In situ synthesis and thermal shock resistance of a cordierite-mullite composite for solar thermal storage

Cordierite-mullite composite ceramic was synthesized in situ by semidry pressing and pressureless sintering from andalusite, kaolin, γ-Al₂O₃, talc, potassium feldspar, and albite in air. The effects of composition and sintering temperature on the density, bending strength, thermal shock stability, crystal phases, and microstructure of the specimens were studied. The results show that specimen B2 (the theoretical content of cordierite was 20 wt%) has excellent performance, that is, a bending strength of 104.59 MPa, 30 cycles of thermal shock resistance without cracking, and a loss rate of 13.12%. X-ray diffractometer (XRD) analysis and scanning electron microscope (SEM) micrographs showed that spherical cordierite crystals were grown on the surface of the mullite, therefore, the specimen possessed a superior bending strength and thermal shock resistance, where a great number of granules combined to restrain crack initiation as well as propagation over time during the thermal shock test. The thermal conductivity of specimen B2 was determined to be 3.83 W/(m·K) (36°C), and the sensible heat storage density was 1136 kJ/kg, with the temperature difference (ΔT) ranging from 0 to 800°C. Consequently, the cordierite-mullite composite is a potentially applicable material for solar thermal storage.     

Preparation and thermal shock resistance of solar thermal absorbing corundum ceramics for concentrated solar power

The absorptivity of solar thermal absorber materials affects the heliothermal conversion efficiency of concentrated solar power systems. The solar absorbing ceramics were prepared by the fixed mixture of bauxit, Fe₂O₃, and TiO₂ with adding CuO in different percentages. The absorptivity and thermal shock resistance with the effect of adding CuO in different percentages were studied. Fe₂O₃ and TiO₂ have excellent optical properties, and CuO decreases the material's band gap to boost the electronic transition and increase the material absorptivity. The results showed that the material is sintered at 1380°C with an excellent absorptivity of 94.00% in the spectrum range of 0.3–2.5 μm, and the bending strength is 132.94 MPa. The bending strength was increased by 21.07% after 30 thermal shock cycles (1000°C-room temperature, air cooling). The liquid phase facilitates the synthesis of hercynite with excellent high temperature properties. The hercynite improves the thermal shock resistance of the material.     

高强抗热震莫来石砖的研制

以优质莫来石作骨料 ,基质中加入电熔白刚玉粉、莫来石细粉、苏州粘土 ,并预先制成混合粉 ,适量添加“三石” ,通过合理的颗粒级配 ,采用高压成型、高温烧成 ,生产出玻璃拉丝窑用高强抗热震莫来石砖。探讨了影响莫来石砖性能的几种因素     

Effect of in situ synthesized and additives on the thermal performance of mullite thermal storage ceramics

High-performance thermal storage ceramics can enable utilization of solar thermal power generation plants. In this work, in situ synthesis was used to prepare mullite thermal storage ceramics. Calcined bauxite, talc, and kaolin were used as raw materials. The effects of additives (e.g., SiC, Si₃N₄, TiC, and ZrB₂) on the density, mechanical durability, phase components, microstructure, and thermal performance of the mullite ceramics were studied. The results showed that the thermal expansion coefficient, thermal conductivity, and heat storage density of the mullite ceramics were affected by their phase components. SiC and Si₃N₄ did not decompose during the in situ syntheses, but TiC and ZrB₂ decomposed. With the addition of 10 wt% SiC, the thermal conductivity improved to 2.72 W (m K)^?1 (298 K). The heat storage density of this material was 688 kJ kg^?1 (273–1073 K). Consequently, the in situ synthesized mullite thermal storage ceramic with added SiC could be a promising candidate material for a compound latent-sensible heat storage system.     

换热器用针状莫来石增强堇青石陶瓷材料

以耐火粘土、高铝矾土及滑石为原料研制了堇青石基陶瓷材料，并对其组织和性能尤其是抗热震性进行了研究。结果表明，堇青石基体上分布着外状莫来石的材料具有更高的抗热震性。对换热器用陶瓷材料抗热震性参数进行了讨论，指出抗热震损伤多数R''更适合于作为优选陶瓷换热器用材料的指标。     

Preparation and thermal shock resistance of anorthite solar thermal energy storage ceramics from magnesium slag

Anorthite solar thermal energy storage ceramics were fabricated from magnesium slag solid waste by pressureless sintering. The effects of CaO/SiO₂ ratio and sintering temperature on the physical, chemical, and thermophysical properties of ceramics were explored. X-ray diffraction results demonstrated that thermal shock process contributed to the formation of anorthite, and increasing CaO/SiO₂ ratio promoted the transformation of anorthite (CAS₂) into melilite (C₂AS). Some micro-cracks were found according to SEM analysis, forming by the mismatch of thermal expansion coefficients among phases. The combined effects of the low thermal expansion coefficient of anorthite and micro-crack toughing endowed the ceramic with good thermal shock resistance. Optimum comprehensive performances were observed in the sample with a CaO/SiO₂ ratio of 0.58 sintered at 1160°C, of which the specific thermal storage capacity was 0.63 J·g^-1·°C^-1(room temperature). The bending strength increased by 0.22% after 30 thermal shock times (room temperature-800°C, wind cooling). Therefore, the anorthite ceramics exhibited great potential for solar thermal energy storage.     

Parameters influencing thermal shock resistance and ionic conductivity of 8 mol% yttria-stabilized zirconia (8YSZ) with dispersed second phases of alumina or mullite

Improved thermal shock resistance for cubic 8 mol% yttria-stabilized zirconia (8YSZ) used in fuel cells and oxygen sensors can be achieved by the addition of higher thermal conductivity second phases. This work compares 10–20 vol% alumina (α-Al₂O₃) and mullite (3Al₂O₃·2SiO₂) additions that increase thermal conductivity, reduce grain size, and increase strength and fracture toughness of 8YSZ. Improvements in thermal shock behavior correlate best with increased thermal conductivity. Second phase additions result in a smaller grain size that reduces the ionic conductivity, measured by electrochemical impedance spectroscopy, primarily through the creation of a higher density of blocking grain boundaries. The blocking effect correlates with decreasing grain size in 8YSZ but also is strongly influenced by the wetting behavior and distribution of intergranular phases. The addition of an appropriate dilute second phase of higher thermal conductivity, however, may compensate for a slightly lower ionic conductivity in certain applications such as oxygen sensors.     

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.     

Mullite whisker toughened mullite coating to enhance the thermal shock resistance of SiC pre-coated carbon/carbon composites

In order to improve the thermal shock resistance of the coated carbon/carbon (C/C) composites, a mullite whisker toughened mullite coating was fabricated on the surface of SiC pre-coated C/C composites (SiC-C/C) by molten-salt method with a later hot dipping process. The phase compositions, surface and cross-section microstructures, high temperature thermal shock resistance of the as-prepared multi-layer coatings were investigated. Results show that the introduction of mullite whiskers can effectively improve the density of the mullite outer coating and decrease the cracking of the coating during the thermal shock cycle process. After 100 times thermal shock cycles between 1773 K and room temperature, only 1.87 × 10⁻³ g cm⁻² weight loss has been detected, indicating the achievement of the excellent thermal shock resistance.     

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.     

红柱石骨料对脱硫喷枪用莫来石浇注料热震稳定性的影响

采用水冷法研究了红柱石骨料对脱硫喷枪用莫来石浇注料于 80 0℃和 14 0 0℃烧后热震稳定性的影响。结果表明 ,随着试样中红柱石骨料含量的增加 ,烧后试样的热震稳定性提高。其原因是由于红柱石骨料和莫来石基质的热膨胀系数不一致 ,在烧后试样中产生了自发裂纹 ;同时 ,自发裂纹也使烧后试样的抗折强度降低。     

Effect of mullite phase formed in situ on pore structure and properties of high-purity mullite fibrous ceramics

Porous mullite ceramics are potential advanced thermal insulating materials. Pore structure and purity are the main factors that affect properties of these ceramics. In this study, high performance porous mullite ceramics were prepared via aqueous gel-casting using mullite fibers and kaolin as the raw materials and ρ-Al₂O₃ as the gelling agent. Effects of addition of mullite fibers on the pore structure and properties were examined. The results indicated that mullite phase in situ formed by kaolin, and ρ-Al₂O₃ ensured the purity of mullite samples and mullite fibers bonded together to form a nest-like structure, greatly improving the properties of ceramic samples. In particular, the apparent porosity of mullite samples reached 73.6%. In the presence of 75% of mullite fibers, the thermal conductivity was only 0.289 W/m K at room temperature. Moreover, the mullite samples possessed relatively high cold compressive strength in the range of 4.9–9.6 MPa. Therefore, porous mullite ceramics prepared via aqueous gel-casting could be used for wide applications in thermal insulation materials, attributing to the excellent properties such as high cold compressive strength and low thermal conductivity.     

ZrO2-莫来石复合耐火材料的反应烧结制备和抗热震性研究

从先进陶瓷精细的制备技术出发 ,以超细ZrSiO4和Al2 O3的反应烧结产物为结合相 ,以粗粒莫来石为骨料 ,制备出ZrO2 -莫来石复合耐火材料。研究了材料的制备工艺、显微结构和力学性能 ,重点探讨了材料的抗热震性。所得ZrO2 -莫来石复合耐火材料同时具有高的致密度 ( >90 % )和优良的抗热震性。     

莫来石加入量对SiC-莫来石材料性能的影响

以SiC颗粒(2～1mm、≤1mm)、SiC细粉(≤0.066mm)、莫来石细粉(≤0.074mm)和SiO2微粉(≤0.045mm)为原料,在w(SiC细粉)=40%的基础配方中分别以质量分数为5%、10%、15%、20%和25%的莫来石细粉取代相应量的SiC细粉,并外加2%的SiO2微粉,成型后分别在1300℃和1500℃的大气气氛中煅烧3h,测定试样煅烧前后的质量变化率以及烧后试样的显气孔率、常温抗折强度和抗热震性,并用扫描电镜观察试样的显微结构。结果表明:在SiC自保护氧化的作用下,试样的抗氧化性较强,而且随着莫来石加入量的增大,1300℃烧后试样的氧化程度减小,1500℃烧后试样的氧化程度先减小,至15%后又增大;1300℃烧后试样比1500℃具有较高的抗热震性,并且随着试样中莫来石加入量的增大,烧后试样的抗热震性提高。     

A multi-scale model for predicting the thermal shock resistance of porous ceramics with temperature-dependent material properties

This paper develops a novel multi-scale thermal/mechanical analysis model which not only can efficiently measure the thermal shock response but also highly reflects the effects of diversiform micro-structures of porous ceramics. Knowledge of the temperature distribution and time-varied thermal stress intensity factors (SIF) is derived by finite element/finite difference method and the weight function method in the macro continuum model. The finite element analysis employs a micro-mechanical model in conjunction with the macro model for the purpose of relating the SIF to the thermal stress in the struts of the porous ceramics. The micro model around the crack tip was established by using Voronoi lattices to accurately explore the micro-architectural features of porous ceramics. Hot shock induced center crack and cold shock induced edge crack are both considered. Effects of relative density and pore size on the thermal shock resistance are investigated and the results are well coincident with the experimental tests. The influence of cell regularity and cross section shape of the cell struts is discussed and the corresponding explanations are provided. The importance of incorporating temperature-dependent material properties on the thermal shock resistance prediction is quantitatively represented. These multi-faceted models and results provide a significant guide to the design and selection of porous ceramics against the thermal shock fracture failure for the future thermal protection system of space shuttle.     

Preparation and thermal shock resistance of corundum-mullite composite ceramics from andalusite

Corundum-mullite composite ceramics have high hardness, small plastic deformation and other excellent performances at high temperature. Corundum-mullite composite ceramics were fabricated from andalusite and α-Al₂O₃ by in-situ synthesis technology. Effects of mullite/corundum ratio and sintering temperatures on the water absorption, apparent porosity, bulk density, bending strength, thermal shock resistance, phase composition and microstructure of the sample were investigated. Results indicated that the in-situ synthesized mullite from andalusite combined with corundum satisfactorily, which significantly improved the thermal shock resistance as no crack formed after 30 cycles of thermal shock (1100 °C-room temperature, air cooling). Formula A4 (andalusite: 37.31 wt%, α-Al₂O₃: 62.69 wt%, TiO₂ in addition: 1 wt%, mullite: corundum=6:4 in wt%) achieved the optimum properties when sintering at 1650 °C, which were listed as follows: water absorption of 0.15%, apparent porosity of 0.42%, and bulk density of 3.21 g⋅cm⁻³, bending strength of 117.32 MPa. The phase composition of the sintered samples before and after thermal shock tests were mullite and corundum constantly. The fracture modes of the crystals were transgranular and intergranular fractures, which could endow the samples with high thermal shock resistance.     

Effect of Sm2O3 on microstructure,thermal shock resistance and thermal conductivity of cordierite-mullite-corundum composite ceramics for solar heat transmission pipeline

Cordierite-mullite-corundum composite ceramics for solar heat transmission pipeline were fabricated via pressureless sintering at a low sintering temperature with added Sm₂O₃. The effects of Sm₂O₃ on sintering behaviors, mechanical property, phase transformation, microstructure, thermal shock resistance and thermal conductivity of the composite ceramics were investigated. TEM analysis results demonstrated that Sm³⁺ located in glass and grain boundaries to facilitate the densification via the liquid-phase sintering mechanism and improve bending strength by grain refinement, respectively. Proper addition (3 wt%) of Sm₂O₃ could promote the crystallization of cordierite, and improve thermal shock resistance of the composite ceramics with an increasing rate of 16.70% for bending strength after 30 thermal shock cycles (air cooling from 1100 °C to RT). The composite ceramics possessed a superior thermal shock resistance, where a large amount of particles were formed to suppress crack initiation and propagation during thermal shock. Cordierite-mullite-corundum composite ceramics with proper Sm₂O₃ addition (3 wt%) had a lower thermal conductivity than that of composite ceramics without Sm₂O₃ addition by strengthening the scattering of phonon, which could reduce the heat loss during solar heat transmission process.     

Microstructure,oxidation and thermal shock resistance of graphene reinforced SiBCN ceramics

SiBCN ceramics were prepared using various volumes of graphene platelets (GPLs) as nanofiller. The effects of the nanofiller on microstructure, and oxidation and thermal shock resistance of as-sintered ceramics were investigated. The phase composition and microstructures were very similar for all investigated ceramics consisting primarily of β-SiC, BNC and small amounts of α-SiC with relatively homogeneously distributed 5–10 nm thick GPLs in the matrix. For SiBCN ceramics incorporating graphene as nanofiller, a porous oxide layer forms at 1500 °C and the oxidation behavior shows a linear kinetics by thickness measurement method. Gas evolution during heating lead to a passive oxidation behavior and weight loss. Graphene reinforced SiBCN ceramics exhibit thermal shock resistance superior to monoliths of the same material. The graphene distributed in SiBCN matrix can dissipate the energy of crack growth and acts as a stopper to cracks. The toughening mechanisms offered by graphene, including pull-out and bridging appear to aid in ameliorating thermal shock effects. Furthermore, the existence of a dense oxide surface layer retards oxygen diffusion into the inner matrix and heals surface pores and cracks, which also contributes to thermal shock resistance.     

Thermal shock resistance study of stereolithographic additive-manufactured Al2O3 ceramics by in situ digital radiography

Thermal shock resistance is critical to ensure the service safety of ceramic hot-end components. The thermal shock performance of stereolithographic additive-manufactured ceramics has not yet been studied. In this study, a series of thermal shock experiments with various temperature differences was conducted on stereolithographic additive-manufactured Al₂O₃ ceramics. The surface cracks were analysed based on photographs captured before and after the thermal shock experiments. Three-point bending tests with in situ X-ray digital radiography were conducted to determine the thermal shock resistance. Crack initiation, propagation, and coalescence were observed under flexural loads. The critical temperature difference of the stereolithographic additive-manufactured Al₂O₃ ceramics was determined to be 267.22 °C. The crack length increased and residual strength decreased with increasing temperature differences. The layered structure of the stereolithographic additive-manufactured ceramics slowed crack propagation. We expect that this study will serve as a reference for the performance of stereolithographic additive-manufactured Al₂O₃ ceramics in extreme environments.     

纳米ZrO2对MgO-CaO材料烧结及抗热震性的影响

在≤0.1mm的MgO-CaO砂中分别加入占其总质量2%、4%、6%和8%的纳米ZrO2,分别经干混、压制成型,1600℃3h煅烧后,检测其体积密度和抗热震性,并进行XRD和SEM分析,以研究添加纳米ZrO2对MgO-CaO材料烧结和抗热震性能的影响及其作用机理。结果表明:添加2%的纳米ZrO2即可显著提高MgO-CaO材料的烧结程度和抗热震性;综合考虑MgO-CaO材料的烧结程度和抗热震性认为,添加6%的纳米ZrO2可使材料获得良好的性能。