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MANUFACTURING TECHNOLOGY RESEARCH

TEXTILES

ADVANCES IN RESEARCH AND APPLICATIONS

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MANUFACTURING TECHNOLOGY RESEARCH

TEXTILES

ADVANCES IN RESEARCH AND APPLICATIONS

BORIS MAHLTIG
EDITOR
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CONTENTS

Preface vii
Chapter 1 Advances in Research and Applications of Smart Textiles 1
Ali Akbar Merati
Chapter 2 Microwave Assisted Preparation for the Realization
of Functional and Colored Textiles 29
Haoqian Miao, Elena Schüll, Kerstin Günther and Boris Mahltig
Chapter 3 Sol-Gel and Layer by Layer Methods for Conferring
Multifunctional Features to Cellulosic Fabrics: An Overview 61
Giulio Malucelli
Chapter 4 Wastewater Treatment from Textile Industry
Using Advanced Oxidation Processes 87
C. López-López, J. Martín-Pascual and J. M. Poyatos
Chapter 5 Green Electrospinning of Nanofiber Mats from Biopolymers
for Medical and Biotechnological Applications 115
Timo Grothe, Nils Grimmelsmann, Sarah Vanessa Homburg
and Andrea Ehrmann
Chapter 6 Achieving Electrical Conductivity in Textiles:
An Overview of Current Techniques 133
Thomas Grethe, Karoline Günther, Thomas Weide
and Anne Schwarz-Pfeiffer
Chapter 7 Metal Coatings Effect Pigments for Textile Functionalization to
Realize UV and IR Protective Applications 151
Jieyang Zhang and Boris Mahltig
vi Contents

Chapter 8 Luminous Textiles for UV-Protection and


Light Effect Applications 167
Egon Dalponte, Boris Mahltig and Christof Breckenfelder
Chapter 9 Double Functional Finishing for Textile Fabrics:
A Combination of UV-Protective and Antimicrobial Properties 183
Ghulam Shabbir, Hajo Haase and Boris Mahltig
Chapter 10 3D-Printing on Textile Fabrics 201
Christoph Döpke, Yasmin Martens, Nils Grimmelsmann
and Andrea Ehrmann
Chapter 11 Simulation Driven Design of Braided Products 217
Yordan Kyosev
Chapter 12 Stab Resistance of Textiles 233
Priscilla Reiners
Chapter 13 Sustainable Knitted Noise Insulation: The Development of
Woolen Interior Elements with Acoustic Absorption Properties 269
Maureen Mann, Sonja Vater, Frank Heimlich and Ellen Bendt
Chapter 14 An Analysis of Impact Behavior of Warp Knit Spacer Fabric for
the Evaluation of Suitability in Protective Applications 285
N. Gokarneshan
Chapter 15 Advances in Research and the Application of Ligno-Cellulosic
Fibres Emphasising Sustainability 319
Sanjoy Debnath
Chapter 16 Textile Applications for German Heath Wool 337
Janina Krolzik, Roland Werner and Ellen Bendt
Chapter 17 Plasma Functionalisation 345
Maike Rabe
Chapter 18 Photochromic Textiles 359
E. Perrin Akçakoca Kumbasar and Seniha Morsunbul
Chapter 19 The Vintage Supply Chain: The Role of Networks 381
Ruth Marciniak and Julie McColl
Index 399
PREFACE

Textile materials or materials made from textiles are probably the most important
materials. Textile materials are present everywhere in daily life in modern times but also
since thousands of years. In this moment you are reading this book and you are also in
tough with textile materials, which are your clothes. In your room you may see now as
well several home textiles as carpet, curtains or as part of your furniture. If you drive
your car or you are passenger in an air plane, you are placed in between many different
types of textiles. Beside these obvious textile applications, there are also many more
hidden applications, which could be e.g., textile filters, textiles in productions processes
or as part of a composite material. Altogether, it can be summarized, modern life without
textiles is not possible.
This book is dedicated to advances in textile research and application. Keep in mind
that the final textile in the final application is the product of many different production
steps, altogether named also as the “textile chain”. Very many different disciplines are
part of this textile chain, as chemistry and machine engineering but also something like
agricultural science, if you think on cotton or wool fiber production. The life of a textile
material starts with the fiber production, this can be a natural process for plant fibers,
animal fibers or regenerated fibers from natural resources. In contrast for chemical fibers,
their origin is the chemical synthesis. After fiber production, the yarn production follows,
which is in the field of spinning technology. From the yarn the textile materials as fabrics
or non-wovens are produced using processes as weaving, knitting, braiding etc. This
textile products are further modified by dyeing and printing processes. Often also
finishing is used to realize special functional properties on a textile product. Finally, the
textile product is realized as cloth, home textile or technical application. Beside technical
aspects, also design and marketing play an important role – especially to realize a
successful product, accepted and bought.
After following this summary, it is obvious that this current book cannot cover every
simple aspect of textile and textile products. Therefore, this book headlines with every
viii Boris Mahltig

chapter a topic in area of textile research and application, which is a topic in actual
scientific research but also in industrial development. According to this statement, this
book is dedicated to readers from universities and industry. For industry, to promote
ideas for new innovative processes and products. For universities, especially for
graduated students, who wish to broaden their expertise in very different fields of the
textile world. Also established scientists could gain a benefit, if they use this book as a
tool to generate new ideas for further research.
Besides all these thoughts on possible benefits, please do not forget one important
benefit for reading or viewing this book: to enjoy it.
In: Textiles: Advances in Research and Applications ISBN: 978-1-53612-855-0
Editor: Boris Mahltig © 2018 Nova Science Publishers, Inc.

Chapter 1

ADVANCES IN RESEARCH AND APPLICATIONS OF


SMART TEXTILES

Ali Akbar Merati*


Advanced Textile Materials and Technology Research Institute and Textile
Engineering Department, Amirkabir University of Technology, Tehran, Iran

ABSTRACT

Smart textiles are a relatively new area of research and convergence of different
science such as materials, physics, chemistry, electrical engineering, wireless & mobile
telecommunication and nanotechnologies. They have many potential applications in the
fields of medical, protection, security communication and textile electronics. Smart
textiles can be defined as textiles that are able to sense and respond to changes in their
environment. The objective of this chapter is to present the latest research results together
with basic concepts related to the main fields of applications of smart textiles. Future
trends in this area of research are presented and issues regarding technology development
and its uptake are highlighted.

Keywords: smart textile, intelligent apparel, chromic materials, conductive materials,


electronic textiles, phase change materials, shape memory materials

INTRODUCTION

Fine and elastic fibers are usually used in order to make comfortable fabric and
clothing. The fibers, yarns and fabrics have to meet special requirements concerning

*
Corresponding Author Email: merati@aut.ac.ir.
2 Ali Akbar Merati

processability and wearability. They should be able to withstand handling that is typical
for textiles, for example weaving, washing and wrinkling, without damaging
functionality. Therefore, fabrics need to have a low mechanical resistance to bending and
shearing so that they can be wearable and comfortable.
The terms “wearable textiles ,” “electronic textiles,” “intelligent textiles” or “smart
textiles,” are associated to those clothing which integrate electronic components, or
which are made of smart materials. Smart textiles are the results of a disciplinary
approach that creates an intersection and overlapping of researches in different fields
such as textile, physics, chemistry, medicine, electronics, polymers, biotechnology,
telecommunications, information technology, microelectronics, wearable computers,
nanotechnology and micro-electromechanical machines. Shape memory materials
(SMMs), phase change materials (PCMs), chromic materials, optic fibers, conductive
materials, mechanical responsive materials, intelligent coating/membranes, micro and
nanomaterials and piezoelectric materials are applied in smart textiles. Smart textiles are
ideal vehicle for carrying active elements that permanently monitor our body and the
environment, providing adequate reaction should something happens.
The objective of this chapter is to present the latest research results together with
basic concepts related to the most advanced researches and applications of smart textile.
This chapter highlights all the main fields of applications of smart textiles such as
healthcare, health monitoring, medicine, personal protective equipment, personal
communication, textile antennas, garments for motion capture and sensors. The scientific
issues and proposed solutions regarding various results, prototypes and achievements
obtained in the best academic and industrial laboratories worldwide are presented in a
rigorous scientific way. At the same time, practical solutions and their realization,
believed to be of the interest to industrial partners, are presented and explained.

SMART TEXTILES

The smart textiles are a new generation of fibers, yarns, fabrics and garments that are
able to sense stimuli and changes in their environments, such as mechanical, thermal,
chemical, electrical, magnetic and optical changes, and then respond to these changes in
predetermined ways (Ibrahim 2014; Tao 2001; Culshaw 1996; Seinivasan & Mcfarland
2001). The objective of smart textile is to absorb a series of active components essentially
without changing its characteristics of flexibility and comfort. Comfort is very important
in textiles. Therefore, adequate actuators are needed that can heat, cool, insulate, ventilate
and regulate moisture to keep the comfort of textiles and prevent the stresses and fatigue.
In order to make a smart textile, firstly, conventional components such as sensors,
devices and wires are being reshaped in order to fit in the textile, ultimately the research
activities trend to manufacture active elements made of fibers, yarns and fabrics
Advances in Research and Applications of Smart Textiles 3

structures. The use of the smart system should not require any additional effort and their
weight should not reduce operation time of the rescue worker. They are multifunctional
textile systems that can be classified into three categories of passive smart textiles, active
smart textiles and very smart textiles (Schwarz et al. 2010).
The smart textiles have some of the capabilities such as biological and chemical
sensing and responding, power and data transmission from wearable computers and
polymeric batteries, transmitting and receiving radio frequency signals and automatic
voice warning systems as to ‘dangers ahead’. These capabilities make the smart textiles
technologies appropriate in military, mountain climbing, sports, healthcare and medicine,
police, and firefighting applications. Smart textiles as a carrier of sensor systems can
measure heart rate, temperature, respiration, gesture and many other body parameters that
can provide useful information on the health status of a person. The smart textiles can
support the rehabilitation process and react adequately on hazardous conditions that may
have been detected. The reaction can consist of warning, prevention or active protection.
After an event has happened, the smart textile is able to analyze the situation and to
provide first aid.
There are many research areas in integrated processes and products of smart textiles
such as wearable electronics and photonics, adaptive and responsive structures,
biomimetic, bioprocessing, tissue engineering and chemical /drug releasing. There are
some areas that the research activities have reached the industrial application. Optical
fibers, shape memory polymers, conductive polymers, textile fabrics and composites
integrated with optical fiber have been already used in smart textiles. Shape memory
polymers have been applied to textiles in fiber, film and foam forms, resulting in a range
of high performance fabrics and garments, especially sea-going garments. Fiber sensors,
which are capable of measuring temperature, strain/stress, gas, biological species and
smell, are typical smart fibers that can be directly applied to textiles. Conductive polymer
-based actuators have achieved very high levels of energy density. Clothing with its own
senses and brain, like shoes and snow coats which are integrated with Global Positioning
System (GPS) and mobile phone technology, can tell the position of the wearer and give
him/her directions. Biological tissues and organs, like ears and noses, can be grown from
textile scaffolds made from biodegradable fibers.

SMART TEXTILES CONTAINING PHASE CHANGE MATERIALS

Phase change materials (PCMs) are thermal storage materials that are used to
regulate temperature fluctuations. The thermal energy transfer occurs when a material
changes from a solid to a liquid or from a liquid to a solid. This is called a change in
4 Ali Akbar Merati

state, or phase. Incorporating microcapsules of PCMs into textile structures improves the
thermal performance of the textiles. PCMs store energy when they change from solid to
liquid and dissipate it when they change back from liquid to solid. It would be most ideal,
if the excess heat a person produces could be stored intermediately somewhere in the
clothing system and then, according to the requirement, activated again when it starts to
get chilly.
The most widespread PCMs in textiles are paraffin-waxes with various phase change
temperatures (melting and crystallization) depending on their carbon numbers. PCMs can
be applied to fibers in a wet-spinning process, incorporated into foam or embedded into a
binder and applied to fabric topically, or contained in a cell structure made of a textile
reinforced synthetic material.
In manufacturing the fiber, the selected PCM microcapsules are added to the liquid
polymer or polymer solution, and the fiber is then expanded according to the
conventional methods such as dry or wet spinning of polymer solutions and extrusion of
polymer melts. Fabrics can be formed from the fibers containing PCMs by conventional
weaving, knitting or nonwoven methods, and these fabrics can be applied to numerous
clothing applications. In this method, the PCMs are permanently locked within the fibers,
the fiber is processed with no need for variations in yarn spinning, fabric knitting or
dyeing and properties of fabrics (drape, softness, tenacity, etc.) are not altered in
comparison with fabrics made from conventional fibers. The microcapsules incorporated
into the fibers in this method have an upper loading limit of 5–10% because the physical
properties of the fibers begin to suffer above that limit, and the finest fiber available is
about 2.2 dtex. Due to the small content of microcapsules within the fibers, their thermal
capacity is rather modest, about 8–12 J/g.
Usually PCM microcapsules are coated on the textile surface. Microcapsules are
embedded in a coating compound such as acrylic, polyurethane and rubber latex, and
applied to a fabric or foam. In lamination of foam containing PCMs onto a fabric, the
selected PCMs microcapsules can be mixed into a polyurethane foam matrix, from which
moisture is removed, and then the foam is laminated on a fabric (Pause 2001). Typical
concentrations of PCMs range from 20% to 60% by weight. Microcapsules should be
added to the liquid polymer or elastomer prior to hardening. After foaming (fabricated
from polyurethane) microcapsules will be embedded within the base material matrix. The
application of the foam pad is particularly recommended because a greater amount of
microcapsules can be introduced into the smart textile. In spite of this, different PCMs
can be used, giving a broader range of regulation temperatures. Additionally,
microcapsules may be anisotropically distributed in the layer of foam. The foam pad with
PCMs may be used as a lining in a variety of clothing such as gloves, shoes, hats and
outerwear. Before incorporation into clothing or footwear the foam pad is usually
attached to the fabric, knitted or woven, by any conventional means such as glue, fusion
or lamination.
Advances in Research and Applications of Smart Textiles 5

The addition of PCMs to fabric-backed foam significantly increases the weight,


thickness, stiffness, flammability, insulation value, and evaporative resistance value of
the material. It is more effective to have one layer of PCM on the outside of a tight-
fitting, two layer ensemble than to have it as the inside layer. This may be because the
PCMs closest to the body did not change phase. PCM protective garments should
improve the comfort of workers as they go through these environmental step changes
(e.g., warm to cold; cold to warm, etc.). For these applications, the PCM transition
temperature should be set so that the PCMs are in the liquid phase when worn in the
warm environment and in the solid phase in the cold environment (Mattila 2006). The
effect of PCMs in clothing on the physiological and subjective thermal responses of
people would probably be maximized if the wearer was repeatedly going through
temperature transients (i.e., going back and forth between a warm and cold environment)
or intermittently touching hot or cold objects with PCM gloves (Mattila 2006).
The PCM microcapsules are also applied to a fibrous substrate using a binder (e.g.,
acrylic resin). All common coating processes such as knife over roll, knife over air,
screen-printing, gravure printing, dip coating may be adapted to apply the PCM
microcapsules dispersed throughout a polymer binder to fabric. The conventional pad–
mangle systems are also suitable for applying PCM microcapsules to fabrics. The
formulation containing PCMs can be applied to the fabric by the direct nozzle spray
technique.
There are many thermal benefits of treating textile structures with PCM
microcapsules such as cooling, insulation and thermo regulating effect. Without PCMs,
the thermal insulation capacity of clothing depends on the thickness and the density of the
fabric (passive insulation). The application of PCMs to a garment provides an active
thermal insulation effect acting in addition to the passive thermal insulation effect of the
garment system. The active thermal insulation of the PCM controls the heat flux through
the garment layers and adjusts the heat flux to the thermal circumstances. The active
thermal insulation effect of the PCM results in a substantial improvement of the
garment’s thermo-physiological wearing comfort (Pause 2000). Intensity and duration of
the PCM’s active thermal insulation effect depend mainly on the heat-storage capacity of
the PCM microcapsules and their applied quantity. In order to ensure a suitable and
durable effect of the PCM, it is necessary to apply proper PCM in sufficient quantity into
the appropriate fibrous substrates of proper design. The PCM quantity applied to the
active wear garment should be matched with the level of activity and the duration of the
garment use. Furthermore, the garment construction needs to be designed in a way which
assists the desired thermo-regulating effect (Mattila 2006). Thinner textiles with higher
densities readily support the cooling process. In contrast, the use of thicker and less dense
textile structures leads to a delayed and therefore more efficient heat release of the PCM.
Further requirements on the textile substrate in a garment application include sufficient
breathability, high flexibility, and mechanical stability.
6 Ali Akbar Merati

In order to determine a sufficient PCM quantity, the heat generated by the human
body has to be taken into account carrying out strenuous activities under which the active
wear garments are worn. The heat generated by the body needs to be entirely released
through the garment layers into the environment. The necessary PCM quantity is
determined according to the amount of heat which should be absorbed by the PCM to
keep the heat balance equalized (Pause 2000). It is mostly not necessary to put PCM in
all parts of the garment. Applying PCM microcapsules to the areas that provide problems
from a thermal standpoint and thermo-regulating the heat flux through these areas is often
enough. It is also advisable to use different PCM microcapsules in different quantities in
distinct garment locations.
There are many applications including apparel, home textiles and technical textiles
for smart textiles containing PCMs (Keyan et al. 2012). PCMs are used in winter and
summer clothing not only in high-quality outerwear and footwear, but also in the
underwear, socks, gloves, helmets and bedding of world-wide brand leaders. Seat covers
in cars and chairs in offices can consist of PCMs. In outdoor apparels, PCMs are being
used in a variety of items such as smart jackets, vests, men’s and women’s hats and
rainwear, outdoor active-wear jackets and jacket lining, golf shoes, trekking shoes, ski
and snowboard gloves, ski boots and earmuffs. In protective garments, PCMs are being
used in a variety of items such as fire fighters protective clothing, bullet proof fabrics,
space suits, sailor suits and so on. The specified roles of PCMs in outdoor and protective
smart textiles are the absorption of body heat surplus, insulation effect caused by heat
emission of the PCM into the fibrous structure and thermo-regulating effect, which
maintains the microclimate temperature nearly constant.
A new generation of military fabrics feature PCMs which are able to absorb, store
and release excess body heat when the body needs it resulting in less sweating and
freezing, while the microclimate of the skin is influenced in a positive way and efficiency
and performance are enhanced. In the medical textiles field, a blanket with PCM can be
useful for gently and controllably reheating hypothermia patients. Also, using PCMs in
bed covers regulates the micro climate of the patient. In domestic textiles, blinds and
curtains with PCMs can be used for reduction of the heat flux through windows. In the
summer months large amounts of heat penetrate the buildings through windows during
the day. At night in the winter months the windows are the main source of thermal loss.
Results of the test carried out by Pause (2000) on curtains containing PCM have indicated
a 30% reduction of the heat flux in comparison to curtains without PCM.
One example of practical application of PCM smart textile is cooling vest (TST
Sweden Ab) (http: //www.tst-sweden.com/en). This is a comfort garment developed to
prevent elevated body temperatures in people who work in hot environments or use
extreme physical exertion. The cooling effect is obtained from the vest’s 21 PCM
elements containing Glauber’s salt which start absorbing heat at a particular temperature
Advances in Research and Applications of Smart Textiles 7

(28ºC). Heat absorption from the body or from an external source continues until the
elements have melted. After use the cooling vest has to be charged at room temperature
(24ºC) or lower. When all the PCMs are solidified the cooling vest is ready for further
use.

SMART TEXTILES CONTAINING SHAPE MEMORY MATERIALS

Shape memory materials (SMMs) are able to ‘remember’ a shape, and return to it
when stimulated, e.g., with temperature, magnetic field, electric field, pH -value and UV
light (Lendlein & Kelch 2002; Okano & Kikuchi 1996; Koshizaki et al. 1992; Srinivasan
& McFarland 2001; Otsuka & Wayman 1998). An example of natural shape memory
textile material is cotton, which expands when exposed to humidity and shrinks back
when dried. Such behavior has not been used for aesthetic effects because the changes,
though physical, are in general not noticeable to the naked eye. The most common types
of such SMMs are shape memory alloys and polymers, but ceramics and gels have also
been developed. Commercialized shape memory products have been based mainly on
metallic shape memory alloys (SMAs), either taking advantage of the shape change due
the shape memory effect or the super-elasticity of the material, the two main phenomena
of SMAs. Shape memory polymers (SMPs) and shape memory gels are developed at a
quick rate.
There are many potential applications of SMPs in industrial components like
automotive parts, building and construction products, intelligent packing, implantable
medical devices, sensors and actuators, etc. SMPs are used in toys, handgrips of spoons,
toothbrushes, razors and kitchen knives, also as an automatic choking device in small-
size engines (Wang et al. 1998). One of the most well-known examples of SMP is a
clothing application, a membrane called Diaplex. The membrane is based on
polyurethane based SMPs developed by Mitsubishi Heavy Industries. Polyurethane is an
example of SMPs which is based on the formation of a physical cross-linked network as a
result of entanglements of the high molecular weight linear chains, and on the transition
from the glassy state to the rubber -elastic state (Mather et al. 2000). Shape memory
polyurethane (SMPU) is a class of polyurethane that is different from conventional
polyurethane in that these have a segmented structure and a wide range of glass transition
temperature (Tg). The long polymer chain s entangle each other and a three-dimensional
network is formed. The polymer network keeps the original shape even above Tg in the
absence of stress. Under stress, the shape is deformed and the deformed shape is fixed
when cooled below Tg. Above the glass transition temperature polymers show rubber-
like behavior. The material softens abruptly above the glass transition temperature Tg. If
the chains are stretched quickly in this state and the material is rapidly cooled down again
8 Ali Akbar Merati

below the glass transition temperature the polynorbornene chains can neither slip over
each other rapidly enough nor become disentangled. It is possible to freeze the induced
elastic stress within the material by rapid cooling. The shape can be changed at will. In
the glassy state the strain is frozen and the deformed shape is fixed. The decrease in the
mobility of polymer chains in the glassy state maintains the transient shape in
polynorbornene. The recovery of the material’s original shape can be observed by heating
again to a temperature above Tg. This occurs because of the thermally induced shape-
memory effect (Mather et al. 2000). The disadvantage of this polymer is the difficulty of
processing because of its high molecular weight (Otsuka & Wayman 1998). Some of the
other SMPs such as polynorbornene, Polyethylene/nylon-6 graft copolymer, styrene -1,
4-butadiene block copolymer, ethylene oxide -ethylene terephthalate block copolymer,
polymethylene-1 and 3-cyclopentane) polyethylene block copolymers are suitable for
textiles applications.
SMPs can be laminated, coated, foamed, and even straight converted to fibers. There
are many possible end uses of these smart textiles. The smart fiber made from the shape
memory polymer can be applied as stents, and screws for holding bones together. Shape
memory polymer coated or laminated materials can improve the thermophysiological
comfort of surgical protective garments, bedding and incontinence products because of
their temperature adaptive moisture management features. Films of SMPs can be
incorporated in multilayer garments, such as those that are often used in the protective
clothing or leisurewear industry. The SMPs reverts within wide range temperatures. This
offers great promise for making clothing with adaptable features. Using a composite film
of SMPs as an inter-liner in multilayer garments, outdoor clothing could have adaptable
thermal insulation and be used as protective clothing. A SMP membrane and insulation
materials keep the wearer warm. Molecular pores open and close in response to air or
water temperature to increase or minimize heat loss. Apparel could be made with shape
memory fiber. Forming the shape at a high temperature provides creases and pleats in
such apparel as slacks and skirts. Other applications include fishing yarn, shirt neck
bands, cap edges, casual clothing and sportswear. Also, using a composite film of SMPs
as an interlining provides apparel systems with variable tog values to protect against a
variety of weather conditions.

SMART TEXTILES CONTAINING CHROMIC MATERIALS

Chromic materials are the general term referring to materials, which their color
changes by the external stimulus. Due to color changing properties, chromic materials are
also called chameleon materials. This color changing phenomenon is caused by the
external stimulus and chromic materials can be classified depending on the external
Advances in Research and Applications of Smart Textiles 9

stimulus of induction. Photochromic, thermochromic, electrochromic, piezochromic,


solvatechromic and carsolchromic are chromic materials that change their color by the
external stimulus of heat, electricity, pressure, liquid and an electron beam, respectively
(Mattila 2006). Most photochromic materials are based on organic materials or silver
particles. Thermochromic materials change color reversibly with changes in temperature.
The liquid crystal type and the molecular rearrangement type are thermochromic systems
in textiles. The thermochromic materials can be made as semi-conductor compounds,
from liquid crystals or metal compounds. The change in color occurs at a pre-determined
temperature, which can be varied. Electrochromic materials are capable of changing their
optical properties (transmittance and/or reflectance) under applied electric potentials. The
variation of the optical properties is caused by insertion /extraction of cations in the
electrochromic film. Piezochromism is the phenomenon where crystals undergo a major
change of color due to mechanical grinding. The induced color reverts to the original
color when the fractured crystals are kept in the dark or dissolved in an organic solvent
(Mattila 2006). Solvatechromism is the phenomenon, where color changes when it makes
contact with a solvent or liquid. Materials that respond to water by changing color are
also called hydrochromic and smart textiles containing this kind of materials can be used,
e.g., for swimsuits.
The majority of applications for chromic materials in the textile sector today are in
the fashion and design area, in leisure and sports garments. In workwear and the
furnishing sector a variety of studies and investigations are in the process by industrial
companies, universities and research centers. Chromic materials are one of the
challenging material groups when thinking about the future textiles. Color changing
textiles are interesting, not only in fashion, where color changing phenomena will exploit
for fun all the rainbow colors, but also in useful and significant applications in soldier and
weapons camouflage, workwear and in technical and medical textiles. The combination
of SMMs and thermochromic coating is an interesting area which produces shape and
color changes of the textile material at the same time Mattila 2006).

SMART TEXTILES CONTAINING OPTICAL FIBERS

Optical fibers are currently being used in textile structures for several different
applications. Optic sensors are attracting considerable interest for a number of sensing
applications (Kersey et al. 1993; Xu et al. 1993). There is great interest in the multiplexed
sensing of smart structures and materials, particularly for the real-time evaluation of
physical measurements (e.g., temperature, strain) at critical monitoring points. One of the
applications of the optical fiber s in textile structures is to create flexible textile-based
displays based on fabrics made of optical fibers and classic yarns (Deflin & Koncar
2002). The screen matrix is created during weaving or knitting, using the texture of the
10 Ali Akbar Merati

fabric. Integrated into the system is a small electronics interface that controls the LEDs
that light groups of fibers. Each group provides light to one given area of the matrix.
Specific control of the LEDs then enables various patterns to be displayed in a static or
dynamic manner. This flexible textile-based displays are very thin size and ultra-
lightweight. This leads one to believe that such a device could quickly enable innovative
solutions for numerous applications. Bending in optical fibers is a major concern since
this causes signal attenuation at bending points. Integrating optical fibers into a woven
perform requires bending because of the crimping that occurs as a result of weave
interlacing. However, standard plastic optical fiber (POF) materials like
polymethylmethacrylate, polycarbonate and polystyrene are rather stiff compared to
standard textile fibers and therefore their integration into textiles usually leads to stiffen
of the woven fabric and the textile touch is getting lost (Markus et al. 2008). Alternative
fibers with appropriate flexibility and transparency are not commercially available yet.

CONDUCTIVE MATERIALS IN SMART TEXTILES

Several conductive materials are in use in smart textiles. Conductive textiles include
electrically conductive fibers, yarns, fabrics and articles made from them (Marchini
1991). Flexible electrically conducting and semi-conducting materials, such as
conductive polymers, conductive fibers, threads, yarns, coatings and ink are playing an
important role in realizing lightweight, wireless and wearable interactive electronic
textiles. Generally, conductive fibers can be divided into two categories such as naturally
conductive fibers and treated conductive fibers. Naturally conductive fibers can be
produced purely from inherently conductive materials, such as metals, metal alloys,
carbon sources, and conjugated polymers (ICPs). Highly conductive flexible textiles can
be prepared by weaving or knitting thin wires of various metals. These textiles have been
developed for higher degrees of conductivity. Metal conductive fibers are very thin
filaments with diameters ranging from 1 to 80 μm produced from conductive metals such
as ferrous alloys, nickel, stainless steel, titanium, aluminum and copper. Since they are
different from polymeric fibers, they may be hard to process and have problems of long
term stability. These highly conductive fibers are expensive, brittle, heavier and lower
processability than most textile fibers.
Treated conductive fibers can be produced by the combination of two or more
materials, such as non-conductive and conductive materials. The conductive textiles can
be produced in various ways, such as by impregnating textile substrates with conductive
carbon or metal powders, patterned printing, and so forth. Conducting polymers, such as
polyacetylene (PA), polypyrrole (PPy), polythiophene (PTh) and polyaniline (PAn), offer
Advances in Research and Applications of Smart Textiles 11

an interesting alternative. Among them, PPy has been widely investigated owing to its
easy preparation, good electrical conductivity, good environmental stability in ambient
conditions and because it poses few toxicological problems (Omastova et al. 1997;
Thiéblemont et al. 1995). PPy is formed by the oxidation of pyrrole or substituted pyrrole
monomers. Electrical conductivity in PPy involves the movement of positively charged
carriers or electrons along polymer chain s and the hopping of these carriers between
chains. The conductivity of PPy can reach the range 102 S cm-1, which is next only to PA
and PAn. With inherently versatile molecular structure s, PPys are capable of undergoing
many interactions. The brittleness of PPy has limited the practical applications of it. The
processability and mechanical properties of PPy can be improved by incorporating some
polymers into PPy (Ruckenstein & Chen 1991; Truong et al. 1998). However, the
incorporation of a sufficient amount of filler generally causes a significant deterioration
in the mechanical properties of the conducting polymer, in order to exceed the
percolation threshold of conductivity (Chen et al. 1991). Another route to overcoming
this deficiency is by coating the conducting polymer on flexible textile substrates to
obtain a smooth and uniform electrically conductive coating that is relatively stable and
can be easily handled (Gregory et al. 1991; Heisey et al. 1993).
The conductive fibers obtained through special treatments such as mixing, blending,
or coating are also known as conductive polymer composites (CPCs), can have a
combination of the electrical and mechanical properties of the treated materials (Markus
et al. 2008). Polymer fibers may be coated with a conductive layer such as PPy, copper or
gold (Tariq 2013). PPy-based composites may overcome the deficiency in the mechanical
properties of PPy, without adversely affecting the excellent physical properties of the
substrate material, such as its mechanical strength and flexibility. The resulting products
combine the usefulness of a textile substrate with electrical properties that are similar to
metals or semi-conductors. Fibers containing metal, metal oxides and metal salts are a
proper alternative for metal fibers. The conductivity will be maintained as long as the
layer is intact and adhering to the fiber. Chemical plating and dispersing metallic particles
at a high concentration in a resin are two general methods of coating fibers with
conductive metals.
Fibers containing conductive carbon are produced with several methods such as
loading the whole fibers with a high concentration of carbon, incorporating the carbon
into the core of a sheath–core bicomponent fiber, incorporating the carbon into one
component of a side–side or modified side–side bicomponent fiber, suffusing the carbon
into the surface of a fiber. Nanoparticles such as carbon nanotubes can be added to the
matrix for achieving conductivity. Conductive fibers can also be produced by coating
fibers with metal salts such as copper sulfide and copper iodide. Metallic coatings
produce highly conductive fibers; however adhesion and corrosion resistance can present
problems. It is also possible to coat and impregnate conventional fibers with conductive
12 Ali Akbar Merati

polymers, or to produce fibers from conductive polymers alone or in blends with other
polymers.
Conductive fibers /yarns can be produced in filament or staple lengths and can be
spun with traditional non-conductive fibers to create yarns that possess varying wearable
electronics and photonics degrees of conductivity. Also, conductive yarns can be created
by wrapping a nonconductive yarn with metallic copper, silver or gold foil and be used to
produce electrically conductive textiles. Conductive threads can be sewn to develop smart
electronic textiles. Through processes such as electrodeless plating, evaporative
deposition, sputtering, coating with a conductive polymer, filling or loading fibers and
carbonizing, a conductive coating can be applied to the surface of fibers, yarns or fabrics.
Electrodeless plating produces a uniform conductive coating, but is expensive.
Evaporative deposition can produce a wide range of thicknesses of coating for varying
levels of conductivity. Sputtering can achieve a uniform coating with good adhesion.
Textiles coated with a conductive polymer, such as PAn and PPy, are more conductive
than metal and have good adhesion, but are difficult to process using conventional
methods. Adding metals to traditional printing inks creates conductive inks that can be
printed onto various substrates to create electrically active patterns. The printed circuits
on flexible textiles result in improvements in durability, reliability and circuit speeds and
in a reduction in the size of the circuits. The printed conductive textiles exhibit good
electrical properties after printing and abrading. The inks withstand bending without
losing conductivity. However, after twenty washing cycles, the conductivity decreases
considerably. Therefore, in order to improve washability, a protective polyurethane layer
is put on top of the printed samples, which resulted in the good conductivity of the
fabrics, even after washing (Kazani et al. 2012). Currently, digital printing technologies
promote the application of conductive inks on textiles.
Electrically conductive textiles make it possible to produce interactive electronic
textiles. There are many applications for conductive textiles. They can be used for
communication and antennas, entertainment, health care, safety, homeland security,
computation, thermal purposes, protective clothing, wearable electronics and fashion.
The application of conductive smart textile in combination with electronic devices is very
widespread. In location and positioning, they can be used for child monitoring, geriatric
monitoring, integrated GPS (global positioning system) monitoring, livestock monitoring,
asset tracking, etc. In infotainment, they can be used for integrated compact disc players,
MP3 players, cell phones and pagers, electronic game panels, digital cameras, and video
devices, etc. In health and biophysical monitoring, they can be used for cardiovascular
monitoring, monitoring the vital signs of infants, monitoring clinical trials, health and
fitness, home healthcare, hospitals, medical centers, assisted-living units, etc. They can
be used for soldiers and personal support of them in the battlefield, space programs,
protective textiles and public safety (firefighting, law enforcement ), automotive,
Advances in Research and Applications of Smart Textiles 13

exposure -indicating textiles, etc. They can be also used to show the environmental
response such as color change, density change, heating change, etc. Fashion, gaming,
residential interior design, commercial interior design and retail sites are other application
of conductive smart textiles.

SMART TEXTILES CONTAINING ELECTRONIC DEVICES AND


CONDUCTIVE MATERIALS

The components of an electronic smart textile that provide several functions are
sensors unit, network unit, processing unit, actuator unit and power unit. On the smart
textile, several of these functions are combined to form services. Providing information,
communication or assistance are possible services. Because mobility is now a
fundamental aspect of many services and devices, these smart textiles can be used for
health applications such as monitoring of vital signs of high-risk patients and elderly
people, therapy and rehabilitee, knowledge applications such as instructions and
navigation and entertainment applications such as audio and video devices (Tao 2005).
In order to form flexible circuit boards, printing of circuit patterns is carried out on
polymeric substrates such as films. Fabric based circuits potentially offer additional
benefits of higher flexibility in bending and shear, higher tear resistance, as well as better
fatigue resistance in case of repeated deformation. Different processes that have been
described in literature for the fabrication of fabric based circuits include embroidery of
conductive threads on fabric substrates, weaving and knitting of conductive threads along
with nonconductive threads, printing or deposition and chemical patterning of conductive
elements on textile substrates.
The insulating fabric could be woven, non-woven, or knitted. The conductive threads
can be embroidered in any shape on the insulating fabric irrespective of the constituent
yarn path in a fabric. One of the primary disadvantages of embroidery as a means of
circuit formation is that it does not allow formation of multi-layered circuits involving
conductive threads traversing through different layers as is possible in the case of woven
circuits.
Conductive threads can be either woven or knitted into a fabric structure along with
nonconductive threads to form an electrical circuit. One of the limitations of using
weaving for making electrical circuits is that the conductive threads have to be placed at
predetermined locations in the warp direction while forming the warp beam or from a
creel during set up of the machine. Different kinds of conductive threads can be supplied
in the weft or filling direction and inserted using the weft selectors provided on a
14 Ali Akbar Merati

weaving machine. Some modifications to the yarn supply system of the machine may be
needed in order to process the conductive threads that are more rigid.
In most conventional weft knitting machines, like a flatbed machine, the conductive
threads can be knitted in the fabric only in one direction, i.e., the course (or cross)
direction. In order to keep the conductive element in a knit structure straight, one can
insert a conductive thread in the course direction such that the conductive thread is
embedded into the fabric between two courses formed from non-conductive threads.
Processes that have been employed to form a patterned conductive path on fabric
surfaces include deposition of polymeric or nonpolymeric conducting materials and
subsequent etching, reducing, or physical removal of the conductive materials from
certain regions. Thus, the conductive material that is not removed forms a patterned
electrical circuit or a region of higher conductivity. The biggest problem associated with
patterning of circuits from thin conductive films (polymeric or metallic) deposited on
fabric substrates is that use of an etching agent for forming a circuit pattern leads to non-
uniform etching, as some of the etching liquid is absorbed by the threads of the
underlying substrate fabric (Locher et al. 2002; DeAngelis et al.1995; Kuhn & Kimbrell
1987; Stoppa & Chiolerio 2014; Spoerry & Co AG, Swiss Shield® 2017; Scheibner et al.
2003; Ohmatex, Smart Textile Technology 2017; Hertleer 2004; Gough 2004; Eleksen
Ltd. 2017; Pressure Profile Systems, Inc. 2017; Swallow and Thompson 2017; Viry et al.
2014). Another problem with deposition of conductive films on fabric substrates is that
bending the fabric may lead to discontinuities in conductivity at certain points.
There are different device attachment methods like raised wire connectors, solders,
snap connectors, and ribbon cable connectors in electronic smart textiles. Soldering
produces reliable electrical connections to conductive threads of an electronic textile
fabric but has the disadvantage of not being compatible with several conductive threads
or materials like stainless steel. Moreover, soldering of electronic devices to threads that
are insulated is a more complex process involving an initial step of removal of insulation
from the conductive threads in the regions where the device attachments are desired and
insulation of the soldered region after completion of the soldering process. The main
advantage of employing snap connectors is the ease of attachment or removal of
electronic devices from these connectors, whereas the main disadvantages are the large
size of the device and the weak physical connection formed between the snap connectors
and the devices. Ribbon cable connectors employ insulation displacement in order to
form an interconnection with insulated conductor elements integrated into the textiles. A
v-shaped contact cuts through the insulation to form a connection to the conductor.
Firstly, the ribbon cable connector is attached to the conductive threads in an e-textile
fabric and subsequent electronic devices and printed circuit boards are attached to the
ribbon cable connector. One of the advantages of employing ribbon cable connectors for
device attachment is the ease of attachment and removal of the electronic devices to form
the electronic textiles.
Advances in Research and Applications of Smart Textiles 15

SOME OTHER RESEARCHES AND APPLICATIONS OF SMART TEXTILES

Each technique of smart textiles manufacturing process shows advantages and


disadvantages and our aim in this section is to highlight some typical commercialized
smart textile products (Stoppa & Chiolerio 2014). Swiss Shield® yarns that are turned
into fabrics ensure an efficient shielding from electromagnet fields. Their degree of
shielding, which can be modulated according to the type of application, ranges to over 80
dB. Swiss Shield® yarn is manufactured in various forms for home textiles, garments,
industrial and military applications (Spoerry & Co AG, Swiss Shield® 2017). Numerous
materials can be employed as the base for Swiss Shield® yarns, from cotton to artificial
fibers such as polyester, polyamide, aramids and the like. The monofilament can be made
from copper, bronze, silver, gold, aluminum, inox or other conductive materials. Swiss
Shield® curtains prevents electro-smog from penetrating into interiors and act as an
invisible protective shield that will effectively and safely protect the room from
unwelcome external electromagnetic radiation (Spoerry & Co AG, Swiss Shield® 2017).
The Textile Research Institute of Thuringia-Vogtland (TITV, Greiz, Germany) has
produced conductive threads by coating a conventional Nylon 66 yarn with sliver layers,
called ELITEX® with a specific conductivity of about 1.2 × 103 S·cm−1 (Scheibner et al.
2003). The Danish company of Ohmatex developed physiological and environmental
sensors for inclusion in medical devices, sportswear, and protective clothing (Ohmatex,
Smart Textile Technology 2017). They produce textile cables, connectors and sensors
using conductive yarns.
A Flemish consortium of universities and companies, among them the textile
department of Ghent University, developed a prototype suit called Intellitex. It is a
biomedical suit meant for the long term monitoring of heart rate and respiration of
children at the hospital. To measure the ECG, a three-electrode configuration is used.
Two measurement electrodes are placed on a horizontal line on the thorax, a third one,
acting as a reference (Right Drive Leg, RDL), is placed on the lower part of the abdomen
(Hertleer et al. 2004). Philips Research Laboratory (Redhill, UK), developed a stretch
sensor integrated into a garment. The stretch sensor, which is produced out of conductive
and elastic yarns knitted together, is based on the fact that the electrical resistance
changes when stretching the sensing material. Thus, it can be used to control the volume
of music or changing the track (Gough 2004). The British company Eleksen Limited,
formerly Electrotextiles (Tunstall, UK), commercializes a soft and flexible textile based
sensory fabric under the tradename ElekTex® Smart Fabric Interfaces. ElekTex is not
composed of wires -instead it is composed of conductive fibers with other traditional
textile fibers. This combination results into a durable, reasonably priced, washable and
even wearable 3D structure (Eleksen Ltd. 2017). Many other researchers in research
institutes and companies have developed various kinds of sensing systems for smart
16 Ali Akbar Merati

textiles (Pressure Profile Systems, Inc. 2017; Swallow, S.; Peta Thompson 2017; Viry et
al. 2014; Benito-Lopez et al. 2009).
Goose Design and product design agency PDD revealed a concept for a new cycling
jacket that combined safety and fashion. The ILLUM jacket was based on emerging
technology including printed electroluminescent ink and printed photovoltaic technology
(solar power), 360 degrees around the body and cut into several ergonomic panels with
red light at the back, white at the front and the photovoltaic source at the shoulders and
top of the back, designed to be discreet once switched off (Consultancy Goose Design,
“PDD Illum Project” 2017).
Thermotron of UNITIKA (Osaka, Japan) is a particular fabric able to converts sun
light into thermal energy while storing heat without wasting it. Inside the Thermotron
there are micro particles of zirconium carbide which allow the fabric to absorb and filter
sunlight. The inner layer of the fabric withholds the heat generated and prevents it from
becoming lost, thus providing a salutary effect on the human body (Unitika LTD. 2017).
This company has developed KOKAGE MAX advanced heat-shielding material that
efficiently shields the wearer against heat, by blocking most visible and ultraviolet rays,
radiation -shielding waterproof sheet and Saracool that efficiently shields the wearer
against the heat-carrying (infrared) rays of the sun, keeping the wearer cool. It has
excellent UV protection and see-through prevention properties.
Researchers at Katholieke Universiteit Leuven and University Malaysia Perlis were
the first to develop a fully textile waveguide antenna using a material inspired unit cell
that is also used in composite right/left-handed transmission lines. The antenna is
compact, robust and can be used for 2.45 and 5.4 GHz dual-band WLAN applications
(50. Yan & Soh 2014). Patria (Halli, Finland) is a company with expertise in textile
antenna design. It develops textile antennas composed by conventional or industrial
fabrics, and typically conductive antenna parts are made out of modern conductive fibers
(Patria. 2017). In this sector TexTrace AG (Frick, Switzerland) provides the
manufacturing line as well as the components for industrial in-house production of woven
RFID labels. Integrate RFID and the label will provide added value from garment
manufacturing through logistics to sales and after-sales management (TEXTRACE
2017).

SMART TEXTILES IN HEALTH

The continuous monitoring of vital signs of some patients and elderly people is an
emerging concept of health care to provide assistance to patients as soon as possible
either online or offline. A wearable smart textile can provide continuous remote
monitoring of the health status of the patient. Wearable sensing systems will allow the
user to perform everyday activities without discomfort. The simultaneous recording of
Advances in Research and Applications of Smart Textiles 17

vital signs would allow parameter extrapolation and inter-signal elaboration, contributing
to the generation of alert messages and synoptic patient tables. In spite of this, a smart
fabric is capable of recording body kinematic maps with no discomfort for several fields
of application such as rehabilitation and sports (Pacelli et al. 2001).
The working principles of these smart textiles and some solutions for integration of
electronic components are summarized to show the current evolution toward ‘embedded
everywhere’. This evolution will only be successful if the devices are unobtrusive and
reliable for the user and for the diagnostician. The advances in electrodes for monitoring,
textile sensors and textile-based actuators are key points in the development of high-
efficiency smart textiles for healthcare, health monitoring and medicine.
The embedding electronics and conductive wires into fabric is a basic requirement to
make smart textiles that can serve as platforms for a wide variety of applications in the
field of healthcare. Wearable body sensor network based on smart textiles for healthcare
applications is a great solution to enable the ubiquitous noninvasive health monitoring in
people's daily life. However, developing smart textile-based body sensor networks poses
significant technical challenges for the sensor and sensor network design such as
miniaturization of sensors, imbedding sensors in noninvasive wearable structures, the
integration of radio integrated circuits and modules with body-worn antennas, energy
consumption minimization, and data security. The challenges of designing electronic
textiles-based body sensor networks, strategies and solutions to overcome the problems
of body sensor network have been the concern of many research activities.

SMART TEXTILES IN PERSONAL PROTECTIVE EQUIPMENT

In the field of the technical textile industry, the personal protective equipment is a
critical and certain requirement that has been an important field of research and
innovation as well as business and technological development for many years. During the
last decade, researches have focused on developing new personal equipment to protect
workers, soldiers, firefighters and other professionals often exposed to hazardous
situations. Getting real-time information about a person's health, his environment, or even
the state of his protective equipment can be essential for both the worker and his team in
order to make relevant strategic decisions. Smart textiles as a new and progressive
technology have many potential applications in personal protective equipment including
fire fighters protective clothing, bullet proof fabrics, space suits, sailor suits and so on.
Smart textiles can be functionalized for their membrane and responsive permeability
properties using SMPs, polymer gels, superabsorbent polymers, grafted polymer brushes,
and polymeric ionic liquids. The smart textiles can be also developed to improve the
thermal comfort using phase change materials that can provide additional heat or
coolness as the need arises. Several types of textile monitoring sensors, including
18 Ali Akbar Merati

electrocardiographic, respiratory, temperature and humidity sensors are used in the


personal protective equipment that can be developed using the smart materials and
technologies. Currently, phase change materials are being used in a variety of outdoor
apparel items such as smart jackets, vests, men’s and women’s hats and rainwear, outdoor
active-wear jackets and jacket lining, golf shoes, trekking shoes, ski and snowboard
gloves, boots, earmuffs and protective garments. In protective garments, the absorption of
body heat surplus, insulation effect caused by heat emission of the PCM into the fibrous
structure and thermo-regulating effect, which maintains the microclimate temperature
nearly constant, are the specified functions of PCM contained smart textile. Phase change
materials are used both in winter and summer clothing. PCM is used not only in high-
quality outerwear and footwear, but also in the underwear, socks, gloves, helmets and
bedding of world-wide brand leaders. Seat covers in cars and chairs in offices can consist
of phase change materials.
The addition of PCMs to fabric-backed foam significantly increases the weight,
thickness, stiffness, flammability, insulation value, and evaporative resistance value of
the material. It is more effective to have one layer of PCM on the outside of a tight-
fitting, two layer ensemble than to have it as the inside layer. This may be because the
PCMs closest to the body did not change phase. PCM protective garments should
improve the comfort of workers as they go through these environmental step changes
(e.g., warm to cold; cold to warm, etc.). For these applications, the PCM transition
temperature should be set so that the PCMs are in the liquid phase when worn in the
warm environment and in the solid phase in the cold environment (Mattila 2006). The
effect of phase change materials in clothing on the physiological and subjective thermal
responses of people would probably be maximized if the wearer was repeatedly going
through temperature transients (i.e., going back and forth between a warm and cold
environment) or intermittently touching hot or cold objects with PCM gloves (Mattila
2006).
One example of practical application of PCM smart textile is cooling vest (TST
Sweden Ab) (http: //www.tst-sweden.com/en 2017). This is a comfort garment developed
to prevent elevated body temperatures in people who work in hot environments or use
extreme physical exertion. The cooling effect is obtained from the vest’s 21 PCM
elements containing Glauber’s salt which start absorbing heat at a particular temperature
(28ºC). Heat absorption from the body or from an external source continues until the
elements have melted. After use the cooling vest has to be charged at room temperature
(24ºC) or lower. When all the PCMs are solidified the cooling vest is ready for further
use (http: //www.tst-sweden.com/en 2017).
A new generation of military fabrics feature PCMs which are able to absorb, store
and release excess body heat when the body needs it resulting in less sweating and
freezing, while the microclimate of the skin is influenced in a positive way and efficiency
and performance are enhanced. In the medical textiles field, a blanket with PCM can be
Advances in Research and Applications of Smart Textiles 19

useful for gently and controllably reheating hypothermia patients. Also, using PCMs in
bed covers regulates the micro climate of the patient. In domestic textiles, blinds and
curtains with PCMs can be used for reduction of the heat flux through windows. In the
summer months large amounts of heat penetrate the buildings through windows during
the day. At night in the winter months the windows are the main source of thermal loss.
Results of the test carried out by Pause (2001) on curtains containing PCM have indicated
a 30% reduction of the heat flux in comparison to curtains without PCM.

SMART TEXTILES IN PERSONAL COMMUNICATION


AND TEXTILE ANTENNAS

A wearable smart textile system basically comprises of sensors to detect body or


environmental parameters, a data processing unit to collect and process the obtained data,
an actuator that can give a signal to the wearer, an energy supply that enables working of
the entire system, interconnections that connect the different components and a
communication device that establishes a wireless communication link with a nearby base
station components that provide several functions (Ajmera et al. 2013). In recent years,
communication, as a part of smart textile functionalities, has attracted the attentions of
many researchers (Hertleer et al. 2008; Roh et al. 2010a; Roh et al. 2010b; Salvado et al.
2012; Sanjari et al. 2013; Sanjari et al. 2014; Sanjari et al. 2015a; Sanjari et al. 2015b). In
practice, communication refers to the transfer of information.
Generally, the majority of electronic components can be placed on the inner clothing
layer. These components include various sensors, a central processing unit (CPU) and
communication equipment. Analogous to ordinary clothing, additional heating to
warming up a person in cold weather conditions is also associated with this layer. Thus,
the inner layer is the most suitable for batteries and power regulating equipment, which
are also sources of heat. The outer clothing layer contains sensors needed for
environment measurements, positioning equipment that may need information from the
surrounding environment and numerous other accessories. The physical surroundings of
smart clothing components measure the environment and the virtual environment
accessed by communication technologies. Soldier and weapons camouflage is possible by
using chromic materials in outer layer of smart textiles.
The data transfer requirements in the smart textiles can be divided into internal and
external. The internal transfer services are divided into local health and security related
measurements. Many of the services require or result in external communications
between the smart textile and its environment. For communication between the different
components of smart textile applications, both wired and wireless technologies are
applicable. An applied solution for data transferring is often a compromise based on
20 Ali Akbar Merati

application requirements, operational environment, available and known technologies,


and costs.
Wired data transfer is in many cases a practical and straightforward solution. Thin
wires routed through fabric are an inexpensive and high capacity medium for information
and power transfer. The embedded wires inside clothing do not affect its appearance.
However, wires form inflexible parts of clothing and the detaching and reconnecting of
wires decrease user comfort and the usability of clothes (Rantanen et al. 2002). The cold
winter environment especially stiffens the plastic shielding of wires. In hard usage and in
cold weather conditions, cracking of wires also becomes a problem (Rantanen et al.
2002). The connections between the electrical components placed on different pieces of
clothing are another challenge when using wires. During dressing and undressing,
connectors should be attached or detached, decreasing the usability of clothing.
Connectors should be easily fastened, resulting in the need for new connector
technologies.
A potential alternative to plastic shielded wires is to replace them with electrically
conductive fibers. Conductive yarns twisted from fibers form a soft cable that naturally
integrates in the clothing’s structure keeping the system as clothing-like as possible. Fiber
yarns provide durable, flexible and washable solutions. Also lightweight optical fiber s
are used in wearable applications, but their function has been closer to a sensor than a
communication medium (Lind et al. 1997; Lee & Kwon 2001). The problem of
conductive fibers is due to the reliable connections of them. Ordinary wires can be
soldered directly to printed circuit boards, but the structure of the fiber yarn is more
sensitive to breakage near the solder connections. Protection materials that prevent the
movement of the fiber yarn at the interface of the hard solder and the soft yarn must be
used. Optical fibers are commonly used for health monitoring applications and also for
lighting purposes (http: //www.lumitex.com/medical -devices 2013).
In practice, the transfer of information in the smart textiles can be divided into two
categories: short-range and long-range. There are different ways to accomplish the first
goal. Using electrical wires in cloths, infrared or Bluetooth technology and personal area
network (PAN) are some of these techniques. From practical point of view, embedded
wiring is very tiresome to the wearer. Low-power wireless connections provide increased
flexibility and also enable external data transfer within the personal space. The infrared
rays to work effectively require a direct connection between sender and receiver. But this
would be difficult or impractical for devices located inside cloths. In view of the fact that
this area needs further development and despite some disadvantages, it seems that
Bluetooth technology and personal area network are more practical ways to connect two
wearable devices on the user (Tao 2005). Also, existing and emerging WLAN and
WPAN types of technologies are general purpose solutions for the external
communications, providing both high speed transfer and low costs. For wider area
Advances in Research and Applications of Smart Textiles 21

communications and full mobility, cellular data networks are currently the only practical
possibility.
The antennas are used for long-range and wireless communication. Antennas are
designed and produced in various types and geometries. Wire antennas (dipole antennas,
loop antennas, helix antennas), aperture antennas, microstrip antennas, reflector antennas,
lens antennas and array antennas are the most common types (Huang & Boyle 2008). It
seems, just planar antennas are suitable for wearable applications. In this case, there is a
possibility to hide the antenna beside of the fact that the comfort of wearer is not affected.
Lamination, embroidery, weaving, knitting and printing are some of the methods
which have been used to produce wearable antennas (Roh et al. 2010; Salonen et al.
2004; Scarpello et al. 2012; Yao & Qiu 2009). Roh et al. (2010) designed and produced
wearable textile antenna with multiple resonance frequencies for the reception of FM
signals using conductive embroidery of metal composite embroidery yarn on a polyester
woven substrate. They attached the antenna to a jacket and evaluated the effect of body
conditions on the antenna performance. Salonen et al. (2004) prepared a wearable WLAN
antenna that made out of knitted copper and aracon fabric. They concluded that to avoid
the adverse effects of discontinuities, the fabrics should be densely knitted. In addition,
they acknowledged that the printed circuit board antennas can be replaced by textile
antennas in wearable systems. Wearable antenna technology has evolved from simple
rectangular patches to more complex topologies and uses a range of textile materials.
Because of their planar structure, microstrip antennas, also called patch antennas, are
more appropriate for embedding into garments. A microstrip antenna in its simplest
configuration consists of a radiating patch on one side of a dielectric substrate (Electrical
permittivity ≤ 10), which has a ground plane on the other side. The patch can assume
virtually any shape, but conventional geometrical shapes are generally used to simplify
analysis and performance prediction. These antennas have several advantages compared
to conventional microwave antennas and therefore many applications over the broad
frequency ranging from 100 MHz to 50 GHz are expected (Bahl & Bhartia 1980). Unlike
rigid antennas, wearable antennas endure a lot of stresses during using or washing. These
stresses can deform the shape of the antenna and consequently change its characteristics.
Due to these challenges, some attempts have been made to provide an understanding of
such situations (Sanjari et al. 2013; Sanjari et al. 2014; Sanjari et al. 2015a; Sanjari et al.
2015b; Bai & Langley 2012; Kaija et al. 2010). Compressive stresses are one of the most
probable stresses which would be applied to the cloths. In compression, because the
thickness of substrate is much greater than the thickness of patch and ground, changing to
its dimensions is more effective on the shift of resonance frequency. Sanjari et al. (2013;
2014; 2015a; 2015b) simulated the deformation caused in antenna under uniaxial
compressive loading and compared the results of simulation with those of experimental
measurements. They showed a good agreement between analytical predictions, full wave
simulations and experimental measurements.
22 Ali Akbar Merati

SMART TEXTILES FUTURE TRENDS

Smart textiles and wearable electronic devices are becoming increasingly popular, as
they offer significant enhancements to human comfort, health and well-being. The
development of high value-added products such as smart fabrics, wearable consumer and
medical devices and protective textiles has increased rapidly in the last decade. Recent
advances in stimuli-responsive surfaces and interfaces, sensors and actuators, flexible
electronics, nanocoatings and conductive nanomaterials has led to the development of a
new generation of smart and adaptive electronic fibers, yarns and fabrics for application
in E-textiles.
However, improvements in sensors, flexible & printable electronics and energy
devices are necessary for wider implementation and nanomaterials and/or their hybrids
are enabling the next phase convergence of textiles, electronics and informatics. They are
opening the way for the integration of electronic components and sensors (e.g., heat and
humidity) in high strength, flexible and electrically conductive textiles with energy
storage and harvesting capabilities, biological functions, antimicrobial properties, and
many other new functionalities.
Nanomaterials such as carbon nanotubes, silver nanowires graphene and other 2D
materials are viewed as key materials for the development of wearable electronics for
implementation in healthcare and fitness monitoring, electronic devices incorporated into
clothing and smart skin’applications (printed graphene-based sensors integrated with
other 2D materials for physiological monitoring). These materials are naturally more
suitable for integration with flexible, soft or glass substrates owing to their two
dimensional nature and can potentially offer the electronic performance needed for low-
power systems.
Unlike today’s ‘wearables’ tomorrow’s devices will be fully integrated into the
garment through the use of conductive fibers, multilayer 3D printed structures and two
dimensional materials such as graphene. Products utilizing two dimensional materials
such as graphene inks will be integral to the growth of wearables. The market for
wearables using smart textiles is forecast to grow rapidly in next decades. Smart textiles
in the military and protection sector accounted for the largest share in comparison with
other segments such as sports & fitness, medical & healthcare, home & lifestyle,
industrial and fashion. Major drivers identified for the growth of the smart textiles market
are growing trends in the wearable electronics market, increasing popularity of
sophisticated gadgets with advanced functions, miniaturization of electronic components,
and rapid growth of low-cost smart wireless sensor networks. There are also some factors
such as high costs, lack of exhaustive standards and regulations which are restraining the
growth of the market.
Advances in Research and Applications of Smart Textiles 23

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In: Textiles: Advances in Research and Applications ISBN: 978-1-53612-855-0
Editor: Boris Mahltig © 2018 Nova Science Publishers, Inc.

Chapter 2

MICROWAVE ASSISTED PREPARATION


FOR THE REALIZATION OF
FUNCTIONAL AND COLORED TEXTILES

Haoqian Miao1, Elena Schüll1, Kerstin Günther2


and Boris Mahltig1,*
1
Niederrhein University of Applied Sciences, Faculty of Textile and Clothing
Technology, Mönchengladbach, Germany
2
Gesellschaft zur Förderung von Medizin-, Bio- und Umwelttechnologien,
GMBU e.V., Jena, Germany

ABSTRACT

The use and the benefit of microwave radiation in textile functionalization processes
are presented. First, a general introduction into microwave radiation and microwave
assisted processes is given. Following, examples from textile dyeing and UV-protective
textiles are given. In the end, the realization of photoactive textiles by microwave
assistant application of titania is presented. Altogether, it is shown, that microwave
assisted procedures can be a powerful tool in textile functionalization methods.

Keywords: photoactivity, textile finishing, microwave synthesis, titania, dyeing, UV


protection, fluorescence, polyester fiber

*
Corresponding Author Email: Boris.mahltig@hs-niederrhein.de.
30 Haoqian Miao, Elena Schüll, Kerstin Günther et al.

INTRODUCTION

Microwave heating is a process which directly introduces the thermal energy into the
heated components and the reactive compounds. For this, microwave heating is in many
cases more effective compared to conventional heating processes (Nimtz 1980).
Especially in high pressure processes the microwave assisted heating can be used to reach
short heating durations and altogether short process duration s, which can be 10 times
faster compared to the analogous processes driven by conventional heating (Gedye et al.
1986; Strauss & Trainor 1995). In chemical synthesis, especially for pharma production,
microwave assisted processes are well established (Larhed & Hallberg 2001; Wathey et
al. 2002). However in the textile world, microwave processes are seldom used for
synthesis purposes. Mainly reported is the use of microwave radiation for textile drying
and fixation after dyeing or finishing is performed (Burkinshaw & Marshall 1986;
Dittrich et al. 1992; Steiner 1982). For this, the aim of the actually presented chapter is to
give the reader a short introduction into microwave technique and introduce him to some
textile functionalization processes realized under microwave assistance.
At first presented is a dyeing process adapted from a conventional HT-process to a
microwave process. Here the microwave is used as heating source in the hydrothermal
process. Following this procedure, UV protective textiles and fluorescence textiles are
realized. Second, the preparation of photoactive textiles by microwave assistance is
presented. Textiles are suitable substrates to carry photocatalytic materials as titania,
which can be introduced for different applications as waste water cleaning or cleaning of
air pollution (Böttcher et al. 2010; Dastjerdi & Montazer 2010). Two approaches are
actually presented to produce photoactive titania onto textile surfaces. One approach aims
on the microwave treatment of a titania containing finishing agent, which is a sol-gel
based system. Photoactive properties can be introduced by this microwave treatment. The
other microwave approach uses the microwave application as part of a hydrothermal
process to promote the condensation of the titaniumorganic precursor to photoactive
titania directly on the textile surface (Mahltig & Miao 2017). The water and acid
necessary for the condensation are transported via the gas phase to the textile. The
photoactivity is determined by different methods especially by decomposition of organic
dye (AcidOrange7) under illumination with UV-light. The determined photocatalytic
effect of the realized titania materials strongly depends on the applied process
temperature but also on process duration. Significant photoactivity is reached even after
short processes of only 5 minutes and moderate process temperatures around 120°C.
Altogether, microwave assisted processes can be as well used for textile
functionalization, especially if short process duration s and mild thermal conditions are
requested.
Microwave Assisted Preparation for the Realization … 31

MICROWAVE TECHNOLOGY

Microwaves belong to electromagnetic radiation. In the electromagnetic spectrum


microwave radiation is placed between infrared light and radiowaves. Microwaves
contain frequencies between 300MHz to 300 GHz – related to a wavelength in the range
of 100 cm to 0.1 cm (Pozar 2009, Gerthsen & Vogel 1993). Microwave spectroscopy
investigates the rotation of molecules with electromagnetic radiation of frequency in the
range of 1 to 1000 GHz, which is related to wavelengths from submillimeter to
centimeter range (Göpel & Ziegler 1994). Microwaves have a lot of utilizations in human
society. In the communication field, microwave technology is extensively used for
telecommunications. In the navigation field, Global Navigation Satellite Systems (GNSS)
including the Chinese Beidou, the American Global Positioning System (GPS) and the
Russian GLONASS broadcast navigational signals in various bands between about 1.2
GHz and 1.6 GHz. Further, radar uses microwave radiation to detect the range, speed,
and other characteristics of moving objects (Bartlett 2013).
Another important application common in daily life is the heating by microwave
radiation (Chandrasekaran et al. 2013).
Microwave heating is not only used in domestic but also industry, e.g., for drying
purposes, in analytics, in production processes and in environmental applications
(Sengutta 2009; Krämer 1999; Menendez et al. 2010; Jones et al. 2002).
Microwave radiation is used during textile dyeing processes for drying and fixation
purposes after application of the dye bath to the textile fabric. The process duration can
be significantly decreased by use of microwave technique (Breuer 2011).
The company Mageba (Bernkastel-Kues, Germany) offers microwave devices
especially for the drying of ropes and narrow fabrics. The advantages of this drying
method – especially in comparison to infrared drying – are the higher penetration depth
of the microwave radiation into the rope and the selected heating of the water compared
to the surrounding fiber material. By this, the drying is possible at lower temperatures,
which is especially advantageous if the fiber material is thermal sensitive. Mainly the
application for pre-drying processes is mentioned in patent literature (Stang 2004; Stang
2011).
The laboratorial and industrial used microwave technology can be applied for acid
digestion, ashing, food testing, drying, curing, compositional analysis, solvent extraction,
and synthesis etc. (Camel 2000; Du et al. 2011; Kappe 2004; Kappe et al. 2012;
Nakashima et al. 1988). Microwave synthesis can be as well used for fast preparation of
silver nanoparticles (Mahltig et al. 2009).
When the microwave is applying to heat up material, it is often named differently,
e.g., dielectric heating, electronic heating, RF heating, high-frequency heating. These
names all describe the same phenomenon that a high-frequency alternating electric field
32 Haoqian Miao, Elena Schüll, Kerstin Günther et al.

or microwave electromagnetic radiation heats a dielectric material (Mingos & Baghurst


1991; Osepchuk 1984).
Molecular rotation and vibration occur in materials containing polar molecules
having an electrical dipole moment, with the consequence that they will align themselves
with an electromagnetic field (Fowler & Raynes 1981; Herman & Wallis 2016). If the
field is oscillating, as it is in an electromagnetic wave or in a rapidly oscillating electric
field, these molecules rotate continuously aligning with it (Bishop 1990). As the field
alternates, the molecules reverse direction. Rotating molecules push, pull, and collide
with other molecules (through electrical forces), distributing the energy to adjacent
molecules and atoms in the material. Once distributed, this energy appears as heat
(Lidström et al. 2001).
Temperature is related to the average kinetic energy of the atoms or molecules in a
material, so stimulating the molecules in this way increases the temperature of the
material. Thus, dipole rotation is a mechanism by which energy in the form of
electromagnetic radiation can raise the temperature of an object (Zlotorzynski 1995;
Göpel & Ziegler 1994).
Microwave chemistry is the science of applying microwave radiation to chemical
reactions (Kappe et al. 2012). Microwaves act as high-frequency electric field s and will
generally heat any material containing mobile electric charge s, such as polar molecules
in a solvent or conducting ions. Semiconducting and conducting samples heat when ions
or electrons within them form an electric current and energy is lost due to the electrical
resistance of the material (Nimtz 1980).

Glass vessel
Metal vessel (transparent to
(conducts heat) microwave energy)

Sample- Sample-
solvent solvent
mixt ure mixt ure
Microwave

Temperature
gradient

Conventional Microwave
heating process heating process

Figure 1. Conventional heating process (left) versus microwave heating process (right). The
temperature gradient in the conventional heating process leads to unevenness of the temperature of
heated sample. The microwave can easily penetrates the whole sample, which heats the sample in
different parts of the vessel evenly.
Microwave Assisted Preparation for the Realization … 33

Angle Clamp

IntelliVent
Pressure
Control System
(10ml vessel)

Pressure Control
System for
80ml vessel
Number Keys

Hot Keys Screen

Figure 2. Laboratory microwave system used for the actual presented investigations and experiments
The Discover System (Model series: 908010, manufacturer: CEM co.).

Conventional heating usually involves the use of a furnace or bath, which heats the
walls of the reactor by convection or conduction. The core of the sample takes much
longer to achieve the required temperature (Kappe 2004).
One of the advantages of microwave heating is the elimination of wall effects.
Microwave heating is able to heat the target compounds without heating the entire
furnace or bath, which save time and energy. Figure 1 shows a comparison between
conventional heating process and microwave heating process. It is also able to heat
sufficiently this objects throughout their volume. Microwave frequencies penetrate
conductive materials, including semi-solid substances like meat and living tissue, to a
distance defined by the skin effect. The penetration essentially stops where all the
penetrating microwave energy has been converted to heat in the substances. In most
laboratory situations, the penetration is considered to be thorough (Kappe 2004).
In literature also an intensive and controversial discussion is presented on the fact
that microwave radiation can influence chemical reactions with other effects additional to
heating (Kuhnert 2002). These other effects are also named “non-thermal effect” and the
background of them could be a direct interaction of the microwave radiation with the
reacting molecule. This image is similar to photoreactions started and driven by
illumination with UV-light (Wöhrle et al. 2012). However, after intensive investigations
34 Haoqian Miao, Elena Schüll, Kerstin Günther et al.

Kuhnert stated that there are obviously no so-called non-thermal effect in microwave-
assisted reactions in organic chemistry (Kuhnert 2002).
Different compounds covert microwave radiation to heat by different amounts. This
selectivity allows some parts of the object being heated to heat more quickly or more
slowly than others. A heterogeneous system, which comprising different substances or
different phases may be heated anisotropic. As a result, it can be expected that the
microwave field energy will be converted to heat by different amounts in different parts
of the system (Schepps & Foster 1980). This inhomogeneous energy dissipation means
that molecular scaled hot spots appear. At those hot spots, the microwave field in the
heating device is especially strong, so the thermal effect at those spots is high (Coleman
1991; Kriegsmann 1997). To avoid so-called hot-spot effects, often sample vessels are
rotated or moved in other way in the microwave field. Also the stirring of liquid
components and solutions can help to avoid hot-spot effects.
Another issue or better limitation of microwave heating is related to the volume of
the heating subject. If the subject is too thick, the microwave radiation is not able to heat
it up regularly (Metaxas & Meredith 1983).
For the current investigations presented in the next sub-sections of this chapter a so-
called focused microwave system available from CEM was used (see Figure 2). This
device is presented in further literature more in detail (Sengutta & Meier 2002; Theis &
Ritter 2011). The aim of this focused microwave device is to gain the same microwave
intensity and by this the same heating rate in the whole volume of the reaction vessel. By
this application the formation of hot-spots is avoided. The used reaction vessel has a total
volume of 80 mL and can be filled up safely with 50 mL of liquid. This vessel can be also
closed and be used as a kind of autoclave system with high pressure of several bar as
process pressure for the microwave assisted synthesis. Such focused microwave heating
system is also reported for the synthesis of azo disperse dyes, which can be afterwards
used for dyeing of polyester (El-Apasery 2008).

OPTICAL MODIFICATION OF TEXTILES BY MICROWAVE PROCESSES

In year 2010, Ahmed & El-Shishtawy describe in a review several new technologies
for dyeing of textile materials (Ahmed & El-Shistawy 2010). One technology they
present is the use of microwave processes. They give examples for natural fibers like
cotton or flax dyed with reactive dyes but also for polyester fabrics dyed with dispersed
dyes.
Reactive dyes are applied on cotton fabrics in a conventional dyeing process and a
dyeing process used microwave irradiation for heating the dye bath. The process
temperature was set to 60°C and the duration of microwave heating is in between 5 to 20
minutes. Compared to the conventional dyeing process the reported microwave driven
Microwave Assisted Preparation for the Realization … 35

process saves 75% of dyeing time. The fastness according to washing, light, abrasion and
perspiration is tested as well (Haggag et al. 2014). The same research group reports also
on the dyeing of polyester with disperse dyes under microwave heating. The experiments
are done with a household microwave and the maximum process temperature for water
based systems is 100°C, because of the boiling point of water. To gain under this
experimental condition s adequate dyeing results on polyester fabric, a carrier system is
added to the dye bath (Haggag et al. 1995). Instead of using a carrier system, also the
addition of organic solvents is reported to enable polyester dyeing with microwave
heating at process temperatures of 100°C or less (Kim et al. 2003).
For application of disperse dyes onto polyester fabrics, the use of microwave is also
reported as a tool for the fixation (Chiao-Cheng & Reagan 1983). In this case the
dispersed dyes are applied by a padding procedure and afterwards analogously to a
thermosol process the microwave method is applied. Important for this application
process is the presence of boiled water (Chiao-Cheng & Reagan 1983).
The microwave for aftertreatment of pad-dyed fabrics is as well demonstrated for
natural fabrics. The fixation of reactive dyes on wool with short fixation times of 30 to 60
seconds by microwave application is possible (Delaney & Seltzer 1972). For such
processes an adequate heating chamber with steam is constructed (Kawaguchi 1979).
Compared to these previous experiments and investigations, the actual study is
related to polyester fabrics functionalized in a HT-process driven by a focused
microwave-system -CEM Focused MicrowaveTM Synthesis System (Model Discover).
This microwave device can work as closed system under high pressure and with process
temperatures above 100°C. No addition of carriers or organic solvent is needed to gain
adequate results of dyeing. The dyeing is performed with two conventional red dyes
(Dianix Deep Red SF and Dianix Red AC-E01 from DyStar) and one fluorescent dye
(Bemacron Luminous Red SEL-4B from CHT – Tübingen, Germany) (Bone et al. 2007;
Avinc et al. 2009; Ferus-Comelo 2009). Further a functionalization is done by application
of a disperse UV-absorber (Tanuval UVL from Tanatex, Netherlands ).
The application of the microwave process is compared with a conventional dyeing
process with same dyes and functional agents. This conventional dyeing is performed in a
dyeing machine – Mathis Polycolor HT. The process temperature is set to 130°C and the
process duration (including heating up and cooling down) is set to 1 h 50min.
For the microwave process a discover system from CEM is used. This microwave
apparatus is equipped with a dyeing vessel of maximal 80mL capacity, which is filled
with 50mL of dyeing bath. The polyester fabric is placed together with a stirrer into this
vessel as depicted in Figure 3.
For the microwave process, temperatures from 80°C to 140°C are set with a process
duration of 5 or 15 minutes. For heating and cooling 10 minutes or less are set. The
microwave operates at the maximum power of 250 Watts. The process pressure is
determined by the process temperature in the autoclave system. An example for relation
36 Haoqian Miao, Elena Schüll, Kerstin Günther et al.

of process temperature and pressure as function of process duration is presented in Figure


4. In this example the process temperature is set to 140°C.

Figure 3. Schematic drawing of placement of textile sample in the reaction vessel containing the dye
bath.

After all performed dyeing procedures, the treated polyester fabric is cleaned by a
reductive process. This reductive cleaning is done to remove the not fixed dye, which is
present on the fiber surface after treatment with the dye bath. For alkaline cleaning, the
chemical Cyclanon Clear ARC in a concentration of 2g/L is applied at 70°C for 10
minutes. A final rinsing is performed with acetic acid. To determine the color properties
of dyed fabrics, a photospectrometer from Shimadzu is used. By this photospectrometer,
the diffuse reflection of light with wavelength in the range of 220nm to 800 is measured.
This device also enables the calculation of the Kubelka-Munk function (KM-function)
from the measured refection spectra.

160 5
run time hold time temperature
140
process temperature [C°]

4
process pressure [bar]

120

3
100

80
2

60 pressure

1
40

20 0
0 3 6 9 12 15 18
process duration [minutes]

Figure 4. Process temperature and pressure for a dyeing process at 140°C driven in the microwave
system. The hold time is set to 15 minutes.
Microwave Assisted Preparation for the Realization … 37

COLOR APPLICATION

For color application under microwave assistance the dyeing of polyester fabrics with
two disperse dyes - Dianix Deep Red SF and Dianix Red AC-E01 – is used. These dyes
are applied in microwave process with different process temperatures and two different
durations 5 minutes or 15 minutes. For comparison, both dyes are applied with a
conventional process driven at 130°C. The reflection spectra of resulted dyed polyester
fabrics with Dianix Deep Red SF are presented in Figure 5. It is clearly seen, that the
color intensity increased with increasing process temperature and process duration of the
microwave process. A color intensity similar to the one reached with the conventional
process is gained for microwave processes driven at 130°C or 140°C. These temperatures
are obviously needed to open up the polyester structure, so the disperse dye can diffuse
into the polymer matrix of the polyester fiber. By a first view on the reflection spectra, it
is clear, with the microwave assisted HT-process the dyeing procedure can be speed up to
few minutes, while the conventional procedure takes more than one hour. Nevertheless,
the minimum at the reflection spectra are of high intensity and closed together. For this, it
is quite difficult to distinguish the color intensity of these strong colored samples. To
enable here a further data evaluation, the minimum of reflection spectra and the
maximum of the related KM-function are recorded as function of process temperatures
(Figures 6 and 7).

60
microwave 60
microwave
process time 5min
process time 15 min
50
50

40
reflection [%]

40
reflection [%]

30 30
80°C
80°C
20 20
100°C
100°C
10 10
130°C conventional conventional
0
140°C 130°C; 140°C
0
300 400 500 600 700 800 300 400 500 600 700 800
wavelength [nm] wavelength [nm]

Figure 5. Spectra of diffuse reflection of polyester fabrics after dyeing with Dianix Deep Red SF. The
dyeing is performed under microwave assistance at different process temperatures of 80°C, 100°C,
130°C or 140°C. The process duration is 5 or 15 minutes. For comparison a reflection spectrum of a
conventional dyed polyester fabric is shown.

It is clearly seen in Figure 6, the reflection minimum which is an indicator for the
color intensity is decreasing as function of the used process temperature of the
microwave process. With the highest microwave process temperatures applied for 15
38 Haoqian Miao, Elena Schüll, Kerstin Günther et al.

minutes similar or even stronger color intensities compared to the conventional process
can be reached. With the dye Dianix Red AC-E01 even with 100°C process temperature
in the microwave same color intensities as with the conventional dyeing are reached. For
this it should be stated, that not only the process parameter but also the type of dye has a
certain influence on the dyeing result. Probably, there are dyes with higher affinity for
microwave processes.

18
dye1; 5min
dye1; 15min
16 dye2; 5min
reflection at minimum [%]

dye2; 15min
14

12

10

6
dye 2; conventional
4
dye 1; conventional
2

0
80 90 100 110 120 130 140
process temperature [°C]

Figure 6. The reflection at minimum for dyed polyester fabrics is given as function of process
temperature of microwave process. The dyeing is performed with Dianix Deep Red SF (dye1) and
Dianix Red AC-E01 (dye2). The duration of microwave process is set to 5 or 15minutes. The reflection
values gained after analogous conventional dyeing are shown as reference lines.

24

20
KM-function [a.u.]

16
dye 1; conventional

12 dye 2; conventional

dye1; 5min
4 dye1; 15min
dye2; 5min
dye2; 15min
0
80 90 100 110 120 130 140
process temperature [°C]

Figure 7. The maximum of KM-function for dyed polyester fabrics is given as function of process
temperature of microwave process. The dyeing is performed with Dianix Deep Red SF (dye1) and
Dianix Red AC-E01 (dye2). The duration of microwave process is set to 5 or 15 minutes. The KM-
function values gained after analogous conventional dyeing are shown as reference lines.
Microwave Assisted Preparation for the Realization … 39

The evaluation of the KM-function leads to similar results (Figure 7). Here the color
intensity is directly correlated to the KM-function which increases with the process
temperature of the microwave process. By evaluation of the KM-values, the differences
between the both process duration s of 5 minutes or 15 minutes are more obviously. It is
clearly seen, that with the longer duration of 15 minutes the reached coloration is of
significant higher intensity. However, even this longer microwave process duration is
significant shorter (less than 20%) compared to the analogous conventional dyeing
process.

FLUORESCENCE EFFECTS AND UV-PROTECTION

For application of fluorescent effects on polyester, the red fluorescent dye Bemacron
Red SEL-4B is applied in the focused microwave device. The process temperature for the
microwave process is set to 80°C to 140°C and the process duration is 5 or 15 minutes.
For comparison an analogous HT-dyeing process at 130°C is performed. The dyeing
results are investigated by measurements of diffuse reflection as depicted in Figure 8. It is
clearly seen, that the microwave process driven at the same process temperature as the
conventional process – 130°C – leads to a deeper coloration of the treated polyester
fabric. By using the microwave process more intensive coloration with significantly
shorter process duration can be realized. However, lower process temperatures with
100°C or even 80°C are not suitable for microwave processes to compete with the
conventional dyeing process.
A systematic evaluation of the dyeing results is given in Figure 9. In Figure 9 the
reflection value at the minimum is depicted as function of microwave process
temperature and shown for both process duration s. In this dyeing process, the process
temperature is the most important parameter influencing the intensity of resulted
coloration. Compared to the temperature, the influence of process duration is low.
Especially for the lower investigated temperatures of 80°C and 100°C, there is no
significant difference, if the microwave process is driven at 5 or 15 minutes. Probably a
certain process temperature is needed to support a certain penetration of the dye into the
fiber by diffusion process es. If this temperature is not reached, even a longer process
duration cannot increase the dye up-take significantly. With the process temperatures of
130°C or 140°C, a longer process duration leads to a stronger coloration of the dyed
polyester. In these cases of higher temperature, obviously an in principal possible
diffusion is further promoted, so more dye molecules penetrate the polyester fiber during
the microwave dyeing process.
40 Haoqian Miao, Elena Schüll, Kerstin Günther et al.

60
microwave
process time 15min
50

80°C
40

reflection [%]
100°C

30
conventional
20 130°C

140°C
10

0
300 400 500 600 700 800
wavelength [nm]

Figure 8. Spectra of diffuse reflection of polyester fabrics after dyeing with the fluorescent dye
Bemacron Luminous Red SEL-4B. The dyeing is performed under microwave assistance at different
process temperatures of 80°C, 100°C, 130°C or 140°C. The process duration is 15 minutes. For
comparison a reflection spectrum of a conventional dyed polyester fabric is shown.

The amount of up-taken fluorescent dye is directly correlated with the strength of
fluorescent effect of the treated polyester fabric. Altogether it can be concluded, that by
microwave assisted process the polyester fabric can reach stronger fluorescent effect after
significantly shorter process duration s.

45
5min
40 15min

35
reflection at minimum [%]

30

25
concentional dyeing process
20

15

10

0
80 90 100 110 120 130 140
process temperature [°C]

Figure 9. The reflection at minimum for dyed polyester fabrics is given as function of process
temperature of microwave process. The dyeing is performed with fluorescent dye Bemacron Luminous
Red SEL-4B. The duration of microwave process is set to 5 or 15minutes. The reflection value gained
after analogous conventional dyeing is shown as reference line.
Microwave Assisted Preparation for the Realization … 41

The effectivity for UV-protection of a textile can be effectively determined by the


spectrum of diffusive transmission for UV-light with a wavelength of 250 nm to 400 nm.
A lower transmission value indicates obviously a better UV-protection (Mahltig et al.
2005). By application of an UV absorber, this transmission can be decreased to small
values. However, some UV-absorbers are also optimized, that they do not absorb visible
light (Rauch et al. 2004). In fact a complete transparence for visible light and a zero
transmission for UV light is an ideal demand, which cannot be fulfilled by real
compounds. For this, uncolored UV-absorbers do not lead to a perfect UV-protection for
UV-light just below 400 nm.
In microwave assisted processes, UV-absorbers can be applied on polyester fabrics to
realize an UV-protective textile. These textile are evaluated by transmission
spectroscopy, as shown in Figure 10.

35 35
untreated reference untreated reference
conventional process, 130°C conventional process, 130°C
30 30
5min microwave, 80°C 5min microwave, 100°C
15min microwave, 80°C 15min microwave, 100°C
25 25
transmission [%]
transmission [%]

20 20

15 15

10 10

5 5

0 0
250 300 350 400 450 250 300 350 400 450

wavelength [nm] wavelength [nm]

35
untreated reference
conventional process, 130°C
30
5min microwave, 140°C
15min microwave, 140°C
25
transmission [%]

20

15

10

0
250 300 350 400 450
wavelength [nm]

Figure 10. Spectra of diffusive transmission of polyester fabrics treated with the UV-absorber Tanuval
under different process conditions in the microwave system. The microwave process is driven at 80°C,
100°C or 140°C for a duration of 5 or 15 minutes. As reference, a spectrum of untreated polyester
fabric and a spectrum of a polyester fabric treated with Tanuval in a conventional process is given.
42 Haoqian Miao, Elena Schüll, Kerstin Günther et al.

It is clearly seen, that the application of the UV-absorber significantly decreases the
transmission of the polyester fabric in the range of 300 to 400 nm. Below 300 nm, the
transmission is even for the untreated polyester near 0%, probable because the aromatic
structure of the polyester fabric. Also the addition of titaniumdioxide as white pigment
could be a reason for a certain decrease in transmission for the untreated polyester
reference (Bajaj et al. 2000). The application of the UV-absorber in a conventional HT-
process is done at 130°C process temperature and improve significantly the UV-
protective properties of the polyester fabric (Figure 10). In Figure 10 this conventional
functionalized fabric is compared to microwave-assisted functionalization at different
process temperatures 80°C, 100°C and 140°C. The composition of the dye bath is the
same for all applications. The microwave process driven at 80°C leads to a significant
decrease in transmission for UV-light but the results are not that good as reached after the
conventional application. Competitive or even better compared to the conventional
application is the microwave application at 100°C and 140°C. The better results are
realized for a microwave treatment of longer duration of 15 minutes. Probable even under
microwave assisted application a certain amount of time is needed to force the UV
absorber molecules into the matrix of the polyester fiber. Nevertheless, the microwave
process with 100°C process temperature is competitive to the conventional process at
130°C. This is a significant lower process temperature, applied for only 25% of the
conventional needed process duration. For further development it is here especially
important, that with a process temperature of 100°C there is no need for using an
autoclave system. For this, it can be a first starting point for a microwave driven non HT-
functionalization of polyester textiles.

PHOTOCATALYTIC MODIFICATION

To give an appropriate introduction, following first a short general introduction into


photoactivity is given. After this, in a further sub-section different microwave assisted
preparations are presented, which enable the preparation of photoactive titania onto
textile substrates. Beside preparation also some rough analytic characterizations of these
titania materials are described.

Short Introduction to Photoactivity

In general, photocatalysis can be defined as the acceleration of a photoreaction in the


presence of a catalyst. This so-called photocatalyst is only working in the presence of
Microwave Assisted Preparation for the Realization … 43

light and absorbs light during the process. It can be included in the category of advanced
oxidation process, if the photocatalyst is working for an oxidation process (Andreozzi et
al. 1999).
Often mentioned is the heterogeneous photocatalysis. In heterogeneous catalysis, the
catalyst is placed in a different phase from the reactants. Mostly the catalyst is a solid
material while the reactant is present in a liquid or in the gas phase, e.g., a dye stuff in
waste water or a toxic gas in air. Heterogeneous photocatalysis is a discipline which
includes a large variety of reactions, as e.g., mild or total oxidations, dehydrogenation,
hydrogen transfer, water detoxification and gaseous pollution removal.
Most common heterogeneous photocatalysts are semiconductors from transition
metal oxides. Unlike the metals which have a continuum of electronic states,
semiconductors possess a void energy region where no energy levels are available to
promote recombination of an electron and hole produced by photoactivation in the solid.
The void region, which extends from the top of the filled valence band to the bottom of
the vacant conduction band, is as well called band gap (Linsebigler et al. 1995).
This band gap is also named as energy gap. It is an energy range in a solid where no
electron state s can exist (Brus 1986). The term "band gap" refers to the energy difference
between the top of the valence band and the bottom of the conduction band (Hybertsen &
Louie 1986). Electrons are able to jump from one band to another. However, in order for
an electron to jump from a valence band to a conduction band, it requires a specific
minimum amount of energy for the transition. The required energy differs with different
semiconductor materials. Electrons can gain enough energy to jump to the conduction
band by absorbing either a phonon (heat) or a photon (light ). A semiconductor will not
absorb photons of energy less than the band gap. The energy of the formed electron-hole
pair produced by a photon is equal to the bandgap energy (Weller 1967).
One of the most prominent photocatalysts is titaniumdioxide TiO2 in the anatase
crystalline type. This titania photocatalyst is activated by UV-light of 390 nm or lower
wavelength according to the band gap of anatase (Mahltig et al. 2007).
Altogether, mainly three different crystalline forms of the TiO2 exist which are rutile,
anatase and brookite (Willmes 1993). Additionally titania can also occur in amorphous
state. The band gap of the titania modifications are different, for anatase it is 3.20eV
related to a wavelength of light 385nm, while for rutile it is 3.05eV related to a
wavelength of 420nm (Veronovski et al. 2010). The photooxidation process with oxygen
is well catalyzed by anatase but not with pure rutile, brookite or amorphous titania. For
this, the preparation of photoactive titania materials is usually aimed on anatase and its
modifications. One prominent commercially available photoactive titania product is P25
supplied by Degussa /Evonik. P25 is a combination of anatase and rutile (Ohno et al.
2001). The modification of photoactive properties of TiO2 by doping with noble metals,
44 Haoqian Miao, Elena Schüll, Kerstin Günther et al.

copper, iron, silica or manganese is as well possible and intensively reported (Sakthivel et
al. 2004; Xin et al. 2005; Zaleska 2008; Mahltig & Textor 2008; Mahltig et al. 2011;
Mahltig et al. 2013; Schmidt et al. 2012).
In the environmental protection area, TiO2 has been a popular subject since years.
Researchers mainly focus on the purification of air and water (Böttcher et al. 2010). Tan
et al. reported the conversion of carbon dioxide into gaseous hydrocarbons using titanium
dioxide in the presence of water (Tan et al. 2006). A form of solar water disinfection,
which is supported titaniumdioxide photocatalyst was described by McCullagh
(McCullagh et al. 2007).
According to the supposed mechanism of photocatalysis by titanium dioxide, during
the process, free radicals are generated. Because of the generation of the highly reactive
free radicals, titaniumdioxide is used by many researchers as an effective antibacterial
material (Brunet et al. 2009; Nonami et al. 2004). In the textile field, photoactive titania
is used to realize self-cleaning and antimicrobial textiles (Bozzi et al. 2005; Meilert et al.
2005; Mahltig & Textor 2008; Mahltig & Haufe 2010)

Modification of Titania Sol-Gel Systems

The idea of this approach is to prepare a sol-gel coating agent for textile
functionalisation based on photoactive titania materials. Most titania sol-gel coating
agents are containing amorphous titania nanoparticles forming after application onto
textile substrate an as well amorphous titania coating. Such amorphous titania materials
usually contain no or only small photoactive properties (Mahltig et al. 2007). If these
coatings are thermal treated at temperatures of >400°C, a transfer to photoactive anatase
type is possible. However, such temperatures would destruct the textile substrates. For
this, several years ago a solvothermal treatment for titania sol-gel systems was developed
which leads to formation of anatase already in the coating solution. By this, anatase
coatings on textile materials without thermal aftertreatment are possible (Mahltig et al.
2007).
According to this approach following two sol-gel systems are treated in a microwave-
assisted solvothermal process. The sol system A is prepared as following: 56ml TTIP
(TiO2 precursor -titaniumtetraisopropoxide) is added into 26ml ethanol. This solution is
stirred for 30min. 13ml ethanol, 3ml distilled water and 1.2ml nitric acid are mixed under
strong stirring and are added dropwise to the first TTIP containing solution. The dropping
process has an approximately duration of two hours. This sol-gel system A is treated in
the microwave at process temperatures between 100°C to 150°C, while the process
pressures are between 11 bar to 18 bar (see Figure 11). The prepared samples exhibit a
strong yellow coloration, with increasing color intensity as function of process
temperature in the microwave process (Figure 12).
Microwave Assisted Preparation for the Realization … 45

Figure 11. Development of process temperature and process pressure at a microwave-assisted reaction
with set for control temperature. The shown curves are recorded for a microwave process with a
duration of 5 minutes driven with the titania sol-system A.

Figure 12. Microwave radiated titania sol system A. The sols which are treated under different
temperature control points are distinguished by the boxes.
46 Haoqian Miao, Elena Schüll, Kerstin Günther et al.

Figure 13. The titania sol-gel system B is more cloudy when the temperature control point of
microwave radiation was higher, samples prepared with process temperatures of 120°C and 140°C are
totally opaque.

The second investigated titania sol-system B is developed according to the synthesis


route of photoactive TiO2 from Qi et al. in Hong Kong Polytechnic University (Qi et al.
2007).
The preparation of sol-system B is described as following. 50 ml distilled water and
2.14ml HNO3 are added into an Erlenmeyer flask, respectively. Afterwards 20ml acetic
acid are added into the same container. Dilution of the as-prepared solution is performed
with distilled water to 200ml. The resulting solution is further named as Solution A.
Afterwards, a dropping funnel is employed to add TTIP into Solution A. When the first
few drops go into the acidic solution, some white precipitate occurres immediately. After
24h stirring, all white precipitate is gone. The final solution is transparent with a hint of
light yellow. These solutions are treated in the microwave device at process temperatures
of 100°C to 140°C for 5 minutes. After this process the solutions turn into a white non-
transparent appearance. This whiteness is increasing as function of process temperature
(see Figure 13).

Vapor Phase Deposition of Photoactive Titania

As a different preparation method for photoactive titania onto textile surfaces a kind
of vapor phase deposition process is developed (Mahltig & Miao 2017). Roughly spoken,
the textile substrate is impregnated by the TTIP precursor for the titania formation. The
water and acid necessary for the hydrolysis and condensation of TTIP to titania are
applied from vapor phase by using a microwave driven evaporation process. The
developed process is described following in detail.
Microwave Assisted Preparation for the Realization … 47

Figure 14. Preparation of the textile substrate with the TTIP-precursor for titania synthesis in the
microwave-assisted process. Two microscope slides are used to squeeze the extra TTIP precursor out of
textile sample.

The scoured cotton fabric is cut into small size. The width of the fabric sample is
equal to the width of microscope slide used as sample holder, but the length of fabric
sample is one-third shorter than that (Figure 14). During the microwave radiation process,
the TTIP treated fabric sample is laying on the slide, and the slide is standing inside an
80ml thick-wall vessel. The vessel will contain a small amount of solution (acid and
water) in the bottom. In order to prevent the TTIP coated fabric sample from touching the
surface of the solution, the samples need to be shorter than the slide (the bottom of the
slide is immersing in the solution). The specific dimensions of the fabric samples are
55mm × 25mm. The preparation route of the used acidic solution is according to a report
of Qi et al.. In their reported synthesis route, the TTIP is added dropwise into the acidic
solution (Qi et al. 2007). However, the actual method is slightly different, because
actually the precursor come in contact to the acidic solution by evaporation of the acidic
medium.
An acidic solution is prepared in the following route. Firstly, 30ml distilled water are
added into a 150ml Erlenmeyer flask. Secondly, 10ml acetic acid and 1.07ml nitric acid
(65%) are added into the same Erlenmeyer flask. Finally, the Erlenmeyer flask is filled
until the volume of the acidic solution is 100ml.
The microwave instrument which is employed here is a Discover System from CEM
Corporation. The model 908010 (shown in Figure 2) is designed to enhance the ability to
perform chemical reactions under controlled conditions on a laboratory scale.
The impregnation of the textile fabric is done with diluted TTIP, in ratio of 1: 1 and
1: 3 with ethanol. For this impregnation, the fabric sample is laid on the microscope slide
(supporting slide) evenly and 1ml precursor (dilute TTIP) is dropped slowly onto the
fabric. Another microscope slide (covering slide) is laid on the top of the fabric and a
200g weight is set on the covering slide to press extra precursor out (Figure 14). The
48 Haoqian Miao, Elena Schüll, Kerstin Günther et al.

squeezing process takes only 5 seconds. A forceps is used to transfer this impregnated
fabric with the supporting slide into the 80ml thick wall vessel which containing 3ml as-
prepared acidic solution (Figure 15).
After placing the vessel into the cavity of the microwave device and closing the
pressure detector, the microwave radiation process is ready to run. During the microwave
radiation process, the fabric sample stays on the slide by the adhesive force of wet
precursor. The fabric sample has no contact to the acidic solution which is on the bottom
of the vessel. However, when the temperature of the system increased, the water
molecules and acid molecules gain the thermal energy and escape from the liquid phase
and enter the gas phase (evaporation ). When the acidic solution gasifies, the gas
molecules have the opportunity to react with the precursor on the surface of fabric and
microscope slide. The hydrolysis of TTIP and condensation polymerization to TiO2 occur
consequently. The proper temperature can transform the amorphous TiO2 into crystalline
states. Different temperatures lead to TiO2 of different crystalline forms (Chen et al.
1995). In most studies, it needs 400°C to transform the TiO2 to anatase phase, and 500°C
to transform to rutile phase (Wang & Ying 1999).
When the microwave system is cooled down, the fabric sample is transferred to an
oven for drying with the supporting slide. The drying process upholds 5min under the
temperature of 80°C.
The process temperatures in the used microwave process are varied in the range
between 60°C to 140°C with a 20°C interval. The hold time (process duration) is pre-set
with 5min and 15min.

Figure 15. Transfer of textile sample with TTIP precursor into the 80ml reaction vessel of the
microwave device.
Microwave Assisted Preparation for the Realization … 49

Figure 16. SEM-image of titania coating on fabric. The preparation is done with 1: 3 diluted TTIP and
microwave process temperature of 120°C applied for 15 minutes.

Figure 17. SEM-image of titania coating on fabric. The preparation is done with 1: 1 diluted TTIP and
microwave process temperature of 120°C applied for 15 minutes.

After the complete process is finished, the formed TiO2 can be clearly detected by
scanning electron microscope SEM onto the textile substrates (see Figures 16 and 17). In
case of the more diluted TTIP application (ratio 1: 3), only nanoscaled TiO2 particles are
detected. These nanoparticles appear as single particles and as aggregates (Figure 16). In
50 Haoqian Miao, Elena Schüll, Kerstin Günther et al.

case of the higher concentrated TTIP application (ratio 1: 1), beside the nanoparticles also
larger structures are deposited. These structures contain also cracks, what is a hint to a
high coating thickness (Mahltig & Textor 2008; Krüger et al. 2006). The formed
structures are almost similar independent from process temperature and duration of the
microwave synthesis. Probably with the application of the more concentrated precursor to
much TiO2 is applied leading to the formation of larger broken structures onto the textile
substrate.
The photoactivity of the prepared titania coated fabrics is determined by
photodecomposition of the organic dye Acid Orange 7, as described in detail previously
(Mahltig et al. 2007; Böttcher et al. 2010). By photooxidation, the organic dye AO7 is
decomposed under illumination with UV-light and the comparison to the dye
concentration under dark conditions indicates the photoactivity of the present titania
material. The concentration of AO7 after the testing is determined in the dye solution
(Figures 18 and 19) and on the textile fabrics (Figures 20 and 21).
In this test the decomposition of the dye AO7 is the parameter for the intensity of the
photocatalytic effect. This dye is solved into the testing solution with a starting
concentration of 0.1 mmol/L. After contact with the titania coated textile samples with
and without illumination with UV-light, the dye concentration in the solution is
determined again by using a UV/Vis spectrometer. A stronger decrease in dye
concentration is probable related to a stronger photocatalytic effect. However, it has to be
kept in mind that beside the photodecomposition also other processes can lead to a
decrease of the dye concentration. One main additional process is the absorption of the
dye molecules by the textile fabric and by the titania coating on it. For this, it is
absolutely necessary to determine the remaining dye concentration with similar test
condition but without UV light (under dark conditions). The reference measurements are
absolutely necessary, to rank the intensity of the photocatalytic effect in an adequate way.
The Figures 18 and 19, summarize both measurements under UV light exposition and
the reference measurements under dark conditions. The remaining dye concentration is
here given as function of temperature in the microwave process. It is obvious, with
increasing microwave process temperature the concentration of the dye is decreased.
Under exposition to UV-light this decrease is stronger, so the photocatalytic activity is
clearly determined and this activity is stronger with higher process temperatures.
Nevertheless, it is also determined that the dye concentration is significantly
decreased even if the reference testing is performed without UV-light. For this, a strong
up-take of the dye AO7 by the textile and the titania material can be stated. Interesting is
that this absorption increases with increased microwave process temperatures. Probably
under these conditions titania material is formed which has a higher absorptive capacity.
Such a higher absorption capacity is also an important aspect for the photocatalytic
effectivity, because for the photocatalytic effect a certain contact of titania material to the
Microwave Assisted Preparation for the Realization … 51

dye molecules is necessary and an absorbed dye has of course an intensive contact to the
absorbing titania matrix.

1:3 ratio application


0,05
5min preparation, dark test
5min preparation, UV test

concentration of AO7 [mmol/l]


0,04 15 min preparation, dark test
15 min preparation, UV test

0,03

0,02

0,01

0,00
60 80 100 120 140

process temperature [C°]

Figure 18. Testing on photoactivity with the dye acid orange 7 AO7. Presented is the remaining dye
concentration after contact with the titania coated fabric under different conditions; dark test – 19 hours
placement of the fabric in the dye solution without light, UV test – 6 hours placement under a UV-
lamp. The results are depicted as function of microwave process temperature. The sample preparation is
done with 1: 3 diluted TTIP and microwave applied for 5 minutes or 15 minutes.

1:1 ratio application


0,05
5min preparation, dark test
5min preparation, UV test
concentration of AO7 [mmol/l]

0,04 15 min preparation, dark test


15 min preparation, UV test

0,03

0,02

0,01

0,00
60 80 100 120 140
process temperature [C°]

Figure 19. Testing on photoactivity with the dye acid orange 7 AO7. Presented is the remaining dye
concentration after contact with the titania coated fabric under different conditions; dark test – 19 hours
placement of the fabric in the dye solution without light, UV test – 6 hours placement under a UV-
lamp. The results are depicted as function of microwave process temperature. The sample preparation is
done with 1: 1 diluted TTIP and microwave applied for 5 minutes or 15 minutes.
52 Haoqian Miao, Elena Schüll, Kerstin Günther et al.

25% dilution; 5 minutes process duration


100
60°C; dark test
60°C; UV test
120°C; dark test
80

diffusive reflection [%]


120°C; UV test

60

40 r
120°C

20 r
60°C

0
486nm
300 400 500 600 700 800
wavelength [nm]

Figure 20. Testing of photoactivity with the dye acid orange 7 AO7. Presented are the reflection spectra
of textile samples after placement in the dye solution under different conditions; dark test – 19 hours
placement of the fabric in the dye solution without light, UV test – 6 hours placement under a UV-
lamp. The results are depicted for microwave process temperature 60°C and 120°C. The sample
preparation is done with 1: 3 diluted TTIP and microwave applied for 5 minutes.

80 ratio 1:3; 5 min


difference reflection r at 486nm [%]

ratio 1:3; 15 min


70
ratio 1:1; 5 min
60
ratio 1:1; 15 min

50

40

30

20

10

0
60 80 100 120 140
microwave process temperature [C°]

Figure 21. Texting of photoactivity with the dye acid orange 7 AO7. Presented is the difference of
reflection of textile samples at wavelength of 480nm between textiles tested with UV test and
placement under dark conditions. The results are depicted as function of microwave process
temperature. The sample preparation is done with 1: 1 or 1: 3 diluted TTIP and microwave applied for 5
minutes or 15 minutes.

Beside the color intensity of the aqueous dye solution, also the color properties of the
textile samples are determined after the testing procedure with the dye AO7. This color
properties are determined by UV/Vis spectroscopy in arrangement of diffusive reflection.
Related spectra are presented in Figure 20. The absorption maxima of the dye AO7 is at
Microwave Assisted Preparation for the Realization … 53

486nm, this is related to the minimum determined in the reflection spectra. A deeper
reflection minimum is correlated to a stronger dye up-take by the textile. The spectra of
samples tested in the UV-test and under dark conditions are compared and the difference
in the reflection minima after both tests is directly related to the photoactivity of the
prepared samples. A stronger difference indicates that the once absorbed dye is
decomposed afterwards by a photocatalytic process driven under UV-light exposure.
To generate here an overview, for all prepared samples this difference in reflection at
the minimum is correlated to the microwave process temperature used for sample
preparation (Figure 21). This difference in reflection is clearly increasing as function of
the process temperature in microwave process. Until a process temperature of 100°C, the
reflection difference increases moderately to values around 20%. The change of process
temperature to 120°C changes the situation drastically to values of 50% or more. For this,
it could be concluded that for preparation of strong photocatalytic titania materials by the
currently presented process a minimum process temperature of 120°C is necessary. For
samples prepared with temperatures till 120°C, the other parameters as concentration of
the precursor or the process duration are of less importance. However, with the highest
investigated process temperature of 140°C, the other parameters show their influence.
Highest activity – with values of 80% - is reached with a process temperature of 140°C,
the lower process duration of 5 minutes and the smaller precursor concentration. In fact,
this is a surprising result. Of course, a higher process temperature can be easily correlated
to a stronger formation of photocatalytic species. However, a lower concentration of
precursor should be also related to less photoactive titania on the textile surface. An
explanation can be done with the structure of the formed titania on the fiber surface, as
shown in Figures 16 and 17. With smaller precursor concentration, the formed titania
occurs mainly in nanoparticular form. These nanoparticles are supposed to have a high
specific surface area and by this a larger area to get in contact with the dye in the
solution. A higher contact area can cause higher reaction rate s for the photocatalytic
process. An analogous argument can be used to explain the difference resulting from the
process duration. Probable with longer process duration the formed titania nanoparticles
can sinter together and by this the photoactive surface area is decreased. By this
argumentation the higher photoactivity gained after the shorter process time of 5 minutes
can be explained.
Altogether it can be concluded that the microwave-assisted process can be a powerful
tool to realize photoactive functionalized textiles. The most important process parameter
is the temperature but also moderate temperatures of 120°C or 140°C are sufficient to
reach significant photoactivity. These temperatures are in the range of temperatures used
in conventional textile processes. Other parameters as concentration of functional
component or process duration influences the gained photoactivity probable mainly by
surface effects. Such surface effects are difficult to predict, so for improvement of the
microwave process usually intensive experimental optimizations are required.
54 Haoqian Miao, Elena Schüll, Kerstin Günther et al.

SUMMARY AND CONCLUSION

Microwave assisted processes are versatile tools for dyeing, finishing and
functionalization of textile materials. Conventional functionalization can be realized
significantly faster and at lower process temperature. This is demonstrated in the current
overview on the examples of dyeing, fluorescent textiles and UV protective textiles.
Beside the improvement of conventional procedures, also new materials can be
realized by using microwave assistance in textile functionalization, this is shown actually
by the preparation of different photocatalytic materials on textile substrates.
However it should be mentioned additionally, that the use of microwave applications
for different textile treatments is known since decades but only few applications have
found the way towards commercially products and procedures. One probable reason for
this are technical challenges in case of an up-scale in microwave devices. The actual
shown experiments are performed with a focused microwave system giving nearly the
same intensity of the microwave field in the whole reaction vessel. In case of up-scaling
the shown procedures, a certain experimental effort has to be done especially to gain
homogenous distributed properties on the whole treated textile fabric.
Nevertheless, the chances of microwave assisted textile functionalization are
obviously clear and a future development of new techniques and materials in this field
can be expected.

ACKNOWLEDGMENTS

The authors would like to thank Thomas Heistermann and Thomas Grethe for many
helpful discussions and experimental help. For funding of the electronmicroscopic
equipment the authors acknowledge very gratefully the program FH-Basis of the German
federal country North-Rhine-Westphalia NRW. Experimental work presented is part of
the Master thesis performed by Haoqian Miao (2016, Hochschule Niederrhein) and the
Bachelor thesis performed by Elena Schüll (2017, Hochschule Niederrhein). All product
and company names mentioned in this chapter may be trademarks of their respective
owners, also without labeling.

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Editor: Boris Mahltig © 2018 Nova Science Publishers, Inc.

Chapter 3

SOL-GEL AND LAYER BY LAYER METHODS


FOR CONFERRING MULTIFUNCTIONAL FEATURES
TO CELLULOSIC FABRICS: AN OVERVIEW

Giulio Malucelli*
Politecnico di Torino,
Dept. Applied Science and Technology, Alessandria, Italy

ABSTRACT

This chapter reviews the recent advances referring to the use of sol-gel processes and
layer by layer (LbL) treatments for conferring multifunctional features to cellulosic
fabrics (namely cotton and its blends with polyester). In fact, these two approaches,
which have been successfully applied to both natural and synthetic fabrics, can be very
effective in providing multifunctional features to the treated fabrics, through the
formation of a ceramic - or polymer /ceramic-based coating (sol-gel ), or by depositing a
nanostructured organic, inorganic or hybrid assembly (LbL) on the underlying textile.
Sol-gel is based on a bottom-up strategy, starting from different precursors, from which it
is possible to tailor the final surface properties of the treated substrates. Conversely, layer
by layer exploits a top-down method, suitable for the design of very thin and, at the same
time, performing coatings. Among the different possible multifunctional properties the
two approaches can provide to cellulosic substrates, fire retardancy, hydrophobicity, wear
resistance and anti-bacterial activity seem to fulfill the up-to-date needs coming from
either the academic or industrial world. This work thoroughly reviews the development
and the recent advances achieved by the two strategies, showing their potentialities and
current limit ations.

*
Corresponding Author Email: giulio.malucelli@polito.it.
62 Giulio Malucelli

Keywords: cotton fabrics, sol-gel processes, layer by layer deposition, surface


engineering, multifunctional surfaces, fire retardancy, wear resistance, hydrophobic
surfaces, anti-bacterial coatings

INTRODUCTION

The recent technological innovations and the need for new functions are engendering
an increasing demand for novel materials and structures, which could remarkably widen
their application fields and markets. In this context, the possibility of conferring
multifunctional features to different substrates through the exploitation of surface
engineering strategies seems to open new pathways towards the development of smart
tailored materials, for which the surface structure and composition represent the key point
affecting their overall behavior. It is worthy to note that this approach, irrespective of the
achieved performances, is very often easy to perform on different types of materials
(plastics, metals, ceramics, composites …), does not imply changes of the bulk properties
and is cost -effective (Martin 2011).
Fabric substrates have emerged from the materials that deserve surface treatment s, as
they can be quite easily modified exploiting the standard finishing treatments already
employed in the industrial processes; furthermore, the surface engineering methods
selected for modification of the fabrics can provide interesting multifunctional features,
making these substrates suitable for wider uses.
In this context, sol-gel and the layer by layer (LbL) techniques are the main strategies
that received great attention over the last 10 to 15 years. The former represents an
example of soft-chemistry bottom-up strategy based on hydrolysis and condensation
reactions taking place in a liquid medium that contains selected alkoxy precursors. This
technique, schematized in Figure 1, allows synthesizing new multifunctional materials
with a high degree of homogeneity at molecular level and with exceptional physico-
chemical features. As clearly reported in the open scientific literature, several parameters
contribute to the development of the sol-gel processes, hence affecting the structure
/morphology of the resulting oxidic networks: temperature and pH, type of (semi)metal
atom and alkyl/alkoxide groups, water /alkoxide ratio, reaction time and presence of co-
solvents (Alongi & Malucelli 2012).
Unlike sol-gel, LbL is a typical top-down approach, suitable for the deposition of
very thin assemblies (ranging from hundreds of nanometers to microns) on several types
of substrates, comprising plastics, metals and also fabrics. Although the first application
of this approach dated in 1966 (Iler 1966), this method was forgotten until the early
1990s, when Decher’s group developed a suitable strategy for its practical use (Decher &
Hong 1991).
Sol-Gel and Layer by Layer Methods for Conferring Multifunctional Features … 63

OR OR
H+
RO M OR + H 2O RO M OH + ROH STEP 1: Hydrolysis

OR OR

OR OR OR OR
H+
M OH + HO M OR RO M O M OR + H2O

OR OR OR OR

STEP 2a: Condensation with water formation

OR OR OR OR
H+
M OH + RO M OR RO M O M OR + ROH

OR OR OR OR

STEP 2b: Condensation with alcohol formation

Figure 1. Scheme of sol-gel reactions occurring in acidic conditions (M=(semi)metal, such as Si, Ti).

From an overall point of view, the LbL assembly mainly consists in an alternate
adsorption of electrically oppositely charged chemical species (namely, polyelectrolytes,
nanoparticles, nano-objects) on a specific substrate. Most of its applications, as clearly
depicted in the open scientific literature, exploit a step-by-step coating build-up based on
electrostatic forces (Malucelli 2016a). However, LbL can also utilize different types of
interactions (e.g., covalent bond s (Ichinose 1998, Fang 1997), hydrogen bonds (Stockton
& Rubner 1997, Shimazaki 1998), stereo-complex formation (Serizawa 2000, Serizawa
2001), donor-acceptor interactions (Wang 2007), etc.).
A general scheme of the most used LbL assembly based on electrostatic interactions
is shown in Figure 2: it essentially exploits the alternate immersion of the substrate into
oppositely charged polyelectrolyte solutions (or nanoparticle dispersions). The
concentration of the solutions/dispersions is very low (usually in between 0.5 and
1 wt.%); besides, water is usually the medium utilized for their preparation, hence
avoiding the use of organic solvents. As a result, an assembly of positively and negatively
charged layers piled up on the underlying substrate is achieved, giving rise to a total
surface charge reversal after each immersion step. In addition, the suitable components
involved in the LbL assembly can be selected from a wide assortment of products: in fact,
cationic or anionic polyelectrolytes, metallic or oxidic colloids, layered silicates, even
biomacromolecules have been successfully used.
64 Giulio Malucelli

Fabric
1 cycle = 1 layer

cationic polyelectrolyte solution/ washing


nanoparticle suspension

washing anionic polyelectrolyte solution/


nanoparticle suspension

Figure 2. Scheme of the layer by layer method based on electrostatic interactions.

Unlike some standard and well-known thin film deposition methods (such as plasma
treatments and impregnation /exhaustion processes, which are very common as finishing
treatments in the textile industry), the layer by layer deposition takes place in “mild” and
somehow “environmentally-friendly conditions.”
In fact, it is usually carried out at atmospheric pressure and room temperature, almost
always using very diluted water -based solutions or suspensions. In addition, it allows
tailoring the final properties of the obtained assembly by easily incorporating selected
functional species in the deposited layers.
Therefore, from an overall point of view, sol-gel and LbL methods can be
successfully exploited for providing fibers or fabrics with multifunctional features,
depending on the structure of the sol-gel precursors or of the LbL constituents, hence
Sol-Gel and Layer by Layer Methods for Conferring Multifunctional Features … 65

finely tuning the desired specific properties to provide the textile with. In particular, it is
possible to coat the underlying textile substrate with a fully inorganic or hybrid organic-
inorganic (referring to both sol-gel and LbL) or with a fully organic coating (as far as the
only LbL strategy is considered).
This chapter reviews the current state of the art related to the use of these surface
engineered strategies for conferring multifunctional features (among them, fire
retardancy, hydrophobicity, wear resistance and anti-bacterial activity), to cellulosic
substrates, discussing both their potential advances and current limit ations.

MULTIFUNCTIONAL FEATURES PROVIDED


BY SOL-GEL COATINGS

The sol–gel method has already demonstrated its outstanding potential for the design
of tailored materials with a high degree of homogeneity at the molecular scale and with
outstanding physico-chemical, thermo-mechanical and barrier properties. As already
shown in Figure 1, this technique is based on two-step hydrolysis /condensation reactions
of (semi)metal alkoxides, among which, tetramethoxysilane, tetraethoxysilane,
aluminium isopropoxide, titanium tetraisopropoxide are very often utilized. The
aforementioned reactions favor the formation of fully inorganic or hybrid organic–
inorganic coatings at or near room temperature, on the basis of the chemical structure and
reactivity of the employed precursors.
Referring to textiles, sol-gel processes have been successfully exploited for providing
them with multifunctional features; more specifically, great attention was directed
towards the design of “smart” textiles. For this purpose, different kinds of properties have
been considered, hence leading to the obtainment of flame retardant, super-hydrophobic,
antimicrobial or UV radiation protective fabrics. Besides, it was also possible to improve
the dye fastness of the treated fabrics (Mahltig & Textor 2006, Cireli & Onar 2008), to
immobilize biomolecules (Li 2007), to perform anti-wrinkle finishing (Huang 2006), and
to provide the treated fabrics with sensor characteristics (Caldara 2012, Van der Schueren
2012) or photocatalytic features (Moafi 2011, Colleoni 2012).

Sol-Gel Flame Retardant Coatings

The sol-gel method has been used from the 1950s, but only quite recently for
providing the textiles with flame retardant properties. In particular, it was found that the
ceramic phases (in form of either coatings or particles) formed on the sol-gel treated
fabrics could behave as a thermal shield during the exposure of the fabrics to a flame or
to a heat source. This physical barrier that limits oxygen and heat transfer impedes the
66 Giulio Malucelli

formation of combustible volatile species that promote the further textile degradation,
favoring, at the same time, the formation of an aromatic stable carbonaceous residue,
called char (Alongi & Malucelli 2012, Alongi & Malucelli 2015).
On the other hand, as the fabrics have a limited thickness, the deposited sol-gel
coatings can protect them only partially. As a consequence, the flame retardant properties
provided by these coatings are really effective only when they work in synergistic or joint
effects with other active components: this situation can be fulfilled by combining the sol-
gel ceramic phases with other flame retardant active species, such as P- and/or N-
containing molecules. In addition, a quite recent step-forward of the sol-gel technique has
allowed designing dual-cure processes, which can be exploited for preparing hybrid
organic-inorganic protective coating s (Malucelli 2016b) through the combination of a
photo-induced polymerization process together with a thermal treatment that promotes
the buildup of sol-gel ceramic phases (Alongi 2011a).
The first researches on the sol-gel method applied to textiles were focused on the
development of fully inorganic coatings on the fabrics. Hribernik et al. applied sol-gel
derived silica coatings (thickness about 350 nm), aiming at reducing the flammability of
regenerated cellulose fibers (i.e., viscose) (Hribernik 2007). In particular,
tetraethylorthosilicate (TEOS) was utilized as precursor of the silica coating: the treated
fibers showed enhanced thermal stability (with 20°C temperature increase of the first
degradation step) and flame resistance with respect to the untreated counterparts;
furthermore, the glowing combustion of the residue showed an important 40°C
temperature increase.
The obtained sol-gel coatings, when applied to cotton, polyester and cotton/polyester-
rich blends, were able to delay the degradation reactions in nitrogen and air, as revealed
by thermogravimetric analyses. In addition, the silica coatings were capable to
significantly lower the peak of the heat release rate (pkHRR) and to increase the time to
ignition (TTI) during cone calorimetry tests (Alongi 2011b).
Pursuing this research, different precursors for silica, even in combination with other
preformed oxidic phases have been applied to cellulosic fabrics, thoroughly assessing the
effect of different adopted process parameters on the morphology of the sol-gel derived
coatings.
Alongi and co-workers investigated the effect of the experimental condition s
adopted for the sol-gel treatments (namely, temperature and time of the thermal treatment
and the precursor: water molar ratio) on the achieved flame retardancy of cotton (Alongi
2011c). More specifically, cone calorimetry tests showed 56% increase of time to ignition
(TTI) and 15% reduction of peak of heat release d rate (pkHRR) when the sol-gel process
was performed at 80°C for 15 h, keeping a 1: 1 water: tetramethylortosilicate (TMOS)
molar ratio. These findings demonstrated that the sol-gel coating acts as a thermal
insulator, shifting the degradation temperature towards higher values and favoring the
Sol-Gel and Layer by Layer Methods for Conferring Multifunctional Features … 67

formation of a stable char, as derived from cellulose dehydration (Alongi &Malucelli


2015).
Then, the role of the chemical structure of the silica precursor (in terms of type and
number of hydrolysable alkoxy functionalities) was thoroughly investigated, comparing
the flame retardant features of cotton treated with TMOS (bearing 4 methoxy groups)
with the fabric treated with TEOS (bearing 4 ethoxy groups) and tetrabuthylorthosilicate
(TBOS, bearing 4 buthoxy groups) (Alongi 2012a). Vertical flame spread tests revealed
that the burning rate lowers in the presence of even a very limited amount of silica
coating (from 2.50 to 1.45 mm/s for untreated cotton and TMOS-treated counterpart,
respectively), hence increasing the total burning time. Furthermore, the final residue was
remarkably increased (from 10, untreated fabric, to 35 and 48 wt.%, for TEOS- and
TMOS-treated counterparts, respectively). Therefore, it was concluded that a shorter
precursor chain length lowers the fabric flammability. In addition, the combustion
behavior, as assessed by cone calorimetry tests, was thoroughly investigated: to this aim,
the combustion behavior of TEOS was compared with that of other alkoxysilanes bearing
a different number of hydrolysable groups, namely diethoxy(methyl)phenylsilane
(DEMPhS), 3-aminopropyl trimethoxysilane (APTES), triethoxy(ethyl)silane (TEES),
1,4-bis(triethoxysilyl)benzene (bTESB) and 1,2-bis(triethoxysilyl)ethane (bTESE). As
revealed by the cone calorimetry results, it was found that:

 the alkoxysilanes bearing a limited number of hydrolysable groups (i.e., 2 or 3)


behave like TEOS, though they promote an increase of smoke release and give
rise to very thin and incoherent residues
 a compact and thicker residue is obtained when an amino group (APTES) is
replaced with an alkyl chain (TEES);
 bTESB and bTESE, which bear a high number of alkoxy groups, are able to
change cotton flammability; more specifically, the fabrics treated by bTESB do
not burn even after repeated flame applications.

The same group also studied the effect of the precursor type on the overall fire
behavior of cotton fabrics: for this purpose, these latter were treated with alumina,
zirconia or titania sol-gel derived coatings, starting from aluminium isopropylate,
tetraethylortho-zirconate and tetraethylortho-titanate precursors (Alongi 2012b). The best
flame retardancy performances were obtained with the silica coating, for which 56% TTI
increase and 20% pkHRR decrease were achieved in cone calorimetry tests. Conversely,
alumina and titania coatings ensured the best enhancements of abrasion resistance,
assessed by Martindale tests.
Pursuing this research, alumina micro- or nano-particles were embedded in sol-gel
silica coatings, aiming at designing new coatings with enhanced fire and tribological
features. In particular, irrespective of the size of the used alumina particles, the sol-gel
68 Giulio Malucelli

systems coated on cotton or cotton-linen fabrics were found to enhance the abrasion
resistance, to decrease the total burning rate by 45% and to increase the final residue
(+46%) after horizontal flame spread tests (Alongi 2013).
As previously mentioned, the fire behavior of sol-gel derived coatings can be further
ameliorated by exploiting their synergistic or joint effects with other flame retardants,
mostly containing P or P and N elements. This goal can be fulfilled either by using
alkoxysilane precursors that bear both silane and phosphate groups or by grafting a
phosphoric acid source to an alkoxysilane precursor. A further method exploits the
incorporation of an alkoxysilane precursor bearing both silane and phosphate groups into
P- and N-containing compounds. Irrespective of the type of chosen strategy, the presence
of phosphate groups promotes the dehydration of the cellulosic substrate, instead of the
formation of flammable volatile organic products, hence giving rise to the creation of a
stable char (Alongi & Malucelli 2015).
The concurrent presence of P and Si elements in the same precursor has been
exploited for obtaining hybrid organic-inorganic coatings, which act as char developers,
due to the presence of the phosphoric acid source, but also as thermal protective coating s
(owing to the inorganic ceramer).
In this context, hybrid phosphorus -silicon organic-inorganic coatings were
synthesized on cotton, starting from diethylphosphatoethyltriethoxysilane (DPTES) as a
precursor and using a multistep sol-gel process (from 1 to 6 deposited layers) (Alongi
2012c). In cone calorimetry tests, the sol-gel treated fabrics showed a decreased burning
time, as revealed by the flame out values (66, 62 and 80 vs. 116 s for 1, 3 and 6 layers
and untreated cotton, respectively). Besides, the obtained hybrid coatings were capable of
limiting the development of volatile species, as indicated by total smoke release (TSR)
values (20, 15 and 6 vs. 26 m2/m2 for 1, 3 and 6 layers and untreated cotton,
respectively). Finally, a further pre-hydrolysis step of the precursor was found to improve
the washing fastness of the treated fabrics (up to 5 washing cycles, according to the ISO
6330 standard) (Alongi 2013).
Pursuing this research, possible synergistic effect s between sol-gel derived silica
coatings, bearing both silane and phosphate groups, with P- and N-containing
compounds, were assessed. For this purpose, DPTES was mixed with APTES or APTES
and a melamine-based resin (M) and applied to cotton (Brancatelli 2011). An increase of
char yields, as revealed by thermogravimetric analyses in air (42 and 38 wt.% for
APTES/DPTES- and APTES/DPTES/M-treated samples, respectively) was found. The
further replacement of the N-source with N,N,N,’N,’N,”N”-hexakis-methoxymethyl-
[1,3,5]triazine-2,4,6-triamine (MF) and the optimization of DPTES/MF relative ratios
were found to enhance the char-forming character of the obtained coatings that
approached 70 wt.% of residue after thermogravimetric analyses in air (Alongi 2012d).
The occurrence of synergistic effect s, estimated through Lewin’s synergistic
effectivity (Lewin 2001) was assessed for sol-gel derived coatings deposited on cotton
Sol-Gel and Layer by Layer Methods for Conferring Multifunctional Features … 69

fabrics and doped with different phosphoric acid sources (i.e., aluminium phosphinate, or
a mixture of aluminium phosphinate, melamine poly(phosphate) and zinc and boron
oxide, or ZrP nano-platelets (Alongi 2011d)). More specifically, time to ignition (TTI,
from 14, untreated cotton, to 40 s) and the limiting oxygen index (LOI, from 19%,
untreated cotton, to 30%) were found to remarkably increase by simply mixing the sol-
gel precursor with 5 wt. % of the above-mentioned phosphorus -based compounds.
Very recently, a new combination of a functional sol-gel coating based on (3-
trimethoxysilylpropyl) diethylenetriamine and phenylphosphonic acid as a phosphorous -
rich component was applied to cotton, polyester and a 65: 35 cotton: polyester blend
(Kappes 2016). The treated fabrics were able to self-extinguish in small-scale flame tests
with either surface or edge ignition (according to EN ISO 15025).
In a very recent work, a two-step process for obtaining flame retardant and
superhydrophobic cotton fabrics was designed by Przybylak and co-workers (Przybylak
2016). In particular, a sol-gel coating based on aminopropyltriethoxysilane was exploited
for immobilizing ammonium dihydrogen phosphate and/or guanidine carbonate: this way,
it was possible to provide cotton with flame retardant features. Subsequently, the flame
retarded cotton was further combined with a fluorofunctional silane or polysiloxane,
hence gaining high hydrophobicity. The occurrence of synergistic effect s between P- and
N-containing compounds and organosilicon species was demonstrated and allowed
reaching high flame retardant properties: in particular, 71.6% limiting oxygen index and
90% decrease in Qmax (i.e., the maximum specific heat release rate assessed in
Pyrolysis-Combustion Flow Calorimetry tests) with respect to the untreated fabric were
documented.
Very recently, a hybrid organic–inorganic coating containing P, Si and N was
synthesized starting from APTES and phenylphosphonic dichloride and applied to cotton
fabrics by using a sol-gel method (Liu 2016). The treated fabrics showed an improved
thermal stability and fire behavior: in particular, the deposited hybrid coating promoted
the self-extinction of the fabrics immediately after the removal of the ignition source. The
obtained results were interpreted on the basis of the formation of both a ceramic layer on
the fiber surface upon heating and of a thermally stable aromatic char.

Sol-Gel Antimicrobial Coatings

Several sol–gel systems with antimicrobial features have been developed up to now,
in order to prevent possible biocontamination phenomena. In particular, the sol-gel
antimicrobial coating formulations for fabrics can be classified into three different
systems:
70 Giulio Malucelli

 Photoactive TiO2–based coatings with permanent antimicrobial features, which


work upon UV exposure due to photomineralization processes occurring on their
surface (Ollis 2000);
 Polycationic coatings, obtained from hydrolysis products of long-chained
tetraalkylammoniumsilane precursors, which show permanent antimicrobial
properties (Isquith 1972);
 Temporary antimicrobial sol–gel coatings with embedded biocides and controlled
release of biocides (Bottcher 1992).

The third strategy seems to be the most performing in the textile world, as it makes
possible to embed a wide selection of inorganic biocides (such as Ag, Cu or boric acid)
and any organic biocides.
Mahltig and co-workers exploited sol-gel silica coatings containing silver, silver salts
or biocidal quaternary ammonium salts (i.e., cetyltrimethylammoniumbromide and
octenidine) for conferring antimicrobial features to cotton /polyester blend fabrics
(Mahltig 2004). In particular, the antimicrobial efficacy, wash-out and long-term
behavior were thoroughly investigated on the basis of the type of embedded biocides. All
the prepared sol-gel coatings were found to inhibit the growth of fungi and bacteria,
especially when embedding octenidine or silver.
Xing and co-workers treated cotton fabrics with silica sols from water glass and then
with silver nitrate solution (Xing 2007). Using E. coli as a model for Gram-negative
bacteria assessed the antimicrobial activity. The results showed that the treated cotton
fabrics possess an excellent antimicrobial effect and washing fastness (up to 50 washing
cycles ). Furthermore, XPS analyses revealed the presence of silver in two different
states, i.e., Ag+ and Ag2+, on the surface of the treated fabrics: both the states turned out
to contribute to the observed antimicrobial activity.
Tomsic and co-workers exploited a sol-gel method for preparing water and oil
repellent and antimicrobial coatings for cotton fibres (Tomsic 2008). To this aim, a
commercially available fluoroalkyl functional water-borne siloxane (FAS ), nanosized
silver (Ag) and a reactive organic–inorganic binder (RB) were used and applied
according to two different procedures: cotton fabrics were impregnated with a sol mixture
containing all three components or first impregnated with the Ag–RB sol and then with
the FAS sol. Apart from the good hydrophobic/oleophobic features shown by the sol-gel
treated fabrics even after 10 washing cycles, their antibacterial activity against E. coli and
S. aureus was found to depend on the application procedure of the sol-gel coatings. In
particular, the separate deposition of antibacterial Ag nanoparticles followed by the
application of the oleophobic and antibacterially non-active fluoroalkyl functional water-
borne siloxane turned out to be preferable to the application of the sol mixture in one step
only.
Sol-Gel and Layer by Layer Methods for Conferring Multifunctional Features … 71

Pursuing this research, the same group treated cotton fabrics with a
diureapropyltriethoxysilane [bis(aminopropyl)-terminated polydimethylsiloxane (1000)]
(PDMSU) sol−gel hybrid coating, also in the presence of 1H,1H,2H,2H-
perfluorooctyltriethoxysilane (PFOTES) (Vilčnik 2009). The obtained mixed
PFOTES−PDMSU finishes applied on cotton fabrics turned out to enhance both
hydrophobicity and oleophobicity of the treated substrates. The antibacterial activity of
sol-gel treated fabrics was assessed with the transfer method (EN ISO 20743: 2007): the
reduction of E. coli bacteria on unwashed cotton fabrics was nearly 100% and was still
high after 10 washing cycles (60.6%).
Tarimala et al. exploited a sol–gel method for synthesizing a dodecanethiol-capped
silver nanoparticle–doped silica coating (Tarimala 2006). The antibacterial activity tests
performed on woven cotton fabrics treated with the prepared doped sol revealed an
excellent performance of the silica coating against E. coli, hence suggesting the
possibility of using the so-treated fabrics as disposable bandages.

Sol-Gel UV-Protective Coatings

The emission of UV radiation in the spectral region from 280 to 400 nm may be
responsible of such health issues as sunburn, allergies or even, in very limited cases, skin
cancer (Lapidot 2003).
Thus, the development of effective systems able to ensure protection from UV
radiation is an up-to-date issue. Apart from the products that are directly put on the skin,
the design of UV-protective fabrics may represent a solution in order to face this issue. In
this context, different parameters directly related to the fabrics, such as their chemical
structure and composition, grammage, porosity, color, play an important role.
Xin et al. developed a UV-blocking sol-gel derived coating for cotton fabrics: to this
aim, a nanosol, prepared at room temperature by mixing titanium tetraisopropoxide with
absolute ethanol, was directly applied to the cellulosic substrate (Xin 2004). The presence
of titania domains on the surface of the fabrics provided an excellent UV protection;
furthermore, the deposited coating showed a good adhesion to the underlying fibers and a
high washing fastness (the UPF – ultraviolet protection factor – was equal to 50+ even
after 55 home launderings). Finally, the sol-gel coating did not show any detrimental
effect on the mechanical strength of the treated substrates, as confirmed by bursting
strength tests.
Abidi and co-workers exploited a sol-gel method and applied nanosols containing
tetraethyl orthotitanate and tetraethyl orthosilicate to lightweight 100% cotton fabric
(Abidi 2007). After drying and curing, the modified fabrics show a high UV protection,
which was strictly correlated to the titania content in the nanosol: this finding was
ascribed to the increase of the refractive index of the sol-gel coatings deposited on the
72 Giulio Malucelli

fabric surface. Furthermore, the obtained UV protective systems showed a high washing
fastness, due to the formation of covalent bond s between the hydroxyl groups of
cellulose and those of the titania and titania–silica network.
Pursuing this research, the same group modified cotton fabrics by titania nanosols
derived from a sol-gel method, using tetrabutyl orthotitanate as the active species (Abidi
2009). The treated substrates showed a good UV protection, which was not affected by
repeated home launderings (for up to 18 cycles according to AATCC TM 124);
furthermore, it was found that coffee and red wine stains were successfully decomposed
by exposing of the stained fabric to the UV radiation. Paul et al. compared the UV
protection effect provided by preformed ZnO nanoparticles deposited on cotton fabrics,
with that of titania nanoparticles obtained by sol-gel reactions starting from titanium
isopropoxide (Paul 2010). As compared to ZnO nanoparticles, the sol-gel derived titania
counterparts were found to be more performing in the UV protection of the underlying
fabrics and more resistant to washing treatments (i.e., to 10 cycles of domestic washings).
Wang and co-workers investigated the effect of dumbbell-shaped ZnO crystallites
obtained from a sol-gel method on the UV-protection of cotton fabrics (Wang 2005). In
particular, in the UV-range, complete blocking was achieved using the obtained ZnO
crystallites.
Onar and co-workers treated cotton fabrics by a pad–dry–cure method with different
amounts of Ag-doped, Ti-based transparent solutions prepared with a sol–gel technique
(Onar 2007). The fabrics modified with a 30 atom % Ag doped, Ti-based solution,
exhibited a good UPF rating of 15+, which was 200% higher with respect to the untreated
fabric. Furthermore, the proposed treatments also showed a good washing fastness after
10 washing cycles according to BS EN ISO 105-C06-A1S Standard. Sundaresan et al.
designed a multifunctional treatment based on the application of titania nanoparticles,
obtained through a sol-gel method, on cotton fabrics. In particular, two different average
TiO2 nanoparticle sizes (i.e., 7 and 12 nm), were obtained and applied to the cellulosic
substrate (Sundaresan 2012). The proposed treatment provided the cellulosic fabrics with
UV-protection, antimicrobial and self-cleaning activity. In particular, as far as UV-
protection is considered, 12 nm TiO2 nanoparticles showed higher UPF values as
compared to the smaller nanoparticles; besides, the UV-protection was retained until 10
washing cycles.

MULTIFUNCTIONAL FEATURES PROVIDED BY LAYER


BY LAYER COATINGS

In the first research works appeared in the scientific literature, the layer by layer
technique was addressed to the build-up of coatings with outstanding oxygen barrier
Sol-Gel and Layer by Layer Methods for Conferring Multifunctional Features … 73

properties (Jang 2008, Grunlan & Jang 2008, Priolo 2010); then, it was also utilized for
providing different substrates with anti-reflection (Podsiadlo 2007), electrical
conductivity (Rivadulla 2010) or antibacterial properties (Dvoracek 2009, Gentile 2015).
In general, the LbL coatings have been intentionally designed for modifying the
surface of substrates having a high surface to bulk ratio, such as plastic films and fabrics:
in fact, these substrates possess a high surface accessible for the LbL assembly with
respect to the bulk.
In the following, the state of the art about the multifunctional features that can be
conferred to cellulosic fabrics by designing specific LbL assemblies is thoroughly
reported.

Multifunctional Layer by Layer Coatings

During the last 10 years, several types of LbL assemblies have been designed for
expressly providing flame retardant features (i.e., to enhance thermal stability and fire
retardancy of the cellulosic substrate) to different fabrics; in particular, fully inorganic,
hybrid organic/inorganic and fully organic coatings have been proposed.
As far as fully inorganic LbL systems are considered, one of the pioneering works
was done by Laufer and co-workers, who assembled positive alumina-coated silica (10
nm) and negative silica nanoparticles (10 or 40 nm) on cotton fabrics, exploiting a
dipping method (Laufer 2011). In particular, the deposition of up to 20 silica/silica
bilayers was able to provide self-extinction to the treated fabrics during vertical flame
spread tests and to increase the time to ignition in cone calorimetry experiments.
The same silica /silica architectures were then applied to cotton fabrics by using a
spray-assisted layer by layer deposition; the obtained results were compared with those
achieved by dipping. More specifically, the horizontal spray method was found to
homogeneously cover the fabric surface, conferring, at the same time, the best thermal
protection to the underlying substrate during combustion tests (Alongi 2013, Carosio
2013b).
Among the other types of inorganic nanoparticles utilized for assembling fully
inorganic LbL coatings, Polyhedral Oligomeric Silsesquioxane (POSS®) salts, positively
or negatively charged, have been considered. The first example refers to the use of water
-soluble OctaAmmonium POSS ((+) POSS) and OctaTetramethylammonium POSS
((-)POSS), respectively as cationic and anionic components, for the design of 20 bilayers
thin coatings (Li 2011a). Aminopropyl silsesquioxane oligomer was also considered as
possible substitute cationic species. Micro cone calorimetry tests performed on the LbL
treated cotton fabrics showed the formation of more than 12 wt.% char; furthermore, the
afterglow time was found to significantly decrease during vertical flame spread tests and
74 Giulio Malucelli

the LbL treatment allowed preserving the fabric texture and the shape of the individual
fibers.
The outcomes from the fully inorganic LbL assemblies pushed the scientific
community towards the design of intumescent LbL coatings: in fact, thanks to their
structure and composition, the intumescent LbL coatings can offer both a barrier effect
(due to the presence of the inorganic layers) and a charring effect (due to the reactive
intumescent layers).
The first example of intumescent LbL coating on cotton combined a poly(allylamine)
(which acted as a carbon source and blowing agent) with sodium phosphates (as acid
source) (Li 2011b). The intumescent LbL-treated fabrics self-extinguished in vertical
flame spread tests; besides, it was not possible to ignite the treated fabrics under the cone,
using 35 kW/m2 heat flux.
Chitosan and ammonium polyphosphate, i.e., a carbon source and a acid
source/blowing agent, respectively, were combined in a layer by layer coating suitable for
conferring flame retardant properties to cotton -polyester blends (Carosio 2012). In
particular, during horizontal flame spread tests, the fabrics treated by 20 bilayers
exhibited decreased combustion kinetics and did not show afterglow phenomena;
furthermore, the obtained residues were coherent and thick.
Instead of using intumescent LbL coatings based on bilayers, quad-layers made
of poly (diallydimethylammonium chloride) / poly (acrylic acid) / poly (diallydimethyl
ammonium chloride) / ammonium polyphosphate, were applied to cotton fabrics. The
proposed LbL assemblies allowed the fabrics achieving self-extinction, decreasing, at the
same time, the heat-related parameters (Alongi 2012e, Carosio 2013a).
An oligoallylamine and its phosphonated counterpart were synthesized (Guirao 2013)
and exploited in intumescent LbL assemblies on cotton fabrics, exploring the effect of the
adopted experimental parameters (namely, molecular weight s of the synthesized
products and pH conditions for the building up of the LbL coatings (Carosio 2015). First,
a high thermal and thermo-oxidative stability was assessed through thermogravimetric
analyses performed in nitrogen and air, along with the formation of very high residues at
800°C (37 and 31%, in nitrogen and air, respectively). The thickness of the LbL
structures was influenced by the pH chosen during the deposition process. Afterglow
phenomena were not detected on the LbL-treated fabrics, irrespective of the molecular
weight of the components of the assembly; furthermore, horizontal flame spread tests
clearly indicated that high molecular weight layers are more effective in lowering the
total burning time and increasing of the final residues at the end of the tests.
Huang et al. applied an intumescent flame retardant-polyacrylamide (derived from
the copolymerization of N1-(5,5-dimethyl-1,3,2-dioxaphosphinyl-2-yl)-acrylamide with
acrylamide) in combination with graphene oxide nanosheets on cotton fabrics (Huang
2012). The thermal stability of cotton was enhanced by the deposition of the LbL
assembly, as assessed by thermogravimetric analyses. Cone calorimetry tests revealed a
Sol-Gel and Layer by Layer Methods for Conferring Multifunctional Features … 75

decrease of pkHRR, as well as an increase of TTI in the presence of the deposited


coating; in addition, the assembly was responsible for the formation of a continuous and
coherent char after the combustion tests.
The possibility of designing multifunctional flame -retardant, self-healing and
superhydrophobic LbL assemblies on cotton fabrics was assessed and demonstrated by
Chen et al., who exploited a solution -dipping method, with the sequential deposition of a
trilayer of branched poly(ethylenimine), ammonium polyphosphate and fluorinated-decyl
polyhedral oligomeric silsesquioxane (Chen 2015). In vertical flame spread tests, the
LbL-treated fabrics showed an intumescent behavior, with the formation of a porous char
layer that allowed achieving self-extinction. Besides, the fluorinated layer provided
superhydrophobic features to the underlying cellulosic substrate, along with a self-
healing behavior. In fact, a simple water rinsing process allowed the LbL assemblies
restoring the superhydrophobicity when this latter was lost.
A significant part of the research activity on LbL coatings carried out during the last
5 to 10 years has been addressed to the setup of low environmental impact renewable
intumescent coatings that, apart from flame retardant purposes, may provide the fabrics
with multifunctional features (as an example, antibacterial properties).
In particular, it was possible to exploit different biomacromolecules for the buildup
of “green” treatments on different textile substrates.
One of pioneering works was done by Laufer and co-workers, who combined
chitosan (carbon source, positively charged) with phytic acid (acid source, negatively
charged) in a 30 bi-layered assembly on cotton fabrics (Laufer 2012). The pH of the
aqueous LbL solutions was found to strongly affect the composition of the obtained LbL
nanocoatings: in particular, those obtained at pH 6 were thicker than the analogous
prepared at pH 4 and with a different phytic acid content (48 vs 66 wt.% for pH 6 and 4,
respectively). Vertical flame spread tests proved self-extinction for the fabrics coated
with high phytic acid content assemblies, while untreated cotton was completely
consumed. In addition, the fabrics treated with pH 4 aqueous solutions exhibited a
significant decrease of pkHRR and of total heat release (-60 and -76%, respectively) with
respect to the untreated fabric, during microcombustion calorimetry tests.
Fang and co-workers applied an LbL intumescent flame retardant coating,
comprising chitosan (positively charged) and ammonium polyphosphate (negatively
charged) on cotton fabrics (Fang 2015a). The deposition of 20 bilayers remarkably
reduced the burning time and efficiently limited fire propagation, with only 27 mm length
in horizontal direction damaged. After vertical flame spread tests, the char formed on the
LbL-treated fabrics was able to preserve the textile texture that showed a considerable
mechanical strength. The occurrence of an intumescent effect was confirmed by the
formation of several bubbles on the surface of the burnt fibers treated with 20 bilayers.
Lastly, both pkHRR and total heat release decreased after the deposition of the LbL
coating, as assessed by microcone calorimetry tests.
76 Giulio Malucelli

The same group further designed a polyhexamethylene guanidine phosphate -


ammonium polyphosphate LbL coating exhibiting flame retardant and antimicrobial
features (Fang 2015b). In particular, vertical flame spread tests carried out on the LbL-
treated fabrics displayed a reduced burning time, no afterglow, and an increased residue,
maintaining the original textile texture. Lastly, antimicrobial tests performed on the
treated fabrics showed an antimicrobial action on E. coli and S. aureus.
Very recently, ammonium polyphosphate was replaced with potassium alginate,
extracted from seaweed: in doing so, it was possible to combine the intumescent effect of
antimicrobial polyhexamethylene guanidine phosphate with the low impact character of
potassium alginate (Fang 2016). The LbL-treated cotton fabrics turned out to show a
significant decrease of peak of heat release rate and total heat release in microcombustion
tests. At the same time, the antimicrobial effect on E. coli and S. aureus exerted by the
LbL assemblies was assessed: more specifically, the inactivation of 100% E. coli and S.
aureus was achieved in 5 and 30 min, respectively.
The possibility of using DNA (deoxyribonucleic acid) in the design of intumescent
LbL coatings has been quite recently assessed. In fact, the structure and chemical
composition of this biomacromolecule mimics that of an all-in-one intumescent system
(Alongi 2013b). In particular, its phosphate groups can behave as acid source, the
deoxyribose units provide carbon and the nitrogen -containing bases may release blowing
agent s (i.e., ammonia and nitrogen) (Alongi 2013c).
Carosio et al. designed LbL anionic DNA /cationic chitosan assemblies on cotton,
depositing up to 20 bilayers (Carosio 2013c). The DNA layers embedded in the assembly
enhanced the char forming character of chitosan, hence leading the fabric to self-
extinction in horizontal flame spread tests. In addition, 40% reduction of heat release rate,
as well as a significant increase of the final residue was assessed in cone calorimetry tests
performed on the fabrics treated with 20 bilayers.
Referring to hybrid organic-inorganic LbL systems, the combination of nanoparticle
layers together with the intumescent properties provided by organic layers has been
repeatedly reported in the open scientific literature as a feasible method for achieving
high performing treatments on different fabric substrates.
Alongi et al. designed one of the first LbL hybrid coating on cotton -polyester blend
fabrics, coupling chitosan, ammonium polyphosphate and silica nanoparticles (bearing
positive or negative charges) (Alongi 2012f). The resulting assemblies provided the
treated substrates with an increased flame retardant behavior, as assessed by horizontal
flame spread and cone calorimetry tests. In particular, this latter was strictly correlated
with both the morphology and the physical stability of the obtained LbL assemblies i.e.,
with the growth of a homogeneous and coherent LbL coating.
Huang and co-workers designed LbL hybrid coatings for cotton, comprising
poly(acrylic acid) and amino -functionalized montmorillonite nanoplatelets layers (Huang
2012). The treated fabrics showed decreased combustion kinetics. In addition, the
Sol-Gel and Layer by Layer Methods for Conferring Multifunctional Features … 77

formation of a blown charred structure including montmorillonite nanoplatelets was


assessed on the residues after combustion tests through SEM microscopy.
Recently, montmorillonite nanoplatelets, in combination with dimethyl diallyl
ammonium chloride-allyl glycidyl ether, were also utilized in LbL hybrid assemblies
deposited on cotton fabrics (Gao 2015). In particular, an LbL modified technique,
involving a dipping step and a subsequent padding, drying and curing, was exploited. The
deposited coatings increased the char residue formed at high temperature, as shown by
thermogravimetric analyses; an increase of the total burning time and of the final residue
was obtained after vertical flame spread tests, as well as a slight increase of LOI values.
Very recently, Chen et al. designed a LbL multifunctional coating with electrical
conductivity, flame retardant and antimicrobial features (Chen 2016). For this purpose,
up to 20 bilayers consisting of polyhexamethylene guanidine phosphate and potassium
alginate-carbon nanotubes were deposited on cotton. The formation CNTs networks on
the fabric surface was responsible for an excellent electrical conductivity. At the same
time, the assembled LbL coating significantly enhanced the thermal stability and fire
behavior of the underlying fabric, notwithstanding an increased inhibition effect of the
growth of E. coli as a function of the number of deposited bilayers.
One of the main drawbacks on the use of LbL coatings on fabrics refers to the water -
soluble character of many active components of the assemblies: as a consequence, the
deposited coatings cannot tolerate repeated washing cycles, which significantly limits
their potential applications. Therefore, several attempts have been carried out in order to
solve this durability issue, although it is still an up-to-date challenge.
In addition, it is also greatly needed to fabricate LbL assemblies in a more efficient
way, i.e., by largely diminishing the number of layer deposition cycles required for
conferring the envisaged final properties to the underlying fabric.
For this purpose, quite recently, Carosio and Alongi combined the LbL process with
the UV-curing technique (Pappas 1992): an anionic UV-curable aliphatic acrylic
polyurethane latex doped with ammonium polyphosphate and in the presence of a
suitable photoinitiator was coupled with chitosan and LbL deposited on cotton fabrics by
dipping (Carosio & Alongi 2015). Subsequently, the obtained assembled coating was
UV-cured: the thin coating formed on cotton fibers showed an enhanced flame retardant
behavior; at the same time, the assembly provided the substrate with the self-extinction
even after a washing cycle performed in water at 65°C for 1 h, hence showing an
enhanced durability.
Very recently, Tian and co-workers exploited the LbL method also for conferring a
robust UV protection to cotton fabrics; to this aim, graphene oxide and chitosan layers
were combined in the LbL assembly (Tian 2015, Tian 2016). The treated fabrics
exhibited more than 40-fold increase of UPF value than control cotton (UPF rating at
9.37). In addition, the LbL-treated cotton showed an excellent washing fastness, even
after 10 times water laundering.
78 Giulio Malucelli

Another effort was very recently made by Casale et al. who obtained cotton fabrics
with enhanced water resistance, self-extinction in flammability tests and good
antimicrobial activity, by combining DNA and chitosan in a LbL assembly, exploiting the
ability of chitosan to undergo UV-curing when exposed to UV radiation in the presence
of a suitable photoinitiator (Casale 2016).
One of the last challenging issues of the LbL method refers to the prospect of
designing a continuous process, reasonably exploitable for commercial and industrial
purposes. Quite recently, Chang and co-workers proposed a continuous layer by layer
system suitable for depositing polymer −clay nanoassemblies on cotton fabrics and for
enhancing their fire behavior (Chang 2014). In particular, layers of branched
polyethylenimine with urea and diammonium phosphate (positively charged) and clay
nanoparticles (negatively charged) were continuously applied to the fabric substrate up to
50 bilayers, using a single “roll-to-roll” process and avoiding the rinsing step. The
proposed continuous LbL technique was found to confer an increased thermal stability to
the fabrics and to enhance the combustion parameters (i.e., to increase TTI and to
decrease the heat release rate) as proved by thermogravimetric analyses and cone
calorimetry tests, respectively.

CONCLUSION

This chapter has clearly demonstrated the importance, practicability and consistency
of sol-gel processes and layer by layer methods as robust surface engineering approaches
for providing cellulosic fabrics (and their blends with polyester) with multifunctional
features (i.e., fire retardancy, anti-bacterial activity, UV-protection, wear resistance ).
This goal can be successfully achieved by simply “playing” with the chemical structure
of the sol-gel precursors or of the LbL components, hence tuning the obtained coatings
towards the final application. Notwithstanding the wide attention, the two strategies have
merited until today, especially from the scientific/academic world, they still represent a
challenging issue for several reasons here summarized.
In particular, referring to sol-gel approaches, their current main limitation may be
ascribed to the “chemistry behind the process” that could limit the scale-up of the
technique to fit the already existing finishing treatments at an industrial scale. A further
limitation refers to the possible detrimental effect of the treatment on the hand/comfort of
the fabrics, even, in some cases, when hybrid organic-inorganic sol-gel treatments are
specifically designed on the cellulosic substrates.
Conversely, at present, the Layer by layer approach shows some limitations in view
to a possible scale-up at an industrial level that should ensure the commercial valorization
/exploitation of this surface engineering method. Besides, the up-to-now weak durability
Sol-Gel and Layer by Layer Methods for Conferring Multifunctional Features … 79

of the proposed multifunctional assemblies seems to limit and to exert a negative


influence on a large-scale exploitation of this strategy.
However, the valuable research work that has been performed in the last years within
the scientific community is intended to demonstrate that a further development and
optimization of these strategies may overcome their current limit ations.

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In: Textiles: Advances in Research and Applications ISBN: 978-1-53612-855-0
Editor: Boris Mahltig © 2018 Nova Science Publishers, Inc.

Chapter 4

WASTEWATER TREATMENT FROM


TEXTILE INDUSTRY USING ADVANCED
OXIDATION PROCESSES

C. López-López1,2, J. Martín-Pascual1,2 and J. M. Poyatos1,2,*


1
Department of Civil Engineering, University of Granada, Granada, Spain
2
Institute for Water Research, University of Granada, Granada, Spain

ABSTRACT

In recent years, the use of natural resources in industrial sectors has increased,
specifically in the textile industry. One of the main problems generated by the textile
industry is related to the wastewater generated. The textile industry is considered one of
the main generators of complex dangerous water pollutants with high contents of organic
and inorganic matter, suspended solids, turbidity and colour, among others. The main
points of generation of these pollutants are focused on the emission of air, solid and
liquid wastes, energy consumption and generation of wastewater with high contents of
slowly biodegradable compounds. Different types of synthetic dyes and pigments are
used in this industry; however, the most used are the azo dyes, followed by
phthalocyanines, both of which contain highly stable molecules.
The removal of this pollution is difficult using conventional biological treatments,
which are insufficient to remove the high pollution load and have a great impact on the
environment. In this chapter we present physical-chemical treatments to treat wastewater.
These more intensive technologies are capable of removing these recalcitrant and toxic
substances characterised by low biodegradability. The technology based on Advanced
Oxidation Processes (AOPs) involves the transformation of organic contaminants in less
complex species and even full mineralisetion. The studies done with H2O2/UV, photo-
Fenton (Fe2+/H2O2/UV) and heterogeneous photocatalysis (TiO2/H2O2/UV) processes
have shown very high efficiency of colour and organic matter removal.

*
Corresponding Author Email: jpoyatos@ugr.es.
88 C. López-López, J. Martín-Pascual and J. M. Poyatos

The high turbidity in the water caused by the colouration can produce a shield that
reduces the penetration of UV light and causes a decrease in the efficiency of AOP.
Therefore, pre-treatment must be considered for these technologies. Coagulation-
Flocculation (CF) as pre-treatment can be a reliable combination to remove excess
turbidity in the wastewater and increase the efficiency of AOPs.

1. PROBLEMS OF WASTEWATER IN THE TEXTILE INDUSTRY

The industrial development and the improvement of analytical methods have led to
the concern about complex bioresistant pollutants in the wastewater effluents, which has
become an important aspect to consider in the textile industry. This industry is one of the
largest groups of industries causing intense water pollution, because it is one of the most
important consumers of resources (energy and water). This high consumption is
especially great during the cleaning of the raw material, which involves numerous steps
of washing throughout the production manufacturing process (Lin and Chen, 1997;
Rodríguez et al., 2002; Al-Kdasi et al., 2004; Scharnk et al., 2007; Blanco et al., 2014).
According to Rajeshwar et al. (2008), each year around 0.7 million tons of organic
synthetic dyes are produced, mainly for use in the textile sector, leather goods, industrial
paint, food, plastics, cosmetics and consumer electronics.
Wastewater from the textile industry is complex and consists of a mixture of many
polluting substances, generally synthetic organic compounds with high complex
molecular structure s and large molecular weight s (McMullan et al., 2001; Fu et al.,
2002). This wastewater contains a wide variety of dyes and chemicals with a relatively
low biological oxygen demand (BOD) and high chemical oxygen demand (COD),
suspended solids (SS) (Correia et al., 1994; Al-Kdasi et al., 2004) and matter in dissolved
and/or colloidal form. Moreover, the dyes also have intense colours and high contents of
other soluble substances (Correia et al., 1994; Dae-Hee et al., 1999). The effects of the
direct discharge of this wastewater into water bodies are water pollution and flora and
fauna disruption (Kumar-Verma et al., 2012), which leads to a considerable
environmental problem (Savin and Butnaru, 2008).
The presence of colour with the high level of organic and reactive compounds could
transform in toxic and/or mutagenic products in contact with a natural water mass
(Weisburger, 2002, Blanco et al., 2012).
Due to the complexity of the compounds contained in textile industrial wastewater,
its biodegradability is a particularly complex parameter. Effluents from the textile
industry contain toxic compounds, most of them non-biodegradable (Ledakowicz and
Gonera, 1999). The high levels of coloured products and toxic chemicals introduced into
the environment are not easily eliminated by conventional biological treatments (Garcia
et al., 2009; Kumar-Verma et al., 2012).
Wastewater Treatment from Textile Industry … 89

About 20% of toxic compounds discharged into the water are caused by the textile
industry; the most of them come from products manufactured outside of the European
Union, especially from Asian countries. The European Commission is concerned with the
use of CMR (Carcinogenic, Mutagenic and Toxic for Reproduction) products in the
textile industry. Some of the pollutants introduced by the textile industries are called
emerging pollutants that are currently unknown or unrecognised pollutants.
The presence of these compounds in the environment is not necessarily new but at
the moment concern regarding the environment and the public health is high. In recent
years, the concern about emerging compounds has increased due to their continued and
excessive use and their release into the environment (Al-Khazrajy and Boxall, 2016). In
the twentieth century alone, more than 100,000 chemicals that are used in daily life,
either in households, industries or agriculture, have been introduced into the environment
(Primel et al., 2012). The detection of these pollutants is possible thanks to new
technologies and emerging pollutants are detected in wastewater, water surfaces, soils
and sediments around the world in very small concentrations (from ng/L to μg/L) (He et
al., 2016). The trace concentrations of these compounds have adverse effects, most of
which are currently unknown. In addition, there are numerous emerging contaminants,
from pharmaceutical products (Martín et al., 2012; Al-Khazrajy and Boxall, 2016; He et
al., 2016), personal care and hygiene products (Camacho-Muñoz et al., 2009; Peña-
Álvarez y Castillo-Alanís, 2015; He et al., 2016), perfluorinated compounds (Arvaniti y
Stasinakis, 2015; Wilkinson et al., 2016; Zahn et al., 2016), hormones (Robles-Molina et
al., 2014), abuse drugs (Martínez-Bueno et al., 2011; Robles-Molina et al., 2014;
Wilkinson et al., 2016) and organic compounds (Pivnenko et al., 2015; Wilkinson et al.,
2016; Zahn et al., 2016).
In spite of the variability of the textile wastewater composition, according to Crespi
(1994), the following general characteristics can be surmised:

1. Great variability of flow and load, depending on the industry.


2. High content of colloidal and suspended particles.
3. Organic load higher than that of an urban wastewater.
4. High pollution in soluble form, therefore the wastewater is generally coloured.
5. Generally do not contain toxic products.
6. Deficient in nutrients.
7. Low concentration of pathogenic microorganisms.

The textile industry uses numerous types of dyes and synthetic pigments depending
on the nature of the industry. These compounds include azo, anthraquinones,
triarylmethanes and phthalocyanine groups. Azo dyes account for 70% of over one
million tons of dyes produced per year, making them the largest group of dyes released
into the environment (dos Santos et al., 2007). Phthalocyanines used to obtain blue and
90 C. López-López, J. Martín-Pascual and J. M. Poyatos

green dyes are the second dye type used (Forgacs et al., 2004; Shu and Chang, 2005).
Initially, the phthalocyanines were used as pigments in the textile industry but were
subsequently used in various applications, such as biology, medicine and industry; this
highlights the importance of these complex molecules (Jancûla and Maršalek, 2011).
Phthalocyanines are present in industrial wastewater, as shown in numerous studies
carried out on textile wastewater (Alinsafi et al., 2007, Fu et al., 2002; Sena and
Deminrer, 2003; Shu and Chang, 2005; Kalsoom et al., 2012; Ghasemi et al., 2013).
These dyes and pigments are generally non-biodegradable and are composed of
chemically stable molecules. In addition, dyes and pigments are designed to resist
degradation by different external agents, which make them difficult to neutralise using
conventional systems, such as biological processes (Khalid et al., 2011). These
characteristics make chemical synthetic dyes highly recalcitrant and capable of inducing
toxicity in aquatic organisms and, in some cases, in humans (Bandala et al., 2008). This
has forced the search for new technologies capable of eliminating these contaminants
using a combination of several physical, chemical and biological methods (Velegraki et
al., 2006; Fatta-Kassinos et al., 2011).
The aim of the present chapter is to summarise the use of Advanced Oxidation
Processes (AOPs) to treat textile wastewater and to show the most relevant results
obtained using three oxidation processes: H2O2/UV, photo-Fenton and heterogeneous
photocatalysis (TiO2/H2O2/UV).

2. TECHNOLOGIES FOR TEXTILE WASTEWATER TREATMENT

As a consequence of the problems caused by this wastewater type, the use of


advanced technologies is necessary for its treatment. Given the recalcitrant and poor
biodegradability of these effluents, biological processes are not efficient. Physical-
chemical treatments, such as coagulation-flocculation, membrane technology, such as
reverse osmosis, ultrafiltration and nanofiltration, adsorption and AOPs, are used reliably
(Salas Colotta, 2003; Holkar et al., 2016).
Coagulation-flocculation is based on the addition of polyelectrolytes that form flocs
with the dye molecules, thereby facilitating their removal by settling. The removal
efficiencies of this process are high, but in the process a polluted concentrated sludge is
generated (GiPavas et al., 2017). The membrane technology based on physical
separation, including reverse osmosis, ultrafiltration and nanofiltration, effectively
separate the dye molecules and other compounds that are larger than the pore size of the
selected membrane. Membrane technologies are widely recognised as an adequate option
for wastewater treatment and reclamation because they can selectively remove
contaminants from wastewater. (Choo et al., 2007; Alventosa-deLara et al., 2014;
Thamaraiselvan and Noel, 2015; Avdicevic et al., 2017). The adsorption process is based
Wastewater Treatment from Textile Industry … 91

on the physical retention of the dye molecules on the surface of the adsorbent used. The
efficiency of this process is influenced by the interaction between the dye and adsorbent,
the specific surface area of the adsorbent, the size of the dye molecule, temperature, pH
and contact time. Activated carbon is an effective adsorbent for a wide range of dyes.
Carbon-based materials have varied applications due their remarkable properties that
enable tailoring to a particular process, however decolourisation has some limitation,
especially when dealing with bulkier and complex species (Holkar et al., 2016;
Khamparia and Jaspal, 2017).
Other alternatives for the elimination of recalcitrant pollutants from textile industry
wastewater are AOPs (Agustina et al., 2005; Sillanpää et al., 1998; Choi et al., 2013; Del
Moro et al., 2013), on which the present chapter is focused. These are a good option
when conventional processes are insufficient to remove persistent pollutants (Moreira et
al., 2005).

2.1. Advance Oxidation Processes

AOPs are physical chemical processes based on the addition of different compounds.
They have been used successfully in the removal of organic matter and colour. AOPs are
a complex and synergistic treatment of textile wastewater, involving the conversion of
organic pollutants to short species and even their complete mineralisetion through the
generation of highly reactive free radical oxidants (Rodrigues et al., 2008). These
processes can eliminate toxic substances and increase the biodegradability of organic
pollutants (Zayas Perez et al., 2007). AOPs have been extensively studied and are
considered as an improved technological alternative to conventional wastewater
treatment (Yonar et al., 2006). The AOPs based on the use of UV radiation and oxidants
such as hydrogen peroxide (H2O2) have been used successfully for removing many
different substances.
The aim of these processes is to eliminate non-biodegradable soluble compounds
and/or high chemical stability in wastewater (Poyatos et al., 2010). Due to the high
reactivity of the OH• radicals it is possible to remove both organic and inorganic
compounds, often to the point of extensive mineralisetion of the target pollutant
(Pignatello et al., 1999), thus achieving a reduction of COD, Total Organic Carbon
(TOC) and toxicity in the treated wastewater (Del Moro et al., 2013).
AOPs are technologies based on physical-chemical processes that lead to the
chemical oxidation of a large range of pollutants, under low pressure and temperature
conditions. This oxidation causes the formation of highly reactive oxygen species,
specifically OH• radicals, with an oxidation potential equal to 2.8 Volts (Papoutsakis et
al., 2015). These oxidising species can be generated by photochemical means (including
sunlight) or other forms of energy, thereby achieving a high efficiency in the oxidation of
92 C. López-López, J. Martín-Pascual and J. M. Poyatos

organic matter. OH• radicals are often combined with metal or semiconductor catalysts
and UV radiation (Homem and Santos, 2011).
AOPs can be used as the main treatment or as part of the purification process to
increase their efficiency. AOPs are especially useful as a pre-treatment prior to a
biological treatment to remove contaminants resistant to biodegradation (Pulgarin et al.,
1999; Kajitvichyanukul and Suntronvipart, 2006; Tantak and Chaudhari, 2006; Lucas et
al., 2007) or as a post-treatment process (Scott and Ollis, 1995) to improve the
characteristics of the water before discharge to water bodies. In addition, AOPs are
considered as a potential future treatment for water due to their high efficiency in
disinfecting most viruses, bacteria and protozoa (Guo et al., 2009; Rubio et al., 2013),
with Escherichia coli being the most common method used to microbiologically control
water quality (Pitkänen et al., 2007).

ADVANCED
OXIDATION
PROCESSES

HOMOGENEOUS HETEROGENEOUS
PROCESSES PROCESSES

WITHOUT Heterogeneous
WITH ENERGY
ENERGY photocatalysis

ULTRAVIOLET ULTRASOUND ELECTRICAL O3 in alkaline Photocatalytic


MICROWAVE
RADIATION ENERGY ENERGY medium ozonation

Electrochemical Catalytic
O3/UV O3/US MW/H2O2 O3/H2O2
oxidation ozonation

H2O2/UV H2O2/US Anodic oxidation MW/catalyst H2O2/catalyst

O3/H2O2/UV Electro-Fenton

Photo-Fenton
Fe2+/H2O2/UV

UV vacuum

Figure 1. Classification of Advanced Oxidation Processes. Abbreviations used: O3 ozonation, H2O2


hydrogen peroxide, UV ultraviolet, US energy with ultrasound, Fe2+ ferrous ion. (Modified from
Poyatos et al., 2010).

Figure 1 shows the numerous existent AOPs, which can be classified as


heterogeneous or homogenous. In the more commonly used homogeneous process, the
Wastewater Treatment from Textile Industry … 93

oxidant and the catalyst exist in single phase, whilst in the heterogeneous process the
catalyst has a different phase. Homogeneous processes can be further subdivided into
processes that use energy and processes that do not use energy (Poyatos et al., 2010).
AOPs include a combination of oxidants (e.g., H2O2 or ozone ), catalysts (e.g., Fe2 + or
TiO2) and energy (UV radiation or ultrasounds). The AOPs most investigated in
wastewater treatment are heterogeneous and homogeneous photocatalytic methods based
on UV radiation or solar irradiation, ozonisetion, Fenton process, ultrasonic,
electrochemical and wet-air oxidation (Rizzo, 2011). A chemical wastewater treatment
using AOPs can produce complete mineralisetion of the pollutants in CO2, water and
inorganic compounds, or these compounds can be transformed into innocuous products
(Poyatos et al., 2010; Del Moro et al., 2013). In addition, partial decomposition of non-
biodegradable organic pollutants can lead to biodegradable intermediates (Sarria et al.,
2002).
Of these different processes, the present chapter is focused on the UV/H2O2, photo-
Fenton and photocatalysis heterogeneous (TiO2/H2O2/UV).

2.1.1. H2O2/UV
This process, which involves the combination of UV radiation with hydrogen
peroxide (UV/H2O2), is one of the most appropriate and promising technologies for the
removal of toxic organic compounds from wastewater (Alnaizy and Akgerman, 2000;
Aleboyeh et al., 2005). This AOP involves the formation of potent and non-selective
hydroxyl radicals (OH•) generated by the photolysis of H2O2 when UV radiation (hv) is
applied, as shown in reaction R(1) (Alaton et al., 2002; Poyatos et al., 2010):

H2O2+hν→ν2OH• (1)

This photolysis rate does not depend on pH and increases under more alkaline
conditions, so the total photolysis of the system could be affected by pH. The following
propagation reactions are given in R(2), R(3) and R(4) (Glaze et al., 1987):

H2O2+OH•→OH2•+H2O (2)

H2O2+OH2•→OH• +O2+H2O (3)

2OH2•→H2O2+O2 (4)

The advantages of the H2O2/UV process include the wide range of applications for
the degradation of contaminants such as dyes, phenols and pesticides, with an accelerated
rate of oxidation, potential disinfection and meticulous mineralisation of contaminants in
the wastewater (Cao and Mehrvar, 2011).
94 C. López-López, J. Martín-Pascual and J. M. Poyatos

This system has been applied for the degradation of several azo dyes in industrial
wastewater, suggesting that it is an effective method for the treatment of wastewater
contaminated with dye (Zuorro et al., 2013). Some studies report the efficiency of the
process on particular dyes and the effect of the variables in the process.
López-López et al. (2013) reported COD and colour removal efficiencies of 86.38
and 68.95%, respectively, by operating the process under a pH of 7 for a treatment time
of 120 minutes. However the efficiency of the process is severely affected by the
colouring type: Lopez-Lopez et al. (2015), using the same process on commercial dyes,
attained higher efficiencies for organic matter and colour removal (91.42 and 99.60%,
respectively), operating at pH 3 for a treatment time of 120 minutes. Schrank (2007)
obtained only 52% for Vat Green 01 dye removal with the H2O2/UV process and 0.5 g/L
H2O2.
One of the most important parameters to consider in the design of an AOP in general,
and the H2O2/UV process in particular, is the concentration of oxidant. For example,
López-López et al. (2013) reported averages of 86.38 ± 2.9%, 63.03 ± 3.7%, 45.73 ±
3.9%, 35.49 ± 4.5% and 22.94 ± 8.9% using H2O2 concentrations of 5, 2, 1, 0.5 and 0.25
g/L, respectively. Similarly, the colour removal obtained at pH 7 was 68.95, 55.68, 26.44,
10.96, and 2.75% using H2O2 concentrations of 5, 2, 1, 0.5 and 0.25 g/L, respectively.
Obviously, the higher oxidant concentration is, the higher efficiency became.
López-López et al. (2013) studied the effect of pH on the process by using a pigment
that changed the pH from 3 to 11 and operating at concentrations of H2O2 between 0.25
and 5 g/L. The results obtained in that study showed that under neutral pH the H2O2/UV
process removed more organic matter and colour, independent of the concentration of
H2O2
Another fundamental aspect studied by Lopez-López et al. (2014) was the influence
of the exposure time in the process. For example, the rate of colour removal in the
H2O2/UV process was relatively constant at 90 minutes for 0.25 g/L (47.4%) and 75
minutes with 0.5 g/L (82.2%). However, for TOC removal, indicated values increased
with time for all concentrations of H2O2, while removal rates increased with H2O2
concentration independent of time.
According to the results attained by these authors, the H2O2/UV process is an
effective technology for removing many contaminants in wastewater. However, the
selection of the conditions and the influences between them affect the organic matter and
colour removal.
Figure 2 shows a schematic diagram of the laboratory-scale photoreactor used by
López-López et al., (2013). The reactions are carried out in a batch or continues reactor,
which includes a lamp for UV generation. To remove the heat produced from the lamp,
the temperature must be controlled with a refrigeration system to maintain it at a constant
temperature. Normally, the photoreactor is covered with an opaque material to avoid
Wastewater Treatment from Textile Industry … 95

interference with other external radiation and is placed on a magnetic stirrer in order to
keep the sample homogeneous.

Figure 2. Photoreactor diagram used for the Advanced Oxidation Process.

2.1.2. Photo-Fenton
Henry J. Fenton first described the photo-Fenton oxidation reagent (H2O2 in the
presence of Fe2+) and demonstrated that H2O2 could be activated in the presence of Fe2+
ions to oxidise tartaric acid (Fenton, 1894). As such, the photo-Fenton process has proved
to be a good alternative for treating textile wastewater containing high levels of dyes,
recalcitrant organic compounds and suspended solids by improving the biodegradability
of the effluent (Vedrenne et al., 2012; Yu et al., 2013). This process appears to have the
ability to completely decolourise and mineralise the dyes from the textile industry in a
short reaction time (Lucas and Peres, 2006).
Fenton’s oxidation appears to be the most promising method, in terms of cost -
effectiveness and simplicity of operation (Tekin et al., 2006). Fenton is a homogeneous
oxidation process and is considered to be a metal-catalysed oxidation reaction, in which
iron is the catalyst (Tekin et al., 2006; Saritha et al., 2007) and includes reactions of
peroxides (usually H2O2) with iron ions to form active oxygen species (OH•) that oxidise
organic or inorganic compounds present in the wastewater (Pignatello et al., 2006).
The mixture of ferrous sulphate and H2O2 generates OH• radicals that are capable of
oxidising organic pollutants in wastewater (Sivakumar et al., 2013) and the additional
formation of hydroxyl radicals could increase with UV light. Thus, by increasing the Fe2+
concentration the overall reaction is accelerated (Modirshahla et al., 2007). As the
concentration of dye increases, it is necessary to increase the concentration of both Fe 2+
and H2O2 to ensure the presence of OH• radicals to degrade organic matter (Arslan-
Alaton et al., 2009, Prato-Garcia and Buitrón, 2013).
The reactions for the production of OH• radicals in the photo-Fenton process can be
represented by the reactions given below (Sun and Pignatello, 1993; Poyatos et al., 2010;
Maezono et al., 2011):
96 C. López-López, J. Martín-Pascual and J. M. Poyatos

Fe2++H2O2→Fe3++OH- +OH• (5)

H2O2+hv→2OH• (6)

Fe3++H2O+hv→Fe2++OH•+H+ (7)

The photo-Fenton process has been used successfully in the removal of organic
compounds and can completely decolourise water. Employing the same conditions as in
the H2O2/UV process, López-López et al. (2015) studied the removal of organic matter
and colour using the photo-Fenton process.
The rates of colour removal for the photo-Fenton process were 87.2, 91.0 and 93.3%
for 1, 2 and 5 g/L peroxide, respectively, after 120 minutes. These rates were lower than
those reported by Elmorsi et al. (2010) for photo-Fenton treatment of the Mordant red 73
dye, where 99% decolourisation was seen within 15 min. In relation to the organic matter
removal, the photo-Fenton process was achieved more than 94% removal after 120 min
with 5 g/L of H2O2.
When Fe2+ was used as the catalyst, after 15 minutes of reaction, for all
concentrations of H2O2, the colour yields are very high, with the lowest concentration of
H2O2 achieving a colour removal above 58%.

2.1.3. Heterogeneous Photocatalytic (TiO2/H2O2/UV)


The term photocatalysis is applied to the acceleration of a photoreaction by the action
of a catalyst. The use of TiO2 in these processes is of great interest due to its high
photocatalytic activity, lack of toxicity, biological and photochemical stability in aqueous
solutions and its chemically inert nature (Pekakis et al., 2006; Sakkas et al., 2009).
Processes consisting of a heterogeneous photocatalysis (TiO2/H2O2/UV), which degrade
pollutants by the generation of hydroxyl radicals using a catalyst (TiO2), an oxidant
(H2O2) and UV radiation, are advantageous due to the lack of limitations of mass transfer,
operation under environmental conditions and the possible use of solar irradiation
(Pekakis et al., 2006). In addition, the catalyst itself is inexpensive and readily available
(Velegraki et al., 2006).
In these systems, the hydroxyl radicals (OH•) are more likely to form and a larger
number of oxidant species may appear in the electron (e) and proton (h+) generation
processes (García et al., 2007):

TiO2+hv→TiO2 (e-+h+) (8)


Wastewater Treatment from Textile Industry … 97

TiO2h++OH-ad→TiO2+OH• (9)

H2O2+e-→OH•+OH- (10)

The heterogeneous photocatalysis process (TiO2/H2O2/UV) is a technology that can


also easily decolourise and greatly reduce the organic load of dyes and related effluents
(Velegraki et al., 2006; Chen et al., 2009).
The TiO2/H2O2/UV process was found to be the most effective method for colour and
organic matter removal by López-López et al. (2015). At lower H2O2 concentrations,
colour removal rates were higher (77.6 and 85% for 0.25 and 0.5 g/L of H2O2,
respectively) and organic matter removal rates were 46.81 and 73.85%, respectively, at
the same H2O2 concentrations after 120 minutes. At higher H2O2 concentrations the
colour and organic matter removal rates were 99.9% and 94.55%, respectively, at 120
minutes.

3. COAGULATION-FLOCULATION PROCESS AS A PRE-TREATMENT

Considering the principles of AOPs based on UV, the presence of turbidity is a


limiting aspect for the efficiency of the treatment (Islam et al., 2011). Textile wastewater
contains particles of a wide variety of shapes, sizes and densities (Aguilar et al., 2003;
Sörensen and Larssson, 1992) and the removal of these particles from the wastewater is
of great interest because they can absorb the chemical and microbiological contaminants
present in the water (Lawler, 1997). Additionally, high concentrations of particles in
water promote greater heat absorption from solar radiation and, consequently, the
dissolved oxygen in the sample decreases.
Furthermore, due to the turbidity present in the water, the penetration of UV into the
water sources is reduced; therefore, the efficiency of the process can be affected (Prado
and Espulgas, 1999). As a consequence of an excessive level of turbidity, the efficiency
of the photomineralisation and photodisinfection of the contaminants present in the water
is reduced due to the effect of shielding, which attenuates the light penetration (Chin et
al., 2004, Rincon and Pulgarin, 2005). Turbidity leads to weakened penetration of direct
light and decreased absorption of light photons (Seien and Soleymani, 2012). For this
reason, Yonar et al. (2006) recommended a pre-treatment to eliminate turbidity to ensure
the success of the oxidation process. One of the alternative solutions for this turbidity
problem in the influent of AOP could be Coagulation-Flocculation (CF).
CF process is a common treatment used in water effluents (Rodrigues et al., 2008), as
it is a versatile method that has shown high efficiency of removal in the COD and SS
98 C. López-López, J. Martín-Pascual and J. M. Poyatos

(Guida et al., 2007). The flocculation is a process based on two stages, which cannot be
applied independently.
Coagulation is the phase in which colloidal particles are destabilised by the
neutralisation of their electrical charges through the addition of chemical compounds.
The amount of coagulant that it is added to the water should be taken into account in this
process, as the turbidity of the water can be increased when the concentration is higher
than necessary. Flocculation is the stage that follows the coagulation, in which all the
electrically discharged particles are put into contact with one another so that the
destabilised particles enter into an equilibrium around inert particles (flocculants),
thereby resulting in the formation of larger flocs that can be decanted or separated by
membranes.
The CF process usually consists of the rapid dispersion of a coagulant into the
wastewater, followed by an intense agitation, commonly defined as a rapid mixing
(Rossini et al., 1999). This can achieve a greater removal of particles in the effluent and
provide improved filtered water compared to conventional treatment processes (Rahman
et al., 2010). This process also removes colour and turbidity in industrial wastewater
(Meriç et al., 2005; Oller et al., 2011), and is a favoured option for this process (Oller et
al., 2011).
The coagulants most commonly used for treating contaminated water are aluminium
and iron salts; although a great variety of them, both of inorganic and organic nature, can
be found. In general, the hydrolysis reactions of trivalent metals can be presented as
R(11) (Ching et al., 1994a; Stephenson and Duff, 1996):

xMe3++yH2O2 → Mex(OH)y(3x-y)++yH+ (11)

The hydrolysis reactions that take place with the hydrated ferric ion are R(12) and
R(13) (Fair et al., 1971):

[Fe(H2O)6]3++H2O → [Fe(H2O)5(OH)]2++H3O+ (12)

[Fe(H2O)5(OH)]2++H2O → [Fe(H2O)4(OH)2]++H3O+ (13)

Hydroxo ferric complexes have a great tendency to polymerise, thereby producing


the simplest reaction R(14) or R(15):

2[Fe(H2O)5(OH)]2+ → [Fe2(H2O)8(OH)2]4++2H2O (14)

[Fe2(H2O)8(OH)2]4++H2O → [Fe2(H2O)7(OH)3]3++H3O+ (15)


Wastewater Treatment from Textile Industry … 99

Al3+ behaves very similarly to Fe3+ but its hydrolysis is apparently more complicated.
Aluminium salts are easily hydrolysed and the acidity of the aqueous aluminium ion is
lower than that of the ferric ion. The species formed during the hydrolytic reactions for
aluminium are shown in reaction (16) (Fair et al., 1971; Hutchison and Healy, 1990):

[Al(H2O)6]3+→[Al(H2O)5OH]2+→[Al6(OH)15]3+→[Al8(OH)20]4+→Al(OH)3(s)
→ Al(OH)4]-
(16)

pH is one of the most important factors because it determines, for each coagulant, the
nature of the species present in the water and its solubility. There is a pH zone for each
coagulant where a good flocculation occurs in the short term using a given dose of
coagulant (Aguilar et al., 2002).
It is important to keep in mind that the colloidal particles tend to remain in
suspension when they are stable. As such the stability must be reduced so that it is easier
to join larger nuclei and increase their density to make facilitate removal by
sedimentation. Therefore, the chemical reagents in the process are added, which eliminate
the electrical charge that keeps them separated and can be agglomerated more easily. This
charge can be positive or negative, although most of the colloids of wastewater developed
a negative charge (Fair et al., 1971; Narkis and Rebhun, 1983; Van Benschoten and
Edzwald, 1990a; Nemerow and Dasgupta 1991; Aguilar et al., 2002).
Some novel pre-hydrolysed coagulants, such as Polyaluminium chloride (PACl),
Polyaluminium ferric chloride (PAFCl), Polyferrous sulphate (PFS) and Polyferric
chloride (PFCl) were found to be more effective and suggested for the decolourisation of
textile wastewater (Kumar Verma et al., 2012). López-López et al. (2016) tested five
coagulants of this type (SICOAG C-21, FLOCUSOL-PA/18, FLOCUSOL-CM/1,
SIFLOC C 40 L PLUS and SIFLOC C-3) in order to analyse the effect of CF as pre-
treatment to colour, turbidity and total organic carbon (TOC) removal from effluent by
AOPs.
After the CF process the colour removal was higher than 84.48% in all cases;
however, the coagulant used presented differences in the turbidity and TOC removal. The
TOC removal presented lower efficiencies than colour, which changed between 52.90
and 82.19% with SICOAG C-21 and FLOCUSOL-CM/1, respectively. In relation to the
turbidity removal, a high range of values was obtained for the efficiencies, ranging from
9.52 to 98.21% (López-López et al., 2016).
Table 1 shows the results of total colour, turbidity and TOC removal after CF and
AOP. It can be seen that the colour removal in all cases is practically 100%.
In the case of turbidity removal, there are differences depending on the coagulant-
flocculants used. The coagulants-flocculants SICOAG C-21 and FLOCUSOL-PA/18
produce a turbidity removal higher than 92 and 98%, respectively. However, in the case
100 C. López-López, J. Martín-Pascual and J. M. Poyatos

of the other three coagulants-flocculants, turbidity removal is very low. The different
turbidity removal obtained can allow us to analyse the effect of the turbidity in the
behaviour of the AOP, due to the fact that turbidity removal plays a crucial role as the
penetration of UV light through the wastewater is important for the success of the process
in the long run (Yonar et al., 2006). The TOC removal, for all cases, is higher than 79%.

Table 1. Total removal (%) of colour, turbidity and TOC from the raw effluent after
CF and AOP (López-López, 2016)

Colour Turbidity TOC


% total removal
H2O2/UV 99.94 92.86 97.10
SICOAG C-21 (5 g/L) photo-Fenton 100.00 92.86 98.39
TiO2/H2O2/UV 100.00 92.86 99.29
H2O2/UV 99.66 98.21 95.12
FLOCUSOL-PA/18 (5 g/L) photo-Fenton 99.77 98.21 98.20
TiO2/H2O2/UV 99.94 98.21 98.20
H2O2/UV 99.69 10.58 79.51
FLOCUSOL-CM/1 (0.1 g/L) photo-Fenton 99.62 11.11 86.90
TiO2/H2O2/UV 99.93 11.64 94.43
H2O2/UV 99.33 19.79 89.95
SIFLOC C 40 L PLUS (0.1
photo-Fenton 99.12 19.79 93.25
g/L)
TiO2/H2O2/UV 99.73 20.32 94.91
H2O2/UV 99.28 30.77 91.11
SIFLOC C-30 (1 g/L) photo-Fenton 99.09 30.77 94.23
TiO2/H2O2/UV 99.84 31.79 97.01

The use of CF as a pre-treatment of an AOP that uses catalyst improves the efficiency
in colour and organic matter removal with respect to the process without pre-treatment.

KINETIC MODELLING OF AOPS

A significant advantage of AOPs is that they can be mathematically modelled at


several different levels to determine the optimum conditions of H2O2 and exposure time,
based on known kinetic pathways and constant reaction rate s that can provide the most
information best fit between model and laboratory data (Crittenden et al., 1999). Table 2
shows the kinetic equations used by López-López et al. (2015).
Wastewater Treatment from Textile Industry … 101

1 a)
0,8

Ct/Co
0,6
0,4
0,2
0
0 15 30 45 60 75 90 105 120
Time (minutes)

1 b)
0,8
Ct/Co
0,6
0,4
0,2
0
0 15 30 45 60 75 90 105 120
Time (minutes)

1 c)
0,8
Ct/Co

0,6
0,4
0,2
0
0 15 30 45 60 75 90 105 120
Time (minutes)

1 d)
0,8
Ct/Co

0,6
0,4
0,2
0
0 15 30 45 60 75 90 105 120
Time (minutes)

1 e)
0,8
Ct/Co

0,6
0,4
0,2
0
0 15 30 45 60 75 90 105 120
Time (minutes)

Figure 3. Ct/C0 ratio for AOP TiO2/H2O2/UV for each concentration of H2O2: 0.25 (a), 0.5 (b), 1 (c),
2 (d) and 5 (e) g/L for each type of water used in the different investigations: synthetic water with
commercial dye, real water with commercial dye and pre-treated water with CF pre-treatment prior to
the AOP: experiment 1 (SICOAG C-21), experiment 2 (FLOCUSOL-PA/18), experiment 3
(FLOCUSOL-CM/1), experiment 4 (SIFLOC C 40 L PLUS) and experiment 5 (SIFLOC C-30) (López-
López, 2016).
102 C. López-López, J. Martín-Pascual and J. M. Poyatos

Table 2. Kinetic equations (modified of López-López et al., 2015)

Model Equation Parameter

C0: initial TOC concentration


Pseudo-first Order 𝐶𝑡 = 𝐶𝑜 − (𝐶𝑒 ∗ (1 − 𝑒 −𝑘1′∗𝑡 ))
(mg/L)

t ∗ k2′ ∗ Ce2
Pseudo-second Order 𝐶𝑡 = Co − Ct: TOC concentration at any
1 + k2′ ∗ Ce time, t, (mg/L)

Zero Order 𝐶𝑡 = 𝐶𝑜 + 𝑘𝑜 ∗ 𝑡
Ce: the removal capacity at
equilibrium (mg/L)

First Order 𝐶𝑡 = 𝐶𝑜 ∗ 𝑒 𝑘1∗𝑡


t: time of process (min)

𝐶𝑜
Second Order 𝐶𝑡 =
1 + 𝑘2 ∗ 𝐶𝑜 ∗ 𝑡 k1’,2’,0,1,2,3: Velocity constant

𝐶𝑜 2
Third Order √ a: initial TOC concentration rate
1 + 𝑘3 ∗ 𝐶𝑜 2 ∗ 𝑡
(mg/L min)

1 1
Elovich type equation 𝐶𝑡 = 𝐶𝑜 + ln(𝑎𝑏) + ln(𝑡)
𝑏 𝑏 b: removal constant (mg/L)

The pseudo-first-order model for the three processes studied by Ho and McKay
(1998), Ho et al. (2000), Calero et al. (2011) and López-López et al. (2013, 2016)
indicated the highest correlation between empirical and modelled data with an average of
0.965, suggesting that this model could be used to design AOPs. The rate constants
increased with H2O2 concentration and indicated that heterogeneous photocatalysis
(Figure 3) was the most rapid way to remove organic matter at the same H2O2
concentration.
With heterogeneous photocatalysis, increasing the concentration of H2O2 increased
the degradability of water, thereby confirming that by using TiO2 as a catalyst, high rates
of organic matter removal are attained; in addition, less processing time is required.

GENERAL DISCUSSION

Considering the results obtained by the numerous authors who have studied the
application of AOPs in the textile industry, some relevant aspect can be summarised. The
Wastewater Treatment from Textile Industry … 103

efficiency of colour and organic matter removal increases with the oxidant
concentrations, up to a limit whereby no more oxidant is consumed. An excess of H2O2
could be hazardous for the environment and so it is important to choose the minimum
concentration to attain the efficiency required. Moreover, an increase in the exposure
time also improved the efficiency to the oxidant; once H2O2 is used up the process
finished. The greater the exposure time, the greater the energetic consumption; thus, it is
especially important for the design of these processes to study the characteristics of the
influent.
In general terms, the addition of a catalyst to a conventional AOP improves the
efficiency of the process; however, the cost of the process increases too. Among the
different process studied, generally the most reliable is TiO2/H2O2/UV, although with
certain textiles wastewater the photo-Fenton can attain similar or even better removal
rates. Considering the negative effect of the turbidity in the efficiency of the AOP, the
use of a pre-treatment must be considered, especially in wastewater with high
concentrations of colloidal particles.

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In: Textiles: Advances in Research and Applications ISBN: 978-1-53612-855-0
Editor: Boris Mahltig © 2018 Nova Science Publishers, Inc.

Chapter 5

GREEN ELECTROSPINNING OF NANOFIBER MATS


FROM BIOPOLYMERS FOR MEDICAL
AND BIOTECHNOLOGICAL APPLICATIONS

Timo Grothe, Nils Grimmelsmann, Sarah Vanessa Homburg


and Andrea Ehrmann*
Bielefeld University of Applied Sciences,
Faculty of Engineering and Mathematics, Bielefeld, Germany

ABSTRACT

Electrospinning can be used to create mats from nanofibers consisting of polymers,


possibly blended with other organic or inorganic components. Compared with other
textile fabrics, such as common nonwovens, these nanofiber mats possess large surface-
volume ratios, allowing for enhanced interactions with their environment. This property
makes them suitable for applications in wound dressing, drug delivery, biotechnological
filter technology, etc., especially if prepared from biopolymers with intrinsically
antimicrobial or other qualities.
In a recent project, the possibilities to create such nanofiber mats from diverse
(bio-)polymers by “green” electrospinning, i.e., electrospinning from aqueous solutions
or other nontoxic solvents, are investigated. The article depicts the latest results from
needleless electrospinning pure polymers and polymer blends as well as typical physical
and chemical properties of the created nanofiber mats.

Keywords: electrospinning, nanospinning, nanofiber, biopolymer, polymer blend, green


electrospinning

*
Corresponding Author Email: andrea.ehrmann@fh-bielefeld.de.
116 Timo Grothe, Nils Grimmelsmann, Sarah Vanessa Homburg et al.

INTRODUCTION

Electrospinning belongs to the primary spinning methods, allowing for producing


fine fibers or fiber mats from polymer solutions or melts. The diameters of electrospun
fibers usually range from some ten nanometers to a few micrometers. Electrospinning can
be performed using a needle through which the polymer solution or melt is pressed or by
coating a rotating drum or a fine wire (Koombhongse et al. 2001; Bognitzki et al. 2000;
Theron et al. 2001), resulting in different positioning of the nanofibers on a substrate. The
process of needleless electrospinning using a wire system is described in detail in the
section “Methods.”
The principle technology of electrospinning has been known for decades and was
patented in 1934 (Formhals 1934). Nevertheless, the electrospinning technology
experienced a revival only in the 1990s when it was shown that a broad variety of
different polymers could be spun from solutions (Reneker and Chun 1996) or melts
(Larrondo and Manley 1981). Besides polymers which are typically used in the textile
industry, such as polyester, polyamides, aramide, poly(acrylonitrile ), etc., biopolymers
are of large interest, such as poly(ethylene glycol ), polypeptides, proteins, etc.
Due to their large inner surface, nanofiber mats are especially used in applications
which necessitate large contact areas between the fiber material and the environment,
e.g., as filters in medical or biotechnological areas, for tissue engineering, wound
dressing, drug delivery, etc. Additional to the fiber diameter, the morphology of the
nanofibers can be modified by carefully tailoring the spinning and solution /melt
parameters. Besides round cross-shapes, flat ribbons were produced (Koombhongse et al.
2001, Frenot and Chronakis 2003) or combinations of fibers and membranes
(Grimmelsmann et al. 2017b). With too low viscosities, nano droplets are formed instead
of fibers. Too low electrode-substrate distances or too high electrical fields may cause
formation of undesired beads, a phenomenon which occurs more or less frequently
depending on the spinning polymer. It was attributed to capillary break-ups of the
polymer jets, thus being dependent on the charge density on the polymer jets, their
surface tension and the viscoelastic properties of the solutions (Deitzel et al. 2001; Fong
et al. 1999). Fiber diameters, on the other hand, depend mainly on the polymer
concentration in the solution (Deitzel et al. 2001).
While most polymers are spun from acids or toxic solvents, the idea of “green”
electrospinning arose around 2010, avoiding harmful organic solvents by spinning from
polymeric solutions (Sun et al. 2001), emulsions or suspensions (Agarwal and Greiner
2011). In the latter case, spinning agents, such as high-molecular weight poly(ethylene
glycol) (PEG), can be used to process a dispersion to water -resistant nanofiber mats
(Bubel et al. 2013).
Spinning from aqueous solutions often necessitates an additional crosslinking step
after the actual spinning process, e.g., by UV irradiation (Giebel et al. 2013a; Giebel et al.
Green Electrospinning of Nanofiber Mats from Biopolymers … 117

2013b) or heat treatment (Shi and Yang 2015; Jiang et al. 2016). The crosslinking
efficiency, on the other hand, often depends on the nanofiber mat properties and thus on
the spinning parameters (Giebel et al. 2013a).
Functionalization of such stabilized nanofiber mats can be achieved by coating them,
e.g., with dyes, antibacterial materials, metal nanoparticles, or the like (Giebel et al.
2013b; Wang et al. 2015; Bunyatova et al. 2016; Castilla-Casadiego et al. 2016). On the
other hand, such nanofiber mats can be used for controlled drug delivery (Salehi et al.
2014; Chen et al. 2015) or protein release (Wang et al. 2015).
The biopolymers used in this examination and their potential applications are
described more in detail in the “Results” section.

METHODS

Electrospinning

The process of needleless electrospinning is depicted in Figure 1. Firstly, a carriage is


filled with the polymer solution or melt. This carriage travels along the high voltage
electrode, formed by a thin stainless steel wire. A fine spinning nozzle surrounds the wire
and allows the polymer solution to coat it.
This coating is forced to the ground electrode due to the high voltage field between
both electrodes before the solvent evaporates. The ground electrode is shielded by a
movable substrate, here a polypropylene mat. During flying, the polymer drops are drawn
in the electric field, resulting in formation of long, thin fibers which form so-called
Taylor cones between the electrodes, i.e., cone-shaped jets of fibers. After impinging on
the substrate, the fibers build a mat of nanofibers which are in most cases rigidly fixed on
each other. It should be mentioned that with needleless electrospinning it is not possible
to create infinitely long fibers which could be carefully drawn away from the substrate
afterwards, as it can be made possible in needle-electrospinning.
Several techniques can be used to implement the basic idea of electrospinning. While
several research groups prefer working with self-built equipment, mostly used for needle-
electrospinning, our group work s with a commercially available machine, the
“Nanospider Lab” produced by Elmarco (Czech Republic ), as depicted in Figure 2. This
equipment enables production of relatively large-scale nanofiber mats in the order of
magnitude of 1 m²/h, with significant dependencies of this value on the spinning
parameters. For industrial applications, the process can be upscaled to larger machines.
The spinning parameters can be modified in large ranges. Typical parameters are,
e.g., high voltages between 25 kV and 80 kV; currents between 0.05 mA and 0.3 mA;
carriage speeds between 100 and 200 mm/s; nozzle diameters between 0.6 mm and 1.5
mm; electrode-substrate distances between 120 mm and 240 mm; and relative humidity
118 Timo Grothe, Nils Grimmelsmann, Sarah Vanessa Homburg et al.

in the spinning chamber between 30% and 40%. Higher relative humidities may result in
severe problems, e.g., with cotton -candy-like fiber connections between high voltage
electrode and substrate, flashovers, etc.

Figure 1. Principle of the electrospinning process.

Figure 2. Electrospinning apparatus “Nanospider Lab.”

Biopolymers and Other Ingredients

For the spinning solutions, a broad variety of different materials was used: aloe vera
(alexmo cosmetics ); chitosan; commercial agar -agar 15% in aqueous solution;
commercial gelatin powder (as used for baking) 15% in aqueous solution; commercial
gelatin leaves 15% in aqueous solution; and pure gelatin powder (Abtei, Germany) 55%
in aqueous solution. In some experiments, the latter was blended with 19% wax
(KahlWax 6592) to increase water resistance.
As a spinning agent as well as for basic tests with the pure material, PEG with a
molecular weight of 600,000 daltons (concentration 8%) purchased from S3 Chemicals
Green Electrospinning of Nanofiber Mats from Biopolymers … 119

was used in some experiments. The concentrations of the spinning solutions were chosen
due to their viscosity which must not be too high for needleless electrospinning.
Different salts (NaCl, KCl and KBr, purity > 99%, Carl Roth) as well as PEDOT:
PSS (poly(3,4-ethylenedioxythiophene) polystyrene sulfonate) were used to modify the
conductivity of the spinning solutions.
Diverse additional materials were integrated into the polymer solutions, e.g., forest
fruit tea (MAYFAIR), a ferrofluid (AstroMedia), and chlorophyll.
Optical evaluation of the nanomats was done using a confocal laser scanning
microscope (CLSM) VK 9000 by Keyence. All images shown here have a nominal
magnification of 2000 x.

RESULTS

Poly(ethylene glycol )

Poly(ethylene glycol) (PEG), also called Poly(ethylene oxide) (PEO), is a water -


soluble biopolymer with very good spinnability. Solely, it can be used in applications
from skin creams or toothpaste to pharmaceutics to medicine. PEG can be used as a
coating for fibers from other materials (Liu et al. 2003; Wang et al. 2000). In
electrospinning, it is often used as a spinning agent, e.g., in combination with collagen,
PVDF or cellulose (Wongchitphimon et al. 2011; Zeugolis et al. 2008; Sungkaew et al.
2010), while only few reports about spinning pure PEG nanofibers can be found in the
scientific literature (Deitzel et al. 2001; Chen et al. 2007; Fortunato et al. 2014).
In an earlier project, we have investigated the morphology of PEG nanofiber mats
created by needleless electrospinning and identified the PEG concentration in the
aqueous solution as the most crucial parameter. Other spinning parameters, such as the
voltage, the electrode-substrate distance, the carriaged speed etc. influenced the fiber mat
density, but a significant influence on the fiber mat morphology was not observed
(Grothe et al. 2017a). On the other hand, the molecular weight of the PEG under
examination had to be chosen carefully to enable fiber formation (Grothe et al. 2017b). It
was found that at too low molecular weights, strong Taylor cones were visible, but no
fibers were formed on the substrate. Too high molecular weights, however, impeded
reaching the necessary concentrations for electrospinning since the viscosity of the
spinning solution became too high. Generally, molecular weights between 300 kD and
600 kD in combination with concentrations between 6% and 12% PEG in aqueous
solution were found to be suitable for needleless electrospinning. It should be mentioned
that these values differ from those found for needle-electrospinning (Grothe et al. 2017a;
Jaeger et al. 1998).
120 Timo Grothe, Nils Grimmelsmann, Sarah Vanessa Homburg et al.

Figure 3 depicts PEG samples produced under different conditions which are given in
Table 1 for an overview of possible morphologies, depending on the spinning solution
and process parameters. By changing these parameters, fiber densities, thicknesses, and
straightness are modified, until transformation from fibers to membrane-like structures
start (cf. sample D).

Figure 3. PEG electrospun nanofiber mats created by different spinning and solution parameters, cf.
Table 1.

Table 1. Parameters of the nanofiber mats depicted in Figure 3

Sample Mol. weight Concentration U Carriage speed Electr. dist.


A 600 kD 6% 35 kV 100 mm/s 140 mm
B 600 kD 6% 25 kV 200 mm/s 140 mm
C 600 kD 8% 70 kV 250 mm/s 190 mm
D 600 kD 8% 75 kV 250 mm/s 140 mm

Aloe Vera

Aloe vera belongs to the materials typically used for medical applications. It contains
more than 70 active components, e.g., minerals, amino acid s, vitamines, or enzymes
(Surjushe et al. 2008). Due to its antiseptic (Surjushe et al. 2008) and anti-inflammatory
properties (Hutter et al. 1996), its ability to increase wound healing (Fulton 1990; Chithra
Green Electrospinning of Nanofiber Mats from Biopolymers … 121

et al. 1998) and collagen cross-linking (Heggers et al. 1996) and to support the immune
system (Ro et al. 2000), it can be used as a part of bandages etc. In electrospinning, aloe
vera cannot be used solely, but is usually co-spun with PEG or another spinning agent
(Grothe et al. 2017c).
Figure 4 depicts a nanofiber mat created from aloe vera 2.5% in aqueous solution and
PEG 8% in aqueous solution. With this relation, relatively thick and homogenous mats
are produced with nanofiber diameters of approximately 500 nm.

Figure 4. Electrospun aloe vera / PEG nanofiber mat.

Casein

Casein can absorb water to a large extend, making it smooth to the skin and
comfortable in contact, especially for people with skin diseases such as neurodermatitis.
It is known to have a natural antibacterial effect, to promote biomineralization (Szyk-
Warzynska et al. 2014) and to work as a size-selective molecular device which attracts
macromolecules like proteins or polysaccharides (Peixoto et al. 2015).
In electrospinning, casein is usually combined with other materials (Grothe et al.
2017; Tomasula et al. 2016) or in graft copolymers (Dong and Gu 2002).
For the experiments shown here, 25% casein in aqueous solution and 8% PEG in
aqueous solution were mixed in different ratios. Figure 5 depicts the result of mixing 5 ml
casein solution with 1.5 ml PEG solution. Apparently, this mixing ratio is not perfect,
leading to an inhomogeneous mat with several thicker and denser parts as well as visible
diameter modifications on the fibers, apparently resulting from droplet formation during
the spinning process.
Combining 5 ml casein solution with only 1 ml PEG solution results in denser and
more regular nanofiber mats (Grothe et al. 2017c), while adding water leads to very fine
fibers with droplets. Spinning casein solely seems to be impossible.
122 Timo Grothe, Nils Grimmelsmann, Sarah Vanessa Homburg et al.

Figure 5. Electrospun casein / PEG nanofiber mat.

Chitosan

Chitosan belongs to the typical filter materials, amongst others due to its antifouling
(Lim 2016) and antibacterial properties (Cooper et al. 2013; Wang et al. 2016). It is used
as a coating on filters for disperse dyes in water (Zhao et al. 2015) or on cotton fabrics for
filtering Gram-positive and Gram-negative bacteria (Ferrero et al. 2014; Periolatto et al.
2014). Additionally, chitosan can be applied for medical or biotechnological scaffolds,
e.g., for growing human mesenchymal stem cells (Muzzarelli et al. 2015; Aljawish et al.
2016).

Figure 6. Electrospun chitosan /PEG nanofiber mat.

In electrospinning, chitosan is usually blended with PEG, resulting in morphologies


which strongly depend on the chitosan: PEG ratio (Wei et al. 2015; Lemma et al. 2016;
Grimmelsmann et al. 2017a; Grimmelsmann et al. 2017b). The nanofiber mat depicted in
Green Electrospinning of Nanofiber Mats from Biopolymers … 123

Figure 6 was produced using a chitosan: PEG ratio of 3: 2, while higher amounts of
chitosan resulted in strong bead formation.

Agar

Agar is a typical cell growth medium for biotechnological applications. It is reported


to be not spinnable solely from aqueous solutions (Sousa et al. 2015a); however, co-
spinning with different polymers from other solution was successfully performed (Sousa
et al. 2015b).

Figure 7. Electrospun agar /PEG coating on PP substrate fibers.

In our experiments, the temperature of the spinning equipment, especially cartridge


and nozzle, was shown to strongly influence the possible spinning duration since at low
temperature the viscosity of the agar solution became too high to be spinnable any longer.
Combining agar and PEG in a weight-ratio of 2: 1 and electrospinning from pre-heated
equipment resulted in dense nanofiber mats which turned into coatings for ratios around
20: 1. Figure 7 depicts such a coating, gained from spinning agar-agar 15% in aqueous
solution in combination with 10% of PEG 8% in aqueous solution.

Gelatin

Gelatin is also a typical material for tissue engineering (Elamparithi et al. 2017)
which can be blended with other materials, such as poly(glycerol sebacate), to increase
the biocompatibility of the resulting nanofiber mat (Hu et al. 2017). Here, different
approaches to electrospin gelatin are depicted.
124 Timo Grothe, Nils Grimmelsmann, Sarah Vanessa Homburg et al.

Figure 8 (upper left panel) shows the results of electrospinning gelatin leaves. This
attempt led to coating the PP fibers of the substrate instead of producing nanofibers.
From pure gelatin (pharmaceutical grade), thick flat fibers were spun.
Adding PEG to the pure gelatin solution interestingly resulted in electrospraying
instead of electrospinning, opposite to previous experiments in which PEG has proven to
work well as a spinning agent. Finally, adding wax to the pure gelatin spinning solution
in order to increase the water resistance resulted in short, wax-coated fibers. Apparently,
gelatin belongs to the materials which should ideally be spun solely or in combination
with other polymers than PEG.

Figure 8. Electrospun gelatin nanofibers from different aqueous solutions.

PEG with Different Dopants

While the former sub-chapters concentrated on the possibility to spin non-solely


spinnable polymers by adding PEG, here different modifications of PEG spinning
solutions and additions are depicted which can be used to add different functions or to
modify the spinning process.
Figure 9, e.g., shows blends of PEG with different concentrations of NaCl. Salts can
be used to modify viscosity (Frenot and Chronakis 2003) and conductivity
(Murugendrappa et al. 2000; Blomberg et al. 2017) of the spinning solutions and thus to
change the physical properties of the resulting nanofiber mats. Here, it is clearly visible
that high concentrations of NaCl destroy fiber formation, most probably due to the
Green Electrospinning of Nanofiber Mats from Biopolymers … 125

extremely increased conductivity of the solution which was approx. one order of
magnitude higher than suggested for needleless electrospinning.

Figure 9. Electrospun PEG nanofibers with different amounts of NaCl.

Another possibility to increase the conductivity of an electrospun nanofiber mat is the


addition of the conductive polymer PEDOT: PSS to a PEG solution, as depicted in Figure
10 (left panel). However, similar problems arise as with the addition of salts – the desired
conductivities cannot be reached with relatively low PEDOT: PSS concentrations (here:
22%), while higher amounts of the conductive polymer result in the typical problems
with too conductive spinning solutions (Grothe et al. 2016).
Another physical property of nanofiber mats which can be increased by blending
PEG with another material is the magnetism of the fiber mat. Figure 10 (right panel)
depicts a nanofiber mat produced from PEG co-spun with a ferrofluid. The different
brightnesses in the nanofiber mat show that not all areas have the same magnetic
properties; however, on larger scales, these results may be sufficient. A problem in
electrospinning this solution is the missing compatibility of water -based PEG solutions
and oil -based ferrofluids. Further research should try to implement magnetic
nanoparticles directly in the aqueous PEG solution.

Figure 10. Electrospun PEG nanofibers with PEDOT: PSS and ferrofluid.
126 Timo Grothe, Nils Grimmelsmann, Sarah Vanessa Homburg et al.

Figure 11. Electrospun PEG nanofibers with chlorophyll and forest fruit tea.

Finally, Figure 11 shows PEG nanofiber mats blended with chlorophyll (coated area
in left panel) and forest fruit tea (dark areas in right panel). In both cases, the color of the
nanofiber mats is changed on macroscopic scales, and their smell allows identification of
the respective additional indegredient. In a similar way, PEG nanofiber mats could also
be used for drug delivery.

CONCLUSION

Nanofiber mats were electrospun from PEG and diverse other biopolymers as well as
additional ingredients, used for modifying the physical properties of the mats. In most
cases, by carefully adjusting the solution and spinning parameters, it was possible to gain
nanofiber mats with different morphologies and other properties.

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In: Textiles: Advances in Research and Applications ISBN: 978-1-53612-855-0
Editor: Boris Mahltig © 2018 Nova Science Publishers, Inc.

Chapter 6

ACHIEVING ELECTRICAL CONDUCTIVITY


IN TEXTILES: AN OVERVIEW
OF CURRENT TECHNIQUES

Thomas Grethe*, Karoline Günther, Thomas Weide


and Anne Schwarz-Pfeiffer
Hochschule Niederrhein – University of Applied Sciences,
Moenchengladbach (Germany )

ABSTRACT

Electronic textiles are subjected to an increasing attention since the combination of


sensory or actuary functions with textile materials is quite promising.
Initially the integration of electronic functions into textiles for recreational purposes
was reported, for example integrating control elements for a music player in a jacket, or
light application in a dress (Post et al. 2000). In this early stage conventional electronic
components were integrated in the textile structures. The ongoing development process
leads to higher integration levels by empowering textile structures themselves to act as
electronic devices. An ambitious example is the fabrication of fiber based transistors,
which was reported in 2005 by Lee et al. (Lee et al. 2005). Less demanding approaches
like realizing resistors and capacitors with textile materials is also often referred to
(Castano et al., 2014). These simple structures can act as sensors to detect for instance
force (Meyer et al., 2010; Shu et al., 2010), elongation (Cochrane et al., 2010; Mattmann
et al., 2011), moisture (Devaux et al., 2011; Weremczuk, 2012), and temperature
(Sibinski et al., 2010; Schwarz-Pfeiffer, 2015). These types of textiles are already
commercialized. This development shifts possible fields of application from consumer
goods to technical appliances. Therefore, electronic functions can be found with
increasing extent in technical textiles. The field of application spans from geo textiles

*
Corresponding Author Email: Thomas.grethe@hsnr.de.
134 Thomas Grethe, Karoline Günther, Thomas Weide et al.

(Heyse et al., 2015), building materials (Davis et al., 2013) to medical textiles (Hoffmann
et al., 2011). In all the addressed sectors the availability of textile integrated reliable
conductive tracks is crucial as well as the connection technology.

INTRODUCTION

Therefore, common approaches like copper printed circuits or even cables cannot be
considered to achieve the goal of a high integration level. Hence, other opportunities have
to be evaluated. Before looking into further details, it is helpful to understand the
different requirements of an electrical conductor: In the first place, obviously, a low
electric resistance is necessary, but on a second look additional functions are crucial,
depending on the field of application. Namely, the isolation against other conductors but
also against surrounding media needs to be addressed. Faulty insulations can lead to
injuries if high energies are transmitted, but also low current applications like sensors or
data lines can suffer from malfunctions due to faulty insulations. In a textile environment
the requirements of insulation materials can also include long-term high flexibility,
washing resistance, and mechanical strain resistance. In the case of signal transmission
lines also the issue of electromagnetic shielding is of high importance. Since in common
electronic applications coaxial cables are widely used, this technique cannot easily be
transferred to textile applications. It is usually desirable to achieve a low capacitance of a
coaxial cable, which is realized by a distance between the signal transmitting wire and the
outer shielding, which gives such cables a diameter of a few millimeters, which is not
well compatible with textile integration for the most parts.
Different techniques can be applied to ensure a conduction of electric signals and
power along the textile material. In general terms, the options can either be fiber or fabric
based. In the first case conductive yarns are applied by different techniques like weaving,
embroidering or braiding dependent on the used yarn and the aimed application. Yarn
materials can be separated in two systems: conductive coated yarns and bulk metal
components as yarn or yarn component. Such approaches show specific challenges, for
example the mechanical properties of these yarns render common textile processing
techniques difficult due to their susceptibility to abrasion or breakage. On the other hand
fabric based concepts often apply coating of conductive compounds like pastes or inks
onto the textile substrate. Here other requirements such as good conductivity, elasticity of
the film, adhesion to the fabric have to be met.

YARN BASED CONDUCTORS

This approach might represent the highest possible integration level for all yarn or
filament based textile materials. A lot of different approaches exist to obtain an electric
Achieving Electrical Conductivity in Textiles 135

conductivity in yarns. First, conductive coatings of nonconductive mono- or


multifilament yarns with conductive materials are often realized. The coating materials
are varying widely and are usually applied by any kind of paste coating, like dip coating,
immersing, etc. by chemical deposition or physical vapor deposition. Examples for the
first approach are dip coating of cotton threads with a CNT containing liquid resulting in
resistances of a few ten ohms per cm (Shim et al. 2008), coating of polyethylene yarns
with polyaniline (a conductive polymer) obtaining resistances in the same order of
magnitude (Devaux et al. 2007), and also other intrinsically conductive polymers (ICPs)
are used like polypyrrole (Xue et al. 2004; Maity et al., 2014) which can be in situ
polymerized on the fiber. The conductivity of ICPs can be explained by the combination
of two concepts: First the molecular orbital s need to be extended along the complete
molecular chain. This can usually be obtained by an extended -System. A primitive
example of such a molecule is polyacetylene (Figure 1).
The conjugated carbon -carbon double bonds lead to a widely delocalized -System
allowing electrons to reside anywhere along the molecular structure. For textile
applications, the most common ICPs are polyethylene dioxythiophene (PEDOT),
polypyrrole (PPy) and polyaniline (PANI). These offer better properties regarding
degradation and processability. The conjugated bond structure of those polymers creating
a delocalized -system is depicted in Figure 2. Beside these structural requirements for
conductivity also a reasonable charge carrier mobility is necessary. A common way to
introduce charge carriers is doping, which is also known for inorganic semiconductors
like silicon. Contrary to the inorganic systems, where doping is usually accomplished by
introducing impurities in the crystal lattice, ICPs are usually doped due to oxidation of
the polymer. The mechanism can be illustrated by looking on the molecular orbital s of
hexatriene (Figure 3). In the neutral state all electrons reside in the highest occupied
molecular orbital (HOMO). It is therefore not possible for an electron to be moved along
the molecular axis, since there are no allowed states for it to reside along its movement.
By introducing an electron (reduction) it will fill in the lowest unoccupied molecular
orbital (LUMO) of the molecule with plenty possible states to fill in while moving along
the molecular axis, therefore conductivity can be achieved. The same mechanism is
present in the case of oxidizing the molecule, where an electron is removed, resulting in
an unoccupied state in the HOMO, which allows electrons to settle in. This will lead to an
apparent movement of the free state, which is commonly referred to as hole conduction.

Figure 1. Structure of polyacetylene, the first synthesized and investigated conductive polymer, but
unfortunately, this substance is sensitive to oxidation (Berets et al. 1968) and therefore gained no
commercial impact.
136 Thomas Grethe, Karoline Günther, Thomas Weide et al.

Figure 2. Structures of different ICPs: a) polyethylene dioxythiophene, b) polyaniline, c) polypyrrole.

In an inorganic semiconductor like silicon, doping is accomplished for example by


aluminum or phosphorous which also leads to freely moveable charge carriers. These
impurities a rather immobilized in the crystal lattice and therefore most inorganic
semiconductors are not really sensitive to oxidation 1. ICPs are mostly amorphous and
due to their electron configuration quite susceptible to oxidation. Besides unintended
doping or dedoping the material can also be permanently degraded by oxidation.

Figure 3. MO structure of hexatriene.

1
In fact, it is possible to adsorb oxygen on an inorganic semiconductor surface, which leads to a change of the
bandgap of the material, but this effect only takes place at the crystal surface. In a bulk material this is usually
not of a concern, but by using a semiconductor with a high surface to volume ratio, this effect can be used to
sense gases.
Achieving Electrical Conductivity in Textiles 137

However, doping of ICPs by oxidation obviously introduces a charge on the


polymeric backbone. Therefore, a compensation by additional ions is necessary. For
example, polyethylene dioxythiophene can be doped with polystyrene sulfonate (PEDOT:
PSS) and polypyrrole (ppy) is usually in situ polymerized using an iron catalyst which
also acts as a dopant. In the case of PEDOT: PSS the charges are located on the sulfonate
ion (negative) and the polymeric backbone (positive) forming polarons. Charge transport
is than accomplished by moving of these polarons along the electric field gradient.
PEDOT: PSS also offers another interesting property: It is mostly transparent to the
visible part of the spectrum, which allows fabricating translucent electrodes. The case
of polyaniline (PANI) is a bit more complicated: The conductive variant of the molecule
consists of an intramolecular blend of oxidized and reduced parts called the emeraldine
base (Figure 4).

NH N

NH
N
m n
Figure 4. Emeraldine base, reduced part left, oxidized part right.

Figure 5. Movement of the oxidized section along the molecular axis by protonation/deprotonation and
valence resonance, according to Focke et al. (Focke et al. 1987).
138 Thomas Grethe, Karoline Günther, Thomas Weide et al.

The proposed conduction mechanism involves both species after a protonation of the
base forming the emeraldine salt (Figure 5, second structure from top). Due to valence
resonance the oxidized section emerges further down the molecular axis, which results in
a net charge movement (Focke et al. 1987). The counter ion can be conceived as the
corresponding anion of the used Brönsted acid.
PANI offers also the ability to transport charge carriers between different polymer
molecule s by a proton exchange.
The further above mentioned in situ polymerization of polypyrrole is an example of a
chemical deposition of conductive materials on fiber surfaces from a liquid phase, a
technique also often utilized to deposit metals on fiber surfaces. This is mostly
accomplished by reducing a noble metal salt in situ leading the reaction to a particulate
precipitation of the metal. For example this can be used to deposit copper (Kim et al.,
2004; Jiang et al., 2011; Schwarz et al., 2012), gold (Schwarz et al. 2010), nickel (Pinto
et al., 2004) and silver (Lu et al. 2010; Feng et al., 2011). Another option is physical
vapor deposition of metals on fibrous surfaces (Shahidi et al, 2014; Amberg et al., 2008).
In this case a low pressure plasma discharge removes neutral atoms from a metal target
which than are deposited on the fiber surface. These technique requires a more complex
machinery than liquid based coating methods. The yarn has either to be placed in the
recipient or a set of differentially evacuated vacuum chambers have to be applied
allowing to transport the yarn material through a small orifice in the outermost chamber.
The latter setup can be used for a continuous coating. It has to be noted, that physical
vapor deposition yields only good results on monofilaments, since the rough surface
topology of spun multifilaments exhibits interruptions in the very thin coating.

Figure 6. SCHEME of a differentially pumped vacuum chamber: a) high volume pump e.g., roots
pump, b) vacuum pump e.g., rotary pump, c) main treatment chamber, d) prechamber, the yarn material
is ducted from left to right across the chambers.
Achieving Electrical Conductivity in Textiles 139

However, coating of yarns comes with a set of drawbacks: Abrasion resistance of the
coating is usually not sufficient to employ these yarns successfully in textile production
processes like weaving, embroidering or knitting. Especially yarns from PVD are
susceptible to abrasion. Furthermore, most yarn based substrates offer an elasticity which
is necessary for the textile processing, but most coatings will alter their conductivity by
elongation mostly due to lateral departing of the conductive elements in the coating
(molecules in intrinsic conductive polymers, metal nano crystallites, or carbon particles,
etc.). This might be interesting for the use in textile sensor systems but is
disadvantageous for current or data lines. Another issue emerges due to the quite low
share of conductive material in the net mass of the yarn leading to a low cross section of
the conductive material itself. The resistance of a metal coated yarn can easily be
calculated using the resistivity of the coated metal. The resistivity can be conceived as a
proportionality factor between the resistance and the ratio of length and cross sectional
area of a conductor.

𝑙
𝑅=𝜌 (1)
𝐴

An exemplary yarn with a diameter of 500 µm and a silver coating (resistivity of


silver: 1.586*10-8 Ohm/m (Matula et al. 1979)) obtained by PVD of about 100 nm
exhibits according to Eq. 1 a resistance of approx. 100 Ohm/m.
Also most of the coated yarns are not isolated, which renders them mostly unsuitable
for commercial applications in the clothing sector and also in the sector of technical
textiles. Intrinsic conductive polymers as coating agents show in most cases a
susceptibility to foreign substances and degradation by UV light and/or oxygen impairing
their conductivity. This is mostly provoked by an unintended doping of the polymers by
these substances changing the band gap of the polymer. However, these effects can be
very interesting to realize sensors based on such polymers.
An approach to gain higher conductivity is to integrate metal filaments in yarns. A
common approach is to entwine a metal wire around a textile yarn. This ensures a higher
elongation of the yarn under strain without rupturing the conductive element, since the
metal is usually less elastic than the yarn. On the other hand, the textile haptics of the
yarn is altered (Schwarz et al., 2011; Guo et al., 2012).
Already commercialized is a blend of stainless steel and polyester staple fibers spun
to a conductive yarn, additionally a variant consisting of pure stainless steel staple fibers
exist. These materials offer electric conductivity combined with a good textile haptics
and a good processing ability. However, due to the use of staple fibers the contact
resistances in the yarn dominate the conductivity leading to a higher resistance than
expected by the metal content. Unfortunately, an insulation of these yarns is not offered
and may possibly be hard to achieve.
140 Thomas Grethe, Karoline Günther, Thomas Weide et al.

Figure 7. Example of a wire entwined around a staple fiber yarn.

Figure 8. Micrograph of a commercially available steel staple fiber yarn.

In our research group the concept of integrating metal wires in textile staple fiber
yarns was taken further while maintaining the textile haptics and realizing an insulation:
Enameled metal wires, e.g., from copper, are widely used in electronic components like
transformers and other inductive components. In first steps, these wires were integrated in
100% cotton material by conventional ring spinning, which was successfully
accomplished. Due to the circular motion of spun yarn in the process, the metal
component exhibits a helical structure, which lead to an only partially positioning of the
wire in the middle of the yarn cross section (Figure 9). However, it was obviously
desirable to keep the wire in the inner core of the yarn to achieve a complete textile
characteristic of the resulting thread.

Figure 9. Left: micrograph of a ring spun yarn with metal core, the highlighted area shows the metal
core penetrating the yarn surface; right: cross sectional view.
Achieving Electrical Conductivity in Textiles 141

An alternate spinning process called friction spinning was also applied to incorporate
such wires into a staple fiber yarn. This technology is an open-end technology which
means the inserted fiber bundle is opened into single fibers to piece them at the end of an
already spun yarn end by friction and twisting. For this process, one or multiple draw
frame slivers can be used. The first friction spinning apparatus was invented by Ernst
Fehrer, Helmut Fuchs, and Franz Koenig in 1976 (Fehrer et al. 1976). The commercial
use of their friction spinning technology is known under the name DREF-3000 and is
mainly used for core-shell yarn structures for technical applications as demonstrated here.
Their spinning technique employs two drums feeding the staple fibers into the process,
while a core yarn is lead axially along the drums. The drums are slightly tapered,
equipped with a mesh surface and connected to a vacuum pump. This leads to an
adhesion of the fibers to the rotating drums, and friction occurs at the gap between the
drums forming the resulting yarn (Figure 10). The tapered geometry increases the friction
in axial direction in order to densify the produced yarn.

Figure 10. Basic working principle of a friction spinning machine creating a core-shell-yarn; a) staple
fibers from a draw frame sliver, b) spinning drums, c) connection to vacuum pump, d) core yarn, e)
core-shell-yarn.

Figure 11. Left: micrograph of a friction spun yarn with metal core; right: cross sectional view.
142 Thomas Grethe, Karoline Günther, Thomas Weide et al.

An enameled copper wire was then introduced as core component and wool staple
fibers were used to create a core-shell-yarn. It is clearly visible that in this case the metal
core is well integrated into the yarn without any surface contact or break through (Figure
11). However, it has to be considered that the coverage ratio is also influenced by the
produced yarn count, the used fiber type and fiber diameter. As mentioned earlier, these
metal core hybrid yarns lack elasticity and tenacity and are therefore prone to breakage
during textile processing. In particular, sewing and embroidering showed to be
impossible. However, other processing techniques were successfully carried out. In the
first place, using a special embroidery head enables one to use these yarns as cover thread
which is fixated by an additional yarn. This allows realizing nearly unlimited designs of
these conductive structures. In a second approach the integration of these yarns in a
narrow woven fabric was realized. In this case the yarn material was introduced as weft
component. Due to the nature of a narrow weaving machine the weft yarn is not cut at the
selvedge but lead back. This resulted in a mesh like conductive surface consisting of a
single, non-crossing conductive strand.

Figure 12. Embroidered patch with metal core yarn.

Figure 13. Narrow fabric with incorporated metal core yarn as weft yarn (white).
Achieving Electrical Conductivity in Textiles 143

APPLICATIONS OF CONDUCTIVE YARNS

Commercially available with a significant market share are only metal based yarns,
being metal coated, incorporating metal filaments or consisting of metal filaments.
Polymer coated yarns are not yet commercialized most probably for the reasons
mentioned above. Since most of these metallic yarns lacking an insulation, the fields of
applications are mostly: Heating, medical electrodes (contact to the skin ), and antistatic
applications. They are also used as power supply lines for smart textiles, however, the
lack of insulation renders these approaches more experimental. It has to be mentioned,
that some yarn suppliers offer silver coated yarns with a polyurethane isolation, rendering
these materials promising for the field of smart textiles, but removing the isolation
without damaging the underlying coating may be difficult.

FABRIC BASED CONDUCTORS

Another approach to introduce an electric conductivity into textile materials can be


accomplished by coating the textile substrate with conductive materials. The integration
level is lower than in yarn based approaches, but some requirements can be met much
better by areal coating of a textile. These requirements can either be structural or being
dictated by the field of application. Structural advantage of areal coating is the ability to
quickly change design patterns of conductive tracks or areas or the ability to use
individual patterns. This can be done either by screen printing or digital printing of
conductive pastes. The field of application may lead to an advantageous coating rather
using conductive yarns if wide areas need to be conductive. This can be the case for
textile electrodes or capacitance based textile sensors.
Different materials exist to realize conductive coatings on textiles. First, carbon
containing coating pastes are already commercially available, which can be applied by a
simple knife coating technique. Usually these pastes contain carbonaceous materials
(mostly sooth) at a sufficient amount to achieve percolation embedded in a polymeric
coating paste. This approach enables easy to process and cost efficient coatings. Also
intrinsically conductive polymers (ICPs) are utilized for conductive coatings. PEDOT:
PSS solution for coating applications are known since quite a long time, but were based
on organic solvents. For textile applications it is highly desirable to replace these solvents
by water. Therefore, water based PEDOT: PSS dispersions are commercially available
today which incorporate water soluble polymers of higher molecular weight. These
provide some assistance in geometrical aligning the ICP molecules during the drying
process which usually leads to higher conductivity than without these auxiliaries.
144 Thomas Grethe, Karoline Günther, Thomas Weide et al.

Also Isolation is an issue for these technique as it is for the conductive yarns. But in
the case of coating this can be addressed much easier by applying a non-conductive top
coating on the conductive layer. On the other hand contacting such coatings is more
challenging than for conductive yarns. The latter can on some cases even be soldered, but
also contacting by embroidery is possible. Conductive areal coatings, especially
multilayer assemblies, cannot be sewn or otherwise penetrated. It is also not possible to
solder on carbonaceous materials or ICPs. Therefore the most applied technique is using
conductive adhesives or coating on a partially metalized substrate. Also clamping and
crimping can be utilized.
Some care hast to be taken by contacting ICP coatings with metals (wires,
connectors, etc.), since an unintended schottky contact could be made. For example
schottky contacts for Al/PEDOT: PSS and Al/PPy are reported (Abthagir et al. 2001).
Choosing metals with a higher work function should avoid this issue.

APPLICATIONS OF CONDUCTIVE AREAL COATINGS

Fabric based coatings are less widespread than conductive yarns. Some applications
are known for heating textiles and electroluminescent textiles in which luminescent
particles are incorporated between to coated electrodes, one being made of PEDOT: PSS.
By applying an alternating electric field, these particles can be excited to emit light
(Graßmann et al. 2017). However, none of these applications gained a market relevance.

Printing Techniques

A sub technique of areal coating is printing of conductors onto textiles. Here either
screen printing (Kazani et al., 2012; Yang et al., 2013; Virkki et al., 2015) or inkjet
printing (Stempien et al., 2016) can be conceived. The latter is of growing attention due
to its high flexibility and resource efficiency in the textile sector especially for
nonconductive applications. While printing inks need to show specific rheological
behavior and sometimes also distinct dielectric properties, printing conductive tracks on
textiles by this technique needs additional requirements to be met. In most cases printing
inks for conductive applications can be divided into two groups: filler based and
intrinsically conductive.
Intrinsically conductive inks usually consist of a share amount of conductive
polymers, like PEDOT: PSS in a suitable dispersion for inkjet printing. Challenges for
these are achieving a sufficient low viscosity to be printable by simultaneously
maintaining a high conductivity. As for knife coated PEDOT: PSS layers, degradation
and oxidation have to be minimized. Textile applications of inkjet printed ICPs are quite
Achieving Electrical Conductivity in Textiles 145

rare but some approaches are known e.g., for the fabrication of textile EL-devices (Hu et
al. 2012) or textile strain sensors (Calvert et al. 2007).
Filler based inks contain metallic or carbonaceous particles and can therefore achieve
higher conductivities than intrinsically conductive inks. However, the particle size of
such fillers is highly crucial as well as the agglomeration behavior of the fillers. Both
effects can lead to clogging of the printing nozzle or, worse, to clogging of the supplying
tubes. To circumvent those issues, nano sized particles are employed in printing inks, but
they need to be sintered after printing to connect the conductive particles together and
allow percolation (Perelaer et al. 2006, Park et al. 2007). Another approach features the in
situ reduction of silver ions on the substrates surface. The authors claim, that due to their
chosen reduction agent, metallic silver forms after passing the nozzle and no annealing is
necessary afterwards (Walker et al. 2012). Textile applications are reported for example
as antennas (Whittow et al. 2014) or elastic conductors (Matsuhisa et al. 2015).
Due to this aforementioned challenges, screen printing of conductive materials on
textile fabrics is much more prevalent. Depending on the mesh size, different particle
diameters and also nano wires can be printed. Furthermore, viscosity is not that crucial,
since it influences the maximal achievable resolution but does not infringe the process at
all. So on textile substrates transmission lines are reported (Locher et al. 2007), all
printed waterproof conductive tracks (Yang et al. 2013), and also electrodes for medical
applications are screen printed on fabrics (Paul et al. 2014).

ACKNOWLEDGMENTS

The authors wish to thank the following members of the Niederrhein University of
applied sciences: Mr. Roland Werner for conducting the spinning experiments, Mr. Frank
Heimlich and Ms. Jiaming Gu for producing the woven structures, and Ms. Marina
Normann for embroidering the conductive yarns.

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and Wearable Fabrics for Human Biomonitoring made by Carbon Nanotube Coating
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pressure measurement and analysis system based on fabric pressure sensing array.
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fibers. Sensors, 10(9), 7934-7946.
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In: Textiles: Advances in Research and Applications ISBN: 978-1-53612-855-0
Editor: Boris Mahltig © 2018 Nova Science Publishers, Inc.

Chapter 7

METAL COATINGS EFFECT PIGMENTS FOR TEXTILE


FUNCTIONALIZATION TO REALIZE UV AND IR
PROTECTIVE APPLICATIONS

Jieyang Zhang and Boris Mahltig


Hochschule Niederrhein – University of Applied Science,
Faculty of Textile and Clothing Technology,
Mönchengladbach, Germany

ABSTRACT

The aim of the actual development is the realization of a coated textile material with
protective properties against ultraviolet light (UV) as well as against infrared light (IR).
To fulfill these demands a double coating is developed for textile substrates. The double
coating contains mainly two different coatings: A first base coating – to equalize the
textile topography and to support UV-protection and a second top coating – containing
metal effect pigments to introduce IR-reflection and coloration effects. The optical
transmission of prepared samples are determined by UV/Vis/IR-spectroscopy in diffusive
measurement arrangement for wavelength from 220 nm to 1400 nm. Surface properties
of coated samples are recorded by using scanning electron microscopy SEM and light
microscopy. The wash fastness as well as the abrasion stability of the coatings are tested.
Altogether the developed coating approach can be the starting point for the final
development for a textile based light protective and light management device.

Keywords: effect pigments, optical spectroscopy, UV-protection, IR-reflection


Corresponding Author Email: Boris.Mahltig@hs-niederrhein.de.
152 Jieyang Zhang and Boris Mahltig

1. INTRODUCTION

In daily life, people are exposed mainly to three different types of light: UV light,
visible light and IR light. Simplest these types of light can be distinguished by their
wavelength ; UV nmVis 750nm > > 400nm; IR> 750nm (Hesse et al.
2008). The radiation of the sun reaching the earth surface contains usually UV light from
290 nm up to IR light with 4000 nm wavelength (Hölzle & Hönigsmann 2005). The light
intensity and composition is of course dependent on the geographical position and the
weather (Krizek et al. 2005). Also artificial light from man-made light sources (lamps)
can contain significant amounts of UV and IR light (Maslowsky 2013; Mahltig et al.
2013). For incandescent lamps (lightbulb), the emission of infrared light is significantly
higher compared to the amount of emitted visible light (MacIssac et al. 1999). For human
eye only visible light of wavelength between 400 to 750 nm is visible, so a decrease of
UV- and IR-light exposure cannot be detected by human eye and will not influence the
lighting situation, e.g., in a building (Hesse et al. 2008). UV light can cause sun burns,
blindness or even skin cancer, so the protection against UV-light is quite reasonable
(Brasch et al. 1991). UV protection by textile materials means that the transmission of
UV-light (<400nm) is near to zero. The best case for an UV protective textile is that the
transmission of visible light is not effected, so the coloration of the textile is not changed
and intensity of useful visible light is not changed. IR light can be also described as
thermal radiation (Howell et al. 2010). IR light is of course not that dangerous as UV
light. Nevertheless, in many situations also a protection against IR light is advantageous.
Just imagine the situation of a hot summer day, there the IR radiation coming inside the
room by transmitting through the windows and heating up the building. In that case, a
textile window coverage exhibiting a low IR transmission could be of course
advantageous, if the transmission of visible light is not too much influenced. The visible
sun light from outside is wished indoors for lighting up the rooms. In case of a significant
shut-down of visible light from outside it is to dark inside and artificial light from lamps
is necessary. This is from energetic point of view not effective, because lamps also
exhibit a significant amount of heat radiation. Additionally the change of the optical
properties of textiles in the infrared area of light is reported for the use in camouflage
applications (Gupta et al. 2001).
With this background it is clear, that a textile which allows the protection against
both UV- and IR-radiation is of a certain demand. Usually textiles with UV protective
function are realized by addition of a compound named UV-absorber. Such an UV-
absorber takes up the UV light without being destroyed by it and by this the UV
transmission of a textile carrying the UV-absorber is significantly decreased. Well known
and used are inorganic UV-absorbers as titanium dioxide or zinc oxide but also organic
compounds as benzophenone derivatives or Tinuvin are in used (Sivakumar et al. 2012;
Sundaresan et al. 2011; Saito 1993; Paul et al. 2010; Mahltig et al. 2005; Mahltig &
Metal Coatings Effect Pigments for Textile Functionalization … 153

Textor 2008). However UV-absorbers from Tinuvin type contain a significant risk to
cause contact allergies (Nikilasson & Björkner 1989). While for UV-protection mostly
UV absorbing materials are used, for IR-protection usually IR-reflection is used.
Appropriate materials are here IR reflective pigments, e.g., from titanium dioxide of
rutile type, iron oxide red or aluminum flake pigments (Berdahl 1994; Gunde & Kunaver
2003; Bendiganavale & Malshe 2008).
The current paper will discuss now the combination of UV and IR protective
properties on one textile substrate by using an effect pigment containing coating system.
In that coating system the UV protective function is gained by a base coating containing
the most prominent UV absorber titanium dioxide TiO2 as fine distributed pigment
particles. The IR protection is gained by a so-called effect coating containing metal effect
pigments. Effect pigments are anisotropic plain pigments which are acting mirror-like
and exhibit a high reflectivity of light (Wißling et al. 2006; Mahltig et al. 2015).
Originally effect pigments are developed to apply special color effects onto different
materials. Nowadays also different functions of effect pigments as the application of
conductive coatings or the realization of antimicrobial effects are reported (Topp et al.
2014; Mahltig et al. 2017). The idea of this paper is to investigate and compare the
property for protection against UV-light and IR-light. Investigations on the coated textiles
are performed with an optical spectrometer enabling the measurement of the diffuse
transmission for UV, Vis and IR light. Supported are these spectroscopic measurements
by additional microscopic studies (scanning electron microscopy – SEM - and light
microscopy) and investigations according washing and abrasion fastness. The developed
materials can be probable in future application used to produce radiation protective
materials and light management materials.

2. EXPERIMENTAL SECTION

2.1. Materials and Preparation

For coating application two types of different textiles are used as substrates, white
cotton fabric and white polyester fabric. The textiles are plain woven materials with the
weight of 112 g/m2 for cotton and 50 g/m2 for polyester. As effect pigments three
different types of pigments supplied by the company Eckart GmbH (Hartenstein,
Germany) are used. These effect pigments are supplied as ready mixed pigment pastes
with a density in the range of 1.2 to 1.4 g/cm3. All effect pigments used together with
their elemental composition are summarized in Table 1. The coating is applied as single
or double layer system containing of a first base coating and a second coating containing
the effect pigment. For base coating a mixture of following composition is used: Lutexal
Thickener HIT 3% (supplied by BASF – Germany) / water 65.5%/binder Edolan GS 30%
154 Jieyang Zhang and Boris Mahltig

(polyurethane dispersion supplied by Tanatex – Netherlands )/crosslinker Edolan XCI


1.5% (supplied by Tanatex – Netherlands). This recipe for the base coating preparation
can be modified with 30% of the pigment suspension Helizarin White RTU TiO2. This
Helizarin White is an aqueous suspension of titanium dioxide white pigment (10 wt-%
pigment concentration) supplied by BASF. For the second effect pigment containing
coating a mixture of following composition is used: Lutexal Thickener HIT (supplied by
BASF – Germany)/water/binder Edolan CA (polyurethane dispersion supplied by
Tanatex – Netherlands)/crosslinker Edolan XCI (supplied by Tanatex Netherlands). The
amount of added shinedecor pigment paste is calculated in respect to their pigment
concentration. The final effect pigment concentration in the coating recipe is set in the
range of 2.5, 10% or 15%.

Table 1. Overview on the used effect pigments. Values for solid content and pH
values are given data by the supplier. The mentioned elementary composition is the
composition on the surface of the pigments and is determined by EDS method from
dried pigment paste (only chemical elements with >0.1% and from the 3.period or
higher are recorded)

Pigment content pH Color Elemental composition [wt-%]


paste value Cu Ag Al Zn Si P
Shinedecor Aluminum 6.5-7.5 Silver --- 0.5 +/- 55.6 +/- --- --- 0.3 +/-
5000 flake; white 0.1 3.0 0.1
24-28%
Shinedecor Gold 7.3-8.3 Copper 52.5 +/- --- --- --- 1.4 +/- ---
9350 bronze; red 1.8 0.1
38-42%
Shinedecor Gold 7.3-8.3 Gold 32.7 +/- --- 0.2 +/- 14.4 +/- 1.5 +/- ---
9355 bronze; yellow 1.2 0.1 1.1 0.1
33-37%

Table 2. Paste recipe for coating agent containing different metallic effect pigments.
All amounts are given in wt-%. The weight content of the metallic effect pigment in
the final coating recipe is 10%

Recipe components Amounts of components used, for recipes with different Shinedecor effect
pigment pastes
Shinedecor 5000 Shinedecor 9350 Shinedecor 9355
Lutexal Thickener HIT 0.5 2.5 3
Water 28 41 36.9
Edolan CA 30 30 30
Edolan XCI 1.5 1.5 1.5
Shinedecor paste 40 25 28.6
Metal Coatings Effect Pigments for Textile Functionalization … 155

In Table 2 the recipe composition of the most used 10% recipe is given. The
application of the coating recipes on the polyester fabric is done by knife on air coating.
Afterwards drying is performed in a Mathis Lab dryer at 80°C for 2 minutes. In the end
of the process a curing is performed at 160°C for a duration of 3 minutes.

2.2. Analytical Methods

Light microscopy is performed with a light microscope VHX-600 from Keyence. The
actual zoom lens is a VH – Z250R with a possible magnification in the range of 250 to
2500. A profile measurement unit VHX – S15 is used to gain profile pictures. Scanning
electron microscopy SEM is performed with a TM 3000 Tabletop microscope from
Hitachi. For SEM measurements the acceleration voltage is set to 15kV. This used SEM
device contains additionally an EDS (energy dispersive spectroscopy) unit Quantax 80
from Bruker, which enables the determination of the elemental composition on sample
surfaces. The optical properties are determined in the spectral range of 220 nm to 1400
nm and give for this information on the coloration of samples but also on their ability to
support protection against UV and IR radiation. These measurements are performed in
arrangement of diffuse transmission. In the measurement arrangement of diffuse
transmission all light which is transmitted through the sample is collected and
summarized. In comparison to common transmission measurements, in case of the
actually used arrangement beside the direct transmitted light also the light scattered
during the transmission is detected. A SHIMADZU UV-2600 UV-VIS Spectrometer is
used as testing devise. This spectrometer is equipped with two detectors. One detector for
detection of UV light and visible light and the other detector for infrared light. These
detectors are switched at a wavelength of 700 nm, leading in the recorded spectra to a
small step in the signal. For determining the washing fastness of coated fabric samples,
fabric samples are washed several times at 40℃ for 75 minutes in the washing device
SIEMENS SIWAMAT IQ 714. The samples are cut into 38 mm diameter round shape by
using James Heal sample cutter. The washing detergent is TANDIL gentle washing
powder containing no brightener. The usage of the detergent is 20 g per 2.5 kg washing
material. The fabric material is added into the washing cylinder to keep the weight of
treated textiles at 2.5 kg. The coated fabric samples are weighed before and after
washing. The optical properties of samples are also evaluated after washing. According to
EN ISO 12947-1, the abrasion testing is operated by using a Martindale from James Heal.
The fabrics samples are cut in 38 mm diameter round shape by using James Heal sample
cutter. According to the abrading fabric requirement in ISO 12947-1, a flat woven wool
fabric from James Heal against the test specimen is abraded. After several abrasion
cycles, the weight and the light transmission of coated fabric samples are evaluated.
156 Jieyang Zhang and Boris Mahltig

3. RESULTS AND DISCUSSION

To support an appropriate structure to the reader, this section is split into three
subchapters. At first the properties of the pure pigments and surface properties of the
coated textile substrates are described. Following the optical properties and the protective
functionalization gained by the coatings are presented. In the end, important properties
related to the practical application, as wash fastness and abrasion fastness, are presented
and discussed.

3.1. Materials and Surface Properties

Altogether three different metal effect pigments are used to prepare the effect
coating. These three metal effect pigments can be sorted into two different categories –
an aluminum pigment and gold bronze pigments (Table 1). The aluminum pigment
Shinedecor5000 is of silver white coloration and contain beside aluminum as main
component also small amounts of the elements silver and phosphorous. These both
elements are probable present to enhance the stability of the aluminum pigments in
aqueous binder systems (Wissling 1999). Without stabilization of pigment surface,
aluminum pigments react with water based solutions under the formation of hydrogen.
This reaction is especially enhanced, if the binder system used for coating preparation
contains an alkaline pH. The pigments contain nearly a round and regular shape with
diameters up to 80 m (Figure 1). This shape of an effect pigment is often also named as
“silver dollar” (Wißling et al. 2006). In contrast, the both gold bronze pigments
Shinedecor9350 and Shinedecor9355 are significantly colored. They are mainly copper
based (Table 1). For Shinedecor9355 also a content of zinc and aluminum is observed,
probably responsible for the yellow coloration of this pigment. Both gold bronze
pigments contain also an amount of around 1.5 wt-% silicon. This silicon is probable a
part of a protective layer on the pigment surface, preventing the corrosion of these copper
containing pigments. The size of the gold bronze pigments is smaller compared to the
aluminum pigments. Also their shape is less regular (Figure 1). Such a shape is often also
named as “corn-flake” structure (Wißling et al. 2006).

3.2. Optical Properties

The optical properties are determined by transmission spectroscopy and recorded for
the samples in transmission spectra for each type of prepared samples (Figures 3 to 5).
Figure 2 shows as references the transmission spectra of the uncoated textiles of polyester
Metal Coatings Effect Pigments for Textile Functionalization … 157

and cotton used as substrates for further coating experiments. The polyester fabric
contains in the range from 400 to 1400 nm transmission values of 50% to 60%. For UV
light with a wavelength below 400 nm, the transmission is decreased and lowest values
with a transmission of only 5% are reached for wavelengths below 300 nm. This low
transmission of UV light can be explained by light absorption caused by the aromatic
structure of the polyester polymer (PET, polyethyleneterephthalate ). Nevertheless the
main UV radiation from sunlight is in the range from 300 nm to 400 nm and in this area
the fabric exhibits a significant transparency. For this, this untreated polyester fabric is
not suitable for UV protection applications and still a further protective finishing or
coating is necessary to introduce UV protective properties. The reference cotton with a
higher weight per area and a denser structure contains a lower transmission from 400 to
1400 nm with transmission values around 35%. However, the transmission against UV
light is higher compared to the values of the polyester reference, so this cotton is as single
material as well not a suitable material for UV protective application. In a first sample
series the effect of a coating containing 10% of the effect pigments is investigated (Figure
3). By application of the effect pigment coating, the transparency is significantly
decreased on the whole investigated spectral range. For all coatings, below a wavelength
of 300 nm the transmission is near zero, so for that range the UV protection is given. This
decrease can be explained by the absorption properties of the metal pigments in the UV
range and the polyurethane component in the binder system. However in the range from
300 to 400 nm still significant transmission values are determined, so a full UV
protection cannot be reached by these effect coatings. The transmission of visible light
and infrared light is strongly determined by the type of used effect pigment. Lowest
transmission values can be reached by use of the aluminum pigment (Shinedecor5000),
which is supposed to contain a higher light reflection property compared to the other both
investigated pigments. The gold bronze pigments contain in the area of visible light a
shoulder in the spectra, which is related to their color. Although a significant decrease in
the light transmission is reached by this first series of coatings, the transmission values
are still too high for a light protective application. For this, following further coating
series are performed to optimize the protective properties. For this improvement, the
effect coating is applied as second coating on a previous applied base coating containing
only the pure binder. The idea for using the base coating is to even the rough textile
surface structure and to optimize by this the arrangement of the flat anisotropic pigments
in the second layer. A certain decrease in transmission can be obtained by this double
coating method (Figure 4). This decrease is stronger for the more rough cotton and
mainly related to the infrared light. In contrast, by this arrangement a full UV protection
cannot be reached. To improve the UV-protection, the addition of another effective UV-
absorber material is required. This improvement is done by addition of titanium dioxide
pigments to the base coating. The transmission spectra of the double coating system
containing a base coating with titania pigments are presented in Figure 5. By use of this
158 Jieyang Zhang and Boris Mahltig

titania additive in the base coating, the transmission in the full UV range up to 400 nm
can be decreased to values below 5% for both types of textile substrates (polyester and
cotton) (Figure 5). For this, a full UV protection can be reached by this double coating
system. Beside the strong influence of the TiO2 on the optical properties in the UV range,
also the TiO2 application decreases significantly the transmission in the range for visible
and infrared light. Titania is an UV absorber but also a white pigment with strong
reflective properties for visible and IR light. This additional reflection is probable the
reason for the further decrease of transmission of visible and IR light, if titania is applied
in the base coating. Lowest transmission values are gained by combination with the used
aluminum pigment Shinedecor5000. So for the current investigation, the combination of
a titania containing base coating and an aluminum pigment top coating is most
advantageous for radiation protection purposes.

5000 9355

Figure 1. Light microscopic images of polyester fabrics coated with recipes containing 10% of metallic
effect pigments Shinedecor 5000 or Shinedecor 9355. The images are recorded in magnification
of 1000X.

70

60
polyester
50
transmission [%]

40

cotton
30

20

10

0
400 600 800 1000 1200 1400
wavelength [nm]

Figure 2. Transmission spectra of the both textile substrates polyester and cotton. Reference spectra
of the uncoated substrates.
Metal Coatings Effect Pigments for Textile Functionalization … 159

70
on polyester fabric 70

60 reference on cotton fabric


60 5000
transmission [%] 50 9350
50
9355

transmission [%]
40
40

30
30

20
reference
20
5000
10 9350 10
9355
0
0
400 600 800 1000 1200 1400 400 600 800 1000 1200 1400
wavelength [nm] wavelength [nm]

Figure 3. Transmission spectra of the fabrics with effect pigment coatings. Applied are four different
effect pigments (Shinedecor types) with a concentration of 10% in the coating recipe.

70
70
on cotton fabric reference
on polyester fabric
60
60 5000
9350
50
50
transmission [%] 9355
transmission [%]

40
40

30
30

20 reference 20
5000
10 9350 10

9355
0 0
400 600 800 1000 1200 1400 400 600 800 1000 1200 1400
wavelength [nm] wavelength [nm]

Figure 4. Transmission spectra of the fabrics with effect pigment coatings. Applied are double coating,
with a first base coating without any pigment and a second top coating containing four different effect
pigments (Shinedecor types) with a concentration of 10% in the coating recipe.

70 70

on polyester fabric on cotton fabric reference


60
60 5000
9350
50 50
transmission [%]

9355
transmission [%]

40 40

30 30

20 reference 20

5000
10 9350 10
9355
0 0
400 600 800 1000 1200 1400 400 600 800 1000 1200 1400
wavelength [nm] wavelength [nm]

Figure 5. Transmission spectra of the fabrics with effect pigment coatings. Applied are double coating,
with a first base coating containing titania white pigments and a second top coating containing four
different effect pigments (Shinedecor types) with a concentration of 10% in the coating recipe.
160 Jieyang Zhang and Boris Mahltig

3.3. Fastness Properties

The fastness properties are investigated with the most advantageous coating system
containing titania in the base coating and the aluminum effect pigment in the second
effect coating.

3.3.1. Washing Stability


To gain information on the washing fastness the transmission spectra of the samples
are recorded before and after 5 or 10 washing cycles (Figure 6). Also the transmission
value at = 1000 nm in the infrared range is recorded as function of pigment
concentration in the coating recipe and the number of washing cycles (Figure 7). Further
the weight of coated samples before and after washing is depicted (Figure 8). The
transmission spectra of samples in the washing tests are depicted in Figure 6 together
with the reference spectrum of the samples containing only the titania base coating. The
change of transmission as function of number of washing cycles is clearly seen but
strongly depends on the type of coated textile and the wavelength of light. On polyester
fabrics, the increase in transmission after washing is stronger compared to coated cotton.
This statement is especially valid for visible and infrared light. Even on polyester after 10
washing cycles, the transmission values are lower compared to the reference spectrum of
the titania containing base coating. For this it could be estimated, that by the washing
process the effect coating is not completely removed and can act still as a protection
component decreasing the transmission of light. Probably the adhesion of the binder layer
onto the polyester fabric is weaker compared to the situation on the cotton fabric. The
change of transmission for UV-light (<400nm) is for both types of substrates polyester
and cotton not detectable. Probable the adhesion of the titania base coating – mainly
responsible for the UV-absorption – is strong and no removement of UV-absorber
happens during the washing procedures. Only effect pigments – responsible for the
interaction with visible and infrared light – from the second top coating are removed
during the washing. To document this statement, in Figure 7 the transmission values at
=1000nm are given as function of pigment concentration in the coating and as function
of the number of washing cycles. It is clearly seen that with increasing pigment
concentration in the coating recipe also the transmission of the resulted coating is
reduced, probably because of the increasing coverage of the textile surface by the
embedded effect pigments. Adequate low transmission values are gained only with high
pigment concentrations of 10% or 15%. After performing the washing procedures, the
transmission values are increasing, especially for the sample prepared with 10% pigment
on the polyester substrate. The decrease of sample weight after washing is related to the
amount of coating components removed from the fabric surface by washing (Figures 7
Metal Coatings Effect Pigments for Textile Functionalization … 161

and 8). This decrease of weight after washing is measurable but not very strong compared
to the whole weight of the coating. For this, it should be supposed that the aim body of
the coating is not removed by washing. Only small parts of the coating are probable
removed. Most favorable components for this kind of removement are the effect
pigments on top of the coating. Effect pigments placed deeper inside the coating or even
the titania pigments of the base coating are mainly not removed. This statement is
strengthened by the microscopic investigations shown in Figure 9. In these images it is
shown that after washing the substrates are still almost completely covered by the binder
layer but effect pigments on the top of the coating surface are removed.

50 on polyester fabric 50 on cotton fabric


reference titania basecoat
40 40 coating after preparation
transmission [%]

transmission [%]
5X washing
10X washing
30
30

20
20

reference titania basecoat


10 coating after preparation 10
5X washing
10X washing
0
400 600 800 1000 1200 1400 0
400 600 800 1000 1200 1400
wavelength [nm]
wavelength [nm]

Figure 6. Transmission spectra of the fabrics with effect pigment coatings before and after performing
several washing cycles. Applied are double coating, with a first base coating containing titania white
pigments and a second top coating containing Shinedecor 5000 effect pigments with a concentration of
10% in the coating recipe.

50 50
on cotton; 10% pigment
45 on cotton fabric 45 on cotton; 15% pigment
on polyester fabric
on polyester; 10% pigment
transmission at 1000nm [%]

40
transmission at 1000nm [%]

40
on polyester; 15% pigment
35 35

30 30

25 25

20 20

15 15

10 10

5 5

0 0
0 2 4 6 8 10 12 14 16 0 2 4 6 8 10
applied concentration effect pigment shinedecor 5000 number of performed washing cycles
[%]

Figure 7. Evaluation of the optical transmission at the wavelength of 1000nm as function of the
pigment concentration (above) and the number of performed washing cycles (below). Applied are
double coating, with a first base coating containing titania white pigments and a second top coating
containing Shinedecor 5000 effect pigments in the coating recipe.
162 Jieyang Zhang and Boris Mahltig

3.3.2. Abrasion Stability


The behavior of developed coatings after abrasion is determined by transmission
measurements (Figure 10) and scanning electron microscopy SEM (Figure 11).
Surprisingly after the abrasion procedure the transmission of the samples decreases. This
decrease in transmission is promoted as function of number of performed abrasion cycles
(Figure 10). This fact is especially surprising, because it mean after abrasion the validated
protection properties of the samples are increased. Usually it would be expected that the
transmission increases by the abrasion procedure, because of the removement of pigment
and coating by this abrasion process. However, this is obviously not the case. After
abrasion the color of the effect coating turns from silver white to dark grey. This change
in coloration could be the result of oxidation processes on the metal pigment surface and
lead to a stronger absorption of light. This absorption is probably the reason for the lower
transmission values detected. Also, the surface topography of the coated samples are
drastically influenced by the abrasion process (Figure 11). Before abrasion, the surface is
nearly completely and regularly covered by effect pigments. The textile structure is
completely covered by the coating and is mostly not detectable by the SEM. After the
abrasion procedure this picture is changed drastically. On the raised areas of the fabric,
the effect pigments on the coating surface are removed, while in the intermediate areas
the pigments are still present. However, in these intermediate areas the thickness of the
textile substrate is lower, so especially in that place a remaining protective coating is
necessary to keep protective properties.

170

160

150
weight of fabric [g/m2]

140

130

120 on cotton; 10% pigment


110
on cotton; 15% pigment
on polyester; 10% pigment
100 on polyester; 15% pigment
90

80

70

60
0 2 4 6 8 10
number of performed washing cycles

Figure 8. Weight of fabric samples before and after applying several numbers of washing cycles.
Applied are double coating, with a first base coating containing titania white pigments and a second top
coating containing Shinedecor 5000 effect pigments in the coating recipe.
Metal Coatings Effect Pigments for Textile Functionalization … 163

Figure 9. SEM-images of cotton samples coated with titania containing basecoat and a top coating
containing 10% pigment Shinedecor 5000 before and after ten washing cycles.

14 after preparation
500 abrasion cycles
12 2000 abrasion cycles
15000 abrasion cycles
transmission [%]

10

0
400 600 800 1000 1200 1400
wavelength [nm]

Figure 10. Transmission spectra of cotton fabric with effect pigment coatings before and after
performing several abrasion cycles. Applied are double coating, with a first base coating containing
titania white pigments and a second top coating containing Shinedecor 5000 effect pigments with a
concentration of 10% in the coating recipe.

Figure 11. SEM-images of cotton samples coated with titania containing basecoat and a top coating
containing 10% pigment Shinedecor 5000 before and after several abrasion cycles.
164 Jieyang Zhang and Boris Mahltig

CONCLUSION

A double layer coating system containing different pigments can be used to realize
protective textiles against UV and IR light. A full protection against UV-radiation was
reached with fine dispersed TiO2 in a first base coating. The IR-protection is gained by a
second top coating containing anisotropic aluminum effect pigments. In comparison to
the washing fastness, the fastness against abrasion is especially excellent. For this, the
developed coating system is probably less suitable for clothing application, where the
washing fastness is absolutely required. However, the good abrasion fastness could be the
key advantage for a textile application development in home textiles. The developed
coating can be e.g., part of a window coverage as a light protection and light management
system.

ACKNOWLEDGMENTS

For funding of the electromicroscopic equipment the authors acknowledge very


gratefully the program FH-Basis of the German federal country North-Rhine-Westphalia
NRW. Many thanks are further owed to Thomas Heistermann for help and advice in the
finishing lab. Experimental work presented is part of the Master thesis performed by
Jieyang Zhang (2016, Hochschule Niederrhein). All product and company names
mentioned in this chapter may be trademarks of their respective owners, also without
labeling.

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Effect Coatings. Appl. Spectros., 57, 1266-1272.
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Hesse, M., Meier, H., Zeeh, B. (2008). Spectroscopic Methods in Organic Chemistry.
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(lightbulb). The Physics Teacher, 37, 520-525.
Mahltig, B., Böttcher, H., Rauch, K., Dieckmann, U., Nitsche, R., Fritz, T. (2005).
Optimized UV protecting coatings by combination of organic and inorganic UV
absorbers. Thin Solid Films, 485, 108-114.
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(2017). Effect pigments for textile coating – a review on the broad range of
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of nano metal oxide finishes on the multifunctional characteristics of cotton fabrics.
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of Industrial Textiles, 41, 259-277.
166 Jieyang Zhang and Boris Mahltig

Topp, K., Haase, H., Degen, C., Illing, G., Mahltig, B. (2014). Coatings with metallic
effect pigments for antimicrobial and conductive coating of textiles with
electromagnetic shielding properties. J. Coatings Technol. Res., 11, 943-957.
Wissling, P. (1999). State-of-the-art technology in aluminium pigments for aqueous
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Vincentz Network, Hannover.
In: Textiles: Advances in Research and Applications ISBN: 978-1-53612-855-0
Editor: Boris Mahltig © 2018 Nova Science Publishers, Inc.

Chapter 8

LUMINOUS TEXTILES FOR UV-PROTECTION AND


LIGHT EFFECT APPLICATIONS

Egon Dalponte, Boris Mahltig* and Christof Breckenfelder


Hochschule Niederrhein, University of Applied Science,
Faculty of Textile and Clothing Technology,
Mönchengladbach, Germany

ABSTRACT

The current work describes the development of a fluorescent fabric in combination


with UV emitting light sources. The construction is based on a 3D knitted fabric in which
UV emitting LEDs are inserted. Additionally, a layer of fabrics is placed over the 3D
knitted fabric. This fabric layer is as well dyed with a fluorescent dye or an optical
brightener. This applied dye transfers the emitted UV light into visible light. One
advantage is that in absence of an ultraviolet light emitting source, the dyed fabric is
transparent. By this, a switch on and off light effect can be created. Further, the realized
textiles have certain UV-protective properties. Presented is at first an intensive
classification of the used dye systems. Than textile processing is presented, followed by
spectroscopic investigations on the realized textile materials. Altogether a suitable textile
construction for light effect application is presented.

Keywords: fluorescence dyes, optical brightener, UV emitting LED, smart textiles

*
Corresponding Author Email: Boris.Mahltig@hs-niederrhein.de.
168 Egon Dalponte, Boris Mahltig and Christof Breckenfelder

INTRODUCTION

Textile materials are often more than simple clothing or textiles used in technical
applications. Often textiles are used to give optical signals. Most fashion is related to
optical signals indicating the status of the person wearing it. Remember for example the
German society in the Middle Age. Each class and group of professionals was wearing
typical clothes presenting the status and place in the society. Nowadays, also optical
signals can be enhanced by using so-called light effects. For working clothes it is often
required to have a high visible effect (Porter 1997). Imagen e.g., the safety vests which
are obligatory for many workers and as safety equipment in a car. These vests will give
you a high visibility at evening time or at night in case of an accident, if you have to
leave the car (Desjardin 2005; Dan Turner et al. 1997).
Other examples are textiles containing an effect of “after glowing” (Pourdeyhimi &
Little 2001). These textiles will emit light for a certain time after they were illuminated,
so in case of a suddenly darkness, e.g., as result of an accident, these textiles could lead
you to the emergency exist.
High visible clothes are often realized by use of so-called fluorescence dyes
(Truesdale 2004). These fluorescence dyes do not only support a certain coloration to the
textile, they also add a fluorescence effect to the textile fabric. Simply spoken,
fluorescence means that a substance absorbs light of higher energy and emits light of
lower energy. By this, light of lower wavelength is transferred to light of higher
wavelength. The physicochemical background of fluorescence is described in detail in
several text books and should not be the focus of this chapter (Hesse et al. 2008; Wöhrle
et al. 1998; Christie 2001; Göpel & Ziegler 1994; March 1992). For textile application it
is of importance that fluorescence transfers UV-light, which is not visible by human eye,
into visible light. In consequence the amount of visible light is significantly increased and
a higher visibility of the textiles can be realized. The emission of fluorescence light is
immediately stopped after the exposition to the exciting light source is stopped.
The above mentioned textiles with an “after glowing” effect are therefore not realized
by fluorescence dyes. To realize these after glowing textile materials, phosphorescence
dyes or pigments are used. This phosphorescent afterglow is reported for textile
application with 30 minutes up to 12 hours (Wadely 1957). In simple understanding,
phosphorescence is quite similar to fluorescence but the light is emitted in case of
phosphorescence for a longer duration. The reason for this delay in emission is in
literature often described by the term of “intersystem crossing” and should not be
described more in detail in the current chapter (Hesse et al. 2008; Christie 2001).
For textile application it could be remarked, that for fluorescence applications often
dye stuffs with fluorescence properties are used (Christie 1993; Christie et al. 2008). In
contrast, for phosphorescence effects on textiles mainly pigments are used.
Luminous Textiles for UV-Protection and Light Effect Applications 169

Phosphorescent pigments are applied on textiles as part of a coating or printing


(Goldstein 1966) or as additive at production of synthetic fiber s (Owens 1994).
Optical brightener can be understood as special type of fluorescence dyes, which are
almost uncolored in the visible range of light (Wagner et al. 1966). Optical brighteners
absorb UV-light and emit visible fluorescence light. The UV-light absorbed is described
to be in the range of 340 nm to 375 nm. The emitted visible light contains usually
wavelengths from 400 nm to 500 nm, with colors in the range from violet, blue or
greenish blue. By this transfer of not visible UV-light into blue visible light the fabric
appears whiter, so optical brighteners are also named as whitening agents (Tiki et al.
2010; Kabir et al. 2014).
Optical brighteners can be roughly classified into two categories, as direct
brighteners and disperse brighteners – simply related to direct dyes and disperse dyes
(Clark 2011). The direct or substantive brighteners can be used similar to direct dyes for
textile application. Direct brighteners exhibit a good water solubility and are used mainly
for hydrophilic natural or regenerated fibers, as e.g., cotton, wool or viscose (Fort et al.
1966). Also analogous to acid dyes, they can be applied onto polyamide fabrics. Higher
washing stability on natural fibers can be reached by use of reactive brighteners,
containing a reactive anchor group forming a permanent covalent bond to the fiber
surface (Schinzel & Lebkucher 1964; Eckhardt et al. 1997). Disperse brighteners are
similar to disperse dyes in relation for their application onto textiles (Daubach et al.
1980). They are insoluble in water and applied as dispersion for treatment of hydrophobic
synthetic fiber s, mainly for polyester fabrics (Tiki et al. 2010).
Usually fluorescence dyes or optical brighteners applied on a textile are interacting
with light from an external light source like the sun or surrounding artificial light sources,
as lamps. In contrast, the current chapter describes a 3D textile construction where the
light sources are integrated inside a textile functionalized with brighteners and
fluorescence dyes. By this direct contact to the emitting light source, special luminous
textiles with strong light effects can be realized.

MATERIALS

For the focused application, it is important to specify the characteristics of demand


for the textile product. In order to insert the UV-emitter inside the fabric a certain height
of the fabric is needed. However, not only the height of the fabric is crucial. It is also
necessary that the structure is open to ensure that the emitted UV-radiation can pass
through the structure and can interact with the fluorescence dyes placed on the fibers. On
the other hand it would be advantageous to have a closed structure to be able to test the
effect of a 3D fabric with inserted UV-emitter and to gain also a certain UV-protective
effect. Therefore, it has been decided to produce a knitted structure open on one side and
170 Egon Dalponte, Boris Mahltig and Christof Breckenfelder

closed on the opposite side. To realize a fabric according to the mentioned demands a
double layered 3D knitted fabric is chosen.
The textile material used is prepared from polyester monofilament by using a Raschel
machine (DR 7 E-ST; number of needles 2x450 with a working width of 635 mm). By
this, a double-faced fabric is produced. The maximum height, which can be produced by
the used device is 5 mm. The produced knitted structure is shown as photographs in
Figure 1. Additionally images taken by a scanning electron microscope are presented in
Figure 2. The open mesh structure of the knitted fabric is clearly seen. As well the tunnel
structure building up the space between the two layers is clearly visible. In this tunnel
structure ideally a small UV-emitting device can be placed (Figures 1 and 2).

Figure 1. Photographs of double layered knitted fabric – top view (left) and side view (right); the tunnel
structure of the 3D-knitted fabric is clearly seen.

As source for UV-light different types of commercially available LEDs are taken into
account. Important for the wished application is a small dimension of the light source, so
that it can be inserted and placed in the 3D knitted fabric. The dimension of the chosen
LED is fitting excellent to the size of the tunnel structure of the prepared 3D fabric.
Beside the size of the light source, also the lightening power and the wavelength of
emitted UV-light are of importance. The emitted UV-light should be able to interact with
the optical brighteners and the fluorescence dyes but has to be also in the range of UV-A
light. UV-A light exhibits lower health risk compared to the more energy rich UV-B and
UV-C light. With this background, for the developed application a UV-emitting LED
Luminous Textiles for UV-Protection and Light Effect Applications 171

“OCU_400_UC375” is used, which is supplied by the company Osa Opto Light GmbH.
The emitted UV-light is in the range of 375 nm to 380 nm (OSA Opto Light 2013).

Figure 2. SEM-images of double layered knitted fabric – top view (above) and side view directly into
the tunnel structure (below).

DYE PROPERTIES

In comparison to other fibers, the dyeing of polyester fabrics is challenging, because


the surface of the polyester fiber does not contain functional groups, which enable the
adhesion or formation of covalent bond s to dye molecules (Clark 2011). This adhesion
or the chemical bonding of dye molecules to the fiber is the main condition for a
sufficient washing and abrasion stability of the coloration reached by the dyeing process.
For this, for polyester fabrics the use of simple direct dyes or acid dyes is not possible.
The dyeing of polyester is usually done with disperse dye stuffs applied in a HT-process
or a thermosol process (Clark2011).
In actual investigation, the two fluorescence dyes Bemacron Leuchtgelb SEL-EN
(further also named: yellow dye) and Bemacron Leuchtrot SEL-4B (further also named:
172 Egon Dalponte, Boris Mahltig and Christof Breckenfelder

red dye) supplied by CHT (Tübingen, Germany) are used. These both dyes are dedicated
especially for the application onto polyester fabrics and described to have a very bright
blue supplementary element. There are originally dedicated for the production of warning
clothes, sportswear and leisure clothing (Ferus-Comelo 2009; CHT Bezema 2017).
The second category of components applied in actual investigation are optical
brightener. Optical brightener are compounds absorbing UV light and transfer it into
visible light, which is emitted. One advantage of optical brightener for the current
application is the colorless in the absence of UV-light but one UV radiation activates it,
the brightener shines blue. For this, there is a clear color difference between the fabric
under normal light conditions and under exposition to UV light, which emphases the
wished light effect. In current investigations two optical brighteners are used – Ultraphor
BN and Ultraphor SFG. Both brighteners are supplied by German company BASF and
are described as non-ionic fluorescent brightening agents dedicated especially for the use
on polyester fibers and fabrics (Tutak 2013; BASF 2001).

447nm brigthener - ultraphor BN


0,4 brigthener - ultraphor SFG
yellow dye
red dye
absorption [a.u.]

0,3

0,2

347nm
353nm
0,1

0,0
250 300 350 400 450 500 550 600
wavelength [nm]

Figure 3. Optical absorption spectra of the used brighteners and dyes solved in iso-propanol.

These four components are applied as water based dispersion. From this dispersion,
they can be extracted into organic solvents like iso-propanol. This clear and
homogeneous solution in iso-propanol is used to measure the optical absorption spectra
of both fluorescence dyes and optical brighteners (Figure 3). It is clearly indicated that
the optical brighteners do not show any light absorption in the visible range. Beside
strong absorption of UV-C and UV-B light, they also contain a significant absorption
maximum for UV-A light around 350 nm. Bemacron SEL-EN exhibits a clear yellow
coloration (yellow dye) and has a strong absorption maximum for visible light at 447 nm.
Luminous Textiles for UV-Protection and Light Effect Applications 173

Bemacron SEL-4B exhibits a red coloration (red dye) but has no clear absorption
maximum for visible light. This red dye absorbs mainly visible light in the range from
400 nm to 550 nm. For light with a wavelength of 600 nm or more no absorption is
determined.
The solutions of the dyes in iso-propanol are also used to determine the fluorescence
properties of those compounds. The yellow dye Bemacron SEL-EN emitted fluorescence
light in the range from 200 nm to 800 nm, for exposure for excitation light from 200 nm
to 400 nm. For excitation mainly three region around 210 nm, 280 nm and 395 nm are
determined leading to strong emission of fluorescence light. However, for the actual
developed textile application only the excitation region around 390 nm is of relevance,
because of the light emission of the used LED -device in that region. Also for other
applications of this fluorescence dye, e.g., for warning clothes, this excitation with UVA-
light is significant, because this type of UV-light is present in daily life (Brennan et al.
1988). The excitation with UVC-light is not important, even if the fluorescence effect is
stronger, because UV-C light does not occur in common situations. The occurrence of
UV-C light is almost limited to industrial applications and production processes and due
to its high potential health risks, it should be only used in closed systems (Marquardt &
Schäfer 1994).
The optical brightener Ultraphor SFG exhibits as well fluorescence properties. A
clear maximum in fluorescence is determined for excitation light with around 210 nm.
For UVA-light no significant single maximum is indicated. If UV-light with 390 nm is
excited, fluorescence light with around 400 nm is emitted. Exactly this emission of
visible blue light is necessary for the application as optical brightener.

DYEING PROCESS

The dyeing of the 3D knitted fabric is done by a thermosol process. For this, aqueous
dispersions of the both fluorescence dyes and the both optical brightener are prepared and
applied with a padding machine. The concentration of the optical brightener Ultraphor
BN and Ultraphor SFG are set to 5 g/L in the dye bath. The concentrations of the
fluorescence dye Bemacron leuchtgelb SEL-EN is set to 10 g/L and of the dye Bemacron
leuchtrot SEL-4B to 20 g/L in the dye bath. The padding process is done with a pressure
of 6 bar. If the padding pressure is set to lower values, the liquid up-take is too much.
After padding, the fabrics are dried at 120°C for 2 minutes and a thermofixation is
performed afterwards at 190°C for 1 minute. To remove the unfixed dye stuff from the
fiber surface, all fabric samples are washed for seven minutes under alkaline conditions
in water at 80°C. After rinsing with conventional water, the fabrics are tumble dried for 1
minute. Finally a drying step is performed for 30 seconds in an oven at 130°C. The
resulted colored 3D-fabrics are shown in Figure 4.
174 Egon Dalponte, Boris Mahltig and Christof Breckenfelder

Figure 4. Dyed 3D knitted fabrics.

Beside the 3D knitted fabric, also a conventional woven polyester fabric is treated
with the fluorescence dyes and the brighteners. For this dyeing of polyester fabric, a HT-
process is used. HT stands for high temperature, meaning that the process temperature is
above 100°C and the process pressure is above 1bar. In the actually used dyeing
procedure, the process temperature is set to 135°C. The aqueous dispersions containing
following concentrations: 0.6% Ultraphor BN; 1.25% Ultraphor SFG; 2.0% Bemacron
SEL-EN or 6.0% Bemacron SEL-4B. Additionally the dispersing agents CHT-
Dispergator XHT-S and Opticid PB are used in concentrations of 2%. The dyeing process
is performed at 135°C in a dyeing machine Mathis Polycolor HT. After dyeing the textile
samples are rinsed with conventional water and dried at air.

TEXTILE PROPERTIES

To gain optimal light effect textiles, combinations of different materials are


developed. The focus of optimization and investigation is primarily optical, related to
best light effect. Second, also the safety issue of the product is a concern. Not only single
layer constructions but also products that consist of several layers are in focus of
development. Presented single layer products consist only of a 3D knitted fabric with
embedded electrical component. Whereas the double layer construction consists of a 3D
knitted fabric with an additional conventional woven polyester fabric on top. Both
Luminous Textiles for UV-Protection and Light Effect Applications 175

polyester materials are dyed with fluorescence dye or optical brightener. By this, various
combinations are possible when overlaying the two fabrics. The textile samples are
analyzed according to their properties of diffuse transmission and reflection (Figures 5
and 6). Further a visual evaluation is done with the full textile configuration (Figures 7
and 8).
The transmission for UV-light should be as low as possible, due to safety reasons but
also as an indicator for the effectivity of the fluorescence effect to transfer UV-light to
visible light. UV light which is not transferred to visible light is lost for the wished light
effect. The reflection measurements are performed mainly for color determination of the
fabrics.
In Figure 5 the transmission and reflection spectra of the conventional polyester
fabric dyed with the different fluorescent components are depicted. The spectra
summarize a range from 220 nm (UV light) to 800 nm (visible light ). The both fabrics
with optical brightener exhibit over the complete visible range nearly the same
transmission of around 45%. For the UV-range, the transmission behavior could be
roughly separated into two parts. From 220 nm 320 nm, the transmission is below 20%,
this decrease is probably related to the absorption of UV-light by the polyester material
itself (Bajaj et al. 2000). From 320 nm to 400 nm, the transmission is around 30%, this
decrease is probably related to the absorption of UV-light by applied brighteners.
This decrease of UV-transmission by the applied optical brighteners is clearly seen.
However, it has to be stated that for UV protective purposes a remaining UV
transmission of around 30% is still too high. For UV protective materials usually
transmission values of 5% or less are expected for the complete range of UV light (Rauch
et al. 2004; Mahltig et al. 2005; Bajaj et al. 2000; Saravanan 2007). For textile materials
these values can be reached by several methods, e.g., sol-gel coatings or metal effect
pigments (Böttcher et al. 2006; Mahltig & Textor 2008; Topp et al. 2014; Mahltig et al.
2017).
Compared to the both applied brighteners, the application of both fluorescence dyes
leads to lower UV-transmission of around 20% in the spectral range from 300nm to
400nm. Due to the coloration of the applied fluorescence dyes, also the transmission of
visible light is significantly influenced. Significant transmission minima in the visible
range are detected at 413 nm for the red dye and at 520 nm for the yellow dye. Due to
this coloration, analogously the reflectance is influenced (Figure 5). These determined
minima for the fluorescence dyes after application onto polyester textile are different
from the values determined for the same dyes in solution of iso-propanol.
A change of optical properties depending on the surrounding solvents or polymeric
matrix is known and described by the term “solvatochromism” (Liptay 1969; Reichardt
1992). This solvatochromism effect could be also appear with the currently used dyes, if
they are placed in different media – on one side the hydrophilic solvent iso-propanol and
on the other side the hydrophobic polyester fiber.
176 Egon Dalponte, Boris Mahltig and Christof Breckenfelder

100
Brightener - Ultraphor BN
90 Brightener - Ultraphor SFG
80
red dye
yellow dye
70

transmission [%]
60

50

40

30

20

10
413 nm
520 nm
0
300 400 500 600 700 800
wavelength [nm]

100
Brightener - Ultraphor BN
90
Brightener - Ultraphor SFG
80 red dye
yellow dye
70
reflection [%]

60

50

40

30

20 394 nm
497 nm
10

0
300 400 500 600 700 800
wavelength [nm]

Figure 5. Optical spectra of diffuse transmission and reflection of polyester woven fabrics with different
optical brighteners and fluorescence dyes.

Figure 6 shows the transmission and reflection spectra of the 3D knitted fabric dyed
with the different fluorescent components. The determined maximum transmission in the
visible range of around 35% are lower compared to the values of the woven polyester
material. For this, the 3D construction could be described as less transparence for light
compared to the woven material described in Figure 5. For both fluorescence dyes
transmission minima are detected, which are mainly at the similar position as for the
woven fabric. More differences between the both types of fabrics are found for the
Luminous Textiles for UV-Protection and Light Effect Applications 177

reflection spectra. Probably the reflection is also strongly influenced by the surface
topography of the textile samples.

100
Brightener
90
red dye
80 yellow dye
transmission [%] 70

60

50

40

30

20

10
436 nm 520 nm
0
300 400 500 600 700 800
wavelength [nm]

100

90 Brightener
red dye
80 yellow dye
70
reflection [%]

60

50

40
493 nm
30

20
393 nm
486 nm
10

0
300 400 500 600 700 800
wavelength [nm]

Figure 6. Optical spectra of diffuse transmission and reflection of polyester 3D knitted fabrics with
optical brightener and both applied fluorescence dyes.

TEXTILE APPLICATIONS

A bilayer construction is considered advantageous not only from aesthetical but also
from a customer friendly point of view. In case, it is necessary to clean the surface of the
product, the top polyester fabric can be easily removed and washed without the necessity
178 Egon Dalponte, Boris Mahltig and Christof Breckenfelder

to remove also the electronic components from the construction. Another important point
is, that with a bilayer or even multilayer construction the amount of fluorescent active
materials around the UV emitting source is increased, so the intensity of the gained light
effect is improved. Further, different color effects can be realized by combination of
textiles containing different fluorescent dyes.

Figure 7. 3D-Fabric with yellow fluorescence dye above and 3D-Fabric covered with standard polyester
fabric (both dyed with the same yellow fluorescence dye) below. The presented textile construction
contains four LED as UV-emitters.

Examples for double-layer constructions are shown in Figures 7 and 8. Figure 7


contain a 3D-knitted fabric and a polyester woven material both equipped with the yellow
fluorescence dye. By this, a light green effect can be realized. It is also clear that the top
polyester woven fabric leads to a brighter light effect covering the full textile area,
Luminous Textiles for UV-Protection and Light Effect Applications 179

probably because of light scattering. The same effect is as well demonstrated in Figure 8,
with a 3D-fabric containing the optical brightener half covered by a polyester fabric with
yellow fluorescent dye. In the not covered part, the two LEDs can be clearly identified.
After coverage with the fluorescent fabric, the whole textile area is full illuminated and
the place of the light source cannot be identified.

Figure 8. Half-covered assembled sample. The presented textile construction contains four LED as UV-
emitters.

CONCLUSION

The aim of the current development is to investigate the possibility of a product that
creates a unique optical effect using a 3D warp knitted fabric with embedded UV-emitter
and dyed with different UV-light sensitive fluorescent dyes.
To develop the aimed product, three different challenges have to be overcome:
First, the creation of the necessary 3D warp knitted structure in which the electrical
components for UV-emission are meant to be embedded. Due to the limited height of the
fabric, a special tunnel construction has to be designed.
Second, different finishing methods have been tested. Here, for material development
only polyester fiber materials are taken into account, making it possible to use the same
category of dyes and optical brightener on the different fabrics. The 3D knitted fabric are
dyed using a thermosol process. Other woven polyester fabric are dyed by using a
conventional HT-process.
Third, embedding the UV emitter inside the fabric is not been without difficulties.
Even with components so small to create difficulties while handling them, the tunnels of
3D knitted fabrics are hardly big enough to embed the electronic components. In the case
180 Egon Dalponte, Boris Mahltig and Christof Breckenfelder

of the 3D knitted fabrics the shrinkage caused by the thermosol process makes it
impossible to embed the component. Alternatively, the fabric has been cut open in order
to make the electrical components fit. To deliver electricity to the embedded UV-emitter
an own power supply and electrical circuit are built.
Altogether, it was demonstrated that luminous textiles can be realized by application
of fluorescence dyes and optical brightener constructed in 3D knitted fabrics, which are
ideal carriers for small electronic devices used as emitter of UV-light. The fabrics are
able to decrease the emitted UV-light intensity and convert the UV-light into visible light.
By this in a proof-of-concept for light effect textiles are realized and presented in a first
approach. These textiles are able to switch on / off the emitted light and coloration, while
being mainly uncolored without the presence of UV-light.

ACKNOWLEDGMENTS

The authors would like to thank Thomas Heistermann for many helpful discussions
and experimental help. For help with spectroscopic measurements following persons
have to be mentioned – Amir Fahmi and Duygu Disci-Zayed from Hochschule Rhein-
Waal. For funding of the electronmicroscopic equipment the author acknowledges very
gratefully the program FH-Basis of the German federal country North-Rhine-Westphalia
NRW. Experimental work presented is part of the Bachelor thesis performed by Egon
Dalponte (2016, Hochschule Niederrhein). All product and company names mentioned in
this chapter may be trademarks of their respective owners, also without labeling.

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In: Textiles: Advances in Research and Applications ISBN: 978-1-53612-855-0
Editor: Boris Mahltig © 2018 Nova Science Publishers, Inc.

Chapter 9

DOUBLE FUNCTIONAL FINISHING FOR TEXTILE


FABRICS: A COMBINATION OF UV-PROTECTIVE
AND ANTIMICROBIAL PROPERTIES

Ghulam Shabbir1, Hajo Haase2 and Boris Mahltig1,*


Hochschule Niederrhein – University of Applied Science,
1

Faculty of Textile and Clothing Technology, Mönchengladbach, Germany


2
Technische Universität Berlin, Institute for Food Technology
and Food Chemistry, Berlin, Germany

ABSTRACT

Double functional finishing provides two new functional properties on a textile


fabric by using only one application step during a finishing process. In the present
investigation an example is given applying UV-protection and antimicrobial activity in
one step by using an aqueous based finishing agent. This finishing agent contains as
active component zinc pyrithione ZnPh and is applied on both cotton and polyamide
fabrics. Both functional properties UV-protection and antimicrobial activity are reached
by this method. However for satisfactory UV-protection higher amounts of ZnPh applied
are necessary. In contrast, to reach antimicrobial activity only small ZnPh concentrations
have to be applied.
In fact, by this study it is demonstrated that already well established finishing agents
could be suitable for application of a second functional property with the aim of a double
functional finishing.

Keywords: UV-protection, antibacterial, antimicrobial, zinc compounds, zinc pyrithione

*
Corresponding Author Email: Boris.Mahltig@hs-niederrhein.de.
184 Ghulam Shabbir, Hajo Haase and Boris Mahltig

INTRODUCTION

Bifunctional finishing of a textile summarizes application processes which allow the


application of two functional properties on one textile substrate. It can be also named as
double functional finishing.
Very attractive are bifunctional textiles for several areas. Applications are found for
sport and outdoor clothes, e.g., a sport T-shirt with UV-protective function and humidity
management or a T-shirt offering both UV-protection and deodorating effects gained
from antimicrobial function. Another type of application is a swim suit with UV-
protection and the property of fast drying effect. After this short list of possible and
useful applications, which could be only a short selection, also different methods, how to
realize bifunctional textiles should be mentioned. Usually a certain functional property
can be applied by using an agent carrying this function, e.g., if a flame retardant agent is
applied onto cotton fabrics, by this flame retardant cotton is realized.
From that point, a simple approach to realize bifunctional textiles is the step by step
application of different functional finishing agents. For example, at first a flame retardant
component is applied and in a second step an agent with water repellent properties is
applied. This kind of a two-step process is of high flexibility but also increases the efforts
in application.
With this background it is an interesting approach to have a view on finishing agents
developed for a specific functionalization and evaluate them for a second possible
function which can be also reached with this agent.
A very simple approach in this direction is the use of dye stuff (especially basic dyes
or metal-complex dyes) which can have also antimicrobial properties (Ma et al. 2003;
Simoncic & Tomsic 2010; Zhao et al. 2008; Abedi et al. 2008). The two applied
functions are here the color and the antimicrobial property. More difficult is the
combination of antistatic and water repellent properties (Textor & Mahltig 2010).
Antistatic properties are often reached by hydrophilic treatments decreasing the surface
resistance of textiles by increasing their ability to water up-take.
This mechanism to reach antistatic properties is obviously contradictive to the aimed
hydrophobic properties. A suitable approach is here developed with a sol-gel system
allowing the self-orientation of a hydrophilic part towards the fiber surface and a
hydrophobic part oriented to the air interface (Textor & Mahltig 2010).
In the actual presented investigation, a bifunctional treatment is focused which is
aiming the combination of antimicrobial function together with an UV-protection
property. If those two functions are wished to apply in one finishing step, it should be
evaluated if there is an antimicrobial agent which can be as well used to generate UV-
protection. Vice versa, also an UV-protective agent could be evaluated for its possible
antimicrobial properties.
Double Functional Finishing for Textile Fabrics 185

An excellent UV protective agent is titanium dioxide TiO2, which is as well used as


white pigment (Saravanan 2007; Braun et al. 1992). The white pigment is of rutile type
(Braun et al. 1992; Wang et al. 2010). Another titania type is anatase, which is reported to
be photoactive and this photoactivity can also support antimicrobial properties (Amiano
et al. 2012, Mahltig et al. 2007; Mahltig & Textor 2008; Mahltig & Haufe 2010; Mahltig
& Miao 2017). For this, photoactive TiO2 can be used for preparation of bifunctional
textiles containing both UV-protective and antimicrobial properties (Ren et al. 2010;
Nazari 2014). However, photoactive materials have significant disadvantages, if they are
used as antimicrobial agents for textiles.
These disadvantages are mainly related to two points. First, the photocatalytic effect
is only working under presence of UV-A light (Amiano et al. 2012). If a modification is
done to support also photoactivity with visible light, the samples get a significant
coloration, which is in most cases not wished (Liu et al. 2009).
Second, the photoactivity effects not only the bacteria also polymers can be degraded
by it. For this, the organic textile material is damaged by photooxidative processes
(Worsley & Searle 2002).
Alternatively to the TiO2 approach, zinc oxide ZnO can be aimed to realize a
bifunctional modification of textile substrates. ZnO is as well a white pigment with UV-
absorbing properties. Also the antimicrobial properties of ZnO is well reported. The
realization of both antimicrobial and UV-protective functions on cotton fabrics by using
zinc oxide nanoparticles and nanostructures is described (Shaheen et al. 2016; Shateri-
Khalilabad & Yazdanshenas 2013; Rajendran et al. 2010).

Figure 1. Chemical structure of zinc pyrithione complex (1-Hydroxypyridine-2-thione zinc salt,


C10H8N2O2S2Zn; 317.7 g/mol).

Compared to TiO2, the advantage of ZnO as antimicrobial agents is, that its
antimicrobial property is not based on a photoactive process, so the disadvantages
mentioned for TiO2 above are not valid for ZnO. The antimicrobial property of ZnO is
mainly based on the release of zinc ions Zn2+ (Castro-Mayorga et al. 2017). However, it
should be remarked that the antimicrobial effect of released zinc ions is significantly
lower compared to other metal ion s, as e.g., silver Ag+ ions (Mahltig et al. 2013).
186 Ghulam Shabbir, Hajo Haase and Boris Mahltig

Alternatively to ZnO, also other zinc containing compounds are developed to realize
antimicrobial textiles. One already well established agent is based on zinc pyrithione
ZnPh (Figure 1) (Morris & Welch 1983; Morris & Welch 1984; DeMeyer 2016). In the
actual presented investigation beside the capability to apply antimicrobial properties also
the focus is set to possible UV-absorbing properties of ZnPh. If there are sufficient UV-
absorption properties of ZnPh, a double functional finishing with UV-protection and
antimicrobial properties would be easily possible.

EXPERIMENTAL SECTION AND ANALYTICS

For application of both antimicrobial and UV-protective properties, a finishing agent


is used, which is originally dedicated and commercialized for antimicrobial
functionalization of textiles. The used agent is RUCO-BAC ZPY supplied by Rudolf
GmbH (Germany ). This finishing agent is especially dedicated for realization of a silver
free antimicrobial effect. The antifungal and the deodorizing effect is especially claimed
by the supplier (Müller 2015). According to the safety data sheet this readymade recipe
contains up to 50% zinc pyrithione ZnPh complex as antimicrobial active agent (see
Figure 1). Other components are sodium polynaphthalenformaldehydesulfonate. It is a
white liquid with a pH in the range of 6 to 9 at 20°C. The density is around 1.1 g/cm3
(Rudolf 2016).
For the actual experiments, this recipe is applied onto cotton and polyamide fabrics.
The cotton textile is a plain woven fabric with a weight of around 240 g/m2. The
polyamide textile is a warp knitted fabric with a weight of around 155 g/m2.
On these fabrics the RUCO BAC ZPY is applied in concentrations of 1 g/L to 30 g/L
as aqueous dilution. Further, diluted acetic acid is used to adjust the pH in the range of
4.0 to 4.5.
The application of the recipe onto the textile fabrics is done by a lab scale padder
from Mathis (type HVF-72206). The roller pressure is set to 2 bar and the speed of the
roller is 15 m/min. Under this set-up the wet pick-up for application on polyamide is in
the range of 86wt-% to 93 wt-%. For cotton fabrics the wet pick-up is in the range from
67 wt-% to 71 wt-%. The drying of samples is performed at 130°C by using an oven from
Mathis (type LTE-76207).
The surface topography of the textile samples is investigated by scanning electron
microscopy SEM performed with a TM 3000 Tabletop microscope from Hitachi. The
chemical surface composition of the samples is additionally determined by EDS (energy
dispersive spectroscopy) using a unit Quantax 80 from Bruker. The UV protective
properties are determined as optical transmission for UV-light in arrangement of
diffusive transmission. A SHIMADZU UV-2600 UV-VIS Spectrometer is used as testing
devise for determination of the optical transmission.
Double Functional Finishing for Textile Fabrics 187

Antimicrobial testing is done with gram-negative (Escherichia coli) and gram-


positive (Staphylococcus warneri) bacteria. Glycerol stocks (10 µl) are grown over night
in 75 ml LB medium. For testing their impact on viability, textile samples (circles of 5
mm diameter) are placed in sterile 96-multiwell cell culture plates together with 200 µl
bacterial suspension (diluted 1: 250 in LB medium) per well and incubated for 3h at
37°C, rotating at 120 rpm in an PST -60HL-4 orbital incubator (Biosan, Latvia ).
Subsequently, bacterial viability is tested by measuring the reduction of
methylthiazolyldiphenyl
tetrazolium bromide (MTT) as previously described (Kaltenberg et al. 2010; Mahltig et
al. 2011). Briefly, cells are incubated with 0.01% (w/v) MTT in LB medium, followed by
lysis of a 100 µl aliquot in isopropanol and determination of the absorption at 570 nm
(reference wavelength 700 nm) in a Tecan M200 multiwell-plate reader (Tecan,
Crailsheim, Germany ). Data are shown as % viability relative to bacteria in the absence
of fabric samples. For each textile sample the measurements are conducted at least three
times independently with different cutouts from the same sample.

RESULTS AND DISCUSSION

Material Properties

Before investigating the specific functional properties after the finishing application,
at first a view is done onto some material properties of the realized textile samples. The
material properties are related to the surface topography and surface composition of the
samples. A first view is done by SEM onto the surface topography of the cotton fabric
before and after recipe application (Figures 2 and 3). After application of recipes
containing only small amounts of zinc pyrithione (ZnPh) no difference in the surface
topography of textile samples compared to the untreated can be determined (Figure 2). In
contrast textiles treated with higher concentrated recipes exhibit white spots on the SEM
topographies. Especially after applications with highest ZnPh concentrations this is
obvious (Figure 3). In the used measurement modus of the SEM device, beside the
surface topography also a certain chemical contrast is supported. In this modus surface
area s containing chemical elements of higher atomic weight are depicted brighter.
Compared to the cotton substrate, the applied ZnPh contains with zinc and sulphur
heavier chemical elements and areas containing ZnPh in larger amounts will be shown
brighter.
The detection of ZnPh on the cotton surface in larger amounts and unregularly is a
hint that the applied ZnPh is not up-taken completely by the cotton fiber and some
material is left on the fiber surface.
188 Ghulam Shabbir, Hajo Haase and Boris Mahltig

Figure 2. SEM-images of untreated cotton substrate and cotton substrate after application of the lowest
applied amount of ZnPh.
Double Functional Finishing for Textile Fabrics 189

Figure 3. SEM-images of cotton substrates after application of the highest applied amounts of ZnPh.
190 Ghulam Shabbir, Hajo Haase and Boris Mahltig

10000
C

8000

signal intensity [a.u.]


O
6000

4000

2000
Si Ca

0
0 1 2 3 4
photon energy [keV]

C
8000
signal intensity [a.u.]

O
6000

4000

2000
Si Ca
Zn S
0
0 1 2 3 4
photon energy [keV]

Figure 4. EDS-spectra of untreated cotton reference fabric and a cotton fabric treated with ZnPh
(highest concentration 30 g/L).

By EDS analysis also the composition of chemical elements on the surface of textile
samples can be determined (Figure 4). The EDS spectra of the untreated cotton exhibit
clear peaks related to the elements carbon and oxygen (Figure 4). The chemical element
hydrogen cannot be detected by this method. From the cellulosic structure of the cotton
this appearance of the elements oxygen and carbon is clear. Also small peaks are detected
related to the elements silicon and calcium. The occurrence of those both elements can be
explained from earlier cleaning and washing processes performed with common water or
by the application of sizing agents during textile production processes. The textile
samples after the ZnPh application exhibit as well peaks related to zinc and sulphur
Double Functional Finishing for Textile Fabrics 191

(Figure 4). However from those both elements, the zinc can be only determined on the
sample surface, if the ZnPh is applied in higher concentrations of 10 g/L or more (Figure
5). In contrast the sulphur can be also determined after application of smallest ZnPh
amounts and the surface concentration of sulphur is consequently increasing as function
of applied ZnPh concentration. From this, it could be estimated that during application
and fixation process the applied ZnPh is splitted and the zinc component penetrates the
fiber deeper compared to the sulphur containing component. The zinc is placed deeply in
the fiber and cannot be detected by EDS method, while the remaining sulphur is clearly
observed. Only with higher amounts of applied ZnPh the zinc is also determined on the
surface by EDS. In this situation, probably the cotton fibers are already saturated by the
zinc component and a not penetrating zinc is now visible on the fiber surface.

1,0
zinc
0,9
sulphur
0,8
on treated textile [wt-%]
surface concentration

0,7

0,6

0,5

0,4

0,3

0,2

0,1

0,0
0 5 10 15 20 25 30
concentration of ZnPh
in finishing solution [g/L]

Figure 5. Surface concentration of zinc and sulphur on the treated cotton fabrics as function of ZnPh
concentration in the finishing solution.

Antimicrobial Properties

The antimicrobial properties of the textiles after application of the ZnPh recipes are
summarized in the Figures 6 and 7. These figures show the remaining bacterial viability
after contact with the textile samples. This viability is depicted as function of increasing
amount of ZnPh applied on the textiles and given for the two bacteria E.coli and
S.warneri.
192 Ghulam Shabbir, Hajo Haase and Boris Mahltig

E.coli on cotton fabric


120
on polyamide fabric

remaining bacterial viability [%]


100

80

60

40

20

0
0 5 10 15 20 25 30
concentration of ZnPh
in finishing solution [g/L]

Figure 6. Antimicrobial activity of ZnPh containing textile samples. Shown is the remaining bacterial
viability of E.coli after contact with cotton or polyamide fabrics containing ZnPh in increasing
concentration.

on cotton fabric
120 S.warneri on polyamide fabric
remaining bacterial viability [%]

100

80

60

40

20

0
0 5 10 15 20 25 30
concentration of ZnPh
in finishing solutin [g/L]

Figure 7. Antimicrobial activity of ZnPh containing textile samples. Shown is the remaining bacterial
viability of S.warneri after contact with cotton or polyamide fabrics containing ZnPh in increasing
concentration.
Double Functional Finishing for Textile Fabrics 193

For both bacteria it is clearly seen that even with the smallest applied amount of
antimicrobial finishing agent a significant antimicrobial effect is reached. This is
especially remarkable, because the lowest applied concentration of 1g/L ZnPh is
significantly below the concentration recommended by the supplying company. With
application of higher ZnPh concentrations no significant further improvement of
antimicrobial activity is reached. For this, it should be stated that the applied ZnPh is a
highly effective antimicrobial agent, which has already in lowest applied concentration
excellent antimicrobial results.

UV-Protection

To determine the properties of developed textile fabrics for purposes of UV


protection, their optical properties are investigated in arrangement of diffusive reflection
and diffusive transmission. First requirement for an ideal UV protective finishing agent is
that it will decrease the transmission of the treated textiles for UV light to low values
(Fuso & Reinert 1998). In best case for light with wavelength smaller 400nm the
transmission is 0%. A second often mentioned requirement for UV protective agents is
that they do not change the optical properties for visible light. Additionally an UV
protective agent should not influence the color of the textile, if it is applied on it (Mahltig
et al. 2005; Rauch et al. 2004).
The diffusive reflection of investigated samples is presented in Figure 8 and related
to the color properties of the samples. In this image the untreated textile samples are
compared to the samples treated with the highest amount of ZnPh. It is clearly seen, for
visible light in the range of 400 to 600nm, the reflection is nearly constant in the range of
70% to 80%. All these samples exhibit a high reflectivity for visible light and appear for
this in a white color shade. This white color is not influenced even if the finishing agent
ZnPh is applied in highest concentration, so an influence of the UV-absorber on the color
is not determined. Only the reflection spectra is changed in the range of UV light with
wavelength smaller 400nm.
To evaluate the UV protective properties the transmission spectra of the prepared
textile samples are recorded and presented in Figures 9 and 10. Figure 9 shows all spectra
of prepared cotton samples with increasing amount of applied ZnPh agent. By higher
amounts of applied ZnPh the transmission values for UV-light with wavelength smaller
350nm can be significantly decreased below 2.5%. For this, the application of ZnPh onto
cotton can lead to a significant UV protective functionalization.
A different result is found for the application of the ZnPh recipes on polyamide
textile (Figure 10). The transmission spectrum of the untreated polyamide and the
spectrum of the polyamide textile after application of the highest ZnPh concentration are
194 Ghulam Shabbir, Hajo Haase and Boris Mahltig

nearly the same. The untreated polyamide exhibits already a very low transmission for
UV light which is not further decreased by application of ZnPh.

100

90

diffusive reflection [%] 80

70

60

50

40

30
untreated cotton
20 cotton / 30 g/L ZnPh
10 untreated polyamide
polyamide / 30 g/L ZnPh
0
250 300 350 400 450 500 550 600
wavelength [nm]

Figure 8. Optical spectra of diffuse reflection of cotton fabrics treated with recipes containing ZnPh in
increasing concentrations.

25
UV-range visible range

20
diffusive transmission [%]

15
increasing
ZnPh amount

10

250 300 350 400 450 500 550 600


wavelength [nm]

Figure 9. Optical spectra of diffuse transmission of cotton fabrics treated with recipes containing ZnPh
in increasing concentrations.
Double Functional Finishing for Textile Fabrics 195

White polyamide fiber s are often spin -doped with titaniumdioxide TiO2 as white
pigment (Bajaj et al. 2000). Beside its function as white pigment, TiO2 is an excellent UV
absorber and its presence in the polyamide fiber would explain the low transparence for
UV-light. An application of an additional UV-light absorbing agent as ZnPh does not
lead to an additional decrease of UV-transmission.

25
UV-range visible range
untreated
20
diffusive transmission [%]

polyamide

15
polyamide with
highest application
of ZnPh / 30g/L
10

250 300 350 400 450 500 550 600


wavelength [nm]

Figure 10. Optical spectra of diffuse transmission of polyamide fabrics with and without treatment with
ZnPh containing recipe.

A further data evaluation of UV protective properties of prepared textile samples is


given with Figure 11. In this image the transmission values at the wavelength of UV-light
at 320 nm and 370nm are depicted as function of applied ZnPh agent. For application on
the polyamide textile it is observed that the transmission values are nearly not influenced
by the applied ZnPh, even if this component is applied in highest concentration. A
different result is gained for the application on cotton fabrics. In the cotton case, the
transmission for UV light decreases consequently, if the amount of applied ZnPh is
increased. For the lower wavelength of 320 nm, only an amount of 2g/L ZnPh in the
finishing recipe are adequate to reach transmission values of <5%. For the higher
wavelength of 370 nm, significantly higher amounts of ZnPh have to be applied to reach
a transmission of <5%.
If a transmission of <5% is requested to fix a sufficient UV protection, it has to be
concluded that amounts of 20g/L or higher of ZnPh have to be applied. Also it has to be
stated that in the range from 385nm to 400nm the transmission values for UV-light are
even after application of highest amounts of ZnPh still around 10% or higher. For this,
196 Ghulam Shabbir, Hajo Haase and Boris Mahltig

the UV protection against UV-A light is not complete. However, agents which are
decreasing the UV-transmission in the range near to 400nm are usually often influence
the color properties of the treated textiles.

16
cotton; 320nm
14 cotton; 370nm
value of diffusive transmission polyamide; 320nm
at a certain wavelength [%] 12 polyamide; 370nm

10

0
0 5 10 15 20 25 30
concentration of ZnPh
in finishing solution [g/L]

Figure 11. Transmission for UV-light for cotton and polyamide fabrics at the certain wavelengths 320
nm or 370 nm after treatment with recipe of increasing ZnPh concentration.

CONCLUSION

The bifunctional modification of textiles with antimicrobial and UV-protection in a


one step is possible by using a ZnPh recipe originally developed for antimicrobial
finishing of textiles. To reach adequate antimicrobial functions only the application of
low amounts of ZnPh are necessary. This agents is highly effective against the
investigated types of bacteria and only small amounts of active agent are enough to
introduced antibacterial effects. In contrast, to reach a satisfactory UV-protection higher
amounts of ZnPh have to be applied. To reach an UV-protection, the UV-light has to be
absorbed in adequate amounts and for this a certain amount of ZnPh agent has to be
present on the textile to reach a good UV-protection.
Altogether it can be stated that both functions – antimicrobial and UV-protection –
can be applied to textile by ZnPh agent in a one-step application process, because this
agent contain both functional properties inherently. However, one functionalization can
be only reached sufficiently, if the amount of ZnPh is high while the antimicrobial
function is gained even with lowest applied ZnPh amounts.
Double Functional Finishing for Textile Fabrics 197

In general, it is clear the UV-protection is a kind of optical functionalization and a


higher amount of applied functional active agent will improve the optical function. In
contrast the antimicrobial function can be understood as kind of biofunctionalisation
interacting with a biological system. If the antimicrobial component has a strong
interaction with the focused and investigated biological system – here the bacteria E.coli
and S.warneri – even lowest applied amounts of active agents can lead to good results.
The approach for realizing bifunctional textiles by using bifunctional finishing agents
is working. However, beside on the simple presence of the functional properties also the
necessary concentrations have to be taken into account. This statement is especially valid
if functional properties from different areas have to be combined.

ACKNOWLEDGMENTS

The authors would like to thank Thomas Heistermann for many helpful discussions
and experimental help. For funding of the electronmicroscopic equipment the authors
acknowledge very gratefully the program FH-Basis of the German federal country North-
Rhine-Westphalia NRW. Experimental work presented is part of the Master thesis
performed by Ghulam Shabbir (2017, Hochschule Niederrhein). All product and
company names mentioned in this chapter may be trademarks of their respective owners,
also without labeling.

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In: Textiles: Advances in Research and Applications ISBN: 978-1-53612-855-0
Editor: Boris Mahltig © 2018 Nova Science Publishers, Inc.

Chapter 10

3D-PRINTING ON TEXTILE FABRICS

Christoph Döpke, Yasmin Martens, Nils Grimmelsmann


and Andrea Ehrmann*
Bielefeld University of Applied Sciences,
Faculty of Engineering and Mathematics, Bielefeld, Germany

ABSTRACT

3D printing belongs to the emerging technologies which may significantly alter


production processes. This is why 3D printing often is referred to as part of the 4th
industrial revolution.
This technology, however, is not yet capable of creating large numbers of large
objects due to the time-consuming production process. While 3D printing is getting faster
and faster during the last years, it is still much slower than common technologies, such as
die casting for rigid forms or weaving for textile fabrics.
This is why combinations of 3D printing with such common technologies give rise to
fast produced objects with novel properties. Creation of 3D-print/textile composites,
however, necessitates a high adhesion at the borders between both materials.
The article describes the parameters influencing the polymer /textile adhesion, e.g.,
material combinations, textile structure, nozzle-textile distance, printing temperature,
printing speed, nozzle diameter, etc., and depicts the opportunities and limits of such
multi-material composites.

Keywords: 3D printing, textile fabric, adhesion, FDM process, polymer melt, printing
parameters

*
Corresponding Author Email: andrea.ehrmann@fh-bielefeld.de.
202 Christoph Döpke, Yasmin Martens, Nils Grimmelsmann et al.

INTRODUCTION

3D printing is an additive manufacturing technology, allowing for creation of three-


dimensional shapes. Different technologies are merged under this name, e.g., selective
laser sintering (sintering selected areas in a powder bed), stereo-lithography
(polymerizing selected areas in a fluid photo-polymer ), or fused deposition modeling
(FDM), which have different advantages and drawbacks and are thus more or less suited
for different applications (Chua et al. 2003). In spite of the recent technological problems
– e.g., the long printing times and the often nonsatisfying mechanical properties –, 3D
printing is often regarded as a new industrial revolution (Bermann 2012; Rifkin 2012).
Thinking about combinations of textile fabrics or yarns with 3D printing (Robinson
2014), the FDM method is most suitable. Additionally, FDM printers are usually less
expensive than machines working with other technologies and thus more interesting for
industrial applications.
In the FDM technology, a polymer filament is molten in an extruder nozzle (Figure 1,
left panel). The molten material is placed on the printing bed.
After finishing the first layer, the printing bed is lowered, and the next layer is printed
on the previous one (Figure 1, right panel) (Novakova-Marcincinova 2012). Typical
FDM printing materials include PLA (polylactic acid ), ABS (acrylonitrile butadiene
styrene, PA 6.6 (polyamide 6.6, “nylon”), PC (polycarbonate ), etc. (Noorani 2005).

Figure 1. Cross section of the printing head (left panel) and FDM printing principle (right panel).

Possibilities to combine FDM printed polymers with textile fabrics or yarns have
been examined in different projects recently to increase the adhesion between both
partners, partly taking into account specific textile structures or yarns (Melnikova et al.
3D-Printing on Textile Fabrics 203

2014; Richter et al. 2015; Sabantina et al. 2015). Special applications, such as contacting
SMD-LEDs on conductive paths in textile fabrics by 3D printing with electroconductive
polymers, were also investigated (Grimmelsmann et al. 2016). The chemical adhesion
between both materials was recently investigated using ABS, PLA and nylon on different
textile fabrics (Pei et al. 2015). Another group studied the influence of washing or plasma
treatment the textile fabrics before printing on the adhesion of imprinted 3D objects
(Korger et al. 2016). In our and another research group, on the other hand, physical
printing parameters were examined with respect to their effect on fabric-polymer
adhesion (Grimmelsmann et al. 2017; Sanatgar et al. 2017).
Here, we give a basis overview of typical problems in 3D printing on textile fabrics
and approaches to solve them, starting from the challenge to extrude soft printing
polymers – which often adhere very strongly on textiles – reliably and going on to typical
issues influencing the adhesion between 3D printed objects and textile fabrics or yarns.

METHODS

3D printing was performed using the FDM printer “Orcabot XXL” (produced by
Prodim, The Netherlands ), equipped with a 1 mm nozzle or an 0.4 mm nozzle,
depending on the desired precision. Layer heights were 0.5 mm or 0.2-0.25 mm,
respectively. The printer settings were chosen with respect to the printing material, i.e.,
nozzle temperatures of 200 °C for PLA and 240 °C for ABS. Besides these materials, the
elastic printing filament “Filaflex” was used. The printing bed was heated whenever
appropriate.
Different textile materials were used for printing, especially woven and knitted
fabrics from cotton (CO), polyester (PES ), polyamide (PA), and viscose (VI).

PRINTER MODIFICATIONS

One of the problems occuring when 3D printing on a textile fabric is planned, is the
adjustment of the fabric on the printing bed. In the printer used for this examination,
taking out the complete printing bed with heating plate and instead using clamps to fix
the textile was hard to realize; besides, the possibility to heat up the printing bed and thus
the fabric should be conserved. This is why other possibilities to fix a fabric on the
existing printing bed were examined.
A simple method is using strong adhesive tape and gluing the borders of the textile
fabric onto the printing bed. This works for several woven fabrics or nonwovens;
204 Christoph Döpke, Yasmin Martens, Nils Grimmelsmann et al.

however, it is useless for elastic – especially knitted – fabrics since they can be shifted
strongly by the printing nozzle.
In the next approach, double-sided adhesive tape was glued onto the whole printing
bed, and the textile fabric was placed without crincles on top of it and pressed down. In
most cases, printing on the fabrics worked well with this adjustment method. Afterwards,
however, it was hard to take the imprinted textile material out of the printer again without
pulling so strongly at it that the 3D printing was often destroyed or torn apart by the
undesired elongation of the knitted fabric. Additionally, the remains of the glue tended to
sticking at the back of the textile, inhibiting its use.
The next solution was inspired by the cloth rolls of weaving machines – instead of
gluing the complete textile fabric onto the printing bed, the middle part of the printing
bed was covered with sand paper, and only the borders of the fabrics were glued onto the
printing bed with single-sided or double-sided adhesive tape (Figure 2). In this way, even
quite elastic knitted fabrics could be fixed during printing.
Another problem occurred during 3D printing with soft, elastic materials, such as
Filaflex or Ninjaflex. The rubber -like filament surface shows a significantly increased
friction along metal and plastic filament guides, compared with other filament materials.
Additionally, transporting the filament to the hot-end with the heating nozzle is impeded
by the necessity to reduce the pressure of the transport gear onto the filament in order to
avoid damaging the soft filament. Finally, this results in an interrupted filament transport,
resulting in a loss of printing material in the nozzle and thus holes in the printed object or
even a complete stop of extrusion. Figure 3 shows a typical printing issue when one area
of the transport gear is clogged by abraded filament and another area still works as
desired – both samples on the left side show regular stripes, belonging to “functioning”
areas of the transport gear, alternating with areas with significantly reduced extrusion.
After cleaning the transport gear completely with a needle or the like, transport works
well again (right sample in Figure 3).

Figure 2. Printing bed with sand paper area in the middle as a preparation for 3D printing on knitted and
other elastic fabrics.
3D-Printing on Textile Fabrics 205

Figure 3. Samples printed with clogged transport gear (left side) and sample printed after carefully
cleaning the transport gear (right side).

Figure 4. New filament feeding construction for soft printing materials.

To reduce this problem, we decided to reduce friction in the filament supply. For this,
it was firstly tested to take out the filament supply channels which usually aim at
directing the filament from the coil to the extruder without bending it too strongly. This
led to the filament being pulled along sharp edges of the printer housing, not reducing the
friction.
Thus, in a second step, a new filament supply was constructed, consisting of two
parts (Figure 4). The dark part replaces the original Bowden filament guide (white guides
in the middle-grey part), the light -grey part is placed on the extruder instead of the other
end of the original Bowden guide. With two rotating ball bearing wheels leading the
flexible 3D printing filament in their middle channels, friction is significantly reduced in
206 Christoph Döpke, Yasmin Martens, Nils Grimmelsmann et al.

comparison with the Bowden guide. Both parts can simply and fast be exchanged with
the Bowden guide elements.
With these modifications, printing soft materials on textile fabrics is enabled.

3D PRINTING ON TEXTILE FABRICS

After these preparations, diverse objects can be printed onto textile fabrics. For this,
it is firstly necessary to create the desired object in a 3D CAD software, e.g., Autodesk
Inventor (Autodesk), Solid Edge (Siemens PLM Software), Sketchup (Trimble
Navigation Ltd.), etc. Afterwards, the CAD file is exported into an stl file which can be
interpreted by most 3D printer control softwares (often called “repetier host ”). This
repetier host is used for the complete communication between 3D printer and user. After
reading the stl file, it converts the 3D data into the G-Code, containing each single
command which is sent from the computer to the printer during the printing process, by
using the so-called slicer.
Slicing is the process used to cut a 3D model into a certain number of layers which
shall be printed subsequently. For this, different profiles can be chosen from a given list
or can be modified or created from scratch. These profiles contain, e.g., information
about the filament materials, defining the possible printing speed and the necessary
nozzle temperature; the layer heights with are correlated with the nozzle diameter; the
desired z-distance between nozzle and printing bed; etc.

Figure 5. Repetier host with several controlling buttons, depicting the rectangular object to be printed
and the manual control buttons in the right sub-window.
3D-Printing on Textile Fabrics 207

Figure 6. 3D-printed rectangle on a textile fabric (2 layers printed with a 1 mm nozzle), surrounded by
the so-called skirt (1 layer, printed at the beginning of the whole process).

The G-Code controls, e.g., heating the hot-end and the printing bed, moving the
printing bed, moving the printing head with the nozzle, extruding filament through the
nozzle, etc. This code is readable as plain text in each text editor and thus can be
modified in most printers, e.g., to include pauses if textile parts shall be integrated
between two successive layers.
After these preparations, printing can be started. Figure 6 shows a rectangle which is
typically used for adhesion tests according to DIN 53530, printed on a knitted fabric. A
so-called skirt surrounds the actual 3D printed object which normally serves as a pre-
printing job to allow modifying the distance between nozzle and printing bed manually, if
necessary, or detecting in time when the filament does not sufficiently fill the nozzle.
When printing on textile fabrics, opposite to printing on the usual glas bed, it must be
taken into account that usually the skirt cannot be pulled apart from the textile fabric
afterwards, since it should show the same adhesion as the actual 3D printed object. Thus
in most situations it is switched off if a 3D object is planned to be printed on a textile
fabric. Here, however, it served as a border for the adhesion test and did not create any
problems.
During printing on textile fabrics, several parameters influence the adhesion between
both materials which have been investigated by different research groups.
Firstly, combinations of 3D printed elements on relatively “open,” net-like structures
often show a good adhesion (Sabantina et al. 2015; Döpke et al. 2017). The reason for
this finding can be recognized in Figure 7. Apparently, the filament does not stay on top
of the textile fabric in this case, but is printed “through” the substrate, creating a form-
locking adhesion between 3D printed object and textile fabric. In this case, there is no
necessity to increase the adhesion by modifying the materials chemically; adhesion tests
often show that the net-like textile fabric breaks before both materials are separated
(Sabantina et al. 2015).
208 Christoph Döpke, Yasmin Martens, Nils Grimmelsmann et al.

Figure 7. 3D-printed rectangle on an “open” warp-knitted fabric, photographed from the back, showing
the polymer penetrating through the textile.

Figure 8. 3D printed object from soft PLA after manual pull-out test.

Problematic textile materials, on the other hand, include very dense and thin fabrics
as well as untwisted yarns or fabrics containing such yarns, especially carbon yarns
(Richter et al. 2015). Here, the very low fiber -fiber friction results in only the outer
fibers of a yarn being connected with the 3D printing material, while the inner fibers can
be drawn out even by hand (Figure 8).
In recent studies, it was found that deposition of PLA on PET bundles using a
pressure on the melt directly after printing resulted in a certain penetration of the 3D
printing material into the textile fabric and thus a certain bonding between both materials
(Brinks et al. 2013). Especially PLA was found to have a good adhesion when printed on
textile fabrics in applications for printed orthopedic braces on textiles, allowing for a
combination of the flexible and breathable textile with the rigid 3D printed supporting
structure (Pei et al. 2015). In a recent study, nylon and PLA, the latter partly filled with
conductive material, were printed on different PLA fabrics (Sanatgar et al. 2017). Here it
was found that several printing parameters influenced the adhesion between polymer and
textile fabric, e.g., extruder temperature and printing speed, while the printing bed
3D-Printing on Textile Fabrics 209

temperature only showed a significant effect on the adhesion if it was higher than the
glass transition temperature of the used fabric.
One of the most important parameters, however, is the distance between printing
nozzle and textile surface (Grimmelsmann et al. 2018; Döpke et al. 2016a; Döpke et al.
2016b). This parameter can be modified manually, as described above, or in the slicer
settings, allowing for a reproducible examination of its influence on the adhesion
between 3D printing polymer and textile fabric. Figure 9 depicts the effect of the so-
called z-distance on the measured adhesion force s.
The adhesion force s F are given in N/cm, as described in DIN 53530. The z-distance
was measured in the following way: The distances between printer nozzle and glass
printing bed were measured along five points on the printing bed. With the adjusting
screws of the printing bed, the distances were levelled out until all values coincided
within 0.01 mm. The whole procedure was carried out with the heated printing bed since
it was known that temperature changes would deform the glass plate on the heated
printing bed.
A z-distance of 0 mm is identical with the situation that the nozzle just touches the
printing bed without any pressure on it. Positive values indicate an open space between
nozzle and printing bed, while for negative values, the nozzle presses onto the glass plate
and thus compresses the springs on which the printing bed is mounted. For a usual 3D
printing process directly on the glass bed, the distance should typically be equal to half
the nozzle diameter, i.e., 0.2-0.25 mm for a usual 0.4 mm nozzle and 0.5 mm for the 1
mm nozzle used for the examination shown here.

40
PLA on fabric knitted from ...
35 PES / 0.58 mm
30 PA/nylon / 0.61 mm
PAN / 1.04 mm
25 Nozzle diameter = 1.0 mm
F / (N/cm)

20
15
10
5
0
-0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0
z-distance / mm
Figure 9. z-distance dependent adhesion force s for 3D printing with PLA on different textile fabrics.
From (Döpke et al. 2016b), modified.
210 Christoph Döpke, Yasmin Martens, Nils Grimmelsmann et al.

Here, the results are significantly different from the above described approach.
Printing on a textile fabric with 0.5 mm distance – or even 0.5 mm plus the respective
fabric’s thickness – leads to relatively low adhesion force s. Only for the thickest fabric
(PAN, polyacrylonitrile), measurable adhesion forces can be achieved with these
distances between nozzle and printing bed – here, a distance of 0.6 mm is equivalent to
the nozzle being located more than 0.4 mm “inside” the imprinted fabric.
For all textile fabrics under examination, the adhesion force s increase significantly
for negative z-distances. In this area of the graph, the nozzle does not only penetrate into
the fabric but even press against the strong springs under the heating bed. While this
effect is common to all knitted fabrics investigated here, the slopes of the curves differ
significantly. For the thickest fabric, only an increase by a factor 3 can be achieved by
pressing the printing polymer into the textile fabric with maximum force. For both other
knitted fabrics, the effect of decreasing the z-distance is much stronger pronounced, yet
there are also differences between these two slopes which can be attributed to the special
mechanical and other properties of the fabrics under examination (Döpke et al. 2016b).
The principle effect of the decreased z-distance can easily be explained. If the 3D
printing material is pressed into the textile fabric with higher force, it will tend to build a
form-locking connection, instead of simply laying on top of the fabric (Grimmelsmann et
al. 2018). This finding is consistent with the results of another investigation, indicating
that severe differences occur between different printing polymers (Grimmelsmann et al.
2018). In these experiments, PLA showed highest adhesion force s due to its low
viscosity during printing, allowing the polymer to be pressed deeply into the textile
fabric, while the rigid ABS always stayed on top of the textile fabric and impeded
formation of a form-locking connection.

40
35 PLA on fabric knitted
from PA/nylon
30 Nozzle diameter:
25 1.0 mm
F / (N/cm)

0.4 mm
20
15
10
5
0
-0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0
z-distance / mm

Figure 10. z-distance dependent adhesion force s for 3D printing with PLA using different nozzle
diameters. From (Döpke et al. 2016b), modified.
3D-Printing on Textile Fabrics 211

An additional effect is visible when comparing adhesion force s in systems printed


with different nozzle sizes (Figure 10). Here, on the one hand a shift in the curve is
visible which can simply be explained by the different first layer heights for the different
nozzle diameters, as described above. On the other hand, the curves additionally show
different slopes, indicating that there are more effects which have to be taken into
account when using different nozzle sizes.
While the aforementioned investigations were mostly related to physical properties of
the printing process, experiments also dealt with possible chemical modifications of the
textile fabric to increase the adhesion force s (Bergschneider et al. 2017; Korger et al.
2016). For these, PLA was printed on fabrics prepared from cotton, polyester, or glass.
Pre-processing was performed by washing the fabric, applying a hydrophilic finishing, or
using a plasma treatment in low pressure plasma with argon, nitrogen, or carbon dioxide
as process gas ses. It was found that a stronger hydrophilicity resulted in better
wettability by the imprinted PLA and thus stronger adhesion. This effect could be utilized
by either using more hydrophilic cotton rather than more hydrophobic polyester, or by
using hydrophilic finishing agents on polyester. Interestingly, plasma pretreatments on
cotton reduced the adhesion forces, while for polyester, plasma pretreatments with CO2
plasma increased the adhesion properties. It was assumed that by the CO2 plasma, the
polyester was hydrophilized (Bergschneider et al. 2017; Korger et al. 2016).

NEW POSSIBILITIES BY 3D PRINTING ON TEXTILE FABRICS

While the previous part concentrated on technological problems and possible


solutions, now an overview of the broad spectrum of possible applications will be given.
In a recent paper, several ideas were depicted how to combine textile fabrics and 3D
printed items, partly with integrated actors, such as rolling lids actuated by strings, the
band of a watch, or a crown for children (Rivera et al. 2017).
Creating textile-like structures has also been investigated. Relatively simple
structures, similar to chain-mail, were produced from ABS and other materials, with the
expected lack of stability and rigidity (Passlack et al. 2013). Structures similar to single-
face knitted fabrics were 3D printed by Selective Laser Sintering (SLS) as well as FDM
printing with different materials, partly using an additional support material (Beecroft et
al. 2016; Melnikova et al. 2014). These structures were also found to be either too fragile
for utilization in real clothes or – if a soft printing material is used – to stick together at
the binding points of the printed “stitches,” thus showing a completely different behavior
than real knitted fabrics. On the other hand, 2D shapes, e.g., inspired by Plauen Lace, can
be printed in an easier way and tend to showing better results (Melnikova et al. 2014).
The mechanical properties of 3D printed objects can significantly be modified by
embedded textile fabrics. Integration of a carbon fiber woven fabric in an ABS printed
212 Christoph Döpke, Yasmin Martens, Nils Grimmelsmann et al.

item, e.g., results in a severe increase of the maximum deformation in a 3-point bending
test, correlated with significantly decreased bending stress, and thus in the creation of a
new form of composite with novel mechanical properties (Julius et al. 2016).
On the other hand, 3D imprinted objects can be used as accessories on textiles.
Printing Braille patterns on textile fabrics could, e.g., supports blind and visually
impaired people during purchasing clothing and afterwards delivers care information.
Printing single dots on a textile, however, causes several problems, starting from the
necessary separation between them – which may be not given if the printer does not work
exactly – to possible problems with the roughness of the printed dots (Kreikebaum et al.
2016).
Principally, it is also possible to print buttons, snap fasteners or zip fasteners directly
on textile fabrics. For these applications, the adhesion between polymer and textile fabric
is of special importance due to the regular mechanical loads the objects are exposed to
(Martens et al. 2017). Figure 11 depicts parts of zip fasteners, printed for washing tests,
with their respective skirts, one of which can apparently be pulled away from the textile
fabric easily, indicating that the corresponding zip fastener will soon be torn away from
the textile during the washing tests.
Surface modifications can also be performed by 3D printing elastic materials, such as
Filaflex or Ninjaflex, on a textile surface, resulting in increased water resistance and
stiffness at selected positions (Martens et al. 2017). Printing with magnetic or electro-
conductive materials translates the respective physical properties to the textile fabric. In
this way it is possible, e.g., to combine mechanical and electrical contacting of small
LEDs on the conductive paths in textile fabrics (Grimmelsmann et al. 2016; Bosowski-
Schönberg et al. 2017), as depicted in Figure 12.
Finally, imprinted 3D shapes on textile fabrics can be used to modify the elastic or
bending properties of the textile substrates, with the 3D printed patterns either
automatically modifying the fabrics’ shape (Neuß et al. 2016) or increasing its stability
and thus allowing for creating new multi-material objects, as depicted in Figure 13.

Figure 11. Zip fasteners, 3D printed on a textile fabric.


3D-Printing on Textile Fabrics 213

Figure 12. 3D printed SMD-LED holders on a woven fabric with integrated wires.

Figure 13. 3D printed shapes modifying the bending properties of textile fabrics.

CONCLUSION

To conclude, the adhesion between textile fabrics and 3D imprinted polymers is still
not completely understood, often resulting in severe problems due to wear and tear,
washing and abrasion tests. Here, more investigations of physical and chemical
parameters are necessary which influence the adhesion in these systems.
When methods are developed to increase the adhesion between both materials in a
reliable way, 3D printing on textile substrates enables creation of new multi-material
objects with novel mechanical, haptical and other properties.
214 Christoph Döpke, Yasmin Martens, Nils Grimmelsmann et al.

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Brinks, G. J., Warmoeskerken, M. M. C., Akkerman, R., Zweers, W. (2013). The Added
Value of 3D Polymer Deposition on Textiles. Proc. of 13th AUTEX World Text.
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Chua, C. K., Leong, K. F., Lim, C. S. (2003). Rapid Prototyping: Principles and
Applications, 2nd Edition, World Scientific Publishing Co. Pte. Ltd., Singapore.
Döpke, C., Grimmelsmann, N., Ehrmann, A. (2016a). 3D-Druck auf Gestricken.
Melliand Textilberichte, 97, 195-196.
Döpke, C., Grimmelsmann, N., Ehrmann, A. (2016b). 3D printing on knitted fabrics.
Proceedings of 48th IFKT Congress, Mönchengladbach, June 8-11, 2016.
Döpke, C., Grimmelsmann, N., Ehrmann, A. (2017). A new dimension in finishing
textiles: 3D printing onto warp-knitted textiles – possibilities and technical
limitations. Kettenwirk-Praxis, English Edition, 01/2017, 25-27.
Grimmelsmann, N., Martens, Y., Schäl, P., Meissner, H., Ehrmann, A. (2016).
Mechanical and Electrical Contacting of Electronic Components on Textiles by 3D
Printing. Procedia Technology, 26, 66-71.
Grimmelsmann, N., Lutz, M., Korger, M., Meissner, H., Ehrmann, A. (2018). Adhesion
of 3D printed material on textile substrates. Rapid Prototyping Journal, accepted 14-
03-2017.
Julius, A., Lutz, M., Finsterbusch, K., Ehrmann, A. (2016). Integration of woven fabrics
in 3D printed elements to enhance the mechanical properties. Technical Textiles, 59,
E72-E73.
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Possible Applications of 3D Printing Technology on Textile Substrates. IOP Conf.
Series: Materials Science and Engineering, 141, 012011.
Kreikebaum, E., Lutz, M., Doerfel, M., Finsterbusch, K., Ehrmann, A. (2016). 3D
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3D-Printing on Textile Fabrics 215

Martens, Y., Ehrmann, A. (2017). Composites of 3D-printed polymers and textile fabrics.
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forms with textile structures – mechanical and geometrical properties of multi-
material systems. IOP Conference Series: Mat. Sci. Eng., 87, 012005.
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of FDM printing process parameters. Applied Surface Science, 403, 551-563.
In: Textiles: Advances in Research and Applications ISBN: 978-1-53612-855-0
Editor: Boris Mahltig © 2018 Nova Science Publishers, Inc.

Chapter 11

SIMULATION DRIVEN DESIGN


OF BRAIDED PRODUCTS

Yordan Kyosev *

Faculty of Textile and Clothing Technology,


Research Institute of Textile and Clothing,
Hochschule Niederrhein – University of Applied Sciences,
Mönchengladbach, Germany

ABSTRACT

This chapter presents the latest original developments of the author in the area of
engineering design of braided products. Braids are used as ropes, medical stents and as
reinforcement of overbraided parts in airplanes, cars and other constructions. In all these
fields, the properties of the products have to be chosen precisely. Until now, this is done
mainly based on the experience of the engineering personal in the companies and based
on large sets of trials. The engineering process of design of braids can be speeded up
using FEM Software as demonstrated in several works. Even though the usage of FEM
Software is beneficial, it requires well qualified personal and the availability of the
geometry of the braids.
This chapter presents two technologies – parametric models and emulative models -
which solve these problems successfully. The geometry of the standard braided structures
– like tubular and flat braids – can be created based on parametric models and used later
in FEM computations. Such models are known to use very short computational time and
to give good results for the cases, which they are created for. Several aspects about the
presentation of the form of the cross-section of the rovings and its deformation are
discussed.
The emulative models help in the case of more special structures, for which the
orientation of the yarns is not known before the calculations. In such a case, the motion of

*
Corresponding Author Email: yordan.kyosev@hs-niederrhein.de
218 Yordan Kyosev

the carriers is emulated and the resulting braid geometry is created based on the
information of this motion. This approach is universal, but its flexibility costs the user
computational time and accuracy.

Keywords: braided ropes, composites, medical braids, simulation, engineering design

INTRODUCTION

Braided products are used in almost all areas of the modern environment. These are
seldom detected and recognized as separated, engineered product. In several of the
mobile phone s the antennas are fine braided cables (Kyosev & Müller 2016). According
to the braiding machinery producer Herzog Gmbh, every car contains at least 1500 meter
of braided products. The braids are used to ensure electric, heating or cut resistance and
are used in the shielding of cables and hoses and as reinforcement of rubber sleeves for
brake hoses. In the light weight construction, the covering of light mandrels with
complex forms can often be done using overbraiding (van Ravenhorst & R. Akkerman
2016).
For each type of application, the braids must fulfil different requirements completely.
The optimal parameters can rarely be fo& by trials and errors or simple analytical
relations. This work gives an overview of a few simulation driven methods for
engineering and optimizing braided structures.

DESIGN OF TUBULAR AND FLAT BRAIDED PRODUCTS

Structure of Tubular and Flat Braided Structures

The majority of braided products have tubular or flat cross sections and are produced
on “standard” braiding machines. “Standard” means, that the number of carriers of an
fully occupied machine (for instance 16 or 64) and the machine stitch (for instance
80mm) (Kyosev 2014b) are enough information for the machine producer, to provide a
suitable machine for such a product. For these kinds of standard braids, the yarn
architecture is predictable by using parametric geometrical models and can be used for
initial design and optimisation of the braids.
There are several researchers, like (Rawal, Potluri & Steele 2005; Alpyildiz 2012;
Kyosev 2007), which tried to describe the architecture of braids using periodic functions,
mostly trigonometric functions, but these models can only be applied for one single type
of structure. Simple changes of the floating length or of the number of the yarns in a
group require the application of different models. A generalized model, which avoids
Simulation Driven Design of Braided Products 219

these disadvantages is developed, proposed (Kyosev 2015b) and implemented in the


professional software (Kyosev 2012) TexMind Braider. Using this model and software
the engineer can quickly check the yarn orientation for the different kinds of
interlacements. Figure 1 demonstrates generated braids with one yarn per group and
Figure 2 with two yarns in a group.

Figure 1. Simulated tubular braids with different floating length (a-1, b-2, c-3, d-4 and one yarn per
group), using TexMind Braider.

Figure 2. Simulated tubular braids with two yarns in a group a) with floating length of one, b) with
floating length of two, using TexMind Braider.
220 Yordan Kyosev

Colour Design

The created virtual braids allow playing with colour configurations without the need
of producing the real samples. The colour of each yarn can be assigned with two mouse
clicks (select colour, select yarn). This way, the braiders can create and evaluate a set of
different colour arrangements within only one minute. The virtual colour design is
especially useful for braids with more yarns and for customers with more specific
requirements regarding the optical appearance and when the braid has to suit the design
of the remaining clothing. Figure 3 demonstrates three colouring variations of the same
tubular braid.

Geometrical Properties

For various applications, the geometrical parameters of the braids as its outer and
inner diameter and the limits of its axial deformation (jamming angles), pore size, cover
factor and other aspects, are important.

Figure 3. Tubular braids with different colour arrangement, created using TexMind Braider.
Simulation Driven Design of Braided Products 221

The generated 3D geometries of the braids, using the implemented generalized


algorithms for the tubular and flat braids (Kyosev 2015b), provide the required data for
all these calculations. The maximal and the minimal braiding angle (jamming limits) for a
tubular structure for instance, can be calculated on the base on the following equation
(Popper Nov. 1992), (Yordan Kyosev 2016):

1 2∙𝑁∙(𝑤+𝑑) ∙sin 𝛼0
𝛼1 = 2 ∙ arcsin 𝜋∙𝐷0
(1)

𝜋
𝛼2 = 2 − 𝛼1 (2)

Figure 4. Calculated jamming angles, the corresponding braid diameters and the complete curve of the
pairs (diameter-braiding angle), which describes the same structure at different states of axial
deformation, using TexMind Braider.
222 Yordan Kyosev

The braiding angle and the diameters between these two angles can be calculated
based on simple geometrical relations (Yuksekkaya & Adanur 2009) and can be shown as
a complete curve (Figure 4).
This way, the experts get an impression of not only how the current braid looks like,
but also, what will be the braid geometry at some level of axial deformation. This
information is important, if for instance, the structure has to be deformed after the
production in order to be removed from the mandrel, if it has to be used during the
production or needs to be pulled over another mandrel, for example for a suitable
thermosetting. In such cases, the limitations of the diameters and the changes in the
braiding angle must be known before the production.
The calculation of the cover factor of the braids is another parameter, which is
important for the production of composites, for cable shielding and also in the medical
area. In this context, most of the researchers make use of the simple equation (3), based
on geometrical relation,

𝑤∙𝑁 2
𝐶
𝐶𝐹 = 1 − (1 − 2∙𝜋∙𝐷∙ cos 𝛼
) (3)

but do not mention the range of the validity of this equation as explained in (Yordan
Kyosev 2016):

𝑤∙𝑁 2 𝑤
𝐶
1 − (1 − 2∙𝜋∙𝐷∙ cos 𝛼
) ; 𝑖𝑓 q∙sin 2𝛼 ≤ 1
𝐶𝐹 = { 𝑤
(4)
1; 𝑖𝑓 >1
q∙sin 2𝛼

Here, CF is the cover factor, NC is the number of the carriers, D is the mandrel
diameter, α the braiding angle, w is the width of the yarn or the roving, and q is the
distance between two crossing points of the yarns, which is at the same time the unit cell
length. The application of the equation (3) without proper understanding, often leads to
wrong results, as the equation is not valid, if the surface between the yarns is already
covered by yarns.
The calculations using equation (3) for a braiding machine with 48 carriers, for
overbraiding a mandrel with diameter 60 mm, for braiding angles between 35° and 65°
and yarn widths between 0.1 and 10 mm are shown in Figure 5. The right branch of the
parable curve of the equation (3) has no physical meaning. It lies in the area of closed
braids with the cover factor 1. Implementing the correct equation (4) in any software
makes sure, that during the design stage the proper value will be used.
The situation becomes more complex for triaxial braids, because the conditions for
the validity of the equation are larger (5) and therefore the implementation in any kind of
calculation software makes sense (Kyosev 2016):
Simulation Driven Design of Braided Products 223

Figure 5. Cover factor, calculated according the equation (3) for different braiding angles and different
yarn widths. As the figure demonstrates, the equation (3) represents typical parable curve where the
right branch does not have physical meaning.

𝑁𝑐 ∙𝑤 𝑁𝑐 ∙ 𝑤𝑖𝑛𝑙𝑎𝑦
𝑖𝑓 + <2
2∙𝜋∙𝐷∙cos 𝛼 2∙𝜋∙𝐷
𝑁𝑐 ∙𝑤 𝑁𝑐 ∙ 𝑤𝑖𝑛𝑙𝑎𝑦 2
𝐶𝐹 = 1 − (1 − − ) (5)
2∙𝜋∙𝐷∙cos 𝛼 2∙𝜋∙𝐷

𝑖𝑛 𝑜𝑡ℎ𝑒𝑟 𝑐𝑎𝑠𝑒
𝐶𝐹 = 1

Mechanical Properties

The prediction of the mechanical properties of the braids is a more complex task.
Next to the strength, also the breaking elongation is often required and for some
applications even the complete force -elongation curve must be known. The prediction of
all these parameters requires information about the orientation of the yarns, their
interaction and their properties. The previously mentioned generalized geometrical model
is able to predict idealized yarn geometry only. This model does not consider the
interaction between the yarns, as its goal is to allow quick calculations for fast evaluation
of the properties during the trials and errors in the early design phase.
224 Yordan Kyosev

Figure 6. Computed Key points of the force elongation curve of a tubular braid.

Still this initial geometry and the calculated jamming angles (Eq. (1) and (2)) allow
the determination of some key points of the force -elongation curve of the braids
(Figure 6).
The tensile tests are starting with a predefined tension, but the braided structure,
especially if the braids are open (as it can be the case in medical applications), can easily
change the braiding angle and its configuration during axial load. The part between point
0 and point A on the curve of Fig. 6 represents this region and the configuration of the
yarns at the point A can be predicted, as it is the one of the jamming states of the braids
(Eq. (1) or (2)). The reacting tensile force in the braid can only be predicted accurately, if
the friction between the yarns, their bending rigidity and their lateral compression, are
considered. Theoretically, this can be done well by using FEM modelling, but practically,
getting correct and useful results for this region is extremely difficult. The reason for this
is, that there are no unified and accurate methods for the measurement of the bending
stiffness, lateral compression and friction of fibrous assemblies and, if in some cases
these measurements can be done, the configuration of the yarn in the contact places often
differs from the configuration during the test. The modelling of the behaviour in the
region between the points A and B relates to the same difficulties, because in this region
the movement of the yarn axes is minimal and is only caused by changes of the yarn
cross section. The last region (B-C) is characterised with predominant tensile loading of
the yarn material, so the elasticity modulus in this region can be predicted based on the
current braiding angle of the braid and the yarn properties. The prediction of the exact
breaking force (Point C) is, again, a more complex issue, because it depends on the
variance of the tensile forces of the single yarns of the braid, their load history during the
production and finishing processes and the interaction between all the yarns during the
load.
Simulation Driven Design of Braided Products 225

Figure 7. Simulated tensile test of braided rope using finite element method (Kyosev 2015a).

This interaction can be predicted by using modern computational methods as the


Finite Element Method or the Digital Chain Method. Figure 7 demonstrates a simulation
of the tensile behaviour. The initial braid geometry is generated by applying the
generalized geometrical model, (Kyosev 2015b) implemented in TexMind Braider, and
then exported to Impact-FEM code (Impact 2015) as a set of beam elements and finally it
is simulated. The explicit FEM allows the deactivation of elements when a certain stress
or strain value has been reached. This way, even after one yarn breaks, the simulation
continues with less number of yarns and one broken yarn, which represents the reality
very well.
At the first sight, the simulation using the digital chain method seem to provide the
same features and advantages, as the finite element method, but it works significantly
faster. Figure 8 presents several steps of tension load of a braided structure. The speed
has its price – when using the finite element method, complex material models are
possible. This feature is not possible yet for the digital chain method.
In the future, the combination of both methods will allow realistic simulations of the
tensile behaviour of the braids. The simulation flow in this case could look like this:
226 Yordan Kyosev

Figure 8. Simulated tubular braids with application of the digital chain method, using geometry
generation with TexMind Braider (Kyosev 2012) and tensile simulation using VMTS (Zhou,
Mollenhauer & Larve 2009).

 Initial geometry using geometrical methods (as Texmind Braider)


 Relaxation of the open structure to receive close to the reality geometry using
Digital Chain Method (as VMTS)
 Load simulation of the relaxed structure using finite element method (using one
of the various available explicit FEM solvers).
Simulation Driven Design of Braided Products 227

DESIGN OF BRAIDS WITH COMPLEX CROSS SECTION

In the field of tubular and flat braids, the geometry of the yarns can be described
parametrically. This is not possible for more complex structures, because solid profiles
with several layers in different orientation must be produced or some mandrel has to be
overbraided. For these two cases the emulation of the braiding process can help in the
speeding up of the design of these products.

3D Solid Braids

The main tasks in production of solid braids with complex cross sections, is the
definition of the braiding machine – the number, position and orientation of all horn
gears. In order to emulate such a machine, its main elements have been implemented in
software (Kyosev 2014a).
Figure 9 presents these main elements. The carriers, their track and the horn gears
with its slots have to be defined as objects in some programming language. For the
Texmind Braiding Machine Configurator, it is implemented in pure C++. Each slot has
one starting point, defined in polar coordinates, radius and angular velocity. For the
simulation of the machine, first all horn gears are placed and oriented so that their slots
can build transfer pairs. The motion of the machine is simulated using explicit time
integration – all horn gears rotate at an angle Δφ and the carriers change their
coordinates. The most complex part of the simulation is the implementation of the carrier
transfer from horn gear to horn gear. The simplest algorithm checks if the carrier reaches
a transfer region and after that, it is “deleted” from the current horn gear and “inserted”
into the receiving horn gear. If the corresponding slot of the receiving horn gear is full
with another carrier, the program stops and gives a message. This way, different
arrangements of carriers on any braiding machine can be checked, before a machine is
completely designed and produced, which in the end saves time and costs. Figure 10
presents an example of a T-cross section braid. The left configuration leads to collision
and is not suitable, but the right one will work (Kyosev & Küster 2016).

Figure 9. a) Horn gear, slot, track and carrier, b) main properties of the object "horn gear".
228 Yordan Kyosev

Figure 10. Configuration for T-profile, based on an extension of a flat braid. Left – trial to arrange the
carriers 1Full – 1 Empty, which leads to collision and is not possible. Right – arrangement of carriers 1
Full – 3 Empty, which can be used.

Figure 11. Simulated idealized braid 3D geometry with the T-configuration and 1Full – 3 Empty carrier
arrangement (Figure 4) in top and side view.

The emulation of the carrier motion also allows the calculation of idealized geometry
of the braids. The resulting 3D image gives a first impression about the new product and
allows evaluation of its properties. Figure 11 presents such a simulated braid, created on
the basis of the machine configuration from figure 10. Figure 12 and 13 present the
machine configuration and 3D geometry of the braids of I-profile, created in the same
way.
Simulation Driven Design of Braided Products 229

Figure 12. Configuration for double-T-profile, based on an extension of a T-braid. Left – trial to arrange
the carriers 1Full – 1 Empty, which leads again to collision. Right - configuration with 1 Full – 3
empty.

Figure 13. Simulation of braided double-T-profile in top and side view.

Overbraided Products

The overbraided products are normally produced using circular or radial braiding
machines. In this case, the motion of the carriers can be described in a simplified way by
using trigonometric or another period function. The main objective in this case is the
simulation of the interaction between the yarns and the mandrel. Here, two approaches
are used. In this context, most of the researchers are explicitly using the FEM software
(Pickett, Sirtautas & Erber 2009), which allows the freedom of the element type
selection, material properties and all other options, which can be provided by large
230 Yordan Kyosev

commercial FEM. This approach gives very good results, but requires corresponding
licenses, highly qualified personal and a lot of time for the preparation of the simulation.
Akkerman and van Ravenhorst implemented kinematic based simulation in a standalone
product (Akkerman & Villa 2006; van Ravenhorst & R. Akkerman 2016), which
produces the simulation in an easier way and in a shorter time, but it only uses the yarn
axis for calculations. Depending on the resources and the required accuracy, it has to be
decided, which of the methods are more suitable for the different applications.

CONCLUSION

This chapter reports about several new simulations based tools for the design of
braided products, created during the last years. These offer a more efficient and more
accurate way for the development of braided products, than the analytical methods, used
until now. From another point of view, the flexibility of the fibres and yarns do not allow
the prediction of their exact geometry directly, so multistep methods must be used in
order to get more realistic results. The combination of geometrical models, the digital
chain method and the finite element method have the potential to provide reliable
prediction of the new products based on pure simulation only.
The emulation of the braiding machine, implemented as a software, allows efficient
evaluation of complex configurations of braiding machines, which was not possible until
now.

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In: Textiles: Advances in Research and Applications ISBN: 978-1-53612-855-0
Editor: Boris Mahltig © 2018 Nova Science Publishers, Inc.

Chapter 12

STAB RESISTANCE OF TEXTILES

Priscilla Reiners *

Niederrhein University of Applied Sciences,


Mönchengladbach, Germany

ABSTRACT

In this chapter a summary in the area of stab resistance is presented. The protection
against sharp edges, such as knifes, increases in significance, since stab attacks against
police or military personnel are also increasing. Against stab attacks, just limited
solutions are available. The stab mechanism is a complex and variable process. An attack
can only be inhibited, but an injury cannot be completely prevented. The goal is always
to absorb as much energy as possible, so that the penetration is thus reduced and the risk
of injury decreases. The review showed the demand on research in this area, because the
most solutions involve hard body armour parts in combination with fibrous materials.
This chapter presents the interdependencies between the physical properties of the
material but also the mechanism during a stab attack is recognized, to developed higher
protection levels. It is demonstrated, that the multitude of factors causes the problem to
define a level of protection. Several investigations are done to analyse the test
parameters, which are defined in the test standard but also this one, which are missing. To
predict the stabbing behaviour of textiles the resistance mechanism of woven fabric
against the falling knife and its influence factors are explained.

BODY ARMOUR- THE PERSONAL PROTECTIVE EQUIPMENT PPE

PPE has to cover or replace the every day’s clothing to give a certain level of
protection against different threats. These textiles for protection determine an important

*
Corresponding Author Email: priscilla.reiners@hs-niederrhein.de
234 Priscilla Reiners

field of research and are also one of the most growing fields for industry and leisure time
(Byrne 2000). PPE should protect to a required level and maintain the health, without
affecting the natural movements or the circulation of the body. That means, that a good
comfort is guaranteed, which encloses, that the PPE is light and flexible and the heat and
moisture transport from the body to the environment is given. It is essential, that the PPE
is not noticed by the wearer. At the same time it should reduce the risk of injuries.
According to the PPE guideline, the PPE has to protect against all defined risks and
should be suitable for the given conditions and meet the ergonomic requirements
(Directive 1989). Therefore the best compromise between efficiency, comfort and costs
have to be found.
The cut and puncture resistances are part of these mechanical threats, which mostly
occur during attacks on humans. This work focusses on the different danger areas where
the puncture and cut protection is applied. In the following, the importance of body
armour against puncture and slash threats are presented.

COMMON APPLICATION AREAS OF BODY ARMOUR FOR STAB


AND SLASH RESISTANCE

Normally it is expected that textiles give no high resistance against cut during
production (Reumann 2000). But for some application areas a high cut resistance of
textiles is an important factor to protect against unintended or wanton destruction by
sharp-edged objects. These textiles have to resist against forces, which occur during the
cut processes, to a certain level (Finkelmeyer 2002). Not only cut resistant textiles, but
also stab resistant textiles are required for some fields of application (Alpyildiz et al.
2011). The main goal in this application area is to absorb the maximum impact energy to
protect human beings against injuries. Personal protection includes all kinds of protective
clothing in the areas of PPE and the sports area. In general, stab-resistant clothing is
manufactured, to protect humans against accidental stab wounds and cuts (BGR196).
This applies to the whole body, as well as high-risk areas such as hands and arms
(BGR200), which means that the wearer is protected during his working sufficiently
against cut and stab injuries. In general, personal protective equipment is required for
professional groups, who work every day with sharp objects like sharp knives, saws,
scissors or other sharp objects. Forest workers are in the exercise of their activities
permanently in contact with heavy, sharp saws. Workers in the field of cutting in the
textile and clothing industry also use sharp knives, to cut multi-layer fabrics. Especially
in the food industry accidents with hand knives are not uncommon. About 30-40% of all
accidents occur with hand knives (BGI 2004).
Stab Resistance of Textiles 235

Applications in the sports arena for puncture and cut resistant garments are among
others for motorcyclists, ski clothing, diving equipment and the fencing clothing
(Finkelmeyer 2002).
However stab resistant textiles are not only used to prevent accidental stab injuries,
but also to protect against unintentional injuries by other people. Another risk group are
the employees of the Security Forces, such as police, Special Forces and security
services. They also have to be protected against stab and cut injuries adequately, because
they are constantly exposed to hazards in their profession, such as attacks with knives or
other sharp objects. Protection must be given to these life-threatening hazards. Due to the
diverse dangers, protection equipment needs to be adjusted respectively to the threat.
Primarily stab protective vests that protect the torso against serious or fatal dangers
are used. Since users mainly come from the police sector the police takes influence on the
testing methods or the development of new vests (Scott 2005; Fenne 2005, 2005). There
are two different kinds of body armour vests available- one type is worn under the
garments and cannot be seen and the other kind of vest is worn visibly on top of the
clothing. The armour also differs in the extent of their protection capability. Some models
give primarily a ballistic protection against projectiles, where the stab protection panel
can optionally be introduced through appropriate stab protection inserts. Another type is a
protective vest that combines ballistic and stab protection and the components cannot be
separated. In addition to the vest there do exist more body protection equipment, which is
used to protect the neck, trunk and extremities. This equipment may consist of several
components, which are intended to enable a modular construction and can be worn in
various combinations or alone (Damm 1997).
The need is also shown in the increase in violence. Insults of the worst kind, threats
and even physical assaults are happening in Job Centres, in customs, in classrooms, social
service offices and in many other jobs. And not just from time to time, but often (Peters
2015).
Wearing body armour is necessary if an increased probability of threat is given. This
protection means reducing the risk of injury to limit the potential harm. Due to the
different.

IMPORTANCE OF BODY ARMOUR

PPE with stab and cut protection are required by professional groups, in which the
use or contact with sharp knives, saws, scissors or other sharp objects are an everyday
occurrence. These areas include among others the forestry sector, the food production
sector, such as butcher, or the clothing sector. According to the professional association
of industry, about 45% of injuries with hand tools happen with knives (BGI 2004). Only
in the food sector 30 - 40% of all accidents happen with knives. Not only accidents but
236 Priscilla Reiners

also intentional injuries with sharp weapons lead to an increased demand for stab
resistant body armour (Aromaa und Viljanen 2010).
Another risk group are the employees of the Security Forces, such as the police or
security services (Jager 2013; Ohlemacher 2003). They also need to be protected
adequately against stitches and cuts. An important group of these were police officers
who are in their profession constantly exposed to the danger of attacks by knives and
other sharp instruments, which are used as weapons (Scott 2005). The annual report 2014
of the German Federal Police reported 2089 attacks on law enforcement officers. This
means, that 6.8% of all police officers were attacked during their work and 1.8% were
injured (Vegesack 2014). A study out of the year 2012 showed that just 53.5% of police
officers wore their safety vest during an attack and only 36.7% were protected against
stab attacks (Ellrich et al. 2012).
Another study in 2009 showed, that 84% of all attacks against police officers were
body attacks with the use of violence and 20% of them with weapons (Hunsicker 2015).
The protection of the police officer is given only conditionally, since most injuries in the
neck and back area occur. Therefore a PPE which protects these areas without limiting
the freedom of movement would be desirable (Hunsicker 2015).
The development of appropriate protective equipment should therefore be adapted to
a large extent to the needs of police officers (Fenne 2005).

TECHNOLOGY OF THE STAB EVENT

The stab and cut resistance include very different and varying applications, like
presented in the previous chapter. This means that the mechanical stress, caused by sharp
or pointed objects in the respective areas vary widely (Horsfall und Arnold 2010). The
threat of a stab attack can be classified in two steps of mechanism. The pure stabbing or
punching means a penetration by a pointed item, but without cutting, like an ice peak,
awl, nail or needle, where the stab instrument penetrates the fabric, using the tip and
displaces the fibres to the sides and slips through the fabric. The slash or cut mechanism
describes the penetration of the fabric, before it slices through the fibres and cuts the
fabric (Egres Jr et al. 2004). A threat by a knife includes both mechanisms, like shown in
Figure 1.1. The tip of the knife penetrates the fabric and displaces the fibres and slips
through the yarns, while the sharp edge slices through the fabric and cuts the yarns. It is
important to understand the principle of both mechanisms in order to understand the
variety of materials, which are used in dependency to their properties for designing
suitable protection garments. In the following chapter, the mechanism of stab and slash
penetrations are further characterized. In addition, the influencing factors beside the
penetration instrument are given and the interactions between them are analysed. The
resultant threats for human bodies complete this analysis.
Stab Resistance of Textiles 237

Basics of the Penetration Mechanisms

There is no general or unique process to describe the mechanism of a stab attack,


while there are a huge variety of stab instruments and stab processes, which can be
cutting, punching or the displacements of fibres. The degree of blade sharpness causes
different damages onto the fibres (Aming und Chitaree 2010). In general, a stab
instrument gives energy to the surrounding material during the penetration until it comes
to a standstill. With regard to the development of stab resistant equipment it makes sense
to analyse the individual procedures since each of them absorbs energy and prevents a
further penetration of the textile layers to the human body. The goal is to reduce the total
puncture energy in a short period of time in order to stop the acting subject as early as
possible.
During the impact of a knife, the directly affected fibres are displaced or destroyed.
The energy on impact is derived in longitudinal and transverse directions, and is spread
over the threads. Thereby the energy is weakened. The high strength of fibres in a fabric
or a shield ensures that the energy is exhausted. Another part of the energy is transformed
in deformation energy, which leads to the deformation of the overall structure; it results
in a trauma and a stab wound. This energy absorption prevents a deep pointed injury. The
cutting process is depending on the nature of the cut, the cutting tool and the movement
characteristics. Due to the high contact forces, the blade will initially penetrate the fabric.
The frictional forces can prevent a further opening through the penetration process so that
each system, which increases the frictional forces acting on a blade, is adapted to reduce
the penetration. Also surface damage to the knife, its blade and the tip minimize
penetration into the other layers significantly. In order to dissipate the energy caused by
the knife blade, a particularly hard material is required (Horsfall 2012).
Summarizing, the cutting process itself can be divided up into three processes after
Feiler (Feiler 1970):

1. The work or energy to overcome the molecular bonding forces. It depends on the
material´s specification.
2. The deformation work, which is the sum out of the elastic and plastic
deformation, depending on the physical properties of the material and the
displaced volume.
3. The frictional force, which depends on the material´s properties, the surface
structure of the cutting instrument and forces acting on the surface.

This theoretical approach is often different from the practice, because as shown on
the one hand, in real life, a variety of instruments is used and secondly, a classification of
the injury `s energy is difficult, as it will be shown in the following chapter. Also the
distinction between the two mechanisms of stab and cut injuries is difficult, because some
238 Priscilla Reiners

instruments include both mechanisms, like shown. Therefore the mechanisms are
summarized in the following chapters as one threat. Also a lot of influencing factors have
to be taken into account.

Influencing Factors

The cutting process is influenced by different parameters, which interact with each
other. They can be split up in two areas, the technological factor, which includes the
stabbing weapon itself with its geometry and the kinematic energy of action and the
material factor of the cut material itself (Feiler 1970; Finkelmeyer 2002).

Technological Factor
From the technological point of view, the threat level is influenced by the kinetic
energy of the knife-arm-system, which depends on the instrument´s factors like size and
shape of the weapon and its blade, the diameter and the angle of attack (Finkelmeyer
2002; Yahya et al. 2014). Also the steel hardness, blade hardness and the knife grip
influence the threat level (Scott 2005). Both cut energy and failure initiation strain
decrease with a decreasing slice angle. The cut energy drops greatly when the blade angle
decreases from 90° it falls from 50 to 75% at a blade angle of 82.5° and decreasing
further, but more gradually, at lower angles. At a 45° blade angle, cut energies fall
between 3 to 10% (Shin et al. 2003). The different kind of cutting methods can also vary.
As a basis for testing procedures Heudorfer gave an overview about the different
methods. These differ by the cutting tool and the characteristics of movements. The
movement characteristics depend especially on the cutting angle, which is different for
the types of cutting methods (Reumann 2000).
A falling cut and a cut through with a put on blade are similar to a stab attack. A
typical tool for this mechanism is the cutter knife. The continue cut relates to a method,
where an already damaged fabric is further cut with a sharp knife. The movement
characteristics depend especially on the cutting angle, which is different for each type of
cutting method. As a result, the test speed and thus the impact energy varies. To analyse
the kinetic influencing factors, also the physical strength and emotional state of the
assailant have to be considered (Govarthanam et al. 2010). The gender, fitness level,
body size and experience of the assailant are also important factors (Scott 2005). The
values, which are assumed for a stab impact, vary greatly between the countries, because
of the different principle of experience which is used. In the United States and Germany
maximum impact energy of 100 Joule is assumed, while in Great Britain values of 42
Joule are supposed. Experiments in Switzerland brought mean values of 35 Joule (Damm
1997). Horsfall found out, that an overarm attack can reach up to 115 Joule and 64 Joule
was reached by an underarm attack (Horsfall et al. 1999). In another research study,
Stab Resistance of Textiles 239

energy levels of 103 Joule were reached by volunteers (Chadwick et al. 1999). One study
compared over- and underarm attacks with a long- and a short stabbing action. Long way
attacks show higher speed values with up to 3.8 m/s for long overarm, 3.1 m/s for long
underarm attacks, 2.8 m/s for short overarm attacks and 2.4 m/s for short underarm
attacks. Longer ways cause higher speeds and result in higher impacts (Miller und Jones
1996).

Material Structure Factor


To produce soft body armour, it is necessary to manufacture textile structures out of
the previous mentioned materials. Due to their construction, textile structures have the
advantage to be flexible and can be woven, non-woven, knitted or laminated structures
made of yarns or fibres and due to their construction they have different properties. The
main goal of the fabric is to absorb energy in case of an impact and make sure that no
perforation occurs. Therefore an inelastic structure is most favourable, because the fibre
itself absorbs the energy and is not influenced by the construction, which gives way from
the amount of yarn reserve and varies on the type of construction.
Stab or cut resistant fabrics should resist against impact as long as possible. The
material, which is penetrated, influences the impact by its chemical and microscopic
structure and therefore by its mechanical properties. Also the sample size, the thickness
and the density are important influencing factors. A higher number of fabric layers absorb
more energy and especially spacer fabrics absorb more energy than plied fabric layers
(Cunniff 1992).

Influence on Human by the Threat


To classify the threat level, the energy of the threat has to be known, whereby the
energy level, which can be reached, varies greatly. Sharp weapons cause wounds, which
can be characterized by their depth and width in the skin. Most of the time the injury is a
combination of stab and cut, because usually both the attacker and the victim are in
motion (DiMaio und Dana 2006). A study in 1986 in Great Britain with 539 adult victims
showed, that 20% of them were attacked by sharp weapons, from which 11% were
broken drinking glasses and 6% were sharp knives. In total 54% of them were injured
through laceration (Shepherd et al. 1990). A simulation of stab penetrations is difficult to
do. Ankersen made stab tests on synthetic chamois and pigskin, which is similar to the
human skin (Ankersen et al. 1999). The most dangerous influences on the injury level are
the depth of the stab injuries and the body areas, which are penetrated. The depth of the
of stab injuries determines the extent of the injury additionally to the shape of the
stabbing instrument and the fabric structure. The depth depends on the victim’s body
mass, his reaction and the position of the assailant, which means the angle of attack. The
stabbing potential is also influenced by the assailant. Here the influencing factors are the
gender, his fitness level and body mass, the physical size, mental state and the training
240 Priscilla Reiners

experience (Scott 2005). Connor made computer tomographic measurements, carried out
on 71 subjects to evaluate the distances of organs to the skin. The results show that with
stab wounds at a depth of up to 9 mm no organs are injured because the smallest distance
of an organ to the skin with 9 mm was measured to the liver. The spleen lies in a distance
of 12 mm to the skin and the kidneys 19 mm. The pleura have a distance to skin of 10
mm and the pericardium 12 mm. There is no difference between male and female
subjects (Connor et al. 1998). Bleetman comes to the same conclusion, (Bleetman und
Dyer 2000) after which the Home Office Police Department has taken those parameters
into account and has set a maximum allowable penetration depth of 7 mm in their
standards (Croft und Longhurst 2007b).

Conclusion

The stab mechanism is a complex and variable process. To design improved body
armour, the physical properties of the material but also the mechanism during a stab
attack has to be recognized. Only if the interdependencies are taken into account, better
panels can be developed for a higher protection level.
From the multitude of factors it is difficult to define a level of protection. This is also
reflected in the large number of standards, which will be discussed later. Also high
kinetic energies are not always critical. A needle bends for example during a fast
penetration while it perforates the fabric at a slow penetration level.
An attack can only be inhibited, but an injury cannot be completely prevented. The
goal is always to absorb as much energy as possible, so that the penetration of the
weapon is thus reduced and the risk of injury decreases. Due to the high variation in
blades, mechanism, sharpness and geometry of the blade and many other factors, like
presented before, it is difficult to characterize the threat level of impact and define a test
method which covers the variety of stab mechanisms and other relevant factors. That is
one reason, why any comprehensive solution is currently not available.

BODY ARMOUR TECHNOLOGY

Composition and Construction of Body Armour

Every stab resistant vest consists of three main parts, which are in most cases,
manufactured from completely different materials, chosen due to their specific properties,
ensuring, that the final product offers the best possible safety to its wearer. The simplest
construction of a vest is a panel out of two layers which build the carrier. In these layers
Stab Resistance of Textiles 241

the stab resistant package panel then can be inserted. The carrier is the only part of an
impact resistant vest that actually allows any design alterations, which makes it most
valuable for organizations like Police Forces or Armies, since it provides space for
additional equipment and any other specifics that reflects the profession of its wearer.
There are two basic options available for the carrier: a carrier with removable stab
resistant packets and / or a carrier in which the panel is permanently inserted. Minds
argue about the pros and cons of both options, but in the context of female body armour it
should be mentioned, that removable plates allow the wearer and bearer of such a vest a
major reduction of weight when several plates are not necessarily needed. Further design
options are also closely related to the functionality of the vest and the field of
employment of the wearer (Moureaux et al. 1999). The carrier and its mode of
functioning are mostly independent of the style of the stab resistant panel and
manufactured for hard or soft body armour.
The stab resistant package panel part is the most important one of any type of body
armour, because it is designed and destined to stop the impact and save its owner. It has
to fulfil many requirements and testing standards such as a superior tensile strength (for
soft body armour only), specific weight requirements, and the ability to distribute the
energy that needs to be absorbed to the highest possible amount of available space and,
lastly, a very low value in terms of elongation during breaking load. They have to fulfil
their protection level also after ten years of use (Gäbler et al. 2011). These standards and
requirements apply to soft as well as hard body armour panels. But apart from these
common goals, the two types of ballistic panels differ greatly from each other. The first
type of body armour to be regarded in this thesis is the hard body armour.

Hard Body Armour


The hard ballistic panel is, opposed to the soft ballistic panel, made out of some sort
of rigid material, including ceramic tiles, metal plates and silicone carbide or boron
carbide plates (Hani et al. 2012). From a historical point of view, this working principle
made up the very first types of body armour. In history, steel was the only preferably
used material that could perform well under the given stress of a mechanical impact.
However, nowadays, a producer of body armour garments can also choose from oxide
ceramics, polyethylene and boron carbide or silicone carbide ceramic, mostly fusing
several materials with specific properties together into one hard ballistic package, which
has a very specific wavy form (Horsfall 2000). Plate armour is the simplest manufactured
body armour and gives a high level of protection. It consists of rigid plates in different
sizes. The disadvantage lies in the missing flexibility and thus a bad comfort. Also
because of the kind of manufacturing, the openings at the neck and armholes have to be
large enough to give a certain level of freedom to the movement. In 1987 Fritch
registered a patent out of multiple panels with front and back body armour inserts to be
worn under regular clothing. Each panel consists of a ply of titanium metal bonded to a
242 Priscilla Reiners

ply of aramid fibre woven cloth. The panels are arranged overlapping (Fritch 1987).
Another innovation is scaled armour out of small rigid plates, which are much more
flexible (Beck 2006; Sacks und Jones 1996). But in case of an angled attack it gives a
very poor protection, because the knife can slip between the plates. To give a better
comfort, some researchers combined the plates with cut resistant yarns, which are
wrapped around the plates. This gives a better breathability to the wearer (Harpell et al.
1993). Another used material is granular ceramic armour, which consists of an array of
small ceramic elements which is bonded together on a rigid backing (McLean und
Frutiger, S. Dabek, R. Reeves, J. 2010). This is mostly done to create a higher degree of
adaption to the body for the vest as well as to better handle the energy that needs to be
adsorbed when an impact hits the garment. In theory, hard ballistic packages are
sufficient to stop any kinds of impacts; nevertheless, they are mostly used in a
combination with soft body armour panels to maximize comfort and safety for the wearer
of the vest. The working principle for hard ballistic packages underlies one simple
principle: the panel should be harder than the impacting threat. Depending on the
materials used for panel and weapon, both can deform during the impact due to the high
energies and forces working against each other at this point. Furthermore, energy can be
led away from the wearer if impact fragments rebound in the opposite direction. With
steel, the molecular structure at the hitting point can be destroyed during the shock,
causing the performance of the vest to decrease dramatically.

Soft Body Armour


Soft body armour is part of the PPE, most times in form of a vest, which protects the
body against impacts, like ballistic impacts or other impacting objects like knives or
spikes.
In the construction of soft body armour, several layers of textiles are put together to a
system against impact threats. The panel should maintain the freedom of movement while
still covering the most important areas, which are the organs of the body. That is why
they are designed in an ergonomically cut with consideration to the human anatomy. The
panel also needs to provide protection against light and humidity, because some stab
performance materials are sensitive to these influences and can lose their properties.
Therefore they are sealed into a waterproof and impermeable light plastic foil and further
encased into a textile carrier. This prevents the effect of light and moisture to the fabric
and therefore reduces the loss of performance.
A soft body armour panel consists of high performance fibres or filaments that are
fused in a woven or other bonded layering. Flexible body armour is also made out of
multi-layered fibre material or a blend of cut resistant fibres with a metal core (Kolmes
und Pritchard, C. E. Mussinelli, M. 2007; Donovan 1984; Zhu und Prickett 2003).
In general, the application of soft ballistic packages is limited to prevent knives to
penetrate, however, with the right amount of layering and a proper high performance
Stab Resistance of Textiles 243

fibres as a base, the soft ballistic panel can be improved, to prevent threads entering the
human body tissue.
Apart from the general valid and needed properties of the fibre type, the type of
weaving or bonding that fuses the fibres together is of highest importance to the
functioning of the finished garment, as described before (Cavallaro 2011).
In principle, two different fabric constructions are used for manufacturing soft body
armour. On the one hand are conventional fabrics and on the other hand are
unidirectional laminate nonwovens (UD), which are also called shields.

Woven Fabrics

In the field of soft body armour construction, woven structures are very common
among other fabric constructions. Up to a certain velocity and density, square woven
fabrics can be more resistant than equivalent hard body armour (Shepherd et al. 1990).
The pattern that is used the most is square woven plain or basket weaves, like presented
in following.

Figure 1.1. Square plain weave.

Figure 1.2. Basket weave.


244 Priscilla Reiners

A balanced weave is normally used for the construction of protection garments,


because unbalanced weave structures lead to an asymmetric transverse deflection
(Cunniff 1992). In this context, the cover factor of the fabric is from high importance.
Studies have shown that cover factors between 0.6 and 0.95 give an optimal performance
(Scott 2005, S. 537). Values below are too loose and such loose yarn structures lead to a
displacement of the yarns, which then lead to a penetration of the fabric (Cheeseman und
Bogetti 2003). Values above 0.95 result in a degradation of the yarns under tension
during the weaving process. Also the crimp of the inserted yarns increases with a higher
density, which is not desirable; because the energy dissipation mechanism is depending
on the crimp of the fabric, which has to extend first until the main mechanism can take its
effect on the energy absorption (Bilisik und Korkmaz 2011). But a high yarn pre-tension
can reduce the cut resistance (Shin et al. 2006).

Laminates
Laminates are a combination of two or more materials to combine the useful
properties of the individual components. These laminates are called unidirectional
laminate fabrics (UD-fabrics). They are nonwoven matrix systems, where yarns are
aligned unidirectional in one layer and the following layer is aligned in another direction,
normally 90° to the first one. They are permanently bonded together by heat, pressure or
adhesives. The properties of these UD-fabrics depend on the type of fibre, the type and
amount of resin, the number of layers and the bond between resin and fabric (Bhatnagar
2006). Different structures are used for stab resistant PPE and are discussed in the
following sub-sections.

Spectra Gold Flex®


One of these structures or shields is the trademark Spectra Gold Flex® by
Honeywell, which is made out of four layers aligned aramid fibres fixed with resin (Park
1999). The produced vests out of this material are thin and resultant of this light and
flexible.

Dyneema UD
Dyneema UD is a unidirectional laminate made of two layers of polyethylene
filaments cross plied and sandwiched in a thermoplastic film. It is one of the strongest
laminates for protection.
The advantage of the shields is that it has no crimp issues, due to the different
processing techniques and lighter weight. Apart from that also brittle materials like glass
or carbon can be inserted. A disadvantage of these constructions is that there are no
linkages between the yarns. They are just connected by the resin, which is not as strong
as the mechanical linkage of woven fabrics.
Stab Resistance of Textiles 245

Improvements of Woven Fabrics


Furthermore, the manufacturer might want to add special coatings to his product to
support functions, especially when working with para-aramids, a hydrophobic finish to
ensure that the live-saving capillary system existing between the single filaments of the
impact resistance package cannot fill with water and thus fail the wearer when it does not
take up the lethal energy properly in the very moment a knife penetrates the vest. This
effect can be achieved through the usage of a resin-like coating that soaks the filaments,
which not only provides water-repellence but unfortunately simultaneously makes the
weave heavier and harder (Jenkins und Ren 2000; Breukers 2003). The simple equation
every company producing and designing soft body armour needs to face is: the better the
waterproofness, the harder and less flexible the fabric. Also a polymer film between the
layers prevents the slippage and fixes the yarns (Fuchs et al. 2003).
Another way to improve the performance of such a panel is to add a liquid, called
Shear Thickening Fluid. The Shear Thickening Fluid, short STF, as the name already
indicates, behaves like a solid when encountering mechanical stress or shear. STF is a
colloid, which is highly filled with miniscule, rigid and colloidal particles that repel each
other slightly and are suspended in a liquid. Due to the fact, that the particles repel each
other, they can easily float through the liquid without clumping together of forming a
layer at the bottom.
With the energy of a sudden impact, hydrodynamic forces overwhelm the repulsive
forces that exist between the tiny particles, driving them to stick together and forming
hydro clusters.
As soon as this energy is taken away, the particles start repelling each other again,
causing the hydro clusters to fall apart and the STF to be liquid once again.
The production of STF is fairly simple: it is made of colloidal silica particles, a
component, only a few nanometres (∼450nm) in diameter of sand and quartz, suspended
in polyethylene glycol, which is a polymer commonly used in e.g., lubricants. Due to the
size of the particles, some reports describe this fluid as nanotechnology. The STF acts
like a liquid, providing high flexibility and no restriction to movement, until an object, in
this case a blade, strikes it forcefully. At this point the relative motion of the high
performance yarns or fibres deform the fluid within milliseconds, forcing a transition into
a rigid state, providing less flexibility but high protection. Studies show, that the addition
of STF improves the stab behaviour of fabrics (Li 2012).

Conclusion

Multi-layer fabric packages of aramid, which are used for mechanical impact
protection, often don´t offer the required protection against stab protection with a sharp
pointed weapon. While developments of fabrics are already found, that enable adequate
246 Priscilla Reiners

stab resistance, there is still a large part of the solutions where combinations of different
structures of textiles with metals are used (Scott 2005). Also materials with the required
mechanical properties like strength or shear in form of plates or metal rings are used.
Stainless steel and titanium plates are also applied for this application. Ceramic plates are
also an ideal material, typically made of aluminium or boron carbide (Scott 2005). A
combination of textile materials such as aramid with steel or ceramic in form of
composite structures or sandwich constructions can give improved stab resistant results,
while they are lightweight and flexible. Also cut resistance gloves give a better protection
using a combination of cut-resistant fibre materials such as para-aramid with steel wire.
Also gloves out of leather with a high material thickness are established as an important
cut-resistant material (Heudorfer et al. 1996). Pure textile solutions often still do not offer
the required protection. Therefore it is important to analyse those influential factors that
cause the decreased stab resistance and develop improvements for better panels (Karahan
2008).

Materials

In the manufacturing of textiles for protection against mechanical risks, like stab- or
slash resistant materials, different materials are used. The main task of these materials is,
to absorb and dissipate the energy, which is transmitted by the stab instrument. As a
result of this, the different kind of stab instruments can be stopped or not (Damm 1997).
The current development of stab resistant equipment often consists of one textile layer in
combination with an additional layer, which has the task, to increase the stab resistance.
In the following materials are presented, which are common used as personal protective
equipment against mechanical risks, because of their high breaking strength and high
modulus properties to be able to absorb a high amount of energy (Fenne 2005).
The most common fibres that are used for body armour products are Kevlar®,
Spectra®, Dyneema® and Zylon®. These fibres provide excellent tenacity properties and
a high modulus. All the fibres listed provide excellent strength-to-weight (tenacity)
property and a high modulus.
But not just the high tech fibres have to be taken into account; also other fibre types
show an important role in this field.
Studies of the properties of wool have shown that the rough surface of wool, caused
by the scales, have very high friction forces (Bahadir und Jevsnik 2014; Frishman et al.
1948; Lindberg und Gralén 1948; Mercer 1945; Zurek und Frydrych 1993).
During the stab test the yarns slide apart when the blade penetrates the fabric.
Therefore Sinnppoo (Sinnppoo et al. 2010) describes the use of wool fabrics in his
studies. He put mid-micron wool fibres into the woven structure to restrict the separation
of the aramid yarns and therefore also the friction behaviour of the fabrics. The function
Stab Resistance of Textiles 247

of the wool is not to replace the aramid as the stab resistant material. As the friction is
most important in the area, where the knife penetrates the aramid fabric, the function of
the wool layer is to decrease the lateral separation of the yarns of the outer fabric layer.
The expected effect of decreasing the friction between the yarns is established in the
special surface of wool. The scales effect like barbed hooks, which claw into the surface
of the nearest yarn and avoid the sliding of them. The wool yarns prevent that the
filaments slide apart, they hold the directly impacted yarns in place for a better
dissipation of the impact energy. The scales stuck into each other or into other surface
irregularities. (Simpson und Crawshaw 2002) Because of the longitudinal friction
between the yarns of the wool and the filaments of the para-aramid the pull-out behaviour
will decrease (Sinnppoo et al. 2010).
In the following, the fibre properties are explained in detail.

Para-Aramid
The most common material for protective vests is para-aramid, because it can be
found in the most commonly manufactured products (Fenne 2005). For the first time, the
yellow organic synthetic fibres appeared in 1965 under the brand name Kevlar® from
DuPont. The other well-known brand is Twaron®, produced from Teijin Aramid and is
basically the same material as Kevlar®. Para-aramid is an aromatic polyamide, consisting
of cyclic aromatic elements and the amide group, namely phenyl group, which is
responsible for the high performance properties, like shown in Figure 1.9. Not just these
groups, but also the linear structure of the polymer chain s are responsible for these
properties, because they can form easily strong intermolecular bonds.
Para-aramid has very good strength-to-weight properties, like high strength, high
modulus, high dimensional stability and hence an excellent cut resistance, which is a
result of the crystalline structure with the molecular chains oriented along the fibre axis
(Teijin Aramid 2012).
The main problem of the para-aramid fibres is the susceptibility to hydrolysis and
sensitivity to light, why it has to be protected from light and moisture. The low resistance
to UV radiation can cause the fibre to lose up to 75% of its strength. Therefore the
material is wrapped by an opaque and impermeable cover to prevent any kind of
degradation and loss of performance (Horrocks und Anand 2000).

Figure 1.3. Chemical formula of aramid.


248 Priscilla Reiners

Figure 1.4. Formula of Polyethylene.

Figure 1.5. Formula of PBO.

Ultra-High Molecular Weight Polyethylene (UHMWPE)


UHMWPE is a special produced polyethylene with extremely long chains of
polyethylene, which are all aligned in one direction. The fibre production is carried out
by solvent or gel spinning and allows the molecules already to align in the solution,
which leads to extremely long molecular chains. The additional drawing process makes
the molecules become even more orientated.
Under the current used fibre types for protection against mechanical threats, it is the
lightest material and the best material referring to its strength to weight ratio. It is
stronger than steel but also stronger than aramid and is not prone to degradation. The low
melting point of 150°C restricts its use to low temperature applications (Horrocks und
Anand 2000). The most known trademarks for UHMWPE products are Dyneema® from
DSM and Spectra® from Honeywell.

Poly-Para-Phenylene-2,6-Benzo-Bisoxazole (PBO)
PBO has very good mechanical properties, caused by the benzene ring structure and
the rigid rod-like chain molecules. The module of elasticity of PBO is much higher than
the one of para aramids. The famous known trademark of PBO is Zylon® from Toyobo
(Toyobo Co. 2005). Since the failure of a Zylon® body armour vest, the assumption of
degradation was taken into account. Due to the protective performance loss a few years
after the production of a vest made of Zylon® as well as the loss of performance through
moistening of the substance, Zylon® based body armour cannot provide the intended
level of protection. As there is no visible indication of aging, PBO vests are not used
anymore (Polizeitechnisches Institut (PTI) 2001).

Wool
In the following, the wool characteristics related to the stab resistance is presented in
detail. Wool can absorb between 14-18% of moisture in standard atmosphere. This is an
important fact due to the increase in moisture on the aramid yarns, which leads to a higher
Stab Resistance of Textiles 249

yarn slippage. Furthermore the comfort of a panel made of blend of wool and aramid
increases because of the water vapour absorption (Mahbub et al. 2014). The friction is
available at two stages – one is fibre to fibre friction inside of the yarns, which influences
the compressibility of the yarns and thus as well the forces, which act to the neighbour
yarns during penetration. Another stage is at the yarn level – the fibres on the yarn
surface contact with the fibres of the other wool and aramid yarns and causes again a
higher friction. Furthermore, the hairiness of the wool yarns influences the friction
between the wool yarns and the aramid yarns. It can be assumed, that in general at every
level single fibre surfaces connect to another one, independent if it is on fibre or yarn
level. The second important characteristic of wool is the friction behaviour, which can
vary significantly depending on several parameters. Because of the random orientations
of the scales of fibres in a yarn, the coefficient of friction µ depends on the surface,
direction of scales (with/against scales), the kind of wool, e.g., fine or coarse, and the
surrounding conditions like temperature and air humidity (Frishman et al. 1948; Mercer
1945). Another influence is caused by the different contact points of the scales parts and
angles (Mahbub et al. 2014). The structured surface of a wool fabric has a higher friction
coefficient in comparison to the smooth surface of an aramid fabric, due to the imbricate
structure (Zurek und Frydrych 1993). Some exemplary friction values µ of wool are
between 0.11 and 0.13 in direction with scales, between 0.15 and 0.21 for the same fibre
direction and between 0.38 and 0.61 against scales (Simpson und Crawshaw 2002). The
values are differentiated between static and kinetic values.

Figure 1.6. Direction of fibres in a wool yarn.

The mean frictional coefficient against scales is higher than with the scales,
(Frishman et al. 1948; Lindberg 1953) but a microscopic analysis of a typical wool yarn
shows that the fibres lay uniformly distributed in both directions, like the example in
Figure 1.6.
250 Priscilla Reiners

Therefore it is assumed, that the mean frictional force of a yarn and also of a fabric is
an average of the frictional force of both directions, with and against scales. Ajayi (Ajayi
und Elder 1997) tested several different fabrics with a wide range of physical properties
to show all these influences on the friction coefficient. He also found out, that the friction
is also affected by experimental condition s, like changes in the normal pressure and a
limited influence to the test velocity.

PROTECTION LEVELS AND CLASSIFICATION OF BODY ARMOUR

Since there are many different levels of threats, there is no single vest that can protect
the wearer against all kind of threats. Different constructions of soft body armour create
different levels of protection and each has its own field of application. The usage of each
construction of soft body armour is restricted to certain threats, respectively kind of
blades, impact forces and speeds. The use of most constructions of textiles are not
sufficient for protection, thus soft body armour cannot give enough protection against a
penetration through sharp pointed weapons like knives or ice picks (Bhatnagar 2006).
That is why it is necessary to classify the different types of body armour.

Technical Guideline of the German Police (TR)

The Technical guideline (TR) Ballistic body armour of police forces of the Federal
Government describes the demands on protective vests of different protection classes
(Polizeitechnisches Institut (PTI) 2008). A vest is designed to protect the wearer against
projectile impacts or other mechanical impacts like attacks with knives. The freedom of
movement of the wearer's body armour may be only slightly restricted. The scope is
generally limited to the upper part of the body. Neither humidity nor temperature or other
external influences may influence the protective effect. The protection of vests against
impacts is specified with the protection class (SK for German: Schutzklassen). The
classification is subdivided in five classes with different properties. In Germany, there is
no safety class system that deals with stab-resistant vests only a system built up on the
one already introduced, with the addition of “ST” in the nomenclature, which stands for
“Stichschutz,” meaning stab-resistance. The protection level SK L ST and SK 1 ST
requires “Stab retardant against attacks with knives (blades),” while the other three levels
give protection against “Largely stab retardant against attacks with knives (blade) and
pointed objects (e.g., needles and cannulas).”
Combinations of bullet resistant specimen with integrated puncture protection have to
be tested according to the guideline VPAM- KDIW 2004 class K1 and bulletproof test
specimen with upgraded puncture resistance should be tested according to VPAM-BSW
Stab Resistance of Textiles 251

2006 (Test Standard VPAM KDIW 2004; Test Standard VPAM BSW 2006). Stab
resistant panels, which are conform to the TR, should resist according to test class K1 of
the guideline VPAM- KDIW 2004, which means, that body armour vests are allowed to
be penetrated with maximum 20 mm at an energy level of 25 Joule.

The NIJ Armour Classification System

In the most important standard of stab protection of the USA, the NIJ (National
Institute of Justice 2000) for stab resistance of personal body armour, two protection
classes are described. The protection classes distinguish between two different risk types
caused by different type of threat instruments. The first protection class, the “Edged
Blade class,” protects against blades or knives, which are of high quality. Weapons of
this quality are expected on streets. In this classification, the knife is allowed to penetrate
a maximum of 7 mm. The “Spike class,” however, offers protection against weapons,
which are of less qualitative or improvised weapons, as they are used in prisons for
example. They are allowed to penetrate a maximum of 20 mm. Within each protection
class, the panel is further classified into one of three protection levels, which are
depending on the stab energy the threat is expecting. Level 1 armour is a low-level
protection armour, which is suitable for an extended wear and is generally covert. Level 2
armour is a general duty garment suitable for an extended wear and can be worn either
overt or covert. Level 3 is a high level protection armour suitable to wear in high risk
situations. It is usually overt. The protective garment of the level 1 provides the lowest
protection. It is mainly used as additional equipment and against low energy attacks up to
24 Joules. Body armour of level 2 is required for all policemen and can fend attacks with
energy levels up to 33 Joules. Level 3 protective equipment is used in risky supported
operations, and thus forms the highest level of security with a protection against attacks
of 43 Joules (National Institute of Justice 2000).

The UK Standard HOSDB

According to the HOSDB (Home Office Scientific Development Branch Body


Armour Standards) for UK Police Part 1: General Requirements (Croft und Longhurst
2007a), protective clothing should protect in case of attacks with knives with edged
weapons or spikes with edged weapons plus blurred weapons against injuries. The
protective clothing is according to its protective function marked and divided in
protection types. Equipment, which is marked as stab resistant, provides protection
against sharp weapons and possibly in addition also against blurred weapons, like nails.
252 Priscilla Reiners

Protective garments which protect against bullets and knives are defined as “dual-
purpose.” In relation to protection against knives and spikes HOSDB Body Armour
Standards for UK Police Part 3: Knife and Spike resistance classifies three levels. KR1
and KR1+SP1 are the lowest level of protection, which is tested with energy values of 24
Joules. Protective clothing of this level is worn in cars or situations in less risky
environments. The average protection level corresponds to KR2 and KRS+SP2, tested
with energy of 33 Joules. This protection level is required for policemen to be worn daily.
Protective clothing of the highest levels KR 3 and KR3+SP3 are only briefly worn in
very risky situations and are tested with an energy level of 43 Joule. The penetration must
not exceed 30mm to be permitted at E2 knife testing and one penetration (no depth limit)
is permissible for spike testing (Croft und Longhurst 2007b).

TESTING METHODS OF STAB RESISTANCE

The stab resistance of stab resistant textiles can be tested according to different test
standards. In Germany or other German-speaking countries, the VPAM test instruction
VPAM KDIW 2004 “Stab and impact protection ” is widely used.
The principle of measurement is shown in Figure 1.12: a blade of a defined sharpness
and size drops from a defined height which depends on the energy level for the stabbing
impact. The penetrated fabric layers are positioned on plasticine, a modelling material
that on the one hand absorbs the penetration of the knife and on the other hand gives the
opportunity to measure the different depths of penetration. The knife is mounted on a
sample holder and the drop mass of this unit is 2.5 kg. To ensure that the knife can fall on
the sample in such a way that the tool strikes it at a 90° angle, the sample holder is led by
rails. As samples of different thicknesses are tested, the drop height is adjusted depending
on application, to determine differences between the samples. Afterwards, the stab depth
in the plasticine is measured by using a ruler.
According to the standard VPAM KDIW 2004, the fall height should be set, that a
potential energy of 15 Joule has to be ensured to reach results of a stab depth lower than
10 mm or 25 Joule for a maximum stab depth of lower than 20 mm.
With the assumption, that the knife falls down without creating frictional forces at the
rails, the falling height can be calculated by:

𝑊𝑃𝑂𝑇 = 𝑚 ∗ 𝑔 ∗ ℎ (1)

where WPOT is the potential energy, m is the mass of the knife with the holder in kg, g is
the gravity and h is the falling height. The weight by the knife plus holder is given by 2.5
kg and the defaulted potential energy is 15 Joule or 25 Joule. Due to this, the adjustment
of the fall height has to be calculated as follows:
Stab Resistance of Textiles 253

𝑊𝑃𝑂𝑇
ℎ= 𝑚∗𝑔
(2)

The outcome of this is a height of 0.61 m for 15 Joule potential energy and 1.02 m
for 25 Joule.
The preliminary tests showed that with a falling height according to the standard of
1.02 m the knife goes through all structures and the differences cannot be seen. Also a
height of 0.61 m gave no significant differences. To find out differences between the
fabrics, the falling height was reduced to 28.5 cm, which is equal to 6.9 Joule for the
following test series. With respect to this, the test speed was also reduced, due to:

𝑣 = √2 ∗ 𝑔 ∗ ℎ (3)

where v represents the velocity of the falling knife in m/s during the test. According to
this equation, the test speed for a height of 1.02 m is 4.47 m/s, but for the height of 0.28
m a reduced speed of 2.34 m/s was measured.

𝑠=𝑑𝑝𝑒𝑛𝑒𝑟𝑡𝑟𝑎𝑡𝑖𝑜𝑛
∆𝐸 = 𝑊 = ∫𝑠=0 𝐹(𝑠) ∙ 𝑑𝑠 = 𝐹𝑎𝑣𝑒𝑟𝑎𝑔𝑒 ∙ 𝑑𝑠 (4)

Figure 1.7. Test equipment stab resistance.

The kinetic energy EKIN, which occurs during the test results of these adjustments like
the following:

1
𝐸𝐾𝐼𝑁 = 2 ∗ 𝑚 ∗ 𝑣 2 (5)
254 Priscilla Reiners

For the falling weight of 2.5 kg and the height of 0.285 m the mean impact force will
be calculated like this:

∆𝐸 𝑚∗𝑔∗ℎ
𝐹𝑎𝑣𝑒𝑟𝑎𝑔𝑒 = 𝑑 =𝑑 (6)
𝑝𝑒𝑛𝑒𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑝𝑒𝑛𝑒𝑡𝑟𝑎𝑡𝑖𝑜𝑛

where dpenetration is the stab depth of the knife in the plasticine.

∆𝐸 = 𝑊 = 𝐸𝐾𝐼𝑁 = 𝑊𝐶 + 𝑊𝑃𝑃 + 𝑊𝐹𝐵𝑌 + 𝑊𝐹𝐶𝑌 (7)

where WC is the cutting work, WPP the work to penetrate the plasticine, WFBY the work of
the friction between the yarns and WFCY the work of friction of the cut yarns. From initial
tests with pure plasticine without fabric, the knife goes through the complete plasticine,
so we can assume that the energy loss for WPP is a negligible part of the complete energy
during this penetration. The energy of friction between the yarns and the energy of
friction during the cutting are in this case also negligible, because for the practical
evaluation it is important to have an idea about the average resistance of the fabric
against penetration. This average force is a calculated value, which would correspond to
the force if the penetration speed is constant, according to equation 7 and can be used for
the comparison of different fabrics. This force accumulates all above mentioned
influences and resistances, which are important during the development and optimisation
of the fabric, but for the final evaluation the average penetration force is relevant.
This is an important factor to demonstrate the interdependence between the stab
depth results and the impacted energy, which leads to fewer injuries during the stabbing.
The drop height is measured as the distance between the tip of the blade and the box
with plasticine. The penetration depth of the blade in the plasticine is measured with a
ruler. Therefore the resultant hole is excavated. According to the standard, tests are
carried out three times per sample. The evaluation of the test results are explained as
follows.

Evaluation of Measurement Results

The VPAM stab resistance tests (Test Standard VPAM KDIW 2004) are carried out
with a standard knife which falls from a specific height, depending on the required
energy level. Therefore it is driven by a defined weight onto the test sample, which is
lying on a box with ballistic plasticine. The penetration depth in the plasticine is
measured after removing the plasticine on one side of the penetration channel. Due to the
correlation of blade width and length in the front part of the blade, additionally the width
can be measured and the depth can be calculated out of it.
Stab Resistance of Textiles 255

According to the Guideline the deformation depth is determined by measuring the


deepest point of the stab impact, where the trauma impact isn´t taken into account. This
means that the hole, which is caused by the stab test, has to be dug out carefully and the
exposed hole has to be measured using a ruler.

Frictional Test Parameters


The friction behaviour of fabrics has to be split in two areas. First there is the friction
behaviour itself, which includes the fibre, yarn and fabric friction. The second parameter
is the yarn pull-out test. This test is a practical method to investigate the material
properties of a fabric. It provides useful information about the fabric`s deformations and
its ability to absorb energy, especially protective applications and therefore the frictional
behaviour of the fabric (Asayesh et al. 2012). It is influenced by many mechanical
properties like the yarn geometry and fabric weave structure (Pan und Yoon 1993). A
similar test to the pull-out test is the seam slippage. Here yarns are also pulled out of a
seam. It is explained in detail after the other methods.

Friction
The performance of textiles is greatly influenced by its frictional behaviour. Due to
the smooth surface of aramid fabrics, the stab resistant performance is affected by textile
frictions and their influencing factors (Ramkumar et al. 2005). They have to be taken into
account to increase stab resistant properties. The influencing factors of textile friction
behaviours can be divided into fibre friction, yarn friction and fabric friction.

Fibre Friction
Fibre friction is related to the structural parameters and the bulk properties of fibres.
Fibre structural properties can be the crimp, or in case of wool, the scales type and size,
the fibres surface roughness or the molecular orientation. Some bulk properties are for
example the diameter, the fineness and the length of the fibres. Also the fibre material
itself influences the frictional behaviour. To determine the fibre-to-fibre friction and
fibre-to-other surface friction, also the test conditions have to be taken into account
(Hong et al. 2004).

Yarn Friction
Yarn friction is related to both surface properties and bulk properties of yarns. Yarn
friction is determined by the before mentioned fibre parameters and the yarn structure
and bulk parameter, like yarn twist, spinning method (Ramkumar et al. 2003) or yarn
fineness. The coefficient of friction of yarn increases with an increasing yarn linear
density, due to the larger contact area and with an increasing yarn twist of ring and rotor
spun yarns, friction decreases for different materials. High twist results in a smaller area
256 Priscilla Reiners

of contact, and thus results in a lower frictional force. The yarn friction decreases with an
increased roughness of the yarn surface. However, with a very rough yarn surface and
increased unevenness, the yarn friction tends to increase.
Also here the test conditions to determine the frictional behaviour of yarns are
important, like the normal load, the frictional speed, contact geometry and the boundary
conditions (Ramkumar et al. 2004; Ajayi und Elder 1997). On top of that the friction of
the yarn is also influenced by finishing (Hwang et al. 2015).

Fabric Friction
Fabric friction is related to both surface properties and bulk properties of fabrics.
Parameters affecting the fabric structure are the weave pattern and the fabric finishing
(Bazhenov und Goncharuk 2014). Twill weave pattern show higher friction forces than
plain weave pattern, due to the floating length of the yarns (Behera und Hari 2010; Ajayi
1992). The influence of operational parameters, like load pressure or the sliding speed,
was reported by several researchers (Ajayi und Elder 1997; Abghari 2011; Arshi et al.
2012; Hermann et al. 2004; Mihail 2015).

Friction Measurement
In general the friction is the force that opposes the relative motion of two surfaces in
contact with the friction coefficient µ.
The frictional force F is mainly determined by the nature of the surfaces which are in
contact and the force that holds the surfaces in contact, which is known as the normal
force. The friction is governed by Amonton’s laws with: (Saville 1999)

𝐹 = 𝜇 ∙ 𝐹𝑁 (8)

After Coulomb the friction is divided into static friction and sliding friction, which
can´t be separated strictly, because they can occur simultaneously or alternatively. It is
the force, which is required to move a carriage on the surface of a test sample to
determine the coefficient of static friction and kinetic friction. When a resting object
starts to slide, a force is required to start the object moving. It is known as the static
friction. The static friction force is proportional the normal or pressing force FN:

𝐹𝑆 = 𝜇𝑆 ∙ 𝐹𝑁 (9)

The coefficient μs is the coefficient of static friction. It depends on the material


combination, but has on the other hand almost no dependency of the contact area of the
surfaces. Already Coulomb has determined that μs increases with the lifetime. Once the
object is moving, the force required to keep it moving is lower than the original starting
force and is known as sliding or dynamic friction. This movement in total is defined as
Stab Resistance of Textiles 257

the frictional force. The frictional force FR is independent of the size of the contact area
and increases mostly linear with normal force FN. The coefficient of friction µ depends on
the surface (EN 14882: 2005; Langston und Rainey 1954; Timble 2014).
The sliding or kinetic frictional force FK is the force, which acts after overcoming the
adhesion. Coulomb has found experimentally that the sliding friction is proportional to
the pressing force N and has no significant dependence of the contact area and roughness
of the surfaces. The kinetic coefficient of friction is approximately equal to the static
friction coefficient:

𝜇𝐾 ≈ 𝜇𝑆 (10)

Hereby the sliding friction depends not, or only very weak, on the sliding speed.
These laws are practicable well for hard materials, but not for textile materials
particularly at low values of normal force. In most cases it is the sliding friction that is of
practical interest. To analyse the sliding process, several operational parameters which
can influence the results of the friction, are determined.

Pull-Out

The pull-out effect is defined as the force, which is required to pull out one single
yarn out of the fabric structure, calculated as the sum of the frictional resistances at the
crossing points to overcome (Kirkwood et al. 2004; Bilisik 2011). Friction in turn is most
dependent on the linear density and the pattern (Rebouillat 1998).
The required force to pull out the yarn is more, the higher the friction coefficient is.
Some energy has to be mustered to move and displace the yarns out of their structure and
this leads to a higher energy absorption by the fabric (Cheeseman und Bogetti 2003). The
resistant energy which has to be overcome is due to friction forces. The friction of the
fabric plays a role, especially for lower impact velocities. There the frictional forces at
the yarn crossover points lead to the destruction of the fibres, which happens under
energy absorption. A higher fabric density will lead to more energy absorption, because
crossover points represent a higher resistance in form of friction (Bilisik und Korkmaz
2011). If the friction between the yarns is too high they would rather cut each other than
displace themselves. In case the friction is too low, there is no resistance against the
impact and yarn slippage occurs. Therefore the coefficient of friction has to be high
enough that yarns cannot be easily pulled out or moved aside. Some coefficients of
friction for interyarn friction, depending on the absorption capacity are (Zeng et al. 2006)

 µ = 0.0 – 0.06 for low friction forces


 µ = 0.06 – 0.2 for medium friction forces
258 Priscilla Reiners

 µ = 0.2 – 1.0 for high friction forces

A high coefficient of friction leads to additional energy absorption, because more


energy is required for the pull-out force. The friction forces between aramid yarns
decrease in the state of wet yarns, because the blade can slide through easier and
therefore lead to a lower protection level (Bazhenov und Goncharuk 2014).

Pull-Out Measurements
The pull-out mechanism means that one yarn is pulled out of a fabric structure by
motion of the penetrator (Bilisik 2011). After Bilisik (Bilisik 2011), the test is split in two
regions, the static and kinetic region. He divided the static region again into two areas;
the area, where the crimped yarn expenses till it is uncrimped, and the fabric
displacement region, which is the extensional stress in the fabric area, when a yarn is
pulled out. In this region, the force increases to a maximum value, which corresponds to
the maximum static friction force Fs. The kinetic region is the motion, when the yarn is
pulled through all crossing points. Hereby a stick-slip effect occurs. Stick is the moment,
when a warp yarn is passing over or under a filling yarn. The slip area is the area between
two picks. (Bilisik 2012) This region corresponds to the dynamic or kinetic friction force
Fk.
The measurements are most times idealized. Local effects are neglected, because they
are too small in comparison to the yarn pull-out forces (Pan und Yoon 1993). Also it is
assumed that the axial tension is dominant, so the shear stress can be neglected in
comparison to the movement at the crossing points (Pan und Yoon 1993).
Other researchers made tests, where they found out, that the yarn pull-out is
dependent on the fabric density, the number of pulled yarns and also the sample size
(Bilisik 2013). Tight fabric structures show higher values than loose structures.
Additionally, the impact energies are absorbed by the friction between the yarns (Bilisik
und Korkmaz 2011). Also the test methods are quite different. One method is to clamp
the fabric at the sides and one or more yarns are pulled out (Bilisik 2011). This leads to
extensional stress in the fabric area, like shown in Figure 1.18. Guo carried out pull-out
tests with the out-of plane method, where the thread is pulled out of the fabric surface
(Guo et al. 2014). The inter yarn friction decreases with the remaining number of
crossing points (Guo et al. 2014). Also the pretension influences the pull-out rate. Results
lead to a higher pull-out load if the pretension is smaller (Nilakantan und Gillespie 2013).

Seam Slippage
In the quality evaluation of ready-made garments is the slippage of yarn at the seam
an important factor. The seam slippage can be defined as the ability of the displacement
of yarns, where the yarns in the fabric slip away from the seam under stress, what means,
that the weft yarns slip over the warp yarns or the warp yarn over the weft yarns
Stab Resistance of Textiles 259

crosswise to the seam, occurred through a given load and cause an opening of the fabric,
like the example in Figure 1.8 shows.

Figure 1.8. Seam opening of a plain weave aramid fabric.

The value of the seam slippage is expressed as the seam slippage resistance FS, which
is the force to open a defined seam LS through the displacement of yarns crosswise to the
seam direction (Reumann 2000).
It can be defined as:

𝐹𝑆 ≈ 𝐹∑𝐿𝑆 (11)

with ∑LS = Sum of openings to both directions in the seam area.


This phenomenon leads to a reduced range of the end-use of possible areas. The
characteristic of migration or slippage is an important parameter and depends on different
fabric structure properties, like fibre type, pattern, the linear density of the yarns and the
number of yarns per unit length, but also the thread seam construction and stich density
(Milašius 2012). One important factor is also the yarn -to-yarn friction. Especially very
smooth fibre types lead to a high yarn migration, particular in the seam area during high
stress. Resultant of this, it is assumed, that the yarn friction is linked to the seam slippage
(Daukantiene und Lapinskienė 2012; Behera und Hari 2010; Malčiauskiene et al. 2011).
The seam slippage will decrease by higher friction forces (Backauskaite et al. 2013).
In the area of stab resistance of textiles, special for high strength fibres like aramid,
the effect is given, that during the penetration with the knife, the yarns are not cut; they
migrate and cause an opening of the fabric. This phenomenon is given for all smooth
fibres, which are penetrated by a sharp shape like a knife. It is assumed that there is
interdependence between this displacement and the seam slippage.

CONCLUSION

The analysis shows that a lot of research has been done in the field of protective
garments against stab attacks. The need for stab resistant materials, the materials which
260 Priscilla Reiners

are currently used for slash and cut resistant applications and their properties were
reviewed in the state of the art. A main problem of these materials is the missing friction
behaviour, why a knife can penetrate a fabric easily. Therefore a lot of layers are used to
ensure adequate protection, but this leads to bad comfort behaviour because of stiffness
and heaviness. Also the test procedure s to define the protection level are incomplete or
for improvement.
The research goal is to examine various aramid fabrics with regard to their stabbing
behaviour and to find influencing factors to this. An attack can only be inhibited, but an
injury cannot be completely prevented. The goal is always to absorb as much energy as
possible, so that the penetration is thus reduced and the risk of injury decreases. The stab
mechanism is a complex and variable process. The review showed the demand on
research in this area, because most solutions involve hard body armour parts in
combination with fibrous materials. This material combinations show many
disadvantages with regards to the high weight and the missing flexibility. Other
researchers also recommend textile solutions, (Horsfall 2012) because they are flexible
and in the field of ballistic panels they are already used. Therefore the interdependencies
between the physical properties of the material but also the mechanism during a stab
attack have to be recognized, to developed higher protection levels. It is shown, that the
multitude of factors causes the problem to define a level of protection.

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Chapter 13

SUSTAINABLE KNITTED NOISE INSULATION:


THE DEVELOPMENT OF WOOLEN INTERIOR
ELEMENTS WITH ACOUSTIC
ABSORPTION PROPERTIES

Maureen Mann1, Sonja Vater2, Frank Heimlich1 and Ellen Bendt1,


1
Niederrhein University of Applied Sciences, Faculty of Textile and Clothing
Technology, Mönchengladbach, Germany
2
Thamm GmbH /e3-raumakustik, Bonn, Germany

ABSTRACT

One of knitting’s unique qualities is the ability to create design, shape and material
properties within the same process. As an example for a beneficial use of 3D structures
and surfaces in product design this presentation discusses the results acquired in the
research project “Development of woollen interior elements with acoustic absorption
properties.” The project´s aim is: designing/developing sustainable acoustic panels with a
knitted woollen surface for interior application in homes, offices and other premises.
Wool was chosen as a sustainable fibre, possessing outstanding sound-absorbing
properties by nature.
Main methods and techniques used for the development process were the testing of
flat knitting constructions, several finishing tests and the discussion of the shape of the
panels. Measurements in a reverberation chamber confirmed the products anticipated
sound-absorbing properties.
Compared to other noise insulating objects, the exterior material of the developed
products does not only create a unique, innovative and aesthetic 3D design, it also


Corresponding Author Email: ellen.bendt@hs-niederrhein.de
270 Maureen Mann, Sonja Vater, Frank Heimlich et al.

enhances the material’s acoustic properties by generating an enlarged and voluminous


surface.

Keywords: noise insulation, 3d surfaces, living comfort, functional wool, sustainable


interior, knitted sound absorption

INTRODUCTION

In the quest for innovative and sustainable design solutions knitting technology can
give way to new opportunities. One of the inimitable aspects of the knitting process is the
ability to create design, shape and material properties within the same process. Especially
flat knitting allows the construction of unique 3D structures and surfaces with unique
properties, which can be utilised in product design.
Noise is a significant and ever present environmental stress or. Particularly in the
workplace noise can interfere with communication and disrupt concentration. Resulting
in a decrease in productivity and elevated stress levels making it a rising health concern
(VGB, 2012). The project ’s aim is to design and develop prototypes of sustainable
acoustic panels with a knitted woolen surface for interior application in homes, offices
and/or other premises.
Though there are various building acoustical measures these are often not specifically
taken into account during construction. Especially in older buildings and were the
intended use does not necessarily point towards an increased demand for special
acoustical conditions. The demand to improve a room’s acoustical quality can be notable
e.g., when repurposing rooms as to create a new conference room or a shared office
space.
To reduce unwanted reverberation and thus improve acoustic quality sound absorbers
can be installed to a room. The volume and type of needed noise insulation depends on
the room size and the room’s acoustic properties i.e., used surfaces and furniture. In small
to medium sized rooms (up to 250 m3) the frequency dependant design for the octave-
centre frequency ranges between 125 Hz and 4000 Hz or the three-frequency frequencies
between 100 Hz and 5000 Hz is generally sufficient, neglecting the sound attenuation of
the air (EN ISO 18041, 2004).
Sound reduction through a passive medium, typically porous materials are a common
way to control reverberation. Porous materials reduce sound by disseminating energy and
converting it into heat due to friction. The sound absorption quality of porous materials
relies on the existence of pores which are open, deep and narrow enough for sound waves
to enter and friction to take place (Fasold & Veres, 2003). Next to porosity and tortuosity
other factors influencing sound absorption need to be taken into account. These are
airflow resistance, surface impedance, material density and thickness and when
Sustainable Knitted Noise Insulation 271

evaluating fibrous materials fibre size and material compactness (Seddeq, 2009). The
thickness of the absorbent layer determines the range of frequencies that can be reached.
Generally for the high frequency range thinner, more compact fibrous mats and for the
lower frequency range thicker, less compact ones are the most suitable (Fasold & Veres,
2003). Textiles, primarily non-wovens, as a kind of porous material have gained attention
for application as noise insulators largely on account of their low-cost and low
environmental impact. Investigations of non-wovens has show the difficulty of producing
an aesthetically pleasing textured surface despite their promising sound absorbing
qualities (Yanping Liu & Hong Hu, 2010) giving knitting an advantage due to the better
control over design of the material surface.
As sustainable material, the wool fibre naturally has high performance fibre qualities,
many of which are specifically desirable for this product. Most importantly is the
materials sound absorbing capability. The increased use and investigation of wool as a
thermal insulator has also spiked the investigation of wools acoustic properties and has
proven useful in the reduction of room reverberation (Ballagh, 1996). Also wool fabrics
applied as covers for conventional acoustic panels have shown to improve sound
absorption in the midfrequency range (Miao, 2005). Used as carpeting wool can also be
applied effectively to reduce airborne noise, echoing and surface noise (Mcneil, 2014).
Further the materials capability to absorb up to one third of its weight in water (Hearle,
2002) additionally supports control of humidity and improves the room climate. Equally
wools good flame -retardant properties (Simpson, 2002) are favourable for a product in
an interior setting for safety reasons.
The basic idea is to generate a sustainable product that incorporates functional
aspects, which add to the creation of an amiable environment in an aesthetically pleasing
design.

2. PRODUCT DEVELOPMENT

Main methods and techniques used for the product development process are the
testing of several flat knitting constructions, finishing tests, and the selection of the
panels shape and measurements in a reverberation chamber.

2.1. Development of Flat Knitting Constructions

The knitted material forms the outer shell of the acoustic elements. Therefore, the
material must incorporate both design and functional aspects. On the grounds that
material volume and density are proportional to the efficiency of the sound-absorbing
272 Maureen Mann, Sonja Vater, Frank Heimlich et al.

properties (Seddeq, 2009), the focus was on finding flat knitting constructions that are
voluminous and have a certain material density to create a large surface, which is also
pleasing to the eye. Thus the focus is on creating 3D structured surfaces.

Figure 1. Different 3D structured surfaces.

All prototyping is realised with the M1Plus pattern software from Stoll. The knitting
is conducted on Stoll flat knitting machines, the CMS 340 TC KW (E6.2) and the CMS
302 TC (E8). The selected yarn for the developments is “Jawalan,” Nm 2/28, 100%
Merino wool (26 µ) of wool specialist “Suedwolle GmbH & Co.KG”. Ranges of different
constructions, especially based on double bed knitting constructions like full needle rib
and jacquards with bold relief structures, are worked out and tested with one or two ends
of yarn and with two different machine gauges. A selection of swatches knitted with two
ends of yarn with gauge E8 can be seen in Figure 1.

2.2. Finishing Tests

For the final fabric a slightly felted finish is anticipated to increase the material´s
compactness, density, firmness and volume without losing the visibility of the stitches
and porosity. To achieve the anticipated finish several finishing tests are conducted. The
swatches are all measured for determination of the shrinkage through the fulling process.
Subsequently the swatches are soaked in a mild soapy solution. Considering that the
selected wool yarn felts easily no aggressive treatment is needed for the fulling process.
The solution contains 60 ml liquid detergent per 2 l of soft water with a pH level of 7.5-8.
Sustainable Knitted Noise Insulation 273

Afterwards the soaked swatches are fulled for different time periods ranging from 30-45
minutes in 15-minute steps without any additional liquid and temperature. The fulling is
realised using an Ipso HC 60 washing machine. Then the swatches are thoroughly rinsed
and spin -dried. To let the swatches dry completely they are laid out flat and air-dried at
room temperature. Additionally, the influence on the fulling process of pre-washing the
swatches for 20 minutes is tested, but without any significant effect on the results.

2.3. Design and Production of the Acoustic Elements

After revision of the swatches the tuck stitch pattern with 3D surface is selected as
cover material with a colour gradient. The base colour for these acoustic elements is a
mid grey tone highlighted with cyan, blue, light green and an emerald green tone. The
substructure of the acoustic elements consists of a 50 mm wide reusable aluminium
frame, filled with a recyclable pure high standard polyester fleece, CARUSO-ISO-
BOND. The knitted fabric acts as a cover and encompasses the entire frame. Not leaving
any metal exposed to reflect sound thus ensuring that the entire panel’s surface is utilised
to absorb sound. The cover can be opened and closed via a Velcro fastener. All
elements/materials can be separated again. A series of three products are realised as
prototypes: Three elements to be hanged on the wall (Figure 2), two elements that can be
installed hanging parallel to the ceiling and two free standing partitions.

Figure 2. Sound absorber wall elements.


274 Maureen Mann, Sonja Vater, Frank Heimlich et al.

2.4. Measurements in a Reverberation Chamber

To confirm the anticipated sound-absorbing properties the prototypes are tested in a


reverberation chamber, at SG Bauakustik (Mülheim an der Ruhr, Germany ). The testing
procedure follows the DIN EN ISO 354 protocol for measurements in a reverberation
chamber. The test is designed to evaluate the sound absorption efficiency across the mid
frequency spectrum (100-5000 Hz) off a diffuse sound field for absorbers intended for
application in rooms e.g., placed on walls and/or ceilings.

Figure 3. Testing in a reverberation chamber.

The test measures the reverberation time of a diffuse sound field in a reverberation
room with the test objects against the reverberation time of the empty room. The
collected data is then used to determine the equivalent sound absorption surface A and the
rated sound absorption coefficient 𝛼𝑤 . Thus giving a good proximate, comparable value
to other products of the same type (EN ISO 354, 2003). Five cycles of tests are
Sustainable Knitted Noise Insulation 275

completed. The first measurement tests the reverberation time of the acoustic elements
placed on a wall, the second test cycle determines the reverberation time of the acoustic
elements applied with a 100 mm gap from the ceiling, the third determines the
reverberation time for a 300 mm gap application from the ceiling and the 4th test cycle
measures the reverberation time of the partition walls. The 5th measurement cycle
determines the reverberation time of the partition walls without the polyester fleece inlay.
The acquired data is then further used to determine the equivalent sound absorption
surface A, the sound absorption coefficient 𝛼𝑠 , 𝛼𝑝 , and the rated sound absorption
coefficient 𝛼𝑤 . To determine the equivalent sound absorption surface A of the measured
objects following equation (1) is used:

𝟓𝟓,𝟑 𝑽 𝟏 𝟏
𝑨𝑻 = 𝑨𝟐 − 𝑨𝟏 = ( − ) (1)
𝒄𝟎 𝑻𝟐 𝑻𝟏

The sound absorption coefficient is calculated based on the equation (2) depicted
below.

𝑨𝑻 𝟓𝟓,𝟑 𝑽 𝟏 𝟏
𝜶𝒔 = 𝑺
= (
𝒄𝟎 𝑺 𝑻𝟐
−𝑻 ) (2)
𝟏

The sound absorption coefficient 𝛼𝑝 and the rated sound absorption coefficient 𝛼𝑤
are ascertained according to DIN EN ISO 11654 (EN ISO 11654, 1997).

3. RESULTS

3.1. Flat Knitting Constructions for 3D Structured Surfaces

The swatches are examined focusing on structure and characteristic of the relief,
shape, size and compactness of the fabric. Important for selection as well: The general
aesthetic appearance and design potential of the patterns with regard to the application as
acoustic elements. The swatches’ knitted using a single thread and a fine gauge (CMS
340 TC KW E6.2, with all needles) are too light and delicate for the anticipated
application purpose. Whereas the swatches knitted on the CMS 302 TC (E8) using two
ends of yarn are more voluminous and denser. Similarly the quality of the 3D structure is
a lot better without appearing coarse. Likewise, the jacquard constructions with a relief
structure on the front gives a satisfactory result with the special characteristic that these
constructions generate especially compact and material-dense knits with high potential
for interior application. Figure 4 shows the tuck stitch swatch with a 3D knobbed surface.
The construction is presented in Figure 5.
276 Maureen Mann, Sonja Vater, Frank Heimlich et al.

Figure 4.1. Tuck-stitch pattern.

Figure 4.2. Tuck stitch detail.

Figure 4.3. Jack relief.


Sustainable Knitted Noise Insulation 277

Figure 5. Construction & Repeat 3D Racked Full Cardigan.

3.2. Finishing Tests

The fulling process applied in the tests is scalable. The best results in the course of
this project are achieved with a fulling time of 30 minutes. Moreover, pre-washing the
swatches scarcely influenced the fulling process and can therefore be forgone. Through
shrinkage the anticipated increase of volume and compactness of the knit fabric is
achieved with all swatches. It is noticeable that the shrinkage is unequally distributed
depending on shape and construction as shown by the before- and after measurements of
width and height in Table 1. This factor needs to be taken into consideration for a
potential production process and could require additional testing.

3.3. Evaluation of the Measurement Data

The evaluation of the conducted measurements confirms the products anticipated


sound-absorbing property. Especially for the middle and high frequency range the sound
absorption coefficients show the products efficiency.
278 Maureen Mann, Sonja Vater, Frank Heimlich et al.

Table 1. Finishing tests

Table 2. Sound absorption coefficients αs, measurements 1-5

Table 2.1. Sound absorption coefficients αs, measurements 1-5

Notable sound absorption can be detected from frequencies 125 Hz upward. As


shown by the determined sound absorption coefficients for the measurement of the wall
elements 𝛼𝑠1 depicted in the first column of tables 2 and 2.1. The product placement also
Sustainable Knitted Noise Insulation 279

plays an important role. The more of the surface is receptive to sound the more sound can
be absorbed. The efficiency of the sound absorption property is proportional to the
amount of sound-absorbing surface. Therefore, the products efficiency increases if not
directly placed against the wall. This is specifically notable for the lower range
frequencies. Furthermore, this also demonstrates the influence of the fabric covering the
frame and the fabric’s voluminous surface structure. This is particularly evident in the
data acquired from the measurement without the fleece inlay.
A further determination of the rated sound absorption coefficient shows the products
outstanding sound-absorbing property. For all three product types the rated sound
absorption coefficient determined is 𝛼𝑤 = 1.00. According to the classification system
given by DIN EN ISO 11654 all three products comply with the sound absorber class A.

3.4. Overview: Design and Technical Data of the Sound Absorber

The sound absorber wall elements are constructed with the following parameters and
materials :

3.4.1. Size
Height & Width: 100 cm x 100 cm
Depth with cover: 7 cm

3.4.2. Materials
100% Merino wool
100% Polyester fleece
100% Aluminium

3.4.3. Construction of the Absorbers


The substructure is made of a 50 mm aluminium frame filled with a 100%
polyester fleece. The knitted wool cover is equipped with a Velcro fastener.

3.4.4. Cover
3D racked tuck stitch pattern = Full Cardigan (every coarse)
with a colour gradient and full finish.

3.4.5. Recycling
All elements/materials can be separated and recycled.

3.4.6. Sound Absorption


The rated sound absorption coefficient is 𝛼𝑤 = 1.00 (DIN EN ISO 11654)
280 Maureen Mann, Sonja Vater, Frank Heimlich et al.

Figure 6. Schematic drawing showing the design, size, amount of sound absorbing surface and the
positioning on the wall.

Table 3. Sound absorption coefficients for wall elements determined during


the first measurement
Sustainable Knitted Noise Insulation 281

Figure 7. Sound absorption coefficient αs for wall elements determined during the first measurement.

Table 4. Absorption coefficients αp for wall elements as function of frequency


determined during the first measurement

DISCUSSION AND CONCLUSION

The resulting product prototypes meet all the desired outcomes. The 3D-structured
surface lets the product stand out visually and haptically giving it an innovative design
appeal while enhancing the sound absorption properties. Moreover, the product also
benefits from wool ´s other unique qualities like moisture absorption and odour
neutralising properties’ that support the regulation of the indoor climate and add to the
creation of an amiable environment. Also wool´s flame -retardant nature is crucial to a
282 Maureen Mann, Sonja Vater, Frank Heimlich et al.

product for indoor application. Not only do the products provide an energy -efficient and
aesthetic possibility for noise reduction and indoor climate regulation; at the end of the
products’ life cycle they can be fully mechanically dismantled and recycled as well.
Despite the aforementioned results, further advances need to be made to enhance
distribution in the interior market:

a) The reduction of costs by researching other, even coarser wool types.


b) The development of a product generator that helps with regard to individual
customer requirements and offers special colours and other 3D structures with
the same efficiency.
c) Improvement of processing times in knitting and finishing based on higher
production quantities.

Not only regarding reduction of material cost is the investigation of coarser wool
types amiable in addition more sustainable options can be explored e.g., by taking other
wool types which are not suitable for clothing because of too thick fibre diameters,
recycled wool or even waste wool into consideration. Waste wool could also be an
alternative for the polyester fleece inlay. Hence further testing would be needed to ensure
reproducibility especially regarding knitting and finishing of the surface material
concerning production. However a lager fibre diameter in this context would suggest
equal to improved product performance concerning sound absorption. In the light of
tackling larger production quantities all aspects of the applied processing method need to
be reviewed pertaining to keeping production cost at a minimum. Though all applied
methods are scalable various improvements can be implemented e.g., shortening
processing times for knitting and finishing as well as optimizing the assembly. As to
product market ing a product generator would not only help to assess the costumer’s
needs but moreover enhance the costumer journey. With the product generator predefined
options for colour, size and 3D structure can be presented to the customer which can be
then individually be mixed and matched by the costumer creating a unique product
tailored to the costumers’ requirements while ensuring efficiency and producibility.

ACKNOWLEDGMENTS

Special acknowledgments go to the supporters and enablers of this project. Especially


to the company Thamm GmbH for their great general support and providing the
substructures’ for the acoustic elements. As well as Suedwolle GmbH & Co.KG for the
material support and SG Bauakustik for supporting and enabling the measurements in the
reverberation chamber.
Sustainable Knitted Noise Insulation 283

APPENDIX

𝛼𝑠 sound absorption coefficient


𝛼𝑝 practical sound absorption coefficient
𝛼𝑤 rated sound absorption coefficient
A equivalent sound absorption surface
𝐴 𝑇 equivalent sound absorption surface of the test object, in square meters
𝐴1 equivalent sound absorption surface of the empty reverberation chamber, in square
meters
𝐴2 equivalent sound absorption surface of the reverberation chamber containing the test
object, in square meters
𝑉 volume of the empty reverberation chamber, in cubic meters
𝑇1 reverberation time of the empty reverberation chamber, in seconds
𝑇2 reverberation time of the reverberation chamber containing the test object, in seconds
𝑐0 velocity of sound in air, in meters per second
𝑆 area of the floor or wall covered by the test object

REFERENCES

Ballagh, K. O. (1996). Acoustical properties of wool. Applied Acoustics, 48(2), 101–120.


DIN 18041. (2004). Acoustical quality in small to medium-sized rooms.
EN ISO 11654. (1997). Acoustics – Sound absorbers for use in buildings – Rating of
sound absorption (ISO 11654: 1997) German version EN ISO 11654: 1997.
EN ISO 354. (2003). Acoustics — Measurement of sound absorption in a reverberation
room (ISO 354: 2003); German version EN ISO 354: 2003.
Fasold, W., Veres, E. (2003). Schallschutz + Raumakustik in der Praxis. Huss-Medien
GmbH Verlag Bauwesen, Berlin, 2nd edition.
Hearle, J. (2002). Physical properties of wool. Wool: Science and Technology, 80–129.
McNeil, S. (2014). Acoustic Advantages of Wool Carpeting. Technical Bulletin,
AgResearch, Christchurch, New Zealand.
Miao, M. (2005). Wool for acoustic absorption. In Proc. 11th Int. Wool Text Res. Conf.,
Leeds, UK.
Seddeq, H. S. (2009). Factors Influencing Acoustic Performance of Sound Absorptive
Materials. Australian Journal of Basic and Applied Sciences, 3(4), 4610–4617.
Simpson, W. S. (2002). Chemical Processes for Enhanced Appearance and Performance.
Wool: Science and Technology, 215–236.
284 Maureen Mann, Sonja Vater, Frank Heimlich et al.

VBG. (2012). Acoustics in the office, aids for the acoustic design of offices. VBG
expertise, BGI/GUV-I (34-5-2468–9).
Yanping Liu, & Hong Hu. (2010). Sound Absorption Behavior of Knitted Spacer Fabrics.
Textile Research Journal, 80(18), 1949–1957.
In: Textiles: Advances in Research and Applications ISBN: 978-1-53612-855-0
Editor: Boris Mahltig © 2018 Nova Science Publishers, Inc.

Chapter 14

AN ANALYSIS OF IMPACT BEHAVIOR OF WARP KNIT


SPACER FABRIC FOR THE EVALUATION OF
SUITABILITY IN PROTECTIVE APPLICATIONS

N. Gokarneshan*
Professor and Head Department of Textile Technology
Park College of Engineering and Technology, Coimbatore, Tamil Nadu, India

ABSTRACT

The article focuses on impact and compression behavior of warp knit spacer fabrics
to determine suitability in protective applications. The protective properties of the spacer
fabrics in protecting the human body against impact have been investigated. Testing has
been done on fabrics in hemispherical form so as to simulate the use of impact protectors
in real life. The impact behavior of spacer fabrics impacted at different levels of energy
has been analyzed taking into account the impact process, energy absorption and force
attenuation of the spacer fabric. The impact behavior of the fabric under impact in the
hemispherical form differs from that in planar form, and also the fabric curvature can
reduce energy absorption during the impact process and therefore reduce the attenuation
properties of the spacer fabric. The influences of structural parameters and lamination on
the impact force attenuation properties of warp knitted spacer fabrics designed for impact
protectors have been studied, and found that all the structural factors significantly affect
the impact force attenuation properties of the fabrics, and also the lamination of the
spacer fabrics can effectively improve the force attenuation performance. The effect of
structures of different warp knit spacer fabrics with regard to different surface structure s,
fabric thicknesses on the impact and compression-after-impact properties have been
studied. The results show that with the closed surface structure and coarser spacer yarns,
the fabrics have the characteristics of lower peak forces, higher energy-absorption ability,

*
Corresponding Author Email: advaitcbe@rediffmail.com.
286 N. Gokarneshan

lower damage depths, and higher drop-off rates of residual strength. Fabrics with higher
thickness are of the features above but they do have lower drop-off rates. A spacer fabric
with good protection performance was considered to have lower peak force, more
absorbed energy, lower damage depth, and a lower drop-off rate of residual strength. The
impact compressive behavior of warp-knitted spacer fabrics developed for human body
protections has been studied. It has been shown that the warp-knitted spacer fabrics can
be used as a type of effective material for human body protection due to their high energy
absorption capacity and reduction of the contact peak force. The finding also reveals that
all the structural parameters significantly affect the impact compressive behavior of the
warp-knitted spacer fabrics with respect to peak contact force, peak transmitted force, and
energy absorbed at different impact compressive stages. The results show that the warp-
knitted spacer fabrics considered can reduce the peak contact force to around 33%.

Keywords: impact, compression, protective, warp knit, spacer fabrics, structural


parameters, energy absorption, peak transmitted force

INTRODUCTION

The impact and compression behavior of warp knit spacer fabrics have been
thoroughly analyzed. An experimental investigation has been carried out on the
protective properties of warp-knitted spacer fabrics developed for protection of human
body from impact. The fabrics have been tested in a hemispherical form by using a drop
weight impact tester, so as to simulate the use of impact protectors in real life (Yanping et
al. 2014). The impact behavior of a typical spacer fabric impacted at different energy
levels, has been studied. The impact behavior of the fabric under impact in the
hemispherical form is different from that in the planar form. The curvature of the fabric
can reduce energy absorption during the impact process and hence decrease the force
attenuation properties of the spacer fabric. This study provides a better understanding of
the protective properties of spacer fabrics. The influences of structural parameters and
lamination on the impact force attenuation properties of warp-knitted spacer fabrics
developed for impact protectors has been studied (Yanping et al. 2014a). The effects of
fabric structural parameters, impact energy levels, and laminated layers on the protective
performance of the spacer fabrics were tested and analyzed based on the assessment of
the peak transmitted force. The results showed that all the structural parameters
significantly affect the impact force attenuation properties of the warp-knitted spacer
fabrics. It was also found that lamination of the spacer fabrics can effectively improve the
force attenuation performance. Three layers of the developed warp-knitted spacer fabrics
in a total thickness of about 2.5 cm can meet the requirement of the transmitted force
lower than 35 kN at an impact energy of 50 J based on European testing standards. The
effects of spacer fabric structures on the impact and compression after impact properties
have been studied (Xiaofang G et al. 2013). The study on impact compressive behavior of
warp knit spacer fabrics intended for human body protection has shown that that the
An Analysis of Impact Behavior of Warp Knit Spacer Fabric... 287

warp-knitted spacer fabrics can be used as a type of effective material for human body
protection due to their high energy absorption capacity and reduction of the contact peak
force (Yanping et al. 2013). Also, all the structural parameters significantly affect the
impact compressive behavior of the warp-knitted spacer fabrics in terms of peak contact
force, peak transmitted force, and energy absorbed at different impact compressive
stages.

HEMISHPERICAL IMPACT BEHAVIOR


ANALYSIS OF IMPACT BEHAVIOR

Since a number of years many types personnel protective equipment (PPE) has been
developed to protect wearers from different kinds of risks or hazards to their health and
safety (Viano et al. 2000; Rønning et al. 2001; Lemair et al. 2007; Bernhardt et al. 2008;
Parker et al. 2006; Van Schoor 2006; Laing et al. 2011). The generally used impact
protectors, PPE, are usually produced to include energy -absorbing material in the form
of pads, which are integrated or inserted into protective clothing or equipment specially
designed for protecting the human body from impact, blows or falls (Bellfy et al. 2009;
Dlugosch et al. 2012). There are many kinds of impact protectors commercially available
for protecting various areas of the body in different circumstances (Viano et al. 2000;
Rønning et al. 2001; Lemair et al. 2007; Bernhardt et al. 2008; Parker et al. 2006). A
series of standard tests have been evolved for assessment of the protective performance
of commercial impact protectors for different sporting applications so as to ensure
adequate protection is provided for the intended use. In these standards impact protection
is generally measured by the force transmitted during impact; a striker of specified shape,
size and weight drops freely onto the protector placed on a hemispherical anvil with the
required velocity and impact energy. The hemispherical anvils are of varied curvatures to
simulate the areas of the body to be protected. Among these standards the two European
Standards for motorcyclists impact protectors are those most commonly quoted for
evaluating protective performance, one for limbs and shoulders and the other for back
protection. Recently there has been great focus on the use of warp-knitted spacer fabrics
in clothing and equipment providing protection against impact because of their
combination of protection and comfort in use. The static and dynamic compression
behavior of a series of warp-knitted spacer fabrics has been studied and the energy
absorption performance and force attenuation capability of these fabrics under flatwise
static and impact compression has been analyzed in detail (Liu et al. 2012, Yanping et al.
2013). The investigations show that the fabrics mainly behave as cushioning materials,
involving three distinct phases in static and dynamic compression, explained as linear
elasticity, plateau and densification. But, to provide required combination of protection
288 N. Gokarneshan

and comfort, the protective material should conform to the shape and curvature of the
body part being protected. It is known that the impact properties of a protective material
of curved shape differ from those of a planar shape, because the boundary conditions
during loading change. The impact behavior of warp-knitted spacer fabrics of
hemispherical shape has been recently reported (Guo et al. 2013). However the
relationship between energy absorption capacity and force attenuation properties has been
overlooked, which is crucial in designing fabrics to meet protective requirements. The
evaluation of the protective properties of warp-knitted spacer fabrics obtained from
impact tests has been conducted strictly in accordance with European Standard in
hemispherical form, so as to simulate the realistic requirements of human body
protection. In the first step focuses on the analysis of the impact behavior of a typical
spacer fabric in order to understand the impact process, energy absorption and force
attenuation mechanism of the spacer fabric. The second step focuses on the influence of
structural parameters and lamination on the impact protective performance of the fabrics.
Such an investigation could provide a deeper understanding of the impact properties of
warp-knitted spacer fabrics for protection of the human body.
A warp-knitted spacer fabric has been developed for human body protection against
impact and tested in the hemispherical form at various levels of impact energy, and the
impact resistance, energy absorption and force attenuation properties have been studied.
The spacer fabric has been analyzed for its different deformation and damage modes
using special techniques. The impact response of the spacer fabric is based on the
boundary condition. The plateau stage of the spacer fabric under impact in the
hemispherical form is not clearly observed due to the change of the contact area of the
fabric during the impact process and different deformation stages of spacer yarns under
similar displacement of the striker. The level of impact energy influences the energy
absorbed by the fabric. The impact energy can be absorbed completely by the elastic and
elastoplastic deformations of the fabric, when the impact energy is lower than the energy
absorption capacity of the fabric. But, fabric damage occurs, as the impact energy
exceeds the energy absorbed by the elastic and elastoplastic deformation of the fabrics,
and increases with the increase of impact energy. The energy absorption capacity of the
fabric reduces under impact in the hemispherical form. The energy absorption capability
is reduced by high curvature of the spacer fabric and thus also its force attenuation
properties. The energy absorption capacity and the applied impact kinetic energy of
spacer fabric determine its peak contact force. These determine the densified level of the
spacer fabric under impact. High densification results in high contact stiffness, and hence
a high peak contact force. High densification also causes the stress wave to transmit
easily and produce a high peak in the transmitted force. Some extent of destruction is
beneficial to dissipate energy through reduction of the densification and thereby reducing
the peak transmitted force. By the use of Hilbert–Huang transform technique, the
deformation and damage modes of the fabric under different levels of impact energy can
An Analysis of Impact Behavior of Warp Knit Spacer Fabric... 289

be identified by means of the frequency domain analysis. The higher the impact energy,
the higher the frequency range distributed in the marginal spectra.

TECHNICAL ASPECTS

The warp-knitted spacer fabric used in the analysis of impact behavior, has been
knitted with polyester multifilament yarn. A polyester monofilament yarn has been used
as a spacer yarn to connect the two outer layers of fabric. The impact tests were
conducted on a drop-weight impact tester (Yanping et al. 2014). A striker is released and
drops down a vertically guided path onto the sample located on the anvil. In order to
obtain more information during the impact process, the acceleration of the striker was
measured by means of accelerometers glued or screwed to it. The acceleration readings
obtained were used for deriving the displacement of the striker (or the compression depth
of the fabric) and the contact forces between striker and fabric. Three accelerometers
were used.

IMPACT PROCESS ANALYSIS

Figure 1(a) and (b) show typical acceleration and transmitted force signals for
various levels of impact energy. During the initial stage the acceleration gives a lower
value over a relatively longer time, and then rapidly rises to a peak in the second stage. A
higher peak acceleration response is achieved at greater energy impact in a shorter
duration. A shorter impact time will lead to a higher acceleration and a higher reactive
force. As the fabric in its densified condition has greater compression resistance it is able
to stop the striker more quickly, and at the peak point the increase in impact energy will
thus lead to a decrease in impact time and an increase in acceleration (Yanping et al.
2014). When the impact occurs, the force is transmitted to the anvil through the deformed
fabric and hence the transmitted force curves are similar to the acceleration curves. A
greater degree of impact energy will lead to a higher peak transmitted force in a shorter
time, for a similar reason. There are two clear stages noticed in the contact force similar
to the acceleration and transmitted force signals, of which the first increases very slowly
and the second increases rapidly. The slowly increasing stage of the curves is generally
located in the displacement range below 5.5 mm, corresponding to a compression strain
of 73%. Further, the contact force increases rapidly with the increase in displacement.
Since the dropping height of the striker controls the impact energy, the change in impact
energy indicates a change in initial contact velocity or strain rate. The impact properties
290 N. Gokarneshan

of the spacer fabric are also sensitive to strain rate, since it is made up of polyester fibers
with strain rate sensitivity.

Figure 1. Impact signals during various energy levels. (a) Acceleration, and (b) Transmitted force.

The fabric can be more quickly be compressed into its densification stage and with a
larger displacement by a striker of higher kinetic energy. This is one of the reasons why
the fabric has a higher peak contact force when it is impacted at higher kinetic energy. It
is interesting to compare the impact behavior of the same fabric impacted in different
shapes. Earlier investigation reveals that the force–displacement curve of the fabric under
flat wise impact comprises of three main stages, linear elasticity, plateau and
An Analysis of Impact Behavior of Warp Knit Spacer Fabric... 291

densification (Yanping et al. 2013). But, there are only two stages seen in the impact
contact force–displacement curves of the spacer fabric in the hemispherical form, as
mentioned above, and under hemispherical impact, plateau stage is not noticed. The
varied boundary conditions of the spacer fabric in planar and hemispherical shapes gives
rise to this difference originates. One reason is that, under flatwise impact, the contact
area between the striker face and the fabric surface remains constant throughout the entire
impact process. However, during impact process the contact area for the fabric in the
hemispherical form is changed and increases with the displacement of the striker.
With the increase in the displacement of striker, the contact area of the fabric with the
striker rapidly increases. The contact force changes as the contact area increases. Hence,
in the case of a hemispherical shaped impact, the plateau stage of the contact force–
displacement curves obtained under the flatwise impact condition is not possible. Under
impact of the fabric in hemispherical form and under flatwise impact the spacer
monofilaments within the fabric deform in various ways, which also attributes for no
plateau stage that is seen. Under flatwise impact all the spacer monofilaments
simultaneously withdraw the impact load and are subjected to the same deformation. On
the other hand, in the hemispherical form the spacer monofilaments at different positions
experience different deformations. Under the impact of the fabric in the hemispherical
form, the linear elasticity, plateau and densification of the spacer monofilaments within
the fabric can all be seen at the same time, when the displacement of the striker is larger
than the densification displacement of the fabric obtained under flatwise impact. It can be
seen that the closer the position of a spacer monofilament to the central axis of the anvil,
the greater the deformation it experiences. As the displacement of the striker increases,
all the deformations on the contact surface also increase. The plateau stage is not seen in
the contact force–displacement curves of the fabric under impact in the hemispherical
form, as the spacer monofilaments within the fabric can deform differently.

ENERGY ABSORPTION AND FORCE ATTENUATION PROPERTIES

In a spacer fabric of hemispherical shape, the impact process is of a complex nature.


The kinetic energy of the impacting striker transforms into various forms of energy as
follows:

a) Energy absorbed by the deformation and damage to the fabric


b) Energy absorbed by the deformation of the testing system (striker, anvil and
supporting mechanism), and
c) Energy lost due to the propagation of stress wave.
292 N. Gokarneshan

The total kinetic energy of the striker at the point of maximal deflection and
acceleration, gets completely transformed into deformation energy and the dissipated
energy, which include the energy stored by the elastic deformation of the fabric and the
testing system, the energy dissipated by the plastic and damage to the fabric and the
testing system, and the energy dissipated by the propagation of the stress wave (Yanping
et al. 2014). The striker rebounds beyond this point due to the transfer of stored energy to
the kinetic energy of the striker. As the impact energy increases, the absorbed energy also
increases. The fabric absorbs more energy owing to its greater deformation, as impact by
the striker at a greater kinetic energy level can lead to a greater final displacement of the
fabric. The elastic and elastoplastic deformation of the fabric absorbs nearly full kinetic
energy of the striker without generation of heat, as the impact energy is below 10 J.
However, when the impact energy is greater than 10 J, the kinetic energy of the striker
cannot be totally absorbed by the elastic and elastoplastic deformation of the fabric,
although the energy absorbed by such deformations of the fabric increases as the impact
energy increases. In this case, the kinetic energy of the striker not absorbed by elastic and
elastoplastic deformation of the fabric is transferred to the residual energy. The residual
energy of the striker also increases as the impact energy increases. Filament damage
occurs as the purely elastic and elastoplastic deformations of the fabric cannot totally
absorb the higher kinetic energy of the striker. It should be noted that while one part of
the residual energy is transformed into heat, the other part together with elastic and the
elastic deformation energy of elastoplastic makes the striker rebound.
The deformation and damage of the fabric after impact at different levels of impact
energy can be categorized as follows –

a) At lower impact energies severe plastic deformation of the monofilaments occurs


(5 J and 10 J), wherein the monofilaments become kinked, distorted or squashed.
b) Some breakage of the monofilaments is also observed at 10 J impact energy. But,
in the outer fabric layers no obvious deformation of the multifilaments is seen.
c) At higher impact energies (20J), some breakage of the multifilaments occurs in
the outer layers, besides plastic deformation and breakage of the monofilaments.
d) At even higher impact energies (30 J), a hole in the outer upper layer of the fabric
is produced by the impact, and simultaneously a number of mono- and
multifilaments are broken. At still higher impact energy (40 J), the heat generated
both mono- and multifilaments are broken and become fused together.
e) When the impact energy reaches 50 J, mono- and multifilaments are broken and
become a rigid plastic through a thermoplastic process.

The above analysis shows that the fabric is deformed and damaged in different modes
when subject to different impact energies. The impact energy is totally absorbed by the
fabric when the energy absorption capacity of the fabric due to elastic and elastoplastic
An Analysis of Impact Behavior of Warp Knit Spacer Fabric... 293

deformations is higher than the kinetic energy of the striker. Whereas, damage occurs in
fabric when the impact energy is higher than the energy absorption capacity due to the
elastic and elastoplastic deformations, as it absorbs the remainder of the kinetic energy of
the striker. A highly densified fabric has a high modulus and hence a high contact
stiffness. Hence, the kinetic energy of the striker is preferably absorbed before the fabric
is compressed to its high densification stage. As pointed out earlier, there is a longer
plateau stage for the contact force under flatwise impact, the response of which permits
the fabric to absorb a large amount of kinetic energy at a lower constant contact force by
elastoplastic deformation. Thus, under flatwise impact, the spacer fabric possesses
superior force attenuation performance. The contact force curves have a monotonal
increasing trend with the displacement under impact in the hemispherical form, as the
spacer monofilaments within the spacer fabric in the hemispherical shape cannot
effectively resist the impact load. The energy absorbed by spacer fabric increases non-
linearly with the contact force. In order to absorb more kinetic energy, the spacer fabric
must be compressed with a larger displacement into a highly densified stage, which
results in higher contact stiffness, a larger contact area, and a bigger peak contact force
between the striker face and the fabric surface. Compared with the impact in the planar
shape, the lower efficiency of force attenuation of the spacer fabric in the hemispherical
shape is due to the fact that not all of the spacer monofilaments are able to contribute to
the resistance to impact loading.
The contact force gets transmitted to the anvil through the deformed specimen in the
form of stress waves, during impact. As the impact energy increases, the peak contact
force and peak transmitted force increase nonlinearly. Also, the peak transmitted force
remains below the peak contact force for all impacts. But, the ratio between them is not
constant when the impact energy changes. This difference may arise from their different
modes of deformation and damage, which can affect the stress wave propagation and
damping behavior of the fabric. A single layer of this particular fabric is inadequate to
offer necessary protection if the motor cycle impacts is severe. The fabric structure has to
be optimized in this case, and lamination used to enable the protective performance of
spacer fabrics to give the protection necessary.

FREQUENCY DOMAIN ANALYSIS

In order to provide a deeper understanding of the impact behavior of the fabric in the
hemispherical shape, a frequency domain analysis was carried out using the Hilbert–
Huang transform (HHT), fast Fourier transform (FFT ), wavelet transform, etc
(Walker1996; Diniz et al. 2010; Huang et al. 1996; Huang et al. 1998; Huang et al. 1999).
HHT has been used to perform the frequency domain analysis of the transmitted force
signals and establish the frequency features that correspond to the deformation and
294 N. Gokarneshan

damage modes of the fabric. Different deformation and damage modes occur under
different levels of impact energy. Also, the frequency distribution varies with time, which
indicates that the deformation mode changes during the impact process. The marginal
spectra are always used to identify the deformation and damage modes (Yu et al. 2005).
The frequency distributions can be divided into a number of ranges, each of which
corresponds to a certain deformation or damage mode. The plastic deformation of
monofilaments has specific frequency ranges. It is possible to determine the related
deformation and damage modes, after measuring the frequency ranges. A relationship
between the frequency ranges and the deformation and damage modes can be established.
The higher the impact energy, the higher is the range of the frequency distributed in the
marginal frequency spectra. The greater transmitted forces are related to the higher
frequency ranges, and correspond to severe damage to the fabric. The deformation and
damage modes in the spacer fabric can be identified from the frequency domain analysis.
By knowing the frequency ranges, the protective performance of the warp knit spacer
fabric can be evaluated.

INFLUENCE OF STRUCTURAL FACTORS OVERVIEW

The transmitted forces of warp-knitted spacer fabrics particularly designed for


protective application have been measured. The influence of various structural factors
including spacer monofilament inclination and fineness, fabric thickness, and outer layer
structure as well as fabric lamination on the peak transmitted forces have been evaluated
(Yanping et al. 2014a). The protective performance of a spacer fabric is significantly
influenced by its structural parameters. A higher force attenuation capacity is seen in the
spacer fabric knitted with higher inclination and coarser spacer monofilaments, a bigger
fabric thickness, and a more stable outer layer structure, if its destruction modes under
different levels of impact energies are not different from other fabrics tested. The
influence of spacer monofilament inclination and outer layer fabric structure on the force
attenuation properties of the spacer fabrics can be changed by the boundary condition in
the hemispherical shape. The force attenuation properties of spacer fabrics can be
significantly improved by laminating them.

RELATED ASPECTS

In order to protect the human body from impact strokes, blows, or falls, impact
protectors which are a type of energy -absorbing material, are integrated or inserted into
protective clothing or equipment (Laing et al. 2011). Different types of impact protectors
An Analysis of Impact Behavior of Warp Knit Spacer Fabric... 295

have been designed and used to protect various zones of human body like shoulders,
elbows, hips, knees, and tibias from impact injuries in intense sports, like motorcycling,
cycling, horse riding, skiing, skating, rugby, and hockey (Yu et al. 2005; Laing et al.
2011; Schmitt et al. 2010; Melissa et al. 2010). Impact protectors due to their wide
applications have resulted in an increasing market demand. Polymeric foams, rubbers,
gels, and plastics are the commonly used materials for assembling impact protectors. But
such materials have a serious setback, since they exhibit poor comfort properties. As
these materials have lower air permeability and moisture transmission ability, they cannot
satisfy the comfort requirement of most protective clothing used in sports and other
extreme activities, involving generation of sweat. Another constraint is that the protectors
made of these materials are too heavy and have low flexibility. Hence such materials are
generally laminated in two or three layers by means of binding or gluing so as to obtain a
better balance of protection and flexibility. On the contrary, the shock -absorbing ability
of impact protectors is good. Owing to their poor wearing comfort, the impact protectors
available in market are not favoured by customers.
The warp knitted spacer fabric is highly suited for impact protection, due to
combination of good out-of-plane flexibility, excellent compressibility, high moisture
conductivity, and good thermoregulation capability. The earlier investigations have
proved that warp-knitted spacer fabrics can be an ideal class of energy absorbers for
cushioning applications and their energy-absorbing capacity can be tailored to meet
specific end-use requirements by varying their structural parameters (Liu et al. 2012).
But, a systematic experimental study on the protective performance of warp-knitted
spacer fabrics used as impact protectors in curved shapes for human body protection
needs to be researched. It is thus necessary to understand how the structural parameters
and lamination of spacer fabrics in curved shapes affect their impact force attenuation
properties. The impact behavior of a warp-knitted spacer fabric with a typical structure
has been elaborately investigated, and has revealed that the force attenuation of the spacer
fabric is determined by its energy absorption ability and the relevant destruction modes
under different kinetic energies, including plastic deformation, filament breakages, and
thermoplastic transformation. According to the frequency domain analysis, these
destruction modes correspond to the specific frequency bands. The study also indicated
that the spacer fabric in the hemispherical shape has a lower efficiency in force
attenuation than that in the planar shape because the spacer monofilaments of the fabric
in the hemispherical shape do not effectively resist the impact loading. Also, a single
layer of the spacer fabric cannot offer sufficient protection as per prescribed standard for
limb protection. While the initial study focused on the energy absorption and force
attenuation properties of a typical spacer fabric in a single layer, a further study on the
effects of structural parameters and lamination of spacer fabrics is the main objective of
discussion. The analysis can provide useful information in the optimized structural design
of warp-knitted spacer fabrics for human body protection against impact in curved forms.
296 N. Gokarneshan

TECHNICAL DETAILS

Twelve warp-knitted spacer fabrics with various fabric thicknesses, outer layer
structures, spacer monofilament diameters, and inclinations have been used for analyzing
the effects of structural parameters on their impact behavior, and knitted on a high speed
double-needle bar Raschel warp knitting machine. Polyester multifilaments have been
used to create the binding of the structure in the knitting process between the top outer
layer and the bottom outer layer. Polyester monofilaments have been used as spacer yarns
to connect the two outer layers together. Four different structures, i.e., locknit, chain plus
inlay, small-size rhombic mesh, and large-size hexagonal mesh have been used for
knitting the outer layers (Yanping et al. 2014a). Three different spacer monofilament
inclinations corresponding to underlapping one, two, or three needles between the front-
and back-needle bars have been used for linking the two outer layers together,
respectively. The spacer fabrics laminated in single, double, and triple layers have been
tested with various levels of kinetic energies ranging between 5 - 50 J, following the
method indicated by the European Standard for “Motorcyclists’ protective clothing
against mechanical impact- requirements and test methods for impact protectors.”

INFLUENCE OF THE SPACER MONOFILAMENT INCLINATION

A group of three fabrics having the same outer layer structure and the same spacer
monofilament yarn but with different spacer monofilament inclinations is used to analyze
the effect of the spacer inclination on the impact force attenuation properties of warp-
knitted spacer fabrics. The fabric thickness and stitch density of the outer layers are
maintained almost the same. With the increase in spacer monofilament inclination, the
duration from the beginning point where the striker contacts the fabric upper surface to
the peak point where the transmitted force reaches the maximal value increases, and also
the peak transmitted force decreases. It implies that the spacer fabric having greater
spacer monofilament inclination and a longer spacer monofilament length more
effectively resists the impact due to a lower peak transmitted force. It differs from the
flatwise impact test result discussed previously, which has shown that the fabric with
moderate inclination spacer monofilaments (two needles underlapped) has the lowest
peak transmitted force (Yanping et al. 2014). According to the theory of elastic stability,
a longer elastic rod which is less oriented to the direction of the compression has a lower
critical load. Hence, the fabric having moderate inclination spacer monofilaments
exhibits the best compression resistance to the flatwise impact, which makes it absorb
more impact energy at the plateau stage. The peak transmitted force is thus the lowest.
But, under impact in the hemispherical shape, the situation gets complex. The upper outer
An Analysis of Impact Behavior of Warp Knit Spacer Fabric... 297

layer of a planar spacer fabric will be extended and the bottom layer will be contracted,
when it is placed on the hemispherical surface of the anvil. This special boundary
condition renders the spacer monofilaments to shear more easily than to buckle under
impact. Under such situation, the stability of the spacer monofilaments becomes a critical
point for the spacer fabric to resist the impact, since the shear movements will reduce the
compression resistance of the spacer yarns to the impact load, and results in a high peak
transmitted force. Since the fabric with higher inclination spacer monofilaments has a
higher shear resistance, it will have a lower peak transmitted force. Hence, among the
fabrics considered, their force attenuation performance increases as the length and
inclination of spacer yarns increase under impact in the hemispherical shape. In the case
of other levels of impact energies and laminated layers the similar trend is achieved,
wherein the peak transmitted force reduces as the spacer monofilament inclination
increases. But with the increase in number of fabric layers, the values of the peak
transmitted force get considerably decreased. The effect is not evident in a single layer,
eventhough the peak transmitted force reduces with the increase of the spacer
monofilament inclination. But, the influence of spacer monofilament inclination becomes
very significant with increase of the fabric layers, since a single layer of the spacer
fabrics is not strong enough to resist the impact with a high kinetic energy and is easier to
be compressed into a high densification stage. Fabrics have been compressed into their
high densification stages in a single layer, in which the striker compressed the
monofilament material rather than making the spacer monofilaments buckle. The
transmitted force depends on the contact stiffness of the compressed yarn material. As all
the fabrics are of polyester monofilaments, the difference in peak transmitted force
among fabrics is not significant. But, with the increase in the fabric layers, the energy
absorption of the laminated fabrics increases and hence will not be compressed into a
high densification stage. In this case, the post-buckling of spacer monofilaments plays the
key role in resisting the impact loading and the spacer monofilament inclination effect
works. Hence, in the case of flatwise impact, a high difference in the value of the peak
transmitted force is seen for the flatwise impact, and the fabric with too vertical spacer
yarns becomes less stable and shear can easily occur between the two outer layers.
Whereas, for spacer monofilaments that are much inclined in a fabric have a longer
length, and are less oriented to the direction of impact compression. The best
compression resistance to the flatwise impact occurs in the fabric with moderate
inclination of spacer monofilaments, which makes it absorb more impact energy at the
plateau stage. Thus, the peak transmitted force is the lowest. But, the situation gets
complex under impact in the hemispherical shape. When a planar spacer fabric is placed
on the hemispherical surface of the anvil, its upper outer layer will be extended and the
bottom layer will be contracted. Such a boundary condition renders the spacer
monofilaments easier to shear rather than to buckle under impact. Here, the stability of
the spacer monofilaments is important for the spacer fabric to resist the impact, since the
298 N. Gokarneshan

shear movements will reduce the compression resistance of the spacer yarns to the impact
load, resulting in a high peak transmitted force. As the fabric having greater inclination
spacer monofilaments exhibits a higher shear resistance, it will have a lower peak
transmitted force. Hence, under impact in the hemispherical shape, the force attenuation
performance of the spacer fabrics increases as the length and inclination of spacer yarns
increase, among the tested fabrics. There is similar trend at other levels of impact
energies and laminated layers, in which the peak transmitted force decreases as the spacer
monofilament inclination increases. But, with the increase in the number of fabric layers,
the values of the peak transmitted force decrease drastically. In a single layer, although
the peak transmitted force decreases with the increase of the spacer monofilament
inclination, the effect is not evident. However, by increasing the fabric layers, the effect
of the spacer monofilament inclination becomes very significant. It is due to a single
layer of the spacer fabrics which is not strong enough to resist the impact with a high
kinetic energy and is easier to be compressed into a high densification stage. All three
fabrics have been compressed into their high densification stages in a single layer. In
these cases, the striker compressed the monofilament material rather than making the
spacer monofilaments buckle. The contact stiffness of the compressed yarn material
depends on the transmitted force. There is no significance among the tested fabrics, as all
the fabrics have been made of polyester monofilaments. But, the energy absorption of the
laminated fabrics increases with the increase in fabric layers, and hence they will not be
compressed into a high densification stage. In this case, the post-buckling of spacer
monofilaments plays the key role in resisting the impact loading and the spacer
monofilament inclination effect works. Therefore, a high difference in the value of the
peak transmitted force can be observed for the specimens with more layers. Also, better
impact force attenuation of spacer fabrics can be achieved when the impact energy is at a
lower level by increasing the fabric layers. As an example, adding one layer of the fabric
can nearly reduce the peak transmitted force by half under impacts with the kinetic
energies of 5 J and 10 J.

INFLUENCE OF THE SPACER MONOFILAMENT FINENESS

In order to investigate the influence of the spacer monofilament fineness on the


impact force attenuation properties of warp-knitted spacer fabrics, two fabrics having
similar spacer monofilament inclination (underlapping three needles) and the same outer
layer structure (chain plus inlay) but with two different spacer monofilament diameters
(0.2 and 0.16 mm) have been selected. Almost the same thickness and outer layer stitch
density have been maintained for the two fabrics. In order to analyze the influence of the
spacer monofilament fineness with the same impact energy, the transmitted force–time
curves of these two fabrics in a single layer under impact at a kinetic energy of 5 J have
An Analysis of Impact Behavior of Warp Knit Spacer Fabric... 299

been used. The spacer fabric having coarser spacer monofilament exhibits a lower peak
transmitted force and a longer time to the peak point and, hence, shows a better impact
force attenuation property (Liu et al. 2010). Even though the boundary condition is
changed to the hemispherical form, this result is consistent with that obtained from the
flatwise impact test. This is normal because the fabric with coarser spacer monofilaments
has higher compression resistance which can decelerate the striker more quickly and
make the striker experience a longer time to reach the peak transmitted force point than
the fabric with finer spacer monofilaments. Since the duration of deceleration is essential
to the impact protection, the impact process should be as long as possible to absorb more
energy in order to reduce the peak transmitted force. This result is also valid for other
impact energy levels and fabric laminated layers. The force attenuation properties of
spacer fabrics in the hemispherical shape can be improved considerably by increasing the
spacer monofilament diameter, just as with the flatwise impact. By increasing the spacer
monofilament diameter, the fabric stiffness increases and thereby reduces the comfort
property, even though increasing the spacer monofilament diameter can considerably
improve the force attenuation capacity of the spacer fabric in the hemispherical shape. By
the choice of an appropriate spacer monofilament fineness for particular protective
application, the balance between the comfort and protective performance can be
achieved.

INFLUENCE OF THE FABRIC THICKNESS

The influence of the fabric thickness on the impact force attenuation properties of
warp-knitted spacer fabrics in the hemispherical form has been evaluated by a group of
four fabrics produced with the same spacer monofilament diameter (0.20 mm), the same
spacer monofilament inclination (underlapping two needles), and the same outer layer
structure (chain plus inlay) but with different thicknesses. The peak transmitted force is
found to reduce and the duration from the starting point to the peak transmitted force
point increases with the increase in thickness of the fabric (Yanping et al. 2014). The
phenomenon is described as follows. For a larger displacement it needs more time to
compress a thicker fabric to its densification stage. As the increase of the compression
time and displacement permits a thicker fabric to absorb more impact energy, a lower
peak transmitted force can be obtained for a thicker fabric. On the other hand, with the
increasing displacement of the striker the contact area of the fabric with the striker
rapidly increases. A thicker fabric can be compressed into a larger displacement and
therefore more spacer monofilaments are involved in resisting impact loading. Therefore,
the thicker fabric has a lower peak transmitted force under impact in the hemispherical
shape. Same trend can be seen, wherein the peak transmitted force reduces with the
300 N. Gokarneshan

increase of fabric thickness. It is also obtained for other impact energy levels and
laminated layers when all the fabric samples have the same destruction modes under
impact. However, two exceptions are found for a single layer of the fabrics under impact
with 20 J and double layers of the fabrics under impact with 50 J. In these two special
cases, the thickest fabrics do not have the lowest peak transmitted forces due to the
different destruction modes compared with other fabric samples. Under impact at a
kinetic energy of 20 J, the obvious damage of multifilaments in the top outer layers of
fabrics in single layer can be observed, but no obvious damage can be observed in the
thickest layer fabric. In the case of double layers of the fabrics under impact with 50J,
similar phenomenon is achieved. The peak transmitted force of a thicker fabric can be
higher than that of the thiner one, as thicker fabric cannot absorb additional impact
energy due to the damage of the fabric structure in these two cases. The analysis
discussed herein shows that the fabric thickness needs to be properly chosen based on the
destruction modes when a spacer fabric will be subjected to impact with higher levels of
kinetic energies during use.

INFLUENCE OF THE OUTER LAYER STRUCTURE

The outer layer structures are found to have an obvious effect. The greatest peak
transmited force is seen in fabric knitted with large-size hexagonal meshes for both outer
layers and the shortest duration from the starting is also obtained for other levels of
impact energies and laminated layers. Such differences mainly arise from various
geometric features of outer layer structures that result from various geometric
arrangements of multifilaments and different inclinations and binding conditions of
spacer monofilaments. Owing to highly buckled and inclined spacer monofilaments, the
fabric knitted with large-size meshes shows the poorest impact protective performance, as
highlighted in flatwise impact. The best impact protection ability is shown by the fabric
knitted with small-size meshes because of tight binding conditions (4). Because of the
combined effect s of loose binding structures and lowly buckled and inclined spacer
monofilaments the fabrics knitted with a close structure have moderate impact protection
performance because of under impact in the hemispherical shape. Besides the factors
stated herein, the deformation of the outer layer structures to fit the shape of the anvil
also significantly affects the impact force attenuation properties of the fabrics (Yanping et
al. 2014). A close structure is certainly more stable and stiffer than an open or mesh
structure. In the case of the close structures, the chain plus inlay structure is more stable
out-of-plane than the locknit structure, since the chain loops and the inlay yarns are
crossed in a perpendicular manner which are more difficult to extend and shear than the
locknit stitches. When placed onto the hemispherical surface of the anvil, a fabric with a
An Analysis of Impact Behavior of Warp Knit Spacer Fabric... 301

more stable outer layer structure can be less extended and sheared than a fabric with a
less stable outer layer structure. Therefore, the number of spacer monofilaments which
can resist the impact cannot be significantly reduced due to a lower deformation of the
stable outer layer structure. Whereas, the stable outer layers render the fabric stiffer,
which enables to disperse the stress wave to a larger area and absorb more energy. Hence,
the best force attenuation performance can be seen in the fabric knitted with the most
stable outer layer structure (chain plus inlay). The knitted fabric having large-size
hexagonal meshes exhibit the poorest impact force attenuation due to combined effects of
low stable outer layer structure and highly buckled and inclined spacer monofilaments.
The discussion indicates that the effects of outer layer structure on the force attenuation
properties under impact in the planar form differ from that of hemispherical forms. The
comfort and formability of fabrics stand in contradiction to the impact force attenuation
properties. The fabric knitted with a stable and stiff outer layer structure has better force
attenuation ability than the fabric with a flexible structure. However, the stiff outer layer
structure makes the fabric uncomfortable and difficult to fit a curved shape. Hence, more
studies are needed to det