Crystallization kinetics of poly(phenylene sulfide) (PPS) and PPS/carbon fiber composites

The evolution of crystallinity of neat PPS and of the carbon fiber reinforced polymer under different processing conditions is studied. Crystallization from the amorphous state at low temperatures (cold crystallization), crystallization from the melt during cooling, and crystal melting processes are analyzed using calorimetric techniques under both isothermal and nonisothermal conditions. Cold and melt crystallization kinetics are described using an Avrami equation and an Arrhenius expression for the temperature dependence of the kinetic constant. Also, the melting kinetics of the, reinforced and of the unreinforced polymer are studied in this work. The effect of carbon fibers on the crystallization kinetics of PPS is analyzed, and a comparison of the crystallization behavior of PPS and other semicrystalline thermoplastic matrices, such as poly(etheretherketone) (PEEK), is presented.     

表面处理对碳纤维/聚苯硫醚复合材料性能的影响

以碳纤维(CF)平纹织物、聚苯硫醚(PPS)纤维为原材料,通过混杂铺丝及热压的方法制备出CF/PPS热塑性复合材料。研究了不同表面处理方法对CF表面官能团、碳(C)与氧(O)元素含量比、单丝拔出强度及复合材料两相浸润性、界面性能、力学性能等的影响。结果表明:丙酮处理可以有效去除CF的上浆剂,利于PPS熔体在CF之间的均匀分散与浸渍,在一定程度上提升了CF/PPS复合材料的力学性能;硝酸溶液处理可以增加CF平纹织物表面的O/C摩尔比,且CF表面轴向产生缺陷和沟壑;CF与PPS之间的界面剪切强度随硝酸处理时间的增加而明显增加,但CF/PPS复合材料的力学性能呈现先增加后降低的趋势;通过表面处理改善CF与PPS之间的浸润性以及界面相互作用力,可以提升CF/PPS复合材料的力学性能。     

Effect of polyphenylene sulfide containing amino unit on thermal and mechanical properties of polyphenylene sulfide/glass fiber composites

Three kinds of high‐molecular‐weight compatibilizers [copoly(1,4‐phenylene sulfide)‐poly(2,5‐phenylene sulfide amine)] (PPS‐NH₂) containing different proportions of amino units in the side chain) were synthesized by the reaction of dihalogenated monomer and sodium sulfide via nucleophilic substitution polymerization under high pressure. The intrinsic viscosity of the obtained copolymers was 0.354–0.489 dL/g and they were found to have good thermal performance with melting point (T_m) of 271.3–281.0 °C and initial degradation temperature (T_d) of 490.0–495.7 °C. There was an excellent physical compatibility between PPS‐NH₂ and the pure industrial PPS. The results of dynamic mechanical analysis and macro‐ and micromechanical test showed that the selective compatibilizer PPS‐NH₂ (1.0) (1.0% mol aminated ratio) can improve the mechanical and interfacial properties of polyphenylene sulfide/glass fiber (PPS/GF) composite. The macro‐optimal tensile strength, Young's modulus, bending strength, and notched impact strength of 5%PPS‐NH₂ (1.0)/PPS/GF composite raised up to 141 MPa, 1.98 GPa, 203 MPa, and 6.15 kJ/m², which increased 12.8%, 9.4%, 4.1%, and 13.8%, respectively, comparing with the pure PPS/GF composite (125 MPa, 1.81 GPa, 195 MPa, and 5.40 kJ/m², respectively). © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45804.     

Transport and solubility of fluids into polyphenylene sulfide (PPS)

The solubility and transport of toluene and carbon disulfide into amorphous and crystalline polyphenylene sulfide (PPS) was investigated. The rates of sorption, desorption, and resorption of both fluids were measured as a function of temperature. The sorption of these fluids into amorphous PPS produces a semi‐crystalline material by solvent induced crystallinity (SIC). Although the rate of diffusion of carbon disulfide (CS₂) into crystalline PPS, (produced either thermally or by SIC), is several orders of magnitude slower than that observed in amorphous PPS, the solubility is only slightly reduced, by approximately 10%. The PPS films exhibit highly stressed surface regions that rapidly sorb the penetrant. Thermal annealing at temperatures as high as 100°C (note T_g of PPS is 85°C) has little or no effect on the surface stress, the diffusion process or the solubility of toluene into PPS. In addition to SIC, PPS undergoes cold crystallization at 130°–140°C; however, the degree of crystallinity induced by cold crystallization is approximately 60% of that formed by cooling from the melt. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 615–625, 2003     

炭黑改性聚苯硫醚纤维性能研究

在聚苯硫醚(PPS)树脂中加入少量的炭黑制成切片,采用熔融纺丝法制得改性PPS纤维。研究了炭黑的加入量对改性PPS纤维的取向、结晶和热性能的影响,以及改性PPS纤维经紫外光老化前后力学性能的变化。结果表明:加入炭黑可使PPS纤维取向度降低,结晶度提高;炭黑质量分数为1.5%的改性PPS纤维耐热性较好;经紫外光照射192 h后,与纯PPS纤维相比,其断裂强度保留率提高了30.3%,断裂伸长保留率提高了41.4%,抗紫外光老化性能得到了改善。     

Mechanical and thermal properties of polyphenylene sulfide/multiwalled carbon nanotube composites

Polyphenylene sulfide (PPS)/multiwalled carbon nanotube (MWCNT) composites were prepared using a melt‐blending procedure combining twin‐screw extrusion with centrifugal premixing. A homogeneous dispersion of MWCNTs throughout the matrix was revealed by scanning electron microscopy for the nanocomposites with MWCNT contents ranging from 0.5 to 8.0 wt %. The mechanical properties of PPS were markedly enhanced by the incorporation of MWCNTs. Halpin‐Tsai equations, modified with an efficiency factor, were used to model the elastic properties of the nanocomposites. The calculated modulus showed good agreement with the experimental data. The presence of the MWCNTs exhibited both promotion and retardation effects on the crystallization of PPS. The competition between these two effects results in an unusual change of the degree of crystallinity with increasing MWCNT content. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Crystallization kinetics of polyphenylene sulfide

The crystallization kinetics of unfilled and glass-reinforced grades of polyphenylene sulfide has been investigated by using differential scanning calorimetry. The maximum rate of crystallization is observed at about 170°C. From the crystallization data, it is recommended that the molding parameters should be so specified that the polymer spends 10–15 s over the temperature range of 155–190°C during cooling, before demolding, in order to ensure stable morphology of the molded part. The glass fibers have an accelerating influence on crystallization resulting in a 15–25% reduction in crystallization time. The kinetic data have been interpreted by using Avrami analysis followed by a discussion of the possible crystallization mechanisms.     

Thermal percolation behavior of graphene nanoplatelets/polyphenylene sulfide thermal conductivity composites

The volume fraction of functionalized graphene nanoplatelets (GNPs) influencing on the thermal conductivities of GNPs/polyphenylene sulfide (GNPs/PPS) composites are investigated. Results reveal that a great improvement of the thermal conductivities with the addition of functionalized GNPs, and the thermal conductivity of the GNPs/PPS composite is 4.414 W/mK with 29.3 vol% functionalized GNPs, 19 times higher than that of the pure PPS matrix. The significantly high improvement of the thermal conductivities is ascribed to good thermal transmission through GNPs networks in the PPS matrix, following a thermal percolation behavior. Meantime, the GNPs have strong ability to generate continuous thermally conductive chains, and the formation of thermally conductive networks becomes much easier. POLYM. COMPOS., 35:1087–1092, 2014. © 2013 Society of Plastics Engineers     

Thermal aging performance of glass fiber/polyphenylene sulfide composites in high temperature

In order to use the glass fiber reinforced polyphenylene sulfide composites (GF/PPS) in high temperature environments, thermal aging performance of two kinds of commercial grade PPS composites, reinforced by 40% glass fiber, PPS-G40 HM and 1140L4, in thermal aging temperature of 250°C was compared by tensile strength, oxidized layer, color, crystallization and melting behavior. The results showed that tensile strength of GF/PPS composites is significantly decreased with increasing of aging time below 200 h and the tensile strength of aged PPS-G40 HM is higher than that of aged 1140L4. The thickness of dark color area is increased with increasing of aging time. The thickness of oxidized layer of 1140L4 is thinner than that of PPS-G40 HM. However, the color of oxidized layer of PPS-G40 HM is lighter than that of 1140L4. The recrystallization in thermal aging results in the formation of crystal with higher melting point and increased melting temperature of GF/PPS composites. It is found that addition of epoxy resin can increase the initial mechanical property and improve the thermal aging performance of GF/PPS composites. A novel modified GF/PPS composite with higher thermal aging properties was obtained.     

Crystallization of poly(etheretherketone) (PEEK) in carbon fiber composites

The tendency of carbon fiber to nucleate the zation of poly(etherettterlcetone) (PEEK) has been evaluated by DSC and other techniques. As the carbon fiber content was increased, the supercooling necessary for PEEK crystallization decreased. The repeated melting (at 396°C) of the same PEEK sample results in a decrease of the number of nuclei for crystallization. At equivalent thermal histories, PEEK with carbon fiber was found to have a higher nucleation density than PEEK itself. The surface of carbon fibers and nuclei in the PEEK matrix compete for crystallization growth. As the holding time in melt was increased, the number of matrix spherulites formed on cooling decreased, hence a more pronounced transcrystalline region was developed. Correspondingly, the composites preheated in the melt for 100 min showed about two times the transverse tensile strength and strain-to-failure of those preheated for only 30 min. Corresponding fracture surface produced in tension showed that the former samples had a greater matrix adhesion to the carbon fiber than the latter. A strong interfacial bond is thus developed by crystallization on carbon fiber surface. Destroying nuclei in the PEEK matrix by long preheating enhances crystallization on the carbon fiber.     

表面涂覆改性后聚苯硫醚纤维的耐用性能初探

利用溶胶—凝胶法在常规聚苯硫醚纤维的表面涂覆了以陶瓷材料为主体的保护层。试验结果表明,该保护层不仅能提高纤维的抗氧化性,而且能延长其高温环境下的使用寿命,无论耐酸、碱和高温环境性能都较常规的聚苯硫醚纤维有了提高。经表面涂覆改性后的聚苯硫醚纤维产品有望在过滤材料领域发挥突出作用。     

Crystallization behavior of polyphenylene sulfide in blends with a liquid crystalline polymer

Blends of polyphenylene sulfide (PPS) with a commercial, wholly aromatic, liquid crystal copolyesteramide (Vectra-B950) have been prepared by meltblending. The crystallization behavior of neat and blended PPS has been studied by differential scanning calorimetry (DSC), under both non-isothermal and isothermal conditions. It has been found that blending PPS with Vectra-B leads to an increase of the temperature of non-isothermal crystallization and to a pronounced acceleration of the isothermal crystallization, without any reduction of the degree of crystallinity. All these effects have been found to occur independent of the Vectra-B concentration, within the investigated range (2 to 20%, w/w). The results have been interpreted in terms of an incrased nucleation density of the blends, probably due to heterogeneous substances, initially present in the Vectra-B bulk, which dissolve to saturation in the PPS phase, during melt-blending.     

Preparation of conductive polyphenylene sulfide/polyamide 6/multiwalled carbon nanotube composites using the slow migration rate of multiwalled carbon nanotubes from polyphenylene sulfide to polyamide 6

Conductive polyphenylene sulfide (PPS)/polyamide 6 (PA6)/multiwalled carbon nanotube (MWCNT) composites having 10–30 wt % PA6 and 1 wt % MWCNTs are prepared by melt mixing at 300°C for 8 min using a high concentration PPS/MWCNT masterbatch approach, and the migration kinetics of MWCNTs from thermodynamically unfavored PPS to favored PA6 was investigated. The morphology of the composites was investigated by field emission scanning electron microscopy and transmission electron microscopy, showing the localization of most MWCNTs in the PPS phase and at the interface, being different from the case of direct melt mixing where non‐conductive materials were obtained with most MWCNTs found in the PA6 phase and at the interface. The electrical resistivity and morphology of the materials as a function of time were investigated, showing that the conductive materials can be prepared within a mixing time of 4–16 min because of the slow migration rate of MWCNTs from PPS toward PA6, and MWCNTs can eventually migrate into the PA6 phase after a long mixing time of 30 min. The slow migration rate of MWCNTs was attributed to the high viscosity ratio of the two phases. This article shows a good example where the migration of MWCNTs was slow enough to control and can be used to prepare conductive polymer blends. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42353.     

Crystallization and thermal behavior of multiwalled carbon nanotube/poly(butylenes terephthalate) composites

Multiwalled carbon nanotube/poly(butylene terephthalate) composites (PCTs) were prepared by melt mixing. The nonisothermal crystallization and thermal behavior of PCTs were respectively investigated by X‐ray diffractometer, polarized optical microscope, differential scanning calorimeter, dynamic mechanical thermal analyzer, and thermogravimetric analyzer. The presence of nanotubes has two disparate effects on the crystallization of PBT: the nucleation effect promotes kinetics, while the impeding effect reduces the chain mobility and retards crystallization. The kinetics was then analyzed using Ozawa, Mo, Kissinger, Lauritzen‐Hoffman, and Ziabicki model, and the results reveal that the nucleation effect is always the dominant role on the crystallization of PBT matrix. Thus the crystallizability increases with increase of nanotube loadings. In addition, the presence of nanotubes nearly has no remarkable contribution to thermal stability because nanotubes also play two disparate roles on the degradation of PBT matrix: the Lewis acid sites to facilitate decomposition and the physical hindrance to retard decomposition. Hence the nanotubes act merely as inert‐like filler to thermal stability. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

聚苯硫醚/有机蒙脱土复合材料热氧化研究

以十六烷基三甲基溴化铵作为插层剂,采用阳离子交换法对钠基蒙脱土粉体进行有机改性制备有机蒙脱土(OMMT);采用熔融插层法制得聚苯硫醚(PPS)/OMMT复合材料并将复合材料进行热处理;利用红外光谱技术研究热处理前后PPS树脂及其复合材料的结构变化,对PPS的热氧化机理进行探讨;利用电脑测色配色仪对热处理前后的PPS树脂及其复合材料颜色的变化值进行测试。结果表明:与纯PPS树脂相比,OMMT的添加可以在一定程度上提高PPS树脂的抗氧化性;经过热处理后PPS树脂及PPS/OMMT复合材料均发生不同程度的氧化,苯环上发生交联,C—S键上发生氧化;C—H的面外弯曲振动峰及苯环C—O伸缩振动峰均发生蓝移;PPS/OMMT复合材料的色度变化程度明显降低,其中添加质量分数为5%的OMMT的复合材料的抗氧化效果较好。     

非等温热重法研究聚苯硫醚热分解动力学

采用非等温热重法对聚苯硫醚的热分解动力学进行研究,通过比较计算结果选定拟合结果更好的迭代法计算反应活化能,采用积分法结合36种动力学函数来判断聚苯硫醚热分解的机理函数。得到了聚苯硫醚热分解动力学参数平均活化能E、指前因子A和对应的热分解动力学方程。     

聚苯硫醚/富勒烯复合纤维的制备及性能研究

采用1-氯萘溶液溶解聚苯硫醚(PPS),将富勒烯(C60)分散到PPS的1-氯萘溶液中,通过溶剂蒸馏和萃取分离,制得PPS/C60复合材料,通过熔融纺丝法制备PPS/C60复合纤维,研究了复合材料及其复合纤维的结构与性能。结果表明:PPS/C60复合材料中C60质量分数小于4%时,能够实现C60均匀分散于复合材料中;与机械混合相比,溶液分散法制备的复合材料C60分散更均匀;C60添加质量分数为4%时,PPS/C60复合纤维的断裂强度达到最高为3.07 c N/dtex,与PPS纤维相比,PPS/C60复合纤维的断裂强度提高了38%;C60与PPS发生π-π共轭作用,使复合材料的力学性能得到提高。     

聚苯硫醚纤维的制备及性能研究

对聚苯硫醚(PPS)切片进行了熔融纺丝,测定了拉伸倍率、拉伸温度、热定型温度对纤维性能的影响。结果发现,随着拉伸倍率和热定型温度的提高,纤维的断裂强度和熔点都提高,断裂伸长则下降;随着拉伸温度的提高,纤维的熔点降低,断裂强度和双折射率则先降低后升高,出现最低值。在初生纤维的冷结晶温度110℃附近进行拉伸,纤维的断裂强度最低。在310℃对PPS进行纺丝,初生纤维在90℃拉伸4.5倍后,再在180℃紧张热定型5min,获得了断裂强度为3.9 cN/dtex的PPS纤维。     

聚苯硫醚纤维的研究开发

介绍聚苯硫醚(PPS)纤维的性能、应用,以及PPS纤维工艺研究的进展。