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In this study, we report the three-point flexural strength and fracture toughness of monolithic hafnium carbide up to 2000 °C. HfC with different grain sizes was consolidated using the spark plasma sintering method. Coarse-grained monoliths showed a weak dependence on the strain rate during high-temperature tests at 1600 °C–2000 °C. In contrast, results for the ceramics with a grain size below 20 μm indicated a positive dependence of the yield strength vs strain rate. This allowed us to identify the activation energy for high-temperature deformation in flexure as 370 kJ/mol. This level of activation energy is in satisfactory agreement with reports about the diffusion of C in hafnium carbide.

We report for the first time the effect of temperature on the mechanical properties of (Ta1/3Ti1/3Zr1/3)C carbide. Flexural strength and fracture toughness were investigated using the three-point bending technique in argon. Using commercially available carbide powders with an equimolar ratio and performing spark plasma consolidation at 1973°C, we obtained a bulk single-phase medium-entropy carbide ceramic with the lattice parameter a= 4.458 Å. The flexural strength and fracture toughness at room temperature reached on average 700 MPa and 3.2 MPa m1/2, respectively. At 1800°C, local decomposition of the medium-entropy carbide took place as a structure with a local chemical gradient was observed after high-temperature tests, which increased fracture toughness by 30% (to 4.4 MPa m1/2).

The liquidus surface projection and isothermal section at 1,800°C in the Mo–Ti–C ternary system are examined using arc-melted alloys. A ternary transition peritectic reaction (L + Mo2C → Mo + TiC) takes place during solidification, which is apparently different from the ternary eutectic reaction (L → Mo + TiC + Mo2C) observed in a previous report. Since the composition of the eutectic reaction (L → Mo + TiC) shifts toward the Mo–Ti binary line with increasing Ti concentration, the volume fraction of the Mo phase and the interlamellar spacing of the Mo and TiC phases increase in the eutectic microstructure. At 1,800°C, the TiC phase in equilibrium with the Mo phase can contain more than 28 at% Mo and a Mo/TiC/Mo2C three-phase region exists at around Mo–15Ti–10C.

Microstructural evolution in the TiC-reinforced Mo–Si–B-based alloy during tensile creep deformation at 1,500°C and 137 MPa was investigated via scanning electron microscope-backscattered electron diffraction (SEM-EBSD) observations. The creep curve of this alloy displayed no clear steady state but was dominated by the tertiary creep regime. The grain size of the Moss phase increased in the primary creep regime. However, the grain size of the Moss phase was found to remarkably decrease to ss phase occurred by continuous dynamic recrystallization including the transformation of low-angle grain boundaries to high-angle grain boundaries. Accordingly, the deformation of this alloy is most likely to be governed by the grain boundary sliding and the rearrangement of Moss grains such as superplasticity in the tertiary creep regime. In addition, the refinement of the Moss grains surrounding large plate-like T2 grains caused the rotation of their surfaces parallel to the loading axis and consequently the cavitation preferentially occurred at the interphases between the end of the rotated T2 grains and the Moss grains.

A negative Poisson's ratio refers to the phenomenon of a material expanding along the transverse direction upon uniaxial tension. Here, we show a negative Poisson's ratio observed directly by experiments in a single-crystal Heusler-type Cu–16.9Al–11.6Mn (at%) shape memory alloy, in addition to the alloy's superelasticity. When stretched along the vicinity of the [110] direction, the alloy expands along the [ 1 1 ¯ 0 ] direction, showing a significant negative Poisson's ratio of −0.51, while shrinking along the [001] direction with a large positive Poisson's ratio of 1.36. These experimental results agree well with the values calculated from the elastic constants and elastic anisotropy.

MoSiBTiC alloys are promising candidates for next-generation ultrahigh-temperature materials. However, the phase diagram of these alloys has been unknown. We have developed an ultrahigh-temperature thermal analyser based on blackbody radiation that can be used to analyse the melting and solidification of the alloy 67.5Mo–5Si–10B–8.75Ti–8.75 C (mol%). Furthermore, electromagnetic levitation (EML) was used for in-situ observation of solidification and microstructural study of the alloy. On the basis of the results, the following solidification pathway is proposed: Mo solid solution (Moss) begins to crystallize out as a primary phase at 1955 °C (2228 K) from a liquid state, which is followed by a (Moss+TiC) eutectic reaction starting at 1900 °C (2173 K). Molybdenum boride (Mo2B) phase precipitates from the liquid after the eutectic reaction; however, the Mo2B phase may react with the remaining liquid to form Moss and Mo5SiB2 (T2) as solidification proceeds. In addition, T2 also precipitates as a single phase from the liquid. The remaining liquid reaches the (Moss + T2 + TiC) ternary eutectic point at 1880 °C (2153 K), and the (Moss + T2 + Mo2C) eutectic reaction finally occurs at 1720 °C (1993 K). This completes the solidification of the MoSiBTiC alloy.

In this study, first, power densities by using SOFC system for APU of regional jets were estimated based on metal supported SOFC system and compared with those in gas turbine APU. As the second, based on the results of power density analysis in the SOFC system, all materials making up the cell stacks are examined and developed for the weight reduction. Such material development strategy is the first trial without precedent in SOFC development history.

The solid solution formation and consolidation of the (Ta,Zr,Nb)C single-phase ceramic made from commercial TaC, ZrC and NbC powders prepared by spark plasma sintering at the temperature of 1920 °C was investigated. Phase analysis and lattice parameter measurements by X-ray diffraction showed multi-stage formation of the single-phase high-entropy-type carbide with the lattice parameter of 4.535 A. The flexural strength and fracture toughness at room temperature were 460 ± 24 MPa and 2.9 MPa m1/2, respectively. With an increase in temperature, the flexural strength showed an increase up to 1600 °C to 496 ± 44 MPa, then decreased after 1800 °C to 366 ± 46 MPa.

A novel procedure of ODS alloy fabrication was examined using a model alloy in the Fe Al O ternary system. Nano-sized Al oxides were precipitated within the α-Fe matrix through a reaction between Fe Al and Fe2O3 powders. Two types of oxides, FeAl2O4 and γ-Al2O3, were found to precipitate during sintering at 1000 °C and the subsequent annealing at 800 °C. The oxides showed sluggish coarsening at 800 °C, which then provided high resistance to coarsening for the α-Fe grains. Microstructure observation and Vickers hardness measurement indicated that the homogeneous dispersion of oxides was achieved through the present procedure without ball milling.

The relation of creep rupture life to minimum creep rate, namely Monkman-Grant (MG) relation is examined by using a creep database of modified 9Cr-1Mo steel. The database covers wide ranges of creep rupture life up to 1.2 × 105 h and of minimum creep rate down to 7.6 × 10−8 h−1. The MG plot exhibits a low overall value of MG exponent (p = 0.85) together with wide scatter of data points at long rupture life. Causes of the low p value and the wide scatter are discussed in the present study paying attention to change in creep curve shape with creep rupture life. There are four regions H, M, L1 and L2 showing different creep behavior in the steel. Regional MG relations are examined also in each region. Values of p are less than unity and change among the four regions. The p value is especially low (0.62) in long-term region L2. The regional p values less than unity result in the low overall p value of 0.85. The especially low regional value of p in the long-term region causes the wide scatter of data points in the overall MG plot. A modified Monkman-Grant equation (Eq. (29)) is proposed taking account of creep deceleration rate A (=−1/(dln e ˙ /de), where e ˙ and e are the creep strain rate and the creep strain) in primary creep and creep acceleration rate B (=1/(dln e ˙ /de)) in tertiary creep. The rates characterize shape of a creep curve. The modified equation can explain the difference of p values among the four regions.

The MoSiBTiC alloy is one promising candidate for ultrahigh–temperature materials. However, it faces severe challenges in the machining of complex shapes because of its significant brittleness, high melting point, and stiffness. To overcome this challenge, we have successfully fabricated MoSiBTiC alloy parts via laser powder bed fusion (L-PBF). A combination of arc-melting and controllable high-energy ball milling (HEBM) was employed to prepare suitable MoSiBTiC powders for L-PBF. The evolution of powder morphology, constituent phases, and laser absorptivity, as well as particle size and distribution during HEBM, was investigated. Moreover, the effects of L-PBF parameters on the densification, microstructure, and mechanical performance of MoSiBTiC alloy builds were studied. A dense MoSiBTiC alloy, mainly consisting of a Mo solid-solution, Mo5SiB2, Mo2C, and TiC phases, was obtained at an energy density of 156 J mm−3 using the laser power of 70 W. Compared to the as-cast alloy, the L-PBF-processed MoSiBTiC alloy possessed more uniform and finer grain structures, while exhibiting a lower Vickers hardness due to the existence of internal microcracks. It was also proved that the small quantity of ZrO2 particles from HEBM processing was uniformly imbedded in L-PBF builds. This work may offer significant guidance for designing and producing complexly shaped refractory intermetallics with unique microstructures in ultrahigh–temperature applications.

Previously, we isolated jacalin-related lectins termed PPL2, PPL3 (PPL3A, 3B and 3C) and PPL4 from the mantle secretory fluid of Pteria penguin (Mabe) pearl shell. They showed the sequence homology with the plant lectin family, jacalin-related &beta, prism fold lectins (JRLs). While PPL3s and PPL4 shared only 35%&ndash, 50% homology to PPL2A, respectively, they exhibited unique carbohydrate binding properties based on the multiple glycan-binding profiling data sets from frontal affinity chromatography analysis. In this paper, we investigated biomineralization properties of these lectins and compared their biomineral functions. It was found that these lectins showed different effects on CaCO3 crystalization, respectively, although PPL3 and PPL2A showed similar carbohydrate binding specificities. PPL3 suppressed the crystal growth of CaCO3 calcite, while PPL2A increased the number of contact polycrystalline calcite composed of more than one crystal with various orientations. Furthermore, PPL4 alone showed no effect on CaCO3 crystalization, however, PPL4 regulated the size of crystals collaborated with N-acetyl-D-glucosamine and chitin oligomer, which are specific in recognizing carbohydrates for PPL4. These observations highlight the unique functions and molecular evolution of this lectin family involved in the mollusk shell formation.

In situ phase transformation and change in the grain size were observed during high-temperature flexural tests performed on tantalum nitride bulks consolidated by spark plasma sintering. This study, for the first time, shows that tantalum nitride with cubic structure is the main phase at temperatures between 25 °C and 2000 °C, while previous studies suggested it should be hexagonal TaN. Cubic TaN phases with lattice parameters of a = 4.338 A and a = 4.45 A were observed below 1600 °C and above 1600 °C, respectively. The possibility of the formation of multiple TaN phases during the flexural tests significantly increases the high-temperature strength as values of greater than 500 MPa were observed at 1600 °C. This strength level is typical for the bulk TaC at room temperature.

Accepted: 2022-02-16, 資料番号: PA2220031000

Grade 91 steel is widely used as steam pipes in ultrasupercritical (USC) steam boilers. In residual creep life assessment of the pipes by calculation, one needs creep rupture life of the steel as a function of stress and temperature in a time range longer than 105 h. Four regions with different creep rupture characteristics appear in a stress versus creep rupture life diagram of the steel. Main steam pipes made of the steel are used in a long-term region with low values of stress exponent and activation energy for creep rupture life (referred to as region G in this paper). Creep rupture lives of the steel in this region vary from heat to heat depending on their prior austenite grain size. This paper proposes a grain size-dependent equation representing creep rupture life of the steel in region G. The equation is verified with creep rupture data up to 232,833 h at 600 °C. Region G is absent in some heats with a large grain size. The equation can rationalize the absence in the heats. In a stress versus creep rupture life diagram of grade 92 steel, there is the same long-term region G. In the region, a creep rupture life of each heat is dependent on its grain size as is the case in grade 91 steel. The proposed equation accords well with the creep rupture lives of the grade 92 steel in region G.

In this study, we explore a simple and effective method for producing a quaternary solid-solution of carbides, a medium-entropy (Ti1/4Ta1/4Zr1/4Nb1/4)C. Using commercially-available carbide powders with an equimolar ratio and performing spark plasma consolidation at 1927 ​°C and 1977 ​°C, we demonstrated that the phase formation and high-temperature flexural strength can be controlled using the processing conditions. The flexural strength and fracture toughness at room temperature were reached an average of 560 ​MPa and 3.2 ​MPa ​m1/2, respectively. The high-temperature performance of these ceramics was analyzed and compared with the available data for the group IV and V transition metal carbide monoliths.

In this study, the ultrahigh-temperature tensile creep behaviour of a TiC-reinforced Mo-Si-B-based alloy was investigated in the temperature range of 1400–1600 °C at constant true stress. The tests were performed in a stress range of 100–300 MPa for 400 h under vacuum, and creep rupture data were rationalized with Larson-Miller and Monkman-Grant plots. Interestingly, the MoSiBTiC alloy displayed excellent creep strength with relatively reasonable creep parameters in the ultrahigh-temperature range: a rupture time of ~400 h at 1400 °C under 137 MPa with a stress exponent (n) of 3 and an apparent activation energy of creep (Qapp) of 550 kJ/mol. The increasing rupture strains with decreasing stresses (up to 70%) and moderate strain-rate oscillations in the creep curves suggest that two mechanisms contribute to the creep: phase boundary sliding between the hard T2 and (Ti,Mo)C phases and the Moss phase, and dynamic recovery and recrystallization in Moss, observed with orientation imaging scanning electron microscopy. The results presented here represent the first full analysis of creep for the MoSiBTiC alloy in an ultrahigh-temperature range. They indicate that the high-temperature mechanical properties of this material under vacuum are promising.

A strategy utilizing carbon nanotubes (CNTs) was put forward to synthesize in situ TiC/Mo-based composites via laser powder bed fusion (laser PBF). The functionalized CNTs were dispersed with MoTiAl powders under electrostatic attraction by heteroagglomeration. During laser PBF, individual CNTs reacted with Ti elements and were completely transformed into monocrystalline TiC. Those TiC reinforcements were homogeneously dispersed and intimately contacted the matrix, giving rise to the morphological evolution of a MoTiAl matrix from the nearly columnar to fine equiaxed grains as well as improved mechanical performance. Our finding offers significant guidance for designing and producing advanced Mo-based composites in the application of heat-resistant materials. Keywords: Laser powder bed fusion (laser PBF), Metal matrix composites (MMCs), Carbon nanotubes, Molybdenum, Microstructure

Laser powder bed fusion (PBF) offers many technological opportunities for producing high-performance composite parts with tailored structures. However, fabrication of suitable composite powders possessing homogenous dispersion, good flowability, suitable particle size and distribution is a prerequisite and main challenge currently faced. In this study, a novel strategy was developed to prepare nanoceramic/metal powders by using acid-treated carbon nanotubes (ATCNTs) as an agent. In detail, a 3 wt% ATCNT/Al2O3 colloid, in which the negatively-charged ATCNTs were partially covered with positively-charged Al2O3 nanoparticles under electrostatic attraction, was obtained by heteroagglomeration; subsequently, the uncovered surface areas of ATCNTs were intimately bonded to the positively-charged MoTiAl powders during their mixing. This ATCNT bridging made individual Al2O3 uniformly wrap on the surface of MoTiAl without aggregation. The Al2O3-coated MoTiAl powders remained similar in shape, particle size, and distribution to uncoated ones, simultaneously showing higher laser absorptivity due to an increased surface roughness. The PBF-processed Al2O3-ATCNT/MoTiAl composite was dense, in which Al2O3 nanoparticles were homogenously dispersed and intimately contacted with MoTiAl, giving rise to an increase in the hardness of the matrix. Keywords: Laser powder bed fusion, Metal matrix composites (MMCs), Carbon nanotubes, Dispersion, Laser absorptivity

Larson-Miller (LM) and Orr-Sherby-Dorn (OSD) parameters are widely used when formulating and predicting creep rupture life tr. The LM constant C and the activation energy Q in the OSD parameter characterize temperature dependence of tr. Q = QLSD (QLSD: activation energy for lattice self-diffusion) and C = 20 are often assumed in the formulation. Creep rupture datasets of 11 heats of nickel alloy A617, 304H and 304J1 stainless steels, 6 heats of A3004N aluminum alloy and four Mg-Al alloys are formulated with the parameters for determining C and Q of each dataset. Based on the correlation between C and Q among similar materials, it is discussed what is the C value equivalent to Q = QLSD. It is also examined how the C value changes with melting temperature of the material. The value of C equivalent to Q = QLSD varies from 14 to 9.5 depending on average values of log(rupture life) and of reciprocal temperature of the dataset. These values of C point out that C = 20 is not equivalent to Q = QLSD. The equivalent C values are similar in all the materials independently of their melting temperatures.

The liquidus projection and the invariant reactions associated with the liquid phase in the Zr-Si-Al ternary system were experimentally determined. Seventeen primary phase regions were identified from metallographic observation and analysis of the as-cast microstructures. There are at least sixteen invariant reactions and three local maxima associated with congruent melting in the ternary system. The ZrSi primary solidification region covers a wide range of compositions in the Zr-Si-Al ternary system. A variety of the solidification paths were described.

TaN samples were prepared using the spark plasma sintering at 1800 °C. Samples consisted of cubic tantalum nitride with the lattice parameter of a = 4.338 A. The formation of hexagonal and cubic (a = 4.44 A) TaN phases in situ during the flexural tests was analyzed using X-ray diffraction.

Boron segregation behavior during tempering at 600 and 790 °C was examined in a boron-doped 9Cr-steel by using high-resolution SIMS imaging (nano-SIMS). Boron segregation that developed at prior austenite grain boundaries (PAGBs) during austenitizing was found to decrease reduced during tempering because the equilibrium concentration of B segregation for austenite is larger than that for ferrite so that the segregated boron atoms diffused into block and packet boundaries. The size and the volume fraction of the carbide precipitates at PAGBs were smaller than those at packet boundaries, suggesting that boron segregation at PAGBs suppresses the carbide precipitation upon tempering.