Synergistic effect of boron nitride and tetrapod‐shaped zinc oxide whisker hybrid fillers on filler networks in thermal conductive HDPE composites

In this paper, in order to investigate and predict the synergistic effect of the tetra‐needle‐shaped zinc oxide whisker (T‐ZnO) and boron nitride (BN) hybrid fillers in the thermal conductive high‐density polyethylene (HDPE) composites, the filler networks were studied through dynamic rheological measurement. Moreover, the crystallinity of the HDPE in the composites, and the thermal and electrical conductivity of the composites were also investigated. It was found that when the ratio of the BN and T‐ZnO in hybrid fillers was 20:10, the HDPE/hybrid fillers composite not only had the highest thermal conductivity but also can maintain the electrically insulating. Furthermore, the gel point of the HDPE/hybrid fillers composites was 11.2 wt%, and it was close to the 10 wt%. Therefore, the synergistic effect of the T‐ZnO and BN hybrid fillers in the HDPE/hybrid fillers composites can be successfully predicted through dynamic rheology date. Simultaneously, the Scanning electron microscope results showed that the T‐ZnO and BN particles can contact each other to form the thermal conductive paths so that the thermal conductivity of the HDPE can be enhanced through addition of the hybrid fillers. In addition, it was also found that the improved thermal conductivity of the HDPE/hybrid fillers composites was not because of a change in the crystallinity of the HDPE in the HDPE/hybrid fillers composites. POLYM. COMPOS., 38:1902–1909, 2017. © 2015 Society of Plastics Engineers     

A study on the tribological behavior of hybrid PTFE/Kevlar fabric composites filled with nano‐SiC and/or submicron‐WS2 fillers

The tribological behaviors of hybrid PTFE/Kevlar fabric composites filled with nano‐SiC and/or submicron‐WS₂ fillers were studied. Scanning electron microscopy and energy‐dispersive X‐ray spectrometer were used for analysis of the worn surface, transfer film, and debris of the PTFE/Kevlar fabric composites. In addition, the wear volume loss of the composite was measured by means of a laser microscopic 3D and profile measurement apparatus. The results indicate that although both single fillers and hybrid fillers can reduce the wear rate of composites, but hybrid fillers filled composites could achieve the desired comprehensive tribological properties in dry sliding. The improved tribological performance of filled composites can be attributed to two aspects: the formation of a thin and tenacious transfer film on the counter‐surface, and the restrain the formation of larger debris. Tiny wear debris was easily trapped in the gap of a worn surface and can repair the damaged surface. In addition, the trapped debris could be considered as a secondary source of lubricant. POLYM. COMPOS., 37:2218–2226, 2016. © 2015 Society of Plastics Engineers     

Thermal conductivity of polypropylene composites with hybrid fillers of boron nitride and vapor‐grown carbon fiber

High thermal conductivity fillers of boron nitride (BN) and vapor‐grown carbon fiber (VGCF) were used alone or incorporate to prepare polypropylene (PP) composites. The effects of filler content, particle size and shape, and single vs. hybrid BN/VGCF fillers were investigated with respect to the thermal conductivity of the PP composites. The thermal conductivity of PP/BN composites depended upon the content and particle size of the BN. Increased content and length of VGCF had the effect of increasing the thermal conductivity of the PP composites. Hybrid fillers were created with a mixture of medium‐sized BN and long‐length VGCF; hybrid BN/VGCF fillers enhanced the thermal conductivity of PP composites with a lower total content compared with PP composites containing only medium‐sized BN particles. POLYM. COMPOS., 37:936–942, 2016. © 2014 Society of Plastics Engineers     

The effects of hybrid fillers on thermal,mechanical, physical,and antimicrobial properties of ultrahigh‐molecular‐weight polyethylene‐reinforced composites

The effects of hybrid filler of zinc oxide and chitosan (chitosan–ZnO) on thermal, flexural, antimicrobial, chemical resistance, and hardness properties of ultrahigh‐molecular‐weight polyethylene (UHMWPE) composites with varying concentration of zinc oxide (ZnO) and further hybridized by chitosan (CS) were successfully studied. The composites were prepared using mechanical ball milling and followed by hot compression molding. The addition of ZnO to the UHMWPE matrix had lowered the melting temperature (T _m) of the composite but delayed its degradation temperature. Further investigation of dual filler incorporation was done by the addition of chitosan to the UHMWPE/ZnO composite and resulted in the reduction of UHMWPE crystallization. The flexural strength and modulus had a notably high improvement through ZnO addition up to 25 wt% as compared to neat UHMWPE. However, the addition of chitosan had resulted in lower flexural strength than that of 12 wt% ZnO UHMWPE composite but still higher than that of neat UHMWPE. It was experimentally proven that the incorporation of ZnO and chitosan particles within UHMWPE matrix had further enhanced the antimicrobial properties of neat UHMWPE. Chemical resistance was improved with higher ZnO content with a slight reduction of mass change after the incorporation of chitosan. The hardness value increased with ZnO addition but higher incorporation of chitosan had lowered the hardness value. These findings have significant implications for the commercial application of UHMWPE based products. It appears that these hybrid fillers (chitosan–ZnO)‐reinforced UHMWPE composites exhibit superior overall properties than that of conventional neat UHMWPE. POLYM. COMPOS., 38:1689–1697, 2017. © 2015 Society of Plastics Engineers     

Effect of nano fillers on the properties of polytetrafluoroethylene composites: Experimental and theoretical simulations

Polytetrafluoroethylene (PTFE) has excellent corrosion resistance and a low coefficient of friction; however, its high wear rate and low hardness severely limit its use. In the work, nano particles were used as fillers for PTFE. The composites were prepared by the homogeneous mixing of PTFE and other fillers and sintered at high temperatures. The work aimed to investigate the effect of various nano fillers (nanocarbon powders, graphene, fullerene, nano graphite powders, and nano copper powders) on the mechanical, thermal, and frictional properties of composites. The results of the experiments showed that the addition of graphene could improve the stress and strain values of the composites, and all the nano fillers could improve the thermal conductivity of the PTFE composites. The friction experiments showed that fullerenes could significantly improve the wear resistance of PTFE composites. In the theoretical simulation, the thermal conductivity of PTFE composites was predicted using ANSYS software, with the changes in the temperature and friction force in the friction process. The theoretical simulation results matched with the experimental values, which proved the accuracy of the theoretical simulations.     

Preparation of nano‐zinc oxide/EPDM composites with both good thermal conductivity and mechanical properties

In this article, nano‐zinc oxide (ZnO) filled ethylene propylene diene monomer (EPDM) composites are prepared, and the mechanical (static and dynamic) properties and thermal conductivity are investigated respectively, which are further compared with the traditional reinforcing fillers, such as carbon black and nano‐silica. Furthermore, influence of in‐situ modification (mixing operation assisted by silane at high temperature for a certain time) with the silane‐coupling agent Bis‐(3‐thiethoxy silylpropyl)‐tetrasufide (Si69) on the nano‐ZnO filled composites is as well investigated. The results indicate that this novel reinforcing filler nano‐ZnO can not only perform well in reinforcing EPDM but can also improve the thermal conductivity significantly. In‐situ modification with Si69 can enhance the interfacial interaction between nano‐ZnO particles and rubber matrix remarkably, and therefore contribute to the better dispersion of filler. As a result, the mechanical properties and the dynamic heat build‐up of the nano‐ZnO filled composites are improved obviously by in‐situ modification, without influencing the thermal conductivity. In comparison with traditioanl reinforcing fillers, in‐situ modified nano‐ZnO filled composites exhibit the excellent performance in both mechanical (static and dynamic) properties and better thermal conductivity. In general, our work indicates that nano‐ZnO, as the novel thermal conductive reinforcing filler, is suitable to prepare elastomer products serving in dynamic conditions, with the longer expected service life. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Influence of filler type and content on thermal conductivity and mechanical properties of thermoplastic compounds

Combining thermal conductivity with electrical isolation is a very interesting topic for electronic applications in order to transfer the generated heat. Typical approaches combine thermally conductive fillers with a thermoplastic matrix. The aim of this work was to investigate the influence of different fillers and matrices on the thermal conductivity of the polymer matrix composites. In this study, various inorganic fillers, including aluminum oxide (Al₂O₃), zinc oxide (ZnO), and boron nitride (BN) with different shapes and sizes, were used in matrix polymers, such as polyamide 6 (PA6), polypropylene (PP), polycarbonate (PC), thermoplastic polyurethane (TPU), and polysulfone (PSU), to produce thermally conductive polymer matrix composites by compounding and injection molding. Using simple mathematical models (e.g., Agari model, Lewis–Nielson model), a first attempt was made to predict thermal conductivity from constituent properties. The materials were characterized by tensile testing, density measurement, and thermal conductivity measurement. Contact angle measurements and the calculated surface energy can be used to evaluate the wetting behavior, which correlates directly with the elastic modulus. Based on the aforementioned evaluations, we found that besides the volume fraction, the particle shape in combination with the intrinsic thermal conductivity of the filler has the greatest influence on the thermal conductivity of the composite.     

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.     

硅灰石与石墨对聚四氟乙烯摩擦磨损性能的影响

以针状的硅灰石和鳞片石墨为填料,采用冷压—烧结工艺制备了不同填料含量的聚四氟乙烯（PTFE）复合材料,考察了复合材料的摩擦磨损性能,并利用扫描电子显微镜对磨痕和转移膜进行了分析。结果表明,单独填充硅灰石和石墨时,PTFE的磨损率都会随填料含量的增加而降低,硅灰石的作用要强于石墨;但硅灰石会使PTFE的摩擦因数明显增大,而石墨会使PTFE的摩擦因数降低;2种填料提升PTFE耐磨性的作用机理不同,硅灰石在摩擦过程中会在滑动界面区域上逐渐堆积,起到优先承担载荷的作用;而石墨在摩擦过程中会发生片层的滑移与剥离,有助于转移膜的形成;适量的硅灰石（含量为20 %,质量分数,下同）与石墨（含量为5 %或10 %）复合填充能产生协同效应,使PTFE的磨损率进一步降低,耐磨性比未填充的PTFE提高200倍。     

环氧树脂/氧化锌晶须/氮化硼导热绝缘复合材料的研究

以环氧树(脂EP)为基体,分别以氧化锌晶(须ZnOw)和ZnOw/氮化硼(BN)混合物为导热填料,制备了EP导热绝缘复合材料。研究了填料含量对复合材料导热性能、电绝缘性能及力学性能的影响,并利用扫描电镜对复合材料的断面形貌进行了观察。结果表明:随着导热填料含量的增大,复合材料的导热系数和介电常数增大,体积电阻率下降,而拉伸强度呈先增大后减小的趋势;在填料含量相同的情况下,EP/ZnOw/BN复合材料比EP/ZnOw复合材料具有更好的导热性能;当填料体积分数为15%时,EP/ZnOw/BN复合材料的热导率为1.06W/(mK)而,EP/ZnOw复合材料的热导率仅为0.98W/(mK)。     

Mechanism of filler action in reducing the wear of PTFE polymer by differential scanning calorimetry

Two types of representative nanometer materials, i.e., fibroid nanometer attapulgite and approximate spherical ultrafine diamond, were selected as fillers of polytetrafluoroethylene (PTFE) to study the mechanism of the wear‐reducing actions of the fillers in PTFE composites. The friction and wear tests were performed on a block‐on‐ring wear tester under dry sliding conditions. Differential scanning calorimetry (DSC) was used to investigate material microstructure and to examine modes of failure. No significant change in coefficient of friction was found, but the wear rate of PTFE composites was orders of magnitude less than that of pure PTFE. DSC analysis revealed that nanometer attapulgite and ultrafine diamond played a heterogeneous nucleation role in PTFE matrix and consequently resulted in increasing the crystallinity of PTFE composites. Moreover, the PTFE composite with higher heat absorption capacity and crystallinity exhibited improved wear resistance. A propositional “sea‐frusta” frictional model explained the wear mechanism of filler action in reducing the wear of PTFE polymer, i.e., fillers in the PTFE matrix effectively reduced the size of frictional broken units for PTFE composites and restrained the flowability of the units, as well as supporting the applied load. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Effects of various kinds of fillers on the tribological behavior of polytetrafluoroethylene composites under dry and oil‐lubricated conditions

Polytetrafluoroethylene (PTFE)‐based composites filled with various inorganic fillers in a volume fraction of 30% were prepared. The tribological behavior of the PTFE composites sliding against AISI52100 steel under dry and liquid paraffin‐lubricated conditions was investigated on an MHK‐500 model ring‐on‐block test rig. The morphologies of worn surfaces and wear debris were observed with a scanning electron microscope (SEM) and an optical microscope. As the results, different fillers show different effects on the tribological behavior of the PTFE composites, while the composite shows much different tribological behavior under lubricated conditions as compared with dry sliding. The tribological behavior of the PTFE composites under dry sliding is greatly related to the uniformity and thickness of the transfer films. Only the PTFE composites with a transfer film of good uniformity and proper thickness may have excellent tribological behavior. The PTFE composites show much better tribological behavior under lubrication of liquid paraffin than under dry sliding, namely, the friction coefficients are decreased by 1 order of magnitude and the wear rate by 1–3 orders of magnitude. Observation of the worn composite surfaces with SEM indicates that fatigue cracks were generated under lubrication of liquid paraffin, owing to the absorption and osmosis of liquid paraffin into the microdefects of the PTFE composites. The creation and development of the fatigue cracks led to fatigue wear of the PTFE composites. This would reduce the mechanical strength and load‐supporting capacity of the PTFE composites. Therefore, the tribological behavior of the PTFE composites under lubrication of liquid paraffin is greatly dependent on the compatibility between the PTFE matrix and the inorganic fillers. In other words, the better is the compatibility between PTFE and fillers the better is the tribological behavior of the composites. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1891–1897, 2001     

Influence of organic montmorillonite nanoparticles on the microstructures and thermal and tribological properties of polyethersulfone and polytetrafluoroethylene composites

Because of high wear rate and low thermal deformation temperature, the generalization and application of polytetrafluoroethylene (PTFE) in the field of tribology is restrained to a certain extent. In order to improve the wear resistance and thermal stability of this self‐lubricating polymer, organic montmorillonite (OMMT) nanoparticle reinforced polyethersulfone (PES) and PTFE ternary composites were prepared by the cold molding and vacuum sintering technology. The effects of sodium montmorillonite (Na‐MMT) and OMMT on the microstructures, thermal stabilities and tribological properties of PTFE composites were comparatively studied. The results show that the thermal stability of the PES/PTFE composites is clearly improved by the incorporation of OMMT nanoparticles. Not only the friction coefficients but also the wear rates of OMMT/PES/PTFE composites are less than those of Na‐MMT/PES/PTFE composites under identical tribological tests. Of all these PTFE composites, the PES/PTFE composite containing 10.0 wt% OMMT nanoparticles exhibits the best friction and wear properties (μ = 0.14, k = 5.78 × 10^?15 m³ N^–1 m^?1). This can be attributed to the existence of a polymer multicomponent layer consisting of PTFE, PES and OMMT on the composite surface as well as the formation of uniform PTFE transfer film on the worn surfaces of metal counterparts.     

Polymer composites with enhanced thermal conductivity via oriented boron nitride and alumina hybrid fillers assisted by 3-D printing

Herein, oriented boron nitride (BN)/alumina (Al₂O₃)/polydimethylsiloxane (PDMS) composites were obtained by filler orientation due to the shear-inducing effect via 3-D printing. The oriented BN platelets acted as a rapid highway for heat transfer in the matrix and resulted in a significant increase in the thermal conductivity along the orientation direction. Extra addition of spherical Al₂O₃ enhanced the fillers networks and resulted in the dramatic growth of slurry viscosity. This, together with filler orientation induced the synergism and provided large increases in the thermal conductivity. A high orientation degree of 90.65% and in-plane thermal conductivity of 3.64 W/(m∙K) were realized in the composites with oriented 35 wt% BN and 30 wt% Al₂O₃ hybrid fillers. We attributed the influence of filler orientation and hybrid fillers on the thermal conductivity to the decrease of thermal interface resistance of composites and proposed possible theoretical models for the thermal conductivity enhancement mechanisms.     

BN／Al2O3／环氧树脂导热复合材料的制备与性能

分别采用氮化硼（BN）、氧化铝（Al2O3）和复配BN／Al2O3作为导热填料制备环氧树脂导热复合材料。结果表明,环氧树脂热导率随导热填料用量的增加而增大;同等用量下,BN／Al2O3／环氧树脂复合材料的导热性能均优于BN／环氧树脂和Al2O3／环氧树脂。当BN／Al2O3质量分4~50％[m（BN）／m（Al2O3）=3／1J,复合材料热导率为08194W／mK。此外,随BN／Al2O3用量的增加,环氧树脂的介电常数和介电损耗角正切增加,而弯曲强度和冲击强度则先增加后降低。     

Preparation and properties of epoxy/BN highly thermal conductive composites reinforced with SiC whisker

A simple method is reported to increase the thermal conductivity and improve the poor mechanical properties caused by high filler loadings of epoxy composites, simultaneously. Epoxy composites were prepared with micro‐boron nitride (BN) and silicon carbon whisker (SiCw) chemically treated by 3‐aminopropyltriethoxysilane (KH550) and 3‐glycidyloxypropyltrimethoxysilane (KH560), respectively. Effects of surface modification of BN particles on the thermal conductivity and flexural strength of epoxy/BN composites were investigated. About 3% SiCw particles grafted with KH560 were incorporated into composites with BN grafted with KH550, which led to about 13.8–17.8% increase of the flexural strength as well as a marginal improvement of the thermal conductivity of composites, and they possessed good dielectric properties. In addition, dynamic mechanical analysis results showed that the storage modulus of composites increased significantly with the addition of fillers, while the glass transition temperature exhibited a slight decrease. POLYM. COMPOS., 37:2611–2621, 2016. © 2015 Society of Plastics Engineers     

An investigation of thermal and tribological behaviors of PTFE‐based silicon composites filled with AlN and flake graphite particles

The thermal and tribological properties of silicon composites were improved by choosing polytetrafluoroethylene (PTFE) as a thickener and alumina nitride (AlN) and flake graphite (FG) as thermal conductive additives, producing AlN‐modified, FG‐modified, and AlN/FG‐modified PTFE‐based thermal silicon composites (AlN–PTSC, FG–PTSC, and AlN/FG–PTSC, respectively). Three‐dimensional network‐configuration representative volume element models were built to investigate the thermal properties of these composites by applying a Monte Carlo, controllable, spatial distribution algorithm. The composites’ thermal conductivity and volume resistance were also measured. Tribological tests were conducted using a ball‐on‐disk reciprocating friction and wear tester. Scanning electron microscopy and energy dispersive spectroscopy were used to analyze the morphologies and elements of worn surfaces. The results showed that AlN/FG–PTSC possessed the best thermal properties, which were ascribed to a compact thermal conductive network; thermal conductivity was 88.8% and 44.8% greater than the highest value of AlN–PTSC and FG–PTSC, respectively. The numerical values of thermal conductivity were in a good agreement with experimental results. The optimal electrical tribological properties of AlN/FG–PTSC were ascribed to the functions of thermal and electrical properties combined, which could be helpful in abating the arc erosion on friction contacts. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45263.     

Thermal and electrical properties of aluminum nitride/boron nitride filled polyamide 6 hybrid polymer composites

The effects of boron nitride (BN) and aluminum nitride fillers on polyamide 6 (PA6) hybrid polymer composites were investigated. In particular, the thermal and electrical conductivity, thermal transition, thermal degradation, mechanical and morphological properties and chemical bonds characteristic of the materials with crystal structure of BN and aluminum nitride (AlN) filled PA6 prepared at different concentrations were characterized. Thermal conductivity of hybrid systems revealed a 1.6-fold gain compared to neat PA6. The highest thermal conductivity value was obtained for the composite containing 50 vol% additives (1.040 W/m K). A slight improvement in electrical conductive properties of composites appears and the highest value was obtained for the 50 vol% filled composite with only an increase by 3%. The microstructure of these composites revealed a homogeneous dispersion of AlN and BN additives in PA6 matrix. For all composites, one visible melting peak around 220°C related to the α-form crystals of PA6 was detected in correlation with the X-ray diffraction results. An improved thermal stability was obtained for 10 vol% AlN/BN filled PA6 composite (from 405.41°C to 409.68°C). The tensile strength results of all composites were found to be approximately 22% lower than pure PA6.     

Reinforced thermal conductivity and mechanical properties of in situ microfibrillar composites through multistage stretching extrusion

To surmount difficulty of the melt processing and deterioration of mechanical properties of polymer composites induced by high fraction of the reinforced fibers and thermal conductive fillers, polyethylene (PE)/boron nitride (BN)/polyamide 6 (PA6) and PE/BN/poly(‐hydroxybenzate‐co‐DOPO‐benzenediol dihydrodiphenyl ether terephthalate) (PHDDT) in situ microfibrillar composites were prepared through multistage stretching extrusion. The experimental results showed that both the tensile and impact strength of the PE/BN/PA6 and PE/BN/PHDDT composites were improved. Meanwhile, the thermal conductivities of the PE/BN, PE/BN/PA6, and PE/BN/PHDDT composites were also reinforced. Based on the equation proposed by Y. Agari, the new modified equations can well predict the thermal conductivity of the composites prepared through multistage stretching extrusion with different number of laminating‐multiplying elements. In addition, it was found that PHDDT can act as a “processing aid” to reduce the viscosity of the PE/BN composites. POLYM. COMPOS., 38:2663–2669, 2017. © 2015 Society of Plastics Engineers     

Friction and wear characteristics of metal sulfides and graphite‐filled PTFE composites under dry and oil‐lubricated conditions

Five kinds of polytetrafluoroethylene (PTFE)‐based composites, pure PTFE, PTFE + 30(v)% MoS₂, PTFE + 30(v)% PbS, PTFE + 30(v)% CuS, and PTFE + 30(v)% graphite (GR) composites, were first prepared. Then the friction and wear properties of these PTFE composites, sliding against GCr15‐bearing steel under both dry and liquid paraffin‐lubricated conditions, were studied by using an MHK‐500 ring‐on‐block wear tester. Finally, the worn surfaces and the transfer films of the PTFE composites formed on the surface of GCr15 bearing steel were investigated by using a scanning electron microscope (SEM) and an optical microscope, respectively. Experimental results show that filling with MoS₂, PbS, CuS, or graphite to PTFE can reduce the wear of the PTFE composites by two orders of magnitude compared to that of pure PTFE under dry friction conditions. However, the friction and wear‐reducing properties of these PTFE composites can be greatly improved by lubrication with liquid paraffin. Investigations of transfer films show that MoS₂, PbS, CuS, and graphite promote the transfer of the PTFE composites onto the surface of GCr15‐bearing steel under dry friction conditions, but the transfer of the PTFE composites onto the surface of GCr15‐bearing steel can be greatly reduced by lubrication with liquid paraffin. SEM examinations of worn surfaces show that with lubrication of liquid paraffin, the creation and development of the cracks occurred on the worn surfaces of the PTFE composites under load, which reduces the load‐supporting capacity of the PTFE composites. This would lead to the deterioration of the friction and wear properties of the PTFE composites under higher loads (>600N). © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 751–761, 1999