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.     

Synthesis and properties of homogeneously dispersed polyamide 6/MWNTs nanocomposites via simultaneous in situ anionic ring‐opening polymerization and compatibilization

Toluene 2, 4‐diisocyanate (TDI) functionalized multiwalled carbon nanotubes (MWNTs‐NCO) were used to prepare monomer casting polyamide 6 (MCPA6)/MWNTs nanocomposites via in situ anionic ring‐opening polymerization (AROP). Isocyanate groups of MWNTs‐NCO could serve as AROP activators of ?‐caprolactam (CL) in the in situ polymerization. Fourier transform infrared (FTIR) showed that a graft copolymer of PA6 and MWNTs was formed in the in situ polymerization. MWNTs‐PA6 covalent bonds of the graft copolymer constituted a strong type of interfacial interaction in the nanocomposites and increased the compatibility of MWNTs and MCPA6 matrix. The nanocomposites were characterized for the morphology, mechanical, crystallization, and thermal properties through field emission transmission electron microscopy (FETEM), tensile testing, differential scanning calorimeter (DSC), and thermogravimetric analysis (TGA). FETEM analysis showed that MWNTs were homogeneously dispersed in MCPA6 matrix. The initial tensile strengths and tensile modulus of the nanocomposite with 1.5 wt % loading of MWNTs were enhanced by about 16 and 13%, respectively, compared with the corresponding values for neat MCPA6. DSC analysis indicated that the crystallization temperature of the nanocomposites was increased by 8°C by adding 1.5 wt % MWNTs compared with pure MCPA6. Besides, it was found that the thermal stability of MCPA6 was improved by the addition of the MWNTs. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

PA6/PPO共混物的非等温结晶动力学

采用差示扫描量热法研究了聚酰胺6/聚苯醚（PA6/PPO）共混物的非等温结晶动力学。通过Jeziorny法、Mo法分别对非等温结晶过程进行处理。结果表明,PPO对PA6结晶起促进作用,而马来酸酐接枝聚苯醚（PPO-g-MAH）、氢化聚苯乙烯-丁二烯-苯乙烯嵌段共聚物（SEBS）和SEBS-g-MAH对PA6的结晶起阻碍作用;随着冷却速率的增大,共混物的结晶度下降,半结晶时间减小;Jeziorny和Mo法都适合分析PPO/PA6的非等温结晶过程。     

Non-isothermal crystallization kinetics of poly (lactic acid)/modified carbon black composite

A novel method was employed to modify the surface of carbon black (CB) by an organic small molecule in a Haake Rheomix mixer. Jeziorny equation, the Ozawa model and Mo equation were employed to describe the non-isothermal crystallization process of poly (lactic acid) (PLA), PLA/CB and PLA/modified carbon black (MCB) composites. It is found that the Ozawa model fail to describe the non-isothermal crystallization process for PLA and its composites, while Jeziorny equation and Mo’s theory provide a good fitting. The comparison of crystallization kinetics between PLA/MCB and PLA through Lauritzen–Hoffman model indicates that there appears a transition from regimes II to III in PLA and PLA/MCB. The fold surface free energy σ _e of PLA/MCB composite is higher than that of neat PLA, implying that the existence of nucleating agent is unfavorable for the regular folding of the molecule chain.     

Non-isothermal crystallization kinetics of poly(ethylene terephthalate)/mica composites

The non-isothermal crystallization kinetics of pure poly(ethylene terephthalate) (PET), PET/mica and PET/TiO₂-coated mica composites were investigated by differential scanning calorimetry with different theoretical models, including the modified Avrami method, Ozawa method and Mo method. The activation energies of non-isothermal crystallization were calculated by Kissinger method and Flynn–Wall–Ozawa method. The results show that the modified Avrami equation and Ozawa theory fail to describe the non-isothermal crystallization behavior of all composites, while the Mo model fits the experiment data fair well. It is also found that the mica and TiO₂-coated mica could act as heterogeneous nucleating agent and accelerate the crystallization rates of PET, and the effect of TiO₂-coated mica is stronger than that of mica. The result is further reinforced by calculating the effective activation energy of the non-isothermal crystallization process for all composites using the Kissinger method and the Flynn–Wall–Ozawa method.     

硅灰石填充尼龙-6复合体系的非等温结晶行为及动力学研究

用差示扫描量热法(DSC)考察了硅灰石填充尼龙-6复合体系的非等温结晶行为,并用Avrami以及Mo法研究了其非等温结晶动力学。结果表明,随着降温速率的增加,复合体系的结晶峰变宽并向低温方向移动,结晶速率增加。通过对比,Mo法能很好地描述硅灰石填充尼龙-6复合体系的非等温过程。     

In situ synthesis of polyamide 6/MWNTs nanocomposites by anionic ring opening polymerization

In situ anionic ring opening polymerization is used to prepare monomer casting polyamide 6 (MCPA6)/carbon nanotubes (CNTs) nanocomposites, whereby water is used as auxiliary dispersing agent of hydroxyl functionalized multiwalled carbon nanotubes (MWNTs‐OH) and ε‐caprolactam (CL) monomer. The MWNTs‐OH were dispersed homogenously in MCPA6 matrix when being observed through transmission electron microcopy. The well dispersed MWNTs‐OH existed at the center of many radial texture phases in MCPA6 matrix. Polarizing microscope analysis showed that these radial texture phases were MCPA6 spherulitic crystallities. Differential scanning calorimetry analysis revealed that the crystallization temperature of the MCPA6/MWNTs‐OH nanocomposites had been improved by adding only 0.2 wt % MWNTs‐OH when compared with pure MCPA6. The influence of MWNTs‐OH on the thermal stability of MCPA6 under nitrogen and air environments was also investigated by thermal gravimetric analysis (TGA). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Nonisothermal crystallization behavior and mechanical properties of poly(butylene succinate)/silica nanocomposites

Silica nanoparticles and poly(butylene succinate) (PBS) nanocomposites were prepared by a melt‐blending process. The influence of silica nanoparticles on the nonisothermal crystallization behavior, crystal structure, and mechanical properties of the PBS/silica nanocomposites was investigated. The crystallization peak temperature of the PBS/silica nanocomposites was higher than that of neat PBS at various cooling rates. The half‐time of crystallization decreased with increasing silica loading; this indicated the nucleating role of silica nanoparticles. The nonisothermal crystallization data were analyzed by the Ozawa, Avrami, and Mo methods. The validity of kinetics models on the nonisothermal crystallization process of the PBS/silica nanocomposites is discussed. The approach developed by Mo successfully described the nonisothermal crystallization process of the PBS and its nanocomposites. A study of the nucleation activity revealed that the silica nanoparticles had a good nucleation effect on PBS. The crystallization activation energy calculated by Kissinger's method increased with increasing silica content. The modulus and yield strength were enhanced with the addition of silica nanoparticles into the PBS matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

原位聚合制备PBT/nano-ZnO复合材料及其结晶性能研究

以精对苯二甲酸（PTA）和1,4-丁二醇（BDO）为基本原料,在5 L熔融缩聚反应釜中,采用原位聚合工艺,通过加入自制纳米氧化锌（nano-ZnO）,制备得到聚对苯二甲酸丁二醇酯（PBT）/nano-ZnO复合材料。采用差示扫描量热仪对PBT/nano-ZnO复合材料的结晶性能进行测试,并研究了复合材料的非等温结晶行为。结果表明,加入nano-ZnO后,不影响PBT的聚合工艺,nano-ZnO对PBT有异相成核作用;Jeziorny法可以很好地分析PBT及其复合材料的非等温结晶过程。     

纳米二氧化硅／MC尼龙6原位复合材料非等温结晶动力学

通过阴离子开环聚合法制各纳米二氧化硅／MC尼龙6原位复合材料,采用差示扫描量热法研究MC尼龙6及其原位纳米复合材料非等温结品行为,并利用修正Avrami方程的Jeziomy和Liu的方法进一步处理原位纳米复合材料的非等温结晶动力学,结果表明在纳米二氧化硅／MC尼龙6原位复合材料中,纳米二氧化硅对基体MC尼龙6的结晶有一定的成核作用,并提高了其结品速率。     

硫酸钙晶须及硅灰石纤维填充PA6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)研究了尼龙6(PA6)及其两种复合材料的非等温结晶行为,分别采用Jeziorny法和Mo法对非等温结晶动力学进行了分析,经计算得到相应的非等温结晶动力学参数。结果表明,硫酸钙晶须和硅灰石纤维的加入都能降低复合材料体系的结晶温度;硅灰石纤维的加入可以很好的促进PA6复合材料的结晶,有效的提高体系的结晶速率,而相同含量的硫酸钙晶须对PA6复合材料有一定的阻碍作用,降低了体系的结晶速率。     

原位增容PA6/PE-HD共混物的非等温结晶动力学研究

利用差示扫描量热仪研究了原位增容的聚酰胺6/高密度聚乙烯（PA6/PE-HD）共混物的非等温结晶过程,用经Jeziorny 修正的Avrami方程和Mo法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,该方程和方法适合于处理纯PA和PA6/PE-HD共混物的非等温结晶过程;在PA6/PE-HD共混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,并且PE-HD的加入,起到异相成核的作用,促进了晶核的生长。此外, 还利用Vyazovkin的方法求出PA6/PE-HD共混物结晶活化能与温度之间的关系。     

Non-isothermal crystallization kinetics of polypropylene/MAP-POSS nanocomposites

Non-isothermal crystallization kinetics of polypropylene (PP)/methylacryloypropy polyhedral oligomeric silsesquioxanes (MAP-POSS) nanocomposites (PP/MAP-POSS) were investigated by DSC at various cooling rates. Jeziorny and Mo method were used to study the non-isothermal crystallization kinetics. The results show that the Jeziorny and Mo method are all successful in describing the non-isothermal crystallization kinetics of PP/MAP-POSS nanocomposites. The MAP-POSS can act a role of heterogeneous nucleation and increase the crystallization rate constant Z _c and decrease crystallization half time t _1/2, and the spherulite crystal size decreases, the inter-spherulitic action or crosslinking structure each other appear at the appropriate content. The DSC peak temperature T _p increase about 5 °C, t _1/2 reduce 0.21 min at 6 % content of MAP-POSS and heating rate of 10 °C/min. The MAP-POSS can also increase the mechanical property of PP/MAP-POSS nanocomposites, the tensile strength and impact strength increase from 12.97 to 19.93 MPa and from 33.2 to 52.6 kJ/m², respectively, at 4 % content of MAP-POSS. But the spherulitic crystal becomes larger and boundaries become clearer again; the macrophase separation will occur and mechanical properties decrease when more and more MAP-POSS was added. The nanocomposite has the best mechanical property at 4 % content of MAP-POSS.     

Non-isothermal crystallization kinetics of TiO2 nanoparticle-filled poly(ethylene terephthalate) with structural and chemical properties

The present research work includes non-isothermal crystallization kinetics of poly(ethylene terephthalate) (PET)–titanium dioxide (TiO₂) nanocomposites as well as structural and chemical properties of these nanocomposites. The average grain size of chemically synthesized TiO₂ nanoparticles has been calculated 19.31 nm by TEM and XRD. The morphology and structural analysis of PET–TiO₂ nanocomposites, prepared via solution casting method, has been investigated using SEM and XRD, respectively. The nature of chemical bonds has been discussed on the basis of FTIR spectra. The effect of TiO₂ nanoparticles and cooling rates on non-isothermal crystallization kinetics of PET was examined by differential scanning calorimetry at various heating and cooling rates. It has been observed that TiO₂ nanoparticles accelerate the heterogeneous nucleation in PET matrix. The crystallization kinetics could be explained through Avrami–Ozawa combined theory. TiO₂ nanoparticles cause to make molecular chains of PET easier to crystallize and accelerate the crystallization rates during non-isothermal crystallization process; this conclusion has also been verified by Kissinger model for crystallization activation energy.     

Crystallization kinetics study of dynamically vulcanized PA6/NBR/HNTs nanocomposites by nonisothermal differential scanning calorimetry

Investigation of crystallization behavior and kinetics of thermoplastic elastomer nanocomposites was the subject of limited works because of complexities associated with semiexperimental modeling of such phenomenon in a system containing components having completely different behavior in the molten state. Nonisothermal crystallization kinetics of dynamically vulcanized PA6/NBR/HNTs thermoplastic elastomer nanocomposites was mathematically modeled applying well‐known Avrami, Ozawa, and Mo theoretical models to the differential scanning calorimetry data gathered at various cooling rates. It was found that HNTs contribute as nucleating agents to the crystallization kinetics and cause acceleration of crystallization. Activation energy of the crystallization was calculated by correlating the crystallization peak temperature with the cooling rate using Kissinger model. It was found that Mo equation could properly describe nonisothermal crystallization kinetics of the PA6/NBR/HNTs thermoplastic elastomer nanocomposites. This was recognized from the obtained parameters of Mo equation in terms of HNTs loading level, which suggested a higher rate for dynamic crystallization. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46488.     

可熔融加工聚乙烯醇的非等温结晶分析

通过差示扫描量热法(DSC)测试了成核剂对可熔融加工改性聚乙烯醇(PVA)结晶行为的影响,并在DSC的基础上用Ozawa法、Jeziorny法以及莫志深方法分析了改性PVA以及改性PVA/成核剂两种材料的非等温结晶动力学。结果表明:结晶度、结晶峰温度、结晶半衰期、结晶速率对降温速率有很强的依赖性;随着降温速率的增加,结晶速率常数增大,结晶度提高;在相同的降温速率下,复合体系的结晶速率常数较大,即成核剂的加入使改性PVA的结晶速率增加,具有异相成核的作用;其中莫志深方法能够较好地解释改性PVA的非等温结晶过程。     

杜仲胶与合成反式-1,4-聚异戊二烯非等温结晶性能对比

本文首先通过红外光谱(IR)、核磁共振(1H-NMR)和渗透凝胶色谱(GPC)等测试手段表征了本实验选用的杜仲胶(EUG)和合成反式-1,4-聚异戊二烯(TPI)的化学组成和结构差异,进而采用差示扫描量热仪(DSC)和偏光显微镜(POM)分别测试了EUG和TPI的非等温结晶行为,Mo法研究了两者的非等温结晶动力学并进行了对比。结果表明,Mo法处理EUG和TPI的非等温结晶过程较为理想。非等温结晶动力学研究得到的t1/2和FT等结晶参数表明,随降温速率的增加,EUG和TPI的结晶速率增大,EUG结晶速率快于TPI。根据Kissinger方程求得EUG的结晶活化能为102.8 kJ/mol,TPI为97.4 kJ/mol。这些非定温结晶性能的差异主要来源于二者不同的合成机理所造成的杂质种类、分子链端基以及分子量分布的不同。     

不同相对黏度PA6的非等温结晶动力学研究

以相对黏度(ηr)为2.0,2.4,2.8,3.4,4.0的5种聚酰胺6(PA6)切片为研究对象,采用差示扫描量热法测试其在不同冷却速率(?)下的非等温结晶过程;基于Jeziorny法和Mo法对不同 ηr的PA6的非等温结晶动力学进行对比分析,并采用Kissinger法计算其结晶活化能(△E).结果表明:PA6的 ηr...     

PBT/PTT合金的非等温结晶行为

采用差示扫描量热法(DSC)研究了聚对苯二甲酸丁二酯(PBT)/聚对苯二甲酸丙二酯(PTT)合金的非等温结晶动力学.随着降温速率的增大,PBT/PTT合金的结晶峰温均降低,结晶峰均加宽.采用Jeziorny法、莫志深法和Flyn-Wall-Ozawa法分析非等温结晶过程,Jeziorny法能够描述PBT/PTT合金的初期结晶过程,对后期结晶存在一定偏差,各PBT/PTT合金的结晶维数变化不大;莫志深和Flyn-Wall-Ozawa法能很好地描述PBT/PTT合金的非等温结晶过程,随PTT含量增加,由Flyn-Wall-Ozawa法求得PBT/PTT合金的活化能呈增加趋势.相对结晶度为0.5,m(PBT)/m(PTT)分别为90∶10,70∶30,50∶50时,PBT/PTT合金的活化能分别为-201.9,-116,0,-66.6 kJ/mol;相对结晶度为0.5时,m(PBT)/m(PTT)为50∶50的合金活化能比PTT(-77.4 kJ/mol)还高.