In situ composite: Phenolphthalein polyethersulfone—thermotropic liquid crystalline polymer blends

Phase behavior, thermal, rheological and mechanical properties plus morphology have been studied for a binary polymer blend. The blend is phenolphthalein polyethersulfone (PES-C) with a thermotropic liquid crystalline polymer (LCP), a condensation copolymer of p-hydroxybenzoic acid with ethylene terephthalate (PHB-PET). It was found that these two polymers from optically isotropic and homogeneous blends by means of a solvent casting method. The homogeneous blends undergo phase separation during heat treatment. However, melt mixed PES-C/PHB-PET blends were heterogeneous based upon DSC and DMA analysis and SEM examination. Addition of LCP in PES-C resulted in a marked reduction of melt viscosity and thus improved processability. Compared to pure PES-C, the charpy impact strength of the blend containing 2.5% LCP increased 2.5 times. Synergistic effects were also observed for the mechanical properties of blends containing < 10% LCP. Particulates, ribbons, and fibrils were found to be the typical morphological units of PHB-PET in the PES-C matrix, which depended upon the concentration of LCP and the processing conditions.     

Morphology and mechanical properties of liquid crystalline copolyester and poly(ethylene 2,6-naphthalate) blends

Blends of poly(ethylene 2,6-naphthalate) (PEN) and a liquid crystalline copolyester (LCP), poly(benzoate-naphthoate), were prepared in a twin-screw extruder. Specimens for mechanical testing were prepared by injection molding. The morphology and mechanical properties were investigated by scanning electron microscopy (SEM) and an Instron tensile tester. SEM studies revealed that finely dispersed spherical domains of the liquid crystalline polymer (LCP) were formed in the PEN matrix, and the inclusions were deformed into fibrils from the spherical droplets with increasing LCP content. The morphology of the blends was found to be affected by their composition and a distinct skin-core morphology was found to develop in the injection molded samples of these blends. Mechanical properties were improved with increasing LCP content, and synergistic effects have been observed at 70 wt% LCP content whereas the elongation at break was found to be reduced drastically above 10 wt% of LCP content. This is a characteristic typical of chopped-fiber-filled composites. The improvement in mechanical properties is likely due to the reinforcement of the PEN matrix by the fibrous LCP phase as observed by scanning electron microscopy. The tensile and modulus mechanical behavior of the LCP/PEN blends was very similar to those of the polymeric composite, and the tensile strength and flexural modulus of the LCP/PEN 70/30 blend were two times the value of PEN homopolymer and exceeded those of pure LCP, suggesting LCP acts as a reinforcing agent in the blends.     

PA6含量对PVC/PA6共混物形态结构与力学性能的影响

以EVA-g-MAH为相容剂,将PVC与自制的低熔点PA6共混制备了PVC/PA6共混物。通过扫描电子显微镜(SEM)和力学性能测试研究了PA6含量对PVC/PA6共混物形态结构及力学性能的影响。SEM分析结果显示:随着PA6含量的增加,PVC/PA6共混物的分散相尺寸逐渐增大,当PA6含量为10%时,共混物中分散相的分散尺寸最小为1μm;当PA6含量为50%时,共混物为两相共连续结构;当PA6含量为60%时,共混物中PA6为连续相,PVC为分散相。力学性能测试结果表明:当PA6含量为10%时,共混物的缺口冲击强度和拉伸强度都较PVC有明显提高,分别提高了约50%与30%,达到了6.29kJ/m2和60MPa。采用差示扫描量热仪(DSC)研究了PVC/PA6共混物的结晶温度,检测结果显示:PVC/PA6共混物呈现非晶结构。     

Morphology and mechanical properties of liquid crystalline copolyester and polyester elastomer blends

Blends of a polyester elastomer (PEL) having a hard segment of polyester (PBT) and soft segment of polyether (PTMG) and a liquid crystalline copolyester (LCP), poly(benzoate-naphthoate), were prepared in a twin-screw extruder. Specimens for mechanical testing were prepared by injection molding. The morphology of the LCP/PEL blends was characterized under different processing conditions. To determine what conditions were necessary for the development of a fibrillar morphology of LCP, we have studied the effect of processing method (extrusion and injection molding), injection molding temperature (below and above the melting point of LCP), and gate position in the mold (direct gate and side gate). SEM studies revealed that some extensional flow was required for the fibrillar formation of LCP and the fibrillar structure of LCP was controlled by the processing method. The morphology of the blends was found to be affected by their compositions and processing conditions. SEM studies revealed that finely dispersed spherical domains of LCP were formed in the PEL matrix and the inclusions were deformed in fibrils from the spherical droplets with increasing LCP content and injection temperature. The mechanical properties of the LCP/PEL blends were also found to be affected by their compositions and processing conditions. The mechanical properties of LCP/PEL blends were very similar to those of polymeric composite. An attempt was made to correlate the structure of the blends from the scanning electron microscope with the measured mechanical properties. All of the aspects of the morphology were possible to explain in terms of the mechanical properties of the blends. A DSC study revealed that the crystallization of PEL was accelerated by the addition of LCP in the matrix and a partial compatibility between LCP and PEL was predicted. The rheological behavior of the LCP/PEL blends was found to be very different from that of the parent polymers, and significant viscosity reductions were observed in the blend consisting of only 5 wt% of LCP.     

Study on in situ reinforcing and toughening of a semiflexible thermotropic copolyesteramide in PBT/PA66 blends

Ternary in situ composites based on poly(butylene terephthalate) (PBT), polyamide 66 (PA66), and semixflexible liquid crystalline polymer (LCP) were systematically investigated. The LCP used was an ABA30/PET liquid crystalline copolyesteramide based on 30 mol % of p‐aminobenzoic acid (ABA) and 70 mol % of poly(ethylene terephthalate) (PET). The specimens for thermal and rheological measurements were prepared by batch mixing, while samples for mechanical tests were prepared by injection molding. The results showed that the melting temperatures of the PBT and PA66 phases tend to decrease with increasing LCP addition. They also shifted toward each other due to the compatibilization of the LCP. The torque measurements showed that the ternary blends exhibited an apparent maximum near 2.5–5 wt % LCP. Thereafter, the viscosity of the blends decreased dramatically at higher LCP concentrations. Furthermore, the torque curves versus the PA66 composition showed that the binary PBT/PA66 blends can be classified as negative deviation blends (NDBs). The PBT/PA66/LCP blends containing up to 15 wt % LCP were termed as positive deviation blends (PDBs), while the blends with the LCP ≥25 wt % exhibited an NDB behavior. Finally, the tensile tests showed that the stiffness and tensile strength of ternary in situ composites were generally improved with increasing LCP content. The impact strength of ternary composites initially increased by the LCP addition, then deteriorated when the LCP content was higher than 10 wt %. The correlation between the mechanical properties and morphology of the blends is discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1975–1988, 2000     

Mechanical,morphological, and thermal properties of poly(ethylene 2,6-naphthalate) and copolyester LCP blends

Binary blends of a liquid crystalline polymer (LCP) and poly(ethylene 2,6-naphthalate) (PEN) were melt blended and injection molded. The mechanical properties were studied as a function of LCP content. Both the ultimate tensile strength and Young's modulus are higher than the theoretical values predicted by the rule of mixtures and they display a synergistic behavior at 70 wt % LCP content. However, the tensile strength decreases with LCP content and Young's modulus remained unchanged at lower LCP contents (10 to 30 wt %). The poor mechanical property is attributed to the immiscibility between PEN and LCP and the fibrillation behavior of LCP as revealed by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) results. However, LCP and PEN are found to be partially miscible at higher LCP content, ascertained by DSC and dynamic mechanical analysis (DMA). This is attributed to the transesterification reaction between PEN and PET moiety in the LCP molecules. SEM micrographs reveal a skin/core morphology in the tensile bars, that is, the LCP is better oriented in the skin than in the core region. At lower LCP content, the dispersed LCP phase is spherical in the core and ellipsoidal in the skin, with long axes oriented in the flow direction. DSC studies show that the crystallization rate is significantly enhanced by the presence of LCP up to 50 wt %, where the LCP acts as a nucleating agent for PEN crystallization. The melting temperature decreases with LCP content, probably as a result of imperfect crystals formed in the presence of LCP heterogeneous nucleating centers and the increasing miscibility between LCP and PEN. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 477–488, 2001     

异氰酸酯对聚乳酸/热塑性聚氨酯共混物性能的影响

以4,4^′-二苯基甲烷二异氰酸酯（MDI）为反应增容剂，采用熔融共混法制备了不同MDI含量的聚乳酸/热塑性聚氨酯（PLA/TPU）共混物，采用傅里叶变换红外光谱仪（FTIR）、万能试验机、冲击试验机、扫描电子显微镜（SEM）、差示扫描量热仪（DSC）和旋转流变仪对共混物力学性能、微观形态、热性能和流变性能进行了研究。结果表明：MDI可以有效改善共混物的力学性能，当MDI质量分数为1%时，共混物力学性能最佳，缺口冲击强度为40.0kJ/m²，断裂伸长率为214.1%，与未加MDI的共混物相比，分别增加了4.3倍和5.8倍，拉伸强度稍有下降（47.6MPa）；SEM表明，MDI的加入提高了共混物的相容性，加入MDI后，共混物的断面由海-岛结构变为核-壳包覆结构，相界面作用力增强；DSC测试表明，共混物的玻璃化转变温度、冷结晶温度和熔融温度随着MDI含量的增加而升高；流变测试表明，MDI质量分数的增加，共混物呈现更显著的剪切变稀行为，推测共混反应机理为：MDI质量分数的增加，体系内依次发生PLA的扩链、支化和TPU的交联。     

环氧树脂对PA6/EPDM-g-MAH共混体系性能的影响

将两种不同型号的环氧树脂（EP(903)、EP(619D)）分别与PA6/EPDM-MA体系进行共混,制备了PA6/EPDM-MA/EP三元共混物。通过力学测试、动态流变(DMA)、差示扫描量热法（DSC）研究了不同EP添加量和环氧当量对PA6/EPDM-MA/EP共混体系性能的影响。实验结果表明：添加EP可以提高PA6/EPDM-MA共混物的拉伸强度,缺口冲击强度,并随着EP含量的增加而增加;而PA6/EPDM-MA/EP三元共混体系的动态储能模量（G′）,复合黏度（η*）随着EP含量的增加而增大,损耗因子（tanδ）减小;结晶度比未加环氧的共混物的结晶度稍高,并且随着环氧含量增加先增加后降低。此外,添加EP(903)的共混物各种性能变化比EP(619D)快。     

Rheological and physical properties of in situ composite based on liquid crystalline polymer and poly(ethylene 2,6‐naphthalate) blends

The in situ composites based on poly(ethylene 2,6‐naphthalate) (PEN) and liquid crystalline polymer (LCP) were investigated in terms of thermal, rheological, and mechanical properties, and morphology. Inclusion of LCP enhanced the crystallization rate and tensile modulus of the PEN matrix, although it decreased the tensile strength in the PEN‐rich phase. The orientation effect of this blend system was composition and spin draw ratio dependent, which was examined by Instron tensile test. Further, the addition of dibutyltindilaurate (DBTDL) as a reaction catalyst was found to increase the viscosity of the blends, enhance its adhesion between the dispersed LCP phases and matrix, and led to an increase of mechanical properties of two immiscible blends. Hence DBTDL is helpful in producing a reactive compatibilizer by reactive extrusion at the interface of this LCP reinforced polyester blend system. The optimum catalyst amount turned out to be about 500 ppm, when the reaction proceeded in the 75/25 PEN/LCP blend system. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2448–2456, 1999     

Blends of low‐density polyethylene and liquid crystalline polymer

Blends of low‐density polyethylene (LDPE) and a glass‐filled thermotropic liquid crystalline polymer (LCP‐g) have been prepared by melt mixing techniques. The thermal transitions, dynamic behavior, morphology and crystalline properties of the blends have been measured by DSC, DMTA, SEM and XRD respectively. The crystallinity decreased with increase in LCP‐g content in the blends. At higher levels of LCP‐g, crystal growth is favored in the PE phase. From DSC, it is found that the thermal stability of the blends increased with the LCP‐g content. The variation of storage modulus, loss modulus and stiffness as a function of blend ratio suggested the phase inversion at the 40–50% level of LCP‐g in the blend. SEM studies revealed that with the increase in LCP‐g content, the flow of the matrix was restricted.     

聚苯醚接枝马来酸酐/聚酰胺66共混物的制备与性能

通过辐照法将马来酸酐(MAH)基团接枝到聚苯醚(PPE)上,制备了PPE-g-MAH,将其和聚酰胺(PA)66通过熔融共混挤出方法制备了PPE-g-MAH/PA66共混物。采用差示扫描量热、吸水性实验、维卡软化和热变形实验、拉伸和冲击性能测试及动态力学性能测试等对PPE-g-MAH/PA66共混物性能进行了研究。结果表明,与PPE/PA66共混物相比,PPE-g-MAH/PA66共混物的耐热性能、力学性能和吸水性能均得到改善;随PPE-g-MAH含量的增加,PPE-g-MAH/PA66共混物中PA66的熔融温度和玻璃化转变温度均向PPE方向移动,表明两者的相容性有所提升,且共混物的维卡软化温度、热变形温度、25℃之前的储能模量均升高,吸水率降低;当PPE-g-MAH含量较低时,共混物拉伸强度提升明显而冲击强度升幅较小,当PPE-g-MAH含量较高时,共混物冲击强度提升明显而拉伸强度基本不变。因此,可以根据实际的应用要求选择合适的PPE-g-MAH含量。     

PEN/PA6共混体系的结晶形态与性能研究

以聚酰胺6(PA6)作为第二组分对聚芳醚腈（PEN）进行了改性,通过熔融共混制备了PEN/ PA6共混体系。用扫描电镜、差示扫描量热分析仪、X-射线衍射等方法对共混体系的形态结构和结晶行为进行了研究;用同步分析仪、万能电子试验机对共混材料的耐热性能和力学性能进行了研究。结果表明,PEN与PA6两者具有较好的相容性,随着PA6含量的增加共混体系中PA6的结晶能力逐渐提高,同时由于PA6的加入使得共混体系的加工性能较纯PEN有所改善,共混体系的拉伸强度较纯PEN提高了34 %。     

共聚聚丙烯(cPP)/线型低密度聚乙烯(LLDPE) 共混体系的流变与结晶形为

用毛细管流变仪研究了共聚聚丙烯(cPP)与线型低密度聚乙烯(LLDPE)共混物熔体的流变行为.讨论了共混物的组成、切应力和剪切速率对熔体流变行为和熔体粘度的影响.测定了不同配比共混物熔体的非牛顿指数.结果表明共混物熔体属假塑性流体,但共混体系粘度随LLDPE加入量的增加变化不大.DSC结晶曲线及扫描电镜(SEM)照片表明,LDPE的加入使cPP的结晶温度变化不大,但对晶体形态有一定影响.LLDPE对cPP有一定的增韧改性作用,当LLDPE质量分数为15%时,共混物的冲击强度增幅在40%左右,而拉伸强度保持率为80%.     

Polyblends containing a liquid crystalline polymer

Polyblends of a liquid crystalline thermotropic polymer (LCP) and an amorphous polyamide (PA) were prepared by melt blending. The blends' rheological behaviour was found to be very different from that of the individual components and very significant viscosity reductions were observed for blends consisting of only 5% LCP. The blends viscosity was always much lower than that of the parent polymers. The tensile mechanical behaviour of LCP/PA blends is very similar to that of polymeric composites. The blends' two phase morphology was found to be affected by their compositions. The LCP phase changed gradually with increasing LCP content from ellipsoidal particles to rod-like and fibrillar structure. A good interphase adhesion was observed.     

Effect of Addition of HDPE and LDPE on Rheological,Mechanical, Elastic and Compatibility Behavior of SBR/NBR Rubber Blend System

The influence of adding low density polyethylene (LDPE) and high density polyethylene (HDPE) to different ratios of styrene butadiene copolymer (SBR) and acrylonitrile butadiene copolymer (NBR) rubber blend has been studied. The experimental methods performed are based on measurements of rheological, mechanical, elastic properties, phase morphology, density, ultrasonic studies, thermal stability and differential scanning calorimetry (DSC). Results showed that rheological and mechanical properties of the blend are improved, especially at SBR/NBR blend (50/50), when incorporated with LDPE. Results indicated also a clear stability of the cure rate index (CRI) of the blend. Morphological structure analysis obtained from scanning electron microscope (SEM) showed a reduced domain size for blends containing LDPE. Ultrasonic and density investigations revealed the efficiency of adding LDPE in improving the compatibility behavior of this blend. Results also showed an improvement in elastic properties and thermal stability by adding LDPE. DSC scans of the blends filled with LDPE showed high shift in the glass transition temperature which can be attributed to the increased strength at the interface.     

尼龙1010／马来酸酐接枝聚乙烯共混体系结晶行为和力学性能的研究

将尼龙1010与马来酸酐接枝聚乙烯进行熔融共混,使用DSC、扫描电镜等方法研究了共混物的结晶行为、共混物形态以及力学性能。结果表明:接枝聚乙烯通过与尼龙1010在熔融共混时生成的接枝共聚物改善了共混组份两相之间的相容性和共混形态;共混物中尼龙组份的结晶熔融热焓下降;共混物在保持较高刚性的同时其干态及低温冲击性能较纯尼龙1010有明显提高。     

The effect of composition on thermal,mechanical, and morphological properties of thermotropic liquid crystalline polyester with alkyl side-group and polycarbonate blends

A thermotropic liquid crystalline polymer (LCP) with an alkyl side-group was synthesized. Blends of the LCP with polycarbonate (PC) were prepared by coprecipitatton from a common solvent. The rheological behavior of the LCP/PC blends was found to be very different from that of PC, and significant viscosity reductions were observed in the temperature range of 200–230°C. Blends of different LCP compositions were extruded with different draw ratio from a capillary rheometer. The ultimate tensile strength showed a maximum at a 10 wt% LCP composition in the blends. It decreased for compositions greater the 10 wt% LCP, whereas the initial modulus increased with increasing LCP content. The morphology of the blends was found to be affected by their compositions. Scanning electron microscopy (SEM) studies revealed finely dispersed spherical LCP domains in the PC matrix. The SEM micrographs also showed a poor adhesion between the two phases.     

Rheology and thermal properties of liquid crystalline copolyester and poly(ethylene 2,6-naphthalate) blends

Blends of a poly(ethylene 2,6-naphthalate) (PEN) and a liquid crystalline copolyester (LCP), poly(benzoate-naphthoate) were prepared in a twin-screw extruder. Specimens for thermal properties were investigated by means of an instron capillary rheometer (ICR) and scanning electron microscopy (SEM). The blend viscosity showed a minimum at 10 wt% of LCP and increased with increasing LCP content above 10 wt% of LCP. Above 50% of LCP and at higher shear rate, phase inversion occured and the blend morphology was fibrous and similar to pure LCP. The ultimate fibrillar structure of LCP phase appeared to be closely related to the extrusion temperature. By employing a suitable deformation history, the LCP phase may be elongated and oriented such that a microfibrillar morphology can be retained in the solid state. Thermal properties of the LCP/PEN blends were studied using DSC and a Rheovibron viscoelastomer. These blends were shown to be incompatible in the entire range of the LCP content. For the blends, the T_g and Tm were unchanged. The half time of crystallization for the LCP/PEN blends decreased with increasing LCP content. Therefore, the LCP acted as a nucleating agent for the crystallization of PEN. The dimensional and thermal stability of the blends were increased with increasing LCP content. In studies of dynamic mechanical properties, the storage modulus (E′) was improved with increasing LCP content and synergistic effects were observed at 70 wt% of LCP content. The storage modulus for the LCP/PEN 70/30 blend is twice that of PEN matrix and exceeded pure LCP.     

Strengthening of poly(butylene adipate-co-terephthalate) by melt blending with a liquid crystalline polymer

Poly(butylene adipate-co-terephthalate) (PBAT) is a soft biodegradable polymer with a low melting temperature. PBAT has been melt-blended with a liquid crystalline polymer (LCP) aiming at preparing a new biodegradable polymer blend with improved mechanical properties. The phase structure and crystalline morphologies of the PBAT/LCP blends were investigated using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS), and transmission electron microscopy (TEM). It was found that the LCP domains are precisely dispersed in the PBAT matrix and that these domains act as the nuclei for PBAT crystallization. The nonisothermal crystallization temperature from the melt was dramatically shifted from 50°C to about 95°C by the addition of 20% LCP. In addition, the tensile modulus of the prepared blends increases gradually with increasing LCP content, indicating the excellent strengthening effects of LCP on the PBAT matrix. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Compatibilizing effect of styrene–maleic anhydride copolymer on the properties of polyamide‐6/liquid crystalline copolyester composites

Liquid crystalline polymer–polyamide‐6 (LCP/PA6) composites containing 20 wt % LCP content were compatibilized by a random styrene–maleic anhydride copolymer (RSMA). The blending was performed via extrusion followed by injection molding. The LCP employed was a commercial copolyester, Vectra A950. The dynamic mechanical (DMA), rheological, thermal, and mechanical properties as well as the morphology of the composites were studied. The DMA and rheological results showed that RSMA is an effective compatibilizer for LCP/PA6 blends. The mechanical measurements showed that the stiffness, tensile strength, and toughness of the in situ composites are generally improved with increasing RSMA content. However, these mechanical properties deteriorated considerably when RSMA content was above 10 wt %. The drop‐weight dart impact test was also applied to analyze the toughening behavior of these composites. The results show that the maximum impact force (F_max) and crack‐initiation energy (E_init) tend to increase with increasing RSMA content. From these results, it appeared that RSMA prolongs the crack‐initiation time and increases the energies for crack initiation and impact fracture, thereby leading to toughening of LCP/PA6 in situ composites. Finally, the correlation between the mechanical properties and morphology of the blends is discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1964–1974, 2000