PTT/MMT纳米复合材料的研究

采用熔融共混的方法制备了聚对苯二甲酸丙二醇酯/有机蒙脱土（PTT/MMT）纳米复合材料,通过DSC、热台偏光显微镜等研究了PTT/MMT纳米复合材料的结晶行为,测定了纳米复合材料的力学性能,并用熔体流变仪研究了PTT/MMT纳米复合材料熔体流变性能。结果表明：随着PTT/MMT纳米复合材料中蒙脱上含量的增加,PTT/MMT纳米复合材料的熔融结晶温度增高,纳米复合材料的力学性能有一定的提高;PTT-蒙脱土纳米复合材料熔体的流变性能随MMT含量的增加非牛顿性减弱,熔体的粘流活化能减小。     

PP／POE／纳米CaCO3复合材料流变性能的研究

研究了聚丙烯/聚烯烃热塑性弹性体/纳米CaCO3(PP/POE/纳米CaCO3)复合材料的流变性能,探讨了纳米CaCO3、POE添加量、剪切速率和温度对复合材料黏度的影响。实验数据显示,在较低剪切速率下,随纳米CaCO3添加量的增加,体系熔体黏度增加;在较高剪切速率下,随纳米CaCO3添加量的增加,体系黏度降低;增加POE添加量,复合体系的熔体黏度增大;纳米CaCO3的加入使复合体系的非牛顿指数减小,非牛顿性增强。PP/POE/纳米CaCO3(100/10/10质量份数,下同)体系具有高流动性,熔体流动速率达19.58g/10min。     

ABS／纳米CaCO3复合材料流变性能的研究

采用双螺杆挤出机，通过熔融共混工艺制备了丙烯腈-丁二烯-苯乙烯共聚物／纳米碳酸钙（ABS／nano-CaCO3）复合材料，利用转矩流变仪研究了其流变行为，探讨了nano-CaCO3用量、剪切速率和温度对复合材料黏度的影响。实验数据显示：ABS／nano-CaCO3熔体为假塑性流体，非牛顿指数n〈1；适量加入nano-CaCO3使复合体系熔体的n值增加，“柱塞流动”现象降低；在低剪切速率下，ABS／nano-CaCO3复合体系的熔体黏度较纯ABS熔体低；在高剪切速率下,复合体系的熔体黏度较纯ABS熔体高。     

PTT/mPE共混物的制备和性能研究

研究了聚对苯二甲酸丙二酯(PTT)/茂金属聚乙烯(mPE)共混体系的流变性能、结晶熔融行为、力学性能以及增容剂对共混物相形态的影响。结果表明：PTT/mPE共混物熔体为假塑性流体,熔体表观黏度随PTT含量的增加而迅速降低,PTT含量高于40％时共混物表观黏度迅速下降,PTT含量越多对温度变化的敏感性越强。PTT和mPE可分别结晶,但PTT组分的结晶峰温度Tpc和结晶熔融峰温度Tm均比纯PTT的明显提高,而mPE组分的Tpc和Tm与纯mPE的相近,mPE可以促进PTT熔体结晶,但已经形成的PTT晶体不影响mPE的结晶,mPE的结晶行为主要发生在mPE微相区内。增容剂马来酸酐接枝乙丙橡胶提高了PTT与mPE间的相容性,共混物的冲击强度随着增容剂的增加而提高,mPE和增容剂共同发挥了增韧作用。     

玻纤增强PTT复合材料流变性能研究

通过熔融共混挤出制备加入不同玻纤(GF)和硅烷偶联剂的玻纤增强聚对苯二甲酸丙二醇酯(PTT)复合材料,并用扫描电镜(SEM)观察玻纤与PTT树脂基体的界面黏结形态,用毛细管流变仪研究了不同温度条件下玻纤增强PTT复合材料熔体的流变性能,得到了熔体流变性能关系曲线。实验结果表明：复合材料的流变行为符合假塑性流体的流动规律。随着玻纤的增加,复合材料的黏度增大、非牛顿指数变小、黏流活化能变大；偶联剂的加入,使熔体黏度变大、非牛顿指数变小、黏流活化能变小。     

PET-PTT共聚酯的流变性能

利用毛细管流变仪研究了聚对苯二甲酸乙二酯(PET)-聚对苯二甲酸丙二酯(PTT)共聚酯(简称PETT)熔体的剪切流动性能,且与对应纯组分的流变性能进行了比较.结果表明:PETT熔体属于非牛顿流体,在相同温度下,PETT的剪切速率和黏度均小于纯PTT的值,且均随PTT链段含量的增加而减小.PETT的非牛顿指数和结构黏度指数均小于纯PTT.在相同剪切速率下,PETT的黏流活化能介于纯PET和纯PTT之间,且随PTT链段含量的增加而减小.     

关于纳米蒙脱土影响聚己内酰胺结晶行为及流变行为的研究

通过双螺杆挤出机熔融挤出生产有机改性纳米蒙脱土(MMT)增强聚己内酰胺(PA6)。使用差示扫描量热仪开展自成核试验及非等温结晶行为研究,了解纳米MMT含量对PA6结晶行为的影响,结果表明:少量的纳米MMT可以明显提高成核效率和结晶速率,但继续增加纳米MMT会抑制PA6结晶生长,降低结晶速率和结晶度。使用广角X射线衍射仪研究PA6的结晶行为,结果表明:纯PA6同时存在α及γ晶型,添加纳米MMT的PA6发生α-γ晶型转变,证实纳米MMT与PA6的作用可以改变PA6的结晶行为。使用毛细管流变仪分析纳米MMT含量对PA6熔体受剪切时流变行为的影响,结果表明:纳米MMT含量影响PA6熔体的黏度及非牛顿流体特征,尤其是高纳米MMT含量的PA6在不同剪切速率下表现出明显的黏度变化。     

PTT/MMT纳米复合材料的制备及性能的研究

采用熔融共混的方法制备了聚对苯二甲酸丙二醇蘸/蒙脱土(PTT/MMT)纳米复合材料,并用红外光谱表征了PTT/MMT纳米复合材料的结构.通过DSC、热台偏光显微镜等研究了PTT/MMT纳米复合材料的结晶行为,测定了纳米复合材料的力学性能.结果表明,随着PTT/MMT纳米复合材料中蒙脱土含量的增加,PTT/MMT纳米复合材料的熔融结晶温度增高.其结晶过程为异相成核,纳米复合材料的力学性能有一定的提高.     

双螺杆挤出机螺杆组合对聚丙烯/纳米CaCO3复合材料在线流变性能的影响

采用啮合型同向旋转双螺杆挤出机制备聚丙烯(PP)/纳米碳酸钙(nano-CaCO3)复合材料,制备过程中在双螺杆挤出机末端连接Haake在线流变仪进行在线流变性能测试。研究了两种螺杆组合结构、纳米CaCO3含量对PP/纳米CaCO3复合材料在线剪切黏度的影响,比较了在不同聚合物加工流场下PP/纳米CaCO3复合材料的在线流变性能。结果表明,引入分布混炼有利于降低复合材料的剪切黏度,复合材料剪切黏度随纳米粒子的加入先呈下降趋势,当达到某一含量后,再提高纳米粒子含量会使黏度提高。     

改性埃洛石纳米管/聚丙烯纳米复合材料的制备与性能

采用KH-550硅烷偶联剂对HNTs进行表面改性,通过溶液共混法制备出了m-HNTs/PP纳米复合材料,并对其流变性能、结晶行为、热稳定性能及力学性能进行了深入研究。流变结果表明:m-HNTs/PP纳米复合材料为熔体假塑性流体,且剪切黏度随HNTs质量分数的增加而逐渐增加。DSC结果表明:复合材料的结晶温度呈现先增加后减小的趋势,但都高于纯PP的结晶温度。力学性能测试和TGA结果表明:加入适当质量分数的m-HNTs明显提高了PP基体的力学强度和热稳定性。     

Melting behaviors,isothermal crystallization kinetics,and morphology of poly(trimethylene terephthalate)/stainless steel fiber composites

The melting behavior and crystallization kinetics of poly(trimethylene terephthalate) (PTT)/stainless steel fiber (SSF) composites were investigated with differential scanning calorimetry. The morphology was studied with scanning electron microscopy and polarized optical microscopy. Differential scanning calorimetry analysis revealed that the crystallization temperature increased by 27°C with the addition of 1 vol % SSF to the matrix. The Avrami exponents, analyzed in isothermal crystallization kinetics, were determined to be 2–3 for both neat PTT and PTT/SSF composites. SSF, as a nucleating agent in the composites, greatly increased the crystallization rate. The activation energies of the composites were obviously lower than that of pure PTT, and this indicated much easier crystallization of the composites. All these samples exhibited banded spherulites, and the spherulite size gradually decreased with the SSF loading increasing. Subsequent melting behaviors revealed that all of these samples, especially of the composites, exhibited triple melting peaks at all crystallization temperatures studied. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

纳米CaCO3对FEP非等温结晶动力学的影响

采用熔融共混法制备了聚全氟乙丙烯（FEP）/纳米碳酸钙（nano-CaCO3）复合材料,利用差示扫描量热法研究了FEP及其复合材料的非等温结晶行为,并通过Avrami方程修正的Jeziorny法、Ozawa法以及Mo法对其非等温结晶动力学进行了处理分析。结果表明,Jeziorny法及Mo法均适用于处理FEP和FEP/nano-CaCO3的非等温结晶过程,但Ozawa法不合适;在同一降温速率下,FEP/nano-CaCO3复合材料的初始结晶温度、最大结晶温度均比相应的纯FEP高,且半结晶时间延长,这说明nano-CaCO3对FEP具有一定的诱导和促进成核的作用,但由于FEP/nano-CaCO3复合材料的长链分子结构及大的空间位垒导致FEP的结晶总速率下降。     

聚己内酯/酯化淀粉/纳米碳酸钙复合材料的制备及性能

以玉米淀粉(ST)和马来酸酐为原料,采用干法改性方法制备了酯化淀粉(EST),将EST与聚己内酯(PCL)、纳米碳酸钙通过密炼机混炼制备可降解PCL/EST/纳米碳酸钙复合材料。利用红外光谱仪、扫描电子显微镜、广角X射线衍射仪和热重-差示扫描量热同步热分析仪研究了PCL/EST/纳米碳酸钙复合材料的微观形态、力学性能、结晶以及热性能。结果表明,随着纳米碳酸钙含量的增加,PCL/EST/纳米碳酸钙复合材料的拉伸强度先升高后降低,当纳米碳酸钙含量为6份(质量份数,下同)时材料的拉伸强度和断裂伸长率达到最大值,与未添加纳米碳酸钙的复合材料相比分别提高了49.8%和34.8%;与PCL/ST/纳米碳酸钙复合材料相比,PCL/EST/纳米碳酸钙复合材料中淀粉颗粒尺寸减小,复合材料的熔点和结晶度有所提高,拉伸强度和熔体流动速率增加,热分解温度下降。     

Isothermal crystallization kinetics and melting behaviors of nanocomposites of poly(trimethylene terephthalate) filled with nano‐CaCO3

The isothermal crystallization and subsequent melting behavior of poly(trimethylene terephthalate) (PTT) composites filled with nano‐CaCO₃ were investigated at designated temperatures with differential scanning calorimetry. The Avrami equation was used to fit the isothermal crystallization. The Avrami exponents were determined to be 2–3 for the neat PTT and PTT/CaCO₃ composites. The particles of nano‐CaCO₃, acting as nucleating agents in the composites, accelerated the crystallization rate, with the half‐time of crystallization decreasing or the growth rate constant (involving both nucleation and growth rate parameters) increasing. The crystallization activation energy calculated from the Arrhenius formula was reduced as the nano‐CaCO₃ content increased from 0 to 2%, and this suggested that nano‐CaCO₃ made the molecular chains of PTT easier to crystallize during the isothermal crystallization process. Subsequent melting scans of the isothermally crystallized composites exhibited triple or double melting endotherms: the greater the content was of nano‐CaCO₃, the lower the temperature was of the melting peak. The degree of crystallization deduced from the melt enthalpy of composites with the proper concentration of nano‐CaCO₃ was higher than that of pure PTT, but it was lower when the nano‐CaCO₃ concentration was more than 2%. The transmission electron microscopy pictures suggested that the dispersion state of nano‐CaCO₃ particles in the polymer matrix was even when its concentration was no more than 2%, whereas some agglomeration occurred when its concentration was 4%. Polarized microscopy pictures showed that much smaller or less perfect crystals formed in the composites because of the interaction between the molecular chains and nano‐CaCO₃ particles. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

MPO改性PTT共聚酯熔融结晶行为研究

采用直接酯化熔融缩聚法合成了一系列不同含量的2-甲基-1,3-丙二醇（MPO）改性的共聚酯,并采用差示扫描量热仪（DSC）研究了其熔融结晶行为。结果表明,MPO的加入使聚对苯二甲酸丙二醇酯（PTT）熔点和结晶温度降低,加入摩尔比为20 %的MPO可以使PTT熔点由原来的226.64 ℃降至201.78 ℃,加入摩尔比为10 %的MPO可以使PTT结晶温度由原来的159.01 ℃降至137.50 ℃,同时使半结晶时间(t1/2)增大;随降温速率的提高,各样品的结晶温度向低温方向移动,放热峰由窄变宽,t1/2变小;不同降温速率下,改性共聚酯的结晶速率常数(Zc)比纯PTT的Zc减小。     

Effects of crystalline and orientational memory phenomena on the isothermal bulk crystallization and subsequent melting behavior of poly(trimethylene terephthalate)

The effects of crystalline and orientational memory phenomena on the subsequent isothermal crystallization and subsequent melting behavior of poly(trimethylene terephthalate) (PTT) were investigated by studying the effect of prior melt‐annealing temperature, T_f, on the subsequent isothermal crystallization kinetics, crystalline structure and subsequent melting behavior of neat and sheared PTT samples. On partial melting, choices of the T_f used to melt the samples played an important role in determining their bulk crystallization rates, in which the bulk crystallization rate parameters studied were all found to decrease monotonically with increasing T_f. The decrease in the values of these rate parameters with T_f continued up to a critical T_f value (ie ca 275 °C for neat PTT samples and ca 280 °C for PTT samples which were sheared at shear rates of 92.1 and 245.6 s^?1). Choices of the T_f used to melt neat PTT samples had no effect on the crystal structure formed. The subsequent melting behavior suggested that the T_f used to melt both neat and sheared samples had no effect on the peak positions of the melting endotherms observed and that the observed peak values of these endotherms for all sample types studied were almost identical. Copyright © 2004 Society of Chemical Industry     

IPP/Nano-CaCO_3复合材料的制备及其结晶行为的研究

通过熔融共混,制备了等规聚丙烯(iPP)/纳米碳酸钙(nano-CaCO3)复合材料,研究了不同剪切环境下nano-CaCO3粒子在聚丙烯(PP)基体中的分散性能及其对基体熔融过程的影响,并利用广角X射线散射仪(WAXS)、差示扫描量热仪(DSC)、偏光显微镜(PLM)、扫描电镜(SEM)考察了该复合材料的结晶行为。结果表明:在剪切环境中,nano-CaCO3粒子与基体的摩擦、碰撞几率增加;随着nano-CaCO3用量的增加,体系剪切热升高,加快了基体熔融的速度,并改善了nano-CaCO3的分散效果。当nano-CaCO3用量低于3%时,其在PP基体中起到成核剂的作用,提高了PP的结晶度,并诱导β型晶体的生成;当其用量超过3%时,nano-CaCO3在基体中的分散效果降低,导致粒子团聚,对基体的成核作用降低,进而降低了复合材料的结晶度,并且削弱了粒子对基体的诱导形成β型晶体的能力。     

Effect of Inorganic Filler on the Crystallization,Mechanical Properties and Rheological Behavior of Poly(trimethylene terephthalate)

Poly(trimethylene terephthalate) filled with nano-CaCO₃ and ultra-fine talc was prepared by melt blending using a co-rotating twin screw extruder. The effect of these two inorganic filler on the crystallization and melting behavior, mechanical properties and rheological behavior of PTT were characterized. The DSC results indicated that both nano-CaCO₃ and ultra-fine talc exhibited heterogeneous nucleation effect on the crystallization of PTT, and more significant nucleation effect were observed in PTT/nano-CaCO₃ composite due to the smaller size and better dispersion of nano-CaCO₃ in PTT matrix. Mechanical properties study suggested that the incorporation of nano-CaCO₃ and ultra-fine talc greatly improved the tensile and flexural properties of PTT. Ultra-fine talc tends to lower the impact properties, while nano-CaCO₃ tend to increase the impact strength of the PTT/nano-CaCO₃ composite. When 2 wt.% of nano-CaCO₃ was added, the impact strength increased by one time. Rheological behavior study indicated nano-CaCO₃ exhibited plasticization effect on PTT melt and decreased the viscosity of PTT, while ultra-fine talc increased the viscosity of PTT due to the hindrance of the layer structure of talc.     

Morphological features and crystallization behavior of the conductive composites of poly(trimethylene terephthalate)/graphene nanosheets

Poly(trimethylene terephthalate) (PTT) composites filled with well‐dispersed graphene nanosheets (GNSs) were prepared through a coagulation method. The effects of increased GNS concentration on variations in the structure and properties of the PTT matrix, such as its electrical conductivity, crystallization kinetics, melting behavior, and crystal morphology, were investigated. Several analytical techniques were used, including electrical conductivity measurement, differential scanning calorimetry, Fourier transform infrared spectroscopy, wide‐angle X‐ray diffraction, polarized light microscopy, transmission electron microscopy (TEM), and thermo‐gravimetric analysis (TGA). Electrical conductivity increased from 1.8 × 10^?17 S/cm for neat PTT to 0.33 ± 0.23 S/cm for PTT/GNS composites with 2.97 vol % GNS content. Percolation scaling laws were applied, and then threshold concentration and exponent were determined. In the case wherein liquid nitrogen was used to quench the melt, a mesomorphic phase was formed despite the extremely short crystallization time after adding high GNS contents. PTT crystallization rate increased with the gradual addition of GNSs. The enhanced crystallization kinetics was attributed to the high nucleation ability of GNSs to induce epitaxially grown lamellae on their surfaces, as revealed by TEM. PTT nuclei were randomly developed on the GNS surface to form the lamellae. However, crystallinity reached its maximum value near the electrical percolation threshold because the PTT chain mobility was confined after the GNS–GNS network formed. The growth of PTT banded spherulites in the bulk was still observed for composites with high GNS content, and TGA results revealed that the GNS‐filled PTT composites had excellent thermal stability. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43419.