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.     

Crystallization morphology and crystallization kinetics of poly(lactic acid): effect of <Emphasis Type="Italic">N</Emphasis>-Aminophthalimide as nucleating agent

The effect of N-Aminophthalimide compound (NA-S) as nucleating agent on crystallization behavior and morphology of poly(lactic acid) was studied. With polarized optical microscope (POM), the unique phenomena of nucleation and epitaxial crystallization of PLA/NA-S system were observed. Dynamic morphology of crystallization was also studied by POM to investigate the relationship between growth behavior of PLA and nucleating agent. Isothermal and non-isothermal crystallization behavior of PLA were studied by differential scan calorimeter (DSC). When nucleating agent was added, a new peak appeared in wide angle X-ray diffraction (WAXD) compared with pure PLA, indicating the nucleating effect of NA-S on crystallization of PLA. All the results indicate that the nucleating agent of NA-S shows obvious nucleating effect on isothermal crystallization above 120 °C and in non-isothermal crystallization after it is added in PLA, that is, the induction crystallization time is reduced, the crystallization rate and nucleation density of PLA are increased.     

聚乙二醇增塑聚乳酸的等温结晶动力学研究

采用DSC方法对聚乙二醇(PEG)增塑聚乳酸的等温结晶动力学进行了研究。结果表明,PEG的加入提高了聚乳酸的结晶速度,在相同结晶温度下,随着PEG摩尔质量的增大,结晶速率增大,结晶活化能先减小后增大。不同摩尔质量PEG增塑PLA的结晶成核机理和生长方式一样。     

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℃。     

聚乙二醇增塑聚乳酸的非等温结晶动力学研究

采用DSC方法对聚乙二醇(PEG)增塑聚乳酸的非等温结晶动力学进行了研究。结果表明,PEG的加入明显提高了聚乳酸的结晶速度。对所得数据分别用Ozawa方程和莫志深方法进行了处理,发现在给定温度范围里非等温结晶时,PLA/PEG主要是以均相成核的三维生长方式结晶;PLA的结晶速度随着PEG分子质量的增加而升高。     

The nucleation effect of modified carbon black on crystallization of poly(lactic acid)

The nonisothermal crystallization of poly(lactic acid) (PLA), PLA/carbon black (CB), and PLA/modified carbon black (MCB) composites were investigated using differential scanning calorimetry (DSC) analysis. The rate of crystallization and the spherulitic morphologies of the PLA and PLA/MCB composites during isothermal crystallization were investigated using DSC and observed by means of polarizing optical microscopy (POM), respectively. The results show that either CB or MCB acts as an efficient nucleating agent for PLA. The nucleation activities of CB and MCB were quantitatively determined. It is shown that MCB has higher nucleating activity than CB in PLA. An isoconversional method correlates the temperature dependence of the effective activation energy and was used to evaluate the effective activation energy of PLA and PLA/MCB composites. It is confirmed that MCB advances the nuclei density and promotes the crystallization rate of the PLA matrix significantly. In addition, an interesting phenomenon of the periodic cracks of PLA spherulites observed by using POM is reported. The unbalanced surface stresses arising from growth features and thermal shrinkage may be the two main factors accounting for the formation of target pattern cracks. POLYM. ENG. SCI., 50:1658–1666, 2010. © 2010 Society of Plastics Engineers     

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     

Crystallization kinetics of chain extended poly(lactic acid)/clay nanocomposites

The poly(lactic acid)/clay nanocomposites (PLACNs) were prepared by melt mixing method, then multiepoxide chain extender (CE) was added into PLACNs to induce the branched structure of poly(lactic acid) (PLA) chains. The nonisothermal cold crystallization and isothermal melting crystallization of PLA, PLACNs, and chain extended PLACNs (CEPLACNs) were characterized by DSC and studied by Avrami analysis. The results showed that the inducing of clay and CE affected the crystallization behavior of PLA in different way. Adding CE increased the overall crystallinity of PLA at cooling process, but clay had an opposite effect. Besides that, the addition of CE and clay increased the crystal nuclei number due to the heterogeneous nucleation mechanism. According to the crystallization kinetics study, the inducing of clay almost no effect on the crystal growth rate of PLA, but the branched structure had a pronounced effect for improving crystal growth rate of PLA. POLYM. COMPOS., 36:2123–2134, 2015. © 2014 Society of Plastics Engineer     

Isothermal Cold Crystallization and Melting Behaviors of Poly(lactic acid)/Epoxy Vinyl Polyhedral Oligomeric Silsesquioxanes Nanocomposites

Poly(l-lactic acid) (PLA)/epoxy vinyl polyhedral oligomeric silsesquioxane (EP-POSS) nanocomposites were prepared via melt blending. The isothermal cold crystallization and melting behavors of pure PLA and its nanocomposites were investigated using differential scanning calorimetry (DSC). The crystal growth model of PLA was a mixture of two-dimensional discotic growth and three-dimensional spherulite growth, as evidenced by the values of the Avrami exponent ranging from 2.15 to 2.66. The crystallization rate displayed a great dependence on the EP-POSS loading level and crystallization temperature, and a transition from regime II to regime III was observed around 115°C. The values of fold surface free energy were calculated from the nucleation parameter which was determined by the Hoffman-Lauritzen equation. Polarizing microscope images (POM) indicated that EP-POSS promoted the nucleation of PLA.     

Effect of sepiolite on the crystallization behavior of biodegradable poly(lactic acid) as an efficient nucleating agent

To enhance the crystallization kinetics of poly(lactic acid) (PLA), fibrous sepiolite was explored for nucleating the crystallization of PLA. PLA/sepiolite nanocomposites were prepared via the melt‐extrusion method. The effect of sepiolite on the crystallization behavior, spherulite growth and crystal structure of PLA were investigated by means of differential scanning calorimetry (DSC), polarized optical microscope (POM), wide angle X‐ray diffraction (WAXD), Fourier transform infrared (FTIR), and scanning election microscope (SEM). On the basis of DSC and POM results, the overall crystallization kinetics of PLA/sepiolite nanocomposites were significantly enhanced leading to higher crystallinity and nucleation density, faster spherulite growth rate (G) and lower crystallization half‐time (t_1/2) compared with the neat PLA. Under non‐isothermal conditions, the PLA blend comprising 1.0 wt% of sepiolite still revealed two crystallization peaks upon cooling at a rate of 35°C/min. Above phenomena strongly suggested that sepiolite was an effective nucleating agent for PLA. FTIR and WAXD analyses confirmed that the crystal structure of PLA matrix was the most common α‐form. SEM micrographics illustrated the fine three‐dimensional spherulite structures with the lath‐shape lamellae regularly arranged in radial directions. POLYM. ENG. SCI., 55:1104–1112, 2015. © 2014 Society of Plastics Engineers     

不同PEG含量对PLA/PEG共混物结晶动力学的影响

采用溶液共混法制备了一系列不同配比的聚乳酸(PLA)/聚乙二醇(PEG)共混物。通过偏光显微镜(POM)、扫描电镜(SEM)和差式扫描量热仪(DSC)研究了不同PEG含量的PLA/PEG共混物在不同结晶温度下,聚乳酸的晶体形貌、球晶生长速率及热力学性能。研究发现,PEG能够显著提高聚乳酸球晶的生长速率。当PEG含量为60%时,PLA/PEG共混物中聚乳酸球晶的生长速率最快,达到23.6μm/min,比纯聚乳酸的最快球晶生长速率(0.5μm/min)高47倍。但是,当PEG含量高于60%时,聚乳酸球晶的生长速率有所降低。同时,PLA/PEG共混物中聚乳酸球晶速率随结晶温度变化的取向,均向低温移动。另外,PLA/PEG共混物中聚乳酸球晶呈现环状花纹。DSC测试结果表明,随着PEG含量的增加,PLA/PEG共混物的玻璃化转变温度明显降低。     

Isothermal crystallization kinetics and spherulite morphologies of poly(lactic acid)/ethylene acrylate copolymer blends

Isothermal crystallization kinetics and spherulite morphologies of partially immiscible blends of poly(lactic acid) (PLA) and ethylene acrylate copolymer (EAC) were investigated by differential scanning calorimetry (DSC) and polarized optical microscopy. The DSC data obtained was analyzed using the Avrami equation. Crystallization kinetics of PLA from the melt was strongly influenced by the blend composition and the crystallization temperature. At a given crystallization temperature, the overall crystallization rate value was greater in the blends than in PLA suggesting that the presence of EAC enhanced crystallization of PLA. Polarized optical micrographs showed that the crystallization of PLA initially took place at the PLA/EAC interface. At high EAC content (>1 wt %), EAC domains acted as hindrance to crystallization reducing the overall crystallization rate of PLA in the blends. Based on the DSC analysis, the crystallization rate was maximum when PLA blend with 1 wt % EAC was isothermally crystallized at 103 °C. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45487.     

Crystallization of itaconic anhydride grafted poly(lactic acid) during annealing

The effect of annealing poly(lactic acid) (PLA) and PLA grafted with itaconic anhydride (IA) at different temperatures was studied using differential scanning calorimetry (DSC) and wide angle X‐ray scattering (WAXS). For PLA, two crystal forms were obtained when annealed between 110 and 120 °C, transforming into only the α‐form at 130 °C while a mixture of α′ and α‐form were obtained in grafted PLA. Grafting increased the percentage crystallinity of PLA, but it was mostly unaffected by the degree of grafting. The rate of crystallization was strongly dependent on the degree of grafting; when annealed at 100 °C, the crystallinity increased from 27.7 to 43.1% while the crystallization halftime reduced from 10.7 to 4.4 min at the lowest degree of grafting. It was thought that the increase in crystallization rate was likely due heterogeneous nucleation in the presence of grafted chains. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44614.     

聚乳酸/环氧化聚丁二烯抗冲树脂结晶性能的研究

采用差示扫描量热仪(DSC)对聚乳酸/环氧化聚丁二烯抗冲聚乳酸树脂(PLA/PB(EPB))的结晶性能进行了考察,并与纯聚乳酸(PLA)的结晶行为进行了对比,研究了环氧化聚丁二烯(EPB)对PLA等温/非等温条件下结晶行为的影响规律。结果表明:聚丁二烯橡胶(PB)对PLA的结晶行为影响较小,而EPB对PLA的晶体完善程度影响较为明显。PLA和PLA/PB更倾向于在低温条件下结晶,而PLA/EPB20.9%和PLA/EPB46.5%更倾向于在高温条件下结晶。抗冲聚乳酸树脂的结晶速率高于纯PLA,并且随着EPB环氧化度的增大,抗冲聚乳酸树脂的结晶速率呈逐渐增大的趋势。     

Crystallization behavior and morphology of poly(lactic acid) with a novel nucleating agent

To improve the crystallization ability of poly(lactic acid) (PLA), a novel nucleating agent with a benzoyl hydrazine compound was used in this study. The crystallization behaviors of PLA/talc and PLA/bibenzoylhydrazinepropane (BBP) with or without poly(ethylene glycol) (PEG) were investigated with differential scanning calorimetry (DSC) and polarized optical microscopy. The DSC curves showed that the crystallization temperature and crystallinity of PLA/BBP (PBBP) was higher than that of PLA/talc. With the addition of PEG, a synergistic effect was found. According to the results of nonisothermal crystallization kinetics, the values of F(T) of PBBP_0.5PEG₅ were usually smaller than those of PTa₃PEG₅, so the nucleation efficiency of BBP was much better than that of talc. From a polarized optical microscopy photo, it was easy to determine that the nucleation density of BBP was higher than that of PTa₃PEG₅, and the spherulitic diameter increased linearly with the crystallization time no matter the impingements. The spherulitic growth rate of PBBP_0.5PEG₅ was faster than that of PTa₃PEG₅, and the induction time of PBBP_0.5PEG₅ was the shortest among all of the samples. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41367.     

Polylactide/nano‐ and micro‐scale silica composite films. II. Melting behavior and cold crystallization

Nonisothermal crystallization of polylactide (PLA)/silica composites prepared by (i) directly blending the PLA with nanoscale colloidal silica sol and by (ii) a sol–gel process are studied by differential scanning calorimeter (DSC) at various heating rates. Samples quenched from the molten state exhibited two melting endotherms (T_ml and T_mh) due to melt‐recrystallization during the DSC scans. Lower heating rate and the presence of silica particles generate a lower peak intensity ratio of T_ml /T_mh. The nonisothermal crystallization kinetics is analyzed by modified Avrami model, Ozawa model, and Liu‐Mo models. The modified Avrami and Liu‐Mo models successfully described the nonisothermal cold crystallization processes, but Ozawa is inapplicable. The nucleation constant (K_g) is calculated by modified Lauritzen‐Hoffman equation and the activation energy by Augis‐Bennett, Kissinger, and Takhor models. These calculated parameters indicate consistently that the nanoscale silica particles seem to form more heterogeneous nucleation to increase crystallization, but microscale one form hindrance to retard crystallization. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

癸二酸二苯甲酰肼对PLA等温结晶行为及拉伸性影响

采用熔融共混法制备聚乳酸/癸二酸二苯甲酰肼(PLA/SBH)共混物。通过差示扫描量热(DSC)分析研究成核剂SBH添加量以及等温温度对PLA熔体等温结晶行为的影响。由结晶动力学分析可知,随着SBH添加量增大,PLA半结晶时间大幅缩短,结晶速率显著加快。加入SBH后,Avrami指数在2.51~3.14之间,PLA熔体结晶以异相成核为主,晶体生长为三维生长。对于PLA急冷模压样条,结晶度仅为2.9%。而加入1.0份SBH后,PLA熔体在134℃下经过3 min等温结晶处理后,所得PLA/SBH(100/1.0)模压样条结晶度达到42.0%。相对于急冷PLA样条,经过热处理的PLA/SBH(100/1.0)样条的维卡软化点由64.3℃大幅提升至160.6℃,而拉伸强度也有所增大。     

Influence of pearlescent pigments on mechanical properties and crystallization behavior of polylactic acid

Polylactic acid (PLA)/pearlescent pigments (PEPs) composites were fabricated by melt blending method and their properties were studied using a rotational rheometry, field emission scanning electron microscopy (FESEM), differential scanning calorimetry (DSC) and X-ray diffractometry (XRD). Because PEP could disperse uniformly in PLA matrix and would form PEP networks, there were improvements made in the flexural strength, tensile strength and impact strength of PLA composites. Interestingly, the viscosity of PLA composites reduced significantly as compared with neat PLA, indicating an improvement in processing properties. The rheological tests confirmed that the storage modulus of PLA composites decreased as PEP content increased at a given frequency. Also, there was a plateau at low frequency range, which was a sign of PEP networks formation. The DMA tests showed that the storage modulus of PLA composite increased with PEP content, suggesting the enhancement of rigidity. According to the XRD results, no change was observed in the crystal structure of PLA in the presence of PEP. The addition of PEP did not change melting temperature, but the glass transition temperature increased a little, and the cold crystallization temperature of PLA decreased largely. The DSC results also showed that nucleation ability of PLA was enhanced by addition of PEP at low cooling rates, but the whole crystallization process of PLA in composite was inhibited at higher cooling rates. This conclusion was also confirmed by the results of crystallization kinetics.     

PLA/PEO共混物的结晶行为研究

共沉积技术制备了聚乳酸(PLA)/聚氧化乙烯(PEO)共混物,通过DMA和相差显微镜考察了共混物的相行为。用DSC研究了PLA/PEO共混物的结晶形貌及其动力学,由于部分相容的熔融态PEO提高了PLA分子链的运动能力,导致显著促进了PLA的结晶速率;结合偏光显微镜(POM)观察分析,结晶速率的提高源于结晶生长速率的促进,而且在低的结晶温度时的结晶速率的增加更为明显。