Effect of propylation on the characteristics of corn starch and variation of properties with different degrees of substitution

Corn starch was modified by propylation with different degree of substitution (DS). DS of four starch modifications were 0.61, 1.56, 2.27, and 2.51. Samples were characterized by FTIR, XRD, TG‐DTA, swelling power, solubility, water binding capacity, and light transmittance. Results of the systematic physico‐chemical characterization of the starch modification in comparison with the native starch have been documented in the article. Results showed that during propylation, the crystalline structure of starch got destroyed and surface of the starch was eroded. Propylated starch (DS 2.51) showed 85% weight loss at temperatures from 300 to 400°C, whereas the native starch underwent similar weight loss (83%) from 250 to 300°C. Swelling power and water binding capacity of native starch (DS 0.0) were 3.09 g/g and 89.8%, respectively. However, in propylated starch at low DS (DS 0.61), swelling power and water binding capacity increased to 10.55 g/g and 136.8% under same conditions. At high DS (DS 2.51), swelling power was similar to native starch at 65°C, whereas solubility and water binding capacity decreased to below that of native starch. Light transmittance of propylated starch with high DS (DS 2.51) increased dramatically compared with native starch. Propylation improved the hydrophobic transformation and thermal stability of starch at high DS. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Photobiodegradation of low‐density polyethylene/banana starch films

The effects of the starch content, photosensitizer content, and compatibilizer on the photobiodegradability of low‐density polyethylene (LDPE) and banana starch polymer blend films were investigated. The compatibilizer and photosensitizer used in the films were PE‐graft‐maleic anhydride (PE‐g‐MA) and benzophenone, respectively. Dried banana starch at 0–20% (w/w) of LDPE, benzophenone at 0–1% (w/w) of LDPE, and PE‐g‐MA at 10% (w/w) of banana starch were added to LDPE. The photodegradation of the blend films was performed with outdoor exposure. The progress of the photodegradation was followed by determining the carbonyl index derived from Fourier transform IR measurements and the changes in tensile properties. Biodegradation of the blend films was investigated by a soil burial test. The biodegradation process was followed by measuring the changes in the physical appearance, weight loss, and tensile properties of the films. The results showed that both photo‐ and biodegradation rates increased with increasing amounts of banana starch, whereas the tensile properties of the films decreased. The blends with higher amounts of benzophenone showed higher rates of photodegradation, although their biodegradation rates were reduced with an increase in benzophenone content. The addition of PE‐g‐MA into polymer blends led to an increase in the tensile properties whereas the photobiodegradation was slightly decreased compared to the films without PE‐g‐MA. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2725–2736, 2006     

Radiation‐assisted morphology modification of LDPE/TPS blends: A study on starch degradation‐processing‐morphology correlation

Potato starch was radiolytically degraded to different extents by irradiating with Co‐60 gamma radiation in wide dose range. The degraded starch was plasticized using glycerol and water to obtain radiation processed thermoplastic starch (RTPS). Blends of different RTPS and low density polyethylene (LDPE) were prepared by internal melt mixing. Characterization of blends using differential scanning calorimetry, thermogravimetric analysis, X‐ray diffraction, Fourier transformed infrared spectroscopy, scanning electron microscope, melt flow, contact angle, and soil burial studies indicated changes in the blend morphology and biodegradation behavior with the increase in the dose imparted to the starch fraction. Molecular weight of starch decreased substantially in the dose range of the study. The melt viscosity of LDPE/RTPS blend decreased whereas crystallinity of LDPE phase increased with the incorporation of RTPS. No significant change in the carbonyl index and thermal stability of the blends was observed in the dose range studied; therefore, the observed changes in the physical and thermal properties of the blends were attributed primarily to the kinetic factors affecting crystallization and time‐dependent phase separation process. Biodegradability of blends varied with the radiation dose imparted to starch component of blend, suggesting better encapsulation of RTPS by LDPE chains. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and characterization of low‐density polyethylene/banana starch films containing compatibilizer and photosensitizer

Composite films containing various percentages of banana starch and low‐density polyethylene (LDPE) were prepared. The effects of the compatibilizer, banana starch content, and photosensitizer content on the thermal and tensile properties of these films were investigated. The banana starch content was varied from 5 to 20 wt % of LDPE, whereas benzophenone was added as a photosensitizer in three different amounts (0.25, 0.5, and 1 wt %) based on LDPE. In these films PE‐graft‐maleic anhydride (PE‐g‐MA) was used as a compatibilizer at 10 wt % banana starch. It was found that the thermal stability of the composite films remained unchanged with respect to the amount of banana starch and benzophenone content. The addition of banana starch had no effect on the melting temperature and degree of crystallinity of the films. Similarly, PE‐g‐MA had no effect on the melting temperature but decreased the degree of crystallinity of the LDPE phase. Benzophenone caused an increase in the melting temperature but decreased the degree of crystallinity of LDPE in the films. Increasing the amount of banana starch decreased the tensile properties of the composite films. The addition of PE‐g‐MA as a compatibilizer increased the tensile properties compared with the uncompatibilized films. However, benzophenone had no effect on the tensile properties of the blend films. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2717–2724, 2006     

Properties of fatty-acid esters of starch and their blends with LDPE

In the present study, starch octanoates OCST1.8 and OCST2.7 with degrees of substitution (d.s.) of 1.8 and 2.7, respectively, and dodecanoate DODST2.7 (d.s. = 2.7), were prepared by esterification of native starch with fatty acid chlorides. Our analyses, including elemental analysis, FTIR, contact angle, DSC, and TGA measurements confirmed the esterification reaction of starch and the degree of substitution. The ester group was found to act like an internal plasticizer, with an increase in the number and the size of fatty acyl chains grafted onto starch. These starch esters were mixed with low density polyethylene (LDPE) at various proportions in a Haake Rheomixer. Water and moisture absorption, thermal and mechanical properties, and biodegradation were investigated as a function of blend composition. The DODST2.7/LDPE blends showed, in general, better thermal stability and higher elongation, but lower tensile strength and water absorption, than did corresponding OCST/LDPE blends. The addition of starch esters to LDPE led to a very slow rate of biodegradation of these blends. © 1997 John Wiley & Sons, Inc. J Appl Polym 65: 705–721, 1997     

Biodegradable Composition Based on Low Density Polyethylene

ABSTRACT

Sodium salt of partially carboxymethylated starch (Na-PCMS) with degree of substitution DS 0.58 and starch acetate with DS 1.7 were synthesized from starch. These starch ethers and acetates along with starch, poly(vinyl acetate) (PVAc) and poly(vinyl alcohol) (PVA) were blended with low density polyethylene (LDPE) in various proportion using Brabender mixer. Addition of 5% stearic acid as a plasticizer improves the blend compatibility. Change in mechanical properties were monitored and optimum composition of blend were prepared. This blend was studied for growth of Bacillus species (BS) and degradation by means of weight loss and change in mechanical properties viz., tensile strength and % elongation, and total cellular protein. Degradation of pure polymers within one month period was also examined.     

Properties of starch‐based blend films using citric acid as additive. II

Starch/polyvinyl alcohol (PVA) blend films were prepared by using corn starch, polyvinyl alcohol (PVA), glycerol (GL), and citric acid (CA) as additives and glutaraldehyde (GLU) as crosslinking agent for the mixing process. The additives, drying temperature, and the influence of crosslinker of films on the properties of the films were investigated. The mechanical properties, tensile strength (TS), elongation at break (% E), degree of swelling (DS), and solubility (S) of starch/PVA blend film were examined adding GL and CA as additives. At all measurement results, except for DS, the film adding CA was better than GL because hydrogen bonding at the presence of CA with hydroxyl group and carboxyl group increased the inter/intramolecular interaction between starch, PVA, and additives. CA improves the properties of starch/PVA blend film compared with GL. TS, % E, DS, and S of film adding GLU as crosslinking agent were examined. With increasing GLU contents, TS increases but % E, DS, and S value of GL‐added and CA‐added films decrease. When the film was dried at low temperature, the physical properties of the films were clearly improved because the hydrogen bonding was activated at low temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2554–2560, 2006     

Tensile properties,morphology, and biodegradability of blends of starch with various thermoplastics

In the present study, blends of starch with different thermoplastics were prepared by a melt blending technique. The tensile properties and morphology of the blends were measured. It was found that with increasing starch content in starch/ionomer blends, the tensile strength and modulus increase. But for starch/low‐density polyethylene (LDPE) and starch/aliphatic polyester (APES) blends, tensile strength and modulus decrease with increasing the starch loading. Elongation at break values of all the blend systems decrease with increasing starch loading. The scanning electron micrographs (SEM) support the findings of tensile properties. Better homogeneity is observed in starch/ionomer systems compared with that in starch/APES and starch/LDPE systems. Up to 50% starch content, the starch/ionomer blends appear as a single phase. The extent of phase interactions of starch/APES system lies in between the starch/LDPE and starch/ionomer systems. From the biodegradability studies of the blends it was found that, although the pure LDPE and ionomer are not biodegradable, the starch/LDPE and starch/ionomer blends are biodegradable with an appreciable rate. The rate of biodegradation of the starch/APES is very high as both the components are biodegradable. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2907–2915, 2002     

Preparation and properties of biodegradable thermoplastic starch/poly(hydroxy butyrate) blends

The vital differences using three types of thermoplastic starches (TPS), including potato starch, corn starch, and soluble potato starch, with two different gelatinization degrees to blend with poly(hydroxy butyrate) (PHB) are thoroughly discussed in this study. For blends containing a certain amount of PHB, thermal stability remains in a certain degree. In all cases of this study, mechanical properties of TPS blended with PHB confer higher performance than those of pristine TPS. In particular, a significant increase on tensile strength and tear strength is observed for TPS (potato starch) blended with PHB at low gelatinization degree. A suitable degree of gelatinization of starch is critical to achieve optimum performance. The investigation on the morphological observation partly features the supporting evidence of the above findings. The assessment of biodegradability indicates that the values of water absorption and weight loss increase with increasing treatment period and glycerol content, but decrease with increasing amount of PHB content. Among three types of starches investigated, the TPS (soluble starch)/PHB blend gives the highest level of water absorption and weight loss. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2371–2379, 2006     

Nano-SiO_2改性氧化淀粉/PVA复合薄膜的制备及表征

采用溶液法制备了氧化淀粉（OS）/PVA/SiO2生物可降解薄膜,并研究了薄膜的物理和生物可降解性。随着Nano-SiO2含量的增加,薄膜的拉伸性能和防水性能得到了增强。土埋降解实验表明,Nano-SiO2的加入对薄膜的生物降解性能没有影响。另外,FT-IR和DSC的分析结果表明,Nano-SiO2和氧化淀粉/PVA之间产生了氢键和C-O-Si化学键,增加了材料的物理性能和耐热性能。     

Grafting of vinyl acetate onto low density polyethylene—starch biodegradable films for printing and packaging applications

Starch‐based biodegradable low‐density polyethylene (LDPE) films were used for graft copolymerization of vinyl acetate with ceric ammonium nitrate (CAN) in aqueous acidic medium as redox initiator with nitric acid. The extent of grafting was examined by Fourier‐transform infrared (FTIR) spectroscopy, attenuated total reflectance (ATR) spectroscopy, X‐ray diffraction (XRD) and scanning electron microscopy (SEM). The objective behind the grafting of vinyl acetate onto the LDPE–starch biodegradable films is to make these suitable for printing and packaging applications without affecting the biodegradability of the original films. Copyright © 2004 Society of Chemical Industry     

Morphology,thermomechanical properties,and biodegradability of low density polyethylene/starch blends

The biodegradability of low density polyethylene (LDPE)/starch and LDPE/starch/starch acetate (STAc) blends was tested and observed to be dependent on STAc content. The binary and ternary blends containing up to a maximum concentration of 30% starch were examined for their thermal, mechanical, and morphological properties. The blends with no STAc or 2.5% STAc show almost no adherence of two phases. With 10% STAc, dispersion of starch was observed to increase with some adherence to LDPE. Tensile strength, elongation at break, and Izod impact strength of the blends decreased with increased starch content. However, incorporation of STAc along with starch improved all these properties, particularly elongation at break and toughness. The melt flow index was also improved on partial substitution of starch by STAc. Maximum biodegradability was observed for the blends containing 30% (starch + STAc). Cell growth was observed to increase with increasing concentration of (starch + STAc) in the blends. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2791–2802, 1999     

Mechanical,thermal, and biodegradation studies of polystyrene–phthalated starch blends using epoxy functionalized compatibilizer

Blends of polystyrene (PS) and esterified starch has been prepared using an epoxy functionalized PS as compatibilizer along with zinc stearate as prooxidant. The starch phthalate (Stph) loading was varied from 20 to 60%. The mechanical, thermal, and biodegradability studies of the blends were carried out as per the ASTM standards and the results were compared with that of neat PS. The blends exhibited enhanced mechanical properties with the addition of compatibilizer although the biodegradation rate slows down. The blend containing 40% starch ester with 12% compatibilizer showed maximum tensile strength. Thermogravimetric and differential scanning colorimetric analyses has been done for the blends, and the neat PS and the glass transition temperature of the blend has been obtained at 327 K. The water absorbency of the blends showed an increase with the increase in loading of Stph and a reduction with the addition of compatibilizer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

改性淀粉/LLDPE共混体系生物降解材料性能的研究

将自制接枝改性淀粉与LLDPE、玉米淀粉以及另外两种相容剂进行共混。通过对共混体系的形态结构、力学性能、流变性能、热性能以及对共混物薄膜的生物降解性能等的研究说明:复合相容剂MAH-g-PE+LA-g-starch的加入改善了淀粉和LLDPE的相容性,使得共混物体系具有适宜的拉伸强度及断裂伸长率;LLDPE/淀粉/(MAH-g-PE+LA-g-starch)共混物薄膜具有很好的生物降解性能。     

Structure and properties of casting films blended with starch and waterborne polyurethane

A series of casting films blended from starch and waterborne polyurethane (STPU) in aqueous solution were prepared. The structure and properties of the films were investigated by infrared spectroscopy, ultraviolet spectroscopy, scanning electron micrography, strength test, thermogravimetric analysis, and different scanning calorimetry. The results showed that the tensile strength and modules of air‐dried STPU blend films increased with the increase of starch content, while elongation decreased. When starch content was in the range from 80 to 90 wt %, the blend films showed significantly higher tensile strength, breaking elongation, water resistivity, and light transmittance than that of pure starch film, resulting from the miscibility between starch and waterborne polyurethane. Moreover, the STPU films containing 90 wt % starch have higher thermal stability than pure waterborne polyurethane film, and their light transmittance was close to the polyurethane, due to the existence of a strong intermolecular hydrogen bonding between starch and polyurethane. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2006–2013, 2001     

Effects of plasticizer/cross-linker on the mechanical and thermal properties of starch/PVA blends

Biodegradable blends of potato starch and polyvinyl alcohol were prepared by solution casting method. Citric acid was employed to introduce the plasticizing effect into the starch materials. Glutaraldehyde as cross-linker was used to enhance the properties of the blend films. Cross-linking is a common method to improve the strength and stability of starch products. The effects of citric acid and glutaraldehyde on the mechanical properties, thermal properties and swelling degree were investigated. The prepared films were measured for their antibacterial activities and biodegradability. The blend samples were characterized by the thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and FTIR analysis techniques. From the mechanical properties study, it was analyzed that the blend films showed improvement in their tensile strength after cross-linking with glutaraldehyde. The SEM micrographs indicated that the blend films were smooth without any cracks, pores and were well cross-linked. The TGA curves showed that there was an increase in the thermal stability of the blend films after cross-linking as compared to uncross-linked blend films. The prepared films showed good antibacterial properties against Gam-positive and Gram-negative bacteria. The biodegradability of the blends was determined by placing the samples in compost soil for different time intervals and were found to be biodegradable in nature.     

Effects of additives with different functional groups on the physical properties of starch/PVA blend film

The effects of additives with different functional groups, that is, hydroxyl and carboxyl groups, on the physical properties of starch/PVA blend films were examined. Starch/PVA blend films were prepared by the mixing process. Glycerol (GL) with 3 hydroxyl groups, succinic acid (SA) with 2 carboxyl groups, malic acid (MA) with 1 hydroxyl and 2 carboxyl groups, and tartaric acid (TA) with 2 hydroxyl and 2 carboxyl groups were used as additives. The results of measured tensile strength and elongation verified that hydroxyl and carboxyl groups as functional groups increased the flexibility and strength of the film. The degree of swelling (DS) and solubility (S) of the GL/SA‐added films were low. However, the DS and S of the films with added MA or TA with both hydroxyl and carboxyl groups were comparatively high. When the film was dried at low temperature, the properties of the films evidently improved, probably because hydrogen bonding was activated at low temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3733–3740, 2006     

Properties of compatibilized polylactide blend films with gelatinized corn and tapioca starches

Blend films containing two types of starch, various amounts of methylenediphenyl diisocyanate (MDI), and polylactide were prepared. The effects of MDI level and starch type on the tensile, thermal, and morphological properties of these films were investigated. The MDI amount was varied from 0 to 10 wt % on the basis of gelatinized starch (GS) content, whereas two types of starch (corn and tapioca) were added as fillers. In this study, the blend films were hot‐mixed at 180°C by an internal batch mixer and then compression‐molded to form test specimens. The results show that the addition of MDI as a compatibilizer led to an increase in the tensile properties compared with the uncompatibilized films. Furthermore, the thermal properties indicated some improving interfacial adhesion between the two phases, as evidenced by the morphological results. These behaviors were observed in the blends with both gelatinized tapioca starch and gelatinized corn starch. The different types of starch had no effect on the glass‐transition and melting‐temperature shifts, including water absorption of the blend films. On the other hand, the mechanical properties of the blends with gelatinized corn starch were higher than those of the others. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Environmentally Degradable Blends of Low Density Polyethylene (LDPE) and Partially Carboxymethylated Starch (PCMS)

Abstract

Sodium - salt of partially carboxymethylated starch (Na-PCMS) with degree of substitution (DS) 0.21 and 0.58 was synthesized by etherification of starch. These starch ethers and low density polyethylene (LDPE) were mixed with and without poly(vinylacetate) (PVAc) in various proportions using Brabender mixer. FTIR confirmed the etherification reaction of starch and blending. Positive changes in the mechanical properties as a function of blending, and environmental degradation have been observed. Addition of 5 wt% PVAc improves the blend quality. Samples were exposed to direct sunlight for one month and environmental degradation was measured in terms of change in tensile strength and per cent elongation.     

抗消化乙酰酯淀粉结构和结肠靶向性能研究

采用扫描电镜、X射线衍射和生物体外(In-V itro)降解等方法,对不同取代度DS的抗消化乙酰酯淀粉的颗粒形貌、结晶结构和生物降解性能进行了研究。结果表明:乙酰酯淀粉的颗粒表面变得粗糙并发生破损;随着乙酰基团取代度的增大,淀粉的抗消化性能不断提高,当DS>2时,淀粉中抗消化淀粉质量分数达到90%以上,其结晶结构也由A型向V型转变。生物体外降解试验表明,抗消化乙酰酯淀粉薄膜在模拟人体上消化道环境中的降解程度低于2.5%,在人工模拟结肠环境中的微生物降解程度为30%—50%,显示出潜在的结肠靶向性和微生物降解性。由此可见,抗消化乙酰酯淀粉适合作为菌群触发型口服结肠靶向药物控释载体材料。