Composites Science and Technology 71 (2011) 541547

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Composites Science and Technology

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Development of aligned-hemp yarn-reinforced green composites with soy protein resin: Effect of pH on mechanical and interfacial properties
Jun Tae Kim, Anil N. Netravali
Dept. of Fiber Science & Apparel Design, Cornell University, Ithaca, NY 14853-4401, United States

a r t i c l e

i n f o

a b s t r a c t
Unidirectional hemp yarn-reinforced green composites were fabricated with soy protein concentrate (SPC) resin processed at various pH values. To preserve the yarn alignment during the fabrication of green composites, hemp yarn was wound onto a metal frame with slight tension and precured SPC resin was applied to the yarns. Effects of pH values on the tensile properties of the SPC resin and hemp yarn/SPC resin interfacial shear strength (IFSS) were investigated. Increasing pH of the SPC resin from 7 to 12 decreased its fracture stress and Youngs modulus from 13.1 MPa and 357.5 MPa to 8.1 MPa and 156.2 MPa, respectively. At the same time fracture strain and moisture content increased from 31.5% and 15.65% to 53.4% and 19.30%, respectively, indicating resin plasticization. However, hemp yarn/SPC resin IFSS increased from 17.7 MPa at pH 7 up to 28.0 MPa at pH 10, after which it decreased. The fracture toughness of the composites increased up to pH of 10 but further increase in pH reduced the toughness. SEM photomicrographs showed fracture surfaces of hemp yarn-reinforced green composites that indicated better resin/ber interaction at pH of 10 than 7 or 12. 2011 Elsevier Ltd. All rights reserved.

Article history: Received 20 September 2010 Received in revised form 23 December 2010 Accepted 6 January 2011 Available online 11 January 2011 Keywords: A. Polymer-matrix composites (PMCs) A. Textile composites B. Fiber/matrix bond B. Interfacial strength B. Mechanical properties

1. Introduction In the past couple of decades the use of natural cellulosic bers has increased, particularly in ber-reinforced composites, as a result of increased consciousness and concerns regarding the environmental problems created by the use of petroleum-based bers and resins [1]. Due to their annually renewable, sustainable and biodegradable features as well as high specic mechanical properties, plant-based bers such as ramie, jute, ax, sisal and hemp have been used as reinforcements to fabricate green composites with biopolymer resins such as polysaccharides and proteins. These green composites are meant to replace the traditional composites such as synthetic ber-reinforced or synthetic resin-based non-degradable or partially degradable composites [26]. Although advanced green composites have high strength and toughness because they have been fabricated using high strength liquid crystalline cellulose bers, most green composites still have the drawback of lower mechanical strength since both resin and bers are relatively low strength and stiffness. In addition, these green composites also exhibit poor water resistance because both bers and polymer resins are hydrophilic [7]. It is well known that mechanical strength and stiffness of the ber-reinforced composites primarily depend on the ber strength,
Corresponding author. Tel.: +1 607 255 1875; fax: +1 607 255 1093.
E-mail address: ann2@cornell.edu (A.N. Netravali). 0266-3538/$ - see front matter 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.compscitech.2011.01.004

the ber content, the ber length, the ber alignment as well as the resin properties and ber/resin interfacial strength [813]. To improve the ber strength and stiffness, various chemical modications have been applied to the natural bers that have shown significant improvements in their mechanical properties [1416]. Although the ber properties were signicantly improved by chemical treatments such as mercerization, the composite strength and stiffness did not reect these improved properties because of the ber misalignment in the composites [17]. Since the soy protein resin is prepared with high water content, it shrinks signicantly by water evaporation during the drying process. This resin shrinkage distorts the ber alignment in the composites even if all bers are aligned along to the ber axis before fabricating the composite. In order to keep the ber alignment in the composites, bers need to be long enough to be held tight on a mold. Although some bers are much longer than the mold size, in many cases it is hard to hold all bers tightly on the mold. However, spun yarn is a continuous form of twisted bers and where the short bers make an angle to the yarn axis. As a result, the strength of the yarn is lower than the individual bers. At the same time, however, due to the continuous length of the yarn, it is easier to control and maintain their alignment in the composites. Hemp is a bast ber obtained from Cannabis sativa L. plant which has been widely cultivated in Asia, Europe and Canada. Hemp ber or yarn has a great potential for reinforcement in green composites due to its high specic mechanical strength and low price [18].

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Soybean is one of the most useful industrial crops because it contains high level of edible oil (about 20%) and protein (about 40%). Soy protein has been used as a good nutritional source in food industry because it contains signicant amounts of the essential amino acids [19]. Soy protein could be classied into three commercially available products such as defatted soy our (SF), soy protein concentrate (SPC), and soy protein isolate (SPI) based on the protein content. SF contains 53% protein and 32% carbohydrate whereas SPC and SPI contain 72% protein and over 90% protein, respectively. Soy protein is now being used as a polymeric resin with natural cellulosic bers to fabricate green composites due to their good strength and compatibility to the cellulosic bers [5,2023]. It has been reported that mechanical strength and interfacial adhesion of soy protein are a function of their protein content [24]. It has also been known that the soy protein could not form a lm at or near its isoelectric point (pH 4.5) due to the coagulation [25]. However, proteins can be denatured and unfolded at pH values away from their isoelectric point, thus exposing their functional groups and increasing the intermolecular interactions. Thus the mechanical properties of soy protein can be affected by its pH. Most protein-based lms show better physical properties when processed in alkaline conditions compared to those processed in acidic conditions [26]. In the present study, SPC resin was prepared at various pH values ranging from 7 to 12. The effect of pH on the tensile properties and moisture content of SPC resins was investigated. Hemp yarn/ SPC resin interfacial shear strength (IFSS) was measured using a microbond test. In order to fabricate the aligned-hemp yarn reinforced (unidirectional) composites, hemp yarns were tightly wound on a metal mold frame to minimize their shrinkage and distortion during the application and drying of the SPC resin. Tensile properties and fracture surfaces of the composites were characterized. 2. Experimental 2.1. Materials Hemp yarns were provided from Hemplee Korea Co. Ltd. (Seoul, Korea). Soy protein concentrate (SPC), ARCON S, was provided by Archer Daniels Midland (ADM) Company (Decatur, IL). Glycerol and analytical grade sodium hydroxide (NaOH) was purchased from Fisher Scientic. 2.2. Preparation of SPC resin SPC resin was prepared by dissolving SPC in 15 times (w/v) of deionized (DI) water with a magnetic stirring. When SPC was completely dissolved, 15% (w/w SPC) glycerol was added to the SPC solution as a plasticizer to avoid the brittleness of the SPC resin. The pH of the native SPC resin was approximately 7 and was adjusted to pHs of 8, 9, 10, 11, and 12 by adding 1 M NaOH solution. Then, the SPC resin was precured at 75 C water bath for 30 min. The precured resins were cast on a Teon coated glass plate and dried at 35 C in an air circulated drying oven for about 16 h. Dried SPC resin sheets were cured using a Carver Hydraulic Hot Press (model 3891-4PROAOO, Wabash, IN) at 120 C for 25 min under pressure of 5 MPa. The cured sheets were conditioned at 21 C and 65% relative humidity (RH) for 72 h prior to testing of their tensile properties. 2.3. Characterization of hemp yarn Hemp yarn was characterized for its linear density, twist angle, moisture content, and tensile properties. Since the mechanical

properties of yarns are a function of its linear density and ber twist angle with respect to yarn axis, yarn characterization is helpful and necessary to understand the composite properties. Fiber twist angles at the yarn surface were measured using an optical microscope, model Nicolet Continulm (Spectra-Tech Inc., USA) and a protractor. At least twenty yarn specimens were measured to obtain the average value of the ber twist angle. Linear density (tex: g/1000 m) of hemp yarn was determined by weighing 10 m length hemp yarn according to ASTM D1577-07. Ten meter of long yarn pieces were conditioned at 21 C and 65% RH for 24 h and then the weights of yarns were measured individually. Average linear density value was obtained from three measurements. Tensile properties such as fracture stress, fracture strain, and Youngs modulus of the hemp yarn were characterized using an Instron, model 5566 (Instron Co., Canton, MA) according to ASTM D2256-01. The cross-sectional area of hemp yarns to obtain the stress was calculated from linear density (tex: g/1000 m) and hemp ber density, 1.48 g/cm3 [27]. Linear density of individual yarn specimens with 100 mm length were measured using a balance with 0.0001 mg resolution. To perform the tensile tests, individual yarn specimens were mounted on the rectangular shape paper tabs and then glued at an equal distance to the gauge length of 50 mm. Yarn specimens were conditioned at 21 C and 65% RH for 24 h. The strain rate of 0.02 min1 was used. At least 20 specimens were tested to obtain the average values.

2.4. Hemp yarn/SPC resin interfacial shear strength (IFSS) Hemp yarn/SPC resin IFSS was characterized by a microbond test [2,24]. A small microbead (microdrop) was placed on the hemp yarn using the precured SPC resins at various pH values. The microbeads on the hemp yarn were kept in drying oven at 120 C for 1 h to cure the SPC resin. All specimens were equilibrated at 21 C and 65% RH for 24 h before performing the IFSS test. Fig. 1 shows the schematic of microbond test for IFSS of hemp yarn and SPC resin. The ber diameter (D) and embedded length (L) were measured using an optical microscope. The microbond test was performed using an Instron with a special microvise. The microvise plates were placed above the microbead and brought closer until they barely touched hemp yarn surface. The yarn was then pulled out from the microbead at a crosshead speed of 0.2 mm/min until

Fig. 1. Schematic of IFSS test by microbond.

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the microbead debonded. The IFSS (s) was calculated using the following equation:

Interfacial shear strength s

pDL

where F is the force required to debond the microbead. Twenty successful tests were conducted to obtain the average IFSS values. 2.5. Preparation of unidirectional hemp yarn-reinforced green composites Unidirectional and aligned-hemp yarn-reinforced green composites were fabricated with the SPC resins at pHs 7, 10, and 12. As shown in Fig. 2, hemp yarns were wound onto a metal frame under small tension to minimize the yarn shrinkage and misalignment during the drying of the SPC resin. Metal frame with the hemp yarn was soaked into the precured soy resins individually to obtain as complete impregnation of the resin as possible into the yarns. The excess resin was removed and the yarn was dried in a drying oven for about 16 h at 45 C. Yarn volume fraction was controlled to be in the range of 50%. Dried composites were cured at 120 C for 25 min under 5 MPa. The cured composites were conditioned at 21 C and 65% RH for 5 day prior to testing of their tensile properties. At least seven specimens were tested to obtain the average values. The thicknesses of the composites varied between 0.9 and 1.0 mm. 2.6. Tensile properties of SPC resins The cured SPC resin sheets were cut into rectangular strips of 100 mm 10 mm. The thickness of SPC resin sheet was between 0.22 and 0.25 mm. The tensile tests of SPC resins were performed according to ASTM D882-02. The gauge length of 50 mm and the strain rate of 1 min1 were used. Ten specimens were tested to obtain the average values. 2.7. Tensile properties of hemp yarn-reinforced composites Tensile properties of the unidirectional and aligned-hemp yarnreinforced composites were characterized in the parallel (longitudinal) direction to the yarn axis. Tensile tests of the composites were performed according to ASTM D3039-00. The rectangular

specimens with 10 mm width and 0.91.0 mm thickness were tested to obtain fracture stress, fracture strain, Youngs modulus, and toughness of the composites. To prevent the specimen slippage from the grip during the tensile testing, both ends of the composite specimens were mounted on a paper tab using a cyanoacrylate glue. A gauge length of 50 mm was maintained and the strain rate was set at 0.05 min1. Seven specimens were tested to obtain the average values. 2.8. Surface characterization Scanning electron microscope (SEM; Leica model 440X, Cambridge, UK) was used to characterize the surface/cross-section of pure hemp yarn and the fracture surfaces of the SPC resins and the green composites. The specimens were loaded on the SEM mount with double sided electrically conductive adhesive carbon tape (SPI Supplies, West Chester, PA), then the specimen mounts were coated with gold/palladium (Au/Pd) for 30 s with 45 mA current in sputter coater. The coated specimens were observed on the SEM using a low accelerating voltage of 5 kV. 3. Results and discussion 3.1. Characterization of hemp yarn Table 1 presents hemp yarns characteristics such as linear density, average diameter, twist angle, moisture content and tensile properties. The average linear density of hemp yarn was obtained by weighing three 1000 m specimens and taking the average value. The yarn was found to be 40.74 tex (g/1000 m) and the average diameter of single hemp yarn was 216.2 lm. Linear density and average diameter of hemp yarn was relatively lower than those (4753 tex and 221242 lm) of other previous study [28]. Fig. 3 shows the plot of twist angle vs. diameter of hemp yarns. As expected, the diameter of hemp yarns reduced slightly when the twist angle increased. For most hemp yarns twist angles were in between 23 and 26 and their diameters ranged between 190 and 230 lm. The average twist angle of hemp yarn was 24.5. Since a yarn has an irregular diameter and a non-circular cross-section, linear density of each yarn specimen and hemp ber density (1.48 g/cm3) were used to obtain more accurate cross-sectional area and thus calculate the yarn fracture stress. Fracture stress, fracture strain, and Youngs modulus of hemp yarn were 449.5 MPa, 4.3%, and 11.9 GPa, respectively. But tensile strength and modulus of single hemp ber would be expected to be much higher than those of hemp yarn because yarn is a twisted form of many short bers. In the twisted form the bers cannot contribute fully to the strength of the yarn because of the angle they make with the yarn axis. Fig. 4 shows the SEM photomicrographs of longitudinal and cross-sectional views of a typical hemp yarn. As shown in Fig. 4a, hemp bers are twisted in right handed direction (Z-twist) and only few inter-ber voids or crevices are observed in the cross-section of the yarn. 3.2. Effect of pH on tensile properties of the SPC resins Table 2 shows the tensile properties and moisture content of the SPC resins processed at pHs 712. It has been shown that soy protein cannot form good lms around its isoelectric point (pH 4.5) as well as at extreme acidic (below pH 1) and alkaline (over pH 12) conditions because of the protein coagulation at its isoelectric point and strong electrostatic repulsive forces at extreme pH conditions, respectively [15,29,30]. At pH 7, in current experiments, SPC resin showed the highest fracture stress of 13.1 MPa and Youngs modulus of 357 MPa while fracture strain and mois-

Fig. 2. Schematic of aligned-hemp yarn winded in a metal frame.

544 Table 1 Characteristics of hemp yarn. Linear density (tex: g/1000 m) 40.74 (0.62)
a a

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Yarn diameter (lm) 216.2 (13.76)

Twist angle () 26.11 (14.31)

Fracture stress (MPa) 449.9 (14.94)

Fracture strain (%) 4.28 (11.20)

Youngs modulus (GPa) 11.91 (14.06)

Moisture content (%) 8.33

The numbers in parentheses indicate the percent coefcient of variation.

400

300

200

100

0 0 10 20 30 40 50
Twist angle (degrees)
Fig. 3. Twist angle vs. diameter of hemp yarns.

ture content showed the lowest, 31.5% and 15.7%, respectively. On the other hand, the lowest fracture stress of 8.1 MPa and Youngs modulus of 156 MPa were observed at pH 12. Increasing pH showed the same effect of plasticizer on the tensile properties of the SPC resin. Fracture stress and Youngs modulus of SPC resin decreased signicantly with increasing pH values while at the same time fracture strain and moisture content increased signicantly. But fracture stress and Youngs modulus of SPC resin were not sig-

nicantly different between pH values of 7 and 8, 8 and 9, and 9 and 10 as shown in Table 2. Although the tensile properties keep changing with pH values, small change of pH may not be enough to distinguish the difference. As a globular protein, soy protein is thermodynamically the most stable folded structure at its isoelectric point [31]. The aggregation or folding of protein can give more compact structure by the formation of various intermolecular interactions resulting in stronger lms [32]. When it is fully denatured, however, globular protein molecule unfolds or forms a random coil conformation by cleavage of some intermolecular interactions such as hydrogen bond, hydrophobic interaction, and disulde bonds resulting in exposing reactive groups [33]. It has been known that tensile strength and stiffness of protein-based lms are largely dependent on the type and density of interactions in the lm network [30]. Increasing pH may reduce the density of inter- and intra-molecular interactions in the lm network by unfolding of protein but it will also increase the exposure of the reactive groups. It can be therefore expected that the exposure of the reactive groups in alkaline condition will increase the interactions with the cellulosic hemp bers resulting in improved in interaction as measured by the IFSS. Lower modulus and strength values and increased fracture strain for resins processed at higher pH values also indicate that there was signicant effect of plasticization at higher water content. Addition of NaOH to increase the pH does seem to make the resin more hydrophilic and more negatively charged. More hydrophilic and negatively charged features of soy protein at higher pH value increased its capacity to hold more polar groups such as carbohydrate and water resulting in in-

Diameter (um)

Fig. 4. SEM photomicrographs of (a) hemp yarn and (b) the cross-section.

Table 2 Effect of pH on the tensile properties and moisture content of SPC resins. pH of SPC resin 7 8 9 10 11 12
a

Fracture stress (MPa) 13.07 12.56 12.30 11.70 10.44 8.12 (1.31)a (4.01) (4.18) (4.16) (3.25) (5.10)

Fracture strain (%) 31.50 34.40 38.47 40.90 48.25 53.42 (11.99) (5.59) (8.64) (4.38) (7.36) (9.87)

Youngs modulus (MPa) 357.8 333.7 306.5 291.2 232.8 156.2 (8.32) (8.21) (7.02) (6.32) (4.65) (6.71)

Moisture content (%) 15.65 16.05 16.63 16.82 17.76 19.30

The numbers in parentheses indicate the percent coefcient of variation.

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40

3.3. Hemp yarn/SPC resin interfacial shear strength (IFSS) Fig. 5 shows IFSS between hemp yarn and SPC resins in various pHs. Hemp yarn/SPC IFSS increased with increasing the SPC resin pH. Although tensile strength and Youngs modulus of the SPC resin decreased with increasing pH, SPC resin/hemp yarn IFSS increased signicantly from 17.7 MPa at pH 7 to 28.0 MPa at pH 10. Unfolding of soy protein, by addition of NaOH, can expose the reactive groups on the peptide chain resulting in increasing intermolecular interaction with hydroxyl groups of cellulosic hemp yarn. On the other hand, soy protein at neutral pH will prefer to fold and maintain the intramolecular interactions within the SPC resin network. As per the results of the present study, the maximum IFSS was observed at pH 10 beyond which it decreased as a result of increased moisture absorption. This suggests that soy protein and cellulosic ber may have optimum intermolecular interactions at pH 10. Extreme alkaline conditions seem to increase the electrostatic repulsive forces along soy protein molecules resulting in reducing the interactions with cellulosic bers [31]. Fig. 6 shows the SEM photomicrograph of a typical microbead after debonding test. The SEM images of the microbeads were not different with resin pH. Some SPC resin was observed on the debonded hemp yarn

30

IFSS (MPa)

20

10

0 7 8 9 10 11 12

pHs
Fig. 5. Effect of pH on IFSS of hemp yarn and SPC resin.

creased moisture absorption [34]. This phenomenon has been seen in mercerization of cotton as well as for sisal bers which makes it more moisture absorbent [15].

Fig. 6. SEM photomicrograph of microbead after debonding test.

Table 3 Tensile properties of hemp yarn-reinforced composites. Yarn volume fraction (%) Composite I (pH 7) Composite II (pH 10) Composite III (pH 12) Theoretical Values
a

Fracture stress (MPa) 253.3 (5.74)a 277.0 (5.49) 262.5 (4.36) 229.5232.4

Youngs modulus (GPa) 6.56 (5.57) 6.54 (9.51) 6.61 (8.71) 6.046.16

Fracture strain (%) 7.73 (4.51) 9.70 (6.72) 8.36 (5.59)

Toughness (MPa) 11.80 (5.57) 15.42 (12.88) 12.00 (9.41)

50.2 49.9 50.1

Numbers in parentheses indicate the percent coefcient of variation.

Fig. 7. SEM photomicrographs of the fracture surface of (a) composite I (pH 7), (b) composite II (pH 10) and (c) composite III (pH 12).

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500
(a) Hemp yarn

400

300
(c) Composites I

200

100
(b) SPC resin

0 0 10 20 30

Tensile Strain (%)

Fig. 8. Typical stressstrain plots of (a) hemp yarn, (b) SPC resin at pH 7 and (c) composite I.

alignment [15]. In case of the unidirectionally aligned yarnreinforced composites, however, the yarn stretching during the fabrication of the composites by winding in a metal mold can increase the composite properties. In fact, their stress and modulus values were 1020% higher than the theoretical values. This effect is similar to the results obtained for prestressed concrete where the rebars are stressed prior to pouring of concrete. Fig. 8 shows typical stressstrain plots of (a) hemp yarn, (b) SPC resin at processed pH 7 and (c) composite I. Hemp yarn shows linear behavior and brittle fracture as the stress falls down abruptly. In our previous research [35], green composites made using sisal ber and SPC/gelatin resin showed non-linear behavior and the fracture occurred in several steps as the bers kept breaking at different strains. Non-linear behavior of the green composites was mainly because of the non-uniform ber alignment and tension during composite fabrication that allowed bers to fracture at different composite trains. However, better yarn alignment in composites should result in better linear behavior as shown in Fig. 8c. Even then the tension in the yarns during composite fabrication was not as uniform as it could be if machines were used. As a result, there still seems to be slight nonlinearity. 4. Conclusions Mechanical properties and IFSS of the SPC resin were seen to be signicantly affected with the pH during resin preparation. Fracture stress and Youngs modulus of the SPC resin decreased with increasing pH values from 7 to 12 while their fracture strain and moisture content increased. Hemp yarn/SPC resin IFSS, however, increased with increasing alkaline condition and the maximum IFSS of 28 MPa was observed at pH 10. Unfolding of soy protein by addition of NaOH could reduce its mechanical strength but increase the IFSS because of more exposure of the reactive groups for enhanced interaction with the bers. The toughness of the composites increased up to pH of 10 and then decreased with further increase in the pH. Acknowledgements The authors acknowledge NYSTAR-TTIP (Grant# C020154) for nancial support and Cornell Center for Materials Research (CCMR) and the Department of Fiber Science & Apparel Design (FSAD) for providing the facilities. References
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surface and in between twisted yarn strands. This SEM image is a clear evidence for the high value of hemp yarn/SPC resin IFSS. 3.4. Tensile properties of aligned-hemp yarn-reinforced composites Tensile properties of aligned-hemp yarn-reinforced green composites in longitudinal direction are presented in Table 3. In our recently published study of cellulosic ber and similar soy protein based unidirectional composites [17], the tensile stress and modulus, in transverse direction, were around 6.0 MPa and 0.6 GPa, respectively. These values were close to the resin properties, as can be expected. While the composites were not tested in transverse direction in this study, we expect the transverse strength and modulus values to be in the same ballpark since similar resin was used in this study. Composites IIII were fabricated with the precured SPC resins containing 15% (w/w SPC) glycerol at pHs 7, 10, and 12, respectively. Tensile properties of the composites are slightly different depending on the pH values at which the SPC resins were prepared. The composite I showed the lowest fracture stress of 253 MPa, fracture strain of 7.7%, and toughness of 11.8 MPa while the composite II showed the highest fractures stress, strain, and toughness of 277 MPa, 9.7% and 15.4 MPa, respectively. Tensile properties of the composite III were in between the composites I and II. Although the SPC resin showed higher mechanical strength and stiffness with pH 7 and kept decreasing with higher pH values, the composite strength was higher for resins processed at pHs 10 and 12 than at pH 7. This is believed to be mainly because of the higher IFSS between yarn and SPC resin at pH of 10. As discussed in the previous section, IFSS was significantly higher with pHs 10 and 12 than that with pH 7. Higher IFSS is known to increase the strength of the composites [17]. Fig. 7 shows SEM photomicrographs of the fracture surfaces of (a) composite I, (b) composite II, and (c) composite III. While most SPC resin was observed on the fracture surface of the composite II, less resin was observed on composite III and almost no resin was seen on the fracture surface of the composite I. The IFSS study also showed highest ber/resin interaction in the case of pH of 10. At pH of 10, the fracture strain of the composites increased as well. This resulted in increased toughness. However, Youngs modulus was around 6.5 GPa for all three composites. Fracture stress and Youngs modulus of alignedhemp yarn-reinforced composites were much higher than those of the theoretical values as shown in Table 3. Theoretical values of fracture stress and Youngs modulus were calculated using the rule of mixture and compared to the experimental values. In most cases for ber-reinforced composites, the actual stress and modulus are observed to be lower than the theoretical values due to the ber mis-

Tensile Stress (MPa)

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