Poly(lactic acid)/coplasticized thermoplastic starch blend: Effect of plasticizer migration on rheological and mechanical properties

Polylactic acid (PLA) and thermoplastic starch (TPS) are known as bio‐based and biodegradable thermoplastic polymers that can be used in different applications owing to their inherent physical and mechanical properties. In order to reduce the higher costs of PLA and tuning its physical and mechanical properties suitable for short life packaging applications, blending of PLA with the TPS, more economical biodegradable polymer, has been considered in academic and industrial researches. However, melt blending of PLA with TPS without compatibilization process caused some drawbacks such as coarsening morphology and declining mechanical properties and ductility because of thermodynamic immiscibility, which may restrict its usage in packaging applications. Subsequently, our approach in this research is compatibilization of PLA/TPS blends by utilization of primary well tuning of TPS formulation with a combination of sorbitol and glycerol plasticizers. In this work, the wide composition range of melt mixed PLA/TPS blends was prepared using a laboratory twin screw extruder. The effects of microstructure on the rheological and mechanical properties of PLA/TPS blends were studied using different methods such as scanning electron microscopy (SEM) images, contact angle, oscillatory shear rheological measurements, and tensile and impact strength mechanical tests. The rheological and mechanical properties were interpreted according to the morphological features and considering the possibility of plasticizer migration from TPS to PLA phase during melt blending. Reduction in complex viscosity and storage modulus of PLA matrix samples indicates the improved melt processability of blends. Finally, in comparison with mechanical results reported in literature, our simple approach yielded the blends with elastic modulus and ductility comparable with those of chemically compatibilized PLA/TPS blends.     

接枝聚乳酸/塑化淀粉共混物的制备与性能研究

为提高聚乳酸(PLA)/淀粉共混物界面作用和降低成本,引入甲基丙烯酸缩水甘油酯(GMA)接枝聚乳酸和塑化淀粉(TPS),通过挤出和注射成型制备接枝聚乳酸/塑化淀粉共混物(PLA-g-GMA/TPS)。红外光谱分析证实,GMA成功接枝到PLA分子链上。对共混物的力学性能、热机械性能、微观形貌、热性能及亲水性等进行了系统研究,结果表明,选择GMA用量为6%(接枝率为1.51%)和TPS用量为10%时的拉伸强度、断裂伸长率及弹性模量最佳,分别为42.6MPa、8.9%及260MPa。FE-SEM观察结果表明,低含量TPS中颗粒被基体包覆或嵌入,界面平整,界面结合力强。DMA和DSC结果显示,不同质量配比的PLA-g-6%GMA/TPS共混物的Tg、储存模量、结晶度、结晶温度及熔融温度仅在小范围内发生变化。吸水率和接触角结果表明,低含量TPS的共混物吸水率和接触角变化幅度均小于高含量TPS体系。     

醋酸淀粉/聚乳酸的制备及性能的影响研究

采用自设计的双螺杆结构挤出制备聚乳酸(PLA)/醋酸淀粉(AS)的全生物降解材料,考察材料的AS的含量和取代度对复合材料动态流变性能、机械性能的影响。研究结果表明,AS含量明显影响复合材料的力学性能、复合黏度和储能模量:当AS含量从45%增加到70%,材料的拉伸强度下降,复数黏度和储能模量则提高。随着AS取代度由1.0上升为3.0,复合材料的复数黏度和储能模量下降,拉伸强度由12.0MPa上升为15.5MPa。对复合材料进行电镜扫描分析发现,AS以海岛结构形式分散在PLA的连续相中,取代度2.0的AS与PLA相容性最好,当其质量含量达到70%,材料的拉伸强度仍然不低于10.0MPa,具有较好的机械强度。     

甲酰胺塑化热塑性淀粉的性能研究

用甲酰胺作为塑化剂制备了热塑性淀粉 (TPS) ,扫描电镜显示甲酰胺可以使淀粉塑化 ,形成均一的连续相 ;流变性能说明在加工温度范围内 ,甲酰胺塑化淀粉 (FPTPS)的剪切应力对温度变化敏感性要小于甘油塑化淀粉 (GPTPS) ;用热重和DSC研究了热稳定性和玻璃化转变 ;FPTPS在 13%～ 2 3%的水含量时有较好的力学性能 ,水含量为 13%时 ,FPTPS有最大的断裂强度 3 9MPa ;水含量为 17%时 ,FPTPS最大的伸长率为 95 % ;与GPTPS相比 ,在RH(Relativehumidity) =0 5 0 %and 10 0 %环境下 ,FPTPS有良好的耐回生性能 ,这主要是因为甲酰胺可以和淀粉羟基形成更稳定的氢键     

Physical and degradation properties of binary or ternary blends composed of poly (lactic acid), thermoplastic starch and GMA grafted POE

Binary and ternary blends composed of poly (lactic acid) (PLA), thermoplastic starch (TPS) and glycidyl methacrylate grafted poly (ethylene octane) (GPOE) were prepared using Haake Mixer. The mechanical morphology, thermal properties, water absorption, and degradation properties of the blends were also investigated. The elongation at break and impact strength of the ternary blends were greatly increased by the filling of GPOE. Compared to non-GPOE binary blends, the morphology of ternary blends with GPOE indicated that starch granules melted and there was good compatibility between PLA matrix and TPS. The mechanism and schematic diagram of the reactions in PLA, TPS, and GPOE were proposed and proved by testing and observing the morphology. Moreover, the biodegradation and thermal decomposition were studied through compost testing and thermal gravimetric analysis, respectively. Biodegradation results indicated that the blends have the excellent biodegrade ability.     

尿素和甲酰胺塑化热塑性淀粉

用甲酰胺和尿素作为塑化剂制备了热塑性淀粉 (TPS) .扫描电镜显示甲酰胺和尿素混合物可以使淀粉塑化 ,形成均一的连续相 ;根据FT IR谱图可以确定 ,与甘油相比 ,甲酰胺可以使热塑性淀粉体系在保存时更稳定 ,各基团的化学环境变化更小 ,这是由于甲酰胺可以和淀粉羟基形成更稳定的氢键 .X ray衍射说明甲酰胺和尿素 (重量比为 10 % 2 0 % )作为混合塑化剂可以有效抑制淀粉的回生 ,同时防止尿素结晶析出 .在RH=33%的湿度环境保存 1周 ,这种热塑性淀粉有良好的拉伸强度、伸长率和断裂能 ,分别达到 4 83MPa ,10 4 6 %和 2 17N·m .水含量对热塑性淀粉的力学性能的影响也被研究 .另外 ,热失重实验和吸水实验说明这种热塑性淀粉的热稳定性和耐水性也要优于常用的甘油塑化热塑性淀粉     

Efficient barrier properties of mechanically enhanced agro-extracted cellulosic biocomposites

The objective of this work was to prepare the mechanically stable hydrophobic biocomposites by incorporating the cellulose fibers into the polymer matrices for their applications in biomedical and food packaging. Herein, two different types of biocomposites were prepared by mixing polylactic acid (PLA) and polyhydroxybutyrate (PHB) with the agro-extracted cellulose, separately at 170 °C. The influence of the cellulose fibers on the thermal, mechanical, and barrier properties of polymer matrices (PLA and PHB) was observed. With an increase in the cellulose content in PLA and PHB, the tensile strength of the biocomposite materials significantly improved with the enhancement of 24.45% and 32.08%, respectively, compared with the pure PLA and PHB. Furthermore, a decrease of 74.16% and 73.49% in the water vapor transmission rate and oxygen transmission rate, respectively, was observed for cellulose/PHB biocomposites. This study highlights that adding cellulose fibers significantly improves the mechanical and the barrier properties of PLA and PHB, suggesting their biocomposites for use in biodegradable polymer industries.     

Preparation,characterization and performances of biodegradable thermoplastic starch

A biodegradable thermoplastic starch (TPS) was successfully prepared from plasticizer ethanolamine and native cornstarch. The hydrogen bonding interaction between starch and ethanolamine was investigated using Fourier transform infrared (FT‐IR). When the ethanolamine mass content was 30%, after the ethanolamine‐plasticized thermoplastic starch (ETPS) was stored at RH 50% for 14 days, the mechanical testing showed that the maximum tensile stress of the ETPS reached 5.98 MPa, the tensile strain reached 106.52%, Young's modulus increased from 38.14 MPa of glycerol‐plasticized thermoplastic starch (GTPS) to 75.32 MPa of ETPS, and the breaking energy increased from 1.921 N·m to 2.305 N·m, which indicated that the mechanical properties of ETPS evidently excelled those of the GTPS. The effects of water contents on the mechanical properties of ETPS and GTPS were studied. A differential scanning calorimetry (DSC) analysis revealed that the low‐temperature transition and the glass transition temperature (T_g) of the ETPS were ?58 and 22°C respectively, which were lower than that of the GTPS. The ETPS effectively restrained the re‐crystallization of traditional GTPS, which was proved by the X‐ray diffraction (XRD). The scanning electron microscopy (SEM) images presented that ethanolamine made starch uniform. Copyright © 2007 John Wiley & Sons, Ltd.     

热塑性淀粉/乙烯-乙烯醇共聚物复合材料的制备与性能

利用熔融共混的方法,制备得到热塑性淀粉/乙烯-乙烯醇共聚物（TPS/EVOH）复合材料,并对该复合体系的加工性能、机械性能、动态力学性能、流变性能以及吸水性进行了研究.结果表明：随着EVOH含量增加,复合材料中分子间作用力加强;复合体系的机械性能得到改善;当EVOH含量到达30%后,复合材料的吸水性明显降低.     

Morphologies and properties of plasticized starch/polyamide compatibilized blends

A new sodium carboxymethylcellulose (CMC) compatibilized glycerol-plasticized starch/polyamide PA11 blend having improved mechanical properties was realized in a one step extrusion process. Blends were prepared in internal mixer and twin screw extruder. Mechanical properties (stress and strain at break) are improved by adding 1 wt% of CMC. Rheological characterization and scanning electron microscopy show that a co-continuous morphology is observed on a wide range of TPS amount.     

Preparation and Characterisation of Thermoplastic Starches from Cassava Starch,Cassava Root and Cassava Bagasse

Summary: Thermoplastic starches (TPS) based on cassava starch have been produced by extrusion at 120 °C, using glycerol as plasticizer. Three forms of cassava starch were employed, viz: cassava root (CR), cassava bagasse (CB) and purified cassava starch (PCS). The main differences between these are the presence of sugars and a few fibres in CR and high fibre concentration in CB. Conditions of processing and characteristics such as amylose and fibre content, crystallinity, water absorption and mechanical behaviour in the tension x deformation test were evaluated. The results demonstrated that the PCS and CR had amylose contents consistent with literature values (14–18%) and that CB is a material constituted mainly by amylopectin. It was found that fibres in high proportions (as in the bagasse) can confer reinforcement properties and are thus able to generate natural composites of TPS with cellulose fibre. The sugars naturally found in the root reduce the elongation of the TPS under tension. The PCS and CR TPS were stable with respect to indices of crystallinity after processing; and during a period of 90 d in a relative humidity of 53%, while the CB TPS tended to vary its crystallinity, probably because its amylose chain had low degree of polymerization.     

水发泡淀粉挤出泡沫的结构与性能

以水为发泡剂,普通玉米淀粉为原料,采用双螺杆挤出机制备淀粉泡沫材料,研究了发泡剂用量及聚乙烯醇的加入量对泡沫材料结构与性能的影响。 用扫描电子显微镜观察了泡沫材料截面的形态,用万能材料试验机测试了泡沫材料的力学性能。 结果表明,水的质量分数为8%时淀粉泡沫径向膨胀率和发泡倍率最高,分别为22倍和17.6倍,压缩模量最高（4.07 MPa）。 加入质量分数10%的聚乙烯醇(PVA)使淀粉泡沫的孔径变大至1.29 mm,壁厚增加至82.43 μm,同时压缩模量增加至9.70 MPa。     

Synthesis of aliphatic amidediol and used as a novel mixed plasticizer for thermoplastic starch

In this paper,aliphatic amidediol was synthesized and mixed with glycerol used as a plasticizer for preparing thermoplastic starch（AGPTPS）.The yield of aliphatic amidediol was 91%.FF-IR expressed that the mixture of aliphatic amidediol and glycerol formed stronger and stable hydrogen bond with starch molecules compared to the native cornstarch.By scanning electron microscope（SEM）native cornstarch granules were proved to transfer to a homogeneous continuous system.After being stored for a period time at room temperature,the mechanical properties of AGPTPS were also studied.As a mixed plasticizer,aliphatic amidediol and glycerol would be practical to extend TPS application scopes.     

Optimization and infrared spectrometric evaluation of the mechanical properties of PLA-based biocomposites

In this work polylactic acid (PLA)/starch biocomposite samples with optimized mechanical properties and suitable cost have been prepared by extrusion and thermal mixing. The variables to be optimized were PLA, corn starch, ethyl vinyl acetate (EVA), carboxy methyl cellulous (CMC) and glycerol mono- stearate (GMS) contents. The experiments were carried out based on the experimental design using D-optimal mixture methods. The analysis of variance indicated accuracy of the model. It was observed that biocomposite sample with PLA 59.5%, Starch 20%, EVA 10%, CMC 6.5%, GMS 2% and CaCO₃ 2% would be attained noticeable improvement in the mechanical properties. Fourier transform infrared spectroscopy (FTIR) in combination with partial least square (PLS) chemometric technique was used to estimate the mechanical properties in five different spectral regions. Results show good accuracy between calibration and validation sets also denoted that O-C?=?O stretching and C?=?O stretching functional groups of PLA, EVA, CMC and GMS have the most positive effect on tensile strength and hydrogen bonded hydroxyl group of starch has the minimum positive effect. This research provided a method to improve the mechanical properties of biocomposite samples by using the D-optimal design and PLS chemometric techniques and Obtained results demonstrated that PLS could accurately predict mechanical properties in these spectral regions.     

Morphological characteristics and properties of TPS/PLA/cassava pulp biocomposites

The effect of cassava pulp (CP) on morphological, tensile, and thermal properties of a thermoplastic cassava starch (TPS)/poly (lactic acid) (PLA) blend was investigated. TPS/PLA/CP biocomposites were manufactured by melt extrusion and then converted into specimens using an injection molding. The weight fraction of PLA to TPS/CP was fixed at 40:60, whereas the final CP concentration in the composites was varied in the range of 4.4–22.1 wt%. CP could act as a reinforcement for TPS/PLA blend to enhance its tensile strength up to 354% and Young's modulus up to 722% when 22.1 wt% of CP was loaded and a nucleating agent for PLA as confirmed from the reduced T_cc. In addition, TPS/PLA/CP composites showed a discrete phase structure (i.e., droplets in matrix) when CP with lower concentration (i.e., 4.4 wt%, 8.8 wt%, and 13.3 wt%) was incorporated and a bicontinuous phase structure (i.e., co-continuous) when higher concentration of CP (i.e., 17.7 wt% and 22.1 wt%) was employed. The results suggest that TPS/PLA/CP biocomposites have potential to be used in the manufacturing of injection-molded articles, particularly when biodegradability and renewability of the material are required.     

Preparation and Characterization of Poly(Lactic Acid)-g-Maleic Anhydride + Starch Blends

Poly(lactic acid) (PLA) and starch copolymers are obtained by reactive blending - varying the starch compositions from 0 to 60%. PLA is functionalized with maleic anhydride (MA), obtaining PLA-g-MA copolymers using dicumyl peroxide as an initiator of grafting in order to improve the compatibility and interfacial adhesion between the constituents. PLA + starch blends without a compatibilizer do not have sufficient interfacial adhesion. Decomposition temperature of PLA is not affected by grafting. Glass transition temperatures and dynamic mechanical properties are affected since MA has a plasticizing effect. Along with an increasing starch content friction decreases while wear loss volume in pin-on-disk tribometry has a minimum at nominal 15% wt. starch but increases at higher starch concentrations. The residual depth in scratching and sliding wear testing has a maximum at 15% starch; there is a minimum of storage modulus E′ determined in dynamic mechanical testing at the same concentration. Microhardness results also reflect the plasticization by MA.     

Biodegradable Poly(3-hydroxybutyrate) Nanocomposite

This work seeks bringing a technological and social contribution by searching blends and composites of poly(3-hydroxybutyrate) (PHB) and polyethylene widely used in packaging films, and colloidal silica. The mixtures were prepared by extrusion using a single-screw extruder and were analyzed regarding their thermal and mechanical properties and morphology. The results have shown PHB toughness in the studied compositions, which elongation at break was in the range 5–80% compared to 2% for neat PHB. The small amount (0.2 to 0.4%) of added silica seemed to increase in 20% the tensile strength. The thermal degradation by thermogravimetry from room temperature to 800 °C revealed a mixed behavior for the composites between PHB and polyethylene.     

大米淀粉膜的制备及其性能

大米淀粉颗粒粒径较小且均匀,在水中有较好的分散性,具有良好的成膜性并且可以在自然中降解,在食品包装、医用敷料及化妆品行业中有着广泛的应用。以大米淀粉为原料,NaOH为糊化剂,甘油为增塑剂,柠檬酸为交联剂和pH调节剂,采用流延法制备了淀粉膜。通过对淀粉颗粒的形貌观察及糊化温度、淀粉溶液的表观粘度及pH值测定、淀粉膜的力学性能、透光率及承载甘草酸二钾释放性能等的测定,研究了大米淀粉的糊化条件,柠檬酸、淀粉和甘油质量分数对淀粉膜性质的影响以及承载物质的释放情况。结果表明,大米淀粉呈光滑的多边形颗粒,直径为5~8 μm,在偏光显微镜下呈现马耳他十字结构,糊化温度范围为82.5~100.8 ℃。柠檬酸在淀粉成膜过程中会与淀粉分子相互作用,同时能够调节溶液的pH值以适应人体皮肤。淀粉质量分数越高,淀粉膜断裂伸长率越低,拉伸强度越高;甘油质量分数越高,淀粉膜断裂伸长率越高,拉伸强度越低。在甘油质量分数为3.0%时淀粉膜透光率最佳,结晶度最低。制备的淀粉膜能够承载且能高效释放抗炎物质甘草酸二钾,在护肤领域具有广泛的应用前景。     

Modification of mechanical and thermal property of chitosan–starch blend films

Chitosan–starch blend films (thickness 0.2 mm) of different composition were prepared by casting and their mechanical properties were studied. To improve the properties of chitosan–starch films, glycerol and mustard oil of different composition were used. Chitosan–starch films, incorporated with glycerol and mustard oil, were further modified with monomer 2-hydroxyethyl methacrylate (HEMA) using gamma radiation. The modified films showed improvement in both tensile strength and elongation at break than the pure chitosan–starch films. Water uptake of the films reduced significantly than the pure chitosan–starch film. Thermo gravimetric analysis (TGA) and dynamic mechanical analysis (DMA) showed that the modified films experience less thermal degradation than the pure films. Scanning electron microscopy (SEM) and FTIR were used to investigate the morphology and molecular interaction of the blend film, respectively.     

Rheological,thermal and mechanical properties of biodegradable poly(propylene carbonate)/polylactide/Poly(1,2-propylene glycol adipate) blown films

Poly(propylene carbonate)(PPC) was blended with polylactide(PLA) and poly(1,2-propylene glycol adipate)(PPA) using a twin screw extruder. Then the PPC/PLA/PPA films were prepared using the blown film technique. DMA results showed that PPA could act as a plasticizer and improve the miscibility between PPC and PLA. Crystal morphology displayed that blending PLA with the amorphous PPC led to a decrease of the spherulite size of PLA. The results of mechanical tests indicated that PPC-rich films showed high elongation at break and PLA-rich films showed high tear strength and good optical properties. The content of PPC and PLA significantly affected the physical properties of the films. With increasing PPC content, the melt strengths of the PPC/PLA/PPA films were enhanced. These findings contributed to the biodegradable materials application for designing and manufacturing polymer packaging.