Starch–poly(vinyl alcohol) foamed articles prepared by a baking process

Composite foam plates were prepared by baking a mixture of granular starch and aqueous poly(vinyl alcohol) (PVOH) solution inside a hot mold. Foam strength, flexibility, and water resistance were markedly improved by addition of 10–30% PVOH to starch batters. The improvement in strength at low humidity was greater for partially (88%) hydrolyzed PVOH while strength at higher humidities improved most with fully (98%) hydrolyzed PVOH. Foam flexibility increased with higher PVOH molecular weight. Scanning electron micrographs of the surface of the foams revealed a phase-separated morphology in which swollen starch granules were embedded in a matrix of PVOH. The starch component was gelatinized (melted) during baking while the PVOH component crystallized to a high degree during baking. Crosslinking agents such as Ca and Zr salts were added to starch batters to give further increases in water resistance. Respirometry studies in soil showed that the starch component of starch–PVOH foams biodegraded relatively rapidly (weeks) while the PVOH component degraded more slowly (months). Baked foams prepared from starch and PVOH have mechanical properties that are adequate for use as packaging containers over a wide range of humidity. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 2129–2140, 1998     

Twin‐screw extrusion production and characterization of starch foam products for use in cushioning and insulation applications

Cylindrical starch foam shapes were produced on a small scale (～11–12 kg/hr) Werner Pfleiderer ZSK‐30 twin‐screw extrusion (TSE) process using water, which functions as a plasticizer as well as a blowing agent. The properties of the starch foams depend on the type of starch used (hydroxypropylated high amylose corn starch, 70% amylose), the amount of water and additives (poly(hydroxyamino ether)) (PHAE) used, and extrusion conditions such as temperature and the screw configuration. PHAE offers the adhesion and durability of epoxy resins with the flexibility and processibility of thermoplastic resins. PHAE was successful in imparting mechanical strength and toughness, cell integrity, weather and water resistance to the foam structure. The purpose of this work was to study the effects of the extrusion (melt) temperature, amount of water added and the screw configuration on the density of starch foams. The water externally added was varied from 3% to 12%, while the PHAE content was varied from 3% to 15% of the starch used (on a wet basis). The foaming was carried out at melt temperatures in the range from 85 to 145°C. A match of material properties with process engineering conditions was achieved to facilitate the control of expansion to a structure with valuable commercial properties. The effects of processing conditions on the foaming process were studied using a Werner Pfleiderer ZSK‐30 twin screw extruder. The optimum temperature, blowing agent content, and PHAE content were determined. The density of the cylindrical foam extrudates obtained was 22–25 kg/m³. The screw configuration, temperature and pressure profiles, and additives affected the morphology, expansion ratio (ER), resilience, and compressibility of the product. These results were then employed on an industrial scale (410–420 kg/hr) twin‐screw food extruder, a Wenger‐80, to manufacture foam sheets. The density of the foam sheets was 27–30 kg/m³. The cushioning and insulation properties were studied and are reported. POLYM. ENG. SCI., 46:438–451, 2006. © 2006 Society of Plastics Engineers     

Poly(vinyl alcohol) composite films with high percent elongation prepared from amylose‐fatty ammonium salt inclusion complexes

Amylose inclusion complexes prepared from cationic fatty ammonium salts and jet‐cooked high amylose starch were combined with poly(vinyl alcohol) (PVOH) to form glycerol‐plasticized films. For the octadecylammonium salt complexes, elongation was significantly higher than the PVOH control when the amount of complex incorporated was from 20% to 70%. For the dodecyl‐ and hexadecylammonium salt complexes, elongation was significantly higher than PVOH films for 20% to 40% incorporation of cationic complex. Tensile strength declined with increasing levels of amylose‐ammonium salt complex, and surface hydrophobicity (contact angle) was significantly higher than PVOH films. Microscopy showed no phase separation or phase inversion, suggesting intimate mixing due to ionic interactions between cationic ammonium salt complexes and the hydroxyl groups of PVOH. The high elongations of these films and increased water contact angles are marketable advantages, along with the lower cost and increased biodegradability of the starch‐based component. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44110.     

Properties of extruded starch–poly(methyl acrylate) graft copolymers prepared from spherulites formed from amylose–oleic acid inclusion complexes

Mixtures of high‐amylose corn starch and oleic acid were processed by steam jet cooking, and the dispersions were rapidly cooled to yield amylose–oleic acid inclusion complexes as micron‐ and submicron‐sized spherulites and spherulite aggregates. Dispersions of these spherulite particles were then graft polymerized with methyl acrylate, both before and after removal of uncomplexed amylopectin by water washing. For comparison, granular, uncooked high‐amylose corn starch was also graft polymerized in a similar manner. Graft copolymers with similar percentages of grafted and ungrafted poly(methyl acrylate) (PMA) were obtained from these polymerizations. The graft copolymers were then processed by extrusion through a ribbon die, and the tensile properties of the extruded ribbons were determined. Although extruded ribbons with similar tensile strengths were obtained from the three starch–PMA graft copolymers, much higher values for % elongation were obtained from the spherulite‐containing systems. Also, the tensile properties were not significantly affected by removal of soluble, uncomplexed amylopectin by water washing before graft polymerization. These results are consistent with the observation that these PMA‐grafted starch particles did not melt during extrusion, and that continuous plastic ribbons were formed by fusing these particles together in the presence of small amounts of thermoplastic PMA matrix. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40381.     

Effect of stearic acid and sodium stearate on cast cornstarch films

Stearic acid and sodium stearate were used as lipids to form inclusion complexes with cornstarch through a cooking process, respectively. The complexing index and the surface tension of the cooked pastes were measured. The films of the pastes were formed by casting, paper‐sizing, and paper‐coating methods. X‐ray diffraction and scanning electron microscopy were used to characterize the crystal and surface structures. Such properties of the complex films as the moisture absorption, friction coefficient, and tensile properties were tested. The results reveal that the two lipids could form an inclusion complex with amylose in the cornstarch more or less as a result of forming V‐type crystals that restrained the crystallite size of the B‐type crystal in the starch film. The addition of lipids reduced the sensitivity of the complex films to environmental moisture, decreased the friction coefficient of the films, and visibly increased the smoothness of the surfaces of the films. When the lipids were added in the starch at a weight content of 1%, the elongation at break of the complex film increased and the strength decreased slightly, and above a 1% content of the lipids, the tensile properties of the starch film were greatly deteriorated. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Understanding polymeric amylose retrogradation in presence of additives

Polymeric aging in starch is an important equilibrating process leading to long‐chain amylose recrystallization and anisotropic properties of material made from starch. Investigations into a number of plasticizers and hydrocolloids showed that their water retention/binding capability influence the starch polymer's crystallinity. Addition of up to 8 wt % glycerol and 3 wt % xylitol acted as an antiplasticizer and apparently increased the total crystalline phase, which reduced the degree of elongation of amylose matrix by 15%. Maltodextrin and xanthan gum also reduced matrix elongation capability but X‐ray diffraction (XRD) analysis showed samples with varying crystallinity, and the extent of crystallinity did not correlate with respective tensile properties. Additives such as maltodextrin, with similar molecular structure as amylose, were ineffective in increasing degree of elongation even at 15 wt % addition rate, because of formation of pockets of crystalline region, as observed by XRD analysis. Both xylitol and xanthan gum samples showed similar tensile strength and elongation properties, but the water retention capability of xylitol‐filled starch samples was about 27% lower than xanthan gum samples, at their respective higher concentrations. A dynamic structural unit is proposed to satisfy the isotropic increase in tensile strength and degree of elongation in oriented starch matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Shrinkage and re‐expansion of extruded starch acetate foams

The effects of concentration of steam, heating time, pretreatment, and cooling conditions on the shrinkage and re‐expansion of extruded starch acetate foam were investigated. The re‐expansion ratio was determined from the degree by which the foam cells were moistened under the condition tested. The higher the concentration of steam used, the faster and greater the foam re‐expanded. Shrinkage was a result of the negative pressure resulting from cooling and condensation of steam or ethanol inside the foam and the unbalanced osmosis of steam transported out of the foam and air transported into the foam and the resistance of foam cell walls. Quenching re‐expanded foams led to significant shrinkage, especially for foams re‐expanded with highly concentrated steam. Shrinkage cannot be avoided even if the foam is kept at the same temperature it was expanded at the nozzle. Gradually reducing the degree of concentration of steam could reduce the shrinking tendency of the re‐expanded foam. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4264–4268, 2006     

Biodegradable foams of poly(lactic acid)/starch. II. Cellular structure and water resistance

Biodegradable foams were prepared with poly(lactic acid) and starch by extrusion. The compression modulus of the foams was negatively related to the foam bulk density. The foam consists of both open‐ and close‐cell structures. The presence of PLA significantly improved the water resistance of the foam, and significantly improved the foam recovery capacity, especially in high‐moisture conditions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Melt processing and characterization of polyvinyl alcohol and polyhydroxyalkanoate multilayer films

Multilayer films for food packaging applications composed of polyvinyl alcohol (PVOH) as the core layer and polyhydroxyalkanoate (PHA) as the outer skin layers were produced by the co‐extrusion process. Rheological properties of PVOH and PHA were performed and analyzed before co‐extruding into a cast film. Analysis of the rheological data indicated the processing temperatures and grades of the PVOH and PHA polymers that would produce similar viscosity and melt flow properties. To improve adhesion of the layers, PHA was grafted with maleic anhydride using a dicumyl peroxide initiator to provide a tie layer material, which improved the peel strength of the PHA and PVOH layers by over 2×. Oxygen transmission rate (OTR) testing showed that the multilayer sample provided an OTR of 27 cc/m²‐day at 0% relative humidity (RH) and rates of 41 and 52 cc/m²‐day at relative humidity values of 60% and 90% RH, respectively. This indicates significant barrier performance enhancement over monolayer PVOH that provided an OTR of 60 cc/m²‐day at 0% RH and 999 cc/m²‐day at 60% RH. Biodegradation testing of the films in the marine environment showed that both the unmodified and maleated PHA polymers displayed high levels of mineralization, whereas the PVOH material did not. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation and characterization of kaolin/starch foam

The objective of this work was to study the effect of the kaolin content on the properties of starch foams. The kaolin/starch foams were made with kaolin contents that ranged from 0 to 15 m% by baking in a hot mold. The starch and kaolin/starch foams were stored at room temperature with a relative humidity (RH) of 55% for 7 days prior to testing. An increase in the kaolin content increased the foam density. The izod impact strength increased up to 1151.37 J/m² at the highest kaolin content (15 m%). The improvement was about five times the izod impact strength of pure starch foam. Moreover, the presence of any kaolin reduced the water absorption ability of the starch foam. Scanning electron microscopy revealed that kaolin increased the size of the starch foam cells and was itself well dispersed. Kaolin/starch foams showed a higher thermal stability than pure starch foam.     

Biodegradable packaging foams of starch acetate blended with corn stalk fibers

Starch acetate–corn fiber foams were prepared by extrusion. Corn starch was acetylated (DS 2) to introduce thermoplastic properties. Corn stalks were treated with sodium hydroxide to remove the lignin and to obtain purified cellulose fibers. Starch acetate was blended with treated fiber at concentrations of 0, 2, 6, 10, and 14% (w/w) and extruded in a corotating twin‐screw extruder with 12 to 18% w/w ethanol content and 5% talc as a nucleating agent. The samples were extruded at 150°C and selected physical and mechanical properties were evaluated. Micrographic properties were analyzed using scanning electron microscopy to observe the interaction of fiber and starch. Fiber incorporation at the lower concentrations enhanced the physical properties of the foams. Fiber contents greater than 10% decreased expansion and increased density and shear strength. Good compatibility between starch and corn fiber was observed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2627–2633, 2004     

Formation of hydrophilic starch coatings on polyethylene films

Thin starch coatings were deposited onto polyethylene (PE) film surfaces when PE films were immersed in 1% jet cooked starch solutions and the hot solutions were allowed to cool. Normal cornstarch, waxy cornstarch, high amylose cornstarch, and solvent‐extracted normal cornstarch (to remove native lipid) were used in these experiments. Amounts of adsorbed starch varied from about 0.03–0.05 mg per cm² of PE, and these starch coatings imparted hydrophilic properties to film surfaces, as evidenced by contact angle measurements. Although starch could be removed by gently rubbing water‐wet PE surfaces, air‐dried coatings were more firmly attached, and did not separate from the PE surface when films were bent or flexed. SEM images of starch‐coated film surfaces showed that starch was deposited as particles less than 1 μm in diameter, and also as aggregates of these submicron particles. Despite the fact that some starch samples contained only very small amounts of amylose and native lipid, surface‐deposited starch in all experiments contained 90–100% amylose; and exhibited the same V_h X‐ray diffraction pattern, indicative of helical inclusion complex formation. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1781–1788, 2002; DOI 10.1002/app.10589     

Processing and properties of an ethylene–vinyl acetate blend foam incorporating ethylene–vinyl acetate and polyurethane waste foams

Waste polyurethane foam (w‐PU) and waste ethylene–vinyl acetate foam (w‐EVA) were used as fillers for the production of an ethylene–vinyl acetate (EVA) blend foam. Two different foaming techniques (single‐stage and heat–chill processes) were used for this purpose. The waste foam concentration was varied up to 30 wt % of the original EVA. The physical, mechanical, and morphological properties of the filled foam were studied. The single‐stage process produced blend foams with a lower density and a greater cell size than the foams obtained by the heat–chill process. The density and compression strength of the blend foam increased as the percentage of w‐PU foam increased. However, for the w‐EVA/EVA blend foams, the addition of w‐EVA foam did not significantly affect the density or compression strength compared to the original EVA foams. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44708.     

Optimal Operating Conditions to Produce Nutritious Partially Parboiled Brown Rice in a Humidified Hot Air Fluidized Bed Dryer

V-type amylose–lipid complexes present in partially parboiled rice can decrease starch digestibility. Formation of such complexes can be accomplished using high-temperature fluidized bed drying; the degree of the complexes depends on the thermal condition. The effects of drying media (hot air and humidified hot air), operating conditions (drying air temperature and relative humidity [RH]), and the initial moisture content on the degree of V-type crystallinity and subsequent starch digestibility (or glycemic index, GI) and brown rice texture were examined experimentally. The results showed that paddy drying with humidified hot air (HHA) requires a longer time than hot air (HA). Higher drying air temperature, RH, and initial moisture content of paddy yield higher degrees of starch gelatinization and V-type amylose–lipid complexes. The brown rice dried by HA or HHA had lower starch digestibility and a harder texture than the reference sample. Within the range of parameters studied, to obtain the lowest GI for the dried brown rice, paddy at an initial moisture content of 33% (db) should be dried by HHA at 150°C and 6.4% RH.     

Physical and mechanical properties of plasticized butenediol vinyl alcohol copolymer/thermoplastic starch blend

The poly(vinyl alcohol) (PVOH) is an eco‐friend polymer and has an excellent oxygen barrier property due to its strong intermolecular force, but difficulty in processing with conventional extrusion process gives it a limitation for various industrial applications, especially packaging industry. Many studies have attempted to plasticize PVOH to improve its processability, but high cost of PVOH is still drawback for a variety of industrial applications. Therefore, PVOH often blended with other biodegradable polymers such as starch to acquire the cost benefit. Nowadays, the butenediol vinyl alcohol copolymer (BVOH) is getting a great attention due to its melt processability and bio‐degradability, but its high cost is barrier to the industrial application as well. In this study, thermoplastic starch (TPS)/plasticized BVOH (P‐BVOH) were prepared by melt mixing technique, and the plasticization effect of glycerol on starch and BVOH with different composition was observed for optimized processing condition. Based on our preliminary study, TPS was blended with varying amount of P‐BVOH (100:0, 90:10, 80:20, 70:30, 60:40, and 50:50 weight ratio). Physical, oxygen barrier, and mechanical properties of the TPS/P‐BVOH blends were evaluated by various analytical instruments to achieve balanced property and performance. J. VINYL ADDIT. TECHNOL., 25:109–116, 2019. © 2018 Society of Plastics Engineers     

Biodegradable polyurethane foam from liquefied waste paper and its thermal stability,biodegradability, and genotoxicity

Liquefaction of waste paper (WP) was conducted in the presence of polyhydric alcohols to prepare biodegradable polyurethane foam. The liquefied‐WP‐based polyol had suitable characteristics such as apparent molecular weight, hydroxyl value, and viscosity for the preparation of rigid polyurethane foam and was successfully applied to produce polyurethane foam with the appropriate combinations of foaming agents. The obtained foams showed satisfactory densities and mechanical properties as good as those of foams obtained from liquefied wood‐ and starch‐based polyols. The foams had almost the same thermal stability at initial weight loss and seemed to be potentially biodegradable because they were degraded to some extent in leaf mold. There were no mutagens or carcinogens in the water extracts of the foams. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1482–1489, 2002     

Effect of potassium persulfate on graft copolymerization and mechanical properties of cassava starch/natural rubber foams

The aim of this study was to improve the mechanical properties of thermoplastic starch foams prepared from cassava starch blended with natural rubber latex by reactive blending. Potassium persulfate was used as an initiator for graft copolymerization between the starch and natural rubber during baking. The starch–natural rubber graft copolymer (starch‐g‐NR copolymer) was successfully produced during both suspension and melt blending based on ¹H‐NMR and FTIR characterization. Natural rubber increased the flexural modulus of starch/natural rubber foams without potassium persulfate, thus indicating the compatibility of the blends. The starch‐g‐NR copolymer, acting as a compatibilizing agent, enhanced the impact strength of foams, but it did not improve the flexural modulus. This may be due to the potassium persulfate decreasing the molecular weight of the natural rubber. Relative humidity also played an important role on the mechanical properties. Foams became more ductile at higher relative humidities. Since foam density increased with an increasing natural rubber content, the specific impact strength was also considered. A soil burial test showed that the cassava starch foams and foams containing 15 pph of natural rubber were fully biodegraded within 8 and 18 weeks, respectively. The starch‐g‐NR copolymer delayed biodegradation of foams and foams containing high natural rubber content, i.e., 35 pph, showed a low ability to be biodegraded. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Reinforcement of soy polyol‐based rigid polyurethane foams by cellulose microfibers and nanoclays

Water‐blown rigid polyurethane foams from soy‐based polyol were prepared and their structure–property correlations investigated. Cellulose microfibers and nanoclays were added to the formulations to investigate their effect on morphology, mechanical, and thermal properties of polyurethane foams. Physical properties of foams, including density and compressive strength, were determined. The cellular morphologies of foams were analyzed by SEM and X‐ray micro‐CT and revealed that incorporation of microfibers and nanoclays into foam altered the cellular structure of the foams. Average cell size decreased, cell size distribution narrowed and number fractions of small cells increased with the incorporation of microfibers and nanoclays into the foam, thereby altering the foam mechanical properties. The morphology and properties of nanoclay reinforced polyurethane foams were also found to be dependent on the functional groups of the organic modifiers. Results showed that the compressive strengths of rigid foams were increased by addition of cellulose microfibers or nanoclays into the foams. Thermogravimetric analysis (TGA) was used to characterize the thermal decomposition properties of the foams. The thermal decomposition behavior of all soy‐based polyurethane foams was a three‐step process and while the addition of cellulose microfibers delayed the onset of degradation, incorporation of nanoclays seemed to have no significant influence on the thermal degradation properties of the foams as compared to the foams without reinforcements. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Blending of poly(lactic acid) and starches containing varying amylose content

Four dry corn starches with different amylose content were blended at 185°C with poly(lactic acid) (PLA) at various starch:PLA ratios using a lab‐scale twin‐screw extruder. Starch with 30% moisture content also was blended with PLA at a 1:1 ratio. Each extrudate was ground and dried. The powder was mixed with about 7.5% plasticizer, and injection molded (175°C) into test tensile bars. These were characterized for morphology, mechanical properties, and water absorption. Starch performed as a filler in the PLA continuous matrix phase, but the PLA phase became discontinuous as starch content increased beyond 60%. Tensile strength and elongation of the blends decreased as starch content increased, but no significant difference was observed among the four starches at the same ratio of starch:PLA. The rate and extent of water absorption of starch/PLA blends increased with increasing starch. Blends made with high‐amylose starches had lower water absorption than the blends with normal and waxy corn starches. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3639–3646, 2003     

A Simple Direct Casting Route to Ceramic Foams

A simple direct foaming and casting process using ovalbumin-based aqueous slurries for fabricating ceramic and metal foams is demonstrated. Foaming of aqueous ceramic slurries and the foam microstructure were seen to be a strong function of slurry rheology. Setting of foams with ceramic solids loading above 20 vol% was achieved by addition of acid, which also prevented binder migration. Acid addition resulted in excessive shrinkage, causing cracking of foams with ceramic loading below 20 vol%. Addition of sucrose to the slurries suppressed shrinkage leading to defect-free foams with porosity exceeding 95%. Overall porosity and foam microstructure could be controlled through ceramic solids loading, ovalbumin–water ratio, foaming time and sucrose amount, and sintering temperature. The ceramic foams fabricated by the process were strong enough to be green machined to different shapes.