Densification and grain growth during sintering of porous Ce0.9Gd0.1O1.95 tape cast layers: A comprehensive study on heuristic methods

The sintering behavior of porous Ce_0.9Gd_0.1O_1.95 (CGO10) tape cast layers was systematically investigated to establish fundamental kinetic parameters associated to densification and grain growth. Densification and grain growth were characterized by a set of different methods to determine the dominant sintering mechanisms and kinetics, both in isothermal and at constant heating rate (iso-rate) conditions. Densification of porous CGO10 tape is thermally activated with typical activation energy which was estimated around 440–470 kJ mol^?1. Grain growth showed similar thermal activation energy of ～427 ± 22 kJ mol^?1 in the temperature range of 1100–1250 °C. Grain-boundary diffusion was identified to be the dominant mechanism in porous CGO10 tapes. Grain growth and densification mechanism were found strictly related in the investigated temperature range. Porosity acts as a grain growth inhibitor and grain boundary mobility in the porous body was estimated around 10^?18–10^?16 m³ N^?1 s^?1 at the investigated temperature range.     

Porous anorthite ceramics with ultra-low thermal conductivity

Porous anorthite ceramics with an ultra-low thermal conductivity of 0.018 W/m K have been fabricated by hydrous foam-gelcasting process and pressureless sintering method using γ-alumina, calcium carbonate and silica powders as raw materials. Microstructure and phase composition were analyzed by SEM and XRD respectively. Properties such as porosity, pore size distribution and thermal conductivity were measured. High porosity (69–91%) and low thermal conductivity (0.018–0.13 W/m K) were obtained after sintering samples with different catalyst additions at 1300–1450 °C. Porosity, pore size, pore structure and grain size had obvious effect on heat conduction, resulting in the low thermal conductivity. The experimental thermal conductivity data of porous anorthite ceramics were found to be fit well with the computed values derived from a universal model.     

Parametric study of intrinsic thermal transport in vertically aligned multi-walled carbon nanotubes using a laser flash technique

The thermal diffusivity of vertically aligned carbon nanotube (VACNT, multi-walled) films synthesized by thermal chemical vapor deposition was measured by a laser flash technique, and shown to be ～30 mm² s^?1 along the tube-alignment direction. The calculated thermal conductivities of the VACNT films and the individual CNTs were ～27 and ～540 W m^?1 K^?1, respectively. The technique was verified to be reliable although a proper sampling procedure is critical. A systematic parametric study of the effects of defects, buckling, tip-to-tip contacts, packing density, and tube–tube interaction on the thermal diffusivity was carried out. Defects and buckling decreased the thermal diffusivity dramatically. An increased packing density was beneficial in increasing the collective thermal conductivity of the VACNT film; however, the increased tube–tube interaction in dense VACNT films decreased the effective thermal conductivity of the individual CNTs in the films. The tip-to-tip contact resistance was shown to be ～1 × 10^?7 m² K W^?1. The study will shed light on the potential application of VACNTs as thermal interface materials in microelectronic packaging.     

Processing and properties of cordierite-silica bonded porous SiC ceramics

Cordierite-silica bonded porous SiC ceramics were fabricated by infiltrating a porous powder compact of SiC with cordierite sol followed by sintering at 1300–1400 °C in air. The porosity, average pore diameter and flexural strength of the ceramics varied 30–36 vol%, ~ 4–22 µm and ~ 13–38 MPa respectively with variation of sintering temperature and SiC particle sizes. In the final ceramics SiC particles were bonded by the oxidation-derived SiO₂ and sol-gel derived cordierite. The corrosion behaviour of sintered SiC ceramics was studied in acidic and alkaline medium. The porous SiC ceramics were observed to exhibit better corrosion resistance in acid solution.     

Compressive mechanical properties of partially sintered porous alumina of bimodal particle size system

This paper examined theoretically and experimentally packing behavior, sintering behavior and compressive mechanical properties of sintered bodies of the bimodal particle size system of 80 vol% large particles (351 nm diameter)–20 vol% small particles (156 nm diameter). The increased packing density as compared with the mono size system was explained by the packing of small particles in 6-coordinated pore spaces among large particles owing to the similar size relation between 6-coordinated spherical pore and small particle. The sintering between adjacent large particles dominated the whole shrinkage of the powder compact of the bimodal particle size system. However, the bimodal particle size system has a high grain growth rate because of the different curvatures of adjacent small and large particles. The derived theoretical equations for the compressive strengths of both mono size system and bimodal particle size system suggest that the increase in the grain boundary area and relative density by sintering dominate the compressive strength of a sintered porous alumina. The experimental compressive strengths were well explained by the proposed theoretical models. The strength of the bimodal particle size system was high at low sintering temperatures but was low at high sintering temperatures as compared with that of mono size system of large particles. This was explained by mainly the change of grain boundary area with grain growth. The stress–strain relationship of the bimodal particle size system showed an unique pseudo-ductile property. This was well explained by the curved inside stress distribution along the sample height. The inside stress decreases toward the bottom layer. The fracture of one layer of sintered grains over the top surface proceeds continuously with compressive time along the sample height when an applied stress reaches the critical fracture strength.     

Highly porous nano-SiC with very low thermal conductivity and excellent high temperature behavior

Highly porous nano-SiC is fabricated by partial sintering and decarburizing process using SiC nano-powders as starting materials and graphite flakes as pore forming agents. The prepared porous nano-SiC ceramics possess multiple pore structures, including well-distributed meso-pores in the skeleton and interconnected flakelike micro-pores. The samples prepared at 1800 °C have relatively low thermal conductivities of 5.61 ～ 0.25 W m^?1 K^?1 with porosities of 55.5–76.1%. While the samples sintered at 1500 °C with porosities between 54.0% to 76.3% show very low thermal conductivities of 0.74 ～ 0.14 W m^?1 K^?1, which is attributed to the integrated nano-scale phonon-scattering mechanisms and duplex pore structures. Porous nano-SiC ceramics also show good retention of elastic stiffness up to 1350 °C and low thermal conductivity at 1400 °C. Our results shed light on porous nano-SiC as a promising thermal insulator used in extreme thermal and chemical environments.     

Preparation of sulfur-doped microporous carbons for the storage of hydrogen and carbon dioxide

Structurally well ordered, sulfur-doped microporous carbon materials have been successfully prepared by a nanocasting method using zeolite EMC-2 as a hard template. The carbon materials exhibited well-resolved diffraction peaks in powder XRD patterns and ordered micropore channels in TEM images. Adjusting the synthesis conditions, carbons possess a tunable sulfur content in the range of 1.3–6.6 wt.%, a surface area of 729–1627 m² g^?1 and a pore volume of 0.60–0.90 cm³ g^?1. A significant proportion of the porosity in the carbons (up to 82% and 63% for surface area and pore volume, respectively) is contributed by micropores. The sulfur-doped microporous carbons exhibit isosteric heat of hydrogen adsorption up to 9.2 kJ mol^?1 and a high hydrogen uptake density of 14.3 × 10^?3 mmol m^?2 at ?196 °C and 20 bar, one of the highest ever observed for nanoporous carbons. They also show a high CO₂ adsorption energy up to 59 kJ mol^?1 at lower coverages (with 22 kJ mol^?1 at higher CO₂ coverages), the highest ever reported for any porous carbon materials and one of the highest amongst all the porous materials. These findings suggest that S-doped microporous carbons are potential promising adsorbents for hydrogen and CO₂.     

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 and properties of mullite-bonded porous fibrous mullite ceramics by an epoxy resin gel-casting process

Porous fibrous mullite ceramics with a narrow range of pore size distribution have been successfully prepared utilizing a near net-shape epoxy resin gel-casting process by using mullite fibers, Al₂O₃ and SiC as raw materials. The effects of sintering temperatures, different amounts of fibers and Y₂O₃ additive on the phase compositions, linear shrinkage, apparent porosity, bulk density, microstructure, compressive strength and thermal conductivity were investigated. The results indicated that mullite-bonded among fibers were formed in the porous fibrous mullite ceramics with a bird nest pore structure. After determining the sintering temperatures and the amount of fibers, the tailored porous fibrous mullite ceramics had a low linear shrinkage (1.36–3.08%), a high apparent porosity (61.1–71.7%), a relatively high compressive strength (4.4–7.6 MPa), a low thermal conductivity (0.378–0.467 W/m K) and a narrow range of pore size distribution (around 5 µm). The excellent properties will enable the porous ceramics as a promising candidate for the applications of hot gas filters, thermal insulation materials at high temperatures.     

Sinterability,microstructure and compressive strength of porous glass-ceramics from metallurgical silicon slag and waste glass

Porous glass-ceramics have been prepared by the direct sintering of powder mixtures of metallurgical silicon slag and waste glass. The thermal behavior of silicon slag was examined by differential thermal analysis and thermogravimetry to clarify the foaming mechanism of porous glass-ceramics. The mass loss of silicon slag below 700 °C was attributed to the oxidation of amorphous carbon from residual metallurgical coke in the silicon slag, and the mass gain above 800 °C to the passive oxidation of silicon carbide. The porosity of sintered glass-ceramics was characterized in terms of the apparent density and pore size. By simply adjusting the content of waste glass and sintering parameters (i.e. temperature, time and heating rate), the apparent density changed from 0.4 g/cm³ to 0.5 g/cm³, and the pore size from 0.7 mm to 1.4 mm. In addition to the existing crystalline phases in the silicon slag, the gehlenite phase appeared in the sintered glass-ceramics. The compressive strength of porous glass-ceramics firstly increased and then decreased with the sintering temperature, reaching a maximal value of 1.8 MPa at 750 °C. The mechanical strength was primarily influenced by the crystallinity of glass-ceramics and the interfaces between the crystalline phases and the glassy matrix. These sintered porous glass-ceramics exhibit superior properties such as light-weight, heat-insulation and sound-absorption, and could found their potential applications in the construction decoration.     

Oxidation-bonded SiC membrane for microfiltration

Porous SiC is a proven viable material for microfiltration membranes, but its application has been limited by high fabrication cost. In this study, the oxidation bonding technique was used for the first time to fabricate SiC microfiltration membrane. The study was divided into two parts: optimization of the slurry used to dip coat the SiC particles over a porous SiC ceramic support and controlling the oxidation behaviour of SiC with respect to temperature. The oxidation behaviour during different thermal treatments was related to pore morphology and ultimately the membrane permeance. By coating the clay-bonded SiC support with oxidation-bonded SiC and sintering the coating at 1100 °C for 1 h, we prepared a defect-free microfiltration membrane with pure-water membrane permeance of >210 L m^?2 h^?1 bar^?1, an average pore size of 93 nm, and a narrow pore-size distribution.     

Preparation of porous Y2SiO5 ceramics with relatively high compressive strength and ultra-low thermal conductivity by a TBA-based gel-casting method

Porous Y₂SiO₅ ceramics with relative high compressive strength (as high as 24.45 MPa) and ultra-low thermal conductivity (～0.08 W/m K) were successfully fabricated by a tert-butyl alcohol based gel-casting method. The formation mechanism of the 3D interconnected pores and the properties of the green body are discussed. The porosity, pore size, compressive strength and thermal conductivity could be controlled by varying the initial solid loading and the sintering temperature. When regulating the initial solid loading (from 20 to 50 wt%) and sintering temperature (from 1200 to 1500 °C), the porosity can be controlled between 47.74% and 73.93%, and the compressive strength and the thermal conductivity of porous Y₂SiO₅ ceramics varied from 3.34 to 24.45 MPa and from 0.08 to 0.55 W/m K, respectively. It should be noted that the porous Y₂SiO₅ ceramics with 30 wt% solid loading and sintering at 1400 °C had an open porosity of 61.80%, a pore size of 2.24 μm, a low room-temperature thermal conductivity of 0.17 W/m K and a relatively high compressive strength of 13.91 MPa, which make this porous Y₂SiO₅ ceramics suitable for applications in high-temperature thermal insulators.     

Master sintering curves of a nanoscale 3Y-TZP powder compacts

The sintering behavior of commercially available granulated ZrO₂–3 mol% Y₂O₃ (3Y-TZP) powder compacts with an aggregate size of 75 nm was studied. The shrinkage response of the powder compacts during non-isothermal sintering was measured in a sensitive dilatometer at different heating rates. Densification and grain growth were also studied after isothermal firing in air according to different sintering cycles. The sintering and grain growth activation energy was estimated to be Q_S = 485 ± 12 kJ mol^?1 and Q_G = 546 ± 23 kJ mol^?1, respectively. Using the estimated Q-values, the master curves for sintering and grain growth were established and used for prediction of the densification and microstructural development under different thermal histories. A good agreement between the model predictions and experimental result was obtained.     

Macro-porous ceramic supports for membranes prepared from quartz sand and calcite mixtures

A new type of porous ceramic supports for membranes has been designed. The new supports have been fabricated from polycrystalline quartz sand and calcite raw materials. In this work, two configurations of support (tubular and flat) have been produced using extrusion method. The open porosity, the pore size distribution, the average pore size (APS), the strength and the permeability of sintered supports have been found to depend mainly on the weight ratio of calcite (CaCO₃) additive. The results showed that with the addition of 15–35 wt.% of calcite and sintering temperature of about 1375 °C for 1 h the best characteristics of sintered supports could be obtained. The developed tubular ceramic supports with the APS 6.3–12 μm, open porosity 42–55%, the water permeability (16–68 m³/h m² bar) and flexural strength 8–18 MPa hopefully offer many perspectives for a wide use in membranes technology.     

Synthesis and characterization of porous Y2SiO5 with low linear shrinkage,high porosity and high strength

The emerging porous Y₂SiO₅ ceramic is regarded as a promising candidate of thermal insulator owing to its very low thermal conductivity. However, recent works on porous Y₂SiO₅ are confronted with severe problems such as large linear shrinkage (18.51–20.8%), low porosity (47.74–62%) and low strength (24.45–16.51 MPa) at high sintering temperatures (1450–1500 °C). In this work, highly porous Y₂SiO₅ ceramic with low shrinkage and excellent high-temperature strength was fabricated by in-situ foam-gelcasting method at 1550 °C. The as-prepared sample has unique multiple pore structures, low linear shrinkages of 6.3–4.5%, controllable high porosities of 60.7–88.4%, high compressive strengths of 38.2–0.90 MPa, and low thermal conductivities of 0.126–0.513 W/(m K) (porosity: 87.1–60.2%). The effects of relative density on relative strength, as well as porosity on thermal conductivity were quantitatively discussed. The present results indicate that porous Y₂SiO₅ is the potential high-temperature thermal insulation material of light weight, low thermal conductivity, and high strength.     

Micrometer-sized mesoporous diamond spherical particles

Micrometer-sized porous diamond spherical particles (PDSPs) were fabricated from nanodiamond (ND) particles using spray drying and microwave plasma-assisted chemical vapor deposition (MPCVD). Nitrogen gas sorption measurement revealed that the PDSP fabricated from 5 nm detonation ND particles had a Brunauer–Emmett–Teller (BET) surface area of ca. 300 m² g^− 1 and a narrow pore diameter distribution around 10 nm. Nitrogen sorption analysis of PDSP fabricated from various ND particle sizes (diameters from 20 to 50 nm) showed that the BET surface area decreased (200–85 m² g^− 1) and the average pore diameter increased (4.6–9.3 nm) as the ND diameter increased from 20 to 50 nm. Calculation with a simple model revealed that the pores of the PDSP were derived from the interparticle space of the NDs. The PDSP was durable to immersion in aqueous solutions of HF and NaOH, which indicates the extremely high chemical stability of the diamond-based mesoporous material. The PDSP surface was modified with octadecyl groups using a photochemical method. A column packed with the modified PDSP was successfully employed in a reverse phase high performance liquid chromatography (HPLC) column, and the successful separation of organic compounds was demonstrated with a water/acetonitrile mixture mobile phase.     

Silicon carbide ceramics: Mechanical activation,combustion and spark plasma sintering

Single-stage fabrication of SiC ceramics by a combination of self-propagating high temperature synthesis (SHS) and spark plasma sintering (SPS) is reported. SHS+SPS is demonstrated to be an efficient method for production of SiC ceramics with density 3.1 g/cm³, hardness of 24 GPa and toughness of 5 MPa m^1/2. The starting material for the process is fine (50–300 nm in size) highly reactive powder, which involves composite particles of elemental carbon and silicon. This powder was prepared using a high-energy ball milling (HEBM). To optimize precursor preparation conditions, the structure transformation in nano-composite Si/C particles at different HEBM stages is also investigated.     

Effect of surfactant and heat treatment on morphology,surface area and crystallinity in hydroxyapatite nanocrystals

Hydroxyapatite (HA) powders were synthesized by the wet precipitation method, with and without surfactant, under identical processing parameters. These powders were then heat treated at 900 °C for 3 h in air. The detailed characterization of the powders was done by using SEM, dynamic light scattering, nitrogen adsorption, XRD, Raman spectroscopy, and FTIR techniques. The HA phase, identified by well defined PO₄^3? and OH^? ion peaks in Raman and FTIR spectra, was observed in all the powder samples. The addition of surfactant changed the morphology of the particles from spherical to needle/rod-like structure and increased the surface area up to three times (from 33 to 96 m²/g). Also, suppression in the evolution of β-TCP phase was observed along with decrease in the crystal size and crystallinity of the powder due to the addition of surfactant. Synthesized nano-HA crystals were found to have diameters and lengths in the range 10–25 nm and 75–150 nm, respectively. The heat treatment changed the architecture of the particles, increased the crystallinity and reduced the surface area to ≈7 m²/g. However, the relative increase in crystallinity was much higher for the powder synthesized with surfactant. The ratio of the average crystallite size to the crystallinity degree was about 0.53±0.07 for all the powders. The particle size distribution was bimodal and coarser for the powder synthesized without surfactant. The pore size analysis showed transformation of a predominantly mesoporous structure into a meso- plus macroporous one on heat treatment. The intensity of OH^? group peak in Raman spectra was found to be highly sensitive to the crystalline state of the HA powder and may be used to assess crystallinity.     

Foam-gelcasting preparation,microstructure and thermal insulation performance of porous diatomite ceramics with hierarchical pore structures

Hierarchically pore-structured porous diatomite ceramics containing 82.9∼84.5% porosity were successfully prepared for the first time via foam-gelcasting using diatomite powder as the main raw material. Sizes of mesopores derived from the raw material and macropores formed mainly from foaming were 0.02∼0.1 μm and 109.7∼130.5 μm, respectively. The effect of sintering temperature, additive content and solid loading of slurry on pore size and distribution, and mechanical and thermal properties of as-prepared porous ceramics were investigated. Compressive strength of as-prepared porous ceramics increased with sintering temperature, and the one containing 82.9% porosity showed the highest compressive strength of 2.1 ± 0.14 MPa. In addition, the one containing 84.5% porosity and having compressive strength of 1.1 ± 0.07 MPa showed the lowest thermal conductivity of 0.097 ± 0.001 W/(m·K) at a test temperature of 200 ̊C, suggesting that as-prepared porous ceramics could be potentially used as good thermal insulation materials.     

Low temperature preparation and electrical properties of sodium–potassium bismuth titanate lead-free piezoelectric thick films by screen printing

Sodium–potassium bismuth titanate (NKBT) thick films with thickness of 40 μm were prepared by screen printing. To improve the homogeneity, the sintering aids were added into the pastes as a chemical liquid-phase doping method. The results show that the addition of Bi–Li sintering aids was beneficial for both the reduction of the sintering temperature and the improvement of the electrical performance of the thick films. The thick films containing 5 wt.% Bi–Li sintering aids demonstrated optimal dielectric properties with the maximum dielectric constant of 725 and minimum dielectric loss of 2.5%. Moreover, the NKBT thick films containing 3 wt.% Bi–Li sintering aids sintered at 950 °C exhibited the remanent polarization of 19.6 μC/cm², room-temperature pyroelectric coefficient of 1.56 × 10^?4 C/(m² °C), figure of merit for specific detectivity of 0.48 × 10^?5 Pa^?0.5, and effective longitudinal piezoelectric coefficient of 88 pm/V, which are comparable to that of the high-temperature sintered thick films without sintering aids.