JFS:

Food Engineering and Physical Properties

Tensile Properties of Soy Protein Isolate Films Produced by a Thermal Compaction Technique
P. CUNNINGHAM, A.A. OGALE, P.L. DAWSON, AND J.C. ACTON ABSTRACT: Soy protein isolate (SPI) was utilized as a biopolymer and glycerol was used as a plasticizer to successfully produce light-yellow, transparent protein films by a thermal compaction technique. Flexible films, approximately 180 micrometers, could be produced at a processing temperature of 150 C and compaction pressure and time of 10 MPa and 2 min, respectively. The dispersion of glycerol among SPI macromolecules was found to be a diffusion-limited process that could be accelerated by intensive mixing. Films containing 30 wt% glycerol made from intensively mixed material had average tensile strength and elongation values that were, respectively, 6% and 300% higher than those of films made from unaged, manually mixed material. Key Words: soy protein isolate, films, thermal compression, tensile strength, elongation

Introduction
waste are discarded into municipal waste systems each year. More than 8 million tons of plastic packaging waste were generated in 1993 (EPA 1994). To reduce such synthetic polymer waste, a considerable amount of research has been devoted to the production of biodegradable polymer films derived from natural sources. Biodegradable films can be composted and eventually converted into natural elements by the metabolic activity of microbes. Much of the research into biodegradable films has involved the production of films from the method of solvent casting (McGrath and Kaplan 1996; Roy and others 1999). Thermal processing methods such as compression molding and extrusion have received only limited attention. Jane and Wang (1996) and Huang and others (1995) report an extrusion and/or molding technique, whereas Paetau and others (1994), Jane and others (1994), and Paulk and Ogale (1995) used compression molding to produce films from soy protein. Other studies, such as that of Spence (1994), discuss the compression molding of starch and corn-zein films. Some of these films were reported to be rigid and brittle due to the absence of a plasticizer in the preprocessed mixture. The main objectives of the present study were to investigate such thermal processing methods and to characterize the resulting films for their tensile properties.

NCREASING AMOUNTS OF PACKAGING

yellow to light brown in color. In an earlier study (Paulk and Ogale 1995), it was demonstrated that a compaction temperature of 175 C resulted in a dark-brown film with evidence of degradation of the material. It was found that a temperature of 150 C was the optimum temperature that resulted in semitransparent films with a light yellow or amber tinge. In general, the clarity of the films improved with increasing plasticizer content. The clarity also increased with increasing processing temperature, but at the highest temperature, a light-brown coloration was evident.

Tensile properties
The average tensile strength (TS), percent elongation at failure (%E), and film thickness for soy-protein films containing various amounts of plasticizer are displayed in Table 1; the films were made from intensively mixed and manually mixed (both unaged and aged for 6 wk) materials. The average %E of films ranged from 1.5% to 106% and increased with increasing plasticizer content. The average TS and thickness of films decreased with increasing plasticizer content. The average thickness and TS values ranged, respectively, from 0.16 mm and 1.6 MPa at the highest plasticizer content (40 wt%) to about 0.35 mm and 15.8 MPa at the lowest plasticizer content (20 wt%) investigated in this study. The effect of intensive mixing on the tensile properties of films was varied. A significant increase was observed on the TS of only those films containing 20 wt% glycerol. On the contrary, it is evident from Table 1 that intensive mixing resulted in a significant improvement of the flexibility of these films (as evidenced by the increase in the %E values) at all plasticizer

levels. Typically, a 3- to 4-fold increase was observed in %E values of intensively mixed materials over those of films made from unaged mixtures. Properties of films made from SPI/glycerol mixture aged for 6 wk are also reported in Table 1. Whereas the average TS value of the aged films is lower than that of the films made from intensively mixed materials, the %E values are very similar. The overall appearance and the texture of the aged films also started approaching those of the films made by intensively mixed materials. An interesting phenomenon was observed during the processing of the 40 wt% glycerol films. When unaged mixture was thermally compacted, the periphery of the sample (approximately 1 mm wide) was observed to have a high plasticizer content and a sticky feel. However, during thermal compaction of both aged and intensively mixed materials, no such sticky periphery was observed. Thus, it may be inferred that intensive mixing, similar to natural aging, increases the dispersion of plasticizer in soy-protein particles and ultimately yields films with improved mechanical properties.

FoodEngineeringandPhysicalProperties

Aged mixtures
The effect of aging of mixtures at 25 C on the mechanical properties of the resulting samples with 30 and 40 wt% plasticizer levels is displayed in Table 2. For films containing 30 wt% glycerol, the average TS of samples changed from 5.8 MPa (for unaged mixture) to an asymptotic value of about 2.6 MPa after 1 wk of aging of the mixture. For samples containing 30 wt% glycerol, the average %E values of samples increased from 24% (for unaged mixture) to 80% after 1 wk of aging. Thus, the aver 2000 Institute of Food Technologists

Results and Discussion

Color and clarity
The films produced by the thermal compression technique ranged from light

668 JOURNAL OF FOOD SCIENCEVol. 65, No. 4, 2000

age TS and %E values indicate that the mixtures containing 30 wt% glycerol reach a reasonable extent of aging in approximately 1 wk. Similar results were observed for films containing 40 wt% glycerol, except that the TS and %E reached asymptotic values after a longer duration of 4 wk of mixture aging.

Table 1Average ( std. dev.) tensile strength (TS), percent elongation (%E), and film thickness at 25 C and 50% RH for soy-protein films containing various plasticizer content and made from intensively mixed and manually mixed (both unaged and aged) blends Average Tensile Strength (MPa) wt% glycerol Mixture 20% 25% 7.3 0.3 8.9 0.3 30% 5.4 0.2 5.8 0.4 2.5 0.3 35% 3.7 0.4 2.7 0.4 40% 2.6 0.4 2.4 0.6 1.6 0.4

Intensively Mixed 15.8 0.2 Unaged 4.1 0.4 Aged 6 wk

Aging of films
The effect of post-process aging on the properties of SPI films made from intensively mixed materials was investigated because it was observed that some plasticizer diffused out of films over time, giving the samples a sticky surface. The effect of post-process aging on the TS and %E of soy-protein films containing 30, 35, and 40 wt% glycerol are displayed in Table 3. A significant loss of the plasticizer would be expected to alter the tensile strength of samples. However, results presented in Table 3 indicate a slight decrease in the mean TS of the aged films. Only the 0.8 MPa decrease in the TS values for the 30 wt% glycerol films was determined to be statistically significant (at a 95% confidence level). The out-diffusion of plasticizer would be expected to decrease the percent elongation of samples. Table 3 indicates that the percent elongation of the films containing 40 wt% glycerol did drop significantly (at a 95% confidence level) after aging, but the % E value for the films containing 30 and 35 wt% glycerol did not change significantly. However, it is possible that aging periods longer than 14 wk may affect samples containing 30 and 35 wt% glycerol. It is noted that, although visually obvious, the out-diffusion of the plasticizer was minimal and could not be measured quantitatively in terms of mass change. This was further confirmed by film thickness data presented in Table 3, which indicate that the thickness of the aged films did not differ significantly (at a 95% confidence level) from the thickness of the unaged films.
Average Percent Elongation (%E) wt% glycerol Mixture Intensively Mixed Unaged Aged 6 wk 20% 4.2 1.4 1.5 0.5 25% 67.4 7.8 8.1 30% 96.5 6.2 24.0 7.0 64.8 19.7 35% 106.0 19.0 21.6 5.6 40% 74.5 32 13.2 4.9 71.3 12.4

Average Film Thickness (mm) wt% glycerol Mixture 20% 25% 0.29 0.02 0.32 0.01 30% 0.26 0.01 0.30 0.01 0.15 0.02 35% 0.22 0.02 0.28 0.01 40% 0.18 0.02 0.25 0.03 0.16 0.01

Intensively Mixed 0.25 0.02 Unaged 0.35 0.01 Aged 6 wk

Impact energy
Table 4 displays the effect of plasticizer content on the average impact energy of SPI films produced from intensively mixed materials; the average values ranged from about 150 to 200 kJ/m for films containing 20 to 40 wt% glycerol. It is noted that the values reported in Table 4 are normalized with respect to the sample thickness and sometimes referred to as impact strength (particularly in the plastics literature). From Table 4 it is evident that the impact energy of films increases with increasing plasticizer levels. This is expected because films with plasticizer levels of 35

and 40 wt% exhibit ductile behavior as evident from tensile results. Materials with high impact energies display ductile behavior, whereas low impact energies are indicative of brittle failure. No studies on the impact strength of biopolymer films were found in the literature. Many studies on the impact strength of synthetic polymer films were found in the literature. However, a direct comparison with the results presented here for soy-protein films could not be made because most studies in the literature used ASTM D 1709 or D 256 to conduct impact testing. Krohn and Jordy (1995) did use the same type of testing procedure as used in the present study to measure the impact strength of extruded HDPE films of various thicknesses. However, Krohn and Jordy reported the peak load (lb) as the impact strength instead of the impact energy. It is observed that the SPI films from this study have considerably lower impact strengths than those of synthetic polymer films such as HDPE and LDPE.

Table 2Average ( std. dev.) tensile strength (TS), percent elongation (%E), and film thickness at 25 C and 50% RH for films made from manually mixed blends; the blends were aged at 25 C in sealed polyethylene bags for various times as indicated in the table. 30 wt% glycerol Aging time unaged 2d 1 wk 2 wk 3 wk 5 wk 6 wk TS (MPa) 5.8 0.4 2.6 0.4 2.5 0.2 2.6 0.2 2.8 0.5 2.5 0.3 %E 24 7 80.6 27.5 102 25 67.5 9.4 60.6 30 64.8 19.7 40 wt% glycerol Aging time unaged 2d 2 wk 3 wk 4 wk 5 wk 6 wk TS (MPa) 2.4 0.6 1.9 0.3 1.7 0.6 2.1 0.4 2.1 1.0 1.6 0.4 %E 13.2 4.9 37.4 9.4 42 22.2 88.4 27.6 81 25 71.3 12.4 Thickness (mm) 0.25 0.03 0.17 0.02 0.16 0.01 0.15 0.02 0.16 0.01 0.16 0.01 Thickness (mm) 0.30 0.01 0.22 0.03 0.26 0.04 0.16 0 0.16 0.01 0.15 0.02

Comparison with selected biopolymer and synthetic polymer films

The TS, %E, and thickness for selected biopolymer and synthetic polymer films are presented in Table 5. Soy-protein films made from aged or intensively compounded mixtures have mechanical properties similar to those of other biopolymer films produced by solvent casting. Films made from a compounded mixture containing 30 wt% glycerol had a TS of 5.4

MPa and a %E of 96%, which compares well with that of solvent-cast soy-protein films made by Brandenburg and others (1993) that had a TS and %E of 5.2 MPa and 90%, respectively. Films made in the present study had much higher %E values compared to the values of 2% and 4% reported by Spence (1994) and Paetau and others (1994), respectively; the higher values in the present study resulted from the plasticization effect afforded by glycerol.

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FoodEngineeringandPhysicalProperties

Tensile Properties of Soy Protein Isolate Films . . .

Table 3Average ( std. dev.) tensile strength (TS), percent elongation (%E), and thickness at 25 C and 50% RH of post-process aged soy-protein films; the films were aged at 25 C in sealed polyethylene bags. wt% glycerol 30 TS (MPa) %E Thickness (mm) 5.4 0.2 96.5 6.2 0.26 0.01 30PA 4.6 0.7 104 35 0.26 0.01 35 3.7 0.4 106 19 0.22 0.02 35PA 3.6 0.2 104 6 0.21 0.03 40 2.6 0.4 74.5 32 0.18 0.02 40PA 2.3 0.1 37 14 0.20 0.01

However, the TS and %E of synthetic polymers such as LDPE and HDPE are significantly higher than those of biopolymer films reported in the present and literature studies.

Conclusions

PA = post-process aged 14 wk

HIN , FLEXIBLE FILMS WERE PRODUCED BY thermal compaction of soy protein

Table 4The effect of plasticizer content on the average ( std. dev.) normalized impact energy of soy-protein films at 23 C and RH of 55% wt% glycerol 20 Impact strength (kJ/m) Thickness (mm) 151 7 0.260.01 25 144 9 0.280.02 35 187 3 0.210.003 40 216 14 0.180.01

Table 5Tensile strength (TS) and percent elongation (%E) values for selected biopolymer and synthetic polymer films Film Typeab WGc WPI:Glyd DAS-CZe CZf SPIg SPIh SPI:Glyi ATSPI:Glyj MSPI-PEO-LDPEk Cellophane HDPE LDPE Thickness (mm) 0.101 0.11 N.A. 0.089 0.083 N.A. 0.066 0.066 0.20 0.036 0.025 0.025 TS (MPa) 2.6 13.9 16 0.4 3.6 37 5.23 4.33 2.4 114.0 17.3 to 34.6 8.6 to 17.3 %E 276.2 30.8 2.0 < 1.0 169.3 4.0 90.27 115.2 100 20.0 300 500 Reference Gennadios and others (1993a) McHugh and Krochta (1994b) Spence (1994) Aydt and others (1991) Gennadios and others (1993b) Paetau and others (1994) Brandenburg and others (1993) Brandenburg and others (1993) Ghorpade and Hanna (1996) Aydt and others (1991) Briston (1988) Briston (1988)

aAll films were made by solvent casting unless otherwise noted. bAbbreviated terms stand for: WG = wheat gluten. WPI = whey protein isolate. Gly = glycerol. DAS = dialdehyde starch. CZ =

corn zein protein. SPI = soy protein isolate. ATSPI = alkali-treated soy protein isolate. MSPI = modified soy protein isolate. PEO = polyethylene glycol. LDPE = low density polyethylene. HDPE = high density polyethylene. N.A. = not available. cWG:Gly (15:6) w/wdWPI:Gly (2.3:1) w/w eDAS:CZ (4:1) w/w, 5%Gly, 9.3% moisture, compression molded at 113 C fCommercial product Cozeen _ 303NFgSPI:Gly (5:3) w/w, solution pH adjusted to 10 by NaOH h8% moisture, compression molded at 160 CiSPI:Gly (5:3) w/w, solution pH adjusted to 10 with NH4OH jATSPI:Gly (5:3) w/w, protein allkali-treated with NaOH, solution pH adjusted to 10 with NH OH kMSPI:PEO:LDPE (8:8:84) w/ 4 w, film extruded by twin-screw extruder

isolate (SPI) and glycerol mixtures. The films were semitransparent and light yellow in color. As expected, the properties of thermally compacted SPI films were dependent upon the plasticizer content; SPI films made without glycerol were brittle and unusable. In general, higher plasticizer content improved processability of the material and led to thinner films. Due to its high viscosity, the dispersion of glycerol among SPI molecules was determined to be a diffusion-limited process. The rate of dispersion was accelerated by intensive mixing of SPI/glycerol mixtures under controlled conditions of temperature, mixing speed, and mixing time. Films containing 30 wt% glycerol made from such intensively mixed material had average tensile strength (TS) and percent elongation (%E) values that were, respectively, 6% and 300% higher than those of films made from an unaged, manually mixed material. Also as expected, TS decreased, and %E increased with increasing glycerol levels. The mechanical properties of SPI films were comparable to those made of other biopolymers. Thus, the proposed process represents the initial development of a thermal technique for producing SPI films. If suitably scaled-up, the process may lead to a rapid technique for the production of SPI-based biopolymeric films.

FoodEngineeringandPhysicalProperties

Materials and Methods

Reagents
Soy protein isolate (PC 9000z) with an average molecular weight of 230,000 and initial moisture content of 10% to 12% was provided by Protein Technologies International, St. Louis, Mo., U.S.A. The protein was freeze-dried 24 h to obtain a final moisture content of 5% to 7% using a Virtis Freeze Dryer (The Virtis Company, Inc., Gardiner, N.Y., U.S.A.). This step was incorporated in the process to ensure consistent water content in materials mixed at various times during the experimental study. Glycerol (Fisher Scientific, Fairlawn, N.J., U.S.A.) was used as a plasticizer in the protein films.

Mixing
Soy protein was intensively mixed

with glycerol in amounts of 20, 25, 30, 35, and 40 wt% glycerol using a Brabender Plastic-Corder PL 2000 with a roller-type mixing head. The mixing was conducted at a temperature of 62 C using a mixing speed of 42 rpm. Mixing times used were 5, 10, 20, 25, and 30 min for mixtures containing 20, 25, 30, 35, and 40 wt% glycerol, respectively. These materials (henceforth referred to as intensively mixed) were processed into films within 24 to 48 h of mixing. In addition to the intensively mixed protein/glycerol mixtures, other mixtures were also investigated that were manually blended in a mortar and pestle for a period of about 10 min. These mixtures were either processed within 24 to 48 h (henceforth referred to as unaged mixture) or were aged for different times (ranging up to 6 wk) at 25 C in a poly-

ethylene storage bag (henceforth referred to as aged mixture) before being processed into films.

Production of films
Soy protein/glycerol mixtures were thermally compacted using a Carver Laboratory Press (Fred S. Carver Inc., Menomonee Falls, Wis., U.S.A.). The procedure consisted of placing about 3 g of mixture between 2 sheets of aluminum (0.34 mm thick, 60 mm wide, and 200 mm long) and then inserting the aluminum sheeting between the platens of the press heated to 150 C. A pressure of about 10 MPa (at the film) was applied for 2 min followed by the removal of the aluminum sheeting from the press and a cool-down time of 3 min. The protein film could be easily removed from the aluminum sheeting and cut to the re-

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quired gage dimensions (13 mm wide and 50 mm long) for further testing. To determine the effect of post-process aging, tensile samples were prepared using the standard processing protocol and subsequently aged for 14 wk at 25 C in sealed polyethylene bags. For impact testing, the processing conditions had to be modified slightly from those used to make tensile specimen because larger-size samples (approximately 75 mm dia) were needed for impact testing. Intensive mixing temperature and speed remained unchanged at 62 C and 42 rpm, respectively. Mixing times were also approximately the same as those described earlier. Thermal compaction conditions consisted of a processing temperature of 160 C, an applied pressure of approximately 10 MPa (at the film), and a processing time of 2 min. The samples were stored in sealed polyethylene bags in a controlled environment room at 25 C and RH of 50% for

24 h before testing.

mm/min). TS was determined at the maximum load, and %E was calculated Film thickness at break. Testing was conducted at a The thickness of tensile specimen temperature of 25 C and a relative huwas measured to the nearest 0.005 mm midity of 50%. (Digimicro ME-50HA, Nikon Corporation, Nikon, Japan) at 5 points along the Impact testing sample length between the grip lines. The films were tested at 23 C and a The thickness of impact-test specimen RH of approximately 55% using a Dynatwas measured at 9 points across the up impac t-t esting unit (model 8250, sample surface. General Research Corporation, Santa Barbara, Calif., U.S.A.). The procedure Tensile testing outlined in ASTM D 3763 was used for The tensile strength (TS) and appar- testing. The average impact velocity was ent percent elongation (%E) were calcu- 3.72 m/s. The normalized impact energy lated for soy-protein films following the was calculated by dividing the impact procedures outlined in ASTM D 638-94, energy by the average film thickness. Standard Test Method for Tensile Prop- Samples were tested within 24 to 48 h of erties of Plastics (ASTM 1995). Type I production. Measurements for TS, %E, and imspecimens were used for all tensile tests using a SATEC mechanical testing device pact testing were typically performed on (model APEX T10000, 1114 N load cell, 5 replicates. A = 0.05 significance level SATEC Systems, Inc., Grove City, Pa., (or 95% confidence level) was used for all U.S.A.) and a crosshead speed of 19.05 statistical analyses.

References
ASTM 1995. ASTM D 638-94b, Standard Test Method for TensileProperties of Plastics, Annual Book of ASTM Standards. Philadelphia: American Society For Testing and Materials. p 47-58. Aydt TP, Weller CL, Testin RF. 1991. Mechanical and barrier properties of edible corn and wheat protein films. Transactions of the ASAE 34(1):207-211. Brandenburg AH, Weller CL, Testin RH. 1993. Edible films and coating from soy protein. J Food Sci 58(5): 1086-1088. Brinston JH. 1988. Plastic films. 3rd ed. New York: Wiley. 380 p. EPA 1994. Characterization of Municipal Solid Waste in the United States: 1994 Update. Executive Summary. Washington, D.C.: United States Environmental Protection Agency, Office of Solid Waste. Gennadios A, Weller CL, Testin RF. 1993a. Property modification of edible wheat, gluten-based films. Am Soc Agri Eng 36(2):465-470. Gennadios A, Brandenburg AH, Weller CL, Testin RF. 1993b. Effect of ph on properties of wheat gluten and soy protein isolate films. J Agri Food Chem 41(11):1835-1839. Ghorpade VM, Hanna MA. 1996. Mechanical properties of soy protein-polyethylene ribbon and film extrudates. Am Soc Agri Eng 39(2):611-615. Huang HC, Hammond EG, Reitmeir CA, Myers DJ. 1995. Prop-

erties of fibers produced from soy protein isolate by extrusion and wet-spinning. J Am Oil Chem Soc 72(12):145360. Jane J, Lim S, Paetau I, Spence K, Wang S. 1994. Biodegradable platics made from agricultural biopolymers. In: Kaplan D, editor. Polymers from agricultural coproducts. Lancaster: Technomic Publishing Co. p 92-100. Jane J, Wang S, 1996. inventors. Iowa State Universitys Research Foundation Inc., Ames, Iowa, assignee. 1994 May 25. Soy protein-based thermoplastic composition for preparing molded articles. U.S. patent 5,523,293. McGrath K, Kaplan D, editors. 1996. Protein-based materials. Boston: Birkhauser. 429 p. Krohn JV, Jordy DW. 1995. Method for measuring the impact strength of heavy-gauge films. TAPPI J 78(12):167-170. McHugh TH, Krochta JM. 1994 b . Sorbitol- vs glycerol-plasticized whey protein edible films: integrated oxygen permeability and tensile property evaluation. J Agri Food Chem 42(4):841-845. Paetau I, Chen C, Jane J. 1994. Biodegradable plastic made from soybean products. 1. Effect of preparation and processing on mechanical properties and water absorption. Ind Eng Chem Res 33(7):1821-1827. Paulk JM, Ogale AA. 1995. Thermal Processing of Food Grade Proteins. Proceedings of the Annual Technical Conference, ANTEC 95; 1995. 5-9 May 1995. Boston, Mass. Brook-

field, Conn.: Society of Plastics Engineers. p 3139-3140. Roy S, Weller CL, Gennadios A, Zeece MG, Testin RF. 1999. Physical and molecular properties of wheat gluten films cast from heated film-forming solutions. J Food Sci 64(1):57-60. Spence KE. 1994. Biodegradable plastic made from dialdehyde starch and zein [Ms thesis]. Ames, Iowa: Iowa State University. 70 p. Available by interlibrary loan from Iowa State University Library. MS 19990735 received 7/21/99; revised 1/5/00; accepted 4/ 10/00. Financial support from the South Carolina Agricultural Experimental Station is gratefully acknowledged.

Authors Cunningham and Ogale are with the Department of Chemical Engineering and Center for Advanced Engineering Fibers and Films, Clemson University, Clemson, SC 29634. Authors Dawson and Acton are with the Department of Food Science, Clemson University. Direct correspondence to A.A. Ogale (E-mail: amod.ogale@ ces.clemson.edu).

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