Composites: Part A 56 (2014) 280289

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Composites: Part A
journal homepage: www.elsevier.com/locate/compositesa

Review

Green composites: A review of material attributes and complementary applications

Michael P.M. Dicker , Peter F. Duckworth, Anna B. Baker, Guillaume Francois, Mark K. Hazzard, Paul M. Weaver
Advanced Composites Centre for Innovation and Science (ACCIS), University of Bristol, Queens Building, University Walk, Bristol BS8 1TR, UK

a r t i c l e

i n f o

a b s t r a c t
Despite the large number of recent reviews on green composites, limited investigation has taken place into the most appropriate applications for these materials. Green composites are regularly referred to as having potential uses in the automotive and construction sector, yet investigation of these applications reveals that they are often an inappropriate match for the unique material attributes of green composites. This review provides guidelines for engineers and designers on the appropriate application of green composites. A concise summary of the major material attributes of green composites is provided; accompanied by graphical comparisons of their relative properties. From these considerations, a series of complementary application properties are dened: these include applications that have a short life-span and involve limited exposure to moisture. The review concludes that green composites have potential for use in a number of applications, but as with all design, one must carefully match the material to the application. 2013 Elsevier Ltd. All rights reserved.

Article history: Received 11 June 2013 Received in revised form 1 October 2013 Accepted 18 October 2013 Available online 25 October 2013 Keywords: A. Fibres A. Polymermatrix composites (PMCs) B. Environmental degradation B. Mechanical properties

Contents 1. 2. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1. Natural fibres. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2. Biopolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Attributes of green composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1. Mechanical properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2. Variable fibre properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3. Renewability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.4. Low embodied energy and CO2 emissions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.5. Biodegradability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.6. Low cost . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.7. High natural fibre water absorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.8. Poor durability. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.9. Non-toxicity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.10. Biocompatibility and bioactivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.11. Fibre degradation at elevated temperatures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Defining complementary applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Complementary applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.1. Short life-span products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.2. Sporting equipment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.3. Biomedical applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281 282 282 283 283 283 284 284 284 284 285 285 285 286 286 286 286 286 286 287 287 287 288 288

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Corresponding author. Tel.: +44 (0) 117 33 15768.

E-mail address: michael.dicker@bristol.ac.uk (M.P.M. Dicker). 1359-835X/$ - see front matter 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.compositesa.2013.10.014

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1. Introduction As global societies continue to grow, increasing emphasis is being placed on ensuring the sustainability of our material systems. Topics such as greenhouse gas emissions, embodied energy, toxicity and resource depletion are being considered increasingly by material producers. Some of this practice is being driven by reg-

Fig. 1. Structural constitution and arrangement of a natural vegetable bre cell [9].

ulations (particularly in Europe as a result of legislation such as the end of life vehicle directive [1]), but increasingly, anecdotal evidence would suggest consumers are also demanding improved environmental credentials from the products they consume. Improving the sustainability of our material systems will require not just the development of new sustainable materials, but also the increased application of existing green materials. One existing class of materials with good environmental credentials are green composites. Green composites are dened, in this work, as biopolymers (bio-derived polymers) reinforced with natural bres. More specically, this work will only look at the subset of green composites that are commonly considered as being biodegradable (counter intuitively, not all biopolymers are biodegradable), as dened by an appropriate standard (EN 13432 [2], EN 14995 [3]). There are several recently published reviews on green composites, but unlike those, this work is not application specic, nor does it present the detailed chemistry of natural bre and biopolymer enhancement. Instead, this work provides guidelines for engineers and designers on the appropriate application of green composites. For a detailed review of aspects relating to the materials science of green composites or their application in the automotive and construction sectors, the reader is referred to [48]. The initial part of this review provides a concise summary of the major material attributes of green composites. Signicant results from literature are presented, as well as techniques and prospects

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Fig. 2. Density specic mechanical properties. Dashed lines indicate constant material performance for tie stiffness E/q and strength r/q, beam stiffness E1/2/q and strength r2/3/q and plate stiffness E1/3/q and strength r1/2/q. Green composite properties from [76] (Long ax slivers/Randy PL-1000 PLA resin, 0.610.72 bre volume fraction), [77] (10 mm length kenaf/PLA 3051D resin, 0.20.4 bre weight fraction, only exural strength and modulus reported), [78] (Woven jute fabric/soy resin, 0.40.6 bre weight fraction), [79] (10 mm NaOH treated jute bres/starch resin injection moulded, 0.10.3 bre weight fraction), [80] (Abaca bre pellets/PLA injection moulded, 0.3 bre weight fraction), [81] (Jute bre pellets/PLA injection moulded, 0.3 bre weight fraction), [82] (Flax bres/PLA and PHB resins, 0.3 bre weight fraction, lm stacking compression moulding), [83] (Flax bres/PLA resin, 0.3 bre weight fraction, lm stacking compression moulding). (For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)

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for future advances. Discussions of the relative merit of each attribute are included, with Ashby charts (Figs. 24) being employed to allow easy comparison of the relative mechanical, environmental and economic properties of green composites compared to other materials. These material attributes are then used to dene a series of complementary application attributes. For example, one attribute of green composites is their tendency to absorb water and degrade, a complementary application attribute would be: limited exposure to moisture. As a result, a list is developed that combined with the mechanical properties of green composites can be used as a guide for their successful application. Applications that maximise the advantages of green composites, minimise the disadvantages and are obtainable with the necessary mechanical performance are then investigated, before general conclusions are made.

2. Materials 2.1. Natural bres Natural bres are generally classed as either vegetable or animal. Vegetable bres are principally composed of cellulose, whilst animal bres are composed of proteins [6]. Vegetable bres are the most commonly used in composite applications and, as such, are the primary focus of this work. The cell structures of natural bres are relatively complicated, with each bre being a composite of rigid cellulose microbrils embedded in a soft lignin and hemicellulose matrix. This structure is illustrated in Fig. 1; where it can be seen that the microbrils are helically wound along the hollow bre axis. Mechanical failure requires a large amount of energy to uncoil these spirally oriented brils [9]. These vegetable bres can be

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Fig. 3. Material production embodied energy specic mechanical properties, expected accuracy 10% [13]. Dashed lines indicate constant material performance for tie stiffness E/H and strength r/H, beam stiffness E1/2/H and strength r2/3/H and plate stiffness E1/3/H and strength r1/2/H. (For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)

Fig. 4. Cost specic mechanical properties [13]. Dashed lines indicate constant material performance for tie stiffness E/C and strength r/C, beam stiffness E1/2/C and strength r2/3/C and plate stiffness E1/3/C and strength r1/2/C. (For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)

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Table 1 Summary of bre properties, values primarily taken from [13], with additional values for bre length, diameter, composition and all values for bamboo sourced from [5,8,22,31,8486]. Fibre type Density (kg/m3) Carbon HS E-glass Coir Cotton Flax Hemp Jute Kenaf Ramie Sisal Bamboo 18001840 25502600 11501220 15201560 14201520 14701520 14401520 14351500 14501550 14001450 6001100 Price (USD/kg) 124166 1.633.26 0.250.5 2.14.2 2.14.2 12.1 0.351.5 0.260.52 1.52.5 0.60.7 0.50.5 Youngs modulus (GPa) 225260 7285 46 712 7590 5570 3560 6066 3844 1025 1132 Tensile strength (MPa) 44004800 19002050 135240 350800 750940 550920 400860 195666 500680 550790 140800 Elongation (%) 0.0 1.84.8 1535 512 1.21.8 1.41.7 1.72 1.35.5 22.2 46 2.53.7 Length (mm) 20150 1060 5900 555 1.5120 9001200 900 1.54 Diameter (lm) <17 <10 10460 1045 12600 25500 20200 2080 8200 2540 Moisture content (wt.%) 8 7.858.5 812 6.212 12.513.7 7.517 1022 Cellulose (wt.%) 3243.8 82.790 6272 6874.4 5971.5 3172 68.685 6078 2665 Hemicellulose (wt.%) 0.1520 5.7 18.620.6 1522.4 13.620.4 20.321.5 1316.7 1014.2 30 Lignin (wt.%) 4045 <2 25 3.710 11.813 819 0.50.7 814 530

Synthetic Fruit Bast

Leaf Grass

Table 2 Summary of polymer properties, values taken from [4,8,10,13,8790]. Polymer type Bio PLA PHB Starch Epoxies Polyester Polypropylene Density (kg/m3) 12101250 11801260 10001390 11101400 10401400 890910 Glass transition temp. (C) 4558 415 66.9167 147207 0.91.55 Melt temp. (C) 150162 168182 110115 Youngs modulus (GPa) 0.353.83 3.54 0.1250.85 2.353.08 2.074.41 0.91.55 Tensile strength (MPa) 2160 2440 56 4589.6 41.489.6 2841 Elongation (%) 2.56 58 3144 210 22.6 100600 Price (USD/kg) 2.43 3.24 5.5 810 44.4 1.852.05

Synthetic

harvested from the stems, leaves, or seeds of various plants [5], which classies them as a distinctly renewable resource. Table 1 provides an overview of natural bre properties and composition. 2.2. Biopolymers As with natural bres, there is a wide range of biodegradable biopolymers [10]. These are derived from a variety of renewable sources and include both thermosetting and thermoplastic polymers. However, if these thermosets are formed by polymerisation with synthetic monomers as many are they are no longer 100% green materials [11,12]. A review of the current state of development of both thermosetting and thermoplastic biopolymers, highlighting their respective biodegradability is presented in [6]. Bio-thermoplastics are commonly used in green composites and will be highlighted in this work. These include poly(lactic acid) (PLA), polyhydroxybutyrate (PHB), polysaccharides of plant origin; cellulose and alginate, animal origin; chitin and of microbe origin; hyaluronate. Thermoplastic starch is another polysaccharide commonly used as a matrix for green composites, it is comprised of both linear regions, that form helical structures, and branched regions. Proteins such as collagen (gelatin) and albumin are also biopolymers. Table 2 provides an overview of some of these polymers. 3. Attributes of green composites 3.1. Mechanical properties Fig. 2 shows two Ashby plots, where the densities of a variety of materials are plotted against tensile strength and Youngs modulus on logarithmic scales. An Ashby plot facilitates easy comparison of materials for differing design criteria. The dashed lines in Fig. 2 are guidelines for minimum weight tie, beam and plate design. By this it is meant that from any material that falls on the same guideline

or on any line parallel to these a structure, classed as either a tie, beam or plate can be designed with equal weight and equivalent stiffness or strength [13]. Ashby plots are also used in this paper to examine embodied energy and cost, here the dashed lines relate to structures with equal embodied energy or cost and equivalent stiffness or strength. Such a plot allows for a comparative evaluation of the mechanical properties of green composites to be made. The plots also provide a convenient way of reporting the mechanical properties of the wide range of green composites reviewed in this work. In the interests of fair comparison, the majority of the properties presented in these plots are extracted from the 2012 edition of Materials and the Environment by Ashby [13] (excluding the values for biopolymers and of course the green composites). Values for the green composites are extracted from several different research papers (references in the caption of Fig. 2); due to the often limited nature of the information provided in these, much of the density data for green composites is calculated from reported weight/volume fractions, with constituent densities used from Ashby [13]. It should be noted that the attribute values used for natural bres do not always align exactly with those reported in other publications (although they are similar). In addition, the plotted ellipses in these charts are made within a bounding box, dened by the extremes of the reported values. Thus one must allow for some error when considering these plots, but they are deemed to be acceptable for the desired purpose of comparison. It can be seen in Fig. 2 that natural bres and glass bres are comparable in terms of specic stiffness and specic strength. However, a wide gap appears when comparing the mechanical properties of composite materials constructed from each of these bres. This disparity between the properties of the raw material and those of the manufactured composite has several root causes; in part it is due to the use of low volume fractions of short, unaligned, reinforcement in green composites. However, the chemical incompatibility between the hydrophilic natural bre and hydrophobic polymer matrix is also responsible as it leads to poor bre

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wetting which produces an inferior interface and encourages bre agglomeration. Overcoming this issue is the subject of much research which is touched upon in the following paragraphs. Fibre alkali treatment, also referred to as mercerisation (see Section 3.7.) is both a common and effective method for reducing water absorption and improving the bre/matrix adhesion. The process improves the capacity for chemical interaction between the matrix and bres, while allowing for better mechanical interlocking through rougher topography and larger numbers of individual brils [14]. The treatment can also dissolve hemicellulose; the most hydrophilic part of natural bre structures which contributes little to the strength [15]. In an alkali treatment study by De et al. the tensile strength of a grass/phenolic composite improved 52% after alkali treatment [16]. In the work of Van de Weyenberg et al. the effect of alkali treatment on a unidirectional ax/epoxy composite was investigated. An average increase in strength of 30% was found in the material bre direction, while an increase of 138% was found in the transverse (matrix dominated) direction [14]. This large increase in the matrix dominated property compared to the bre direction shows that alkali treatment has a large impact, specically, upon bre/matrix bonding. Despite such work, structural applications of green composites have been extremely limited. Further work is needed to translate the good specic mechanical properties of the natural bres into those of a composite material. However, care should be taken to ensure any chemical modication of the bres in order to achieve this does not adversely affect the inherent environmental credentials of these materials. 3.2. Variable bre properties Due to natural bres being obtained from natural sources, they suffer from natural variability in properties, including bre shape, length and chemical composition. Crop variety, seed density, soil quality, fertilisation, eld location, bre location on the plant, climate and harvest timing are all factors that induce variation in these properties [5]. This variability can be seen in the value ranges reported in Table 1 and seen graphically in Fig. 2. Variability is a major issue to be resolved if these materials are to be relied upon in structural applications where failure is unacceptable and thus must be accurately predicted. Attempts have been made to model the size, shape and tensile properties through statistical analysis of individual bres [17,18], but few consider modelling of lamina and laminates, where three dimensional discontinuities such as microbeads may cause variation. Fibre lengths being tested in most green composites are relatively small (up to around 300 mm) compared with higher performance man-made bres. Although this reduces the chance of bres containing critical aws which reduce the materials tensile strength [19,20], their non-uniform length and shape leads to increased variability [4]. To effectively utilise the properties of brous composites, bre length should be maximised and bre direction aligned with the applied load. Increased bre alignment also allows for higher bre volume fractions to be achieved [20]. 3.3. Renewability The majority of traditional polymer matrix materials are derived from non-renewable petroleum which is formed from biomass over the course of 106 years; yet when consumed as plastic products or fuel, it is usually converted into CO2 within 110 years [8]. Thus the use of this distinctly nite and often volatilely priced resource is unsustainable. This is a large part of the incentive for pursuing green composites where both the reinforcement and matrix materials are derived from plants usually in the time

span of less than a year [8]. Using renewable resources in this way; whereby the rate of CO2 sequestered is balanced with the rate of consumption, contributes signicantly to developing carbon neutral materials. 3.4. Low embodied energy and CO2 emissions Values for the embodied energy and CO2 emissions of materials can be highly subjective [13], yet are increasingly useful measures by which the environmental impact of a material can be determined. In addition, it provides an indicator of the materials cost sensitivity to energy prices and emission regulations. In this work, we highlight embodied energy for the materials primary production only. This is the most signicant component of the materials life-cycle energy ow (as opposed to processing) and eliminates some of the variability/uncertainty regarding system boundaries and how the material may eventually be disposed of (for example, one could gain energy back through incineration with energy capture). Ashby plots, as presented in Section 3.1 can also be applied to the comparison of material environmental credentials. Weaver et al. show how such plots can be used to aid material selection for reduced environmental impact, demonstrated through a case study of refrigerator insulation [21]. Fig. 3 presents plots of embodied energy vs. mechanical properties. Unlike CO2 gures, embodied energy is independent of assumptions of the greenhouse gas intensity of electricity generation. The values in Fig. 3 are mostly from Ashby [8] and thus are suitably comparable. Similar techniques were used to calculate the embodied energy from volume/weight fractions, as for density, in Fig. 2. Here we are using only the embodied energy to produce the constituent materials, not any that is associated with creating the composite, nor that associated with any bre treatment. This is a signicant limitation of the analysis. In Fig. 3 it can be seen that a large number of natural bres have both an energy specic stiffness and strength advantage compared to synthetics, which still holds when they are implemented as reinforcements in polymers. In absolute terms, the embodied production energy in synthetic bres is in the order of 10 times greater than natural bres, whilst synthetic composites require around ve times more energy for production than green composites. Looking at a wider range of results in the literature, natural bre production has been reported to involve 2025% [22], 3040% [23] and 5055% [24] the energy of synthetics (glass bres). For green composites more generally, it is reported by Martin and Ramani [24] that a saving of 20 MJ/kg is achievable, with an associated reduction of 1 kg of CO2/kg, and an overall environmental impact reduction of 20%. Pervaiz and Sain [25] investigated a polypropylene (PP) composite reinforced with hemp and found that an energy saving of 50 MJ/kg (3 kg of CO2/kg) was possible by replacing a glass bres component with a bre weight fraction of 0.3, with a hemp bre component with a 0.65 bre weight fraction. Clearly there is an environmental benet in regards to energy use and CO2 emissions that can be achieved through the use of green composites. 3.5. Biodegradability Materials are dened as biodegradable if they degrade through the actions of living organisms; this denition is often widened to include degradation through non-enzymatic hydrolysis [26]. Natural bres are inherently biodegradable, as are many polymers the degradation rate of which is dictated by the chemistry along its backbone [26]. For example, polyanhydrides and polyesters both degrade through hydrolysis but at signicantly different rates; 0.1 h and 3.3 years respectively [27], whilst polyethers are

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non-biodegradable since they do not contain a hydrolysable bond. By making copolymers from polymers with different degradation rates, this property can be tailored to the application [28,29]. Biodegradation is a desired quality since it prevents accumulation of solid waste, which is a major consideration for composite materials in general and hinders their use in products with a limited service life [8,30]. Green composites could allow composite materials to enter new markets such as these, as their biodegradability offers a serious advantage over synthetic composites. For example, pure PLA will degrade to carbon dioxide, water and methane, within 2 years, whereas petroleum-based plastics require hundreds of years [15]. 3.6. Low cost Fig. 4 plots the production cost of a variety of materials against tensile strength and Youngs modulus. As with Figs. 2 and 3, the majority of values are taken from [13]. Green composite values are calculated from the reported volume/weight fractions and thus do not consider the cost of creating the composite itself, only the constituent elements. It can be seen from Fig. 4 that natural bres have a clear cost advantage over synthetic bres. However, biopolymers can be slightly out performed by their synthetic counterparts, although this situation is improving. In 2000 it was regarded that the cost of biopolymers was too high to sustain the industry [31]; since then, petroleum prices have risen and biopolymer production methods have improved. The result of this economic change has been quite signicant, for example, adjusting for ination, the cost of PP has increased by 111%, while the cost of PLA has fallen 73% [13,31]. Despite this turnaround in cost, it is remarked in [32], that linking performance with cost is still a difcult task. Thus, although work continues to improve the properties of biopolymers, the cost effectiveness of green composites depends heavily on the bre volume fraction used. Despite natural bres being currently inexpensive, two additional points should be considered. The rst is that the bre treatment and processing techniques required for adequate performance add additional cost to green composites [22]. The second point relates to the nature of the natural bre industry; in that these are materials with a young market for their supply and use. As such, there is great uncertainty around the future price of these materials. The North American market for natural bres is projected to grow from USD 155 million in 2000 to USD 1.38 billion by 2025 [8]. Whether this growth leads to shortages and price increases, or the development of a more mature and robust production industry remains to be determined. 3.7. High natural bre water absorption With three alcohol groups per glucan repeating unit, cellulose is a highly hydrophilic molecule and this property is imparted to natural bres comprised of cellulose [22]. The manufacturing issues this raises were discussed in Section 3.1. However, a further result of this property is that of water absorption of the nished composite material. Water absorption causes bre swelling which leads to delamination, surface roughening and a subsequent loss of strength of the material reported at up to 31% [5]. The moist environment can also facilitate the growth of fungus and bacteria which leads to rotting, this will be discussed in Section 3.8 where the durability of green composites is presented. In addition, bio-derived polymers also have a tendency to absorb more water than their synthetic counterparts, compounding the problem. It was found by Masoodi and Pillai [33] that for 40% (by mass) jute/epoxy composites, water absorption stabilised at

17.5% (by mass of total specimen); this value jumped to 26% when a bio-derived epoxy was used instead. The effect of moisture on the mechanical properties of natural bres was investigated in detail by Symington et al. [34]. This work concluded that moisture plays a signicant role in inuencing the mechanical properties of natural bres. Whilst the tensile strength of bres such as kenaf, jute and abaca centre around similar values when at room temperature/humidity conditions compared to being fully soaked, bres such as ax and coir undergo a notable decrease. Hemp was so degraded it was unable to be tested, raising concerns around its stability when exposed to various environmental conditions. In this work abaca was found to have the highest capacity to absorb moisture (164% by weight), which, especially concerning for the performance of a composite, led to volume swelling of 245.85%. Signicant research has been undertaken into improving the properties of natural bres through chemical modications to their surface, this work is presented and reviewed in a number of papers, including [22,35,36]. These reviews suggest that the most common and efcient chemical modication method for reducing moisture absorption is alkali treatment (also referred to as mercerisation), which has been used to treat almost all natural bres with successful results (although quantiable results are difcult to nd). Exposure of the bres to alkali solutions (most commonly KOH or NaOH) causes dissolution of the noncellulosic cementing substances; hemicellulose and lignin (Fig. 1) which reduces moisture absorption by the bre [34]. The alkali treatment must be carefully controlled, as too long an exposure will degrade the structural cellulose [34]. Other issues with the process include the creation of high pH waste products which compromises the environmental credentials of green composites [5]. One alternative to alkali treatment is the Duralin process which, by utilising steam to degrade and remove the hemicellulose and lignin, is more environmentally friendly [37,38]. In an investigation by Stamboulis and Baillie involving ax bres, the maximum moisture content (by mass) after exposure to 100% humidity was reported at 14.33% for a Duralin treated sample, compared with 42.58% for an untreated specimen [38]. Other benets of the Duralin process include better bre dimensional and temperature stability, better resistance to fungal attack and generally improved mechanical properties. However, the high temperatures required adds signicant energy costs to the material which again compromises the environmental credentials of green composites [5]. Material coatings are another method that can be used to prevent water absorption. But this is not 100% effective [39] and is often only a short to medium term solution. 3.8. Poor durability As one would expect from biodegradable materials, green composites have limited durability. Exposure to environmental conditions can lead to a rapid degradation of the material. Accurately predicting the lifetime of green composites is a major challenge to their widespread implementation [8]. One concerning cause of degradation in green composites is the growth of fungus and bacteria. Stamboulis and Baillie observed fungal growth on ax bres after just three days exposure to moisture [38]. In the work of Nadali et al. a bagasse/polypropylene composite was exposed to rainbow fungus (Coriolus versicolor): after 4 months a 3050% reduction in bending strength, bending modulus and hardness was observed [40]. Singh and Gupta show that weathering over a two year period of a jute/phenolic composite resulted in colour fading, resin cracking, bulging, brillation and black spots [41]. In addition, signicant reductions in mechanical properties were logged: for example, exural strength reduced by 22%. Similar results were reported in [42,43].

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Table 3 Summarised green composite attributes, matched to complementary application attributes. Material attributes Excellent weight specic stiffness Good weight specic strength Variable bre properties Renewable resource Low embodied energy Biodegradable Non-toxic Biocompatible Low cost High water absorption Poor durability Application attributes Weight critical vehicles/products (transport, mobile electronics, sport equipment Non-safety critical/low required reliability applications Short life-span product (disposable and high obsolescence rate products) Childrens toys, consumer handled items, hobbyist built items Medical devices and implants Competitive consumer products Dry use products Short life-span products, limited exposure to harsh environments

3.9. Non-toxicity Natural bres are generally non-toxic [6], providing scope for manufacturing composites with no or heavily reduced human health hazards and environmental damage throughout their life cycle (production, processing, use and disposal). A life cycle assessment by Corbiere et al. of biobre pallets compared to glass bre equivalents found reductions of: human toxins (43%), carcinogenic substances (63%) and heavy metals (71%) [44]. However, as shown in the work of Alves et al. bre treatment can have an effect on the level of respiratory irritants contained in the resulting composite [45]. 3.10. Biocompatibility and bioactivity A biocompatible material exists in harmony within a biological system, whilst a bioactive material facilitates a (in this instance benecial) biological response from the system through a direct interaction [26,46]. Non-toxicity is a fundamental requirement of a product for in vivo use and should the material biodegrade in situ, it is important that the by-products also meet these criteria. Here the hydrophilicity of green composites allows cellular interactions; cellulose, collagen, starch, chitin and PLA have all demonstrated biocompatibility [26,47]. 3.11. Fibre degradation at elevated temperatures Natural bres can begin to degrade at temperatures exceeding 170200 C, limiting the range of suitable applications, matrix systems and processing methods [8,22,36]. However, for manufacturing of green composites with a bio-derived polymer matrix (such as PLA) this has not proved a limiting factor, as these materials have low processing temperatures [5]. 4. Dening complementary applications Green composites are often touted for application in the automotive [4] and construction [5] industries. The potential for green composites to have a positive environmental impact when applied to these industries is large, as carbon can be effectively sequestered in these products for many years. Green composites can also provide weight saving and vibration damping of benet to the automotive sector. However, excluding non-structural, interior applications, the material properties required in automotive and construction uses are not always the best match for the currently obtainable attributes of green composites (variable bre properties, poor durability). Similarly, the attributes of green composites do not make them a potential substitute for glass bre reinforced composites (GFRP); not only are their absolute mechanical properties inferior, but their water absorption tendencies may exclude them from use in the vast array of wet GFRP applications (boats, kayaks, piping, tanks, etc.). Even if designs and manufacturing techniques for the structural intensive GFRP applications such as wind turbine blades could be modied to make use of the good specic mechanical

properties of green composites, great challenges would still obstruct their implementation in the form of bre property variability and low durability. In light of these observations a list has been compiled (Table 3) that attempts to match the material attributes of green composites with complementary application attributes. This list should be thought of as a guide for the successful applications of green composites. Applications that maximise the advantages of green composites (environmental), minimise the disadvantages (durability) and are obtainable with the mechanical performance offered. This paper does not want to rule out the use of green composites in any application, it simple tries to better promote the use of green composites in a wider array of applications, beyond the already heavily investigated areas of automotive and construction. In the following sections relevant current, developing and future applications of green composites are discussed. 5. Complementary applications 5.1. Short life-span products Short life-span products are typically thought of as those that are disposable, such as plastic cutlery and packaging. So called commodity plastics such as polyethylene, polystyrene, polypropylene, and polyvinyl chloride are used heavily in packaging causing several environmental concerns due to their non-biodegradability. Bio-composites that incorporate a biodegradable polymer comparable to the price and material performance of commodity polymers may well be a solution to the problem [7,31]. However, short life-span products are not only those items that we consider disposable, they are also items such as consumer electronics for example, smart phones. With such items, changes in style and improvements in technology can quickly lead to a product becoming obsolete, despite it still being functional [48]. Although research on product life-spans is limited [49], anecdotal evidence would suggest that as consumers become more involved in the fast paced development of electronics, the rate of product obsolescence is increasing; coupled to a reduction in product lifespans. A study into discarded products in the UK from 1993 to 1998 found that computers, telephones, faxes, radios, stereos, CD players, mobile phones, pagers and toys had a mean age of six years or under [49]. The very fact that some of these items can no longer be purchased and there is no mention of smart phones would suggest that the mean age of discarded items in the UK today would be substantially less. More recently, the European Consumer Centre has reported average life-spans for smart phones of just 20 months, not from failure or planned obsolescence, but rather style obsolescence [48]. The same report found average life-spans for rst, second and third generation iPods of just 18 months before battery failure [48]. Such products like many other modern designs for consumer electronics turn out to be more cost effective to replace rather than repair or replace the damaged subcomponent. The electronics company NEC has been working with green composites since 2004 when they used a PLA/kenaf composite in

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dummy cards in personal computers [50]. In 2006 NEC developed an eco phone with this material and in 2007 began using some green composites in the housing of their personal computers [51]. The green credentials of mobile phones are an increasingly popular area of development. US mobile phone retailer Sprint declared in January 2012 that it would require all phones it sells to meet a minimum environmental standard [52]. While a June 2012 report by Juniper Research has stated that 392 million green handsets (those with at least 50% recycled content and made without certain hazardous chemicals) will be shipped by 2017 [53]. Clearly phones, and electronics in general, are a potential application for green composites due to the high rates of obsolescence along with their limited exposure to moisture during use. Toys are another potential short life-span application for green composites. Although no current examples of biodegradable green composite toys were found excluding wooden toys the company Sprigwood manufactures toys from cellulose reinforced recycled plastics [54]. This shows that there is both consumer and business interest in using materials with improved environmental credentials in toy applications. The non-toxic attributes of green composites could also be highly desirable in toy applications particularly for very young children. From these considerations, we conclude that consumer electronics and toys are potential applications for green composites since they would complement their renewable, low embodied energy, biodegradability and low durability properties. 5.2. Sporting equipment The varying properties of natural bres and their limited absolute strength present a challenge for their use in load bearing applications. The issues associated with maintaining this strength when formed into a composite material are another obstacle for this type of application. However, the weight specic properties particularly stiffness of these bres is excellent, thus there is potential and incentive for them to be used in applications where mechanical properties are important. Sporting equipment may be a good starting point since failure (resulting from material variation or degradation) is less likely to cause serious injury or expensive property damage than more critical applications. Despite this, sporting equipment applications to date have involved either the use of hybrid composites (natural and synthetic bres combined) and/or non-biodegradable matrix polymers, negating one of the materials principal benets biodegradability. Examples included ax reinforced snowboards [55,56], ax and carbon (25:75%) reinforced tennis rackets [57] and ax and carbon (80:20%) reinforced bicycle frames [58]. In these applications the ax bres impart enhanced performance, since they provide superior vibration dampening compared to those of carbon or glass. It is claimed that this leads to snow boards that can navigate uneven terrain more uidly and with greater speed [55], tennis rackets that give added comfort when striking the ball [57], and bicycles that absorb micro-shocks for superior comfort [58]. Although many of these claims may be based more on marketing than engineering, the concept is aligned with one of the messages of this review; that the most successful green composite applications will be those that complement the inherent material attributes. 5.3. Biomedical applications The hydrophilicity of green composites facilitates interactions with other hydrophilic surfaces and substances such as living cell tissue. This property of bioactivity, coupled with their biocompatibility and biodegradability, distinguishes green composites from their synthetic counterparts for use in biomedical applications. By opening up this eld to composites, materials can be produced

which offer signicant advantages over those traditionally used or those of just a single component [59,60]: Superior material properties such as strength and toughness without sacricing weight, The ability to tailor other properties such as, Biodegradation kinetics, Cell permeability, The possibility of incorporating other materials within the cell support such as growth factors or nutrients [61], Shapability [62]. One biomedical application for which green composites have demonstrated these advantages is the interdisciplinary eld of tissue engineering; here a material scaffold acts as an extra cellular matrix to which cells adhere and grow. Specically, green composite materials have shown promise as scaffolds for soft tissue growth: Highly tailorable three-dimensional composite structures of poly(lactic-co-glycolic acid) (PLGA)/collagen have demonstrated success in regeneration of articular cartilage [62]. The biodegradation of PLGA is easily tailorable through the monomer ratio [63] and the by-products produced are naturally present in the body so this material poses minimal toxicity risk [61]. Similarly, by using these two polymers in their homopolymer form a highly tailorable scaffold for cartilage tissue growth has been produced. Here, a brous mesh of poly(glycolic acid) (PGA) was embedded within a poly(lactic acid) (PLA) matrix, and an increase in the proportion of the matrix was found to lead to an increase in both stiffness and degradation rate [64]. Cellulose has been studied in a range of biomedical applications [6569]. Bacterially sourced cellulose (from Gluconacetobacter xylinus) has been successfully incorporated into a PLA matrix and the material was touted for biomedical applications [70], as have cellulose/chitosan composites [71]. Human mesenchymal stem cells (MSCs) can be seeded onto a scaffold and directed to differentiate down a desired cell lineage to grow tissues or organs. A trachea has been successfully grown using this technique and the subsequent transplant proved ground breaking since the procedure allowed the patient an immunosuppressant-free life, unlike normal transplantees [72]. The trachea was grown ex vivo on a donated extracellular matrix and differentiation was induced using growth factors. Cell differentiation can be inuenced by a number of factors, one of which is the stiffness of the scaffold material [73]. It can be envisioned that by using a green composites bioactivity to induce differentiation, the tissue growth could occur in vivo without the need for growth factors [73]. A composite of cellulose and silk was found to initiate bioactively chondrogenic differentiation of human MSCs, and lead to the deposition of cartilage matrix material in vitro. The hydroxyl and amide functional groups were found to be important factors along with the materials stiffness, all of which are tailorable through the proportions of the two materials used [74]. Biopolymers are already widely used in medical applications [75]; however it is only recently that natural bres have been incorporated into these systems to yield new green composite materials which offer unique performance and functionality [60,70,71]. This eld is very much in its infancy and with the real advances being made, it could one day offer some truly life changing medical treatments.

6. Conclusion This review has provided a concise summary of the major material attributes of green composites. These include: good specic but variable mechanical properties, good environmental creden-

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M.P.M. Dicker et al. / Composites: Part A 56 (2014) 280289 [19] Virk AS, Hall W, Summerscales J. Tensile properties of jute bres. Mater Sci Technol 2009;25:128995. [20] Summerscales J, Dissanayake NPJ, Virk AS, Hall W. A review of bast bres and their composites. Part 1 Fibres as reinforcements. Compos Part A: Appl Sci Manuf 2010;41:132935. [21] Weaver PM, Ashby MF, Burgess S, Shibaike N. Selection of materials to reduce environmental impact: a case study on refrigerator insulation. Mater Des 1996;17:117. [22] Mohanty AK, Misra M, Drzal LT. Surface modications of natural bers and performance of the resulting biocomposites: an overview. Compos Interfaces 2001;8:31343. [23] Mueller DH, Krobjilowski A. New discovery in the properties of composites reinforced with natural bers. J Ind Text 2003;33:11130. [24] Martin P, Ramani N. How sustainable are biopolymers and biobased products? The hope, the doubts, and the reality. Natural bers, biopolymers, and biocomposites. CRC Press; 2005. [25] Pervaiz M, Sain MM. Carbon storage potential in natural ber composites. Resour Conserv Recycl 2003;39:32540. [26] Ikada Y, Tsuji H. Biodegradable polyesters for medical and ecological applications. Macromol Rapid Commun 2000;21:11732. [27] Gpferich A. Mechanisms of polymer degradation and erosion. Biomaterials 1996;17:10314. [28] Guarino V, Lewandowska M, Bil M, Polak B, Ambrosio L. Morphology and degradation properties of PCL/HYAFF11 composite scaffolds with multi-scale degradation rate. Compos Sci Technol 2010;70:182637. [29] Baker BM, Gee AO, Metter RB, Nathan AS, Marklein RA, Burdick JA, et al. The potential to improve cell inltration in composite ber-aligned electrospun scaffolds by the selective removal of sacricial bers. Biomaterials 2008;29:234858. [30] Klemchuk PP. Degradable plastics: a critical review. Polym Degrad Stabil 1990;27:183202. [31] Mohanty AK, Misra M, Hinrichsen G. Biobres, biodegradable polymers and biocomposites: an overview. Macromol Mater Eng 2000;276277:124. [32] Luckachan GE, Pillai CKS. Biodegradable polymers a review on recent trends and emerging perspectives. J Polym Environ 2011;19:63776. [33] Masoodi R, Pillai KM. A study on moisture absorption and swelling in biobased juteepoxy composites. J Reinforced Plast Compos 2012;31:28594. [34] Symington MC, Banks WM, West OD, Pethrick RA. Tensile testing of cellulose based natural bers for structural composite applications. J Compos Mater 2009;43:1083108. [35] Kalia S, Kaith BS, Kaur I. Pretreatments of natural bers and their application as reinforcing material in polymer composites a review. Polym Eng Sci 2009;49:125372. [36] John MJ, Anandjiwala RD. Recent developments in chemical modication and characterization of natural ber-reinforced composites. Polym Compos 2008;29:187207. [37] Pott GT. Reduction of moisture sensitivity in natural bres. In: Wallenberger FT, Weston NE, Ford R, Wool RP, Chawla K, editors. Advanced bers, plastics, laminates and composites; 2002. p. 8798. [38] Stamboulis A, Baillie CA. Environmental durability of ax bres and their composites based on polypropylene matrix. Appl Compos Mater 2000;7:27394. [39] Newill JF, Mcknight SH, Hoppel CPR, Cooper GR. Effects of coatings on moisture absorption in composite materials. Army Research Laboratory Weapons and Materials Reseach Directorate, ARL, Aberdeen Proving Ground, MD 210055069. <http://www.dtic.mil/cgi-bin/GetTRDoc?AD=ADA372503> [cited 14.05.13]; 1999. [40] Nadali E, Karimi A, Tajvidi M, Naghdi R. Natural durability of a bagasse ber/ polypropylene composite exposed to rainbow fungus (Coriolus versicolor). J Reinforced Plast Compos 2009;29:102837. [41] Singh B, Gupta M. Performance of pultruded jute bre reinforced phenolic composites as building materials for door frame. J Polym Environ 2005;13:12737. [42] Mehta G, Mohanty AK, Drzal LT, Kamdem DP, Misra M. Effect of accelerated weathering on biocomposites processed by SMC and compression molding. J Polym Environ 2006;14:35968. [43] Ahmad Thirmizir MZ, Mohd Ishak ZA, Mat Taib R, Rahim S, Mohamad Jani S. Natural weathering of kenaf bast bre-lled poly(butylene succinate) composites: effect of bre loading and compatibiliser addition. J Polym Environ 2010;19:26373. [44] Corbiere-Nicollier T, Gfeller Laban B, Lundquist L, Leterrier Y, Manson J-AE, Jolliet O. Life cycle assessment of biobres replacing glass bres as reinforcement in plastics. Resour Conserv Recycl 2001;33:26787. [45] Alves C, Ferro PMC, Silva AJ, Reis LG, Freitas M, Rodrigues LB, et al. Ecodesign of automotive components making use of natural jute ber composites. J Cleaner Prod 2010;18:31327. [46] Athanasiou KA, Agrawal CM, Barber FA, Burkhart SS. Orthopaedic applications for PLAPGA biodegradable polymers. Arthrosc: J Arthrosc Relat Surg: Off Publ Arthrosc Assoc N Am Int Arthrosc Assoc 1998;14:72637. [47] Dugan JM, Gough JE, Eichhorn SJ. Directing the morphology and differentiation of skeletal muscle cells using oriented cellulose nanowhiskers. Biomacromolecules 2010;11:2498504. [48] European Consumer Centre. LObsolescence programme ou les drives de la socit de consommation. <http://www.europe-consommateurs.eu/leadmin/ user_upload/eu-consommateurs/PDFs/publications/etudes_et_rapports/ Etude-Obsolescence.pdf> [cited 14.05.13]; 2013.

tials (renewable, biodegradable, low embodied energy, non-toxicity), low cost, high water absorption, low durability and biocompatibility. As work continues to improve the attributes of green composites, particular care must be taken to ensure the inherent green characteristics of these materials are not undermined. This review investigates a series of potential application for these materials. Applications such as consumer electronics, sporting equipment and medical devices that have been deemed to have complementary attributes to those of green composites have been presented. These are only examples of potentials applications and are by no means meant to represent an exhaustive list of green composite applications. Instead, they simply demonstrate the message of this review; that the most successful green composite applications will be those that complement their inherent material attributes. Green composites have potential for use in a number of applications, but as with all design, one must carefully match the material to the application. Although the information presented in this review does not delve into the details of green composite material science, it is hoped it does allow engineers and designers to have a better grasp of the most appropriate applications for green composites. It is anticipated that this will lead to the increased application of green composites, ultimately leading to an improvement in the sustainability of our material systems. Acknowledgments The authors gratefully acknowledge the support of the EPSRC under its ACCIS Doctoral Training Centre grant, EP/G036772/1. References
[1] The European Parliament and The Council of The European Union. Directive 2000/53/EC; 2000. [2] The European Standard EN, 13432:2000 Requirements for packaging recoverable through composting and, biodegradation; 2000. [3] EN 14995 Plastics evaluation of compostability test scheme and specications; 2006. [4] Koronis G, Silva A, Fontul M. Green composites: a review of adequate materials for automotive applications. Compos Part B: Eng 2013;44:1207. [5] Dittenber DB, GangaRao HVS. Critical review of recent publications on use of natural composites in infrastructure. Compos Part A: Appl Sci Manuf 2012;43:141929. [6] Zini E, Scandola M. Green composites: an overview. Polym Compos 2011;32:190515. [7] La Mantia FP, Morreale M. Green composites: a brief review. Compos Part A: Appl Sci Manuf 2011;42:57988. [8] Satyanarayana KG, Arizaga GGC, Wypych F. Biodegradable composites based on lignocellulosic bers an overview. Prog Polym Sci 2009;34:9821021. [9] Rong MZ, Zhang MQ, Liu Y, Yang GC, Zeng HM. The effect of ber treatment on the mechanical properties of unidirectional sisal-reinforced epoxy composites. Compos Sci Technol 2001;61:143747. [10] Van de Velde K, Kiekens P. Biopolymers: overview of several properties and consequences on their applications. Polym Test 2002;21:43342. [11] Shogren RL, Petrovic Z, Liu Z, Erhan SZ. Biodegradation behavior of some vegetable oil-based polymers. J Polym Environ 2004;12:1738. [12] Li F, Larock RC. Synthesis, properties, and potential applications of novel thermosetting biopolymers from soybean and other natural oils. In: Mohanty AK, Misra M, Drzal LT, editors. Natural bers, biopolymers, and biocomposites. Boca Raton: Taylor & Francis; 2005. p. 72750. [13] Ashby MF. Materials and the environment: eco-informed material choice. Butterworth-Heinemann; 2012. [14] Van de Weyenberg I, Chi Truong T, Vangrimde B, Verpoest I. Improving the properties of UD ax bre reinforced composites by applying an alkaline bre treatment. Compos Part A: Appl Sci Manuf 2006;37:136876. [15] Hu R, Lim J-K. Fabrication and mechanical properties of completely biodegradable hemp ber reinforced polylactic acid composites. J Compos Mater 2007;41:165569. [16] De D, Adhikari B, De D. Grass ber reinforced phenol formaldehyde resin composite: preparation, characterization and evaluation of properties of composite. Polym Adv Technol 2007;18:7281. [17] Summerscales J, Virk AS, Hall W. A review of bast bres and their composites: Part 3 Modelling. Compos Part A: Appl Sci Manuf 2013;44:1329. [18] Virk AS, Hall W, Summerscales J. Modelling tensile properties of jute bres. Mater Sci Technol 2011;27:45860.

M.P.M. Dicker et al. / Composites: Part A 56 (2014) 280289 [49] Cooper T. Reections on product life spans and the throwaway society. J Ind Ecol 2005;9:5167. [50] Iji M, Kiuchi Y. ITR 2012 Highly functional PLA composites used for electronic products. Green Innovation Reseach Laboratories NEC Corporation <http:// www.innovationtakesroot.com/~/media/ITR2012/2012/presentations/ durables/01_Highly-Functional-PLA-Composites_Iji_pdf.pdf> [cited 14.05.13]; 2012. [51] NEC Corporation. Bioplastics. <http://www.nec.com/en/global/onlinetv/en/ society/bio_plastic_l.html> [cited31.10.12]; 2006. [52] Herrera T. Sprint to require green certication for all cell phones. <http:// www.greenbiz.com/blog/2012/01/09/sprint-require-green-certication-allcell-phones> [cited 31.10.12]; 2012. [53] Ashdown D. Press release: Green handset shipments to reach almost 400 million by 2017. <http://www.juniperresearch.com/ viewpressrelease.php?pr=310> [cited 24.04.13]; 2012. [54] Sprig Toys. Sprig on being green sprigwood. <http://www.sprigwood.com/> [cited 31.10.12]; 2012. [55] Lucintel. XBoards introduces snowboard made from ax bre composite. <http://www.lucintel.com/news/ xboards_introduces_snowboard_made_from_ax_bre_composite.aspx> [cited 01.11.12]; 2012. [56] JEC Composites. Biocomposite snowboard using Biotex ax fabric. <http:// www.jeccomposites.com/news/features/biocomposites/biocompositesnowboard-using-biotex-ax-fabric> [cited 01.11.12]; 2012. [57] Artengo. Artengo Flaxber. <http://www.artengo.com/EN/tennis-178543753/ > [cited 14.05.13]; 2011. [58] Museeuw. MF-5. <http://en.museeuwbikes.be/bikes/race/mf-5> [cited 01.11.12]; 2012. [59] Lv Q, Feng Q, Hu K, Cui F. Three-dimensional broin/collagen scaffolds derived from aqueous solution and the use for HepG2 culture. Polymer 2005;46:126629. [60] Cheung H-Y, Lau K-T, Tao X-M, Hui D. A potential material for tissue engineering: silkworm silk/PLA biocomposite. Compos Part B: Eng 2008;39:102633. [61] Rezwan K, Chen QZ, Blaker JJ, Boccaccini AR. Biodegradable and bioactive porous polymer/inorganic composite scaffolds for bone tissue engineering. Biomaterials 2006;27:341331. [62] Dai W, Kawazoe N, Lin X, Dong J, Chen G. The inuence of structural design of PLGA/collagen hybrid scaffolds in cartilage tissue engineering. Biomaterials 2010;31:214152. [63] Gupta B, Revagade N, Hilborn J. Poly(lactic acid) ber: an overview. Prog Polym Sci 2007;32:45582. [64] Moran JM, Pazzano D, Bonassar LJ. Characterization of polylactic acid polyglycolic acid composites for cartilage tissue engineering. Tissue Eng 2003;9:6370. [65] Carlsson DO, Nystrm G, Zhou Q, Berglund LA, Nyholm L, Strmme M. Electroactive nanobrillated cellulose aerogel composites with tunable structural and electrochemical properties. J Mater Chem 2012;22:19014. [66] Czaja W, Krystynowicz A, Bielecki S, Brown RM. Microbial cellulose the natural power to heal wounds. Biomaterials 2006;27:14551. [67] Klemm D, Schumann D, Udhardt U, Marsch S. Bacterial synthesized cellulose articial blood vessels for microsurgery. Prog Polym Sci 2001;26:1561603. [68] Ferraz N, Carlsson DO, Hong J, Larsson R, Fellstrm B, Nyholm L, et al. Haemocompatibility and ion exchange capability of nanocellulose polypyrrole membranes intended for blood purication. J Roy Soc, Interface/Roy Soc 2012;9:194355.

289

[69] Boyd S. An investigation into the use of cellulose nanobre mats in the production of an aesthetic orthodontic bracket. University of Bristol, Thesis (Ph.D.); 2011. [70] Quero F, Nogi M, Yano H, Abdulsalami K, Holmes SM, Sakakini BH, et al. Optimization of the mechanical performance of bacterial cellulose/poly(Llactic) acid composites. ACS Appl Mater Interfaces 2010;2:32130. ska D. Multifunctional bacterial cellulose/chitosan composite [71] Ciechan materials for medical applications. Fibres Text Eastern Europe 2004;12:6972. [72] Macchiarini P, Jungebluth P, Go T, Asnaghi MA, Rees LE, Cogan TA, et al. Clinical transplantation of a tissue-engineered airway. Lancet 2008;372:202330. [73] Even-Ram S, Artym V, Yamada KM. Matrix control of stem cell fate. Cell 2006;126:6457. [74] Singh N, Rahatekar SS, Koziol KKK, Ng TS, Patil AJ, Mann S, et al. Directing chondrogenesis of stem cells with specic blends of cellulose and silk. Biomacromolecules 2013;14:128798. [75] Nair L, Laurencin C. Polymers as biomaterials for tissue engineering and controlled drug delivery. Tissue Eng I 2006;102:4790. [76] Ren B, Mizue T, Goda K, Noda J. Effects of uctuation of bre orientation on tensile properties of ax sliver-reinforced green composites. Compos Struct 2012;94:345764. [77] Han SO, Karevan M, Sim IN, Bhuiyan MA, Jang YH, Ghaffar J, et al. Understanding the reinforcing mechanisms in kenaf ber/PLA and kenaf ber/PP composites: a comparative study. Int J Polym Sci 2012;2012:18. [78] Behera AK, Avancha S, Basak RK, Sen R, Adhikari B. Fabrication and characterizations of biodegradable jute reinforced soy based green composites. Carbohydr Polym 2012;88:32935. [79] Vilaseca F, Mendez JA, Plach A, Llop M, Caigueral N, Girons J, et al. Composite materials derived from biodegradable starch polymer and jute strands. Process Biochem 2007;42:32934. [80] Bledzki AK, Jaszkiewicz A, Scherzer D. Mechanical properties of PLA composites with man-made cellulose and abaca bres. Compos Part A: Appl Sci Manuf 2009;40:40412. [81] Bledzki AK, Jaszkiewicz A. Mechanical performance of biocomposites based on PLA and PHBV reinforced with natural bres a comparative study to PP. Compos Sci Technol 2010;70:168796. [82] Bodros E, Pillin I, Montrelay N, Baley C. Could biopolymers reinforced by randomly scattered ax bre be used in structural applications? Compos Sci Technol 2007;67:46270. [83] Oksman K, Skrifvars M, Selin J-F. Natural bres as reinforcement in polylactic acid (PLA) composites. Compos Sci Technol 2003;63:131724. [84] Halley PJ, Dorgan JR. Next-generation biopolymers: advanced functionality and improved sustainability. MRS Bull 2011;36:68791. [85] Malkapuram R, Kumar V. Recent development in natural ber reinforced polypropylene composites. J Reinforced Plast Compos 2008;28:116989. [86] Ray AK, Mondal S, Das SK, Ramachandrarao P. Bambooa functionally graded composite-correlation between microstructure and mechanical strength. J Mater Sci 2005;40:524953. [87] Averous L, Moro L, Dole P, Fringant C. Properties of thermoplastic blends: starchpolycaprolactone. Polymer 2000;41:415767. [88] Ahankari SS, Mohanty AK, Misra M. Mechanical behaviour of agro-residue reinforced poly(3-hydroxybutyrate-co-3-hydroxyvalerate), (PHBV) green composites: a comparison with traditional polypropylene composites. Compos Sci Technol 2011;71:6537. [89] Curvelo A. Thermoplastic starchcellulosic bers composites: preliminary results. Carbohydr Polym 2001;45:1838. [90] Avrous L. Biodegradable multiphase systems based on plasticized starch: a review. J Macromol Sci, Part C: Polym Rev 2004;44:23174.