I

STATE OF THE ART

Eco-efficient composite materials

OCTOBER 2010

Laura Laine 1 and Liva Rozite 2

1

Tampere University of Technology, Department of Material Science/Plastics and Elastomer Technology, Kokkola unit, Finland
2

Lule University of Technology, Division of Polymer Engineering, Sweden

II

II

CONTENTS
1 2 INTRODUCTION ................................................................................................................... 1 MATERIAL CANDIDATES .................................................................................................. 3 2.1 2.2 2.3 3 Bioresins ........................................................................................................................... 3 Biofibers ........................................................................................................................... 5 Bio core materials........................................................................................................... 11

PERFORMANCE IN HARSH CONDITIONS .................................................................... 13 3.1 Definition of harsh conditions ........................................................................................ 13

4 TESTING AND CHARACTERIZATION METHODS FOR DURABILITY EVALUATION............................................................................................................................. 14 4.1 4.2 Mechanical testing.......................................................................................................... 14 Physical testing............................................................................................................... 16 Moisture and water sorption testing........................................................................ 17

4.2.1 5

SURFACE TREATMENT METHODS FOR BIOFIBERS ................................................. 18 5.1 5.2 5.3 Chemical treatment ........................................................................................................ 18 Physical treatment .......................................................................................................... 20 Effects on long term properties ...................................................................................... 21

CONCLUSIONS ................................................................................................................... 22 6.1 6.2 6.3 Best choice material candidates ..................................................................................... 22 Identification of most critical harsh conditions .............................................................. 22 Surface treatment options and recommendations........................................................... 22

REFERENCES ............................................................................................................................. 23

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1 INTRODUCTION

This state-of-the-art is part of EU INTERREG IV A North -project called ANACOMPO (Application of natural fiber reinforced composites in harsh environments) and contains discussion about eco-efficient composite materials, test methods and fiber surface treatment methods. The aim is to find commercially available biobased resins and natural fibers, make a literature search of composite testing and fiber surface treatments and define the project objectives based on the findings. In this report, only thermoset resins used in structural composites are discussed, thermoplastic resins are excluded. Increased interest in using natural fibers as reinforcement in polymer composites is due to higher environmental awareness and the great potential of natural fibers. Natural fibers have many advantages to be used as reinforcements in polymer composites. They are considered as biodegradable and sustainable alternatives to other fibers. They are CO2 neutral and leave no residues when they are incinerated. Their mechanical properties are very good and they are not abrasive or toxic. Natural fibers have low density and low price. However, they also have disadvantages like inhomogeneous quality and supply cycles. They have low water resistance and dimensional stability. Natural fibers absorb moisture and lack good properties in toughness. [1] In this report, the term biofiber stands for natural fiber. Resins used in polymer composites are typically thermoset resins, like epoxies and unsaturated polyesters, and thermoplastic resins, like polypropylene. Their raw material is normally crude oil. The resin material can also be biobased and in that case it is based on renewable resources. Biobased resin means that some amount of the raw materials is derived from biomass, in other words renewable resources. The rest is crude oil based raw materials. The motive to develop biobased resins is to have more environmentally friendly composite materials and to use less crude oil. On the market, also biodegradable resins are available. These are thermoplastics which decompose by microorganisms into carbon dioxide and water in a short time. Biodegradable resins, like polylactic acid, are mainly used in short lifetime applications, such as packaging. In structural composites, biodegradation is not a main issue. The percentage of the bio-derived content in a thermoset resin varies greatly and only a few are nearly 100 % biobased. The biobased content varies from 12 % to 90 %, according to manufacturers own reports. The characterization of true biobased content is more difficult but there is also a standard for defining it, ASTM D6866. In this state-of-the-art, biobased thermosetting resins are of interest and bioresin is used as a synonym for biobased resins for simplicity. However, the word bioresin is used in different meanings in other sources.

2 In Chapter 2, bioresins, biofibers and bio core materials are reviewed. In Chapter 3, the definition of harsh conditions is discussed. Characterization methods for durability evaluation and literature values are presented in Chapter 4. Surface treatment methods for natural fibers are discussed in Chapter 5 and conclusions are made in Chapter 6.

2 MATERIAL CANDIDATES

Possible material candidates in this project are environmentally friendly composite materials that have potential to be used in structural applications and in difficult environmental conditions. The aim is that both resins and reinforcements are to some extent made from biobased raw materials or constituents with the ideal target a composite made from 100 % biobased raw materials. Concerning reinforcements, natural fibers have shown very promising mechanical properties. Biobased resins are quite comparable with crude-oil resins, except the price is higher and therefore the usage of biobased resins is growing slowly. In this chapter, commercial bioresins, biofibers and bio core materials are discussed.

2.1 Bioresins
The term bioresin means that a resin is composed of raw materials, which are wholly or partly derived from renewable resources. Bioresin can be a thermoplastic, a thermoset or a biodegradable plastic. Here, only thermoset bioresins are discussed. A thermoset polymer is highly cross-linked and is cured by using a curing agent and heat or heat and pressure, and the result is a material with high strength, modulus and durability [2]. In a review article [2], thermosetting bioresins are divided into phenolics, epoxies, polyurethanes, polyesters and other resins. The article contains detailed information on raw materials used in different resins, including chemical formulas. To produce bioresins, commonly used renewable raw materials are plant oils (for instance soybean oil, castor oil, pine oil), polysaccharides (cellulose, starch) and proteins. Currently, petroleum-based raw materials are added to renewable raw materials to make bioresins. In Table 1, current manufacturers for commercial thermosetting bioresins are presented with information about raw materials, chemical formula or manufacturing method and application areas. As can be seen, used raw materials are diverse, including soybean oil, epoxidised pine oil waste, castor oil, furfuryl alcohol and lactid acid. In this group, biobased content varies from 18% to 50-90%. Three of them are unsaturated polyester based, one is an epoxy and others are varied.

4 Table 1 Commercially available bioresins, their raw materials and applications.

Manufacturer (trade name) Ashland e.g. ENVIREZ 1807 Amroy Europe Oy EpoBioXTM Raw materials Unsaturated polyester Soybean oil Bio 18% Natural phenols distilled from forest industry waste stream, eg. epoxidised pine oil waste Bio 50-90% Unsaturated polyester Bio 55% Furfuryl alcohol based resins from biomass Lactic-acid based Chemical formula Applications e.g. tractor panels Sour ce [3]

kayaks, boats, tent poles, glues, electrical cars

[4]

DSM Palapreg ECO P 55-01 TransFurans Chemicals bvba BioRez furfuryl resin JVS-Polymers Ltd. LAIT-X / POLLITTM

Not available

SMC/BMC applications Varied applications

[5]

Furfural (FF) is produced from hemicellulosic agricultural wastes and source for FA production via catalytic hydrogenation. Aliphatic hydroxyl acids, such as lactic acid, are polymerized into poly(lactic acid) by direct polycondensation with a use of suitable catalyst Not available Not available

[6]

Bioresin Bioresin Reichhold ENVIROLITE

castor oil Unsaturated polyester Soya oil Bio 25% acrylate functional resin system derived from soya oil Soybean oil: Methacrylated, Methacrylic anhydride modified, Acetic anhydride modified

composites, impregnated products, coatings and biomedical applications Automotive, marine SMC/BMC and pultrusion applications

[7]

[8] [9]

Cognis Tribest

[10]

University of Bors

Eg. Methacrylated soybean oil

O O O O O O O O 2 OH OH 3 O O 7 3 OH 3 O O

2.2 Biofibers
Natural fibers can be divided in groups of bast, leaf, seed, fruit, wood and grasses. Flax and hemp fibers belong to bast fibers. [11] Here, the inspection is limited mainly to flax and hemp. Some of commercial natural fiber and biofiber reinforcement producers are presented in Table 2. Natural fibers for composite applications are available typically in the form of yarns and fabrics, which can be woven or non-woven. Some manufacturers provide fibers as preimpregnated to different resins or plastics. As shown, flax providers are easier to find than hemp providers. Table 2 Manufacturers of natural fibers and natural fiber reinforcements.
Manufacturer Libeco-Lagae, Belgium Engtex AB, Sweden Composites Evolution Ltd, UK Group Depestele, France Lineo NV, Belgium Safilin, France/Poland Fimalin, France Stemergy: Renewable fibre technologies, Canada HP Johannesson Trading AB, Sweden CORDENKA GmbH, Germany Fiber flax flax flax flax flax flax flax hemp jute regenerated cellulose Webpage www.libeco.be www.engtex.se www.compositesevolution.com e.g. www.lbn-lin.com www.lineo.eu www.safilin.fr www.fimalin.com www.hempline.com www.hpjtrading.se www.cordenka.com

The natural fiber has a very complex multi-scale internal structure: it consists of elements with different size scales. The main constituents involved in composition of plant fibers are polymers themselves: cellulose, hemicellulose, lignin and pectin (see Table 3). [12] Figure 1 shows a schematic picture of composition and built of a flax stem (see also the micrograph in Figure 2). Technical fibers (approximately 1 m long) are isolated from the flax plant and consist of elementary fibers with length generally between 2 and 5 cm, and diameters between 19 and 25 m. The elementary fibers are glued together by a pectin interface. These fibers have polyhedron shape (see Figure 3) with 5 to 7 sides to improve the packing in the technical fiber. [12]

Table 3 The chemical composition of different natural fibers. [13] Fiber Type Flax Hemp Wood Sisal Cellulose, % 81 74 ~ 46 73 Hemicellulose, % Lignin, % 14 3 18 4 ~ 27 ~ 27 13 11 Pectin, % 4 1 2

Figure 1 Composition and built of flax stem. [14]

Figure 2 Micrograph showing multi-scale structure of the flax stem. (Constructed from individual images published in [15]).

Figure 3 SEM image of elementary flax fiber. [46]

Elementary fibers are single plant cells and the most common chemical material in plant cell walls is cellulose (C6H10O5)n. The chemical structure of cellulose monomer is showed in Figure 4. Most of the elementary fibers consist of oriented, highly crystalline cellulose fibrils and amorphous hemicellulose. The crystalline cellulose fibrils in the cell wall are oriented at an angle 10 with the fiber axis and give the fiber its high tensile strength (see Figure 5). [12]

Figure 4 The chemical structure of cellulose monomer. [12]

Figure 5 Different layers in cell wall. Middle lamella (ML), Primary wall (P), Secondary wall (S), Lumena (L). Natural fibers have many properties that make them interesting as reinforcement in composites. These fibers are renewable, recyclable, have high specific properties and good isolation properties. Also these fibers have low bulk cost and low weight. However, natural fibers have several disadvantages compared with synthetic fibers. The main drawback is quality variations, depending on growth conditions, processing and other reasons, which may also influence the price of fibers. Natural fibers are sensitive to moisture and have lover durability.

9 The maximal processing temperature is lower than for synthetic fibers. Table 4 shows some properties for the most popular natural fibers, E-glass and wood fibers. Table 4 Properties of different fibers. [12,16,17] Fibers E-glass Wood Flax Hemp Sisal Cordenka Density (g/cm3) 2.54 1.54 1.4-1.5 1.48 1.45 1.5 Modulus (GPa) 72 30-40 50-70 30-60 9-20 ~20 Strenght (MPa) 3530 400-800 500-900 300-800 510-700 700-800 Strain (%) 1.8-3.2 1.5-2.4 1.1-2 2.2-2.9 13-15 Diameter (m) 10 20-40 10-30 10-50 10-40 12.5 Specific modulus 28.2 ~ 25 ~ 41 ~ 30 ~ 10 ~ 13 Specific Strenght 1390 ~ 390 ~ 480 ~ 370 ~ 420 ~ 470

The process to make flax or hemp plant into a reinforcement fiber has several stages. Fibers are in fiber bundles, so first the bundle is broken down by retting. Retting is done by spreading the crop in the fields and leaving there for 3-8 weeks or immersing the crop in water for 1-2 weeks. At present, also many industrial retting methods are being developed, like enzyme retting. When the retting has broken down the bundle into single fibers, fibers are dried and mechanically separated from the straw by stripping and combing. [18] Natural fibers have been used in lines, ropes and other one dimensional products, textiles, canvas, and papers. As natural fiber mechanical properties can be competitive to glass fibers, they can substitute glass fibers in composites. However the adhesion between natural fibers and polymer is a problem. Adhesion can be improved by fiber treatment or by the use of more compatible polymers (for example bio-based resins). Also the length of natural fiber and orientation is an issue for using them in the composites.

10

Figure 6 The viscose process. [19] One of the latest revelations in the type of reinforcement with plant origin is regenerated cellulose fibers. These fibers, similar to flax and hemp fibers, have high cellulose content, but unlike flax and hemp they are manmade. Terms regenerated cellulose, rayon, and viscose rayon tend to be used interchangeably [19]. The flow diagram for the viscose process is given in Figure 6. First wood pulp is dissolved in caustic soda. Then steeping is performed - for a specified period of time composition is shredded and allowed to age. The period of aging determines the viscosity of the viscose. The longer is the ageing time the higher will be the viscosity of solution. Afterwards aged pulp is treated with carbon disulphide to form a yellow-colored cellulose xanthate, which is dissolved in caustic soda. This is the starting stage of viscose formation [20].

11 Although these are manmade fibers, they are made out of the natural polymer directly on contrary to the fibers made out materials with fossil origin. These fibers are continuous and it is easy to arrange them into fabrics with stable orientation and geometry. At the moment, the main application for these fibers is in textile industry. However, currently there are many on-going studies dealing with the evaluation of these fibers as perspective reinforcement for bio-based polymer composites.

Figure 7 Stress-strain curves of CA (Cordenka EHM), CB (Cordenka 1840), CC (Enka Viscose), CD (Cordenka 700), CE (Alternative cellulose) and CF (Lyocell) regenerated cellulose fibers and steam exploded flax and field retted hemp fibers. [21] There are several types of regenerated cellulose fibers. Typical stress-strain curves for different fibers are presented in Figure 7. One of the regenerated fibers considered for this particular project are Cordenka fibers. These fibers are produced by the German company, Cordenka GmbH, and the main application is for reinforcing rubber in car tires.

2.3 Bio core materials

The most used natural core material in composites is balsa wood. Commonly balsa is used as a plate which consists of balsa pieces cut to the same thickness. Balsa has good strength properties. [22] For example, 3A Composites (Switzerland) manufactures balsa for sandwich structures with

12 trade name BALTEK (more information: www.corematerials.3acomposites.com/baltekbalsa.html). In this project, also other biobased core materials are interesting. For instance, Saarpella Oy (Finland) produces non-woven flax felt as an insulation material, which could be used as core material. Bioresin (Brazil) has derived polyurethane foam, BIOFOAM, from castor oil. Interesting is also the possibility to use the bioepoxy of Amroy Europe Oy (Finland) as foam. In literature, Burgueo et al. [23] studied load-bearing natural fiber composite cellular beams and plates made of hemp or flax fibers and unsaturated polyester. Dweib et al. [24] used acrylated epoxidized soybean oil (AESO) resin and flax mats to produce biocomposite sandwich beams for structural applications. Faruk et al. [25] has made a review of microcellular foamed wood-plastic composites.

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3 PERFORMANCE IN HARSH CONDITIONS

Reinforced composites are normally used in applications, where good mechanical and other properties are required, such as technical and structural applications. They can also be exposed to difficult or extreme environment conditions in their applications. These conditions can affect the properties of composites and decrease their performance. Therefore, studies in difficult conditions are relevant and aid to choose a right application and predict the performance of composite. In this chapter, the definition of harsh conditions of biobased composites is discussed.

3.1 Definition of harsh conditions

Biobased composites can be used in applications, where the conditions are challenging to composites, in other words harsh conditions. In marine industry for instance, composites are exposed to water and in sea areas to saline water. Also humidity can sometimes be very high and have influence on composites. Biofibers tend to absorb moisture. In a report [26], harsh weather conditions are said to contain humidity, elevated temperature, UV radiation and rain. Low temperatures can be added to the list, because outdoor temperature in the Nordic countries is several degrees below zero in winter. UV radiation from sunlight is at its highest in summer. Rarely these conditions are present separately and thus they have a combined effect on composites. During this project, the effect of these conditions on biobased composites is going to be studied. In literature, Mehta et al. [26] tested hemp reinforced UPE composite samples in an accelerated weatherometer. They used the measurement cycle of 48 cycles of UV treatment (340 nm) at 60 C for 2.5 h followed by water spray for 30 min and condensation at 45 C for 24 h. They repeated it 12 times with total duration 2016 h. Weight loss was less than 2% for untreated hemp composite and 1.25% for acrylonitrile treated hemp composite, surface roughness increased with exposure time and color changed. Storage modulus decreased only slightly (values 6-8 GPa) and Tg decreased less than 3C.

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4 TESTING AND CHARACTERIZATION METHODS FOR DURABILITY EVALUATION

Testing and characterization methods in order to evaluate the durability of composites are divided into mechanical tests, physical tests and chemical tests. Mechanical testing is the most used test method of these. Mechanical tests provide information on strength, compression, impact, bending and shear properties. In many applications, the strength properties of composite are of interest. Physical tests give knowledge of thermal, absorption and structural properties. Chemical tests give insight into the chemical properties or structure of composites. In this chapter, numerical data from various studies are collected mainly in tables to show their performance.

4.1 Mechanical testing

Typical mechanical tests for composites are tensile, flexural, impact and fatigue tests. In structural applications, composites are required to carry load and good tensile properties are demanded. In Table 5, data from various studies are collected for flax reinforced composites and hemp reinforced composites. The composite structure of test samples varies and that has effect on their properties. Reinforcements are in the form of mats, woven fabrics, fibers or non-woven mats. Also the resin is varied: epoxies, polyesters, soybean oil resin and acrylated epoxidized resins. Mechanical test results differ quite lot, probably partly due to the composite structures. For instance, tensile strength for flax reinforced composites is between 15 to 90 MPa. In this project, one purpose is to study, if biofibers are suitable for being used in applications, where good strength properties are required.

15 Table 5 Test data from the literature for flax and hemp reinforced composites. X means that tests are done but figure is not found.
Fiber/ Matrix Flax / Soybean oil resin (MMSO) (60:40) Flax / Vinylester or Modified acrylic resin Flax / Acrylated epoxidized soy oil (AESO) Flax / EP Flax / EP Processing Compression moulding, air laid / woven fabric RTM, mats (25kN, 2 mm/min) 70-90 MPa 7.5-9.5 GPa Tensile strength Tensile modulus Flexural (5kN) Strength 90 MPa, Mod. 5 GPa Fatigu e Impact strength (Charpy) 24-29 kJ/m2 Refere nce [27]

[28]

RTM, fiber

(5mm/min) 15-30 MPa

3.2-4.7 GPa

Strength 42- 64 MPa, Mod. 2.7 - 4.2 GPa X

[29]

yarns Laminates, non-woven mat

Hemp / Acrylated epoxidized soy oil (AESO) Hemp / UPE

RTM, mats

(1mm/min) 47 MPa (untreated) 60-75 MPa (treated) 35 MPa

4.5-4.8 GPa

[30] [31] [32]

4.4 GPa

Hemp / UPE

Compression moulding, non-woven mat RTM, mat

70 MPa (AN treated hemp)

8 GPa (AN treated)

Strength 35.7 5.9 MPa / 51.3 2.7MPa, Mod. 2.6 0.2 GPa / 2.7 0.2 GPa X

[29]

(notched Izod) 26 J/m

[33]

Strength 22 3 MPa / (Fungal treated) 26 3.5 MPa, Mod. 3.3 0.3 GPa / (Fungal treated) 3.7 0.5 GPa

[34]

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4.2 Physical testing

Data from physical tests, including thermal analysis, are collected in Table 6. Typical physical tests are water absorption, swelling and moisture content. They are discussed in chapter 4.2.1. Thermal analysis methods can be thought as physical testing. In the table, the numerical values of tests from differential scanning calorimetry (DSC), thermogravimetry (TG), dynamic mechanical analysis (DMA) and scanning electron microscope (SEM) are used to give the scale to physical properties. In addition to the table, Gulati et al. [35] used inverse gas chromatography (IGC) to investigate acid-base characteristics of hemp fibers. They found that highest improvements in acid-base interactions between fiber and matrix are correlated with actual improvement in the mechanical properties of RTM manufactured hemp reinforced unsaturated polyester composites. Table 6 Physical test data from the literature.
Fiber/ Matrix Flax/Soyb ean oil resin (60:40) Flax / Acrylated epoxidize d soybean oil (AESO) Hemp / UPE Processing Compression moulding, air laid / woven fabric Vacuum RTM / infusion, mat (different kinds of vol%) Compression moulding, non-woven mat Vacuum RTM / infusion, mat DSC TG Relative low thermal stability (370C) (3-point bending) E 1500 2000 MPa E 200 -260 MPa Tg 57 70C Tg = 95C (max tan ) DMA SEM Shorter fiber pullout with styrene Refere nce [27]

[32]

Smaller degree of fiber pullout (AN treated)

[33]

Hemp / Acrylated epoxidize d soybean oil AESO Hemp / Waterbased acrylic thermoset

(3-point bending) E 2200 MPa E 270 MPa Tg 65C (20-100C) heat capacity of cured resin 1.98-2.7 J g -1 K-1 / of hemp 2.2-3.4 J g -1 K-1

[32]

[36]

17 In Table 6, when comparing DMA results, hemp reinforced AESO composite has better strength than flax reinforced according to higher storage modulus, E, value. The larger E, the better strength composite has. Glass transition temperature, Tg, of flax and hemp reinforced AESO composites can be somewhat lower than it could be due to an incomplete curing process. Otherwise, the values seem to be moderate. Typically, biofibers are thought to have a limited processing temperature at approximately 200 C, which must be taken into account when choosing a processing method.

4.2.1 Moisture and water sorption testing Moisture and water sorption tests are important in order to study the water resistance of biofiber reinforced composites. Natural fibers are commonly known as to easily absorb moisture. In Table 7, rather different values for water sorption are collected from literature. Water uptake varies from 2 % to 18 % increase in composite weight. The reason for variation can be found in different matrices and surface treatments. Moisture absorption for hemp is found to be about 1 to 3 weight-%. Fiber surface treatments can decrease water and moisture absorption. Table 7 Moisture and water test data from the literature.
Fiber/ Matrix Flax / Acrylated epoxidized soy oil (AESO) Hemp / UPE Processing RTM, fiber Water sorption (24h) 2.3 - 4.1 wt% (7 weeks) 10.4 - 12.4 wt% (30C, 90% RH) 0.7 wt% (untreated) 0.3 wt% (AN treated) (23C, 94% RH, 200 days) 1.5 2.7 wt% No saturation Moisture absorption Refere nce [29]

Compression moulding, mat

[26]

Hemp / UPE

RTM, randomly oriented mat (different kinds of vol-%)

(23C, saturation 200 days) 2 4 wt%

[37]

Flax / EP Hemp / EP

(816 h) 17.2% (flax) 18.4% (hemp)

[38]

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5 SURFACE TREATMENT METHODS FOR BIOFIBERS

Natural fibers have typically poor adhesion and wettability with resin materials because biofibers are hydrophilic in nature and resins are hydrophobic. If the reinforcement is not properly adhered to the matrix, it does not add the strength of the composite. Therefore, different surface treatment methods for biofibers have been invented and tested to improve the adhesion between biofibers and polymer matrices. Treatments naturally raise the price of end products. Generally, treatment methods can be divided into chemical treatments and physical treatments. Chemical treatment can be defined as a chemical reaction between some reactive constituents of chemical reagent and biofiber to form a covalent bond [39]. Physical treatment methods do not change the chemical structure of biofibers, only the surface properties. In this chapter, the literature search results of treatment methods are presented and their effect on the long term properties of composites is discussed.

5.1 Chemical treatment

Common chemical treatments are dewaxing, mercerization, bleaching, cyanoethylation, silane treatment, benzoylation, peroxide treatment, isocyanate treatment, acrylation, acetylation, latex coating and steam-explosion. [39] John et al. [40] also adds the condensation of coupling agents onto the cellulose surface. Many studies have been made to investigate the effect of different surface treatments on the properties of fibers. Good review articles [39-41] are found in the scientific literature. For example, possible silanes to be used in silane treatment are various and Xie et al. [42] have made a table with references about Silanes used for the natural fiber/polymer composites. The main things from the literature articles are collected into Table 8 and Table 9. The articles that studied only fibers [42,43] are left out of the tables. Surface treatments for flax and for hemp are separated into different tables.

19 Table 8 Effect of different chemical treatments on hemp reinforced composite properties.

Fiber/ Matrix Hemp/ EP Chemical treatment Mercerizati on Conditions Processing Effect on composite properties + Flex. strength 45% Flex.mod. of elast. 100% Higher improvement with alkali in flex. mod. and strength Flex. strength 21%, flex. mod. 12 % (improved interfacial adhesion) Tensile strength 80%, tensile mod. 25%, elast.mod. 30%, impact strength 50%, storage mod. & loss mod. increased Treatment not significantly improve the water resistance Lower impact strength, Low toughness Pyridine: no effects on properties Effect on Referenc composite e properties [44]

22% NaOH, 60 min, 10C

Filament winding, UD RTM, contains also glass fiber mats RTM, mat

Hemp/ UPE

Alkalizatio n/ Acetylation

Hemp/ UPE

Fungal modificatio n

6% NaOH for 48h, room temp. / glacial acetic acid for 1h, room temp. 0.5% glucose and 0.1% yeast, in rotary shaker for 4, 6 or 8 days 3% acrylonitrile, 0.5% dicumyl peroxide, 96.5% ethanol, 15 min

[35]

[34]

Hemp/ UPE

Acrylonitril e grafting

Compressio n moulding, non-woven mat

[33]

Hemp/ UPE

Alkali / Silane treatment

Hemp/ UPE

Esterificati on

Alkali: 2% NaOH, 23C, 1h, dried Silane: 1% 3aminopropyltriet hoxysilane, 30 min, dried Methacrylic anhydride + pyridine: 100C, 48h, dried / Pyridine (same)

RTM, randomly oriented mat

[37]

RTM, non- Better interfacial woven mat adhesion Higher flex. mod., flex. stress at break no change except in mode of failure

[45]

20 Table 9 Effect of different chemical treatments on flax reinforced composite properties.

Fiber/ Matrix Chemical treatment Conditions Processing Effect on composite properties + Tensile and flexural properties and fiber wettability improved Tensile strength 50% Effect on composite properties Refere nce [46]

Flax/Acryl Lignin ated treatment epoxidized soybean oil + styrene Flax/EP Ethylene diamine tetraacetic acid Flax/EP Alkalizatio n

Aqueous VARTM, NaOH solution mat of kraft lignin

NaOH, 60 C, 3h

Laminates, non-woven mat Autoclave, UD mat

[31]

NaOH 1% 3%, 20 min, room temperature

Flax/EP

Alkali / Silane / Isocyanate

NaOH 1% / 3aminopropyltri ethoxysilane / Phenyl isocyanate

Autoclave, UD mat / Random non-woven mat

(Improved interface quality) Increased longitudinal and transverse flex.mod. and strength Tensile strength 17%, tensile mod. 25% No change in impact toughness

(fiber strength decreased)

[47]

[48]

As can be seen in the tables, the surface treatments influence mainly positively to the properties of natural fiber reinforced thermoset polymer composites. The comparison of results is quite challenging, because the results depend on fiber content, composite manufacturing method and test methods. In generally, in many studies tensile strength, tensile modulus, flexural strength and flexural modulus increased because of the surface treatment. Mercerization, also called alkalization, seems to be the most used treatment for flaw and hemp fibers.

5.2 Physical treatment

Typical physical treatment methods are stretching, calendaring, thermotreatment, production of hybrid yarns, corona and cold plasma. Also other interesting methods have been tested. Gouanv et al. [49] studied the effect of autoclave treatment and helium cold plasma treatment on the water sorption of flax fiber (no matrix). The moisture resistance increased after autoclave treatment, but the plasma treatment had no effect on the resistance. Hepworth et al. [50] used a urea treatment to penetrate epoxy resin into the cell walls of flax fibers. Treated fiber reinforced composites had higher tensile modulus (15 GPa) than untreated fiber composites (11.5 GPa) although strength was not affected (118 MPa).

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5.3 Effects on long term properties

Composites are typically used in applications, whose time of use is long, from years to decades. Hence, the effect of surface treatments on the long term properties of composites should be studied. The question, how biofiber reinforced composites maintain their properties during a long period, is interesting. For instance, water and fungus can cause harm to biofibers within time. Many studies cover short or relatively short term property changes. Changes in long term properties are one of the main objectives to be explored in this project.

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6 CONCLUSIONS

The purpose of this state-of-the-art is to give insight into eco-efficient composite materials and make conclusions that operate as guidelines to further actions in the ANACOMPO project. Materials that are chosen to be good material candidates tested in this project are discussed, likewise the recommended surface treatment to be used. The most critical harsh conditions concerning the use of biocomposites are considered.

6.1 Best choice material candidates

A few from commercially available bioresins are selected for further characterization. The bioepoxy, EpoBioXTM, is a good material candidate because epoxies typically have very good properties and this bioepoxy also has a large bio content percent. Epoxies perform presumably well in harsh conditions. It is also produced in Finland and hence quite near to all project partners. ENVIREZ unsaturated polyester bioresins can also be purchased from Finland and ENVIREZ resins have been in the market for almost a decade, so they are worth to take as good candidates. Also the unsaturated polyester bioresin, Palapreg ECO P55-01, from DSM has quite high bio content percent, a half of the raw materials. These four resins are selected for further tests.

6.2 Identification of most critical harsh conditions

Data from harsh condition testing is quite limited available. Probably a good way is to start tests in all typical condition areas that are known to be difficult. UV radiation, water, humidity and temperature and also the combined effect of those are commonly of interest.

6.3 Surface treatment options and recommendations

In tables 8 and 9, the most commonly used surface treatment is chemical treatment with sodium hydroxide. This treatment is quite easy and inexpensive.

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REFERENCES
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