Study of flame-retarded silicone rubber with ceramifiable property

Fire-resistant ceramifiable silicone rubber composites with excellent comprehensive property were prepared in this paper. Silicone rubber was used as the base polymer, aluminum hydroxide, magnesium hydroxide, zinc borate, and glass frits were additives. The flammability and thermal stability properties, essentially focusing on the use of the limiting oxygen index and thermogravimetric analysis, were all studied. Besides, the ceramic residues were also studied by mechanical testing, scanning electron microscopy, and X-ray diffraction. The ceramifying silicone rubber could achieve a limiting oxygen index value of 34.8%, and the flexural strength of ceramic residues formed at 800°C was 9.7 MPa. The residue of composites was approximately 58.6% at 700°C, which is significantly higher than that of neat silicone rubber. The scanning electron microscopy analysis depicted that a dense structure was formed as formed.     

Dielectric,Mechanical, and Thermal Properties of Low-Permittivity Polymer–Ceramic Composites for Microelectronic Applications

A new low-permittivity polymer–ceramic composite for packaging applications has been developed. The ceramic-reinforced polyethylene and polystyrene composites were prepared by melt mixing and hot molding techniques. Low-loss, low-permittivity Li₂MgSiO₄ (LMS) ceramics prepared by the solid-state ceramic route were used as the filler to improve the dielectric properties of the composites. The relative permittivity and dielectric loss were increased with the increase in the ceramic loading at radio and microwave frequencies. The mechanical properties and thermal conductivity of the Li₂MgSiO₄-reinforced polymer–ceramic composite were also investigated. The stability of the relative permittivity of polymer–ceramic composites with temperature and frequency was investigated. The experimentally observed relative permittivity, thermal expansion, and thermal conductivity were compared with theoretical models.     

Enhanced dielectric and mechanical properties of CaCu3Ti4O12/Ti3C2Tx MXene/silicone rubber ternary composites

Dielectric polymer composites with conducting fillers would have great potential for diverse applications if their severe leakage loss could be addressed. In this regard, ternary composites using both ceramic and conducting materials as fillers might be an enabler for high dielectric constant and low dielectric loss. Herein, ternary composites with both Ti₃C₂T_x MXene conducting nanosheets and CaCu₃Ti₄O₁₂ (CCTO) dielectric particles embedded in silicone rubber were studied. It was found that a ternary composite with 1.2 wt% (0.40 vol%) Ti₃C₂T_x MXene and 12 wt% (2.58 vol%) CCTO could provide an overall superior performance that include a high dielectric constant of 8.8, low dielectric loss of less than 0.0015, good thermal stability up to 450 °C, and excellent mechanical properties with tensile strength of 569 kPa, elastic module of 523 kPa and elongation at break of 333%. The outstanding performance is attributed to the improved uniform dispersion and good interfacial compatibility of mixed fillers in the polymer matrix, suggesting ternary composites might be a better option over their binary counterparts in preparing high performance dielectric composites.     

Improved flame retardancy and ceramifiable properties of PE composites by the combination of aluminum hypophosphite and zinc borate

Ceramifiable polyolefin materials protect circuits by forming compact ceramic layers under fire conditions, and can have an excellent application prospect in the refractory cable field. In this paper, Aluminum hypophosphite (AHP) and zinc borate (ZB) were added to further improve flame retardancy and ceramifiable properties of polyethylene (PE)/silicon powder (SP)/wollastonite (WS)/glass frits (GF) composites. The LOI values of composites with AHP/ZB can reach 23.5%, significantly higher than that of PE/SP/WS/GF composites (19.6%). The thermal stability behavior and char yield behaviors of composites could also be characterized by the TG test. The incorporation of AHP/ZB enhances the flexural strength of residue formed at 1000°C from 0.1 to 20.5 MPa. In addition, a new crystal is formed at high temperatures and is identified as the calcium aluminum phosphate phase [CAP, Ca₉Al (PO₄)₇] by XRD analysis. The flow of molten ZB accelerates the reaction of AHP and WS, and this eutectic reaction promotes the formation and stability of ceramics. Furthermore, the SEM analysis reveals the fluxing effect of ZB at low temperatures and AHP at high temperatures. The incorporation of AHP/ZB with a ratio of 1:1 could effectively avoid the vitrification of ceramics and improve their dimensional stability.     

铜及其氧化物填充UHMWPE力学、摩擦学性能研究

在超高分子量聚乙烯(UHMWPE)中分别填充铜粉、氧化铜粉和氧化亚铜粉,用万能材料试验机、摩擦磨损试验机等研究了三种填料对UHMWPE复合材料力学性能和摩擦磨损性能的影响,利用扫描电子显微镜对几种材料的磨损表面进行了观察和分析。结果表明,在填料添加量相同时,铜粉的减摩耐磨效果最好,氧化铜粉的减摩耐磨效果次之,氧化亚铜粉的减摩耐磨效果最差;以体积分数25％的铜粉填充的UHMWPE复合材料,具有良好的力学性能和摩擦学性能,是一种有应用前景的聚合物基减摩抗磨材料。     

Effect of the filler morphology on the crystallization behavior and dielectric properties of the polyvinylidene fluoride-based composite

Ceramic/polymer composites can be chemically stable, mechanically strong, and flexible, which make them candidates for electric devices, such as pressure or temperature sensors, energy storage or harvesting devices, actuators, and so forth. Depending on the application, various electrical properties are of importance. Polymers usually have low dielectric permittivity, but increased dielectric permittivity can be achieved by the addition of the ceramic fillers with high dielectric constant. With the aim to enhance dielectric properties of the composite without loss of flexibility, 5 wt% of BaTiO₃-Fe₂O₃ powder was added into a polyvinylidene fluoride matrix. The powder was prepared by different synthesis conditions to produce core/shell structures. The effect of the phase composition and morphology of the BaTiO₃-Fe₂O₃ core/shell filler on the structure and lattice dynamics of the polymer composites was investigated. Based on the results of the thermal analysis, various parameters of ceramic/polymer composites were determined. Differences in the phase composition and morphology of the filler have an influence on the formation of various polyvinylidene fluoride allomorphs and the degree of crystallinity. Furthermore, the dielectric performances of pure polyvinylidene fluoride and the polymer/ceramic composites were measured.     

Effects of aluminium nitride silane-treatment on the mechanical and thermal properties of polybenzoxazine matrix

A new kind of polymer composite, produced from the typical polybenzoxazine and 0–30 wt-% native and silane-treated aluminium nitride (T-AlN), was investigated. The mechanical tests revealed a significant increase in the microhardness and flexural properties upon adding the T-AlN particles compared to that obtained from the untreated ones. By adding 0–30 wt-% T-AlN, the tensile moduli were accurately reproduced by the Halpin-Tsai and Nielsen models. At 30 wt-% T-AlN, dynamic mechanical analysis showed a significant increase in the storage moduli and the glass transition temperature (T_g), reaching 3.2?GPa and 217°C, respectively. The thermal stability of these materials was significantly improved upon the addition of the T-AlN fillers. These improvements are attributed to the high thermal and mechanical properties of the fillers and their good dispersion and adhesion in and to the matrix as revealed by a morphological analysis.     

Mechanical and fracture properties of zircon–mullite composites obtained by direct sintering

Refractory materials based on zircon (ZrSiO₄) are applied in high temperature applications (1400–1500 °C). They are demonstrated to have an excellent chemical attack resistance, such as corrosion or degradation due to molten glass or metals. On the other hand mullite (3Al₂O₃2SiO₂) is important both in traditional and advanced ceramics. Although multi-phase ceramic materials were always used, nowadays composite materials have an important industrial and technological development, to enlarge the designing capability of the manufacturer in properties and behaviors. The objective of the present work is to study the influence of the starting composition on the mechanical and fracture properties of zircon–mullite composites obtained by direct sintering of consolidated samples by slip cast of concentrated aqueous suspensions in plaster molds. Zircon–mullite composites using 15–45 wt% mullite were prepared and compared with pure zircon material obtained in the same conditions. Flexural strength (σ_f), dynamic elastic modulus (E), toughness (K_IC) and initiation fracture surface energy (γ_NBT) were evaluated. The results were explained by microstructure and the XRD analysis. The presence of mullite increased the zircon thermal dissociation. The ZrO₂ was a product of this reaction and also influence the mechanical and fracture properties of these materials through several combined mechanisms.Zircon composites prepared with 45 wt% of mullite in the starting powder showed a higher fracture toughness and initiation energy than ceramics derived from pure zircon. Microstructure consisting in mullite as a continuous predominant phase in which zircon and zirconia grains were distributed improved almost all the mechanical and fracture properties.     

Self‐Generating High‐Temperature Oxidation‐Resistant Glass‐Ceramic Coatings for C–C Composites Using UHTCs

Carbon–carbon (C–C) composites are ideal for use as aerospace vehicle structural materials; however, they lack high‐temperature oxidation resistance requiring environmental barrier coatings for application. Ultra high‐temperature ceramics (UHTCs) form oxides that inhibit oxygen diffusion at high temperature are candidate thermal protection system materials at temperatures >1600°C. Oxidation protection for C–C composites can be achieved by duplicating the self‐generating oxide chemistry of bulk UHTCs formed by a “composite effect” upon oxidation of ZrB₂–SiC composite fillers. Dynamic Nonequilibrium Thermogravimetric Analysis (DNE‐TGA) is used to evaluate oxidation in situ mass changes, isothermally at 1600°C. Pure SiC‐based fillers are ineffective at protecting C–C from oxidation, whereas ZrB₂–SiC filled C–C composites retain up to 90% initial mass. B₂O₃ in SiO₂ scale reduces initial viscosity of self‐generating coating, allowing oxide layer to spread across C–C surface, forming a protective oxide layer. Formation of a ZrO₂–SiO₂ glass‐ceramic coating on C–C composite is believed to be responsible for enhanced oxidation protection. The glass‐ceramic coating compares to bulk monolithic ZrB₂–SiC ceramic oxide scale formed during DNE‐TGA where a comparable glass‐ceramic chemistry and surface layer forms, limiting oxygen diffusion.     

An experimental design approach in formulating a ceramifiable EVA/PDMS composite coating for electric cable insulation

The study used d ‐optimal mixture design of experiments to formulate a ceramifiable EVA/PDMS composite with optimized ceramified flexural strength properties after being exposed to elevated temperatures. The ideal amounts of inorganic fillers and their interaction within the polymer composite were studied. It was found that good polymer and ceramic properties were achieved when using 59% EVA/PDMS polymer blend with inorganic fillers of 11% calcium carbonate, 10% aluminium hydroxide, 11% muscovite mica, and 9% calcined kaolinite, respectively. TGA, SEM, and PXRD were employed to study the behavioral changes of the EVA/PDMS composite during and postceramification process. Although all inorganic fillers used were important, muscovite mica played a special role not only in the ceramification process, but also in keeping the ceramic product physically stable. Microstructural analysis of the cross‐sectional area of the ceramic product showed that it was multilayered with an inhomogeneous distribution of the chemical composition across its layers. POLYM. COMPOS., 38:371–380, 2017. © 2015 Society of Plastics Engineers     

The dynamic mechanical analysis of epoxy–copper powder composites using azole compounds as coupling agents

The dynamic mechanical properties of cured epoxy resin have been studied in which copper powder treated or untreated with azole compounds was used as fillers. The untreated fillers do not shift the glass transition temperature of the matrix polymer of the composites, whereas the storage modulus rises with increasing content of fillers. The application of azole compounds as coupling agents, which could react with both copper and epoxy resin, extended the polymer–filler interactions. The composite filled with copper powder treated with benzotriazole shows a strong reinforcement effect and high resistance to moisture.     

Characterization and transport properties of ceramic filler incorporated natural rubber composites

Crystalline glass–ceramic fillers were prepared from calcium carbonate, silica, alumina, and calcium fluoride by heating and subsequent quenching in cold water. The fillers were incorporated into natural rubber (1,4-cis-polyisoprene) and the filled rubber composites were crosslinked with sulfur in the presence of different rubber additives. The unfilled and filled rubber composites were characterized. The transport properties of benzene, toluene, and p-xylene (BTX) through the rubber composites were studied in terms of sorption, diffusion, permeation, and mass transfer coefficients. The effect of the ceramic fillers on the mechanical, thermal and transport properties were studied. The sorption data at different temperatures were used for calculating activation energy of diffusion, permeation, free energy, and enthalpy of sorption. The BTX remained in the liquid state within the composite matrix as evident from negative ΔS. The diffusion coefficient (D) and mass transfer coefficient (k_mtc) of BTX decreased with the increase in filler loading. Accordingly, for the transport of BTX the unfilled rubber showed a D (D × 10⁷ cm²/s) and mass transfer coefficient (k_mtc × 10⁴ cm/s) of 5.67/3.97/2.96 and 7.71/7.08/7.04, respectively which decreased to 5.06/2.95/2.57 and 7.53/6.95/6.90, respectively for the composite containing 50 wt.% ceramic filler.     

Retention of Mechanical and Thermal Properties of Hydrothermal Aged Glass Fiber-Reinforced Polymer Nanocomposites

The combined effect of nano-Al₂O₃ and TiO₂ fillers on residual mechanical and thermal properties of glass fiber-reinforced polymer composites has been evaluated. The results reveal that the addition of 0.1?wt% of Al₂O₃ and 0.1?wt% of TiO₂ into the epoxy matrix reduces the water diffusivity by 12%. The residual flexural and interlaminar shear strength of the nanocomposite have been increased by 19 and 21%, respectively, as compared to those of neat epoxy glass fiber-reinforced polymer composite. In spite of reduction in water diffusivity and increase in strength, there was no improvement in glass transition temperature of the nanocomposites.     

Enhanced dielectric response of ternary polymeric composite films via interfacial bonding between V2C MXene and wide-bandgap ZnS

Increasing the dielectric constant of polymer/sulfide ceramic composites by using wide-bandgap semiconducting sulfide ceramic fillers like ZnS is difficult because of their low interface polarization. To increase the dielectric constant, in this study, ternary polymer-based composite films were designed and fabricated using a hybrid filler consisting of shell-like ZnS particles and core-like V₂C MXene particles. First, V₂C MXene with a multi-layered structure was synthesized from the simplest raw materials followed by the in-situ hydrothermal growth of ZnS particles around the V₂C particles. Then, binary polymer/ZnS and ternary polymer/V₂C–ZnS composites were fabricated, and their dielectric, conductive, and electrical breakdown properties were investigated. Finally, the effect of interfacial bonding between the V₂C and ZnS phases was investigated by density functional theory calculations, and the contribution of V₂C/ZnS interfacial bonding to the higher dielectric constant of the ternary composites than that of the binary composites was explained. The ternary composites exhibited balanced electrical properties suitable for energy storage applications. The ternary composite with 10 wt% hybrid filler loading exhibited a high dielectric constant of ~52, a low dielectric loss of ~0.11 at 100 Hz, and a high electrical breakdown strength of ~202 MV m⁻¹. This study paves the way for the facile fabrication of high-performance composite dielectrics for application in advanced capacitors.     

Properties and processing characteristics of dielectric-filled epoxy resins

A family of casting composites, epoxy resins with mineral fillers, having a range of electrical properties, are being developed. In such composites, the dielectric constant is controlled primarily by varying the filler material in composition and proportions. The present work reports on the mechanical properties of composites made with two types of filler, an alumina powder (XA3500 from ALCOA) and a BaTiO₃/TiO₂ ceramic powder (ATD-50 from Ampex). Dependence of mechanical properties on curing agents was also determined. Filler contents from 0 to 40 percent volume were used. Epoxy systems contained single epoxy resin with both amine and anhydride hardeners. Processing of the anhydride-cured systems was easier than that of the amine-based systems because of their lower viscosity and longer gel time of the former. However, the anhydride-cured systems required higher processing temperatures. Curing kinetics and molecular bonding were investigated using a combination of differential scanning calorimetry, dynamic mechanical thermal analysis, and scanning electron microscopy. Activation energies of 11.2 kcal/mole and 12.1 kcal/mole were obtained for the curing of the amine-based and the anhydride-based composites respectively, and a small difference in the glass transition temperature was also observed. These effects can be attributed to the difference in the structure of the curing agents. The epoxy resin cured with NMA is less ductile compared with those cured with MTHPA or MHHPA due to slight chemical modification on the ring structures. This dependence of ductility on curing agent was observed in specimens with different filler contents. Although the presence of the filler materials was found to enhance the mechanical properties of the epoxy, the fracture mode in these materials is still brittle.     

Improvement of mechanical performance of epoxy resins filled with cobalt and chromium powders

Epoxy/ powder metal composites have interesting electrical properties, becoming conductors above the percolation threshold. To complete this study, mechanical investigations have been carried out to show the influence of the fillers on the mechanical performance of these composites. In this framework, different epoxy/metallic powders (Cobalt, Chromium) composites were prepared. Scanning Electron Microscopy showed that the dispersion of the metallic fillers in the matrix is almost homogeneous. The dynamic mechanical thermal analysis (DMTA) measurements showed the dependence of the viscoelastic parameters with the frequency, temperature, nature, and content of fillers. The main relaxations observed are the primary α relaxation (associated to the glass transition, T_g) and a secondary β relaxation. A second DMTA run on the same samples showed a slight increase of the T_g. It clearly showed that the used metallic fillers improve the mechanical properties of the obtained composites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

The synergistic effects on enhancing thermal conductivity and mechanical strength of hBN/CF/PE composite

In this work, a simple and novel method was applied to prepare polymer composites by taking the advantage of melt flow shear force driving orientation of the fillers. By using this method, hexagonal boron nitride/polyethylene (hBN/PE) and hexagonal boron nitride/carbon fibers/polyethylene (hBN/CF/PE) composites were fabricated to be possessed of high thermal conductivity and mechanical properties. A high thermal conductivity of 3.11 W/mK was realized in the composite containing 35 wt% hBN and 5 wt% CF, which was over 1,200% higher than that of unfilled PE matrix. Under this component, the compressive strength and modulus of hBN/CF/PE composite were determined to be 30.1 and 870.9 MPa, respectively, which were far higher than that of unfilled PE accordingly. The bending performance was also somewhat enhanced. Meanwhile, the bulk resistivity of the composite material reached 2.55 × 10¹¹ Ω·cm, which was basically the same as that of pure PE. The novel composites with high thermal conductivity, excellent mechanical properties, and controllable electrical insulation could be a potential thermal management material for electrical and electronics industries.     

Microstructure and mechanical properties of B4C–TiB2 ceramic composites prepared via a two-step method

B₄C–TiB₂ ceramic composites were fabricated by a two-step method. First, B₄C–TiB₂ composite powders were synthesized from TiC–B powder mixtures at 1400 ℃, then mixed with commercial B₄C powders by ball milling and the B₄C–TiB₂ ceramic composites were prepared by hot pressing at 1950 ℃. This two-step method not only effectively refined TiB₂ grains, but also allowed the composition of the composites to be freely designed. The microstructure and mechanical properties of the composites were investigated. The results showed that the B₄C–TiB₂ ceramic composite with a 10 wt% TiB₂ content obtained the ideal comprehensive performance, with a volume density, Vickers hardness, bending strength, and fracture toughness of 2.61 g/cm³, 35.3 GPa, 708 MPa, and 5.82 MPa m^1/2, respectively. The advantages of the in-situ reaction process were fully exerted by the two-step method, which made a remarkable contribution to the excellent properties of B₄C–TiB₂ ceramic composites.     

Improved dielectric and mechanical properties of Ti3C2Tx MXene/silicone rubber composites achieved by adding a few boron nitride nanoplates

MXenes have attracted great attentions in the fabrication of dielectric polymer composites because of their excellent electrical conductivity. However, the high dielectric loss tangent would suppress the application of such polymer-based composites. Incorporating insulating fillers might be a solution. Herein, Ti₃C₂T_x MXene/silicone rubber (SR) composites incorporated with boron nitride (BN) nanoplates were prepared. The homogeneous distribution of fillers was obtained in the composites, which was also thermally stable up to 400 °C. Dielectric constant of 7.06 (2.54 times of pure SR) and dielectric loss tangent of 0.00131 were achieved when the filling contents of MXene and BN in SR composite were 1.2 wt% and 5 wt%, respectively. The improved dielectric constant can be ascribed to the enhanced interfacial polarization and the formation of conductive network, while the low dielectric loss tangent can be due to the insulating interlayers of BN which could inhibit the transfer of free electrons from conductive fillers to the insulating polymer matrices. BN/MXene/SR composites displayed improved mechanical properties (tensile stress of 671 kPa and elongation at break of 353%) and good flexibility (elastic modulus of 540 kPa) due to the low filling content of fillers. This work is promising for preparing dielectric polymer composites in applications of electronic devices.     

Effect of fiber orientation on viscoelastic properties of polymer matrix composites subjected to thermal cycles

Fibers in polymer composites can be designed in various orientations for their usage in service life. Various fiber orientated polymer composites, which are used in aeroplane and aerospace applications, are frequently subjected to thermal cycles because of the changes in body temperatures at a range of −60 to 150°C during flights. It is an important subject to investigate the visco‐elastic properties of the thermal cycled polymer composite materials which have various fiber orientations during service life. Continuous fiber reinforced composites with a various fiber orientations are subjected to 1,000 thermal cycles between the temperatures of 0 and 100°C. Dynamic mechanic thermal analysis (DMTA) experiments are carried out by TA Q800 type equipment. The changes in glass transition temperature (T_g), storage modulus (E′), loss modulus (E′′) and loss factor (tan δ) are inspected as a function of thermal cycles for different fiber orientations. It was observed that thermal and dynamic mechanical properties of the polymer composites were remarkably changed by thermal cycles. It was also determined that the composites with [45°/−45°]_s fiber orientation presented the lowest dynamic mechanical properties. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers