Microstructure characterization of nanocrystalline (Ti0.9W0.1) C prepared by mechanical alloying

The microstructural characteristics of nanocrystalline (Ti_0.9W_0.1)C during mechanical alloying were investigated by using X-ray diffraction. The diffraction crystallite size (DCS) and the microstrain of (Ti_0.9W_0.1) C ball milled powders have been determined according to various models. The Scherrer and the Stokes–Wilson relations, the Williamson–Hall plot and the Rietveld refinement methods have been employed. The Rietveld method seems to be the best since it gives homogeneous results. The results obtained showed that the (Ti_0.9W_0.1)C diffraction crystallite size decreases tremendously and its microstrain increases as the milling duration increases. With the further milling of the nanocrystalline (Ti_0.9W_0.1)C within the stage of the steady-state diffraction crystallite size (8–6 nm), we observed a grain boundary relaxation process that was manifested by evident decreases in the root-mean-square strain, as well as important increases in the dislocation density and the volume fraction. Thus, when the (DCS) is higher than the critical value (8 nm), the plastic deformation is governed by the dislocation sliding mechanism. In the contrary, when the (DCS) is lesser than 8 nm, the plastic deformation is governed by the grain-boundary sliding mechanism.     

Sintering of tungsten powder with and without tungsten carbide additive by field assisted sintering technology

Tungsten powder (0.6–0.9 μm) was sintered by field assisted sintering technology (FAST) at various processing conditions. The sample sintered with in-situ hydrogen reduction pretreatment and pulsed electric current during heating showed the lowest amount of oxygen. The maximum relative density achieved was 98.5%, which is from the sample sintered at 2000 °C, 85 MPa for 30 min. However, the corresponding sintered grain size was 22.2 μm. To minimize grain growth, nano tungsten carbide powder (0.1–0.2 μm) was used as sintering additive. By mixing 5 and 10 vol.% WC with W powder, densification was enhanced and finer grain size was obtained. Relative density above 99% with grain size around 3 μm was achieved in W–10 vol.% WC sintered at 1700 °C, 85 MPa, for 5 min.     

Effect of ball-milling time on structural characteristics and densification behavior of W-Cu composite powder produced from WO3-CuO powder mixtures

Understanding the microstructure of W–Cu nanocomposite powder is essential for elucidating its sintering mechanism. In this study, the effect of milling time on the structural characteristics and densification behavior of W-Cu composite powders synthesized from WO₃-CuO powder mixtures was investigated. The mixture of WO₃ and CuO powders was ball-milled in a bead mill for 1 h and 10 h followed by reduction by heat-treating the mixture at 800 °C in H₂ atmosphere with a heating rate of 2 °C/min to produce W-Cu composite powder. The microstructure analysis of the reduced powder obtained by milling for 1 h revealed the formation of W–Cu powder consisting of W nanoparticle-attached Cu microparticles. However, Cu-coated W nanocomposite powder consisting of W nanoparticles coated with a Cu layer was formed when the mixture was milled for 10 h. Cu-coated W nanopowder exhibited an excellent sinterability not only in the solid-phase sintering stage (SPS) but also in the liquid-phase sintering stage (LPS). A high relative sintered density of 96.0% was obtained at 1050 °C with a full densification occurring on sintering the sample at 1100 °C. The 1 h-milled W-Cu powder exhibited a high sinterability only in the LPS stage to achieve a nearly full densification at 1200 °C.     

Hydrogen solubility and diffusion studies of Zr-based AB2 alloys and sol–gel encapsulated AB2 alloy particles

Hydrogen solubility and hydrogen diffusion coefficients have been studied in Ti_0.1Zr_0.9(Mn_0.9V_0.1)_1.1Fe_0.5Ni_0.5, Ti_0.1Zr_0.9Mn_0.9V_0.1Fe_0.55Ni_0.55 and (Ti_0.1Zr_0.9)_1.1Mn_0.9V_0.1Fe_0.5Co_0.5 in the temperature range 450–650 °C with hydrogen gas pressure up to 100 mbar and hydrogen concentration up to 0.03 hydrogen atoms per formula unit. H₂ absorption is exothermic, and the values of partial enthalpy of solution per H atom are in the range from −370 ± 10 meV to −466 ± 50 meV. The silica embedded AB₂ alloy particles have been prepared by sol–gel technique. P–C isotherms of encapsulated AB₂ alloy particles have been obtained in the pressure and temperature ranges 0–30 bar and 30–100 °C, respectively. Diffusion of H interstitials in sol–gel encapsulated Ti_0.1Zr_0.9Mn_0.9V_0.1Fe_0.5Ni_0.5, (Ti_0.1Zr_0.9)_1.1Mn_0.9V_0.1Fe_0.5Ni_0.5 and (Ti_0.1Zr_0.9)_1.1Mn_0.9V_0.1Fe_0.5Co_0.5 alloy particles have been studied between 500 and 650 °C with H₂ gas pressure up to 100 mbar and H concentration up to 0.014 H atoms per formula unit. Diffusion coefficient (D) of H interstitials has been determined for all these samples from the kinetics of hydrogen absorption. The activation energies have been calculated from temperature dependence of diffusion coefficient and the values are in the range 416 ± 15–897 ± 50 meV.     

Formation of porous metallic glass compacts by electro-discharge sintering

A single pulse of 0.1–0.9 kJ/0.45 g atomized amorphous Cu₅₄Zr₂₂Ti₁₈Ni₆ powders in size range of 90–150 μm was applied to fabricate porous metallic glass compacts using electro-discharge sintering (EDS) with 3 and 4 mm in diameter. The structural and thermal analysis of the samples indicated that formation of the porous metallic glass compacts occurs only when low electrical input energy was induced on the amorphous powders. Furthermore, the critical input energy inducing crystallization of the amorphous phase during EDS is strongly dependent on the size of the sample.     

Densification and grain growth during early-stage sintering of Ce0.9Gd0.1O1.95−δ in a reducing atmosphere

The present work investigates the processes of densification and grain growth of Ce_0.9Gd_0.1O_1.95?δ (CGO10) during sintering under reduced oxygen partial pressure. Sintering variables were experimentally characterized and analyzed using defect chemistry and sintering constitutive laws. Based on the results achieved, the grain size–relative density relationship, the densification rate and the grain-growth rate were determined. The activation energies for densification and grain growth were evaluated, and the dominant densification mechanism was indicated. For comparison, the densification behavior of CGO10 sintered in air was also studied. Accelerated densification was observed in early-stage sintering of CGO10 in a reducing atmosphere. This might be attributed to the oxygen vacancies generated by the reduction of Ce⁴⁺ to Ce³⁺ in the reducing atmosphere, which facilitate the diffusion of ions through the lattice. The densification activation energy of CGO10 in the reducing atmosphere was evaluated to be 290 ± 20 kJ mol^?1 in the relative density range of 0.64–0.82, which was much smaller than that of CGO10 sintered in air (770 ± 40 kJ mol^?1). The grain-growth activation energy of CGO10 sintered in the reducing atmosphere was evaluated to be 280 ± 20 kJ mol^?1 in the grain size range of 0.34–0.70 μm. The present work describes a systematic investigation of sintering behavior of CGO10 under reduced oxygen partial pressure, which contributes to the first known determination of the fundamental parameters associated with densification and grain growth during early-stage sintering of CGO10 in a reducing atmosphere.     

The effects of ball-milling treatment on the densification behavior of ultra-fine tungsten powder

Ultra-fine tungsten powder with a BET particle size of 210 nm was synthesized by sol spray drying, calcination and subsequent hydrogen reduction process. Then this powder was treated by ball-milling, the characteristic changes of this powder before and after milling were investigated. Then the sintering densification behavior of these powders with different ball-milling time (0 h, 5 h, 10 h) were also studied. The results show that ball-milling treatment greatly activates the sintering process of ultra-fine tungsten powder. The relative density of the powder ball-milled for 10 h could reach 97.3% of theoretical density (TD) when sintered at 1900 °C for 2 h, which is 600 °C lower than the required temperature of the traditional micro-scaled powder sintered for the same density. At the same time, ball-milling treatment could substantially reduce the onset temperature of sintering as well as recrystallization, and bulk tungsten materials with more uniform and finer microstructure and much better mechanical properties (hardness) could be obtained.     

Spark plasma sintering of TiC particle-reinforced molybdenum composites

In order to improve the recrystallization resistance and the mechanical properties of molybdenum, TiC particle-reinforcement composites were sintered by SPS. Powders with TiC contents between 6 and 25 vol.% were prepared by high energy ball milling. All powders were sintered both at 1600 and 1800 °C, some of sintered composites were annealed in hydrogen for 10 h at 1100 up to 1500 °C. The powders and the composites were investigated by scanning electron microscopy and XRD. The microhardness and the density of composites were measured, and the densification behavior was investigated. It turns out that SPS produces Mo–TiC composites, with relative densities higher than 97%.The densification behavior and the microhardness of all bulk specimens depend on both the ball milling conditions of powder preparation and the TiC content. The highest microhardness was obtained in composites containing 25 vol.% TiC sintered from the strongest milled powders. The TiC particles prevent recrystallization and grain growth of molybdenum during sintering and also during annealing up to 10 h at 1300 °C. Interdiffusion between molybdenum and carbide particles leads to a solid solution transition zone consisting of (Ti_1 −x Mo_x)C_y carbide. This diffusion zone improves the bonding between molybdenum matrix and TiC particles. A new phase, the hexagonal Mo₂C carbide, was detected by XRD measurements after sintering. Obviously, this phase precipitates during cooling from sintering temperature, if (Ti_1 −x Mo_x)C_y or molybdenum, are supersaturated with carbon.     

Nano-sized zirconium carbide powder: Synthesis and densification using a spark plasma sintering apparatus

Nano-sized zirconium carbide powder was synthesized at 1600 °C by the carbothermal reduction of ZrO₂ using a modified spark plasma sintering (SPS) apparatus. The synthesized ZrC powder had a fine particle size of approximately 189 nm and a low oxygen content of 0.88 wt%. The metal basis purity of the synthesized powder was 99.87%. The low synthesis temperature, fast heating/cooling rate and the effect of current during the modified SPS process effectively suppressed the particle growth. Using the synthesized powder, monolithic ZrC ceramics with high relative density (97.14%) were obtained after the densification at 2100 °C for 30 min at a pressure of 80 MPa by SPS. The average grain size of the densified ZrC ceramics was approximately 9.12 μm.     

Forming and sintering behaviors of commercial α-Al2O3 powders with different particle size distribution and agglomeration

The Al₂O₃ structure ceramics have been investigated extensively in previous studies. In order to compare micron- with submicron-scale powder on forming and sintering behaviors, three commercial α-Al₂O₃ powders were studied: 0.15 μm (denoted S as small in the paper) (granulating), 0.43 μm (denoted M as middle) (granulating), and 1.8 μm (denoted L as large) (granulate-free) at d₅₀ (median size). Although the (M) powder contains hard agglomerates, it forms more easily than the (S) powder. This is principally because the (M)'s soft agglomeration strength (0.03 MPa) is weaker than (S) (7 MPa). The (L) bulk formed easily with lower pressure 10 MPa because of wider starting-particle size distribution, 0.2–15 μm. The (S) primary particles rearranged before sintering, so it postponed its sintering onset temperature to about 1200 °C. Additionally, its shrinkage rate becomes maximal and concentrated at the 2nd stage of sintering from 1300 to 1400 °C. (M) bulk revealed the longest shrinkage range from 1000 to 1500 °C because the sintering occurred with its hard agglomerates at first. Although (L) powder formed rather easily, its sintering was impeded by a much wider particle size distribution.     

Influence of SPS parameters on the density and mechanical properties of sintered Ti3SiC2 powders

The densification of Ti₃SiC₂ MAX phase was performed by the Spark Plasma Sintering (SPS) technique. The SPS parameters, such as sintering temperature, pressure and soaking time, were optimized to obtain fully densified samples which were characterized to obtain the best mechanical properties. The sintering temperature was varied from 1070 to 1300 °C, the soaking time from 1 to 10 min and the applied pressure from 60 to 180 MPa. The best full densified samples were sintered at 1300 °C applying 60 MPa for 7 min. Ti_xC_y and TiSi₂ secondary phases were found in samples densified at 1200, 1250 and 1300 °C, due to decomposition of Ti₃SiC₂. These secondary phases, detected by XRD patterns, were confirmed by microhardness testing, FESEM observations and EDAX analyses.     

Combined effect of Ni and nano-Y2O3 addition on microstructure,mechanical and high temperature behavior of mechanically alloyed W-Mo

Nanostructured tungsten (W) based alloys with the nominal compositions of W₇₀Mo₃₀ (alloy A), W₅₀Mo₅₀ (alloy B), and 1.0 wt.% nano-Y₂O₃ dispersed W₇₉Ni₁₀Mo₁₀ (alloy C) (all in wt.%) have been synthesized by mechanical alloying followed by compaction at 0.50, 0.75 and 1 GPa pressure for 5 mins and conventional sintering at 1500 °C for 2 h in Ar atmosphere. The microstructure, evolution of phases and thermal behavior of milled powders and consolidated products has been investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), High resolution transmission electron microscopy (TEM), Energy dispersive spectroscopy (EDS) and differential scanning calorimetry (DSC). Minimum crystallite size of 29.4 nm and maximum lattice strain and dislocation density of 0.51% and 18.93 (10¹⁶/m²) respectively has been achieved in alloy C at 20 h of milling. Addition of nano-Y₂O₃ reduces the activation energy for recrystallization of W based alloys. Alloy C compacted at 1 GPa pressure shows enhanced sintered density, hardness, compressive strength and elongation of 95.2%, 9.12 GPa, 1.51 GPa, 19.5% respectively as well as superior wear resistance and oxidation resistance (at 1000 °C) as compared to other W-Mo alloys.     

Effect of Al addition on SiC–B4C cermet prepared by pressureless sintering and spark plasma sintering methods

SiC–B₄C–Al cermets containing 5, 10 and 20 wt.% of Al were fabricated by high-energy planetary milling followed by conventional sintering and spark plasma sintering (SPS) techniques separately. The average particle size reduced to ~ 3 μm from an initial size of 45 μm after 10 h of milling. The as-milled powders were conventionally sintered at 1950 °C for 30 min under argon atmosphere and SPS was carried out at 1300 °C for 5 min under 50 MPa applied pressure. The formation of Al₈B₄C₇ and AlB₁₂ phases during conventional sintering and SPS were confirmed by X-ray diffraction (XRD) and scanning electron microscopy (SEM) analyses. The formation of Al₈B₄C₇ at 700 °C and AlB₁₂ at 1000 °C was well supported by XRD and differential scanning calorimetry (DSC). The maximum relative density, microhardness and indentation fracture resistance of SiC–B₄C–10Al consolidated by SPS are 97%, 23.80 GPa and 3.28 MPa·m^1/2, respectively.     

Reactive sintering of TiAl–Ti5Si3 in situ composites

TiAl with between 0 and 20 vol%Ti₅Si₃ was produced by reactive sintering (700 °C for 15 min in vacuum) of cold pressed compacts of elemental Ti, Al and Si powder. The results show that adding Si to Ti and Al reduces the swelling associated with reactive sintering of TiAl, as composites containing more than 5 vol%Ti₅Si₃ densified during reactive sintering. However, composites containing more than 10 vol%Ti₅Si₃ did not retain their shape and the TiAl+20 vol%Ti₅Si₃ composite completely melted during the sintering process. A thermodynamic analysis indicated that the simultaneous formation of TiAl and Ti₅Si₃ increases the adiabatic flame temperature during the reaction between the powders. In fact, the analysis predicted that the maximum temperature of the reaction associated with the formation TiAl+20 vol%Ti₅Si₃ should exceed the melting point of TiAl, and this was observed experimentally. Differential thermal analysis (DTA) revealed that an Al–Si eutectic reaction occurred in mixtures of Ti, Al and Si powders prior to the formation of the TiAl and Ti₅Si₃ phases. There was no such pre-reaction formation of a eutectic liquid in Ti and Al powder mixtures. The formation of the pre-reaction liquid and the increase in adiabatic flame temperature resulted in the melting that occurred and the enhanced densification (minimization of swelling) during reactive sintering of the in situ composites.     

Development of electroless (Ni-P)/BaNi0.4Ti0.4Fe11.2O19 nanocomposite powder for enhanced microwave absorption

Ni-, Ti-substituted nanocrystalline M-type barium hexaferrite powder (BaNi_xTi_xFe_12?2xO₁₉ (x = 0.4) of size ～10 nm) was coated with Ni-P by electroless (EL) coating technique to form EL Ni-P/BaNi_0.4Ti_0.4Fe_11.2O₁₉, a radar absorbing material (RAM) nanocomposite powder. Under TEM, the particle size of RAM powders before and after Ni-P coating were found to be in the range of 10–15 nm and 15–25 nm respectively. A uniform layer of 5–10 nm thick coating is deposited due to the controlled growth of EL Ni-P nanoglobules onto the powder. A growth mechanism was proposed to understand the deposition of EL Ni-P layer onto the RAM powder. The reflection loss (RL) of the EL (Ni-P)/RAM nanocomposite powder in Ku band (12.4 ?18 GHz) was evidently enhanced to ?28.70 dB, as compared to the EL Ni-P nanoglobules (?16.20 dB) and nanocrystalline RAM powder (?24.20 dB). After annealing at 400 °C for 4 h, the RL and bandwidth of EL (Ni-P)/RAM nanocomposite powder was further improved from ?24.20 to ?35.90 dB and 1.50 to 4.00 GHz respectively. The RL enhancement mechanism was explained on the basis of VSM study (hysteresis loops) and electromagnetic theory.     

Synthesis of high purity titanium silicon carbide from elemental powders using arc melting method

The objective of this study is to investigate the formation of Ti₃SiC₂ from Ti/Si/C powders using the arc melting method. The results show that the sample sintered at 80 s produced a near single-phase of Ti₃SiC₂ (99.2 wt.%) with a relative density of 88.9%. These results were confirmed by phase determination using XRD analysis and were supported with micrographs from FESEM/EDX analyses. The relative density and porosity of all samples were dependent on the formation of macropores in bulk samples and micropores in TiC_x grains. The proposed reaction mechanisms for the synthesis of Ti₃SiC₂ by arc melting is that Ti₃SiC₂ might be formed from TiC_x + Si, Ti₅Si₃C_x + C, and Ti₅Si₃C_x + TiC_x at early arcing time (≤ 10 s), while TiC_x + TiSi₂ take place at 15 s to 80 s. After 80 s, decomposition of Ti₃SiC₂ into TiC_x, TiSi₂ and C was observed.     

In situ synthesis and sintering of ZrB2 porous ceramics by the spark plasma sintering–reactive synthesis (SPS–RS) method

Zirconium diborides (ZrB₂) porous ceramics were synthesized by the Spark Plasma Sintering-Reactive Synthesis (SPS–RS) technique using ZrO₂ and B₄C as precursors which undergo solid state reaction that lead to pore formation. Phase analysis of the products indicated that the reaction started between 1200 °C and 1300 °C and was carried out at 1600 °C within 10 min under SPS conditions, which was consistent with the thermodynamic calculations. The as-prepared ZrB₂ porous ceramics had a relatively smaller crystallite size (~ 1 μm), a lower oxygen content (~ 1.04 wt.%) and a relative density of 29.9%. The oxygen impurities decreased with the sintering temperature and holding time. In addition, the measured results showed that the reaction was carried out within 10 min holding time at the temperature of 1600 °C and the synthesized ZrB₂ products had high purity in comparison to commercial ZrB₂ powder product.     

Ti50Cu23Ni20Sn7 bulk metallic glasses prepared by mechanical alloying and spark-plasma sintering

A powder metallurgy technology was developed to prepare Ti₅₀Cu₂₃Ni₂₀Sn₇ bulk metallic glasses (BMGs). Firstly, amorphous powder was prepared by mechanical alloying (MA) method successfully after being milled for 30 h. Phase transformation of the as-milled powder was characterized by X-ray diffraction (XRD). Morphology of the as-milled amorphous powder was observed by scanning electron microscopy (SEM). Onset temperature of glass transformation and onset temperature of crystallization (T_x and T_g) of the as-milled amorphous powder were evaluated by differential scanning calorimeter (DSC). Secondly, the as-milled amorphous powder was then consolidated by spark-plasma sintering (SPS) method into a specimen with the shape of cylindrical stick, with a diameter and height of about 20 and 10 mm, respectively. The SPS experiment was conducted under a pressure of 500 MPa at a heating rate of 40 K/min, sintering and holding for 1 min at the temperature of 763 K. It was confirmed that the as-milled powder is of fully amorphous however the consolidated specimen shows to be an amorphous matrix with partial crystallization. Compressing strength, Young's modulus, micro-hardness, friction and density of the consolidated specimen are about 975 MPa, 121 GPa, 13 GPa, 0.12 and 6599 kg/m³, respectively. Fractograph of the specimen appears to be shear fracture and very few defects can be seen from the picture of SEM.     

Experimental and atomistic simulation based study of W based alloys synthesized by mechanical alloying

The present research work represents the synthesis of nanostructured W based alloys with the nominal compositions of W₉₀Mo₁₀ and W₈₀Ni₁₀Mo₁₀ (all in wt.%) by mechanical alloying and followed by conventional sintering at 1500 °C for 2 h in Ar atmosphere. The microstructure and evolution of phases during milling and consolidated products are investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Energy dispersive spectroscopy (EDS). Crystallite size of 38.7 nm and 40 nm and lattice strain of 0.41% and 0.33% are achieved in W₉₀Mo₁₀ and W₈₀Ni₁₀Mo₁₀ alloy respectively at 20 h of milling. The lattice parameter of all the investigated alloys shows initial expansion at 10 h of milling and then contraction at 20 h of milling. W₈₀Ni₁₀Mo₁₀ shows maximum sintered density of 94.8% as compared to W₉₀Mo₁₀. The hardness as well as the compressive strength of W₈₀Ni₁₀Mo₁₀ alloy records maximum value of 8.57 GPa and 1.18 GPa, respectively. The minimum wear depth is attained in W₈₀Ni₁₀Mo₁₀ alloy to that of W₉₀Mo₁₀. Molecular dynamic simulation based study is also performed to reveal the mechanisms responsible for deformation. Atomistic simulation shows that addition of nickel lowers the flow stress and increases ductility of W-Mo alloy studied at nanoscale. Results of atomistic simulation based study correlates well with experimental analysis.     

Processing and characterization of porous Ti2AlC with controlled porosity and pore size

In this work, we demonstrate a simple and inexpensive way to fabricate porous Ti₂AlC, one of the best studied materials from the MAX phase family, with controlled porosity and pore size. This was achieved by using NaCl as the pore former, which was dissolved after cold pressing but before pressureless sintering at 1400 °C. Porous Ti₂AlC with samples a volume fraction of porosity ranging from ～10 to ～71 vol.% and different pore size ranges, i.e. 42–83, 77–276 and 167–545 μm, were successfully fabricated. Fabricated samples were systematically characterized to determine their phase composition, morphology and porosity. Room temperature elastic moduli, compressive strength and thermal conductivity were determined as a function of porosity and/or pore size. For comparison, several samples pressureless-sintered without NaCl pore former, or fabricated by spark plasma sintering, were also characterized. The effects of porosity and/or pore size on the room temperature elastic moduli, compressive strength and thermal conductivity of porous Ti₂AlC are reported and discussed in this work. It follows that porosity can be a useful microstructural parameter to tune mechanical and thermal properties of Ti₂AlC.