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。     

Processing and characterization of LDPE/starch/PCL blends

Low-density polyethylene/plasticized starch/polycaprolactone blends were processed by conventional extrusion, injection molding, and film blowing techniques. The glass transition temperatures of plasticized starch were determined using differential scanning calorimetry. The blends were characterized by mechanical property measurements and scanning electron microscopy. The blend properties were found to depend not only on composition but also on the generated morphology. In films the fine dispersion of polycaprolactone phase in the polyethylene/starch matrix resulted in mechanical property increase, while in injection specimens there was property decrease due to phase coalescence. It appears that the different conditions existing at the two different shaping processes i.e. film blowing and injection molding could account for the final obtained morphology.     

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     

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.     

A Mixed Plasticizer for the Preparation of Thermoplastic Starch

In this paper, formamide was firstly used as plasticizer to prepare thermoplastic starch (TPS), which could suppress the retrogradation of TPS by X-ray diffractometry (XRD) and show a good flexibility, but was weaker than conventional glycerol-plasticized TPS (GPTPS). When urea was introduced into plasticizer, both the retrogradation and mechanical properties were ameliorated. The tensile stress, strain and energy break of TPS plasticized by urea (wt. 20%) and formamide (wt.10%), respectively, reached 4.83 MPa, 104.6 % and 2.17 N-m (Newton-meter) after it had been stored at relative humidity (RH) 30% for one week.     

热塑性淀粉/聚乙烯醇/蒙脱土三元纳米复合材料

用熔融挤出的方法制备了甘油塑化热塑性淀粉（TPS）/聚乙烯醇（PVA）/蒙脱土（MMT）纳米复合材料,添加蒙脱土和聚乙烯醇用以提高热塑性淀粉材料的力学性能。 在相对湿度50%的条件下,复合材料的XRD衍射谱图和透射电子显微镜测试表明,MMT以剥离状态均匀分布在TPS/PVA基体中;力学测试表明,当MMT的质量分数从0％增至5％时,复合材料的力学性能明显提高。 当蒙脱土的质量分数为3%时,复合材料最大抗张强度达到13.24 MPa,杨氏模量达到61.46 MPa。 这说明蒙脱土在复合材料中可以起到物理交联点的作用,提高了复合材料的力学性能。     

Thermoplastic starch blends: A review of recent works

The aim of this review is to discuss the recent developments in thermoplastic starch blends. Starch has been considered as an excellent candidate to partially substitute synthetic polymer in packaging, agricultural mulch and other low-cost applications. Recently, the starch granules were plasticized using different plasticizers under heating and shearing, giving rise to a continues phase in the form of a viscous melt which can be processed using traditional plastic processing techniques, such as injection molding and extrusion. This kind of starch composites is called thermoplastic starch. Unfortunately, thermoplastic starch presents some drawbacks, such as low degradation temperatures, which make it difficult to process, poor mechanical properties and high water susceptibility. Much work has been carried out to overcome these drawbacks, including the combination of thermoplastic starch with other polymers, aiming at lowering the cost and enhancing the biodegradability of the final product.     

Effect of PHB on the properties of biodegradable PLA blends

Blends of biodegradable polymers polylactic acid/thermoplastic starch/polyhydroxybutyrate (PLA/TPS/PHB) were prepared using a twin-screw extruder. The TPS content was constant (50 %) and the PHB content in the blends was gradually changed from 0 mass % to 20 mass %. TPS was prepared by melting, where a mixture of native starch, water and glycerol was fed into the twinscrew extruder. Average temperature of extrusion was 180°C and the concentration of glycerol was 40 mass %. Influence of the PHB concentration in the blend and that of the processing technology on the mechanical and rheological properties of the PLA/PHB composition containing TPS were studied. Mechanical properties were measured 24 h after the film and monofilament preparation and also after the specific storage time to study the effect of storage on the properties. The results indicate that differences in morphology strongly influence the mechanical properties of the studied materials with identical material composition.     

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.     

生物医用材料自增强工艺的研究现状及前景展望

介绍了生物医用材料自增强的概念,重点介绍了纺丝、熔体注塑和挤出、纤维集束模压成型、定向自由拉伸、固态挤出、成纤模压等自增强工艺,对这些自增强工艺的原理作了简要的介绍,并对生物医用材料的发展前景进行了展望。     

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.     

Formulation study for orally disintegrating tablet using partly pregelatinized starch binder

In this study, we aimed to design orally disintegrating tablets by employing a formulation design approach that enables the production of such tablets in the same facilities used for the production of solid dosage forms on an industrial scale. First, we examined the relationships between the types of binders used in the tablets and the properties of orally disintegrating tablets prepared by the wet granulation method. Results revealed that partly pregelatinized starch is a relatively suitable binder for orally disintegrating tablets as it also serves as a disintegrant. Next, we employed a central composite design for 2 factors, namely, corn starch and partly pregelatinized starch, in order to design granules suited for orally disintegrating tablets composed of D-mannitol, corn starch or partly pregelatinized starch. The effects of these 2 factors on 3 types of responses, namely, 50% granule size, compressing index and disintegrating index, were analyzed with a software package, and responses to changes in the factors were predicted. This study investigated the effects of binder type and binder content in orally disintegrating tablets, and provided evidence that the binder exerts a strong influence on tablet properties, and is therefore an important component of orally disintegrating tablets.     

Crystalline structure and reinforcement in hybrid PP composites

Journal of Thermal Analysis and Calorimetry - Hybrid composites were prepared from a PP homopolymer, talc and PVA fibers by twin-screw extrusion and injection molding. Talc was added to improve...     

改性淀粉材料生物降解性分析体系的建立及应用

测定了热塑性淀粉(TPS)和热塑性双醛淀粉(TPDAS)在堆肥条件下的生物降解能力。根据ISO 14855建立了一套新的测试体系并且验证了这个体系测定高分子材料生物降解性能的可行性。对热塑性淀粉材料生物降解性的测试结果发现化学改性对于淀粉的降解速率和降解速度都有很大的影响。在可控堆肥条件下TPS比TPDAS降解的要快。TPDAS的降解速度和最终的生物降解百分率和双醛淀粉(DAS)的氧化度有密切的关系。文中讨论了存在这种关系的可能原因。有不同降解速率的TPS和TPDAS的降解过程呈现出三个阶段,即迟滞阶段。降解阶段和平稳阶段。     

Recycling of mixed automotive plastics

Mixed plastics from junked autos were homogenized by milling or extrusion, modified by addition of low-molecular-weight low-melt-viscosity polymers, and processed by compression or injection molding. Properties were comparable with high-density polyethylene and common building panel materials.     

The effect of processing additives on the surface properties of polyvinyl chloride

Stabilizers, plasticizers and lubricants play an important part in the formulation of polymer materials for use in manufacturing. For polyvinyl chloride, they are used to achieve stability, together with suitable flow and release behavior, during extrusion, molding, and other processing steps. However, the additives remain after manufacturing and may affect the properties of the product for the rest of its useful life. We have investigated the surface properties of polyvinyl chloride containing organotin stabilizers and calcium stearate, and the surface properties of the additives themselves. We used zeta-potential measurements to determine the charge on the surface of additive-containing polyvinyl chloride and have related this to chemical reactions of the additive materials. This chemistry is important for understanding what goes on during the period when the polymer product comes in contact with a humid environment. The major chemical reactions are those involving hydrolysis of tin-ester linkages in the organotin compounds and dissociation of carboxylic acid groups. These groups may be the carboxylic acid groups originally present or those formed by hydrolysis. As a result of these reactions, the surface charge of the polymer depends strongly on the pH of the aqueous medium in contact with the surface.     

用模压成型方法制备HDDR粘结NdFeB磁体的成型性研究

在形状复杂或大尺寸的模压成型粘结磁体制备过程中，由于粉末颗粒间以及磁粉与模壁间的摩擦，造成沿压制方向的压制压力递减，使得磁体密度的不均匀分布的现象，成为不可避免，为了改善磁体密度分布不均匀的现象，本研究选取用HDDR NdFeB磁粉模压成型制备的薄壁环作为研究对象，系统地研究了润滑剂的添加量以及润滑剂和增强剂的添加方式对磁体密度、密度分布的均匀性以及磁体抗压强度的影响，通过复合添加润滑剂和增强剂的方法，可以保证在磁体抗压强度不降低的前提下，提高磁体的密度，改善密度分布的均匀性，从而改善粘结磁体的成型性。     

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     

Crystallization,Mechanical and Flame-retardant Properties of Poly(lactic acid) Composites with DOPO and DOPO-POSS

Poly(lactic acid)(PLA) composites with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO) and DOPOcontaining polyhedral oligomeric silsesquioxane(DOPO-POSS) were prepared via melting extrusion and injection molding. The crystallization, mechanical, and flame-retardant properties of PLA/DOPO and PLA/DOPO-POSS were investigated by differential scanning calorimetry(DSC), X-ray diffraction(XRD), tensile testing, thermogravimetric analysis(TGA), limiting oxygen index(LOI),and cone calorimeter test. The DSC results showed that the DOPO added could act as a plasticizer as reflected by lower glass transition temperature and inhibited crystallization of part of the PLA; the DOPO-POSS acted like a filler in the PLA matrix and slightly improved the crystallinity of the PLA matrix. The XRD and DSC analyses indicated that the PLA composites by cold molding injection were amorphous, and the PLA composites following a heat treatment in an oven at 120 °C for 30 min achieved crystallinity. All the PLA and its composites after heat treatment had improved mechanical properties. The thermogravimetric analysis(TGA) tests showed that the PLA,DOPO and DOPO-POSS decomposed separately in the PLA/DOPO and PLA/DOPO-POSS, respectively. The cone calorimeter tests offered clear evidence that addition of the DOPO-POSS resulted in an evident reduction of 25% for the peak of heat release rate(p-HRR).It was also confirmed that the crystalline flame-retardant PLA composites after heat treatment had better flame retardant properties than the amorphous PLA composites prepared by the cold molding.     

Aggregation of particulate fillers: factors,determination, properties

The aggregation tendency of 11 different CaCO₃ fillers with widely differing particle sizes was studied in polypropylene (PP) composites. The fillers were characterized by different techniques in powder form and in suspension. Homogenization and sample preparation were carried out by extrusion and injection molding, or in an internal mixer and compression molding, respectively. Thin slices were prepared from the composites and the relative area of aggregates was determined by image analysis. Tensile and fracture properties were studied as a function of filler content. The results proved that the extent of aggregation increases with decreasing particle size and increasing filler content. Surprisingly, extruded and injection molded samples contained more aggregates than those prepared by homogenization in an internal mixer followed by compression molding. Good agreement was found between the powder properties of the fillers and their performance in the composites. Deviations from the general tendency indicate that some factors, which were not accounted for in the study, also influence aggregation and composite properties.