Preparation of in situ and ex situ reinforced Fe–10Cr–1Cu–1Ni–1Mo–2C containing NbC particles by milling and hot pressing

An in situ and ex situ reinforced powder metallurgy(PM) steel was prepared by the combination of high-energy ball milling and subsequent hot pressing of elemental mixed powders of Fe–10Cr–1Cu–1Ni–1Mo–2C by mass with the addition of Nb C particles. A 40-h milling pretreatment makes the powder particles nearly equiaxed with an average diameter of ~8 μm, and the ferrite grain size is refined to ~6 nm. The sintered density reaches 99.0%–99.7% of the theoretical value when the sintering is conducted at temperatures greater than 1000°C for 30 min. In the sintered bulk specimens, the formation of an in situ M7C3(M = Cr, Fe, Mo) phase is confirmed. M7C3 carbides with several hundred nanometers in size are uniformly distributed in the matrix. Some ultra-fine second phases of 50–200 nm form around the ex situ Nb C and in situ M7C3 particles. The sintered steel exhibits an excellent combination of hardness( Hv 500) and compressive strength(2100–2420 MPa).     

In situ reaction mechanism of MgAlON in Al–Al_2O_3–MgO composites at 1700°C under flowing N_2

The Al–Al_2O_3–MgO composites with added aluminum contents of approximately 0wt%, 5wt%, and 10wt%, named as M_1, M_2, and M_3, respectively, were prepared at 1700°C for 5 h under a flowing N_2 atmosphere using the reaction sintering method. After sintering, the Al–Al_2O_3–MgO composites were characterized and analyzed by X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The results show that specimen M_1 was composed of MgO and MgAl_2O_4. Compared with specimen M_1, specimens M_2 and M_3 possessed MgAlON, and its production increased with increasing aluminum addition. Under an N_2 atmosphere, MgO, Al_2O_3, and Al in the matrix of specimens M_2 and M_3 reacted to form MgAlON and AlN-polytypoids, which combined the particles and the matrix together and imparted the Al–Al_2O_3–MgO composites with a dense structure. The mechanism of MgAlON synthesis is described as follows. Under an N_2 atmosphere, the partial pressure of oxygen is quite low; thus, when the Al–Al_2O_3–MgO composites were soaked at 580°C for an extended period, aluminum metal was transformed into AlN. With increasing temperature, Al_2O_3 diffused into AlN crystal lattices and formed AlN-polytypoids; however, MgO reacted with Al_2O_3 to form MgAl_2O_4. When the temperature was greater than(1640 ± 10)°C, AlN diffused into Al_2O_3 and formed spinel-structured AlON. In situ MgAlON was acquired through a solid-solution reaction between AlON and Mg Al_2O_4 at high temperatures because of their similar spinel structures.     

Preparation of CaB_6 powder via calciothermic reduction of boron carbide

The method of calciothermic reduction of B_4C was proposed for preparing CaB_6. The phase transition and morphology evolution during the reaction were investigated in detail. The experimental results reveal that Ca first reacts with B_4C to generate CaB_2C_2 and CaB_6 at a low temperature and that the CaB_2C_2 subsequently reacts with Ca to produce CaB_6 and CaC_2 at a high temperature. After the products were leached to remove the byproduct CaC_2, pure CaB_6 was obtained. The grain size of the prepared CaB_6 was 2–3 μm, whereas its particle size was 4–13 μm; it inherited the particle size of B_4C. The residual C content of the product was decreased to 1.03 wt% after the first reaction at 1173 K for 4 h and the second reaction at 1623 K for 4 h.     

Interfacial behavior of Fe76Si9B10P5/Zn0.5Ni0.5Fe2O4 amorphous soft magnetic composite during spark plasma sintering process

Fe_(76)Si_9B_(10)P_5/Zn_(0.5)Ni_(0.5)Fe_2O_4 amorphous composite with micro-cellular structure and high electrical resistivity was prepared by spark plasma sintering(SPS) at 487 °C. XRD and SEM results showed that the Fe_(76)Si_9B_(10)P_5 alloy powders remained the amorphous state and the composite was dense. A fusion zone at interface of Fe_(76)Si_9B_(10)P_5 cell body and Zn_(0.5)Ni_(0.5)Fe_2O_4 cell wall was observed by TEM, which also indicates the formation of local high temperature. The interface bonding based on the formation of local high temperature in SPS process was observed. It is believed that the tip effect of Zn_(0.5)Ni_(0.5)Fe_2O_4 nanoparticles promotes the local discharging and plasmas creation in the gaps, and the discharging energy forms an instantaneous local high temperature to complete the local sintering and the densification of Zn_(0.5)Ni_(0.5)Fe_2O_4 particles at a low nominal sinter temperature. Simultaneously, the local high temperature stimulates the adjacent gaps discharging, thus facilitate the continuous formation of new discharging path. Finally, sintering and densification of the amorphous composite is complete.     

Synthesis, Characterization and Calorimetry of Ni（C4H8N2O3）2Cl2

A coordination complex was synthesized from NiCl2 and dipeptide glycylglycine（GG）. It was characterized by element analysis, NMR and TG methods, and then was determined to be Ni（C4HsN2O3）2Cl2. Using an isoperibolic reaction calorimeter, the standard molar enthalpy of formation of Ni（GG）2Cl2（solid） has been determined to be -（1 674.66±2.02） kJ · mol^-1 at 298.15 K.     

Oxide coating mechanism during fluidized bed reduction: solid-state reaction characteristics between iron ore particles and MgO

Experiments on the solid-state reaction between iron ore particles and MgO were performed to investigate the coating mechanism of MgO on the iron ore particles’ surface during fluidized bed reduction. MgO powders and iron ore particles were mixed and compressed into briquettes and, subsequently, roasted at different temperatures and for different time periods. A Mg-containing layer was observed on the outer edge of the iron ore particles when the roasting temperature was greater than 1173 K. The concentration of Fe in the Mg-containing layer was evenly distributed and was approximately 10wt%, regardless of the temperature change. Boundary layers of Mg and Fe were observed outside of the iron ore particles. The change in concentration of Fe in the boundary layers was simulated using a gas–solid diffusion model, and the diffusion coefficients of Fe and Mg in these layers at different temperatures were calculated. The diffusion activation energies of Fe and Mg in the boundary layers in these experiments were evaluated to be approximately 176 and 172 kJ/mol, respectively.     

Novel approaches to produce Al2O3– TiC/TiCN– Fecomposite powders directly from ilmenite

Al2O3 –TiC/TiCN–Fe composite powders were successfully prepared directly from ilmenite at 1300–1400℃.The effects of Al/C ratio,sintering atmosphere,and reaction temperature and time on the reaction products were investigated.Results showed that the nitrogen atmosphere was bene cial to the reduction of ilmenite and the formation of Al2O3 –TiC/TiCN–Fe composite powders.When the reaction temperature was between 600 and 1100℃,the intermediate products,TiO2,Ti3O5 and Ti4O7 were found,which changed to TiC or TiCN at higher temperature.Al/C ratio was found to affect the reaction process and synthesis products.When Al addition was 0.5 mol,the Al2O3 phase did not appear.The content of carbon in TiCN rose when the reaction temperature was increased.     

Effect of Yb2O3 doping on the grain boundary of NiFe2O4–10NiO-based cermets after sintering

xYb2O3–15(20Ni–Cu)/(85?x)(NiFe2O4–10NiO) (x=0, 0.25, 0.5, 0.75, 1.0, 2.0, and 10.0) cermets for aluminum electrolysis were prepared to investigate the effect of Yb2O3 doping on the grain boundary of the cermets after sintering. The results showed that each interface was very clear and that with increasing Yb2O3 content, most of the Yb was evenly distributed at the grain boundary. Moreover, according to the phase composition and microstructural analysis by X-ray diffraction (XRD), scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDX), and electron probe microanalysis (EPMA), YbFeO3 was produced along the grain boundary. The YbFeO3 was concluded to not only have formed from the interaction between the NiFe2O4 or Fe2O3 component and Yb2O3 at the grain boundary of the cermets, but also from the decomposition of NiFe2O4 into NiO and Fe2O3 and the subsequent reaction of Fe2O3 with Yb2O3. Thus, the pro-duction of YbFeO3 resulted in a cermet with high relative density, good electrical conductivity, and good corrosion resistance.     

粉末冶金法制备混杂增强铜基复合材料的增强体竞争析出行为研究

Copper matrix composites reinforced by in situ-formed hybrid titanium boride whiskers (TiB_w) and titanium diboride particles (TiB_2p) were fabricated by powder metallurgy. Microstructural observations showed competitive precipitation behavior between TiB_w and TiB_2p, where the relative contents of the two reinforcements varied with sintering temperature. Based on thermodynamic and kinetic assessments, the precipitation mechanisms of the hybrid reinforcements were discussed, and the formation of both TiB_w and TiB_2p from the local melting zone was thermodynamically favored. The precipitation kinetics were mainly controlled by a solid-state diffusion of B atoms. By forming a compact compound layer, in situ reactions were divided into two stages, where Zener growth and Dybkov growth prevailed, respectively. Accordingly, the competitive precipitation behavior was attributed to the transition of the growth model during the reaction process.     

Microstructure and electrolysis behavior of self-healing Cu-Ni-Fe composite inert anodes for aluminum electrowinning

The microstructure evolution and electrolysis behavior of(Cu_(52)Ni_(30)Fe_(18))–x Ni Fe_2O_4(x=40wt%,50wt%,60wt%,and 70wt%)composite inert anodes for aluminum electrowinning were studied.Ni Fe_2O_4 was synthesized by solid-state reaction at 950°C.The dense anode blocks were prepared by ball-milling followed by sintering under a N_2 atmosphere.The phase evolution of the anodes after sintering was determined by scanning electron microscopy and energy-dispersive X-ray spectroscopy.The results indicate that a substitution reaction between Fe in the alloy phase and Ni in the oxide phase occurs during the sintering process.The samples were also examined as inert anodes for aluminum electrowinning in the low-temperature KF–NaF–AlF_3 molten electrolyte for 24 h.The cell voltage during electrolysis and the corrosion scale on the anodes were analyzed.The results confirm that the scale has a self-repairing function because of the synergistic reaction between the alloy phase with Fe added and the oxide phase.The estimated wear rate of the(Cu_(52)Ni_(30)Fe_(18))–50Ni Fe_2O_4 composite anode is 2.02 cm·a~(-1).     

Effect of Yb_2O_3 doping on the grain boundary of NiFe_2O_4–10NiO-based cermets after sintering

xY b2O3–15(20Ni–Cu)/(85- x)(NiF e2O4–10NiO)(x = 0, 0.25, 0.5, 0.75, 1.0, 2.0, and 10.0) cermets for aluminum electrolysis were prepared to investigate the effect of Yb2O3 doping on the grain boundary of the cermets after sintering. The results showed that each interface was very clear and that with increasing Yb2O3 content, most of the Yb was evenly distributed at the grain boundary. Moreover, according to the phase composition and microstructural analysis by X-ray diffraction(XRD), scanning electron microscopy with energy dispersive X-ray spectroscopy(SEM/EDX), and electron probe microanalysis(EPMA), YbF eO 3 was produced along the grain boundary. The YbF eO 3 was concluded to not only have formed from the interaction between the NiF e2O4 or Fe2O3 component and Yb2O3 at the grain boundary of the cermets, but also from the decomposition of NiF e2O4 into NiO and Fe2O3 and the subsequent reaction of Fe2O3 with Yb2O3. Thus, the production of YbF eO 3 resulted in a cermet with high relative density, good electrical conductivity, and good corrosion resistance.     

Influence of Mo and Ta additions on solidification behavior of Ni3Al single crystal alloys

Ni3Al(Ni75Al25) and Ni3Al–2Mo/Ta(Ni73.5Al24.5Mo/Ta2) single crystals were prepared by the Bridgman method under high temperature gradient(~170℃/cm) at the withdrawal rates of 5 and 20 μm/s. The experimental results showed that the addition of Mo decreased the liquidus and solidus temperatures, and the addition of Ta increased the liquidus and solidus temperatures. Meanwhile, both Mo and Ta additions were found to increase the solidi fi cation range of experimental alloy. It has been found that for solidi fi cation of stoichiometric Ni3Al at low withdrawal rate(5 μm/s), β/γ'eutectic first solidi fied from liquid(L→β+γ') and then β phase completely transformed into pure γ'(β→γ') after the completion of solidi fi cation. However, at high withdrawal rate of 20 μm/s, the remaining β phase was found in the as-cast microstructure of Alloy Ni3Al. Different from stoichiometric Ni3Al, the solidi fi cation sequence of Alloy Ni3Al–2Mo was identi fi ed as L→β+γ'+Mo-rich phase(ternary eutectic reaction). In addition, the addition of Ta led to the formation of primary γ'phase and then subsequent intercellular/interdendritic β/γ'eutectic microstructure. Based on above study, a new Ta and Mo containing Ni3Al based single crystal alloy with superior tensile strength at ultra-high temperature(1100℃) was designed.     

Effect of TiB2 content on microstructure and properties of in situ Ti-TiB composites

This study determined the optimal concentration of titanium diboride (TiB₂) particles for the development of in situ titanium-titanium boride (Ti-TiB) metal matrix composites (MMCs) prepared by a conventional powder metallurgy route to be used for industrial applications. The effect of concentration of TiB₂ particles was studied by reinforcing TiB₂ powder in different mass fractions (2wt%, 5wt%, 10wt%, and 20wt%) into pure Ti powder during the fabrication process. The MMCs were sintered at high temperatures under vacuum. The transmission electron microscopy (TEM) results revealed the formation of needle-shaped TiB whiskers, indicating that in situ reaction occurred during vacuum sintering of the powder compacts. All the composite samples had a high sintered density, and the hardness of the composites increased with an increase in the mass fraction of reinforcement. Mechanical and tribological properties such as flexural strength, impact, and wear properties were determined and found to be dependent on the mass fraction of the reinforcement. However, the mechanism for the in situ reaction needs further investigation by high-energy in situ X-ray diffraction techniques.     

Rapid synthesis of MoSi2-Si3N4 nanocomposite via reaction milling of Si and Mo powder mixture

The nanocomposite of MoSi2-SiaN4 （molybdenum disilicide-silicon nitride） was synthesized by reaction milling of the Mo and Si powder mixture. Changing the processing parameters led to the formation of different products such as a- and B-MoSi2, SiaN4, Mo2N, and M05Si3 at various milling times. A thermodynamic appraisal showed that the milling of Moa2Siss powder mixture was associated with highly exothermic mechanically induced self-sustaining reaction （MSR） between Mo and Si. The MSR took place around 5 h of milling led to the formation of a-MoSi2 and the reaction between Si and N2 to produce Si3N4 under a nitrogen pressure of 1 MPa. By increasing the nitrogen pressure to 5 MPa, more heat is released, resulting in the dissociation of Si3N4 and the transformation of a-MoSi2 to β-MoSi2. Heat treatment was also performed on the milled samples and led to the formation of Mo2N and the transformation of a-MoSi2 to β-MoSi2 at the milling times of 10 and 40 h, respectively.     

Tin recovery from a low-grade tin middling with high Si content and low Fe content by reduction–sulfurization roasting with anthracite coal

A new method for separating and recovering tin from a low-grade tin middling with high Si content and low Fe content by roasting with anthracite coal was researched by studying the reaction mechanism and performing an industrial test, in which the Sn was sulfurized into Sn S(g) and then collected using a dust collector. The Fe–Sn alloy may be formed at roasting temperatures above 950°C, and like the roasting temperature increases, the Sn content and Sn activity in this Fe–Sn alloy decrease. Also, more FeS can be formed at higher temperatures and then the formation of FeO–FeS with a low melting point is promoted, which results in more serious sintering of this low-grade tin middling.And from the thermodynamics and kinetics points of view, the volatilization of the Sn decreases at extremely high roasting temperatures. The results of the industrial test carried out in a coal-fired rotary kiln show that the Sn volatilization rate reaches 89.7% and the Sn is concentrated in the collected dust at a high level, indicating that the Sn can be effectively extracted and recovered from the low-grade tin middling with a high Si content and low Fe content through a reduction–sulfurization roasting process.     

In situ(α-Al_2O_3+ZrB_2)/Al composites with network distribution fabricated by reaction hot pressing

In situ(α-Al_2O_3+ZrB_2)/Al composites with network distribution were fabricated using low-energy ball milling and reaction hot pressing. Differential thermal analysis(DTA) was used to study the reaction mechanisms in the Al–Zr O2–B system. X-ray diffraction(XRD) and scanning electron microscopy(SEM) in conjunction with energy-dispersive X-ray spectroscopy(EDX) were used to investigate the composite phases, morphology, and microstructure of the composites. The effect of matrix network size on the microstructure and mechanical properties was investigated. The results show that the optimum sintering parameters to complete reactions in the Al–Zr O2–B system are 850°C and 60 min. In situ-synthesized α-Al2O3 and Zr B2 particles are dispersed uniformly around Al particles, forming a network microstructure; the diameters of the α-Al2O3 and Zr B2 particles are approximately 1–3 μm. When the size of Al powder increases from 60–110 μm to 150–300 μm, the overall surface contact between Al powders and reactants decreases, thereby increasing the local volume fraction of reinforcements from 12% to 21%. This increase of the local volume leads to a significant increase in microhardness of the in situ(α-Al2O3–Zr B2)/Al composites from Hv 163 to Hv 251.     

Joining of Si3N4 ceramic using PdCo(Ni SiB)–V system brazingfi ller alloy and interfacial reactions

The wettability of V-active PdCo-based alloys on Si3N4ceramic was studied with the sessile drop method. And the alloy of Pd50.0–Co33.7–Ni4.0–Si2.0–B0.7–V9.6(wt%),was developed for Si3N4ceramic joining in the present investigation. The rapidly-solidified brazing foils were fabricated by the alloy Pd50.0–Co33.7–Ni4.0–Si2.0–B0.7–V9.6. The average room-temperature three-point bend strength of the Si3N4/Si3N4joints brazed at 1453 K for 10 min was 205.6 MPa,and the newly developed braze gives joint strengths of 210.9 MPa,206.6 MPa and 80.2 MPa at high temperatures of 973 K,1073 K and 1173 K respectively. The interfacial reaction products in the Si3N4/Si3N4joint brazed at 1453 K for10 min were identified to be VN and Pd2Si by XRD analysis. Based on the XEDS analysis result,the residual brazing alloy existing at the central part of the joint was verified as Co-rich phases,in which the concentration of element Pd was high up to 18.0–19.1 at%. The mechanism of the interfacial reactions was discussed. Pd should be a good choice as useful alloying element in newer high-temperature braze candidates for the joining of Si-based ceramics.     

Effects of Cr and Mo elements on the microstructures and compressive properties of the in situ (TiC_xN_y–TiB_2)/Ni cermets

In-situ(TiC_xN_y–TiB_2)/Ni cermets with 70 wt%TiC_xN_y–TiB_2 were successfully fabricated by combustion synthesis and hot pressing sintering in Ni-Ti-B_4C-BN powder systems.The microstructures,density,compressive properties,and hardness of the TiC_xN_y–TiB_2/Ni cermets with the addition of 0–8 wt%Cr/Mo to the Ni-Ti-B_4C-BN powder systems were compared and analysed.The results showed that the ceramic particles distributed uniformly in the cermets,and the size of the ceramic particles reduced with the Cr/Mo addition.Both Cr and Mo addition can improve the hardness,compressive properties,and fracture strains of the cermets.The hardness,compressive strength,and fracture strain of the(TiC_xN_y–TiB_2)/(Ni+Cr)cermets increased from 1561 HV,2.94 GPa,and 2.9%to 1864 HV,3.65 GPa,and 3.4%,respectively when the Cr content increased to 5 wt%.The hardness and compressive strength of the(TiC_xN_y–TiB_2)/(Ni+Mo)cermets increased from 1561 HV and 2.94 GPa to 1902 HV and 3.43 GPa,respectively when the Mo content increased to 8 wt%.The cermets with Cr had better compressive properties than the cermets with Mo.     

Influence of isothermal aging on σ precipitation in super duplex stainless steel

The time-temperature-transformation (TTT) curve of the 00Cr25Ni7Mo4N duplex stainless steel was obtained with a Formastor-digital thermal dilatometer, and the influence of isothermal aging on σ precipitation was studied by metallographic observation, X-ray diffraction (XRD), and transmission electron microscopy (TEM). The results show that the decomposition of ferrite phase is accompanied by the formation of σ phase at 750–1000℃, especially in the range of 800–900℃. The longer the aging time, the higher the amount of σ precipitation. The area fraction of various phases remains at a certain value upon the completion of ferrite deformation. The temperature of 850℃ is the most sensitive transaction temperature, the incubation time for the formation of σ precipitation is less than 1 min, and aging for 20 min leads to the complete transformation of ferrite. The σ phase is formed preferentially at the α/α/γ junction, and then grows along the α/α boundary in the matrix.     

Bulk Al–Al_3Zr composite prepared by mechanical alloying and hot extrusion for high-temperature applications

Bulk Al/Al_3Zr composite was prepared by a combination of mechanical alloying(MA) and hot extrusion processes. Elemental Al and Zr powders were milled for up to 10 h and heat treated at 600℃ for 1 h to form stable Al_3Zr. The prepared Al_3Zr powder was then mixed with the pure Al powder to produce an Al–Al_3Zr composite. The composite powder was finally consolidated by hot extrusion at 550℃. The mechanical properties of consolidated samples were evaluated by hardness and tension tests at room and elevated temperatures. The results show that annealing of the 10-h-milled powder at 600℃ for 1 h led to the formation of a stable Al_3Zr phase. Differential scanning calorimetry(DSC) results confirmed that the formation of Al_3Zr began with the nucleation of a metastable phase, which subsequently transformed to the stable tetragonal Al_3Zr structure. The tension yield strength of the Al-10wt%Al_3Zr composite was determined to be 103 MPa, which is approximately twice that for pure Al(53 MPa). The yield stress of the Al/Al_3Zr composite at 300℃ is just 10% lower than that at room temperature, which demonstrates the strong potential for the prepared composite to be used in high-temperature structural applications.