Microwave and conventional treatment of low-cement high-alumina castables with different water to cement ratios; Part I. Drying

The aim of this study was to determine the effect of the microwave and conventional drying method on the strength, porosity and composition of low-cement alumina castables with various water to cement ratios (wcr). High-alumina low-cement castable samples were prepared with different w/c ratios: 0.64, 0.75, 0.82 and 1.13. Changes in wcr were effected through volumetric replacement of cement with 0–0,045-mm tabular alumina having a comparable particle size. Water content in all the composition was constant (4,5%). After curing, the samples were dried conventionally in a laboratory electric drier or in a laboratory microwave drier. After drying open porosity and modulus of rupture were determined. The pore size distribution, pore median and tortuosity of the samples were measured by the mercury porosimetry method. Phase composition was determined using X-ray diffraction. The Rietveld method was used for quantitative analysis. It was found that at low wcr (0.62) the main hydrate formed in the castable was C₃AH₆, which caused a release of a smaller amount of water during the drying process, mainly pore water, resulting in lower open porosity and lower pore size than in the castables with a high wcr (1.13). At a low wcr, the strenght of castable was higher due to a higher amount of hydrates, low porosity and small pore size. On the other hand, at a high wcr, the strength of castable was lower owing to a higher amount of water released in the drying process, which led to loosening the structure of castable. With an increased water-to-cement ratio the degree of CA₂ hydration decreased. The temperature rise due to cement hydration probably influenced the kinetics of this process.     

The effect of nano-size additives on the electrical conductivity of matrix suspension and properties of self-flowing low-cement high alumina refractory castables

Influence of two nano-size additives on electrical properties of suspension matrix of self-flowing low-cement high alumina refractory castable is investigated. For this purpose, castament FS 10 and FS 20 on the basis of polycarboxylate ether were considered. The self-flow value, workability and mechanical strength of the castable are evaluated and their relations with electrical conductivity are determined. Using these relations, the type and optimum amount of proper additive for these refractory castables are determined. It was shown that if the electrical conductivity of matrix suspension is less than 0.71 mS/cm, high alumina low-cement self-flowing refractory castable can be obtained. The best self-flow, sufficient working time and adequate mechanical strength in the castables are obtained with 0.08 wt.% FS 20.     

The relationship between electric processing condition and microstructure in the solidification of multicomponent oxides

Systematic characterization for the relationship between the electropulse processing conditions and microstructure has been carried out in the present work. It is found that electropulse can refine porosity and alter grain morphology considerably. A processing with optimum electropulsing parameters can reduce over 75% volume fraction of porosity and more than 70% average pore diameter in comparison with that of reference sample without electric treatment. Electric current treatment promotes the growth of dendrites with smaller thickness of primary arms dendrite and prevents the liquid entrapping between the growing solid grains. The former is caused by the effect of electricity-enhanced kinetic mobility on the radius of curvature at the tip of dendrite. The latter is attributed to the effects of electric thermodynamics on the microstructural formation such as the enhanced connectivity of conductive phase. The microstructures obtained by electropulsing treatment are favourable for heat conduction, structural strength and crack prohibition. However, the excess pulse frequency and pulse width can generate unwanted heat to counteract electric effect. The research reveals the relationship between electric processing conditions and microstructure in a perfectly controversial solidification condition in oxide materials to that of the metals and alloys. The results confirm from the opposite side the validity of the pulsated solidification.     

Investigations of SiC aggregates oxidation: Influence on SiC castables refractories life time at high temperature

This paper reports results concerning the oxidation of silicon carbide of pure SiC powder (98% of SiC) and the oxidation of two silicon carbide castables, used in waste-to-energy plants (WTE), and containing 60% and 85% of SiC, respectively. The investigated temperature range (800-1200 °C) corresponds to typical service conditions in WTE. Thanks to thermogravimetric and thermal expansion tests, kinetics of oxidation of the powder of SiC and of the castables has been investigated. According to these tests, several important points have been underlined. Firstly, the oxidation of SiC aggregates has a high influence on the thermal expansion and on the weight gain of SiC castables. Secondly, the grain size distribution of SiC aggregates within castables plays a dominating role (especially enhanced for the fine particles) in castable expansion behaviour induced by oxidation. This is a key point according to the evolution of thermal expansion of such materials.     

Characterization of IT-SOFC non-symmetrical anode sintered through conventional furnace and microwave

This work investigated the mechanical and electrical properties of NiO–SDC/SDC anode sintered by two different methods: in a microwave at about 1200 °C for 1 h and in a conventional furnace at 1200 °C with a holding time of 1 h (total sintering time of 21 h). Nano-powders Sm_0.2Ce_0.8O_1.9 (SDC) and NiO were mixed using a high-energy ball mill, followed by the co-pressing technique at a compaction pressure of 400 MPa. No binder was used between the layers. The electrical behaviors of all sintered samples were studied using electrochemical impedance spectra in the frequency range of 0.01–10⁵ Hz under 97% H₂–3% H₂O, an amplitude of 10 mV, and at high temperature range of 600–800 °C. Results indicate that the non-symmetrical NiO–SDC/SDC anode achieved through microwave sintering has finer grain size and higher electrochemical performance. However, hardness and Young׳s modulus increased in the samples sintered through a conventional furnace.     

Pore-forming agent induced microstructure evolution of freeze casted hydroxyapatite

There were interconnected small lamellar pores, big spherical pores and ceramic walls in the hydroxyapatite (HAP) ceramics fabricated by a freeze casting/pore-former method. As keeping the content of polymethyl methacrylate (PMMA) constant and decreasing the size of PMMA, the size of spherical pores and length of ceramic wall both decreased, and the compressive strength increased. As keeping the size of PMMA and decreasing the content of PMMA, the open porosity decreased and compressive strength increased. The shapes of pores caused by ice crystals were reticular, lamellar and treelike, in turn. The HAP ceramics with the spherical pores of 150-250 μm, open porosity of 62.13% and compressive strength of 7.01 MPa are prospective to have biomedical application.     

Evaluation of aluminum dross waste as raw material for refractories

An aluminum dross waste from plasma processing for Al metal reclamation was tested as a replacement raw material in refractories. The main phases of the starting Al dross waste material were MgAl₂O₄ and AlN. The waste was tested to replace calcined alumina in castables and refractory clay in a molded refractory at levels below 6.5%. The results of physical and mechanical tests indicated that the waste may be applied directly, without prior calcination, as a substitute for fine structural components in refractories. The waste and water contents used in processing, however, must be optimized to avoid the formation of crack-like defects in the microstructure. The origin of these defects is related to the generation of gas from the waste at high temperatures. It is not known if these crack defects impact physical properties. The waste was also tested as a replacement for anti-oxidant elements (Al and Si powders) in a resin-bonded refractory. Oxidation tests, however, indicated a negative effect on oxidation resistance.     

TBA-based freeze/gel casting of porous hydroxyapatite scaffolds

Porous ceramic scaffolds with a controlled “designer” pore structure have been prepared by the freeze/gel casting route using a TBA-based hydroxyapatite slurry system with 20–40 wt.% solid content. The products were characterized in terms of sintered microstructure, together with physical and mechanical properties. After sintering at 1050–1250 °C, the advantages of freeze casting and gel casting appeared in the pore structure and compressive strength of the ceramics, i.e., unidirectional aligned macro-pore channels developed by controlling the solidification direction of the TBA solvent used in the freeze casting together with small diameter (micron sized) isolated pores formed in the dense outer walls of the pore channels when processed by gel casting. The sintered porosity and pore size generally resulted in a high solid loading giving low porosity and small pore size, this leading to higher compressive strengths. The scaffolds obtained exhibited an average porosity and compressive strength in the range 41.9–79.3% and 35.1–2.7 MPa, respectively, depending on the processing conditions used.     

Acidic and basic binders for magnesite based aggregate in plaster of tundish

Binders are generally inorganic, organic or organomineral and have an important influence on the performance and corrosion resistance of slag line and deskulling. Since silicate and phosphate binders have some side effects, in this work sulphate binders such as sulphamic acid, H₂NSO₃H; aluminum sulphate, Al₂(SO₄)₃; ammonium sulphate, (NH₄)₂SO₄; magnesium sulphate, MgSO₄; calcium sulphate, CaSO₄; sodium sulphate, Na₂SO₄; and potassium sulphate, K₂SO₄, are investigated. Cold crushing strength at different heat treatments of room temperature, 110 °C, 1100 °C, 1400 °C is measured. Apparent porosity of samples without pulp and bulk density together with pH of the binder solution is evaluated and XRD and SEM studies are performed. Among these sulphate binders MgSO₄ was found to be the best. It is acidic in nature and develops strong bonds to the basic aggregate, MgO, at low temperatures. At high temperatures it dissociates from MgO(s) and SO₃(g) and the remained portion of MgO is the same as host oxide, with no corrosion and easy deskulling. Basic binders such as calcium sulphate, sodium sulphate and potassium sulphate could not strongly bond the MgO aggregates.     

Non-destructive investigations of pore morphology of micropore carbon materials

Pore morphology of experimental micropore carbon materials was explored using non-destructive methods. The influence of the heat treatment on porosity of two micropore carbon materials was investigated using helium porosimetry (HP) and X-ray micro-computed tomography (µCT). Methodology of µCT image processing and separation of the total and the open porosity is presented. In both materials open pores were found over the whole height of the sample. The local pore thickness and tortuosity of the materials were calculated. The increase of the porosity after heat treatment is observed for both materials.     

Processing and in vitro bioactivity of high-strength 45S5 glass-ceramic scaffolds for bone regeneration

In this paper, the compressive strength and in vitro bioactivity of sintered 45S5 bioactive glass scaffolds produced by powder technology and polymer foaming were investigated. The sintering temperature of scaffolds was 975 °C. The characterization of scaffolds before immersion in SBF was performed by scanning electron microscopy (SEM) and microtomography (μCT). The scaffolds were also tested for compression, and their density and porosity were measured. After immersion, the samples were observed through SEM and analyzed using EDS, X-ray diffraction (XRD), and infrared spectroscopy (FT-IR). Mass variation was also estimated. The glass-ceramic scaffolds showed a 61.44±3.13% interconnected porosity and an average compressive strength of 13.78±2.43 MPa. They also showed the formation of a hydroxyapatite layer after seven days of immersion in SBF, demonstrating that partial crystallization during sintering did not suppress their bioactivity.     

Fabrication of porous SiC ceramics having pores shaped with Si grain templates

SiC porous ceramics were prepared by heating mixtures of Si powder and carbon black at 900 °C for 24 h in Na vapor. The grains of the Si powder were not only the source of Si for SiC but also served as templates for the pores in the SiC porous ceramics. Angular-shaped pores with sizes of 2-10, 10-150 and 50-150 μm were formed by angular Si grains with sizes of ≤10, ≤50 and ≤150 μm, respectively. The porosity of the SiC porous ceramics was around 55-59%. Spherical pores were also formed when spherical Si grains were used. A bending strength of 14 MPa was measured for the SiC porous ceramics prepared with the Si grains (≤50 μm).     

Microwave hydrothermal synthesis of Sr doped ZnO crystallites with enhanced photocatalytic properties

Pure and Sr²⁺ doped ZnO crystallites were successfully synthesized via a microwave hydrothermal method using Zn(NO₃)₂·6H₂O and Sr(NO₃)₂·6H₂O as source materials. The phase and microstructure of the as-prepared Zn_1−xSr_xO crystallites were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Ultraviolet–visible spectrum (UV–vis) and photochemical reaction instrument were used to analyze the photocatalytic properties of the particles. XRD results show that the diffraction peaks of the as-prepared Zn_1−xSr_xO crystallites shifted slightly toward lower 2θ angle with the increasing of Sr²⁺ doping concentration from 0% to 0.3%. The pure ZnO crystallites with lamellar structure are found transforming to a hexagonal columnar morphology with the increase of Sr²⁺ doping concentration. UV–vis analysis shows that the particles have a higher absorption in UV region with a slightly decreased of optical band (E_g) gap. The photocatalytic activity of Sr²⁺ doped ZnO crystallites was evaluated by the Rhodamine B (RhB) degradation in aqueous solution under visible-light irradiation. Compared with the pure ZnO particles, the photocatalytic properties of the Sr²⁺ doped ZnO crystallites are obviously improved. The photocatalysis experiment results demonstrate that the 0.1% Sr²⁺ doped ZnO exhibits the best photocatalytic activity for the degradation of Rhodamine B.     

Fabrication of corrosion resistant, bioactive and antibacterial silver substituted hydroxyapatite/titania composite coating on Cp Ti

The present work is aimed at developing a bioactive, corrosion resistant and anti bacterial nanostructured silver substituted hydroxyapatite/titania (AgHA/TiO₂) composite coating in a single step on commercially pure titanium (Cp Ti) by plasma electrolytic processing (PEP) technique. For this purpose 2.5 wt% silver substituted hydroxyapatite (AgHA) nanoparticles were prepared by microwave processing technique and were characterized by X-ray diffraction (XRD), Fourier-transform infrared (FT-IR) spectroscopy and transmission electron microscopy (TEM) methods. The as-synthesized AgHA particles with particle length ranging from 60 to 70 nm and width ranging from 15 to 20 nm were used for the subsequent development of coating on Cp Ti. The PEP treated Cp Ti showed both titania and AgHA in its coating and exhibited an improved corrosion resistance in 7.4 pH simulated body fluid (SBF) and 4.5 pH osteoclast bioresorbable conditions compared to untreated Cp Ti. The in vitro bioactivity test conducted under Kokubo SBF conditions indicated an enhanced apatite forming ability of PEP treated Cp Ti surface compared to that of the untreated Cp Ti. The Kirby-Bauer disc diffusion method or antibiotic sensitivity test conducted with the test organisms of Escherichia coli (E. coli) for 24 h showed a significant zone of inhibition for PEP treated Cp Ti compared to untreated Cp Ti.     

Microwave assisted sintering of CaCu3Ti4O12

CaCu₃Ti₄O₁₂ electroceramic was prepared by a microwave assisted solid-state reaction technique from CaCO₃, CuO and TiO₂ powders. Processing involved the preparation of raw material, mixing and milling, calcination, pellet forming and sintering processes. Conventional furnace and microwave assisted sintering processes were employed in order to improve phase structures, morphology and dielectric properties of CaCu₃Ti₄O₁₂ ceramics. Surface and fracture FESEM analysis showed that the microwave assisted sintered CaCu₃Ti₄O₁₂ produced better densification and more uniform grain size compared to the conventional sintered sample.     

Synthetic carbons activated with phosphoric acid: II. Porous structure

Synthetic activated carbons were prepared by H₃PO₄ activation of a chloromethylated and sulfonated copolymer of styrene and divinylbenzene, using an impregnation weight ratio of 0.75 and carbonization temperatures in the 400-1000 °C range. Other impregnation ratios (0.93 and 1.11) were also used at a carbonization temperature of 800 °C. The porous texture of the resulting carbons was characterized by N₂ adsorption at −196 °C and CO₂ adsorption at 0 °C. All carbons exhibited a multimodal pore size distribution with maxima in the micropore and meso/macropore regions. Maxima in pore volume were attained at 900 °C for micropores and at 500 and 900 °C for mesopores. The mesopore volume was less sensitive than the micropore volume to changes in the impregnation ratio. It is concluded that the porous texture is not a prime factor in determining the outstanding cation exchange capacities of these carbons.     

Enhanced performance of Fe2O3 doped yttria stabilized zirconia hollow fiber membranes for water treatment

Fe₂O₃ powders were introduced as sintering aid to fabricate yttria-stabilized zirconia (YSZ) hollow fiber membranes using a combined wet-spinning and post-sintering method. The obtained Fe₂O₃-YSZ hollow fiber membranes show enhanced performance for water treatment with fine crystal structure in terms of bending strength and pure water permeability. Scanning electron microscopy (SEM), X-ray powder diffraction (XRD), and thermogravimetric analysis (TGA) along with mechanical tests were employed to investigate the structural evolution in the sintering process and the effect of Fe₂O₃. It is suggested that the Fe₂O₃ dopants dissolve into YSZ at elevated temperatures, providing defect sites and vacancies for fast ion migration, favoring for densification and grain growth of the YSZ, which yields dense microstructures of fine crystallites at relatively low sintering temperature. The Fe₂O₃-YSZ hollow fiber membranes sintered at 1150 °C show a 3-fold increase of the permeate flux of pure water (F) (743 L m⁻² h⁻¹) along with comparable bending strength (152 MPa) compared to pure YSZ membranes. This modified method can reduce sintering costs and therefore fabrication costs which should pave the way for scale-up production for ceramic hollow fiber membranes.     

XPS and optical studies of different morphologies of ZnO nanostructures prepared by microwave methods

Zinc oxide (ZnO) nanostructures of various morphologies were prepared using a microwave-assisted aqueous solution method. Herein, a comparative study between three different morphologies of ZnO nanostructures, namely nanoparticles (NPs), nanoflowers (NFs) and nanorods (NRs) has been reviewed and presented. The morphologies of the prepared powders have been studied using field effect scanning electron microscopy (FESEM). X-ray diffraction (XRD) results prove that ZnO nanorods have biggest crystallite size compared with nanoflowers and nanoparticles. The texture coefficient (T_c) of three morphologies has been calculated. The T_c changed with varying morphology. A comparative study of surfaces of NPs, NFs and NRs were investigated using X-ray photoelectron spectroscopy (XPS). The possible growth mechanisms of ZnO NPs, NFs and NRs have been described. The optical properties of the ZnO nanostructures of various morphologies have been investigated and showed that the biggest crystallite size of ZnO nanostructures has lowest band gap energy. The obtained results are in agreement with experimental and theoretical data of other researchers.     

Coarse-grained refractory composites based on Nb-Al2O3 and Ta-Al2O3 castables

Coarse-grained refractory composites, with grain sizes between 20 and 5000?µm, based on Nb-Al₂O₃ and Ta-Al₂O₃ castables were produced for the first time and characterised in terms of shrinkage after sintering, splitting tensile strength, compressive strength, porosity and the measurement of the elastic properties (E, G and $\nu$). After sintering at a temperature of 1600?°C, the shrinkage of the composites was 1.5% and 0.3%. Measured values of splitting tensile strength were between 5.5 and 15?MPa and the ones of compressive strength were between 23 and 89?MPa. Values of E and G were between 117 and 45?GPa and 48–17?GPa, respectively, for samples with 11–45?vol% refractory metal. Poisson's ratio was found to be very sensitive to the bonding between the fine matrix and coarse-grained particles of the composites. Its value increased from 0.25 for good bonding to $\nu =0.43$ in case of poor bonding between the coarse metal particles and the fine ceramic matrix. DTA/TG measurement under air atmosphere showed that the metal-ceramic composites start to oxidise at temperatures above 450?°C.