Low thermal conductivity of atomic layer deposition yttria-stabilized zirconia (YSZ) thin films for thermal insulation applications

Thermal insulation applications have long required materials with low thermal conductivity, and one example is yttria (Y₂O₃)-stabilized zirconia (ZrO₂) (YSZ) as thermal barrier coatings used in gas turbine engines. Although porosity has been a route to the low thermal conductivity of YSZ coatings, nonporous and conformal coating of YSZ thin films with low thermal conductivity may find a great impact on various thermal insulation applications in nanostructured materials and nanoscale devices. Here, we report on measurements of the thermal conductivity of atomic layer deposition-grown, nonporous YSZ thin films of thickness down to 35 nm using time-domain thermoreflectance. We find that the measured thermal conductivities are 1.35–1.5 W m⁻¹ K⁻¹ and do not strongly vary with film thickness. Without any reduction in thermal conductivity associated with porosity, the conductivities we report approach the minimum, amorphous limit, 1.25 W m⁻¹ K⁻¹, predicted by the minimum thermal conductivity model.     

Graphite foam from pitch and expandable graphite

Graphite foams were prepared from a coal tar pitch that was partially converted into mesophase. Expandable graphite was used instead of an inert gas to “foam” the pitch. The resulting foam was subjected to a series of heat treatments with the objective of first crosslinking the pitch, and thereafter carbonizing and graphitizing the resulting foam. XRD confirmed that the graphitization at 2600 °C resulted in a highly graphitic material. The porosity of this foam derives from the loose packing of the vermicular exfoliated graphite particles together with their internal porosity. During the foaming process the pitch tends to coat the outside surface of the expanding graphite flakes. It also bonds them together. The graphite foam prepared with 5 wt.% expandable graphite had a bulk density of 0.249 g cm⁻³, a compressive strength of 0.46 MPa and a thermal conductivity of 21 W m⁻¹ K⁻¹. The specific thermal conductivity (thermal conductivity divided by the bulk density) of this low-density carbon foam was 0.084 W m² kg⁻¹ K⁻¹ which is considerably higher than that of copper metal (0.045 W m² kg⁻¹ K⁻¹) traditionally used in thermal management applications.     

Preparation by tape casting and hot pressing of copper carbon composites films

During this last decade, the use of metal matrix composites (MMCs) such as AlSiC or CuW for heat dissipation in microelectronic devices has been leading to the improvement of the reliability of electronic power modules. Today, the continuous increasing complexity, miniaturization and density of components in modern devices requires new heat dissipating films with high thermal conductivity, low coefficient of thermal expansion (CTE), and good machinability. This article presents the original use of copper carbon composites, made by tape casting and hot pressing, as heat dissipation materials. The tape casting process and the sintering have been adapted and optimised to obtain near fully dense, flat and homogeneous Cu/C composites.A good electrical contact between carbon fibres and copper matrix and a low porosity at matrix/copper interfaces allow obtaining a low electrical resistivity of 3.8 μΩ cm⁻¹ for 35 vol.% carbon fibre (electrical resistivity of copper = 1.7 μΩ cm⁻¹). The CTE and the thermal conductivity are strongly anisotropic due to the preferential orientation of carbon fibres in the plan of laminated sheets. Values in the parallel plan are, respectively, 9 × 10⁻⁶ °C⁻¹ and 160–210 W m⁻¹ K⁻¹ for 40 vol.% fibres. These CTE and thermal conductivity values are in agreement with the thermo-elastic Kerner's model and with the Hashin and Shtrikman model, respectively.     

Fabrication and thermal conductivity of highly porous alumina body from platelets with yeast fungi as a pore forming agent

A highly porous alumina body was fabricated by heating a green clinker body consisting of platelets and yeast fungi as a pore forming agent. Four kinds of alumina platelets were used. When green clinker bodies of platelet aggregates (A11) with 10 and 30 mass% of yeast fungi were heated at 1500 °C for 2 h, their porosities reached 72% and 78%, respectively. In contrast, when the green clinker bodies composed of platelets with an average size of 10 µm and an aspect ratio of 25–30 (SERATH①), and 20 mass% of yeast fungi were heated at 1400 °C for 2 h, the porosity of the resultant porous alumina body was also approximately 72%. However, the room temperature thermal conductivities of the porous alumina bodies with 72% porosity derived from A11 and SERATH① were 0.86 and 0.50 W m⁻¹ K⁻¹, respectively. The decrease in the thermal conductivity of the porous alumina body produced from SERATH① is caused by the long path route for heat transfer.     

Effects of porous C/C density on the densification behavior and ablation property of C/C–ZrC–SiC composites

C/C–ZrC–SiC composites were prepared by precursor infiltration and pyrolysis process using a mixture solution of organic zirconium-containing polymer and polycarbosilane as precursors. Porous carbon/carbon (C/C) composites with density of 0.92, 1.21 and 1.40 g/cm³ were used as preforms, and the effects of porous C/C density on the densification behavior and ablation resistance of C/C–ZrC–SiC composites were investigated. The results show that the C/C preforms with a lower density have a faster weight gain, and the obtained C/C–ZrC–SiC composites own higher bulk density and open porosity. The composites fabricated from the C/C preforms with a density of 1.21 g/cm³ exhibit better ablation resistance with a surface temperature of over 2400 °C during ablation. After ablation for 120 s, the linear and mass ablation rates of the composites are as low as 1.02 × 10⁻³ mm/s and −4.01 × 10⁻⁴ g/s, respectively, and the formation of a dense and continuous coating of molten ZrO₂ solid solution is the reason for their great ablation resistance.     

Porous Ca3Co4O9 with enhanced thermoelectric properties derived from Sol–Gel synthesis

Highly porous Ca₃Co₄O₉ thermoelectric oxide ceramics for high-temperature application were fabricated by sol–gel synthesis and subsequent conventional sintering. Growth mechanism of misfit-layered Ca₃Co₄O₉ phase, from sol–gel synthesis educts and upcoming intermediates, was characterized by in-situ X-ray diffraction, scanning electron microscopy and transmission electron microscopy investigations. The Ca₃Co₄O₉ ceramic exhibits a relative density of 67.7%. Thermoelectric properties were measured from 373 K to 1073 K. At 1073 K a power factor of 2.46 μW cm⁻¹ K⁻², a very low heat conductivity of 0.63 W m⁻¹ K⁻¹ and entropy conductivity of 0.61 mW m⁻¹ K⁻² were achieved. The maintained figure of merit ZT of 0.4 from sol–gel synthesized Ca₃Co₄O₉ is the highest obtained from conventional, non-doped Ca₃Co₄O₉. The high porosity and consequently reduced thermal conductivity leads to a high ZT value.     

Improvement on characteristics of porous alumina from platelets using a TEOS treatment

A porous alumina body was synthesized from anisotropic alumina particles, namely platelets. When green compacts, which had been uniaxially pressed at 1 MPa, were heated at 1200 and 1500 °C for 1 h, the average porosity of the resulting alumina bodies was 75.5 and 71.0%, respectively. The thermal conductivity of the porous alumina fabricated at 1400 °C for 1 h with 72.3% in porosity was 0.8 W m^?1 K^?1. In an attempt to increase the compressive strength of the porous alumina bodies, TEOS (tetraethyl orthosilicate) solution treatment was carried out, followed by reheating to 1400 °C for 1 h. The compressive strength of the porous alumina body increased from 3.8 MPa (without TEOS solution treatment) to 10.2 MPa (with three rounds of TEOS treatment), with the porosity decreasing to 65.5% and the thermal conductivity increasing to1.2 W m^?1 K^?1.     

Preparation processes and characterizations of alumina-coated alumina support layers and alumina-coated natural material-based support layers for microfiltration

Recently, porous ceramic membranes have become a subject of significant interest due to their outstanding thermal and chemical stability. To reduce the high manufacturing costs of these porous ceramic membranes, recent research has focused on the utilization of inexpensive natural materials. However, there have not been any well-established direct comparisons of the membrane properties between typical alumina-based membranes and novel natural material-based membranes. Therefore, we compared alumina-coated alumina support layers (with average pore sizes ranging from 0.10 µm ~0.18 µm), alumina-coated diatomite-kaolin composite support layers (with an average pore size of 0.12 µm), and alumina-coated pyrophyllite-diatomite composite support layers (with an average pore size of 0.11 µm) via the dip-coating method and subsequent heat treatment ranging from 1200 °C–1400 °C for 1 h. The pure water permeability of the alumina-coated diatomite-kaolin composite support layer and the alumina-coated pyrophyllite-diatomite composite support layer was found to be approximately 2.0×10² L m⁻² h⁻¹ bar⁻¹, which is similar to that of an alumina-coated alumina support layer. Therefore, we suggest that the average pore size of an alumina-coated natural material-based support layer can be effectively controlled while exhibiting acceptable water permeability.     

Silicon carbide-based foams derived from foamed SiC-filled phenolic resin by reactive infiltration of silicon

Macro-cellular porous silicon carbide-based foams were fabricated by reactive infiltration of melt silicon into porous carbonaceous preforms pyrolyzed from foamed SiC-filled phenolic resins (PF). The SiC-filled PF foams were prepared at 80 °C with different heating rate. The effect of heating rate on the foaming behavior of the liquid SiC-filled PF mixture and the microstructure of the foams were investigated. The foamed SiC-filled PF was then pyrolyzed at 1000 °C and infiltrated by melt Si at 1600 °C, leading to the formation of open macro-cellular structure. At a heating rate of 6 °C min⁻¹, Si-infiltrated foams with a porosity of ~72% and a mean pore size of ~0.5 mm were obtained. The Si-infiltrated foams with dense struts mainly inherited the pore structure of pyrolyzed preforms. The main phases of SiC-based foams were α-SiC, β-SiC and the remnant Si, which contributed to high compressive strength of the SiC-based foams.     

Dielectric properties of silicon nitride ceramics produced by free sintering

The silicon nitride ceramics with a beneficial combination of low dielectric losses and improved physical properties was fabricated by cold isostatic pressing and pressureless sintering. The fine grain microstructure, three-phase composition based on the β-SiAlON, the small amount of the glass phase and relatively small porosity promote a unique combination of a low thermal conductivity 14.51 W m⁻¹ K⁻¹ and low dielectric loss 1.4·10⁻³. A novel method is proposed to overcome the main drawbacks of the commercial and high-cost technologies.     

Thermal analysis of submicron nanocrystalline diamond films

The thermal properties of sub-μm nanocrystalline diamond films in the range of 0.37–1.1 μm grown by hot filament CVD, initiated by bias enhanced nucleation on a nm-thin Si-nucleation layer on various substrates, have been characterized by scanning thermal microscopy. After coalescence, the films have been outgrown with a columnar grain structure. The results indicate that even in the sub-μm range, the average thermal conductivity of these NCD films approaches 400 W m^− 1 K^− 1. By patterning the films into membranes and step-like mesas, the lateral component and the vertical component of the thermal conductivity, k_lateral and k_vertical, have been isolated showing an anisotropy between vertical conduction along the columns, with k_vertical ≈ 1000 W m^− 1 K^− 1, and a weaker lateral conduction across the columns, with k_lateral ≈ 300 W m^− 1 K^− 1.     

Highly thermal conductive composites with polyamide-6 covalently-grafted graphene by an in situ polymerization and thermal reduction process

The thermal conductive polyamide-6/graphene (PG) composite is synthesized by in situ ring-opening polymerization reaction using ε-caprolactam as the monomer, 6-aminocaproic acid as the initiator and reduced graphene oxide (RGO) as the thermal conductive filler. The generated polyamide-6 (PA6) chains are covalently grafted onto graphene oxide (GO) sheets through the “grafting to” strategy with the simultaneous thermal reduction reaction from GO to RGO. The homogeneous dispersion of RGO sheets in PG composite favors the formation of the consecutive thermal conductive paths or networks at a relatively low GO sheets loading, which improves the thermal conductivity (λ) from 0.196 W m⁻¹ K⁻¹ of neat PA6 to 0.416 W m⁻¹ K⁻¹ of PG composite with only 10 wt% GO sheets loading.     

Heat transport enhancement of thermal energy storage material using graphene/ceramic composites

Graphene/ceramic composites are proposed by directly depositing graphene on the insulating Al₂O₃ particles by chemical vapor deposition without any metal catalysts. Carbothermic reduction occurring at the Al₂O₃ surface is vital during the initial stage of graphene nucleation and the graphene sheet can connect with neighboring sheets to completely cover Al₂O₃ particles. The quality and layer number of graphene on Al₂O₃ can be finely tailored by changing the growth temperature and gas ratio. Graphene coated Al₂O₃ (G-Al₂O₃) composites are used as effective fillers of stearic acid (SA) to increase the thermal transport property. By the optimization of the layer number of graphene, size of Al₂O₃ particles and ratio of G-Al₂O₃/SA in a quantitative, their thermal conductivities significantly increase up to 11 folds from 0.15 to 1.65 W m⁻¹ K⁻¹. The great improvement is attributed to the high thermal transfer performance of graphene and excellent wettability between graphene and SA. When the G-Al₂O₃/SA composites with the graphene coated porous Al₂O₃ foam, the thermal conductivity further reaches to 2.39 W m⁻¹ K⁻¹, and the corresponding latent heat is 38 J g⁻¹. It demonstrates the potential applications of graphene in thermal transport and thermal energy storage devices.     

Ultralow cost reticulated carbon foams from household cleaning pad wastes

A very simple method is described for preparing ultra lightweight and ultralow cost carbon foams (density 0.04–0.075 g cm⁻³ and porosity 98–96%) by impregnation with sucrose of household cleaning pad wastes used as sacrificial templates, followed by pyrolysis in inert atmosphere. Scanning electron microscopy showed that the resultant reticulated vitreous carbon (RVC) foams had a fully open and interconnected porous structure. These materials are more thermally insulating (thermal conductivity 0.042–0.065 W m⁻¹ K⁻¹) than commercial RVC foams having similar compressive strengths (0.11–0.23 MPa) and similar densities.     

Thermal,mechanical and electrical properties of hard B4C,BCN, ZrBC and ZrBCN ceramics

We study the thermal, mechanical and electrical properties of B₄C, BCN, ZrBC and ZrBCN ceramics prepared in the form of thin films by magnetron sputtering. We focus on the effect of Zr_x(B₄C)_1−x sputter target composition, the N₂+Ar discharge gas mixture composition, the deposition temperature and the annealing temperature after the deposition. The thermal properties of interest include thermal conductivity (observed in the range 1.3–7.3 W m⁻¹ K⁻¹), heat capacity (0.37–1.6×10³ J kg⁻¹ K⁻¹ or 1.9–4.1×10⁶ Jm⁻³ K⁻¹), thermal effusivity (1.6–4.5×10³ J m⁻² s^−1/2 K⁻¹) and thermal diffusivity (0.38–2.6×10⁻⁶ m² s⁻¹). We discuss the relationships between materials composition, preparation conditions, structure, thermal properties, temperature dependence of the thermal properties and other (mechanical and electrical) properties. We find that the materials structure (amorphous×crystalline hexagonal ZrB₂-like×nanocrystalline cubic ZrN-like), more than the composition, is the crucial factor determining the thermal conductivity and other properties. The results are particularly important for the design of future ceramic materials combining tailored thermal properties, mechanical properties, electrical conductivity and oxidation resistance.     

The impact of heat treatment on the microstructure of a clay ceramic and its thermal and mechanical properties

This paper presents the results of an experimental study on the microstructure, the thermal and the mechanical properties of a clay-based ceramic used in building applications. The X-ray tomography analysis showed a layered microstructure of clay with 200 µm sheets of porosity after the extrusion process. The gas release from the dehydration, dehydroxylation and decarbonation induced a 7 vol% formation of porosity during the heat treatment of the clay-based ceramic up to 850 °C. The porosity increase and the development of metakaolin led to a 38% decrease in the thermal conductivity. On the other hand, the Young's modulus of the clay-based ceramic was conserved due to the formation of smaller pores than the 200 µm sheets of porosity. The densification and the crystallization of amorphous phases also led to a 110% increase of the Young's modulus from 850 °C to 1050 °C. The Young's modulus of the clay-based ceramic was only decreased by the β→α quartz inversion of the cooling due to sand addition. Hence, this study provided a useful insight into how the microstructure of fired clay bricks can be specifically transformed by the porosity during the heat treatment to control the thermal and mechanical properties.     

Fabrication of insulated metal substrates with organic ceramic composite films for high thermal conductivity

Insulated metal substrates (IMSs) were fabricated and characterized using an organic ceramic composite as a coating mixture. Organic‐inorganic sol solutions were prepared by a sol‐gel process using TEOS (tetraethylorthosilicate), MTMS (methyltrimethoxysilane) and PhTMS (phenyltrimethoxysilane). Ceramic fillers were composed of aluminum oxide (1 and 4 µm) and silicon nitride. The optimal ratio of ceramic filler in the coating mixture was found to be 70 wt%. A thermal conductivity of 3.16 W/mK and a breakdown voltage of 4 kV with a leakage current of 0.17 mA/cm² were obtained for the 122 µm-thick film. A well-networked microstructure between the sol resin and filler in the organic ceramic composite films enhanced the properties of the IMS, such as thermal conductivity and electric insulation.     

Dense carbon monoliths for supercapacitors with outstanding volumetric capacitances

A commercially available dense carbon monolith (CM) and four carbon monoliths obtained from it have been studied as electrochemical capacitor electrodes in a two-electrode cell. CM has: (i) very high density (1.17 g cm⁻³), (ii) high electrical conductivity (9.3 S cm⁻¹), (iii) well-compacted and interconnected carbon spheres, (iv) homogeneous microporous structure and (v) apparent BET surface area of 957 m²g⁻¹. It presents interesting electrochemical behaviors (e.g., excellent gravimetric capacitance and outstanding volumetric capacitance). The textural characteristics of CM (porosity and surface chemistry) have been modified by means of different treatments. The electrochemical performances of the starting and treated monoliths have been analyzed as a function of their porous textures and surface chemistry, both on gravimetric and volumetric basis. The monoliths present high specific and volumetric capacitances (292 F g⁻¹ and 342 F cm⁻³), high energy densities (38 Wh kg⁻¹ and 44 Wh L⁻¹), and high power densities (176 W kg⁻¹ and 183 W L⁻¹). The specific and volumetric capacitances, especially the volumetric capacitance, are the highest ever reported for carbon monoliths. The high values are achieved due to a suitable combination of density, electrical conductivity, porosity and oxygen surface content.     

Effect of phase composition of natural quartz raw material on characterization of microfiltration ceramic membranes

The results of development of multi-layer ceramic membranes on the basis of natural quartz raw material from Mongolia are presented. The influence of the phase composition and temperature of calcination on the porosity, morphology and mechanical strength of large-porous ceramic support obtained by the method of isostatic pressing was studied. It was established that multi-layer ceramic membranes obtained by the application of water suspension of high-disperse quartz sand of Mongolia and alumosilicate binder with the addition of 15–35 wt% of quartz are characterized by optimal properties. The developed tubular ceramic membranes with the average pore size 5.3 µm, coefficient of air permeability (4.17–4.41)×10⁻¹³ m², productivity by water 46.3–48.0 m³/(h×m²×bar) and mechanical strength 2.27–2.53 MPa are perspective for wide use in microfiltration processes.