Controlling conditions for synthesis of iron-titanium carbide using two different titanium precursors

Preparation of Fe–TiC composite from mixtures of carbon black and two different titanium bearing minerals (black sand ilmenite and natural rutile) was studied. Milled (mechanically activated) and unmilled carbon containing mixtures were prepared and then heated at temperatures 1200 °C and 1300 °C for 3 h under an inert atmosphere. The reaction progress, as well as reaction products, was evaluated using thermogravimetric analysis (TGA-DTA), X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), and energy dispersive X-ray spectroscopy (EDX). The feasibility of producing Fe–TiC composites from titanium bearing materials mixed with carbon black was proved. Fe–TiC could be produced by carbothermic reduction of mechanically activated black sand ilmenite containing mixtures milled for 50 h and heated up to 1200 °C. On the other hand, 60 h milling followed by heating up to 1300 °C was needed in case of natural rutile containing mixture. The morphology of the Fe–TiC produced from black sand ilmenite showed a homogeneous distribution of Fe and TiC enriched areas, while the Fe–TiC produced from natural rutile showed intense distribution of TiC phase with traces of iron and lower titanium oxide.     

Oxidation behavior of micro-sized Al2O3–TiC–Co composites prepared from cobalt-coated powders

The oxidation behavior of hot-pressed Al₂O₃–TiC–Co composites prepared from cobalt-coated powders has been studied in air in the temperature range from 200 °C to 1000 °C for 25 h. The oxidation resistance of Al₂O₃–TiC–Co composites increases with the increase of sintering temperature at 800 °C and 1000 °C. The oxidation surfaces were studied by XRD and SEM. The oxidation kinetics of Al₂O₃–TiC–Co composites follows a rate that is faster than the parabolic-rate law at 800 °C and 1000 °C. The mechanism of oxidation has been analyzed using thermodynamic and kinetic considerations.     

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.     

Thermomechanical properties of TiC particle-reinforced tungsten composites for high temperature applications

Tungsten and tungsten alloys are widely used in high temperature environments where arc ablation or mechanical deformation and damage are the main sources of materials failure. For high temperature critical applications in thermomechanical environments, however, the low strength limits the use of tungsten and tungsten alloys. Hence, new tungsten based materials with good high temperature thermomechanical properties need to be developed in order to extend the use of tungsten. TiC particle-reinforced tungsten based composites (TiC_p/W) were fabricated by hot pressing at 2000 °C, 20 MPa in a vacuum of 1.3×10⁻³ Pa. The composites were examined with respect to their thermophysical and mechanical properties at room temperature and at elevated temperature. Vickers hardness and elastic modulus increased with increasing TiC content from 0 to 40 vol.%. The highest flexural strength, 843 MPa, and the highest toughness, 10.1 MPa m^1/2, of the composites at room temperature were all obtained when 20 vol.% TiC particle were added. As the test temperature rose, the flexural strength of the TiC_p/W composites firstly increased and then decreased, except in the monolithic tungsten. The highest strength of 1155 MPa was measured at 1000 °C in the composite containing 30 vol.% TiC particles. The strengthening effect of TiC particles on the tungsten matrix is more significant at high temperatures. With the addition of TiC particles, the thermal conduction of tungsten composites was drastically decreased from 153 W m⁻¹ K⁻¹ for monolithic W to 27.9 W m⁻¹ K⁻¹ for 40 vol.% TiC_p/W composites, and the thermal expansion was also increased. The new composites are successfully used to make high temperature grips and moulds.     

Effect of oxide scale on temperature-dependent interfacial heat transfer in hot stamping process

An optimization-based numerical procedure was developed to determine the temperature-dependent interfacial heat transfer coefficient (IHTC). The effects of temperature, pressure and oxide scale thickness were analyzed, for oxide thickness between 9 μm and 156 μm and pressure from 8 MPa to 42 MPa. Oxide scales and contact pressure both show distinctive effects on IHTC in the cooling process. The average IHTC decreases about 2461 W/(m² °C) with the increase of oxide scale thickness and increases 2620 W/(m² °C) with the increase of pressure. Based on the two-way ANOVA, the effect of contact pressure influences the IHTC most. Their mutual interaction is negligible. The IHTC decreases when the average temperature between the blank and die surface is above 250 °C and increases when the latent heat release.     

Formation of TiC via interface reaction between diamond grits and Sn-Ti alloys at relatively low temperatures

In this paper, interfacial reaction between diamond grit and Sn-6Ti alloy was systematically studied at brazing temperatures from 600 to 1030 °C. A thin and uniform layer of scallop-like nano-sized TiC grains was formed after brazing for 30 min at 600 °C, and interfacial TiC grains subsequently coarsened as brazing temperature increased to 740 and 880 °C. Strip-like columnar TiC grains in a bilayer structure was further grown as brazing temperature increased to 930 °C. After brazing at 1030 °C, a dense layer of columnar TiC grains were formed. Based on the TEM micrographs of interfacial TiC, the formation and evolution of the growth morphologies of interfacial TiC was believed to be controlled by the diffusion of C flux from diamond grits, which is dependent on the brazing temperatures.     

Unlubricated friction and wear behaviors of Al2O3/TiC ceramic cutting tool materials from high temperature tribological tests

The unlubricated friction and wear behaviors of Al₂O₃/TiC ceramic tool materials were evaluated in ambient air at temperature up to 800 °C by high temperature tribological tests. The friction coefficient and wear rates were measured. The microstructural changes and the wear surface features of the ceramics were examined by scanning electron microscopy. Results showed that the temperature had an important effect on the friction and wear behaviors of this Al₂O₃ based ceramic. The friction coefficient decreased with the increase of temperature, and the Al₂O₃/TiC ceramics exhibited the lowest friction coefficient in the case of 800 °C sliding operation. The wear rates increased with the increase of temperature. During sliding at temperature above 600 °C, oxidation of the TiC is to be expected, and the formation of lubricious oxide film on the wear track is beneficial to the reduction of friction coefficient. The wear mechanism of the composites at temperature less than 400 °C was primary abrasive wear, and the mechanisms of oxidative wear dominated in the case of 800 °C sliding operation.     

Effect of sintering process on the microstructures and properties of in situ TiB2–TiC reinforced steel matrix composites produced by spark plasma sintering

Spark plasma sintering (SPS) is a new technique to rapidly produce metal matrix composites (MMCs), but there is little work on the production of TiB₂–TiC reinforced steel matrix composites by SPS. In this work, in situ TiB₂–TiC particulates reinforced steel matrix composites have been successfully produced using cheap ferrotitanium and boron carbide powders by SPS technique. The effect of sintering process on the densification, hardness and phase evolution of the composite is investigated. The results show that when the composite is sintered at 1050 °C for 5 min, the maximum densification and hardness are 99.2% and 83.8 HRA, respectively. The phase evolution of the composite during sintering indicates that the in situ TiB₂–TiC reinforcements are formed by a hybrid formation mechanism containing solid–solid diffusion reaction and solid–liquid solution-precipitation reaction. The microstructure investigation reveals that fine TiB₂–TiC particulates with a size of ～2 μm are homogeneously distributed in the steel matrix. The TiB₂–TiC/Fe composites possess excellent wear resistance under the condition of dry sliding with heavy loads.     

Microstructure and stress rupture property of titanium-containing 11Cr ferritic/martensitic steels

The microstructure and stress rupture behavior of 11Cr ferritic/martensitic steels with 0.02 wt.%Ti (low Ti) and 0.14 wt.%Ti (high Ti) have been studied. The steels are prepared by vacuum induction melting followed by hot forging and rolling into plates. The results show that titanium is easy to combine with oxygen and other elements to form complex inclusions. Large MX particles with 1–3 μm are found in the high titanium steel. Most of the large MX particles have a TiO₂ cored structure. After normalizing at 1100 °C for 1 h, cooled in air and tempering at 750 °C for 1 h, nano-sized MX precipitates distribute densely near martenstic lath boundaries in the high titanium steel. The large MX particles cannot be dissolved even at austenitizing temperature up to 1300 °C. Creep cracks nucleate at the interface between matrixes and the large MX particles or titanium-containing oxide inclusions.     

Titanium to steel joining by spark plasma sintering (SPS) technology

The bonding of Ti–6Al–4V to low alloy steel (AISI4330) using SPS technique in the 850–950 °C temperature range was examined. The formation of a thin (～1 μm) titanium carbide interfacial layer was observed with a thickness only slightly dependent on the joining temperature. This layer separates the joined metals and prevents the formation of Fe–Ti intermetallics in the bonding zone. The maximal tensile strength of the joints (of about 250 MPa) was achieved for bonding at 950 °C for 3.6 ks. The formation of the titanium carbide layer and its evolution are discussed based on the isothermal section of the ternary Fe–Ti–C phase diagram.     

Influence of nanocrystalline Ni–Ti reaction agent on self-propagating high-temperature synthesized porous NiTi

Nanocrystalline Ni–Ti was used in self-propagating high-temperature synthesis (SHS) to fabricate porous NiTi. The SHS of porous NiTi using elemental powders was also prepared for comparison. Results showed that the main phase was NiTi with unreacted Ni when using elemental powders, which is detrimental to medical use. A large amount of Ti₂Ni secondary phase was also detected. By employing mechanically alloyed nanocrystalline Ni–Ti as a reaction agent, the secondary intermetallic phase (i.e. Ti₂Ni) was significantly reduced and the unreacted Ni was eliminated. The addition of 25 wt% nanocrystalline Ni–Ti reaction agent produced porous NiTi with an average porosity of 52–55 vol% and a general pore size of 100–600 μm under preheating temperatures of 200 and 300 °C. This general pore size in the range of 100–600 μm is beneficial to biomedical application for osseointegration. By further increase of the reaction agent to 50 wt% in the reactant, a porous NiTi part was produced at ambient temperature (i.e. no preheating was necessary) and a dense part was formed at preheated temperature of 200 °C due to the large amount of energies in the nanocrystalline reaction agent. This revealed that the use of nanocrystalline reaction agent effectively lowered the activation barriers for combustion synthesis reaction.     

Microstructure characterization of large TiC-Mo-Ni cermet tiles

A detailed characterization of large (150 mm × 150 mm), 6 to 12 mm thick, commercially produced tiles of a TiC-Mo-Ni cermet with ~ 13 vol% Ni binder and a microstructure consistent with processing via self-propagating high temperature synthesis (SHS) has been conducted. Many mechanical property defining attributes of the materials were highly reproducible, including the composition, phase content, TiC particle size distribution (with an average particle diameter of 8–10 μm), and density of 5.52 × 10³ kgm^− 3. However, sufficient variability in the distribution of metal elements within the carbide particles, interparticle contiguity, the distribution of porosity, and residual stress were discovered that the mechanical behavior is expected to exhibit significant variability. The spheroidal shaped TiC particles had a multilayered (onion ring like) composition with rings of locally higher Mo concentration, rather than the more usual Ti-rich core and a single Mo-rich rim that enhances wetting with the Ni-binder. The TiC particles also had a high contiguity factor of 0.30–0.47. Recent assessments of liquid phase sintered cermets indicate significant loss of fracture resistance as the contiguity increases above 0.25. Hot isostatic pressing (HIP) at 1250 °C and 100 MPa was unable to reduce the porosity, which remained as large pockets of insufficient metal binder material (a form of shrinkage porosity) between the spheroidal carbide particles. X-ray diffraction measurements indicated the presence of significant residual stress in the as-received and the HIP condition materials. A stress relief heat treatment at 900 °C succeeded in eliminating this residual stress consistent with its origination from thermal gradients associated with rapid cooling.     

Effect of ultrasonic treatment on the Fe-intermetallic phases in ADC12 die cast alloy

The ultrasonic treatment temperatures were varied from about 100 °C above the liquidus temperature down to the Al–Si eutectic temperature, for different treatment times (0–15 s). The results showed that the ultrasonic melt treatment was very effective to convert the long plate-like Fe-intermetallic phases (up to 200 μm length) to a highly compacted fine polyhedral/globular form (<15 μm size). The critical ultrasonic treatment temperature to affect the morphology of Fe intermetallics was found to be in the range of 596–582 °C. The eutectic Si was mostly not affected by ultrasonic treatments carried out in this study (in the temperature range of 670–581 °C and for up to 10 s). It was also observed that the nucleation undercooling, which is a measure of nucleation efficiency, at the start of solidification was lowered from ～2.9 to ～0.4 °C by ultrasonic treatment. The variation of horn temperature within 20 °C above pouring temperature to 10 °C below it had no noticeable effect. The ultrasonically treated samples showed better tensile properties than the untreated samples, due to the change in morphology of the Fe-intermetallic particles.     

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.     

Effect of initial particulate and sintering temperature on mechanical properties and microstructure of WC–ZrO2–VC ceramic composites

Owing to improving the mechanical properties of cemented carbides in high speed machining fields, a new composite tool material WC–ZrO₂–VC (WZV) is prepared from a mixture of yttria stabilized zirconia (YSZ) and micrometer VC particles by hot-press-sintering in nitrogenous atmosphere. Commercial WC, of which the initial particle sizes are 0.2 μm, 0.4 μm, 0.6 μm and 0.8 μm, is mixed with zirconia and VC powder in aqueous medium by following a ball mill process. The sintering behavior is investigated by isostatic pressing under different sintering temperature. The relative density and bending strength are measured by Archimedes methods and three-point bending mode, respectively. Hardness and fracture toughness are performed by Vickers indentation method. Microstructure of the composite is characterized by scanning electron microscopy (SEM). The correlations between initial particles, densification mechanism, sintering temperature, microstructure and mechanical properties are studied. Experimental results show that maximum densification 99.5% is achieved at 1650 °C and the initial particle size is 0.8 μm. When temperature is 1550 °C and particle size is 0.4 μm, the optimized bending strength (943 MPa) is obtained. The best hardness record is 19.2 GPa when sintering temperature is 1650 and particle size is 0.8 μm. The indention cracks propagate around the grain boundaries and the WC particles fracture, which is associated with particle and microcrack toughening mechanism.     

Mechanical properties of as-fabricated and 2300 °C annealed tungsten wire tested up to 600 °C

Recent efforts dedicated to the mitigation of tungsten brittleness have demonstrated that tungsten fiber-reinforced composites acquire pseudo ductility even at room temperature. Crack extension and fracture process is basically defined by the strength of tungsten fibers. Here, we move forward and report the results of mechanical and microstructural investigation of different grades of W wire with a diameter of 150 μm at elevated temperature up to 600 °C. The results demonstrated that potassium doping to the wire in the as-fabricated state does not principally change the mechanical response, and the fracture occurs by grain elongation and delamination. Both fracture stress and fracture strain decrease with increasing test temperature. Contrary to the as-fabricated wire, the potassium-doped wire annealed at 2300 °C exhibits much lower fracture stress. The fracture mechanism also differs, namely: cleavage below 300 °C and ductile necking above. The change in the fracture mechanism is accompanied with a significant increase of the elongation to fracture being ~ 5% around 300 °C.     

Effect of Fe3O4, Fe and Cu doping on magnetic properties and behaviour in physiological solution of biological hydroxyapatite/glass composites

The effect of Fe, Fe₃O₄ and Cu additives on magnetic properties and behaviour in physiological solution of glass-reinforced biological hydroxyapatite composites has been investigated. 1 wt% of additive was admixed before the final sintering of composites at 500 or 780 °C. The relative green and sintered densities of the samples were analyzed for the influence of additives and sintering temperature on the composite properties. The morphology of composites exhibited a porous structure with a pore size of 0.1–200.0 μm for OK 015 and 0.2–600.0 μm for OK 6 samples. It has been found that the magnetic properties of the doped composites depend on their compositions, the nature of additive and sintering conditions. The influence of the additive phases on the degradation of the composites in physiological solution was studied in vitro. It has been shown that Fe₃O₄-doped OK 015, which has ferromagnetic properties, can be the most suitable material for targeted delivery of drugs.     

Fabrication and characterization of pure tungsten using the hot-shock consolidation

Crack-free pure W bulks have been fabricated by SHS assisted hot-shock consolidation (HSC). The tungsten powders were preheated by the heat released through a SHS (self-propagating high-temperature synthesis) reaction before shock wave loading. The duration of preheating was less than 3 min and the preheating temperature was controlled in the range of 700 ~ 1300 °C by adjusting the mass of the SHS mixture. The highest relative density of compacted samples can reach 96.7% T.D. (theoretical density) at 1300 °C under the shock pressure of 3.14GPa. The grain sizes of all compacted samples are nearly the same as the initial powder size of 2 μm. The hardness and modulus of the consolidated pure W bulks were measured using nanoindentation test; and the microstructure was investigated using light microscopy (LM) and scanning electron microscopy (SEM). It is found that the shock pressure plays a more important role than preheating temperature, after the pressure exceeding the crush strength of tungsten powder during the sintering process. At the preheating temperature of 1300 °C, the increase in shock pressure leads to obvious surface melting. For HSC of pure tungsten, the void collapse and surface melting are the main sintering mechanisms. The former one contributes to the densification behavior of powders, and the later one is responsible for the inter-particle bonding; and both of which are dominated by the shock pressure. The advantage of preheating for eliminating the cracks is also demonstrated by the experimental results.     

Ultra high-pressure spark plasma sintered ZrC-Mo and ZrC-TiC composites

Ultra-high-pressure spark plasma sintering was applied to ZrC-20 wt%Mo and ZrC-20 wt%TiC composites with a pressure up to 7.8 GPa and temperatures of 1550 °C and 1950 °C. Mechanical performance of the composites was benchmarked against a plain ZrC produced by the same method. Both composites outperformed the pure ZrC with superior hardness and indentation fracture toughness of 2239 HV1 and 5.4 MPa m^1/2, and 1896 HV1 and 5.9 MPa m^1/2, respectively, for ZrC-Mo and ZrC-TiC composites. It was shown that ultra-high compaction pressure affected the ZrC-20 wt%TiC miscibility gap by lowering the temperature threshold from the usually applied 1800 °C down to 1550 °C resulting in formation of the solid state solution of (Zr,Ti)C. In contrast, the high pressure does not inhibit the carburisation of Mo with ZrC to form MoC, even when experiments were performed in a graphite free environment. The equiaxed morphology of ZrC grains along with a right-shift in XRD peaks for ZrC indicates dissolution of Mo in ZrC resulting in formation of the solid solution of (Zr,Mo)C. High-temperature X-ray diffraction analysis under oxidation conditions was performed on the samples showing degradation of ZrC-20 wt%Mo due to the oxidation of Mo at high-temperature leading to MoO₃ vaporisation. Conversely, the oxidation of ZrC-20 wt%TiC composites was characterised by formation of ZrO₂ and TiO₂ remaining stable up to 1500 °C.     

β Phase decomposition in Ti–5Al–5Mo–5V–3Cr

The decomposition of the β phase during rapid cooling of the near β titanium alloy Ti–5Al–5Mo–5V–3Cr has been studied using in situ X-ray synchrotron diffraction combined with ex situ conventional laboratory X-ray diffraction and transmission electron microscopy (TEM). Evidence is found supporting the suggestion by De Fontaine et al. (Acta Mater. 1971;19) that embryonic ω structures form by the correlation of linear (1 1 1)β defects at high temperatures. Further cooling causes increased correlation of these defects and the formation of athermal ω structures within the β matrix at temperatures ～500 °C. Post-quench aging at 570 °C resulted in the nucleation of α laths after ～90 s at temperature, with the laths all initially belonging to a single variant type. Aging for 30 min produced an even distribution of α precipitates with a lath morphology ～1.5 μm × 0.2 μm in size composed of both the expected Burgers variants. Mechanical property data suggests that the ω structures alone have no real effect; however, hardness increases were observed as the α phase developed. The utilization of thermal regimes similar to those presented in this paper could offer a method to engineer the α phase in near β titanium alloys and hence control mechanical properties.