PET/PEN/DBS共混体系结构与形貌的研究

共混是改善聚合物性能的一种简单而又行之有效的方法,PET和PEN均为结晶性聚酯,由于PEN合成原料的影响,致使PEN的价格较高,但性能比PET优良,通过二者的共混,既可以提高PET的性能,又可以降低PEN成本,有关PET／PEN共混体系的研究已引起人们的关注,而对于共混体系结晶形态和结晶条件的研究较少,由于成核剂能够提高结晶速率,减小球晶尺寸,因此本文对PET／PEN／DBS共混体系中,组分组成的影响及不同结晶条件下共混物的结晶形貌进行研究。     

具有环状结构的二氧化硅微聚集体的制备、表征及应用

通过溶胶-凝胶法制备二氧化硅溶胶,并采用喷雾干燥法对其进行形态调控.扫描电镜(SEM)结果表明,喷雾干燥使二氧化硅颗粒发生了形态重组,形成均匀的具有环状结构的二氧化硅微聚集体(PC16MS).通过熔融共混制备了二氧化硅/聚丙烯(PP)纳米复合材料,研究了PC16MS的加入对其微观结构、晶体结构、结晶行为、球晶形态、结晶成核密度和球晶生长速率等方面的影响.采用差示扫描量热(DSC)、偏光相差显微镜(POM)和广角X射线衍射(WAXRD)分析表明,在PP结晶初始阶段,PC16MS的加入大幅度提高了基体材料的成核密度,且使晶粒细化,缩短了结晶时间;当添加2%(质量分数)的PC16MS时,复合材料的结晶温度相对于纯PP提高了10.4℃,成核效率达到39.1%,优于大部分无机成核剂的成核效率.在相同条件下,添加2%未经过喷雾干燥处理的纳米二氧化硅(NC16MS),复合材料的结晶温度相对于纯PP提高3.26℃,成核效率达到12.3%.结果表明,喷雾干燥使二氧化硅颗粒发生了形态重组,形成的均匀介稳态微聚集体在熔融挤出过程中重新分散成纳米粒子,从而有效提高了二氧化硅作为成核剂的成核效率.     

不同分子量聚L-乳酸的非等温结晶动力学研究

采用DSC方法研究了不同分子量聚乳酸在不同降温速率下的结晶过程,利用Ozawa方程和Kissinger方程研究了其非等温结晶动力学。结果表明,随着降温速率的增大和分子量增加,结晶峰向低温偏移,且峰形趋于平缓。求得分子量为2.6×104的聚乳酸的Ozawa指数m接近3,以异相成核的三维球晶生长为主,而分子量为14.3×104和19.2×104的聚乳酸的Ozawa指数m接近4,以均相成核的三维球晶生长为主,结晶活化能分别为-165.8kJ/mol、-82.1kJ/mol和-75.4kJ/mol。建立的"铰链"模型解释了不同分子量聚乳酸结晶活化能的显著差异,得到了聚乳酸分子量与结晶活化能的关系。     

GMA/苯乙烯多组分单体接枝聚丙烯结晶行为研究

使用差示扫描量热计 (DSC)研究了甲基丙烯酸缩水甘油酯 苯乙烯 (GMA St)多单体熔融接枝聚丙烯[PP g (GMA co St) ]的等温和非等温结晶行为 ,用偏光显微镜观察了结晶的形态 ,并利用Avrami方程对其结晶动力学进行了分析 .研究发现接枝聚丙烯的结晶模式与PP相似 ,属于异相成核控制的球晶三维生长 ;但接枝聚丙烯的结晶温度 (Tc)显著提高 ,幅度高达 16～ 19℃ ,总结晶速率与纯PP相比明显加快 .接枝聚丙烯上GMA co St支链的存在 ,降低了成核界面自由能 ,促进了聚丙烯结晶的异相成核 .在接枝率不太高的情况下 ,随着接枝率的提高 ,接枝聚丙烯的结晶温度升高 ,总结晶速率加快 .在高接枝率范围内 ,随着接枝率的提高 ,接枝PP的Tc 不再升高 ,且由于接枝链的增长严重阻碍了球晶生长 ,导致接枝PP的总结晶速率反而随接枝率的升高而下降     

PET/PEN/DBS共混物非等温结晶动力学研究

采用DSC方法, 用修正的Avrami, Ozawa, Ziabicki宏观动力学模型描述PET/PEN/DBS[PET: 聚对苯二甲酸乙二醇酯; PEN: 聚2,6-萘二甲酸乙二醇酯; DBS: 1,3∶2,4-二(亚苄基)-D山梨醇]共混物的非等温熔融结晶过程, 研究结果表明, 修正的Avrami模型能很好地描述此共混物非等温结晶过程. 冷却速率在5-20 ℃/min范围内, Ozawa方程能很好地描述初期结晶过程, 但结晶后期由于忽略次级结晶而不适宜. 由Ziabicki结晶动力学参数可知, 该共混物的结晶随着成核剂DBS含量的增加而降低, 结晶速率随着成核剂DBS含量的增加而提高. 在非等温结晶条件下, 共混物结晶同时受到冷却速率和共混物组成的影响, 与共混物非等温结晶过程的有效能垒分析结果基本一致.     

聚苯硫醚及其聚醚砜共混物结晶形态的研究

本文借用偏光显微镜(PLM)、扫描电子显微镜(SEM)、小角激光光散射仪(SALS)及蚀刻的方法,研完了聚苯硫醚及其与聚醚砜共混物的结晶形态和织构,讨论了共混方法及其共混组成对其共混物的结晶形态的影响。结果表明,聚苯硫醚在应力作用下能生成横晶;溶液共混物和粉末机械共混物呈现不同的共混结晶形态;随着聚醚砜组分的增加,共混物的织构从聚苯硫醚为连续相逐渐转变为聚醚砜为连续相,同时,聚醚砜的聚集区域从分散在聚苯硫醚的球晶之间转变为聚集在聚苯硫醚的球晶内,使聚苯硫醚的球晶形态逐渐变得不规整。     

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.     

长链支化聚丙烯结晶行为及发泡性能研究

通过广角X射线衍射(WAXD)、示差扫描量热(DSC)和偏光显微镜(POM)研究了长链支化聚丙烯(LCBPP)和线性等规聚丙烯(PP)的结晶行为.WAXD和DSC的结果显示LCBPP样品有利于β结晶,出现了少量β晶.DSC和POM的结果显示在等温结晶过程中长链支化结构起到促进异相成核和细化晶粒的作用,LCBPP样品的结晶温度提高,结晶速度增大,球晶尺寸显著减小.采用间歇釜式超临界二氧化碳发泡法对LCBPP和线性PP样品进行发泡,由于LCBPP结晶温度高,结晶速率更快,有利于泡孔的固化定型,可以提高发泡温度,研究结果表明在相同的发泡压力下LCBPP样品发泡温度窗口较宽,为5 K左右,而线性PP样品的发泡温度窗口较窄,仅为2 K左右,同时在相同的发泡条件下LCBPP样品的发泡倍率较大.     

β晶型成核剂对聚丙烯力学及结晶性能的影响

研究了N,N′-二环己胺基对苯二酰胺作为β成核剂对聚丙烯(PP)力学性能及结晶性能的影响。结果表明,成核剂具有使聚丙烯增韧的优异性能,当添加质量分数为0.3%时,其抗冲击强度由原来的36.06 J/m2提高到65.79 J/m2。DSC研究表明,添加β成核剂可以诱导PP中β晶生成。考察了冷却速率对结晶温度的影响,当冷却速率为10℃/m in时,结晶温度从118.38℃提高到124.53℃,表明该成核剂的加入使结晶向高温方向偏移,结晶速度加快。     

硅氧烷液晶共聚物作为β晶成核剂对等规聚丙烯结晶结构与形态的影响

采用广角X射线衍射(WAXD)与偏光显微镜(POM)等手段研究了硅氧烷液晶共聚物(LCP-O2)作为新型成核剂对聚丙烯(PP)共混样品结晶结构与形态的影响.结果表明,低浓度的LCP-O2在PP共混体系中起到异相成核的作用,使PP的晶核数目增多,球晶细化,并提高了结晶速度,同时也诱导出了β晶的形成.LCP-O2的成核效果主要依赖于其在PP中的相对含量、液晶的分子结构与结晶的热处理过程,且随着结晶温度或成核剂含量的增加,对应PP试样的β晶含量(Kβ)呈现先增加,后降低的趋势.当LCP-O2质量分数为1.0%,在130℃等温结晶1h,对应PP试样的Kβ最大,为58%.此外,属于单斜晶的α球晶呈现黑白颜色,晶束呈放射状生长,边界清晰;而属于三方晶的β球晶亮度要高于α球晶,其颜色艳丽多彩,束状晶片聚集体呈支化生长,内部排列比α晶疏散,边界相对模糊,且β晶与α晶的形态分别在157和171℃完全消失.     

Crystallization and morphology of poly(ethylene‐2,6‐naphthalene dicarboxylate) in the presence of nucleating agents

The crystallization and morphology of poly(ethylene‐2,6‐naphthalene dicarboxylate) (PEN) containing, as nucleating agents, a sodium salt of a copolymer of ethylene and acrylic acid or a sodium salt of a copolymer of ethylene and methacrylic acid, were investigated with differential scanning calorimetry, polarized optical microscopy, and small‐angle light scattering. The nucleating agents accelerated the crystallization rate at high temperatures by decreasing the surface free energy barrier hindering nucleation. Meanwhile, the nucleating agents with flexible chains could also improve the mobility of the PEN chains and increase the crystallization rate at low temperatures. Hedrites were observed when PEN was crystallized at high temperatures, whereas crystallization at low temperatures led to the formation of spherulites. Similar but smaller morphologies were obtained in the presence of nucleating agents. With nucleating agents, the spherulites formed at low temperatures were less perfect, although the optical properties of the spherulites were not influenced. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2387–2394, 2002     

高顺式-1,4-聚丁二烯的结晶形态研究

用稀土催化剂得到的顺-1,4-聚丁二烯具有顺式含量高,支化度小及分子链结构规整性好等特点。在常温下为非晶态,但在低温下易于结晶,因而具有较高的力学性能。本文详细讨论了高顺式稀土顺丁生胶的低温结晶行为。用电子显微镜观察了在低温下球晶结构的形成及其分子结构规整性、结晶条件对结晶形态及结晶速率的影响。     

聚十二烷二元酸丁二酯及其共聚酯的结晶行为研究

聚十二烷二元酸丁二酯是长碳链脂肪族聚酯中的一种新的聚合物材料．近年来，随着对环境问题的日益重视，利用脂肪族聚酯容易水解的特性，开发生物降解脂肪族聚酯材料的研究得到广泛开展．目前脂肪族二元酸酯的研究大多是围绕聚丁二酸酯、聚乙二酸酯及其共聚酯这一类降解速度较快的材料进行的．虽然这些聚酯已有部分商品化，但远远不能满足对特定降解速率材料的需求．长碳链脂肪族聚酯由于其具有类似PE的结构特征，又兼具聚酯的结构特征，有望在可降解包装材料、书籍装订、服装用热熔胶等方面获得广泛的应用．     

羧酸盐类成核剂在聚2,6-萘二甲酸乙二酯中的化学成核

采用与PEN分子结构单元相似的 2 ,6 萘二甲酸二甲酯 (DMN)和熔点较低的邻氯苯甲酸钠 (SOCB)为模型化合物 ,用DSC、FTIR、带热台偏光显微镜 (HPOM)和HPLC等方法 ,研究了DMN和SOCB在热处理过程中的化学反应 .DSC和HPOM研究也证明了PEN与SOCB在高温下发生化学反应 .因而提出羧酸盐类成核剂在PEN中的成核是“化学成核” .即在高温下羧酸盐类成核剂和PEN发生化学反应 ,生成PEN的羧端基离子盐 ,该离子盐是真正的成核剂 ,起到成核作用     

全氟乙丙烯共聚物的超分子结构与结晶性质

本文用激光小角光散射技术研究了全氟乙丙烯共聚物的超分子结构。发现它的结晶形态主要依赖于熔体温度。当共聚物从315—320℃以下降温结晶时得到无规排列晶片所固有的圆对称散射图象。从315—320℃以上温度冷却时,形成球晶结构。这些结果与DSC测得的结晶性质之间存在对应关系。结晶性质在上述温度区间上下也有突变。这些结果可用熔体中存在有序微区来解释,它在结晶时起晶核的作用,在温度高于315—320℃时消失。     

Isothermal crystallization of poly(vinylidene fluoride) in the presence of high static electric fields. II. Effect of crystallization temperature and electric field strength on the crystal phase content and morphology

The melt crystallization of poly(vinylidene fluoride) in a static electric field was studied for different fields strengths and undercooling conditions. The γ-phase nucleation process was examined directly by polarized optical microscopy and indirectly by small-angle light scattering. The crystal phase content was assessed by differential scanning calorimetry. It is shown that the γ-phase nucleation density and γ-phase content increase with field strength and that the higher the crystallization temperature, the larger the effect of the field. These experimental results confirm the predictions of the model of nucleation in an electric field that we published previously. It is also noted that the degree of crystallinity and the perfection of crystal orientation along the γ-phase spherulite radical direction decrease with field strength. The homogeneity of morphology resulting from the crystallization in the field is also examined by polarized optical microscopy on specimens microtomed across their thickness. When the crystallization is carried out under high field (E ≈ 0.1 MV/cm) and high temperature (T > 166°C) a nonuniform morphology results, characterized by a higher nucleation density at the positive electrode than at the negative electrode. Near the negative electrode very large disklike spherulites are seen to grow parallel to the substrate.     

Morphology of cold-crystallized polyamide 6

The structure of cold-crystallized polyamide 6 (PA 6) has been analyzed by wide-angle X-ray scattering, atomic force microscopy, and polarizing optical microscopy. It has been found that ordering of initially fully amorphous and glassy PA 6 on slow heating to temperatures higher than the glass transition temperature results in formation of spatially non-organized short lamellae/nodules with a size depending on the maximum annealing temperature. In contrast, melt crystallization at low supercooling is connected with formation of spherulites and laterally extended lamellae. The observed experimental results demonstrate that crystals of qualitatively different morphology and higher-order organization can be generated by variation of the pathway of crystallization. It is assumed that the different structures obtained in melt- and cold-crystallized samples are related to heterogeneous and homogeneous nucleation, respectively.     

Transcrystallization of PTFE fiber/PP composites (I) crystallization kinetics and morphology

Transcrystallization of polypropylene (PP) on the polytetrafluoroethylene (PTFE) fiber was investigated. Both nucleation rate and crystal growth rate were determined by a polarized optical microscope. Based on the theory of heterogeneous nucleation, it has been found that the induction time can correlate well with the nucleation rate in determining the interfacial free energy difference function Δσ. The ratio of Δσ in the bulk matrix to that at the interface is 1.63 which implies the transcrystalline growth is favorable from a thermodynamic point of view. No difference in crystal growth rate of PP has been found in either spherulites or transcrystalline layers. On the basis of regime theory, a transition between regimes II and III was observed at ΔT = 48K. From the morphology studies, it has been found that the thickness of the transcrystalline layer increases with crystallization temperature, from 30 to 120 μm in the temperature range of 110–140°C. The growth of transcrystalline layer is hindered by the spherulites nucleated in the bulk. Moreover, the radius of spherulites adjacent to the transcrystalline layer is much smaller than that distant to the fiber. No significant increase in nucleation density at fiber ends is observed. Effect of internal stresses of fibers on the fiber's nucleating ability is not pronounced. © 1996 John Wiley & Sons, Inc.     

THE EFFECT OF CLAY DISPERSION ON THE CRYSTALLIZATION AND MORPHOLOGY OF POLYPROPYLENE／CLAY COMPOSITES

PP/clay composites with different dispersions, namely, exfoliated dispersion, intercalated dispersion and agglomerates and particle-like dispersion, were prepared by direct melt intercalation or compounding. The effect of clay dispersion on the crystallization and morphology of PP was investigated via PLM, SAXS and DSC. Experimental results show that exfoliated clay layers are much more efficient than intercalated clay and agglomerates of clay in serving as nucleation agent due to the nano-scale dispersion of clay, resulting in a dramatic decrease in crystal size (lamellar thickness and spherulites) and an increase of crystallization temperature and crystallization rate. On the other hand, a decrease of melting temperature and crystallinity was also observed in PP/clay composites with exfoliated dispersion, due to the strong interaction between PP and clay. Compared with exfoliated clay layers, the intercalated clay layers have a less important effect on the crystallization and crystal morphology. No effect is seen for samples with agglomerates and particle-like dispersion, in regard to melting temperature, crystallization temperature, crystal thickness and crystallinity.     

Study of crystallization kinetics of trans-1,4-polyisoprene

The concentrations and the growth rates of high- and low-melting type spherulites of trans-1,4-polyisoprene were measured in the temperature range 39–49°C. It was shown that above about 40°C., the crystallization rate of trans-1,4-polyisoprene is determined primarily by the radial growth rate of high-melting form (HMF) spherulites, whereas the predominance of the low-melting form (LMF) crystals below 40°C. can be attributed to the high rate of formation of LMF primary nuclei at lower crystallization temperatures. Temperature-independent rate parameters were calculated from optical and dilatometric measurements and were found to be in good agreement. Both the change in nucleation habit and spherulite growth rate with temperature can be explained on the basis of a lower end surface free energy of LMF crystals of trans-1,4-polyisoprene compared to that of the HMF crystals.