Structural characteristics of biodegradable thermoplastic starch/poly(ethylene–vinyl alcohol) blends

To establish relationships among the blend composition, processing history, and the resultant properties of starch-based thermoplastics, three varieties of corn starch: (1) Waxy Maize, (2) Native Corn, and (3) high-amylose Hylon VII were extrusion-blended with poly(ethylene-vinyl alcohol) (EVOH) containing 56 mol % VOH. Wide-angle X-ray scattering (WAXS), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) were used to examine the structural characteristics of the blends. All starches were destructurized upon compounding and a fine dispersion was achieved with EVOH. The Native Corn and Hylon VII blends were phase-separated and exhibited some miscibility between the polymer components as evident in EVOH melting-point depression, smaller domain sizes, lower contrast between phases in TEM, and increased resistance to moisture and enzyme-etching treatments. Starches containing amylose exhibited complexation and crystallinity in the starch fraction, although most of the crystallinity in the blends was due to the EVOH component. Waxy Maize blends were well phase-separated with larger domain sizes and underwent phase coarsening as a function of time in the melt. When subjecting the blends to capillary flow, orientation of both starch-rich and EVOH-rich domains was observed at various compositions, with the EVOH component undergoing significantly more orientation relative to starch as evident by the presence of EVOH-rich fibrils. Finally, EVOH was found to coat the surfaces of filaments produced from the blends even at rather high levels of starch (70%), which is expected to improve moisture sensitivity and slow down the initial rate of biodegradation. © 1995 John Wiley & Sons, Inc.     

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     

不同直链含量热塑性淀粉的制备及性能研究

利用转矩流变仪,以丙三醇为增塑剂对不同来源的淀粉进行改性制备热塑性淀粉（TPS）。采用X射线衍射仪（XRD）、热重分析仪（TG）、水接触角测量仪、傅里叶变换红外光谱仪（FTIR）和扫描电子显微镜（SEM）等对获得的热塑性淀粉进行了表征。结果表明,4种热塑性淀粉均含有颗粒状和颗粒状碎片,并且在热塑性木薯淀粉中所含比例更高;淀粉在增塑过程中达到稳态的扭矩依次为木薯淀粉（23 N·m）>玉米淀粉（21 N·m）>马铃薯淀粉（17.8 N·m）>蜡质玉米淀粉（15.2 N·m）,这与不同种类来源淀粉的直链淀粉比例差异直接相关;不同类型的淀粉与增塑剂形成氢键的能力存在差异,蜡质玉米淀粉的能力最强;4种热塑性淀粉的亲水性依次为热塑性木薯淀粉（75.9 °）>热塑性玉米淀粉（69.2 °）>热塑性马铃薯淀粉（67.9 °）>蜡质玉米淀粉（64.9 °）。     

Structure and properties of compression-molded thermoplastic starch materials from normal and high-amylose maize starches

The structural and mechanical properties of compression-molded normal and high-amylose maize starches were studied as a function of processing water content and ageing time. Rubbery thermoplastic starches were produced by compression molding of four maize starches with differences in amylose content and amylopectin structure. Glycerol (30% on the basis of dry starch) and water (between 10 and 35% on the basis of total mass) were used as plasticizers. After processing, the amorphous thermoplastic starch materials crystallized during ageing. The semicrystalline materials contained both E-type and V-type, as well as B-type crystallinity. The properties of the thermoplastic starch materials are dependent on water content during processing, starch source, and ageing time. The normal maize starch materials are highly flexible with elongations between 56 and 104%. The elongations of the high-amylose maize starch materials were between 5–35%. The tensile stress and E-modulus of the normal maize starch materials were in the range of 3.9–6.7 and 27–131 MPa, respectively. The tensile stress and E-modulus of the high-amylose maize starch materials increased from approximately 0.5 to 23 and 5 to 700 MPa, respectively, with increasing water content during processing from 10 to 35%. The differences in mechanical properties of the normal and high-amylose materials were explained by differences in the structure of the amylose and amylopectin structure. It was concluded that both lead to differences in the starch network. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 631–644, 1997     

Irradiation-modification of starch-containing thermoplastic blends. I. Modification of properties and microstructure

Irradiation-modification of the blends of various starches with a synthetic polymer [poly(ethylene-co-vinyl alcohol)] was carried out using an electron beam. The effect of irradiation on neat starches was studies using gel permeation chromatography. Changes in the thermal and mechanical properties of the blends, as well as in their microstructures, were also evaluated. The data indicate, consistent with other reports in literature, that starch molecules fragment under the effect of ionizing radiation, while the EVOH is relatively unaffected. These substantial (mainly physical) modifications to the starch molecules manifest themselves in changes in the thermal behavior of the blends. Furthermore, the mechanical properties of filaments obtained from molten irradiated pellets were quite different from those of control filaments, at least for some starches. Micrographic examination of some blends indicated a correspondence between a modification in the microstructure of the filaments and a change in their mechanical properties. It seems likely that the enhanced mobility of the fragmented starch molecules in the melt is responsible for these changes in the microstructure and concomitantly, the mechanical properties of the blend. Such an irradiation-based physical modification of starch may be of use in tailoring the properties of commercial blends of starches with synthetic thermoplastics. © 1996 John Wiley & Sons, Inc.     

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     

Effect of blend composition and structure on biodegradation of starch/ecoflex‐filled polyethylene films

A method to blend starches and polyethylene, and thus improve the environmental footprint, was investigated. Unlike traditional methods that utilize compatibilizers or rely on reactive extrusion to achieve the desired material compatibility, a high amylose starch, such as Gelose 80, was mixed with native starch, converted to thermoplastic starch, and compounded with Ecoflex and polyethylene. Films showed good integrity and were evaluated for mechanical properties, anaerobic biodegradability, and structure changes both before and after anaerobic sludge digestion. Mechanical properties were sufficient that these films might be utilized in a number of applications but were not recommended as a sustainable solution. Biodegradation was below the theoretical maximum, was not a linear function of the amount of biodegradable materials incorporated in the films, and was depressed further as the proportion of polyethylene increased due to an encapsulation effect. Structural evaluation showed the components of the blends remained as separate phases and the structure of the Gelose 80 was reminiscent of interphase material. Biodegradation yield appeared to be principally driven by connectivity of the starches within the films to the anaerobic sludge digestion environment. Recommendations for additional studies were given. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Incorporating amylopectin in poly(lactic acid) by melt blending using poly(ethylene‐co‐vinyl alcohol) as a thermoplastic carrier. (I) morphological characterization

In this study, the possibility of using a biodegradable grade of thermoplastic poly(ethylene‐co‐vinyl alcohol) with high (71 mol %) vinyl alcohol (EVOH‐29), as a carrier to incorporate the renewable and biodegradable component amylopectin (AP) into poly(lactic acid) (PLA) through melt blending, was investigated. The effect of using a plasticizer/compatibilizer (glycerol) in the blend systems was also investigated. In a first step, the EVOH/AP blends were produced and thereafter, in a second step, these were mixed with PLA. In this first study, the blend morphology was investigated using optical microscopy, scanning electron microscopy and Raman imaging spectroscopy and the thermal properties were measured by differential scanning calorimetry. Despite the fact that EVOH and AP are both highly polar, their blends were immiscible. Still, the blends exhibited an excellent phase dispersion on a micron level, which was enhanced further by the addition of glycerol. A good phase dispersion was finally observed by incorporation of the latter blends in the PLA matrix, suggesting that the proposed blending route can be successfully applied for these systems. Finally, the Differential scanning calorimetry (DSC) data showed that the melting point of EVOH dropped in the EVOH/AP blends, but the properties of the PLA phase was still relatively unaffected as a result of blending with the above components. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effects of jet-cooking conditions upon intrinsic viscosity and flow properties of starches

This work examined the sensitivity of intrinsic viscosity values of jet-cooked waxy maize starch to initial pH conditions and the effects of jet-cooker steam pressure parameters upon the intrinsic viscosity and flow viscosity values of four jet-cooked starches. Flow viscosities of the 10 wt % cooked starches and intrinsic viscosities in 90% DMSO-H₂O were the lowest when mixing and turbulence during steam jet-cooking was increased (i.e., by adjusting steam line pressure vs. pressure within the cooking chamber to allow greater amounts of steam to flow through the apparatus). The percent decreases of the intrinsic viscosity caused by the most severe cooking conditions compared to gentle cooking conditions were 52, 45, 32, and 12, respectively, for waxy maize, waxy rice, normal maize, and 70% high amylose maize starches. Initial pH values, from 3 to 10.5, of waxy maize starch had minor effects upon the intrinsic viscosity of the jet-cooked material. © 1996 John Wiley & Sons, Inc.

1 This is a U.S. Government work and, as such, is in the public domain in the United States of America.

     

Properties of poly(lactic acid) blends with various starches as affected by physical aging

Poly(lactic acid) (PLA) and starch are both biodegradable and renewable polymers derived from agricultural feedstock. A previous study showed that a small amount (0.5%) of methylenediphenyl diisocyanate (MDI) could enhance the mechanical properties of starch and PLA blends by improving the interfacial interaction. In this study, blends of PLA (1/1, w/w) and starch with or without MDI were evaluated for thermal and mechanical properties as well as morphology, as affected by physical aging when stored up to 12 months at 25 °C and 50% relative humidity. The blends were prepared by thermally blending PLA with wheat starch, corn starch, and/or high amylose corn starch, with or without MDI. All samples exhibited phenomena of physical aging. The samples with MDI aged more slowly, showing a slower reduction rate of excess enthalpy relaxation, than those without MDI. The mechanical properties decreased slowly as aging proceeded. Microstructure showed a reduced interaction between starch and PLA around the interface with aging. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3683–3689, 2003     

New breathable films using a thermoplastic cross‐linked starch as a porogen

Breathable films, which find in variety of product applications, are conventionally made using mineral porogens such as calcium carbonate (CaCO₃). This article addresses a novel biodegradable and highly breathable film without inorganic porogens. Unexpectedly, a thermoplastic cross‐linked natural polymer (corn starch) was used successfully to create tortuous passages for film breathability. This concept was demonstrated using two types of thermoplastic cross‐linked corn starches as porogens and contrasted to control samples: native corn and chemically cross‐linked starches, respectively. The films discussed had increased breathability and mechanical properties relative to the control samples. The film morphology reveals that filler was irregular when thermoplastic starch or CaCO₃ was used. The difference in filler from chemically modified cross‐linked starch and thermoplastic cross‐linked starch was observable as well. It is believed that spherical particles provided by thermoplastic cross‐linked starch helps film debonding and porosity during the film stretch processes. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41016.     

Thermal,mechanical, and morphological characterization of biobased thermoplastic starch from agricultural waste/polypropylene blends

The thermal, mechanical, and morphological properties of biobased thermoplastic starch (TPS) obtained from agricultural waste seed (AWS) and agricultural waste tuber (AWT) blended with polypropylene (PP) were investigated in this article. The grounded (pulverized) AWS and AWT were different in amylose/amylopectin ratios and contained relatively low starch content (≤50%). The commercial grade of TPS (CS) and native tapioca starch blended PP (NTS/PP) were also prepared for comparison. The performances of the TPS/PP blends were dependent on the starch composition (e.g., amylose‐to‐amylopectin ratio), particle size, dispersion, and interfacial adhesion with matrix. The high‐amylopectin starch blend (i.e., AWS/PP) was more susceptible to thermal degradation than the amylose‐rich material (i.e., NTS/PP). The addition of starch to PP not only led to a stiffening effect (i.e., increase in storage modulus), but it also affected the relaxation of polymer matrix by shifting the thermal transition (i.e., glass transition temperature) to a higher temperature. POLYM. ENG. SCI., 54:1357–1365, 2014. © 2013 Society of Plastics Engineers     

Morphology and rheological properties of blends of chemically modified thermoplastic starch and polycaprolactone

Polycaprolactone (PCL) was blended in a twin‐screw extruder with chemically modified thermoplastic starch (CMPS) to provide biobased and biodegradable resin composition. Reacting starch with maleic anhydride (MA) in the presence of a plasticizer and a free radical initiator provided the CMPS. The starch modification improved interfacial adhesion and processability in blending with other thermoplastic polyesters. The rheological, mechanical, thermal, and morphological properties of the blends were examined. Differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and Fourier transform infrared (FTIR) studies revealed that the PCL/CMPS blends are thermodynamically immiscible. However, they formed compatible blends due to the reaction of the carboxyl groups on starch backbone with hydroxyl groups of the PCL chain ends. The tensile strength and elongation decreased with increasing CMPS content, whereas the modulus increased. Dynamic viscoelastic measurements showed that the flow behavior of PCL was that of Newtonian fluid within the tested frequencies, whereas the CMPS exhibited strong shear thinning characteristics. The flow behavior of the blends varied with the CMPS content. The complex viscosity, storage, and loss moduli of the blends containing more than 40% of CMPS were higher than those of pure CMPS and PCL. In addition, the properties of CMPS to those of chemically unmodified thermoplastic starch (TPS) were compared. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Structure and properties of starch/poly(ethylene-co-vinyl alcohol) blown films

Blends of native corn starch and poly(ethylene-co-vinyl alcohol) (EVOH), with starch: EVOH ratios of 1 : 1 (SE-50) and 2 : 1 (SE-67A, SE-67B), were processed into blown films. SE-67A had a higher glycerol and water content and was processed at 5°C higher than was SE-67B. The films were conditioned to various moisture contents by equilibrating at a constant relative humidity and by oven drying at 41°C. Equilibrium moisture content, which ranged from 2 to 11%, increased with increasing starch content at a given relative humidity. Mechanical properties depended strongly on starch and moisture content as well as on processing history. The extension to break of SE-50 was only about one-third that of EVOH, while that of the 2 : 1 blends was even lower. SE-67A exhibited a higher extension to break, lower tensile strength and modulus, and greater moisture sensitivity than those of SE-67B. Differential scanning calorimetry and dynamic mechanical analysis revealed evidence of interactions between starch and EVOH, probably indicative of extensive intermixing but not necessarily miscibility. Scanning electron micrographs of fracture surfaces revealed extensive differences in texture with microcracking in SE-50 and SE-67A. The combination of the analytical results provide a basis for explaining many aspects of the mechanical behavior including the marked difference in properties between SE-67A and SE-67B. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 2613–2622, 1997     

Tailoring morphology to improve the gas‐barrier properties of thermoplastic polyurethane/ethylene‐vinyl alcohol blends

The morphology and helium‐barrier properties of thermoplastic polyurethane (TPU)/ethylene‐vinyl alcohol (EVOH) blends with and without dicumyl peroxide (DCP) were investigated by melting blending. A lamellar dispersion of EVOH with good helium‐barrier properties was observed in the TPU matrix with DCP. The evolution of the morphology of the blends is mainly related to the variation of the viscosity ratio between the dispersed phase and the matrix phase. Compared with pure TPU, lamellar morphology increased the helium‐barrier properties of the TPU/EVOH (60/40) blend by as much as 10‐fold. We also explored the effects of composition, DCP content, and blending sequence on the morphology and helium‐barrier properties of the TPU/EVOH blends. The morphology of the blends ranged from a droplet‐matrix to a lamellar structure. We determined the optimum amount of DCP to improve the helium barrier of the blends. The helium‐barrier properties of the blends prepared by direct blending were superior to those of the blends prepared by two‐segment blending, and the blends prepared by direct blending exhibited a well‐developed lamellar morphology. We compared the permeability of the samples with the theoretical results to explain the relationship between morphology and helium‐barrier properties. POLYM. ENG. SCI., 56:922–931, 2016. © 2016 Society of Plastics Engineers     

Structural changes of injection molded starch during heat treatment in water atmosphere: Simultaneous wide and small‐angle X‐ray scattering study

Native starches with wide varying amylose content were processed by injection molding. The injection‐molded materials were conditioned in water for 20 days and sealed in glass capillaries. Simultaneous wide‐ and small‐angle X‐ray scattering (WAXS and SAXS, respectively) were recorded during thermal heating using a synchrotron source. Crystallinity, SAXS invariant, Q, and long period, L, were measured as a function of heating temperature. The injection‐molding process provokes a destruction of the crystal forms A (cereal starch) and B (tubercle starch) but favors a development of the crystal form V_h. After wet conditioning, WAXS of the injection‐molded samples shows again the appearance of the crystal forms A or B, and crystallinity reaches values similar or larger than those of native starch. A constant heating rate (5°C/min) was particularly used for a comparison of potato and corn starch with a similar amylose content. While the crystallinity associated to forms A and B slowly decreases below 55°C and then rapidly decreases until its disappearance at 85–90°C, the invariant shows a maximum around 40°C and rapidly decreases thereafter. The total nanostructure disappearance occurs at temperatures about 10°C higher for the case of potato starch. In addition, a recovery of the WAXS and SAXS maxima during the subsequent cooling process before reaching room temperature was observed only for potato starch. Analysis of WAXS and SAXS for the rest of the starch materials reveals clear differences in the structural parameters of the samples that cannot be easily explained solely on the basis of the amylose content. Thus, for Cerestar and Roquette, it is noteworthy that there was a continuous decrease of L until its total disappearance as well as the persistence of crystallinity (form B), presumably stabilized by the presence of the V_h structure (12–15%). Real‐time crystallization experiments on two amorphous injection molded samples, waxy maize (free amylose starch) and potato starch, are also discussed. It is shown that the absence of amylose delays the recrystallization of amylopectine during the experiment. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 301–309, 2004     

The effect of temperature on the observed flow-induced structure in semidilute solutions of gently solubilized starches

The effect of temperature on the unexpected shear-thickening behavior exhibited by semidilute solutions of waxy maize starch during a repeated shear-loop experiment was evaluated. Shear-thickening behavior, characterized using power law models, was observed for waxy maize starch, but not for normal maize starch at the same concentration. The shear-thickening region was observed for waxy maize starch at temperatures ranging from 25°C to 80°C and shear rates from 2–100 s^?1 during the initial part of the shear-loop experiment. For waxy maize starch, the power law exponent, n, was found to be 0.539 ± 0.017 in the shear-thinning region. For normal maize starch, the value of n was found to be equal to 0.751 ± 0.015 and only shear-thinning behavior was observed. The values of n for both waxy maize and normal maize starch were found to be temperature independent within the precision of the experimental measurements. The differences in n indicate the differences in the conformational dynamics of waxy maize and normal maize starches in solution.     

Film processability and properties of polycaprolactone/thermoplastic starch blends

In this work, the processing and properties of blown films prepared from thermoplastic corn starch (TPS) and polycaprolactone (PCL) were studied, in particular at high TPS content. The influence of processing parameters and material moisture content on the tensile properties was also studied. The results show that final film properties are mainly controlled by the draw ratio, blow‐up ratio and PCL concentration in the blends. The results also show that PCL/TPS films are less hydrophilic as PCL content increases. Finally, it was found that a very narrow processing window exists for this blend. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

The distribution of lipids in the germ,endosperm, pericarp and tip cap of amylomaize,LG-11 hybrid maize and waxy maize

The quantitative distribution of 23 acyl lipid classes and unsaponifiable matter in kernels of amylomaize, LG-11 hybrid maize and waxy maize is described. LG-11 and waxy maize were normal (oil content) varieties, containing 4.9% and 5.1% lipid, respectively, while amylomaize (9.3% lipid) was a high oil variety. The distribution of kernel lipids was 76–83% in germ, 1–2% in pericarp, 1% in tip cap, 1–11% in starch, and 13–15% in aleurone plus the nonstarch fraction of the starchy endosperm. Germ contained 39–47% lipid, which was nostly triglyceride (TG), with some steryl esters (SE) and diglycerides (DG), and small amounts of glycolipids (GL) and phospholipids (PL). Aleurone lipids appeared to be TG with some free fatty acids (FFA) and SE. The other nonstarch lipids in starchy endosperm were FFA with very small amounts of SE, DG, GL and PL. The starches had a little surface lipid (FFA) and true (internal) starch lipid (FFA, lyso-PL) in quantities roughly related to amylose content (amylomaize =ca. 73% amylose, 1.0% lipid; LG-11=23% amylose, 0.7% lipid; waxy maize =<5% amylose, 0.2% lipid). Pericarp lipids (0.8–2.5%) were mainly unsaponifiable matter, the acyl lipids being TG, SE, DG and FFA. Tip cap lipids (2.5–2.9%) had more TG, GL and PL than pericarp lipids, but were otherwise similar. Pericarp lipids and endosperm nonstarch lipids appeared to have suffered extensive degradation at some time during kernel development or after harvesting, while lipids in starch, germ and tip cap were evidently unaffected. FFA and lyso-PL are regarded as normal components of maize starch (rather than degradation products) and may occur as amylose inclusion complexes.     

Morphology and properties of compatibilized polylactide/thermoplastic starch blends

This paper investigates the properties and interfacial modification of blends of polylactide (PLA) and glycerol-plasticized thermoplastic starch (TPS). A twin-screw extrusion process was used to gelatinize the starch, devolatilize the water to obtain a water-free TPS and then to blend into the PLA matrix. The investigated TPS concentration ranged from 27 to 60 wt%. In the absence of interfacial modification, the TPS/PLA blend morphology observed through scanning electron microscopy was very coarse with TPS particles sizes between 5 and 30 μm. Interfacial modification was achieved by free-radical grafting of maleic anhydride (MA) unto the PLA and then by reacting the modified PLA with the starch macromolecules. Blends comprising MA-grafted PLA showed much finer dispersed phase size, in the 1–3 μm range and exhibited a dramatic improvement in ductility. The paper discusses the effects of two interfacial modification strategies on the blend morphology and tensile properties and investigates the compatibilization efficiency for glycerol plasticizer contents between 30 and 39 wt% and for starches from three different sources: wheat, pea and rice.