Microstructure and Thermal Conductivity of Silicon Carbide with Yttria and Scandia

A fully dense SiC ceramic with high thermal conductivity was obtained by conventional hot pressing, with 1 vol% Y₂O₃–Sc₂O₃ additives. The ceramic had a bimodal microstructure consisting of large and small equiaxed SiC grains. Observation with high‐resolution transmission electron microscopy (HRTEM) showed two kinds of homophase (SiC/SiC) boundaries, that is crystallized and clean boundaries, and a fully crystallized junction phase. The thermal conductivity of the SiC ceramic was 234 W (m·K)^?1 at room temperature. The high thermal conductivity was attributed to a clean SiC lattice and good contiguity between SiC grains.     

Effects of starting powder on microstructure and thermal conductivity of pressureless-sintered fully ceramic microencapsulated fuels

The effects of the starting SiC powder (α or β) with the addition of 5.67 wt% AlN–Y₂O₃–CeO₂–MgO additives on the residual porosity and thermal conductivity of fully ceramic microencapsulated (FCM) fuels were investigated. FCM fuels containing ～41 vol% and ～37 vol% tristructural isotropic (TRISO) particles could be sintered at 1870 °C using α-SiC and β-SiC powders, respectively, via a pressureless sintering route. The residual porosities of the SiC matrices in the FCM fuels prepared using the α-SiC and β-SiC powders were 1.1% and 2.3%, respectively. The thermal conductivities of FCM pellets with ～41 vol% and ～37 vol% TRISO particles (prepared using the α-SiC and β-SiC powders, respectively) were 59 and 41 Wm^?1K^?1, respectively. The lower porosity and higher thermal conductivity of FCM fuels prepared using the α-SiC powder were attributed to the higher sinterability of the α-SiC powder than that of the β-SiC powder.     

Electrical and Thermal Properties of SiC Ceramics Sintered with Yttria and Nitrides

The electrical and thermal properties of SiC ceramics containing 1 vol% nitrides (BN, AlN or TiN) were investigated with 2 vol% Y₂O₃ addition as a sintering additive. The AlN‐added SiC specimen exhibited an electrical resistivity (3.8 × 10¹ Ω·cm) that is larger by a factor of ~10² compared to that (1.3 × 10^?1 Ω·cm) of a baseline specimen sintered with Y₂O₃ only. On the other hand, BN‐ or TiN‐added SiC specimens exhibited resistivity that is lower than that of the baseline specimen by a factor of 10^?1. The addition of 1 vol% BN or AlN led to a decrease in the thermal conductivity of SiC from 178 W/m·K (baseline) to 99 W/m·K or 133 W/m·K, respectively. The electrical resistivity and thermal conductivity of the TiN‐added SiC specimen were 1.6 × 10^?2 Ω·cm and 211 W/m·K at room temperature, respectively. The present results suggest that the electrical and thermal properties of SiC ceramics are controllable by adding a small amount of nitrides.     

Pressureless sintered silicon carbide matrix with a new quaternary additive for fully ceramic microencapsulated fuels

This study suggests a new additive composition based on AlN–Y₂O₃–Sc₂O₃–MgO to achieve successful densification of SiC without applied pressure at a temperature as low as 1850 °C. The typical sintered density, flexural strength, fracture toughness, and hardness of the SiC ceramics sintered at 1850 °C without applied pressure were determined as 98.3%, 510 MPa, 6.9 MPa·m^1/2, and 24.7 GPa, respectively.Fully ceramic microencapsulated (FCM) fuels containing 37 vol% tristructural isotropic (TRISO) particles could be successfully sintered at 1850 °C using the above matrix without applied pressure. The residual porosity of the SiC matrix in the FCM fuels was only 1.6%. TRISO particles were not damaged during processing, which included cold isostatic pressing under 204 MPa and sintering at 1850 °C for 2 h in an argon atmosphere. The thermal conductivity of the pressureless sintered FCM pellet with 37 vol% TRISO particles was 44.4 Wm^?1 K^?1 at room temperature.     

High‐Temperature Deformation Mechanisms in Monolithic 3YTZP and 3YTZP Containing Single‐Walled Carbon Nanotubes

Monolithic 3YTZP and 3YTZP containing 2.5 vol% of single‐walled carbon nanotubes (SWCNT) were fabricated by Spark Plasma Sintering (SPS) at 1250°C. Microstructural characterization of the as‐fabricated 3YTZP/SWCNTs composite shows a homogeneous CNTs dispersion throughout the ceramic matrix. The specimens have been crept at temperatures between 1100°C and 1200°C in order to investigate the influence of the SWCNTs addition on high‐temperature deformation mechanisms in zirconia. Slightly higher stress exponent values are found for 3YTZP/SWCNTs nanocomposites (n~2.5) compared to monolithic 3YTZP (n~2.0). However, the activation energy in 3YTZP (Q = 715 ± 60 kJ/mol) experiences a reduction of about 25% by the addition of 2.5 vol% of SWCNTs (Q = 540 ± 40 kJ/mol). Scanning electron microscopy studies indicate that there is no microstructural evolution in crept specimens, and Raman spectroscopy measurements show that SWCNTs preserved their integrity during the creep tests. All these results seem to indicate that the high‐temperature deformation mechanism is grain‐boundary sliding (GBS) accommodated by grain‐boundary diffusion, which is influenced by yttrium segregation and the presence of SWCNTs at the grain boundary.     

The effect of graphene nanoplatelets on the thermal and electrical properties of aluminum nitride ceramics

The thermal conductivity (κ) of AlN (2.9 wt.% of Y₂O₃) is studied as a function of the addition of multilayer graphene (from 0 to 10 vol.%). The κ values of these composites, fabricated by spark plasma sintering (SPS), are independently analyzed for the two characteristic directions defined by the GNPs orientation within the ceramic matrix; that is to say, perpendicular and parallel to the SPS pressing axis. Conversely to other ceramic/graphene systems, AlN composites experience a reduction of κ with the graphene addition for both orientations; actually the decrease of κ for the in-plane graphene orientation results rather unusual. This behavior is conveniently reproduced when an interface thermal resistance is introduced in effective media thermal conductivity models. Also remarkable is the change in the electrical properties of AlN becoming an electrical conductor (200 S m⁻¹) for graphene contents above 5 vol.%.     

Novel in-situ constructing approach for vertically aligned AlN skeleton and its thermal conductivity enhancement effect on epoxy

As one of the key components of electronic devices, thermal management materials (TMMs) with high thermal conductivity are essential to ensure their safety and long service life. For polymer-based TMMs, AlN is one of the preferred fillers, but it has some drawbacks such as high cost and easy hydrolysis. Herein, a controllable and continuously oriented three-dimensional AlN skeleton (3D-AlNNS) was in-situ transformed from a low-cost 3D Al-containing skeleton (3D-AlNS) by combining the ice-templating and nitriding reaction sintering. Subsequently, AlN/epoxy composites were obtained by a vacuum infiltration. The composite containing 39.69 vol% AlN had the highest thermal conductivity of 4.29 W m^?1·K^?1, which was 21.45 times higher than that of pure epoxy. The composite substrates showed excellent heat dissipation performance in practical applications due to their high thermal conductivity. The continuous directional alignment of AlN powders in the 3D skeleton and intersection of AlN whiskers between the skeleton walls produced in-situ contributed to the formation of effective multichannel heat transferring paths and improvement in thermal conductivity. This novel approach has the advantages of low-cost, short processing time, simple operation and repeatability, and provides a new idea for developing heat-conducting polymer composites, which can also be extended to the preparation of similar TMMs.     

Zirconium Diboride with High Thermal Conductivity

Thermal properties were characterized for zirconium diboride produced by reactive hot pressing and compared to ZrB₂ ceramics that were hot pressed from commercial powders. No sintering additives were used in either process. Thermal conductivity was calculated from measured values of heat capacity, thermal diffusivity, and density for temperatures ranging from 298 to 2273 K. ZrB₂ produced by reactive hot pressing achieved near full density, but had a small volume fraction of ZrO₂, whereas hot‐pressed ZrB₂ contained porosity and carbon inclusions. Reactive hot pressing produced a ceramic with higher thermal diffusivity and heat capacity, resulting in thermal conductivities of 127 W·(m·K)^?1 at 298 K and 80 W·(m·K)^?1 at 2273 K, which were up to ~30% higher than typically reported for hot‐pressed ZrB₂.     

Single-walled carbon nanotube/silicone rubber composites for compliant electrodes

Single-walled carbon nanotube (SWCNT)/silicone rubber composites that can be used in fabricating compliant electrodes are prepared by spraying a mixed solution of ionic-liquid-based SWCNT gel and silicone rubber onto an elastic substrate. Subsequently, the composites are exposed to nitric acid vapor. Scanning electron microscopy and atomic force microscopy images of the composites show that the SWCNTs are finely dispersed in the polymer matrix due to the addition of the ionic liquid. Doping of the SWCNTs by nitric acid can significantly lower the sheet resistance (R_s) of the composites; samples with 4 wt% of SWCNT content exhibit the lowest R_s value (50 Ω sq^?1). This sheet resistance corresponds to a conductivity value of 63 S cm^?1. In addition, the composites retain a high conductivity after several tensile strains are applied. Stretching the composite sample to 300% of the original length increased the R_s value to 320 Ω sq^?1 (19 S cm^?1). Even after 20th stretch/release/stretch cycle, the conductivity remains constant at a value of 18 S cm^?1. These results provide a scalable route for preparing highly stretchable and conductive SWCNT composites with relatively low SWCNT concentrations.     

Influence of the Processing Route on the Carbon Nanotubes Dispersion and Creep Resistance of 3YTZP/SWCNTs Nanocomposites

3YTZP matrix composites containing 2.5 vol% of single‐walled carbon nanotubes (SWCNT) were fabricated by Spark Plasma Sintering (SPS) at 1250°C, following different processing routines with the aim of optimizing the SWCNTs dispersion throughout the ceramic matrix. Microstructural characterization of the as‐fabricated samples has been performed by means of scanning electron microscopy (SEM). The specimens have been crept at 1200°C to correlate creep resistance and SWCNTs distribution. There are no creep experimental results on these nanocomposites reported in literature. Mechanical results show that the incorporation of SWCNTs into a 3YTZP matrix produces an increase in the strain rate at high temperature with respect to monolithic zirconia. The creep resistance of these nanocomposites decreases with the improvement of the SWCNTs dispersion, where a smaller SWCNTs agglomerate size and consequently a higher concentration of carbon nanotubes surrounding the 3YTZP grain boundaries is found. This fact indicates that SWCNTs act as a lubricant making grain‐boundary sliding easier during deformation of these composites.     

Electrical performance of orthotropic and isotropic 3YTZP composites with graphene fillers

3 mol% yttria tetragonal zirconia polycrystal (3YTZP) composites with orthotropic or isotropic microstructures were obtained incorporating few layer graphene (FLG) or exfoliated graphene nanoplatelets (e-GNP) as fillers. Electrical conductivity was studied in a wide range of contents in two configurations: perpendicular (σ_?) and parallel (σ_//) to the pressing axis during spark plasma sintering (SPS). Isotropic e-GNP composites presented excellent electrical conductivity for high e-GNP contents (σ_? ～ 3200 S/m and σ_// ～ 1900 S/m for 20 vol% e-GNP), consequence of their misoriented distribution throughout the matrix. Optimum electrical performance was achieved in the highly anisotropic FLG composites, with high electrical conductivity for low contents (σ_? ～ 680 S/m for 5 vol%), percolation threshold below 2.5 vol% FLG and outstanding electrical conductivity for high contents (σ_? ～ 4000 S/m for 20 vol%), result of the high aspect ratio and low thickness of FLG.     

Cellular structures of carbon nanotubes in a polymer matrix improve properties relative to composites with dispersed nanotubes

A new processing method has been developed to combine a polymer and single wall carbon nanotubes (SWCNTs) to form electrically conductive composites with desirable rheological and mechanical properties. The process involves coating polystyrene (PS) pellets with SWCNTs and then hot pressing to make a contiguous, cellular SWCNT structure. By this method, the electrical percolation threshold decreases and the electrical conductivity increases significantly as compared to composites with well-dispersed SWCNTs. For example, a SWCNT/PS composite with 0.5 wt% nanotubes made by this coated particle process (CPP) has an electrical conductivity of ∼3 × 10⁻⁴ S/cm, while a well-dispersed composite made by a coagulation method with the same SWCNT amount has an electrical conductivity of only ∼10⁻⁸ S/cm. The rheological properties of the composite with a macroscopic cellular SWCNT structure are comparable to PS, while the well-dispersed composite exhibits a solid-like behavior, indicating that the composites made by this new CPP are more processable. In addition, the mechanical properties of the CPP-made composite decrease only slightly, as compared with PS. Relative to the common approach of seeking better dispersion, this new fabrication method provides an important alternative means to higher electrical conductivity in SWCNT/polymer composites. Our straightforward particle coating and pressing method avoids organic solvents and is suitable for large-scale, inexpensive processing using a wide variety of polymers and nanoparticles.     

Main‐chain poly(1,2,3‐triazolium hydroxide)s obtained through AA+BB click polyaddition as anion exchange membranes

A series of aromatic poly(1,2,3‐triazolium iodide)s were synthesized by step growth polymerization of dipropargyl bisphenol A with aliphatic and aromatic diazides followed by quantitative or partial N‐alkylation of the main‐chain 1,2,3‐triazole groups using iodomethane. After characterization by ¹H NMR spectroscopy, SEC and DSC the corresponding self‐standing membranes were obtained by hot pressing. Poly(1,2,3‐triazolium iodide) membranes were converted to the corresponding hydroxide‐containing membranes by anion exchange. Structure–property correlations are discussed based on the evolution of water uptake and ionic conductivity with respect to the ionic exchange capacities of the different materials having distinct chemical structure, quaternization degree and counter‐anion structure. Poly(1,2,3‐triazolium hydroxide) anion exchange membranes exhibit water uptakes below 150% and ionic conductivity in the hydrated state up to 4 mS cm^?1 for ionic exchange capacities up to 3.2 meq g^?1. © 2019 Society of Chemical Industry     

Densification and properties of AlN ceramic bonded carbon

To obtain light and tough materials with high thermal conductivity, AlN ceramic bonded carbon (AlN/CBC) composites were fabricated at temperatures from 1600 to 1900 °C in a short period of 5 min by the spark plasma sintering technique. All AlN/CBCs (20 vol% AlN) have unique microstructures containing carbon particles of 15 μm in average size and continuous AlN boundary layers of 0.5-3 μm in thickness. With an increase in sintering temperature, AlN grains grow and anchor into carbon particles, resulting in the formation of a tight bonding layer. The AlN/CBC sintered at 1900 °C exhibited a light weight (2.34 g/cm³), high bending strength (100 MPa), and high thermal conductivity (170 W/mK).     

Transition metal diboride-silicon carbide-boron carbide ceramics with super-high hardness and strength

Three phase boride and carbide ceramics were found to have remarkably high hardness values. Six different compositions were produced by hot pressing ternary mixtures of Group IVB transition metal diborides, SiC, and B₄C. Vickers’ hardness at 9.8 N was ~31 GPa for a ceramic containing 70 vol% TiB₂, 15 vol% SiC, and 15 vol% B₄C, increasing to ~33 GPa for a ceramic containing equal volume fractions of the three constituents. Hardness values for the ceramics containing ZrB₂ and HfB₂ were ~30% and 20% lower than the corresponding TiB₂ containing ceramics, respectively. Hardness values also increased as indentation load decreased due to the indentation size effect. At an indentation load of 0.49 N, the hardness of the previously reported ceramic containing equal volume fractions of TiB₂, SiC and B₄C was ~54 GPa, the highest of the ceramics in the present study and higher than the hardness values reported for so-called “superhard” ceramics at comparable indentation loads. The previously reported ceramic containing 70 vol% TiB₂, 15 vol% SiC, and 15 vol% B₄C also displayed the highest flexural strength of ~1.3 GPa and fracture toughness of 5.7 MPa·m^1/2, decreasing to ~0.9 GPa and 4.5 MPa·m^1/2 for a ceramic containing equal volume fractions of the constituents.     

Cold sintering process of Li1.5Al0.5Ge1.5(PO4)3 solid electrolyte

The recently developed technique of cold sintering process (CSP) enables densification of ceramics at low temperatures, i.e., <300°C. CSP employs a transient aqueous solvent to enable liquid phase‐assisted densification through mediating the dissolution‐precipitation process under a uniaxial applied pressure. Using CSP in this study, 80% dense Li_1.5Al_0.5Ge_1.5(PO₄)₃ (LAGP) electrolytes were obtained at 120°C in 20 minutes. After a 5 minute belt furnace treatment at 650°C, 50°C above the crystallization onset, Li‐ion conductivity was 5.4 × 10^?5 S/cm at 25°C. Another route to high ionic conductivities ~10^?4 S/cm at 25°C is through a composite LAGP ‐ (PVDF‐HFP) co‐sintered system that was soaked in a liquid electrolyte. After soaking 95, 90, 80, 70, and 60 vol% LAGP in 1 M LiPF₆ EC‐DMC (50:50 vol%) at 25°C, Li‐ion conductivities were 1.0 × 10^?4 S/cm at 25°C with 5 to 10 wt% liquid electrolyte. This paper focuses on the microstructural development and impedance contributions within solid electrolytes processed by (i) Crystallization of bulk glasses, (ii) CSP of ceramics, and (iii) CSP of ceramic‐polymer composites. CSP may offer a new route to enable multilayer battery technology by avoiding the detrimental effects of high temperature heat treatments.     

High thermal conductivity of spark plasma sintered silicon carbide ceramics with yttria and scandia

A fully dense SiC ceramic with a room‐temperature thermal conductivity of 262 W·(m·K)^?1 was obtained via spark plasma sintering β‐SiC powder containing 0.79 vol% Y₂O₃‐Sc₂O₃. High‐resolution transmission electron microscopy revealed two different SiC‐SiC boundaries, that is, amorphous and clean boundaries, in addition to a fully crystallized junction phase. A high thermal conductivity was attributed to a low lattice oxygen content and the presence of clean SiC‐SiC boundaries.     

Optimization of non-aqueous tape casting of high solid loading slurry for aluminum nitride ceramic substrates

Aluminum nitride (AlN) ceramic substrates have been fabricated using non-aqueous tape casting and pressureless densification under flowing N₂ atmosphere. Considering the economic and environmental impact, a new strategy of solvent and dispersant system was adopted to prepare AlN slurries with high solid loading. According to the viscosity characteristics of AlN slurries, dispersant content was adjusted to be 0.5 wt% of AlN powder in order to optimize the rheological behavior of AlN slurries. The addition contents of binder and plasticizer were both optimized as 5 wt% of AlN powders by combining the viscosity of slurries and tensile strength of green tapes. Green AlN tapes were fabricated with an optimized tape casting process such as dry temperature. The exclusion process of organic additives was investigated by employing thermogravimetric analysis. Flat and dense AlN ceramic substrates with a relative bulk density over 99.75 % were achieved after being sintered under 1800°C for 6 hours, which had a maximum size of 110 × 110 mm. The thermal conductivity of the AlN substrate could reach 145 Wm⁻¹K⁻¹.     

Effects of SmF3 addition on aluminum nitride ceramics via pressureless sintering

Aluminum nitride (AlN) ceramics with dense structure, high thermal conductivity, and exceptional mechanical properties were fabricated by pressureless sintering with a novel non-oxide sintering additive, samarium fluoride (SmF₃). The results showed that the use of a moderate amount of SmF₃ promoted significant densification of AlN and removed the oxygen impurity. This led to the formation of fine and isolated secondary phase that cleaned the grain boundaries and increased the contact between AlN grains, remarkably enhancing thermal conductivity. Furthermore, SmF₃ also exhibited grain refinement and grain boundary strengthening effects similar to traditional sintering additive, samarium oxide (Sm₂O₃), leading to high mechanical properties in SmF₃-doped AlN samples. The most optimal characteristics (thermal conductivity of 190.67 W·m⁻¹·K⁻¹, flexural strength of 403.86 ± 18.27 MPa, and fracture toughness of 3.71 ± 0.19 MPa·m^1/2) were achieved in the AlN ceramic with 5 wt% SmF₃.     

Effect of the starting AlN content on the phase formation and property of the novel in-situ fabricated X-SiAlON/BN composites

Novel in-situ X-SiAlON reinforced BN composites were first fabricated via the procedure of mechanical alloying plus hot press sintering. The effects of the starting AlN content (0∼25 vol%) on phase formation, evolution and microstructure were carefully investigated. XRD results indicated that AlN content was the crucial factor in the phase composition and evolution in the composites, for instance, excess AlN leading to the transformation from X-SiAlON to β-SiAlON. The relationships of AlN content with mechanical, thermal and dielectric properties of the composites were also involved in this study. The composite with the 15 vol% AlN, mainly consisting of X-SiAlON and BN, exhibited the best mechanical properties (flexural and fracture strength were 337.5 MPa and 4.15 MPa.m^1/2, respectively), low thermal conductivity as well as the excellent dielectric properties (ε < 5.71), which enabled it to be a promising candidate for the application of high-temperature structural/ functional materials.