Crystallization of glass fiber‐reinforced poly(p‐phenylene sulfide) nanocomposites

Ternary composites of glass fiber‐reinforced poly(p‐phenylene sulfide) (PPS/GF) filled with nanometric calcium carbonate (nano‐CaCO₃) were prepared by means of a twin‐screw extruder. The nano‐CaCO₃ surface was treated with stearate and treated with titanate, the composites being called SI composite system and SII composite system, respectively. The crystallization and heatproof properties of the PPS/GF/nano‐CaCO₃ composites were measured using a differential scanning calorimeter, to investigate the influence of the nanometric filler content on the crystallinity. The results show that the variation of the starting crystallization temperature, crystallization temperature and crystallinity with an increase of the particle weigh fraction (?_f) of SI composite system is different from that of SII composite system. When ?_f is less than 4 wt%, the crystallinity of the two composite systems increases and then decreases slightly with increasing ?_f. Moreover, the crystallization behavior and mechanisms are discussed. Copyright © 2011 Society of Chemical Industry     

Thermal studies of blends of poly(phenylene sulfide) (PPS) with poly(phenylene sulfide sulfone) (PPSS) and with poly(phenylene sulfide ether) (PPSE)

The miscibilities of poly(phenylene) sulfide/poly(phenylene sulfide sulfone) (PPS/PPSS) and poly(phenylene) sulfide/poly(phenylene sulfide ether) (PPS/PPSE) blends were invesigated in terms of shifts of glass transition temperatures T_g of pure PPS, PPSS, a dn PPSE. The crystallization kinetics of PPS/PPSS blends was also studied as a function of molar composition. The PPS/PPSS and PPS/PPSE blends are respectively partially and fully miscible. PPSE shows a plasticizing effect on PPS as does PPS on PPSS, which necessarily improves te processibility in the respective systems. We can control T_g and melting temperature T_m of PPS by varying amounts of PPSE in blends. The melt crystallization temperature T_mc of PPS/PPSE blends was higher than that of the PPSE homopolymer. Therefore, these blends require shorter cycle times in processing than pure PPSE. The overall rate of crystallization for PPS/PPSS blends follows the Avrami equation with an exponent ?2. The maximal rate of crystallization for PPS/PPSS blends occurs at a temperatre higher by 10°C than that for PPS, while the crystallization half time t_1/2 is 4 times shorter. In the cold crystallization range, crystal growth rates increase and Avrami exponents decrease significantly as the temperature increases.     

Plasma surface modification of poly(phenylene sulfide) films for copper metallization

Poly(phenylene sulfide) (PPS) films were modified by Ar, O₂, N₂ and NH₃ plasmas in order to improve their adhesion to copper metal. All four plasmas modified the PPS film surfaces, but the NH₃ plasma modification was the most effective in improving adhesion. The NH₃ plasma modification brought about large changes in the surface topography and chemical composition of the PPS film surfaces. The peel strength for the Cu/plasma-modified PPS film systems increased linearly with increasing surface roughness, R _a or R _rms, of the PPS film. The plasma modification also led to considerable changes in the chemical composition of the PPS film surfaces. A large fraction of phenylene units and a small fraction of sulfide groups in the PPS film surfaces were oxidized during the plasma modification process. Nitrogen functional groups also were formed on the PPS film surfaces. The NH₃ plasma modification formed S—H groups on the PPS film surfaces by reduction of S—C groups in the PPS film. Not only the mechanical interlocking effect but also the interaction of the S—H groups with the copper metal may contribute to the adhesion of the Cu/PPS film systems.     

Processing,structure, and properties of multiwalled carbon nanotube–poly(phenylene sulfide) composite fibers

To improve the processability and properties of the poly(phenylene sulfide) (PPS) fibers at room temperature and high temperatures, a series of composite fibers based on PPS and multiwalled carbon nanotubes were prepared by melt spinning. We researched the processability with a high‐pressure capillary rheometer, and the properties of the composite fibers were investigated in detail by scanning electron microscopy, differential scanning calorimetry, fiber sonic velocity measurement, and single‐fiber strength testing. The results show that the carbon nanotubes (CNTs) had good interfacial adhesion with PPS and dispersed homogeneously in the PPS matrix. When the shear rate was higher than 500 s^?1, the oriented CNTs induced the orientation of PPS molecular chains; this resulted in a decline in the apparent viscosity and an increase in the orientation degree of the molecular chains. Meanwhile, the CNTs acted as nucleating agents to effectively improve the crystallization of PPS. The strength of the fibers at room temperature were improved by 28.8% after the addition of 0.2% CNTs, and the initial modulus was also significantly enhanced. The strength retention at 160 °C was promoted from 60.58 to 88.32% with the addition of 1.0% CNTs. The shrinking percentage decreased to almost zero from higher than 15%; this suggested that the CNTs could efficiently improve the dimensional stability at high temperatures. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44609.     

Microcellular foams of glass–fiber reinforced poly(phenylene sulfide) composites generated using supercritical carbon dioxide

Microcellular foaming of poly(phenylene sulfide) (PPS) and its glass–fiber (GF) reinforced composites using supercritical CO₂ as a blowing agent presents a promising approach to produce novel cellular materials with tailored microstructures. This study investigated the effects of the material composition and process conditions on the foaming behaviors and final morphologies of the microcellular foamed PPS and PPS/GF composites. The rheological and thermal properties as well as the saturation and desorption behaviors of CO₂ in the pure PPS and PPS/GF composites were also detailedly discussed. The results show that microcellular foams with various relative densities, cell sizes, cell‐size distributions, and cell densities can be attained by tailoring the fiber content and key process parameters. At low foaming temperatures below the cold crystallization temperature, the microcellular foamed PPS and PPS/GF composites both present a unimodal cell‐size distribution. At elevated temperatures, the generated crystalline superstructures including spherulites in the polymer matrix and transcrystals around the GF will cause a secondary heterogeneous cell nucleation. This leads to the observations of bimodal and trimodal cell‐size distributions in the pure PPS and the PPS/GF composites, respectively. The mechanisms for the solid‐state foaming behaviors of pure PPS and PPS/GF composites have been illustrated by establishing theoretical models. POLYM. COMPOS., 37:2527–2540, 2016. © 2015 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.     

Properties of polyphenylene sulphide/glass fibre composites with negative thermal expansion ceramic fillers

The high coefficient of thermal expansion (CTE) of polymeric composites can cause large deformation under temperature changes, affecting coupling with devices made of other materials in radio frequency (RF) communication systems and limiting their application in RF systems. In order to obtain polyphenylene sulphide (PPS)-based composites with low CTE, a series of PPS-based composites containing different loadings of ceramic powders (including Zr₂WP₂O₁₂, BN, AlN, Al₂O₃) were fabricated by melt extrusion method using PPS with 40 wt% glass fibre (GF) as matrix material. The experimental results showed that the PPS composites with Zr₂WP₂O₁₂ (ZWP) as a filler had a lower CTE compared to the samples with other fillers at the same filler loading. The CTE of PPS/GF/ZWP steadily decreased with increasing ZWP addition. At 20 vol% ZWP loading, a 67% (about 18 ppm/°C) reduction of CTE compared to the PPS/GF was achieved. The addition of ZWP powder to PPS/GF also led to an improvement in the dielectric loss of the composite. When the ZWP content is 20 vol%, the dielectric loss of the composites is about 0.0035, which is 24.4% lower than PPS/GF. Hence, the PPS/GF/ZWP composites have great potential for applications in RF communication systems.     

Molecular weight distribution of polyphenylene sulfide by high temperature gel permeation chromatography

Poly(phenylene sulfide) (PPS) has been characterized using a novel high temperature gel permeation chromatograph (GPC). Samples were injected in slurry form at ambient temperature, and redissolved by an in-line precolumn heater at 250°C. A viscometer consisting of a capillary tube with inlet and outlet taps connected to a sensitive differential pressure transducer was used as sole detector, with deflections converted to concentration using the column calibration. Columns and viscometer were operated at 210°C. Universal calibration was carried out using intrinsic viscosity/molecular weight relations for polystyrene and PPS, determined by light scattering. Satisfactory operation was confirmed by agreement between intrinsic viscosity calculated from GPC with independently measured values, and comparisons with melt flow data. Samples of PPS tested were found to be of relatively narrow distribution, with M_w/M_n typically less than two.     

Mechanical and morphological study of polyphenylene sulfide/liquid crystalline polymer blends compatibilized with a maleic anhydride grafted copolymer

Blends of thermotropic liquid crystalline polymer (LCPA‐950), based on a copolyester of hydroxynapthoic acid and hydroxybenzoic acid with an engineering thermoplastic, poly(phenylene sulfide) (PPS), were prepared using a corotating twin‐screw extruder. Addition of a third component, a functionalized polypropylene (maleic anhydride grafted polypropylene, MA‐PP), that interact with the thermotropic liquid crystalline polymer (TLCP) facilitates the structural development of the TLCP phase by acting as a compatibilizer at the interface. Differential scanning calorimetry and dynamic mechanical thermal analysis results, however, show that there is an interaction between the polymers in the presence of compatibilizer. This means that MA‐PP can be used as a compatibilizer for the PPS/LCP in situ composite system. The viscosity of the compatibilized in situ composite was decreased by the compatibilizer, and this is mainly due to the fibrous structure of the LCP at the high shear rate. The mechanical properties of the ternary blends were increased when a proper amount of MA‐PP was added. This is attributed to fine fibril generation induced by the addition of MA‐PP. Morphological observations determined the significance of the third component in immiscible polymer blends, and an optimum amount of MA‐PP exists for the best mechanical performance. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Mechanical and thermal enhancements of benzoxazine‐based GF composite laminated by in situ reaction with carboxyl functionalized CNTs

An easy and efficient approach by using carboxyl functionalized CNTs (CNT‐COOH) as nano reinforcement was reported to develop advanced thermosetting composite laminates. Benzoxazine containing cyano groups (BA‐ph) grafted with CNTs (CNT‐g‐BA‐ph), obtained from the in situ reaction of BA‐ph and CNT‐COOH, was used as polymer matrix and processed into glass fiber (GF)‐reinforced laminates through hot‐pressed technology. FTIR study confirmed that CNT‐COOH was bonded to BA‐ph matrices. The flexural strength and modulus increased from 450 MPa and 26.4 GPa in BA‐ph laminate to 650 MPa and 28.4 GPa in CNT‐g‐BA‐ph/GF composite, leading to 44 and 7.5% increase, respectively. The SEM image observation indicated that the CNT‐COOH was distributed homogeneously in the matrix, and thus significantly eliminated the resin‐rich regions and free volumes. Besides, the obtained composite laminates showed excellent thermal and thermal‐oxidative stabilities with the onset degradation temperature up to 624°C in N₂ and 522°C in air. This study demonstrated that CNT‐COOH grafted on thermosetting matrices through in situ reaction can lead to obvious mechanical and thermal increments, which provided a new and effective way to design and improve the properties of composite laminates. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Optimization of structure and properties of polyphenylene sulfide porous membrane by controlling the process of thermally induced phase separation

Polyphenylene sulfide (PPS) porous membranes were successfully prepared from miscible blends of PPS and polyethersulfone (PES) via thermally induced phase separation followed by subsequent extraction of the PES diluent. The morphologies, crystalline structures, mechanical properties, pore structures and permeate fluxes of the PPS porous membranes obtained from different phase separation processes were characterized and are discussed. During the phase separation in the heating process, PPS and PES mainly underwent liquid–liquid phase separation, and then a nonhomogeneous porous structure with a mean pore size of 100 μm and a honeycomb‐like internal structure formed on the membrane surface. The phase separation of PPS/PES occurring in the cooling process was easier to control and the related pore diameter distribution was more regular. In the process of direct annealing, as the phase separation temperature decreased, the pore size distribution became more homogeneous and the mean diameter of the pores also decreased gradually. When the phase separation temperature decreased to 200 °C, PPS membranes with a network structure and a uniform as well as well‐interconnected porous structure could be obtained. In addition, the maximum permeation flux reached 1718.03 L m^–2 h^–1 when the phase separation temperature was 230 °C. The most probable pore diameter was 6.665 nm, and the permeate flux of this membrane was 2.00 L m^–2 h^–1; its tensile strength was 17.07 MPa. Finally, these PPS porous membranes with controllable pore structure as well as size can be widely used in the chemical industry and energy field for liquid purification. © 2020 Society of Chemical Industry     

Microcellular foaming of poly(phenylene sulfide)/poly(ether sulfones) blends using supercritical carbon dioxide

Microcellular foaming of poly(phenylene sulfide)/poly(ether sulfones) (PPS/PES) blends presents a promising approach to produce high‐performance cellular materials with tailored microstructures and enhanced properties. This study investigated the effects of multiphase blend composition and process conditions on the foaming behaviors and final cellular morphology, as well as the dynamic mechanical properties of the solid and microcellular foamed PPS/PES blends. The microcellular materials were prepared via a batch‐foam processing, using the environment‐friendly supercritical CO₂ (scCO₂) as a blowing agent. The saturation and desorption behaviors of CO₂ in PPS/PES blends for various blend ratios (10 : 0, 8 : 2, 6 : 4, 5 : 5, 4 : 6, 2 : 8, and 0 : 10) were also elaborately discussed. The experimental results indicated that the foaming behaviors of PPS/PES blends are closely related to the blend morphology, crystallinity, and the mass‐transfer rate of the CO₂ in each polymer phase. The mechanisms for the foaming behaviors of PPS/PES blends have been illustrated by establishing theoretical models. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42634.     

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     

Isothermal crystallization of pure and glass fiber reinforced poly(phenylene sulfide) composites

The isothermal crystallization of poly(phenylene sulfide) (PPS) and its glass fiber (GF) reinforced composite has been investigated by differential scanning calorimetry (DSC) and polarized optical microscope (POM) equipped with a hot stage. During the isothermal crystallization process of PPS the Avrami exponent value decreases with time, indicating the change of crystallization mechanism and presence of mixed growth mechanism (bidimensional and three‐dimensional growth of crystals). The presence of GF greatly accelerates the bulk crystallization rate of PPS and changes the crystalline morphology of PPS from the spherulites to transcrystallization. And the reason for development of transcrystallization is considered to be relevant with the compatibility of the interface between GF and PPS. POLYM. COMPOS., 2009. © 2009 Society of Plastics Engineers     

Synthesis and characterization of novel poly(phenylene sulfide) containing a chromophore in the main chain

A kind of novel poly(phenylene sulfide)s (PPSs) containing a chromophore group were synthesized by the reaction of dihalogenated monomer and sodium sulfide (Na₂S.xH₂O) via nucleophilic substitution polymerization under high pressure. The polymers were characterized by Fourier transform infrared spectroscopy, ultraviolet spectroscopy, fluorescence spectroscopy, XRD, DSC, TGA, mechanical testing and dissolvability experiments. The intrinsic viscosity of the polymers obtained with optimum synthesis conditions was 0.22 ? 0.38 dl g^?1 (measured in 1‐chloronaphthalene at 208 °C). These polymers were found to have good thermal performance with a glass transition temperature (T_g) of 90.5 ? 94.6 °C and initial degradation temperature (T_d) of 475–489 °C, showing improved thermal properties compared with homo‐PPS. At the same time the resultant resins had a high tensile strength of 67.5 ? 74.1 MPa and compressive strength of 70.7 ? 85.4 MPa. Additionally, these polymers exhibited a weak UV ? visible reflectivity minimum at 450–570 nm, and the fluorescence spectra of the polymers showed maximum emission around nearly 370 nm. Also they showed excellent chemical resistance and another special property ? bright shiny colors changed into different colors in acid solution. © 2014 Society of Chemical Industry     

Isothermal crystallization kinetics of poly(phenylene sulfide)/TLCP composites

The isothermal crystallization kinetics, the morphology, and the melting behavior of melt‐processed composites of poly(phenylene sulfide) (PPS) with a thermotropic liquid crystalline copolyester, Vectra A950, (TLCP) were studied by differential scanning calorimetry (DSC) and optical microscopy. The crystallization behavior of PPS in PPS/TLCP composites is observed to be highly sensitive to T_c and immiscible TLCP content in the composites. The spherulite growth rate, the overall crystallization rate, and the activation energy of PPS in PPS/TLCP composites are markedly depressed by the presence of TLCP. The analysis of the Avrami kinetic parameters (n and k) indicates that blending of TLCP with PPS causes heterogeneous growth process and nucleation mechanisms. At low T_cs, the PPS crystallization rate is faster than that neat PPS with ≤30 wt% TLCP loading whereas at high T_cs it remains almost unchanged. The analysis of the melting behavior of these composites indicates that the stability of PPS crystals and their reorganization is influenced both by the T_cs and the composite compositions. The sizes and the number of spherulites change a great extent with composite composition with a drop of spherulite rapid growth rate, at constant T_c, with increasing content of TLCP in composites. The analysis based on the Lauritzen‐Hoffmann secondary nucleation theory, using present DSC data, indicates that present data predominantly follow a linear growth trend over a present range of T_cs and PPS crystallization in composites still occurs according to regime II kinetics, whereby multiple surface nuclei form on the substrate with multiple nucleation acts commencing before initially formed growth layer is completed. The fold surface free energy of PPS chains in composites is found higher than that of neat PPS, leading to an average higher work of chain folding and is ascribed to a general development of the PPS chain mobility in the composite melt. POLYM. ENG. SCI., 2009. © 2008 Society of Plastics Engineers     

Synergistic effects of hybrid fillers on the development of thermally conductive polyphenylene sulfide composites

The future of integrated circuits with three‐dimensional chip architecture hinges on the development of practical solutions for the management of excessive amounts of heat generation. This requires new polymer–matrix composites (PMCs), with good processibility, high effective thermal conductivity (k_eff), and low but tailored electrical conductivity (σ). This article explores the synergy of hybrid fillers: (i) hexagonal boron nitride (hBN) platelets with different sizes and shapes; (ii) hBN platelets with carbon‐based fillers promoting the k_eff of the polyphenylene sulfide (PPS) composites. It explores the promotion of interconnectivity among the fillers in the PPS matrix, leading to higher k_eff, by the uses of hybrid fillers. It discusses using carbon‐based fillers as secondary fillers to tailor the PMCs' σ. Finally, it presents the effects of hybrid fillers on the PMCs' coefficient of thermal expansion. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Realization of reinforcing and toughening poly (phenylene sulfide) with rigid silica nanoparticles

Reinforcing and toughening poly (phenylene sulfide) (PPS) with rigid SiO₂ nano-particles was realized simultaneously under the suitable thermodynamic state of PPS, and the key issue about the effect of matrix/filler interaction was also demonstrated. The strong matrix/filler interaction realized by grafting reactive groups onto nanoparticles was beneficial for stress transfer and thus in favor of the increase in tensile strength of PPS. Meanwhile, this interaction provided nanoparticles with certain mobility to move with molecular chains and align along the tensile direction when T > T_g of PPS, thus the nanoparticles could significantly improve the tensile toughness of PPS according to the energy dissipation mechanism. Consequently, the tensile strength and elongation to break values of PPS increased to 59.0 MPa and 112.1 % from the initial values of 48.0 MPa and 78.5 % by adding 1 wt% grafted SiO₂ nano-particles. The work provided a promising method to reinforce and toughen rigid-chain polymer simultaneously and prepare high-performance PPS nanocomposites.     

Synthesis of polyphenylene polysulfur

Summary Polymers with conjugated double bonds are both of theoretical and practical interest. Poly (thio-1, 4 phenylene), which is called poly (phenylene sulfide) (or PPS), is an original class of polymers capable of displaying conductive properties. Usually, PPS are prepared by Friedel-Crafts reaction or by Macallum synthesis. In this paper we describe another way to obtain poly (phenylene polysulfane). They are prepared in a one-pot reaction with alcali metal, S₈ and p-dichlorobenzene. The reaction is studied on model molecules.     

An investigation of the friction and wear behaviors of polyphenylene sulfide filled with solid lubricants

Composites of polyphenylene sulfide (PPS) filled with solid lubricant particles of graphite (C), molybdenum disulfide (MoS₂), and polytetrafluoroethylene (PTFE) were prepared by compression molding. The size of the solid lubricant particles was 3‐;5 µm. The friction and wear behaviors of the composites were examined with a pinon‐disk test rig. The worn composite pin surfaces and the transfer films formed on the counterface were analyzed with scanning electron microscopy. An X‐ray photo‐electron spectroscope (XPS) was used to characterize the chemical states of the elements in the transfer film. It has been found that graphite and PTFE as the fillers increase the wear resistance of PPS considerably, while MoS₂ as the filler decreases the wear resistance of PPS greatly. The fillers promote the decomposition of PPS and generate compounds, which accounts for the changes in the wear resistance of the composites.