Bioabsorbable Soy Protein Plastic Composites: Effect of Polyphosphate Fillers on Biodegradability

The use of biodegradable polymers made from renewable agricultural products such as soy protein isolate has been limited by the tendency of these materials to absorb moisture. A straightforward approach for controlling the inherent water absorbency of the biodegradable polymers involves blending special bioabsorbable polyphosphate fillers, biodegradable soy protein isolate, plasticizer, and adhesion promoter in a high-shear mixer followed by compression molding. The procedure yields a relatively water-resistant, biodegradable soy protein polymer composite, as previously reported. The aim of the present study is to determine the biodegradability of the new polyphosphate filler/soy protein plastic composites by monitoring the carbon dioxide released over a period of 120 days. The results suggest that the composites biodegrade satisfactorily, with the fillers having no significant effect on the depolymerization and mineralization of the soy protein plastic, processes that would otherwise result in nonbiodegradable composites. Further, the results indicate that the biodegradation and useful service life of these biocomposites may be controlled by changing the filler concentration, making the biocomposites useful in applications in which the control of water resistance and biodegradation is critical.     

Processing and Characterization of Glycerol-Plasticized Soy Protein Plastics Reinforced with Citric Acid-Modified Starch Nanoparticles

Citric acid-modified starch nanoparticles with an average size of 82 nm were prepared through precipitation from gelatinized starch solution by ethanol and further modification with citric acid. When being incorporated in glycerol-plasticized soy protein plastics, citric acid-modified starch nanoparticles displayed dramatic reinforcing effect. The resulted nanocomposite plastics exhibited improvement in mechanical performance. Also, the water uptake decreased, indicating an increase of water resistance. The modified starch nanoparticles had a good compatibility with soy protein matrix. Possessing a relative hydrophobic surface, the filler would prefer to interact with protein-rich domains in glycerol-plasticized soy protein. The work provided a green approach of biodegradable materials based on naturally occurring biopolymers.     

Thermal and Mechanical Properties of Plastics Molded from Sodium Dodecyl Sulfate-Modified Soy Protein Isolates

Soybean protein is a potential material for manufacturing of biodegradable plastics. The objective of this investigation was to characterize the thermal and mechanical properties of plastics made from sodium dodecyl sulfate (SDS)-modified soy proteins. Soy protein isolate (SPI) was prepared from defatted soy flour, modified with various concentrations of SDS, and then molded into plastics. The temperatures of denaturation of the modified soy protein increased at low SDS concentration and then decreased at high SDS concentration. At the same SDS concentration, the plastics molded from the modified soy proteins showed a similar temperature of denaturation, but a lower enthalpy of denaturation compared to the modified soy protein. Young's modulus of the plastics decreased as SDS concentration increased, and the tensile strength and strain at break of the plastics reached a maximum value at 1% SDS modification. Two glass transition temperatures were identified corresponding to the 7S and 11S globulins in SPI by dynamic mechanical analysis, and they decreased as SDS concentration increased. The SDS modification increased the water absorption of the plastics.     

Modification of Soy Protein Plastic with Functional Monomer with Reactive Extrusion

Chemical modification of soy protein with monomers such as maleic anhydride, glycidyl methacrylate and styrene was accomplished using reactive extrusion technology. Thermal and mechanical properties of the modified soy protein plastics were characterized with differential scanning calorimetry (DSC), a dynamic mechanical analyzer (DMA) and a United Testing System load frame. It was found that the denaturation temperature and the glass transition temperature of soy protein plastic changed. In addition, the tensile properties of modified soy protein plastic improved. Attenuated total reflection Fourier transform infrared (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS) were used to characterize the structure of modified soy proteins. A suggestion of the interaction between soy protein and functional group in functional polymers is given. Through the in-situ interaction between the polymer and soy protein plastic, the mechanical properties of the soy protein plastic can be adjusted and controlled.     

A study on engineering characteristics of asphalt concrete using filler with recycled waste lime

This study focuses on determining the engineering characteristics of asphalt concrete using mineral fillers with recycled waste lime, which is a by-product of the production of soda ash (Na(2)CO(3)). The materials tested in this study were made using a 25%, 50%, 75%, and 100% mixing ratio based on the conventional mineral filler ratio to analyze the possibility of using recycled waste lime. The asphalt concretes, made of recycled waste lime, hydrated lime, and conventional asphalt concrete, were evaluated through their fundamental engineering properties such as Marshall stability, indirect tensile strength, resilient modulus, permanent deformation characteristics, moisture susceptibility, and fatigue resistance. The results indicate that the application of recycled waste lime as mineral filler improves the permanent deformation characteristics, stiffness and fatigue endurance of asphalt concrete at the wide range of temperatures. It was also determined that the mixtures with recycled waste lime showed higher resistance against stripping than conventional asphalt concrete. It was concluded from various test results that a waste lime can be used as mineral filler and, especially, can greatly improve the resistance of asphalt concrete to permanent deformation at high temperatures.     

Tensile Strength, Elongation, Hardness, and Tensile and Flexural Moduli of PLA Filled with Glycerol-Plasticized DDGS

Rapid growth of the biofuel industry is generating large amounts of coproducts such as distillers dried grains with solubles (DDGS) from ethanol production and glycerol from biodiesel. Currently these coproducts are undervalued, but they have application in the plastics industry as property modifiers. The objective of this research effort is to quantify the effects on mechanical properties of adding DDGS and glycerol to polylactic acid (PLA). The methodology was to physically mix DDGS, as filler, with PLA pellets and injection mold the blends into test bars using glycerol as a plasticizer. The bars were subject to mechanical testing procedures to obtain tensile strength, tensile and flexural moduli, elongation to break, and surface hardness of blends from 0 to 90?%, by weight, of plasticized filler. Blends were typically relatively brittle with little or no yielding prior to fracture, and the addition of glycerol enabled molding of blends with high levels of DDGS but did not increase strength. Any presence of filler decreased the tensile strength of the PLA, and 20?C30?% filler reduced strength by 60?%. The 35?C50?% filled PLA had about one-fifth the value for pure PLA; at 60?C65?% filler level, about 10?% tensile strength remained; and over 80?% filler, 95?% of the strength was lost. Over 20?% filler, the tensile modulus decreased. The 35?% plasticized, filled blend yielded about one-half the stiffness as the pure PLA case; flexural modulus trended in the same manner but demonstrated a greater loss of stiffness. Most blends had less than 3?% elongation to break while surface hardness measurements indicated that up to 60?% filler reduced Shore D hardness by less than 20?%. The tensile strength and modulus data are consistent with the findings of other researchers and indicate that the type of filler and amount and sequence of plasticization are secondary effects, and the total PLA displaced is the dominant factor in determining the mechanical strength of the PLA and DDGS blends. Up to 65?% plasticized DDGS filler can be injection molded, and sufficient mechanical strength exists to create a variety of products. Such a novel material provides higher-value utilization of the biofuel coproducts of glycerol and DDGS and maintains the biodegradable and biocompatible nature of PLA.     

Characterization of poly(lactic acid) biocomposites filled with chestnut shell waste

The aim of this study was to determine thermal and mechanical properties and applicability of ground chestnut shell waste as a filler for poly(lactic acid) composites. The used amount of filler was ranging from 2.5 to 30 wt%. Spectroscopic analysis of composites and its ingredients was conducted by means of FT-IR method. The mechanical and thermal properties of the composites were determined in the course of static tensile test, Dynstat impact strength test, DMTA analysis, and DSC method. The fractured surface morphology of biocomposites was evaluated by SEM analysis. Incorporation of the filler influenced the overall mechanical properties of the composites characterized by high stiffness and lowered impact resistance. Fabricated composites with different amounts of non-reactive natural waste filler exhibited acceptable mechanical and thermal properties. Therefore, these composites can be used as eco-friendly, biodegradable materials for low-demanding applications.     

Tensile Strength, Elongation, Hardness, and Tensile and Flexural Moduli of Injection-Molded TPS Filled with Glycerol-Plasticized DDGS

Continuing growth of biofuel industries is generating large amounts of coproducts such as distillers dried grains with solubles (DDGS) from ethanol production and glycerol from biodiesel. Currently these coproducts are undervalued, but they have application in the plastics industry as property modifiers. This research effort has quantified the effects on mechanical properties of adding DDGS and glycerol to a commercial thermoplastic starch (TPS). The methodology was to physically mix DDGS, as filler, with the TPS pellets and injection mold the blends into test bars using glycerol as a processing aid. The bars were then mechanically tested with blends from 0 to 65 %, by weight, of plasticized filler. The test bars were typically relatively brittle with little yielding prior to fracture with elongation between 1 and 3 %. The addition of glycerol enabled molding of blends with high levels of DDGS but did not increase strength. Any presence of filler decreased the tensile strength of the starch, and up to 30 % filler, the tensile strength drops about 15 %. The 20 and 50 % blends (without glycerol) have slightly greater stiffness than pure starch. With some other blends, the presence of plasticized filler degrades the tensile modulus with 35 % filler yielding about 1/3 the stiffness. Changes in the flexural modulus are much more pronounced as 20–25 % filled TPS has a 30 % increase in flexural stiffness. In terms of surface hardness, blends up to 60 % filler are within 20 % of the TPS baseline.     

Utilization of limestone dust waste as filler in natural rubber

The possibility of using limestone dust waste (LDW) as a filler in natural rubber (NR) was investigated. First, the basic properties of LDW were characterized; LDW was then incorporated into NR and the compound properties were determined. Comparison of the reinforcing effect of LDW and other commercial fillers such as light-precipitated calcium carbonate (PCC) and nanoprecipitated calcium carbonate (NPCC) was made. The results revealed that even though the addition of LDW has little effect on compound processability, it has a negative effect on most mechanical properties, e.g., tensile strength, tear strength, and abrasion resistance, of the vulcanizate. Among the three fillers, the degree of reinforcement could be placed in the following order: NPCC > PCC > LDW. Due to their relatively low specific surface area and thus low reinforcement ability, both LDW and PCC can be grouped as nonreinforcing fillers, whereas NPCC, the specific surface area of which is relatively high, could be grouped as a semi-reinforcing filler for rubber.     

Processing and Physical Properties of Plastics Made from Soy Protein Polyester Blends

Blending soy protein with polyesters using a polyvinyllactam as a compatibilizer successfully made soy protein-based plastics. The polyesters used to produce blends included polycaprolactone (PCL) and Biomax (a commercial biodegradable polyester). The blends were processed by compounding extrusion and injection molding. Blends containing soy protein/Biomax-poly(vinyl alcohol) had tensile strengths ranging from 16–22 MPa, with samples containing larger percentages of the synthetic polymer exhibiting greater strengths. Blends made from soy protein, Biomax, and PCL had tensile strengths ranging from 27–33 MPa. All the blends had high Young's moduli but demonstrated brittle characteristics as evident from their low elongations at break, ranging from 1.8–3.1%. Plastics made from soy protein/polyester blends exhibited low water absorption and had good stability under ambient conditions relative to the plastics made from soy protein alone. Blends made from soy protein flour produced plastics with the lowest water absorption.     

Viscosity of Soy Protein Plastics Determined by Screw-Driven Capillary Rheometry

Soy protein plastics are a renewable, biodegradable alternative to fossil fuel-based plastic resins. Processing of soy protein plastics using conventional methods (injection molding, extrusion) has met with some success. Viscosities of processable formulations that contain soy protein along with the necessary additives, such as glycerol and cornstarch, have not been reported, but are necessary for extrusion modeling and the design of extrusion dies. Resins consisting of soy protein isolate-cornstarch ratios of 4:1, 3:2, and 2:3 were plasticized with glycerol and soy oil, compounded in a twin screw extruder and adjusted to 10% moisture. The effects on viscosity of added sodium sulfite, a titanate coupling agent and recycling were evaluated using a screw-driven capillary rheometer at shear rates of 100–800/s. The viscosities fit a power-law model and were found to be shear thinning with power-law indices, n, of 0.18–0.46 and consistency indices, m, of 1.1 × 10⁴–1.0 × 10⁵. Power-law indices decreased and consistency indices increased with increasing soy protein-to-cornstarch ratio and in the absence of sodium sulfite. Addition of the titanate coupling agent resulted in increased power-law index and decreased consistency index. Viscosities at a shear rate of 400/s decreased with recycling, except for the 4:1 soy protein isolate to cornstarch formulation, which displayed evidence of wall slip. Power-law indices were unaffected by recycling. Viscosities in the tested shear rate range were comparable to polystyrene and low-density polyethylene indicating soy protein plastics are potential drop-in replacements for commodity resins on conventional plastics processing equipment.     

Injection Molded Wheat Straw and Corn Stem Filled Polypropylene Composites

Environmentally friendly composite materials can be prepared using wood fibers and/or various types of agro-derived fibers as reinforcements. In this study, agro-residues such as wheat straw and corn stem filled polypropylene were prepared and their suitability was investigated as a reinforcing filler in thermoplastics and as an alternative to the wood flour filled plastics. Effect of compounding techniques, compatibilizer and fungal treatment of agro-residues on the mechanical properties of the composites were evaluated. It was found that high shear compounding of wheat straw fibers exhibited similar properties to that produced by the milled wheat straw. This may be due to the extensive fiber breakage occurred during the high shear compounding that results in a similar aspect ratio to that of milled straw. Compatibilizer is needed for improving the strength properties of the agro-residue filled PP composites. Fungal treatment of milled wheat straw did not show much improvement in the strength properties of the composites. Comparison of mechanical properties of the agro-residue filled PP with that of the wood flour and the old newsprint filled PP showed the suitability of the agro-residues as alternative filler for thermoplastics.     

Fabrication and Properties of Acid Treated Carbon Nanotubes Reinforced Soy Protein Nanocomposites

Acid treated multiwalled carbon nanotubes (MWNTs) were incorporated into glycerol plasticized soy protein to form MWNTs/soy protein nanocomposite plastics. The influence of the polar groups grafted on carbon nanotubes by acid treatment on the compatibility would be studied. The results showed that aggregation of carbon nanotubes was reduced by acid treatment and some polar groups were grafted on the nanotubes. The modified MWNTs were dispersed in soy protein matrix homogeneously and exhibited good compatibility with soy protein matrix. The crystalline structure of soy protein was not changed by MWNTs. The mechanical properties were dramatically enhanced through MWNTs incorporation due to the strong hydrogen bonding between them and the homogeneously dispersion of MWNTs in protein matrix, indicating the reinforcing effect of MWNTs in soy protein matrix. The water uptake was reduced and the thermal stability was enhanced by MWNTs incorporation.     

Development and Application of Green Composites: Using Coffee Ground and Bamboo Flour

Environmental degradation and global warming are increasing as a result of the use of petroleum. Therefore, many industries are seeking more eco-friendly materials that will decrease the level of environmental contamination and economic cost. Recently, the level of coffee consumption has increased rapidly. Therefore, the amount of coffee grounds discarded is increasing. In this study, polylactic acid, coffee grounds and bamboo flour were compounded for green composites. Coffee grounds are used in the recycling of food waste. In addition, 4,4-methylene diphenyl diisocyanate (MDI) was used as a coupling agent. The mechanical strength of green composites decreased with increasing natural filler content. However, mechanical and thermal properties were increased by the addition of MDI as a coupling agent. The hydroxyl groups of natural fillers reacted with the isocyanate group of MDI, and a urethane linkage was created between the polymer and natural fillers.     

Effects of Storage Time on Properties of Soybean Protein-Based Plastics

Soybean protein has been considered as a potential biodegradable polymer in the manufacture of plastics. The purpose of this investigation was to characterize the effect of storage time on thermal and mechanical properties of soybean protein isolate (SPI) plastics. SPI was separated from defatted soy flour, modified with 1M or 2M urea, or plasticized with glycerol, and compression molded into plastics. Plastic made from SPI alone was used as a control. For all SPI plastics, glass transition temperatures and dynamic storage modulus increased and loss tangent decreased during storage. Excess enthalpy of relaxation of all SPI plastics had an exponential relationship with storage time, indicating a fast aging rate at the beginning of storage. All SPI plastics tended to be stiff and brittle during storage. The plastics with glycerol had the slowest aging rate and were fairly stable after 60 days, with about 8.8 MPa tensile strength and 168% strain at break. Plastics with the 2M urea-modification SPI also had a slow aging rate and became relative stable after 60 days, with about 10 MPa tensile strength and 72% elongation.     

Water Aided Fabrication of Whey and Albumin Plastics

Development of polymeric materials that can reduce the reliance on petroleum derived synthetic polymers involves biopolymers such as proteins, starch, cellulose and lipids which can be obtained as agricultural co-products or by-products. Specifically, bioplastics from protein feedstock may have significant advantages over traditional plastics, especially in areas such as packaging, agriculture, horticulture and medical materials. This article focuses on fabricating plastics from whey and albumin proteins and describing properties of plastics made from them. These protein biomasses were plasticized using water and compression molded into plastic samples. Results indicated the importance of water on plasticization during fabrication and on mechanical performance later due to densification during drying.     

Study of Graft Copolymerization of Soy Protein-Methyl Methacrylate: Preparation and Characterization of Grafted Films

Hybrid materials represent the family of compounds comprising mixtures of natural and synthetic materials. The study of this field is in a marked expansion since their preparation represents a valid methodology for optimizing the insufficient properties exhibited by materials integrally formed from naturally-occurring sources. In the present work, we describe soy protein modification by grafting reaction with methyl methacrylate. The reaction was confirmed by Fourier Transform Infrared Analysis and Carbon Nuclear Magnetic Resonance. In addition, films were prepared with the material by heat compression. Films were physically and mechanically characterized by determining contact angle with water, total soluble matter, moisture content, swelling in water, water vapor permeability, tensile strength, elongation at break and Young’s modulus. These measurements suggest that the material increased its hydrophobic character as compared with that of the control film since marked reductions in water vapor permeability, swelling and water solubility were determined. Moreover, their mechanical properties were improved by obtaining a more rigid material. These results represent an interesting advance in the preparation of hybrid biocomposites.     

An Overview on the Mechanical Behaviour of Biodegradable Agricultural Films

The mechanical behavior of various types of biodegradable materials depends, mainly, on their chemical composition and the application conditions. Various additives are added into the bioblends to improve their properties, which sometimes even reach the levels of the conventional plastics. It is well known that the environmental conditions during production, storage, and usage of these materials influence their mechanical properties. Ageing during the useful lifetime also causes great losses in the elongation. In the present paper, the overall mechanical behavior of biodegradable films, which may be considered suitable for agricultural applications, but also of partially biodegradable films, is reviewed and analyzed. Selected critical mechanical properties of films before their exposure to biodegradation are investigated and compared against those of conventional agricultural films.     

Water-Blown Castor Oil-Based Polyurethane Foams with Soy Protein as a Reactive Reinforcing Filler

To decrease the usage of petroleum based materials, a kind of bio-resource based composite foams were developed with soy protein isolate (SPI) as reactive reinforcing filler in castor oil based polyurethane foams (PUF) prepared by self-rising method using water as a blowing agent. The resulting composite foams were evaluated for their morphology, density, mechanical and biodegradation properties, etc. Fourier transform infrared spectroscopy study exhibited characteristic peaks for SPI and PUF and indicated that the amino groups and hydroxyl groups on SPI reacted with polyphenyl polymethylene polyisocyanates (PAPI) to increase the crosslinking degrees of the composite foams. Densities of the resultant composites were found to increase with increasing SPI content. Mechanical properties of the samples were improved with the increase of SPI content. The compost tests further proved that the composite PUF had better biodegradability than neat PUF. Therefore, this research has provided a simple method of preparing the bio-resource based polyurethane foams, while exploring the potential of using SPI in polyurethane foam applications.     

Dialdehyde starch and zein plastic: Mechanical properties and biodegradability

Dialdehyde starch (DAS) and zein, a hydrophobic corn protein, were investigated to produce biodegradable plastics with improved water resistance and mechanical properties. In the study, dialdehyde starch and zein ratio, plasticizers, and degree of starch oxidation were examined. Increased molding temperature and level of starch oxidation decreased water absorption of the plastic. Tensile strength and Young's modulus increased with starch oxidation. The biodegradation of starting materials and ground plastic specimens was studied in aerobic soil reactors maintained at 25°C for 180 days. Biodegradation of corn starch, zein, and dialdehyde starch for 180 days produced CO₂ equivalent to 64, 63, and 10% of theoretical carbon, respectively. Specimens of molded DAS and zein (3 : 1) plastic showed accelerated CO₂ evolution compared to DAS and other raw materials alone. By 180 days, specimens made with starch of low oxidation (1 and 5% oxidized) demonstrated a 60% biodegradation, and specimens with highly oxidized starch (90% oxidized) achieved 37% biodegradation.Paper presented at the Bio/Environmentally Degradable Polymer Society—Third National Meeting, June 6–8, 1994, Boston, Massachusetts.Journal Paper J-15927 of the Iowa Agriculture and Home Economics Experiment Station, Ames, Project No. 3258.