Crystallization kinetics of amorphous alumina–zirconia–silica ceramics

Crystallization kinetics of amorphous alumina–zirconia–silica ceramics was studied by nonisothermal differential scanning calorimetry (DSC). Different amorphous materials were produced by plasma spraying of near-eutectic Al₂O₃–ZrO₂–SiO₂ mixtures. Phase composition and microstructure of the amorphous materials and nanocrystalline products were analyzed. All of the investigated materials show an exothermic peak between 940 and 990 °C in the DSC experiments. The activation energies calculated from DSC traces decrease with increasing SiO₂ concentration. Values of the Avrami coefficients together with results of the microstructural observations indicate that tetragonal zirconia crystallization from materials containing more than 10 wt.% SiO₂ proceeds by a diffusion-controlled mechanism with nucleation occurring predominantly at the beginning of the process. In contrast, material with almost no SiO₂ exhibited a value of the Avrami exponent consistent with the crystal growth governed by processes at the phase boundary.     

Direct synthesis of CeO2/SiO2 mesostructured composite materials via sol–gel process

A series of CeO₂/SiO₂ mesostructured composite materials was synthesized by sol–gel process using Pluronic P123 as template, tetraethylorthosilicate as silica source and hexahydrated cerium nitrate as precursor under acid condition. The as-synthesized materials with Ce/Si molar ratio ranging from 0.03 to 0.3 were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), laser Raman spectroscopy (LRS), and N₂ adsorption. Characterization revealed that all samples possess ordered hexagonal mesoporous structure similar to SBA-15 and possess high surface area, large pore volume and uniform pore size. The fact that cerium species are present as highly dispersed CeO₂ nanocrystals in hexagonal matrix was confirmed by XRD combined with high-resolution TEM and selected area electron diffraction (SAED) analysis. Introduction of ceria to silica matrix can cause a distortion of hexagonal ordering structure and decrease pore diameter and increase the wall thickness of mesopores. Moreover, it can be found that this sol–gel route is a feasible, effective and simple method for templating synthesis of CeO₂/SiO₂ composite materials.     

Synthesis of vicinal diamines via Zn–H2O–CO2-induced reduction of aromatic imines in supercritical carbon dioxide

Zn–H₂O–CO₂ is a good reducing reagent for the reduction of imines in supercritical carbon dioxide (scCO₂). They provide the corresponding vicinal diamines in moderate to good yields. The results showed that carbon dioxide plays an important role as both solvent and reagent.     

Oxidation behavior of silicon carbide based biomorphic ceramics prepared by chemical vapor infiltration and reaction technique

The oxidation behavior of biomorphic SiC based ceramics with different microstructure and composition was studied at 1450 °C in airflow for 50 h by thermal gravimetric analysis (TGA). SiC with amorphous, coarse grain, crystalline and fine grain crystalline microstructures as well as SiC–Si₃N₄ composite ceramics were processed from paper preforms by chemical vapor infiltration and reaction technique. The ceramics were characterized by X-ray diffraction and scanning electron microscopy coupled with energy dispersive spectroscopy (SEM/EDX) before and after oxidation. The results show that the crystalline SiC with fine grain structure and SiC–Si₃N₄ composite ceramics show very good oxidation resistance at a temperature of 1450 °C.     

炭/陶复合材料的抗热震性能研究

对含石墨的炭／陶复合材料优良的抗热震性能进行了讨论。这种性质与石墨的导热系数大、断裂功高、热膨胀和弹性模量小密切相关。     

Catalytic combustion of chlorobenzene over MnOx–CeO2 mixed oxide catalysts

A series of MnOx–CeO₂ mixed oxide catalysts with different compositions prepared by sol–gel method were tested for the catalytic combustion of chlorobenzene (CB), as a model of volatile organic compounds of chlorinated aromatics. MnOx–CeO₂ catalysts with different ratios of Mn/Ce + Mn were found to possess high catalytic activity in the catalytic combustion of CB, and MnOx(0.86)–CeO₂ was identified as the most active catalyst, on which the temperature of complete combustion of CB was 254 °C. Effects of systematic variation of reaction conditions, including space velocity and inlet CB concentration on the catalytic combustion of CB were investigated. Additionally, the stability and deactivation of MnOx–CeO₂ catalysts were studied by various characterization methods and other assistant experiments. MnOx–CeO₂ catalysts with high Mn/Ce + Mn ratios present a stable high activity, which is related to their high ability to remove the adsorbed Cl species and a large amount of active surface oxygen.     

Improvements on the mechanical properties and thermal shock behaviours of MgO-spinel composite refractories by ZrO2 incorporation

Microstructural features and improvements on the mechanical properties and thermal shock behaviours of MgO-spinel composite refractories with ZrO₂ addition were examined. ZrO₂ incorporation into MgO-spinel led to improvements around ∼1.5-fold ratios on mechanical properties, R_st values and thermal shock results. The basic parameters improving mechanical properties and thermal shock resistance of MgO-spinel-ZrO₂ composite refractories were determined as follows: (i) propagation of microcracks for a short distance by interlinking each other, (ii) stopping or deviation of microcracks when reaching pores or ZrO₂ particles, (iii) concurrent occurrence of mostly intergranular and some transgranular cracks on fracture surfaces, and with the addition of ZrO₂ (iv) the increase in bulk density, and (v) a significant decrease in MgO grain size. The improvements observed in thermo-mechanical properties confirmed that MgO-spinel-ZrO₂ refractories showed a low strength loss and high thermal shock damage resistance at high temperatures, leading to longer service lives for using industrial applications.     

Microstructure, mechanical properties and thermal shock resistance of plasma sprayed nanostructured zirconia coatings

Nanostructured yttria stabilized zirconia (YSZ) coatings were deposited by Atmospheric Plasma Spraying (APS). X-ray diffraction (XRD) was used to investigate their phase composition, while scanning electron microscopy (SEM) was employed to examine their microstructure. The coatings showed a unique and complex microstructure composed of well-melted splats with columnar crystal structure, partially melted areas, which resembled the morphology of the powder feedstock, and equiaxed grains. Vickers microhardness of nanostructured zirconia coatings was similar to that of the conventional ones and strongly depended on the indentation load. Otherwise, a higher thermal shock resistance was found. This effect was addressed to the retention of nanostructured areas in coating microstructure and to the corresponding high porosity.     

Preparation and thermal shock resistance of cordierite-spodumene composite ceramics for solar heat transmission pipeline

Cordierite-spodumene composite ceramics with 5, 10, 15 wt% spodumene used for solar heat transmission pipeline were in-situ prepared via pressureless sintering from kaolin, talc, γ-Al₂O₃ and spodumene. Effects of spodumene on densification, mechanical properties, thermal shock resistance, phase composition and microstructure of the composite ceramics were investigated. The results showed that spodumene used as flux material decreased the sintering temperature greatly by 40–80 °C, and improved densification and mechanical properties of the composite ceramics. Especially, sample A3 with 10 wt% spodumene additive sintered at 1380 °C exhibited the best bending strength and thermal shock resistance. The bending strengths of A3 before and after 30 thermal shock cycles (wind cooling from 1100 °C to room temperature) were 102.88 MPa and 96.29 MPa, respectively. XRD analysis indicated that the main phases of the samples before 30 thermal shock cycles were α-cordierite, α-quartz and MgAl₂O₄, and plenty of β-spodumene appeared after thermal shock. SEM micrographs illustrated that the submicron β-spodumene grains generated at the grain boundaries after thermal shock improved the thermal shock resistance. It is believed that the cordierite-spodumene composite ceramics can be a promising candidate material for heat transmission pipeline in the solar thermal power generation.     

Effect of sintering temperature on varistor properties and aging characteristics of ZnO–V2O5–MnO2 ceramics

The microstructure, electrical properties, dielectric characteristics, and DC accelerated aging behavior of the ZVM-based varistors were investigated for different sintering temperatures of 800–950 °C. The microstructure of the ZVM-based ceramics consisted of mainly ZnO grain and secondary phase Zn₃(VO₄)₂, which acts as liquid-phase sintering aid. The Zn₃(VO₄)₂ has a significant effect on the sintered density, in the light of an experimental fact, which the decreases of the Zn₃(VO₄)₂ distribution with increasing sintering temperature resulted in the low sintered density. The breakdown field exhibited the highest value (17,640 V/cm) at 800 °C in the sintering temperature and the lowest value (992 V/cm) at 900 °C in the sintering temperature. The nonlinear coefficient exhibited the highest value, reaching 38 at 800 °C and the lowest value, reaching 17 at 850 °C. The varistor sintered at 900 °C exhibited not only high nonlinearity with 27.2 in nonlinear coefficient, but also the highest stability, in which %ΔE_1 mA = −0.6%, %Δα = −26.1%, and %Δ tan δ = +21.8% for DC accelerated aging stress of 0.85 E_1 mA/85 °C/24 h.     

Thermal shock resistance of in situ formed Si2N2O–Si3N4 composites by gelcasting

Thermal shock resistance of Si₂N₂O–Si₃N₄ composites was evaluated by water quenching and subsequent three-point bending tests of strength diminution. Si₂N₂O–Si₃N₄ composites which was prepared with in situ liquid pressureless sintering process using Yb₂O₃ and Al₂O₃ powders as sintering additives by gelcasting showed no macroscopic cracks and the critical temperature difference (ΔT_c) could be up to 1400 °C. A mass of pores existed in the sintered body and the irregular shaped fibers extended from the pores increased the thermal shock property.     

Sintering behavior and thermal shock resistance of aluminum titanate (Al2TiO5)-toughened MgO-based ceramics

In order to improve the thermal shock resistance of MgO-based ceramics, aluminum titanate (Al₂TiO₅)-toughened MgO-based ceramics were successfully prepared by solid state sintering at 1450 °C and 1550 °C for 3 h starting from MgO and as-synthesized Al₂TiO₅ powders. The effects of various contents of Al₂TiO₅ second phase on the sintering behavior and thermal shock resistance of MgO-based ceramics were investigated. The sintering behavior of sintered samples was evaluated by comparing the relative density, apparent porosity, bending strength, phase composition as well as microstructure. The thermal shock resistance of sintered samples was characterized by using the residual bending strength after three thermal cycles and thermal expansion coefficient. The obtained samples with 10 wt% Al₂TiO₅, which were sintered at 1550 °C for 3 h, showed the highest relative density, lowest apparent porosity as well as optimum bending strength. In addition, the samples added 15 wt% Al₂TiO₅ at 1550 °C with a dwell time of 3 h were the highest residual bending strength and lowest thermal expansion coefficient. It revealed that the enhancement in thermal shock resistance was ascribed to the reduction of thermal expansion coefficient.     

Influence of Ru segregation on the activity of Ru–Co/γ-Al2O3 during FT synthesis: A comparison with that of Ru–Co/SiO2 catalysts

γ-Al₂O₃ and SiO₂ supported Co catalysts, with varying amounts of Ru, were prepared and evaluated for Fischer–Tropsch synthesis (FTS). The composition of Ru for optimum activity was found to be support-dependent. The reducible Co₃O₄ was high in the region of 0–1.64 wt.% of Ru in Co/SiO₂ catalysts. Co/γ-Al₂O₃ displayed a maximum for reducible Co species at 0.42 wt.% Ru. Segregation of Ru occurred beyond this composition decreasing the extent of reduction. Co/γ-Al₂O₃ catalysts showed lower activity and olefin selectivity, in spite of higher Co dispersion, than Co/SiO₂ catalysts. The catalytic performance depends on the amount of reducible Co species, which again depends upon the optimum content of Ru.     

Investigation of the morphological changes promoted by heating of Si–C–O ceramics derived from a phenyl-rich hybrid polymer. Effect of Ni in the polymeric precursor

This study focuses on the structural and morphological changes promoted by heating of silicon oxycarbide ceramics obtained from hybrid polymeric precursors based on poly(methylsiloxane) and divinylbenzene, with or without nickel acetate, by pyrolysis under Ar at different temperatures. The increase of the temperature from 950 to 1500 °C promoted the densification and crystallization of SiC and graphite nanodomains in the ceramic bulk with or without Ni, as identified by HRTEM. Moreover, the Ni-containing precursor led to the formation of ultra-long amorphous nanowires on the surface and voids in the ceramic body obtained at 1500 °C. These nanowires presented different sizes and morphologies, but similar compositions, basically composed by silicon and oxygen, with the presence of carbon at their external layers. The growth mechanism and the nature of the nanowires are also proposed. The addition of nickel acetate in the polymeric precursor induced the formation of nanowires with different morphologies in the Si–O–C system.     

Synergetic effect of combined use of Cu–ZnO–Al2O3 and Pt–Al2O3 for the steam reforming of methanol

Commercial Cu–ZnO–Al₂O₃ catalysts are used widely for steam reforming of methanol. However, the reforming reactions should be modified to avoid fuel cell catalyst poisoning originated from carbon monoxide. The modification was implemented by mixing the Cu–ZnO–Al₂O₃ catalyst with Pt–Al₂O₃ catalyst. The Pt–Al₂O₃ and Cu–ZnO–Al₂O₃ catalyst mixture created a synergetic effect because the methanol decomposition and the water–gas shift reactions occurred simultaneously over nearby Pt–Al₂O₃ and Cu–ZnO–Al₂O₃ catalysts in the mixture. A methanol conversion of 96.4% was obtained and carbon monoxide was not detected from the reforming reaction when the Pt–Al₂O₃ and Cu–ZnO–Al₂O₃ catalyst mixture was used.     

Effect of CaF2 on sintering behavior and thermal shock resistance of Y2O3 materials

Y₂O₃ materials have become a popular candidate for preparing refractory crucibles for ultra-pure high-temperature alloy melting in recent years. However, its difficulty in sintering and poor thermal shock resistance limited its industrial application. The effect of CaF₂ on the densification microstructure, mechanical properties, and thermal shock resistance of Y₂O₃ materials was investigated in this paper. The main purpose of this study was to optimize the amount of CaF₂ added in the preparation of Y₂O₃ materials to improve its thermal shock resistance and get better mechanical properties. The mechanism of the densification process of CaF₂-doped Y₂O₃ materials was analyzed by phase analysis and microstructure. The results showed that successive doping of large Ca²⁺ ions caused more lattice distortion in the Y₂O₃ materials, and the diffusion rate of Y³⁺ was increased, thus enhanced grain boundary diffusion and promoted sintering densification in the Y₂O₃ materials. Meanwhile, the addition of CaF₂ also significantly reduced the apparent porosity and enhanced the mechanical properties of the materials. The improvement of these properties was attributed to the increased relative density of CaF₂-doped Y₂O₃ materials and the high sintering activity of CaF₂. In addition, crack deflections effectively improved the thermal shock resistance of the materials. The residual flexural strength ratio of Y₂O₃ materials doped with 1 wt % CaF₂ was increased by 21.2% after thermal shock test compared with undoped specimens.     

热驱动CO2多相催化合成化学品研究进展

由于CO₂分子较高的化学惰性,导致其选择性活化及可控转化极具挑战。相比于电和光驱动CO₂催化转化,热驱动CO₂多相催化转化反应是操作简便、目标产物可调且产品收率较高的方法。通过该类反应实现CO₂还原或非还原制备多种化学品既可促进CO₂的资源化利用,又可有效缓解温室效应,在环保、能源和材料等领域具有重要意义。本综述基于作者在CO₂捕集和转化方面的研究工作,结合近年来国内外的相关文献,对目前热驱动多相催化CO₂转化为CO、CH₄、甲酸、甲醇、碳氢化合物和其它精细化学品的研究现状进行综合评述。重点讨论反应机理、所用催化剂及反应体系的研究进展,并对其未来的研究方向进行了前景展望和探讨。     

Nanocomposite Fe2O3–SiO2 inclusion pigments from post-functionalized mesoporous silicas

High-surface mesoporous silicas with different pore sizes were employed for the first time as silicon precursors in the synthesis of reddish Fe₂O₃–SiO₂ inclusion pigments. Interestingly, the size of included Fe₂O₃ nanoparticles was partially controlled through confinement effects into silica mesopores. Notably, impregnated samples showed a more homogeneous and efficient encapsulation of smaller and monodisperse hematite nanoparticles (sizes around 10–35 nm). Moreover, they resulted in an improved reddish color at 1000 °C within a ceramic glaze. The best red shade (a* ≈ 18) was associated to nanocomposite with smaller hematite nanoparticles (around 5 nm). These promising results suggest the possibility to improve the reddish coloration and thermostability of Fe₂O₃–SiO₂ ceramic pigments through and adequate control of confinement effects into sintered mesoporous silicas.     

Solid acidities of SiO2–TiO2/montmorillonite composites synthesized under different pH conditions

SiO₂–TiO₂/montmorillonite composites were prepared under acidic, neutral and basic conditions and the solid acidity of the resulting composites were determined. All the SiO₂/TiO₂ ratio of the colloidal particles was set at 10 but the resulting SiO₂/TiO₂ ratios were significantly richer in TiO₂. The XRD patterns of the acidic composite showed expanding and broadening of the (001) reflection by intercalation of colloidal SiO₂–TiO₂ particles, but the neutral and basic composites showed only broadening of the reflections and no intercalation. The specific surface areas of the acidic, neutral and basic composites (375, 237 and 247 m²/g, respectively) were much larger than of montmorillonite (6 m²/g). The average pore sizes were about 4, 15 and 50 nm, and the amounts of solid acidic sites measured by the NH₃-TPD were 178, 95 and 86 µmol/g for the acidic, neutral and basic composites, respectively. The solid acid amount of the acidic composite was twice that of a commercial catalyst, K-10, (85 µmol/g) and much higher than the guest phase SiO₂–TiO₂ gel (16 µmol/g) or the host phase montmorillonite (6 µmol/g). The TPD peak temperatures reflect the acid strength, and were similar in all the samples, ranging from 175° to 200 °C.     

Effect of print path process on sintering behavior and thermal shock resistance of Al2O3 ceramics fabricated by 3D inkjet-printing

In this study, Al₂O₃ ceramics parts were printed by inkjet printing technology with different printed paths distributions, such as the spiral printed path, round trip straight printed path and ladder lap printed path. The influences of inkjet printed paths on sintering performance and thermal shock resistance of the Al₂O₃ green bodies were investigated. The sintering performance of the green sample with the ladder lap printed path is the highest among the three samples. Sintered at 1550?℃, its bulk density and porosity reached 3.73?g/cm³ and 10.80%, respectively. In addition, the thermal shock resistance of the sample with the step print path reached 11 times. The results suggest that the optimization of the printed path provides an effective way to print 3D ceramics with good performances through 3D inkjet-printing technology.