间规立构聚丙烯非等温结晶行为研究

使用DSC对间规立构聚丙烯（sPP）和等规聚丙烯（iPP）的非等温结晶行为进行了研究。发现间规聚丙烯具有与等规聚丙烯不同的结晶结构。修正的Avrami方程和Ozawa方程对非等温结晶过程处理得到的结晶动力学参数表明两种聚丙烯非等温结晶过程中的成核和生长机理不同;由于立构规整性的差异,间规聚丙烯的结晶速度明显低于等规聚丙烯。     

尼龙6/11共聚物的非等温结晶动力学研究

以尼龙11预聚物和尼龙6预聚物为原料,采用熔融聚合的方法制备了尼龙6/11共聚物.利用差示量热扫描热分析仪(Differential Scanning Calorimetry,DSC)研究了尼龙6/11共聚物的非等温结晶过程,用经Jeziorny修正的Avrami方程对其非等温结晶动力学进行了研究,计算并得到非等温结晶动力学参数.结果表明:该方程适合于处理尼龙6/11共聚物的非等温结晶过程.在尼龙6/11共聚物非等温结晶过程中,在其初期结晶阶段可能同时包含了均相成核和异相成核,在二次结晶阶段结晶生长可能是一维生长;此外,还利用Kissinger方法求得尼龙6/11共聚物非等温结晶的结晶活化能为-201.76 kJ/mol.     

氢化棉籽油非等温结晶动力学研究

应用差示扫描量热仪(DSC)研究氢化棉籽油的非等温结晶行为.考察了两种氢化棉籽油在5、10、15和20℃/min降温速率下的非等温结晶行为,并用Ozawa方程进行动力学分析.非等温结晶曲线表明:随着降温速率的增大,结晶的温度范围增大;Ozawa方程解析非等温结晶曲线表明:当温度升高时,结晶常数m值增大,结晶速率常数K(T)减小.与等温结晶常数相比,非等温结晶常数偏大,说明非等温状态下氢化棉籽油结晶时可能会发生异相成核.     

间规聚丙烯与等规聚丙烯共混物的结晶行为

使用ＤＳＣ和偏 光显微镜对间规聚丙烯（ｓＰＰ）和等规聚丙烯（ｉＰＰ）共８混物的形态和结晶行为和结晶动力学进行了研究。发现ｓＰＰ和ｉＰＰ共混后形成了不相容的多相共混体系,两共混组分在各自微区形成结晶。在ｓＰＰ一方面发迹了ＳＰＰ结晶的成核机理和生长方式,另一方面对ｓＰＰ的结晶起到明显的促进作用,使ＳＰＰ的结晶速率常数增大、半结晶时间减少、结晶活化能下降。同时共混还可以提高ＳＰＰ的结晶度和结晶熔点。     

动态交联聚丙烯/乙烯-醋酸乙烯酯共聚物结晶行为

通过差示扫描量热法(DSC)和X射线衍射(XRD)来研究动态交联聚丙烯(PP)/乙烯-醋酸乙烯酯共聚物(EVA)共混物中PP非等温结晶动力学和晶体结构.结果表明:Ozawa方程适合于描述动态交联PP/EVA共混物中PP的非等温结晶动力学过程.EVA颗粒和动态交联的EVA颗粒都能够对PP的结晶起到异相成核剂的作用,促进PP的结晶.PP/EVA共混物和动态交联PP/EVA共混物中的PP结晶活化能(△E)均小于纯PP的△E,且后者略小于前者.共混和动态交联都没有改变共混物中PP的晶体结构.     

聚乙烯醇对聚丙烯等温结晶行为的影响

利用差示扫描量热仪（DSC）研究了聚乙烯醇（PEG）的加入对聚丙烯（PP）结晶速度的影响,并用Avrami方程分析了聚丙烯在PP／PEG共混物中的结晶动力学。结果表明,当PEG的含量较低时能增加PP的结晶速度,PEG的含量增加,PP的结晶速度有降低的趋势。等温结晶动力学参数表明,PEG的加入对PP起着异相成核作用,但同时又有溶剂化的作用,使其对PP的结晶速度的影响比较复杂。PEG加入使共混物对结晶温度的敏感性降低。     

高聚物结晶动力学方程的研究

对国内外学者提出的高聚物结晶动力学方程进行了归纳,列举了较成熟的2种等温结晶动力学方程和7种非等温结晶动力学方程,分析不同方程产生的基础和存在的意义,总结现有方程的局限性,提出高聚物结晶动力学方程的研究方向。     

全同立构聚丙烯等温结晶行为的研究

采用偏光显微镜对全同立构聚丙烯（iPP）等温结晶行为进行系统的研究，并与聚丙烯／蒙脱土（PP/MMT）复合材料的结晶行为进行比较．结果表明，引入蒙脱土后，结晶速率提高，球晶尺寸变小，蒙脱土起到异相成核的作用、并对iPP本体，特别是对iPP熔体在剪切应力作用下的晶体生长和晶体形态进行研究．柱状晶、纤维晶、树枝晶等晶体形态的形成，都进一步证实聚合物熔体并非完全处在无序的状态，而是部分有序的．     

PET分子量对结晶性能与热性能的影响

研究不同分子量聚酯(PET)的等温结晶、非等温结晶、热失重和恒温热降解等性能。结果表明:在等温结晶过程中,随着分子量的增加结晶速度逐步降低,结晶速度与分子量的倒数成线性关系;在非等温结晶过程中,随分子量的增加,熔体结晶峰峰温逐步向低温推移,过冷程度增大,峰形由高尖形变为宽矮形;在热失重和恒温热降解过程中,随分子量的增加,热失重程度减少而热降解幅度增大。     

间规聚丙烯与等规聚丙烯共混物的结晶行为

使用DSC和偏光显微镜对间规聚丙烯(Spp)和等规聚丙烯(Ipp)共混物的形态和结晶行为和结晶动力学进行了研究。发现Spp与Ipp共混后形成了不相容的多相共混体系,两共混组分在各自微区形成结晶。在Spp中混入少量Ipp一方面改变了Spp结晶的成核机理和生长方式,另一方面对Spp的结晶起到明显的促进作用,使Spp的结晶速率常数增大、半结晶时间减少、结晶活化能下降。同时共混还可以提高Spp的结晶度和结晶熔点。     

聚丙烯MI及成核剂添加量对TIPS法多孔膜结构与透过性能的影响

研究了等规聚丙烯(iPP)/邻苯二甲酸二丁酯(DBP)/邻苯二甲酸二辛酯(DOP)/成核剂TM-1体系的热致相分离(TIPS)行为,采用熔融指数(MI)较低的聚丙烯T30S与MI较高的F401作对比研究.采用示差扫描量热仪(DSC)测定成核效应,采用光学显微镜观察iPP成核与晶粒生长.经过加热模压并控制冷却速率制备iPP多孔膜,对膜结构及其透过性能进行了表征.结果表明:相比于F401/DBP/DOP体系,TM-1对T30S/DBP/DOP体系表现出更强的成核效应;不同MI聚丙烯制备的多孔膜结构明显不同,加入成核剂后,T30S型iPP多孔膜结构由紧密融合、内含胞腔孔的球晶结构转变为晶粒组成胞腔壁、相对开放的胞腔孔结构,而F401型iPP多孔膜的结构仍为紧密融合、内含胞腔孔的球晶结构,只球晶尺寸变小;相同成核剂添加量下,用T30S制备的多孔膜透过性能更好.     

Non-isothermal Melt Crystallization Kinetics of Anhydrite-Filled Polypropylene Composites

The non-isothermal crystallization kinetics of polypropylene (PP), PP/anhydrite composites were investigated by differential scanning calorimetry (DSC) with various cooling rates. The Avrami analysis modified by Jeziorny and a method developed by Mo were employed to describe the non-isothermal crystallization process of these samples. The difference in the exponent n between PP and PP/anhydrite composites indicated that non-isothermal kinetic crystallization corresponded to tri-dimensional growth with heter...     

Preparation and crystallization action of SiO2 -Al2O3 -CaO-ZnO-R2O porous glass-ceramics

Using powder-sintering method,SiO2-Al2O3-CaO-ZnO-R2O porous glass-ceramics were produced for analysis. Five samples with different SiO2 /CaO ratios were used in the research. The mechanical properties, microstructures and textures of porous glass-ceramics are investigated by using differential thermogravimetric analysis/differential thermal analysis ( TGA/SDTA) ,X-ray diffraction ( XRD) ,and scanning electron microsco- py ( SEM) . The activity energy of crystallization ( E) and crystallization kinetics parameter ( k) were calculated based on the modified JMA equation. The Avrami parameter n was obtained according to Augis-Bennett function. The results show that the k value of No. 1 sample ( SiO2 /CaO = 61∶ 18) is the largest among all samples, which tends to crystallize more easily,and crystallization processes of all samples are observed bulk crystallization. The main crystal phase observed is parawollastonite ( clinorhombic system) with puncheon shape. Poreforming agents decomposed at 100 - 500 ℃ form a large number of closed pores with micron dimension and several semi-open pores distribute uniformly in the glass-ceramics matrix. This work may be expected to be favorable for industrial scale applications of porous glass-ceramics in the field of building thermal insulation.     

热致相分离法iPP/Nano-SiO_2共混微孔膜的结构与透过性能

研究了等规聚丙烯(iPP)/邻苯二甲酸二丁酯(DBP)/邻苯二甲酸二辛酯(DOP)/纳米二氧化硅(Nano-SiO2)体系的热致相分离(TIPS)行为,光学显微镜测定体系的液-液相分离温度,示差扫描量热仪(DSC)测定体系的iPP动态结晶温度.加热模压并控制冷却速率制备iPP/Nano-SiO2共混平板微孔膜,对膜结构与透过性能进行了表征.发现Nano-SiO2提高了体系的液-液相分离温度;Nano-SiO2起到了成核剂作用,提高了iPP的动态结晶温度.X光电子能谱(XPS)表明Nano-SiO2向膜表面发生了迁移,膜的亲水性有所提高.随Nano-SiO2添加量增加,膜结构由粒子形态为主向胞腔形态为主转变;膜的孔隙率和纯水通量均呈现先上升后下降的趋势.研究表明:通过向制膜体系中添加Nano-SiO2,可以调控膜结构,并改善膜的透过性能.     

透闪石/尼龙1010复合材料等温结晶动力学研究

将经过表面修饰的透闪石与尼龙1010按一定比例共混制成复合材料,采用差示扫描量热法(DSC)研究了该复合材料的等温结晶行为,并应用Avrami方程对其进行了等温结晶动力学分析。结果表明:透闪石对尼龙1010结晶起到了异相成核的作用,尼龙1010的结晶速率随透闪石的含量的增加而提高,Avrami指数n略有降低。对尼龙1010及其复合材料样品结晶活化能的计算表明,后者高于前者,结晶速度对温度的敏感性增加。     

高分子量聚对二氧环己酮结晶性能的研究

利用差示扫描量热法（DSC）,配带热台的偏光显微镜（POM）和X衍射法（XRD）研究了高分子量聚对二氧环己酮（poly p-dioxanone, PPDO）的结晶行为。研究结果表明,当分子量达到一定程度以后（MW>30000g/mol）,不但PPDO的结晶行为不受分子量的影响,同时PPDO的晶体结构也不会受到其影响,然而PPDO的球晶生长过程受却受到分子量的显著影响,其球晶生长速度与PPDO的分子量与等温结晶温度均成反比,当分子量达到277300g/mol时,其在高温100°C时就无法结晶。     

β晶型成核剂对聚丙烯结晶行为和力学性能的影响

以2,6-苯二甲酸环己酰胺（TMB-5）为β晶型成核剂,采用熔融共混的方法制备β晶改性聚丙烯. 利用示差扫描量热仪、偏光显微镜、拉伸实验机以及冲击试验机对改性聚丙烯的微观结构、热性能、结晶性能、力学性能进行研究. 实验结果表明,在聚丙烯中添加β晶型成核剂进行改性后,由于成核剂在体系中起到了异相成核的作用,聚丙烯中部分晶型由α晶型向β晶型转变,改性聚丙烯的结晶温度向高温方向移动,且聚丙烯球晶尺寸明显减小,球晶之间无明显的边界. 随着β晶型成核剂含量的增加,改性聚丙烯的拉伸强度、弯曲强度和弯曲模量呈现先降后升的趋势,而其断裂伸长率和冲击强度呈先升后降的趋势,并且当β晶型成核剂含量为0.4份时,改性聚丙烯的拉伸强度、弯曲强度和弯曲模量为最小值,断裂伸长率和冲击强度达到最大值.     

Limitation of the Johnson-Mehl-Avrami equation for the kinetic analysis of crystallization in a Ti-based amorphous alloy

The primary crystallization of the Ti40Zr25Ni8Cu9Be18 amorphous alloy was studied by isochronal differential scanning calorimetry (DSC). The activation energy was determined by the Kissinger-Akahira-Sunose method. Trying to analyze the crystallization kinetics of the Ti40Zr25Ni8Cu9Bei8 amorphous alloy by two different methods, it was found that the crystallization kinetics did not obey the John-son-Meh1-Avrami equation. A modified method in consideration of the impingement effect was proposed to perform kinetic analysis of the isochronal crystallization of this alloy. The kinetic parameters were then obtained by the linear fitting method based on the modified kinetic equation. The results show that the isochronal crystallization kinetics of the amorphous Ti40Zr25Ni8Cu9Be18 alloy is heating rate dependent, and the discrepancy between the Johnson-Meh1-Avrami method and the modified method increases with the increase of heating rate.     

Non-isothermal melt crystallization kinetics of anhydrite-filled polypropylene composites

The non-isothermal crystallization kinetics of polypropylene (PP), PP/anhydrite composites were investigated by differential scanning calorimetry (DSC) with various cooling rates. The Avrami analysis modified by Jeziorny and a method developed by Mo were employed to describe the non-isothermal crystallization process of these samples. The difference in the exponent n between PP and PP/anhydrite composites indicated that non-isothermal kinetic crystallization corresponded to tri-dimensional growth with heterogeneous nucleation. The values of half-time, Z _c and F(T) showed that the crystallization rate increased with the increasing of cooling rates for PP and PP/anhydrite composites, but the crystallization rate of PP/anhydrite composites was faster than that of PP at a given cooling rate. The method developed by Ozawa did not describe the non-isothermal crystallization process of PP very well. Moreover, the method proposed by Kissinger was used to evaluate the activation energy of the mentioned samples. The result showed that the activation energy of PP/anhydrite was greatly larger than that of PP.