Synthesis of nanostructured WC-12 pct Co coating using mechanical milling and high velocity oxygen fuel thermal spraying

A nanostructured WC-12 pct Co coating was synthesized using mechanical milling and high velocity oxygen fuel (HVOF) thermal spraying. The variation of powder characteristics with milling time and the performance of the coatings were investigated using scanning electron microscope (SEM), X-ray, transmission electron microscope (TEM), thermogravimetric analyzer (TGA), and microhardness measurements. There is no evidence that indicates the presence of an amorphous phase in the sintered WC-12 pct Co powder, and the binder phase in this powder is still crystalline Co. Mechanical milling of up to 20 hours did not lead to the formation of an amorphous phase in the sintered WC-12 pct Co powder. During the initial stages of the milling, the brittle carbide particles were first fractured into fragments and then embedded into the binder phase. This process gradually formed polycrystal nanocomposite powders of the Co binder phase and W carbide particles. The conventional cold welding and fracturing processes primarily occurred among the Co binder powders and polycrystal composite powders. The nanostructured WC-12 pct Co coatings, synthesized in the present study, consist of an amorphous matrix and carbides with an average particle diameter of 35 nm. The coating possesses an average microhardness of 1135 HV and higher resistance to indentation fracture than that of its conventional counterpart.     

WC粒度对超音速火焰喷涂WC-10Co-4Cr涂层耐腐蚀性能的影响

采用制粒?高温快速烧结法制备两种分别含亚微米级和微米级WC粒径的WC-10Co-4Cr喷涂粉末,并用超音速火焰喷涂(HVOF)技术在45#钢基体上制备涂层;利用扫描电子显微镜和电化学工作站分别对涂层的显微形貌及耐腐蚀性能进行分析检测,探讨WC粒度对涂层耐腐蚀性能的影响和涂层的电化学腐蚀机理。研究结果表明：两种涂层组织致密,界面结合良好;含亚微米级WC粒径的涂层具有相对较低的孔隙率,使其涂层的耐腐蚀性能优于含微米级WC粒径的涂层。在3.5%NaCl溶液中涂层的硬质相WC和粘结相Co发生电偶腐蚀,且低电位的Co相优先腐蚀,导致WC颗粒脱落,出现凹坑及点蚀现象。     

Interfacial reaction-controlled reprecipitation of W atoms in liquid matrix phase during the sintering of W-8 pct Mo-7 pct Ni-3 pct Fe

Microstructural evolution and variation in phase composition of W-8 pct Mo-7 pct Ni-3 pct Fe alloy were investigated with respect to various isothermal holding times, ranging from 5 to 240 minutes, at a sintering temperature of 1480 °C. Mass transfer was found to proceed actively in both the liquid matrix phase and the tungsten-based solid phase during the initial stage of the isothermal hold. Formation of large jagged grains was found to be a result of excessive interdiffusion between molybdenum and tungsten. The jagged grains gradually developed into spheroidal grains with the reprecipitation of supersaturated tungsten atoms in the liquid matrix phase, which also resulted in crystallization of the matrix phase with less lattice dilation during cooling. Based on model fitting, reprecipitation of tungsten atoms from the liquid matrix phase to grains is proposed to be controlled by a first-order interfacial reaction.     

WC粉末粒度对超音速火焰喷涂WC-CoCr涂层组织性能的影响

采用超音速火焰喷涂(HVOF)工艺制备了纳米结构、双峰结构和常规结构3种WC-CoCr复合涂层。探讨了不同WC粉末粒度对涂层沉积过程的脱碳行为、涂层微观组织及力学性能的影响。结果表明:随WC颗粒尺寸减小,涂层脱碳率增大,W_2C含量增加,孔隙率降低,涂层的显微硬度和界面结合强度增大;但是纳米结构涂层中粘结相的非晶化现象严重,断裂韧度显著下降;双峰结构涂层因纳米、亚微米WC颗粒的合理搭配和协同效应表现出最好的断裂韧性,同时兼具较高的显微硬度和界面结合强度。     

Precipitation of Fe2W laves phase and modeling of its direct influence on the strength of a 12Cr-2W steel

Precipitation of Fe₂W Laves phase in a 12Cr-2W power plant steel is investigated by using transmission electron microscopy (TEM). Fe₂W Laves phase is found to be coherent with the matrix and has a stacking fault structure. The influence of formation of Fe₂W Laves phase on the yield strength of the steel is quantitatively evaluated. The modeling result indicates that the strengthening effect from the formation of Laves phase particles is diminished by the loss of solid solution strengthening of alloying elements, and, as a result, the strength of the steel remains similar. The effect of clustering and coarsening of Laves precipitates on the strength of the steel is also studied. It is showed that clustering and coarsening decreases the strengthening effect of Laves phase. The limitation of the modeling approach currently adopted is also discussed.     

Free energies of formation of WC and W2C,and the thermodynamic properties of carbon in solid tungsten

The activity of carbon in the two-phase regions W + WC and W + W₂C has been obtained from the carbon content of iron rods equilibrated with mixtures of metal plus carbide powders. From this activity data the standard free energies of formation of WC and W₂C have been calculated to be ΔG _f ⁰(WC) = -10,100 + 1.19T ± 100 cal/mole (-42,300 + 4.98T ± 400 J/mole) (1150 to 1575 K) ΔG _f ⁰(W₂C) = - 7300 - 0.56T ± 100 cal/mole (- 30,500 - 2.34T ± 400 J/mole). (1575 to 1660 K) The temperature of the eutectoid reaction W₂C = W + WC was fixed at 1575 ± 5K. Using available data for the solubility of C in solid W, the relative partial molar free energy of C in the dilute solid solution was calculated to be $$\Delta \bar G_C^\alpha {\text{ = 23,000 }} - {\text{ }}[{\text{0}}{\text{.68 }} - R\ln X_C^\alpha ]{\text{ }}T \pm 3000 cal/mole (96,200 - [2.85 - R\ln X_C^\alpha ]{\text{ }}T \pm 12,600 J$$ The heat solution of C in W obtained was \(\Delta \bar H_C^\alpha {\text{ = 23,000 }} \pm {\text{ 5000 cal/mole (96,200 }} \pm {\text{ 20,000 J/mole)}}\) and the excess entropy for the interstitial solid solution, assuming that the carbon atoms are in the octahedral sites, \(\Delta \bar S_C^\alpha {\text{ = (}}xs,i{\text{) }} = - {\text{1}}{\text{.5 }} \pm {\text{ 2 cal/deg - mole (}} - {\text{6}}{\text{.3 }} \pm {\text{ 8 J/deg - mole)}}\) .     

Characterization of sulfur-centered radical intermediates formed during the oxidation of thiols and sulfite by peroxynitrite. ESR-spin trapping and oxygen uptake studies

Using a novel phosphorylated spin trap, 5-diethoxy-phosphoryl-5-methyl-1-pyrroline N-oxide (DEPMPO), an analog of the commonly used trap 5,5'-dimethyl-1-pyrroline N-oxide (DMPO), we have investigated the reactions of sulfur-centered radicals produced from the oxidation of thiols and sulfite by peroxynitrite. The predominant species trapped in all cases are the corresponding sulfur-centered radicals, i.e. glutathionyl radical (GS) from glutathione (GSH), N-acetyl-DL-penicillamine thiyl radical (S-NAP) from N-acetyl-DL-penicillamine (NAP) and sulfate anion radical (SO3-) from sulfite. These radicals consume molecular oxygen forming either peroxyl or superoxide anion radicals. GS, S-NAP, and (SO3-)-derived radicals react with ammonium formate to form the carbon dioxide anion radical (CO2-). Further support of spin adduct assignments and radical reactions are obtained from photolysis of S-nitrosoglutathione and S-nitroso-N-acetyl-DL-penicillamine. We conclude that the direct reaction of peroxynitrite with thiols and sulfate forms thiyl and sulfate anion radicals, respectively, by a hydroxyl radical-independent mechanism. Pathological implications of thiyl radical formation and subsequent oxyradical-mediated chain reactions are discussed. Oxygen activation by thiyl radicals formed during peroxynitrite-mediated oxidation of glutathione may limit the effectiveness of GSH against peroxynitrite-mediated toxicity in cellular systems.     

Evaluation of the surface tension of tungsten carbides WC and WC-W2C by the results of the laser diffraction analysis of their milling with iron powder

The data on the experimental determination of surface tension coefficients (σ) of tungsten carbides WC and WC-W₂C by the force of simultaneous grinding their powders with iron powder in a RM 400 planetary mill are presented. Coefficients σ are evaluated and confidence intervals of their expected values are determined.     

On the transition from pushing to engulfment during directional solidification of the particle-reinforced aluminum-based metal-matrix composite 2014+10 vol pct Al2O3

Microstructural evolution in the commercial aluminum-based metal matrix composite 2014+10 vol pct Al₂O₃ was investigated during directional solidification with planar interface within the initial transient. Investigations were directed toward phase formation and phase distribution, with special emphasis on the critical conditions for the transition from particle pushing to engulfment. In situ nucleation of intermetallic particles, identified as being the complex silicides (Fe, Mn)₃Si₂Al₁₅, their growth, pushing, and subsequent engulfment are shown to be interactively coupled to the pushing and engulfment of the inert alumina particles. The experimental conditions for engulfment of the inert particles are in good agreement with predictions according to the “critical velocity” model of Pötschke and Rogge, the critical velocities ranging from 0.3 to 1.0 μm/s, due to the effect of the solutal field. This indicates that in castings with equiaxed dendritic solidification patterns, the radial growth velocities are not necessarily responsible for pushing the particles into the interdendritic spaces. For the intermetallic particles, the dependence of the critical velocity on particle size is not linear as for inert particles, but deflected upward for increasing size. This is probably due to the fact that they act as a sink for certain species of segregated solute atoms, meaning that size and solutal distortions are reactively coupled.     

Vaccinia virus induces Ca2+-independent cell-matrix adhesion during the motile phase of infection

Vaccinia virus (VV) induces two forms of cell motility: cell migration, which is dependent on the expression of early genes, and the formation of cellular projections, which requires the expression of late genes. The need for viral gene expression prior to cell motility suggests that VV proteins may affect how infected cells interact with the extracellular matrix. To address this, we have analyzed changes in cell-matrix adhesion after infection of BS-C-1 cells with VV. Whereas uninfected cells round up and detach from the culture flask in the presence of EGTA, infected cells remain attached to the culture flask with a stellate morphology. Ca2+-independent cell-matrix adhesion was evident by 10 h postinfection, after the onset of cell motility but before the formation of virus-induced cellular projections. Progression to Ca2+-independent adhesion required the expression of late viral genes but not the formation of intracellular enveloped virus particles or intracellular actin tails. Analyses of specific matrix proteins identified vitronectin and fibronectin as optimal ligands for Ca2+-independent adhesion and the formation of cellular projections. Adhesion to fibronectin was mediated via RGD motifs alone and was not inhibited by 500 micrograms of heparin/ml. Kistrin, a disintegrin which binds preferentially to the alphav beta3 (vitronectin/fibronectin) receptor inhibited the formation of cellular projections without disrupting preformed matrix interactions. Finally, we show that Ca2+-independent cell-matrix adhesion is a dynamic process which mediates changes in the morphology of VV-infected cells and uninfected cells which exhibit a transformed phenotype.     

Thermal analysis of the compositional shift in a transient liquid phase during sintering of a ternary Cu-Sn-Bi powder mixture

In this work, differential scanning calorimetry (DSC) and microstructural analysis were used to study the transient-liquid-phase sintering (TLPS) of a Cu-Sn-Bi powder mixture. During sintering, the liquid phase shifts from a Sn-rich (i.e., ∼90 wt pct Sn) to a Bi-rich (i.e., >78 wt pct Bi) composition. In addition, the presence of Bi creates two melting events: a Sn:Bi eutectic reaction at 139 °C and a reaction involving the melting of (Bi) at 191 °C. The Sn:Bi eutectic melting event was fully transient. The melting event at 191 °C was consistent with the formation of a terminal Bi-rich liquid phase. The rate of compositional shift toward this terminal liquid phase at 260 °C was dependent on the rate of the reaction of the Sn with the Cu powder to form intermetallic phases. For mixtures made with medium and fine Cu powder, the terminal Bi-rich composition was reached after isothermal hold times of 20 and 15 minutes, respectively. This resulted in a new melting point for the mixture of 191 °C. For coarse Cu powders, the rate of the compositional shift toward a Bi-rich composition was much slower. The liquid phase remained at a hypoeutectic Sn-Bi composition estimated at 80 wt pct Sn, while the mixture maintained a melting point of 139 °C.     

基于基元反应动力学观点的CO／H2／N2燃气高温低氧燃烧的数值模拟

应用FLUENT软件,采用k-ε模型对CO/H2/N2的湍流高温低氧燃烧进行模拟,得到不同空气预热温度下温度场、流场、组分分布特性及变化规律.针对模拟结果,从自由基基元反应动力学理论出发,采用详细的化学反应模型,结合Kintecus化学计算软件进行煤气高温低氧燃烧的数值模拟,得出火焰温度、各种自由基浓度、NOx浓度等变化规律.结合两方面分析结果找出变化规律,为实际燃烧中污染物的有效控制提供理论依据.     

Ordering in the carbide W2C and phase equilibria in the tungsten — carbon system in the region of its existence

We have studied alloys in the W - C system with compositions 24 to 48 at.% C, melted in an arc furnace, homogenized and quenched from temperatures of 1450°C to 2650°C or cooled stepwise from a subsolidus temperature down to 850°C, and annealed for a prolonged period at this temperature or at temperatures close to it. We studied the specimens by x-ray single-crystal and powder diffraction, metallography, and differential thermal analysis. We have shown that the carbide W₂C exists in two modifications: an hexagonal phase with structure of type L′₃ crystallizes from the melt, which at T ≈ 1850°C transforms to an ordered hexagonal phase of the ε-Fe₂N type. The latter, for a carbon content of about 32 at.% and T ≈ 1250°C, also decomposes according to a eutectoid reaction to 〈W〉 and WC. This decomposition is accompanied by formation of a metastable phase of the ξ-Fe₂N type as an intermediate. Taking the results obtained and literature data into consideration, we have corrected the phase diagram for the W - C system.