Composites: Part A 42 (2011) 579588

Contents lists available at ScienceDirect

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

Review

Green composites: A brief review

F.P. La Mantia a, M. Morreale b,
a b

Universit di Palermo, Dipartimento di Ingegneria Chimica dei Processi e dei Materiali, Viale delle Scienze, 90128 Palermo, Italy Libera Universit Kore Enna, Facolt di Ingegneria e Architettura, Cittadella Universitaria, 94100 Enna, Italy

a r t i c l e

i n f o

a b s t r a c t
The rising concern towards environmental issues and, on the other hand, the need for more versatile polymer-based materials has led to increasing interest about polymer composites lled with naturalorganic llers, i.e. llers coming from renewable sources and biodegradable. The composites, usually referred to as green, can nd several industrial applications. On the other hand, some problems exist, such as worse processability and reduction of the ductility. The use of adhesion promoters, additives or chemical modication of the ller can help in overcoming many of these limitations. These composites can be further environment-friendly when the polymer matrix is biodegradable and comes from renewable sources as well. This short review briey illustrates the main paths and results of research (both academic and industrial) on this topical subject, providing a quick overview (with no pretence of exhaustiveness over such a vast topic), as well as appropriate references for further in-depth studies. 2011 Elsevier Ltd. All rights reserved.

Article history: Received 6 June 2010 Received in revised form 20 January 2011 Accepted 24 January 2011 Available online 31 January 2011 Keywords: A. Polymermatrix composites (PMCs) A. Wood B. Mechanical properties

Contents 1. 2. 3. 4. 5. 6. 7. 8. 9. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Polymer matrices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Chemical modification and use of adhesion promoters . Processability and rheology . . . . . . . . . . . . . . . . . . . . . . . Processing and processability . . . . . . . . . . . . . . . . . . . . . Industrial applications . . . . . . . . . . . . . . . . . . . . . . . . . . . Towards complete environmental sustainability . . . . . . Environmental impact considerations. . . . . . . . . . . . . . . Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 579 580 580 582 582 583 583 585 586 586

1. Introduction Polymer composites have been widely used for several years and their market share is continuously growing. It is widely known that the use of a polymer and one (or more) solid llers allows obtaining several advantages and, in particular, a combination of the main properties of the two (or more) solid phases. Among the llers used, it is worth citing [1] calcium carbonate, glass bers, talc, kaolin, mica, wollastonite, silica, graphite, synthetic llers (e.g. PET- or PVA-based bers), high-performance bers (carbon, aramidic, etc.). However, this leads also to one of the main limitations of polymer composites: the two different components make the reuse and

Corresponding author.
E-mail address: marco.morreale@unikore.it (M. Morreale). 1359-835X/$ - see front matter 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.compositesa.2011.01.017

recycling quite difcult, to such an extent that it is often preferred to perform the direct disposal in a dump, or incineration [2,3]. This way is often considered to be unsatisfactory (especially in the rst case), because of the high costs, the technical difculties and the environmental impact. The latter is, indeed, a problem of primary importance. Furthermore, it is worsened by the fact that plastics production requires a remarkable consumption of oil-based resources, which are notoriously non-renewable. These problems have begun to be particularly evident for about 10 years, thus leading the scientic research to look for new alternatives, able to replace traditional polymer composites with substitutes having lower environmental impact and thus often referred to as ecocomposites or green composites. This task can be made easier by the fact that many of the typical applicative elds of these composites do not require excellent mechanical properties (i.e. secondary and tertiary structures, panels, packaging, gardening items, cases, etc.) [2,4].

580

F.P. La Mantia, M. Morreale / Composites: Part A 42 (2011) 579588

In chronological order, the rst attempts in this direction were focused on the production and characterization of polymer composites based on recyclable polymers (e.g. polyolens) lled with natural-organic llers, i.e. bers and particles extracted from plants. Several points support this choice; rst of all, the use of natural-organic llers in replacement for traditional mineralinorganic ones allows a considerable reduction in the use of nonbiodegradable polymers and non-renewable resources. Furthermore, these llers are usually drawn from relatively abundant plants (often from wastes), therefore they are very cheap. They are also much less abrasive than inorganic-mineral counterparts to processing machinery, less dangerous for the production employees in case of inhalation, easy to be incinerated, they lead to nal composites with lower specic weight (in comparison to mineral-lled counterparts) and allow obtaining interesting properties in terms of thermal and acoustic insulation [13,510]. The most widely known and used natural-organic llers are wood our and bers. Wood our can be easily and cheaply obtained from sawmill wastes and it is usually used after proper sieving. Wood bers are produced by thermo-mechanical processes on wood waste. Besides wood derivatives, other natural-organic llers have begun to nd application as well. Among these, some examples are cellulose, cotton, ax, sisal, kenaf, jute, hemp, starch [1,8,11,12]. Further environment-friendliness can be achieved upon using post-consumer recycled plastics in place of virgin polymer matrices. Wood our and bers are quite interesting because of the low cost, dimensional stability, elastic modulus, while tensile properties do not improve; the main shortcomings are the poor adhesion between the ller particles and the polymer matrix, low impact strength, thermal decomposition at temperatures over 200 C [2,4]. Flax, sisal, hemp and kenaf are relatively similar and are basically long bers extracted from the bast of the plants; they can be used as llers by proper cutting into long or short bers. Starch is a polysaccharide present in many plants acting as an energy reservoir. It is made of glucose monomers linked by a-(1-4) bonds [13,14]. In general, the addition of granular starch to a polymer leads to a reduction of the elongation at break (and often of the tensile stress as well), as high as the starch content increases, while the elastic modulus is enhanced. A limitation of this ller type is the tendency to absorb water because of its very high surface area and its hygroscopic nature. Other less used natural-organic llers can include rice husk ash, nutshells, oil palm empty fruit bunch bers, corn plants extracted bers, etc. [3,1517].

mitigated by using polar adhesion promoters such as maleic anhydride grafted polyethylene (MAgPE), maleic anhydride grafted polypropylene (MAgPP), or ethyleneacrylic acid copolymer [13, 25,30]. Polypropylene Literature reports several studies on polypropylene in combination with llers derived from wood, ax, sisal, hemp, kenaf, and starch. The spur towards alternate cellulose sources nds a justication in the fact that these are more easily renewable than the wood itself. Adhesion promoters are used as well. Some examples reported in the literature regard silane-based compounds [18], maleic anhydride grafted polypropylene (MAgPP), styreneethylenebutadienestyrene rubber grafted with maleic anhydride (MAgSEBS), ethylenepropylenediene copolymer grafted with maleic anhydride (MAgEPDM), which allowed obtaining a signicant improvement of mechanical and morphological properties[31,32]. Interesting results have been also found regarding the effect of wood bers on crystallization and morphology of polypropylene-based composites. It has been conrmed that wood bers do not inuence signicantly the crystal growth kinetics, while can enhance nucleation rates. The addition of MAgPP further increased nucleation phenomena, but it is not clear whether the observed improvement of mechanical properties should be attributed mainly to an enhancement of woodpolymer adhesion, to a better wood dispersion, or both. It is also proposed that the polymer structure, in particular the presence of amorphous regions, may have an important role on the worsening of some mechanical properties [33]. Others Examples of research regarding other kinds of polymers in combination with wood (and other natural-organic llers) include sisal bers and polystyrene [8], wood our [34] or starch [35] and polycaprolactone, phenolic resins and several natural bers [2], palm tree our and polyester resins [36], isora bers and natural rubber [37].

3. Chemical modication and use of adhesion promoters As previously mentioned, research is particularly focused on the modication of ller surface in order to improve the interfacial adhesion between ller particles (hydrophilic) and polymer macromolecules (generally hydrophobic) and their dispersion in the matrix. This is a very important issue, since the simple addition of natural-organic llers to a polymer matrix may lead to poor mechanical properties in comparison to the neat polymer; this can be especially true when ller particles with low length-todiameter ratios are used. An example of the trends of the main mechanical properties upon simple addition of 30 wt.%, low aspect ratio natural-organic llers (OS = olive stones our, SDc = coarse wood our, SDf = ne wood our, SS = sago starch) to a recycled polyethylene (RPE) is provided in Table 1. The overall comment which can be drawn is that the green composites can achieve greater stiffness and thermomechanical resistance but, on the other hand, the ductility and the tensile strength are signicantly reduced. It is therefore clear that chemical modication or use of adhesion promoters can be interesting paths in order to improve the overall mechanical properties. Modication relies on chemical and physical techniques, mainly focused on grafting chemical groups capable of improving the interfacial interactions between ller particles and polymer matrix. The main techniques may be summarized as follows [5,37 47]: Alkali treatment (also called mercerization): it is usually performed on short bers, by heating at approx. 80 C in 10% NaOH aqueous solution for about 34 h, washing and drying in

2. Polymer matrices The main polymer matrices used in the eld of green composites (excluding biodegradable ones, which are overviewed in a following paragraph) could be summarized as follows. Polyethylene The scientic literature reports polyethylene based composites, including a number of llers, e.g. wood chips and bres [1821], corn starch [13,22], sago, tapioca and rice starch [23,24], sisal bers [5], kenaf bers [12]. Furthermore, papers exist regarding post-consumer recycled polyethylene, e.g. wood bers and HDPE coming from food containers [25], wood bers and HDPE coming from milk bottles [26], polyethylene coming from greenhouse lms and wood bers, sago starch, ground olive stones [27]. Wood bers (as well as the other main natural-organic llers) are usually added to the polymer matrix up to 4070% by weight [28,29]. In general, an increase of stiffness and exural strength, and a reduction of ductility are observed. This problem can be

F.P. La Mantia, M. Morreale / Composites: Part A 42 (2011) 579588 Table 1 Main mechanical properties of RPE-based green composites without the use of any adhesion promoter/chemical modication technique (data taken from Ref. [27]). Property Elastic modulus (MPa) Tensile strength (MPa) Elongation at break (%) Heat deection temperature (C) Impact strength (J/m) RPE 129 12.5 100 27 No break RPE-OS 163 8 36 35 No break RPE-SDc 264 10.9 29 38 185 RPE-SDf 282 10.4 17 42 99 RPE-SS

581

193 9.9 45 37 No break

ventilated oven. It allows disrupting ber clusters and obtaining smaller and better quality bers. It should also improve ber wetting. Acetylation: the bers are usually immersed in glacial acetic acid for 1 h, then immersed in a mixture of acetic anhydride and few drops of concentrated sulphuric acid for a few min, then ltrated, washed and dried in ventilated oven. This is an esterication method which should stabilize the cell walls, especially in terms of humidity absorption and consequent dimensional variation. Treatment with stearic acid: the acid is added to an ethyl alcohol solution, up to 10% of the total weight of the bers to be treated the obtained solution is thus added drop wise on the bers, which are then dried in oven. It is an esterication method as well. Benzylation: the bers are immersed in 10% NaOH and then stirred with benzoyl chloride for 1 h, ltrated, washed and dried, then immersed in ethanol for 1 h, rinsed and dried in oven. This method allows decreasing the hydrophilicity of the bers. TDI treatment: the bers are immersed in chloroform with few drops of a catalyst (based on dibutyltin dilaurate) and stirred for 2 h after adding toluene-2,4-diisocyanate. Finally, bers are rinsed in acetone and dried in oven. Peroxide treatment: the bers are immersed in a solution of dicumyl (or benzoyl) peroxide in acetone for about half an hour, then decanted and dried. Recent studies have highlighted signicant improvements in the mechanical properties. Anhydride treatment: it is usually carried out by utilizing maleic anhydride or maleated polypropylene (or polyethylene) in a toluene or xylene solution, where the bers are immersed for impregnation and reaction with the hydroxyl groups on the ber surface. Literature reports signicant reduction of water absorption. Permanganate treatment: the bers are immersed in a solution of KMnO4 in acetone (typical concentrations may range between 0.005 and 0.205%) for 1 min, then decanted and dried. Investigations have pointed out a decreased hydrophilic nature of the bers upon performing this treatment. Silane treatment: the bers are immersed in a 3:2 alcohol water solution, containing a silane-based adhesion promoter for 2 h at pH  4, rinsed in water and oven dried. Silanes should react with the hydroxyl groups of the bers and improve their surface quality. Isocyanate treatment: isocyanate group can react with the hydroxyl groups on ber surface, thus improving the interface adhesion with the polymer matrix. The treatment is typically performed with isocyanate compounds at intermediate temperatures (around 50 C) for approximately 1 h. Plasma treatment: this recent method allows signicantly modifying the ber surface. However, chemical and morphological modication can be very heterogeneous depending on the treatment conditions, therefore it is not easy to generalize; process control is a critical aspect and the nal surface modications strongly depend on it.

More specically, TDI, dicumylperoxide and silane treatment seem to guarantee the best results with concern to mechanical properties, while alkali treatment and acetylation seem to give better improvements in thermal and dimensional stability. Chemical modication, therefore, is an interesting way to improve the properties of natural organic/polymer composites, though having a primary drawback represented by the costs that, especially in the case of complicated techniques, can rise to such a level to make this method not suitable for industrial applications. These, in fact, require quicker and cheaper methodologies and it necessary to assure constant product quality. It is therefore clear that chemical modication of bers is unlikely to meet all of these requirements [33]. Other solutions are therefore preferred in order to produce green composites with improved matrixber interfacial adhesion and ber dispersion, and to reduce the formation of voids inside the material (due to the hydrophilic nature of natural-organic llers) [48]. At present, the preferred solution for industrial applications does not rely on chemical modication of bers, but rather on the addition of small amounts of a third component which, by its intrinsic chemical characteristics, may act as an adhesion promoter between polymer matrix and cellulosic llers, by forming chemical bonds (either covalent, or Van der Waals kind) [32]. Of course, the adhesion promoter molecule should contain a hydrophilic part, able to create the bonds with the polar groups typically present on cellulosic bers, and a hydrophobic part, which can show higher afnity to the macromolecular chains. A number of recent papers exist regarding the use of adhesion promoters/compatibilizers for green plastic composites [32,49 68]. The most investigated matrices are polyolens, while the adhesion promoters are mainly based on the same polyolens modied with maleic anhydride. The results are quite variable, depending on the polymer matrix used, the ller type and quantity, the adhesion promoter used (i.e. the base polymer on which it is prepared, its molecular weight, the modier percentage, etc.) and its amount, the processing techniques, etc. In general, it could be observed that these adhesion promoters, on average, can signicantly improve tensile properties and processability, while water absorption is reduced. However, in some cases, impact strength may not be enhanced, therefore specic elastomeric impact modiers should be used. An example of the improvements that a maleated adhesion promoter can assure to a green composite based on polypropylene and 30 wt.% wood our is reported in Table 2.

Table 2 Main mechanical properties of polypropylene/wood our green composite without and with the use of a maleated adhesion promoter (reproduced from Ref. [32] with permission from Brill). Property Elastic modulus (MPa) Tensile strength (MPa) Elongation at break (%) Impact strength (unnotched) (J/m) PP + 30% WF 954 19.5 4.2 83 PP + 30% WF + 3% MAPP 1035 27.2 4.6 98

582

F.P. La Mantia, M. Morreale / Composites: Part A 42 (2011) 579588

4. Processability and rheology With concern to processability of polymer-natural-organic ller composites, in comparison to the neat polymer, it can be stated, as a general rule, that an increase in the viscosity is observed (and thus a decrease of the processability), and it is higher upon increasing the ller content [27,36,69,70]. However, processability is not compromised (except, in some case, for very long bers) since torque and viscosity increases are not too high and, at high shear rates (typical of the industrial processing techniques) these gaps tend to reduce [27,69,70]. There are not many papers regarding the rheology of polymer systems lled with natural organic materials. Early studies pointed out an increase of viscosity in polyethylene or polypropylenebased composites lled with wood our [7173]; it was also found that viscosity increases upon increasing the ller content [27,69,74]. Li and Wolcott [70] investigated the behavior of HDPEwood bers composites, upon changing the ller content (40 and 60 wt.%) and the wood type (maple or pine), using a capillary rheometer. They found wall slip phenomena to be present and largely dependent on ller weight percentage and nature; similar considerations can be done for the yield stress. Elongational ow analysis showed that viscosity depends more on the ller content than the ller nature; a comparison of the Trouton ratio showed it to be strongly dependent on ber typology and a strong interaction between the bers was also observed (thus justifying yield stress during the shear ow). La Mantia and Morreale [32] investigated also the rheological behavior of PP-wood our composites with and without the addition of a PPgMA based adhesion promoter. The latter acted as a mild processing aid, however, upon increasing the ller content, rheology was signicantly modied by the formation of ller polymer bonds, mediated by the adhesion promoter.

5. Processing and processability Literature data on green composites show, as discussed before, a clear prevalence of wood, in combination with polyolens: this inuences, of course, also the information available on processing and processability. Typical processing techniques include extrusion and subsequent injection or compression molding [27,30,48,69,7577]. Filler amount seldom exceeds 5060 wt.%, even though sometimes higher percentages, up to 7080%, are reported (especially in the US). Of course, being the conditions more extreme, compression molding is preferred to injection molding. Some typical problems related to the processing of these materials are due to the hydrophilic and hygroscopic nature of the llers, and to their poor thermal resistance (so that processing temperatures should be kept below approx. 200 C). In particular, the hydrophilic and hygroscopic nature of the llers is one of the main problems in this eld: in fact, it tends to signicantly inuence ller dispersion in the matrix and the interfacial adhesion. The presence of humidity generally leads, during the processing, to the formation of water vapor which can, in turn, give rise to several problems, especially in the following molding step (in the case of injection molding), if a venting or drying system is not present. In general, the formation of water vapor (but also of gases/vapors of different kind) leads to the formation of voids in the material and thus to poor mechanical properties. On the other hand, the presence of volatile substances inside the material can negatively inuence the following steps of the products life cycle. However, it should be also pointed out that small amounts of humidity are not detrimental but, on the contrary, may help to soften the cellulosic component, thus acting as a sort

of lubricant [75]. Furthermore, it is a widely accepted technique to dry the natural-organic ller prior to processing, by different ways such as hot air jets, rotating driers, ventilated ovens, in order to reduce the humidity level to approx. 23%. The early processing techniques basically relied on melt mixing and extrusion of seminished products in the shape of at boards, to be then used especially for car panels [78]. Extruded PP-wood our sheets soon showed their potential: low humidity absorption, dimensional stability, reduced ame propagation in case of re, good processability especially for compression molding, versatility and recyclability. Some years ago, the most used technique was based on the preparation of the solid blend through a high-speed mixer and the following feeding of the blend to a counter-rotating twin screw extruder. During the last years, processing techniques have been tailored to operative and market needs, leading to a gradual reduction of the importance of components preliminary mixing, in favor of gravimetric dosage along the extruder, in order to reduce power consumption and assure higher uniformity and regularity of dosage. At the same time, counter-rotating extruders have been gradually replaced by co-rotating ones. Newer extrusion systems are also modular, meaning that they are made up of independent, inter-changeable modules. Literature reports several studies on new technological solutions related to WPC processing, e.g. investigations on trial-and -error methodologies for the design of moulds for automotive panels production, starting from WPC sheets made of polyolens and wood bers [79]; simulation of non-newtonian ow of polymernatural ller systems inside mixers and extruders in order predicting nal product quality and heat production through viscous stress [79]; various attempts of reactive extrusion [80]; processing with particular reactive additives or electron beam [81]; turbine mixing [82]. Japanese researchers have recently proposed an electromagnetic induction method for jute fabric reinforced thermoplastic molding [83]. According to the Authors, the system allows an instantaneous heating of the mold surface, thus shortening the production cycle times and leading to a reduction of the production costs related to composite panels molding. Other Authors have found a signicant inuence of ber area fraction (besides molding temperature and forming pressure) on the mechanical and thermomechanical properties of green composites [84]. Scaffaro et al. have studied the inuence of process variables and processing techniques on the mechanical behavior of green composites lled with wood our [85,86]. They found, by means of statistical analysis, that the most inuencing process variable on the materials rigidity is the ller content, even though preliminary treatments and mixing speed exert some inuence as well; the impact strength was mainly inuenced by mixing speed and ller aspect ratio, while temperature had only a minor effect. With concern to the role of the processing technique (beyond the basic batch mixing), they found that injection molding caused a partial degradation of the macromolecules, leading to a reduction of the viscosity and the stiffness of the material, while twin-screw extrusion and single-screw extrusion followed by calendering allowed obtaining nal materials with higher moduli. On the other hand, a particularly compact morphology was found in the injection molded samples. The comparison between extrusion and mixing is not easy, since similar results were found for the elastic modulus, while the tensile strength deeply depended on the ller content (Table 3). Other Authors [87] found partially comparable trends on PVCcoconut ber composites. However, the above mentioned investigations also pointed out that the role of ller type, ller content, ller aspect ratio and processing temperature is of great importance, so it may be very difcult (and sometimes even inappropri-

F.P. La Mantia, M. Morreale / Composites: Part A 42 (2011) 579588 Table 3 Tensile properties of wood our lled green composites as a function of the processing technique (data taken from Ref. [85]). Mechanical property Elastic modulus (MPa) Processing Mixing Single-screw extrusion Twin-screw extrusion Injection molding Mixing Single-screw extrusion Twin-screw extrusion Injection molding Neat polymer 410 378 373 200 17 27 28 15

583

Composite, 15 wt.% WF 537 535 563 295 11 17 12 18

Tensile strength (MPa)

ate) to search and propose general rules which might apply to the mechanical behavior. Takagi and Asano [88] have prepared green composites based on dispersion-type biodegradable resin and cellulose nanobers, by using a stirring technique at relatively low speed and long times and upon changing the mold pressure. They found signicant increases in exural modulus and strength (up to 100%), upon increasing the mold pressure, in comparison to the control composites (which had not undergone the same stirring process). 6. Industrial applications With concern to the industrial applications, several paths have been undertaken. In short, it can be stated that the most used natural-organic ller is wood (either our or bers), especially as low cost ller for polyolens [2]. Wood our is usually obtained from sawmill waste after a simple sieving treatment; wood bers are produced from sawmill waste by a wet thermomechanical process. Already explored industrial applications include window and door frames, furniture, railroad sleepers, automotive panels and upholstery, gardening items, packaging, shelves and in general those applications which do not require very high mechanical resistance but, instead, low purchasing and maintenance costs [2,4,8991]. Furthermore, it is possible and convenient to use recycled polymers in place of virgin ones, thus assuring improved cost-efciency and eco-sustainability. Some examples of industrial applications can be easily found on the technical literature and on the Internet; these include, for instance, indoor furniture panels, footboards and platforms, automotive panels and upholstery, noise insulating panels, etc., mainly produced by American, German, Japanese, British and Italian rms [2,78,92]. In particular, the role of automotive industry in this eld is of primary importance. The rst carmaker to use polymers lled with natural bers was Mercedes-Benz in the 90s, by manufacturing door panels containing jute bers [92]. This example was soon followed by other main carmakers, which have started to utilize polymer composites with natural-organic llers as materials for door panels, roof upholstery, headrests, parcel shelves, etc., thanks to the advantages they can assure in terms of environmental impact, weight, elastic modulus and costs. Depending on the applications, it was sometimes necessary to improve the mechanical properties through ber pre-treatment (acetylation, use of MAgPP, etc.), and the treated bers were then used in several ways, in order obtaining mats, non-woven structures, etc. Some authors assert also that, by means of special treatments on natural bers, these could lead to the production of high-quality composites with mechanical properties comparable to glass ber lled composites [92]. A result which would be impossible to obtain otherwise, since the hydrophilic nature of natural-organic llers favors agglomeration, humidity absorption and lack of adhesion with the polymer matrix; in fact, many efforts are being done to overcome the problem of interfacial adhesion. Among these, the investigations on silane-based adhesion promoters [60,92] or some ber treatments with alkaline substances or dilute resins. How-

ever, a proper use of long (i.e. more than approx. 5 cm, at least) bers can already allow obtaining composites suitable to semistructural applications. 7. Towards complete environmental sustainability Some recent developments are pushed by the fact that, unfortunately, even these green composites are not fully ecocompatible, since their recyclability has some limitations (temperatures cannot exceed 200 C during recycling and all the main properties will worsen because of the degradation phenomena) [2,92] and their biodegradability regards only the ller but not, of course, traditional (petroleum-based) polymer matrices. For this reason, research developments during the last years have been focused on the production on 100% eco-sustainable and green composites, by replacing non-biodegradable polymer matrices with biodegradable ones. Several biodegradable, natural-derived polymers exist, such as polysaccharides (starch, chitin, collagen, gelatines, etc.), proteins (casein, albumin, silk, elastin, etc.), polyesters (e.g. poly(hydroxyalcanoate), poly(hydroxybutyrate), polylactic acid), lignin, lipids, natural rubber, some polyamides, polyvinyl alcohols, polyvinyl acetates, and polycaprolactone [2,93105]. In the majority of cases, they degrade through enzymatic reactions in suitable environments (typically, humid). As a general rule, biodegradable polymers can be classied according to their origin, i.e. into agropolymers (e.g. starch), microbial-derived (e.g. PHA) and chemically synthesized from agrobased monomers (e.g. PLA) or conventional monomers (e.g. synthetic polyesters) [106]. Several examples are available in literature. For instance, Japanese researchers have investigated on composites based on starch and bamboo bers [2]. Others have studied the interesting properties of composites based on Monsanto Biopol (a polyhydroxy butyratehydroxyvalerate copolymer) with ananas and jute bers. In some cases, natural bers were pre-treated by alkali treatment and chemical groups grafting [9395,107109]. Work has also been done to use matrices based on soy proteins. For instance, Netravali and coworkers [2,95] used soy proteins in combination with several natural bers, obtaining interesting composites which, in some cases, show global characteristics even superior to many wood types. An interesting system for automotive applications is a composite where the polymer matrix is based on soy and corn oil, which are used as raw materials for the production of the polymer (in a way which is comparable with the one by which commodity polymers come from oil) with good resistance, exibility, lightness and durability properties [92]. Examples of possible applications are panels, seats, packaging, furnishing, etc. Some companies have been working on synthetic silk production by genetic engineering, which may be used for biodegradable materials as well [2,110]. A very interesting class of biodegradable polymers which could be used for eco-composites production is the Novamonts Mater-Bi. It is known that Mater-Bi family polymers are usually

584

F.P. La Mantia, M. Morreale / Composites: Part A 42 (2011) 579588

Table 4 Main mechanical properties for a neat Mater-Bi grade (MB) and the corresponding 30 wt.% wood our (SDc = coarse, SDf = ne) lled green composites, without (humid) and with (dry) drying treatment on the polymer before processing (data taken from Ref. [111]). Property Elastic modulus (MPa) Tensile strength (MPa) Elongation at break (%) Heat deection temperature (C) Impact strength (J/m) MB 88 6 73 39 No break MB + 30%SDc (humid) 457 5.5 2.8 49 86 MB + 30%SDf (humid) 483 6.4 2.7 54 54 MB + 30%SDc (dry) 442 7 2.3 48 63 MB + 30%SDf (dry) 530 6.7 2.3 55 44

based on modied starch and synthetic polymers (polyesters in prevalence) [111113] and are compostable [113]. Literature reports that Mater-Bi can be conveniently used for the realization of fully biodegradable composites, however mechanical properties, processability and biodegradability strongly depend on the Mater-Bi and the ller used, ller content, processing techniques [113122]. For instance, rigidity of the materials usually increases upon increasing ller content [85,86,116,118,121], while ultimate properties can change signicantly depending on ller content, processing techniques (mixing, extrusion, injection molding, etc.), processing parameters (speed, temperature, etc.) [85,119,120,122, 123]. Scaffaro et al. [85] found that injection molding can signicantly reduce the polymers molecular weight in comparison to extrusion followed by compression molding but, on the other hand, it can improve both surface and internal morphology of the composite samples, thus leading to signicant increases of tensile strength if compared to the neat, unlled samples. An example of the way how the main mechanical properties can change upon going from a neat Mater-Bi grade to the corresponding, 30 wt.% lled green composites, is provided in Table 4. The composites were lled with coarse (SDc) and ne (SDf) wood our. The ller was always dried before processing, while the polymer was dried only in the case of dry-labeled samples. It can be observed that wood our signicantly enhances the stiffness and the thermomechanical resistance of the materials; furthermore, tensile strength keeps practically constant, probably thanks to the hydrophilic nature of the chemical groups present in the Mater-Bi matrix; only the ductility is worsened. However, since polyesters are typically present in the composition of most Mater-Bi grades, a drying pre-treatment is advisable in order reducing the hydrolytic chain-scission reactions due to the presence of water in the system during processing. Biodegradability of Mater-Bi based green composites has not been much investigated so far. The papers available regard biodegradation of composites in soil [112,113,124] and found that the composites underwent biodegradation after burial in soil. Rutkowska et al. [125,126] studied biodegradation in different natural environments, nding a complete biodegradation after 4 weeks. However, these investigations regarded just neat materials. Scaffaro et al. [114] have studied Mater-Bi/wood our composites biodegradation in active sewage sludge, nding that the composites undergo biodegradation with higher weight loss rates than the neat Mater-Bi. This effect was attributed primarily to the morphology achieved and to the capability of wood bers to act as support for the bacterial growth [114]. Another interesting thermoplastic polymer coming from renewable sources is polylactic acid (PLA). In general, PLA shows good mechanical properties, is biocompatible and is rather easy to produce. Literature reports some studies on PLA and naturalorganic llers. Nishino et al. [127] prepared PLA/kenaf bers composites with good mechanical properties, thanks to the orientation imparted to the bers. Lee and Wang [128] have studied PLA/bamboo bers composites and the effect of a lysine-based coupling agent, obtaining an improvement of the mechanical properties and an increased thermal stability, even though this may worsen

the biodegradability. Further studies exist on PLA/ax composites [129] and the main problem encountered regards matrixbers adhesion. Huda et al. [130] investigated the properties of PLA/recycled cellulose composites prepared by extrusion and injection molding, nding that the ller (up to 30 wt.%) signicantly improved the rigidity without affecting the crystallinity degree or thermal stability. Plackett et al. [131] prepared PLA/jute composites, by a lm stacking technique, nding signicant improvements of the tensile properties, although brittle fracture was observed, affecting also the impact strength. Unfortunately, some limitations have still to be overcome in order to support the development and use of fully biodegradable composites. First comes the still high price of biodegradable polymers in comparison to traditional commodity polymers, which of course discourages their use. Price is slowly decreasing upon increasing of their utilization, however the latter need to increase more and more to get to very competitive prices; this is one of the major challenges that biodegradable polymers are facing. Another problem regards, as predictable, ller dispersion and its interface adhesion with the polymer matrix, which are of fundamental importance for the overall properties of the product. Depending on the biodegradable polymer used, the results may be more satisfactory than in the case of polyolens, etc. because of the presence of polar groups along the macromolecules [85,86,111,114] but, sometimes, it is necessary to improve the properties by treatments such as alkali treatment, acetylation, and silane or maleic anhydride treatments [2,13,18,132,133]. However, from the point of view of industrial applications, chemical modication of bers is usually neither convenient nor cheap, therefore being mostly a niche solution. Finally, it must be pointed out that thermoplastic polymers have been investigated also for use with nano-sized llers in replacement for traditional micro-sized ones, thus leading to the green nanocomposites eld. An extensive review of such subeld would be out of the scope of the present paper. However, excellent reviews on it currently exist. Samir et al. [134] reported on the processing and behavior of nanocomposites obtained by thermoplastic polymers and polysaccharide microcrystals, nding that the use of high aspect ratio cellulose whiskers can lead to signicant improvements of the mechanical properties. Polysaccharide nanocrystals may be obtained from several sources such as, for instance, chitin and starch by acid hydrolysis. Hubbe et al. [135] focused on possible industrial application of cellulose nanocrystals, pointing out that retention of properties over time should be guaranteed and the use of water-miscible polymer matrices such as latex, starch products, polyvinyl alcohol should be preferred, in order to make cellulose preparation and compatibilization with the matrix easier. Eichhorn et al. [136] reported (similarly as in the previous references cited) the possible methods of cellulose nanollers recovery, then focusing on the use of cellulose nanowhiskers for the manufacturing of shape memory nanocomposites, as well as on the interfacial phenomena occurring in polymer/nanocellulose ller composites.

F.P. La Mantia, M. Morreale / Composites: Part A 42 (2011) 579588

585

8. Environmental impact considerations It has been already pointed out that the use of natural-organic llers allows obtaining several environmental advantages in comparison to mineral-inorganic counterparts. The environmental impact, in fact, can be improved mainly due to the reduction in the use of fossil-based resources (especially petroleum). Furthermore, if biodegradable polymers are used, fully biodegradable systems may be obtained, thus signicantly reducing the problems related to the everyday production of solid, plastic-derived waste [121,137139]. These aspects have been further investigated by invoking also the data which life cycle assessment (LCA) may provide as further evidence [2,132]. In particular, a detailed paper has been written by Joshi et al. [9] collecting and discussing some LCA assessment studies on composites lled with, respectively, natural-organic llers (NFR) and glass bers (GFR). It is known that LCA analysis allows determining a detailed overview of all the environmental impacts related to products and/or processes, by a cradle to grave approach, thus determining all of the mass and energy ows deriving from the manufacturing of a product, but also from the use during its life cycle. All these steps and ows are then linked to their direct and indirect environmental impacts, which must be determined quantitatively. The entire process is regulated by ISO 14040 to 14043 standards [9]. For instance, the life cycle of a generic GFR item includes glass and monomer production, starting from the raw materials (minerals and oil, respectively); then the monomer must be subjected to polymerization, while glass must be treated in order to manufacture the bers. These raw materials are then processed to make the product. The latter will be then purchased, used for a certain time period, until the end of its life cycle, which can thus consist in waste disposal, incineration or recycling. It is therefore clear that every step is combined with mass and energy ows (and of course with all the emissions), often difcult to quantify, with subsequent environmental impacts, which are usually quantied by specic environmental indicators: total energy ow; CO2, CH4, SO2, NOx, CO emissions; nitrates, phosphates, BOD emissions in water, etc. The above mentioned brief review [9], therefore, accurately examines the outcomes of three different LCA studies available in the literature. The rst [140] regards the use of a PP + EPDM blend respectively lled with glass bers or hemp bers for an automotive insulating item, nding that the green composites led to significant reduction of non-renewable energy demand and CO2, SO2, NOx, CO emissions. The second [141] regards the comparison between car panels made respectively by ABS or epoxy resins with hemp bers. Remarkable reduction in energy consumption and carbon emissions was calculated, however NOx, but also nitrates and phosphates emissions (in water) were not reduced at all, mainly because of the use of articial fertilizers for hemp cultivation. Finally, the third one [142] directly compared pellets made of polypropylene and, respectively, glass or bamboo bers. The results showed an enhancement of the main environmental indicators: non-renewable energy consumption, CO2, CO, SO2, NOx emissions, BOD emissions in water, and also some indicators related to toxicity and carcinogenetic impact. The only worsening regarded, once more, nitrates and phosphates emissions due to the use of articial fertilizers. Joshi then proposes a generalization of the results, identifying and presenting four interesting indicators of the superior relative environmental performance of NFR composites in comparison to GFR ones. These can be summarized as follows: (A) environmental impacts of natural ber vs. glass ber production: NF win because of energy consumption (solar energy vs. thermal energy from fossil

fuels) and lower emissions (except for nitrates); (B) replacement of higher polymer volume percentages: in order obtaining comparable mechanical properties, higher volume fractions of NF are used and this favors a lower use of oil-derived polymers; (C) reduced emissions during service life of the product, due to lower weight: NFR composites have lower specic weights than GFR composites and this, in turn, reduces energy consumption both directly (e.g. in the case of composites used for automotive applications) and indirectly (reduction of emissions due to product transport and delivery); (D) carbon and energy credits from natural bers incineration: differently from glass bers, natural bers can be conveniently incinerated at the end of products service life, with a double advantage of energy recovery and no net additional CO2 emission, since the CO2 released during combustion is theoretically the same which was taken up by the plant from the atmosphere, during its growth. More recently, other Authors have performed LCA assessments on green composites as well. It should be noted that, at least, some aspects are not taken into account in these LCA studies. These deciencies can typically include some steps of the life cycle itself (for instance, related to ller cultivation and/or manufacturing, use and disposal), the energy contribution from fertilizers or other additives, or some environmental burdens. Vidal et al. [143] have studied the environmental impact of green composites made of recycled polyolens (PP, HDPE) and biodegradable waste (rice husks and recycled cotton). The environmental impact was thus compared to the impact of virgin PP and HDPE through LCA. Two different scenarios, namely incineration and landlling, were taken into account and four impact categories were considered for the LCA: global warming over 100 years, nonrenewable energy depletion, acidication, and eutrophication. The Authors pointed out that the following environmental impacts were beyond the scope of their study: (a) the impact of compounding additives (their environmental burdens were considered as negligible), (b) the impacts of cotton cultivation (cotton was assumed to be recovered from fabric waste), (c) the impacts of further processes that might be applied to the composite materials to obtain nished products (they were assumed as equivalent for composites and virgin plastics). The Authors found that the composites showed a signicantly reduced environmental impact during the materials supplying and processing in all of the impact categories considered. However, rice husk lled composites slightly suffered from the impact originating from the use of fertilizers for rice cultivation, related to the eutrophication category. The Authors also pointed out that the environmental impact is expected to reach even lower levels than those found, as soon as the production and use of these materials becomes more widespread. However, the Authors highlighted that it would be also advisable to take the land use impact category into consideration when performing comparative studies between composites and conventional polymers; they reported the reliability of current methodologies for assessing this impact category to be questionable [144]. Alves et al. [145] performed a LCA on the replacement of glass bers with jute bers, in the reinforcement of automotive structural parts. In particular, the front bonnet was taken as the functional unit and the related impact categories were: carcinogens, respiratory organics, respiratory inorganics, climate change, radiation, ozone layer, ecotoxicity, acidication/eutrophication, land use, minerals, fossil fuels. Recycling, incineration and landll scenarios were taken into account. They found that the jute ber composites allow improving the environmental performance. In particular, fuel consumption proves to be lower due to the weight reduction of the vehicle, although some unknown impacts in the production and disposal phases were found, related to the logistics of jute bers transportation and the recycling scenario.

586

F.P. La Mantia, M. Morreale / Composites: Part A 42 (2011) 579588

Furthermore, the Authors highlighted that phases such as cultivation, harvesting, mercerizing, drying and ber rening were attributed with no impacts, reporting that jute production for several small farmer communities along the Amazon River was considered, with the river providing also the humus and all of the nutrients required. Luz et al. [146] investigated the environmental impact of sugarcane bagasse - polypropylene composites for automotive components applications, in comparison to talc-PP composites, through a complete LCA. Three scenarios were taken into account, namely Scenario 1 (contemplating a reuse for the 50% of materials otherwise incinerated), Scenario 2 (one half of the composite material is considered to be disposed municipally) and Scenario 3 (analyzing the contribution of a hypothetical talc-lled composite having the same specic weight as sugarcane bagasse composite). Impact categories were abiotic depletion, acidication potential, eutrophication potential, global warming potential (100 years basis), ozone layer depletion potential and photochemical ozone creation potential. The investigation was accurate, since it took into account auxiliary processes such as diesel, phosphate, nitrogen, potassium, phosphorus and lime production/sources; however, still no land use impacts were explicitly included. The overall analysis suggested that the green composites are better that the talc-lled composites in automotive applications, especially when weight reduction is particularly important. It is also suggested that sugarcane bagasse ber production leads to lower environmental impacts compared to talc production, the composites are lighter, sugarcane has a positive contribution in terms of carbon credits and the reuse of the end-of-life material is the optimum way to minimize the environmental impacts. The same Authors [147] evaluated the technical performance and environmental impacts of the same composites in comparison to neat polypropylene. Different end-of-life options included incineration, recycling and landll. The composites showed better environmental performance during the entire life cycle, especially in the cultivation phase (with sugarcane consuming carbon during its growth, thus contributing to decrease global warming effects). Also in this case, recycling with economic reuse of the composites was the best alternative to minimize the environmental impacts. For further in-depth study, an interesting review by Jorge [148] on environmental impact and LCA of lignocellulosic-derived products (including lignocellulosic-lled plastic composites) can be taken into account.

much can still be done in order nding new applications, improving the properties, the appearance and the marketability of these materials. All of these issues require, and continue to require, signicant research efforts in order to nd new formulations (virgin or recycled polymers, traditional or biodegradable polymers; type, appearance, quality and amount of the llers), characterize them, apply them for the most suitable applications and, in general, to rene processing techniques. As soon as the market for these composites increases, reduction of costs and improvement of the quality will be achieved. References
[1] Gachter R, Muller H. Plastics additives, 3rd ed. Hanser Publishers; 1990. [2] Netravali AN, Chabba S. Composites get greener. Mater Tod 2003;6:226. [3] Rozman HD, Lai CY, Ismail H, Mohd Ishak ZA. The effect of coupling agents on the mechanical and physical properties of oil palm empty fruit bunchpolypropylene composites. Polym Int 2000;49:12738. [4] Carroll DR, Stone RB, Siringano AM, Saindon RM, Gose SC, Friedman MA. Structural properties of recycled plastic/sawdust lumber decking planks. Res Cons Recycl 2001;31:24151. [5] Joseph K, Thomas S, Pavithran C. Effect of chemical treatment on the tensile properties of short sisal bre-reinforced polyethylene composites. Polymer 1996;37:513949. [6] Joseph PV, Joseph K, Thomas S. Effect of processing variables on the mechanical properties of sisal-ber-reinforced polypropylene composites. Compos Sci Technol 1999;59:162540. [7] Canch-Escamilla G, Rodriguez-Laviada J, Cuich-Cupul JI, Mendizabal E, Puig JE, Herrera-Franco PJ. Flexural, impact and compressive properties of a rigidthermoplastic matrix/cellulose ber reinforced composites. Compos Part A 2002;33:53949. [8] Nair KCM, Kumar RP, Thomas S, Schit SC, Ramamurthy K. Rheological behavior of short sisal ber-reinforced polystyrene composites. Compos Part A 2000;31:123140. [9] Joshi SV, Drzal LT, Mohanty AK, Arora S. Are natural ber composites environmentally superior to glass ber reinforced composites? Compos Part A 2004;35:3716. [10] Selke SE, Wichman I. Wood ber/polyolen composites. Compos Part A 2004;35:3216. [11] Raj RB, Kokta BV, Dembele F, Sanschagrain B. Compounding of cellulose bers with polypropylene: effect of ber treatment on dispersion in the polymer matrix. J Appl Polym Sci 1989;38:198796. [12] Chen HL, Porter RS. Composite of polyethylene and kenaf, a natural cellulose ber. J Appl Polym Sci 1994;54:17813. [13] Willett JL. Mechanical properties of LDPE/granular starch composites. J Appl Polym Sci 1994;54:168595. [14] Bagheri R. Effect of processing on the melt degradation of starch-lled polypropylene. Polym Int 1999;48:125763. [15] Sreekala MS, Kumaran MG, Thomas S. Oil palm bers: morphology, chemical composition, surface modication, and mechanical properties. J Appl Polym Sci 1997;66:82135. [16] Ahmad Fuad MY, Zaini MJ, Jamaludin M, Mohd Ishak ZA, Mohd Omar AK. Determination of ller content in rice husk ash and wood-based composites by thermogravimetric analysis. J Appl Polym Sci 1994;51:187582. [17] Ahmad Fuad MY, Yaakob I, Rusli O, Mohd Ishak ZA, Mohd Omar AK. Determination of ller content in thermoplastic composites by FTIR analysis. J Appl Polym Sci 1995;56:155760. [18] Coutinho FMB, Costa THS, Carvalho DL. Polypropylenewood ber composites: effect of treatment and mixing conditions on mechanical properties. J Appl Polym Sci 1997;65:122735. [19] Simpson B, Selke S, Composite materials from recycled multilayer polypropylene bottles and wood bers. In: Andrews G, Subramamian P, editors. Emerging technologies in plastic recycling. ACS Symp Series; 1992. p. 513. [20] Balasuriya PW, Ye L, Mai YW, Wu J. Mechanical properties of wood ake polyethylene composites. II. Interface modication. J Appl Polym Sci 2002;83:250521. [21] Raj RB, Kokta VB. Reinforcing high density polyethylene with cellulosic bers. I: the effect of additives on ber dispersion and mechanical properties. J Appl Polym Sci 1991;31:135862. [22] Wool RP, Raghavan D, Wagner GC, Billieux S. Biodegradation dynamics of polymerstarch composites. J Appl Polym Sci 2000;77:164357. [23] Sharma N, Chang LP, Chu YL, Ismail H, Ishiaku US, Mohd Ishak ZA. Study on the effect of pro-oxidant on the thermo-oxidative degradation behaviour of sago starch lled polyethylene. Polym Degrad Stabil 2001;71:38193. [24] Danjaji ID, Nawang R, Ishiaku US, Ismail H, Ishak ZA Mohd. Sago starch-lled linear low-density polyethylene (LLDPE) lms: their mechanical properties and water absorption. J Appl Polym Sci 2001;79:2937. [25] Selke SE, Childress J. Wood ber/high density polyethylene composites: ability of additives to enhance mechanical properties. In: Wolcott MP, editor. Wood berpolymer composites: fundamental concepts, processes and material options. Forest Product Society, Madison, Wisconsin; 1993. p. 10911.

9. Conclusions The use of polymer composites lled with natural-organic llers, in replacement of mineral-inorganic llers, is of great interest in the view of the reduction in the use of petroleum-based, nonrenewable resources, and in general in a more intelligent utilization of environmental and nancial resources. These green composites can nd several industrial applications, although some limitations occur regarding mainly ductility, processability and dimensional stability. Worldwide research has been spending much effort in order developing suitable solutions through chemical modication of the ller, use of adhesion promoters and additives. However, a full biodegradability, and thus a really improved environmental impact, can be obtained only by replacing traditional polymers (coming from non-renewable resources) with biodegradable ones. In these cases, however, new limitations arise and current scientic investigation has been focusing on the selection of the most suitable biodegradable matrix and the optimization of all of the preparation and processing parameters. As regards the commercial situation, it can be stated that the market is still in an opening phase (especially in Europe), therefore

F.P. La Mantia, M. Morreale / Composites: Part A 42 (2011) 579588 [26] Yam KL, Gogoi BK, Lai CC, Christopher C, Selke SE. Composites from compounding wood bers with recycled high density polyethylene. Polym Eng Sci 1990;30:6939. [27] La Mantia FP, Tzankova Dintcheva N, Morreale M, Vaca-Garcia C. Green composites of organic materials and recycled post-consumer polyethylene. Polym Int 2004;53:188891. [28] Park RD, Balatinecz JJ. Short term exural creep behavior of woodber/ polypropylene composites. Polym Compos 1997;19:37782. [29] Liao B, Huang YH, Cong GM. Inuence of modied wood bers on the mechanical properties of wood ber-reinforced polyethylene. J Appl Polym Sci 1997;66:15618. [30] Myers GE, Chahyadi IS, Gonzales C, Coberly CA. Wood our and polypropylene or high-density polyethylene composites: inuence of maleated polypropylene concentration and extrusion. In: Wolcott MP, editor. Wood berpolymer composites: fundamental concepts, processes and material options. Forest Product Society, Madison, Wisconsin; 1993, p. 4956. [31] Kolosick PC, Myers GE, Koutsky JA. Bonding mechanisms between polypropylene and wood: coupling agent and crystallinity effects. In: Wolcott MP, editor. Wood berpolymer composites: fundamental concepts, processes and material options. Forest Product Society, Madison, Wisconsin; 1993. p. 159. [32] La Mantia FP, Morreale M. Improving the properties of polypropylenewood our composites by utilization of maleated adhesion promoters. Compos Interf 2007;14:68598. [33] Harper D, Wolcott M. Interaction between coupling agent and lubricants in woodpolypropylene composites. Compos Part A 2004;35:38594. [34] Nitz H, Semke H, Landers R, Mulhaupt R. Reactive extrusion of polycaprolactone compounds containing wood our and lignin. J Appl Polym Sci 2001;81:197284. [35] Odusanya OS, Manan DMA, Ishiaku US, Azemi BMN. Effect of starch predrying on the mechanical properties of starch/poly(e-caprolactone) composites. J Appl Polym Sci 2003;87:87784. [36] Khalil HPSA, Rozman HD, Ahmad MN, Ismail H. Acetylated plant-berreinforced polyester composites: a study of mechanical, hygrothermal, and aging characteristics. Polym Plast Tech Eng 2000;39:75781. [37] Lovely M, Joseph KU, Rani J. Isora bres and their composites with natural rubber. Prog Rubber Plastics Recycl Technol 2004;20:33749. [38] Belgacem MN, Bataille P, Sapieha S. Effect of corona modication on the mechanical properties of polypropylene/cellulose composites. J Appl Polym Sci 1994;53:37985. [39] Gassan J, Gutowski VS. Effects of corona discharge and UV treatment on the properties of jutebre epoxy composites. Compos Sci Technol 2000;60:285763. [40] Khalil HPSA, Ismail H, Rozman HD, Ahmad MN. The effect of acetylation on interfacial shear strength between plant bres and various matrices. Eur Polym J 2001;37:103745. [41] Valadez-Gonzalez A, Cervantes-Uc JM, Olayo R, Herrera-Franco PJ. Effect of ber surface treatment on the bermatrix bond strength of natural ber reinforced composites. Compos Part B 1999;30:30920. [42] Dipa R, Sarkar BK, Rana AK, Bose NR. Effect of alkali treated jute bres on composite properties. Bull Mater Sci 2001;24:12935. [43] Samal RK, Mohanty M, Panda BB. Effect of chemical modication on FTIR spectra: physical and chemical behavior of jute. J Polym Mater 1995;12:23540. [44] Raj RG, Kokta BV, Daneault C. Effect of chemical treatment of bers on the mechanical properties of polyethylene-wood ber composites. Adhes Sci Technol 1989;3:5564. [45] Sapieha S, Allard P, Zhang YH. Dicumyl peroxide-modied cellulose/LLDPE composites. J Appl Polym Sci 1990;41:203948. [46] Dominkovics Z, Dnydi L, Puknszky B. Surface modication of wood our and its effect on the properties of PP/wood composites. Compos Part A 2007;38:1893901. [47] Kalia S, Kaith BS, Kaur I. Pretreatments of natural bers and their application as reinforcing material in polymer compositesa review. Polym Eng Sci 2009;49:125372. [48] Bledzki AK, Letman M, Viksne A, Rence L. A comparison of compounding processes and wood type for wood brePP composites. Compos Part A 2005;36:78997. [49] Kuo PY, Wang S-Y, Chen JH, Hsueh HC, Tsai MJ. Effects of material compositions on the mechanical properties of woodplastic composites manufactured by injection molding. Mater Des 2009;30:348996. [50] Tasdemir M, Biltekin H, Caneba GT. Preparation and characterization of LDPE and PPwood ber composites. J Appl Polym Sci 2009;112:3095102. [51] Madhoushi M, Nadalizadeh H, Ansell MP. Withdrawal strength of fasteners in rice straw bre-thermoplastic composites under dry and wet conditions. Polym Test 2009;28:3016. [52] Nourbakhsh A, Ashori A. Preparation and properties of wood plastic composites made of recycled high-density polyethylene. J Compos Mater 2009;43:87783. [53] Zhang 53Y, Toghiani H, Zhang J, Xue Y, Pittman CU. Studies of surfacemodied wood our/polypropylene composites. J Mater Sci 2009;44:1432151. [54] Nygard P, Tanem BS, Karlsen T, Brachet P, Leinsvang B. Extrusion-based wood brePP composites: wood powder and pelletized wood bresa comparative study. Compos Sci Technol 2008;68:341824.

587

[55] Srebrenkoska V, Gaceva GB, Avella M, Errico ME, Gentile G. Recycling of polypropylene-based eco-composites. Polym Int 2008;57:12527. [56] Nourbakhsh A, Kokta BV, Ashori A, Jahan-Latibari A. Effect of a novel coupling agent, polybutadiene isocyanate, on mechanical properties of woodber polypropylene composites. J Reinf Plast Comp 2008;27:167987. [57] Kaboorani A, Faezipour M, Ebrahimi G. Feasibility of using heat treated wood in wood/thermoplastic composites. J Reinf Plast Comp 2008;27: 168999. [58] Kim SJ, Moon JB, Kim GH, Ha CS. Mechanical properties of polypropylene/ natural ber composites: comparison of wood ber and cotton ber. Polym Test 2008;27:8016. [59] Mansour SH, Asaad JN, Iskander BA, Tawk SY. Inuence of some additives on the performance of wood our/polyolen composites. J Appl Polym Sci 2008;109:22439. [60] Prachayawarakorn J, Khunsumled S, Thongpin C, Kositchaiyong A, Sombatsompop N. Effects of silane and MAPE coupling agents on the properties and interfacial adhesion of wood-lled PVC/LDPE blend. J Appl Polym Sci 2008;108:352330. [61] Yuan Q, Wu D, Gotama J, Bateman S. Wood ber reinforced polyethylene and polypropylene composites with high modulus and impact strength. J Thermoplast Compos Mater 2008;21:195208. [62] Cui Y, Lee S, Noruziaan B, Cheung M, Tao J. Fabrication and interfacial modication of wood/recycled plastic composite materials. Compos Part A 2008;39:65561. [63] Kumari R, Ito H, Takatani M, Uchiyama M, Okamoto T. Fundamental studies on wood/cellulose-plastic composites: effects of composition and cellulose dimension on the properties of cellulose/PP composite. J Wood Sci 2007;53:47080. nya di L, Renner K, Mo czo J, Puka nszky B. Wood our lled polypropylene [64] Da composites: interfacial adhesion and micromechanical deformations. Polym Eng Sci 2007;47:124655. [65] Nachtigall SMB, Cerveira GS, Rosa SML. New polymeric-coupling agent for polypropylene/wood-our composites. Polym Test 2007;26: 61928. [66] Karimi AN, Tajvidi M, Pourabbasi S. Effect of compatibilizer on the natural durability of wood our/high density polyethylene composites against rainbow fungus (Coriolus versicolor). Polym Compos 2007;28:2737. [67] Renner K, Mcz J, Puknszky B. Deformation and failure of PP composites reinforced with lignocellulosic bers: effect of inherent strength of the particles. Compos Sci Technol 2009;69:16539. nya di L, Janecska T, Szabo Z, Nagy G, Mo czo J, Puka nszky B. Wood our [68] Da lled PP composites: compatibilization and adhesion. Compos Sci Technol 2007;67:283846. [69] La Mantia FP, Morreale M, Mohd Ishak ZA. Processing and mechanical properties of organic llerpolypropylene composites. J Appl Polym Sci 2005;96:190613. [70] Li TQ, Wolcott M. Rheology of HDPEwood composites. I. Steady state shear and extensional ow. Compos Part A 2004;35:30311. [71] Mamunya EP, Mishak VD, Shumskii VF, Lebedev EV. Rheological properties of polymerwood material based on polyethylene. USSR Vysokomol Soedin Ser B 1991;33:83945. [72] Natov M, Wasilewa S. S. Kowachewa Welewa, Rheologische eigenschaften von mit holzmehl geflltem polypropylen. Angew Makromol Chem 1995;225:7381. [73] Maiti SN, Hassan MR. Melt rheological properties of polypropylenewood our composites. J Appl Polym Sci 1989;37:201932. [74] Sain M, Khunova V, Hurst J, Balatinecz J. The inuence of llers on composite rheological properties. Plasty Kauc 1998;35:199202. [75] Rietveld JX, Simon MJ. The inuence of adsorbed moisture on the processability and properties of a wood our-lled polypropylene. In: Wolcott MP, editor. Wood ber/polymer composites: fundamental concepts, and material options; 1993. p. 3948. [76] Rana AK, Mandal A, Bandyopadhyay S. Short jute ber reinforced polypropylene composites: effect of compatibiliser, impact modier and ber loading. Compos Sci Technol 2003;63:8016. [77] Bledzki AK, Faruk O. Wood bre reinforced polypropylene composites: effect of bre geometry and coupling agent on physico-mechanical properties. Appl Compos Mater 2003;10:36579. [78] La Mantia FP, Morreale M. Mechanical properties of recycled polyethylene ecocomposites lled with natural organic llers. Polym Eng Sci 2006;46:11319. [79] Igl SA, Osswald TA. A study on the thermoformability of wood ber-lled polyolen composites. In: Wolcott MP, editor. Wood ber/polymer composites: fundamental concepts, and material options; 1993. p. 338. [80] Mohanakrishnan CK, Narayan R, Nizio JD. Reactive extrusion processing of polypropylene-lignocellulosic blend materials. In: Wolcott MP, editor. Wood ber/polymer composites: fundamental concepts, and material options; 1993. p. 5762. [81] Czvikovszky T, Lopata V, Boyer G, Kremers W, Saunders C, Singh A. Electronbeam processing of wood ber-reinforced polypropylene. In: Wolcott MP, editor. Wood ber/polymer composites: fundamental concepts, and material options; 1993. p. 6874. [82] Woodhams RT, Law S, Balatinecz JJ. Intensive mixing of wood bers with thermoplastics for injection-moulded composites. In: Wolcott MP, editor. Wood ber/polymer composites: fundamental concepts, and material options; 1993. p. 758.

588

F.P. La Mantia, M. Morreale / Composites: Part A 42 (2011) 579588 [117] Alvarez VA, Fraga AN, Vazquez A. Effects of the moisture and ber content on the mechanical properties of biodegradable polymersisal ber biocomposites. J Appl Polym Sci 2004;91:400716. [118] Alvarez VA, Vazquez A, Bernal C. Fracture behavior of sisal ber-reinforced starch-based composites. Polym Compos 2005;26:31623. [119] Alvarez VA, Iannoni A, Kenny JM, Vazquez A. Inuence of twin-screw processing conditions on the mechanical properties of biocomposites. J Compos Mater 2005;39:202338. [120] Alvarez VA, Terenzi A, Kenny JM, Vazquez A. Melt rheological behavior of starch-based matrix composites reinforced with short sisal bers. Polym Eng Sci 2004;44:190714. [121] Puglia D, Tomassucci A, Kenny JM. Processing, properties and stability of biodegradable composites based on Mater-Bi and cellulose bres. Polym Adv Technol 2003;14:74956. [122] Johnson RM, Tucker N, Barnes S. Impact performance of Miscanthus/ Novamont Mater-Bi biocomposites. Polym Test 2003;22:20915. [123] Johnson M, Tucker N, Barnes S, Kirwan K. Improvement of the impact performance of a starch based biopolymer via the incorporation of Miscanthus giganteus bres. Ind Crop Prod 2005;22:17586. [124] Alvarez VA, Ruseckaite RA, Vazquez A. Degradation of sisal bre/Mater Bi-Y biocomposites buried in soil. Polym Degrad Stabil 2006;91:315662. [125] Rutkowska M, Heimowska A, Krasowska K, Janik H. Biodegradation of thermoplastic starchcaprolactone in different natural environments. In: Capparelli Mattoso LH, Leao A, Frollini E, editors. Natural polymers and composites. Embrapa Instrumentaao Agropecuaria: Sao Carlos; 2000. [126] Rutkowska M, Krasowska K, Steinka I, Janik H. Biodeterioration of Mater-Bi Y class in compost with sewage sludge. Polish J Environ Stud 2004;13:859. [127] Nishino T, Hirao K, Kotera M, Nakamae K, Inagaki H. Kenaf reinforced biodegradable composite. Compos Sci Technol 2003;63:12816. [128] Lee SH, Wang S. Biodegradable polymers/bamboo ber biocomposite with bio-based coupling agent. Compos Part A 2006;37:8091. [129] Bax B, Mussig J. Impact and tensile properties of PLA/Cordenka and PLA/ax composites. Compos Sci Technol 2008;68:16017. [130] Huda MS, Mohanty AK, Drzal LT, Schut E, Misra M. Green composites from recycled cellulose and poly(lactic acid): physico-mechanical and morphological properties evaluation. J Mater Sci 2005;40:42219. [131] Plackett D, Lgstrup Andersen T, Batsberg Pedersen W, Nielsen L. Biodegradable composites based on L-polylactide and jute bres. Compos Sci Technol 2003;63:128796. [132] Nickel J, Riedel U. Activities in biocomposites. Mater Tod 2003;6:448. [133] Li TQ, Ng CN, Li RHY. Impact behavior of sawdust/recycledPP composites. J Appl Polym Sci 2001;81:14208. [134] Samir M, Alloin F, Dufresne A. Review of recent research into cellulosic whiskers, their properties and their application in nanocomposite eld. Biomacromolecules 2005;6:61226. [135] Hubbe MA, Rojas OJ, Lucia LA, Sain M. Cellulosic nanocomposites: a review. Bioresource 2008;3:92980. [136] Eichhorn SJ, Dufresne A, Aranguren M, Marcovich NE, Capadona JR, Rowan SJ, et al. Review: current international research into cellulose nanobres and nanocomposites. J Mater Sci 2010;45:133. [137] Klemchuk PP. Degradable plastics: a critical review. Polym Degrad Stabil 1990;27:183202. [138] Lim ST, Chang EH, Chung HJ. Thermal transition characteristics of heatmoisture treated corn and potato starches. Carbohyd Polym 2001;46: 10715. [139] Tezuka Y, Ishii N, Kasuya K, Mitomo H. Degradation of poly(ethylene succinate) by mesophilic bacteria. Polym Degrad Stabil 2004;84:11521. [140] Schmidt WP, Beyer HM. Life cycle study on a natural ber reinforced component. SAE Technical Paper 982195, SAE Total Life-Cycle Conf. Austria: Graz; 1998. [141] Wotzel K, Wirth R, Flake R. Life cycle studies on hemp bre reinforced components and ABS for automotive parts. Angew Makromol Chem 1999;272:1217. [142] Corbiere-Nicollier T, Gfeller Laban B, Lundquist L, Leterrier Y, Manson JAE, Jolliet O. Life cycle assessment of biobres replacing glass bres as reinforcement in plastics. Resour Conserv Recycl 2001;33:26787. [143] Vidal R, Martnez P, Garran D. Life cycle assessment of composite materials made of recycled thermoplastics combined with rice husks and cotton linters. Int J Life Cycle Assess 2009;14:7382. [144] Mil i Canals L, Clift R, Basson L, Hansen Y, Brando M. Expert workshop on land use impacts in life cycle assessment (LCA). Int J Life Cycle Assess 2006;11:3638. [145] Alves C, Ferrao PMC, Silva AJ, Reis LG, Freitas M, Rodrigues LB, et al. Ecodesign of automotive components making use of natural jute ber composites. J Clean Prod 2010;18:31327. [146] Luz SM, Caldeira-Pires A, Ferro PMC. Environmental benets of substituting talc by sugarcane bagasse bers as reinforcement in polypropylene composites: ecodesign and LCA as strategy for automotive components. Resour Conserv Recycl 2010;54:113544. [147] Luz SM, Ferro PMC, Alves C, Freitas M, Caldeira-Pires A. Ecodesign applied to components based on sugarcane bers composites. Mater Sci Forum 2010;636637:22632. [148] Caldeira Jorge F. Reducing negative environmental impacts from the manufacturing and utilization of lignocellulosics-derived materials: an overview on research in 20072009. Molec Cryst Liq Cryst 2010;522:32835.

[83] Tanaka K, Katsura T, Kinoshita Y, Katayama T, Uno K. Mechanical properties of jute fabric reinforced thermoplastic moulded by high-speed processing using electromagnetic induction. WIT Trans Built Environ 2008;97:2119. [84] Dauda M, Yoshiba M, Miura K, Takahashi S. Processing and mechanical property evaluation of maize ber reinforced green composites. Adv Comp Mater 2007;16:33547. [85] Scaffaro R, Morreale M, Lo Re G, La Mantia FP. Effect of the processing techniques on the properties of ecocomposites based on vegetable oil-derived Mater-Bi and wood our. J Appl Polym Sci 2009;114:285563. [86] Morreale M, Scaffaro R, Maio A, La Mantia FP. Mechanical behaviour of MaterBi/wood our composites: a statistical approach. Compos Part A 2008;39:153746. [87] Ferreira RL, Furtado CRG, Visconte LY, Leblanc JL. Optimized preparation techniques for PVC-green coconut ber composites. Int J Polym Mater 2006;55:105564. [88] Takagi H, Asano A. Effects of processing conditions on exural properties of cellulose nanober reinforced green composites. Compos Part A 2008;39:6859. [89] Klason C, Kubat J, Stromwall HE. Efciency of cellulosic llers in common thermoplastics. Part 1. Filling without processing aids or coupling agents. Int J Polym Mater 1984;10:15987. [90] Dalvag H, Klason C, Stromwall HE. The efciency of cellulosic llers in common thermoplastics. Part II. Filling with processing aids and coupling agents. Int J Polym Mater 1985;11:938. [91] Bataille P, Ricard L, Sapieha S. Effects of cellulose bers in polypropylene composites. Polym Compos 1989;10:1038. [92] Marsh G. Next steps for automotive materials. Mater Tod 2003;6:3643. [93] Luo S, Netravali AN. Mechanical and thermal properties of environmentfriendly green composites made from pineapple leaf bers and poly(hydroxybutyrate-co-valerate) resin. Polym Compos 1999;20:36778. [94] Luo S, Netravali AN. Interfacial and mechanical properties of environmentfriendly green composites made from pineapple bers and poly(hydroxybutyrate-co-valerate) resin. J Mater Sci 1999;34:370919. [95] Lodha P, Netravali AN. Characterization of interfacial and mechanical properties of green composites with soy protein isolate and ramie ber. J Mater Sci 2002;37:365765. [96] Van de Velde K, Kiekens P. Biopolymers: overview of several properties and consequences on their applications. Polym Test 2002;21:43342. [97] Rodriguez-Gonzalez FJ, Ramsay BA, Favis BD. High performance LDPE/ thermoplastic starch blends: a sustainable alternative to pure polyethylene. Polymer 2003;44:151726. [98] Scott G. Green polymers. Polym Degrad Stabil 2000;68:17. [99] Doi Y. Microbial polyesters. New York: VCH Publishers; 1990. [100] Saad GR, Seliger H. Biodegradable copolymers based on bacterial poly((R)-3hydroxybutyrate): thermal and mechanical properties and biodegradation behaviour. Polym Degrad Stabil 2004;83:10110. [101] Dufresne A, Vignon MR. Improvement of starch lm performances using cellulose microbrils. Macromolecules 1998;31:26936. [102] Lenz RW, Marchessault RH. Bacterial polyesters: biosynthesis, biodegradable plastics and biotechnology. Biomacromolecules 2005;6:18. [103] Godbole S, Gote S, Latkar M, Chakrabarti T. Preparation and characterization of biodegradable poly-3-hydroxybutyratestarch blend lms. Bioresour Technol 2003;86:337. [104] Averous L. Biodegradable multiphase systems based on plasticized starch: a review. J Macromol Sci 2004;44:23174. [105] Yu L, Dean K, Li L. Polymer blends and composites from renewable resources. Prog Polym Sci 2006;31:576602. [106] Satyanarayana KG, Arizaga GC, Wypych F. Biodegradable composites based on lignocellulosic bersan overview. Prog Polym Sci 2009;34:9821021. [107] Khan MA, Idriss Ali KM, Hinrichsen G, Kopp C, Kropke S. Study on physical and mechanical properties of biopol-jute composite. Polym Plast Technol Eng 1999;38:99112. [108] Mohanty AK, Khan MA, Sahoo S, Hinrichsen G. Effect of chemical modication on the performance of biodegradable jute yarn-Biopol composites. J Mater Sci 2000;35:258995. [109] Mohanty AK, Khan MA, Hinrichsen G. Surface modication of jute and its inuence on performance of biodegradable jute-fabric/Biopol composites. Compos Sci Technol 2000;60:111524. [110] Gould P. Exploiting spiders silk. Mater Tod 2002;5:427. [111] Morreale M, Scaffaro R, Maio A, La Mantia FP. Effect of adding wood our to the physical properties of a biodegradable polymer. Compos Part A 2008;39:50313. [112] Di Franco CR, Cyras VP, Busalmen JP, Ruseckaite RA, Vazquez A. Degradation of polycaprolactone/starch blends and composites with sisal bre. Polym Degrad Stab 2004;86:95103. [113] Bastioli C. Properties and applications of Mater-Bi starch-based materials. Polym Degrad Stab 1998;59:26372. [114] Scaffaro R, Morreale M, Lo Re G, La Mantia FP. Degradation of Mater-Bi/ wood our biocomposites in active sewage sludge. Polym Degrad Stabil 2009;94:12209. [115] Alvarez VA, Vazquez A. Thermal degradation of cellulose derivatives/starch blends and sisal bre biocomposites. Polym Degrad Stabil 2004;84:1321. [116] Alvarez VA, Vazquez A, Bernal C. Effect of microstructure on the tensile and fracture properties of sisal ber/starch-based composites. J Compos Mater 2006;40:2135.