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     

Extrusion Foaming of Poly (lactic acid)/Soy Protein Concentrate Blends

Poly(lactic acid) (PLA) and soy protein concentrate (SPC) were compounded using poly(2‐ethyl‐2‐oxazoline) as compatibilizer by twin‐screw extrusion, and the resulting blends were foamed by a chemical blowing agent (CBA) using the same extruder. Effects of foaming temperature and CBA content on cell density and foam density were investigated. Polymeric methylene diphenyl diisocyanate (pMDI) as a co‐compatibilizer was added prior to foaming extrusion and its effects on foam morphology and properties were also studied. The results showed that cell density and foam density were greatly influenced by foaming temperature and CBA content. Using the strong interfacial modifier pMDI in PLA/SPC blends resulted in high‐cell density and low‐foam density when CBA concentration was low.

     

Crystallinity development in cellular poly(lactic acid) in the presence of supercritical carbon dioxide

This article investigates the crystallinity development in cellular poly(lactic acid) (PLA) and the effect of the achieved crystalline content on its properties and microstructure. Carbon dioxide (CO₂) in its supercritical state was used as the expansion agent for three different grades of PLA that differed in terms of L‐lactic acid content. Cellular PLA was produced on a twin‐screw extrusion line using capillary dies of various diameters. The obtained crystalline contents were measured by differential scanning calorimetry and X‐ray diffraction techniques. The morphology of the cellular structures was examined using scanning electron microscopy. The crystallinity developed on expansion depended on L‐lactic acid content, on supercritical CO₂ concentration, polymer flow rate, and die diameter. Cellular PLA, with densities as low as 30 kg/m³, was obtained under the most favorable conditions. It was shown that the crystallinity development in PLA enhances its cellular structure formation and enables the fabrication of quality cellular materials at lower CO₂ concentration. The presence of PLA crystallites within expanded cell walls leads to a peculiar 2D‐cavitation phenomena observed only in the cell walls of semicrystalline foams. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Thermal degradation and biodegradability of poly (lactic acid)/corn starch biocomposites

Thermal degradation and biodegradability of poly (lactic acid) (PLA) and poly (lactic acid)/corn starch (PLA/CS) composites with and without lysine diisocyanate (LDI) were evaluated by thermogravimetric analysis measurement and enzymatic degradation using Proteinase K and burial tests, respectively. Thermal stability was decreased by addition of CS and the composites with LDI showed higher thermal degradation temperature than those without LDI. In enzymatic biodegradation, the weight remaining of all samples decreased almost linearly with time. The addition of CS resulted in a faster rate of degradation and the composites with LDI were more difficult to degrade than those without it. In the composite without LDI, the degradation was faster at the interface between PLA and CS, showing deep and wide clearance, but degradation starting at the interface was not clearly observed in the composite with LDI. There was no considerable difference in molecular weight and distribution of the samples after enzymatic degradation. The lactic acid content of the water‐soluble product obtained after enzymatic degradation increased with degradation time. In burial tests, pure PLA was little degraded but the composites gradually degraded. The degradation of the composite without LDI was faster than that of the composite with LDI. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3009–3017, 2006     

Biodegradable polymer blends of poly(lactic acid) and poly(ethylene glycol)

Poly(lactic acid) (PLA) and poly(ethylene glycol) (PEG) were melt-blended and extruded into films in the PLA/PEG ratios of 100/0, 90/10, 70/30, 50/50, and 30/70. It was concluded from the differential scanning calorimetry and dynamic mechanical analysis results that PLA/PEG blends range from miscible to partially miscible, depending on the concentration. Below 50% PEG content the PEG plasticized the PLA, yielding higher elongations and lower modulus values. Above 50% PEG content the blend morphology was driven by the increasing crystallinity of PEG, resulting in an increase in modulus and a corresponding decrease in elongation at break. The tensile strength was found to decrease in a linear fashion with increasing PEG content. Results obtained from enzymatic degradation show that the weight loss for all of the blends was significantly greater than that for the pure PLA. When the PEG content was 30% or lower, weight loss was found to be primarily due to enzymatic degradation of the PLA. Above 30% PEG content, the weight loss was found to be mainly due to the dissolution of PEG. During hydrolytic degradation, for PLA/PEG blends up to 30% PEG, weight loss occurs as a combination of degradation of PLA and dissolution of PEG. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1495–1505, 1997     

连续挤出发泡聚乳酸泡孔结构的影响因素

介绍了采用超临界CO2作为发泡剂,连续挤出聚乳酸泡沫塑料的方法。在不同的实验条件下,对聚乳酸进行挤出发泡,得到聚乳酸发泡样品。通过对样品的ESM照片的分析研究,得出了不同的发泡条件对挤出聚乳酸泡沫泡孔结构的影响。结果表明螺杆转速的增加使得泡孔数量增加,泡孔形态更加规整均匀。模头温度影响了泡孔形态,较高的温度会使得样品的泡孔形态受到不利的影响。水分的存在不利于聚乳酸发泡成为均匀发泡倍率高的泡沫制品。成核剂促进异相成核,使发泡样品的泡孔结构更加均匀,大大提高了聚乳酸泡沫塑料的泡孔密度。     

Strengthening blends of poly(lactic acid) and starch with methylenediphenyl diisocyanate

Poly(lactic acid) (PLA) is a biodegradable polymer, but its applications are limited by its high cost. Blending granular starch with PLA reduces the cost, but the blend has poor strength properties. In this study, a 55/45 (w/w) mixture of PLA (weight‐average molecular weight = 120,000 Da) and dried wheat starch was blended thermally in an intensive mixer with or without a low level of methylenediphenyl diisocyanate (MDI). Blends with MDI had enhanced mechanical properties that could be explained by the in situ formation of a block copolymer acting as a compatibilizer. Scanning electron micrographs showed reduced interfacial tension between the two phases. The presence of MDI also enhanced the mechanical properties of the blend at temperatures above the glass‐transition temperature. Water uptakes by the PLA/starch blends with and without MDI did not differ. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1761–1767, 2001     

Mechanical and thermal properties of poly(lactic acid)/starch blends with dioctyl maleate

Poly(lactic acid) (PLA)/starch blends were prepared blending with dioctyl maleate (DOM). DOM acted as a compatibilizer at low concentrations (below 5%), and markedly improved tensile strength of the blend. However, DOM functioned as a plasticizer at concentrations over 5%, significantly enhancing elongation. Compatibilization and plasticization took place simultaneously according to the analysis of, for example, mechanical properties and thermal behavior. With DOM as a polymeric plasticizer, thermal loss in the blends was not significant. Water absorption of PLA/starch blends increased with DOM concentration. DOM leaching in an aqueous environment was inhibited. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1697–1704, 2004     

微孔发泡聚乳酸/木纤维复合材料的泡孔结构

引言聚乳酸(PLA)因具有环境友好性和降解性而被用于制备不同泡孔结构的泡沫制品[1],然而PLA呈现低的熔体强度和窄的加工窗口,这不利于以超临界流体(如超临界二氧化碳Sc-CO2)发泡制备微孔PLA材料[2-3]。加入填料(如二氧化硅[4]、羟基磷灰石[5]和蒙脱土[6]等)可改善PLA     

Biodegradable poly(L‐lactic acid)/TiO2 nanocomposites: Thermal properties and degradation

Poly(L ‐lactic acid)‐titanium dioxide nanocomposites (with various loadings of TiO₂: 0.5, 1, 2, 5, and 10 wt %) were produced by solution casting method. The influence of TiO₂ on thermal properties and crystallinity of PLA was investigated by DSC and FTIR spectroscopy. The TiO₂ nano filler has no significant influence on the characteristic temperatures (T_g, T_c, and T_m), but has high impact on the crystallinity of these systems. The degree of crystallinity X_c significantly increases for PLA nanocomposites loaded with up to 5 wt % of TiO₂, while for 10 wt % load of TiO₂ it drops below X_c of the pure resin. The degradation of the prepared composites was evaluated hydrolytically in 1N NaOH, enzymatically in α‐amylase solutions, and under UV irradiation. The catalytic effect of TiO₂ nano particles on the degradation processes under UV light exposure (λ = 365 nm) and hydrolytic degradation was confirmed with the increase of the filler content. The opposite effect was identified in enzymatic degradation experiments. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

聚乳酸/聚乙烯醇纳米纤维的制备及结构

以二甲基亚砜为溶剂,制备不同配比的聚乳酸(PLLA)和聚乙烯醇(PVA)的混合溶液,静电纺丝制得PLLA/PVA纳米纤维。采用红外光谱仪、原子力显微镜等对PLLA/PVA纳米纤维结构与性能进行了表征。结果表明:PLLA/PVA纳米纤维中PVA上的羟基与PLLA上的羰基形成了氢键,PLLA与PVA之间存在一定的相互作用,但PLLA/PVA纳米纤维存在相分离现象;混合溶液的PLLA质量分数为11%,PVA质量分数为8%时可以得到较好的PLLA/PVA纳米纤维,但PVA质量分数为6%时出现液滴及珠丝,PVA质量分数为4%时,不能制得纳米纤维。     

Properties of mineral filled poly(lactic acid)/poly(methyl methacrylate) blend

This study examines the influence of three different minerals, that is, clay, calcium carbonate, and quartz on the physical, thermal, and mechanical properties of poly(lactic acid) (PLA)/poly(methyl methacrylate) blend. Rheological behavior and phase structure were initially studied by small-amplitude oscillatory shear rheology. Clay- and quartz-filled materials presented an increase in viscosity at low frequency associated with the presence of a yield stress. However, this behavior was not observed for calcium carbonate filled materials due to a matrix degradation effect. To elucidate this aspect, thermal stability and thermal properties were examined by thermogravimetric analysis and differential scanning calorimetry, showing that calcium carbonate promotes degradation of the PLA phase. No nucleating effect was observed in the presence of the minerals. Dynamical mechanical analysis and mechanical characterization revealed an increase of the overall softening temperature and, a reinforcing effect for clay- and quartz-based composites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46927.     

Effects of moisture content and heat treatment on the physical properties of starch and poly(lactic acid) blends

Starch, a hydrophilic renewable polymer, has been used as a filler for environmentally friendly plastics for about 2 decades. Starch granules become swollen and gelatinized when water is added or when they are heated, and water is often used as a plasticizer to obtain desirable product properties. The objective of this research was to characterize blends from starch and poly(lactic acid) (PLA) in the presence of various water contents. The effects of processing procedures on the properties of the blends were also studied. Blends were prepared with a lab‐scale twin‐screw extruder, and tensile bars for mechanical testing were prepared with both compression and injection molding. Thermal and mechanical properties of the blends were analyzed, and the morphology and water absorption of the blends were evaluated. The initial moisture content (MC) of the starch had no significant effects on its mechanical properties but had a significant effect on the water absorption of the blends. The thermal and crystallization properties of PLA in the blend were not affected by MC. The blends prepared by compression molding had higher crystallinities than those prepared by injection molding. However, the blends prepared by injection molding had higher tensile strengths and elongations and lower water absorption values than those made by compression molding. The crystallinities of the blends increased greatly with annealing treatment at the PLA second crystallization temperature (155°C). The decomposition of PLA indicated that PLA was slightly degraded in the presence of water under the processing temperatures used. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3069–3082, 2001     

The morphology,rheological, and mechanical properties of wood flour/starch/poly(lactic acid) blends

An entirely biosourced blend composed of poly(lactic acid) (PLA), starch, and wood flour (WF) was prepared by a co‐extruder with glycerol as a plasticizer. The morphology, rheological properties, and mechanical properties of the WF/starch/PLA blends were comprehensively analyzed. The results showed that with the decrease of the starch/WF ratio, the morphology experienced a large transformation, and the compatibility of the blends was found to be superior to other blends, with a starch/wood flour ratio of 7/3. The dynamic mechanical thermal analysis (DMA) results demonstrated the incompatibility of the components in WF/starch/PLA blends. Following the decrease of the starch/WF ratio, the storage modulus (G″) and the complex viscosity (η*) of the blends increased. The mechanical strength first increased, and then decreased with the increase of the WF concentration. The water absorption results showed that the water resistance of the blends was reduced with the lower starch/WF ratio. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44743.     

Improved processability and performance of biomedical devices with poly(lactic acid)/poly(ethylene glycol) blends

To improve the processability of micropolymer‐based devices used for biomedical applications, poly(lactic acid) (PLA) was melt‐blended with poly(ethylene glycol)s (PEGs) of different molecular weights (MWs; weight‐average MWs = 200, 800, 2000, and 4000; these PEGS are referred to as PEG200, PEG800, PEG2000, and PEG4000, respectively, in this article). The thermal properties, mechanical properties, and rheological properties of the PLA and the PLA–PEG blends were investigated. The tensile samples’ morphologies showed that the low‐MW PEGs filled molds well. The rheological properties confirmed that the low‐MW PEGs decreased the complex viscosity, and improved the processability. With decreasing PEG MW, the PLA glass‐transition temperature decreased. The nanoindenter data show that the addition of PEG decreased the modulus and hardness of PLA. The morphologies of the tensile samples showed that with increasing PEG MW, the thicknesses of the core layers increased gradually. The elongation at break was improved by approximately 247% with the addition of PEG200. Such methods can produce easily processed biological materials for producing biomedical products. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45194.     

Relationship between the crystallization behavior of poly(ethylene glycol) and stereocomplex crystallization of poly(L‐lactic acid)/poly(D‐lactic acid)

Poly(l ‐lactic acid) (PLLA) is a good biomedical polymer material with wide applications. The addition of poly(ethylene glycol) (PEG) as a plasticizer and the formation of stereocomplex crystals (SCs) have been proved to be effective methods for improving the crystallization of PLLA, which will promote its heat resistance. In this work, the crystallization behavior of PEG and PLLA/poly(d ‐lactic acid) (PDLA) in PLLA/PDLA/PEG and PEG‐b‐PLLA/PEG‐b‐PDLA blends has been investigated using differential scanning calorimetry, polarized optical microscopy and X‐ray diffraction. Both SCs and homocrystals (HCs) were observed in blends with asymmetric mass ratio of PLLA/PDLA, while exclusively SCs were observed in blends with approximately equal mass ratio of PLLA/PDLA. The crystallization of PEG was only observed for the symmetric blends of PLLA_39k/PDLA_35k/PEG_2k, PLLA_39k/PDLA_35k/PEG_5k, PLLA_69k/PDLA_96k/PEG_5k and PEG‐b‐PLLA_31k/PEG‐b‐PDLA_27k, where the mass ratio of PLLA/PDLA was approximately 1/1. The results demonstrated that the formation of exclusively SCs would facilitate the crystallization of PEG, while the existence of both HCs and SCs could restrict the crystallization of PEG. The crystallization of PEG is related to the crystallinity of PLLA and PDLA, which will be promoted by the formation of SCs. © 2017 Society of Chemical Industry     

聚乳酸/羟丙基淀粉复合降解型材料的制备和表征

羟丙基改性淀粉作为填充剂,在偶联剂作用下与聚乳酸共混、挤出制备聚乳酸/羟丙基淀粉复合降解型材料。随着羟丙基改性淀粉含量的增加,共混材料的硬度略有增加、拉伸强度和断裂伸长率都先减小后增大,材料的吸水率和降解速率增加,且改性淀粉取代度的增加有利于提高材料的韧性。     

可生物降解聚乳酸发泡材料研究进展

综述了聚乳酸(PLA)发泡材料在包装领域、汽车领域和生物医疗领域的多种应用现状,概括了釜压发泡法、连续挤出发泡法、注塑发泡法以及其他发泡成型法制备PLA发泡材料的成型机理及泡孔结构特点,重点介绍了分子链结构改性、共混改性和微米/纳米级填充改性等较为有效的PLA改性方法,以及各种改性方法所制备的PLA发泡材料的泡孔形态特征。     

Biodegradation study of a coextruded starch and poly(lactic acid) material in various media

The biodegradation of a coextruded starch/poly(lactic acid) polymeric material was studied in a liquid, in an inert solid, and in composting media. Mineralization of the material's carbon content was followed using the appropriate ASTM standard experimental methods. The final percentage of biodegradation depended on the nature of the medium used. The percentage of mineralization (Cg) was better with the liquid medium (65%) than with either the compost medium (64%) or the inert medium (59%). To understand the workings of the biodegradability of the polymer material, a measurement of the carbon balance seemed essential A repartitioning of the material's carbon between the various degradation products to biomass carbon (Cb), to carbon dioxide carbon (Cg), to dissolved organic carbon (Cs), and to residual insoluble material carbon (Cnd) produced was quantified throughout the experimental runs. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 825–831, 2003     

Recyclability Studies on Poly(lactic acid)/Poly(butylene succinate-co-adipate) (PLA/PBSA) Biobased and Biodegradable Films

Poly(lactic acid)/poly(butylene succinate-co-adipate) (PLA/PBSA) blends are found promising for film packaging applications because of their flexibility, resistance, and compostability. Industrially extruded granules and films based on PLA and containing different amounts of PBSA are reprocessed through mini-extrusion, to simulate recycling, and tested in terms of their melt flow rate as a function of PBSA content. Moreover, pure PLA commercial granules and the film produced extruding the PLA/PBSA 60/40 blend are reprocessed several times by injection molding and characterized in terms of melt flow rate, mechanical properties, thermal properties, and color as a function of injection molding cycles. The variation in melt fluidity and thermo-mechanical properties is negligible up to 3 injection molding cycles for both pure PLA granules and PLA/PBSA blend. In the case of blend the change in color (yellowing and darkening) is more evident and slight local compositional change in injection molded items can be evidenced as well as a slight decrease in PBS crystallinity as a function of injection molding cycles. Nevertheless, in applications where these aspects are not critical, these materials can be recycled by extrusion or injection molding before being composted, thus prolonging their life cycle and storing carbon in them as longer as possible.