Production of nepheline/quartz ceramics from geopolymer mortars

This research has investigated the mechanical properties and microstructure of metakaolin derived geopolymer mortars containing 50% by weight of silica sand, after exposure to temperatures up to 1200 °C. The compressive strength, porosity and microstructure of the geopolymer mortar samples were not significantly affected by temperatures up to 800 °C. Nepheline (NaAlSiO₄) and carnegieite (NaAlSiO₄) form at 900 °C in the geopolymer phase and after exposure to 1000 °C the mortar samples were transformed into polycrystalline nepheline/quartz ceramics with relatively high compressive strength (～275 MPa) and high Vickers hardness (～350 HV). Between 1000 and 1200 °C the samples soften with gas evolution causing the formation of closed porosity that reduced sample density and limited the mechanical properties.     

The influence of process parameters on in situ inorganic foaming of alkali-bonded SiC based foams

Silicon carbide (SiC) foams were developed with a low temperature process by using an inorganic alkali aluminosilicates binder, also known as geopolymer. The foaming agent was the metallic silicon present as impurity in the SiC powder. Si⁰ in the alkaline solution led to gas evolution that induced the foaming of the slurries. The binder was a geopolymeric resin with atomic ratio Si/Al = 2 and potassium as alkaline cation, classified as (K)poly(silalate-siloxo). The geopolymeric resin was prepared using metakaolin as aluminosilicatic raw powder, while the alkali aqueous solution was KOH/K₂SiO₃. Metakaolin in alkaline conditions dissolved and re-precipitated to form geopolymeric nano-particulates that acted as a glue to stick together SiC particles (90 wt.%). Process parameters such as water addition, mixing time and curing temperature were correlated to the foam structure. The formation of prolate pores induced anisotropy in the compressive strength. The foams were studied by dilatometric analysis in inert and oxidative atmospheres up to 1200 °C.     

Sintered material from alkaline basaltic tuffs

The possibility to obtain sintered material from alkaline basaltic tuffs is demonstrated. The parent rock was milled for 10–15 min, the resulting powder was pressed at 100 MPa and the obtained samples were heat-treated in the range of 1000–1140 °C. The sintering behaviour and the phase formation were studied by pycnometry, dilatometry, DTA, XRD and SEM.The final material was obtained by sintering at 1100 °C and is characterized by zero water absorption, 8–9 vol.% closed porosity and a structure similar to a glass-ceramic. Due to high crystallization trend of used composition, phase formation takes place during the sintering and cooling steps; this leads to a crystallinity of ～60% and formation of different crystal phases (pyroxene, anorthite, spinel and hematite).Despite the low-cost production cycle the obtained material is characterized by high mechanical properties: bending strength of 100 MPa and Young modulus of 90 GPa.     

From nanometric zirconia powder to transparent polycrystal

Coprecipitated zirconia-yttria (8 mol%) gel subjected to hydrothermal treatment at 240 °C resulted in the solid solution powder of 8 nm particle sizes and specific surface area 132.7 m²/g. Uniaxial compaction followed by cold isostatic pressing under 300 MPa resulted in samples of the extremely small and narrow pore size distribution. Such samples start to shrink at about 200 °C which is related to the desorption of water layers surrounding particles. The state of closed porosity is achieved at 1150 °C. Pore closing was performed in air or oxygen atmosphere. Hot isostatic pressing at 1150 °C for 2 h under 250 MPa argon pressure led to transparent materials. Some pores remained in the material whose preliminary pore closure was performed in air. The samples initially sintered in oxygen atmosphere show no porosity and higher light transmittance than the former ones.     

Microporous alumina substrate with porosity >70% by gelcasting

Microporous alumina membrane substrate in tubular and planar configurations have been prepared by gelcasting of alumina powder slurry using high amount of urea–formaldehyde as gelling agent followed by humidity controlled drying, binder removal and sintering of the gelled bodies. Porosity of the substrate samples sintered at 1350 °C was more than 70% as measured by mercury porosimeter. More than 51% porosity could be retained even after sintering of the samples at 1450 °C. Average pores size of the membrane substrate samples sintered at temperature in the range from 1250 to 1550 °C varied between 0.42 and 0.56 with a maximum at 1350 °C. More uniform pores were observed in sample sintered at 1450 °C. Urea-formaldehyde polymer present in the gelcast body acts as template for micropores.     

Fabrication and compressive strength of porous hydroxyapatite scaffolds with a functionally graded core/shell structure

A novel type of porous hydroxyapatite (HA) scaffolds with a functionally graded core/shell structure was fabricated by freeze casting HA/camphene slurries with various HA contents into fugitive molds containing a graphite template with three-dimensionally interconnected pores for the creation of a highly porous core. All the fabricated samples had functionally graded core/shell structures with 3-D periodic pore networks in a core surrounded by a relatively dense shell. The overall porosity of the sample decreased from 60 to 38 vol% with increasing HA content in the HA/camphene slurry from 20 to 36 vol% due to a decrease in porosity in both the core and shell regions. In addition, the compressive strength was improved remarkably from 12 ± 1.1 to 32 ± 3.0 MPa. The in vitro cell test using a pre-osteoblast cell line showed that the samples had good biocompatibility.     

Fabrication of porous silicon carbide ceramics with high porosity and high strength

Unique porous SiC ceramics with a honeycomb structure were fabricated by a sintering-decarburization process. In this new process, first a SiC ceramic bonded carbon (SiC/CBC) is sintered in vacuum by spark plasma sintering, and then carbon particles in SiC/CBC are volatized by heating in air at 1000 °C without shrinkage. The honeycomb structure has at least two different sizes of pores; ∼20 μm in size resulting from carbon removal; and smaller open pores of 2.1 μm remaining in the sintered SiC shell. The total porosity is around 70% and the bulk density is 0.93 mg/m³. The bending and compressive strengths are 26 MPa, and 105 MPa, respectively.     

Preparation and characterization of porous mullite ceramics via foam-gelcasting

Porous mullite ceramics were prepared via foam-gelcasting using industrial grade mullite powder as the main raw materials, Isobam-104 as the dispersing and gelling agent, sodium carboxymethyl cellulose as the foam stabilizing agent, and triethanolamine lauryl sulfate as the foaming agent. The effects of processing parameters such as type and amount of additive, solid loading level and gelling temperature on rheological properties and gelling behaviors of the slurries were investigated. The green samples after drying at 100 °C for 24 h were fired at 1600 °C for 2 h, and the microstructures and properties of the resultant porous ceramic samples were characterized. Based on the results, the effects of foaming agent on the porosity level, pore structure and size and mechanical properties of the as-prepared porous mullite ceramics were examined. Porosity levels and pore sizes of the as-prepared samples increased with increasing the foaming agent content up to 1.0%, above which both porosity levels and pore sizes did not change. The compressive strength and flexural strength of the as-prepared sample with porosity of 76% and average pore size of 313 μm remained as high as 15.3±0.3 MPa and 3.7±0.2 MPa, respectively, and permeability increased exponentially with increasing the porosity.     

Fabrication and properties of ultra highly porous silicon carbide by the gelation–freezing method

Silicon carbide (SiC) with ultra high porosity and unidirectionally oriented micrometer-sized cylindrical pores was prepared using a novel gelation–freezing (GF) method. Gelatin, water and silicon carbide powder were mixed and cooled at 7 °C. The obtained gels were frozen from ?10 to ?70 °C, dried using a vacuum freeze drier, degreased at 600 °C and then sintered at 1800 °C for 2 h. The gels could be easily formed into various shapes, such as cylinders, large pipes and honeycombs using molds. Scanning electron microscopy (SEM) observations of the sintered bodies showed a microstructure composed of ordered micrometer-sized cylindrical cells with unidirectional orientation. The cell size ranging from 34 to 147 μm could be modulated by changing the freezing temperatures. The numbers of cells for the samples frozen at ?10 and ?70 °C were 47 and 900 cells/mm², respectively, as determined from cross-sections of the sintered bodies. The resulting porous SiC with a total porosity of 86%, exhibited air permeability from 2.3 × 10^?11 to 1.0 × 10^?10 m², which was the same as the calculated ideal permeability, and high compressive strength of 16.6 MPa. The porosity, number of cells, air permeability and strength of the present porous SiC were significantly higher than that reported for other porous SiC ceramics.     

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.     

Effect of ageing on microstructure changes in EB-PVD manufactured standard PYSZ top coat of thermal barrier coatings

The ceramic top coat of thermal barrier coatings (TBC) manufactured by electron beam-physical vapour deposition (EB-PVD) process is a crucial part of a system which protects the high pressure turbine blades of aero engines and stationary gas turbines. Under service conditions, turbine blades are exposed to temperatures above 1100 °C, typically with short-term peaks. Ceramic top coat has a unique microstructure made up of individual primary columns, growing in a preferred crystal direction. This columnar growth produces an inter-columnar spacing exhibiting a weak bonding between the neighbouring columns, and providing the TBCs with high strain tolerance. Rotation of the substrates during vapour phase deposition produces an additional intra-columnar closed porosity. Furthermore, this causes formation of a feather-like sub-columnar structure at the periphery of each primary column due to over-shadowing, increasing total porosity and thus contributing to low thermal conductivity of the material.On thermal exposure during service, both inter- and intra-columnar porosity decrease as a result of sintering induced surface area reduction. The driving force for this process is the decrease in surface energy. As a result, thermal conductivity increases due to the alteration of the porosity distribution, size and morphology. In addition the in-plane strain tolerance decreases after the primary columns sinter together to form bridges at the contact points. These are two important factors which affect the performance of the entire system. Thus, analysis of the involvement of each pore family (feather-arm, intra- and inter-columnar pores) in thermal insulating capabilities of yttria stabilized zirconia (PYSZ) TBC may provide a guideline for engine manufacturers in designing more efficient coatings with optimised thermal properties, in all probability solely by controlled adjustment of the process parameters.This work reports the thermal-induced microstructural changes in terms of total porosity at EB-PVD produced top coats before and after annealing at 900 °C, 1000 °C, 1100 °C, 1200 °C, 1300 °C and 1400 °C for 1 h, as well as at 1100 °C for 20 min, 1 h, 3 h, 10 h and 100 h. For the analysis of the changes in pore surface area, methods such as SANS (small angle neutron scattering) and BET (Brunauer–Emmett–Teller) were applied. Alteration of surface area with time and temperature commonly gives an indication of the type of diffusion mechanism. Hence, kinetic and the activation energy of the mechanism are calculated and determined with the help of the data obtained by SANS and BET-analysis. Due to the presence of a large number of nano-sized closed porosity in the coatings, SANS measurements were crucial to distinguish those from the remaining open porosity. A mean porosity representative for pores smaller than 180 nm is obtained by interaction of neutrons diffracting parallel to the primary column axis.     

Processing of silica foam using steam heating and its characterization

Silica foams with 50–86 vol.% porosity have been developed through steam-heating route using slurries containing ovalbumin as binder, as well as sucrose and colloidal silica as additives. On steam-heating, only 1 h is required for drying of as-cast foams, as the cell-walls being restrained from shrinking by intra-cellular gas pressure, and simultaneously strengthened by ovalbumin protein coagulation, show minimum damage. Scanning electron microscopic studies of sintered foams have shown near-spherical pores with size distribution having mean of ≈250–300 μm. These pores appear interconnected through finer pores of ≈15–25 μm size along their walls. Solid loading, binder and sucrose concentrations of slurries for optimum viscosity have been obtained through rheological studies to tailor desirable pore content and size distributions in the sintered foams. Young's moduli and compressive strengths are found to be in the ranges of 14.4–544 MPa and 0.3–8.6 MPa, respectively for sintered foams having ≈55–90 vol.% porosity content.     

Differentiation of the solid-state NMR signals of gel,zeolite phases and water species in geopolymer-zeolite composites

Geopolymer-zeolite composites were synthesized using a silica-rich industrial byproduct from chlorosilane production and sodium aluminate. Pastes were cured at 80 °C and 80% RH, and subsequently dried in two different climates: at 23 °C and 50% RH, and under vacuum. ¹H MAS, ²³Na MAS and ²⁹Si MAS NMR and XRD measurements were performed after the drying procedures as well as after subsequent aging. Zeolite Na-A was found beside traces of faujasite-type zeolite and zeolite EMT as major crystalline phases in the cured composites; the fraction of geopolymeric gel in the reaction products was determined to be ~18% on a molar basis. Various water species could be distinguished using ¹H MAS and ¹H-²⁹Si CP MAS NMR, applying rotor-synchronized echo experiments. The largest fraction of the pore water resides in the α-cages of the zeolite Na-A and in the geopolymeric gel; in addition, water exists in the β-cages of the zeolites and adsorbed at sodium ions. The water species in α-cages and in the pores of the geopolymeric gel exhibit slightly different chemical shifts of 4.7 ppm and 4.9 ppm, respectively, in the ¹H MAS NMR spectra. Changes of the water content in the geopolymer pores of differently dried samples were observed and led to slightly varied chemical shifts in the ²⁹Si MAS NMR spectra too. Measurements after more than 500 days revealed no significant aging effects of the composites, which confirm their chemical stability.     

Preparation of Si3N4 ceramic foams by simultaneously using egg white protein and fish collagen

Fish collagen, a kind of fibrous protein, and egg white protein were selected as foaming agent to prepare ceramic foams by protein foaming method. Ceramic foams with open porosity of 84.8–86.9%, average pore size of 216–266 μm and compressive strength of 8.7–13.7 MPa were fabricated. Studies of fish collagen addition on the influence of open porosity, pore size distribution and mechanical property of ceramic foams were investigated. In comparison with single addition of 8 wt% egg white protein, the combinational addition of 2 wt% fish collagen and 6 wt% egg white protein results in 23% increase in average pore size. In addition, the introduction of fish collagen decreases the count of small pores. Moreover, with the introduction of fish collagen, pores become regular in shape.     

Microstructural and compositional change of NaOH-activated high calcium fly ash by incorporating Na-aluminate and co-existence of geopolymeric gel and C–S–H(I)

This study explores the reaction products of alkali-activated Class C fly ash-based aluminosilicate samples by means of high-resolution synchrotron X-ray diffraction (HSXRD), scanning electron microscope (SEM), and compressive strength tests to investigate how the readily available aluminum affects the reaction. Class C fly ash-based aluminosilicate raw materials were prepared by incorporating Na-aluminate into the original fly ashes, then alkali-activated by 10 M NaOH solution. Incorporating Na-aluminate reduced the compressive strength of samples, with the reduction magnitude relatively constant regardless of length of curing period. The HSXRD provides evidence of the co-existence of C–S–H with geopolymeric gels and strongly suggests that the C–S–H formed in the current system is C–S–H(I). The back-scattered electron images suggest that the C–S–H(I) phase exists as small grains in a finely intermixed form with geopolymeric gels. Despite providing extra source of aluminum, adding Na-aluminate to the mixes did not decrease the Si/Al ratio of the geopolymeric gel.     

Effects of heating rate on the structure and properties of SiOC ceramic foams derived from silicone resin

Silicon oxycarbide ceramic foams were fabricated in a single step manufacturing process using in situ foaming of SiOC powders loaded silicone resin. The effects of heating rate on the porosity, compressive strength and microstructure of the ceramic foams were investigated. The porosity (total and open) increased firstly and then decreased with increasing heating rate. It was possible to control the total and open porosity of ceramic foams within a range of 81.9–88.2% and 62.4–72.5% respectively, by adjusting the heating rate from 0.25 °C/min to 3 °C/min while keeping the silicone resin content at 90 vol%. However, the compressive strength decreased with increasing the heating rate progressively, and the average compressive strength of the foams was in the range of 1.0–2.3 MPa. Micrographs indicated that the ceramic foams which cross-linked at a heating rate less than 1 °C/min had a well-defined open-cell and regular pore structure.     

New multifunctional porous Yb2SiO5 ceramics prepared by freeze casting

New porous Yb₂SiO₅ ceramics were prepared by a water-based freeze casting technique using synthesized Yb₂SiO₅ powders. The prepared porous Yb₂SiO₅ ceramics exhibit multiple pore structures, including lamellar channel pores and small pores, in its skeleton. The effects of the solid content and sintering temperature on the pore structure, porosity, dielectric and mechanical properties of the porous Yb₂SiO₅ ceramics were investigated. The sample with 20 vol% solids content prepared at 1550 °C exhibited an ultra-low linear shrinkage (i.e. 4.5%), a high porosity (i.e. 79.1%), a high compressive strength (i.e. 4.9 MPa), a low dielectric constant (i.e. 2.38) and low thermal conductivity (i.e. 0.168 W/(m K)). These results indicate that porous Yb₂SiO₅ ceramics are good candidates for ultra-high temperature broadband radome structures and thermal insulator materials.     

Improving compressive strength of fly ash-based geopolymer composites by basalt fibers addition

In this study, ASTM Class C fly ash used as an alumino-silicate source was activated by metal alkali and cured at low temperature. Basalt fibers which have excellent physical and mechanical properties were added to fly ash-based geopolymers for 10–30% solid content to act as a reinforced material, and its influence on the compressive strength of geopolymer composites has been investigated. XRD study of synthesized geopolymers showed an amorphous phase of geopolymeric gel in the 2θ region of 23°–38° including calcium-silicate-hydrate (C-S-H) phase, some crystalline phases of magnesioferrite, and un-reacted quartz. The microstructure investigation illustrated fly ash particles and basalt fibers were embedded in a dense alumino-silicate matrix, though there was some un-reacted phase occurred. The compressive strength of fly ash-based geopolymer matrix without basalt fibers added samples aged 28 days was 35 MPa which significantly increased 37% when the 10 wt%. basalt fibers were added. However, the addition of basalt fibers from 15 to 30 wt% has not shown a major improvement in compressive strength. In addition, it was found that the compressive strength was strong relevant to the Ca/Si ratio and the C-S-H phase in the geopolymer matrix as high compressive strength was found in the samples with high Ca/Si ratio. It is suggested that basalt fibers are one of the potential candidates as reinforcements for geopolymer composites development.     

Processing and properties of low cost macroporous alumina ceramics with tailored porosity and pore size fabricated using rice husk and sucrose

The present study demonstrates a cost effective way to fabricate porous ceramics with tailored microstructures using rice husk (RH) of various range of particle sizes as a pore former and sucrose as a binder as well as a pore former. Sample microstructures reveal randomly oriented elongated coarse pores and fine pores (avg. size 4 μm) created due to burnout of RH and sucrose, respectively. Porous alumina ceramics with 20–66 vol% porosity and 50–516 μm avg. pore size (length), having isolated and/or interconnected pores, were fabricated using this process. Mechanical properties of the porous samples were determined as a function of porosity and pore microstructure. The obtained porous ceramics exhibited flexural strength of 207.6–22.3 MPa, compressive strength of 180–9.18 MPa, elastic modulus of 250–18 GPa and hardness of 149–18 HRD. Suggested application area includes thermal, filtration, gas purging etc.     

Fabrication and characterization of porous ZrO2 with a high volume fraction of fine closed pores

A novel technique for the fabrication of porous ZrO₂ with a high volume fraction of fine closed pores was investigated. A partially stabilized ZrO₂ (3 mol% Y₂O₃; Y-PSZ) body, with a 97–99% relative density and containing a small amount of impurities, exhibited a large volume expansion related to the formation of closed pores after heating at 1700 °C for 10 min in N₂. These closed pores seemed to mainly form due to the vaporization of hydroxyl apatite: Ca₁₀(OH)₂(PO₄)₆ as an impurity and superplasticity of the ZrO₂ during heating. Porous ZrO₂ with approximately 24.6% closed pores (total porosity: 26.7%) was successfully fabricated by the addition of 1 mass% SiO₂, 1 mass% TiO₂, and 1 mass% hydroxyl apatite. The closed pore size and morphology of the resultant porous ZrO₂ bodies were investigated, and the formation mechanism of the closed pores was examined on the basis of chemical thermodynamics.