等温冷结晶对PLA/PBAT共混物冲击韧性和耐热性能的影响

通过熔融共混法制备了聚乳酸/聚己二酸-对苯二甲酸丁二醇酯(PLA/PBAT)共混物,并对其微观形貌、热性能、冲击性能和耐热性能进行了研究。结果表明,随着PLA/PBAT共混物中PBAT含量的增加,共混材料的无缺口冲击强度逐渐增大,其中当PBAT含量为30%时,共混材料的无缺口冲击强度达到最大值。再通过等温冷结晶提高PLA/PBAT材料的结晶度,以改善材料的耐热性能。结果表明,等温冷结晶样品的维卡软化温度(VST)明显高于急冷样品,且结晶度越高,VST值则越大;此外,90℃等温冷结晶20 min的样条无缺口冲击强度高于急冷样条,但当等温冷结晶温度提高至130℃时,样条的无缺口冲击强度下降,且低于急冷样条。因此,较低冷结晶温度有利于得到兼具良好耐热性能和冲击性能的PLA/PBAT材料。     

多元环氧扩链剂对聚乳酸等温结晶行为及力学性能的影响

采用多元环氧扩链剂(ADR)对聚乳酸(PLA)进行熔融扩链改性,得到PLA/ADR共混物。采用差示扫描量热仪(DSC)对共混物的熔体等温结晶行为进行表征和分析。结果表明:在110~120℃温度范围内,ADR的加入提高了PLA熔体的结晶速率;随着ADR用量的增加,PLA等温结晶速率明显提高,半结晶时间缩短。结合熔体流动速率和偏光显微镜分析,从分子运动能力和熔体黏度的角度解释了ADR对PLA等温结晶行为的影响机理。此外,研究了结晶度变化对PLA/ADR共混物拉伸性能和维卡软化温度(VST)的影响。当PLA/ADR(100/1.0)共混物的结晶度由1.7%提高到32.2%时,其拉伸强度由55.6 MPa提高到63.2 MPa,VST由61.9℃提高到156.9℃。结晶度的增大有利于PLA/ADR共混物力学性能和耐热性能的进一步提高。     

聚己内酯对聚乳酸熔融结晶的影响

聚合物共混材料的结晶行为对材料性能有重要的影响,结晶行为是共混材料研究的主要问题。选用聚乳酸(PLA)和聚己内酯(PCL)共混材料,采用偏光显微镜和差示扫描量热仪,对PLA/PCL共混材料的结晶行为进行研究。通过等温结晶动力学,分析PCL对PLA在100和120℃时等温结晶的影响。结果表明,PCL相作为异相成核剂加入PLA相,使得PCL/PLA共混物中异相结晶成核效率提高,晶体直径减小,半结晶时间减小,提高PCL/PLA共混物的结晶能力。随着PCL相的占比增大,PCL/PLA(40/60)试样中出现"海-岛结构",异相成核效率增大,半结晶时间较小,结晶直径减小,结晶度减小。     

纳米二硫化钼对聚乳酸等温结晶行为的影响

采用熔融共混法制备聚乳酸/二硫化钼(PLA/MoS_2)纳米复合材料。通过差示扫描量热法(DSC)研究纳米MoS_2含量对PLA等温结晶行为的影响,采用Avrami方程分析纳米复合材料的等温结晶动力学,并采用X射线衍射(XRD)测试材料的结晶结构。由等温结晶动力学计算结果可知,加入MoS_2纳米粒子后,PLA基体的结晶速率显著提高。例如,当结晶温度(Tc)为110℃,MoS_2含量由0增至2.0%时,试样的结晶半时间(t1/2)可由纯PLA的8.5 min大幅降低至3.2 min。而当Tc为120℃,MoS_2含量由0增至2.0%时,试样的t1/2由纯PLA的11.4 min降低至3.8 min。同时,随着MoS_2含量的增大,PLA基体的最大结晶度也有一定程度增大,说明MoS_2起到异相成核剂作用。PLA/MoS_2试样的Avrami指数在2.6~3.1之间,可知在MoS_2存在下,PLA晶体主要为异相成核和三维生长。     

滑石粉对PLA/PBAT共混物非等温结晶行为的影响

采用差示扫描量热法研究了滑石粉(Talc)对聚乳酸/聚己二酸-对苯二甲酸丁二醇酯(PLA/PBAT)共混物非等温结晶行为的影响。结果表明,随着Talc用量的增加,结晶完成时间缩短,结晶温度向高温移动,且结晶度增大,这说明Talc可以起到异相成核剂的作用,显著提高共混物的结晶能力。此外,降温速率对共混物的非等温结晶行为也有显著影响。较低的降温速率有利于得到结晶度更高的PLA/PBAT共混材料。利用Jeziorny法对共混物的非等温结晶动力学进行研究。结果发现,在相同降温速率下,随着Talc含量的增加,结晶速率常数显著增大,而半结晶时间随之减小。在不同降温速率下得到的含Talc共混物的Avrami指数(n)接近3,故其成核机理是以异相成核为主,球晶生长方式为三维生长。     

生物降解PBS/MMT共混体系结晶行为研究

通过差示扫描量热仪及Avrami方程对聚丁二酸丁二醇酯/蒙脱土(PBS/MMT)共混体系的结晶熔融行为和非等温结晶动力学进行了表征和分析。结果表明:PBS在86.9℃处出现结晶峰;随着无机成核剂MMT的添加(添加量1%~5%),PBS/MMT共混体系在120℃以上出现高温区结晶峰。PBS/MMT共混体系的低温区结晶温度、绝对结晶度和结晶活化能均高于纯PBS。随着MMT加入量的增加,共混体系的低温区结晶温度和绝对结晶度逐渐降低,结晶活化能呈现先升高后下降的趋势;高温区的结晶温度和结晶活化能逐渐升高,绝对结晶度则迅速下降,且当MMT加入量达到7%时,高温区结晶峰消失。MMT具有明显的异相成核作用,可以改变PBS结晶过程中的成核和增长方式,而对其结晶速率影响不显著,其结晶速率受降温速率的影响较大。     

有机膨润土和退火对PLA结晶及耐热性能的影响

以有机膨润土(OBT)作为聚乳酸(PLA)的成核剂,采用熔融共混法制备了PLA/OBT共混物,通过偏光显微镜(POM)、X射线衍射仪(XRD)、差示扫描量热仪(DSC)和维卡软化温度测定仪分析了在不同退火条件下,成核剂OBT对PLA结晶及耐热性能的影响。研究表明:加入成核剂OBT后,短时间的退火能够有效提高PLA的结晶度和耐热性能。当OBT的含量为0.5%时,PLA/OBT共混物在100℃下退火10 min后,其结晶度为46.3%,热变形温度(HDT)为97.8℃。     

增塑剂对生物降解塑料聚乳酸结晶形态的影响

采用熔融共混方法制备了聚乙二醇(PEG)和聚乳(酸PLA)的共混物,并借助差示扫描量热仪和广角X射线衍射仪研究了在80~140℃等温结晶时PEG对PLA结晶形态和熔融行为的影响。结果表明:100℃以上时PLA的结晶度随结晶温度的升高逐渐增加;100℃以下时PLA的结晶度随PEG含量的增加逐渐增大。110℃以下时,晶面间距随结晶温度的升高和PEG含量的增加而逐渐减小;110℃以上时,晶面间距保持不变;当加入15%的PEG时PLA的晶面间距不受结晶温度的影响结,晶生成的是稳定的α晶。     

聚乳酸/四针状氧化锌晶须非等温冷结晶行为的研究

采用熔融共混法制备了聚乳酸(PLA)/四针状氧化锌晶须(T-ZnOw).用差示扫描量热仪研究了PLA及PLA/T-ZnOw的非等温冷结晶行为;用Jeziorny法和Mo法对其非等温冷结晶动力学进行了分析研究,并计算了相关的结晶动力学参数.结果表明,Jeziorny法和Mo法均能很好地描述PLA及PLA/T-ZnOw的非等温冷结晶过程,且结果一致.Jeziorny法分析表明,初次结晶阶段PLA及PLA/T-ZnOw的Avrami指数n1值范围分别为4.22～5.43和3.11～4.80,而二次结晶阶段的Avrami指数n2值范围分别为3.10～4.66和2.69～5.57,说明T-ZnOw的加入改变了PLA的成核和晶体生长规律.Mo法分析表明,在相同的X(t)下,PLA/T-ZnOw的F(T)值整体大于PLA,T-ZnOw的加入降低了PLA的结晶速率.偏光显微镜观察结果显示,随着T-ZnOw的加入,PLA球晶尺寸减小,数目增多,T-ZnOw促进了PLA的成核.     

偶联改性棉花纳米纤维素/聚乳酸复合材料的非等温结晶性能和疏水性能研究

采用偶联剂3-氨丙基三乙氧基硅烷(KH550)对棉花纳米纤维素(CNF)进行表面改性,得到偶联改性棉花纳米纤维素(cCNF),将cCNF与聚乳酸(PLA)的氯仿溶液直接共混,通过溶液浇铸得到偶联改性棉花纳米纤维素/聚乳酸复合材料(cCNF/PLA)。研究cCNF的加入量对PLA的非等温结晶性能和疏水性能的影响。结果表明:复合材料的结晶峰温度及结晶度先升高后降低,当cCNF的添加量为0.125%时,复合材料结晶峰温度及结晶度升高至最大值,分别为107.2℃、32.1%,比纯PLA分别升高2.4℃、5.5%;PLA及其复合材料的半结晶时间(t_(1/2))也缩短。采用改进的Avrami方程研究PLA及cCNF/PLA的非等温结晶过程,在2、4、6℃/min的降温速率下,n值的范围为1.85～2.54,表明晶体的生长模式为二维和三维并存,当cCNF的添加量为0.125%时,结晶速率常数均升高到最大值。当cCNF的添加量为1%时,cCNF/PLA复合材料的接触角降到最小值69°,比纯PLA降低11.5°。     

Isothermal melt crystallization and performance evaluation of polylactide/thermoplastic polyester blends with multi‐functional epoxy

A multi‐functional epoxy (ADR) was used to improve compatibilization of poly(lactic acid) (PLA)/ thermoplastic polyester elastomer (TPEE) blends. Influence of ADR on isothermal melt crystallization of the blends was investigated. The results show that isothermal melt crystallization rate of the samples increases with ADR loading. It can be attributed to a nucleation enhancement resulted from an increase of molecular weight and melt viscosity created by the chain extension/branched process of PLA in the presence of ADR. In addition, the maximum crystallinity of the samples shows a decrease with increasing ADR loading because of the chain extended and branched reaction. Quenched and crystallized samples were fabricated using compression molding under different cooling conditions in‐mold. Effects of crystallinity and ADR on mechanical performances of the PLA/TPEE sample were investigated. With increasing the crystallinity, the PLA/TPEE sample shows a marked enhancement in heat resistance. However, the tensile ductility of the crystallized PLA/TPEE sample drastically decreases due to the formation of firm crystal crosslinking and the incompatibility between PLA and TPEE. It is notable that the tensile ductility of the crystallized samples is improved with the introduction of ADR owing to its reactive compatibilization effect. Finally, the crystallized PLA/TPEE/ADR samples with improved heat resistance and relative higher ductility are obtained. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46343.     

Preparation, Crystallization Behavior, and Morphology of Poly(lactic acid) Clay Hybrids via Wet Kneading Masterbatch Process

Modified masterbatch method comprising of the wet kneading and intercalated modifiers process was successfully applied to prepare exfoliated polylactic acid (PLA) clay hybrids. The crystallization rate of PLA/clay nanocomposite was improved by introducing alkylamide, an intercalated modifier with higher crystallinity. Both XRD and TEM analyses showed that the exfoliated and partially intercalated PLA nanocomposites can be obtained. The effect of clay and intercalated modifier on the nonisothermal, isothermal crystallization kinetics, and morphology of PLA was investigated using DSC instrument. The PLA nanocomposites showed faster crystallization rate because the alkylamide modifier act as a nucleation agent that successfully promoted crystallization. Notably, the crystallinity of PLA/clay hybrids dramatically increased from 9.0 to 42.1 %. The nucleation and crystal growth rate of PLA when crystallized from melt state is greatly influenced by the presence of organoclays. Therefore, as revealed from this isothermal crystallization investigation, the crystallization rate is enhanced by a factor of about 7–17.     

Enhanced crystallization of poly(lactide) stereocomplex by xylan propionate

The effect of xylan propionate (XylPr) as a novel biomass‐derived nucleating agent on the poly(lactide) sterecomplex was investigated. Addition of XylPr to an enantiomeric blend of poly(l ‐lactide) (PLLA) and poly(d ‐lactide) (PDLA) was performed in either the solution state or molten state. The solution blend of PLLA/PDLA with XylPr was prepared by mixing equal volumes of 1 wt% XylPr/PLLA and 1 wt% XylPr/PDLA solutions in chloroform and precipitating in methanol. The solution blend with XylPr showed shorter half‐time crystallization than the solution blend without XylPr in isothermal crystallization between 80 and 140 °C, although homocrystallization occurred. Enhanced stereocomplex crystallization in the solution blend with XylPr was observed at 180 °C, where no crystallization occurred in the solution blend without XylPr. Addition of XylPr to PLLA/PDLA blend in the molten state was performed at 240 °C. Thereafter, the melt blend of PLLA/PDLA with or without XylPr was either quenched in iced water or isothermally crystallized directly from the melt. Isothermal crystallization of the melt‐quenched blend with XylPr gave a similar result to the solution blend with XylPr. In contrast, the melt‐crystallized blend with XylPr formed only stereocomplex crystals after crystallization above 140 °C. Furthermore, the melt‐crystallized blend with XylPr showed a higher crystallinity index and melting temperature than the melt‐crystallized blend without XylPr. This shows that XylPr promotes stereocomplex crystallization only when the blend of PLLA/PDLA with XylPr is directly crystallized from the molten state just after blending. © 2016 Society of Chemical Industry     

Hydrolytic degradation behavior of poly(butylene succinate)s with different crystalline morphologies

The effect of crystalline morphology on the hydrolytic degradation behavior of poly(butylene succinate) (PBS) in an alkaline solution was investigated by using scanning electron microscopy, gel permeation chromatography, and weight loss measurement. Morphological changes were induced on PBS samples by different thermal treatments (i.e., melt quenching or isothermal crystallization) at a constant overall degree of crystallinity. It was found that even with a similar degree of crystallinity, the hydrolytic degradation rate of an isothermally crystallized sample at 60°C was higher than that of a melt‐quenched sample. This was due to the difference in the internal morphology of the spherulites: the internal structure of spherulite in an isothermally crystallized sample consists of coarse and loosely packed fibrils whereas a melt‐quenched sample contains finer and tightly packed fibrils. This result suggested that the internal structure of the spherulite of PBS samples plays an important role in the hydrolytic degradation for this experimental condition. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1025–1033, 2001     

PLA/T-ZnOw等温冷结晶及熔融行为的研究

采用熔融共混法制备了PLA/T-ZnOw复合物。用差示扫描量热仪（DSC）研究了PLA/T-ZnOw的等温冷结晶及其熔融行为,Avrami方程分析表明,Avrami方程能很好的描述PLA/T-ZnOw的等温冷结晶过程,Avrami指数n值在1.78~3.10之间,表明PLA/T-ZnOw是以二维盘状生长和三维球晶生长并存的球状晶体。偏光显微镜观察结果显示,随着T-ZnOw的加入,PLA球晶尺寸变小,数目增多,说明T-ZnOw促进了PLA的成核但未提高其结晶速度。     

Borassus powder-reinforced poly(lactic acid) composites with improved crystallization and mechanical properties

This article reports on the development of biocomposites based on polylactic acid (PLA) and borassus powder. Borassus powder was treated with alkali to remove hemicelluloses and lignin. The treated borassus improved the homogeneous mixing with PLA and increased the crystallinity of PLA. Dispersibility of the borassus was studied by scanning electron microscopy (SEM) and X-ray MicroCT. PLA/borassus composites were prepared by melt mixing of PLA with 5, 10, and 15 wt % treated/untreated borassus. Composites were examined for mechanical properties and crystallization. Composites showed enhanced tensile strength compared to neat PLA. The PLA/treated borassus powder composites displayed higher crystallinity than PLA. The isothermal cold crystallization study showed increase in the crystallization rate of PLA in the presence of treated borassus. The spherulitic growth was studied using polarized optical microscopy. The enhanced performance of the PLA-borassus composites was observed in the presence of borassus. This study demonstrates that the PLA-borassus composites show great promise for bioplastics applications. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47440.     

Thermal properties and non‐isothermal crystallization behavior of poly(trimethylene terephthalate)/poly(lactic acid) blends

Thermal properties and non‐isothermal melt‐crystallization behavior of poly(trimethylene terephthalate) (PTT)/poly(lactic acid) (PLA) blends were investigated using differential scanning calorimetry and thermogravimetric analysis. The blends exhibit single and composition‐dependent glass transition temperature, cold crystallization temperature (T_cc) and melt crystallization peak temperature (T_mc) over the entire composition range, implying miscibility between the PLA and PTT components. The T_cc values of PTT/PLA blends increase, while the T_mc values decrease with increasing PLA content, suggesting that the cold crystallization and melt crystallization of PTT are retarded by the addition of PLA. The modified Avrami model is satisfactory in describing the non‐isothermal melt crystallization of the blends, whereas the Ozawa method is not applicable to the blends. The estimated Avrami exponent of the PTT/PLA blends ranges from 3.25 to 4.11, implying that the non‐isothermal crystallization follows a spherulitic‐like crystal growth combined with a complicated growth form. The PTT/PLA blends generally exhibit inferior crystallization rate and superior activation energy compared to pure PTT at the same cooling rate. The greater the PLA content in the PTT/PLA blends, the lower the crystallization rate and the higher the activation energy. Moreover, the introduction of PTT into PLA leads to an increase in the thermal stability behavior of the resulting PTT/PLA blends. Copyright © 2011 Society of Chemical Industry     

Modification of the thermal properties and crystallization behaviour of poly(ethylene terephthalate) by copolymerization

Poly(ethylene terephthalate) (PET) is a widely used polyester, which can be crystallized from the melt over a wide range of supercooling conditions or, alternatively, quenched into the amorphous state and, subsequently, crystallized by thermal treatment above the glass‐transition temperature. It is well known that the crystallization of PET can be hindered by means of copolymerization or reactive blending. The incorporation of comonomeric units into the polymer backbone leads to an irregular chain structure and thereby inhibits regular chain packing for crystallization. The crystallization of PET copolyesters is strongly influenced by the chain microstructure regarding comonomer distribution, randomness and length of the crystallizable ethylene terephthalate sequences. This paper is mainly devoted to the thermally induced crystallization behaviour of PET and to reviewing the efforts that have been made in the last decade to modify the glass‐transition and melting temperatures, the crystallinity and the crystallization rate of this polyester. Furthermore, some illustrative experimental data obtained from isothermal and non‐isothermal crystallization of PET are included in this study. © 2003 Society of Chemical Industry     

Effects of size and shape of dispersed poly(butylene terephthalate) on isothermal crystallization kinetics and morphology of poly(lactic acid) blends

The isothermal crystallization kinetics and morphology of the poly(lactic acid) (PLA) blends containing three different sizes of both spherical and fibrous poly(butylene terephthalate) (PBT) domains have been comparatively investigated by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). The dynamic DSC measurement reveals that PBT domains significantly increase the degree of crystallinity of the PLA. Furthermore, the Avrami model is employed to evaluate the crystallization kinetics under isothermal conditions and it is found that PBT acts as nucleating agent, leading to a high overall crystallization rate constant k and shortened crystallization half time t_1/2. Furthermore, the crystallization rate of PLA is promoted with the incorporation of PBT with a large specific surface area. The average Avrami index n of all samples lies within the range of 3.3 ? 4.0, suggesting that morphologies of PBT do not affect the nucleation mechanism; however, the depression of equilibrium melting temperature in the blends ascribes the reductions of perfectness and size of the PLA crystallites. Besides, the nucleation of PLA crystallites around PBT fibers is probably faster than those around PBT spheres because the PBT chains oriented at the fiber surface as a result of flow‐induced crystallization during melt stretching may serve as the primary nuclei for PLA chains to drastically crystallize at the fiber surface. POLYM. ENG. SCI., 56:258–268, 2016. © 2015 Society of Plastics Engineers