10.1002/spepro.

000065

Material characterization of novel bioplastics for food packaging

Sunny Modi, Kurt Koelling, and Yael Vodovotz Composite polymers based on bioresins have attractive advantages, but require additional research for use in foodstuff industries. Petroleum-based resins (thermoplastics) are used in many foodpackaging applications. However, the recent oil shortage, concern regarding the formation of greenhouse gases, and the saturation of landll sites with thermoplastic waste has steered research toward the development of green polymeric materials, such as polyhydroxybutyrates (PHBs). These high-molecular-weight polyesters are produced by a broad spectrum of microorganisms and have characteristics similar to those of conventional thermoplastics. However, the commercial use of PHBs is limited by availability and cost. Furthermore, PHB homopolymers have narrow processing temperatures due to degradation and brittleness at room temperature.1, 2 Therefore, initial material characterization, such as exibility at desired temperatures, gas and water permeability, and thermoforming capability, is needed to assess the feasibility of using PHB-based bioplastics for food-packaging applications.3 There are various methods for improving the thermal, mechanical, and rheological (ow) properties of PHB. For example, one technique incorporates 3-hydroxyvalerate (HV) during the fermentation process, which results in a lower melting point of the copolymer, broadens the processing window, improves the melt stability, and decreases brittleness. We characterized various properties of PHB synthesized with different valerate contents (5, 12, and 20%) and related these properties to potential food-packaging applications. Polyhydroxybutyrate-valerate (PHBV) with 5 and 12% HV content (Sigma-Aldrich, Milwaukee, WI) and PHBV 5 and 20% HV content (Tianan Biologic Material Co., Ltd., China) were used to perform the experiments. Currently, Tianan 5% is available in bulk quantities and Tianan 20% is still in development, while available quantities of Sigma-Aldrich PHBV are limited. Differential scanning calorimetry (DSC) and rheology were used to characterize the material properties of the polymers by assessing

Figure 1. Differential scanning calorimetry (DSC) melting transition scans of PHBV at 10 C/min (rst melting behavior). T: Tianan. A: Aldrich.

Figure 2. DSC melting transition scans of PHBV at 10 C/min (second melting behavior).

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Table 1. Average thermal parameters of PHBV. Crystallization transition Tpc ( C) 66.1 * * * Melting transitions (rst melting) Tpm1 ( C) Tpm2 ( C) 132 171 171 143 156 166 Glass transitions (second melting) Teig ( C) Tmg ( C) 3.1 0.05 2.6 4. 7.4 2.7 0.89 2.0 Melting transitions (second melting) Tpm1 ( C) Tpm2 ( C) 130 163 165 149 158 144 159

Tianan 20% Tianan 5% Aldrich 12% Aldrich 5%

*Material did not show results during rst heating. Teig : Extrapolated onset temperature. Tmg : Midpoint temperature. Tpm : Melting peak temperature.

Figure 3. DSC glass-transition scans of PHBV at 20 C/min (second melting behavior).

Figure 4. Complex viscosity-frequency sweeps of four PHBV materials at 150 C. Pa: Pascals. rad: Radians.

phase-transition temperatures that dene the crystalline, melting, glass/rubber, and ow behaviors. Table 1 summarizes the phase transitions observed with the crystallization and melting temperatures obtained from thermograms of the rst heating cycle (see Figure 1). The melting temperatures obtained ranged from 132 to 171 C. The higher HV content appeared to give two melting transitions to Aldrich 12% (143 and 156 C) and Tianan 20% (132 and 171 C). The presence of two or more melting transitions can be attributed to crystal thickening or recrystallization that occurs during the DSC heating cycle.4 The 5% PHBV samples had a uniform melting behavior at 171 C. The Aldrich 5% sample resulted in a broader melting peak ranging from 130 to 166 C. When the rst heating runs were compared to rescan thermograms, some sample degradation was observed after they were kept isothermally at 200 C for 5min (see Figure 2). Signicant changes in melting behaviors were observed for Tianan 20% and Aldrich 5% and 12%, with the materials showing two melting transitions. The

Figure 5. Complex viscosity-frequency sweeps of four PHBV materials at 160 C.

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Author Information Sunny Modi The Ohio State University Columbus, OH Sunny Modi is a graduate student working on his MSc. He received his undergraduate degree in food science and technology from the University of Georgia. Currently, his research explores bioresins for food packaging in place of petroleum-derived plastics. Kurt Koelling Department of Chemical and Biomolecular Engineering The Ohio State University Columbus, OH Kurt Koellings research interests include the rheology and processing of complex uids, including polymer melts and solutions as well as carbon nanotube and nanoplate polymer composites. He is codirector of the Center for Advanced Polymer and Composite Engineering. Yael Vodovotz Department of Food Science and Technology The Ohio State University Columbus, OH Yael Vodovotz researches the physical and chemical properties of food materials to enable product developers to tailor formulations to increase the shelf life, quality, bioactive delivery, and acceptability of food.
References 1. B. M. P. Ferreira, C. A. Zavaglia, and E. A. R. Duek, Films of PLLA/PHBV: thermal, morphological, and mechanical characterization, J. Appl. Polym. Sci. 86 (11), p. 2898, 2002. 2. L. Chen, M. Zhu, L. Song, H. Yu, Y Zhang, Y. Chen Adler, and H. J. C. Long, Crystallization behavior and thermal properties of blends of poly(3-hydroxybutyrateco-3-valerate) and poly(1,2-propandiolcarbonate), J. Macromol. Symp. 210 (1), pp. 241250, 2004. 3. C. J. Weber (ed.), Biobased Packaging Materials for the Food Industry, p. 4, Royal Veterinary and Agricultural University, Frederiksberg, Denmark, 2000. 4. H. Verhoogt, B. A. Ramsay, B. D. Favis, and J. Ramsay, The inuence of thermal history on the properties of poly (3-hydroxybutyrate-co-12%-3-hydroxyvalerate), J. Appl. Polym. Sci. 61 (11), p. 87, 1996.

Figure 6. Complex viscosity-frequency sweeps of four PHBV materials at 170 C.

lower melting peak closely represents the original unannealed crystal behavior.4 The melting peak at 150 C resulted from a crystal size similar to that of HV, and at about 170 C from a crystal size similar to that of PHB.2 The second heating cycle was used to determine glass transitions, and all PHBV materials displayed a glass transition between 10 and 20 C (see Figure 3). The melt rheology is shown in Figures 4 6. The results suggest a more severe degradation of samples as the complex viscosity decreased versus the frequency around the polymers melting temperature. The Aldrich 5% material showed severe degradation as temperatures increased, and the complex viscosity decreased by ve orders of magnitude. In summary, the use of PHBV bioresin for food-packaging applications has been limited due to its performance, processing, and cost compared to traditional thermoplastics. The PHBV copolymers (Aldrich 5 and 12%, and Tianan 20%) show two melting transitions, suggesting an immiscible blend between the PHB homopolymer and HV comonomer. The rheological data showed that the Tianan 5% polymer is thermally unstable at temperatures higher than 160 C because of random-chain polymerization that causes the longer polymer chains to break down. Additional studies under way in our laboratory aim to improve the exibility of bioplastics using PHBV. The authors would like to thank Tianan Biologic Material Co., Ltd., China, for supplying raw materials and technical assistance. This work was supported by Institute for Materials Research and Center for Advanced Processing and Packaging Studies grants through Ohio State Universitys research foundation.

c 2009 Society of Plastics Engineers (SPE)