Fabrication and performances of WC-Co cemented carbide with a low cobalt content

WC-Co cemented carbides with a low cobalt content (≤3 wt.%) were successfully manufactured by the powder metallurgy method. The cobalt content is lower than conventional cemented carbide (3–30 wt.%), which makes the prepared alloys possess excellent hardness. The effects of cobalt content on the densification behavior, phase composition, micromorphology, and mechanical performances of cemented carbides were investigated in detail. The results revealed that all the sintered alloys were almost completely consolidated with a relative density of greater than 98.0%. Moreover, abnormal grain growth was observed, and the inhomogeneity of WC grains decreased with the increment in cobalt content. In order to obtain cemented carbides with homogeneous microstructure and outstanding performances, VC was added to inhibit grain growth. Microstructure and performances were significantly affected by the addition of VC. The maximum Vickers hardness of cemented carbides without the addition of vanadium was 2234 HV30, while the fracture toughness was 7.96 MPa·m^1/2 after sintering WC-2 wt.%Co. After adding VC, the ultimate hardness and fracture toughness of WC-3 wt.%Co-0.5 wt.%VC alloy could reach 2200 HV30 and 8.61 MPa·m^1/2, respectively. In addition, the obvious crack deflexion and transgranular behavior can be noticed, which can prevent the extension of crack and achieve an increase in fracture toughness of cemented carbides.     

Stabilization of 6H-Hexagonal SrMnO3 Polymorph by Al2O3 insertion

We demonstrate the structural evolution of polymorphic phases in Al₂O₃-inserted SrMnO₃ ceramics synthesized by solid state reaction. While the 4H-hexagonal phase is predominant in pure SrMnO₃ ceramics, a small amount of 6H-hexagonal polymorph is identified in addition to the primary 4H-hexagonal SrMnO₃ and the secondary hexagonal SrAl₂O₄ phases in the as-sintered ceramics, evidenced by x-ray diffraction and subsequent Rietveld refinement analyses. The existence of the 6H-hexagonal SrMnO₃ phase is corroborated using Raman spectroscopy. The chemical compositions and electronic structures of the Al₂O₃-inserted SrMnO₃ compounds are also examined using energy dispersive spectroscopy and x-ray photoelectron spectroscopy, respectively. The first-principles calculations reveal that there is no clear difference between the total energies of 4H- and 6H-hexagonal polymorphs regardless of the presence/absence of Sr and oxygen vacancies. Possible origins are discussed with the estimation of actual strain based on the refined lattice parameter of 6H SrMnO₃.     

Growth,characterization and thermo-mechanical analysis of Al/Al2O3 core/shell nanoparticles obtained under H2 atmosphere

In this work, growth, characterization and thermo-mechanical behavior of Al/Al₂O₃ core/shell nanoparticles (NP) is performed. The growth was carried out by gas condensation methods using H₂ as carrier gas at a pressure of 100 Pa and with a temperature of the evaporation source of 1315 °C. The prepared NP were characterized by Energy Dispersive X-ray Spectroscopy for chemical information, transmission electron microscopy for morphological study, and electron diffraction patterns for structural information. The prepared Al NP exhibit a thin Al₂O₃ passivating oxide shell due to the air exposure when removed from the preparation vacuum chamber. Afterwards, the growth of the Al₂O₃ oxide shell of the Al NP and the thermo-mechanical interaction between this growing oxide shell and its Al core was studied by performing in-situ thermal X-ray diffraction from RT up to 505 °C. Coefficients of thermal expansion of both Al core and Al₂O₃ oxide shell were obtained by means of X-ray strain analysis. It was found that the thickness of the Al₂O₃ shell increases with temperature and the thermal stress induced in the system increases linearly with temperature. Our results highlight that these NP overcome higher values of fracture toughness compared with Al₂O₃ NP used in micro-nano composites, thus improving their mechanical properties for nanofluid applications.     

Thermodynamic Modeling of the HfO2–La2O3–Al2O3 System

Based on phase equilibria, thermodynamic, and crystal structure data, the thermodynamic modeling of HfO₂–La₂O₃–Al₂O₃ system is presented. Liquid phase is described by the modified quasichemical model considering the short‐range ordering in liquid solution. Solid solutions are described by the ionic sublattice model considering respective crystal structure. The model (La³⁺, Hf⁴⁺)₂(Hf⁴⁺, La³⁺)₂(O^2?, Va)₆(O^2?)₁(Va, O^2?)₁ successfully describes the structure defect, homogeneity range, and thermodynamic property of pyrochlore solid solution. A set of optimized model parameters is obtained which reproduces most experimental data well. Isothermal sections, liquidus and solidus projections, and Scheil reaction scheme are constructed.     

液相法制备棒状Al2O3及Al2O3-ZrO2陶瓷复合粉体

采用二乙三胺五乙酸（DTPA）为配合剂,以简易的液相法合成出微纳米纤维状Al和Al-Zr前体,煅烧处理制备了棒状α-Al₂O₃和Al₂O₃-ZrO₂复合陶瓷粉体。同时研究了DPTA∶Al³⁺质量比、反应温度与时间对陶瓷粉体形态的影响。利用X射线衍射（XRD）、热分析（TG/DSC）以及扫描电子显微镜（SEM）对粉体进行了表征。结果表明：较高的DTPA∶Al³⁺质量比以及较长的反应时间有利于制备高长径比的纤维棒状Al和Al-Zr配合物前体。合成纳米纤维状α-Al₂O₃和Al₂O₃-ZrO₂前体的最优条件是反应温度60℃,反应时间5.5h,DTPA∶Al³⁺比例为1.2∶1。相应地,该前体煅烧后可以制备出棒状α-Al₂O₃和Al₂O₃-ZrO₂复合陶瓷粉体。     

反应结合Al2O3—ZrO2—SiC复合陶瓷的制备工艺与性能

采用反应结合技术研究了Ａｌ２Ｏ３－ＺｒＯ２－ＳｉＣ复合陶瓷的制备工艺与材料性能，比较孙同的原料来源对致密化行为及材料性能的影响，含细Ａｌ２Ｏ３和粗ＳｉＣ的配方获得了最快的致密化速率及最高的烧结密度，该材料经１５５０℃烧结３０ｍｉｎ后再热等静压获得了近１００％的致密度和７６０ＭＰａ的弯曲强度。     

Pt-Sn/Al2O3 sol-gel catalysts: Metallic phase characterization

Highly dispersed platinum was found in Pt-Sn/Al₂O₃ catalysts prepared by the sol-gel method, i.e., cogelation of aluminum tri-sec-butoxide and tetrabutyltin and subsequent impregnation with hexachloroplatinic acid. X-ray diffraction studies showed that the cell parameter of pure platinum is not modified in bimetallic Pt-Sn samples. Moreover, energy dispersive X-ray analysis studies (EDX) showed that platinum, but not tin, was detected in the catalysts where tin was incorporated by the sol-gel coprecipitation of tin and aluminum. Incorporation of tin into the alumina network is suggested.     

Al2O3/Al2O3-ZrO2(3Y)层状纳米陶瓷复合材料的显微结构及弯曲强度

在Al2O3-ZrO2(3Y,即含3%Y2O3,摩尔分数,下同)纳米陶瓷的基础上,以原位合成的Al2O3和Al2O3-ZrO2(3Y)纳米粉体为原料,采用干压成型及热压烧结的方法制备了Al2O3/Al2O3-ZrO2(3Y)层状纳米陶瓷复合材料,研究了ZrO2(3Y)含量对材料显微结构及力学性能的影响.结果表明:复合材...     

Al2O3/Cu的界面微观结构及封接性能

采用活化Mo-Mn法和活性金属钎焊(AMB)工艺对Al₂O₃陶瓷进行金属化处理,分别研究了两种金属化工艺的界面形貌、新相的形成及显微结构的演变,并测试了Al₂O₃/Cu的力学性能和气密性。研究表明:采用活化Mo-Mn法的封接界面处出现玻璃相的迁移,形成了立方相MnAl₂O₄,可以提高封接强度。AMB工艺中活性元素Ti与Al₂O₃反应依次形成厚度为0.64 μm的TiO和1.03 μm的Cu₃Ti₃O。各层间热膨胀系数(CTE)的差异给钎焊接头提供了良好的热弹性相容性且降低了残余应力。活化Mo-Mn法的封接强度((60.2±7.7) MPa)比AMB工艺((43.1±6.9) MPa)高,但在气密性方面两者并无明显差别(均在2.3×10^-11 Pa·m³·s^-1左右)。     

Phase development of phosphate-bonded Al2O3-MgAl2O4 high-temperature ceramics: XRD and solid-state NMR investigations

This article describes investigations on the phase development (T ≤ 1500℃) of phosphate-bonded Al₂O₃-MgAl₂O₄ high-temperature ceramics by a combination of solid-state MAS NMR and X-ray diffraction analyses. The ceramic body was bonded with inorganic hydrogen orthophosphates (Al, Mg, Ca, Zr) with a total binder content of 3 wt.% P₂O₅. The binding mechanisms of these phosphate-bonded ceramics could be extensively deduced by analyses of phase developments during hardening, strength development, and high-temperature phase formation at T ≤ 1500℃: The formation of a network of aluminum phosphate compounds by acid and condensation reactions of the phosphate with the ceramic body is proven to be the active binding process. The binding process is initiated by the formation of active phosphoric acid phosphate phases, which in principle prerequisites water solubility of the binder. Thermal treatment, especially at T ≤ 600℃, promotes the degree of P-cross-linking of the phosphate structures. In addition to these phosphate-ceramic reactions, it was also possible to identify parallel pure phosphate–phosphate conversions of the initial phosphates (via condensation and polymerization) without reactions with ceramic components. The contribution of these structures to the binding effect can be estimated to be minor. Only at temperatures of T ≥ 600℃, these Ca, Mg and Zr phosphates begin to react with the ceramic material to form aluminum phosphates. The phosphate bond has a permanent effect until the formation of the ceramic bond (T > 1000℃). High-temperature phases are usually crystalline PO₄-sintered structures which are formed by reaction with MgAl₂O₄.     

Tribological behavior of GNPs doped Al2O3 coating fabricated by SHVOF thermal spraying on cemented carbide

This paper aims to experimentally investigate the effect of graphene nanoplatelets (GNPs) doped Al₂O₃ coating deposited on the surface of cemented carbide substrate using suspension high velocity oxy fuel (SHVOF) thermal spraying technique. Scanning electron microscopy was applied to characterize GNPs doped Al₂O₃ feedstock, the surface morphologies of cemented carbide before and after spraying, and the wear track morphology of cemented carbide after wear tests. The phases of GNPs doped Al₂O₃ feedstock, uncoated and coated cemented carbide were analyzed by X-ray diffraction. The existence of GNPs was analyzed by Raman spectroscopy. A mixture of un-molten and molten splats formed on the surface of cemented carbide substrate after SHVOF thermal spray. The average coefficient of friction (CoF) of coated samples was slightly lower than that of uncoated samples, which might be due to the friction-reduction effect of GNPs. The wear rate of the samples was one order of magnitude higher than that of the alumina ball, showing that the wear of samples was the main wear between the friction couples. The wear mechanism of uncoated sample was mainly fatigue spalling, and that of cemented carbide substrate coated with GNPs doped Al₂O₃ coating was mainly plowing and abrasive wear.     

Measurement of thermal residual stresses in ZrB2-SiC composites

Neutron diffraction, Raman spectroscopy, and x-ray diffraction were employed to measure the stresses generated in the ZrB₂ matrix and SiC dispersed particulate phase in ZrB₂-30 vol% SiC composites produced by hot pressing at 1900 °C. Neutron diffraction measurements indicated that stresses begin to accumulate at ∼1400 °C during cooling from the processing temperature and increased to 880 MPa compressive in the SiC phase and 450 MPa tensile in the ZrB₂ phase at room temperature. Stresses measured via Raman spectroscopy revealed the stress in SiC particles on the surface of the composite was ∼390 MPa compressive, which is ∼40% of that measured in the bulk by neutron diffraction. Grazing incidence x-ray diffraction was performed to further characterize the stress state in SiC particles near the surface. Using this technique, an average compressive stress of 350 MPa was measured in the SiC phase, which is in good agreement with that measured by Raman spectroscopy.     

Al2O3-ZrO2-CeO2系陶瓷的微观组织结构及强度性能

列出了对在Al_2O_3-ZrO_2-CeO_2(Al_2O_3 50%克分子)系中在粉料早期产物凝胶体合成的过程中,各组份的沉淀顺序对相关陶瓷材料的形态及微观组织结构的影响的研究结果。表明了陶瓷的强度和操作使用性能与微观组织结构尺寸因素之间的依存关系。查明,利用早期产物各组份同时沉淀的方法合成的粉料制造的刀具拥有更高的切削寿命。     

Microstructural evolution during the brazing of Al2O3 ceramic to kovar alloy by sputtering Ti/Mo films on the ceramic surface

Alumina (Al₂O₃) ceramics were metallized by magnetron sputtering Ti/Mo bilayer films on the surface with a subsequent high temperature sintering and were brazed to Kovar alloy (Fe-Ni-Co) using Ag-Cu eutectic alloy. The Ti/Mo metallization film and the brazing seam microstructures were investigated and the correlation between the Al₂O₃/Kovar joining strength and the microstructures of the brazing seam was discussed. The results show that the joining strength is related to the thickness of the Ti/Mo adhension layer which depends on the holding time during brazing. The mutual diffusion of the elements at the interface firstly increases the thickness of the adhension layer as the holding time increases and the Mo film acts as a barrier layer to block the diffusion of Ti atoms into the seam. The optimal brazing joining strength of 72.6±5.0 MPa could be achieved at a brazing temperature of 810 °C for 14 min However, if the holding time is further prolonged, Mo atoms will diffuse into the (Ni, Cu) solid solution, resulting in the diffusion of Ti atoms and the adhension layer becoming indistinguishable. Therefore, the intermetallic Ni₃Ti forms in the seam and the titanium oxide changes from TiO to Ti₂O₃ or Ti₃O₅, which leads to the joint strength decreasing.     

Thermodynamic assessment of the pseudoternary Na2O–Al2O3–SiO2 system

Vitrified high‐level radioactive waste that contains high concentrations of Na₂O and Al₂O₃, such as the waste stored at the Hanford site, can cause nepheline to precipitate in the glass upon cooling in the canisters. Nepheline formation removes oxides such as Al₂O₃ and SiO₂ from the host glass, which can reduce its chemical durability. Uncertainty in the extent of precipitated nepheline necessitates operating at an enhanced waste loading margin, which increases operational costs by extending the vitrification mission as well as increasing waste storage requirements. A thermodynamic evaluation of the Na₂O–Al₂O₃–SiO₂ system that forms nepheline was conducted by utilizing the compound energy formalism and ionic liquid model to represent the solid solution and liquid phases, respectively. These were optimized with experimental data and used to extrapolate phase boundaries into regions of temperature and composition where measurements are unavailable. The intent is to import the determined Gibbs energies into a phase field model to more accurately predict nepheline phase formation and morphology evolution in waste glasses to allow for the design of formulations with maximum loading.     

锆莫来石对Al2O3-ZrO2-C材料性能的影响

以电熔白刚玉、锆莫来石、鳞片石墨、SiC粉和酚醛树酯为原料,通过改变锆莫来石的加入量和粒度制备了7种不同的A l2O3-ZrO2-C试样,主要研究了锆莫来石加入量和试样的粒度组成对A l2O3-ZrO2-C材料的体积密度、显气孔率、常温耐压强度、气孔孔径分布和透气度等性能的影响。结果表明:1)锆莫来石加入量对A l2O3-ZrO2-C材料的体积密度、显气孔率、耐压强度、气孔孔径分布和透气度都有一定的影响,但影响都不大;2)试样的粒度组成对A l2O3-ZrO2-C材料的体积密度和透气度的影响较大,但对显气孔率、常温耐压强度、气孔孔径分布的影响较小。     

On the growth and structure of Al2O3-Y3Al5O12-ZrO2:Y solidified eutectic

Structural features of Al₂O₃-YAG-ZrO₂:Y eutectic plates grown by the EFG process have been studied. X-ray tomography shows that all three phases are continuous along the whole sample, suggesting a fully coupled ternary eutectic growth. However the growth of alumina and YAG is well described by a classical binary coupled growth, in spite of the facetted structure of their growth interface. Colonies are observed at high growth rate and have been related to the chemical rejection of zirconium ions at the solid-liquid interface, possibly due to a slight off-stoechiometry of the raw material.     

新型合成气甲烷化催化剂La2O3-ZrO2-Ni/Al2O3的制备与性能

针对常规合成气甲烷化催化剂高热结构稳定性差、活性低、适应性差等不足,本文创新地引用稀土金属氧化物La₂O₃复配过渡金属氧化物ZrO₂作为多功能复合助剂,利用反向沉淀法制备了新型合成气甲烷化催化剂La₂O₃-ZrO₂-Ni/Al₂O₃,同时制备催化剂Cr₂O₃-Ni/Al₂O₃作为参照组。采用X射线衍射（XRD）、透射电子显微镜（TEM）表征了催化剂的微观结构,并利用N₂吸附仪（BET）测量催化剂经高温水热处理前后的微孔结构参数,以考察催化剂的高热结构稳定性。结合国内某大型煤制天然气项目工艺特征和运行实践,应用Aspen Plus软件模拟了四段甲烷化工艺理论平衡值。基于自主固定床合成气甲烷化评价实验装置,考察了反应压力、空速和原料气H₂O(g)含量等因素对La₂O₃-ZrO₂-Ni/Al₂O₃催化性能的影响,并开展了1000h长周期寿命评价实验。结果表明,La₂O₃-ZrO₂-Ni/Al₂O₃比Cr₂O₃-Ni/Al₂O₃具有更优的高热结构稳定性;可使CO和CO₂反应达到或接近催化剂床层出口温度下的理论平衡状态,呈现显著的宽温活性;活性组分NiO晶粒尺寸介于7~10nm,分散度较高;对反应压力、空速和原料气H₂O(g)含量的变化不敏感,具有良好的操作弹性;1000h反应后仍能保持较高的活性和稳定性。     

铝锆碳质转炉挡渣闸阀开发与应用

主要研究了膨胀石墨含量对低碳铝碳耐火材料的显微结构,力学性能和抗热震性的影响;在此基础上选择合适含量的膨胀石墨引入铝锆碳质转炉挡渣闸阀中,考察了转炉挡渣闸阀的现场服役行为.结果表明:膨胀石墨引入铝碳耐火材料中有助于促进碳化硅晶须的生长;正是由于碳化硅晶须以及膨胀石墨自身的强韧化作用,铝碳耐火材料热震后的残余强度由空白样的4.87 MPa提高至9.31 MPa,残余强度保持率由38%提高至54%.工业试验结果显示引入0.5wt%膨胀石墨的铝锆碳质转炉挡渣闸阀的平均使用寿命较传统滑板提高0.77次.     

炭黑包裹燃烧法制备Al_2O_3-ZrO_2复合粉

研究了采用炭黑包裹燃烧法制备Al2O3-ZrO2复合粉体溶液pH值和炭黑氧化温度对复合粉体制备团聚及粒度组成的影响。结果表明:pH值控制为3,经过500℃×10h+600℃×2h脱炭后制得的粉体粒径最小,通过激光粒度分布仪测定得Al2O3-ZrO2复合粉体粒径分布均匀,d10=0.6μm,d50=2.06μm,平均粒径为2.62μm,复合粉体的比表面积为440m2/cm3。