聚酰胺11/白炭黑纳米复合材料的非等温结晶动力学研究

采用原位聚合法制备了聚酰胺11（PA11）及PA11/白炭黑纳米复合材料,利用差示扫描量热仪研究了PA11及其纳米复合材料的非等温结晶过程,用经Jeziorny修正的Avrami方程、Mo法对其非等温结晶动力学进行了研究,计算并得到了非等温结晶动力学参数。结果表明,Avrami方程和Mo法都适用于处理PA11及其纳米复合材料的非等温结晶过程;在其非等温结晶过程中,PA11及其纳米复合材料都包括初期结晶和二次结晶两个阶段;Mo法表明,复合材料的结晶速率比PA11的小。此外,用Huffman-Lauritzen理论计算了PA11及其纳米复合材料非等温结晶的结晶活化能,结果表明,纳米复合材料的结晶活化能的绝对值小于PA11。     

PA6/硅灰石纤维复合材料的非等温结晶动力学研究

采用差示扫描量热法(DSC)研究了PA6/硅灰石纤维复合材料的非等温结晶行为,分别采用Jeziorny法、Ozawa法和Mo法对非等温结晶动力学进行了分析,经过计算得到相应的非等温结晶动力学参数。结果表明:复合材料的结晶分为初期结晶阶段和二次结晶阶段,随着降温速率的增大,结晶温度降低,结晶温度范围变大,结晶速率增大。Jeziorny法和Mo法能较好地描述复合材料的非等温结晶过程,而Ozawa法不适合描述该过程。     

MCPA6/纳米TiO2原位复合材料的熔融行为

采用差示扫描量热法(DSC)研究了铸型尼龙6(MCPA6)及其纳米TiO2原位复合材料的等温结晶与非等温结晶晶体的熔融行为。结果表明：MCPA6／纳米TiO2原位复合材料等温结晶晶体的熔融行为呈现三重熔融峰,非等温结晶晶体的熔融行为呈现二重熔融峰;其高温熔融峰温随等温结晶温度或降温速率的变化基本不变,而低温熔融峰温则随等温结晶温度的升高或降温速率的减小而提高;纳米TiO2的加入对MCPA6有一定的成核作用,使其熔点提高。     

TPU和纳米SiO2改性聚丙烯的非等温结晶动力学

采用示差扫描量热法研究PP、PP/TPU、PP/TPU/纳米SiO2复合材料的非等温结晶动力学.采用 Jeziorny法、Ozawa法和莫志深法研究结晶动力学参数.研究发现Ozawa法不适合处理PP及其复合材料的非等温结晶行为,而Jeziorny法和莫志深法则能很好处理.结果表明:TPU和纳米SiO2起到异相成核的作用,使PP的结晶峰温升高,结晶速率加快.TPU和纳米粒子的填充使PP的结晶活化能增大.     

聚酰胺6/可反应性纳米SiO2复合材料的非等温结晶动力学

通过双螺杆挤出机制备出聚酰胺（PA）6/可反应性纳米SiO2（RNS）复合材料,并采用Jeziorny法和Mo法对其非等温结晶行为进行了研究。结果表明,RNS具有较强的异相成核能力,能提高PA6的结晶速率,并使其晶体结构和生长机制发生改变。通过对比纯PA66及其复合材料的结晶活化能还发现,RNS能够降低PA66的结晶活化能。     

PA6/HBPA共混物的非等温结晶动力学研究

采用熔融共混法制备了聚酰胺6/含磷超支化聚酰胺(PA6/HBPA)共混物。通过差示扫描量热法(DSC)考察了该共混物的非等温结晶行为,并利用改进Avrami方程的Jeziorny法、Ozawa法和Mo法对DSC测试结果进行了非等温结晶动力学分析。结果表明:当HBPA用量为2%时,PA6基体的结晶度和结晶速率均有所提高,而进一步增大HBPA用量则会对PA6的结晶产生阻碍作用,致使结晶速率降低。另外,Ozawa法不适于描述PA6/HBPA共混物的非等温结晶动力学,Jeziorny法则仅适用于PA6/HBPA的结晶初期和中期,而Mo法很好地描述了PA6/HBPA共混物的非等温结晶行为,因而可用于PA6/HBPA的非等温结晶动力学分析。     

聚丙烯/纳米碳酸钙原位聚合复合材料非等温结晶动力学研究

用原位聚合复合法制备PP/纳米CaCO3复合材料,用DSC法研究了不同纳米粒子含量的等速结晶性能和非等温结晶行为。对所得数据分别用修正Avrami方程的Ozawa法和Mo法进行处理,表明Mo法处理PP/CaCO3纳米复合材料非等温结晶过程比较理想。Mo法所得的参数F(T)随结晶度的增加而增大,a随结晶度的增加而增大,但幅度不大。表明降温速率越快,单位结晶时间达到的结晶度越高,各降温速率下的结晶方式基本不变。等速结晶研究表明,纳米碳酸钙的加入起到了结晶成核剂作用。用Kissinger方法计算出PP/纳米CaCO3原位复合材料的活化能为202 4kJ/mol。     

PA11/白炭黑纳米复合材料非等温结晶动力学研究

采用原位聚合法制备了聚酰胺(PA)11/白炭黑纳米复合材料,利用差示扫描量热仪研究了PA11纳米复合材料的非等温结晶过程,用经Jeziorny修正的Avrami方程、Mo法对其非等温结晶动力学进行了分析,计算并得到了非等温结晶动力学参数。结果表明,Avrami方程、Mo法都适用于处理PA11及其纳米复合材料的非等温结晶过程;在非等温结晶过程中,PA11及其纳米复合材料都包括初期结晶和二次结晶两个阶段;Avrami方程和Mo法表明,白炭黑含量较低时可提高复合材料的结晶速率,含量过高时则阻碍晶体的生长。     

PA66/可反应性纳米SiO_2复合材料的非等温结晶动力学

通过双螺杆挤出机制备出聚酰胺(PA)66/可反应性纳米SiO2(RNS)复合材料,采用Jeziorny法和Mo法对其非等温结晶行为进行了研究。结果表明,RNS具有较强的异相成核能力,能提高PA66的结晶速率,并使PA66的晶体结构和生长机制发生改变;通过对比PA66及其复合材料的结晶活化能发现RNS能够降低PA66的结晶活化能。     

聚甲醛／共聚酰胺共混物的非等温结晶动力学研究

采用差示扫描量热法（DSC）研究了聚甲醛（POM）和聚甲醛／共聚酰胺（POM／CADPA）二元共混体系在不同降温速率下的非等温结晶行为，并用Jeziomy法、Ozawa法和莫志深法计算了聚甲醛及其共混物的非等温结晶动力学参数。结果表明：提高降温速率，POM和POM／COPA共混物的结晶峰均向低温方向移动，且结晶放热峰逐渐变宽；COPA的加入使POM的结晶温度提高、结晶速率加快，在体系中起到了异相成核的作用；Jeziomy法和莫志深法处理该体系的非等温结晶过程比Ozawa法更为合适。     

聚酰胺612的非等温结晶动力学研究

采用差示扫描量热仪研究了聚酞胺612在不同降温速率下的非等温结晶行为,并用Jeziorny法、Ozawa法和莫志深法对DSC测试数据进行了处理。结果表明,随降温速率的增加,其结晶峰从高温向低温方向移动,峰形变宽,结晶时间缩短,结晶加快。聚酚胺612的非等温结晶动力学能较好地符合莫志深法和Jeziomy法。采用Kissinger方程计算出聚酞胺612的非等温结晶活化能为293.0U/mol。     

NONISOTHERMAL CRYSTALLIZATION KINETICS AND MECHANICAL PROPERTIES OF PP/NANO-SiO2 COMPOSITES

The nonisothermal crystallization kinetics of polypropylene (PP)/nano-SiO₂ composites was studied by means of differential scanning calorimetry (DSC). The modified Avrami theories by Jeziorny, Ozawa, and Mo were used to analyze the data of DSC. The results showed that both the Jeziorny and Mo methods could describe this system very well, but the Ozawa analysis failed. The activation energy was evaluated by the Kissinger method. It was found that the crystallization activation energy of PP was higher than that of PP/nano-SiO₂ composites. The determined results of mechanical properties showed that the addition of nano-SiO₂ increased the mechanical properties of the PP. Micrographs of Polarized optical micrograph (POM) further demonstrated that nano-SiO₂ could toughen the PP.     

La_2O_3/LDPE复合材料非等温结晶性能研究

利用差示扫描量热仪(DSC)考察了氧化镧(La2O3)/低密度聚乙烯(LDPE)复合材料的非等温结晶行为。通过Jeziorny法、Ozawa法及莫志深法研究了复合材料的非等温结晶动力学。结果表明:在添加La2O3后,LDPE成核速率降低,结晶度下降,晶体粒径分布变宽。在非等温结晶动力学分析中,Jeziorny法lg[-ln(1-Xt)]～lgt关系曲线在结晶前期和中期具有较好的线性关系,结晶后期产生较大偏离;Ozawa法并不适用;而莫志深法适用于该体系的研究,表明La2O3的加入使LDPE结晶速率增大。     

POM /TPU共混物非等温结晶动力学研究

采用差示扫描量热法(DSC}研究了不同冷却速率下聚甲醛( POM)以及POM/热塑性聚氨酷弹性体(TPU)共混物的非等温结晶过程,分别采用Jeziorny法、Ozawa法和Mo法进行处理。结果表明:随着冷却速率的增大,POM及其共混物的结晶峰都变宽,结晶峰值温度(Tc)都降低;在相同冷却速率下,POM /TPU共混物的Tc。较纯POM有所提高;Jeziorny法和Mo法处理非等温结晶过程比较理想,而由于次级结晶的存在Ozawa法并不适用;Jeziorny法和Mo法处理所得的数据表明,TPU的加人能够提高POM的结晶速率,减小半结晶时间(t1/2),并且导致POM的结晶成核和生长发生了改变。     

Investigations of the Non-Isothermal Crystallization Behavior of Polyamide 6/Polyethylene-Octene/Organomontmorillonite Nanocomposites

The crystallization behavior of polyamide 6/polyethylene-octene/organomontmoril- lonite (PA 6/POE/OMMT) nanocomposites fabricated via melting intercalation route was investigated using differential scanning calorimeter (DSC). The crystallization kinetics under non-isothermal conditions was analyzed by Jeziorny method and Mo method, and the crystallization kinetics parameters were obtained. It was found that nano-clay acted as a heterogeneous nucleation agent and the semi-crystallization time was prolonged with the OMMT loading increasing. The activation energy for non-isothermal crystallization of such nanocomposites was calculated according to the Huffman-Lauritzen theory. The average size of the composite nanocrystals was reduced with introduction of OMMT to the synthetic system.     

Nonisothermal Crystallization and Melting Behaviors of PP/PA6/TiO2 Nanocomposites

Titanium dioxide nanoparticles were functionalized with toluene-2,4-diisocyanate and then polypropylene/polyamide 6 blends containing functionalized titanium dioxide were prepared using a twin-screw extruder. The nonisothermal crystallization and melting behaviors of the as-prepared nanocomposites were investigated using differential scanning calorimetry. The nonisothermal crystallization differential scanning calorimetry data were analyzed by the modified-Avrami (Jeziorny) and combination of Ozawa and Avrami (Mo) methods. It can be found that the Jeziorny method can be used to describe the main crystallization process, and the Mo method can better deal with nonisothermal crystallization kinetics of the polypropylene and polyamide 6 phase in polypropylene/polyamide 6-based nanocomposites. The nonisothermal crystallization analysis shows that the titanium dioxide nanoparticles have two effects on polypropylene/polyamide 6 blends, i.e., it can favor the improvement of crystallization ability and decrease the crystallization rate of the polypropylene and polyamide 6 phase in polypropylene/polyamide 6-based nanocomposites. For one thing, the functionalized titanium dioxide nanoparticles in the polypropylene/polyamide 6-based nanocomposites act as effective nucleation agents and result in higher crystallization temperature (T₀) than that of the polypropylene and polyamide 6 in pure polypropylene/polyamide 6 blends, which indicated titanium dioxide nanoparticles favor the improvement of crystallization ability of the polypropylene and polyamide 6 phase. For another, the existence of functionalized titanium dioxide nanoparticles hinders the free movement of polymer chains and results in lower crystallinity than that of the polypropylene and polyamide 6 in pure polypropylene/polyamide 6 blends, which indicated titanium dioxide nanoparticles decrease the crystallization rate of the polypropylene and polyamide 6 phase in polypropylene/polyamide 6-based nanocomposites. The nonisothermal crystallization melting behaviors show that there is single or double melting peak, which varies with different cooling rates for the polyamide 6 phase in polypropylene/polyamide 6-based nanocomposites. Multiple melting peak is mainly caused by the different crystalline structure of the polyamide 6 phase, the melting peak I is mainly caused by γ crystal of the polyamide 6 phase, while the melting peak II corresponds to the thermodynamic stability of α crystal. Besides, the recrystallization of the polyamide 6 phase in the heating process, and the effect of the incorporation of the titanium dioxide nanoparticles may have some contributions to the appeared multiple melting peak of the polyamide 6 phase in the polypropylene/polyamide 6-based nanocomposites.     

LLDPE/粉煤灰复合材料非等温结晶动力学研究简

利用差示扫描量热法（DSC）结合Avrami方程研究了线性低密度聚乙烯（LLDPE）、LLDPE/Fly Ash（粉煤灰）的非等温结晶动力学.通过Jeziomy法、Ozawa法和莫志深法分别对非等温结晶过程进行处理,采用Kissinger法和Takhor法得到迁移活化能.结果显示,粉煤灰粉体的加入阻碍了LLDPE分子链的规则排列,影响了链段的结晶扩散迁移规整排列,使LLDPE的结晶速率变慢,对LLDPE晶体生长起了抑制作用.由Ozawa法分析实验数据,得到的线性关系很差,因此也很难得到可靠的动力学参数.在所有结晶速率下,样品的Avrami指数n值在1.42 ～2.09之间变化,说明粉煤灰的加入对LLDPE的成核与生长方式的影响有限.用莫志深法得出的结论与Jeziorny法一致,b值在0.76～1.13之间变化.     

Non-isothermal crystallization kinetic and compatibility of PTT/PP blends by using maleic anhydride grafted polypropylene as compatibilizer

The crystallization behaviors, non-isothermal crystallization kinetics, and the morphology of poly(trimethylene terephthalate)/Polypropylene (PTT/PP) blends using a maleic anhydride grafted polypropylene (PP-g-MAH) as a compatibilizer were investigated by differential scanning calorimeter (DSC) and scanning electron microscope (SEM), respectively. The results suggested that the blends exhibited different crystallization and melting behaviors due to different content of PP-g-MAH. All of the DSC curves of the blends exhibited two exothermic peaks and endothermic peaks. The commonly used Avrami equation modified by Jeziorny, Ozawa theory and the method developed by Mo were used, respectively, to fit the primary stage of non-isothermal crystallization process. The results suggested that the crystallization rate of PTT component was increased, whereas, that of PP component was retarded with the introduction of PP-g-MAH. The effective activation energy was calculated by differential iso-conversional method developed by Vyazovkin. The SEM result suggested that the introduction of PP-g-MAH greatly improved the compatibility between PTT and PP, and decreased the size of dispersed particles.     

半芳香族聚酰胺6T/6I/6的合成及其非等温结晶动力学研究

采用成盐、高温溶液缩聚两步法成功制备了半芳香族聚酰胺（PA）6T/6I/6。通过傅里叶变换红外光谱（FTIR）、氢核磁共振（¹H⁃NMR）分析了其分子链结构,并对其力学性能进行了测试表征,利用差示扫描量热法（DSC）对PA6T/6I/6的非等温结晶动力学进行了研究,使用Jeziorny法、Oazawa法和莫志深法修正的Avrami方程分别分析了PA6T/6I/6的非等温结晶行为。结果表明,通过Jeziorny法处理发现结晶过程分为主期结晶和次期结晶2个阶段,主期结晶阶段Avrami指数在1.08~1.09之间,晶体为异相成核,呈一维针状生长,次期结晶阶段Avrami指数在2.13~2.21之间,晶体为二维片状生长方式;Ozawa法处理曲线相关性低,表明不适用于描述PA6T/6I/6的非等温结晶过程;莫志深法修正的Avrami方程能较好地描述结晶过程,a值在0.89~0.90之间,F（T）值在7.24~15.85之间;采用Kissinger方程计算求得PA6T/6I/6的非等温结晶活化能为-294.17 kJ/mol。     

s-PB/TPI釜内原位聚合共混物的非等温结晶动力学

采用2种负载型催化体系在反应釜内原位合成了间同聚丁二烯（s-PB）及s-PB/反式-1,4-聚异戊二烯（TPI）（80/20）共混物。用DSC方法研究了s-PB及共混物的非等温结晶行为,结果表明：Jeziorny修正的Avrami法和Mo法对s-PB及s-PB/TPI（80/20）共混物的非等温结晶行为有较好的适用性,Ozawa法则存在一定的缺陷。s-PB及其共混物的结晶活化能分别为-253 kJ/mol和-310 kJ/mol。TPI的加入降低了s-PB的结晶速率,使得共混物的结晶活化能绝对值增大。