聚丙烯/纳米碳酸钙原位聚合复合材料非等温结晶动力学研究

用原位聚合复合法制备PP/纳米CaCO3复合材料,用DSC法研究了不同纳米粒子含量的等速结晶性能和非等温结晶行为。对所得数据分别用修正Avrami方程的Ozawa法和Mo法进行处理,表明Mo法处理PP/CaCO3纳米复合材料非等温结晶过程比较理想。Mo法所得的参数F(T)随结晶度的增加而增大,a随结晶度的增加而增大,但幅度不大。表明降温速率越快,单位结晶时间达到的结晶度越高,各降温速率下的结晶方式基本不变。等速结晶研究表明,纳米碳酸钙的加入起到了结晶成核剂作用。用Kissinger方法计算出PP/纳米CaCO3原位复合材料的活化能为202 4kJ/mol。     

纳米CaCO3及偶联剂对小本体PP结晶的影响

采用熔融共混法制备了小本体聚丙烯/纳米CaCO3复合材料(SBPP/纳米CaCO3),研究了经铝钛复合偶联剂处理前后的纳米CaCO3粒子对SBPP结晶性能的影响.结果表明纳米粒子能够诱导β晶的形成,提高SBPP的结晶度,降低SBPP球晶尺寸,使得球晶均匀程度增加,并且纳米CaCO3经偶联剂处理后以上几种效果更为显著;纳米CaCO3可以提高材料的结晶温度和结晶速率,但经偶联剂处理的纳米粒子的结晶速率却小于未经偶联剂处理的材料的结晶速率,说明偶联剂的加入在一定程度上抑制了纳米CaCO3对SBPP/纳米CaCO3复合材料的结晶过程.     

PLA协同纳米CaCO3增韧PP的研究

通过熔融共混制得聚丙烯/聚乳酸/纳米碳酸钙（PP/PLA/CaCO3）复合材料,考察了PLA和纳米CaCO3对复合材料力学性能、热性能、流变性能与结晶形态的影响及其作用机理。结果表明,复合材料中形成连续空间网络结构的PLA有助于改善PP的性能,PLA含量为20 %（质量分数,下同）时复合材料综合力学性能最佳;与纯PP相比,加入PLA后的复合材料拉伸强度和冲击强度分别提高5.1 %和54.4 %,断裂伸长率降低62.5 %;纳米CaCO3通过“滚珠增韧”和“异相成核”作用明显改善复合材料力学性能,纳米CaCO3含量15 %时产生的晶粒细化作用效果最为显著,复合材料综合力学性能达到最佳,拉伸强度、断裂伸长率和冲击强度分别比未添加CaCO3时提升了15.2 %、2.7 %和5.6 %。     

PP／POE／纳米CaCO3复合材料的制备与性能研究

采用逐级分散共混法，制备了PP/POE／纳米CaCO3复合材料，研究了其力学性能和微观结构。逐级分散法先制备纳米CaCO3母料，然后将PP分多次加入含纳米CaCO3的共混体系中，目的在于改善纳米CaCO3的分散，以提高复合材料的力学性能。研究结果表明：采用逐级分散法制备的PP/POE／纳米CaCO3复合材料的冲击强度为64．2kJ／m^2，比直接共混法高16．9％，比通常的母料法高9．7％。复合材料的微观结构研究表明：纳米CaCO3粒子基本上都分布在连续相PP中。     

HDPE/CaCO3纳米复合材料的制备及性能

通过熔融共混法制备HDPE/纳米CaCO3复合材料,并通过TEM观察复合材料的微观结构.结果表明:纳米CaCO3基本以纳米级均匀分散在HDPE基体中,HDPE/纳米CaCO3复合材料的熔体指数比纯HDPE有所下降,并且当纳米CaCO3含量为5份时,复合材料的冲击强度提高约26.2%;而纳米CaCO3含量为3份时,复合材料的拉伸强度提高约2%,同时热分解温度比纯HDPE提高了49.8℃;热失重残余量在纳米CaCO3含量为8份时提高到了6.98%.     

纳米CaCO3/EPO/PP复合材料性能与结构的研究

研究了纳米CaCO3／EPO／PP复合材料的力学性能、熔体流变性能及纳米CaCO3粒子在PP基体中的分散状况。结果表明：弹性体EPO对PP有很好的增韧效果，当EPO用量为4份时，PP从脆性断裂转变成韧性断裂；当EPO用量为10份时，PP复合材料的室温和低温缺口冲击强度均有大幅度的提高。在EPO／PP复合材料中加入纳米CaCO3不仅可以显著提高复合材料的室温和低温缺口冲击强度，而且可显著提高复合材料的弯曲弹性模量和MFR，改善复合材料的加工流动性能；纳米CaCO3粒子在PP中达到了纳米级分散。     

PP/PA6/SiO_2纳米复合材料的非等温结晶动力学

采用熔融插层法在双螺杆挤出机上制备聚丙烯(PP)/聚酰胺(PA) 6/二氧化硅(SiO_2)纳米复合材料。通过差示扫描量热仪对体系的非等温结晶动力学进行研究,并采用莫志深(Mo)法对PP复合材料的非等温结晶动力学数据进行分析。结果表明,加入PA6和SiO_2,对PP有异相成核的作用,能提高PP的结晶速率和结晶度;随着降温速率增加,PP/PA6/SiO_2复合材料的结晶度增大。运用Mo法研究纯PP和PP/PA6/SiO_2复合材料的非等温结晶动力学过程,效果理想。结果显示,随着结晶度的增大,PP及其复合材料在单位时间内需要更大的冷却速率才能达到特定的结晶度。并且在相同的结晶度条件下,PP/PA6/SiO_2复合材料的结晶速度比纯PP的结晶速度快。     

纳米ZnO/PP及ZnO/CaCO_3/PP复合材料的性能研究

纳米氧化锌(ZnO)与聚丙烯(PP)通过熔融共挤制得了ZnO/PP纳米复合材料.研究了ZnO/PP纳米复合材料的力学、流变学性能与纳米ZnO添加量之间的关系;同时制备了ZnO/CaCO3/PP三元纳米复合材料并对其进行了机械性能和制备成本分析.结果表明,ZnO/PP纳米复合材料的熔体质量流动速率较纯PP有较大程度的提高;纳米CaCO3的加入不但可以降低生产成本,而且可以显著改善体系的冲击韧性;材料的拉伸破坏属于韧性断裂过程.     

纳米CaCO_3含量对PP/SBS/CaCO_3复合材料力学性能的影响

通过双螺杆共混方法制备聚丙烯(PP)/苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)/Ca-CO3复合材料,并采用扫描电镜(SEM)、力学性能测试和偏光显微镜研究了纳米CaCO3用量对该复合体系微观结构、力学性能以及结晶形貌的影响。结果表明:纳米CaCO3粒子在PP中均匀地分散可细化晶粒并起到了增韧增强的效果。当加入纳米CaCO3的质量分数为2%时,其综合性能最好。     

PP/OBC/EPDM-g-MAH复合材料的制备及性能

以聚丙烯(PP)为基体材料,乙烯-辛烯嵌段共聚物(OBC)为增韧材料,三元乙丙橡胶接枝马来酸酐共聚物(EPDM-g-MAH)为相容剂,制备了PP/OBC/EPDM-g-MAH复合材料。用DSC、SEM、转矩流变仪分析了OBC及EPDM-g-MAH对PP结晶性能、断面相结构、流变性能的影响,测试了复合材料的力学性能。结果表明:加入15%OBC,PP/OBC复合材料的熔融温度升高了1.63℃,结晶度降低了5.4%,断裂伸长率及缺口冲击强度明显提高,弯曲强度和拉伸强度有所下降;含4%EPDM-g-MAH的PP/OBC/EPDM-g-MAH复合材料,OBC粒子均匀分散在PP基体中,粒径明显细化,熔融塑化扭矩值降低,结晶速率加快;与纯PP相比,断裂伸长率和缺口冲击强度分别提高了128.57%和107.96%,柔韧性有较大幅度提高。     

己二酸/无水硫酸钙晶须改性PP的等温结晶动力学

通过差示扫描量热(DSC)仪分析了己二酸(AA)和无水硫酸钙晶须(ACSW)复配改性聚丙烯(PP)的等温结晶行为,用偏光显微镜(PLM)观察了AA/ACSW复配改性PP的晶体形貌。DSC分析结果表明,随着结晶温度升高,半结晶时间和最大结晶时间增加,半结晶速率降低;与纯PP相比,ACSW和AA/ACSW复合改性都能使PP的结晶时间降低,结晶效率增加,说明ACSW和AA/ACSW对PP具有异相成核作用,并且AA/ACSW复合改性PP对提高PP的结晶性能有更好的效果,此外ACSW改性PP的等温结晶活化能最低。对改性PP的PLM的观察说明ACSW对PP具有异相成核作用,而AA/ACSW对PP的β晶成核具有协同促进作用。     

Effect of zeolite 5A on the crystalline behavior of polypropylene (PP) in PP/β‐nucleating agent system

The effect of zeolite 5A on the crystalline behavior of polypropylene (PP) in PP/β‐nucleating agent system was investigated with X‐ray diffractometer (XRD), differential scanning calorimeter (DSC), and polarized light microscope (PLM) in this study. Zeolite 5A has less effect on crystalline phase of PP/β‐nucleating agent than does n‐CaCO₃, which is ascribed to the stronger surficial polarity and better dispersibility of zeolite 5A. The data of DSC indicated that the crystallization peak temperature of PP increases by 8.3°C in the presence of zeolite 5A, and n‐CaCO₃ increases 5.7°C in PP/TMB‐5 system, relative to pure PP. And the initial crystallization temperature (T_c0) and the relative crystallinity (X_c) of PP is much more dramatically raised in the presence of zeolite 5A than CaCO₃. The efficiency of zeolite 5A in reducing the spherulites size of PP was seen clearly from the PLM photographs. The mechanical testing results showed that the flexural strength and impact strength of PP/β‐nucleating agent system increased in the presence of zeolite 5A. POLYM. COMPOS., 2008. © Society of Plastics Engineers     

Crystallization behavior and mechanical properties of polypropylene/halloysite composites

In this work, halloysite nanotubes (HNTs), a new type of inexpensive filler, were used for the modification of polypropylene (PP). HNTs were first surface treated by methyl, tallow, bis-2-hydroxyethyl, quaternary ammonium, then melt mixed with PP. Scanning electron microscope (SEM) was used to examine the dispersion of HNTs in PP matrix. Differential scanning calorimetry (DSC), polarized light microscope (PLM), dynamic melt rheometry and wide angle X-ray diffraction (WAXD) were employed to investigate the crystallization behavior of the prepared PP/HNT composites. The mechanical properties were evaluated by Instron and impact tests. SEM results revealed that HNTs could be well-dispersed in PP matrix and had a good interfacial interaction with PP, even up to a high content of 10 wt%. DSC data indicated that HNTs could serve as a nucleation agent, resulting in an enhancement of the overall crystallization rate and the non-isothermal crystallization temperature of PP. PLM showed a constant spherulite growth rate and a decreased spherulite size at given isothermal crystallization temperature, suggesting that nucleation and growth of a spherulite are two independent processes. The result obtained by dynamic melt rheometry indicated that HNTs mainly promoted nucleation and had not much influence on the growth of PP crystallization. Nevertheless, by fast cooling the samples, almost constant spherulite size can be obtained for both pure PP and PP/HNT composites due to the limited nucleation effect of HNTs on PP crystallization. WAXD showed that HNTs mainly facilitated α-crystal form of PP. Though a good dispersion of HNTs in PP matrix was observed, out of our expectation, not much enhancement on mechanical properties of PP/HNT composites had been achieved, and this could be mainly ascribed to the constant crystallinity and spherulite size of PP as well as the small length/diameter ratio of HNTs.     

Crystallization characteristics of polypropylene and low ethylene content polypropylene copolymer with and without nucleating agents

In this paper, the crystallization characteristics of polypropylene and low ethylene content polypropylene copolymers with and without nucleating agents were studied by differential scanning calorimetry (DSC) and polarized light microscopy (PLM). In order to determine the nonisothermal crystallization rate of these materials, a new estimation method was introduced. Comparing with the crystallization rate coefficient (CRC), which was proposed by Khanna, we found the new approach is more reasonable. From the analysis of results of DSC and PLM, it can be concluded that nucleating agent is more efficient than it is in PP homopolymer. © 1994 John Wiley & Sons, Inc.     

Fractionated crystallization of dispersed PA6 phase of PP/PP‐g‐MAH/PA6 blends

Fractionated crystallization behavior of dispersed PA6 phase in PP/PA6 blends compatibilized with PP‐g‐MAH was investigated by scanning electron microscopy (SEM), differential scanning calorimeter (DSC), polarized light microscopy (PLM), and wide‐angle X‐ray diffraction (WAXD) in this work. The lack of usual active heterogeneities in the dispersed droplet was the key factor for the fractionated crystallization of PA6. The crystals formed with less efficient nuclei might contain more defects in the crystal structures than those crystallized with the usual active nuclei. The lower the crystallization temperature, the lesser the perfection of the crystals and the lower crystallinity would be. The fractionated crystallization of PP droplets encapsulated by PA6 domains was also observed. The effect of existing PP‐g‐MAH‐g‐PA6 copolymer located at the interface on the fractionated crystallization could not be detected in this work. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3742–3755, 2004     

Study on the crystallization kinetics of PP/GF composites

The crystallization kinetics and morphology of glass fiber-reinforced polypropylene (PP/GF) were investigated in this work. Both isothermal and nonisothermal crystallization behaviors of 90PP/10GF, 80PP/20GF, and 70PP/30GF were examined with a DSC instrument. It was found that the addition of glass fiber would increase the crystallization rate of PP and increase the content of β spherulite, which was most likely formed at temperatures between 390 and 400 K. The morphology of spherulites of PP/GF composites were examined with SEM and a polarized microscope. All experimental observations conformed rather well with the theoretical approach, a dynamic crystallization model, proposed in our previous work. The size of α spherulites of PP would decrease at lower crystallization temperature, or at higher cooling rate, or by adding glass fiber in it.     

Crystallization behavior of polypropylene in polypropylene/nylon 6 blend

This article describes the crystallization behavior of polypropylene (PP) in the presence of a crystallizable polymer, namely, nylon 6, in the binary blend of PP/nylon 6 in the composition range from 0 to 30 wt % of nylon 6 content in the blend. The crystallization behavior was studied through variation of the crystallinity with the blend composition and changes in the crystallization exotherms were recorded by differential scanning calorimetry (DSC) and the spherulite morphology was observed via polarized light microscopy (PLM). Comparison of the crystallization exotherms and melting endotherms revealed some differences which are attributed to the role of a sufficiently high thermal energy of the nylon 6 crystals on the melting of PP. The crystallinity of PP decreased in the presence of nylon 6, whereas the crystallinity of nylon 6 increased considerably in the presence of PP. The rate of nucleation of PP on addition of nylon 6 decreased rapidly in the region 0–10 wt % nylon 6 content, and, thereafter, at a higher nylon 6 content, decrease of the nucleation rate was relatively slow. PLM observation revealed the presence of composite spherulites with PP spherulites grown on the surface of the already‐formed nylon 6 spherulites. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1153–1161, 1999     

Effects of spatial confinement and selective distribution of CB particles on the crystallization behavior of polypropylene

The effects of selective distribution of carbon black (CB) particles and spatial confinement on the crystallization behavior of isotactic polypropylene (iPP)/Polystyrene (PS)/CB composite were studied. The crystallization behaviors and the morphologies of the composite were studied by differential scanning calorimetry (DSC), polarized light microscope (PLM), and scanning electron microscopy (SEM). The results indicated the typical cocontinuous structure appeared in PP/PS/CB (55/45/1) composite, and CB particles are distributed in PS phase, which follows the theory of interfacial tension. Compared with PP/CB composite, the nucleation effect of CB particles on the crystallization process of PP in PP/PS/CB was greatly weakened by selective distribution. Moreover, the morphologies of cocontinuous structure, which means that the crystallization process of PP had to take place in the micron‐scale spatial confinement formed by continuous PS phase, greatly influenced the crystallization behavior of PP in PP/PS/CB composite. The spherulite radial growth rate of PP in spatial confinement was lower than that of neat PP during isothermal crystallization processes, and the results of the total crystallization activation energy (ΔE) and the nucleation parameter (K_t) implied that in comparison to neat PP, the activation energy of PP chain segments arranged into crystal was higher in composite with cocontinuous structure. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

α-成核剂对聚丙烯结晶性能和形态的影响

用差示扫描量热仪（DSC）、广角X射线衍射（WAXD）研究了不同含量的α-成核剂对聚丙烯的结晶行为和结晶形态的影响，用偏光显微镜观察了结晶尺寸大小的变化，测试了聚丙烯的力学性能，同时对聚丙烯的透光性也进行了表征。结果表明，添加少量α-成核剂提高了聚丙烯的结晶温度和结晶度。且随α-成核剂的添加，聚丙烯的球晶尺寸明显缩小，聚丙烯的拉伸强度也相应增强。当α-成核剂的质量分数为0．3%时，拉伸强度最大，薄片的透光性显著改善。     

复合成核剂对PP/POE共混体系等温结晶行为的影响

以低分子量尼龙6为主体制备了一种新型复合成核剂NF-10,采用差示扫描量热分析仪、偏光显微镜等分析手段研究了该成核剂对聚丙烯/乙烯-辛烯共聚物(PP/POE)共混体系结晶温度、结晶形态、等温结晶及其动力学的影响。结果表明:NF-10可以提高PP/POE体系的结晶温度、结晶度和结晶速率,减小体系结晶球晶的尺寸,提高晶核密度,显著改善PP/POE共混体系结晶性能。