Effect of Crystallization on Thermal Conductivity and Specific Heat of Two Corning Glass-Ceramics

A magnesium aluminosilicate glass-ceramic (Corning Code 9606) has been heat-treated at 900°, 1010°, 1200°, and 1260°C for up to 90 min., and the effect on the thermal conductivity between 30 and 300 K has been studied. It has been shown that the large increase of the thermal conductivity which results from the ceramming occurs predominantly when crystalline cordierite forms. At 1260°C, heat treatment for only 20 min leads to a thermal conductivity identical to that measured for commercial 9606, which has been cerammed for 8 h at the same temperature. This observation provides further evidence for the usefulness of commercial 9606 as a thermal conductivity standard. Measurements of the specific heats of Code 9606 before and after ceramming have been reviewed and have been found to be close to that of crystalline SiO₂ above ∼ 30 K, regardless of the state of ceramming. A review has also been made of thermal conductivity and specific heat of several ZrTiO₄ nucleated lithium aluminosilicate glass-ceramics at various states of ceramming. The thermal conductivity of these glass-ceramics seems to be sufficiently independent of chemical composition as well as of the degree of crystallization to warrant a recommended curve for this class of glass-ceramics.     

Anisotropic thermal diffusivity and conductivity in SiC/SiC tubes studied by infrared imaging and X-ray computed tomography

Traditional flash diffusivity evaluation of thermal diffusivity/conductivity of composite tubes require machining of specimens. For a thin-wall tube, this method can only be used to obtain through-thickness transport property. A novel method to evaluate anisotropic thermal diffusivity in a composite tube has been developed. Braided SiC/SiC composite tubes were subjected to a xenon flash heating pulse. A high-speed, high-sensitivity infrared camera was used to measure surface temperature changes as a function of time and nondestructively detect subsurface defects/damages, such as macroscopic pores. Standard reference material (Pyroceram 9606) and curved SiC/SiC composite tube specimens were used to validate thermal diffusivity obtained from infrared imaging. Unlike the traditional method, there is no need prepare special specimens, and thermal diffusivity values in three orientations are obtained after a single flash. A finite element analysis model based on x-ray computed tomography scans was developed to simulate the heat transfer. This technique is significant in assessing thermal conductivity and inspecting the health of ceramic tubes during and after service.     

Fabrication of lightweight alumina with nanoscale intracrystalline pores

In this study, lightweight alumina containing nanoscale intracrystalline pores was fabricated by introducing zirconia sol and alumina sol into α-Al₂O₃ micropowder. The effects of zirconia sol on the sintering behavior of lightweight alumina were also investigated. With the introduction of zirconia sol, the grain growth and phase transformation of nano-alumina are delayed. Therefore, the structure of the nanoscale pores between nanoparticles can be stabilized during heat treatment, and numerous nanoscale intracrystalline pores with diameters in the range of 50-300 nm are trapped in the alumina grains. Because of the existence of these nanoscale intracrystalline pores, the thermal conductivity of lightweight alumina decreases significantly. Lightweight alumina with the addition of 0.75 wt% zirconia sol exhibits 31% lower thermal conductivity compared to alumina without zirconia sol.     

Porous alumina ceramics with enhanced mechanical and thermal insulation properties based on sol-treated rice husk

To improve the properties of porous alumina ceramics, which were typically prepared by adding pore-forming agents, rice husk (RH) as pore-forming agent was pretreated with zirconia sol. The effects of sol-treatment on the thermal conductivity and compressive strength of the resultant ceramics were characterized. Furthermore, the pore size distribution, pore shape, microstructure, and phase evolution also were studied. The results showed that the RH pretreatment optimizes the microstructure of the ceramic pores. Moreover, complete morph-genetic RH is clearly observed in the pores, which is established as a key factor in improving the properties of the resultant ceramic. The thermal insulation properties are determined to significantly improve, although the thermal conductivity increases slightly with the increment of zirconia sol concentration from 5 to 10?wt%. Meanwhile, after sintering at 1550?°C, the compressive strength is significantly greater for the specimen prepared with 10?wt% zirconia sol-treated RH (65.56?MPa) than that with untreated RH (43.37?MPa). Hence, it was demonstrated that the use of zirconia sol-pretreated RH as a pore-forming agent could enhance the mechanical and thermal insulation properties of porous alumina ceramics.     

Crystallographic Texture and Thermal Conductivity of Zirconia Thermal Barrier Coatings Deposited on Different Substrates

The crystallographic texture and thermal conductivity of zirconia coatings deposited by electron beam evaporation on a variety of substrates have been measured. It was found that the thermal conductivity of coatings deposited at the same temperature was independent of whether they were deposited on polycrystalline alumina, single-crystal sapphire, single-crystal zirconia, or fused silica. The room-temperature thermal conductivity of the coatings deposited at 700°C was 0.32 W/(m·K), increasing to 1.36 W/(m·K) for coatings deposited at 1150°C. Similarly, the crystallographic texture was also independent of the substrate and had a (111) fiber texture at 700° and 900°C, switching to a (200) fiber texture by 1050°C. The exception was the coating deposited at 1150°C on (111) single-crystal zirconia which was epitaxial and exhibited a thermal conductivity of 2.46 W/(m·K). It is concluded that the properties of zirconia thermal barrier coatings are determined by the growth conditions rather than those associated with nucleation on the underlying substrate.     

Effect of carbon nanotubes and aluminum oxide on the properties of a plasma sprayed thermal barrier coating

To protect the structural components of a power generating unit from the corrosive environment, thermal spray coatings are applied to the components. In the present work, four different types of thermal barrier coating (TBC) viz. partially stabilised zirconia (8YSZ), zirconia-20% alumina (ZA) composite coating without carbon nanotube (CNT) reinforcement, and ZA with 1% and 3% CNT reinforcement. The coating was deposited on NiCrAlY coated P91 steel using a plasma spraying process. The coating microstructure and phases were characterised using field emission scanning electron microscope (FE-SEM) with energy dispersive spectroscopy (EDS). The phases of the coating were analyzed using X-ray diffraction technique. The effect of CNT reinforcement on the thermal conductivity, porosity, and hardness of the composite coatings was investigated. The protective behavior of the coatings was characterised by potentiodynamic polarization testing and electrochemical impedance measurements. The thermal conductivity of the composite coating was found to be increased with increasing CNT content. Hardness was found to be highest for 3% CNT reinforcement and the thermal conductivity was found to increase with decreasing porosity. The electrochemical measurements indicate that reinforcement of CNT in zirconia alumina composite coating improved its corrosion resistance.     

Mechanical and electrical properties of ZrO2---6·5 Y2O3 ceramic electrolytes doped with alumina

Two differently prepared series of zirconia-yttria electrolytes doped with 5–50 wt% of Al₂O₃ have been investigated. Bending strength, thermal shock resistance and ionic conductivity of the electrolytes have been measured. There was limited agreement between experimental and calculated (percolation theory) values for the electric properties. The 50% alumina samples exhibited slightly lower conductivity than the pure zirconia electrolyte in both series. It was found that alumina addition causes an increase in Young's modulus and thermal shock resistance, and results in better homogeneity of the microstructure.     

水泥回转窑用含ZrO2耐火材料

含ZrO2耐火材料在水泥窑上的应用不断增加,水泥窑用含ZrO2耐火材料包括含锆白云石砖、含锆镁砖、含锆镁尖晶石砖、含锆高铝砖等.本文从材料的抗化学侵蚀性、热震稳定性、导热性和力学性能等方面讨论了ZrO2的引入对耐火材料使用性能的影响.     

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.     

FEM simulations of microstructure effects on thermoelastic properties of sintered ceramics

A model was developed to simulate macroscopic material properties of polycrystalline ceramics from the material properties of the constituting phases and the microstructure. Cubic and random structures were included. The model allows a variation of volume fractions of the phases, grain size and grain boundary areas. Representative for a large number of material properties, elastic tensor, thermal conductivity, coefficient of thermal expansion and thermal stress are calculated for individual microstructures using finite element methods (FEM). Simulations focus on two types of bi-continuous ceramic composites: zirconia toughened alumina (ZTA) and a porous zirconia ceramic which was infiltrated by a spinel-glass. Microstructure of experimental samples is represented by two different model structures: a Voronoi type structure for the ZTA ceramic and a cubic structure of cubes interconnected by cylinders for the infiltrated zirconia system. A substantial impact of microstructure on macroscopic material properties and internal stress distribution is obtained. A good agreement between measured and simulated material properties was found.     

Failure of the plasma-sprayed coating of lanthanum hexaluminate

Lanthanum magnesium hexaluminate (LaMgAl₁₁O₁₉, LMA) is an attractive material for thermal barrier coatings (TBCs), and the failure of its coating was studied in this work by thermal cycling, X-ray diffraction, dilatometric measurement and thermal gravimetric-differential thermal analysis. The dilatometric measurement indicates that even though the bulk material of LMA has a higher sintering-resistance than the typical TBC material, i.e. yttria-stabilized zirconia (YSZ), the plasma sprayed coating of LMA has two serious contractions due to the re-crystallization of LMA and phase transitions of alumina. LMA has similar thermal expansion behaviour with alumina, leading to a good thermal expansion match between LMA and the thermally grown oxide layer. On the other hand, the plate-like structure of LMA not only results in a low thermal conductivity, low Young's modulus, but also a high stress tolerance, and these are believed to be the reasons for the long thermal cycling life of LMA coating.     

Thermal conductivity of high porosity alumina refractory bricks made by a slurry gelation and foaming method

Alumina has high heat resistance and corrosion resistance compared to other ceramics such as silica or mullite. However, for its application to refractory bricks, its high thermal conductivity must be reduced. To reduce this thermal conductivity by increasing the porosity, a GS (gelation of slurry) method that can produce high porosity solid foam was applied here to produce the alumina refractory brick. This method was successfully applied to produce alumina foam with high porosity and thermal conductivity of the foam is evaluated. At room temperature, the thermal conductivity was about 0.12 W/mK when the foam density was 0.1 g/cm³. At elevated temperature above 783 K, thermal conductivity of the foam was strongly affected by heat radiation and increased with increasing temperature, in contrast to the thermal conductivity of alumina itself, which decreased with increasing temperature. The alumina foams developed here achieved sufficient thermal insulating properties for use in refractory bricks.     

Nano- and micrometre additions of SiO2, ZrO2 and TiO2 in fine grained alumina refractory ceramics for improved thermal shock performance

The present contribution investigates the influence of micro-metre- as well as nano-metre-additions of zirconia (ZrO₂), titania (TiO₂), silica (SiO₂) and magnesia (MgO) into alumina-rich fine grained ceramic materials for refractory applications. Slip casted samples in the system alumina–zirconia–titania (AZT), alumina–zirconia–titania–silica (AZTS) and alumina–zirconia–titania–magnesia (AZTM) were sintered and the physical as well as mechanical properties were investigated as fired and after thermal shock treatments. The generation of a micro-crack network after sintering due to the formation of phases with different thermal expansion coefficients and the formation and decomposition of aluminium titanate (Al₂TiO₅) before and after thermal shock exposure leads to higher strengths after thermal shock attack.     

髋关节整体替代陶瓷材料

许多材料在医学领域应用广泛,例如,整体替换硬组织或软组织的元件(如骨盆、骨头、关节、植牙等)、修补、诊断或矫正仪器(如起搏器、心脏阀等)。这些材料不仅要有好的力学性能,还要保持长期稳定,不能与人体相排斥。由于陶瓷材料在生理环境中具有强度高、生物相容性强和稳定性好的优点,人们研究用陶瓷材料替换骨骼。从20 世纪70 年代起,欧洲人用陶瓷组件置换整个髋关节。这些组件主要由氧化铝和氧化锆单体制成。然而,在有水环境中,氧化锆会发生低温降解。目前人们的研究重点在于提高陶瓷组件的强度和耐磨性,同时缩小其尺寸并延长其使用寿命。研究中使用的材料是氧化锆增韧的氧化铝复合陶瓷和其它氧化铝复合陶瓷,不再是单体陶瓷。另外,还可以使用氧化铝和氧化锆功能梯度复合材料。该梯度材料可以利用电泳沉积法(EPD)制得,其表面为纯氧化铝,中心部分为均匀的氧化铝、氧化锆复合材料,中间过渡部分是呈连续梯度渐变的氧化铝、氧化锆复合材料,烧成后会产生剩余热应力。设计这样的梯度结构是为了使复合材料具有最大表面压应力和最小内部张应力,与纯氧化铝组件相比,提高了强度和耐磨性。     

Electric insulating properties of refractory coatings obtained by flame spraying

Conclusions Coatings of alumina, aluminomagnesia spinel and zirconia have a sufficiently high electrical insulating capacity at 20–700°C.The purity of the material is important for the electrical resistance and dielectric loss of the coatings.Ceramic materials as a rule have a low thermal conductivity. Laminated cermet coatings made from alumina and nickel have a low thermal conductivity; they are electrically insulating in the direction perpendicular to the layers of metal and good current conductors and heat conductors over these layers. They can be used for removing heat from local overheated sites (hot spots) in special units.Coatings of titania with low coefficients of thermal conductivity [8] may be used for heat insulation and also as excellent current conductors in nonoxidizing conditions and at temperatures up to 100°C in oxidizing conditions.The investigation was carried out at the ceramics faculty of the University of Illinois under the direction of A. L. Friedberg.Translated from Ogneupory, No. 6, pp. 52–56, June, 1967.     

Thermal expansion of β-eucryptite in oxide-based ceramic composites

This paper presents an experimental investigation on the thermal expansion behaviour of β-eucryptite (E) when it is used for processing alumina/β-eucryptite (AE) or zirconia/β-eucryptite (ZE) composites. Composite materials were prepared from a β-eucryptite powder synthetised in our laboratory and commercially available alumina or zirconia nanopowders. In order to preserve the β-eucryptite crystalline phase in sintered materials, the pressureless sintered step was performed at relatively low temperatures (<1300 °C). It is experimentally shown that in well-densified oxide-based composites, the β-eucryptite lost its slightly negative thermal expansion coefficient. This behaviour could be related to compressive residual stresses applied on β-eucryptite grains due to the thermal expansion mismatch between alumina or zirconia and the β-eucryptite.     

不同形态ZrO2复合Al2O3陶瓷的抗热震性设计与表征

采用湿化学方法制备了具有不同团聚度及稳定度的氧化锆陶瓷粉体,并将其复合到氧化铝基体中的结构微气孔,以同时提高材料的抗热震性能与强度。研究表明：水洗复合材料的抗热震性能更为优越。其原因在于团聚氧化锆的形成,这也得到显微结构证实。运用函数构造建立了含裂纹脆性材料的具有普话意义的热震方程,进而探讨了几类复合材料的抗热震行为的表征和模拟。     

Mechanical and functional properties of Al2O3–ZrO2–MWCNTs nanocomposites

Multi-walled carbon nanotubes (MWCNTs) are often reported as additives improving mechanical and functional properties of ceramic composites. However, despite tremendous efforts in the field in the past 20 years, the results are still inconclusive. This paper studies room temperature properties of the composites with polycrystalline alumina matrix reinforced with 0.5–2 vol.% MWCNTs (composites AC) and zirconia toughened alumina with 5 vol.% of yttria partially stabilised zirconia (3Y-PSZ) containing 0.5–2 vol.% of MWCNTs (composites AZC). Dense composites were prepared through wet mixing of the respective powders with functionalised MWCNTs, followed by freeze granulation, and hot-pressing of granulated powders. Room temperature bending strength, Young's modulus, indentation fracture toughness, thermal and electrical conductivity of the composites were studied, and related to their composition and microstructure. Slight increase of Young's modulus, indentation fracture toughness, bending strength, and thermal conductivity was observed at the MWCNTs contents ≤1 vol.%. At higher MWCNTs contents the properties were impaired by agglomeration of the MWCNTs. The DC electrical conductivity increased with increasing volume fraction of the MWCNTs.     

Measurement of ceramics cracking during water quenching by digital image correlation

Measuring the thermal shock crack growth process is crucial for revealing ceramic materials and structures’ thermal shock failure mechanisms and evaluating their reliability. We used a self-made water quenching system to conduct thermal shock tests on alumina and zirconia ceramics. The thermal shock process was recorded by high-speed digital image correlation (DIC) during the test. The process of thermal shock crack initiation and propagation in two kinds of ceramics was determined by analyzing the speckle image change on the sample’s surface. It is found that the crack growth rate of alumina is faster than that of zirconia, which is caused by different material parameters. This paper presents an in-situ measurement method for the initiation and propagation of thermal shock cracking in ceramic materials. It can provide a measurement method to identify and predict the thermal shock damage of ceramic components.     

The Tetragonal-Monoclinic Transformation in Zirconia: Lessons Learned and Future Trends

Zirconia ceramics have found broad applications in a variety of energy and biomedical applications because of their unusual combination of strength, fracture toughness, ionic conductivity, and low thermal conductivity. These attractive characteristics are largely associated with the stabilization of the tetragonal and cubic phases through alloying with aliovalent ions. The large concentration of vacancies introduced to charge compensate of the aliovalent alloying is responsible for both the exceptionally high ionic conductivity and the unusually low, and temperature independent, thermal conductivity. The high fracture toughness exhibited by many of zirconia ceramics is attributed to the constraint of the tetragonal-to-monoclinic phase transformation and its release during crack propagation. In other zirconia ceramics containing the tetragonal phase, the high fracture toughness is associated with ferroelastic domain switching. However, many of these attractive features of zirconia, especially fracture toughness and strength, are compromised after prolonged exposure to water vapor at intermediate temperatures (∼30°–300°C) in a process referred to as low-temperature degradation (LTD), and initially identified over two decades ago. This is particularly so for zirconia in biomedical applications, such as hip implants and dental restorations. Less well substantiated is the possibility that the same process can also occur in zirconia used in other applications, for instance, zirconia thermal barrier coatings after long exposure at high temperature. Based on experience with the failure of zirconia femoral heads, as well as studies of LTD, it is shown that many of the problems of LTD can be mitigated by the appropriate choice of alloying and/or process control.