Effects of carbon additives on the properties of ZrB2–based composites: A review

This review presents the recent achievements on carbon additives incorporated in ZrB₂ ceramics, improved properties, and their advancements. Monolithic ZrB₂ ceramics have broad potential applications, but their critical drawbacks such as poor damage tolerance, and weak oxidation and ablation resistance confines their applicability. It is an important issue to resolve these shortages in physiochemical properties by engineering the composite ingredients and process design of the ceramic counterparts for an extensive production and applications, which are especially essential in high–tech industries and products. Carbon additives have exceptional characteristics including low density, low cost, and excellent thermo–mechanical stability. These materials have been incorporated in ZrB₂ ceramics to enhance their efficiency and form practical composite ceramics. Although addition of the secondary carbonaceous phases is generally supposed to improve the mechanical properties of ZrB₂ composites, it may also result in a decrease in other aspects of performance, comparing with monolithic ZrB₂ ceramics. In this work, we reviewed the methods and strategies for the preparation of carbon modulated ZrB₂ ceramic composites. Moreover, the advantages, disadvantages, and the productivity of the introduced composite ceramics have been explored and featured.     

Processing and mechanical properties of hot-pressed zirconium diboride – zirconium carbide ceramics

ZrB₂ was mixed with 0.5 wt% carbon and up to 10 vol% ZrC and densified by hot-pressing at 2000 °C. All compositions were > 99.8% dense following hot-pressing. The dense ceramics contained 1–1.5 vol% less ZrC than the nominal ZrC addition and had between 0.5 and 1 vol% residual carbon. Grain sizes for the ZrB₂ phase decreased from 10.1 µm for 2.5 vol% ZrC to 4.2 µm for 10 vol% ZrC, while the ZrC cluster size increased from 1.3 µm to 2.2 µm over the same composition range. Elastic modulus was ~505 GPa and toughness was ~2.6 MPa·m^½ for all compositions. Vickers hardness increased from 14.1 to 15.3 GPa as ZrC increased from 2.5 to 10 vol%. Flexure strength increased from 395 MPa for 2.5 vol% ZrC to 615 MPa for 10 vol% ZrC. Griffith-type analysis suggests ZrB₂ grain pullout from machining as the strength limiting flaw for all compositions.     

Effect of lattice defects on the thermal conductivity of β-Si3N4

Two types of β-Si₃N₄ were sintered at 1900 °C one for 8 h and the other for 36 h by using Yb₂O₃ and ZrO₂ as sintering additives. The latter specimen was further annealed at 1700 °C for 100 h to promote grain growth. The microstructures of the sintered materials were investigated by SEM, TEM, and EDS. The thermal conductivities of the specimens were 110 and 150 Wm⁻¹K⁻¹, respectively. The sintered material which possessed 110 Wm⁻¹K⁻¹ had numerous small precipitates that consisted of Yb, O and N elements and internal dislocations in the β-Si₃N₄ grains. In the sintered material with 150 Wm⁻¹K⁻¹ neither precipitates nor dislocations were observed in the grains. The microscopic evidence indicates that the improvement in the thermal conductivity of the β-Si₃N₄ was attributable to the reduction of internal defects of the β-Si₃N₄ grains with sintering and annealing time as the grains grew.     

Effect of lattice impurities on the thermal conductivity of β-Si3N4

Effect of impurities in the crystal lattice and microstructure on the thermal conductivity of sintered Si₃N₄ was investigated by the use of high-purity β-Si₃N₄ powder. The sintered materials were fabricated by gas pressure sintering at 1900 °C for 8 and 48 h with addition of 8 wt.% Y₂O₃ and 1 wt.% HFO₂. A chemical analysis was performed on the loose Si₃N₄ grains taken from sintered materials after the chemical treatment. Aluminum was not removed from Si₃N₄ grains, which originated from the raw powder of Si₃N₄. The coarse grains had fewer impurities than the fine grains. Oxygen was the major impurity in the grains, and gradually decreased during grain growth. The thermal conductivity increased from 88 Wm⁻¹ K⁻¹ (8 h) to 120 Wm⁻¹ K⁻¹ (48 h) as the impurities in the crystal lattice decreased. Purification by grain growth thus improved the thermal conductivity, but changing grain boundary phases might also influence the thermal conductivity.     

Theoretical study of the thermal conductivity of silica glass–crystal composites

The heat dissipation of silicate glasses draws much attention for various applications, and the desire for glasses with high thermal conductivity remains an unsolved challenge. The structural origin of thermal conductivity in glass remains not fully understood. The present study aims to elucidate the impact of embedding highly thermally conductive crystalline α-quartz in a silica glass matrix. We consider both nano-thread (NT) (1D) and nano-plate (NP) (2D) structures and use molecular dynamics simulations to evaluate the role of its connectivity on thermal conductivity in the glass–crystal composite as a function of the volume fraction of the α-quartz region. The directional dependence of thermal conductivity was also investigated to obtain percolation threshold behavior along the cross-sectional directions, whereas the parallel circuit model of electricity can be used to account for the change of thermal conductivity along the longitudinal direction. Incorporation of α-quartz NTs or NPs into silica glass offers the opportunity to enhance its thermal conductivity.     

Effect of incorporation of hafnium diboride nanofibers on thermomechanical properties of carbon fiber–phenolic composites

Carbon fiber/phenolic (C/Ph) composites were modified with different weight ratios of hafnium diboride (HfB₂) nanofibers to apperceive thermomechanical properties of C/Ph–Hf nanocomposites. Mechanical properties, thermal stability, and ablation resistance of C/Ph–Hf nanocomposites were found to be optimum when the weight percentage of HfB₂ was equal to one. Maximum flexural strength and modulus were obtained with 118 MPa and 1.9 GPa for C/Ph–1%Hf nanocomposite, respectively. Increasing the proportion of HfB₂, by delaying the temperature of thermal degradation of nanocomposites, enhanced the thermal stability and residual of C/Ph–Hf relative to C/Ph in both nitrogen and air environments. In the oxyacetylene flame test at 2500°C for 160 s, the optimum mass ablation rate of C/Ph–1%Hf nanocomposites was found to be 0.0150 g/s compared to 0.068 g/s for blank C/Ph, along with reducing the back surface temperature by 51%. The ablation mechanism of C/Ph–Hf nanocomposites after the oxyacetylene torch test was concluded from the derivations obtained from X-ray diffraction, energy dispersion spectroscopy, and microstructure analyses. These clarified that the formation of high-temperature species, such as HfO₂, HfC, and B₄C owing to oxidation of HfB₂ and subsequent reaction products with char, resulted in an increased ablation resistance of the nanocomposites.     

Improved ablation resistance of C–C composites using zirconium diboride and boron carbide

Zirconium diboride and boron carbide particles were used to improve the ablation resistance of carbon–carbon (C–C) composites at high temperature (1500 °C). Our approach combines using a precursor to ZrB₂ and processing them with B₄C particles as filler material within the C–C composite. An oxyacetylene torch test facility was used to determine ablation rates for carbon black, B₄C, and ZrB₂–B₄C filled C–C composites from 800 to 1500 °C. Ablation rates decreased by 30% when C–C composites were filled with a combination of ZrB₂–B₄C particles over carbon black and B₄C filled C–C composites. We also investigated using a sol–gel precursor method as an alternative processing route to incorporate ZrB₂ particles within C–C composites. We successfully converted ZrB₂ particles within C–C composites at relatively low temperatures (1200 °C). Our ablation results suggest that a combination of ZrB₂–B₄C particles is effective in inhibiting the oxidation of C–C composites at temperatures greater than 1500 °C.     

Studies on the microwave conductivity of polyaniline–polyvinyl chloride composites

Abstract

Polyaniline/polyvinyl chloride semi-interpenetrating polymer networks were prepared by the chemical oxidative polymerisation of aniline using ammonium persulphate as initiator in the presence of emulsion-grade polyvinyl chloride. The polymerisation was carried out for about 4 h at room temperature. It was then dried under different conditions (room temperature drying, vacuum drying and oven drying). The dielectric properties such as dielectric constant, conductivity, dielectric loss, dielectric heating coefficient and loss tangent were measured using the cavity perturbation technique. Cavity operating at S band was used for the study. The dielectric properties were found to depend on both the frequency and the composition of the mix (polyaniline-polyvinyl chloride).     

Effect of γ-radiation on the electrical conductivity of polycaproamide fibres

The electrical conductivity of polycaproamide fibres decreases by more than 100 times in the γ-radiation dose range of 0≤D≤1.6 MGy. The change in the conductivity of irradiated PCA fibres is unambiguously correlated with a change in their structure, strength, and thermomechanical properties. Rupture of chemical bonds in the polymer chain is the basic process in γ-irradiation of PCA fibres in air. St. Petersburg State University of Technology and Design. Translated fromKhimicheskie Volokna, No. 3, pp. 40–41, May–June, 1999.     

Effect of N–Ni coordination bond on the electrical and thermal conductivity of epoxy resin/nickel-coated graphite

The agglomeration of nickel-coated graphite (NCG) in epoxy resin (EP) composites leads to low electrical conductivity of EP composites, which limits their development in electronic devices and multilayer circuits. In order to improve the electrical and thermal conductivity of NCG/EP composites, ethylenediamine (EDA) was used to modify NCG and compared with pure NCG-filled EP composites. It was found that the conductive effect of modified composites with 20 wt% filler is better than that of unmodified composites with 40 wt% filler. The results of Fourier transform infrared spectroscopy and thermogravimetric analysis of EDA-modified NCG (ENCG) showed that a coordination adsorption reaction occurred between EDA and NCG, forming N–Ni coordination bonds. When the filling amount of ENCG was 40 wt%, the conductivity and thermal conductivity of the composite are improved most significantly. The volume resistivity was reduced from 2.636 to 0.109 Ω cm, a decrease of 95.85%, and the thermal conductivity was improved from 0.517 to 0.968 W/(m K), an increase of 87.23%, respectively. Meanwhile, ENCG has better dispersion in the EP matrix than NCG.     

Effect of the addition of β-Si3N4 nuclei on the thermal conductivity of β-Si3N4 ceramics

Various microstructures of β-Si₃N₄ were fabricated, with or without the addition of β-Si₃N₄ seed particles to high-purity β-Si₃N₄ powder, using Yb₂O₃ and ZrO₂ as sintering additives, by gas-pressure sintering at 1950 °C for 16 h. The thermal conductivity of the specimen without seeds was 140 W·(m·K)⁻¹, and the specimen exhibited a bimodal microstructure with abnormally grown grains. The thermal conductivity of the specimen with 24 vol.% seed addition was 143 W·(m·K)⁻¹, and this specimen had the bimodal microstructure with finer grain size than that without the seeded material, but maintained the same amount of large grains (⩾2 μm in diameter) as in the specimen without the seeds. This finding indicates that the thermal conductivity of β-Si₃N₄ is controlled by the amount of reprecipitated large grains, rather than by the grain size of the β-Si₃N₄.     

Effect of YF3 on densification behavior and thermal conductivity of AlN ceramics with Y2O3–YF3 additives under reducing atmosphere

The effect of yttrium fluoride (YF₃) on the densification behavior, microstructure, phase composition and thermal conductivity of aluminium nitride (AlN) ceramics with yttrium oxide (Y₂O₃) and YF₃ additives were studied. Since YF₃ provided liquid phases and promoted densification at a lower temperature, the sintering temperature required to reach the full density of AlN samples decreased with the increase in YF₃ content. Appropriate addition of YF₃ could improve the thermal conductivity of AlN ceramics, but the values of thermal conductivity decreased as YF₃ increased further. It is attributed to the ability of YF₃ to react with oxygen impurity was worse than that of Y₂O₃. Moreover, the reducing atmosphere significantly affected the phase composition, and the oxygen content in grain boundary phases decreased at 1750 °C and 1800 °C. Therefore, the proper proportion of Y₂O₃–YF₃ additives could simultaneously improve densification and the thermal conductivity of AlN samples at a low sintering temperature.     

Effect of β to α phase transformation on microstructure and thermal conductivity of SiC ceramic densified with Y2O3-MgO additives in argon

SiC ceramic was fabricated by spark plasma sintering of β-SiC powder and Y₂O₃-MgO additives in argon. The effects of β→α phase transformation of SiC on microstructure and thermal conductivity of densified bulks were systematically investigated, in comparison to the counterparts using α-SiC as starting powder. The β→α phase transformation led to a “unimodal to bimodal” transition in grain size distribution. After sintering at 1850 ^oC, the incomplete β→α phase transformation induced the appearance of β/α heterophase boundary with strong effect of phonon-scattering. After sintering at 2050 ^oC, the completion of β→α phase transformation resulted in enlarged grains and disappearance of β/α heterophase boundary in SiC ceramic. The lattice oxygen content was decreased primarily by enhanced grain growth and oxygen picking-up of sintering additives, and possibly some contribution from β→α phase transformation. The optimized microstructure enabled SiC ceramic to obtain a remarkable increase in thermal conductivity from 126 to 204 W/mK after the replacement of α-SiC by β-SiC as starting powder and the accomplishment of β→α phase transformation.     

Effects of silica aerogel particle sizes on the thermal–mechanical properties of silica aerogel – unsaturated polyester composites

Silica aerogels with a surface area as high as 773?m²?g^?1 and a density of 0.077?g?cm^?3 were produced from rice husk via sol–gel process and ambient pressure drying. A particulate composite material was prepared by adding silica aerogel particles of three different particle sizes (powder, granules and bead) to unsaturated polyester resin with a fixed volume fraction of 30%. Thermogravimetric and thermal conductivity studies revealed that silica aerogel composites were having higher thermal stability and thermal insulation than the neat resin. It was suggested that the preservation of aerogel pores from resin intrusion is important for better thermal properties. Larger silica aerogel particles have more porous area (unwetted region) which results in a lower degradation rate and lower thermal conductivity of the base polymer. However, the addition of silica aerogel into resin has reduced the tensile modulus of the polymer matrix where smaller particle size displayed higher toughness than those with bigger particle size.     

Effect of large β-Si3N4 particles on the thermal conductivity of β-Si3N4 ceramics

Mean-field micromechanics model, the rule of mixture is applied to the prediction of the thermal conductivity of sintered β-Si₃N₄, considering that the microstructure of β-Si₃N₄ is composed of a uniform matrix phase (which contains grain boundaries and small grains of Si₃N₄) and the purified large grains (⩾2 μm in diameter) of Si₃N₄. Experimental results and theoretical calculations showed that the thermal conductivity of Si₃N₄ is controlled by the amount of the purified large grains of Si₃N₄. The present study demonstrates that the high thermal conductivity of β-Si₃N₄ can be explained by the precipitation of high purity grains of β-Si₃N₄ from liquid phase.     

The influence of aluminum oxide on the heat resistance of the coatings based on the zirconium boride–silicon composite

The process of the formation of coatings based on zirconium boride, silicon, and aluminum oxide on graphite by the thermal treatment of the mixtures of the initial components in air has been studied. During the chemical reactions, a vitreous melt encapsulating the particles of zirconium boride and silicon is formed, which provides high heat resistance of the material. The effect of the composition, temperature, and mode of heating on the kinetics of oxidation of graphite samples with the coatings during their thermal treatment at 1400°C has been studied via the methods of thermogravimetric, thermal, and X-ray phase (XPA) analyses. The compositions of the coatings that effectively protect graphite from oxidation in air at temperatures of up to 1400°C have been proposed based on the results of the study.     

Aluminum oxide particles/silicon carbide whiskers’ synergistic effect on thermal conductivity of high-density polyethylene composites

Aluminum oxide (Al₂O₃) particles and silicon carbide (SiC) whiskers improved the thermal conductivity of high-density polyethylene (HDPE). To improve the dispersion of inorganic fillers in the matrix, 5 wt% of maleic anhydride-modified polyethylene was added into HDPE as a compatibilizer, and the hybrid matrix was denoted as mHDPE. The thermal conductivity, heat resistance, and tensile properties of resulting HDPE composites were characterized. The results showed that the thermal conductivity reached its maximum value of 0.8876 W/(m K) at 1/4 weight ratio of Al₂O₃/SiC, which was 110.3, 54.8, and 8.8% higher than that of pure HDPE, mHDPE/Al₂O₃, and mHDPE/SiC composites, in the order given, indicating that hybrid fillers have synergistic effect on the thermal conductivity of HDPE composites. Moreover, they also have a synergistic effect on the heat resistance and Young’s modulus. As the SiC content increases, the heat resistance of the composites increases at first and then falls, and the maximum VST is reached at an Al₂O₃/SiC weight ratio of 3/2, which is 5.4 °C higher than that of HDPE. The maximum Young’s modulus of the composites (1160 MPa) is obtained at an Al₂O₃/SiC weight ratio of 1/4, and the yield strength increases gradually as the SiC whiskers’ content increases.     

Influence of stabilizing ions and sintering process on the thermal conductivity of α-SiAlON ceramics

α-SiAlON ceramics with different stabilizing ions of Yb, Dy, Nd, Y, Ca, and binary stabilizing ions of (Yb + Ca) and (Yb + Nd) were prepared by spark plasma sintering at 1600°C and gas pressure sintering at 1800 and 1900°C, and their thermal conductivity was investigated. It was found that α-SiAlON ceramics with larger and heavier stabilizing ions had lower thermal conductivity and the thermal conductivity could be further reduced by using binary stabilizing ions, which can be explained by phonon scattering from point defects. At the same time, the samples prepared at lower sintering temperatures showed smaller grain sizes and lower thermal conductivity. The relationship between the thermal diffusivity of samples and temperature was studied, where the dependence of inverse thermal diffusivity on temperature was better fitted by a quadratic fitting function than the usual linear one over a wide temperature range from 25 to 800°C.     

Eutectic bonding of copper to ceramics for thermal dissipation applications – A review

Metallic copper, which has low electrical resistivity and high thermal conductivity, is widely used as an interconnector or substrate within microelectronic packages. If a small amount of oxygen is introduced to the surface of the copper, a eutectic liquid forms above 1065 °C. The eutectic liquid wets many ceramics well; it is thus possible to bond slightly oxidized copper to many ceramics directly. The present report summarizes previous results on three systems, Al₂O₃/Cu, AlN/Cu, and Si₃N₄/Cu laminates, prepared by the eutectic bonding process. The reported data demonstrate that ceramic/copper interfaces prepared with this technique are strong. Though little attention has been paid to the thermal characteristics of ceramic/copper laminates, the limited data suggest that the thermal conductivity of the laminates is high, the potential for using the laminates for thermal dissipation is thus high. In the present report, the current status for the technique is summarized; critical topics for further improvement are also proposed.