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.     

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.     

Application of Cellulose Microfibrils in Polymer Nanocomposites

Cellulose microfibrils obtained by the acid hydrolysis of cellulose fibers were added at low concentrations (2–10% w/w) to polymer gels and films as reinforcing agents. Significant changes in mechanical properties, especially maximum load and tensile strength, were obtained for fibrils derived from several cellulosic sources, including cotton, softwood, and bacterial cellulose. For extruded starch plastics, the addition of cotton-derived microfibrils at 10.3% (w/w) concentration increased Young’s modulus by 5-fold relative to a control sample with no cellulose reinforcement. Preliminary data suggests that shear alignment significantly improves tensile strength. Addition of microfibrils does not always change mechanical properties in a predictable direction. Whereas tensile strength and modulus were shown to increase during addition of microfibrils to an extruded starch thermoplastic and a cast latex film, these parameters decreased when microfibrils were added to a starch–pectin blend, implying that complex interactions are involved in the application of these reinforcing agents.     

Effects of Temperature and Relative Humidity on Polylactic Acid Plastic Degradation

Three high molecular weight (120,000 to 200,000 g mol^–1) polylactic acid (PLA) plastic films from Chronopol (Ch-I) and Cargill Dow Polymers (GII and Ca-I) were analyzed for their degradation under various temperature and relative humidity (RH) conditions. Two sets of plastic films, each containing 11 samples, were randomly hung in a temperature/humidity-controlled chamber by means of plastic-coated paper clips. The tested conditions were 28, 40, and 55°C at 50 and 100% RH, respectively, and 55°C at 10% RH. The three tested PLA films started to lose their tensile properties when their weight-average molecular weight (M _w) was in the range of 50,000 to 75,000 g mol^–1. The average degradation rate of Ch-I, GII, and Ca-I was 28,931, 27,361, and 63,025 M _w/week, respectively. Hence, GII had a faster degradation rate than Ch-I and Ca-I under all tested conditions. The degradation rate of PLA plastics was enhanced by the increase in temperature and relative humidity. This trend was observed in all three PLA plastics (Ca-I, GII, and Ch-I). Of the three tested films, Ch-I was the first to lose its mechanical properties, whereas Ca-I demonstrated the slowest loss, with mechanical properties under all tested conditions.     

Poly(ethylene oxide)-coated granular starch-poly(hydroxybutyrate-co-hydroxyvalerate) composite materials

Granular cornstarch was coated with several biodegradable polymers in an effort to improve the mechanical properties of starch-poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) composites. Only samples containing poly(ethylene oxide) (PEO)-coated granular starch showed a large improvement in tensile properties over uncoated starch. For example, a 50/50 blend of PEO-coated starch and PHBV had a tensile strength of 19 MPa and an ultimate elongation of 23%, compared to 10 MPa and 11% for a similar blend containing uncoated starch. PEO may act as an adhesive between the starch and the PHBV and/or increase the toughness and resistance to crack growth of PHBV around the starch granules.Paper presented at the Bio/Environmentally Degradable Polymer Society—Third National Meeting, June 6–8, 1994, Boston, Massachusetts.Names are necessary to report factually on available data; however, the USDA neither guarantees nor warrants the standard of the product and the use of the name by the USDA implies no approval of the product to the exclusion of others that may also be suitable.     

A Biobased Blend of Cellulose Diacetate with Starch

Two bio-based polymers, cellulose diacetate (CDA) and starch, were used to prepare blends with reasonable properties and low cost. Due to the poor processing properties, starch was modified in the presence of glycerol and epoxidized soybean oil (ESO), and CDA was plasticized by triacetin (TA) and ESO, respectively. The morphologies of the blends with different amounts of modified starch (MST) were studied by scanning electron microscope (SEM), and the physical properties of the blends, including thermal stability, mechanical property, water and moisture resistance, were investigated. The equilibrium moisture absorption rates of the blends containing 30 and 50 wt% MST at 100 % of relative humidity(RH) were 9.4 and 15.0 %, respectively. SEM and DMA results demonstrated that CDA and MST had a certain extent of compatibility. Due to the partial plasticization of starch, the tensile strength of the blends was nearly not affected by the amount of MST. Even if 50 wt% MST was added, the tensile strength of the blend was as high as 24.7 MPa. The obtained blend containing 30 wt% MST can keep good mechanical properties at 50 % RH, and its tensile strength and elongation at break are 30.2 MPa and 3.6 %, respectively. All the results show that the CDA/MST blends have a potential as an environmental friendly material.     

Effect of Orientation on the Morphology and Mechanical Properties of PLA/Starch Composite Filaments

Polylactic acid (PLA)/starch fibers were produced by twin screw extrusion of PLA with granular or gelatinized starch/glycerol followed by drawing through a set of winders with an intermediate oven. At 30% starch, fibers drawn 2–5x were highly flexible (elongation 20–100%) while undrawn filaments were brittle (elongation 2–9%). Tensile strength and moduli increased with increasing draw ratio but decreased with increasing starch content. Mechanical properties were better for composites made with gelatinized starch/glycerol than granular starch. In conclusion, orientation greatly increases the flexibility of PLA/starch composites and this may be useful not only in fibers but also possibly in molded articles. Other advantages of starch addition could include fiber softness without added plasticizer, moisture/odor absorbency and as a carrier for active compounds.     

Processing and mechanical properties of biodegradable Poly(hydroxybutyrate-co-valerate)-starch compositions

Poly(hydroxybutyrate-co-valerate) (PHBV) is a completely biodegradable thermoplastic polyester produced by microbial fermentation. The current market price of PHBV is significantly higher than that of commodity plastics such as polyethylene and polystyrene. It is therefore desirable to develop low-cost PHBV based materials to improve market opportunities for PHBV. We have produced low-cost environmentally compatible materials by blending PHBV with granular starch and environmentally benign CaCO₃. Such materials can be used for specific applications where product biodegradability is a key factor and where certain mechanical properties can be compromised at the expense of lower cost. The inclusion of granular starch (25 wt%) and CaCO₃ (10 wt%) in a PHBV matrix (8% HV, 5% plasticizer) reduces the cost by approximately 40% and has a tensile strength of 16 MPa and flexural modulus of 2.0 Gpa, while the unfilled PHBV/plasticizer matrix has a tensile strength of 27 MPa and a flexural modulus of 1.6 GPa.Paper presented at the Bio/Environmentally Degradable Polymer Society—Third National Meeting, June 6–8, 1994, Boston, Massachusetts.The mention of firm names or trade products does not imply that they are endorsed or recommended by the U.S. Department of Agriculture over other firms or similar products not mentioned.     

Biodegradable Corn Starch Loose-Fill. II. The Effect of Storage at Different Relative Humidities on the Physical Properties of Loose-Fill

The physical properties of corn starch loose-fill were examined at various relative humidities (r.h.). After 48 h of storage at both 25 and 50% r.h., only a slight change in the dimension and physical properties of the corn starch loose-fill was apparent. A wet environment (75% r.h. for 48 h), however, caused significant shrinkage and the loss of physical properties. The tensile properties, particularly tensile modulus, sharply increased, while the resilience gradually decreased with storage time. Amorphous X-ray diffraction patterns of corn starch loose-fills were transformed into crystalline patterns due to aging at 75% r.h. after 48 h. These changes were attributed to the structural relaxation, which was accelerated by moisture gain. The T _g of corn starch loose-fill decreased with increasing the moisture content in expanded starch. Our proposed model based on Avrami equation was able to describe the time-dependent recrystallization of corn starch by modifying the time-dependent tensile modulus. The growth parameter (n) and time constant (k) for the recrystallization process of corn starch loose-fill were about 3.2 and 8.87 × 10^–18 s^–1, respectively. If the growth parameter of 3.2 is considered, spherulitic growth of crystallization occurred in the corn starch loose-fill in the wet environment.     

Processing and Characterization of Short-Fiber Reinforced Jute/Poly Butylene Succinate Biodegradable Composites: The Effect of Weld-Line

Fabrication of complex injection molded parts often involves the use of multiple gates. In such situations, polymer melts from different gates meld to form the molded part (weld line). This paper reports on the fabrication and characterization of the mechanical and morphological properties of short fiber reinforced jute/poly butylene succinate (PBS) biodegradable composites. The effect of a dual gated mold in the fabrication of welded specimens was a key focus of the investigation. It was observed that incorporation of jute fiber (10 wt%) conferred drastic changes on the stress–strain properties of the matrix as the elongation at break (EB), dropped from 160% in the matrix to just 10% in the composite. The tensile strength of the composite was lower than that of the matrix. However, it is noteworthy that the tensile modulus of the composite increased. Bending test also revealed that both bending strength and modulus increased with the incorporation of jute. Morphological studies of the tensile fracture surface using SEM revealed two types of failure mode. Ductile failure was indicated by plastic deformation at the initiation of fracture followed by brittle failure. The good interfacial bonding indicated between jute and PBS was attributed to positive interaction between the two polar polymers. A comparison of the non-weld and weld-line samples revealed that the weld-line composites have better mechanical integrity than the corresponding polymer matrix with weld line. The results also revealed that elongation at break and toughness are most sensitive to the presence of the weld-line whereas flexural properties are least sensitive.     

Aging properties of extruded high-amylose starch

The structural and mechanical properties of extruded high-amylose and normal cornstarch were studied as a function of time and humidity to determine the suitability of high-amylose cornstarch for use in biodegradable plastic materials. After extrusion at 170°C and 20–30% moisture, high-amylose starch was mostly amorphous, with small amounts of V- and A-type crystal structures. Tensile strengths for the extruded high-amylose starch ribbons were rather stable with time (65, 50, and 35 MPa at 20, 50, and 80% RH) and were higher than those for normal cornstarch (25, 40, and 15 MPa after 84 days at 20, 50, and 80% RH). Elongations at break declined gradually with time for high-amylose starch (6, 11, and 11% after 84 days at 20, 50, and 80% RH), while rapid declines were seen for normal cornstarch at higher humidities (3, 9, and 3% after 84 days at 20, 50, and 80% RH). Differential scanning calorimetry revealed that normal cornstarch aged at a high humidity had much larger sub-T _g endotherms than high-amylose cornstarch. These endotherms reflect decreases in enthalpy and free volume which occur in amorphous polymers due to structural relaxation. It appears, therefore, that plastic materials prepared from gelatinized or melted high-amylose cornstarch should have greater strength and flexibility and slower physical aging than those prepared from gelatinized normal cornstarch.Paper presented at the Bio/Environmentally Degradable Polymer Society—Second National Meeting, August 19–21, 1993, Chicago, Illinois.Product names are necessary to report factually on available data; however, the USDA neither guarantees nor warrants the standard of the product, and the use of the name by the USDA implies no approval of the product to the exclusion of others that may also be suitable.     

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.     

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.     

Preparation and Optimization of Starch/Poly Vinyl Alcohol/ZnO Nanocomposite Films Applicable for Food Packaging

Pollution and destruction of the environment due to the accumulation of non-degradable plastics are some of the most important concerns in the world. A significant amount of this waste is related to the polymers used in food packaging. Therefore, experts in the food industry have been looking for suitable biodegradable alternatives to synthetic polymers. Preparing biocompatible and biodegradable films based on starch is a good choice. In this study, various factors affecting films of starch/polyvinyl alcohol (PVA)/containing ZnO nanoparticles such as the amount of starch, PVA, glycerol, and ZnO were evaluated by response surface methodology (RSM). Film formation by solvent casting method, mechanical properties, swelling, solubility, and water vapor permeability (WVP) were selected as responses of RSM. The results showed that hydrogen bonding interactions between polyvinyl alcohol and starch improved the film formation. The effect of glycerol and PVA content on the mechanical strength was contrary to each other. As the amount of PVA increased, the tensile strength first decreased and then increased. The value of WVP was for all Runs from 0 to 6.77?×?10^??8 g m^??1 s^??1 Pa^??1. Finally, films with high film formation, maximum tensile strength, and high elongation at break, minimum solubility, permeability, and swelling were optimized.

     

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.     

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.     

Extruded Cornstarch-Glycerol-Polyvinyl Alcohol Blends: Mechanical Properties, Morphology, and Biodegradability

Elongation properties of extruded cornstarch were improved by blending with glycerol. Further blending of starch-glycerol with polyvinyl alcohol (PVOH) resulted in significant improvements in both tensile strength (TS) and elongation at break. Samples of starch-glycerol without PVOH equilibrated at 50% relative humidity had a TS of 1.8 MPa and elongation of 113%, whereas those containing PVOH had a TS and elongation of 4 MPa and 150%, respectively. Dynamic mechanical analysis (DMA) of starch-glycerol-PVOH blends showed that decreases in glass transition temperatures (T _g values) were proportional to glycerol content. Scanning electron microscopy (SEM) of fractured surfaces revealed numerous cracks in starch-glycerol (80:20) samples. Cracks were absent in starch-glycerol (70:30) samples. In both blends, many starch granules were exposed at the surface. No exposed starch granules were visible in blends with added PVOH. Starch-glycerol samples incubated in compost lost up to 70% of their dry weight within 22 days. Addition of PVOH lowered both the rate and extent of biodegradation.     

Cellulose Fiber/Bentonite Clay/Biodegradable Thermoplastic Composites

Adding cellulose fiber reinforcement can improve mechanical properties of biodegradable plastics, but fiber must be well dispersed to achieve any benefit. The approach to dispersing fiber in this study was to use aqueous gels of sodium bentonite clay. These clay-fiber gels were combined with powdered compostable thermoplastics and calcium carbonate filler. The composite was dried, twin-screw extruded, and injection molded to make thin parts for tensile testing. An experimental design was used to determine the effect of fiber concentration, fiber length, and clay concentration. Polybutylene adipate/terephthalate copolymer (PBAT) and 70/30 polylactic acid (PLA)/PBAT blend were the biodegradable plastics studied. The composite strength decreased compared to the thermoplastics (13 vs. 19 MPa for PBAT, 27 vs. 38 MPa for the PLA/PBAT blend). The composite elongation to break decreased compared to the thermoplastics (170% vs. 831% for PBAT, 4.9% vs. 8.7% for the PLA/PBAT blend). The modulus increased for the composites compared to the thermoplastic standards (149 vs. 61 MPa for PBAT, 1328 vs. 965 MPa for the PLA/PBAT blend). All composite samples had good water resistance.     

Compatible Blends of Zein and Polyvinylpyrrolidone

Blends of zein and polyvinylpyrrolidone (PVP) were compared based on their tensile properties, thermal properties and morphology. Zein was blended with polyvinylpyrrolidone of varying molecular weights (10, 55, and 1,300 kDa) and films were cast from ethanol solutions. Films cast using the higher molecular weight polymers showed an improvement in tensile strength, up to a 24% increase, compared to control. Differential scanning calorimetry data for the blends showed single T_m and T_g values of an intermediate value between those of zein and PVP control samples. Field emission scanning electron microscopy images show no obvious inhomogeneities, and confocal fluorescence microscopy showed no decreased uniformity in the PVP/zein films compared to control. Electrospun fibers of the zein/PVP blends were also obtained. These findings suggest that zein and polyvinylpyrrolidone combine to form a compatible blend, the first such blend of zein with a synthetic polymer.     

Electroactive Materials Composed of Starch

Extruded films of plasticized starch were doped with metal halides to produce solid ion-conducting materials. The electrical conductance of the material increased from 10^–11 to 10^–6 Siemens/cm. The type and amount of dopant affects the conductance of the material. Although the materials are moisture sensitive, water content does not have a significant effect on the conductance of doped films. Mechanical properties of doped films indicate that the starch is plasticized and that the ion-conducting material is strong and tractable. Unlike intrinsically conductive polymers, electroactive starch materials can be extruded in thin films or molded into any shape.