Preparation and properties of short natural fiber reinforced poly(lactic acid) composites

The natural fiber/poly(lactic acid) (PLA) composites were prepared with ramie and jute short fiber as reinforcement and PLA as matrix. The mechanical and thermal properties of the composites were investigated. The results show that the properties of the composites are better than those of plain PLA. When the content of the fiber is 30%, the composites can get the best mechanical properties. The dynamic mechanical analysis results show that the storage moduli of the PLA/ramie and PLA/jute composites increase with respect to the plain PLA. The Vicat softening temperature of the composites is greatly higher than that of PLA. The results of thermogravimetric analysis show that adding fiber to the PLA matrix can improve the degradation temperature of PLA.

Poly(lactic acid)-starch/Expandable Graphite (PLA-starch/EG) Flame Retardant Composites

This work reports on the effect of commercial expandable graphite(EG)on the flammability and thermal decomposition properties of PLA-starch blend.The PLA-starch/EG composites were prepared by melt-mixing and their thermal stability,volatile pyrolysis products and flammability characteristics were investigated.The char residues of the composites,after combustion in a cone calorimeter,were analyzed with environmental scanning electron microscopy(ESEM).The thermal decomposition stability of the composites improved in the presence of EG.However,the char content was less than expected as per the combination of the wt%EG added into PLA-starch and the%residue of PLA-starch.The flammability performance of the PLA-starch/EG composites improved,especially at 15 wt%EG content,due to a thick and strong worm-like char structure.The peak heat release rate(PHRR)improved by 74%,the total smoke production(TSP)by 40%and the specific extinction area(SEA)by 55%.The improvements are attributed to the ability of EG to exfoliate at increased temperatures during which time three effects occurred:(i)cooling due to an endothermic exfoliation process,(ii)dilution due to release of H2O,SO2 and CO2 gases,and (iii)formation of a protective intumescent char layer.However,the CO and CO2 yields were found to be unfavorably high due to the presence of EG.

The Green Composites: Millet Husk Fiber (MHF) Filled Poly Lactic Acid (PLA) and Degradability Effects on Environment

This study provides an overview on green composites degradability. Practically, the main drawbacks of using natural fibers are their poor dimensional stability, degradability and high degree of moisture absorption. While, end use of product from natural fiber filled or reinforced composites has become subject of concern to material engineers and scientist. The major properties of natural fiber reinforced polymer composites are greatly dependent on the hydrophilic tendency and dimensional stability of the fibers used, morphology aspect ratio for long fiber, while voids for powder fibers. The effects of chemical treatments on cellulosic fibers that are used as reinforcements for thermoplastics were studied. The chemical source for the treatments is alkalization. The significance of chemically-treated natural fibers is seen through the improvement of mechanical properties. The untreated fiber composites degrade faster in municipal soil compared to treated fiber composites.

Multi-porous electroactive poly(L-lactic acid)/ polypyrrole composite micro/nano fibrous scaffolds promote neurite outgrowth in PC12 cells

In this study, poly（L-lactic acid）/ammonium persulfate doped-polypyrrole composite fibrous scaffolds with moderate conductivity were produced by combining electrospinning with in situ polymerization. PC12 cells were cultured on these fibrous scaffolds and their growth following electrical stimulation （0-20.0 μA stimulus intensity, for 1-4 days） was observed using inverted light microscopy, and scanning electron microscopy coupled with the MTT cell viability test. The results demonstrated that the poly（L-lactic acid）/ammonium persulfate doped-polypyrrole fibrous scaffold was a dual multi-porous micro/nano fibrous scaffold. An electrical stimulation with a current intensity 5.0- 10.0 μAfor about 2 days enhanced neuronal growth and neurite outgrowth, while a high current intensity （over 15.0 μA） suppressed them. These results indicate that electrical stimulation with a moderate current intensity for an optimum time frame can promote neuronal growth and neurite outgrowth in an intensity- and time-dependent manner.

Mechanical and Morphological Properties of Wood Plastic Biocomposites Prepared from Toughened Poly（lactic acid） and Rubber Wood Sawdust （Hevea brasiliensis）

The present research aims to utilize the acrylic Core-Shell Rubber （CSR） particles to reduce the brittleness in Wood Plastic Composites （WPC） prepared from poly（lactic acid） （PLA） and rubber wood sawdust （Hevea brasiliensis）. Experimental works consisted of two major parts. The first part concentrated on toughening PLA by using CSR particles. Mechanical tests revealed that PLA had become tougher with a more than five times increment in the impact strength when the CSR was added at only 5 wt%. The modified PLA was less stiff with the significant reductions of both elastic and flexural moduli and strengths. The second part focused on producing WPC from the toughened PLA and rubber wood sawdust. The tensile moduli and the strengths of the PLA composites increased with rubber wood content. The composites turned out to be more brittle with reductions of both the impact strength and the tensile elongation at break at all the sawdust contents. Toughening PLA/wood flour with 5 wt% CSR improved both the impact strength and the tensile elongation at break. The toughness enhancement was also depicted by the plastic deformation observed on the surfaces of fractured PLA/CSR/wood sawdust composites.

Preparation and Characterization of the Covalent-Integrated Poly(lactic acid) and Scrap Leather Fiber Composites

Scrap leather fibers(SLFs) modified with active silane containing epoxide groups were incorporated into poly(lactic acid)(PLA) modified by vinyl trimethoxysilane,i.e.,the PLA/SLF composites were prepared for bio-composites by solvent compounding technology in this article.The effects of silane coupling agents on the structures of PLA and SLF molecules were examined,and the mechanical properties and thermal stability of PLA/SLF composites were also measured.The results of Fourier-transform infrared spectroscopy(FTIR) had proved that silane had been incorporated successfully to PLA and SLF molecules by means of the solvent technology.Scanning electric microscopy(SEM) was used to investigate both the changes in shapes between the pristine SLFs and the treated SLFs and the microscopic structures of composites.According to SEM results,it was shown that there were some significant differences between the untreated and treated SLFs,and a double continuous phase structure had occurred in PLA/SLF composites due to the excellent dispersion of SLFs in matrix.The addition of the treated SLFs into PLA resulted in a distinct improvement of the impact and tensile strengths.When the mass fraction of the treated SLFs was 15%,the notched impact strength and tensile strength of PLA/SLF bio-composites were improved by 34.4%and 21.2%compared with the pristine PLA,respectively. Additionally,with the increase of the modified SLFs content,the thermal stability of PLA/SLF bi-composites was apparently improved.The macroscopic properties of bio-composites were found to be strongly dependent on their components,concentration,dispersion and resulted morphological structures.

Enhanced mechanical properties and flame retardancy of short jute fiber/poly(lactic acid)composites with phosphorus-based compound

In this work, a phosphorous-based compound （DOPO-ICN） was obtained by a two-step process. 9,10-dihydro-9-oxa-10- phosphaphenanthrene-10-oxide （DOPO） reacted with formaldehyde firstly, followed with reacting with 1,6-hexane diisocyanate （HD1）. The chemical structure of DOPO-ICN was confirmed by Fourier transform infrared spectroscopy （FTIR） and 1H NMR. The influence of DOPO-1CN on the mechanical and flammability properties ofjute/PLA composites was studied. Compared to DOPO, DOPO-ICN improved the tensile, flexural and impact strength of the flame retardant jute/PLA composites. Moreover, the flammability ofjute/PLA composites with different DOPO and DOPO-MA loading was investigated by thermogravimetric analysis （TGA）, UL 94 test and limiting oxygen index （LOI） measurements. The results showed that DOPO-ICN imparted the flame retardancy to the jute/PLA composites.

Biodegradation of jute/poly(lactic acid) composites by fungi

Jute/poly(lactic acid)(PLA) composites were firstly prepared by extrusion and injection molding. Then the composites were exposed to a fungi environment for 28 d which consisted with five fungi according to the American Society of Testing Materials(ASTM) standards. Weight loss, morphology and mechanical properties of the samples with different infected days were measured. Gel permeation chromatography(GPC), scanning electron microscope(SEM) and differential scanning calorimetry(DSC) were utilized to analyze the infected process. Mechanism can be concluded that PLA on the surface of composites slowly degraded under the fungi environment. Then surface fiber were exposed in the air, the interface gap between fiber and matrix enlarged, resulting in the decline of the mechanical properties.

Poly(methyl methacrylate)-induced Microstructure and Hydrolysis Behavior Changes of Poly(L-lactic acid)/Carbon Nanotubes Composites

Poly(L-lactic acid)(PLLA)-based composites exhibit wide applications in many fields.However,most of hydrophilic fillers usually accelerate the hydrolytic degradation of PLLA,which is unfavorable for the prolonging of the service life of the articles.In this work,a small quantity of poly(methyl methacrylate)(PMMA)(2 wt%-10 wt%)was incorporated into the PLLA/carbon nanotubes(CNTs)composites.The effects of PMMA content on the dispersion of CNTs as well as the microstructure and hydrolytic degradation behaviors of the composites were systematically investigated.The results showed that PMMA promoted the dispersion of CNTs in the composites.Amorphous PLLA was obtained in all the composites.Largely enhanced hydrolytic degradation resistance was achieved by incorporating PMMA,especially at relatively high PMMA content.Incorporating 10 wt%PMMA led to a dramatic decrease in the hydrolytic degradation rate from 0.19%/h of the PLLA/CNT composite sample to 0.059%/h of the PLLA/PMMA-10/CNT composite sample.The microstructure evolution of the composites was also detected,and the results showed that no crystallization occurred in the PLLA matrix.Further results based on the interfacial tension calculation showed that the enhanced hydrolytic degradation resistance of the PLLA matrix was mainly attributed to the relatively strong interfacial affinity between PMMA and CNTs,which prevented the occurrence of hydrolytic degradation at the interface between PLLA and CNTs.This work provides an alternative method for tailoring the hydrolytic degradation ability of the PLLA-based composites.

基质细胞衍生因子1修饰左旋聚乳酸多孔微球促进软骨细胞增殖和组织形成

背景:二维培养条件下的软骨细胞增殖及表型维持受限,多孔微球作为支架材料可提供三维培养环境,以更好地模拟体内生长条件。基质细胞衍生因子1是有强趋化效力的稳态细胞因子,能够促进细胞的黏附与增殖。目的:明确接枝基质细胞衍生因子1左旋聚乳酸多孔微球对软骨细胞生物学特性及软骨组织形成的影响。方法:(1)体外验证不同质量浓度基质细胞衍生因子1对兔软骨细胞增殖、迁移、表型维持的影响。(2)采用复乳法制备左旋聚乳酸多孔微球,利用碳二亚胺法将基质细胞衍生因子1接枝于左旋聚乳酸多孔微球上,通过酶联免疫吸附实验及孵育基质细胞衍生因子1特异荧光抗体验证接枝情况。(3)将兔软骨细胞分别接种于左旋聚乳酸多孔微球、接枝基质细胞衍生因子1左旋聚乳酸多孔微球上,检测细胞增殖与黏附。(4)在裸鼠背部皮下分别植入甲基丙烯酰胺基明胶-软骨细胞复合体(对照组)、左旋聚乳酸多孔微球-甲基丙烯酰胺基明胶-软骨细胞复合体(多孔微球组)、接枝基质细胞衍生因子1左旋聚乳酸多孔微球-甲基丙烯酰胺基明胶-软骨细胞复合体(多孔微球修饰组),8周后取材,分别进行组织学染色与成软骨相关基因qRT-PCR检测。结果与结论:(1)相较于0,1 000 ng/mL基质细胞衍生因子1,500 ng/mL基质细胞衍生因子1可促进软骨细胞的增殖与迁移,提升软骨细胞内Ⅱ型胶原、弹性蛋白、增殖细胞核抗原、Bcl-2 mRNA表达;(2)基质细胞衍生因子1成功接枝于左旋聚乳酸多孔微球上,接枝率为93.75%;(3)相较于左旋聚乳酸多孔微球,接枝基质细胞衍生因子1左旋聚乳酸多孔微球可促进软骨细胞的增殖、黏附;(4)裸鼠皮下植入8周后,相较于对照组、多孔微球组,多孔微球修饰组具有更明显的软骨陷窝结构、更丰富的软骨特异性基质和Ⅱ型胶原沉积,弹性蛋白、Ⅱ型胶原、增殖细胞核抗原、Bcl-2 mRNA表达升高。结果表明:接枝基质细胞衍生因子1左旋聚乳酸多孔微球有利于软骨细胞的黏附、增殖、表型维持以及体内软骨组织形成。

Dexamethasone-Loaded PLGA Microspheres Incorporated PLLA/PLGA/PCL Composite Scaffold for Bone Tissue Engineering

The combination of micro-carriers and polymer scaffolds as promising bone grafts have attracted considerable interest in recent decades.The poly(L-lactic acid)/poly(lactic-co-glycolic acid)/polycaprolactone(PLLA/PLGA/PCL)composite scaffold with porous structure was fabricated by thermally induced phase separation(TIPS).Dexamethasone(DEX)was incorporated into PLGA microspheres and then loaded on the PLLA/PLGA/PCL scaffoldtopreparethedesiredcompositescaffold.The physicochemical properties of the prepared composite scaffold were characterized.The morphology of rat bone marrow mesenchymal stem cells(BMSCs)grown on scaffolds was observed using scanning electron microscope(SEM)and fluorescence microscope.The resultsshowedthatthePLLA/PLGA/PCLscaffoldhad interconnected macropores and biomimetic nanofibrous structure.In addition,DEX can be released from scaffold in a sustained manner.More importantly,DEX loaded composite scaffold can effectively support the proliferation of BMSCs as indicated by fluorescence observation and cell proliferation assay.The results suggested that the prepared PLLA/PLGA/PCL composite scaffold incorporating drug-loaded PLGA microspheres could hold great potential for bone tissue engineering applications.

木质素在合成可降解高分子材料中的应用研究进展

简述了木质素的结构、特性和分类情况,并综述了近年来国内外使用木质素来增强和改善聚对苯二甲酸-己二酸丁二酯、聚乳酸、聚己内酯和聚丁二酸丁二酯等合成可降解高分子材料性能的研究进展。指出木质素与合成可降解高分子材料复合可以赋予复合材料多种功能特性,如紫外屏蔽、抗菌、阻隔等,并能改善材料的生物降解性能,同时实现降本增效的目标。最后提出当前木质素与合成可降解高分子材料复合材料工业化生产应用存在的问题,并对木质素基全生物降解复合材料的未来研究趋势进行展望。

竹质纤维形态对聚乳酸基竹塑复合材料性能的影响

为高值化利用竹材加工剩余物资源,以聚乳酸(PLA)为基体,竹粉纤维(BF)、竹屑纤维(BS)、竹原纤维(BN)与竹浆纤维(BP)为填料,采用密炼-注塑工艺制备了四种竹塑复合材料,研究了竹质纤维种类对其结构与性能的影响。研究结果显示,BP与BN纤维长径比更大,BS中颗粒形态较多,BF与BS质地较刚硬。BF、BN与PLA共混熔体的混炼扭矩更大,PLA/BP复合材料吸水率最大。BF,BS,BN与PLA的界面相容性较好,其添加改善了复合材料的力学性能,而BP添加降低了复合材料的力学性能。与PLA相比,在纤维质量分数为30%时,PLA/BF,PLA/BS与PLA/BN复合材料拉伸强度分别提高了17.85%,13.6%,11.89%,冲击强度分别提高24.33%,18.70%,35.57%,弯曲强度分别提高19.45%,21.45%,4.99%。PLA/BF复合材料的综合力学性能最优,其次为PLA/BS复合材料,PLA/BP复合材料最差。研究可为竹塑复合材料的开发与应用提供有益参考。

Effect of DOPO-containing Flame Retardants on Poly（lactic acid）： Non-flammability, Mechanical Properties and Thermal Behaviors

The flame retardancies of three kinds of 9,10-dihydro-9-oxa-10-phosphaphenan-threne 10-oxide（DOPO）- containing flame retardant（A1, A2, A3）/poly（lactic acid）（PLA） composites[PA-n/（Ax-y）, n= 1--12; x= l, 2, 3, denoting three kinds of flame retardants; y= 10%, 20%, 30%, 40%, denoting the mass fraction of Ax] were greatly enhanced by melt blending of flame retardant Ax with PLA, including twin-screw extrusion and injection-molding processes. With only 10%（mass fraction） of Ax added to PLA, good flame retardancy with limiting oxygen index（LOI） values of more than 33% was achieved. As the Ax mass fraction was further increased to 20%, PA-n/（Ax-20%） composites showed much better flame retardancy（LOI~〉35% and UL-94 V-0 rating）. Moreover, the thermal degradation behaviors and mechanical properties of PA-n/（Ax-y） composites were investigated via thermogravimetric analysis（TGA）, differen- tial thermal analysis（DTA）, tensile testing, notched impact-bar testing, and dynamic mechanical analysis（DMA）. TGA results show that PA-n/（Ax-y） composites have slower rate of mass loss and much higher char yield, compared to neat PLA. With the addition of Ax to PLA, the DTA and DMA results indicate slight variations in glass transition tcmpe- ratures（Tg） of PA-n/（Ax-y） composites. Based on TGA results under nonisothermal conditions, the thermal degrada- tion kinetics of PA-n/（Ax-y） composites were studied by KAssinger＇s and Ozawa＇s methods. These thermal degrada- tion dynamic analyses show lower activation energies（EK or Eo） for PA-n/（Ax-y） composites, corresponding to higher mass fractions of Ax（from 10% to 40%）. The PA-n/（Ax-y） composites with good flame retardancy and good mecha- nical properties obtained in this study could be potential candidates for fire- and heat-resistant applications in auto- motive engineering and building fields with more safety and excellent performance.

低温冷凝沉积法3D打印骨组织工程左旋聚乳酸/珍珠粉复合支架

背景:大面积骨缺损的修复目前仍面临严峻挑战,研发可个性化定制、低成本且具有成骨诱导活性的组织工程支架用于骨修复意义深远。目的:探索低温冷凝沉积法实现3D打印含珍珠复合材料骨组织工程支架的工艺流程,并进一步测试该复合支架的理化性能和体外生物学功能。方法:采用研磨过筛法制备珍珠粉,将不同质量的珍珠粉加入左旋聚乳酸墨水中,使珍珠粉与左旋聚乳酸的质量比分别为0,0.1,0.2,0.3,0.5,采用低温冷凝沉积法3D打印左旋聚乳酸/珍珠粉复合支架。检测支架的微观形貌、抗压性能、水接触角、细胞相容性以及体外促成骨分化能力。结果与结论:①扫描电镜显示5组支架均有直径2μm甚至更小的微孔,形状不规则且相互连通;②5组支架均具有良好的抗压性能,其中珍珠粉0.5组支架的压缩强度高于其他4组支架(P<0.05),珍珠粉0.2组、珍珠粉0.5组的水接触角小于珍珠粉0组(P<0.01,P<0.001);③将骨髓间充质干细胞分别与5组支架共培养1,3,5 d,珍珠粉0.1组、珍珠粉0.2组、珍珠粉0.3组、珍珠粉0.5组培养3,5 d的细胞增殖均快于珍珠粉0组(P<0.05);培养1 d的活死染色显示,各组支架上的细胞数量较少,但均为活细胞;④将骨髓间充质干细胞分别接种至珍珠粉0组、珍珠粉0.1组支架表面进行成骨诱导分化,珍珠粉0.1组诱导4,6 d的碱性磷酸酶活性高于珍珠粉0组(P<0.05);⑤结果表明,左旋聚乳酸/珍珠粉复合支架具有良好的抗压强度、亲水性、细胞相容性与促成骨性能。

Lignin/PLA复合材料的制备与性能

将聚乳酸(PLA)与木质素(Lignin)通过熔融共混法制备了Lignin/PLA复合材料样品。通过熔体流动速率测试仪、万能试验机、冲击试验机及热台偏光显微镜对样品的结晶形态、熔融指数、拉伸性能及冲击性能进行了表征。结果表明:Lignin的加入可细化PLA的球晶尺寸,破坏PLA的球晶完整性。随着Lignin含量的增加,熔融指数、断裂伸长率及冲击强度呈先升后降趋势。当Lignin质量含量分别为15%时,样品的熔体流动速率有最大值,为60.5 g/(10 min),较空白样提升了23.67%;当Lignin质量含量分别为10%时,样品的断裂伸长率有最大值,为4.86%,较空白样提升了43.36%;当Lignin质量含量分别为5%时,样品的冲击强度有最大值,为3.65 kJ/m^(2),较空白样提升了95.19%。

生物高分子材料聚乳酸的改性研究进展

在对生物医用高分子材料聚乳酸的生物性能、物理力学性能进行概述的基础上,介绍了对聚乳酸进行增塑、共聚、共混、复合等改性的方法及作用。经改性后聚乳酸的力学性能、亲水性能或反应功能可以得到某些改善,且其降解性能不受影响,从而更好地满足了在生物医用及环保中的应用需要。

聚乳酸的改性研究

综述了近几年生物降解材料聚乳酸的改性研究进展。改性方法可分为化学改性、物理改性和复合材料改性。化学改性包括共聚、交联、表面修饰等,物理改性包括共混改性、增塑改性等。

聚乳酸/木粉复合材料的结构与性能研究

以聚乳酸和杨木粉为原料制备了聚乳酸/木粉复合材料,研究了木粉处理、木粉用量对复合材料性能的影响,并对复合材料形态结构进行了观察。结果表明,与未处理木粉相比,木粉表面偶联处理使复合材料力学强度略有下降,碱处理对复合材料力学强度的提高并不明显。随木粉用量增加,复合材料的拉伸强度和弯曲强度分别在木粉质量分数为40%和20%时达到最高值,比纯聚乳酸的强度分别高出41.8%和38.6%。复合材料为假塑性流体,随木粉用量增加,剪切黏度增加。光学显微镜观察发现,未处理木粉能够均匀分散在聚乳酸基体中。

聚乳酸木塑复合材料的增韧及结晶性能

选用不同弹性体乙烯-醋酸乙烯共聚物(EVA)、马来酸酐接枝乙烯辛烯共聚物(POE-MAH)、甲基丙烯酸缩水甘油酯接枝乙烯辛烯共聚物(POE-GMA)与木粉和聚乳酸在Haake转矩流变仪中熔融共混,考察弹性体对聚乳酸木塑复合材料冲击强度的影响,发现POE-GMA对聚乳酸木塑复合材料的增韧效果最好,研究了POE-GMA的用量对聚乳酸木塑复合材料的韧性的影响,并阐述了增韧机理,且当PLA/WF/POE-GMA质量比为80/20/20时,聚乳酸木塑复合材料的综合性能最佳。POE-GMA的加入使得聚乳酸木塑复合材料结晶温度下降,结晶度升高。