Developing Protein-Based Plastics - ACS Publications - American

Chapter 15

Developing Protein-Based Plastics

Downloaded by UNIV OF GEORGIA on September 19, 2015 | http://pubs.acs.org Publication Date (Web): December 23, 2014 | doi: 10.1021/bk-2014-1178.ch015

David Grewell,1,* James Schrader,2 and Gowrishankar Srinivasan3 1Agricultural

and Biosystems Engineering, Iowa State University, Ames, Iowa 50011 2Horticulture, Iowa State University, Ames, Iowa 50011 3Center for Industrial Research & Service, Iowa State University, Ames, Iowa 50011 *E-mail: [email protected]

While most product development strategies are interdisciplinary in nature, products manufactured from soy-protein plastics are intensively interdisciplinary, and there is limited experience with these materials in industry. Despite the challenges, it is clear that industry recognizes the potential of protein-based materials and is strongly interested in adopting them for use in products such as horticulture pots. With success of such applications, it is expected that protein materials will be considered for many more applications. Work is progressing on soy-protein-based fibers for textile products, an application that represents a large potential market. Protein plastics will be most competitive in applications where they provide additional functions over those of petroleum plastics.

Introduction The growing need and demand for bio-renewable and biodegradable materials in the marketplace has led to continuous development and characterization of novel materials. Presently there are numerous bio-renewable, biodegradable plastics on the market, including polyesters such as polylactic acid (PLA) and polyglycolic acid (PGA) and starch based plastics that have not reached product maturity. In addition, there are bio-plastics, such as polyethylene derived from starch based bio-mass or sugars, which are not bio-degradable but have properties © 2014 American Chemical Society In Soy-Based Chemicals and Materials; Brentin; ACS Symposium Series; American Chemical Society: Washington, DC, 2014.


comparable to those of commercial petrochemical plastics. Coca-Cola produces approx. 30% of their polyethylene terephthalate (PET) bottles from biobased resources and they foresee a 100% biobased PET in the future. In the past, other bio-materials, such as protein-based plastics, were developed and tested by industrialists such as Henry Ford and George Washington Carver, but these materials were never commercialized because of the advent of petrochemical feedstocks, see Figure 1.

Figure 1. Photograph of Henry Ford testing his protein automotive body panel. (Permission 2014-2018)

There are a number of other reasons why many bioplastics have not achieved wide commercialization: they currently cost more than petroleum plastics, they have different mechanical, thermal, and chemical properties, and there are manufacturing-related issues that need to be overcome. The best way to address these issues and move toward wider utilization of sustainable biopolymers is to 358 In Soy-Based Chemicals and Materials; Brentin; ACS Symposium Series; American Chemical Society: Washington, DC, 2014.


take a multi-disciplinary approach and to address this complex problem from a multi-scale view: Starting at the molecular level, all the way to the final product concept, including all the critical pathways that contribute to a product. It is also important to include a meaningful life cycle model in order to quantify the real-world economics of bio-plastic based products, an exercise that can also help predict future trends in product consumption. A wide range of aspects must be considered throughout the development of bio-based products in order to successfully realize these products and establish them in the marketplace. Six major areas of interest are involved in this interdisciplinary approach: chemistry, material science, engineering, design, economics, and social science. The importance of each of these disciplines in the development of protein-based plastic products is detailed in the following sections.

Chemistry Because the fundamental building blocks of any material define its behavior, it is critical to fully understand the chemical composition and structure of the materials used for the manufacture of specific products (1). In the case of protein-based plastic, the fundamental building blocks are polymerized amino acids. Nature relies on approximately 21 standard amino acids to serve as building blocks (monomers) for proteins (2, 3). Both plants and animals polymerize these building blocks into short and long chains. Short chains, which typically have a molecular weight of 200-1000 g/mol, are called peptides (4). Longer chains, such as proteins, typically have molecular weights ranging from 100,000-500,000 g/mol. These proteins can function as enzymes, as energy-storage structures, or as structural components such as keratin, which is the main protein found in hair and fingernails. The functionality of proteins is not only defined by their composition, such as the type and number of monomers, but also by their conformation. For example, these long chains can form a wide range of structures when they fold on each other, creating helix and sheet conformations (see Figure 2). Often, these structures are maintained by the formation of secondary bonds, such as hydrogen bonds or by primary bonds, such as di-sulfide bonds. If these structures are reconfigured from their natural state, their functionality will also be altered. This reconfiguration is referred to as denaturing. In order to use soy proteins as the building blocks for plastic materials, their structure must be significantly denatured to unfold the conformations and linearize the molecules (5, 6), rendering them similar to traditional plastic molecules. In order to promote linearization, the protein must be dissolved in a solvent and chemically altered to break the di-sulfide bonds. Further denaturing is accomplished utilizing an extrusion process that heats the protein structure and, through shearing, results in a material that behaves similarly to a traditional petrochemical thermoplastic. The general concept of converting soy protein into plastic is shown in Figure 3. 359 In Soy-Based Chemicals and Materials; Brentin; ACS Symposium Series; American Chemical Society: Washington, DC, 2014.


Figure 2. Protein structure of a typical 11S soy protein

As will be detailed in the applications section of this chapter, it is possible and often useful to compound soy-protein plastics with other plastics to produce blended polymers. With protein plastics, blends are often used to enhance mechanical properties or water stability. Although researchers have shown that the water absorption of soy-protein plastics can be reduced from 200% to less than 20% through chemical modifications, the strength of soy-protein plastics is greatly reduced with as little as 20% water absorption. Compounding soy-protein plastics with other plastics, such as PLA, results in a relatively water resistant blend. In addition, blending with PLA and other polymers can enhance the tensile strength compared to pure soy plastic. Typically, pure soy-protein plastics have a tensile strength of 10 MPa with some reports as high as 30 MPa. Soy and PLA polymers blended at 50/50 by weight have a tensile strength well over 5 MPa.

360 In Soy-Based Chemicals and Materials; Brentin; ACS Symposium Series; American Chemical Society: Washington, DC, 2014.


Figure 3. Illustration of general steps required in producing plastic products from soy protein

While there are many possible formulations of soy-protein plastics, we will provide information on only a few of them here. Details of the compositions, recommended processing conditions, and tensile strengths of two promising soy plastics are shown in Table 1. Other formulations include soy-flour, polyethylene and/or polypropylene composites (7–9). These composites have been used to produce fibers (10) as well as rigid applications that are commercially available from BioBent (Columbus, OH).



Table 1. General soy-protein plastic formulations. Soy (SPA) Formulation

PLA/PEG Formulation

PLA/PEG/SPA Formulation

Water Stable Soy

Extrusion Temperature

90-125 °C

145-210 °C

110-145 °C

Mixed at 60 °C

Injection Molding Temperature

130 °C

145 °C

145 °C

N/A

Tensile Strength (ULT. STR.)

1.11 MPa

13.67 MPa

8.40 MPa

N/A

Stabilizer

75 g phthalic anhydride + 75 g adipic acid

Solvent

650 g water+ 150 g glycerol

Antimicrobial

10 g potassium sorbate

Di-sulfide bond opener

10 g sodium sulfite

Polymer

500 g soy flour + 500 g soy protein isolate

10mL BERSET 2700 (2.5% concentration) crosslinker 10% PEG 8000

90% PLA

355 mL water

60% PLA/PEG + 40% SPA

Material Science Once the chemistry of these protein structures is understood and proper functionality is achieved through chemical pathways, the material properties must be matched to the design requirements. Properties that require careful consideration are stiffness, strength, solvent resistance, temperature deflection, fatigue, among many others. Thus, problem-solving techniques related to material science and informatrix (11) must be applied. Initially, the base materials must be characterized and compared to the design requirements. Depending on the properties, additional chemical treatment may be required, or the properties may be tailored through the addition of fillers, such as reinforcing fibers. Alternatively, blends may be formulated with other resins. Other approaches, such as heat treatment, can be used to alter the chemical and mechanical properties. It is important to note that during the characterization and formulation stage, it is common practice to rely on the fundamental chemistry to ultimately achieve the desired material properties. In addition, it is critical that engineering aspects, such as machinability, formability, and shape stability, be considered during formulation development. For example, formulations that require long reinforcing fibers to provide sufficient strength would eliminate the possibility of processing 362 In Soy-Based Chemicals and Materials; Brentin; ACS Symposium Series; American Chemical Society: Washington, DC, 2014.

by injection molding, and formulations that have a very narrow range of thermal stability would be nearly impossible to thermoform during manufacturing. Thus, formulation and chemistry may greatly affect the engineering aspects of the material and final product.


Engineering The engineering aspects of the product, including design, manufacturing, and costs of the product are all inter-related with material properties, product characteristics, and final requirements. As previously mentioned, the chemistry and formulation of the material will dictate which manufacturing processes are amenable to the product. In addition, the properties of the formulation will influence the design of the final product by determining the material-specific design features needed to accomplish the product requirements. For example, weaker materials will require the incorporation of more rib-stiffeners and/or thicker walls into the final design in order to meet the same performance accomplished by a stronger material. Thus, a design made for a weaker material will require more raw materials and will often be more difficult to fabricate compared to a design made from a stronger material. Hence, engineering aspects are critical throughout the stages of the design process, starting with the chemical modification of the proteins, to the final design and the processing technology. For the protein-based plastics developed so far, mass production was envisioned as a fundamental concept of the design. To achieve this goal, it was considered critical that the material be suitable for injection molding. Consequently, the chemistry and formulation had to be tailored to meet the process requirements to result in a thermoplastic material that could be plasticized in an extruder.

Design One of the most difficult aspects of product development to be measured is the success of the final product design. The product must meet its defined functionality requirements and be sufficiently robust (engineered) to ensure it will not fail, but it must also be accepted by the end user. The perception of the end user can often be counter-intuitive and often is not easily defined. In order to reduce the risk of product rejection by the end user, designers incorporate qualitative aspects such as aesthetics, feel, ergonomics, and smell into the final design. In the case of protein-based plastics, a relevant case study involved an interdisciplinary team that neglected to include this critical aspect of design in a trial of soy-based protein plastics for disposable cutlery. Not only did the prototypes fail because of water solvent issues (an engineering failure), but they were also rejected by the end user because of residual odors. In short, if the end product is not properly designed to meet the expectations of the end user, the product will never successfully enter the market. 363 In Soy-Based Chemicals and Materials; Brentin; ACS Symposium Series; American Chemical Society: Washington, DC, 2014.


Economics As with any product, the economics related to protein-based plastics are among the most important aspects. Only products that create a profit will be successful. Thus, the entire product cost must be considered. These costs include the cost of the design, engineering, testing, manufacturing, distribution, marketing, and opportunity. The costs of the raw material, such as proteins and solvents, as well as the costs to process, design, etc., for a final product will define the final costs of any product. Only when the final cost of a product is equal or below the market price of an existing product, will a product be realized. However, special considerations include subsidized products or products where the market is willing to pay a premium. As an example, the public may be willing to pay a premium for organic foods. It is anticipated that a similar trend may be seen with bio-renewable, biodegradable plastics, such as protein-based plastics. Despite the fact that the raw materials of bio-plastics, such as soy-proteins, may be less appealing in terms of costs, the growing awareness of their ecological advantage may promote economic success. In addition, when considering that the energy consumption during production of protein plastics is lower than that of comparable petroleum-based products, the price of energy will greatly affect the relative costs. Also, from a holistic long-term perspective, biodegradable plastics cause less social-economic damage compared to non-degradable plastics. Considering the importance and cost of CO2 reduction, final waste treatment, and damage caused to the environment by non-degradable petroleum-based plastics, biodegradable plastics can be considered to be more economical for certain applications. The imbalance of CO2-fixation and CO2-release of petroleum-based plastics (which is 105 years vs. 1-10 years) can be reduced by using biodegradable and bio-renewable plastics, which are derived annually from renewable feedstock (12). If it is assumed that CO2 emissions are related to climate changes that result in more severe natural disasters, such as extreme droughts and flooding, then the reduced contribution of bio-based plastics to these environmental costs could arguably make protein-based plastics very cost-effective. While petroleum plastics can be incinerated with energy recovery, their use still results in the release of CO2. In addition, landfilling of these materials can result in CO2 and/or methane from microbial decomposition, depending on the plastic and conditions. In contrast, biodegradable plastics can be composted in a short time period, resulting in a final product (such as horticulture pots) that can be used for soil amendment. In addition to being a natural fertilizer, this composting can decrease ecological damage caused by wind and water erosion of agricultural areas. The cost of the feedstocks for a typical soy protein-based plastic material is less than $1/pound, making it relatively competitive with petrochemical plastics. Composites that incorporate other low-cost fillers, such as dried distillers grains with solubles (DDGS) or corn stover, will be even more cost competitive. In more detail, by using flours instead of protein isolates, it is possible to formulate base resins of soy-protein plastics with ingredient costs of approximately 0.75 $/pound, which is competitive with commodity plastics such as polyethylene and polypropylene, as seen in Table 2. 364 In Soy-Based Chemicals and Materials; Brentin; ACS Symposium Series; American Chemical Society: Washington, DC, 2014.

Table 2. Standard soy-flour plastic formulation and costs estimates (PA: phthalic anhydride, SPI: soy protein isolate) Parts

%

Price

$/lbs

SPI

50

0.26

26.1

2.36

$0.62

Soy flour/meal

50

0.26

26.1

0.28

$0.07

22.5

0.12

11.7

0.1

$0.01

PA

7.5

0.04

3.9

1.1

$0.04

Water

60

0.31

31.3

0

$0.00

1

0.01

0.5

0.9

$0.00

0.5

0.00

0.3

0.31

$0.00

Glycerin

Sodium sulfite Downloaded by UNIV OF GEORGIA on September 19, 2015 | http://pubs.acs.org Publication Date (Web): December 23, 2014 | doi: 10.1021/bk-2014-1178.ch015

Fraction

Potassium sorbate

191.5

100

$0.75

Social Science In order to determine acceptance of a product, and especially of “green” plastic products, social behavior must be considered. For example, a general question that can be asked is: “is it more socially accepted by your peers to be seen buying and using green products?” Only ergonomics and social science can address such issues. However, the assessment of social-science aspects will use assumptions from the chemistry, material science, engineering, and economical aspects to determine the social acceptance of new plastics, such as protein-based plastics. For example, it will be critical that we fully understand the impact of protein-based plastics on the world’s food supply, as well as the environmental impact of such plastics.

Applications There has been a wide range of proposed applications for products made of soy-protein plastics. Some of the most interesting examples utilize the intrinsic advantages of the soy material. One example is golf tees that can biodegrade after use and provide a fertilizing effect made available by the organic nitrogen released from the degrading protein. Another popular idea is using soy-protein plastics in dog toys that can supplement protein intake as the pet enjoys the toy. Other possible applications include disposable utensils and composite boards. Figure 4 shows applications, some of which never went to commercialization because of a variety of factors, including costs and limited mechanical performance. However, there are a few products that utilize the intrinsic advantages of the soy plastic and are currently being commercialized. One of the most interesting is the use of these materials for horticulture pots (containers) that can provide most of the fertilizer required for production of medium- and short-cycle greenhouse crops. 365 In Soy-Based Chemicals and Materials; Brentin; ACS Symposium Series; American Chemical Society: Washington, DC, 2014.


Figure 4. Proposed applications for soy-protein plastics.

Example: Bioplastic Horticulture Containers with Added Functionality Despite the environmental problems related to the use of petroleum plastics for single-use items, the use of petroleum-based plant containers is ubiquitous in the container-crops horticulture industry because plastic is vastly superior in meeting the functional requirements of the application. Although this is the reality of the industry, both the horticulturists and their customers are becoming less and less tolerant of non-sustainable growing practices. Lowering environmental impact of growing systems has become a major priority. Protein-based plastics have attracted much attention for use in horticultural plant containers because there is potential for the protein plastics to fulfill all of the functions met by petroleum plastics, while making a much lower environmental impact. In addition, protein can provide the added function of supplying some or most of the fertilizer required for the growing plant (13). In early efforts to utilize protein-based plastics for plant containers, researchers hoped to tap into an underused byproduct of the poultry industry by using keratin from poultry feathers (14). Evaluations of the material were promising, but the use of keratin polymer for plant containers has not gained momentum, mainly due to the high cost of development and the low profit margin for the application (15). Another protein that was investigated for use in biobased plant containers that can provide fertilizer is zein protein from corn. Prototypes of zein-based plant containers provided a very strong nitrogen-fertilizer effect that was excessive for healthy plant growth (16, 17), indicating that use of zein plastic 366 In Soy-Based Chemicals and Materials; Brentin; ACS Symposium Series; American Chemical Society: Washington, DC, 2014.


for this application would require either blending with a high-carbon polymer to lower the concentration of zein and maintain a suitable carbon-nitrogen ratio or the development of some other mechanism to slow the release of nutrients. Efforts to develop and evaluate soy-based bioplastics for horticultural containers have been strongly interdisciplinary from the beginning, and all of the important considerations listed earlier (chemistry, materials science, economics, social science, etc.) have been major components of the development process. Early results with high-content soy-protein plastics showed an excessive fertilizer effect similar to that of zein, and they also indicated that the material cost for a container made of high-content soy protein would be prohibitive. The next phases of development improved these two issues by formulating a soy-based polymer that included soy flour (lower nitrogen content and lower cost than soy protein isolate) and by evaluating blends of the new soy polymer with carbon-rich biopolymers, including PHA, PLA, and polyamide (18). It was found that blends of PLA/soy and PLA/soy/DDGS provided a balanced fertilizer effect that could significantly reduce the amount of synthetic fertilizer needed for the culture of short- and medium-cycle greenhouse crops (19). Blending these materials resolved many of the issues that made the materials unsuitable for this application when used alone. The soy component provided the plant-available nitrogen source for the fertilizer effect and improved the biodegradability of the used container. The PLA provided strength, durability, carbon-nitrogen balance, and effectively controlled the rate of nitrogen release from the container (20). The DDGS incorporated in some of the formulations helped reduce cost and appeared to balance the nutrient ratios. At each stage of development and evaluation of soy-based plant containers, the composite blends were tested for physical properties, biodegradation rate, performance under application conditions (greenhouse trials), cost of materials, effectiveness of the added function (fertilizer effect), improvements in sustainability, aesthetic appeal, ease of processing, and consumer impression. The results of this interdisciplinary approach provided a soy-based plant container that is cost competitive with petroleum-based containers, especially when the added fertilizer function is considered. The PLA/soy composite container reduced the amount of synthetic fertilizer required to grow an ornamental greenhouse crop like marigold by 87% compared to plants grown in a standard petroleum-based container (see Figure 5), and the amount of fertilizer required to grow a tomato transplant was reduced by 44%. The savings achieved by this added function are realized in thee ways: 1) reduced cost for fertilizer, 2) reduced cost for labor to apply the fertilizer, and 3) reduced environmental impact by the replacement of synthetic fertilizer with the natural fertilizer nutrients from soy. Unlike synthetic nitrogen fertilizer, which is energy intensive and produced by the Haber-Bosh process (21), the nitrogen available from the soy-based plastics comes from natural, biological nitrogen fixation performed in the roots of the soybean plant and is fueled by natural photosynthesis. Along with the reduction in fertilizer cost, the improvement in sustainability afforded by the plant-derived, soy-based nitrogen fertilizer is remarkable. Compared to synthetic fertilizers, the utilization of plant-derived nitrogen fertilizer such as that from soybean uses 7.9 times less energy and causes 6.4 times less global-warming impact, 935 times 367 In Soy-Based Chemicals and Materials; Brentin; ACS Symposium Series; American Chemical Society: Washington, DC, 2014.


less ozone depletion, and 1.8 times less acidifying emissions (22). The use of PLA/soy composites for this application provides a substantial improvement in sustainability by both replacing the fossil-based polymer with a bio-renewable polymer that is biodegradable (23), and by greatly reducing environmental impact through its added function, its intrinsic bio-derived fertilizer.

Figure 5. Marigold plants grown with 87% less synthetic fertilizer than the standard protocol. Plants grown in the control treatment (left, petroleum-based polypropylene container) and in the PLA/soy composite container (right) were provided with the same amount of fertilizer, 100 parts-per-million nitrogen during the first two weeks only. The fertilizer effect of the PLA/soy container is readily apparent, and the plant grown in this container is of better quality than those produced by standard protocols.

Summary While most product development strategies are interdisciplinary in nature, products manufactured from soy-protein plastics are intensively interdisciplinary. Because of the relatively limited experience with these materials in industry, they prove extraordinarily challenging. As they become more common and industry gains more experience, these challenges will diminish, but interdisciplinary development will continue to be an important aspect of efforts to maximize the potential of these materials. Despite the challenges, it is clear that industry recognizes the potential of protein-based materials and is strongly interested in adopting them for use in products such as horticulture pots. With success of such 368 In Soy-Based Chemicals and Materials; Brentin; ACS Symposium Series; American Chemical Society: Washington, DC, 2014.

applications, it is expected that protein materials will be considered for many more applications. Work is progressing on soy-protein-based fibers for textile products, an application that represents a large potential market. In addition, soy-flour composites, such as those from Biobent, are a growing market that demonstrates the increasing importance of these materials. Protein plastics will be most competitive in applications where they provide additional functions over those of petroleum plastics.


References 1.

Harding, K. G.; Dennis, J. S.; Von Blottnitz, H.; Harrison, S. T. L. Environmental analysis of plastic production processes: Comparing petroleum-based polypropylene and polyethylene with biologically-based poly-β-hydroxybutyric acid using life cycle analysis. J. Biotechnol. 2007, 130 (1), 57–66. 2. Locks, J. Properties and applications of compostable starch-based plastic material. Polym. Degrad. Stab. 1998, 59 (1−3), 245–249. 3. Rosentrater, K. A.; Otieno, A. W. Considerations for manufacturing biobased plastic products. J. Polym. Environ. 2006, 14 (4), 225–346. 4. Campbell, M. K.; Farrell, S. O. Biochemistry; Cengage Learning: 2001. 5. Achouri, A.; Zhang, W.; Xu, S. Enzymatic hydrolysis of soy protein isolate and effect of succinylation on the functional properties of resulting protein hydrolysates. Food Res. Int. 1999, 31 (9), 617–623 (Volume Date 1998). 6. Kalapathy, U.; Hettiarachchy, N. S.; Rhee, K. C. Effect of drying methods on molecular properties and functionalities of disulfide bond-cleaved soy proteins. J. Am. Oil Chem. Soc. 1997, 74 (3), 195–199. 7. Liu, B.; Jiang, L.; Liu, H.; Zhang, J. Synergetic Effect of Dual Compatibilizers on in Situ Formed Poly(Lactic Acid)/ Soy Protein Composites. Ind. Eng. Chem. Res. 2010, 49, 6399–6406. 8. Su, J.-F.; Yuan, X.-Y.; Xia, W.-L. Properties stability and biodegradation behaviors of soy protein isolate/poly(vinylalcohol)blend films. Polym. Degrad. Stab. 2010, 95, 1226−1237. 9. Song, L.; Zhi, J.; Zhang, P.; Zhao, Q.; Li, N.; Qiao, M.; Liu, J. Synthesis and characterization of a new soy protein isolate/Polyamic acid salt blend films. J. Food Sci. Technol. 2014, DOI: 10.1007/s13197-014-1349-z. 10. Ozdemir, O.; Lukubira, S.; Ogale, A.; Dawson, P. Fabrication and Analysis of Soy Flour Filled Polyethylene Fibers. Presented at Graduate Research and Discovery Symposium (GRADS), 2014; Paper 100. 11. Domenek, S.; Morel, M.-H.; Redl, A.; Guilbert, S. Thermosetting of wheat protein based bioplastics: modeling of mechanism and material properties. Macromol. Symp. 2003, 197, 181–191 (7th World Conference on Biodegradable Polymers & Plastics). 12. Narayan, R.Drivers for Biodegradable/Compostable Plastics & Role of Composting in Waste Management & Sustainable Agriculture; 2001.



13. Schrader, J. A.; Srinivasan, G.; Grewell, D.; McCabe, K. G.; Graves, W. R. Fertilizer effects of soy-plastic containers during crop production and transplant establishment. HortScience 2013, 48, 724–731. 14. Evans, M. R.; Hensley, D. L. Plant growth in plastic, peat, and processed poultry feather fiber growing containers. HortScience 2004, 39, 1012–1014. 15. Kuack, D.. From coop to container to consumer. HRI News; 2012. www.hriresearch.org/index.cfm?page=Content&categoryID=157&ID=894. 16. Helgeson, M. S.; Graves, W. R.; Grewell, D.; Srinivasan, G. Degradation and nitrogen release of zein-based bioplastic containers. J. Environ. Hortic. 2009, 27, 123–127. 17. Helgeson, M. S.; Graves, W. R.; Grewell, D.; Srinivasan, G. Zein-based bioplastic containers alter root-zone chemistry and growth of geranium. J. Environ. Hortic. 2010, 27, 123–127. 18. Grewell, D.; Srinivasan, G.; Schrader, J.; Graves, W.; Kessler, M. Sustainable materials for a horticultural application. Plast. Eng. 2014, 70 (3), 44–52. 19. Currey, C.; Schrader, J.; McCabe, K.; Graves, W.; Grewell, D.; Srinivasan, G.; Madbouly, S. Bioplastics for greenhouses –Soy what? GrowerTalks 2014, 77 (9), 70–74. 20. Currey, C.; Schrader, J.; McCabe, K.; Graves, W.; Grewell, D.; Srinivasan, G.; Madbouly, S. Soy containers: Growing promise, growing plants. GrowerTalks 2014, 77 (10), 60–65. 21. Pelletier, N.; Audsley, E.; Brodt, S.; Garnett, T.; Henriksson, P.; Kendall, A.; Jan Kramer, K.; Murphy, D.; Nemecek, T.; Troell, M. Energy Intensity of Agriculture and Food Systems. Annu. Rev. Environ. Resour. 2011, 36, 223–246. 22. Pelletier, N.; Arsenault, N; Tyedmers, P. Scenario modeling potential eco-efficiency gains from a transition to organic agriculture: life cycle perspectives on Canadian canola, corn, soy, and wheat production. Environ. Manage. 2008, 42 (6), 989–1001. 23. Groot, W.; Borén, T. Life cycle assessment of the manufacture of lactide and PLA biopolymers from sugarcane in Thailand. Int. J. Life Cycle Assess. 2010, 15 (9), 970–984.


Developing Protein-Based Plastics - ACS Publications - American

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