硼对第二代镍基单晶高温合金显微组织的影响

硼(B)是强化镍基单晶合金小角度晶界的重要微量元素,但目前关于B对镍基单晶合金显微组织影响的系统报道非常有限。通过对3种不同B含量(质量分数分别为0、0.01%、0.02%)的第二代镍基单晶合金DD11铸态及热处理态组织定量表征,研究了B对相转变温度、(γ+γ′)共晶组织、硼化物的影响。结果表明:B显著降低合金的固液相线,提高铸态共晶组织体积分数;0.01%B的加入,合金中未出现M3B2型硼化物相;而0.02%B的加入,显著促进了骨架状硼化物的形成,降低合金初熔点,引起残余共晶含量的大幅度提高;骨架状硼化物吸收较多的Cr、Mo和W等元素,降低合金的固溶强化效果,可导致单晶合金基体的蠕变性能大幅度降低。研究结果对认识单晶合金中微量元素B的作用机理及优化B成分范围具有理论指导意义。     

Effect of trace boron on microstructural evolution and high temperature creep performance in Re-contianing single crystal superalloys

The effect of trace B on the microstructure and creep properties under 1100 °C/130 MPa in three single crystal superalloys with various levels of B(0, 0.01 and 0.02 wt %) additions was investigated. Compared with the boron-free alloy, the creep rupture life decreased slightly for the alloy with 0.01 wt % B, but dropped obviously for the 0.02 wt% B contained alloy. The low B addition had a slight effect on the main element compositions ofγ/γ′ by the high precision atom probe tomography(APT) analysis and no significant change of γ/γ′ misfit was observed. However, the contents of Re, Mo, Cr in γ phase were decreased with the high B addition, resulting in the decrease of γ/γ′ misfit and increase of the spacing of γ/γ′ interfacial dislocation networks. Meanwhile, the residual(γ+γ′) eutectics and borides with a large volume fraction obviously decreased the creep rupture properties in the high B addition alloy. This study is helpful for understanding the boron's role of strengthening mechanism in high temperature creep of Ni-base single crystal superalloys.     

固溶热处理对一种第三代镍基单晶高温合金组织及高温持久性能的影响

研究了固溶热处理对一种Re含量为6.5%(质量分数)的第三代单晶高温合金组织及持久性能的影响,实验结果表明:合金铸态下存在明显的凝固偏析,枝晶间区域存在大量的(γ+γ′)共晶组织。固溶过程中,共晶组织在1 335℃以上开始快速溶解,但难熔元素,尤其是Re元素的偏析需要在1 360℃以上才能有明显改善;经过1 365℃固溶后疏松含量增加至0.21%(体积分数),接近铸态下疏松含量的5.2倍。铸态及经1 360℃和1 365℃固溶热处理后合金的持久性能测试结果显示:固溶热处理显著改善了合金的持久性能,且固溶温度越高,持久性能越高。在高温持久加载过程中,铸态合金的裂纹主要沿枝晶间分布,在(γ+γ′)共晶组织处萌生;当固溶温度较低时,且枝晶干处析出了较多的TCP(topologically close-packed)相,未能充分降低Re元素的偏析可能是导致枝晶干处TCP相大量析出的主要原因;当固溶温度较高时,TCP相析出量较少。     

Fabrication of solid-phase-sintered SiC-based composites with short carbon fibers

Solid-phase-sintered SiC-based composites with short carbon fibers (Csf/SSiC) in concentrations ranging from 0 to 10wt% were prepared by pressureless sintering at 2100°C. The phase composition, microstructure, density, and flexural strength of the composites with different Csf contents were investigated. SEM micrographs showed that the Csf distributed in the SSiC matrix homogeneously with some gaps at the fiber/matrix interfaces. The densities of the composites decreased with increasing Csf content. However, the bending strength first increased and then decreased with increasing Csf content, reaching a maximum value of 390 MPa at a Csf content of 5wt%, which was 60 MPa higher than that of SSiC because of the pull-out strengthening mechanism. Notably, Csf was graphitized and damaged during the sintering process because of the high temperature and reaction with boron derived from the sintering additive B₄C; this graphitization degraded the fiber strengthening effect.     

Alloying effects of refractory elements in the dislocation of Ni-based single crystal superalloys

The alloying effects of W, Cr and Re in the [100] (010) edge dislocation cores (EDC) of Ni-based single crystal superalloys are investigated using first-principles based on the density functional theory (DFT). The binding energy, Mulliken orbital population, density of states, charge density and radial distribution functions are discussed, respectively. It is clearly demonstrated that the addition of refractory elements improves the stability of the EDC systems. In addition, they can form tougher bonds with their nearest neighbour (NN) Ni atoms, which enhance the mechanical properties of the Ni-based single crystal superalloys. Through comparative analysis, Cr-doped system has lower binding energy, and Cr atom has evident effect to improve the systemic stability. However, Re atom has the stronger alloying effect in Ni-based single crystal superalloys, much more effectively hindering dislocation motion than W and Cr atoms.     

Effects of Mo addition on microstructure of a 4th generation Ni-based single crystal superalloy

The effects of Mo addition on the microstructure of a 4th generation Ni-based single crystal superalloy were investigated. Mo addition significantly promoted elements Mo, W and Re partition into γ phase and enhanced absolute lattice misfit at 1100 ?°C. The increase of Mo concentration from 2 ?wt% to 4 ?wt% also decreased the content of eutectic islands and the segregation ratios of other alloying elements in the as-cast state, especially Re and W. After heat treatments, the size of γ′ phase and width of γ channels decreased slightly with higher Mo content. More Mo additions slightly enhanced the segregation behavior of Re while reducing the segregation behavior of Mo. However, it revealed that the primary and secondary dendrite arm spacings were barely affected by Mo addition.     

Effect of the withdrawal rate on the microstructure and thermal durability of a third-generation single crystal superalloy

Single crystal Ni-based superalloys are the typical structural materials for high-pressure turbine blades, and their microstructure is critical in determining their mechanical properties. The withdrawal rate is a key parameter affecting the microstructure during the single crystal growth process. In the present work the effect of the withdrawal rate on the microstructure of a third-generation single crystal superalloy containing 6.8 ?wt% Re has been investigated, and the creep resistance of the alloy determined. The results showed that increased withdrawal rate refined the dendritic structure, reduced dendritic arm spacing, promoted the growth of secondary tertiary dendrites and decreased solidification segregation with a reduced size of γ′ phase. The porosity density of the as-cast alloy first decreased and then increased with the withdrawal rate, while the minimum porosity densityoccurred when the alloy was under the solidification condition of withdrawal rate of 4.5 ?mm/min. The maximum creep rupture life of 326.4 ?h of the heat-treated alloys under the test condition of 1100 ?°C/140 ?MPa also appeared at the alloys under the withdrawal rates of 4.5 ?mm/min. It is believed that the minimum porosity density and reduced size of the γ′ phase may be the main reasons for the enhanced creep rupture life of the alloys with withdrawal rates of 4.5 ?mm/min. This investigation provides theoretical support and a practical basis for the development of third-generation single crystal superalloys.     

Microstructure and stress rupture properties of polycrystal and directionally solidified castings of nickel-based superalloys

A new directionally solidified Ni-based superalloy DZ24, which is a modification of K24 alloy without rare and expensive elemental additions, such as Ta and Hf, was studied in this paper. The microstructure and stress rupture properties of conventionally cast and directionally solidified superalloys were comparatively analyzed. It is indicated that the microstructure of K24 alloy is composed of γ, γ′, γ/γ′ eutectics and MC carbides. Compared with the microstructure of K24 polycrystalline alloy, γ/γ′ eutectic completely dissolves into the γ matrix, the fine and regular γ′ phase reprecipitates, and MC carbides decompose to M₆C/M₂₃C₆ carbides after heat treatment in DZ24 alloy. The rupture life of DZ24 alloy is two times longer than that of K24 alloy. The more homogeneous the size of γ′ precipitate, the longer the rupture life. The coarsening and rafting behaviors of γ′ precipitates are observed in DZ24 alloy after the stress-rupture test.     

Activity coefficients of NiO and CoO in CaO-Al2O3-SiO2 slag and their application to the recycling of Ni-Co-Fe-based end-of-life superalloys via remelting

To design optimal pyrometallurgical processes for nickel and cobalt recycling, and more particularly for the end-of-life process of Ni-Co-Fe-based end-of-life (EoL) superalloys, knowledge of their activity coefficients in slags is essential. In this study, the activity coefficients of NiO and CoO in CaO-Al₂O₃-SiO₂ slag, a candidate slag used for the EoL superalloy remelting process, were measured using gas/slag/metal equilibrium experiments. These activity coefficients were then used to consider the recycling efficiency of nickel and cobalt by remelting EoL superalloys using CaO-Al₂O₃-SiO₂ slag. The activity coefficients of NiO and CoO in CaO-Al₂O₃-SiO₂ slag both show a positive deviation from Raoult's law, with values that vary from 1 to 5 depending on the change in basicity. The activity coefficients of NiO and CoO peak in the slag with a composition near B=(%CaO)/(%SiO₂)=1, where B is the basicity. We observed that controlling the slag composition at approximately B=1 effectively reduces the cobalt and nickel oxidation losses and promotes the oxidation removal of iron during the remelting process of EoL superalloys.     

In situ reaction mechanism of MgAlON in Al-Al2O3-MgO composites at 1700℃ under flowing N2

The Al-Al₂O₃-MgO composites with added aluminum contents of approximately 0wt%, 5wt%, and 10wt%, named as M₁, M₂, and M₃, respectively, were prepared at 1700℃ for 5 h under a flowing N₂ atmosphere using the reaction sintering method. After sintering, the Al-Al₂O₃-MgO composites were characterized and analyzed by X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The results show that specimen M₁ was composed of MgO and MgAl₂O₄. Compared with specimen M₁, specimens M₂ and M₃ possessed MgAlON, and its production increased with increasing aluminum addition. Under an N₂ atmosphere, MgO, Al₂O₃, and Al in the matrix of specimens M₂ and M₃ reacted to form MgAlON and AlN-polytypoids, which combined the particles and the matrix together and imparted the Al-Al₂O₃-MgO composites with a dense structure. The mechanism of MgAlON synthesis is described as follows. Under an N₂ atmosphere, the partial pressure of oxygen is quite low; thus, when the Al-Al₂O₃-MgO composites were soaked at 580℃ for an extended period, aluminum metal was transformed into AlN. With increasing temperature, Al₂O₃ diffused into AlN crystal lattices and formed AlN-polytypoids; however, MgO reacted with Al₂O₃ to form MgAl₂O₄. When the temperature was greater than (1640 ±10)℃, AlN diffused into Al₂O₃ and formed spinel-structured AlON. In situ MgAlON was acquired through a solid-solution reaction between AlON and MgAl₂O₄ at high temperatures because of their similar spinel structures.     

Effect of B2O3 on the aqueous tape casting and microwave properties of Li2O–Nb2O5–TiO2 ceramics

The effect of B2O3 addition on the aqueous tape casting, sintering, microstructure and microwave dielectric properties of Li2O-Nb2O5-TiO2 ceramics has been investigated. The tape casting slurries exhibit a typical shear-thinning behavior without thixotropy, but the addition of B2O3 increases the viscosity of the slurries significantly. It was found that doping of B2O3 can decrease the tensile strength, strain to failure and density of the green tapes. The sintering temperature could be lowed down to 900℃ with the addition of 2 wt% B2O3 due to the liquid phase effect. No secondary phase is observed. The addition of B2O3 does not induce much degradation on the microwave dielectric properties. Optimum microwave dielectric properties of εr 67, Q×f 6560 GHz are obtained for Li2O-Nb2O5-TiO2 ceramics containing 2 wt% B2O3 sintered at 900 1C. It represents that the ceramics could be promising for multilayer low-temperature co-fired ceramics (LTCC) application.     

Improved dehydriding property of polyvinylpyrrolidone coated Mg-Ni hydrogen storage nano-composite prepared by hydriding combustion synthesis and wet mechanical milling

In this work, polyvinylpyrrolidone(PVP) coated Mg_(95)Ni_5 nano-composites were prepared by hydriding combustion synthesis(HCS) plus wet mechanical milling(WM) with tetrahydrofuran(THF) and donated as WM-x wt% PVP(x = 1, 3, 5 and 7) respectively. The phase compositions, microstructures and dehydriding property, as well as the co-effect of PVP and THF were investigated in detail. XRD results showed that the average crystal size of MgH_2 in the milled Mg_(95)Ni_5 decreased from 23 nm without PVP to 18 nm with 1 wt% PVP. The peak temperature of dehydrogenation of MgH_2 in the milled Mg_(95)Ni_5 decreased from 293.0 ℃ without THF to 250.4 ℃ with THF. The apparent activation energy for decomposition of MgH_2 in WM-7 wt% PVP was estimated to be 66.94 kJ/mol, which is 37.70 kJ/mol lower than that of milled Mg_(95)Ni_5 without THF and PVP. PVP and THF can facilitate the refinement of particle size during mechanical milling process. Attributed to small particle sizes and synergistic effect of PVP and THF, the composites exhibit markedly improved dehydriding properties.     

衬底偏压对γ′-Fe4N薄膜磁性的影响

采用直流磁控溅射方法, 以Ar/N₂（N₂/(Ar+N₂)=10％）为放电气体, 在Si(100)单晶衬底上获得了γ′-Fe₄N薄膜样品. 利用X射线衍射(XRD)和振动样品磁强计(VSM)研究衬底偏压对γ′-Fe₄N薄膜样品的影响. 结果表明, 随着衬底负偏压的增大, γ′-Fe₄N薄膜样品的晶胞参数减小, Fe和N的化合效率与样品的致密度提高, 表面缺陷减少, 矫顽力降低.      

Effect of long-term aging treatment on the tensile strength and ductility of GH 605 superalloy

Aging treatment is an effective way to optimize the mechanical properties of Co-based superalloys. In this study, commercial GH 605 superalloy was subjected to aging treatment at 650 ?°C in a wide time range up to 1000 ?h. The effects of aging time on the tensile characteristics, microstructure evolution and mechanical properties were systematically investigated at room temperature (RT) and 900 ?°C. The results showed that the volume fractions of M₆C and M₂₃C₆ carbide increased with the aging time. After long-term aging treatment, the yield strength (YS) at RT was enhanced from 490.3 ?MPa to 805.9 ?MPa, while the alloy still had high tensile ductility (above 20%). Microscopic observations by transmission electron microscopy (TEM) indicated that the strengthening mechanism was related to carbide precipitation inside the grains and the change in the dislocation slipping mode. Moreover, long-term aging treatment can increase the elongation from 24.1% to 47.3% at 900 ?°C accompanied by a slight increase of YS from 299.3 ?MPa to 313.9 ?MPa. Based on detailed microstructure analysis the strengthening mechanism can be attributed to the refined grains as well as carbide precipitation inside the grains and around the grain boundaries.     

硼粉粒度对Li-B合金结构及热稳定性的影响

分别以3种粒度的硼粉为原料,采用相同的成分配比和工艺参数熔炼制备Li-B合金铸锭。合金铸锭经挤出和轧制获得薄带。随后进行X射线衍射（XRD）测试、扫描电子显微镜（SEM）观察、化学成分分析和热稳定性测试。XRD结果显示,Li-B合金由Li₇B₆相和锂相组成,且Li₇B₆相与锂相的衍射峰强度比随硼粉粒度的增大而减小。SEM观察表明,随原料硼粉粒度的增大,Li-B合金的纤维组织变得粗大且不均匀。化学成分测试显示,Li-B合金中化合态硼含量随硼粉粒度的增大而减小。热稳定性测试表明,原料硼粉的粒度越大,Li-B合金的热稳定性越差。     

Influence of laser scanning speed on Cu-Zr-Al composite coatings on Mg alloys

To improve the surface properties of magnesium alloys, a study was conducted on Cu-Zr-Al composite coatings on AZ91HP magnesium alloy by laser cladding. The influence of laser scanning speed on the microstructures and properties of the coatings was discussed. The coatings consist of amorphous phase, Cu8Zr3, and Cu10Zr7. With the increase of laser scanning speed, the amorphous phase content of the coatings increases and reaches 60.56wt% with the laser scanning speed of 2.0 m/min. Because of the influence of laser scanning speed on the amorphous and crystal phases, the coatings show the maximum elastic modulus, hardness, and wear resistance at the laser scanning speed of 1.0 m/min. At the laser scanning speed of 2.0 m/min, the coatings have the best corrosion resistance.     

Growth characteristics of directionally solidified Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/YAG/ZrO<Subscript>2</Subscript> ternary hypereutectic <Emphasis Type="Italic">in situ</Emphasis> composites under ultra-high temperature gradient

Oxide eutectic ceramic in situ composites have attracted significant interest in the application of high-temperature structural materials because of their excellent high-temperature strength, oxidation and creep resistance, as well as outstanding microstructural stability. The directionally solidified ternary Al₂O₃/YAG/ZrO₂ hypereutectic in situ composite was successfully prepared by a laser zone remelting method, aiming to investigate the growth characteristic under ultra-high temperature gradient. The microstructures and phase composition of the as-solidified hypereutectic were characterized by using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and X-ray diffraction (XRD). The results show that the composite presents a typical hypereutectic lamellar microstructure consisting of fine Al₂O₃ and YAG phases, and the enriched ZrO₂ phases with smaller sizes are randomly distributed at the Al₂O₃/YAG interface and in Al₂O₃ phases. Laser power and scanning rate strongly affect the sample quality and microstructure characteristic. Additionally, coarse colony microstructures were also observed, and their formation and the effect of temperature gradient on the microstructure were discussed.     

Effects of boron on the microstructure and thermal properties of Cu/diamond composites prepared by pressure infiltration

Diamond reinforced copper (Cu/diamond) composites were prepared by pressure infiltration for their application in thermal management where both high thermal conductivity and low coefficient of thermal expansion (CTE) are important. They were characterized by the microstructure and thermal properties as a function of boron content, which is used for matrix-alloying to increase the interfacial bonding between the diamond and copper. The obtained composites show high thermal conductivity (>660 W/(m·K)) and low CET (<7.4×10-6 K-1) due to the formation of the B₁₃C₂ layer at the diamond-copper interface, which greatly strengthens the interfacial bonding. Thermal property measurements indicate that in the Cu-B/diamond composites, the thermal conductivity and the CTE show a different variation trend as a function of boron content, which is attributed to the thickness and distribution of the interfacial carbide layer. The CTE behavior of the present composites can be well described by Kerner’s model, especially for the composites with 0.5wt% B.