PLA/MWNTs/HA复合材料的制备和性能研究

采用超声辅助原位湿法合成多壁碳纳米管／羟基磷灰石纳米复合材料(MWNTs／HA),并通过溶液浇铸法制备了PLA／MWNTs／HA复合材料薄膜。考察了MWNTs／HA纳米粒子含量对复合膜性能的影响,并通过力学性能、SEM、FTIR、以及DMTA对复合膜性能进行了表征,结果表明：随着纳米粒子质量分数的增加,复合膜的拉伸强度呈下降趋势;拉伸模量和储能模量呈现先下降后上升的趋势;玻璃化转变温度则呈现不断上升趋势。     

聚甲基乙撑碳酸酯/氧化石墨烯纳米复合材料的制备及性能研究

本文采用改进Hummers法制备氧化石墨烯(GO),通过原子力显微镜对GO片层形貌进行表征;以聚甲基乙撑碳酸酯(PPC)、聚乙烯醇(PVA)和氧化石墨烯(GO)为原料,采用溶液和熔融共混法相结合,制备PPC/PVA/GO纳米复合材料,研究其力学性能、热学性能和动态流变行为。结果表明,当GO含量为0.5 wt%时,拉伸强度达到了22.03 MPa,与纯PPC相比提高了25.8%;当GO含量增大到1.0 wt%时,拉伸强度开始降低;断裂伸长率随GO的加入呈现降低的趋势。GO含量为1.0%时复合材料的热学性能最好,与纯PPC相比,复合材料的完全热分解温度从350℃提高到了400℃以上,并且热分解速率下降了12%/min;复合材料的复数黏度、储能模量和损耗模量随PVA及GO的引入也有一定程度的提高。     

几种不同生物质复合材料的力学性能研究

以聚乳酸(PLA)为基体,以菠萝叶粉(PALF)、玉米秸秆芯粉(CF)、芝麻秸秆粉(SF)及甘蔗渣纤维粉(BF)作增强体,通过挤出加注塑工艺,制备可降解生物质复合材料(BBC),考察了秸秆粉用量对BBC力学性能的影响。并以PALF/PLA复合材料为例,研究了材料的断裂特性。结果表明,随着纤维粉用量的增加,所有BBC的拉伸强度均逐渐降低,当纤维粉添加量相同时,PALF/PLA的拉伸强度始终最低;CF/PLA、SF/PLA复合材料的弯曲模量随着秸秆粉用量的增加逐渐增大,当秸秆粉用量为40%时,弯曲模量分别比纯PLA增加74.15%和71.84%,BF/PLA复合材料的弯曲模量先增加后减小,但始终低于CF/PLA和SF/PLA,PALF/PLA的变化趋势较为复杂,呈现先增后减再增加的趋势;随着纤维粉含量的增加,PALF/PLA复合材料的冲击强度逐渐增加,其它三种均呈现先增加后减小趋势。PALF/PLA复合材料的断裂面无纤维拔出,应力-应变曲线无屈服点,断裂伸长率仅4.80%,属于典型的脆性断裂。     

尼龙6/氯化钾复合材料的结晶与性能

通过熔融共混法制备了不同KCl含量下的尼龙6(PA6)/KCl复合材料,采用示差扫描量热仪(DSC)、流变仪、红外光谱(IR)、电子拉伸机等研究了KCl含量对PA6/KCl复合材料结晶行为、流变性能及力学性能的影响,并研究了其受限机制.力学性能研究结果表明,随着KCl含量的增加,PA6/KCl复合材料拉伸强度和冲击强度呈现出先增大后减小的趋势,在KCl含量为3 phr时,复合材料拉伸强度和冲击强度分别达到最大值82.67 MPa和7.34 k J/m~2,较纯PA6分别增加了10.8%和34.68%,动态力学性能测量结果表明,在测量温度范围内,复合材料的储能模量均高于纯PA6,在25℃体系储能模量(G')随KCl含量的增加而增大,复合体系抵抗弯曲变形能力增加,而结晶行为研究结果表明,增加KCl的含量,PA6/KCl复合材料的成核温度、晶体生长温度、熔融温度及玻璃化转变温度均向低温方向移动,成核密度和成核速率也逐渐减小,结晶能力下降,结晶度减小,结晶度由原来25.30%变为19.34%,而结晶诱导时间逐渐增加.流变性能研究结果表明,随着KCl含量的增加,复合体系的零剪切黏度逐渐增加,且所有的体系均呈现出假塑性流体行为,剪切变稀现象越来越明显,特征松弛时间τ_1、τ_2和τ_3逐渐增加,复合体系的松弛机制发生变化.     

增塑剂对碱木质素/HDPE复合材料性能影响研究

分别采用邻苯二甲酸二辛酯(DOP)、邻苯二甲酸二丁酯(DBP)、环氧大豆油(ESO)作为增塑剂制备碱木质素/HDPE复合材料.研究了不同种类增塑剂对复合材料力学性能的影响,结果表明,3种增塑剂都能提高复合材料的断裂拉伸率,其中DOP的效果最优,当DOP添加量为7.5 phr,复合材料的断裂拉伸率达146.28%,比未添加增塑剂的样品高62.4%.添加DOP制备复合材料,研究DOP对复合材料力学性能、断面形貌、流变性能的影响.复合材料的力学性能结果表明DOP含量的增加有利于复合材料断裂拉伸率的提高;SEM表明DOP的添加使复合材料的断面变的更加粗糙,材料韧性提高;流变性能结果表明DOP能降低复合材料的表观黏度(η)和复数黏度(η*),并且线性黏弹区随着DOP含量的增加而变窄,储能模量(G')和损耗模量(G″)也逐渐下降.分析认为,DOP分子吸附包覆在木质素微颗粒的表面,抑制了木质素微颗粒在HDPE相中的团聚,改善了木质素在HDPE中的分散状况,同时降低了木质素分子和聚乙烯分子链之间的作用力,从而改善了复合材料的力学性能和流变性能.     

碳酸钙/芝麻秸秆/不饱和树脂三元复合材料的力学性能和热稳定性

采用浇注成型工艺制备碳酸钙/芝麻秸秆/不饱和树脂三元复合材料,研究了碳酸钙粉、芝麻秸秆粉相对含量对复合材料力学性能及热稳定性的影响。结果表明,所有复合材料的拉伸强度和弯曲强度均低于不饱和聚酯树脂浇注体。随着碳酸钙粉用量的增多,复合材料的拉伸强度逐渐升高,而弯曲强度先下降后逐渐增大,含10%碳酸钙粉和5%芝麻秸秆粉的复合材料具有最大弯曲模量2 672.11 MPa。复合材料的热稳定性随着碳酸钙粉用量的增加而逐渐上升。复合材料的吸水率高于纯树脂浇注体,在相同的浸泡周期中,秸秆粉含量越高,复合材料的吸水率越高。     

原位缩聚法制备碳纳米管/尼龙11复合材料

用原位缩聚法制备了碳纳米管增强的尼龙11复合材料,用X射线衍射仪、红外(FTIR)、扫描电镜(SEM)、热重(TGA)、机械拉伸测试仪等对其结构、形貌、热性能及机械性能进行了表征测试.扫描电镜结果显示碳纳米管均一地分散在尼龙11/碳纳米管复合材料中.复合材料的拉伸模量比纯尼龙11有较大的提高.当复合材料中碳纳米管含量分别为1%,5%,10%时,材料的拉伸模量分别提高了34.5%,92.9%和113,7%.同时,复合材料的储能模量也有提高.热分析结果显示当复合材料中碳纳米管含量为1%时,其失重5%和10%的温度分别由纯尼龙11的404℃、424℃提高到414℃和437℃.示差扫描量热分析(DSC)显示复合材料的结晶温度随碳纳米管的加入而升高,而结晶度则降低.     

发泡聚乳酸/热塑性聚氨酯/二氧化硅纳米复合材料的泡孔结构

以超临界二氧化碳作为物理发泡剂,通过快速降压法制备聚乳酸(PLA)/热塑性聚氨酯(TPU)/二氧化硅(SiO2)纳米复合材料发泡样品。发泡样品的泡孔结构使用扫面电子显微镜进行观察。在低频区,SiO2增加PLA/TPU共混物的储能模量和复数黏度。SiO2的加入使PLA/TPU共混物发泡样品的泡孔直径减小、泡孔密度增大。SiO2对PLA/TPU共混物发泡样品泡孔结构的改善归因于SiO2的异相成核作用和对共混物流变性能的改善作用。     

淀粉添加量和增塑剂对聚乙烯醇/淀粉复合材料结构与性能影响

近些年来，由于不可再生资源的消耗问题以及塑料垃圾等造成的白色污染等环境问题，人们对绿色环保产品的需求日益增长，高性能生物降解材料的开发受到越来越多的关注。采用醇解度适中的1788型聚乙烯醇(PVA1788)和玉米淀粉为原料，添加少量甘油与氯化钙，通过溶液流延法制得了聚乙烯醇/淀粉(PVA/ST)复合材料。研究了淀粉添加量以及增塑剂配比对PVA/ST复合材料结构与性能的影响。结果表明：淀粉的加入会导致PVA的结晶度明显下降，黏度提高，同时因为淀粉的高脆性，导致复合材料模量明显提高，力学性能明显下降；而加入的甘油和氯化钙作为增塑剂，能够减弱PVA和ST的分子间作用力，降低结晶度，提高材料的柔韧性。当加入甘油与氯化钙的比例均为PVA和ST总含量的10%时，复合材料的力学性能最优，拉伸强度约为16 MPa,断裂伸长率约为410%。     

聚乙烯/氧化铝复合材料形态、流变和力学性能

将聚乙烯（PE）和氧化铝（AO）熔融共混制得综合性能更好的PE/AO复合材料。通过对其进行流变分析、热力学性能分析、力学性能分析、导热性能分析和断面微观结构分析,探究AO质量分数对复合材料结构及性能的影响。结果表明,随着AO质量分数的增加,复合材料逐步转为脆性材料,其弹性模量、屈服强度、导热系数、储能模量同步增加;当AO质量分数为10%时,复合材料的断裂强度为18.2 MPa,综合性能最好。     

Properties of immiscible and ethylene-butyl acrylate-glycidyl methacrylate terpolymer compatibilized poly (lactic acid) and polypropylene blends

Poly(lactic acid) (PLA) and polypropylene (PP) blends of various proportions were prepared by melt-compounding. The miscibility, phase morphology, thermal behavior, and mechanical and rheological properties of the blends were investigated. The blends were immiscible systems with two typical morphologies, spherical droplet and co-continuous, and could be obtained at various compositions. Complex viscosity, storage modulus and loss modulus depend on the PP content. Thermal degradation of all blends led to two weight losses, for PLA and PP. The incorporation of PP improved the thermal stability of the blend. The effect of compatibilizer (ethylene-butyl acrylate-glycidyl methacrylate terpolymer, EBA-GMA) on the morphology and mechanical properties of 70/30 w/w PLA/PP blends was investigated. The tensile strength of these blends reached a maximum for 2.5 wt% EBA-GMA, and impact strength increased with increasing EBA-GMA content, suggesting that EBA-GMA is an effective compatibilizer for PLA/PP blends.     

Poly(lactic acid)/poly(butylene succinate)/calcium sulfate whiskers biodegradable blends prepared by vane extruder: Analysis of mechanical properties,morphology, and crystallization behavior

Ternary blends of PLA/PBS/CSW with different weight fractions were prepared using a vane extruder. The mechanical properties, morphology, crystallization behavior and thermal stability of the blends were investigated. For the PLA/CSW blend, the tensile strength decreased, the flexural strength and modulus increased compared with pure PLA. For PBS, the addition of CSW had little influence on the mechanical properties. For the ternary blends PLA/PBS/CSW, the tensile strength, flexural strength and modulus decreased compared with pure PLA, while the elongation at break and the impact strength increased significantly. The brittle-ductile transition of the blends took place when the PBS weight fraction reaching 30 wt%. As a soft component in the blends, PBS was beneficial to improve the tensile ductility and the toughness of PLA. SEM measurements reveal that PLA/PBS/CSW blends were immiscible. When the weight fraction of PBS was 50 wt%, significant phase separation was observed, and CSW had preferential location in the PBS phase of the blend. DSC measurement and POM observation reveal that CSW had a heterogeneous nucleation effect on PLA and PBS matrix. The addition of PBS improved the crystallization of PLA and the thermal resistance of the PLA/PBS/CSW blends significantly.     

Transparent and ductile poly(lactic acid)/poly(butyl acrylate) (PBA) blends: Structure and properties

Poly(butyl acrylate) was prepared by the free radical polymerization of butyl acrylate as an initiator in the presence of 2,2′-Azoisobu-tyronitrile (AIBN) and the average molecular weight, polydispersity and thermal stability were evaluated. PLA and PBA were melt blended using a Haake Rheometer, and the light transmission, thermal properties, dynamic rheological properties, mechanical properties, phase morphology of blends and toughening mechanism were investigated. Dynamic rheology, SEM and DSC results show that the PLA is partial miscible with PBA. The PBA component improved the crystallization ability of PLA and the crystallinity of PLA increased with content of PBA (<15 wt.%). With the increase of PBA, the tensile strength and modulus of the blend decreased slightly while the elongation at break and toughness were dramatically increased. With the addition of PBA, the failure mode changes from brittle fracture of neat PLA to ductile fracture of the blend. Rheological results revealed the complex viscosity and melt elasticity of the blends decreased with increasing content of PBA and phase segregation occurred at loading above 11 wt.% PBA. UV–vis light transmittance showed that PLA/PBA blends with a high transparency, and the transmittance decreased with the amount of PBA.     

Assessing the mechanical,phase inversion,and rheological properties of poly-[(R)-3-hydroxybutyrate-co-(R)-3-hydroxyvalerate] (PHBV) blended with poly-(l-lactic acid) (PLA)

Poly-(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and poly-(l-lactic acid) (PLA) have attracted much interest in recent years since they are biodegradable, thus can replace synthetic non-degradable materials. In this study, improvements of PHBV, mechanical, phase inversions, and rheological properties were investigated after blending with PLA in varying ratio’s. Three different blends of commercially available PLAs with 92–98% l-lactide units and one grade of PHB with 5% valerate content were blended using a micro-compounder at 175 °C. The composition of PHBV in blends ranged from 50% to 80%. With the addition of PLA, increases in the flexural strength and elastic modulus were observed for several blends, while minor to no changes were detected in the elongation at break and tensile strength as compared to pure PHBV material. Like many conventional plastics, the complex viscosity decreased with increasing rotational frequency due to decreasing entanglements and molecular weight. The complex viscosity with respect to time was very stable for the blends, but no improvements in the PHBV viscosity were observed with the addition of PLA at 170 °C. Three phase inversion models were used to predict the continuity of the blends, and the results showed both dual- and PLA-continuity phase for the blends. In summary, the mechanical results showed improvements in the tensile and flexural properties, while the rheological observation showed minor improvements in the complex viscosity for numerous concentrations.     

Rheological and thermal behavior of PLA modified by chemical crosslinking in the presence of ethoxylated bisphenol A dimethacrylates

Crosslinking structures can be partly introduced into PLA by melt mixing in a twin screw extruder with dicumyl peroxide (DCP) and ethoxylated bisphenol A dimethacrylates (Bis‐EMAs) as a crosslinking coagent. The study of DCP and Bis‐EMA contents on the melt rheology, thermal properties, dynamic mechanical properties and morphology of the reactive extruded pellets is presented. The results show that PLA with a DCP content higher than 3 phr exhibits increases in both the melt modulus and complex viscosity as compared with PLA. The introduction of DCP into PLA improved the thermal stability of the PLA. PLAs with various Bis‐EMA contents showed the optimum storage modulus and complex viscosity to occur at 5 phr Bis‐EMAs. Moreover, the glass transition, cold crystallization and melting temperature of PLAs decreased with increasing Bis‐EMA content. The crystallinity of the partly crosslinked PLAs was lower than that of PLA. Similar to the rheological results, the thermo‐mechanical properties showed that the storage modulus and loss modulus of the partly crosslinked PLAs increased with increasing Bis‐EMA contents up to 5 phr. In addition, these partly crosslinked PLAs showed rough surface or sea island‐like structure. Copyright © 2016 John Wiley & Sons, Ltd.     

Fabrication of open‐porous PCL/PLA tissue engineering scaffolds and the relationship of foaming process,morphology, and mechanical behavior

Tissue engineering scaffolds should provide a suitable porous structure and proper mechanical strength, which is beneficial for the delivery of growth factor and regulation of cells. In this study, the open‐porous polycaprolactone (PCL)/poly (lactic acid) (PLA) tissue engineering scaffolds with suitable porous scale were fabricated using different ratios of PCL/PLA blends. At the same time, the relationship of foaming process, morphology, and mechanical behavior in the optimized batch microcellular foaming process were studied based on the single‐factor experiment method. The porous structures and mechanical strength of the scaffolds were optimized by adjusting foaming parameters, including the temperature, pressure, and CO₂ dissolution time. The results indicated that the foaming parameters influence the cell morphology, further determine the mechanical behavior of PCL/PLA blends. When the PCL content is high, with the increase of temperature and time, the cell diameter and the elastic modulus increased, and the tensile strength and elastic modulus increased with the increase of the average cell size, and decreased as the increase of the cell density. While when the PLA content was high, the cell diameter showed the same trend, and the tensile strength and elastic modulus were higher, and the elongation at break was lower, and tensile strength and elastic modulus decreased with the increase of the average cell size and increased with the increase of cell density. This work successfully fabricated optimized porous PCL/PLA scaffolds with excellent suitable mechanical properties, pore sizes, and high interconnectivity, indicating the effectiveness of modulating the batch foaming process parameters.     

Physical characterization of coupled poly(lactic acid)/starch/maleic anhydride blends plasticized by acetyl triethyl citrate

Acetyl triethyl citrate (ATC) was used as a plasticizer for poly(lactic acid) (PLA)/starch blends coupled with maleic anhydride and an initiator of 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane (L101). Elongation of the blend at break was markedly increased when the ATC content was above the 8% loading level, which is referred to as the percolation threshold. The extended elongation was achieved at the expense of tensile strength and elastic modulus. Thermal transitions of the blend, including the glass transition temperature (T(g)), cold crystallization temperature (T(c)) and melting temperature (T(m)), decreased with ATC content. Thermally induced ATC migration affected the thermal behavior of the plasticized blends and reduced elongation and tensile strength, whereas the elasticity modulus increased. ATC migration increased with ambient temperature, which was controlled by the activation energy of the blend system. Leaching of ATC was slow at room temperature in distilled water, but significant in boiling water. Additionally, the leaching rate was also directly proportional to the ATC content of the blend. Glass transition temperatures of PLA/starch/MA/L101 blends with various acetryl triethyl citrate contents.     

Toughening of polylactide by melt blending with a biodegradable poly(ether)urethane elastomer

Melt blending of polylactide (PLA) and a biodegradable poly(ether)urethane (PU) elastomer has been performed in an effort to toughen the polylactide without compromising its biodegradability and biocompatibility. The miscibility, phase morphology, mechanical properties, and toughening mechanism of the blend were investigated. The blend was found by dynamic mechanical analysis to be a partially miscible system with shifted glass transition temperatures. The PU elastomer was dispersed in the PLA matrix with a domain size of sub-micrometer scale. The addition of PU elastomer not only accelerated the crystallization speed, but also decreased the crystallinity of the PLA. With an increase in PU content, the blend shows decreased tensile strength and modulus; however, the elongation at break and the impact strength were significantly increased, indicating the toughening effects of the PU elastomer on the PLA. The brittle fracture of neat PLA was gradually transformed into ductile fracture by the addition of PU elastomer. It was found that the PLA matrix demonstrates large area, plastic deformation (shear yielding) in the blend upon being subjected the tensile and impact tests, which is an important energy-dissipation process and leads to a toughened, biodegradable polymer blend.     

Morphology and properties of biodegradable poly (lactic acid)/poly (butylene adipate-co-terephthalate) blends with different viscosity ratio

Phase morphology exerts a tremendous influence on the properties of polymer blends. The development of the blend morphology depends not only on the intrinsic structure of the component polymers but also on extrinsic factors such as viscosity ratio, shearing force and temperature in the melt processing. In this study, various poly (butylene adipate-co-terephthalate) (PBAT) materials with different melt viscosity were prepared, and then poly (lactic acid) (PLA)/PBAT blends with different viscosity ratio were prepared in a counter-rotating twin-screw extruder under constant processing conditions. The influence of viscosity ratio on the morphology, mechanical, thermal and rheological properties of PLA/PBAT (70/30 w/w) blends was investigated. The experimental results showed that the morphology and properties of PLA/PBAT blends strongly depended on the viscosity ratio. Finer size PBAT phase were observed for viscosity ratio less than 1 (λ < 1) compared to samples with λ > 1. It was found that the interfacial tensions of PLA and PBAT were significantly different when the viscosity ratio was changed, the lowest interfacial tensions (0.12 mN/m) was obtained when the viscosity was 0.77. Additionally, the maximal tensile strength in PLA/PBAT blends were obtained when the viscosity ratio was 0.44, while the maximal impact properties were obtained when the viscosity ratio was 1.95.