Preparation of AlN ceramic bonded carbon by gelcasting and spark plasma sintering

To obtain light, strong materials with high thermal conductivity, a new carbon-based material, AlN ceramic bonded carbon (AlN/CBC), was fabricated by combining gelcasting and spark plasma sintering techniques. The results showed that AlN/CBC (20 vol% AlN) has a unique microstructure containing carbon grains of 15 μm in size and an AlN grain-boundary layer of 0.5-3 μm in thickness. Continuous AlN ceramic networks bonded the carbon grains together. Compared with the conventional AlN/carbon (AlN/C) material made by a ball-milling method, AlN/CBC showed a higher strength and a higher thermal conductivity by two and four times, respectively.     

Studies on ionic conductivity of stabilized zirconia ceramics (8YSZ) densified through conventional and non-conventional sintering methodologies

Densification studies of 8 mol% yttria stabilized zirconia ceramics were carried out by employing the sintering techniques of conventional ramp and hold (CRH), spark plasma sintering (SPS), microwave sintering (MWS) and two-stage sintering (TSS). Sintering parameters were optimized for the above techniques to achieve a sintered density of >99% TD. Microstructure evaluation and grain size analysis indicated substantial variation in grain sizes, ranging from 4.67 μm to 1.16 μm, based on the sintering methodologies employed. Further, sample was also sintered by SPS technique at 1425 °C and grains were intentionally grown to 8.8 μm in order to elucidate the effect of grain size on the ionic conductivity. Impedance spectroscopy was used to determine the grain and grain boundary conductivities of the above specimens in the temperature range of RT to 800 °C. Highest conductivity of 0.134 S/cm was exhibited by SPS sample having an average grain size of 1.16 μm and a decrease in conductivity to 0.104 S/cm was observed for SPS sample with a grain size of 8.8 μm. Ionic conductivity of all other samples sintered vide the techniques of TSS, CRH and MWS samples was found to be ∼0.09 S/cm. Highest conductivity irrespective of the grain size of SPS sintered samples, can be attributed to the low densification temperature of 1325 °C as compared to other sintering techniques which necessitated high temperatures of ∼1500 °C. The exposure to high temperatures while sintering with TSS, CRH and MWS resulted into yttria segregation leading to the depletion of yttria content in fully stabilized zirconia stoichiometry as evidenced by Energy Dispersive Spectroscopy (EDS) studies.     

Proton exchange membranes based on sulfonated crosslinked polystyrene micro particles dispersed in poly(dimethyl siloxane)

Proton exchange membranes of sulfonated crosslinked polystyrene (SXLPS) particles dispersed in crosslinked poly(dimethyl siloxane) matrix were investigated. Three different sizes of particles—25, 8 and 0.08 μm—were used at loadings from 0 to 50 wt% and the influence of these variables on the water and methanol uptake and proton conductivity were observed. With the reduction in particle size in the composite membrane, more water or methanol uptake was observed. Three different states of water were revealed in the composite membranes by differential scanning calorimetry (DSC). The number of bound water molecules per SO₃H group was 11-15 in membranes with 8- and 25-μm SXLPS. The ratio of bound to unbound water molecules was more than one in these membranes, whereas it was less than one in membranes with 0.08-μm SXLPS. The proton conductivities of the membranes increased with the increase in particle loading. At particle loadings above 35 wt%, membranes containing 8-μm SXLPS had higher conductivity compared to 25-μm SXLPS at room temperature. The conductivity of membranes containing 0.08-μm SXLPS was restricted to 10⁻³ S/cm because of the inherently low IEC of the particles. Increasing the temperature from 30 to 80 °C drastically enhanced the conductivity of the composite membranes compared to Nafion^® 112. At 80 °C, conductivities as high as 0.11±0.04 S/cm were observed for membranes containing more than 30 wt% of 25-μm SXLPS particles.     

Graphite blocks with high thermal conductivity derived from natural graphite flake

In this work, natural graphite flake (NG) and mesophase pitch were used as precursor carbons to prepare the graphite blocks, which were doped with Si and Ti powders. After hot-pressed at 2700 °C, we investigated the effect of mean size of NG on properties and microstructure of the graphite blocks. Results showed that both thermal conductivity and flexural strength of the graphite blocks were improved as mean size of NG in raw material increased from 50 to 246 μm. However, a decrease of thermal conductivity was observed when mean size of NG was higher than 246 μm. The density and open porosity were respectively 2.26 g/cm³ and 5.82% when mean size of NG in raw material was 246 μm. The thermal conductivity was enhanced, however, the flexural strength was reduced as hot-pressing temperature increased from 2300 to 3000 °C. The thermal conductivity and flexural strength of the graphite block were respectively 704 W/m K and 21.1 MPa when hot-pressing temperature was 3000 °C. Phase analysis demonstrated there were diffraction peaks of graphite, TiC and α-SiC crystals in the graphite block as the hot-pressing temperature was less than 2500 °C. No SiC crystals were evident when the hot-pressing temperature was 2700 °C or above.     

The effects of nanoparticle addition on the sintering and properties of bimodal AlN

The effects of nanoparticle addition on the pressureless sintering of injection molded and debound aluminum nitride (AlN) samples were studied. Variations in the densification, microstructure, and properties owing to the increased powder content and reduced particle size are discussed. The results indicate the formation of liquid phase at 1500 °C in the bimodal micro (μ)–nano (n) AlN samples, a temperature that is at least 100 °C lower than typically reported values in the literature. Consequently, a densification ≥ 99% was achieved by pressureless sintering at a relatively lower temperature of 1650 °C with ∼14% isometric shrinkage. Additionally, thermal and mechanical properties of the sintered bimodal AlN samples are presented and compared with sintering studies on conventional monomodal μ-AlN systems reported in the literature.     

Synthesis of α-SiC/α-SiAlON composites by spark plasma sintering: Phase formation and microstructures development

α-SiC/α-SiAlON composites with 80 wt% α-SiC (6H phase) were fabricated by spark plasma sintering at 1800-2000 °C in a 0.6 atm nitrogen atmosphere. The effects of the temperatures on the phase development, microstructures and mechanical properties were investigated. The results showed the Si₃N₄, AlN, Al₂O₃, and Y₂O₃ particles were isolated by the 6H-SiC to prevent α-SiAlON formation at 1800 °C. The Si₃N₄ decomposed at 1900 °C and above, thus added Si in the phase compositions. The α-SiC grains grew anisotropic in the sintering liquids at 1800 °C and 1900 °C, forming the self-reinforcing microstructures, and accordingly increased the flexural strength and fracture toughness. In cooling down immediately after the temperature reached 2000 °C, a transitory hold at 1700 °C transformed the 6H-SiC into the 3C polytype in 30 s. The electric current was suspected of activating this polytype transformation.     

Porous mullite templated from hard mullite beads

Porous mullite bodies were developed by spark plasma sintering (SPS) amorphous mullite beads of about ∼30 μm in diameter at two temperatures, 950 and 1300 °C. Materials showed a close random stacking of solid spheres that retained their original packing but slightly flattened at the contacts in some cases. Depending on the thermal history, the beads were partially or fully crystallized. The thermal conductivity of the different porous mullite materials was analyzed as a function of the microstructure. Owing to the particular porous network, high gas permeability and very low thermal conductivities (1-2 W m⁻¹ K⁻¹) were achieved, among the lowest reported for sintered mullite materials.     

OH and COOH functionalized single walled carbon nanotubes-reinforced alumina ceramic nanocomposites

Alumina ceramics reinforced with 1 wt.% single-walled carbon nanotube (SWCNT) were fabricated via spark plasma sintering (SPS) of composite powders containing carboxyl (COOH) or hydroxyl (OH) group functionalized single-walled carbon nanotubes. The samples were SPS’ed at 1600 °C under 50 MPa pressure for holding time of 5 min and at a heating rate of 4 °C/s. The effects of CNT addition having different surface functional groups on microstructure, conductivity, density and hardness were reported. It was shown that nanotube addition decreased the grain sizeof alumina from 3.17 μm to 2.11 μm for COOH-SWCNT reinforcement and to 2.28 μm for COOH-SWCNT reinforcement. The hardness values of the composites are similar for all samples but there is 4.5 and 7.5 times increase in electrical conductivity with respect to monolithic alumina for COOH-SWCNT and OH-SWCNT, respectively. It was also shown by TEM and FEG SEM observations that transgranular fracture behaviour of alumina was changed to mostly intergranular fracture mode by the addition of both types of CNTs which may be due to location of CNTs along the grain boundaries. A significant grain size reduction in alumina is considered toresult fromthe suppressing effect of CNTs during sintering.     

Densification behavior and properties of hot-pressed ZrC ceramics with Zr and graphite additives

Densifications of hot-pressed ZrC ceramics with Zr and graphite additives were studied at 1800-2000 °C. ZrC with 8.94 wt% Zr additive (named ZC10) sintered at 1900-2000 °C achieved higher relative densities (>98.4%) than that of additive-free ZrC (<83%). The densification improvement was attributed to the formation of non-stoichiometric ZrC_0.9, whereas there had rapid grain growth with grain size about 50-100 μm in ZC10. By adding co-doped additive of Zr plus C and adjusting the molar ratio of Zr/C, ZrC with co-doped additives with Zr/C molar ratio at 1:2 (named ZC12), ZrC ceramics with both high relative density (98.4%) and fine microstructures (grain size about 5-10 μm) were obtained at 1900-2000 °C. Effect of formation of non-stoichiometric ZrC_1−x on densification of ZrC was discussed. The Vickers hardness and indentation toughness of ZC10 and ZC12 samples sintered at 1900 °C were 17.8 GPa and 3.0 MPa m^1/2, 16.2 GPa and 4.7 MPa m^1/2, respectively.     

Epoxy-based carbon films with high electrical conductivity attached to an alumina substrate

Carbon-based films (0.8-13 μm thick) with good bonding to the substrate and high processability were produced at 650 °C on an alumina substrate, using SU 2.5 bisphenol-A type novolac epoxy (plus triethyleneteramine curing agent) as the carbon precursor. This precursor gave crack-free and scratch resistant carbon films. Interconnected filamentary nickel nanoparticles were more effective for conductivity enhancement than silver nanoparticles or multiwalled carbon nanotubes at 5 vol.% or below, in spite of the high conductivity of silver and the high aspect ratio of nanotubes. The carbon film with 2.5 vol.% nickel showed resistivity 6 × 10⁻³ Ω cm.     

Microstructure and electrical conductivity of Mo/TiN composite powder for alkali metal thermal to electric converter electrodes

A Mo/TiN composite powder has been synthesized by a sol–gel method to improve the electrical performance and microstructural stability of the alkali metal thermal to electric converter electrode. The core (TiN)–shell (Mo) structure of the composite powder is confirmed by energy-dispersive X-ray spectroscopy and scanning electron microscopy. The composite powder is primarily composed of submicron (400–800 nm) particles that are coated on a core (>3–5 μm) particle. The Mo/TiN composite electrode exhibits high electrical conductivities of 1000 Scm⁻¹ at 300 °C and 260 Scm⁻¹ at 700  °C in an Ar atmosphere. The electrode exhibits excellent tolerance against grain growth during thermal cycling tests (R.T.↔800 °C), where the average growth rate of Mo grains in the Mo/TiN composite electrodes is controlled less than 0.5%/time (0.62→0.65 μm), while the growth rate in Mo electrodes is 306.7%/time (0.24→3.92 μm). It can be concluded that the Mo/TiN composite powder will suppress the degradation of the electrode and enhance the performance and durability of the unit cell at elevated temperatures.     

Role of interface on electrical conductivity of carbon nanotube/alumina nanocomposite

Interface of multiwalled carbon nanotube (MWCNT)/alumina (Al₂O₃) nanocomposites have been studied using TEM. At low sintering temperature (T_sin=1500 °C), a 3–5 nm thick amorphous interface region was noticed. Nanocomposite sintered at 1700 °C possessed a well-defined graphene layer coating on matrix grains as the interface between CNT and Al₂O₃. A mechanism of such layered interface formation has been proposed. No traceable chemical reaction product was observed at the interface even after sintering at 1700 °C. It was noticed that while DC electrical conductivity (σ_DC) of 1500 °C sintered 2.4 vol% MWCNT/Al₂O₃ nanocomposite was only~0.02 S/m, it raised to ~21 S/m when sintering was done at 1700 °C. Such 10³ times increase in σ_DC of present nanocomposite at a constant CNT loading was not only resulted from the exceptionally high electron mobility of CNT but the well-crystallized graphene interface on insulating type Al₂O₃ grains also significantly contributed in the overall increase of electrical performance of the nanocomposite, especially, when sintering was done at 1700 °C.     

Synthesis and diffused phase transition of Ba0.7Sr0.3TiO3 ceramics by a reaction-sintering process

Ba_0.7Sr_0.3TiO₃ (BST) ceramics prepared by a reaction-sintering process were investigated. BST ceramics could be obtained after 2–6 h sintering at 1330–1370 °C without any calcination involved. BST with density 5.68 g/cm³ (99.8% of the theoretic value) was obtained at 1350 °C for 6 h sintering. Grains of 2–15 μm were formed after 2–6 h sintering at 1330–1370 °C. A diffused ferroelectric–paraelectric transition was observed in pellets sintered at 1330 °C for 2 h and disappeared at a longer soak time or a higher sintering temperature.     

Gas tight sintered material for high temperature sublimation setups

Fine powders of WC, TaC and TaC with W and WC additives were cold-isostatically pressed to ceramic discs and pressurelessly sintered at temperatures up to 2100 °C in a second step. Afterwards, the discs were tested as crucible lid under typical AlN growth conditions. The prepared discs should be gas tight and ensure a better alignment of the thermal expansion coefficients of TaC lid and AlN.Ceramic discs densified by this method reveal a relative density up to 97%. The TaC ceramic discs without additives show a microstructure with grain sizes in the range of 10-200 μm after sintering. The grain enlargement could be reduced by W and WC additives in the range of 1-5 wt.%. The results show that the AlN boules adhere only to WC lids and tungsten containing lids with W contents higher than or equal to 3 wt.%.     

Synthesis and thermal behavior of Cu/Y2W3O12 composite

Cu metal matrix composite with Y₂W₃O₁₂ as a thermal expansion compensator was fabricated by high energy ball milling followed by compaction and sintering, and its thermal properties were explored for the potential applications as heat sinks in electronic industries, high precision optics, and space structures. The volume fraction of reinforcement was varied from 40% to 70% in order to tailor the composite for the simultaneous accomplishment of low thermal expansion and high thermal conductivity. The synthesis technique was optimized by varying the parameters like milling time from 1 to 20 h and sintering temperature from 600 to 1000 °C in order to achieve densified composites. The relative density of the composites is found to be around 90% for the 10 h milled powders followed by compaction at a pressure of 700 MPa and sintering at a temperature of 1000 °C. The thermal expansion of the composites exhibits linear behavior in the temperature range 200 to 800 °C and the low coefficient of thermal expansion (CTE) is found to be for Cu–70%Y₂W₃O₁₂ composite whose value, 4.32±0.75×10⁻⁶/°C, matches with that of Si substrate. The thermal conductivities are found to increase with a decrease in the volume fraction of the reinforcement and decrease with an increase in the temperature for all the samples. The experimentally determined CTE and thermal conductivity values are found to be comparable to those predicted by the thermal expansion based Kerner and Turner model and the thermal conductivity based Maxwell model, respectively.     

Fabrication and thermal conductivity of AlN/BN ceramics by spark plasma sintering

Aluminum nitride/boron nitride (AlN/BN) ceramics with 15–30 vol.% BN as secondary phase were fabricated by spark plasma sintering (SPS), using Yttrium oxide (Y₂O₃) as sintering aid. Effects of Y₂O₃ content and the SPS temperature on the density, phase composition, microstructure and thermal conductivity of the ceramics were investigated. The results revealed that with increasing the amount of starting Y₂O₃ in AlN/BN, Yttrium-contained compounds were significantly removed after SPS process, which caused decreasing of the residual grain boundary phase in the sintered samples. As a result, thermal conductivity of AlN/BN ceramics was remarkably improved. By addition of Y₂O₃ content from 3 wt.% to 8 wt.% into AlN/15 vol.% BN ceramics, the thermal conductivity increased from 110 W/m K to 141 W/m K.     

Thermophysical properties of densified pitch based carbon/carbon materials—II. Bidirectional composites

Bidirectional carbon/carbon composites were developed using high-pressure impregnation/carbonization technique with PAN based carbon fabric as reinforcement and coal tar and synthetic pitches as matrix precursors. Microstructure of these composites has been evaluated using scanning electron microscope and polarized light optical microscope. Thermophysical properties i.e. thermal conductivity and specific heat have been evaluated both at room temperature and between 40 and 300 °C. The temperature dependence of thermal diffusion, specific heat and thermal conductivity has been studied and correlated with microstructure of carbon/carbon composites. It is found that the specific heat of carbon/carbon composites shows increase with temperature with an inverse slope in the temperature range of 150-200 °C. Accordingly, though the thermal conductivity decrease with temperature due to increased phonon interactions, it shows reversible action between 150 and 200 °C.     

Highly dispersed and electrically conductive polycarbonate/oxidized carbon nanofiber composites for electrostatic dissipation applications

The influence of low cost, commercially oxidized carbon nanofibers (ox-CNFs) on the morphological, thermal, mechanical and electrical properties of polycarbonate (PC) composites was examined. Using a simple solution mixing process leads to good dispersion and high packing density of CNFs in the resultant composites. The composite materials exhibit a dramatic improvement in the DC conductivity; for example, increasing from 2.36 × 10⁻¹⁴ S/m for PC to ca. 10⁻² S/m for the composite at only 3.0 wt.% of CNFs, and exhibits a very fast static charge dissipation rate. Dynamic mechanical analysis showed a remarkable increase in storage modulus (282%) at 165 °C, compared to pure PC. Thermogravimetric analysis showed that thermal stability of the composites increased by 54 °C compared to the pure PC. To our knowledge, the measured electrical conductivity and thermal properties for PC/CNF are the highest values yet reported for PC/CNF composites at comparable loadings. The AC/DC conductivity is shown to play an important role to predict the state of dispersion.     

Measurement of through-plane effective thermal conductivity and contact resistance in PEM fuel cell diffusion media

An experimental study was performed to determine the through-plane thermal conductivity of various gas diffusion layer materials and thermal contact resistance between the gas diffusion layer (GDL) materials and an electrolytic iron surface as a function of compression load and PTFE content at 70 °C. The effective thermal conductivity of commercially available SpectraCarb untreated GDL was found to vary from 0.26 to 0.7 W/(m °C) as the compression load was increased from 0.7 to 13.8 bar. The contact resistance was reduced from 2.4×10⁻⁴ m²°C/W at 0.7 bar to 0.6×10⁻⁴ m²°C/W at 13.8 bar. The PTFE coating seemed to enhance the effective thermal conductivity at low compression loads and degrade effective thermal conductivity at higher compression loads. The presence of microporous layer and PTFE on SolviCore diffusion material reduced the effective thermal conductivity and increased thermal contact resistance as compared with the pure carbon fibers. The effective thermal conductivity was measured to be 0.25 W/(m °C) and 0.52 W/(m °C) at 70 °C, respectively at 0.7 and 13.8 bar for 30%-coated SolviCore GDL with microporous layer. The corresponding thermal contact resistance reduced from 3.6×10⁻⁴ m²°C/W at 0.7 bar to 0.9×10⁻⁴ m²°C/W at 13.8 bar. All GDL materials studied showed non-linear deformation under compression loads. The thermal properties characterized should be useful to help modelers accurately predict the temperature distribution in a fuel cell.     

Preparation of AlON ceramics via reactive spark plasma sintering

Al₂O₃ and AlN powder mixtures were used to synthesise AlON ceramics using the reactive spark plasma sintering (SPS) method at temperatures between 1400 and 1650 °C for 15-45 min at 40 MPa under N₂ gas flow. AlON phase formation was initiated in the samples sintered above 1430 °C, according to the X-ray analysis. The complete transformation of the initial phases (Al₂O₃ and AlN) into AlON was observed in the samples that were spark plasma sintered at 1650 °C for 30 min at 40 MPa. A high spark plasma sintering temperature together with a low heating rate produced a greater amount of AlON formation at a constant process time. The densification, microstructure and mechanical properties of the produced ceramics were analysed. The highest hardness value was recorded to be 16.7 GPa, and the fracture toughness of the sample with the highest AlON ratio was measured to be 3.95 MPa m^1/2.