Mechanical properties and microstructure of TiB2–TiC composite ceramic cutting tool material

TiB₂–TiC composite ceramic cutting tool material was prepared by sintering during hot-pressing in vacuum. The effects of nano-scale Ni and Mo additives and sintering heating rate on mechanical properties and grain characteristics were investigated. TiB₂ and TiC grains exhibited prismatic and equiaxed shapes respectively. The diameter and aspect ratio of prismatic TiB₂ grains were influenced by nano-scale Ni/Mo additives. A higher heating rate could cause a higher aspect ratio of prismatic TiB₂ grains. The good mechanical properties of TN1((TiB₂–TiC)/Ni composite ceramic sintered at a heating rate of 50 °C/min) were ascribed to a relatively fine and homogenous microstructure. And a brittle B₄MoTi solid solution phase and wider distribution of grain size induced the lower flexural strength of TNM2((TiB₂–TiC)/(Ni,Mo) composite ceramic sintered at heating rate of 100 °C/min), but the higher aspect ratio of TiB₂ grains could prevent cracks from propagating and ameliorated the fracture toughness. The optimum resultant mechanical properties were obtained by (TiB₂–TiC)/Ni composite ceramic sintered at a heating rate of 50 °C/min.     

A new TiB2 + CrSi2 composite – Densification,characterization and oxidation studies

A new composite of TiB₂ with CrSi₂ has been prepared with excellent oxidation resistance. Dense composite pellets were fabricated by hot pressing of powder mixtures. Microstructural characterization was carried out by XRD and SEM with EDAX. Mechanical and physical properties were evaluated. Extensive oxidation studies were also carried out. A near theoretical density (99.9% TD) was obtained with a small addition of 2.5 wt.% CrSi₂ by hot pressing at 1700 °C under a pressure of 28 MPa for 1 h. The microstructure of the composite revealed three distinct phases, (a) dark grey matrix of TiB₂, (b) black phase – rich in Si and (c) white phase – Cr laden TiB₂. Hardness and fracture toughness were measured as 29 ± 2 GPa and 5.97 ± 0.61 MPa m^1/2, respectively. Crack branching, deflection and bridging mechanisms were responsible for the higher fracture toughness. With increase in CrSi₂ content, density, hardness and fracture toughness values of the composite decreased. Thermo gravimetric studies revealed the start of oxidation of the composite at 600 °C in O₂ atmosphere. Isothermal oxidation of these composites showed better oxidation resistance by formation of a protective oxide layer. TiO₂, Cr₂O₃ and SiO₂ phases were identified on the oxidized surface. Effects of CrSi₂ content, temperature and duration of oxidation on the oxide layer formation are reported. Activation energy of the composite was calculated as ∼110 kJ/mol using Arrhenius equation. Diffusion controlled mechanism of oxidation was observed in all the composites.     

The study of NiAl-TiB2 coatings prepared by electro-thermal explosion ultrahigh speed spraying technology

NiAl-TiB₂ composite coatings with 0, 10 and 20 wt.% TiB₂ were synthesized on the Ni-based superalloy substrate using electro-thermal explosion ultrahigh speed spraying technology. The microstructure analysis shows that the coatings consist of submicron grains. The bond between coatings and substrate is metallic cohesion. TiB₂ as a powerful reinforcement is doped in NiAl for increasing its hardness. The isothermal oxidation test is carried out for the composite coatings at 1100 °C in air. The result shows that the oxidation resistance of NiAl coating is higher than that of NiAl-10TiB₂ and NiAl-20TiB₂ coatings. The phases of oxides on the coatings during the process at high temperature have been analyzed by X-ray diffraction. The results show that Al₂O₃ and Cr₂O₃ coexistence on surface of NiAl coating, while Al₂O₃, Cr₂O₃, TiO₂ and a small amount of NiO form on surface of NiAl-10TiB₂ and NiAl-20TiB₂ coatings after oxidation for 4 h.     

Coating of TiB2 dispersed Ti50Ni50 superelastic alloy layer onto Ti-6Al-4V alloy by spark and resistance sintering

The spark and resistance sintering (SRS) of a mixture of Ti, Ni, and TiB₂ powders was carried out to form a TiB₂ dispersed TiNi alloy layer onto a Ti-6Al-4V alloy substrate. The strength and delamination resistance of the surface layer were evaluated by three-point bending tests. The results showed that the bending strength of the specimen with the TiNi alloy surface layer without TiB₂ particles sintered at 1273 K was low because the crack initiation occurred at an early stage of loading in a thick interface layer containing brittle Ti-Ti₂Ni eutectic. By decreasing the sintering temperature to 1200 K, the bending strength increased and the crack initiation occurred from the surface because the interface layer was thin and did not contain the brittle Ti-Ti₂Ni eutectic. For the specimens with TiB₂ dispersed TiNi surface layer that was sintered at 1273 K, the bending strength was larger than that of the specimens with TiNi surface layer because the interface layer does not contain the Ti-Ti₂Ni eutectic and compressive residual stress generated in the surface layer during cooling process after SRS suppresses the crack initiation on the surface. The coating of TiB₂ dispersed TiNi alloy onto titanium alloys by SRS provides strong interface to prevent delamination of the surface layer, strong surface due to residual compressive stress, and wear-resistant surface due to the existence of hard TiB₂ particles and superelastic deformation of TiNi matrix.     

Effect of partial substitution of Cr for Ni on densification behavior, microstructure evolution and mechanical properties of Ti(C,N)-Ni-based cermets

Four cermets of composition TiC-10TiN-16Mo-6.5WC-0.8C-0.6Cr₃C₂-(32 − x)Ni-xCr (x = 0, 3.2, 6.4 and 9.6 wt%) were prepared, to investigate the effect of the partial substitution of Cr for Ni on densification behavior, microstructure evolution and mechanical properties of Ti(C,N)-Ni-based cermets. The partial substitution of Cr for Ni decreased full densification temperature, and the higher the content of Cr additive was, the lower full densification temperature was. The partial substitution of Cr for Ni had no significant effect of the formation of Mo₂C and Ti(C,N) and the dissolution of WC, and however, it had a significant effect on the dissolution of Mo₂C. Cr in Ni-based binder phase diffused into undissolved Mo₂C to form (Mo,Cr)₂C above 1000 °C at 6.4-9.6 wt% Cr additive, and a small amount of (Mo,Cr)₂C did not dissolve after sintering at 1410 °C for 1 h at 9.6 wt% Cr additive. In the final microstructure, Cr content in Ni-based binder phase increased with increasing the content of Cr additive, and however, regardless of the content of Cr additive, coarse Ti(C,N) grains generally consisted of black core, white inner rim and grey outer rim, and fine Ti(C,N) grains generally consisted of white core and grey rim. The partial substitution of Cr for Ni increased hardness and decreased transverse rupture strength (TRS). Ni-based binder phase became hard with increasing the content of Cr additive, therefore resulting in the increase of hardness and the decrease of TRS. TRS was fairly low at 9.6 wt% Cr additive, which was mainly attributed hardening of Ni-based binder phase and undissolved (Mo,Cr)₂C.     

Synthesis, microstructure and mechanical properties of reaction-infiltrated TiB2-SiC-Si composites

TiB₂-C preforms formed with different compositions and processing parameters were reactively infiltrated by Si melts at 1450 °C to fabricate TiB₂-SiC-Si composites. Phase constituent and microstructure of these composites were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The resulting composites are generally composed of TiB₂ and reaction-formed β-SiC major phases, together with a quantity of residual Si. Unreacted carbon is detected in the samples with a starting composition of 2TiB₂ + 1C formed at higher pressure and in all of the ones at the composition of 1TiB₂ + 1C. The distribution of these phases is fairly homogeneous in microstructure. TiB₂-SiC-Si composites show good mechanical properties, with representative values of 19.9 GPa in hardness, 395 GPa in elastic modulus, 3.5 MPa m^1/2 in fracture toughness and 604 MPa in bending strength. The primary toughening and strengthening mechanism is attributed to the crack deflection of TiB₂ particles.     

Reactive synthesis and mechanical properties of Mo2NiB2 based hard alloy

Using three elementary substances, Mo, Ni, and amorphous B powders as raw materials, the ternary boride based hard alloy Mo₂NiB₂–Ni was prepared successfully. The formation mechanism of the ternary phase was verified by XRD. It was indicated that the formed Mo₂NiB₂ particles at lower temperatures could be as seeds for the further formation of Mo₂NiB₂ directly from the raw materials of Mo, Ni and B at higher temperatures. The appearance of liquid phases between 1100 and 1200 °C was important for the densification of hard alloy. The microstructures of the hard alloys were observed by SEM. The main fracture modes for the hard alloys were different for the samples sintered at different temperatures. The maximum bending strength and the Rockwell hardness reached 1.85 ± 0.04 GPa and 85.7 ± 0.1 HRA, respectively. These values were comparable to those reported in literature.     

Thermal and electrical properties of TiB2–MoSi2

The present communication reports the effect of MoSi₂ addition on high temperature thermal conductivity and room temperature (RT) electrical properties of TiB₂. The thermal diffusivity and the thermal conductivity of the hot pressed TiB₂–MoSi₂ samples were measured over a range from room temperature to 1000 °C using the laser-flash technique, while electrical resistivity was measured at RT using a four linear probe method. The reciprocal of thermal diffusivity of TiB₂ samples exhibit linear dependence on temperature and the measured thermal conductivity of TiB₂-2.5% MoSi₂ composites correlate well with the theoretical predictions from Hashin’s model and Hasselman and Johnson’s model. A common observation is that the thermal conductivity of all the samples slightly increases with temperature (up to 200 °C) and then decreases with further increasing temperature. It is interesting to note that both the thermal conductivity and electrical conductivity of TiB₂ samples enhanced with the addition of 2.5 wt.% MoSi₂ sinter additive. Among all the samples, TiB₂-2.5 wt.% MoSi₂ ceramics measured with high thermal conductivity (77 W/mK) and low electrical resistivity (12 μΩ-cm) at room temperature. Such an improvement in properties can be attributed to its high density and low volume fraction of porosity. On the other hand, both the thermal and electrical properties of TiB₂ were adversely affected with further increasing the amount of MoSi₂ (10 wt.%).     

Electrodeposition of sol-enhanced nanostructured Ni-TiO2 composite coatings

A novel electroplating method has been developed to produce nanocrystalline metal-matrix nano-structured composite coatings. A small amount of transparent TiO₂ sol was added into the traditional electroplating Ni solution, leading to the formation of nanocrystalline Ni-TiO₂ composite coatings. These coatings have a smooth surface. The Ni nodules changed from traditional pyramid-like shape to spherical shape. The grain size of Ni was also significantly reduced to the level of 50 nm. It was found that the amorphous anatase TiO₂ nano-particles (∼ 10 nm) were highly dispersed in the coating matrix. The microhardness was significantly increased from 320 HV₁₀₀ of the traditional Ni coating to 430 HV₁₀₀ of the novel composite coating with 3.26 wt.% TiO₂. Correspondingly, the wear resistance of the composite coating was improved by ∼ 50%.     

Effect of Mo/B atomic ratio on the microstructure and mechanical properties of Mo2FeB2 based cermets

Four series of Mo₂FeB₂ based cermets with the Mo/B atomic ratio in the range from 0.8 to 1.1 were prepared by reaction sintering process. The microstructure and crystalline phases were studied using scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray analysis (EDX) and X-ray diffractometry (XRD). The results indicate that the transverse rupture strength (TRS) of the cermets increases with an increase of Mo/B atomic ratio and shows a maximum value of 1.9 GPa at a Mo/B atomic ratio of 0.9. At a higher atomic ratio the TRS decreases. The hardness of the cermets decreases monotonically from 90.8 HRA to 88.8 HRA with an increase of Mo/B atomic ratio. In Mo-rich cermets with an atomic ratio of Mo/B above 1.0, a new M₂₃B₆ type phase (M₂₃B₆, where M represents a metal) is found. This phase has a lattice parameter a = 1.09 nm containing Mo, Fe, Cr and B with an atomic ratio close to 16:6:1:6 and is precipitated at the interface of Mo₂FeB₂ grains or at the Mo₂FeB₂ grain boundaries.     

Recovery of Mo from Ni-Mo ore leach solution with carrier co-precipitation method

In this paper, “nascent” Fe(OH)₃ as carrier precipitation and NaHCO₃ as buffer agent were used to extract molybdenum from the complex Ni-Mo ore leach solution. The effects of different variables on the molybdenum extraction, such as the dosage of FeCl₃ and NaHCO₃ and the reaction temperature and time, were studied. The results showed that over 99% of molybdenum were extracted in 2 h at 25 ± 1 °C under the conditions of mole ratio of Fe³⁺/Mo 2.2-2.5 and mass ratio of NaHCO₃/Mo 0.7-1.5. About 92% of Mo in the Fe(OH)₃ precipitation can be leached by NH₃⋅H₂O to prepare the ammonium molybdate solution with about 100 g/L Mo. After treating with NH₃⋅H₂O, the Fe(OH)₃ precipitation was dissolved with HCl to obtain the FeCl₃ solution (FeCl₃ 500 g/L) which can be reused for the next round of experiments.     

Brazing of TiBw/TC4 composite and Ti60 alloy using TiZrNiCu amorphous filler alloy

TiB_w/TC4 composite was brazed to Ti60 alloy successfully using TiZrNiCu amorphous filler alloy, and the interfacial microstructures and mechanical properties were characterized by SEM, EDX, XRD and universal tensile testing machine. The typical interfacial microstructure was TiB_w/TC4 composite/β-Ti + TiB whiskers/(Ti, Zr)₂(Ni, Cu) intermetallic layer/β-Ti/Ti60 alloy when being brazed at 940 °C for 10 min. The interfacial microstructure evolution was influenced strongly by the diffusion and reaction between molten fillers and the substrates. Increasing brazing temperature decreased the thickness of brittle (Ti, Zr)₂(Ni, Cu) intermetallic layer, which disappeared finally when the brazing temperature exceeded 1020 °C. Fracture analyses indicated that cracks were initialized in the brittle intermetallic layer when (Ti, Zr)₂(Ni, Cu) phase existed in the brazing seam. The maximum average shear strength of joints reached 368.6 MPa when brazing was conducted at 1020 °C. Further increasing brazing temperature to 1060 °C, the shear strength was decreased due to the formation of coarse lamellar (α+β)-Ti structure.     

Effect of ultrasonic vibration on microstructural evolution of the reinforcements and degassing of in situ TiB2p/Al-12Si-4Cu composites

Some issues such as clustering of TiB₂ particles, formation of long rod-like Al₃Ti particles, as well as high porosity level usually associate with the fabrication of in situ TiB_2p/Al-alloy composites via conventional stir casting technique using Ti and B as reactants. High-intensity ultrasonic vibration was introduced in our research to solve the above issues. The process involved that the original in situ TiB_2p/Al-12Si-4Cu sample with large clusters of TiB₂ particles, large long rod-like Al₃Ti particles and high porosity was remelted at 850 °C, and then ultrasonic vibration was applied to the melt with an ultrasonic probe. The microstructural evolution of the samples treated by ultrasonic vibration with different time was examined by using SEM. After treated by ultrasonic vibration for 12 min, large clusters of TiB₂ particles were broken up effectively and TiB₂ particles were dispersed uniformly in the matrix, and long rod-like Al₃Ti particles were turned into blocky ones with the size of 10 μm due to the effect of ultrasonic stirring. In the meantime, the porosity in the composites decreased from about 6.5% to 0.86% due to the effect of ultrasonic degassing. Microhardness test suggested that a homogeneous microstructure of the composite was achieved after ultrasonic treatment. An effective approach using high-intensity ultrasonic vibration to optimize the microstructures of the particulate reinforced Al-alloy composites was proposed, and the mechanism of the effect of high-intensity ultrasonic vibration on the microstructural evolution of the reinforcements and degassing of composites was also discussed in our research.     

Effects of Pd concentration on the interfacial reaction and mechanical reliability of the Sn-Pd/Ni system

The liquid-solid reaction between Sn-xPd alloy and Ni (x = 0.05-1 wt.%) and the resulting mechanical reliability of the system were examined in this study. The reactions strongly depended on the Pd concentration and the reaction time. When the Pd concentration was low (i.e., x = 0.05 wt.%), the reaction product was only Ni₃Sn₄. In contrast, when the Pd concentration was high (i.e., x ≥ 0.2 wt.%), the reaction product became a dual-layer structure of (Pd,Ni)Sn₄-Ni₃Sn₄. Between 0.05 wt.% and 0.2 wt.% (e.g., x = 0.1 wt.%), discontinuous (Pd,Ni)Sn₄ grains scattered over the Ni₃Sn₄ layer developed. Interestingly, the (Pd,Ni)Sn₄ grains were gradually dispersed in the molten Sn-Pd alloy, leaving the Ni₃Sn₄ at the interface, as the reaction time increased. These Pd-dependent reactions were dictated by thermodynamics and can be rationalized using the Pd-Ni-Sn isotherm. Furthermore, the results of the high-speed-ball-shear (HSBS) test indicated that the mechanical strength of the Sn-Pd/Ni joints dramatically degraded by over one third due to the formation of (Pd,Ni)Sn₄ at the interface. The implication is that the Pd concentration in Sn-Pd solder joints should be reduced to a level below 0.2 wt.% to prevent the creation of an undesired microstructure.     

Microstructure and mechanical properties of TiB2–SiC ceramic composites by Reactive Hot Pressing

TiB₂–SiC ceramic composites with different contents of Ni as additive were prepared by the Reactive Hot Pressing (RHP) process at 1700 °C under a pressure of 32 MPa for 30 min. For comparison, a monolithic TiB₂ ceramic and TiB₂–SiC ceramic composite were also fabricated under the identical temperature, pressure and holding time by the Hot Pressing (HP) process. The effects of the fabrication process and Ni on the microstructure and mechanical properties of the composites were investigated. About 8 vol.% of elongated TiB₂ grains with an aspect ratio of 3–6 and a diameter of 0.5–1 μm were produced in the composite prepared by the RHP process. The improvement of the fracture toughness was attributed to the toughening and strengthening effects of SiC particles and the elongated TiB₂ grains such as crack deflection. The TiB₂–SiC–5 wt.% Ni ceramic composite had the optimum mechanical properties with a flexural strength of 858 ± 87 MPa, fracture toughness of 8.6 ± 0.54 MPa·m^1/2 and hardness of 20.2 ± 0.94GPa. The good mechanical properties were ascribed to the relatively fine and homogeneous microstructure and the strengthening effect of Ni. Ni inhibited the anisotropic growth of TiB₂.     

Investigations on synthesis of HfB2 and development of a new composite with TiSi2

This paper presents the results of investigation carried out on synthesis and densification of monolithic HfB₂ and the effect of TiSi₂ as sinter additive. Pure phase HfB₂ was prepared by boron carbide reduction of HfO₂ and hot pressed to full density with the addition of TiSi₂. Isothermal oxidation study of this composite was carried out at 850 °C up to 64 h. Formation of HfB₂ was seen at 1200 °C but pure HfB₂ was formed at a much higher temperature of 1875 °C in vacuum. Hot pressing of HfB₂ at 1850 °C and 35 MPa pressure gave a compact of 80% TD. Addition of TiSi₂ helped in achieving a much higher density at a lower temperature of 1600 °C and a pressure of 20 MPa. A fully dense composite of HfB₂ and TiSi₂ was obtained with 15% TiSi₂. Hardness and fracture toughness of this composite were 27.4 ± 1.9 GPa and 6.6 ± 0.2 MPa m^1/2, respectively. Considerable deflection was observed in the crack propagation in composites. Oxidation studies indicated the formation of HfO₂, SiO₂, TiO₂ and HfSiO₄ with some glassy phase and the composite with 15% TiSi₂ was seen to be completely covered with a protective glassy layer.     

Synthesis and consolidation of TiN/TiB2 ceramic composites via reactive spark plasma sintering

The simultaneous synthesis and densification of TiN/TiB₂ ceramic composites via reactive spark plasma sintering (RSPS) was investigated. Different component ratios (TiH₂/BN (TiN, B)) and heating rates (112.5-300 °C/min) were used to initiate the chemical reaction for TiN/TiB₂ synthesis. The omit RSPS process was revealed to have three stages, which are described separately. The relationships between the RSPS conditions, the microstructure and the properties of sintered ceramic composites were established. A Vickers hardness of 16-25 GPa and a fracture toughness of 4-6.5 MPa m^1/2 were measured for various compositions. Sintered ceramic composites containing 36 wt% TiB₂ with the highest relative density of 97.4 ± 0.4% and an average grain size of 150-550 nm have been obtained.     

占空比对高频脉冲电沉积( Ni-Co) / 纳米 Al2O3复合镀层的影响

采用高频脉冲电沉积法制备(Ni-Co)/纳米Al2O3复合镀层,研究了占空比对复合镀层沉积速率、成分、形貌及表面显微硬度的影响。结果表明:随着占空比由0.3提高至0.5,复合镀层的沉积速率增加,晶粒尺寸变大,表面变粗糙,并且Co含量降低,Ni含量增加,纳米Al2O3颗粒含量变化不明显,Co含量的降低导致硬度降低。     

热喷涂TiB2-Ni复合涂层组织结构和力学性能

采用团聚烧结方法制备TiB₂-Ni复合粉末喂料,并采用大气等离子喷涂和高速火焰喷涂两种喷涂方法制备了TiB₂-Ni涂层,比较分析了两种涂层的显微组织、物相组成、孔隙率、硬度和断裂韧性.结果表明,与等离子喷涂相比,高速火焰喷涂制备的TiB₂-Ni涂层具有更高的致密度,TiB₂含量,硬度和断裂韧性.两种涂层中TiB₂都没有发生明显的脱硼,氧化,但等离子喷涂过程中TiB₂向金属相中发生了溶解生成了大量脆性Ni₂₀Ti₃B₆相,并降低了涂层中TiB₂的含量,这是涂层硬度和断裂韧性相对较低的主要原因.     

Effects of CeO2 additive on the microstructure and mechanical properties of in situ TiB2/Al composite

In this paper, CeO₂ was investigated as an additive for in situ preparation of TiB₂/Al composite using an exothermic reaction process via K₂TiF₆ and KBF₄ salts. Experimental results indicated that when 0.5 wt.% CeO₂ additive was added, the dispersion of TiB₂ particles was improved significantly. Meanwhile, α-Al matrix grain was further refined. Compared with the composite without CeO₂, the ultimate tensile strength, yield strength, elastic modulus and tensile elongation increased by 8%, 7%, 26% and 14%, respectively in as-cast condition, and the tensile fracture behavior of the composite with CeO₂ belonged to a typical ductile fracture with microvoid coalescence.