Journal of Cleaner Production 161 (2017) 105e126

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Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

Review

A review of progress in the ecological application of ionic liquids in

textile processes
Nizar Meksi a, b, *, Ali Moussa b, c
a
University of Monastir, Faculty of Sciences of Monastir, Research Unity of Applied Chemistry and Environment, 5019, Monastir, Tunisia
b
University of Monastir, National Engineering School of Monastir, Department of Textile Engineering, 5019, Monastir, Tunisia
c
University of Monastir, Textile Engineering Laboratory, Higher Institute of Technological Studies of Ksar Hellal, 5070, Ksar Hellal, Tunisia

a r t i c l e i n f o a b s t r a c t

Article history: Currently, problems related to environmental compliance are meeting growing echo in public opinion.
Received 1 March 2017 This increase in awareness forces manufacturing companies to incorporate the concept of sustainable
Received in revised form development into their processes. The textile industry, in turn, attempts to reduce its environmental
1 May 2017
impact by creating, designing and developing innovative industrial processes, more concerned with
Accepted 2 May 2017
Available online 16 May 2017
ecology, but still ensuring high yields and adapting quickly to fashion trends. In this context, one of the
leading textile engineering research axes concerns the substitution of various textile wet processes often
^ as de
Handling Editor: Cecilia Maria Villas Bo expensive in terms of energy, water, chemicals and auxiliaries consumptions, degradation of textile
Almeida materials and/or wastewater treatment by new cleaner processes using green solvents. One of the
various strategies envisaged is the application of ionic liquids. Recently, it has been proved that these
Keywords: emergent solvents could be successfully used in some important textile processes. This led not only to
Ionic liquids eliminate certain ecological and technical drawbacks of some textile wet processes, but also to create
Green solvents innovative textiles with valuable properties. The aim of this paper is to provide a comprehensive over-
Functionalising agents
view of ionic liquids with particular emphasis on their ecological and industrial potentials. The state of
Auxiliaries
the art of the main researches applied in textile processes using these green solvents was then assessed
Cleaner textile processes
Literature review and discussed.
© 2017 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
2. Overview of ionic liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
2.1. Basic structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
2.2. Technical and ecological performances of ionic liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
2.2.1. Negligible vapour pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
2.2.2. Good thermal properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
2.2.3. Broad liquid range . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
2.2.4. Wide range of solubility and miscibility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
2.2.5. Credential properties for chemical reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
2.2.6. Modular properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
2.2.7. Good recycling properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
2.3. Limitations of ionic liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
2.3.1. High cost . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
2.3.2. High viscosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
2.3.3. Toxicity and biodegradability issues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
2.3.4. Lack of scientific data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108

* Corresponding author. University of Monastir, Faculty of Sciences of Monastir,

Research Unity of Applied Chemistry and Environment, 5019, Monastir, Tunisia.
E-mail address: nizar_meksi@yahoo.fr (N. Meksi).

http://dx.doi.org/10.1016/j.jclepro.2017.05.066
0959-6526/© 2017 Elsevier Ltd. All rights reserved.
106 N. Meksi, A. Moussa / Journal of Cleaner Production 161 (2017) 105e126

3. Methodology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
4. Recent advancements of ionic liquids application in textile processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
4.1. Textile spinning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
4.1.1. Spinning and applications of modified and non modified cellulosic fibres . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
4.1.2. Spinning and applications of non cellulosic fibres . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
4.1.3. Spinning and applications of textile nanofibres . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
4.2. Textile preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
4.3. Textile colouration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
4.4. Textile finishing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
4.5. Textile wastewater treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
4.6. Removal of acid dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
4.6.1. Removal of basic dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
4.6.2. Removal of reactive dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
4.6.3. Removal of other textile dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
5. Concluding remarks and future prospect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124

1. Introduction 2007) as well as gas/liquid and liquid/liquid separation processes

(Selvan et al., 2000; Freemantle, 2003).
In order to develop a textile industry more respectful of the Despite their potential, the use of ionic liquids in textile industry
environment, commonly called “green textile” or “ecologic textile”, remains timid and extremely limited. This may be explained firstly
an increasing interest is observed in recent decades for the appli- by the cost of ionic liquids which is too high for large-scale appli-
cation of new alternative technological fluids to water, traditionally cations. The second reason is probably related to the lack of suffi-
used as a medium in textile processing. This approach offers a cient scientific information about most of these solvents. Ionic
number of advantages when compared to the current water pro- liquids are a novel class of technological fluids which imperatively
cesses which require a great volume of water, more chemicals, requires numerous fundamentally research studies before under-
auxiliaries, etc. and need additional stages of textile drying as well taken in depth applied researches.
as wastewater treatment (Xu et al., 2016). Among the most studied The aim of this paper is to give an in-depth idea about ionic
solvents, it can be cited: liquid ammonia (Greenwood, 1987; liquids, particularly their structures, properties, ecological and in-
Grandjean and Karelle, 2000) and the supercritical carbon diox- dustrial performances as well as their limitations. Then, the state of
ide, which have been widely investigated for the pretreatment, the art and recent developments in the application of ionic liquids
dyeing and finishing processes of textiles (Montero et al., 2000; in textile processes are conducted with a view to enhancing the
Knittel et al., 1993). Some other solvents were also studied for the research activities and the industrial applications in this area.
synthesis and processing of polymers as well as the synthesis of
microcapsules for textile uses (Shiho and DeSimone, 2000; Patra
and Gouda, 2013). Now, there are certain companies in the world 2. Overview of ionic liquids
like Veramtex (Belgium) and Shikibo (Japan) which perform
mercerizing and some finishing treatments of textile materials in 2.1. Basic structures
liquid ammonia. Other companies such as DyeCoo Textile Systems
BV (Nederland) and Hisaka (Japan) have recently started the In literature, the exact definition of ionic liquids is still debat-
manufacture and the commercialisation of machineries designed able. In general, these fluids are described as completely ionised
for dyeing polyester in supercritical carbon dioxide. media whose melting points are below 100
C. Therefore, there are
Since the early 2000s, a new class of solvents, named ionic liq- various terms reported in literature which were used also by au-
uids, has generated unprecedented interest in several fields of thors to define ionic liquids such as liquid electrolytes, ionic melts,
green chemistry (Wasserscheid and Welton, 2007). Thus, it begins ionic fluids, fused salts, liquid salts, or ionic glasses (Tavanaie, 2013;
to attract the attention of researchers worldwide. This ionic liquids Welton, 1999). One of the main advantages of this class of fluids is
class has ecological and industrial prospects very promising. the number of possible combinations anion-cation that can be
The increasing interest in this class of fluids can clearly be theoretically created. According to Seddon (Holbrey and Seddon,
confirmed through the bibliographic boom (Zhang et al., 2009) 1999; Krajian et al., 2009), the number of ionic liquids which can
which has occurred in the research field over the past twenty years. potentially be synthesised is to be of the order of a trillion (up to
This wonderful growth is certainly due to the discovery by scien- 1018 possibilities (Holbrey and Seddon, 1999)).
tists and industry of the importance of ionic liquids in various ap- However, the choice of ions for ionic liquids should meet the
plications thanks especially to their very remarkable properties. requirement of the original concept of these fluids, i.e. to be liquid
Among these applications, we can cite the use of these fluids as at temperatures below 100
C. To satisfy this criterion, ionic liquids
media for several kinds of reactions such as hydrogenation (Dupont consist typically of asymmetric and univalent ions. This prevents
et al., 2002), oxidation (Tzschuche et al., 2002), Diels-Alder reaction tight crystal packing and thus lowers the melting point (Keskin
(Fischer et al., 1999) and dimerisation (Picquet et al., 2004). There et al., 2007). So, the choice of cation and anion forming an ionic
are also some other emerging applications that involve electro- liquid is crucial. Generally, ionic liquids are composed of a bulky
chemical reactions (Gordon, 2001), biocatalysis (Sheldon et al., organic cation and an organic or inorganic anion. The anion tends to
2002), nanomaterials synthesis (Kim et al., 2009), hydrogen stor- have delocalised electron clouds in order to reduce any interionic
age (Doroodian et al., 2010), liquid mirrors production (Borra et al., interactions, and can be either bulky or simple (Stasiewicz et al.,
2008). The choice of ions to form an ionic liquid leads firstly to a
 N. Meksi, A. Moussa / Journal of Cleaner Production 161 (2017) 105e126
change of its physicochemical properties such as: the density, the
viscosity, the acid-base properties, etc., and secondly to behaviour
changes in terms of miscibility and solubility with many organic or
inorganic compounds and polar or non-polar solvents. For this
raison, ionic liquids are often defined as “designable solvents”
(Remsing et al., 2006; Yang et al., 2010a). The ability to modulate
their properties, by a smart choice of the cation and the anion, is a
major asset for this class of fluids.
Currently, nearly thousand ionic liquids are described in the
literature. Their major cations and anions are shown in Figs. 1 and 2,
respectively.
For cations, it can be found many groups from organic chemistry
which can be classified into two categories: The acyclic group
which contains phosphonium, sulfonium, chlonium and ammo-
nium ions and the cyclic group which includes pyridiniums, imi-
dazoliums, pyrazolium and pyrrolidium ions.
For anions, the choice is wider. The most commonly used anions
are: halides like chloride, bromide or iodide, alkyl sulphates de-
rivatives, thiocyanate, triflate (or trifluoromethanesulfonate),
tosylate (p-Toluenesulfonate), hexafluorophosphate, tetra-
fluoroborate and bis(trifluoromethylsulfonyl)imide.
From all these cited examples of ions (Figs. 1 and 2), it can be
observed that to create ionic liquids, the choice is very large. Every
possible combination leads to diverse and varied applications.
However, it appears that imidazolium cation is the most cited in the
literature.
2.2. Technical and ecological performances of ionic liquids
Thanks to many distinctive properties, ionic liquids are
attracting increasing attention as future solvents that can replace
advantageously existing organic solvents. Among the most impor-
tant properties of ionic liquids, it can be cited the following ones:
2.2.1. Negligible vapour pressure
The insignificant volatility is one of the most famous properties
of ionic liquids. Contrary to organic molecular solvents, ionic liquids
possess negligible vapour pressure (Keskin et al., 2007). This pro-
vides the possibility to remove products by distillation without
further contamination by the solvent and also leads low hazards for
atmospheric contamination or intoxication of humans by
inhalation.
Fig. 1. Typical cations present in most ionic liquids.
107
2.2.2. Good thermal properties
Ionic liquids are generally non flammable and remain thermally
stable at temperatures higher than those of conventional organic
molecular solvents. This means that an explosion hazard can be
avoided when chemical reactions are carried out in ionic liquids.
2.2.3. Broad liquid range
Liquid range is defined as the temperature range between
melting point and boiling point or thermal decomposition tem-
perature. As is mentioned previously, ionic liquids have negligible
vapour pressures. So, they generally do not evaporate or boil at high
temperatures. The maximum limit of their liquid range corresponds
to their thermal decomposition temperature. Consequently, ex-
periments can be performed in these solvents at high temperatures
without any solvent degradation and allows good kinetic control.
2.2.4. Wide range of solubility and miscibility
In general, ionic liquids tend to be more strongly solvating than
conventional organic molecular solvents. They can be selected or
designed to dissolve a large variety of organic and inorganic gases,
liquids and solids. For example, carbon dioxide, benzene, carbo-
hydrate, transition metals, enzymes, antibiotics, coal and rocks are
all soluble in certain type of ionic liquids. Ionic liquids can also
dissolve natural and synthetic polymers. The ability of an ionic
liquid to dissolve a substance depends on many factors, especially
on its polarity and the coordination properties of its ions.
2.2.5. Credential properties for chemical reactions
One of the impressive features of ionic liquids is their ability to
act a dual role for a wide variety of chemical reactions. Indeed, ionic
liquids can be used either as reaction media and/or catalysts.
Ionic liquids can possess Bronsted or Lewis acidity and basicity.
These acidic or basic properties depend on the character of the
anions and cations of ionic liquids (Nowicki et al., 2014). This will
offer promising prospects to achieve various new reactions in
organic synthesis and catalysis.
2.2.6. Modular properties
It is possible to tune or tailor the physical, chemical or biological
properties of ionic liquids by:
- Varying the combination of cations and anions.
108 N. Meksi, A. Moussa / Journal of Cleaner Production 161 (2017) 105e126
Fig. 2. Typical anions present in most ionic liquids.
- Designing and adding specific functionalities into the cations
and/or anions.
- Mixing two or more ionic liquids.
2.2.7. Good recycling properties
Ionic liquids can be recycled for next reuse as solvents with an
excellent recovery. The recycling of the catalyst is also possible
using ionic liquids as reaction media. This obviously helps to
minimise waste generation.
2.3. Limitations of ionic liquids
Although ionic liquids are viewed as remarkable class of sol-
vents, there are many issues about some of their features which
slow their development in industrial scale. The main limits of ionic
liquids are:
2.3.1. High cost
It is no doubt one of the most limiting factors. Today, ionic liq-
uids are expensive in comparison to common organic solvents,
even whether produced on an industrial scale. The high cost of ionic
liquids depends not only on the price of raw materials, but espe-
cially on the complexity of their manufacturing processes as well as
the required qualities. However, a recent study by Helmut Kaiser
Consultancy (2015), predicts that there will be a phenomenal in-
crease in demand for ionic liquids during the next fifteen years
which will certainly lead to an important reduction of their cost.
Obviously, in some cases, the use of slightly expensive ionic liquids
may be acceptable if the advantages related to their application are
able to compensate for the additional costs of the solvent.
2.3.2. High viscosity
The most of ionic liquids have viscosities comparable of oils with
orders of magnitude greater than those of typical organic solvents.
This high viscosity is a major disadvantage in many industrial ap-
plications as they depend on mass transfer and mixing. Viscosity
also impacts the conductivity of ionic liquids and thus their use in
electrochemical devices.
2.3.3. Toxicity and biodegradability issues
Ionic liquids are usually viewed and cited as green solvents due
to their negligible volatility, their non flammability and their
recyclability with high product yields. However, the label “green
solvent” should be attentively applied, because, until now, little is
known about the toxicity, biodegradability and mobility in the
environment of the most of ionic liquids. So, more researches will
be necessary in order to establish the correlation between their
ionic structure and toxicity.
2.3.4. Lack of scientific data
The study of ionic liquids is still new; our knowledge about the
physical, chemical, and biological properties of these fluids is
incomplete and limited in comparison with common organic sol-
vents. These data are crucial notably in the design of ionic liquids
for specific applications. Besides, for some properties, like the non
volatility and the non flammability, it is possible to make general-
isations that apply to all classes of ionic liquids. For other proper-
ties, applying generalisations to all ionic liquids or to specific
groups of ionic liquids are not usually possible.
3. Methodology
The information presented in this systematic review was
collected from publicly available sources and covered the main
ecofriendly applications of ionic liquids in the textile engineering
research. For literature search, the following keywords were
selected, based on authors' knowledge in the field: textile/fibre,
ionic liquids, spinning, preparation/pretreatment, dyeing/printing/
colouration, finishing, wastewater treatment, waste recycling, and
composites. The keywords were searched in various suitable
combinations employing Boolean operators “AND”, and “OR” via
major scientific databases including SciFinder, Sciencedirect,
Medline, Google Scholar and Google Scholar Patent without any
geographical or date restrictions. The search covered titles, ab-
stracts and keywords. The most relevant works as exhaustive as
possible: articles, chapters, patents, communications including
some international books published were gathered for screening
and inclusion in this original review. Firstly, special focus has been
given to cleaner textile processes in which ionic liquids were
applied as green media, auxiliaries or functionalising agents. In
these cleaner textile processes, either the used ionic liquids can be
recyclable or the corresponding residual amounts after processing
can be recoverable and reusable. Special focus has also been given
to textile wastewater treatment processes using ionic liquids
because they remain in all situations a sustainable solution to water
scarcity and country's waste increasing. Each selected work was
studied deeply. Then, the nature and the performances of the cor-
responding textile process as well as the used ionic liquid(s) were
determined and compared to other similar applications if possible.
 N. Meksi, A. Moussa / Journal of Cleaner Production 161 (2017) 105e126
4. Recent advancements of ionic liquids application in textile
processes
This section provides a detailed description of the recent eco-
friendly applications of ionic liquids in the main fields of textile
engineering research. Diverse applications of ionic liquids in textile
engineering can be illustrated in the schema presented in Fig. 3.
According to used processes, a number of these applications can
sometimes be overlapped. Through many of these applications,
several innovative cleaner processes were developed in order to
reduce chemical consumption, eliminate the use of water and in
some cases to impart additionally novel properties to textiles. As a
result, negative environmental impacts related to water and
chemical wastages can be minimised compared to conventional
aqueous processes.
4.1. Textile spinning
Spinning is the first stage in the manufacturing line of textile
products. The performances of the final product depend closely on
the chemical, physical and textile properties of the produced fibres
after spinning. This step concerns generally the preparation of
spinning fluids, fibre formation and yarn manufacturing. According
to the use of textile products, the spinning stage can reach non-
woven and composites manufacturing. Table 1 lists various textile
materials obtained through several cleaner spinning processes with
ionic liquids.
4.1.1. Spinning and applications of modified and non modified
cellulosic fibres
One of the most emergent and ecofriendly applications of
ionic liquids is undoubtedly the spinning of regenerated cellu-
losic fibres. More details about that can be found in the excellent
reviews realised by Tavanaie (2013) and Hina et al. (2015). Be-
sides, one of the main targets of this application is to achieve an
Fig. 3. Various applications of ionic liquids in textile engineering.
109
old dream: the development of an ecofriendly and energy-
efficient spinning process for producing regenerated cellulose
fibre, which can replace advantageously the viscose process and
the (N-methylmorpholine N-oxide) NMMO-based Lyocell pro-
cess. These last processes are currently the only two technologies
that have been industrially developed for the production of man-
made cellulosic fibres. However, they show drawbacks, mainly
deriving from the solvents applied in the cellulose dissolution
step. In fact, for the viscose process, the utilisation and the for-
mation of highly toxic chemicals and gases can be harmful for
workers and environment. Consequently, environmental pollu-
tion as well as security costs become a serious concern. For the
NMMO-based Lyocell process which is currently the only com-
mercialised alternative to the viscose process, there are also
several drawbacks such as poor thermal stability of the solvent,
pronounced degradation of both the solvent and the cellulose
due to by-product formation which requires a huge amount of
stabiliser and high safety expenditure.
Due to high market needs for bio-based textiles and sustainable
fashion products, it becomes necessary to develop green spinning
technologies for producing man-made cellulosic fibres. Technically,
this requires finding green solvents capable of effectively dissolving
raw celluloses.
In 2002, Swatloski et al. (2002) were first who studied the
dissolution of cellulose in ionic liquids. The used solvents exhibited
an exceptional potential for cellulose dissolution, processing and
manufacturing of regenerated cellulosic fibres. This result has
opened up new opportunities for new products as well as new
cleaner processes. The first trials towards a technical conversion of
the fibre processing were performed by Bentivoglio and co-workers
(Laus et al., 2005; Bentivoglio et al., 2006). In these studies, many
ionic liquids such as 1-butyl-3-methylimidazolium chloride and 1-
allyl-3-methylimidazolium chloride were investigated as spinning
solvent instead of NMMO in the commercial production of Lyocell
fibres. Fibres obtained from ionic liquids solutions presented lower
110 N. Meksi, A. Moussa / Journal of Cleaner Production 161 (2017) 105e126

Table 1
Various textile materials prepared by spinning processes using ionic liquids.

Process Spinning method Ionic liquid Fibre thickness References

Spinning of non modified cellulosic fibres Dry-jet wet spinning [BMIM]Cl; [AMIM]Cl 0.7e2.2 dtexa (Laus et al., 2005; Bentivoglio
et al., 2006)
Wet spinning [BMIM]Cl; [EMIM]Ac n.d.b (Hermanutz et al., 2006, 2008)
Dry-jet wet spinning
Dry-jet wet spinning [BMIM]Cl n.d.b (Cai et al., 2010)
Wet spinning [BMIM]Cl; [EMIM]Ac 30e70 mm (Vinogradova and Chen, 2015)
Dry-jet wet spinning [EMIM]Ac n.d.b (Hong et al., 2013)
Dry-jet wet spinning [BMIM]Cl; [EMIM]Ac 1.56e3.07 dtex (Wendler et al., 2009)
Meltblown process. [EMIM]Ac 3-40 mm (Luo et al., 2008)
Dry-jet wet-spinning [BMIM]Cl 29-39 dtex (Jiang et al., 2011)
Wet spinning [AMIM]Cl; [BMIM]Ac n.d.b (De Silva et al., 2016)
Dry-jet wet-spinning [DBNH]Ac 1.9 dtex Hummel et al., 2015
Spinning of modified cellulosic fibres Dry-jet wet spinning [BMIM]Cl; [EMIM]Cl [AMIM]Cl 1.77e3.47 dtex (Kosan et al., 2010)
Spinning of functionalised cellulosic fibres Dry-jet wet spinning [EMIM]Cl n.d.b (Sun et al., 2008)
Spinning of functionalised cellulosic Dry-jet wet spinning [EMIM]Cl n.d.b (Maxim et al., 2010)
composite fibres Ultrasonication/Dry-jet [EMIM]Ac 0.110e0.184 mm (Maxim et al., 2012)
wet spinning
Spinning of carbon nanotubes/cellulose Dry-jet wet spinning [EMIM]Ac 14.8e29.6 mm (Rahatekar et al., 2009a, 2009b)
composite fibres Dry-jet wet spinning [EMIM]Ac n.d.b (Zhu et al., 2014a)
Spinning of protein fibres Wet spinning [EMIM]Cl 150 mm (Phillips et al., 2005, 2010)
Wet spinning [EMIM]Cl; [BMIM]Cl n.d.b (Institute of Process
Engineering, 2006)
Wet spinning [BMIM]Cl; [BMIM]Br; [AMIM]Cl; [EMIM] n.d.b (Henan Ding Biotechnology Co.,
I; [EMIM]DEP Ltd., 2013)
Spinning of polyacrylonitrile fibres Dry-jet wet spinning [BMIM]Cl 7.4e23.54 dtex (Wan et al., 2009)
Dry-jet wet spinning [BMIM]Cl 25.68e59.26 mm (Cheng et al., 2014)
Electrospinning [BMIM]Br n.d.b (Yang et al., 2010b)
Spinning of polyamide fibres Wet spinning [EMIM]DEP; [MMIM]DMP; [EMIM]Ac 175-442 dtex (Schwiegk et al., 2010)
Spinning of polyurethane fibres Wet spinning [EMIM]MS 160-1500 dtex (Schuette et al., 2010)
Spinning of cellulose/keratin blends Wet spinning [BMIM]Cl n.d.b (Kuzmina et al., 2009)
Spinning of cellulose/m-aramid blends Dry-jet wet spinning [BMIM]Cl 24.33e30.11 dtex (Lee et al., 2007)
Spinning of cellulose/polyurethane blends Dry-jet wet spinning [EMIM]AC 1.7 dtex (Wendler et al., 2009)
Spinning of cellulosic nanofibres Electrospinning [BMIM]Cl; [EMIM]Ac 100e1000 nm (Vinogradova and Chen, 2015)
Electrospinning [BMIM]Cl 0.5e36.43 mm (Viswanathan et al., 2006)
Electrospinning [AMIM]Cl 100e800 nm (Xu et al., 2008)
Electrospinning [BMIM]Cl 500e800 nm (Quan et al., 2010)
Dry-jet wet [EMIM]Ac 100 nm (Miyauchi et al., 2011)
electrospinning
Electrospinning [EMIM]Ac 470 ± 110 (Freire et al., 2011)
Electrospinning [EMIM]Ac; [DMIM]Cl 120 ± 55 (Freire et al., 2011)
Electrospinning [EMIM]Ac n.d.b (Ahn et al., 2012)
Electrospinning [EMIM]Ac n.d.b (H€ardelin et al., 2012)
Electrospinning [EMIM]Ac n.d.b (H€ardelin et al., 2013)
Electrospinning [EMIM]Ac Less than < 200 nm (Kang et al., 2013)
Spinning of modified poly(L-lactic acid) Electrospinning [HMIM]Cl 323 ± 53 (Seo et al., 2009)
nanofibres e1057 ± 365 nm
Spinning of nylon 6,6 composite Electrospinning [BMIM]PF6 128.9 ± 30.1 (Kang et al., 2012)
nanofibres e239.6 ± 25.3 nm
Spinning of nylon 6 composite nanofibres Electrospinning [BMIM]PF6 100-250 nm (Li et al., 2013)
Spinning of modified polyacrylonitrile Electrospinning [DEA]DHP 200 nm (Jing et al., 2016)
nanofibres
Spinning of modified polyuretrhane Electrospinning [BMIM]PF6 n.d.b (Xing et al., 2015)
nanofibres
a
g/10000 m fibre.
b
No data.

values of tenacity and elongation compared with conventional
Lyocell fibres.
Later, BASF Company, the Institute for Textile Chemistry and
Chemical Fibres (ITCF) and the Institute of Textile and Plastics
Research (TITK) from Germany investigated jointly the properties
of the fibres spun from ionic liquids solutions of cellulose using
pilot plant manufacturing (Hermanutz et al., 2006, 2008). The
production was conducted by 1-butyl-3-methylimidazolium as
ionic liquid solvent. They successfully applied wet and dry-jet wet
spinning processes. However, corrosion, cellulose decomposition
and handling of the ionic liquid with its fairly high melting point
70
C were the most technical drawbacks faced during their studies.
In order to avoid these problems, they tried a second ionic liquid, 1-
ethyl-3-methylimidazolium acetate which is non-corrosive. Then, a
dry-jet-wet spinning process derived from the NMMO process was
developed and adapted to this ionic liquid solvent. They obtained
fibres with higher tenacities than those produced by conventional
wet spinning, which are comparable to Lyocell fibres.
Afterwards, Cai et al. (2010) studied the rheological behaviour of
the cellulose/1-butyl-3-methylimidazolium chloride solution and
the fibres were spun with a dry-jet wet spinning process. In addi-
tion, they investigated the structure and the properties of the
prepared cellulose fibres and compared them to those of Lyocell
fibres. They observed that the prepared fibres have cellulose II
crystal structure just like that of Lyocell fibres, and the orientation
and crystallinity of the fibres increased with the draw ratio
increasing. Consequently, the mechanical properties of the fibres
were improved.
 N. Meksi, A. Moussa / Journal of Cleaner Production 161 (2017) 105e126
Vinogradova and Chen (2015) reported a study in which two
types of ionic liquid, 1-butyl-3-methylimidazolium chloride and 1-
ethyl-3-methylimidazolium acetate, were used as recyclable sol-
vents for dissolving raw cellulose in the spinning of micron- and
nano-scale regenerated cellulose fibres. After comparing the
properties of the obtained fibres in terms of tensile strength,
crystallinity and thermal decomposition, they concluded that 1-
ethyl-3-methylimidazolium acetate is a better candidate for dis-
solving cellulose for the production of regenerated cellulose fibres
because it has lower dissolving and spinning temperatures than 1-
butyl-3-methylimidazolium chloride. Besides, it requires less en-
ergy for fibre formation. Additionally, 1-ethyl-3-
methylimidazolium acetate residuals are not toxic and are safe
for both consumers and healthcare end uses.
Hong et al. (2013) prepared cellulose fibres from cellulose/1-
ethyl-3-methylimidazolium acetate solution under dry-jet wet
spinning conditions. In order to elucidate the fundamental of cel-
lulose spinning mechanism, they investigated the effects of the
processing and the solution conditions on the morphologies and
the properties of the regenerated fibres.
Meanwhile, other researchers were interested in replacing
NMMO by a number of imidazolium-based ionic liquids in cellulose
dissolution for various applications. Wendler et al. (2009) claimed
that the direct dissolution of cellulose and the dry-wet shaping in
1-ethyl-3-methylimidazolium acetate and 1-butyl-3-
methylimidazolium chloride in the presence of functional addi-
tives (nano-scaled silver particles and activated charcoal) provide
regenerated fibres with novel properties. These regenerated fibres
can have various applications in the technical textile field. Similarly,
a process for making inflated fibres of regenerated cellulose formed
from (1-butyl-3-methylimidazolium chloride and 1-allyl-3-
methylimidazolium chloride)/cellulose-dope was patented by
Kokko (2011). These inflated fibres may be incorporated into
absorbent sheets with other paper making fibres in order to pro-
vide softness, bulk, and absorbency. Luo et al. (2008) patented also
a new method for preparing regenerated fibres from cellulose
dissolved in 1-ethyl-3-methylimidazolium acetate solvent and
extruded by the melt blowing process with the purpose of pro-
ducing bonded non-woven webs. The formation of regenerated
cellulose fibres from bagasse and wood under various processing
conditions using 1-butyl-3-methylimidazolium chloride as a recy-
clable solvent was published by Jiang et al. (2011). The regenerated
bagasse fibres showed a higher degree of crystallinity and higher
tenacity than the regenerated wood fibres obtained using the same
ionic liquid solvent and processing conditions.
Researchers in Australia (De Silva et al., 2016) investigated the
key wet spinning parameters for the development of regenerated
cellulose fibres from ionic liquid solutions. They calculated the
coagulation and associated diffusion equilibrium for two
imidazolium-based ionic liquids: 1-allyl-3-methylimidazolium
chloride and 1-butyl-3-methylimidazolium acetate. They found
that the ionic liquid anion largely influences the coagulation ki-
netics due to its association with cellulose.
For ecological and economic reasons, the same Australian team
(De Silva et al., 2014) used also 1-allyl-3-methylimidazolium chlo-
ride to successfully separate polyesterecotton blended textiles,
with polyester recovery rates claimed to be in the region of 99.5%.
This finding presents an environmentally benign approach to
recycling textile waste. Currently, these researchers try to use this
cleaner technology to spin new regenerated cotton fibres that will
be competitive with both viscose and Lyocell.
From these studies, it can be concluded that imidazolium-based
ionic liquids containing halides or carboxylates were identified as
effective cellulose solvents and have thus been adopted for cellu-
lose spinning. However, this class of ionic liquids is not inert toward
111
cellulose and can induce cellulose degradation at high tempera-
tures (>90
C), depending on the substituent on the imidazolium
ring and the chemical nature of the ionic liquid anion (Ebner et al.,
2008).
Recently, Hummel and co-workers (Hauru et al., 2014; Hummel
et al., 2015) have presented a promising Lyocell-type process for the
manufacture of man-made cellulosic fibres. This process, which is
called “Ioncell-F process” uses 1,5-diazabicyclo[4.3.0]non-5-ene
acetate, a non imidazolium-based ionic liquid solvent. This sol-
vent has shown excellent properties for the dissolution of cellulose.
According to these authors, the obtained regenerated fibres
exhibit outstanding properties superior to those of cotton, viscose,
and Lyocell fibres. Besides, they have observed good performances
of the Ioncell spun yarn during knitting and weaving processes
which confirm its suitability for the production of apparels. Finally,
several garments have been produced by this new cleaner spinning
process which present shiny aspect and light feel. In addition, one
of the challenges for the ionic liquids future is the elaboration of the
technology for obtaining thermoplastic cellulose. In this context,
Kosan et al. (2010) investigated the acetylating of cellulose in 1-
butyl-3-methylimidazolium chloride, 1-ethyl-3-
methylimidazolium chloride and 1-allyl-3-methylimidazolium
chloride, followed by the subsequent dry and wet spinning of
these processing solutions. Properties of the resulting fibre were
then studied regarding the degree of dissolution and in comparison
with unsubstituted cellulose fibres.
Sun et al. (2008) were interested in preparing functionalised
cellulosic fibres using ionic liquids. Firstly, they applied dry-jet wet
spinning process with 1-ethyl-3-methylimidazolium chloride for
making magnetically active cellulose fibres. The synthesis of this
functionalised cellulosic fibre requires dissolving the cellulose
material in the ionic liquid, then dispersing particles of magnetite
in the obtained solution, and finally coagulating the fibres in a
water bath under appropriate spinning conditions. During their
experiments, they observed that the fibre texture is related to
overall magnetite concentration, cellulose concentration, and mo-
lecular weight in the spinning solution. The results showed that the
increasing degree of polymerisation (DP) and/or cellulose concen-
tration resulted in more robust fibres, but the addition of magnetite
particles weakens the overall mechanical properties.
In a second work, Sun and co-workers (Maxim et al., 2010) used
the previous procedure to synthesise composite fibres from cellu-
lose/ionic liquid solutions containing suspended titanium particles.
They observed that the surface texture of the cellulose/TiO2 fibres
depends greatly on the concentration of TiO2 used, as the particles
have the tendency to outcrop the surface. Besides, 5% TiO2 was
found to be the optimal concentration that did not cause significant
changes in the mechanical properties of the fibres.
In their most recent work, Sun and co-workers (Maxim et al.,
2012) synthesised composite fibres by homogeneous dispersion
of nanomagnetite in 1-ethyl-3-methylimidazolium acetate using
ultrasonication followed by dissolution of microcrystalline cellu-
lose at 90
C and dry-jet wet spinning into a water coagulation bath.
They observed that the used method has a large influence on the
quality of dispersion and thus the mechanical properties of the fi-
bres. They found that a nanomagnetite load between 0.75 and 1% in
the cellulose matrix offers good mechanical properties of the fibres.
Another use of ionic liquids is to spinning carbon nanotubes.
Indeed, carbon nanotubes (single-wall carbon nanotubes (SWCNT)
and multi-wall carbon nanotubes (MWCNT)) offer a great potential
to be used as electrically conducting inclusions in textiles due to
their excellent electrical conductivity and high aspect ratio (Xie
et al., 2005a). To achieve this target, Rahatekar et al. (2009a;
2009b) prepared successfully multiwall carbon nanotubes
(MWNT)/cellulose composite fibres using dry-jet wet spinning
112 N. Meksi, A. Moussa / Journal of Cleaner Production 161 (2017) 105e126
process with cellulose dissolved in 1-ethyl-3-methylimidazolium
acetate. The scanning electron microscopy analysis of obtained
cellulose fibres shows a very high alignment of MWNT in the fibre
axis direction. Besides, they observed that a moderate improve-
ment (30%) in the tensile strength of MWNT/cellulose composite
fibres is obtained by adding up to 0.07 mass fraction MWNT as
compared to neat cellulose fibres. In a recent work, Rahatekar and
co-workers (Zhu et al., 2014a) developed methods to improve the
dispersion of carbon nanotubes in 1-ethyl-3-methylimidazolium
acetate and in cellulose solution dope. In this work, they studied
especially the effect of fibre spinning parameters such as fibre
extrusion speed and fibre winding speed on the electrical con-
ductivity of the cellulose/carbon nanotube composite fibres.
4.1.2. Spinning and applications of non cellulosic fibres
The search for corresponding publications showed that the main
presented works in spinning and the regenerating of textile fibres
are related to regenerated cellulosic fibres. However, there are also
various promising results about the non cellulosic fibre spinning
with ionic liquids. The purpose of these studies is not only to pro-
duce an innovative fibres generation with good performances using
cleaner spinning processes, but also to develop green processes for
recycling textile wastes.
Among these results, it can be cited the dissolution, the regen-
eration and the spinning of natural protein fibres in different ionic
liquids which presents an area of growing potential. Phillips et al.
(2005, 2010) were first who studied and patented a new cleaner
spinning process of fibre from Bombyx Mori silkworms using 1-
ethyl-3-methylimidazolium chloride as solvent. For the coagula-
tion bath solvent, they indicated that methanol works best for so-
lidifying the fibres because it induces b-sheet crystallite formation.
However, post-spin drawing is required to induce crystallite
alignment.
Later, two Chinese patents (Institute of Process Engineering,
2006; Henan Ding Biotechnology Co. Ltd., 2013) were published
methods for the preparation and the wet spinning of regenerative
keratin solutions from coarse animal hairs, wools and waste wool
textiles using imidazoluim-base ionic liquids. These two Chinese
patents reported various media to regenerate protein fibres, but
they did not provide any details about the properties of the ob-
tained fibres.
Goujon et al. (2012) showed that protic ionic liquids such as
triethylammonium phosphate, triethylammonium lactate, triethy-
lammonium triflate and triethylammonium mesylate cannot
dissolve silk fibroin but they can be advantageously used as coag-
ulation solvents for its regeneration.
In the case of synthetic fibres, polyacrylonitrile has received
special attention from Chinese researchers. Indeed, since 2004 and
the found by Cheng et al. (2004) that ionic liquids are also good
solvents for polyacrylonitrile, the polymerisation (Wan et al., 2009;
Hou et al., 2008), the dissolution (Liu et al., 2007) and the spinning
experiments (Cheng et al., 2014; Yang et al., 2010b) of this synthetic
polymer have been carried out. The rheological properties of
polyacrylonitrile in 1-butyl-3-methylimidazolium chloride (Liu
et al., 2007; Zhu et al., 2014b) and in 1-butyl-3-
methylimidazolium bromide solutions (Yang et al., 2010a, 2010b)
were largely studied. The effects of various experimental conditions
on the rheology properties of such solutions have been reported
comprehensively. The formation of polyacrylonitrile fibres with
ionic liquids as solvents has also been explored in recent years (Zhu
et al., 2015). Wan et al. (2009) successfully obtained acrylic fibres
with round profile and good mechanical properties spun from the
polyacrylonitrile/1-butyl-3-methylimidazolium chloride solution
and using dry-jet wet spinning technology. Yang et al. (2010b)
developed a temperature-controlled apparatus for
electrospinning of polyacrylonitrile fibres.
In 2010, Schwiegk et al. (2010) patented a new method for
producing porous structures from porous polyamide fibres. These
fibres were obtained by dissolving polyamide in 1-ethyl-3-
methylimidazole diethylphosphate, 1,3-dimethylimidazolium
dimethylphosphate or 1-ethyl-3-methylimidazolium acetate.
Then, using a wet-spinning process, the dissolved polyamide was
precipitated in protic solvents and dried.
Meanwhile, wet spinning of polyurethane solution (Spandex)
was performed using 1-ethyl-3-methylimidazulium methanesul-
fonate as a solvent (Schuette et al., 2010). The inventors of this
technique suggested that it can be applied to producing the
Spandex fibres with antistatic properties. These properties were
obtained thanks to ionic properties of residual ionic liquids in the
fibre, for amounts preferably less than 3%. This will prevent charge
build up on the fibres during further processing.
Others researchers were interested in the spinning of fibres
from blending textile polymers. The blending process allows to
obtain advanced polymer blends and composites with high per-
formances and high additional value. This blending process can be
achieved between two different textile polymers or between both a
textile polymer like cellulose, protein and a second polymer which
is generally bio-based material like chitin, chitosane, heparin, etc.
Several investigations using the second way of blending process
were reported in the literature (Viswanathan et al., 2006; Wendler
et al., 2009).
Among the first trials for blending two different textile poly-
mers, it can be cited those of Xie et al. (2005b) who described the
feasibility of preparing cellulose/wool keratin blends in 1-butyl-3-
methylimidazolium chloride with different ratios of cellulose and
wool keratin fibres. According to authors, the obtained solutions
can be used to cast a cellulose/wool keratin blended membrane and
to spin blended fibres directly. Kuzmina et al. (2009) were inter-
ested in the investigation of solutions and films of cellulose/fibroin
blends obtained in 1-butyl-3-methylimidazolium chloride. They
concluded that the strongest intermolecular interaction of the
components of this blend occurs for a fibroin content of 20%. They
also found that the solution corresponding to the mixture 80%
cellulose/20% fibroin has the highest viscosity in comparison with
the other mixtures. Afterwards, Hameed and Guo (2009, 2010)
developed novel wool/cellulose and wool/cellulose acetate blends
using 1-butyl-3-methylimidazolium chloride. Hameed and Guo
(2009) showed that wool/cellulose blend films exhibit signifi-
cantly improved thermal stability and mechanical properties than
the individual components. Besides, they indicated that wool/cel-
lulose acetate blends are homogeneous and possess also an
improved thermal stability. In the same area of investigation, Lee
et al. (2007) used 1-butyl-3-methylimidazolium chloride to pro-
duce cellulose/m-aramid blend fibres using dry-jet wet spinning
process. They reported that up to 10% m-aramid blend fibres did not
lead to any decline in mechanical properties.
In another work, Wendler et al. (2009) indicated that multi-
component fibres with excellent properties can be obtained from
the collective dissolution of cellulose and polyacrylonitrile in 1-
ethyl-3-methylimidazolium acetate. Both textile polymers devel-
oped inside the fibre cluster an ownership structure. The water
retention behaviour and the wet abrasion resistance increase with
the enhancement of polyacrylonitrile content in the fibre.
4.1.3. Spinning and applications of textile nanofibres
In recent years, the production of nanofibres becomes an
emerging technology sector for the development of innovative
materials for biomedical textile applications and protective clothes
such as engineering scaffolds, wound dressing, biosensors, filters
for pathogens (bacteria, viruses), toxic gasses, poisonous or harmful
 N. Meksi, A. Moussa / Journal of Cleaner Production 161 (2017) 105e126
substances in the air, and so forth. The nanofibres are a new class of
nanomaterials with specific properties such as the large surface-to-
area ratio, high porosity, flexibility, stability, and permeability.
These properties distinguish them from conventional non-woven
fibres obtained by other methods like for example melt-blowing.
The technique that is commonly used to prepare nanofibres
with an extremely high surface area to volume ratio, is electro-
spinning (electrostatic fibre spinning). This technique uses electric
forces to draw charged threads of fluid polymer up to fibre di-
ameters in the order of some 10 nm. Electrospinning is habitually
regarded as a simple, rapid and effective method to prepare ul-
trathin fibres from polymers. However, the number of these poly-
mers that can be electrospun is still limited by the availability of
volatile solvents as well as their limited capability of dissolving
them. Thanks to their excellent dissolution ability, their high
thermal stability and their good recyclability, ionic liquids offer in
this case a potential green solution to the poor solubility associated
with many polymers. Obviously, this leads to boost up the devel-
opment of nanofibres sector. In textile engineering research,
various synthetic and natural textile polymers were electrospuned
into nanofibres. Generally, the interest in electrospun cellulosic
nanofibres is gradually increasing from both an environmental and
economic point of view.
Cellulose nanofibres were produced for the first time by elec-
trospinning from cellulose solution (10 wt %, in 1-ethyl-3-
methylimidazolium chloride) by Linhardt and co-workers
(Viswanathan et al., 2006). The formed fibres were washed with
ethanol and then dried. In the same line of investigation, Quan et al.
(2010) applied the same chloride-based ionic liquid for the disso-
lution of cellulose, and subsequent production of non-woven cel-
lulose fibres, through the modification of the electrospinning setup
to operate at 373 K. Xu et al. (2008) investigated the electro-
spinning of cellulose using 1-allyl-3-methylimidazolium chloride
combined with dimethylsulfoxide in order to reduce the surface
tension, viscosity and entanglement density of the network, thus
allowing a continuous jet. Miyauchi et al. (2011) prepared 100 nm
diameter cellulose fibres by dry-jet wet electrospinning using 1-
ethyl-3-methylimidazolium acetate. The obtained nanofibres
were then chemically modified, packed into a column and applied
to investigate bovine serum albumin adsorption/desorption
properties.
In a recent work, Freire et al. (2011) obtained nano sized cellu-
lose fibres with average diameters within (470 ± 110) nm using
electrospinning with 1-ethyl-3-methylimidazolium acetate. They
showed that the addition of another ionic liquid, 1-decyl-3-
methylimidazolium chloride to 1-ethyl-3-methylimidazolium ace-
tate allowed to obtain improved ultrafine cellulose fibres with
average diameters within (120 ± 55) nm.
Ahn et al. (2012) investigated the effects of the type and the
concentration of the co-solvents (dimethylformamide and dime-
thylacetamide) on the spinnability and the properties of the
nanofibre during cellulose electrospinning in 1-ethyl-3-
methylimidazolium acetate. They reported that the addition of
the co-solvent improves the spinnability and produces finer and
more uniform diameter of fibres. In a similar work, Ha €rdelin et al.
(2012) studied the influence of the co-solvents (dimethylsulf-
oxide, dimethylformamide and dimethylacetamide) during elec-
trospinning cellulose from 1-ethyl-3-methylimidazolium acetate.
They showed that co-solvents could decrease viscosity and surface
tension of cellulose solutions. Besides, the rheological properties of
electrospun cellulose solutions can be linked to fibre formation.
In a second work, Ha €rdelin et al. (2013) investigated the influ-
ence of molecular weight and rheological behaviour on electro-
spinning cellulose nanofibres at various concentrations in 1-ethyl-
3-methylimidazolium acetate with dimethylsulfoxide as co-
113
solvent. They observed that neither cellulose concentration nor
molecular weight seems to be decisive for if a solution can be
electrospun into fibres or not. But, it is rather the viscosity of the
solution that is decisive for electrospinnability. Kim and co-workers
(Kang et al., 2013) studied the effects of lignin and hemicelluloses
contents on the spinnability, web morphology, crystallinity and
thermal properties during electrospinning of nanocellulose fibres
using alkali treated-hemp and 1-ethyl-3-methylimidazolium ace-
tate/dimethylformamide as solvent. According to authors, the alkali
treatment reduces the lignin content and hemicelluloses in the
biomass and in turns, significantly improves the spinnability as well
as the crystallinity.
In addition, other researchers were interested in the use of ionic
liquids for electrospinning of textile synthetic nanofibres. Seo et al.
(2009) investigated the effects of adding small amounts of 1-hexyl-
3-methylimidazolium chloride, on the electrospinning process of
poly(L-lactic acid) in chloroform, and compared the effects to that
of a quaternary ammonium salt, triethylbenzylammonium chloride
on solution properties, electrospinning process, and fibre proper-
ties. They reported that both additives increase the conductivity
which decreases in turn the fibre diameter, but differences were
observed on the fibre dispersing and fibre morphology. Recently,
Kang et al. (2012) produced 1-butyl-3-methylimidazolium hexa-
fluorophosphate/nylon 6,6 composite nanofibre via an electro-
spinning process in formic acid as solvent. They claimed that the
obtained material can be a potential candidate for organic vapour
sensing for ethanol, methanol, tetrahydrofuran, and acetone. Af-
terwards, Li et al. (2013) investigated the effect of 1-butyl-3-
methylimidazolium hexafluorophosphate content in 1-butyl-3-
methylimidazolium hexafluorophosphate/nylon 6 solution, the
morphology, mechanical strength, thermal properties and con-
ductivity of the composite nanofibres and fibrous membrane. They
found that the composite nanofibres and their corresponding
fibrous membranes (non-woven mesh of nanofibres) possess
interesting mechanical properties after adding 1-butyl-3-
methylimidazolium hexafluorophosphate mixed in small amounts
with nylon 6. Besides, when the content of 1-butyl-3-
methylimidazolium hexafluorophosphate reaches more than 0.5%,
the composite fibrous membrane presents a significantly enhanced
conductivity. These results prove the potential of 1-butyl-3-
methylimidazolium hexafluorophosphate/nylon 6 composite
membrane in applications such as: nanofibres-based sensors,
antistatic self-cleaning, coating, etc.
Jing et al. (2016) prepared polyacrylonitrile nanofibres by elec-
trospinning in the presence of diethylammonium dihydrogen
phosphate (DEAP), a highly viscous and hydrophilic ionic liquid.
Jing et al. (2016) found that the use of this ionic liquid gives poly-
acrylonitrile nanofibres with rough surface. As a result, the ob-
tained DEAP-modified polyacrylonitrile shows an improved surface
area and hydrophilic character. In a recent work, novel nanofibres
based on a blend containing thermoplastic polyurethane and 1-
butyl-3-methylimidazolium hexafluorophosphate were developed
by Xing et al. (2015). The novel nanofibres have excellent antibac-
terial, anti-electrostatic, and mechanical properties with improved
hydrophilicity. According to Xing et al. (2015), these polyurethane
nanofibres are promising candidates for biomedical and waste-
water treatment applications.
While the literature reports many developments in the eco-
friendly application of ionic liquids in textile spinning, there are still
many areas that deserve to be investigated. Ionic liquids have
proven to be an interesting route to dissolve and regenerate many
textile polymers. However, their full exploitation is still inhibited by
their higher viscosities especially for producing nanofibres by
electrospinning. In order to overcome this problem, many re-
searchers have suggested the addition of co-solvent with ionic
114 N. Meksi, A. Moussa / Journal of Cleaner Production 161 (2017) 105e126
liquids for the dissolution of textile polymers (Meli et al., 2010;
Ha€rdelin et al., 2012; Hina et al., 2015). In spite of its ecological
drawbacks related to the used solvents which should be deeply
clarified, this approach remains very interesting. However, still
more research is needed to understand, for example the kinetics,
the interactions between all components of these polymeric solu-
tions, its rheological behaviour as well as the extent of textile
polymer degradation in these conditions. Furthermore, the role of
the co-solvent in the regeneration of textile polymer by ionic liquid
and the performances of resultant fibres still needed to be
elucidated.
4.2. Textile preparation
To the best of our knowledge, only four reports have investi-
gated the use of ionic liquids to develop novel cleaner textile
preparation processes. Data about these reports are summarised in
Table 2. The first work was elaborated by El-Sayed and co-workers
(Kantouch et al., 2011b) and concerns the application of 1-ethyl-3-
methylimidazolium acetate and 1-butyl-3-methylimidazolium
chloride on the felting resistance of wool. The authors studied the
effect of treatment temperature and time on the yellowing index,
tenacity and elongation at break of the treated wool fibres. They
observed a partial removal of wool scales with a remarkable
reduction in the sulphur content of the treated wool. In the same
area of investigation, Yuan et al. (2012) showed that treating of
wool by 1-butyl-3-methylimidazolium chloride produces a signif-
icant modification of its surface state. Indeed, the epicuticle layer is
partly damaged and some lipids are removed. These changes in the
wool surface characteristics help to improve the effects of protease
processing of wool.
Another reported work focused on the degumming of eri silk
using ionic liquids. In this work, Vyas and Shukla (2016) used 1-
butyl-3-methylimidazolium chloride and 1-butyl-3-
methylimidazolium hydrogen sulphate as green materials for
degumming of silk. Experiments were designed to deduce the op-
timum processing parameters for degumming process of eri silk
using response surface methodology. Then, a comparison, accord-
ing to alkaline hydrogen peroxide degumming process was effec-
tuated. It indicated that the ionic liquids degumming give better
results in terms of weight loss and absorbency.
Musale and Shukla (2017) published also a new process of
alkaline hydrolysis of polyester to imparting hydrophilicity, smooth
surface and brightness. This process consists of treating polyester
with aqueous or methanolic solutions of sodium hydroxide in the
presence of a quaternary ammonium compound, cetyl-
trimethylammonium bromide CTAB and 1-butyl-3-
methylimidazolium chloride. According to these researchers, the
weak methanolic solution of sodium hydroxide shows greater ef-
fect than the aqueous sodium hydroxide solution. Also, the addition
of 1-butyl-3-methylimidazolium chloride enhances the effect bet-
ter than CTAB.
From these works, it can be concluded that the ecofriendly
application of ionic liquids in textile preparation concerns only
three processes: Wool anti-felt treatment, silk degumming and
alkaline hydrolysis of polyester. These works are very original, but
Table 2
Various applications of ionic liquids in textile preparation processes.
Process Textile material
Anti-felting Wool
Degumming Silk
Alkaline hydrolysis Polyester
more informations, especially about the recyclability of ionic liquids
are needed. Besides, some commercialised cleaner processes of
textile preparation involve the use of organic solvents such textile
scouring and wool carbonising. It will be interesting to explore in
these cleaner processes the feasibility of substitution of these
organic solvents by ionic liquids.
4.3. Textile colouration
The main use of ionic liquids in textile colouration concerns
specially the dyeing field. All data about these ionic liquids uses in
textile colouration are summarised in Table 3. In fact, it can be
found in literature three ecofriendly methods for applying of ionic
liquids in textile dyeing. The first method consists of two steps:
pretreating of textile fibre by an ionic liquid, then the dyeing step
with a conventional procedure. The purpose of this method is to
improve the dyeability of textile fibres. Yuan et al. (2010a; 2010b)
studied the effect of 1-butyl-3-methylimidazolium chloride treat-
ment on C.I. Acid Red 249 adsorption by wool fibres. This ionic
liquid possesses good solubility for wool keratin. Yuan and co-
workers observed that the treatment by 1-butyl-3-
methylimidazolium chloride could produce a remarkable modifi-
cation in the surface and internal structure of the wool fibres as
well as a decrease in their degree of crystallinity. Indeed, the scales
and epicuticles of wool were damaged, making the dye molecules
easily adsorbed at the damaged parts of the surface and directly
diffused into the wool fibres (Yuan et al., 2010a; Rouette, 2001).
Dong (2011) examined the influence of four 1-alkyl-3-
methylimidazolium bromine ionic liquids on the sorption proper-
ties of C.I. Acid Red 249 for nylon 6.6 fibres. The studied numbers of
carbon atom of the alkyl chain are 4, 8, 12 and 16. Dong found that
the quantity of dye sorption at pH 5 and 7 is greatly dependent on
the concentrations of the studied ionic liquids as well as the length
of alkyl groups in these ionic liquids. He analysed the sorption
isotherms of dye on nylon 6.6 using three sorption models: Lang-
muir, Langmuir-Nernst and Redlich-Peterson and he observed that
the Redlich-Peterson equation is the most appropriate model. The
isotherm study shows that the mechanism of the increase in dye
sorption in the presence of ionic liquids at appropriate concentra-
tions is due to the existence of the new positively charged dyeing
sites in nylon 6.6. These new sites are induced by the sorption of
ionic liquids on nylon 6.6.
Kantouch et al. (2011a) found that the ionic liquids 1-ethyl-3-
methylimidazolium acetate and l-butyl-3-methylimidazolium
chloride are effective in enhancing the dyeability of wool and silk
fabrics with acid and reactive dyes at relatively low temperature.
This activation depends on the nature of the substrate and/or the
used dye, as well as dyeing conditions. A maximum enhancement
in the dyeability was obtained upon treatment of wool fabrics with
l-butyl-3-methylimidazolium chloride when using C.I. Acid Blue
203.
Besides, new types of ionic liquids called geminal dicationic
ionic liquids have attracted from both industrial and academic
fields (Wang et al., 2006; Liu et al., 2009). They are surfactant
molecules possessing two hydrophobic tails on two ionic groups
that are linked by a spacer (Fig. 4). Gemini ionic liquids are a new
Ionic liquid References
[BMIM]Cl; [EMIM]Ac (Kantouch et al., 2011b)
[BMIM]Cl (Yuan et al., 2012)
[BMIM]Cl; [BMIM]HSO4 (Vyas and Shukla, 2016)
[EMIM]Cl (Musale and Shukla, 2017)
 N. Meksi, A. Moussa / Journal of Cleaner Production 161 (2017) 105e126 115

Table 3
Various applications of ionic liquids in textile colouration processes.

Colouration process Textile material Ionic liquid References

Dyeing by acid dyes Wool [BMIM]Cl (Yuan et al., 2010a, 2010b)

Dyeing by reactive dyes
Dyeing by basic dyes
Dyeing by disperse dyes
Dyeing by direct dyes
Dyeing by metal-complex dyes
Burnout printing
[BMIM]Cl; [EMIM]Ac (Kantouch et al., 2011a)
[HDEA]Ac; [HDEA]Pr; [HDEA]Bu; [HDEA]Pe (Ribero et al., 2013)
Polyamide 6.6 [BMIM]Br; [OMIM]Br; [DDMIM]Br; [HDMIM]Br (Dong, 2011)
[HDEA]Ac; [HDEA]Pr; [HDEA]Bu; [HDEA]Pe (Ribero et al., 2013)
Silk [BMIM]Cl; [EMIM]Ac (Kantouch et al., 2011a)
Cotton [HDEA]Ac; [HDEA]Pr; [HDEA]Bu; [HDEA]Pe (Ribero et al., 2013)
Polyester [HDEA]Ac; [HDEA]Pr; [HDEA]Bu; [HDEA]Pe (Ribero et al., 2013)
Polyacrylonitrile [HDEA]Ac; [HDEA]Pr; [HDEA]Bu; [HDEA]Pe (Ribero et al., 2013)
Acetate [HDEA]Ac; [HDEA]Pr; [HDEA]Bu; [HDEA]Pe (Ribero et al., 2013)
Wool [BMIM]Cl; [EMIM]Ac (Kantouch et al., 2011a)
Silk [BMIM]Cl; [EMIM]Ac (Kantouch et al., 2011a)
[BMIM]Cl (Cheng, 2011)
Cotton Quaternary ammonium salt ionic liquids (See formula in Fig. 6) (Qingdao University, 2012)
[MIM]Ac (Deutsches Textilforschungszentrum Nord-
West E.V., 2008; Knittel and Schollmeyer, 2007)
Flax [BMIM]Cl; [OMIM]Br; [THTDP]Cl; [EMIM]ESO4; [EMIM]NTf2; (Earle and Seddon, 2009)
[EMIM]TFMS; [C]MS
Polyacrylonitrile [BMIM]Br; [OMIM]Br; [DDMIM]Br; [TDMIM]Br [HDMIM]Br (Dong et al., 2011)
[MIM]Ac (Deutsches Textilforschungszentrum Nord-
West E.V., 2008; Knittel and Schollmeyer, 2007)
Polyester [BMIM]Cl; [BMIM]PF6; [BMIM]BF4; [HEMIM]Cl; [BMIM]DCA; (Bianchini et al., 2015)
[HEMIM]DCA; [C]DHP; [C]Cl
[MIM]Ac; [AMIM]Cl; [P]Ac; [EMIM]Cl (Deutsches Textilforschungszentrum Nord-
West E.V., 2008; Knittel and Schollmeyer, 2007)
Wool [BMIM]Cl; [BMIM]PF6; [BMIM]BF4; [HEMIM]Cl; [BMIM]DCA; (Bianchini et al., 2015)
[HEMIM]DCA; [C]DHP; [C]Cl
Cotton [BMIM]Cl; [BMIM]PF6; [BMIM]BF4; [HEMIM]Cl; [BMIM]DCA; (Bianchini et al., 2015)
[HEMIM]DCA; [C]DHP; [C]Cl
Polyester/cotton [AMIM]Cl (Deutsches Textilforschungszentrum Nord-
blend West E.V., 2008; Knittel and Schollmeyer, 2007)
Cotton [MIM]Ac (Deutsches Textilforschungszentrum Nord-
West E.V., 2008; Knittel and Schollmeyer, 2007)
Polyamide 6.6 [MIM]Ac (Deutsches Textilforschungszentrum Nord-
West E.V., 2008; Knittel and Schollmeyer, 2007)
Polyester/viscose [AMIM]Cl; [MIM]Ac; [BMIM]Cl; [BMIM]Ac; [BMIM]HSO4; (Anonymous, 2010)
blend [EMIM]Ac

specific class of ionic liquids. They have chemical and physical
properties which are different from conventional monocationic
ionic liquids such as high densities and viscosities, better thermal
stabilities and longer liquid ranges. This makes them well suited for
various specific applications like electrolytes (Ito et al., 2000; Zhang
et al., 2007), additives in chromatography (Pino et al., 2007; Qi and
Armstrong, 2007), agents for selectively complexing and extracting
metals (Holbrey et al., 2003), solvents for high-temperature organic
reactions (Han and Armstrong, 2005) and high-temperature lu-
bricants (Zeng et al., 2008).
In this context, Zhuang et al. (2014) synthesised a gemini dica-
tionic imidazolium ionic liquid which is 3,3'-[1,2-
ethanediylbis(oxy-2,1-ethanediyl)]-bis[1-methyl-imidazolium]-
dibromide (PEG150-DIL) (Fig. 5). Then, they applied it for the pre-
treatment of ramie fibre to improve its dyeability by C.I. Reactive
Yellow 4. Zhuang et al. (2014) observed that the colour depth
increased obviously with the duration time and temperature of the
PEG150-DIL. The tensile strength and strength retention of PEG150-
DIL-treated ramie fibres decreased with the increase of pretreat-
ment duration and temperature.
A second approach to apply ionic liquids in textile dyeing con-
sists of using them as auxiliaries in dyeing bath. A Chinese patent
published by Qingdao University (2012), can be found in literature
about this approach. This patent describes the synthesis of qua-
ternary ammonium salt ionic liquids and their application in the
dyeing of cotton by triazine reactive dyes. The general formula of

Fig. 4. Schematic representation of geminal dicationic ionic liquid surfactant. Fig. 5. PEG150-DIL synthesised by Zhuang et al. (2014).
116 N. Meksi, A. Moussa / Journal of Cleaner Production 161 (2017) 105e126
Fig. 6. The general formula of quaternary ammonium salt ionic liquids used in dyeing
of cotton by triazine reactive dyes (Qingdao University, 2012).
quaternary ammonium salt ionic liquids is presented in Fig. 6. Ac-
cording to this patent, the ionic liquid was used with a concen-
tration of 10e20 g/L for replacing traditional inorganic salt and
obtaining the same dye uptake and the same fixation rate to those
of traditional dyeing methods. The dyeing was performed at 60
C
and the pH of dyeing bath was fixed at 8e11.
Meanwhile, Cheng (2011) applied 1-butyl-3-
methylimidazolium chloride to substitute sodium chloride in the
dyeing of silk by Reactive Red B. He showed that this ionic liquid
plays an accelerating agent role in silk dyeing because it enhances
the rate of dye uptake. His investigation on the dyeing mechanism
of silk with ionic liquid revealed that 1-butyl-3-methylimidazolium
chloride interacted with acid groups in surface of silk and dyes
through the electrostatic interaction between cation of the ionic
liquid, acetate group of silk and sulphonate group of dye.
However, Dong et al. (2011) indicated that imidazolium-based
ionic liquids can play a successful retarding role in acrylic dyeing
by cationic dyes. Indeed, the imidazolium-based ionic liquids can
reduce the average dyeing rate and increase the dyeing transition
temperature of acrylic fibre. In this study, experiments of acrylic
dyeing were performed using Methylene Blue as cationic dye and
1-alkyl-3-methylimidazolium bromide with variable length of alkyl
groups (the used number of carbon atom are 4, 8, 12, 14 and 16).
Recently, Bianchini et al. (2015) have presented a study which
reports a new sustainable textile dyeing process in open vessels
employing only three components: pure disperse dye (Disperse
Red 13), water, and an adequate ionic liquid. This dyeing process
was applied successfully at 95
C to dye wool, polyester, and cotton
using an appropriate amount of one of the following ionic liquids:
1-butyl-3-methylimidazolium chloride, 1-(2-hydroxyethyl)-3-
methylimidazolium chloride, 1-butyl-3-methylimidazolium dicya-
namide, and 1-(2-hydroxyethyl)-3-methylimidazolium dicyana-
mide. According to these researchers, bright and intense coloured
fibres were obtained with good colour fastnesses to crocking and
washing. Moreover, their work focused on dyeing of polyester and
wool, in the presence of 1-(2-hydroxyethyl)-3-methylimidazolium
chloride. The authors showed that this ionic liquid assures efficient
dyeing of polyester and wool with total dyebath exhaustion, thus
allowing the recycling of the dye bath. Bianchini et al. (2015) tested
also 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-
3-methylimidazolium tetrafluoroborate, choline dihydrogen phos-
phate and choline chloride, but the obtained results are not very
satisfying.
The third approach is really a revolutionary technique in dyeing
field because it leads to substitute totally the water, which is the
conventional solvent in dyeing processes by recyclable ionic liq-
uids. The new developed cleaner dyeing processes may achieve a
lot of economic and technical benefits when compared to con-
ventional aqueous processes (Anderson, 2010; Choudhury, 2013).
Various positive environmental effects may be obtained, such as
reducing water consumption and eliminating hazardous industrial
effluent. Furthermore, economic benefits will be realised including
increased productivity and energy savings. Preliminary trials in this
field were elaborated by Knittel and co-workers from the Deutsche
Textilforschungszentrum Nord-West e.V. (DTNW) (Deutsches
Textilforschungszentrum Nord-West E.V., 2008; Knittel and
Schollmeyer, 2007). In these trials, different textile fibres were dyed
with conventional available dyes in various ionic liquids. Indeed,
cotton was dyed with direct and bifunctional reactive dyes in 1-
methylimidazolium acetate; polyester with disperse dye in 1-
methylimidazolium acetate, 1-ethyl-3-methylimidazolium chlo-
ride, 1-allyl-3-methylimidazolium chloride and piperidinium ace-
tate; polyacrylonitrile with cationic dye in 1-methylimidazolium
acetate; polyamide 6.6 with a metal-complex dye in 1-
methylimidazolium acetate and polyester/cotton blend with
disperse dye in 1-allyl-3-methylimidazolium chloride. Textiles
were treated with dyes solved in ionic liquids in a non-pressure
system, without the addition of supporting auxiliaries and heated
up by a circulating air oven. According to the authors (Deutsches
Textilforschungszentrum Nord-West E.V., 2008; Knittel and
Schollmeyer, 2007), all cleaner processes achieved good dyeing
results, and good washing fastnesses. So, the first trials of dyeing
are very promising, but researches in this area are still needed to
increase output from laboratory scale to industrial levels.
Therefore, a research project has been launched by Centexbel
(the Belgian Textile Research Centre) with the collaboration of the
Deutsche Textilforschungszentrum Nord-West e.V. (DTNW) in or-
der to valorise the first obtained results of DTNW and to develop the
principles of an operational technique to dye natural and synthetic
fibres in ionic liquids (Centexbel, 2012).
Afterwards, Earle and Seddon (2009) from the Queen's Univer-
sity of Belfast published a patent in which they described a novel
ecofriendly method of dyeing of natural cellulosic and protein fi-
bres by reactive dyes in ionic liquids. In this patent, the inventors
presented only some examples of dyeing of linen fabrics by Reac-
tive Blue 116 using various kinds of ionic liquids and under several
conditions of temperature and dyeing duration. From these ex-
amples, Earle and Seddon (2009) found that the following ionic
liquids: 1-butyl-3-methylimidazolium chloride, 1-octyl-3-
methylimidazolium chloride, trihexyltetradecylphosphonium
chloride and 1-ethyl-3-methylimidazolium ethylsulfate can
significantly increase the rate of dyeing. However, choline meth-
anesulfonate produced very poor dyeing results. Besides, 1-ethyl-3-
methylimidazolium bis(trifluoromethylsulfonyl)imide and 1-ethyl-
3-methylimidazolium trifluoromethanesulfonate were found to
have low solubility for the Reactive Blue 116 dye. So, the authors
recommended the addition of a minor amount of a co-solvent to
increase the dye solubility.
Later, textile researchers in Portugal (Ribero et al., 2013) studied
the dyeing of multifibre textile fabrics composed by acetate, cotton,
polyamide 6.6, polyester, acrylic and wool by C.I. Acid Orange 67
using ionic liquids as a solvent instead of water. They used
diethanolamine-based ionic liquids with different anions: 2-
hydroxydiethanolamine acetate, 2-hydroxydiethanolamine propi-
onate, 2-hydroxydiethanolamine butanoate, and 2-
hydroxydiethanolamine pentanoate. It was found that it is
possible to obtain in one dyeing process using only acid dyes and
ionic liquid, the colouration of all textile fibres. According to the
authors, the obtained results confirm those of Knittel and co-
workers (Deutsches Textilforschungszentrum Nord-West E.V.,
2008; Knittel and Schollmeyer, 2007). However, many studies
should still be considered such as: the dyeing yield, the tempera-
ture variation, the dye solubility, the process interaction between
ionic liquid, dye and fibre, the dyeing fastnesses, the dyebath
 N. Meksi, A. Moussa / Journal of Cleaner Production 161 (2017) 105e126
recycling and the costs.
In textile printing, to the best of our knowledge, few works have
been reported on the application of ionic liquids in this field. It can
be found that ionic liquids were firstly applied as a component in
the formulation of aqueous ink compositions for ink jet printing to
replace hazardous solvents, avoid precipitation of the dye and
provide them good heat stability (Schwarz, 2000). Nevertheless,
there is no data about the performances of this ink jet printing
process in textile fibres. The solubility of cellulose fibres in some
ionic liquids was exploited in burnout printing. This technique uses
blended fabrics which combine protein-based fibres or polyester
with cellulose-based fibres such as viscose or cotton. In order to
create the famous 'burnout' pattern, a toxic printing paste con-
taining a thickening agent and sodium hydrogen sulphate is
habitually applied to the fabric in patterns, dissolving away the
cellulose-based fibres and leaving behind the second fibre, which
are not affected by the chemical. Researchers from China
(Anonymous, 2010) explored methylimidazolium-based ionic liq-
uids in the burnout printing of polyester/viscose mix fabric. The
technique is cleaner and promising, but it is still not efficient to
replace completely the sodium hydrogen sulphate technique.
In this area, researchers reported various works about the eco-
friendly application of ionic liquids in textile dyeing. It can be seen
that most of textile dye classes were investigated in these works.
However, some classes like direct dyes and metal-complex dyes are
becoming more and more abandoned by dyers for ecological rea-
sons. So, in order to be effective, future studies should be focused on
the most consumed dye classes in textile industry such as: reactive
dyes, disperse dyes, vat dyes and indigo. Besides, in textile printing,
ink-jet and serigraphy processes are very emerging processes.
Certainly, researches about the ecofriendly application of ionic
liquids in these processes will be very fascinating for textile re-
searchers and industrialists.
4.4. Textile finishing
The applications of ionic liquids in textile finishing are generally
limited to certain classes of them, which in addition to their
ecological benefits are also able to impart novel properties to textile
materials due to the nature of their molecular structures. Data
about these applications are shown in Table 4. Among these ionic
liquids classes, we can cite imidazolium, pyridinium, and quater-
nary ammonium ionic liquids. These groups of ionic liquids were
found to possess antibacterial potential (Pernak et al., 2004;
Kathryn and Charles, 2005). This has encouraged a number of re-
searchers to impart durable antimicrobial functionality to textile
fabrics through ionic liquid treatments. El-Sayed et al. (2011) pre-
pared an anionic agent, dichlorotriazinylaminobenzene sulphonate
Table 4
Various applications of ionic liquids in textile finishing processes.
Finishing process Textile material
Antibacterial finishing Viscose
Wool
Cotton
Antifungal finishing Flax
UV-protection finishing Cotton
Flame-retardant finishing Cotton
Polyamide 6.6/Nylon blend
Water-repellent finishing Cotton
Comfort finishing Polyester
a
No data.
117
and applied it to viscose fabrics. Then, the modified fabrics were
treated with various ionic liquids: 1-butyl-3-methylimidazolium
bromide, 1-butyl-3-methylimidazolium chloride, 1-ethyl-3-
methylimidazolium acetate and 1-ethyl-3-methylimidazolium
ethylsulphate. The researchers claimed that these treated viscose
fabrics have excellent bacterial resistance to gram-positive and
gram-negative bacteria. They also observed that the substantivity
of the ionic liquid agent to viscose fabric and hence the bactericidal
effect increased in the following order (El-Sayed et al., 2011):
[BMIM]Br > [BMIM]Cl > [EMIM]ESO4 > [EMIM]Ac
According to the authors, good durability of the treated fabrics
was observed after 10 washing cycles.
In another study, the same research team (Kantouch et al., 2013)
investigated the effect of pretreatment of wool fabric with another
anionic agent sodium 4-(4,6-dichloro-1,3,5-triazinylamino)-ben-
zenesulfonate, followed by treatment with 1-butyl-3-
methylimidazolium chloride or 1-butyl-3-methylimidazolium
bromide with the purpose of reaching durable antibacterial prop-
erties of the fabric. They found that the pretreatment of wool with
the anionic agent increases the anionic sites along wool keratin
macromolecule and thus increases the exhaustion percent as well
as the fixation of ionic liquid onto keratin. The results showed that
both ionic liquids 1-butyl-3-methylimidazolium bromide and 1-
butyl-3-methylimidazolium chloride give a permanent antibacte-
rial effect towards gram-negative bacteria when fixed on wool
fabric properly.
In a recent work, Shukla and co-workers (Arputharaj et al., 2017)
examined the application of nano zinc oxide (nano-ZnO) as an
antibacterial agent onto cotton fabric by the exhaustion method
using the ionic liquid 1-butyl-3-methylimidazolium chloride. First,
they found that the use of this ionic liquid leads to improve the
uptake and fixation of nano-ZnO on cotton fabrics. Besides, their
results revealed that ZnO-functionalised cotton fabrics have
bacteriostatic activity against both gram-positive and gram-
negative bacteria. The ZnO-functionalised cotton fabrics present
also an excellent UV-blocking ability, particularly in the region of
the 280e370 nm. The authors reported that the use of 1-butyl-3-
methylimidazolium chloride offers to ZnO-treated fabrics more
durability in regard to antibacterial activity and UV protection, after
five hand washes.
Foksowicz-Flaczyk and Walentowska (2013) were interested in
the antifungal activity of ionic liquids applied to linen fabric. In
their work, an ammonium-based ionic liquid with nitrate anion
named didecyldimethylammonium nitrate was tested as an
antifungal agent. They observed that the use of high concentration
of this ionic liquid is necessary to achieve a good antifungal
Ionic liquid References
[BMIM]Cl; [EMIM]Ac; [BMIM]Br; [EMIM]ESO4 (El-Sayed et al., 2011)
[BMIM]Br; [BMIM]Cl (Kantouch et al., 2013)
[BMIM]Cl (Arputharaj et al., 2017)
[DDA]N (Foksowicz-Flaczyk and Walentowska, 2013)
[BMIM]Cl (Arputharaj et al., 2017)
[BMIM]Br (Cheng et al., 2017)
[HMDMIM]Br (Xu, 2011)
[MOMIM]DMP; [AMIM]DMP (Xu, 2014)
[HPMIM]Br; [TBP]DEP (Hariprakasha et al., 2014)
[MTESPIM]Cl; [MTESPP]Cl (Boukhriss et al., 2016)
[TBOP]Br; [TBAP]Br; [TBAP]DBP; [TBAP]Ac (Hariprakasha et al., 2014)
[MTESPIM]Cl; [MTESPP]Cl (Boukhriss et al., 2016)
n.d.a (Opwis et al., 2013)
118 N. Meksi, A. Moussa / Journal of Cleaner Production 161 (2017) 105e126
activity (0.5% of antifungal agent per 1 g of the dry fabric). This
concentration causes visible inhibition of mould growth on the
fabric surfaces. It also provokes less damage to the fabric structure
and surface in comparison to untreated linen fabric. However,
there is no data about the degree of durability of this antifungal
finishing.
Furthermore, the presence of ammonium, phosphonium and
sulfonium cations in many ionic liquids encouraged Xu (2011) to
exploit them in flame-retardant finishes for textile fabrics. Ac-
cording to Xu, this new generation of flame retardants based on
ionic liquids have various advantages; they are halogen free, show
negligible volatility and are thermally stable. They also offer su-
perior flame retarding performances with minimum effects on
mechanical properties. These ecofriendly flame-retardants can be
applied by immersion of the textile in a bath containing the ionic
liquid followed by drying at 90
C and finally curing at 170
C for a
few minutes. They can be also applied through coating process.
Although, Xu tried to provide in his patent (Xu, 2011) an exhaustive
range of ionic liquids which may probably present all classes of
ionic liquids, he reported only the application of hydrox-
ymethylimidazolium ionic liquid derivatives in particular 5-
(hydroxymethyl)-1,1-dimethyl-1H-imidazol-1-ium bromide in the
flame-retardant finishing of cotton fabrics without giving any in-
formation about the performances of this process. Later, a second
patent was published by Xu (2014) about the use of phosphinate
ionic liquids as flame retardants for textile fabrics. In this second
patent, Xu described the application of 1-methyl-3-(oxiran-2-
ylmethyl)-1H-imidazol-3-ium dimethylphosphinate and 1-allyl-3-
methylimidazolium dimethylphosphinate in flame retarding fin-
ishing of cotton using the same process that is reported in his first
patent. All these patented processes are now commercialised by the
start-up, Ionic Flame Retardant Inc.
In 2014, Hariprakasha et al. (2014) published another patent
which is related to the synthesis of amine and hydroxyl function-
alised ionic liquids (especially ionic liquids based on imidazolium
cations and phosphonium cations) and their application as flame
retardants for textile materials. As an example, they reported firstly
the direct application of 3-hydroxypropyl-1-methylimidazolium
bromide on cotton fabrics. They observed that this ionic liquid is
an efficient flame retardant agent because the fire is immediately
extinguished when the flame was disappeared. They also described
a layer by layer process which consists of treating cotton fabric by
tetrabytylphosphonium diethylphosphate followed by coating it
with a solution of acrylamido-2-propane-sulfonic acid (a mono-
mer) and N,N’-methylene bisacrylamide (a crosslinker) and finally
drying. This produces an in-situ polymerisation that strongly binds
the ionic liquid around textile fibres. According to inventors, this
cleaner process improves considerably the flame retardancy of
cotton fabrics. Besides, the inventors presented other examples of
coating solutions which are intended for polyamide 6.6/cotton
(NYCO) blends to impart highly durable flame-retardant effect with
good antielectrostatic properties. Among these coating solutions,
they proposed the use of the following mixtures: hydroxypropyl-
tributylphosphonium bromide/urea, tribu-
tylaminoproppylphosphonium bromide/urea,
tributylaminoproppylphosphonium dibutylphosphate/urea and
tributylaminoproppylphosphonium acetate/urea.
Afterwards, Boukhriss et al. (2016) developed a novel eco-
friendly finishing method which consists of treating cotton fabrics
with sols containing 1-methyl-3-(triethoxysilylpropyl)imidazolium
chloride and 1-methyl-3-(triethoxysilylpropyl)pyridinium chloride
by the pad-dry-cure process followed by an impregnation in a
diluted solution of hexafluorophosphoric acid. After these treat-
ments, the finished fabrics showed excellent water-repellent and
flame-retardant properties. However, the authors indicated that
more studies are still indispensable to improve the durability of this
finish.
Additionally, Cheng et al. (2017) demonstrated that it is possible
to endow to cotton fabric good UV protection property using ionic
liquid iron coordination complex. In their work, Cheng et al. (2017)
prepared the ionic liquid iron coordination complex by in situ re-
action on the surface of the cotton fibre directly using 1-butyl-3-
methylimizolium bromide and iron (II) sulphate. During the in-
situ reaction, Fe2þ cations interact with cotton fibres by electro-
static interaction and simultaneously coordinate with 1-butyl-3-
methylimizolium bromide to form the ionic liquid iron coordina-
tion complex particles on the surface of cotton fabric. The authors
claimed that the modified cotton fabric presents excellent washing
resistance.
Recently, Opwis et al. (2013) developed an innovative finishing
process for polyester fibres. This process which consists of deposing
cellulosic materials onto polyester fibres via ionic liquids solutions
can achieve cotton-like surfaces on the synthetic core fibre. Ac-
cording to the authors, the new cellulose modified-polyester fibre,
promising the “cotton feeling”, can be of interest not only for
apparel, but also in the field of technical textiles.
Most of the studies presented in this section show that ionic
liquids can be successfully applied in textile finishing as function-
alising agents. The results may also be improved if ionic liquids will
be applied in connection with radiations such as gamma, plasma,
microwave, electron beam, ultrasonic, etc. Besides, the high sol-
vating properties of ionic liquids lead us to think that these green
solvents can probably be good media to apply many classic func-
tionalising agents. Certainly, this will generate in the future a lot of
economic and ecological benefits for textile finishers.
4.5. Textile wastewater treatment
Several activities of textile industry generate large volumes of
hazardous species in their wastewater effluents in particular dyeing
and printing. The dyeing wastewaters contain residual amounts of
dyes and chemicals which represent undesirable classes of com-
pounds and require special treatments. These products prevent
photosynthesis of the aqueous flora, and may affect humans,
causing allergies, dermatitis, skin irritations, cancers and
mutagenicity.
So, the treatment of dye wastewaters becomes more indis-
pensable than ever to avoid these ecological problems generated by
the direct release of them into the environment. To remove dyes
from wastewaters, a lot of techniques such as biological treatments,
coagulation/flocculation, chemical oxidation, membrane filtration,
ion-exchange, photocatalytic degradation, reverse osmosis pro-
cesses, electrochemical treatments and adsorption have been
developed. Advantages and disadvantages of each technique have
been extensively reviewed (Forgacs et al., 2004; Singh and Arora,
2011).
In recent years, certain studies demonstrated that ionic liquids
can be successfully used to remove textile dyes from aqueous
medium. The most processes reported in the literature involve the
application of extraction liquid-liquid processes. However, it can be
also found other processes like adsorption and biodegradation.
Many of these studied processes are very promising because they
enable not only to remove textile dyes from aqueous media, but
also to recover and reuse them with high percentages. Among the
investigated processes, azo dyes remain the most studied dyes due
especially to their known potential toxicity. The performances of
the studied extraction liquid-liquid processes are evaluated by
determining generally the distribution coefficient (D) or the parti-
tion coefficient (PIL/W) which represents the ratio between the dye
concentration in the organic layer and the dye concentration in the
 N. Meksi, A. Moussa / Journal of Cleaner Production 161 (2017) 105e126 119

aqueous layer, as well as the dye removal and/or the extraction
efficiencies. The performances of the studied adsorption processes
are evaluated by determining the maximum adsorption capacity
and sometimes the dye removal efficiency. The studied biodegra-
dation processes are only evaluated by measuring the dye removal
efficiency. Data about the developed extraction liquid-liquid pro-
cesses, the targeted dyes, the used ionic liquids as well as the cor-
responding performances are furnished in Table 5, whereas data
corresponding to the developed adsorption and biodegradation
processes are given in Table 6.
4.5.1. Removal of acid dyes
Vijayaraghavan et al. (2006) were the pioneers who successfully
used 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)
imide to extract from water two azo acid dyes (C.I. Acid Blue 113
and C.I. Acid Red 115) with an extraction efficiency of 98%. At the
same time, two kinds of acid dyes were recovered and the ionic
liquid was reused. Later, Li and co-workers (Li et al., 2007; Li and
Xin, 2008) investigated the extraction of azo acid dyes (C.I. Acid
Yellow 25 and C.I. Acid Red 14) and anthraquinone acid dye (C.I.

Table 5
Various applications of ionic liquids in removal of textile dyes via extraction liquid-liquid processes.

Textile dye class Dye generic name Ionic liquid Distribution coefficient (D) or Removal efficiency (%) or References
Partition coefficient (PIL/W) extraction efficiency (%)

Acid dyes C.I. Acid Blue 113 [BMPY]NTf2 2 95 (Vijayaraghavan et al.,

C.I. Acid Red 115 n.d.a 98 2006)
C.I. Acid Yellow 25 [BMIM]PF6 128.92e130.25 81.31e99.98 (Li et al., 2007; Li and
C.I. Acid Blue 80 15.13 60.21 Xin, 2008)
C.I. Acid Red 14 424.8 n.d.a
C.I. Acid Orange 52 [BMIM]PF6 21.5e32.7 85e99 (Pei et al., 2007)
[HMIM]PF6 119e158
[OMIM]PF6 483e657
C.I. Acid Red 87 [BMIM]PF6 0.179e0.627 100
[HMIM]PF6 1.92e10.1
[OMIM] PF6 30.3e117
C.I. Acid Orange 10 [BMIM]PF6 0.174e0.526 69
[HMIM]PF6 0.464e1.66
[OMIM]PF6 4.06e23.3
C.I. Acid Red 2 [BMIM]PF6 0.03e1235.3 n.d.a (Fan et al., 2011)
[HMIM]PF6 1.28e2167.9
[OMIM]PF6 7.97e3218.4
[HMIM]BF4 13.05e2225
[OMIM]BF4 149.5e3367.5
C.I. Acid Orange 52 [TCMA]SCN 42.57e258.97 89.09 (Chen et al., 2013)
[TCMA]DCA 2.75e9.13
[TCMA]Be 1.1e2.76
[TCMA]Hex 1.02e2.98
C.I. Acid Orange 52 [HGU]NTf2 165e1375 n.d.a (Bouchal et al., 2016)
[OGU]NTf2 214e1951
[DGUA]NTf2 226e2494
[BMIM]NTf2 0.29e0.34
Weak Acid Blue 6B [BMIM]PF6 n.d.a >90 (Lin et al., 2014)
Basic dyes C.I. Basic Blue 9 [BMIM]PF6; [BMIM] n.d.a 99 (Ali et al., 2006, 2008)
C.I. Basic Orange 14 BF4; [HMIM]Br;
C.I. Basic Red 5 [BMIM]NTf2
C.I. Basic red 2
C.I. Basic Blue 12
C.I. Basic Blue 9 [TCMA]SCN 1.22e8.95 64.14 (Chen et al., 2013)
[TCMA]DCA 0.77e5.54
[TCMA]Be 0.24e0.64
[TCMA]Hex 0.22e0.57
C.I. Basic Blue 9 [BMIM]PF6 n.d.a 97.8 (Talbi et al., 2014)
C.I. Basic Violet 10 [BBIM]NTf2 40134.83 >88 (Fan et al., 2016)
[BBIM]PF6 12088.38
C.I. Basic Blue 9 [HPIM]NTf2 n.d.a 97.96 (Kermanioryani et al.,
[BEMIM]NTf2 94.84 2016)
[BMIM]NTf2 91.30
[HMIM]NTf2 90.86
[OMIM ]NTf2 85.96
C.I. Basic Blue 9 [TBP]TFMS n.d.a 84.95 (Ullah et al., 2016)
[TBP]NTf2
[TBP]PF6
[TBP]BF4
Reactive dyes C.I. Reactive Black 5 [BMIM]PF6 4.59 81.59 (Li et al., 2007)
C.I. Reactive Yellow 145 n.d.a 82.68
Other dye classes C.I. Direct Red 28 [HMIM]NTf2 n.d.a 95e100 (Gharehbaghi and
Shemirani, 2012)
C. I. Vat Blue 1 [TBP]Br ∞ ~100 (Ferreira et al., 2014)
[TBP]Cl
[TBMP]MS
[TIBMP]Ts
a
No data.
120 N. Meksi, A. Moussa / Journal of Cleaner Production 161 (2017) 105e126

Table 6
Various applications of ionic liquids in removal of textile dyes via adsorption and biodegradation processes.

Textile dye Process Dye generic name Ionic liquid Adsorption capacity Removal efficiency References
class (mg g1) (%)

Acid dyes Adsorption C.I. Acid Blue 74 [BMIM]PF6 n.d.a >95 (Fat'hi et al., 2012)
C.I. Acid Orange 7 [AEVIM]Cl 925.09 n.d.a (Gao et al., 2013)
C.I. Acid Red 27 547.17
C.I. Acid Orange 52 [MTESPIM]Cl 135 n.d.a (Zarezadeh-Mehrizi et al.,
2013)
a
C.I. Acid Red 87 [PMIM]Cl 15e25 n.d. (Tkachenko et al., 2014)
C.I. Acid Red 27 [MDHIM]Br 263.2 >90 (Lawal and Moodley, 2015)
C.I. Acid Red 1 [HDHIM]Br 909 n.d.a (Lawal and Moodley, 2016)
C.I. Acid Orange 7 n.d.a 153.06 n.d.a (Cheng et al., 2016)
C.I. Acid Red 27 84.40
Biodegradation C.I. Acid Blue 113 [C]Sa; [C]DHP; [C]La; [C]Ta e 60e92 (Sekar et al., 2012)
Reactive dyes Adsorption C.I. Reactive Red 120 [HMIM]Br 166.67 99.98 (Absalan et al., 2011)
C.I. Reactive Black 5 n.d.a 161.29 98.5 (Poursaberi and Hassanisadi,
2013)
C.I. Reactive Red 141 [OMIM]Br 71.4 >98 (Kamran et al., 2014)
C.I. Reactive Yellow 62.5
81
C.I. Reactive Blue 4 [PMIM]Cl 10e16 n.d.a (Tkachenko et al., 2014)
Reactive Red B-3BD [BMIM]Br; [OMIM]Br; [BEIM]Br; n.d.a 97 (Cheng et al., 2015a)
[OEIM]Br
C.I. Reactive Blue 19 [BMIM]Br n.d.a 98 (Cheng et al., 2015b)
C.I. Reactive Orange [TDMIM]Br 51.546 >98 (Ahmadi et al., 2016)
122
C.I. Reactive Orange [HEA]Fo 165 n.d.a (Zhou et al., 2016)
5 [HEA]Ac 320
[HEA]La 54
[THEA]Fo 156
[THEA]Ac 105
[THEA]La 280
[HEOA]Fo 128
[HEOA]Ac 233
[HEOA]La 60
a
No data.

Acid Blue 80) from aqueous solutions using 1-butyl-3-
methylimidazolium hexafluorophosphate. In the case of C.I. Acid
Yellow 25, they found a removal efficiency, which varies between
81.31% and 99.98%. However, in the case of C.I. Acid Blue 80, they
obtained a removal efficiency of 60.21%. They also showed that the
extraction process of acid dyes adopts the form of anion exchange
and the soluble part of the ionic liquid plays an important role as
counter-ions. Meanwhile, Pei et al. (2007) studied the following
imidazolium-based ionic liquids: 1-butyl-3-methylimidazolium
hexafluorophosphate, 1-hexyl-3-methylimidazolium hexa-
fluorophosphate and 1-octyl-3-methylimidazolium hexa-
fluorophosphate for the removal of acid dyes from aqueous
solutions including two azo acid dyes (C.I. Acid Orange 10 and C.I.
Acid Orange 52) and one eosin acid dye (C.I. Acid Red 87). They
found that the extraction efficiencies of dyes were strongly affected
by the pH of the aqueous phase. Under the optimised pH condition,
they obtain an extraction efficiency of 85e99% for C.I. Acid Orange
52, 69% for C.I. Acid Orange 10 and almost 100% for the eosin acid
dye. Fan et al. (2011) investigated also the liquid-liquid extraction
using various imidazolium-based ionic liquids for the removal of
C.I. Acid Red 2. In their work, Fan and co-workers reported that the
distribution coefficient D is highly influenced by the pH of the
water phase and the type of salts added. The distribution coefficient
D increases generally with increasing alkyl chain length on the
cations of the ionic liquids and the extraction efficiencies using
tetrafluoroborate-based ionic liquids were higher than that of
hexafluorophosphate. Lin et al. (2014) used also 1-butyl-3-
methylimidazolium hexafluorophosphate to recover the Weak
Acid Blue 6B from dyeing wastewater via liquideliquid extraction
process. They achieved an extraction efficiency, which exceeds 90%.
Then, the collected solvent including Weak Acid Blue 6B was
sequentially applied in the Tussah silk dyeing process as a retarding
agent. The authors claimed that the used ionic liquid was an
excellent retarding agent which offers an increase of dyeing per-
formances of Tussah silk. So, it could be used to replace traditional
inorganic salt in silk dyeing and achieve an environmental friendly
dyeing technology of Tussah.
The extraction of C.I. Acid Orange 52 from water using four non-
fluorine quaternary ammonium-based ionic liquids, i.e. tricap-
rylmethylammonium thiocyanate, tricaprylmethylammonium
dicyanamide, tricaprylmethylammonium benzoate and tricap-
rylmethylammonium hexanoate was performed by Chen et al.
(2013). These researchers indicated that tricaprylmethylammo-
nium thiocyanate exhibits optimal ability for extracting acid dye
with extraction efficiency equal to 89.09%. They also mentioned
that the extraction efficiency is remarkably increased by adding
sodium chloride in the extraction system except in the case of tri-
caprylmethylammonium thiocyanate. Recently, Bouchal and co-
workers (Bouchal et al., 2016) tried other kinds of ionic liquids for
the removal of C.I. Acid Orange 52 from solutions which are mon-
oalkylguanidinium bis-trifluoromethane sulfonimides. They are
functional ionic liquids and non miscible with water. According to
Bouchal et al. (2016) alkylguanidinium-based ionic liquids show
significantly enhanced extraction efficiency compared to conven-
tional imidazolium-based ionic liquids.
Other researchers were interested in using the adsorption pro-
cess to remove acid dyes from wastewaters. Their approach in-
volves the synthesis or the modification of some known adsorbents
by using ionic liquids in order to improve their adsorption capacity.
In their research published in 2012, Fat'hi et al. (2012) immobilised
1-butyl-3-methylimidazolium hexafluorophosphate on the basic
alumina. Then, the modified material was applied as adsorbent to
 N. Meksi, A. Moussa / Journal of Cleaner Production 161 (2017) 105e126
remove indigo carmine (C.I. Acid Blue 74) which is a non azo acid
dye. They observed that indigo carmine is quantitatively adsorbed
due to its interaction with the ionic liquid. They reported that under
optimised conditions, removal efficiencies can achieve percentages
which are superior to 95%. Later, several azo acid dyes were studied
by many researchers. Gao et al. (2013) synthesised a functional
ionic liquid crosslinked polymer by polymerisation of 1-
aminoethyl-3-vinylimidazolium chloride and divinylbenzene.
Then, it was applied as adsorbent for the removal of two acid dyes
(C.I. Acid Orange 7 and C.I. Acid Red 27). Gao and co-workers
showed that this new material possesses a high adsorption ca-
pacity to treat acid dye solutions due to its functional groups. The
maximum adsorption capacities obtained at 25
C are 925.09 and
547.17 mg g1 for C.I. Acid Orange 7 and C.I. Acid Red 27, respec-
tively. Zarezadeh-Mehrizi et al. (2013) synthesised another ionic
liquid functionalised adsorbent by grafting of 1-methyl-3-(trie-
thoxysilylpropyl)imidazolium onto nanoporous silica. This syn-
thesised adsorbent shows an adsorption capacity of 135 mg g1
towards C.I. Acid Orange 52. After that, Tkachenko et al. (2014)
investigated the possibility of removing C.I. Acid Red 87 from so-
lutions using silica chemically modified with 1-propyl-3-
methylimidazolium chloride. They observed that the maximum
dye adsorption occurs from mildly acidic solutions (pH~4) with an
effective capacity of adsorption equal to 15e25 mg g1. The authors
showed also that the modified material can successfully be regen-
erated in an easy and cheap way. Afterwards, Lawal and Moodley
(2015) prepared another ionic liquid (1-methyl-3-
decahexylimidazolium bromide) for the modification of sodium
montmorillonite. Then, the modified montmorillonite was used for
the removal of C.I. Acid Red 27 from aqueous solutions. The authors
indicated that this new material can reach a removal percentage
higher than 90% at an optimum pH of 2 and with an adsorption
capacity which is equal to 263.2 mg g1. Later, in a second study,
Lawal and Moodley (2016) reported the adsorption of C.I. Acid Red 1
on kaolin modified with 1-hexyl-3-decahexylimidazolium bro-
mide. They showed that this modified kaolin offers a high
adsorption capacity (909 mg g1) and the adsorption process is
likely to be chemisorption. Recently, Cheng et al. (2016) have
published a novel work about the synthesis of an amino ionic liquid
modified super paramagnetic mesoporous core/shell nano-
composite and its application as adsorbent to remove two azo acid
dyes: C.I. Acid Orange 7 and C.I. Acid Red 27. They mentioned that
the maximum adsorption capacities are reached at pH 2 due to the
protonation of amino groups. The maximum adsorption capacities
are 153.06 and 84.40 mg g1 for C.I. Acid Orange 7 and C.I. Acid Red
27, respectively.
In 2012, a third promising process to remove acid dyes from
wastewaters was suggested by Sekar et al. (2012). This process
consists of using choline-based ionic liquids as the co-substrate
with S. Lentus in the biodegradation of C.I. Acid Blue 113 in
aqueous solution. Sekar et al. (2012) demonstrated that after 72 h,
this azo acid dye is degraded to less toxic components and the
degradation efficiency varies between 60 and 92%, according to the
nature of the choline-based ionic liquid used.
4.5.2. Removal of basic dyes
The basic or cationic dyes are another class of textile dyes that
have received much attention of researchers. For this dye class, it
can be observed that only the extraction liquid-liquid processes are
studied and Methylene Blue (C.I. Basic blue 9) is the most basic dye
investigated. Ali et al. (2006, 2008) were first researchers who
showed that the addition of a small amount of 1-butyl-3-
methylimidazolium hexafluorophosphate to aqueous solutions of
basic dyes: C.I. Basic Blue 9, C.I. Basic Orange 14, C.I. Basic Red 5, C.I.
Basic Red 2 and C.I. Basic Blue 12, at higher concentrations
121
(1.5 mM), resulted in the precipitation of almost all the cationic dye
from the solution. They also investigated the precipitation of these
basic dyes with three other ionic liquids: 1-butyl-3-
methylimidazolium tetrafluoroborate, 1-butyl-3-
methylimidazolium bis(trifluoromethylsulfonyl)imide and 1-
hexyl-3-methylimidazolium bromide (Ali et al., 2006, 2008). After
the addition of 1.7 wt% of the above ionic liquids to 1.5 mM aqueous
cationic dye solutions, it was found that the precipitation effi-
ciencies of the studied cationic dyes with 1-butyl-3-
methylimidazolium tetrafluoroborate and 1-butyl-3-
methylimidazolium are similar to those observed in the case of 1-
butyl-3-methylimidazolium hexafluorophosphate. Talbi et al.
(2014) were interested in the addition of a non-ionic surfactant
(Triton X-114) during the extraction of C.I. Basic Blue 9 by 1-butyl-
3-methylimidazolium hexafluorophosphate. Talbi and co-workers
indicated that the use of the non-ionic surfactant-ionic liquid sys-
tem, the extraction efficiency could reach 97.8%. In addition to C.I.
Acid Orange 52, Chen et al. (2013) studied the extraction of C.I. Basic
Blue 9 by various non-fluorine quaternary ammonium-based ionic
liquids. Using tricaprylmethylammonium thiocyanate, they ob-
tained extraction efficiency equal to 64.14%. This value is inferior to
that of the acid dye previously mentioned. Later, Fan et al. (2016)
investigated the removal of C.I. Basic Violet 10 by benzyl-
functionalised ionic liquids from water. Their results indicate that
the extraction efficiency of this basic dye by these ionic liquids
remains rather high (>88%) in the range of pH 2e12 and is affected
by the volume ratio as well as the presence of sodium chloride.
Meanwhile, Kermanioryani et al. (2016) prepared two designed
ionic liquids based on bis(trifluoromethylsulfonyl)imide anion: 1-
hexyl-2-phenylimidazolium bis(trifluoromethanesulfonyl)imide
and 1-benzyl-3-methylimidazolium bis(trifluoromethanesulfonyl)
imide. The purpose of their study is to compare the extraction
performances of these functionalised ionic liquids towards three
commercial ionic liquids based also on bis(trifluoromethylsulfonyl)
imide anion: 1-butyl-3-methylimidazolium bis(trifluoromethane
sulfonyl)imide, 1-hexyl-3-methylimidazolium bis(tri-
fluoromethanesulfonyl)imide and 1-octyl-3-methylimidazolium
bis(trifluoromethanesulfonyl)imide. Their results show that the
incorporation of the functional group (aromatic group) not only led
to excellent results of removing C.I. Basic Blue 9 from aqueous so-
lution compared to commercially available ones, but also allowed
easier recovery and subsequent reuse of the functionalised ionic
liquids. In parallel with this work, the removal of the same basic dye
using phosphonium-based hydrophobic ionic liquids with flourous
anions was investigated by Ullah et al. (2016). In this work, the
authors claimed that these ionic liquids show good performances
and offer colour removal efficiency of 84.95%.
4.5.3. Removal of reactive dyes
Currently, reactive dyes occupy an extremely important place in
the textile dyes market. These dyes are mainly used to colour
cellulosic as well as wool materials. The first study about the
removal of reactive dyes from water using ionic liquids was elab-
orated in 2007 by Li et al. (2007) through an extraction liquid-liquid
process. In this work, researchers used 1-butyl-3-
methylimidazolium hexafluorophosphate as an ionic liquid and
two azo reactive dyes (C.I. Reactive Black 5 and C.I. Reactive Yellow
145). The authors indicated that the removal of reactive dyes is low
(5.45% and 31.48% for C.I. Reactive Black 5 and C.I. Reactive Yellow
145, respectively). However, the obtained values can be greatly
increased by the addition of dicyclohexyl-18-crown-6. This reagent,
with the strong complexation ability towards metal ions, enables to
achieve removal efficiencies which are equal to 81.59% and 82.68%
for C.I. Reactive Black 5 and C.I. Reactive Yellow 145, respectively.
Later, many studies looked at the application of the adsorption
122 N. Meksi, A. Moussa / Journal of Cleaner Production 161 (2017) 105e126
process to remove reactive dyes from water. In this regard, Iranian
researchers focused their efforts to modify magnetic nanoparticles
(especially those of Fe3O4) by ionic liquids to improve their
adsorption performances. Pure magnetic nanoparticles have
already shown a high specific surface area and the absence of in-
ternal diffusion resistance (Chang and Chen, 2005). The first work
regarding the modification of Fe3O4 magnetic nanoparticles by
ionic liquids was elaborated by Absalan et al. (2011) using 1-hexyl-
3-methylimidazolium bromide. Then, the new modified materiel
was applied as adsorbent to remove C.I. Reactive Red 120 from
aqueous solutions. The maximum adsorption capacity and the
percent removal of dye achieved are 166.67 mg g1 and 99.98%,
respectively. Similarly, Poursaberi and Hassanisadi (2013) investi-
gated magnetite nanoparticles functionalised with an
imidazolium-based ionic liquid as an efficient nano adsorbent for
the removal of C.I. Reactive Black 5 from dyeing wastewater. They
indicated that the dye removal efficiency of this nano adsorbent is
98.5% and its maximum adsorption capacity is 161.29 mg g1.
Kamran et al. (2014) explored also the modification of nano-
particles of Fe3O4 by another ionic liquid, the 1-octyl-3-
methylimidazolium bromide and its application to remove C.I.
Reactive Red 141 and C.I. Reactive Yellow 81. Their experimental
results indicate that the modified Fe3O4 nanoparticles removed
more than 98% of reactive dyes. The obtained maximum adsorption
capacities are 71.4 mg g1 and 62.5 mg g1, respectively. A third
ionic liquid, the 1-tetradecyl-3-methylimidazolium bromide was
tested for the modification of Fe3O4 nanoparticles by Ahmadi et al.
(2016). Results show that the prepared magnetic adsorbent is able
to remove more than 98% of C.I. Reactive Orange 122 under the
optimum conditions. The maximum adsorption capacity of this
modified magnetic material is equal to 51.546 mg g1. In addition to
C.I. Acid Red 87, Tkachenko et al. (2014) studied the removal of
Reactive Blue 4 from solutions using silica chemically modified
with 1-propyl-3-methylimidazolium chloride. Tkachenko and co-
workers observed that the maximum adsorption capacity of the
reactive dye (10e16 mg g is lower than that of the acid dye pre-
viously mentioned (15e25 mg g1). Other researchers are inter-
ested in the preparation of ionic liquidemetal coordination
complexes and their use as reusable adsorbents to remove reactive
dyes. From these researchers, it can be cited Cheng et al. (2015a)
who synthesised various ionic liquidemetal coordination com-
plexes with different alkyl side chains such as 1-butyl-3-ethyl, 1-
octyl-3-methyl and 1-octyl-3-ethyl for the purpose of comparison
their adsorption capacities towards Reactive Red B-3BD. The best
result was obtained when the alkyl side chain is 1-butyl- 3-methyl
with a percent of dye removal about 97%. The decreasing order of
percent of dye removal is:
1-butyl-3-methyl > 1-butyl-3-ethyl > 1-octyl-3-methyl > 1-octyl-
3-ethyl
This order corresponds to the polarity order of ionic liquid
groups. According to the authors, the reason may be attributed to
the interaction force between the adsorbent and the dye which is
reduced when the polarity of ionic liquid groups increased. In the
same way, Cheng et al. (2015b) explored the hydroxylation of ionic
liquid-iron coordination complexes using 1-butyl-3-
methylimidazolium and OH groups as ligands and the application
of these materials as adsorbents to recover C.I. Reactive Blue 19
(anthraquinone reactive dye) from dyeing wastewater. They
claimed that the achieved adsorption efficiency is 98%, the obtained
desorption efficiency of reactive dye is more than 60% and the re-
covery efficiency is more than 54%. Zhou et al. (2016) synthesised a
series of hydroxyl ammonium ionic liquids/layered double hy-
droxides intercalation composites (modified anionic clay materials)
in order to apply them as adsorbents for the removal of C.I. Reactive
Orange 5 from aqueous solutions. Their experimental results reveal
that the maximum adsorption capacity reaches 300.9 mg g<sup>-1</
sup>
for the case of 2-hydroxyethylammonium acetate/layered
double hydroxides. This value is higher than that of pure layered
double hydroxides (53.9 mg g^-1). According to Zhou et al.
(2016), the process of reactive dye adsorption onto these new
materials is the combination of ion exchange, electrostatic attrac-
tion, hydrogen bond interactions and Van der Waals interactions.
4.5.4. Removal of other textile dyes
Reviewing the available literature indicated that there are also
some other studies which focused on the application of ionic liq-
uids to remove from water other classes of textile dyes. For
instance, Gharehbaghi and Shemirani (2012) developed an efficient
ionic liquid-based dispersive liquideliquid extraction process in
order to extract and remove the Congo Red dye (C.I. Direct Red 28).
In this extraction process, a binary solution, containing an ionic
liquid (1-hexyl-3-methylimmidazolium bis(trifluormethylsulfonyl)
imide) and a suitable disperser solvent (acetone), was injected into
solution containing the azo direct dye. In addition, the removal of
indigo (C.I. Vat Blue 1), which is a very well-known colouring agent
extensively used today for dyeing cotton yarn in the manufacture of
denims and blue jeans (Meksi et al., 2012; Meksi and Mhenni,
2015), was studied by Ferreira and co-workers (Ferreira et al.,
2014). In their work, Ferreira et al. (2014) proposed a very prom-
ising extraction process. It consists of the use of several aqueous
biphasic systems which are composed of various phosphonium and
imidazolium-based ionic liquids and two distinct salts (aluminium
sulphate and potassium citrate). The authors claimed that the uti-
lisation of phosphonium-based ionic liquids in this process lead to
higher partition coefficients when compared with the
imidazolium-based compounds and the extraction efficiencies
reach even 100%.
The use of ionic liquids in textile wastewater treatment is a topic
of burgeoning interest. During the last years, many articles dis-
cussed about the application of ionic liquids in dyeing wastewater
treatment using various promising processes. The presented works
investigated almost all textile dye classes. In addition to that, it can
be found others papers which are related to the use of ionic liquids
to remove colour from wastewaters using pH indicators as models
and not textile dyes. These papers were not cited in this review. All
these works demonstrate the potential of ionic liquids for the
elimination and even the recovery of coloured molecules from in-
dustrial wastewaters. However, the literature shows that there is a
need for more data about these applications of ionic liquids in large
scale. Future studies must also focus on the use of ionic liquids in
more realistic conditions such as multi-component pollutant sys-
tems and the application in real dyeing wastewater.
6. Concluding remarks and future prospect
The application of ionic liquids is growing by leaps and bounds.
It has been introduced in many fields, including textile engineering
because many scientists believe that these green solvents could
play, in the future, an important role in the development of novel
cleaner processes and thus achieve sustainability goals. Indeed,
thanks to their remarkable properties, ionic liquids are real exam-
ples of compounds that could effectively embody in the industry
the environmentally friendly 4 R's approach: “Reduce, Reuse,
Recycle, Recover”. By implementing these principles, negative
environmental impacts can be minimised and economic benefits
can be achieved.
Nowadays, in the textile sector, it is true that until now ad-
vancements in this field have not generally exceeded the laboratory
 N. Meksi, A. Moussa / Journal of Cleaner Production 161 (2017) 105e126
scale; probably in some cases, they have reached the pilot scale, but
undoubtedly, there is a considerable potential for ecofriendly and
profitable applications of ionic liquids in this sector. Among the
textile manufacturing stages, spinning remains the step in which
these applications have been most developed. It is expected that
the new ecofriendly rayon cellulosic fibre elaborated with a cleaner
spinning process using ionic liquids will be soon available in the
market.
The use of ionic liquids in textile processes as green media,
auxiliaries and reagents, allows to reduce water consumptions and
hazardous industrial textile effluents. In addition, certain ionic
liquids can impart novel features to textile materials. As a result,
ionic liquids could be an opportunity to develop novel generations
of textile cleaner processes and also to produce innovative textiles
with high-added value. In this context, task specific ionic liquids
will play crucial role in the design and the development of these
cleaner textile processes. However, sufficient scientific data about
the properties of the used ionic liquids should be established before
their applications and especially those which are related to their
toxicity, biodegradability, mobility in the environment and their
recyclability.
Besides, application of ionic liquids jointly with emerging
technologies and processes such as microencapsulation, sol-gel
technique, plasma technology, ultrasound technology, nanotech-
nology, enzymatic treatments and natural dyeing will certainly
present very attractive research areas but so challenging.
Outstanding results may be expected through that leading to niche
products with high-added value.
Finally, it is hoped that this paper may provide valuable and
useful data for researchers and industrialists working to develop
novel cleaner textile processes using ionic liquids. It is hoped also
that these novel cleaner textile processes will lead to strengthening
both the sustainability and the innovation in the textile industry.
Abbreviations
[AAIM]Cl 1,3-diallylimidazolium chloride
[AEVIM]Cl 1-aminoethyl-3-vinylimidazolium chloride
[AMIM]Cl 1-allyl-3-methylimidazolium chloride
[AMIM]DMP 1-allyl-3-methylimidazolium dimethylphosphinate
[BBIM]NTf2 1-butyl-3-benzylimidazolium
bis(trifluoromethylsulfonyl)imide
[BBIM]PF6 1-butyl-3-benzylimidazolium hexafluorophosphate
[BEIM]Br 1-butyl-3-ethylimidazolium bromide
[BEMIM]NTf2 1-benzyl-3-methylimidazolium
bis(trifluoromethanesulfonyl)imide
[BMIM]Ac 1-butyl-3-methylimidazolium acetate
[BMIM]BF4 1-butyl-3-methylimidazolium tetrafluoroborate
[BMIM]Br 1-butyl-3-methylimidazolium bromide
[BMIM]Cl 1-butyl-3-methylimidazolium chloride
[BMIM]DCA 1-butyl-3-methylimidazolium dicyanamide
[BMIM]HSO4 1-butyl-3-methylimidazolium hydrogen sulphate
[BMIM]NTf2 1-butyl-3-methylimidazolium
bis(trifluoromethylsulfonyl)imide
[BMIM]PF6 1-butyl-3-methylimidazolium hexafluorophosphate
[BMPY]NTf2 1-butyl-1-methylpyrrolidinium
bis(trifluoromethylsulfonyl)imide
[C]Cl choline chloride
[C]DHP choline dihydrogen phosphate
[C]MS choline methanesulfonate
[C]La choline lactate
[C]Sa choline sacchrinate
[C]Ta choline tartarate
CTAB cetyltrimethylammonium bromide
[HDEA]Pe 2-hydroxydiethanolamine pentanoate
123
[HDEA]Pr 2-hydroxydiethanolamine propionate
[HDHIM]Br 1-hexyl-3-decahexylimidazolium bromide
[HDMIM]Br 1-hexadecyl-3-methylimidazolium bromide
[HEA]Ac 2-hydroxyethylammonium acetate
[HEA]Fo 2-hydroxyethylammonium formate
[HEA]La 2-hydroxyethylammonium lactate
[HEMIM]Cl 1-(2-hydroxyethyl)-3-methylimidazolium chloride
[HEMIM]DCA 1-(2-hydroxyethyl)-3-methylimidazolium
dicyanamide
[HEOA]Ac 2-(2-hydroxyethoxy)ammonium acetate
[HEOA]Fo 2-(2-hydroxyethoxy)ammonium formate
[HEOA]La 2-(2-hydroxyethoxy)ammonium lactate
[HGU]NTf2 hexylguanidinium bis(trifluoromethylsulfonyl)imide
[HMDMIM]Br 5-(hydroxymethyl)-1,1-dimethyl-1H-imidazolium
bromide
[HMIM]BF4 1-hexyl-3-methyl-imidazolium tetrafluoroborate
[HMIM]Br 1-hexyl-3-methylimidazolium bromide
[HMIM]Cl 1-hexyl-3-methylimidazolium chloride
[HMIM]NTf2 1-hexyl-3-methylimidazolium
bis(trifluoromethanesulfonyl)imide
[HMIM]PF6 1-hexyl-3-methylimidazolium hexafluorophosphate
[HPIM]NTf2 1-hexyl-2-phenylimidazolium
bis(trifluoromethanesulfonyl)imide
[HPMIM]Br 3-hydroxypropyl-1-methylimidazolium bromide
[MDHIM]Br 1-methyl-3-decahexylimidazolium bromide
[MIM]Ac 1-methylimidazolium acetate
[MMIM]DMP 1,3-dimethylimidazolium dimethylphosphate
[MOMIM]DMP 1-methyl-3-(oxiran-2-ylmethyl)-1H-imidazol-3-
ium dimethylphosphinate
[MTESPIM]Cl 1-methyl-3-(triethoxysilylpropyl)imidazolium
chloride
[MTESPP]Cl 1-methyl-3-(triethoxysilylpropyl)pyridinium chloride
NMMO N-methylmorpholine N-oxide
[OEIM]Br 1-octyl-3-ethylimidazolium bromide
[OGU]NTf2 octylguanidinium bis(trifluoromethylsulfonyl)imide
[OMIM]BF4 1-octyl-3-methylimidazolium tetrafluoroborate
[OMIM]Br 1-octyl-3-methylimidazolium bromide
[OMIM]Cl 1-octyl-3-methylimidazolium chloride
[OMIM]NTf2 1-octyl-3-methylimidazolium
bis(trifluoromethanesulfonyl)imide
[OMIM]PF6 1-octyl-3-methylimidazolium hexafluorophosphate
[P]Ac piperidinium acetate
PEG150-DIL 3,3'-[1,2-ethanediylbis(oxy-2,1-ethanediyl)]-bis[1-
methyl-imidazolium]-dibromide
[PMIM]Cl1-propyl-3-methylimidazolium chloride.
[TBAP]Ac tributylaminoproppylphosphonium acetate
[TBAP]Br tributylaminoproppylphosphonium bromide
[TBAP]DBP tributylaminoproppylphosphonium dibutylphosphate
[TBMP]MS tributylmethylphosphonium methylsulphate
[TBOP]Br hydroxypropyltributylphosphonium bromide
[TBP]BF4 tetrabutylphosphonium tetrafluoroborate
[TBP]Br tetrabutylphosphonium bromide
[TBP]Cl tetrabutylphosphonium chloride
[TBP]DEPtetrabutylphosphonium diethylphosphate
[TBP]NTf2 tetrabutylphosphonium bis((trifluoromethylsulfonyl)
imide,
[TBP]PF6 tetrabutylphosphonium hexafluorophosphate
[TBP]TFMS tetrabutylphosphonium trifluoromethanesulfonate
[TCMA]Be tricaprylmethylammonium benzoate
[TCMA]DCA tricaprylmethylammonium dicyanamide
[TCMA]Hex tricaprylmethylammonium hexanoate
[TCMA]SCN tricaprylmethylammonium thiocyanate
[TDMIM]Br 1-tetradecyl-3-methylimidazolium bromide
[THEA]Ac tri-(2-hydroxyethyl)ammonium acetate
[THEA]Fotri-(2-hydroxyethyl)ammonium formate
124 N. Meksi, A. Moussa / Journal of Cleaner Production 161 (2017) 105e126
[THEA]La tri-(2-hydroxyethyl)ammonium lactate
[THTDP]Cl trihexyltetradecylphosphonium chloride
[TIBMP]Ts tri(isobutyl)methylphosphonium tosylate
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