Materials Science Forum Vols. 631-632

Abstract: Functionally graded material (FGM) is a combined material that has a component gradient from one material at one surface to another material at the opposite surface. 　As one of the fabrication processes of FGM, centrifugal in-situ method has been proposed. Centrifugal in-situ method is a casting that centrifugal force is applied during solidification to both the primary crystal and the matrix. In a previous study, the density and hardness gradients of Al-3mass%Cu FGM ring fabricated by centrifugal in-situ method have been investigated. According to the study, Cu concentration within the FGM ring monolithically increases towards the ring's inner position, and its density also increases toward inner region. This is because the density of the primary -Al crystal is larger than that of the molten Al-Cu alloy in the early stage of solidification. Based on this solidification process, it is considered that the casting condition and the initial Cu concentration of Al-Cu master alloy affect on the density and hardness gradients in the Al-Cu FGM ring. In this study, effects of the casting condition on the density and hardness gradients of Al-Al2Cu FGM rings fabricated by the centrifugal in-situ method were investigated. It was found that density gradient of the Al-Al2Cu FGM rings increases with increasing Cu concentration of Al-Cu master alloys. Also, processing temperature for Al-Cu master alloy can control density gradient of Al-Al2Cu FGM rings. These phenomena were explained by variation of the densities of primary -Al and the molten Al matrix during the solidification.

Abstract: Centrifugal slurry-pouring method has been proposed to fabricate the functionally graded materials (FGMs) with large compositional gradient. This processing method uses the two types of slurries (slurry 1 and slurry 2). The prepared slurry 1 containing one component, particle A, is firstly poured into the mold under the centrifugal force and then the slurry 2 containing two components, particle A and particle B, is poured into the mold. By this process, green body with gradient composition can be obtained and then green body will be sintered by Spark Plasma Sintering method. Finally, it is expected that FGM with gradient from 100% component A at one surface to 100% B at other surface can be fabricated. In this study, the graded distributions of the particle A and particle B within the slurry 2 under the centrifugal force were simulated analyzing the movement of particles in liquid. Moreover, Ti-SiO2 FGMs were experimentally fabricated. The Ti-SiO2 FGM has large compositional gradient on one side of FGM. However, when the size of solid-particle is small, it is difficult to form large compositional gradient in the FGM. This phenomenon obtained by experiment is in agreement with the calculated results. From this result, it is found that the centrifugal slurry-pouring method using different slurries is effective fabrication method for FGMs with large compositional gradient.

Abstract: FGMs with density gradient are of great interest in field of dynamic high-pressure physics. In this paper, tungsten particles reinforced epoxy resin composites, and FGMs with density gradient were prepared by calendering technique. Microstructures of tungsten-epoxy composites with various tungsten contents were analyzed, and the density distribution of the FGMs was characterized. The results show that the distribution of tungsten particles in tungsten-epoxy composites is homogeneous, and the combination of tungsten particles with epoxy matrix is good. The density of tungsten-epoxy composites varies from 1.26gcm-3 to 4.0gcm-3, and the thickness of each layer is about 200μm. Tungsten-epoxy FGMs with density gradient were obtained by laminating thin layers of tungsten-epoxy composites with different tungsten contents. The highly enough bonding strength between these transition layers and good parallelism were achieved. The density distribution of the tungsten-epoxy FGMs can meet the demand of the power function equation of density and thickness.

Abstract: It is difficult to use an ordinary plain bearing under a high load or at a high friction speed because lubricant oil is pushed out from the friction surface or deterioration of the lubricant oil is caused by heat of friction. A solid lubricant, MoS2, is promising in such condition. When the lubricant is dispersed in a matrix, the solid lubricant is always supplied from the matrix. Such a composite bearing needs a back metal to maintain its shape. The heat of friction may cause a crack between the bearing and the back metal due to thermal stress. A bearing with low coefficient of friction is necessary to decrease the heat of friction, and an FGM structure is also promising to decrease the stress. The aim of this experiment is to fabricate and to examine friction properties of the composites. Cu was plated on the lubricant particles by electroless deposition. The lubricant volume fraction (hereafter Vf) was up to Vf 30 %. The Cu plated lubricant particles were hot-pressed to form a composite at 873 K under 30 MPa in a vacuum. Friction properties of the composites were determined by using a ball-on-disk type testing machine. The test was performed in the air without oil at room temperature. The solid lubricant in the composites was effective to decrease the coefficients of friction under a high load when the Vf was higher than 20 %.

Abstract: A new method for processing large flat compositionally graded metal-ceramic parts with connected interpenetrating metal and ceramic network is described. Based on powder metallurgical methods, a metal foam is obtained by slip casting of metal powder slurries on a polyurethane foam, and used as preform to achieve a metallic interpenetration within the composite. The porous metallic preform is infiltrated with a ceramic slip and co-sintered. The metallic part is made from Ni-Cr-alloy, or the P/M superalloy Saratherm 2 and Nimonic 90, the ceramic consists of pure 8Y-ZrO2 or zirconia mixed with ZrSiO4. Composites of nominal same composition sintered without the metal foam preform show no metallic interpenetration.

Abstract: This paper summarises results of a study on graded surface layer composition in porous silicon nitride ceramics with a nominal Yb-silicate, Yb2SiO5-additive content of 3.2 mol%, corresponding to 10wt%. A compositional gradient of the additive is formed within the sintered part, depending upon the sintering conditions. The thickness and the phase content of the compositional gradient is significantly affected by the nitrogen activity of the sintering atmosphere. When argon gas is used during heating up and replaced by nitrogen upon soaking, the surface of the sintered ceramic is free of Yb2SiO5, whereas in N2-atmosphere a silicate-rich coating is found as surface layer of the porous silicon nitride ceramic. In presence of carbon and nitrogen, the surface is covered by SiC. In particular the Yb-silicate enriched surface layer can be used as base for an Environmental Barrier Coating, EBC, to protect the interior of the ceramic from hot gas corrosion.

Abstract: We study the synthesis and physical properties of Pb2-xLnxRu2O7- (Ln = Sm, Eu) compounds with pyrochlore structure. The lead-lanthanoid pyrochlores Pb2-xLnxRu2O7- (Ln = Sm, Eu) have been successfully synthesized by the solid-state reaction. All samples were characterized by X-ray diffraction, magnetic susceptibility, and electrical resistivity measurements. Magnetic susceptibility measurements showed that the spin-glass transition temperature, TSG, decreases with Ln content x and goes to zero at x = 0.2 and 0.6 for Sm and Eu, respectively. From electric resistivity measurements, a crossover from metallic to semiconducting behavior was observed in the range of 0.2 ≤ x ≤ 0.4 and 0.4 ≤ x ≤ 0.8 in Pb2-xSmxRu2O7- and Pb2-xEuxRu2O7-, respectively. These boundaries between metallic and insulating phases mostly correspond to values of x with TSG = 0. These metal-insulator transitions can be caused by the strongly correlated couplings between the itinerant 4d electrons which are possibly attributed to the magnetic frustration.

Abstract: In modern age, much thermal energy is emitted from ceramic and/or steel industries. Their temperature range is between 500 K and 1300 K. Thermoelectric materials are promising to utilize the waste heat, because of no CO2 emission and long life due to no moving parts. The thermoelectric properties of every thermoelectric material have temperature dependence and high performance appears at a specific temperature range. If the proper materials are placed and joined along the temperature gradient to form an FGM, the performance should be higher than a monolithic material. The performance of a thermoelectric material is expressed by the dimensionless figure of merit ZT=α2ρ-1κ -1T, where α is the Seebeck coefficient, ρ is the electrical resistivity, κ is the thermal conductivity, and T is absolute temperature. Thermoelectric oxides are suitable for high temperature materials because of chemical stability. NaxCoO2 shows relatively high ZT value in thermoelectric oxide at the temperature range below 800 K. Ca3Co4O9 shows ZT ~1 at 1000 K. Recently, it is reported that Ca3Co2O6 that is formed by decomposition of Ca3Co4O9 at 1173 K has high performance at 1300 K. The properties and fabrication condition of high density Ca3Co2O6 are, however, not reported in detail. In order to improve the thermoelectric properties and to shift the temperature range for Ca3Co2O6, we investigated the effects of element substitution. In this experiment, the sintered Ca3Co2-xMxO6 (x=0 or 0.2, M= Mn, Mo or V) were prepared by solid-state reaction or hot pressing. Relative density of Ca3Co2O6 by hot-pressing (HP) was over 94% which is larger than one of Ca3Co2O6 by solid-state reaction (SSR). The resistivity of Mo- or V-substituted Ca3Co2O6 (HP-Mo or HP-V) were lower than one of non-substituted Ca3Co2O6 (HP). The resistivity of Mo-substituted Ca3Co2O6 (HP-Mo) showed the lowest value of 4.3×10-2 Ωcm in all specimens at 1181 K. The power factor α2ρ-1 of Ca3Co2O6 (HP-Mo) was 64.2 Wm-1K-2, which is the largest of all specimens at 1178 K, and this value is approximately 1.3 times higher than 48.8 Wm-1K-2 for Ca3Co2O6 (HP).

Abstract: The NbSi2/Nb/-TiAl and NbSi2/Nb functionally graded materials (FGMs) were prepared and their tolerances tested by exposing them to temperatures from 1050 °C to 1250 °C under vacuum and in air. Oxygen resistivity was estimated from metallographic investigations. The FGM lifetime was estimated by using a diffusion equation that considers the disappearance of the NbSi2 and Nb interlayer. These occurred during NbSi2 oxidation and Si diffusion from NbSi2 to Nb and interdiffusion between Nb and -TiAl. The results were validated by diffusion equations.

Abstract: Alloying elements are added to steel for improving surface properties such as corrosion resistance. The alloying elements exhibit different chemical characters, and they are often enriched to the surface of the alloys during annealing at high temperatures. In this study, depth-resolved X-ray absorption spectroscopy (XAS) measurements were carried out using a two-dimensional detector with geometrical arrangement of grazing exit in detection of fluorescence X-ray emitted from sample surface, in order to characterize the enrichment and oxidation of manganese on the surface layers of an Fe-Mn alloy annealed under low oxygen partial pressure. This technique facilitates non-destructive measurement for characterizing the compositional distribution of manganese in the depth direction. The results showed that manganese was enriched to surface layers of the Fe-Mn alloys during annealing at high temperatures and formed as manganese oxide. The preferential oxidation of manganese by annealing under low oxygen partial pressure is considered the driving force for their enrichment on the alloy surface.