Encapsulated carbon black prepared by sol–gel-spraying: A new black ceramic pigment

As a new black ceramic pigment, encapsulated carbon black pigment has been prepared by a sol–gel-spraying method. The obtained pigment sintered at 900 °C for 2 h in air has a deep black hue (L* = 19), indicating carbon black can be fully covered. In the pigment, a dense coating layer on carbon black is formed due to the fast transformation from sol into gel by rapid extraction of solvent. The transparent silica phase spaces out the fine crystalline (zirconia or zircon), which permits to display the color of carbon black. This preparation method provides a way to prepare the encapsulated pigments. It will provide more colorful ceramic pigment applied in ceramic decoration by encapsulating.     

Facile non-aqueous synthesis of high color rendering C@ZrSiO4 encapsulation pigment with carbon-containing precursors as in-situ carbon sources

A zircon encapsulated carbon black (C@ZrSiO₄) pigment with high color rendering was synthesized via facile non-aqueous acetic acid (NAA) assisted sol-gel method using carbon-containing precursors (zirconium n-propoxide and tetraethoxysilane) as in-situ carbon sources. The effects of the NAA amount and heat treatment temperature on the structure and properties of the synthesized encapsulation pigments were characterized by XRD, FT-IR, FE-SEM, HR-TEM, EDS, XPS and CIELAB colorimeter, respectively. The results showed that the C@ZrSiO₄ encapsulated pigments heating at 1000?°C for 2?h in N₂ atmosphere presented a dense and stable encapsulation structure as well as deep dark hue when the mole ratio of NAA and Zr (NAA/Zr) was 3:1, and the chromaticity values were L*?= 21.20, a*?= 0.56, b*?= ?0.09 and C_ab =?0.57, respectively, which were contributed to the high homogeneity at atomic level in ZrSiO₄ sol and the tight bonding between carbon black carbonized by carbon containing group and zircon matrix. In addition, the pigment exhibited excellent chemical stability, thermal stability and tinctorial strength when it was used in water, acid, alkali, organic solvents and ceramic glaze. Especially, these pigments improved the utilization of raw materials and avoided the use of heavy metals or transition metals as coloring agent, which was an environment-friendly black ceramic pigment.     

Morphological control of mesoporous silica SBA-15 synthesized at low temperature without additives

Fiber-like or rod-like mesoporous SBA-15 silicas with different lengths and diameter of macrostructures and pore diameter could be synthesized by the self-assembly of silica-surfactant (commonly used Pluronic P123 (EO₂₀-PO₇₀EO₂₀) as a structure-directing agent) through careful control of the synthetic temperature and stirring time without any additives. X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM), and nitrogen adsorption–desorption isotherms are used to characterize these mesoporous silica materials. Compared with those reports on conventional SBA-15, our work is focused on one-step synthesis and the morphological control of ordered mesoporous silica synthesized at low temperature under low concentration of P123 (0.67 wt%) without the addition of inorganic salts, where pre-hydrolyzed silica species may favor the self-assembly of silica-polymer hybrid micelles. Moreover, the pore diameter of fiber-like SBA-15 synthesized at 40 °C is slightly smaller than that of conventional SBA-15, revealing that the average micellar radius of P123 micelles in this low concentration of P123 solution was almost same as that for the conventional synthesis of SBA-15.     

Development of mullite/zirconia composites from a mixture of aluminum dross and zircon

In order to obtain mullite/zirconia composites, mixtures of aluminum dross and zircon were sintered. Aluminum dross was collected and purified by a milling, sieving and washing process. Stoichiometric mixtures of aluminum dross and zircon were sintered at several temperatures (1400, 1450 and 1500 °C) for several periods of time (2, 4 and 6 h). After the purifying treatment the dross contained mainly Al₂O₃, AlN, MgAl₂O₄, SiO₂ and metallic Al. A homogeneous mullite matrix with small zirconia particles was obtained by sintering the aluminum dross–zircon samples at 1500 °C for 6 h.     

Use of waste water glass as silica supplier in synthesis of pure and Mg-doped lanthanum silicate powders for IT-SOFC application

Water glass in alkali solution (Na₂SiO₃/NaOH) an abundant effluent, generated in the alkaline fusion of zircon sand, represents a potential silica source to be converted in useful silica technological application. Actually, the generation of energy by environmental-friendly method is one of the major challenges for researchers. Solid Oxide Fuel Cells (SOFC) is efficient and environmentally clean technique to energy production, since it converts chemical energy into electrical power, directly. Apatite-type lanthanum silicates are promising materials for application as an electrolyte in intermediate temperature SOFC (IT-SOFC) because of their higher ionic conductivity, in temperatures of range 600–700 °C, than conventional zirconia electrolytes. In this work, pure (La_9,56(SiO₄)₆O_2,34) and Mg-doped (La_9,8Si_5,7Mg_0,3O_26,4) lanthanum silicate were synthesized, from that rich effluent. Using the sol-gel followed by precipitation method, the single crystalline apatite phase of both silicates was obtained by thermal treatment at 900 °C of their precursors. Sintered ceramic samples reached density of higher than 90%.     

Synthesis of high-purity zircon,zirconia, and silica nanopowders from local zircon sand

High-purity zircon (ZrSiO₄) nanopowder was successfully produced from Indonesian natural zircon sand using a low-cost purification approach via magnetic separation, immersion in HCl, and reaction with NaOH, followed by a top-down nanosizing process using wet ball-milling for 10?h and annealing at 200?°C for 2?h. Furthermore, polymorph zirconia (ZrO₂ – amorphous, tetragonal, and monoclinic) and silica (SiO₂ – amorphous and cristobalite) nanopowders were also successfully derived from the purified zircon powder using a bottom-up method via alkali fusion and co-precipitation processes followed by calcination. The crystallite size of the powders was estimated from X-ray diffraction (XRD) data analysis to give 40, 31, 61, and 149?nm, respectively, for the zircon, tetragonal- and monoclinic-zirconia, and cristobalite. Microstructural characteristics of the zircon, silica, and zirconia nanopowders were revealed in transmission electron microscopy (TEM) images which confirmed that the average sizes of the particles were in a good agreement with the XRD estimated values.     

Microstructural evolution of carbon fibers by silicon vapor deposition and its effect on mullite-corundum castables

Carbon fibers (CFs) can be introduced to castables, due to the relative higher thermal conductivity and stronger damping properties. In this research, microstructural evolution of carbon fibers (CFs) in the presence of mixture of silicon and silica powders under the protection of carbon black was studied in the temperature range of 1000–1300 °C by means of X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that some small amorphous SiO_x globules were formed on the surface of CFs at the temperature below 1200 °C. With the increase of the treated temperature, the size of globules became bigger and reached maximum at 1200 °C. The growth of SiO_x globules can be controlled by vapor-solid mechanism. In addition, the effects of these CFs on properties and microstructure of mullite-corundum castables were studied. The results showed that the CFs with SiO_x globules (CFs/SiO_X) could significantly improve the mechanical properties of the castables because the interfacial bonding strength between CFs/SiO_x and matrix is much stronger than the untreated CFs.     

Processing and characterisation of Pr–zircon pigment powder

Abstract

Praseodymium–zircon pigment powders were successfully prepared at different calcination temperatures with sodium fluoride NaF as mineraliser, using the solid state synthesis method. The powders were characterised using techniques such as XRD, SEM and TEM. Qualitative investigation of the phases using XRD showed the presence of large amounts of unreacted zirconia after calcination at 900 and 950°C, whereas from 1000 to 1200°C zircon was found to be the major phase, together with a small amount of zirconia. Quantitative investigation of phases was carried out using an external standard method. The weight fraction of unreacted zirconia at 1000°C was found to be 0·056. SEM observation of powders exposed at various calcination temperatures indicated the presence of tetrahedral crystals, and this was enhanced by the addition of the NaF mineraliser. TEM observations showed lattice defects and elastic strains in the samples at various calcination temperatures.     

Catalytic graphene formation in coal tar pitch- derived carbon structure in the presence of SiO2 nanoparticles

A simple and effective way to manufacture graphene from a coal tar pitch (CTP) is demonstrated. Silica (SiO₂) nanoparticles were used to modify the CTP as carbon precursor. A silica nanofiller introduced into the CTP matrix underwent carboreduction during heat treatment to 2000 °C, resulting in the formation of silicon carbide. Surfaces of SiC grains were sites for graphene formation. The influence of SiO₂ on the structure and microstructure of CTP- based carbon matrix, after annealing up to 2800 °C, was studied. Carbon samples were analyzed using X- ray Diffraction (XRD), Transmission Electron Microscopy (TEM) and Raman Spectroscopy. Crystallite sizes (L_a, L_c) and interplanar distance (d₀₀₂) were determined. The presence of SiO₂ in CTP carbon precursor favored the crystallites’ growth in the ‘a′ crystallographic graphite direction, and inhibited their growth on the ‘c′ axis. The crystallites composing of graphene layers, were characterized by an elongated dimension in the ‘a′ axis direction. Above 2000 °C silicon carbide decomposed, followed by the sublimation of silicon from the carbon matrix.     

Structural Characterization of Mesoporous Silica Nanofibers Synthesized Within Porous Alumina Membranes

Mesoporous silica nanofibers were synthesized within the pores of the anodic aluminum oxide template using a simple sol–gel method. Transmission electron microscopy investigation indicated that the concentration of the structure-directing agent (EO₂₀PO₇₀EO₂₀) had a significant impact on the mesostructure of mesoporous silica nanofibers. Samples with alignment of nanochannels along the axis of mesoporous silica nanofibers could be formed under the P123 concentration of 0.15 mg/mL. When the P123 concentration increased to 0.3 mg/mL, samples with a circular lamellar mesostructure could be obtained. The mechanism for the effect of the P123 concentration on the mesostructure of mesoporous silica nanofibres was proposed and discussed.     

The role of carbon in microstructure evolution of SiBCO ceramics

The composition of polymer derived ceramics could be readily tuned through controlling the structure and element content of the polymer precursors, and investigation on the effect of the element on microstructure evolution is important to the design of advanced ceramics. In this article, the effect of carbon content in SiBCO polymer precursors was systematically investigated. The polymer network and thermal stability of polymer precursors and the carbon content of pyrolyzed SiBCO ceramic could be readily tuned by controlling the DVB amount used. Carbon contributed to the formation of graphitic carbon in SiBC_xO ceramics and inhibited the growth of β–SiC and SiO₂ crystals at 1600 °C, but lead to an increase in the graphitic carbon phase at 1800 °C.     

Preparation of Micro‐/Mesoporous SiOC Bulk Ceramics

Micro‐/mesoporous SiOC bulk ceramics with high surface area and bimodal pore size distribution were prepared by pyrolysis of polysiloxane in argon atmosphere at 1100°C–1400°C followed by etching in hydrofluoric acid solution. Their thermal behaviors, phase compositions, and microstructures at different nano‐SiO₂ filler contents and pyrolysis temperatures were investigated by XRD, SEM, DSC, and BET. The SiO₂ fillers and SiO₂‐rich clusters in the SiOC matrix act as pore‐forming sites and can be etched away by HF. At the same time, the SiO₂ filler promotes SiOC phase separation during the pyrolysis. The filler content and pyrolysis temperature have important effects on phase compositions and microstructures of porous SiOC ceramics. The resulting porous SiOC bulk ceramic has a maximum specific surface area of 822.7 m²/g and an average pore size of 2.61 nm, and consists of free carbon, silicon carbide, and silicon oxycarbide phases.     

Synthesis and characterization of PrxZr1-xSiO4 (x = 0–0.08) yellow pigments via non-hydrolytic sol-gel method

Yellow inorganic pigments Pr_xZr_1-xSiO₄ (x?=?0–0.08) have been prepared by a novel non-hydrolytic sol-gel (NHSG) method at 750?°C for 2?h. Replacing Pr⁴⁺ for Zr⁴⁺ in ZrSiO₄ increased the cell volume and changed the color from white to yellow gradually. The Si―O―Zr and Si―O―Pr bands were observed in the FT-IR spectra of xerogel, indicating it could reach homogeneous mixing at the atomic level. Therefore, it promoted the solid solution reaction between Pr and zircon at low temperature. The samples exhibit high doping limitation (x?=?0.08) and brilliant yellow hue (b^*?=?69.48) in contrast with the previously reported praseodymium zircon yellow pigments. The intense of yellow hue was increased with increasing the Pr doping content due to the increase of Pr⁴⁺/Pr³⁺ species. After applying on bisque ceramic tiles, the pigment exhibited excellent coloration, high thermal stability and low solubility in molten glazes, indicating its potential application in ceramic decoration.     

Worm-hole structured mesoporous carbon monoliths synthesized with amphiphilic triblock copolymer

In the present work, mesoporous carbon monoliths with worm-hole structure had been synthesized through hydrothermal reaction by using amphiphilic triblock copolymer F127 and P123 as templates and resole as carbon precursor. Synthesis conditions, carbonization temperature and pore structure were studied by Fourier transform infrared, thermogravimetric analysis, transmission electron microscopy and N₂ adsorption–desorption. The results indicated that the ideal pyrolysis temperature of the template is 450 °C. The organic ingredients were almost removed after further carbonized at 600 °C and the mesoporous carbon monoliths with worm-hole structure were obtained. The mesoporous carbon synthesized with P123 as single template exhibited larger pore size (6.6 nm), higher specific surface area (747 m² g^?1), lower pore ratio (45.9 %) in comparison with the mesoporous carbon synthesized with F127 as single template (with the corresponding value of 4.9 nm, 681 m² g^?1, 49.6 %, respectively), and also exhibited wider pore size distribution and lower structure regularity. Moreover, the higher mass ratio of template P123/resole induced similar pore size, larger specific surface area and lower pore ratio at the same synthesizing condition. It was also found that the textural structure of mesoporous carbon was affect by calcination atmosphere.     

Self‐Generating High‐Temperature Oxidation‐Resistant Glass‐Ceramic Coatings for C–C Composites Using UHTCs

Carbon–carbon (C–C) composites are ideal for use as aerospace vehicle structural materials; however, they lack high‐temperature oxidation resistance requiring environmental barrier coatings for application. Ultra high‐temperature ceramics (UHTCs) form oxides that inhibit oxygen diffusion at high temperature are candidate thermal protection system materials at temperatures >1600°C. Oxidation protection for C–C composites can be achieved by duplicating the self‐generating oxide chemistry of bulk UHTCs formed by a “composite effect” upon oxidation of ZrB₂–SiC composite fillers. Dynamic Nonequilibrium Thermogravimetric Analysis (DNE‐TGA) is used to evaluate oxidation in situ mass changes, isothermally at 1600°C. Pure SiC‐based fillers are ineffective at protecting C–C from oxidation, whereas ZrB₂–SiC filled C–C composites retain up to 90% initial mass. B₂O₃ in SiO₂ scale reduces initial viscosity of self‐generating coating, allowing oxide layer to spread across C–C surface, forming a protective oxide layer. Formation of a ZrO₂–SiO₂ glass‐ceramic coating on C–C composite is believed to be responsible for enhanced oxidation protection. The glass‐ceramic coating compares to bulk monolithic ZrB₂–SiC ceramic oxide scale formed during DNE‐TGA where a comparable glass‐ceramic chemistry and surface layer forms, limiting oxygen diffusion.     

Effect of carbon black on corrosion resistance of Al2O3–SiC–C castables to SiO2–MgO slag

Metallurgical solid waste recycling is the shape of things to come in green development of Chinese iron and steel industry. Utilization of ironworks slag for producing mineral wool at high temperature is an important approach. However, refractory lining is seriously corroded by the SiO₂–MgO based slag at 1600 °C during the production process. Different production steps need different atmospheres, the changeable service atmospheres (air and reducing atmosphere) put forward high requirements for slag resistance. The Al₂O₃–SiC–C castables containing carbon black are usually used in iron runner, which faces high-temperature service condition of 1450 °C–1500 °C. Nevertheless, the function of carbon black in the Al₂O₃–SiC–C castables at 1600 °C is till essentially unknown. In the current study, the carbon black was introduced to tabular alumina based Al₂O₃–SiC–C castables to improve corrosion resistance to SiO₂–MgO based slag at 1600 °C. The result showed that 0.4 wt% carbon black was suitable for the castables, which the slag resistance of castables was significantly improved. The carbon black had contributed to block slag by wettability resistance. By comparison with the castables without carbon black, the corrosion index and penetration index had been reduced by 20.2% and 28.0%, respectively, under air atmosphere. And there were little corrosion or penetration under reducing atmosphere for castables with 0.4 wt% carbon black. For the mechanical properties, the Al₂O₃–SiC–C castables with 0.4 wt% carbon black could serve production process although the carbon black impaired the physical properties.     

Sintering,microstructure and hardness of Y-TZP- 64S bioglass ceramics

3 mol% yttria-partially stabilized zirconia (Y-TZP) powder and a sol-gel derived CaO- P₂O₅- SiO₂ (64S) bioglass, were used to produce Y-TZP- 64S slip cast compacts. The compacts with 10.5 and 19.9 vol% 64S were sintered at different temperatures up to 1500 °C using 5 and 10 °C/min heating/cooling rates. The densification behaviour, crystalline phase formation and zirconia grain growth were investigated as a function of sintering temperature and 64S glass content. Ca₃(PO₄)₂ along with SiO₂ as a major phase were obtained from thermal decomposition of the 64S glass at 950–1500 °C. Both 64S additions, 10.5 and 19.9 vol%, promoted the sintering process at a lower temperature with respect to Y-TZP (1500 °C); the SiO₂ phase markedly increased the Y-TZP solid state sintering rate at the intermediate stage. The rapidly cooling at 10 °C/min inhibited the t-m transformation of Y-TZP and markedly reduced that of Y-TZP- 64S at 1300–1500 °C. Sintered Y-TZP with 10.5 vol% 64S, nearly fully densified at 1300–1400 °C, was constituted by polygonal ZrSiO₄ particles and elongated Ca₂P₂O₇ particles uniformly distributed in the tetragonal zirconia fine grain matrix. This ceramic exhibited similar hardness to that of Y-TZP sintered at 1500 °C; the in situ formation of calcium phosphate will have the potential to improve the Y-TZP biological properties without significantly affecting its hardness.     

High-temperature oxidation induced layering process for Si–C–B–N ceramic fibers with SiC nanograins

High-temperature oxidation resistance is important for Si–C–B–N ceramic fibers when reinforcing ceramic matrix composites with superior reliability and faulting tolerance. At present, few studies have investigated on the high-temperature oxidation behavior of Si–C–B–N fibers, limiting their further applications. In this work, we analyzed the high-temperature oxidation process of Si–C–B–N ceramic fibers with SiC nanograins (SiBCN-SiCn fibers) at 1000–1500 °C in air. SiBCN-SiCn fibers stated to be oxidized at 1000 °C, with the formation of thin oxide layer. After oxidizing at 1300 °C, obvious oxide layer that mainly consisted of amorphous SiO₂ could be detected. Further oxidizing at 1500 °C caused the thickness increment of oxide layer, which could inhibit the oxidation products (CO, N₂) to release away from the fibers. The remained CO and N₂ may react with SiC nanograins to form SiO₂ and graphite-like g-C₃N₄, causing the formation of additional transition layer. Our finding may support useful information for the applications of SiBCN-SiCn fibers under harsh environment.     

Influence of synthesis method and praseodymium doping on stability and sintering of Ca stabilised zirconia

Abstract

The effects of doping with praseodymium and of preparation method on the Ca-FSZ (fully stabilised zirconia) system were studied. Samples were prepared by a ceramic method (CE) and several sol-gel methods, namely colloidal (CG), citrate (CI) , and polymeric (PG). Two samples with the compositions (ZrO₂)_0·7(CaO)_0·2(Pr₂O₃) _0·05 (doped) and (ZrO₂)_0·8(CaO)_0·2 (undoped) were prepared by each method, in order to study the influence of praseodymium doping. DTA-T G analysis was carried out on all samples. Powders fired for 12 h at 500 and 900°C were sieved at 60 μm, uniaxially pressed at 20 MPa, and fired for 2 h at 1500 and 1600°C. The resulting compacts were characterised by XRD, SEM-EDX, Vickers microhardness testing, and density and lattice parameter measurements. The results indicate that the praseodymium enters the CaO-Z rO₂(c) solid solution, improving densification and microhardness. Samples prepared by sol-gel methods showed better densification and higher microhardness than samples prepared by the ceramic method. Citrate samples stood out for their non-porous microstructure and high Vickers microhardness.     

Active filler controlled polymer pyrolysis – A promising route for the fabrication of advanced ceramics

A novel polyborosiloxane (BoSiVi) containing methyl and vinyl groups with Titanium Silicide (TiSi₂) filler was employed for the preparation of silicon and titanium containing ceramic phases. Ceramic phase evolution was studied from the above mentioned preceramic system at 900, 1200, 1500, 1800 and 2000 °C respectively under argon atmosphere. Reactive nature of TiSi₂ with pyrolytic by-products of BoSiVi led to the formation of different ceramic phases at different firing temperatures. XRD analysis confirmed the evolution of carbide (TiC, TiB, SiC etc.) and oxide (TiOC, SiO₂ etc.) ceramic phases in the temperature regime of 900 °C to 1500 °C. FESEM-EDX analysis of the ceramic phases, heat treated at 1500 °C, proved the formation of Si-Ti-O-C ceramic nano-fibers by Vapor-Liquid-Solid (VLS) method. BoSiVi+TiSi₂ system heat treated at 1800 °C and 2000 °C exhibited the evolution of pure non-oxide ceramic phases along with Ti₃SiC₂ MAX phase.