Time resolved study of oriented crystallisation of poly(lactic acid) during rapid tensile deformation

Poly(l-lactic acid) with 4% d-lactic acid comonomer has been drawn in the amorphous state at 80, 90, 100, 110 and 120 °C at an extension rate of 4 s⁻¹ while simultaneously recording WAXS and SAXS patterns at intervals of 0.12 s. At 80, 90 and 100 °C, crystallisation is very rapid (1-4 s⁻¹) and follows a first order transformation process to give highly oriented crystals. SAXS patterns were barely detectable at these temperatures despite fractional crystallinity of ∼0.2. At 110 and 120 °C, crystallisation was very slow (∼0.01 s⁻¹) and gave rise to crystals with a lower degree of orientation. After eventual crystallisation at 120 °C, a two-point SAXS pattern develops with narrow lateral spread, suggesting ‘shish kebab’ morphology. When the 80 °C drawn sample was annealed at 120 °C, a strong four point SAXS pattern develops. The change in drawing and crystallisation behaviour at higher draw temperature is attributed to the onset of chain retraction relaxation processes. The WAXS fibre pattern after annealing shows sampling on intermediate layer lines that is consistent with the α crystal form with a 10₃ helix. However, prior to annealing, sampling indicates a different, less defined helical configuration.     

紫外线吸收剂在PLA/PBAT生物降解薄膜中的应用

通过挤出共混造粒、吹塑成型工艺制备出了聚乳酸(PLA)/聚对苯二甲酸-己二酸丁二醇酯(PBAT)完全生物降解薄膜。研究了一种二苯甲酮类紫外线吸收剂对PLA/PBAT薄膜抗紫外老化的作用。采用万能拉力试验机、紫外-可见吸光光谱仪、差示扫描量热法(DSC)对PLA/PBAT薄膜在紫外老化过程中的性能进行了测试和表征。结果表明,选择的紫外线吸收剂能有效减缓PLA/PBAT薄膜在老化过程中力学性能的下降。紫外老化更易发生在薄膜的无定型区,该紫外线吸收剂能明显降低薄膜在老化过程中结晶度的变化。同时,添加该紫外线吸收剂能大幅度降低薄膜在紫外老化过程中产生的凝胶含量。     

完全生物降解塑料PLA/PPC合金的结构与性能研究

利用机械共混法,将聚乳酸(PLA)与聚丙撑碳酸亚丙酯(PPC)熔融共混,制备了完全生物降解塑料PLA/PPC合金,并用FTIR、流变仪等手段研究了其结构、力学性能和流变性能。结果表明该共混体系具有良好的相容性、力学性能和熔体流动性,PLA与PPC之间存在着较强的相互作用,PPC的加入使体系拉伸强度下降幅度不大,断裂伸长率升高到23.8%,比纯PLA提高近20倍。共混体系的黏度亦随着PPC的加入逐渐增大,PLA/PPC(50/50)体系的黏流活化能为37.1kJ/mol,同时在一定的温度范围内,提高切应力也会使体系黏度下降。     

聚乳酸（PLA）／己二酸-对苯二甲酸-丁二酯共聚物（PBAT）／乙酰化柠檬酸三丁酯（ATBC）共混物的结晶行为

采用熔融共混法制备聚乳酸（PLA）／己二酸-对苯二甲酸-丁二酯共聚物（PBAT）／乙酰化柠檬酸三丁酯（ATBC）共混物。用差示扫描量热仪（DSC）和偏光显微镜（POM）分析了乙酰化柠檬酸三丁酯（ATBC）对共混物PLA结晶行为的影响。结果表明当PLA／PBAT含量为80／20（质量比）时,随着ATBC量的增加,PLA的Tg、Tc和Tm降低,结晶度提高,球晶生长速率增加。     

Structure-properties of super-tough PLA alloy with excellent heat resistance

Poly(lactic acid) (PLA) was toughed by blending hydrogenated styrene-butadiene-styrene block copolymer (SEBS) with the aid of reactive compatibilizer, poly(ethylene-co-glycidyl methacrylate) (EGMA). The high temperature property and thermal aging resistance were improved by further incorporating polycarbonate (PC), the ductile polymer with high glass transition temperature. On the basis of transmission electron microscopy, differential scanning calorimetry, and dynamic mechanical analysis, the outstanding toughness and aging resistance of the 4 component alloy; e.g., PLA/PC/SEBS/EGMA = 40/40/5/5 (wt. ratio), seems to come from the negative pressure effect of SEBS that dilates the plastic matrix consisting of PLA and PC to enhance the local segment motions.     

聚乳酸增韧改性研究

通过熔融共混法制备了通用注塑级聚乳酸(PLA)材料,研究了刚性粒子种类,增韧剂种类和协同增韧等对PLA力学性能的影响,同时通过控制扩链剂的添加量有效地对注塑级PLA的熔体流动速率(MFR)进行控制。结果表明:协同增韧剂对PLA有较好的增韧效果,冲击强度从3.5 kJ/m2提高到15 kJ/m2,是单一增韧剂的2.5倍。通过引入扩链剂,得到一系列不同MFR的注塑级PLA材料,满足不同的工业化产品需求。     

聚乳酸/淀粉共混复合材料研究进展

综述了近年来国内外聚乳酸/淀粉共混复合材料的研究进展,并对聚乳酸/淀粉共混复合材料的发展前景进行了展望。     

聚乳酸/纤维素及其衍生物共混复合材料的研究进展

介绍了聚乳酸(PLA)/纤维素、PLA/天然植物纤维、PLA/纤维素酯和PLA/纤维素醚共混复合材料最新的研究进展,综述了复合材料在相容性、分散性、力学性能和降解特性等方面存在的优点和缺点,为此类共混复合材料的进一步研究指明方向。     

ACR增韧聚碳酸酯/聚乳酸合金的制备与性能研究

以核壳结构的丙烯酸酯类树脂(ACR)作为增韧剂,对聚碳酸酯(PC/)聚乳(酸PLA)合金进行增韧改性,研究了ACR用量对合金力学性能、热性能和微观形态的影响。结果表明:加入一定用量的ACR,合金的冲击强度大幅度提高,而其他力学性能影响较小;合金比例为PC/PLA=90/10时,二者的相容性良好,体系只有一个玻璃化温度;ACR的用量对合金的微观形态有一定的影响。     

改性剂对聚乳酸/淀粉性能影响的研究进展

针对聚乳酸(PLA)与淀粉直接混合造成力学性能和相容性变差的问题,介绍了添加改性剂对PLA/淀粉热学、力学性能和降解性能的影响,并对PLA/淀粉共混复合材料的发展前景进行展望.     

聚乳酸的改性与成型加工研究进展

结合生物可降解材料聚乳酸的一些缺点,提出了几种改性的方法,并介绍了聚乳酸成型加工常用的两种方法,即挤出成型和注射成型,最后对聚乳酸的应用进行了展望。     

成核剂对聚乳酸结晶行为及热性能的影响

采用熔融共混法制备了聚乳酸/成核剂复合材料,通过结晶速率测试仪、偏光显微镜(POM)、差示扫描量热仪(DSC)、X射线衍射仪(XRD)和负荷热变形温度测定仪对材料的结晶行为及热行为进行了研究。结果表明:与滑石粉相比,多酰胺类化合物(TMC)在聚乳酸基体中的成核效果更为明显,TMC的加入未改变聚乳酸的晶型,但显著提高了聚乳酸的结晶速率和结晶度;当所有样品在120℃下退火2 min时,与纯聚乳酸及滑石粉成核的聚乳酸相比,TMC成核的聚乳酸耐热温度最高,可达105.6℃。     

EVA增容HDPE/PLA共混体系的研究

以乙烯-醋酸乙烯共聚物(EVA)为增容剂,采用熔融共混法制备了高密度聚乙烯(HDPE)/聚乳酸(PLA)/EVA复合材料,研究了EVA用量对复合材料力学性能及热性能的影响,并利用扫描电镜分析了复合材料的微观形态。结果表明:随着EVA用量的增加,复合材料的断裂伸长率及冲击强度逐渐增加;另外SEM结果显示,EVA可以改善HDPE与PLA的相容性,但EVA的加入对复合材料热性能影响较小。     

Polylactide compositions. Part 1: Effect of filler content and size on mechanical properties of PLA/calcium sulfate composites

Starting from calcium sulfate (gypsum) as a fermentation by-product of lactic acid fermentation, novel high performance composites have been produced by melt-blending polylactide (PLA) and previously dried calcium sulfate hemihydrate in a Brabender bench scale kneader at 190 °C. Due to PLA sensitivity towards hydrolysis, it has first been demonstrated that formation of β-anhydrite II (AII) by adequate thermal treatment of calcium sulfate is a prerequisite. Then, the effect of filler content and mean diameter on thermal, mechanical and impact properties has been examined together with the morphology of the resulting materials. It shows that high tensile performances and impact strength are maintained up to a filler content of 20 wt% without any increase of PLA crystallinity. Interestingly enough and provided that AII particles with a mean diameter of ca. 10 μm were considered as PLA fillers, tensile and impact properties proved to be maintained at a very acceptable level at filler content as high as 50 wt%. Such remarkable mechanical behavior can be accounted for by the excellent filler dispersion throughout the polyester matrix and much favorable interactions between CaSO₄ particles and ester functions of PLA chains as evidenced by the use of predictive mathematical models for composite mechanical properties and SEM-BSE imaging of fractured surfaces.     

聚乳酸/环氧基笼型倍半硅氧烷纳米复合材料的流变性能研究

采用毛细管流变仪分析了熔融共混法制备的聚乳酸/环氧基笼型倍半硅氧烷(PLA/EVOS)纳米复合材料的流变行为。结果表明:PLA/EVOS纳米复合材料为假塑性流体,呈现出切力变稀的特征;随着温度的升高,复合材料的非牛顿指数有所提高;随着EVOS含量的增加,复合材料的非牛顿指数先升后降,而稠度和表观黏度先减小后增大;复合材料熔体的黏流活化能相对较低,仅为12~35 kJ/mol。     

Miscibility and crystallisation behaviour of poly(ethylene terephthalate)/polycarbonate blends

Poly(ethylene terephthalate)/polycarbonate blends were produced in a twin-screw extruder with and without added transesterification catalyst, lanthanum acetyl acetonate. The miscibility of the blends was studied from their crystallisation behaviour and variation in glass transition temperature with composition using differential scanning calorimetry, scanning electron microscopy and change in mechanical properties. The blends prepared without the catalyst showed completely immiscible over all compositions, while those prepared in the presence of the catalyst showed some limited miscible. The presence of PC inhibited the crystallisation of PET but this was much greater in the blends prepared in the presence of catalyst suggesting that some reaction had taken place between the two polyesters. The tensile properties showed little differences between the two types of blends.     

聚乳酸/无机填料复合材料结构与性能的研究

采用密炼器熔融共混法,将聚乳酸(PLA)分别与碳酸钙(CaCO3)、蒙脱土(MMT)及滑石粉(Talc)共混制备成生物降解复合材料,研究了PLA/无机填料共混物的力学性能、断面微观结构及结晶性能。结果表明:CaCO3、MMT和Talc均降低了PLA的断裂伸长率;Talc和CaCO3对PLA的拉伸强度影响不大,MMT明显降低了PLA的拉伸强度;Talc和CaCO3相对MMT在PLA基体中的分散较均匀;CaCO3和MMT改善PLA结晶性能的效果不明显,而Talc大大提高了PLA的结晶性能使,PLA的结晶温度下降约20℃结,晶度提高近3%。     

Morphological and rheological characterization of multi-walled carbon nanotube/PLA/PBAT blend nanocomposites

Biodegradable poly (lactic acid) (PLA)/poly (butyleneadipate-co-butyleneterephthalate) (PBAT)/multi-walled carbon nanotube (MWNT) polymer blend nanocomposites were prepared by using a laboratory-scale twin-screw extruder. Fractured surface morphology of the polymer blend/MWNT nanocomposites were examined via SEM. Furthermore, cross sectioned samples obtained using an ultramicrotome was observed via TEM. In addition, effects of both MWNT reinforcement and phase affinity of MWNT on thermal and rheological properties of the PLA/PBAT blends were investigated by TGA and rotational rheometer. Immiscible PLA/PBAT blend with MWNT nanocomposites showed two-step thermal degradation. The onset temperature of thermal degradation started in the PLA much earlier than in the PBAT. Nonetheless, based on TGA data, it was found that the MWNT enhanced thermal property of the PLA/PBAT blend/MWNT nanocomposites. Rheological properties revealed that both shear and complex viscosities showed unique shear thinning behavior due to selectively localized MWNT dispersion state.     

苹果酸对聚乳酸/热塑性淀粉共混物结构与性能的影响

将天然淀粉用甘油改性后制得了热塑性淀粉(TPS),再通过熔融共混法制备了聚乳酸(PLA)/TPS共混物。通过SEM、TG、DSC分析和拉伸性能、吸水性能、流变性能测试,研究了苹果酸对TPS和PLA/TPS共混物结构和性能的影响。结果表明:苹果酸能促进淀粉酸解,使TPS分散相尺寸减小,在PLA基体中的分布更加均匀;苹果酸能提高PLA/TPS共混物的拉伸性能;苹果酸对PLA/TPS共混物的玻璃化转变温度、熔融温度及冷结晶温度影响较小;少量的苹果酸可降低PLA/TPS共混物的吸水率。     

PLA-g-GMA的制备及其对PLA/PPC共混体系性能的影响

采用双螺杆挤出机将甲基丙烯酸缩水甘油酯(GMA)接枝到聚乳酸(PLA)上,而后将接枝产物(PLA-g-GMA)与聚乳酸(PLA)、聚碳酸亚丙酯(PPC)反应性共混,考察了接枝物中GMA加入量变化对PLA/PPC/PLA-g-GMA共混体系的力学性能、热稳定性能的影响,并对共混体系的断裂机理进行了研究。结果表明,PLA-g-GMA的引入能够在一定程度上改善PLA与PPC的相容性。随着接枝物中GMA加入量的增加,共混物的冲击强度、断裂伸长率及拉伸强度均呈现出先升高后降低的趋势,并在接枝物中GMA加入量为3%时达到最大值。扫描电镜结果显示,PLA-g-GMA引入后共混物的韧性断裂特征越发显著,其冲击断裂方式由脆性断裂过渡为韧性断裂。热失重分析结果显示,加入PLA-g-GMA后共混物的起始分解温度和完全分解温度均有一定程度的提高。