赤泥/聚丙烯复合材料非等温结晶动力学研究

采用DSC研究了聚丙烯(PP)及聚丙烯/赤泥复合材料的非等温结晶动力学,对所得的数据采用了Avrami方程的Jeziorny法及Mo法进行处理.结果表明:赤泥的加入提高了PP的结晶温度和结晶速率,PP的结晶活化能降低,赤泥成核活性高于改性的赤泥.在同样含量下,经钛酸酯偶联剂改性的赤泥使PP结晶温度增加,结晶活化能与赤泥/聚丙烯复合材料相比有小幅的增加.赤泥具有异相成核作用,经表面修饰的赤泥异相成核效果降低.     

聚丙烯/高岭土复合材料的结构与性能

以钛酸酯偶联剂(NDZ-105)改性的高岭土为填料、马来酸酐接枝的聚丙烯(PP-g-MAH)为相容剂,与聚丙烯(PP)熔融共混制备复合材料,测定了复合材料的力学性能,并通过X射线衍射(XRD)、红外光谱(Fr-IR)、热失重分析(TG)、扫描电镜(SEM)等手段研究其结构.结果表明,NDZ-105分子包覆到高岭土颗粒表面,有效改善了高岭土与PP基体的相容性;改性高岭土在PP基体中起到异相成核作用,并诱导PP基体产生β晶型;与纯PP及PP/未改性高岭土复合材料相比,PP/改性高岭土复合材料的拉伸强度、冲击强度、屈服强度、弹性模量、维卡软化温度及外推起始失重温度均明显提高,分别增加了7.6％、31％、21％、89.3％、8.4℃及97℃.     

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。     

超声改性无水硫酸钙晶须对聚丙烯等温结晶行为的影响

用超声法对无水硫酸钙晶须(ACSW)进行改性,并利用差示扫描量热法(DSC)研究了聚丙烯(PP)、PP/ACSW和PP/超声改性无水硫酸钙晶须(UACSW)复合材料的等温结晶行为;用Avrami方程全面分析了复合材料的等温结晶过程,并计算出其结晶动力学参数。结果表明:超声改性后的PP/UACSW复合材料的结晶时间缩短,结晶速率显著提高,证明UACSW能促进PP材料的结晶,并在PP结晶过程中起到异相成核作用。     

滑石粉、碳酸钙填充聚丙烯复合材料等温结晶行为的对比研究

用熔融共混法分别制备了聚丙烯（PP）/滑石粉、PP/碳酸钙(CaCO3)复合材料,用差示扫描量热法(DSC)考察了PP及其复合材料的等温结晶过程,并用Avrami方程对纯PP及PP/滑石粉、PP/CaCO3复合材料的等温结晶动力学行为进行了分析。结果表明,PP、PP/滑石粉及PP/CaCO3复合材料的Avrami指数均小于2.3,存在均相成核和异相成核双重成核机理,且其结晶速率常数和结晶速率均随着结晶温度的升高而减小;在该体系中,滑石粉对基体PP有明显的异相成核作用,使PP的结晶速率加快、结晶时间缩短;而CaCO3则没有明显的异相成核作用。     

滑石粉、碳酸钙填充聚丙烯复合材料等温结晶行为的研究

用熔融共混法分别制备了聚丙烯(PP)/滑石粉、PP/碳酸钙(CaCO3)复合材料,用差示扫描量热法考察了PP及其复合材料的等温结晶过程,并用Avrami方程对纯PP及PP/滑石粉、PP/CaCO3复合材料的等温结晶动力学行为进行了分析。结果表明,PP、PP/滑石粉及PP/CaCO3复合材料的Avrami指数均小于2.3,存在均相成核和异相成核双重成核机理,且其结晶速率常数和结晶速率均随着结晶温度的升高而减小;在该体系中,滑石粉对基体PP有明显的异相成核作用,使PP的结晶速率加快、结晶时间缩短;而CaCO3则没有明显的异相成核作用。     

聚丙烯/凹凸棒土复合材料的结晶行为

通过双螺杆挤出机熔融共混制备了聚丙烯(PP)/凹凸棒土(ATP)复合材料样品,分别采用偏光显微镜和差示扫描量热仪对其结晶行为进行了研究。研究表明,复合材料样品的偏光显微镜照片呈现球晶所特有的十字消光现象,球晶尺寸与纯PP球晶的尺寸相比有所减小。非等温结晶测试结果表明,复合材料样品的结晶温度随着ATP含量的增加向高温方向移动,而且半结晶期缩短,PP/ATP复合材料的总体结晶速率增加;ATP的加入改变了PP成核的机制,起到了异相成核的作用。随着降温速率的增大,PP及PP/ATP(95/5)复合材料的结晶起始温度和结晶峰值温度均向低温方向移动,半结晶期变短。     

β晶型聚丙烯专用料的研究

采用β成核剂改性聚丙烯(PP),通过偏光显微镜(POM)、示差扫描量热仪(DSC)、X射线衍射仪(XRD)和悬臂梁缺口冲击仪测试其对PP结晶行为和力学性能的影响。结果表明,利用芳基二酰胺类β晶型成核剂异相成核诱导法对PP-R材料进行结晶改性,能够大幅提高其冲击强度和热变形温度。β成核剂改性PP-R材料使用量小、简单易行且效果突出,非常适合聚丙烯的工程化应用。     

PET纤维对聚丙烯结晶行为与力学性能的影响

以聚丙烯(PP)、聚酯(PET)纤维为主要原料,马来酸酐接枝PP(PP-g-MA)为相容剂,经熔融共混、粉碎、注塑加工成样条后进行表征,并研究了其性能。结果表明:PET纤维对PP具有异相成核作用,主要诱导PP形成α晶,可提高PP结晶温度并降低球晶尺寸;PET纤维可显著提高PP的拉伸强度和弹性模量,但会降低其冲击强度;加入相容剂PP-g-MA对PP/PET纤维共混物的结晶性能基本无影响,但对其力学性能影响显著,与未增容的PP/PET纤维共混物相比,经PP-g-MA增容后,共混物的拉伸强度、冲击强度、弹性模量均得到显著提升。     

超分散剂改性Talc/PP复合材料结晶行为及微观结构分析

合成了YB超分散剂并制备talc/PP复合材料。采用红外光谱(FT-IR)、差示扫描(DSC)、X衍射(XRD)和扫描电镜(SEM)等方法研究了复合材料的结晶行为和微观结构。结果表明:改性后的talc表面连接了新的有机基团;talc的加入具有异相成核作用,提高了PP结晶温度,但无晶型转变,当talc用量超过30%,异相成核作用减弱;超分散剂与talc存在异相成核协同作用,进一步提高结晶温度,并且对β晶型具有诱导效应,YB超分散剂加入,使部分α晶型向β晶型转变;同时使复合材料的冲击断面从脆性断裂转变为强韧性断裂。     

Crystallization kinetics of polypropylene composites filled with nano calcium carbonate modified with maleic anhydride

The subject of this study was the crystallization behavior and thermal properties of polypropylene (PP)/maleic anhydride (MAH) modified nano calcium carbonate (nano‐CaCO₃) composites. In this study, 5 wt % nano‐CaCO₃ modified with different contents of MAH was filled into a PP matrix. X‐ray diffraction and differential scanning calorimetry were used to characterize the crystal morphology and crystallization kinetics of a series of composites. The results demonstrate that the nano‐CaCO₃ modified with MAH had an important effect on the thermal and morphological properties of the nanocomposites. The Avrami exponent of the pure PP was an integer, but those of the composites were not integers, but the crystallization rate constant decreased as the content of MAH in the nano‐CaCO₃ filler increased in isothermal crystallization. In nonisothermal crystallization, the kinetic parameter F(T) and the degree of crystallinity of pure PP were compared with those of the PP composites filled with nano‐CaCO₃. We suggest that heterogeneous nucleation existed in the PP composites and that the transformation and retention of the β‐form crystal into the α‐form crystal took place in the composite system and the β‐form crystal had a higher nucleation rate and growth process than the α‐form crystal in the PP composites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

丙烯酸改性卤锑阻燃聚丙烯的结晶性能

研究了丙烯酸(AA)改性Sb2O3,聚丙烯(PP)母料制备的不同用量卤锑阻燃PP。阻燃PP的差示扫描量热法结果表明,阻燃剂在PP中存在明显的异相成核作用,使PP结晶温度提高,Sb2O3对PP的异相成核作用比十溴二苯醚明显。在无引发剂过氧化二异丙苯(DCP)存在下,AA对阻燃PP中PP结晶温度的影响取决于阻燃剂的用量;在DCP存在下,PP的结晶温度不随AA用量增加而改变。DCP用量增加导致PP严重降解,结晶温度与熔融温度降低。     

聚丙烯／沸石复合材料的结晶行为及其微观形态研究

通过采用PEG10000改性沸石，并与聚丙烯（PP）进行共混制备了聚丙烯／沸石复合材料。对复合材料进行热性能、结晶形态及微观形态测试分析。结果表明，沸石的引入使PP产生了异相成核结晶，结晶度提高；沸石质量分数为3％时，复合材料体系结晶较为完善；而随着沸石用量进一步提高，复合材料的结晶尺寸快速下降，呈现碎晶状。采用PEG10000对沸石进行有机化改性抑制了沸石在PP中团聚，实现了较好的分散。     

Effect of silicon dioxide on crystallization and melting behavior of polypropylene

The crystallization and melting behavior of isotactic polypropylene (iPP) and polypropylene copolymer (co‐PP) containing silicon dioxide (SiO₂) were investigated by differential scanning calorimeter (DSC). SiO₂ had a heterogenous nucleating effect on iPP, leading to a moderate increase in the crystallization temperature and a decrease in the half crystallization time. However, SiO₂ decreased the crystallization temperature and prolonged the half crystallization time of co‐PP. A modified Avrami theory was successfully used to well describe the early stages of nonisothermal crystallization of iPP, co‐PP, and their composites. SiO₂ exhibited high nucleation activity for iPP, but showed little nucleation activity for co‐PP and even restrained nucleation. The iPP/SiO₂ composite had higher activation energy of crystal growth than iPP, indicating the difficulty of crystal growth of the composite. The co‐PP/SiO₂ composite had lower activation energy than co‐PP, indicating the ease of crystal growth of the composite. Crystallization rates of iPP, co‐PP, and their composites depended on the nucleation. Because of its high rate of nucleation, the iPP/SiO₂ composite had higher crystallization rate than iPP. Because of its low rate of nucleation, the co‐PP/SiO₂ composite had lower crystallization rate than co‐PP. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1889–1898, 2006     

Morphology,crystallization and melting properties of isotactic polypropylene blended with lignin

The influence of lignin (L) on the thermal properties and kinetics of crystallization of isotactic polypropylene (PP) is reported in this article. PP blends containing 5 and 15 wt % of L were prepared by mixing the components in a screw mixer. An increase of the thermal degradation temperature of the blends was observed as a function of L content. The crystallization and thermal behavior of the pure PP and of the PP/L blends were analyzed by differential scanning calorimetry (DSC). Isothermal crystallization kinetics were described by means of the Avrami equation, which suggests a three‐dimensional growth of crystalline units, developed by heterogeneous nucleation. The isothermal growth rate of PP spherulites was studied using a polarizing optical microscope. The enhancement of PP crystallization rate for the PP/L blends was observed and ascribed to the nucleating action of lignin particles. Non‐isothermal crystallization kinetics were applied, according to the results elaborated by Ziabicki and the method modified by Jeziorny. The kinetic crystallizability of the PP is not influenced by the L present in the blend. In the presence of L, PP can simultaneously crystallize in both the α and β crystalline forms, and the ratio between the α and β forms was determined by X‐ray diffraction analysis. Two melting peaks relative to the two crystalline form of PP were observed for the PP/L blends, for all isothermal crystallization temperatures investigated by means of DSC. The equilibrium melting temperature for α‐form of pure PP was obtained. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1435–1442, 2004     

Thermal and crystallization behavior of cotton—Polypropylene commingled composite systems

Techniques like thermogravimetric analysis, differential scanning calorimetry, and polarized optical microscopy were used to study the thermal and crystallization behavior of cotton‐polypropylene (PP) commingled composite system. Thermal analysis was used to understand the structure‐property relationship and also to quantify the amount of moisture and volatiles, which causes the deterioration of the composite performance. Thermal stability of the composite was found be intermediate between that of PP and cotton fibers. Presence of treated reinforcements had increased the crystallinity of PP. Also, fibers act as heterogeneous nucleants and favor the early crystallization of PP in the composites. The crystallization and onset crystallization temperature values were increased by the presence of cotton fibers. The theories of heterogeneous nucleation and crystal growth kinetics were used to explain the growth of transcrystalline layer (TCL) of PP on cotton fibers. The interfacial free energy difference for nucleation of PP on fiber was found to be smaller compared with that in the bulk PP. This favors the formation and growth of TCL. The thickness of TCL and radius of the spherulites increase with the increase in the crystallization temperature. Fiber surface roughness and thermal stresses facilitate the growth of transcrystallinity on cotton fiber. POLYM. COMPOS., 31:1487–1494, 2010. © 2009 Society of Plastics Engineers     

聚丙烯/蒙脱土纳米复合材料的结晶性能研究

采用差示扫描量热法研究蒙脱土(MMT)对聚丙烯(PP)等温结晶性能的影响。结果表明：加入MMT后提高了PP的结晶速率，使结晶度增大，但对PP熔点的影响不大；加入相容剂PP-g-MAH后，使有机MMT对PP的成核作用更加明显，从而提高了PP／MMT。纳米复合材料的结晶度；PP／MMT纳米复合材料的n值在3左右，其成核方式是异相成核方式。     

PP/Nano-SiO_2包覆长石复合材料的制备、性能及结构表征

采用纳米二氧化硅(nano-SiO2)对长石填料进行表面修饰改性,且对其表面包覆形貌进行了分析和表征。以nano-SiO2包覆改性长石为填料制备了聚丙烯(PP)/包覆长石复合材料,并对其力学性能、热稳定性进行了研究。结果表明:当包覆长石用量为3%时,复合材料的拉伸强度和断裂伸长率均达到最大值;同纯PP相比,该复合材料的热稳定性和韧性有所提高;另外,nano-SiO2包覆长石粉体对PP具有异相成核作用,提高了PP基体的结晶度。