聚丙烯/累托石纳米复合材料的非等温结晶动力学研究

在双螺杆挤出机上熔融共混制备了聚丙烯 (PP) 有机累托石 (OREC)纳米复合材料 ,采用广角X 射线衍射 (WAXD)定性地分析了PP OREC纳米复合材料及纯PP的结晶形态 ,由半峰宽定性地判断了对应晶面法向的晶粒的大小 .结果表明有机累托石没有改变聚丙烯的结晶晶型 (纳米复合材料主要还是α晶型 ) ,但是细化了晶粒的尺寸 .采用差示扫描量热法 (DSC)定量地研究了复合材料的非等温熔融结晶动力学 ,对所得数据分别用Jeziorny法的Mo法进行了处理 ,表明非等温结晶动力学参数Zc 及Avrami指数n随冷却速率的增加而增加 ,复合材料的Avrami指数n大于纯PP的n ;对相同配比的纳米复合材料 ,随着结晶度的增加 ,单位结晶时间里达到一定结晶度所需要的降温速率F(T)增大 ,对同一个设定的结晶度 ,纳米复合材料的F(T)比纯PP的小 ,说明需要的降温速率减小 .所有这些均说明有机累托石可作为聚丙烯的结晶成核剂 .     

聚丙烯/蒙脱土纳米复合材料的等温结晶研究

采用差示扫描量热法 (DSC)对插层聚合法制备的聚丙烯 /蒙脱土纳米复合材料 (PP MMT)的等温结晶过程进行了研究 .引入蒙脱土 (MMT)后 ,PP MMT的结晶速率大幅度提高 ,相对结晶度略有下降 .采用Avrami方程对结晶动力学进行研究 ,Avrami指数n≈ 3 .0 ,半结晶时间t1 2 大幅度降低 .采用Hoffman理论计算了PP MMT的球晶生长的单位面积表面自由能σe,结果表明σe 随MMT含量的增加逐渐降低     

多壁碳纳米管/聚丙烯复合材料的晶型及非等温结晶动力学

采用熔融共混法制备了多壁碳纳米管/聚丙烯(MWNT/PP)复合材料,利用X射线衍射法(XRD)、差示扫描量热法(DSC)分别研究了纯聚丙烯(PP)及MWNT/PP复合材料的晶型和非等温结晶动力学行为,并运用Mo法研究了纯PP及MWNT/PP复合材料的非等温结晶动力学行为。结果表明,多壁碳纳米管(MWNT)的加入使PP发生了由β晶型向α晶型的转变。MWNT在结晶过程中具有异相成核效应,提高了PP的结晶温度和结晶速率。MWNT/PP复合材料的结晶活化能均明显高于纯PP。MWNT的加入使PP在单位时间内达到一定结晶度所需的降温速率减小。     

碳纤维对聚丙烯结晶行为的影响

本文用偏光显微镜和示差扫描量热计(DSC)方法研究了碛纤维对聚丙烯结晶行为的影响。碳纤维表面对聚丙烯结晶过程具有明显的促进作用,纤维表面成核密度轻高,结晶生长成为横穿结晶,结晶特征温度随碳纤维加入而有不同程度的升高。结晶动力学表明:结晶生长本质仍是球晶机理,促进聚丙烯结晶的原因是碳纤维使结晶过程的表面自由能降低。     

聚丙烯合金PP-c的晶相结构及形态

用偏光显微镜和广角X射线衍射研究了聚丙烯合金PP c的结晶形态.发现PP -c的晶相结构中不仅存在α-晶型聚丙烯(α- PP ) ,也存在着β-晶型聚丙烯(β-PP) .计算了不同乙烯含量PP c的结晶度和β- PP含量.表明随着乙烯含量的增加,β- PP的含量增加,而PP- c的结晶度下降.通过与同等熔融结晶条件下等规聚丙烯(iPP)的结晶形态相比较,发现乙烯组分含量的增加,改变了球晶的生长状况,降低了PP- c晶相的晶体完整性.     

成核剂对聚丙烯及其共聚物的结晶行为和性能的影响

研究了成核剂1,3:2,4-对二乙基苄叉山梨醇(EDBS)对聚丙烯及其乙烯共聚物的结晶行为和结晶形态的影响,并对其薄膜进行了光学性能的表征.结果表明,添加少量(质量分数0.5%)的成核剂,使聚丙烯样品的结晶温度大大提高,结晶度明显增加.而对于乙烯共聚聚丙烯样品,添加少量(质量分数0.5%)成核剂,不仅使其整体结晶温度大大提高,结晶度增加,而且明显强化了低有序部分的结晶.少量成核剂的加入,使聚丙烯及其共聚物的球晶尺寸明显缩小,薄膜的透光性和雾度显著改善.     

稀土β-成核剂对1-丁烯本体聚合和产物聚(1-丁烯)结晶性能的影响

采用Ziegler-Natta催化剂催化1-丁烯本体聚合,稀土β-成核剂经原位聚合的方法加入到体系,并考察成核剂加入量对产物聚(1-丁烯)的分子量和结晶性能的影响.通过凝胶渗透色谱(GPC)、示差扫描量热仪(DSC)、偏光显微镜(POM)和广角X射线衍射仪(WAXD)对聚合物进行表征分析.实验结果表明,随着稀土β-成核剂加入量的增大,催化剂活性有所下降,聚合物等规度略有提高,而聚合的分子量显著提高,分子量分布变窄;聚合时成核剂的加入提高了聚(1-丁烯)的结晶性能,随着成核剂加入量的增多聚合物晶粒变小且尺寸趋向均一化,聚合物结晶度也得到了提高,当成核剂加入量为30 mg时,聚合物结晶度和熔融焓出现突变现象.此外,稀土β-成核剂的加入会改变熔融前聚(1-丁烯)中晶型Ⅰ’和Ⅲ所占比例从而影响聚合物的熔点,成核剂的存在也改变了晶型II向晶型I的转变速率,缩短了晶型转变周期.     

聚丙烯—聚对苯二甲酸乙二酯共混物的扫描电镜观察(Ⅱ)

使用扫描电镜和化学蚀刻的方法研究了聚丙烯(PP)和聚对苯二甲酸乙二酯(PET)共混物(PP:PET:9:1)在不同温度结晶时的形态结构,并与在相应条件下结晶的纯PP样品作比较。结果表明:(1)纯PP在0℃结晶时没有观察到明显的球晶,部分区域呈树枝晶,在30℃以上结晶时呈三类不同形态球晶;在0—140℃范围结晶的PP—PET共混物中都没有观察到第三类球晶和树枝晶。(2)在0—140℃温度下结晶的共混物中两组份互不相溶,PET都是以直径为1—5μ的小球分散在PP连续相的球晶内和球晶之间;PET的加入使PP球晶的尺寸比在相应条件结晶的纯PP球晶小,同时球晶的大小也随结晶温度降低而变小;PET小球与PP连续相之间存在着易受蚀刻的界面层。     

聚丙烯/插层改性水滑石纳米复合材料结构与性能研究

采用离子交换法制备了十二烷基磺酸钠和衣康酸共同改性水滑石(LDHs2),FTIR、XRD分析表明,十二烷基磺酸钠和衣康酸能够同时进入水滑石片层之间,层间距有很大提高。利用改性水滑石,通过马来酸酐-苯乙烯共接枝改性聚丙烯相容剂的熔融共混和聚丙烯与水滑石溶液共混制备母粒,然后与聚丙烯分别熔融共混两种方法制备聚丙烯/水滑石纳米复合材料。TEM分析表明,马来酸酐-苯乙烯共接枝改性聚丙烯作相容剂可以使水滑石在聚丙烯基体中达到更好分散。DSC、XRD分析表明,水滑石、相容剂以及短链共聚聚丙烯对聚丙烯晶型没有影响,但对其结晶速率、结晶度以及晶粒大小有所改变,复合材料中聚丙烯的起始结晶温度、结晶峰温度、结晶速率、结晶度均比纯聚丙烯高,晶粒粒径分布也更均匀。     

聚丙烯与聚酯-聚醚多嵌段共聚物共混的研究

聚丙烯和聚酯-聚醚多嵌段共聚物的熔融共混物是微多相分散体系,其力学性能和软链段的结构有关。DSC和偏光显微镜图分别表明共混物中聚丙烯结晶度以及球晶尺寸随聚酯-聚醚的混入量而变小。聚丙烯和少量聚酯-聚醚多嵌段共聚物共混,可改进聚丙烯的流变性,吸湿性和染色性。     

Attapulgite and ultrasonic oscillation induced crystallization behavior of polypropylene

In this article, the effect of ultrasonic oscillation on the dispersed morphology of attapulgite in polypropylene (PP) and crystallizing kinetics of PP/attapulgite composites prepared through extrusion in the presence and the absence of ultrasonic oscillation were studied. X‐ray diffraction analysis results showed that ultrasonic oscillation did not change attapulgite crystal structure during extrusion in PP/attapulgite composites. On the other hand, scanning electron microscopy and transmission electron microscope photographs indicated that ultrasonic oscillation promoted the dispersion of attapulgite particles in PP matrix. The dispersed morphology of attapulgite and ultrasound oscillation affected the crystalline form, nucleation rate, crystallization temperature, crystallinity, and spherulite size of PP crystals. PP transcrystals were formed on the attapulgite particle surface. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2300–2308, 2007     

聚丙烯催化合金的结晶行为研究

近 1 0年来 ,Montell公司发展的聚丙烯催化合金 (Polypropylene catalloy,PP-c)技术受到广泛关注 .该技术采用具有特定结构的催化剂粒子 ,在适当的聚合条件下 ,得到具有一定大小、形状及内部形貌的聚合物粒子 .由 PP-c技术获得的材料性能可以在非常宽的范围内进行调节 ,其呈现出的高强度可以与工程塑料相比拟 ,柔性可以与聚乙烯相媲美 [1] .结晶性聚合物的结晶度、球晶尺寸等因素对其机械性能 ,尤其是冲击韧性具有重要的影响[2 ,3] .改性聚丙烯的结晶行为及其与物理机械性能之间的关系一直备受关注 .对于纯聚丙烯、聚丙烯与橡胶的共混物…     

插层聚合聚丙烯-蒙脱土纳米复合材料的微观结构形态

使用偏光显微镜，扫描电镜，透射电镜和广角X射线衍射法研究了插层聚合法制备的聚丙烯－蒙脱土（PP－MMT）纳米复合材料的微观结构和形态发展。结果表明，随着插层聚合反应的进行，较大的初级MMT粒子逐渐剥离成较小的次级粒子。次级粒子由2－20片的单个MMT片层组成，其层间充满了PP分子链。提出了插层聚合过程中PP－MMT复合材料的形态发展模型。另外，MMT的加入对PP的球晶形态也有重要影响，PP完整的球晶随MMT的加入逐渐变小和趋于扭曲甚至破坏。     

Isothermal crystallization behavior of exfoliated‐PP/IMMT nanocomposites via in situ polymerization

Highly exfoliated isotactic‐polypropylene/alkyl‐imidazolium modified montmorillonite (PP/IMMT) nanocomposites have been prepared via in situ intercalative polymerization. TEM and XRD results indicated that the obtained composites were highly exfoliated PP/IMMT nanocomposites and the average thickness of IMMT in PP matrix was less than 10 nm, and the distance between adjacent IMMT particles was in the range of 20–200 nm. The isothermal crystallization kinetics of highly exfoliated PP/IMMT nanocomposites were investigated by using differential scanning calorimeter(DSC) and polarized optical microscope (POM). The crystallization half‐time t_1/2, crystallization peak time t_max, and the Avrami crystallization rate constant K_n showed that the nanosilicate layers accelerate the overall crystallization rate greatly due to the nucleation effect, and the crystallization rate was increased with the increase in MMT content. Meanwhile, the crystallinity of PP in nanocomposites decreased with the increase in clay content which indicated the PP chains were confined by the nanosilicate layers during the crystallization process. Although the well‐dispersed silicate layers did not have much influence on spherulites growth rate, the nucleation rate and the nuclei density increased significantly. Accordingly, the spherulite size decreased with the increase in MMT content. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2215–2225, 2009     

聚丙烯/凹凸棒石纳米复合材料的制备与性能研究

以聚丙烯(PP)为聚合物基体,天然凹凸棒石(ATP)为无机组分,经过氧化聚乙烯对ATP表面进行包覆处理,用熔融共混的方法制备了PP/ATP纳米复合材料.扫描电镜结果显示,经本方法处理后的ATP在PP基体中分散较为均匀.ATP棒晶簇直径最佳分散尺寸能达到20~40 nm,比未处理ATP在基体中的棒晶簇直径小10 nm以上;XRD测试表明,未处理ATP和处理后的ATP均有使PP晶粒细化的作用,同时不改变PP的α晶型;DSC结果显示,ATP的加入提高了PP的结晶温度和结晶度,说明ATP有一定的成核作用.通过对复合材料的力学性能测试发现,经过处理的ATP制备的复合材料力学性能优于未处理ATP复合材料对PP力学性能的改善.其中ATP与氧化聚乙烯固含量的质量比为2∶1,ATP含量为3 wt%时复合材料力学性能达到最好.缺口冲击强度比纯PP最高提高了83%,提高幅度显著;经过处理的ATP制备的复合材料拉伸强度提高了6%~11%;弯曲强度提高了33%~45%;弯曲模量提高了90%~106%.     

聚丙烯/凹凸棒土纳米复合材料的非等温结晶动力学

聚丙烯/凹凸棒土纳米复合材料的非等温结晶动力学     

β成核剂修饰多壁碳纳米管增强聚丙烯纳米复合材料的分散及结晶行为

利用非共价键改性方法,用芳香二羧酸酰胺类的β成核剂(β-NA)改性多壁碳纳米管(MWCNTs),采用溶液法制备了聚丙烯(PP)/β-NA-MWCNTs复合材料.通过广角X射线衍射(WAXD)分析了复合材料的结晶形态,结果表明β-NA-MWCNTs诱导聚丙烯生成大量β晶,同时提高了复合材料的结晶度.含5.0 wt％β-N...     

Effect of carbon nanotubes on the crystallization and properties of polypropylene

The effect of different concentrations of single‐walled carbon nanotubes (SWNTs) on the nonisothermal crystallization kinetics, morphology, and mechanical properties of polypropylene (PP) matrix composites obtained by melt compounding was investigated by means of X‐ray diffraction, differential scanning calorimetry, optical and scanning electron microscopy, and dynamic mechanical thermal analysis. Microscopy showed well‐dispersed nanotube ropes together with small and large aggregates. The modulus was found to increase by about 75% at a level of 0.5 wt % nanotubes. The SWNTs displayed a clear nucleating effect on the PP crystallization, favoring the α crystalline form rather than the β form. The crystallization kinetics analysis showed a significant increase in activation energy on incorporating nanotubes. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2445–2453, 2005     

Crystallization and mechanical properties of basalt fiber-reinforced polypropylene composites with different elastomers

In this study, composites based on polypropylene (PP), basalt fiber (BF), polypropylene-graft-maleic anhydride (MAPP) and different elastomers were manufactured by extrusion compounding and injection molding. The main focus of this study was to comparatively investigate the effect of three kinds of elastomers (ethylene–propylene–diene monomer (EPDM), polyethylene–octene (POE) and ethylene–vinyl–acetate (EVA)) on non-isothermal crystallization and mechanical properties of the composites with various BF contents. The tensile test results showed that BF had a reinforcing effect on PP resin, and the addition of MAPP further improved the tensile properties by the enhancement of PP/BF interfacial bonding. Among the elastomers, EPDM was more effective in improving the tensile strength and tensile modulus, while POE significantly toughened the impact strength. Micrographs of scanning electron microscope on the impact fracture surfaces indicated a good dispersion by the addition of POE and EPDM, while some agglomerations were observed in the presence of EVA. The non-isothermal crystallization kinetics were investigated based on Avrami and Mo equations at six different cooling rates by using differential scanning calorimetry. Micrographic images of polarized optical microscopy showed that the spherulite size of PP reduced in the presence of EPDM and EVA.     

Influence of N,N,N′,N′-tetraalkyl terephthalamide on isothermal crystallization kinetics and morphology evolution of polypropylene

The influence of N,N,N′,N′-tetraalkyl terephthalamide (TATA) on the isothermal crystallization kinetics of polypropylene (PP) was studied using differential scanning calorimetry (DSC). It was found that TATA shows a heterogeneous nucleation effect and leads to the formation of β-PP. TATA can not only shorten the crystallization time but also heighten the crystallization temperature of PP. The crystallization rate constant of PP containing TATA is larger than that of pure PP. The evolution of crystalline morphology of PP was investigated on a polarized optical microscopy (POM) equipped with a hot stage and the results showed that the introduction of TATA into PP can quicken the crystallization of PP, which is consistent with DSC results. TATA also leads to a substantial decrease in the spherulite size of PP and the boundaries of spherulites are hardly distinguished.