Preparation of titanium nitride ultrafine powders by sol–gel and microwave carbothermal reduction nitridation methods

Titanium nitride ultrafine powders were prepared from tetrabutyl titanate and sucrose by sol–gel and microwave carbothermal reduction methods. The influences of reaction temperature, molar ratio of Ti to C, addition of crystal seeds and amount of NH₄F on the synthesis of titanium nitride were studied. The results show that excess amount of carbon, addition of crystal seeds and NH₄F plays a positive effect on the preparation of TiN at low temperature. The inceptive formation temperature of TiN ultrafine powders is about 800 °C, and pure TiN can be prepared at 1000 °C. Field emission-scanning electron microscopy (FE-SEM) was used to get the micrograph of the TiN powder, it shows that the size of the powders synthesized at 1000 °C is about 0.1–0.5 μm.     

The influence of different carbon sources in the carbothermal reduction and nitridation (CRN) synthesis of SiAlON from nanocomposite precursors based on Al–SBA-15

Nanocomposites of Al–SBA-15 with the organic polymers poly-4-vinyl pyridine (P4VP) and polyacrylamide (PAM) were synthesized to produce SiAlON precursors containing various carbon contents. These CRN precursors, and their products after firing under N₂ at 1450 °C for 3 h were investigated by XRD, SEM/EDS and surface area analysis (BET) to compare the influence of the organic polymer carbon source. The results were also compared with those from precursors containing carbon black as the carbon source. XRD and SEM/EDS analysis of the Al–SBA-15 confirmed the formation of mesoporous structures, while BET and pore size distribution measurements indicated that the entry of P4VP into the Al–SBA-15 nanocomposite precursor is significantly more efficient than that of PAM. Firing these precursors in nitrogen produced β-SiAlON and β-cristobalite. At all carbon concentrations the P4VP nanocomposite precursors formed significantly more SiAlON than those of the PAM and carbon black precursors, due to the proximity of a greater amount of the organic carbon source to the silica template in the P4VP composite, and possibly also to the lack of oxygen in the P4VP monomer, in contrast with PAM. At least twice the stoichiometric amount of carbon was required in all cases, with optimal SiAlON formation occurring in the P4VP precursor containing 6 times the stoichiometric amount of carbon. Increasing the carbon content further suppresses SiAlON formation, possibly due to the build-up of back pressure of CO by-products in the pores of the nanocomposite.     

Porous SiO2–TiO2–ZrO2 Obtained from Polymeric Systems Prepared by the Sol–Gel Process

An experimental strategy was developed to obtain Si–Ti–Zr transparent sols via the sol-gel process. The chelating agents isoeugenol (2-methoxy-4-propenylphenol, isoH), salicylaldehyde (2-hydroxybenzaldehyde, salH), and itaconic anhydride (2-methylenesuccinic anhydride, anhH) were employed separately to stabilize monomeric Ti and Zr precursors, in order to control their chemical reactivity, avoiding precipitation. In all cases a prehydrolyzed tetraethyl orthosilicate (TEOS) sol was the Si source. The sols were polymerized at room temperature (293 K) to obtain gels and these were dried and calcined at 873 K in air. The radial distribution functions (RDF) of the gels were obtained at room temperature. The solids were studied by scanning electron microscopy (SEM). The porosity and surface area of solids were determined by N₂ adsorption. The surface area results obtained range between 83–198 m²/g. The average pore diameters are 1.44–1.61 nm.     

Agglomeration of α-Al2O3 powders prepared by gel combustion

Ultrafine α-Al₂O₃ powders were prepared by a gel combustion method and the agglomeration characteristic of the resultant powders was studied. A variety of fine crystallite α-Al₂O₃ powders with different agglomeration structures could be obtained by altering the citrate-to-nitrate ratio γ and calcining the precursors at 1050 °C for 2 h. All the powders were of nearly equivalent crystallite size (60–80 nm) except for the P1 powder (113 nm) from the gel with γ = 0.033. The primary crystallites of the obtained α-Al₂O₃ powders were formed into large secondary particles with different degree of agglomeration. Except for the powder P1, the mean particle sizes from specific surface area and particle size distribution measurement increase with increasing citrate-to-nitrate ratio in the fuel-lean condition and decrease in the fuel-rich condition. Densities of alumina ceramics from powders P4 and P5 sintered at different temperatures were relatively low due to the wide particle size distribution.     

Nanostructured ceramic composite coating prepared by reactive plasma spraying micro-sized Al–Fe2O3 composite powders

Nanostructured ceramic matrix composite coating was prepared in-situ by reactive plasma spraying micro-sized Al-Fe₂O₃ composite powders. The microstructure, toughness and Vickers hardness of these coatings were investigated by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and mechanical tests. The results indicated that the coating exhibited nanostructures which consisted of FeAl₂O₄, Al₂O₃, Fe (or Fe solid solution) and a little FeAl. The composite coating showed significantly higher toughness and wear resistance than the conventional Al₂O₃ coating.     

Synthesis of Ti(C,N) ultrafine powders by carbothermal reduction of TiO2 derived from sol–gel process

Experimental results demonstrate that TiC_1−XN_X ultrafine powders can be synthesized by the sol–gel process. The factors influencing the powder synthesizing process, such as temperature, C/Ti ratio in raw materials, holding time and flow rate of nitrogen gas, are discussed. TiC_0.5N_0.5 powders with particle sizes less than 100 nm were produced at 1550°C. The microhardness of hot-pressed TiC_0.5N_0.5 samples at 1750°C was 19.6 GPa and the relative density was 98.9%.     

Formation of α/β-Si3N4 nanoparticles by carbothermal reduction and nitridation of geopolymers

Silicon nitride (Si₃N₄) particles with various α/β-Si₃N₄ ratios were fabricated from geopolymer (GP)-carbon compositions (M₂O·Al₂O₃·4.5SiO₂·12H₂O+18C), where M is an alkali ion (Na⁺, K⁺ and Cs⁺). They were made by carbothermal reduction and nitridation at 1400°, 1500°, and 1600°C for 2 hours under flowing nitrogen. Characterization of carbothermally reacted GP-carbon compositions was based on XRD, SEM-EDS, HRTEM, and selected area electron diffraction analyses. Depending on the alkaline composition of GP, the carbon content and the reaction temperature, a compositionally variable α/β-Si₃N₄ or SiAlON was achieved. Crystallization of the GPs gradually increased by heat treatment over 1400°C with corresponding weight loss. It was found that NaGP, KGP, and CsGP crystallized into a major phase of α-Si₃N₄, β-Si₃N₄, and SiAlON, respectively. Prolonged heating at 1600°C led to an increase in the α/β-Si₃N₄ ratio in NaGP due to the formation of aluminum nitride, while it led to a decrease in α/β-Si₃N₄ ratio in KGP. In the case of CsGP, SiAlON replaced the pollucite which mainly formed at lower temperatures. Transmission electron microscopy revealed that the needle-like particles were of ~0.5 µm in size and consisting of α/β-Si₃N₄ mixtures.     

Synthesis of TiC–TiB2 composite powders via carbothermal reduction and its reaction mechanism

Titanium carbide–titanium diboride (TiC–TiB₂) composite powders were synthesised through a carbothermal reduction method by using titanium dioxide, boric acid, and different carbon sources (namely, carbon black, sucrose, and glucose) as starting materials. The thermal decomposition behaviour of the precursors was studied by thermogravimetry–differential thermal analyser. Phase compositions and morphologies of the synthesised products were characterised by X-ray diffractometer and scanning electron microscope. When n(Ti):n(B):n(C)?=?1.0:2.5:5.0, the blended stock mainly formed TiB₂ with sucrose or glucose as a carbon source, whereas the stock produced TiC when carbon black was the source. At an optimum reaction temperature, the particles of the powders synthesised from carbon black as a carbon source were the smallest at approximately 100?nm. With increasing amount of boric acid in the precursor, the morphologies of the samples changed into less spherical particles, and more flaky grains and small particles with irregular structures were observed.     

Characterisation of urushiol formaldehyde polymer/multihydroxyl polyacrylate/SiO2 nanocomposites prepared by the sol–gel method

Novel anti-ultraviolet UFP/MPA/SiO₂ nanocomposite coatings were prepared from urushiol formaldehyde polymer (UFP) and multihydroxyl polyacrylate resin (MPA) via the sol–gel process. FT-IR spectroscopy was employed to reveal the nanocomposite structure between UFP/MPA and nano-SiO₂. TEM was used to observe the size scale and the distribution of nanoparticles throughout the polymer matrix. Simultaneously, the dynamic mechanical properties were characterised through dynamic mechanical thermal analysis (DMTA). The influence of the SiO₂ content on the physical mechanical and anticorrosive properties of UFP/MPA/SiO₂ nanocomposites was investigated. Moreover, the 1000 h anti-ultraviolet tests showed that the ultraviolet resistance of UFP/MPA/SiO₂ coatings improved. The best anti-ultraviolet and anticorrosive properties were achieved when the SiO₂ content was 5 wt.%.     

Visible-light photocatalytic activity of SiC hollow spheres prepared by a vapor–solid reaction of carbon spheres and silicon monoxide

SiC hollow spheres are obtained by a vapor–solid reaction using carbon spheres as templates. The prepared SiC hollow spheres are characterized by X-ray diffraction, scanning electron microscopy, nitrogen adsorption, and UV–vis diffuse reflectance spectra. The visible-light photocatalytic activity is evaluated by photocatalytic decomposition of the methylene blue in aqueous solution. Results show that the diameter of SiC hollow spheres ranges from 200 to 300 nm and the shell thickness is about 50 nm. The SiC hollow spheres have a high surface area of 83.5 m²/g and exhibit a mesoporous structure characteristic. The photo-response of the SiC hollow spheres expand to visible-light region with band gap energy of 2.15 eV. The SiC hollow spheres exhibit a significantly enhanced photocatalytic activity due to their high surface area as well as large light-harvesting efficiencies.     

Preparation and characterization of ultrafine ZrB2–SiC composite powders by a combined sol–gel and microwave boro/carbothermal reduction method

A combined sol–gel and microwave boro/carbothermal reduction technique was investigated and used to synthesize ultrafine ZrB₂–SiC composite powders from raw starting materials of zirconium oxychloride, boric acid, tetraethoxysilane and glucose. The effects of reaction temperature, molar ratios of n(B)/n(Zr) and n(C)/n(Zr+Si) on the synthesis of ultrafine ZrB₂–SiC composite powders were studied. The results showed that the optimum molar ratios of n(B)/n(Zr) and n(C)/n(Zr+Si) for the preparation of phase pure ultrafine ZrB₂–SiC composite powders were 2.5 and 8.0, respectively, and the firing temperature required was 1300 °C. This temperature was 200 °C lower than that require by using the conventional boro/carbothermal reduction method. Microstructures and phase morphologies of as-prepared ultrafine ZrB₂–SiC composite powders were examined by field emission-scanning electron microscopy (FE-SEM) and transmission electron microscope (TEM), showing that SiC grains were formed evenly among the ZrB₂ grains, and the grain sizes of ZrB₂ in the samples prepared at 1300 °C for 3 h were about 1–2 μm. The average crystalline sizes of these two phases in the as-prepared samples were calculated by using the Scherrer equation as about 58 and 27 nm, respectively.     

Effect of different nucleation catalysts on the crystallization of Li2O–ZnO–MgO–Al2O3–SiO2 glasses

Based on local raw materials, a range of LiZnMg aluminosilicate glasses were prepared to investigate the influence of TiO₂, Cr₂O_3, and ZrO₂ on the crystallization behaviour and thermal expansion characteristics. Differential thermal analysis showed that the crystallization propensity increases in the order TiO₂ > Cr₂O₃ > ZrO₂. Virgilite, β-spodumene ss, gahnite, enstatite and cristobalite were formed in the prepared glass-ceramics. The microstructure of glass-ceramic samples showed growths of rounded and subrounded grains in the base sample, whereas, somewhat rod-like and accumulated growths appeared in samples containing ZrO₂. However, a rather homogeneous texture of accumulated growths was developed in glass-ceramics containing TiO₂ and Cr₂O₃. The coefficient of thermal expansion of parent glasses was sensitive to the type of nucleating agent added (Cr₂O₃ > TiO₂ > ZrO₂) varying from 24.8 × 10⁻⁷ to 65.1 × 10⁻⁷ °C⁻¹ being almost unchanged with the heat-treatment. The microhardness values of glass-ceramic samples were in the 763–779 kg/mm² range.     

In situ synthesis of Al2O3–SiC powders via molten-salt-assisted aluminum/carbothermal reduction method

Al₂O₃–SiC composite powder (ASCP) was successfully synthesized using a novel molten-salt-assisted aluminum/carbothermal reduction (MS-ACTR) method with silica fume, aluminum powder, and carbon black as raw materials; NaCl–KCl was used as the molten salt medium. The effects of the synthesis temperature and salt-reactant ratio on the phase composition and microstructure were investigated. The results showed that the Al₂O₃–SiC content increased with an increase in molten salt temperature, and the salt–reactant ratio in the range of 1.5:1–2.5:1 had an impact on the fabrication of ASCP. The optimum condition for synthesizing ASCP from NaCl–KCl molten salt consisted of maintaining the temperature at 1573 K for 4 h. The chemical reaction thermodynamics and growth mechanism indicate that the molten salt plays an important role in the formation of SiC whiskers by following the vapor-solid growth mode in the MS-ACTR treatment. This study demonstrates that the addition of molten salt as a reaction medium is a promising approach for synthesizing high-melting-point composite powders at low temperatures.     

Structure and properties of nanostructured ceramic matrix composite coatings prepared in-situ by reactive plasma spraying micro-sized Al–Fe2O3–Cr2O3 powders

Nanostructured FeAl₂O₄-based ceramic matrix composite coatings were prepared in-situ by reactive plasma spraying micro-sized Al–Fe₂O₃ and Al–Fe₂O₃–Cr₂O₃ powders. The microstructure, toughness, Vickers hardness, and adhesive strength of these coatings were investigated by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and mechanical tests. The results indicated that both the coatings exhibited a nanostructured microstructure. The grains of coating AFC sprayed with Al–Fe₂O₃–Cr₂O₃ powders are finer than those of the coating AF sprayed with Al–Fe₂O₃ powders. The composite nano-coating sprayed with Al–Fe₂O₃–Cr₂O₃ powders exhibited higher hardness and better wear resistance compared with those of the composite nano-coating sprayed with Al–Fe₂O₃ powders. The adhesive strength, toughness, and wear resistance of the composite coating sprayed with Al–Fe₂O₃–Cr₂O₃ powders were significantly enhanced compared with those of the composite coating sprayed with Al–Fe₂O₃ powders, which were attributed to the Cr₂O₃ addition.     

SiO2载体对Cu/SiO2催化剂的影响

分别以硅溶胶、气相SiO2、介孔SBA-15分子筛为载体,采用共沉淀法制备了Cu/SiO2催化剂,含活性组分Cu质量分数为25%。运用BET、XRD、H2-TPR、NH3-TPD等对催化剂进行表征。结果表明:以硅溶胶和气相SiO2为载体制得催化剂的Cu物种分散性较差,以SBA-15为载体制得催化剂的Cu物种以高度分散的形式存在,且具有较大的比表面积,较低的还原温度和较大的酸量。     

多组元BaO–SrO–CaO–MgO–Al2O3–2SiO2环境障涂层的制备与抗CaO–MgO–Al2O3–SiO2腐蚀性能

采用固相法制备不同摩尔 Ba、Sr、Ca、Mg 配比的 Ba O–Sr O–Ca O–Mg O–Al₂O₃–SiO₂ （BSCMAS）陶瓷材料,研究多组元陶瓷的制备工艺、显微结构及其抗 CMAS 腐蚀性能。结果表明：通过调控 MgO 的含量,在 1 400 ℃条件下制备了Ba_0.3Sr_0.3Ca_0.35Mg_0.05Al₂Si₂O₈ (B_0.3S_0.3C_0.35M_0.05AS)单相多组元陶瓷材料。在 1 250、1 300 ℃和 1 350 ℃对 B_0.3S_0.3C_0.35M_0.05AS 进行 CMAS 腐蚀实验,相比于 Ba_0.5Sr_0.5Al     

Influence of the synthesis route on sol–gel SiO2–TiO2 (1:1) xerogels and powders

Five different sol–gel routes are used in order to synthesize mixed SiO₂–TiO₂ materials. Simple mixing of the Ti and Si precursors, pre-hydrolyzing of TEOS, modification of the Ti alkoxide with acetic acid, isoamyl alcohol and acetylacetone lead to translucent gels with different time of gelation. Different techniques such as TGA, DTA, XRD and IR spectroscopy are used to characterize each material. IR spectroscopy revealed the presence of Si–O–Ti and Si–O–Si bonds for all the xerogels letting suppose a composite microstructure of the gels. Pre-hydrolyzing of TEOS and modification of Ti alkoxide with isoamyl alcohol are the most appropriate routes to retain the anatase phase up to 1100 °C.     

Carbothermal/aluminothermic reduction nitridation synthesis of ZrN–SiAlON refractory composites from zircon and bauxite: a comparative study of the reduction effect of reducers

The ZrN–SiAlON composite refractory powder was successfully synthesised from zircon and bauxite minerals by the carbothermal reduction nitridation or the aluminothermic reduction nitridation method with three typical reducers, including carbon coke, carbon black and aluminium powder. The effect of reaction temperatures on phase composition and microstructure was investigated using X-ray diffraction and a scanning electron microscopy (SEM), respectively. The thermodynamics equilibrium relationships of the condensed phases were analysed as well. The results showed that carbon coke was the most optimum reducer and when it was used as the reducer, the main final products were granular ZrN with a little β-SiAlON. Nevertheless, ZrO₂ was produced during reduction at 1600°C when the reducer was carbon black, because the activity of carbon black was the poorest. Additionally, more byproducts were produced in the case of Al powder used as reducer at 1600°C, such as AlN polytype and Al₂O₃.     

Preparation of hollow mesoporous silica spheres by a sol–gel/emulsion approach

Hollow mesoporous silica spheres were synthesized by a sol–gel/emulsion (oil-in-water/ethanol) approach, in which cetyltrimethylammonium bromide (CTAB) surfactant was employed to stabilize and direct the hydrolysis of oil droplets of tetraethoxysilane (TEOS). The diameters of the hollow spheres can be tuned in the range from 210 to 720 nm by varying the ratio of ethanol-to-water and their shell thickness can be mediated by changing the concentration of CTAB used in the system. BET surface areas of the hollow silica spheres are determined to be in the range of 924–1766 m² g^?1 and their pore sizes are around 3.10 nm as determined by BJH method.     

Synthesis of β-SiC powders by the carbothermal reduction of porous SiO2–C hybrid precursors with controlled surface area

SiO₂–C precursors with various surface areas were derived from tetraethyl orthosilicate and phenolic resin as Si and C sources, respectively, by a modified sol–gel process using the in situ precipitation of phenol resin in a prepared wet gel. The surface area of the SiO₂–C precursors was varied from 20 to 175 m²/g by changing the C/Si molar ratio in the preform. β-SiC powders were synthesized using carbothermal reduction in vacuum at the temperature range of 1200–1600 °C. The effects of the temperature and heat treatment time as well as that of the surface area of the preform on the formation of β-SiC powders were studied. It was determined that the formation of β-SiC started at 1200 °C and was considerably promoted as the heat treatment temperature and time further increased during the carbothermal reduction of SiO₂–C preforms with high surface area. When high surface area SiO₂–C preforms were used, highly crystalline SiC powders were synthesized at 1600 °C in vacuum with a high yield of 85%.