纳米CaCO3包覆长石填充改性PP的性能及结构表征

通过纳米碳酸钙(nano-CaCO3)对长石表面进行了包覆改性,再采用偶联剂KH570进行表面处理,通过熔融共混法制备了聚丙烯(PP)/nano-CaCO3包覆长石复合材料。通过扫描电子显微镜对nano-CaCO3包覆长石的形貌进行了表征,并使用万能材料试验机、扫描电镜、差示扫描量热仪、热重分析仪、X射线衍射仪对复合材料的力学性能、热稳定性能及微观结构进行了研究。结果表明,nano-CaCO3包覆长石含量在1%时,复合材料的拉伸强度和断裂伸长率均达到最大值,其热稳定性与PP基体相比有所提高。nano-CaCO3包覆长石的添加使复合材料由脆性断裂向韧性断裂转变;而且,它会诱导PP-β晶的生长,其在PP中具有异相成核效应,可以提高复合材料的结晶度。     

PP/Nano-CaCO_3复合材料性能的研究

采用熔融共混法制备出了聚丙烯(PP)/纳米碳酸钙(nano-CaCO3)复合材料,研究了nano-CaCO3的加入量对复合材料力学性能的影响,利用扫描电镜(SEM)分析了nano-CaCO3在PP基体中的分散性。结果表明:随着nano-CaCO3用量的增加,PP/nano-CaCO3复合材料的冲击强度和拉伸强度均呈现出先增加后降低的趋势,而弯曲模量呈增加趋势;随着填加量的增加,nano-CaCO3在PP基体中的分散性逐渐变差。     

稀土β晶成核剂改性nano-CaCO_3/PP复合材料的结晶行为

讨论了稀土β晶成核剂(WBGⅡ)对nano-CaCO3/PP复合材料结晶性能的影响,并借助WAXD、DSC及PLM对PP、nano-CaCO3/PP和WBGⅡ/nano-CaCO3/PP复合材料的结晶行为及晶体形态进行了表征。结果表明:加入少量WBGⅡ后,聚丙烯基复合材料的晶型和球晶形态发生明显变化,提高了材料的起始结晶温度和结晶温度,降低了材料的过冷度,半结晶期延长。     

纳米ZnO对等规聚丙烯结晶的异相成核作用

采用熔融共混法制备了nano-ZnO/等规聚丙烯(iPP)复合材料,研究了振荡剪切条件下nano-ZnO对iPP结晶的异相成核作用,并与其静态结晶行为作对比。结果表明:静态结晶下,当nano-ZnO质量分数大于5%时,nano-ZnO对iPP结晶有明显的异相成核作用,使iPP结晶温度大幅度提高,相容剂PP接枝马来酸酐(PP-g-MAH)的加入增强了nano-ZnO粒子与iPP基体的界面相互作用,改善了纳米粒子的分散性,促进了iPP基体的异相成核。振荡剪切作用下,降低结晶温度和加入nano-ZnO均能促进iPP成核,当nano-ZnO质量分数大于3%后,异相成核达到饱和,振荡剪切对nano-ZnO/iPP复合材料存在显著的诱导结晶作用;加入PP-g-MAH后,nano-ZnO分散性的改善及其与iPP基体界面相互作用的加强使得nano-ZnO/iPP复合材料的结晶诱导时间明显缩短。     

交联聚苯乙烯刚性粒子增韧聚丙烯研究

为了解交联聚苯乙烯(XPS)微粒增韧聚丙烯的机理,用双螺杆挤出机将乳液聚合法合成的XPS微粒与均聚丙烯(PP)共混复合,并研究了该复合材料的力学性能、断面形貌和结晶特性.电镜观测发现当XPS粒子的交联剂用量不少于6%(wt)时,它们能在PP热熔融加工时均匀地分散在基体材料中而不团聚.力学性能测试表明PP中加入适量的XPS粒子后,该复合材料的拉伸强度基本保持不变,而冲击强度有较大的提高,经SBS弹性体包覆的XPS粒子与PP复合后得到的改性聚丙烯的冲击强度可达纯聚丙烯的3倍.通过X衍射技术和电镜分析表明韧性增加的主要机理是XPS粒子诱导PP的β结晶成核作用和XPS粒子与基材界面间较大的作用力引起的.当XPS粒子经SBS弹性体包覆后,其诱导β结晶作用明显消失,此时PP的增韧可认为是复合材料受到冲击时,XPS粒子通过相容性优良的界面橡胶层产生大形变和空穴化作用耗散能量的结果.     

表面改性对PP/Nano-CaCO_3复合材料性能的影响

采用熔融共混法制备了聚丙烯(PP)/纳米碳酸钙(nano-CaCO3)复合材料,研究了nano-CaCO3表面改性前后对复合材料力学性能的影响,利用扫描电镜(SEM)分析了nano-CaCO3表面改性前后在PP基体中的分散性。结果表明:加入量较小时,nano-CaCO3表面改性与否对复合材料的力学性能和在PP基体中的分散性基本没有影响;加入量较大时,表面改性nano-CaCO3使复合材料具有更好的力学性能,并且在PP基体中的分散性及其与PP基体间的界面黏结性也更好。     

表面改性高岭土的制备及其在PP中的应用

采用硅烷偶联剂KH550、异佛尔酮二异氰酸酯(IPDI)、十八胺(ODA)对高岭土表面进行三步干法改性,制备出有机高岭土(Kaolin-O),然后将其与聚丙烯(PP)进行熔融共混制备出PP/Kaolin-O复合材料。用FTIR对改性高岭土进行结构表征,并用TEM、SEM、XRD和DSC对复合材料的微观形貌和结晶行为进行研究,通过拉力测试研究了复合材料的力学性能。结果表明:有机物成功接枝到高岭土表面,当Kaolin-O用量低于5phr时,Kaolin-O片层均匀分散在PP基体中;Kaolin-O的加入,促进了聚丙烯β结晶成核,复合材料的结晶度均比纯PP低;Kaolin-O用量为3 phr时,复合材料的拉伸强度、断裂伸长率比PP分别提高了37%、18%。     

β晶型PP/纳米CaCO3/短切PET纤维复合材料的制备

通过熔融挤出共混制备β晶型聚丙烯(PP)/纳米CaCO3/对苯二甲酸乙二酯(PET)纤维复合材料,并用马来酸酐(MAH)接枝PP(PP-g-MAH)改善材料的相容性。研究了PET纤维、β成核剂和相容剂对材料力学性能、相容性和结晶熔融行为的影响。结果表明:CaCO3和PET纤维对PP的结晶具有异相成核作用,能协同诱导形成β晶型PP。加入PET纤维可提高材料的刚性和韧性,但会损坏拉伸性能。PP-g-MAH能改善PP和PET纤维之间的相容性,并能促进成核剂在材料中的分散,形成更多的β晶。     

双螺杆挤出机螺杆组合对聚丙烯/纳米CaCO3复合材料在线流变性能的影响

采用啮合型同向旋转双螺杆挤出机制备聚丙烯(PP)/纳米碳酸钙(nano-CaCO3)复合材料,制备过程中在双螺杆挤出机末端连接Haake在线流变仪进行在线流变性能测试。研究了两种螺杆组合结构、纳米CaCO3含量对PP/纳米CaCO3复合材料在线剪切黏度的影响,比较了在不同聚合物加工流场下PP/纳米CaCO3复合材料的在线流变性能。结果表明,引入分布混炼有利于降低复合材料的剪切黏度,复合材料剪切黏度随纳米粒子的加入先呈下降趋势,当达到某一含量后,再提高纳米粒子含量会使黏度提高。     

两步法制备剥离型聚丙烯/蒙脱土纳米复合材料(Ⅱ)熔融行为及流变性能

采用DSC及XRD研究了聚丙烯/蒙脱土纳米复合材料(PMN)的结晶熔融行为.DSC的结果表明,复合材料熔点升高,但相对结晶度下降.XRD结果表明,蒙脱土作为成核剂促进了聚丙烯β晶型的生成;同时β晶型的增长抑制了α晶体的长大,减小了α晶粒尺寸,提高了复合材料的力学性能.系统研究了复合材料的流变性能,探讨了蒙脱土含量、温度、剪切速率等因素对复合材料黏度特性的影响,结果表明,复合体系总体上呈现剪切变稀的特性,体系表观剪切黏度随蒙脱土含量的升高逐渐下降,材料加工性能优于聚丙烯基体.     

Effect of TMB-5 on dispersion of MWCNTs in iPP and crystallization of β-nucleated iPP/MWCNTs composites

In this work, multiwall-carbon-nanotubes (MWCNTs), β nucleating agent(TMB-5) and isotactic polypropylene(iPP) were mixed to prepare MWCNTs/iPP composites, which were processed by a corotating twin screw extruder at 270 °C. MWCNTs at 0 wt%, 0.05 wt%, 0.3 wt%, 1 wt%, 2 wt% and 3 wt% were added into the composites respectively and the concentration of TMB-5 was 0.3 wt% consistently. Polarized light microscopy (POM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), differential scanning calorimetry (DSC) and Wide-angle X-ray diffraction (WAXD) were used to study the dispersion of MWCNTs in the β-Nucleated iPP and the crystallization of the composites. SEM and TEM graphs showed that MWCNTs dispersed individually in the iPP matrix when TMB-5 was added in the composites. In the contrast, there were many aggregates of MWCNTs in iPP matrix without TMB-5. DSC and WAXD results indicate that TMB-5 and individual MWCNTs have a synergistic effect on inducing the formation of β crystals. However, with the content of MWCNTs increasing in the composites, β crystal content decreased and α crystal content increased, which indicated that MWCNTs aggregating in the iPP matrix acted as α nucleating agent restricting the formation of β crystals and the effect of TMB-5 on dispersion became limited at a relatively high MWCNTs content.     

PTT／纳米CaCO3复合材料流变行为及结晶性能研究

以毛细管流变仪研究了聚对苯二甲酸丙二酯(PTT)/纳米CaCO3复合材料的流变行为,讨论了复合材料的组成、剪切应力和剪切速率及温度对熔体流变行为、熔体黏度的影响,测定了不同配比的复合材料熔体的非牛顿指数 n。结果表明,PTT/纳米CaCO3复合材料熔体为假塑性流体,表观黏度随着剪切速率增加而降低。纳米CaCO3的加入量较少(1％)时,熔体黏度较纯PTT迅速下降;随着纳米CaCO3含量增加(2％-20％),熔体黏度随之上升,但都小于纯PTT的;直到含量为30％时,熔体黏度才超过纯PTT的。差示扫描量热仪测定复合材料的结晶和熔融性能发现,复合材料的熔体结晶温度Tpc和熔融温度Tm较纯PTT、都有所升高,说明纳米CaCO3的加入对PTT的结晶起到了异相成核作用。     

PP/针形纳米CaCO3复合材料的力学性能

用硬脂酸皂化改性针形纳米CaCO3表面后,将其与聚丙烯(PP)共混、挤出和注塑,制成PP／CaCO3纳米复合材料。与纯PP相比,填充针形纳米CaCO3的体积分数为4.21％时,PP体系的冲击强度和断裂伸长率分别提高了49％,339％,拉伸强度下降2．7％。改性后的纳米CaCO3与PP之间的界面作用与改性前相比有所减弱,冲击断面扫描电子显微镜照片显示,针形纳米CaCO3均匀地分散在PP基体中。偏光显微照片显示,针形纳米CaCO3对PP有明显的异相成核作用。     

Isothermal crystallization behavior of isotactic polypropylene blended with small loading of polyhedral oligomeric silsesquioxane

The isothermal crystallization kinetics and morphology development of isotactic polypropylene (iPP) blended with small loading of nanostructure of polyhedral oligomeric silsesquioxane (POSS) were studied with differential scanning calorimetry (DSC), polarized optical microscopy (POM), and wide-angle X-ray diffraction (WAXD). The crystallization behaviors of iPP/POSS composites presented an unusual crystallization behavior during isothermal and nonisothermal crystallization conditions. The exothermic morphologies of isothermal and nonisothermal crystallization of iPP/POSS composites changed remarkably with increasing POSS. Moreover, the developments of spherulitic morphology for iPP/POSS composites showed that the major dispersed POSS molecules became nanocrystals first and then aggregated together forming thread- or network-like morphologies, respectively, depending on POSS content, which was observed. It implies that these major POSS nanocrystals' morphologies appeared as an effective nucleating agent and promoted the nucleation rate of iPP, whereas the minor dispersed POSS molecules that had slight miscibility between iPP retarded the nucleation and growth rates of iPP in the remaining bulk region. Therefore, the isothermal crystallization showed a single exothermic peak at pure iPP and POSS-1.0, whereas at POSS-2.0 and POSS-3.0, displayed the multi-exothermic peaks during isothermal crystallization. These faces indicated that POSS molecules were both influence on the transport of iPP chain in the melted state and on the free-energy of formation the critical nuclei of iPP assisted by the POSS structures were observed. Therefore, we postulated that the crystallization mechanisms of multi-exothermic peaks in isothermal crystallization may proceed to combine the “nucleating agent inducing nucleation of iPP event assisted by the POSS domains” that the nucleation of iPP does occur preferentially on the surfaces of the POSS “threads” or “networks” structures, and “nucleation and growth of iPP in the remaining bulk melted iPP region retarded by dispersed POSS molecules”. Therefore, effects of POSS content on the isothermal and nonisothermal crystallization behaviors of iPP/POSS composites due to the POSS molecules partially miscible with iPP, at very small loading of POSS molecules, promoted or retarded the rates of nucleation and growth of iPP depending on the POSS content and crystallization temperature were discussed.     

聚己内酯/酯化淀粉/纳米碳酸钙复合材料的制备及性能

以玉米淀粉(ST)和马来酸酐为原料,采用干法改性方法制备了酯化淀粉(EST),将EST与聚己内酯(PCL)、纳米碳酸钙通过密炼机混炼制备可降解PCL/EST/纳米碳酸钙复合材料。利用红外光谱仪、扫描电子显微镜、广角X射线衍射仪和热重-差示扫描量热同步热分析仪研究了PCL/EST/纳米碳酸钙复合材料的微观形态、力学性能、结晶以及热性能。结果表明,随着纳米碳酸钙含量的增加,PCL/EST/纳米碳酸钙复合材料的拉伸强度先升高后降低,当纳米碳酸钙含量为6份(质量份数,下同)时材料的拉伸强度和断裂伸长率达到最大值,与未添加纳米碳酸钙的复合材料相比分别提高了49.8%和34.8%;与PCL/ST/纳米碳酸钙复合材料相比,PCL/EST/纳米碳酸钙复合材料中淀粉颗粒尺寸减小,复合材料的熔点和结晶度有所提高,拉伸强度和熔体流动速率增加,热分解温度下降。     

纳米CaCO3对FEP非等温结晶动力学的影响

采用熔融共混法制备了聚全氟乙丙烯（FEP）/纳米碳酸钙（nano-CaCO3）复合材料,利用差示扫描量热法研究了FEP及其复合材料的非等温结晶行为,并通过Avrami方程修正的Jeziorny法、Ozawa法以及Mo法对其非等温结晶动力学进行了处理分析。结果表明,Jeziorny法及Mo法均适用于处理FEP和FEP/nano-CaCO3的非等温结晶过程,但Ozawa法不合适;在同一降温速率下,FEP/nano-CaCO3复合材料的初始结晶温度、最大结晶温度均比相应的纯FEP高,且半结晶时间延长,这说明nano-CaCO3对FEP具有一定的诱导和促进成核的作用,但由于FEP/nano-CaCO3复合材料的长链分子结构及大的空间位垒导致FEP的结晶总速率下降。     

纳米CaCO_3增强增韧PP/弹性体复合材料的研究

采用钛酸酯偶联剂对纳米CaCO_3进行了表面接枝改性,并采用熔融共混法制备了聚丙烯(PP)/乙烯–辛烯嵌段共聚物(OBC)/纳米CaCO_3复合材料,研究了纳米CaCO_3的加入量对复合材料的力学、热力学及流变性能的影响,并观察了复合材料的断面形貌。结果表明,当改性纳米CaCO_3含量为2.5%时,复合材料的力学性能最佳,其中拉伸强度达到27.5 MPa,冲击强度达到16.1 k J/m2,进一步增加纳米CaCO_3含量时,由于纳米粒子之间发生了严重团聚使复合材料力学性能显著下降;纳米CaCO_3的加入对复合材料起到了异相成核的作用,提高了复合材料的结晶温度和结晶度;复合材料中纳米粒子的存在使其复合黏度和储能模量同时升高。     

PP/纳米TiO2复合材料的晶体形貌和非等温结晶行为

用熔融共混法制备了聚丙烯（PP）/纳米TiO2复合材料,用透射电子显微镜、偏光显微镜、差示扫描量热仪和广角X射线衍射仪对其纳米粒子分散性、晶体形貌和非等温结晶行为进行了研究。结果表明,纳米TiO2以纳米级尺寸均匀分散于PP基体中;130 ℃冷却和室温冷却时,PP/纳米TiO2复合材料的晶粒比纯PP的细,并且随着纳米TiO2含量的增加,PP/纳米TiO2复合材料的晶粒尺寸先减小后增大,纳米TiO2含量为2 %（质量分数,下同）时晶粒最细;纳米TiO2对PP结晶具有加速作用;复合材料的结晶活化能高于纯PP的,并且纳米TiO2含量多且均匀时复合材料结晶活化能高;纳米TiO2含量较少时可诱导较多的β晶生成,当纳米TiO2含量为1 %时,复合材料中β晶含量达到25.2 %。     

聚甲醛/弹性体/纳米碳酸钙复合材料的制备及性能研究

采用双螺杆熔融共混的方法,以4种不同的混合顺序,制备了聚甲醛/热塑性聚氨酯弹性体/纳米碳酸钙（POM/TPU/nano-CaCO3）复合材料。通过力学性能测试、偏光显微镜、差示扫描量热仪、熔体流动速率仪和扫描电子显微镜,考察了nano-CaCO3的用量对POM/TPU(90/10)复合材料力学性能的影响,并探讨了共混方式对复合材料力学性能及微观结构形态的影响。结果表明,4 %的nano-CaCO3与TPU预先混合制成母粒再与POM共混得到的复合材料中POM晶粒发生明显细化,缺口冲击强度高达12.5 kJ/m2,冲击性能较为优异。     

Effect of the composition ratio of pimelic acid/calcium stearate bicomponent nucleator and crystallization temperature on the production of β crystal form in isotactic polypropylene

The influence of the composition ratio of pimelic acid/calcium stearate bicomponent nucleator on the β crystal form content of isotactic polypropylene (iPP) had been studied at the crystallization temperature of 120°C and duration of 30 min. It was found that the β crystal form content increased continuously with increasing amount of calcium stearate at the constant amount of 0.15% pimelic acid. High β crystal form content polypropylene could be produced when the amount of calcium stearate was greater than 0.30% (the mass composition ratio of pimelic acid/calcium stearate was less than 1/2, the mole ratio was less than 1.89/1). It was shown that pimelic acid and calcium stearate could react to produce a high effective β nucleator (calcium pimelate) “in situ” during the melt‐mixing of iPP and the bicomponent nucleator. The influence of crystallization temperatures (100–140°C) on the β crystal form content of iPP had also been studied at the constant composition ratio of 0.15% pimelic acid/0.5% calcium stearate (the calcium pimelate produced in situ was 0.16%, which was calculated from stoichiometry). It was found that the β crystal form content increased continuously with increasing crystallization temperature and it maximized at 130°C. β Crystal form content decreased sharply at the crystallization temperature of 140°C. It was shown that β → α modification transformed between 130 and 140°C. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008