Kinetics of thermo-oxidative degradation of zinc borate/microcapsulated red phosphorus with magnesium hydroxide in flame retarded polypropylene composites

The flammability and the thermo-oxidative degradation kinetics of zinc borate (ZB) and microcapsulated red phosphorus (MRP) with magnesium hydroxide (MH) in flame-retardant polypropylene (PP) composites were studied by limiting oxygen index (LOI), TGA, and FTIR spectroscopy. The results show that ZB/MRP is a good synergist for improving the flame retardancy of the PP composites. The Kissinger and Flynn-Wall-Ozawa methods were used to determine the activation energy (E) for degradation of PP composites. The results from the TGA curves indicate that the thermal stability of PP/MH/ZB and PP/MH/ZB/MRP composites is better than that of PP/MH composites. The kinetic results show that the values of E for degradation of PP/MH/ZB/MRP composites is much higher than those of PP/MH and PP/MH/ZB composites. The FTIR spectra data show that the incorporation of MH improves the thermo-oxidative stability of PP, especially for PP/MH composites with suitable content of MRP at higher temperatures. These data indicate that the synergistic flame retardants used in this work have a great effect on the mechanisms of pyrolysis and combustion of PP/MH composites.     

Water absorption behavior of PALF/GF hybrid polyester composites

The water absorption characteristics of pineapple leaf fiber (PALF)/glass fiber (GF) hybrid polyester(PER) composites, and chemically modified PALF/polyester composites were evaluated by immersion in distilled water at 28, 60, and 90°C. The diffusion properties of the intimately mixed (IM) and the layered hybrid composite GPG (Glass skin and PALF core) of different PALF/GF ratio at the three temperatures were compared in order to identify the environmental ageing mechanism at different temperatures. The effect of temperature on the kinetics and thermodynamics of diffusion were also examined. The water uptake of both IM and GPG hybrid composites was decreased with increase in glass fiber content; the lowest water uptake was observed for 0.46 V_f GF hybrid composite. Among the chemically modified composites, vinyl tri 2‐methoxy ethoxy silane treated composites showed the lowest water uptake. Finally, parameters like diffusion, sorption, and permeability coefficients were determined. It was observed that equilibrium water uptake is dependent on the nature of the composite and temperature. Experimental results were also compared with theoretical predictions. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Synthesis,structure, and thermo‐physical properties of Fe2O3.Al2O3 and polyethylene nanocomposites

In this study, Fe₂O₃.Al₂O₃/polyethylene composites were prepared using a two‐step process. In the first step, PE is synthesized using titanium based metallocene catalyst system. While the synthesized PE was subsequently purified, hydrated alumina filled PE (MHFP) composites was formed by the hydrolysis of methylaluminoxane (MAO). In the second step, Fe₂O₃.Al₂O₃/PE was prepared via thermal decomposition of ferric formate in a high temperature solution of MHFP composite. The structure, morphology, and thermal properties of the composites were characterized using the XRD, FTIR, SEM‐EDX, TGA, and DSC analytical techniques. Results showed that the incorporation of a suitable amount of Fe₂O₃.Al₂O₃ into the composites enhances the thermal stability. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Oxidation behavior and kinetics of in situ (TiB2 + TiC)/Ti3SiC2 composites in air

The isothermal oxidation behavior of in situ (TiB₂ + TiC)/Ti₃SiC₂ composite ceramics with different TiB₂ content has been investigated at 900-1200 °C in air for exposure times up to 20 h by means of X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and energy dispersive spectroscopy. The oxidation of (TiB₂ + TiC)/Ti₃SiC₂ composites follows a parabolic rate law. With the increase in TiB₂ content, the oxidation weight gain, thickness of the oxidation scale, and parabolic rate constant decrease dramatically, which suggests that the incorporation of TiB₂ greatly improves the oxidation resistance of the composites. With the increase in oxidation temperature, the enhancement effect becomes more pronounced. Due to the incorporation of TiB₂, the oxidation scale of (TiB₂ + TiC)/Ti₃SiC₂ composites is generally composed of an outer layer of coarse-grained TiO₂ and an inner layer of amorphous boron silicate and fine-grained TiO₂. Only the dense inner layer formed on the surface acts as a diffusion barrier, retarding the inward diffusion of O, and consequently contributing to the improved oxidation resistance of the (TiB₂ + TiC)/Ti₃SiC₂ composites.     

Design of the phthalonitrile‐based composite laminates by improving the interfacial compatibility and their enhanced properties

Phthalonitrile containing benzoxazine (BA‐ph) and cyanate ester (CE) were chosen as the thermosetting matrix and the glass fiber (GF) reinforced laminates formed at low temperature were designed. The polyarylene ether nitriles containing pendent carboxyl groups (CPEN) was selected to modify the interfacial interaction between the resin matrix and GFs. Two methods of introducing CPEN were compared and the effects of CPEN on curing behaviors and properties of the composites were investigated. Results showed that with the CPEN, exothermic peaks shifted to lower temperature and curing temperatures of BA‐ph/CE decreased slightly. The mechanical and thermal properties of GF‐reinforced composites were discussed and the results indicated that the composites of modified GFs with CPEN exhibited outstanding mechanical properties, higher glass transition temperature (T_g > 290 °C) than that of composites composed of CPEN mixed with BA‐ph/CE. Moreover, GF‐reinforced composites showed stable dielectric constants (3.8–4.5) and low dielectric loss (0.005–0.01), which were independent of the frequency. In sum, the various methods of the introduction of CPEN in the GF‐reinforced composites may provide a new route to prepare improved composites, meanwhile, composites with outstanding processability and excellent mechanical and thermal properties are expected to be widely applied in the fields of high‐performance structural materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45881.     

Effect of processing conditions on physical properties of 3‐aminophenoxyphthalonitrile/epoxy laminates

To develop high performances of polymer composite laminates, differential scanning calorimetry and dynamic rheological analysis studies were conducted to show curing behaviors of 3‐aminophenoxyphthalonitrile/epoxy resin (3‐APN/EP) matrix and define cure parameters of manufacturing processes. Glass fiber reinforced 3‐APN/EP (GF/3‐APN/EP) composite laminates were successfully prepared through different processing conditions with three parameters such as pressures, temperatures, and time. Based on flexure tests, dynamic mechanical analysis, thermal gravimetric analysis, and scanning electron microscope, the complementary catalytic effect of the three processing parameters is investigated by studying mechanical behavior, thermomechanical behavior, thermal behavior, and fracture morphology of GF/3‐APN/EP laminates. The 50/50 GF/3‐APN/EP laminates showed a significant improvement in flexural strength, glass transition temperature (T_g), and thermal stability with favorable processing parameters. It was also found that the T_g and thermal stability were significantly improved by the postheated treatment method. The effect of manufacturing process provides a new and simple route for the polymer–matrix composites application, which indicates that the composites can be manufactured at low temperatures. But, they can be used in a high temperature environment. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39746.     

Enhanced thermal conductivity of PE/BN composites through controlling crystallization behavior of PE matrix

In this article, in order to enhance the thermal conductivity of the polyethylene (PE)/boron nitride (BN) composites through controlling the crystallization behavior of the PE matrix, the crystallization and melting behavior of the PE in the PE/BN composites was investigated. When the BN content was more than 10 wt%, an extra weak exothermic peak (T _h) at 130°C was observed. Moreover, after the annealing of the PE/BN composites at 130°C, the extra weak melting peaks (T _mh) of the PE in the PE/BN composites were also observed and shifted to the high temperature with increasing annealing time, which proved that the T _h was induced by PE crystallization. Meanwhile, the results of temperature‐dependent absorbance IR spectra of the PE/BN composites showed that the crystallization peak (729 cm⁻¹) remarkably appeared at 130.2°C, indicating that the crystallization of the PE in the PE/BN composites can occur at 130.2°C. When the annealing time and temperature were 20 min and 130°C, the thermal conductivity of the PE/BN composite was 16% higher than that of the unannealed PE/BN composites. In addition, the results of the wide angle X‐ray diffraction (WAXD) showed that the BN particles had no influence on the PE crystalline form in the PE/BN composites. POLYM. COMPOS., 38:2806–2813, 2017. © 2015 Society of Plastics Engineers     

The role of carbon nanotubes on the stability of tetragonal zirconia polycrystals

The effect of single walled carbon nanotubes (SWNT) at zirconia grain boundaries on the stability of a tetragonal zirconia polycrystalline matrix has been explored in as–sintered composites and after low–temperature hydrothermal degradation (LTD) experiments. For this purpose, highly–dense 3?mol% Y₂O₃–doped tetragonal zirconia polycrystalline (3YTZP) ceramics and SWNT/3YTZP composites were prepared by spark plasma sintering (SPS). Quantitative X–ray diffraction analysis and microstructural observations point out that an increasing amount of well–dispersed SWNT bundles surrounding zirconia grains decreases the metastable tetragonal phase retention in the ceramic matrix after sintering. In contrast, the tetragonal ceramic grains in composites with SWNTs are less sensitive to the presence of water, i.e. to undergo a martensitic transformation under LTD conditions, than monolithic 3YTZP ceramics. The SWNT incorporation diminishes micro–cracking due to tetragonal to monoclinic ZrO₂ phase transformation in the composites.     

Effects of ZnO–B<Subscript>2</Subscript>O<Subscript>3</Subscript> addition on sintering behaviors and microwave dielectric properties of Ba<Subscript>4</Subscript>Sm<Subscript>9.33</Subscript>Ti<Subscript>18</Subscript>O<Subscript>54</Subscript> ceramics

Effects of ZnO–B₂O₃ (ZB) addition on the densification, phase evolution and microwaves dielectric properties of Ba₄Sm_9.33Ti₁₈O₅₄ (BST) ceramics for low-temperature fired applications have been investigated. The sintering temperature of BST ceramics can be effectively lowered to about 1000°C with introduction of ZB. Tungsten bronze like single phase is observed in the BST ceramics with 0.5 and 1.0% ZB. However, Sm₂Ti₂O₇ secondary phase appears when ZB addition reaches 2%, and Sm₂Ti₂O₇ phase gradually increases with the increase ZB addition. Microwave dielectric properties of the present ceramics are strongly dependent on phase constitution and density. Optimal microwave dielectric properties of ε = 63.4, Qf = 2830 GHz, τ _f =–8.8 ppm/°C is obtained for BST ceramics with 1% ZB addition.     

Characterization of polyethylene/kaolin composites by polymerization filling with Cp2ZrCl2/MAO catalyst system

In this work, the preparation and characterization of metallocene‐catalyzed polyethylene (PE)/kaolin composites were presented. The composites was prepared by the so‐called polymerization‐filling method in which the PE matrix was formed directly on the kaolin surface by ethylene polymerization with the prefixed Cp₂ZrCl₂/methylaluminoxane (MAO) catalyst system on the kaolin surface. SEM, FTIR, and DMA were carried out to characterize the composites. The experimental results showed the new composites had homogeneous distribution of kaolin particles in the PE matrix and strong interfacial interaction between the PE matrix and kaolin particles. At the molecular level, the interfacial interaction caused the decrease of the mobility of PE molecular chains. In addition rheological testing showed that the introduction of kaolin by polymerization filling could improve the rheological behavior of prepared composites. The relationship between the rheological behaviors and the interfacial conditions were discussed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2913–2921, 2002     

硼酸锌对氮磷协效阻燃玻纤增强尼龙66性能的影响

为提高三聚氰胺聚磷酸盐(MPP)和二乙基次膦酸盐(OP)协效阻燃玻纤(GF)增强尼龙66(PA66)的综合性能,引入少量的无机阻燃剂硼酸锌(ZB)作为协效剂,系统研究了不同添加量的ZB对阻燃材料的阻燃性能、热稳定性、力学性能和白度的影响。结果表明,当MPP和OP的总添加量为15%,复配0.5%的ZB时,阻燃GF增强PA66的垂直燃烧阻燃等级达到UL94 V–0级,且热释放总量由MPP/OP体系的15.4 k J/g降为13.7 k J/g;ZB的引入促进了连续、致密炭层的形成,增强了凝聚相阻燃;ZB增强了阻燃材料的热稳定性,ZB复配量为1.0%的阻燃材料的初始降解温度提高到了301℃,有效避免了加工过程中的降解;当ZB添加量为1.0%时,阻燃材料的拉伸强度和缺口冲击强度分别为100.9 MPa和4.22 k J/m~2,均优于未添加阻燃剂的纯GF增强PA66;同时,样品的白度得到了明显提升,有利于阻燃GF增强PA66的工业化应用。     

Investigation of non-isothermal crystallization,dynamic mechanical and dielectric properties of poly(ether-ketone) matrix composites

ABSTRACT

Poly(ether-ketone)/hexagonal boron nitride (h-BN) composites reinforced with micrometer-sized h-BN particles were investigated. The composites exhibited glass transition temperature (T_g) and thermal stability over 160°C and 560°C, respectively. The melting point and peak crystallization temperatures of the composites decreased up to 17°C and 12°C, respectively. The linear CTE of the composites decreased both below and above the T_g. The storage modulus increased with increasing h-BN content at all temperatures (50–250°C). The composites possessed excellent dielectric properties with insignificant dispersion with increasing frequency. Thus, resultant composites are promising candidates for the printed circuit boards/electronic substrates.     

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     

A novel B–Si–Zr hybridized ceramizable phenolic resin and the thermal insulation properties of its fiber-reinforced composites

A novel B–Si–Zr hybridized ceramicizable resin(BSZ-PR) was fabricated by chemical reaction of boric acid, zirconium hydroxyl-containing polyhedral oligomeric silsesquioxane(Zr-POSS) and phenolic. The incorporation of boric acid and Zr-POSS improved the thermal stability of the resin effectively, and the residual carbon rate increased to 72.63% at 800 °C under nitrogen atmosphere. The flexural strength of carbon fiber/BSZ-PR and high silica fiber/BSZ-PR composites were increased by 25.7% and 175.5%, and linear ablation rates were reduced by 37% and 44.75%, respectively. It was discovered that the ceramic structures such as SiO₂, ZrO₂ and SiC can be formed at high temperatures as well as under extreme ablative conditions from both BSZ-PR and its fiber-reinforced composites, which may be the key to the improved thermal, ablative properties.     

Effects of glass fiber on the properties of polyoxymethylene/thermoplastic polyurethane/multiwalled carbon nanotube composites

The effects of epoxy‐functionalized glass fiber (GF) on the electrical conductivity, crystallization behavior, thermal stability, and dynamic mechanical properties of polyoxymethylene (POM)/thermoplastic polyurethane (TPU)/multiwalled carbon nanotube (MWCNT) composites are investigated. The electrical resistivities of POM/5%−20% TPU/1% MWCNT composites are significantly reduced by nine orders of magnitude after the addition of 20% GF because of the formation of TPU‐coated GF structure facilitating the construction of conductive networks. GF has no obvious influence on the crystallization temperature, melting temperature, and degree of crystallinity of POM in POM/TPU/MWCNT composites because of their relatively bigger size compared with POM chains and MWCNTs. The storage moduli of POM/TPU/MWCNT composites are improved by the addition of GF, indicating that POM/TPU/MWCNT/GF composites are promising materials with good electrical and mechanical properties. POLYM. COMPOS., 38:1319–1326, 2017. © 2015 Society of Plastics Engineers     

Effect of glass fiber on the electrical resistivities of polyoxymethylene/maleic anhydride‐grafted polyethylene/multiwalled carbon nanotube composites

The effect of glass fiber (GF) on the electrical resistivities of polyoxymethylene (POM)/maleic anhydride‐grafted polyethylene (MAPE)/multiwalled carbon nanotube (MWCNT) composites is investigated. The POM/MAPE/MWCNT composites at a MWCNT loading of 0.75% are nonconductive because most of MWCNTs are isolated in the MAPE islands, and their electrical resistivities decrease significantly after the addition of GF because of the formation of MAPE‐coated GF structure, which facilitates the formation of conductive paths and was confirmed by field emission scanning electron microscopy (FESEM). The formation of MAPE‐coated GF structure is attributed to the interaction between GF and MAPE during melt compounding, as contrasted by the uncoated GF using high‐density polyethylene (HDPE) instead of MAPE. Nonconductive POM/5–20% MAPE/0.75% MWCNT composites become conductive upon the addition of 20% GF. This preparation method for conductive materials can be generalized to POM/5–20% maleic anhydride‐grafted polypropylene (MAPP)/0.75% MWCNT composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41794.     

Ablation properties of zinc borate and aluminum hypophosphite filled silicone rubber composites

The ablative properties of epoxy modified silicone rubber composites filled with zinc borate (ZB) and aluminum hypophosphite (AHP) were studied. The decomposition of the added fillers and covering connection of residual on the substrate contribute to the improvement of heat insulation. The ablation test shows that the formation of a dense char layer with certain strength is key to improving the ablative properties. The optimal ablative performance is achieved when the concentration of ZB and AHP is 10 and 5 phr, respectively. Under such circumstances, the linear ablation rate is as low as 0.032 mm/s, which is about 61% lower than the pure silicone rubber. Furthermore, the structure and composition of the formed char layer were analyzed using X-ray diffraction analysis, scanning electron microscopy, and Fourier transform infrared spectroscopy.     

Synthesis,characterization, and comparative study of conducting polyaniline/lead titanate and polyaniline–dodecylbenzenesulfonic acid/lead titanate composites

To study the effect of a surfactant on the properties of polyaniline (PANI)/metal oxide composites, PANI/lead titanate (PbTiO₃) composites were synthesized with different weight percentages (10, 20, 30, 40, and 50 wt %) of PbTiO₃ in both the absence and presence of dodecylbenzenesulfonic acid (DBSA) by the polymerization of aniline with ammonium persulfate as an initiator. The structural characteristics and stability, surface characteristics, and electric properties of PANI/PbTiO₃ and PANI–DBSA/PbTiO₃ were studied and compared. The interfacial interactions and thermal stability of these composites were characterized with X‐ray diffraction, scanning electron microscopy, transmission electron microscopy, and thermogravimetry techniques. The results indicate significant changes in the physicochemical properties of the composites with the incorporation of DBSA. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effects of ammonium polyphosphate and triphenyl phosphate on the flame retardancy,thermal, and mechanical properties of glass fiber–reinforced PLA/PC composites

The purpose of this study is to increase of the flammability properties of the glass fiber (GF)–reinforced poly (lactic acid)/polycarbonate (PLA/PC) composites. Ammonium polyphosphate (APP) and triphenyl phosphate (TPP) were used as flame retardants that are including the organic phosphor to increase flame retardancy of GF‐reinforced composites. APP, TPP, and APP‐TPP mixture flame retardant including composites were prepared by using extrusion and injection molding methods. The properties of the composites were determined by the tensile test, limiting oxygen index (LOI), differential scanning calorimetry (DSC), and heat release rate (HRR) test. The minimum T_g value was observed for the TPP including PLA/PC composites in DSC analysis. The highest tensile strength was observed in GF‐reinforced PLA/PC composites. In the LOI test, GF including composite was burned with the lowest concentration of oxygen, and burning time was the longest of this composite. However, the shortest burning time was obtained by using the mixture flame retardant system. The flame retardancy properties of GF‐reinforced PLA/PC composite was improved by using mixture flame retardant. When analyzed the results of HRR, time to ignition (TTI), and mass loss rate together, the best value was obtained for the composite including APP.     

Dynamic mechanical analysis of pineapple leaf/glass hybrid fiber reinforced polyester composites

The dynamic mechanical properties of randomly oriented intimately mixed hybrid composites based on pineapple leaf fibers (PALF) and glass fibers (GF) in unsaturated polyester (PER) matrix were investigated. The PALFs have high‐specific strength and improve the mechanical properties of the PER matrix. In this study, the volume ratio of the two fibers was varied by incorporating small amounts of GF such as PALF/GF, 90/10, 80/20, 70/30, and 50/50, keeping the total fiber loading constant at 40 wt%. The dynamic modulus of the compositeswas found to increase on GF addition. The intimately mixed (IM) hybrid composites with PALF/GF, 80/20 (0.2 V_f GF) showed highest E′ values and least damping. Interestingly, the impact strength of the composites was minimum at this volume ratio. The composites with 0.46 V_f GF or PALF/GF (50/50) showed maximum damping behavior and highest impact strength. The results were compared with hybrid composites of different layering patterns such as GPG (GF skin and PALF core) and PGP (PALF skin and GF core). IM and GPG hybrid composites are found more effective than PGP. The activation energy values for the relaxation processes in different composites were calculated. The overall results showed that hybridization with GF enhanced the performance properties. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers