Comparison of Cationic and Unmodified Starches in Reactive Extrusion of Starch–Polyacrylamide Graft Copolymers

Graft copolymers of starch and polyacrylamide (PAAm) were prepared using reactive extrusion in a corotating twin screw extruder. The effect of cationic starch modification was examined using unmodified and cationic dent starch (≈23% amylose) and waxy maize starch (≈2% amylose). For a fixed acrylamide/starch feed ratio, conversion, graft content, and grafting efficiency were essentially unaffected by starch type or modification. Cationic starch graft copolymers generally had lower molecular weight PAAm grafts compared to the unmodified starch, whereas amylose content had little or no significant effect. In addition, the frequency of grafting was higher with cationic starch. These results indicate that cationic modification of starch enhances formation of grafting sites, resulting in graft copolymers with more grafts of lower molecular compared to unmodified starch. Cationic modification may therefore be a way to tailor the properties of starch–PAAm graft copolymers.     

Effect of Glycerin and Starch Crosslinking on Molecular Compatibility of Biodegradable Poly(lactic acid)-Starch Composites

Poly(lactic acid) (PLA) is a biodegradable material. However, PLA is relatively cost effective. Blending starch with PLA is one of the promising efforts because starch is a widely distributed and inexpensive product. PLA and starch were blended using a rheometer to form composites in this report. Glycerin was added into the blends to make the mixture molecular compatible and more homogeneous. The starch was crosslinked using epichlorohydrin to improve the compatibility of starch with PLA. Two series of composite were fabricated. One was PLA and the crosslinked starch containing 32 wt% glycerin. In this group, the crosslinking degree of the modified starch was varied. The second group was PLA and non-crosslinked starch with varied amount of glycerin added. Micro-structure of the blending composites was observed using a SEM to view the homogeneity of the mixture. The SEM pictures indicated that the compatibility of PLA and starch molecules was poor. The addition of glycerin can change the compatibility of PLA and starch. The higher the glycerin content in the composites, the better the compatibility between PLA and starch. Furthermore, when the starch was crosslinked by epichlorohydrin, the compatibility of PLA and starch can be greatly improved. The compatibility increases with the increase of crosslinking degree. This is due to the change of hydrophilicity of starch because the hydroxyl groups on the starch molecules were crosslinked into ether groups by the epichlorohydrin molecules.     

Starch, Poly(lactic acid), and Poly(vinyl alcohol) Blends

Research on biodegradable materials has been stimulated due to concern regarding the persistence of plastic wastes. Blending starch with poly(lactic acid) (PLA) is one of the most promising efforts because starch is an abundant and cheap biopolymer and PLA is biodegradable with good mechanical properties. Poly(vinyl alcohol) (PVOH) contains unhydrolytic residual groups of poly(vinyl acetate) and also has good compatibility with starch. It was added to a starch and PLA blend (50:50, w/w) to enhance compatibility and improve mechanical properties. PVOH (M_W 6,000) at 10%, 20%, 30%, 40%, 50% (by weight) based on the total weight of starch and PLA, and 30% PVOH at various molecular weights (M_W 6,000, 25,000, 78,000, and 125,000 dalton) were added to starch/PLA blends. PVOH interacted with starch. At proportions greater than 30%, PVOH form a continuous phase with starch. Tensile strength of the starch/PLA blends increased as PVOH concentration increased up to 40% and decreased as PVOH molecular weight increased. The increasing molecular weight of PVOH slightly affected water absorption, but increasing PVOH concentration to 40% or 50% increased water absorption. Effects of moisture content on the starch/PLA/PVOH blend also were explored. The blend containing gelatinized starch had higher tensile strength. However, gelatinized starch also resulted in increased water absorption.     

Effects of Starch Moisture on Properties of Wheat Starch/Poly(Lactic Acid) Blend Containing Methylenediphenyl Diisocyanate

Methylenediphenyl diisocyanate was found to improve the interfacial interaction between poly(lactic acid)(PLA) and granular starch. The objective of this research was to study the effect of starch moisture content on the interfacial interaction of an equal-weight blend of wheat starch and PLA containing 0.5% methylenediphenyl diisocyanate by weight. Starch moisture (10% to 20%) had a negative effect on the interfacial binding between starch and PLA. The tensile strength and elongation of the blend both decreased as starch moisture content increased. At 20% moisture level, the starch granules embedded in the PLA matrix were observed to be swollen, resulting in poor strength properties and high water absorption by the blend.     

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.     

The Effect of Starch Composition on Structure of Foams Prepared by Microwave Treatment

A microwave technique was used to prepare foams from different potato starches in granular form, with varying amounts of amylose content, and water. In addition to native potato starch (PN), high amylose potato starch (HAP) and potato amylopectin (PAP) were used, as well as mixtures thereof. In all cases the native crystallinity of starch granules was lost upon microwave treatment and an amorphous material was created. An increased concentration of starch in the initial water dispersion resulted in a less dense foam structure. The potato amylopectin formed open cell foams, whereas increased amylose content, as in native potato starch, yielded a more compact structure with irregular pore shapes. The high amylose potato starch yielded a structure with hardly any porosity. Foaming experiments were done to compare pre-gelatinized and granular starches dispersed in water. The pre-gelatinisation did not affect the pore formation process. These experiments indicated that the molecular architecture of starch polymers is more important for foam formation than starch polymer organization in the granules. Studies of temperature profile and dry matter content during microwave treatment showed that water evaporates more rapidly from a high amylose starch solution than native potato starch and potato amylopectin solutions. Rheological measurements showed that the amylose solution had much lower viscosity than starch and amylopectin. This confirms that polymer – water interaction, such as in amylopectin solution, favours stabilization of bubbles formed upon boiling and evaporation of water, which yields high porosity materials.     

Evaluation of the Biodegradation of Starch and Cellulose Under Controlled Composting Conditions

In order to verify the response of the controlled composting test method (i.e., the ISO/DIS 14855:1997, the ASTM D 5338-92, or the CEN counterpart) to starch at different concentrations, the maximum amount prescribed by the test method (100 g) and lower amounts (60 and 30 g), as if starch were a coingredient in a blend, were tested. After 44 days of incubation (at a constant temperature of 58°C) the biodegradation curves were in a plateau phase, displaying the following final values (referred to a nominal starch initial amount of 100 g): starch 100 g, 97.5%; starch 60 g, 63.7%; and starch 30 g, 32.5%. The data show a CO₂ evolution roughly equal, in each case, to the theoretical maximum, indicating a complete starch mineralization. We cannot discern whether the deviations found at lower concentrations are caused by a priming effect. In any case, the extent of the deviations is not high and is acceptable in biodegradation studies. The average biodegradation of cellulose, obtained gathering four independent experiments with 11 biodegradation curves, turned out to be 96.8 ± 6.7% (SD) after 47 ± 1 days. The data indicate that the controlled composting is a reliable test method also for starch and cellulose and, consequently, for starch-based and cellulose-based materials.     

Evaluation of the Biodegradability of Polyvinyl Alcohol/Starch Blends: A Methodological Comparison of Environmentally Friendly Materials

Polyvinyl alcohol (PVA) and starch are both biodegradable polymers. These two polymers can be prepared as biodegradable plastics that are emerging as one of the environmental friendly materials available now. In this study, after reacting with sodium trimetaphosphate (STMP), modified corn starch was blended with PVA in different ratios by a barbender. Test samples were prepared for mechanical and thermal properties measurements. The surface roughness and morphology of fractured surface of the samples were observed by an atomic force microscopy (AFM) and scanning electron microscope (SEM) measurements. Aqueous degradation by enzyme, water absorption and biodegradability behavior were evaluated for the degradability. The biodegradability of these materials was followed by bio-reactivity kinetics models. Results showed that the addition of modified starch could enhance its water uptake. With an addition of 20 wt% of modified starch, the blend had a maximum weight loss during enzymatic degradation. It was found that the degradability was enhanced with the addition of the starch. Analyzing the results of the biodegradability based on the kinetic models, the growth rate of the microorganism was found to be increasing with the increase of the content of starch in the PVA/starch blends in the first order reaction fashion. In our biodegradability analysis, i.e., based on the China national standards (CNS) 14432 regulations, we estimated the decomposition behavior based on the mentioned first order reaction. We found that the PVA/starch blends would take 32.47, 16.20 and 12.47 years to degrade by 70% as their starch content 0, 20 and 40 wt%, respectively.     

Biodegradation of Injection Molded Starch-Poly (3-hydroxybutyrate-co-3-hydroxyvalerate) Blends in a Natural Compost Environment

Injection molded specimens were prepared by blending poly (hydroxybutyrate-co-valerate) (PHBV) with cornstarch. Blended formulations incorporated 30% or 50% starch in the presence or absence of poly-(ethylene oxide) (PEO), which enhances the adherence of starch granules to PHBV. These formulations were evaluated for their biodegradability in natural compost by measuring changes in physical and chemical properties over a period of 125 days. The degradation of plastic material, as evidenced by weight loss and deterioration in tensile properties, correlated with the amount of starch present in the blends (neat PHBV < 30% starch < 50% starch). Incorporation of PEO into starch-PHBV blends had little or no effect on the rate of weight loss. Starch in blends degraded faster than PHBV and it accelerated PHBV degradation. Also, PHBV did not retard starch degradation. After 125 days of exposure to compost, neat PHBV lost 7% of its weight (0.056% weight loss/day), while the PHBV component of a 50% starch blend lost 41% of its weight (0.328% weight loss/day). PHB and PHV moieties within the copolymer degraded at similar rates, regardless of the presence of starch, as determined by ¹H-NMR spectroscopy. GPC analyses revealed that, while the number average molecular weight (Mn) of PHBV in all exposed samples decreased, there was no significant difference in this decrease between neat PHBV as opposed to PHBV blended with starch. SEM showed homogeneously distributed starch granules embedded in a PHBV matrix, typical of a filler material. Starch granules were rapidly depleted during exposure to compost, increasing the surface area of the PHBV matrix.     

Poly(Ethylene Glycol) Grafted Starch Introducing a Novel Interphase in Poly(Lactic Acid)/Poly(Ethylene Glycol)/Starch Ternary Composites

The main purpose of this study is challenging to dramatically improve the toughness of poly(lactic acid) (PLA)/starch by adding poly (ethylene glycol) (PEG) into the composites and grafting PEG molecules onto the surface of starch particles. It was found that the surface grafting of PEG onto starch induced the presence of PEG-rich regions located around the starch particles, caused by migration and aggregation of free PEG molecules. A novel interphase transition layer between PLA and starch was formed, which showed great ability for cavitation and vested large-scaled plastic deformation to PLA matrix. Further mechanical properties tests indicated the formation of interphase layer significantly increase the elongation at break from 10.2 to 254.5%, and notched impact strength from 1.56 to 2.37?kJ/m² for PLA/PEG/starch ternary composites. The influence of PEG component, ethanol extraction and annealing was also investigated.     

Reactive Blending of Biodegradable Polymers: PLA and Starch

Poly(lactic acid) (PLA) and starch are important biodegradable polymers. Mechanical properties of blends of PLA and starch using conventional processes were very poor because of incompatibility. In this study, PLA and starch were blended with a reactive agent during the extrusion process. The affects of the reactive blending were investigated and significant improvements were confirmed by measuring the tensile strength and elongation at break, IR spectra, and DSC.     

Composites Bioplastic Film for Various Concentration of Zinc Oxide (ZnO) Nanocrystals Towards Physical Properties for High Biodegradability in Soil and Seawater

Journal of Polymers and the Environment - The effect of various amount of ZnO nanocrystals (NCs) in composite starch/ZnO (PZ) and starch/chitosan/ZnO (PK) to the physical, structural,...     

Effect of Starch Granule Size on Viscosity of Starch-Filled Poly(hydroxy ester ether) Composites

The effect of starch granule size on the viscosity of starch-filled poly(hydroxy ester ether) (PHEE) composites was characterized using size-fractionated potato starch, as well as unfractionated starches (rice, corn, wheat, and potato). Potato starch was separated using an air classifier into four particle size fractions: <18 m, 18-24 m, 24-30 m, and >30 m. The starch was dried to a moisture content of 0.5% to minimize moisture effects on composite rheology. PHEE and potato starch were extruded with starch volume fractions of 0.46 and 0.66. Stress relaxation, frequency and strain sweep, and temperature-dependence measurements were carried out. Although small variations in viscosity were seen with the different potato starch fractions, differences were not significant at a volume fraction of 0.46. Viscosity differences between the different particle size fractions were more pronounced at a volume fraction of 0.66. The temperature dependence could be described by an Arrhenius relation, with an apparent activation energy of 84 kJ/mole. At a volume fraction of 0.46, the starch/PHEE viscosities increased in the order potato starch < wheat starch corn starch < rice starch.     

Accessibility of starch to enzymatic degradation in injection-molded starch-plastic composites

Most of the starch in starch-polyethylene-co-acrylic acid (EAA)-polyethylene (PE) composites prepared by injection molding was not accessible to starch-hydrolyzing enzymes. Even when these composites were treated with enzyme in the presence of Triton X-100 for 96 h, little starch hydrolysis was observed. However, when the starch-plastic material was pulverized, both the extent and the rate of starch hydrolysis increased dramatically, with about 70% hydrolysis of the starch within 18 h. Reactions carried out for up to 96 h showed that, while the enzyme was active, the reaction reached a plateau, achieving a total of 80% starch hydrolysis. Fourier transform infrared (FTIR) spectroscopy revealed that only starch, and not EAA or PE, was affected by enzyme in pulverized samples. Results indicated that while 80% of the starch in these composites was transiently inaccessible, perhaps due to EAA and PE forming an impermeable barrier to the enzyme, the other 20% remained inaccessible to enzymes. Also, the rate of starch digestion as determined by solubilized reducing sugar correlated with the particle size of the pulverized material, suggesting that a large available surface area is critical for rapid starch degradation in such composites.The mention of firms names or trade products does not imply that they are endorsed or recommended by the U.S. Department of Agriculture over the firms or similar products not mentioned. All programs and services of the U.S. Department of Agriculture are offered on a nondiscriminatory basis without regard to race, color, national origin, religion, sex, marital status, or handicap.     

Modification of Aliphatic Polyesters and Their Reactive Blends with Starch

Modified polycaprolactone was synthesized by melt reaction of PCL and reactive monomers such as glycidyl methacrylate (GMA) and maleic anhydride (MAH) in the presence of benzoyl peroxide in Brabender mixer. MAH showed a different grafting phenomenon compared to GMA. The reaction mechanism was discussed with different reactive monomers. Reactive blends of the PCL-g-GMA and the gelatinized starch with glycerin were prepared and their mechanical properties and biodegradabilities were investigated. Reactive blends of PCL-g-GMA and starch showed well-dispersed starch domain in the matrix and better mechanical strength than the unmodified PCL/starch blend. However, the reaction between PCL-g-GMA and starch induced a crosslinking during the reactive blending and this crosslinking in the blend lowered the biodegradation of the blend during the composting test. The biodegradability was investigated by the weight loss and surface morphology change of the blend in the composting medium.     

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.     

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.     

Biodegradation by Composting of Surface Modified Starch and PVA Blended Films

Several starch/PVA/glycerol polymer blends were prepared by a solution casting technique and examined for biodegradation by composting over 45 days. Within this time frame, the starch and glycerol components were fully degraded, leaving the PVA component essentially intact. The lowest PVA content film (20%) was selected as a polymer with enough PVA to impart important physical characteristics, but also enough starch to be considered biodegradable. The film characteristics were further improved by surface modification with chitosan. This modification did not interfere with the biodegradation of the starch component. Furthermore, there was slight evidence that PVA biodegradation had been initiated in composted, surface modified starch/PVA blends.     

Biodegradation Properties of Poly-ε-caprolactone,Starch and Cellulose Acetate Butyrate Composites

Blending starches with polymers such as poly-ε-caprolactone (PCL) has been used as a route to biodegradable plastics. The addition of starch has a significant effect on all physical properties including toughness, elongation at break. On blending cellulose acetate butyrate (CAB) with starch and PCL, improvements in most physical and mechanical properties were observed. This is may be due to CAB acts as a compatibilizer between PCL and starch due to the presence of both hydroxyl groups (in starch and CAB) and ester carbonyls (in PCL and CAB). The presence of different compounds affects the way in which other components degrade. For example the structure of CAB within a starch and PCL combination might make the degradation rate different to that when starch was only mixed with PCL. To check whether this was the case, three combinations of different blends were used to calculate the rate of degradation of each of them separately. These degradation rate constants were then used to predict the theoretical degradation which was checked against the experimental value for other different combinations.     

Preparation and Characterization of Compatible and Degradable Thermoplastic Starch/Polyethylene Film

The degradability of the compatible thermoplastic starch/polyethylene film was investigated by weight loss percent (WLP), Fourier Transform Infrared (FT-IR) Spectroscopy, and Scanning Electron Microscope (SEM). The compatible film was prepared by using the particles of thermoplastic starch/polyethylene blends that were produced by one-step reactive extrusion. The weight of the film after degradation reduced more than 3% for 30 days and 4% for 60 days. The FTIR results revealed that both starch and polyethylene in the film exhibited varying degrees of degradation. SEM photographs of the films after degradation showed that starch particles in the film disintegrated into smaller particles or separated out of the film surface. Degradation studies demonstrated that the compatible thermoplastic starch/polyethylene film had increased degradability at the given degradable environment. The information implies that this film could be utilized as a degradable plastic.