You are on page 1of 8

Characterisation of fibre–polymer interactions

and transcrystallinity in short keratin
fibre–polypropylene composites
J. R. Barone* and N. T. Gregoire
Short fibre reinforced composites were made from keratin fibres obtained from poultry feathers.
The matrix material was either polypropylene or a blend of polypropylene and maleic anhydride
modified polypropylene (MaPP). In general, the addition of MaPP to polypropylene (PP) did not
alter the tensile properties of the blend in a significant way. When not using MaPP, composites
had lower breaking stresses than samples without fibres. However, MaPP at concentrations of
.4 wt-% enhanced the breaking stress of the composites to above the value without fibres.
Concurrent thermal analysis using differential scanning calorimetry (DSC) showed a distinct
increase in the amount of transcrystallinity in the composites at MaPP concentrations greater than
4 wt-%. Scanning electron microscopy (SEM) revealed increased interactions between the
protein fibres and the PP/MaPP matrix. Annealing showed that more large polymer crystals near
the fibres were not enough to increase stress transfer across the interface.
Keywords: Composites, Polypropylene, Maleic anhydride, DSC, Properties

Introduction
Agricultural fibres, such as cellulose and protein fibres,
provide an environmentally friendly reinforcement
option for commodity thermoplastic materials such as
polyethylene (PE)1,2 and polypropylene (PP)3–12 and are
a pathway to obtain materials from sustainable
resources. Agricultural fibres typically are of lower
density than inorganic reinforcements such as talc, glass
or calcium carbonate. The absolute physical properties
of agricultural fibres might not be as high as inorganic
reinforcements, but specific or density normalised
properties are comparable with inorganic fillers.
Agricultural fibres are polymeric and have densities
lower than inorganic fibres so synthetic polymers can be
reinforced with little or no cost to unit weight.
The key to successful enhancement of polymers with
fibres of higher modulus or strength is to achieve good
polymer/fibre interaction.13 Good fibre/polymer interaction can be expected if the two components are
chemically compatible. Plant based cellulosic fibres such
as wood, flax, jute and sisal, and inorganic fibres and
fillers are hydrophilic. However, commodity thermoplastics such as PP are hydrophobic. To get chemical
compatibility between the two, additives such as
coupling agents or compatibilisers are used.1,2,7,13
Maleic anhydride has been used to increase the properties of cellulose fibre reinforced PE1,2 and PP.4–9 In most

USDA/ARS/ANRI/EMBUL, BARC West, Bldg. 012, Rm. 1–3, 10300
Baltimore Ave., Beltsville, MD 20705, USA
*Corresponding author, email baronej@ba.ars.usda.gov

ß 2006 Institute of Materials, Minerals and Mining
Published by Maney on behalf of the Institute
Received 19 June 2006; accepted 10 August 2006
DOI 10.1179/174328906X146478

cases, ultimate strength of the composites increased at
maleic anhydride concentrations of 0.1–2%, depending
on the maleic anhydride substitution in the olefin and
the concentration of maleic anhydride modified olefin in
the composite. Scanning electron microscopy (SEM)
revealed increased fibre/polymer interactions.1,4,5
Protein fibres are mixed hydrophobic/hydrophilic
depending on the amino acid sequence. Keratin fibres
obtained from poultry feathers have ,60% hydrophobic
amino acids in the amino acid sequence, with the
balance being hydrophilic amino acids.14 So it can be
expected that there will be some chemical compatibility
between PP and feather keratin fibres. Recently, Barone
and Schmidt showed that it was possible to increase the
tensile properties of low density polyethylene (LDPE)
using keratin feather fibre without the use of coupling
agents or compatibilisers.15 SEM showed good fibre/
polymer interaction.
Maleic anhydride modified polypropylene (MaPP)
has been used in keratin feather fibre–PP composites.
Bullions et al. used MaPP to increase interactions
between PP and a mix of keratin feather fibre and kraft
pulp fibre.10 Schuster made MaPP–keratin feather fibre
composites and observed an increase in properties over
neat PP.11 The proposed interaction mechanism between
MaPP and the fibres is hydrogen bonding between
hydroxyl groups on the MaPP and fibre and covalent
bonding between hydroxyl groups on the fibre and the
carbonyl on the maleic anhydride. The PP portion of the
MaPP is free to entangle with the PP composite matrix.
Investigation of the fibre surface in PP and cellulose
fibre composites shows a ‘transcrystalline’ layer develops.7,8,12 The fibre surface serves as a nucleation site for

Plastics, Rubber and Composites

2006

VOL

35

NO

6/7

287

Composite preparation The PP was ExxonMobil PP9505E1. so it was assumed that the cooling steps were similar. DSC and SEM. The melt temperature was monitored independently.4 and 5. The applied test speed was 2. The first heating cycle proceeded from 30 to 225uC at 10uC min21.1 and the melting temperature during the first heating cycle Tm.8. This means that the polymer volume immediately surrounding the fibres has properties different from the bulk polymer. The melting point and amount of crystallinity as studied by differential scanning calorimetry (DSC) increased with fibre and compatibiliser content. Nunez et al.7 MPa for 1. The first heating cycle yielded information about the state of the polymer as a function of processing conditions. 94:6. Crystallisation at the interface occurred over much longer time periods in absence of shear deformation or compatibiliser.2 cm length were made by grinding feather fibre using a Retsch ZM 1000 centrifugal grinder.5 min. Uniaxial tensile testing was performed using a Com-Ten Industries 95 RC Test System. the room temperature was always 20uC. sandwiched between Teflon coated aluminium foil. and pressed in the Carver Press at 180uC and 0. The resulting plates were .15. 98:2. The transcrystallinity can be affected by shear deformation at the fibre/polymer interface.0.5:12.5. 15).174uC and the composites all achieved melt temperatures of . A TA Instruments DSC 910s was used according to the procedures outlined in ASTM D3417 and D3418.7. Peak assignments and areas were determined according to the ASTM procedures.5:2. 96:4. The MaPP is ExxonMobil Exxelor PO1020 and had a reported maleic anhydride substitution of 0. To prepare samples for testing. so reinforcement of polyolefins with keratin feather fibre is possible.89 g cm23 (Ref. The rotational velocity of the instrument was 15 000 rev min21 and contained a torque feedback so as not to feed in too much material and overload the motor. 97. Fibres of 0. Although there may have been some variation in the cooling step from sample to sample.5–1.17 The feather fibre was semicrystalline and had a diameter of .2 cm length is incorporated into blends of PP and MaPP with the MaPP content varying from 0 to 10 wt-%. The cooling rate could not be controlled. a random copolymer PP with melt flow index (MFI)530 g/10 min at 230uC and 2. The fibre fraction of the composites was held constant at 20 wt-%. After pressing. Immediately after adding the polymer. 92. 95:5. The heat of fusion of the first heating cycle DQm.16 Joseph et al.19 Modulus and strength values of polyolefins are less than the feather values. Four samples of each composite were tested. each sample was sandwiched between Teflon coated aluminium foil and pressed into three thin sheets in a Carver Press Autofour/30 Model 4394 at 180uC and 1 MPa for 18 s. The first heating cycle was followed by a cooling cycle from 225uC back down to 20uC. The polymer was first added into a Brabender mixing head set at 160uC and rotating at 75 rev min21.Barone and Gregoire Characterisation of fibre–polymer interactions and transcrystallinity polymer crystals and the crystals that form at the fibre surface are different from the crystals formed in the bulk polymer.11.2 GPa and yield stress values of 100 and 200 MPa at relative humidity values of 100 and 65% respectively for feather rachis. Previous work showed that pressing did not affect fibre dispersion. The physical properties of the composites are characterised using tensile testing.2 cm length range with a few percentages of smaller ‘fine’ particles. In the present paper.0 wt-%.1 were determined because these values relate to the crystalline structure of the as tested composite.5. stacked on top of each other. A more detailed description of feather fibre can be found elsewhere. Sieving analysis and SEM imaging of the fibres showed that the majority of the fibres were in the 0. Composites were prepared by dry blending the PP and MaPP at PP/MaPP ratios of 100:0. which represented a degree of fill of 70% of the total volume of the mixing head. similar to using shear deformation at the interface. The MaPP content 288 Plastics.8 These researchers also showed that the melting point and crystalline fraction increased with filler and MaPP content. The crystalline fraction of each polymer .5 cm min21. keratin feather fibre of 0. 90:10 and 87. Following mixing.183uC.5:7. The total sample weight of each composite was 40 g.18 Fraser and MacRae report modulus values of 3. Type 4 dogbone samples for testing according to ASTM D638 were machined from the plates.5. the films were air cooled until they reached room temperature. Fibre–polymer interactions are assessed in terms of the transcrystallinity that develops at the interface. The total mixing time for each sample was 15 min. performed a very complete study on the properties of the transcrystalline layer in PP/sisal composites.7 The study showed that the addition of a urethane compatibiliser initiated crystallisation at the fibre/polymer interface in a short amount of time. The film was then removed and cooled under an aluminium block until it reached room temperature.5 mm and a density of 0. Sample sizes of . the three thin sheets were cut into quarters. the chemical nature of the interface and the cooling rate after processing.5 mg were used in a N2 atmosphere. The blends were prepared by mixing PP/ MaPP in ratios of 100:0. Thermal analysis The thermal properties of the polymers and composites were assessed using DSC. 92:8 and 90:10. The polymer control samples all achieved melt temperatures of . After pressing. Experimental Keratin feather fibre Keratin feather fibre was obtained from Featherfiber (Nixa. Composite testing Composite samples were allowed to sit at ambient conditions for one week before testing.15. The heater simply shut off and the DSC cell cooled to 30uC.3 cm in thickness. A second heating cycle then proceeded from 30 to 225uC. MO) using a process patented by the United States Department of Agriculture (USDA).16 kg.20 Good dispersion was observed in all cases. showed that a b crystalline fraction appeared at the PP/wood flour interface when cooled quickly from the melt.12.10. each thin film was inspected to note feather fibre dispersion. Rubber and Composites 2006 VOL 35 NO 6/7 represented the amount of MaPP relative to the total sample weight. 20 wt-% keratin feather fibre was added into the mixing head. The fibre was fed in slowly to avoid motor overload and to minimise frictional heating of the instrument and the fibre.

The sample temperature was raised to 290uC for 10 min to remove surface water from the sample surface. However.Barone and Gregoire 1 Tensile modulus versus MaPP concentration for PP– 20 wt-% 0. The sample was then cooled to below 2120uC and coated with . However.7 Characterisation of fibre–polymer interactions and transcrystallinity 2 Peak stress versus MaPP concentration for PP–20 wt-% 0. the peak stress of the composites was increasing with increasing Scanning electron microscopy (SEM) The fracture surfaces were excised from the failed tensile bars using a scalpel blade and transferred into a modified specimen carrier. determined the crystallinity of PP composites in a similar manner.1 cm keratin feather fibre composites and composite after the first heating cycle X1 was determined from the DSC results using X1 ~ DQm. The cooled holder was then transferred to an Oxford CT1500 HF cryopreparation system attached to a Hitachi S-4100 SEM. the samples had overlapping ranges. Results and discussion Effect of MaPP on tensile properties Figure 1 shows the elastic modulus of the PP/MaPP blends and PP/MaPP/20 wt-% keratin fibre composites. The specimen carrier was known as an ‘indium vise’ because the dissected pieces were clamped between sheets of indium metal and plunge cooled in liquid nitrogen to 2196uC. DQf5(5798 J mol21)/(42 g mol21)5 21 138 J g (Ref. the composite peak stress was lower than the PP/MaPP blends.1 cm keratin feather fibre composites MaPP for the blends. At low MaPP concentration.5 nm of platinum metal using a magnetron sputter coater. and mf is the mass fraction of fibre. Coated samples were transferred to the cold stage in the SEM at 2170uC and observed with an electron beam accelerating voltage of 2 kV. 0–14 phr MaPP for the composites and 0–11 phr 3 Strain at peak stress versus MaPP concentration for PP–20 wt-% 0. 2 and 3 respectively. The addition of MaPP to PP did not affect the peak stress. The peak stress and strain at peak stress showed noticeable differences as MaPP concentration increased as shown in Figs. on a phr basis. Joseph et al.1 DQf (1{mf ) (1) where DQf is the theoretical heat of fusion of 100% crystalline PP. 21).1 cm keratin feather fibre composites Plastics. There was perhaps a minimal enhancement of the elastic modulus as a function of increasing MaPP concentration at a constant fibre loading. The percentage of MaPP relative to the total amount of PP or PP/fibre was kept constant to note how the replacement of PP with fibre affected tensile properties. Rubber and Composites 2006 VOL 35 NO 6/7 289 .

The blends were more ductile than the fibre composites. unlike the blends without fibres. The fibre loading was kept constant for each composite. Therefore. indicating that the PP did not adhere to the fibre. Observation of fibre/polymer interactions Figure 6 shows the fracture surface of a 0 wt-% MaPP composite magnified 62000. At greater MaPP concentration. the melting temperature increased quickly from 0 to 6 wt-% MaPP. At greater MaPP concentrations. then the melting temperature increase was much slower at MaPP concentrations of .1 up to 6 wt-% MaPP.4 wt-% was a critical point in the PPzMaPP/fibre composites. and then there was a discontinuous increase in the crystallinity of the composite after which the crystalline fraction remained relatively unchanged. addition of MaPP increased not only the strength but also the toughness of the composites. Effect of MaPP on thermal properties The effect of MaPP and fibres on PP Tm. Therefore. the peak stress increased discontinuously to peak stress values above the PP/MaPP blends. 3. i.1 versus MaPP concentration MaPP concentration. In Fig. The PP/MaPP blends had increased Tm.Barone and Gregoire Characterisation of fibre–polymer interactions and transcrystallinity 4 Melting temperature from DSC first heating cycle Tm. indicating that this may have been the limiting value necessary to get optimal fibre–polymer interactions. the composites had greater X1 and Tm. However. It should be noted that the samples with higher MaPP contents had some surface ‘freckles’ after moulding and it was possible that this may have contributed to a premature failure.6 wt-% MaPP.1 with increasing MaPP concentration. For the composites.1 and X1 is shown in Figs.1 values meant that there were more large crystals in the composites. with the maximum values being higher than pure PP9505E1 or MaPP PO1020. then the Tm.1 values. The same dependence on MaPP was observed in the peak stress characteristics of the composites. Closer inspection of the surface at 61000 as . an increased crystallinity was observed because of the presence of fibres. The fraction of crystallinity showed a similar trend with maximum values at . There did not appear to be a strong dependence of stress on MaPP concentration above 4 wt-%. At 0 wt-% MaPP. the PP matrix has inhibited crystallinity probably because of a branched chain architecture that the blends assume. Figure 5 shows that the crystalline fraction of the composites increased up to 4– 6 wt-% MaPP.6 wt-%. This indicated that better fibre–polymer interactions required more strain to break.4 wt-%. Tm.1 and X1 at 2–6 wt-% MaPP. the strain immediately decreased upon introduction of MaPP but slowly increased with increasing MaPP back to the 0 wt-% MaPP value. so the fibre surface area for crystal nucleation was the same. the thermal behaviour appeared to reach a limiting value for Tm.15 163. theoretical peak stress values could be higher than the ones reported if samples could be prepared to avoid surface anomalies.22 Again. Larger X1 and Tm. There were voids where ‘pulled-out’ fibres once resided.2 wt-% MaPP. Figure 7a shows a macroscopic view of the fracture surface of a 4 wt-% MaPP composite at 6300.1 up to 4– 6 wt-% MaPP. For pure MaPP. The fibres had ‘clean’ surfaces. At MaPP concentrations .e. The PP–MaPP blends and composites showed a similar trend in Tm. 290 Plastics. MaPP loading of .1 values decreased at . Therefore. Liu et al.57. There were voids in the polymer matrix left by fibres that ‘pulled-out’ and voids around identifiable fibres. increased the wood flour content in composites and saw increased crystallinity because of increased nucleating surface. 4 and 5 respectively. the strain at peak stress did not appear to be greatly dependent on MaPP concentration for the PP/ MaPP blends. there was little fibre–polymer interaction. the PP–MaPP blends reached a maximum in Tm.48uC and X150. Rubber and Composites 2006 VOL 35 NO 6/7 5 Fraction crystallinity from DSC first heating cycle X1 versus MaPP concentration For the composites.

Addition of fibres further narrowed the crystal size distribution after annealing.2 cm fibre composites are plotted in Figs. Annealing the pure PP increased the percentage of crystallinity as shown in Fig. At the end of 8 h. 5. depicted as the middle of the peak and plotted in Fig. the fibres were also strongly adhered to the polymer matrix as shown in Fig. annealing experiments were performed on PP and PP/20 wt-% 0.2 cm keratin feather fibre were prepared and annealed at 0.Barone and Gregoire Characterisation of fibre–polymer interactions and transcrystallinity 6 Image (SEM) of tensile bar fracture surface for 0 wt-% MaPP composite at 62000 8 Image (SEM) of tensile bar fracture surface for 6 wt-% MaPP composite at 63000 shown in Fig. There were not many voids from a macroscopic view. In this manner. 7b shows that some fibres were strongly adhered to the PP matrix. The results of the annealed PP and annealed PP/20 wt-% 0. The data in Figs.23 To test this. PP9505E1 and a composite of PP9505E1 and 20 wt-% 0. concurrent to the thermal analysis and physical property data. 4. However. increased transcrystallinity at the fibre/polymer interface that results in an increased stress at break.1. Analysis of the DSC curves in Fig. 4 and 5 suggested that an increased population of large crystals resided near the fibres. 9. The DSC first heating cycle curves for the annealed and unannealed PP and PP composites without MaPP are shown in Fig. Rubber and Composites 61000 2006 VOL 35 NO 6/7 291 . a definitive transition in the properties of the composites occurred after 4 wt-% MaPP. the oven was turned off and allowed to slowly cool to room temperature. However.2 cm keratin fiber composites not containing MaPP. At 6 wt-% MaPP. The micrographs showed that. The purpose of maleic anhydride is to increase chemical interactions between the hydrophobic PP and hydrophilic fibres (in the case of cellulosic or glass fibres) or partially hydrophilic fibres (in the case of keratin). 9 shows that annealing did not measurably affect the average melt temperature Tm. This concentration was high enough for most of the fibres to bind to the matrix whereas anything less did not provide enough material for all of the fibres to bind and there was still some fibre pull-out. 8 for a fracture surface magnified 63000. 2. Annealing the PP–fibre composite increased the percentage of crystallinity even further to Effect of crystallinity on properties The increased crystallinity observed in the PPzMaPP/ fibre composites manifested as an increased stress to break. the results obtained in the present study suggest that there may be a physical mechanism of interaction manifesting through an 7 Image (SEM) of tensile bar fracture surface for 4 wt-% MaPP composite at a 6300 and b Plastics.1 or small crystal size fraction thus narrowing the crystal size distribution. annealing removed the low Tm. pure PP was used but the transcrystallinity affected through thermal treatment rather than chemical treatment with maleic anhydride.93Tm5135uC in a convection oven for 8 h. SEM analysis showed increased fibre–polymer interactions. 1–5 as open and closed squares respectively.

V. Clemons: J. Gillespie. M. Nunez. M. SC. R. Vinyl Addit. Conclusions Although an increased population of large crystals near a polymer/fibre interface can physically increase stress 292 Plastics. J. the increased fibre/polymer adhesion from maleic anhydride. A. 42. increased chemical interactions are also needed for this efficient stress transfer. Verpoest: Compos. A. 2003. V. Wang: Plast.4 wt-% but increasing MaPP further did not have a marked effect on physical properties. W. 2003. K. 32. P. K. 1503– 1513. Rubber Compos. Wang and Hwang argue that after fibre debonding. Reboredo. C. G.e. 1998. In fact. 7. so the higher yield stress fibres can bear more load. M. Appl.. M. 161–169. Sci. as has been observed previously. T.. English: J. 62. SEM analysis showed this increased interaction and it manifested as increased stress at break. P. A. Kuan. 1259–1264. E. 3. C. Loos: J. increased chemical interactions.Barone and Gregoire Characterisation of fibre–polymer interactions and transcrystallinity 9 DSC first heating cycle curves for annealed and unannealed PP9505E1 and PP9505E1/20 wt-% 0.. Kenny. Myers. 63. 8. 2003. 801–806. Appl. Thomas. Carrasco. Therefore. Y. However. Joseph. K. C. 67. J. J. C. Rana. Sci. M.. 2. i. The present paper is based on a presentation at the AutoPolymers workshop held in Charleston. 1996. Technol. Sci. 122–126.23 The key to polymer composites is still efficient stress transfer across the fibre/polymer interface through increased adhesion. 733–742. While this feature of the transcrystalline region has been shown to increase physical fibre–polymer interactions and therefore increase stress to break in the case of PP. I. 34A. 2004. Sci. Huang.. Rubber and Composites 2006 VOL 35 NO 6/7 transfer across that interface. F. 63. 2002. M. A. M. Eng. P. Appl. Joseph. use of MaPP. A. A. A. X. M. Pillai. Colom. J. Bullions. Prasad and S. for the PP composites studied here. C. Technol. is required to get increased stress at break. C. J. J. Sci. Although the crystallinity of an annealed composite was similar to that of a composite with . there was no increase in peak stress. 10. Sci. Pages and J. 103–108. Best properties were observed at MaPP concentrations of . C.4 wt-% MaPP may have been partially because of a thick transcrystalline region. Ma and F. so addition of fibres again acts as a preferential nucleating surface. The presence of fibres further increased crystallinity and resulted in larger crystals near the fibres. created much more efficient stress transfer across the interface so the fibres could bear load.16 Research has shown that thick transcrystalline layers have increased fibre– polymer interactions. Canavate: Compos. E. Marcovich: Polym. 2003. Oksman and C. which manifest as lower fragment lengths in single fibre fragment tests. 1995. P. Thermal analysis showed that increasing MaPP concentration gave an increased crystallinity with larger crystals in the transcrystalline region. Acknowledgements Mention of trade names or commercial products in this article is solely for the purpose of providing specific information and does not imply recommendation or endorsement by the US Department of Agriculture. Polym..4 wt-% MaPP. The role of the transcrystalline layer in increasing the composite properties is still arguable. Technol. Groeninckx: Compos.. Bandyopadhyay: Compos. H. Sci. References 1. 63. USA in October 2005. 253–266. 5. Price-O’Brien and A. Polym. Mandal and S. there was a decrease in the peak stress of the annealed composite. Wambua. larger transcrystalline layers provide more friction between fibre and polymer. 2003. i. 4. 6. S. Schneider. for PP–keratin fibre composites. 3771–3783. 1147–1151. more large crystals near the fibres. S. as shown first hand by the SEM images. . Polym. S. 1.23 It was possible that the crystallinity values obtained in the annealed composite were enough to overcome any chemical interactions between the fibre and polymer and pulled the matrix from the fibre surface. Technol. Aranguren and M.2 cm keratin fibre composites: no MaPP is used in this experiment the values obtained with MaPP and no annealing. This was performed using maleic anhydride modified PP. Ivens and I.e. Karmaker and J.. A.12 The results shown in the present study indicated that the increased peak stress of the composites with . Clemons and B. 92. 9.. Youngquist: J. an increased transcrystallinity and larger crystals near the fibre/polymer interface are not sufficient criteria for stress transfer across the interface. K.

1980. J. Liu. C. 132. Hu. 1518–1524. J. Prentice-Hall. Biochem. Struct. Takahashi. 1987. M. USA. Lett. S. Yokote and K. R. 395– 405. P. V. M. Macromol.W. R. C. Fried: ‘Polymer science and technology’. Bernardo: J. Paper 4. A. B. D. Gassner. Currey). Cunha. J. Scott: Polym. July 2003. Schmidt. Barone: Compos. 40B. M.. SpringerVerlag. L. Y. K. 34B. Shenton and R. Q. Z. A. 15. 17. B. Schuster: Proc. Technol. 2002. 20. (ed. 12. Chawla: ‘Composite materials’. Polym.. National Science Foundation and The Luso–American Foundation (Portugal). P. B. R. 1996. Rubber and Composites 2006 VOL 35 NO 6/7 293 . San Diego. M. Sci. H. B. Sci. R. K. 23. Plastics. N. M. Vincent and J. Sci. Yi and C. F. 2005. J.. 1435–1442. 14. O’Donnell. J. J. 2001. Compos. Characterisation of fibre–polymer interactions and transcrystallinity 18. 13. 63. 10. Akahane: Eur. 1998. M. C. CA. E. X.. 2005. Dweib. A. 21. Hwang: J. Englewood Cliffs.. 16. Cambridge. 293–297. M. Zafeiropoulos. Fraser and T. A. 2004. 147–157. A. G. 65.A. 501–507.Barone and Gregoire 11. W. Phys. Baillie and F. Water: US Patent 5705030. R. Wang and L. New York. 19. Wool: Compos. Matthews: Adv. Thomas and R. 1983. 529–538. 2001. 1995. Line. AutoPolymers 2005. 23. E. Cambridge University Press. 36A. Compos. J. Schmidt: Compos. D. NJ. Conf. MacRae: in ‘Symposia of the society for experimental biology number XXXIV: the mechanical properties of biological materials’. 173–181. 211–246. F. 22. Murayama-Arai. Kuroda and C. K. Barone and W. H.