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.     

Titanium diboride composite with improved sintering characteristics

Titanium diboride (TiB₂) and its ceramic composites were prepared by hot pressing process. The sintering process, phase evolution, microstructure and mechanical properties of TiB₂ ceramics prepared by using different milling media materials: tungsten carbide (WC/Co) or SiAlON was studied. It was found that the inclusion of WC/Co significantly improved the sinterability of the TiB₂ ceramics. A core/rim structure with pure TiB₂ as the core and W-rich TiB₂, i.e. (Ti,W)B₂ as the rim was identified. Microstructure analysis revealed that this core/rim structure was formed through a dissolution and re-precipitation process. In addition, silicon carbide (SiC) was also introduced to form TiB₂–SiC composites. The addition of SiC as the secondary phase not only improved the sinterability but also led to greatly enhanced fracture toughness. The optimum mechanical properties with Vickers hardness ~ 22 GPa, and fracture toughness ~ 6 MPa m^1/2 were obtained on TiB₂–SiC composites milled with WC/Co.     

Characterization of mechanically alloyed nanocomposites in TiO2–B2O3–Mg–C quaternary system

The influence of the simultaneous presence of magnesium and graphite on mechanosynthesis of various nanocomposite powders in TiO₂–B₂O₃–Mg–C quaternary system was investigated. A mixture of boron oxide and titanium dioxide powders along with different amounts of magnesium and graphite was milled using a high-energy planetary ball mill to provide necessary conditions for the occurrence of a mechanically induced self-sustaining reaction (MSR). In the absence of C (100 wt.% Mg), TiB₂ nanopowder was formed as a result of combustion reaction after 34 min of milling. In the presence of both Mg and C, the mechanochemical reaction was completed after different milling times depending on the weight fraction of the reducing agents in the powder mixture. In the presence of x wt.% Mg–y wt.% C (x = 85 and 90; y = 100 − x), the mechanosynthesized composites contained TiB₂ and TiC as major compounds as well as MgO and Mg₃B₂O₆ as unwanted phases. With further increasing the graphite content to 30 wt.%, no mechanical activation was observed after 90 min of milling. The nanocomposite powders showed a bimodal particle size distribution characterized by the presence of several coarse particles (≈ 250 nm) along with finer particles with a mean size of about 75 nm. Formation mechanism of nanocomposites was explained through the analysis of the relevant sub-reactions.     

B4C/TiB2 composite powders prepared by carbothermal reduction method

B₄C–(10–20 vol%)TiB₂ composite powders have been synthesized with the temperature of 1650–1800 °C by carbothermal reduction process using boron acid, carbon black and TiO₂ powder as the starting materials. B/C mole ratio of the starting materials is ascertained, thermodynamics temperature of the reactions is calculated and the effect of ball milling on the composite powders is discussed. The experimental results indicate that B/C mole ratio of the starting materials and composite powders are 4.4 and 3.98–4.03, respectively. The purity of the gained powders is more than 99 wt%. Wet ball milling eliminates the size of the B₄C/TiB₂ composite powders from 30–40 to 3–5 μm by decreasing the conglomeration of the composite powders. XRD and EDS results show that the composite powders are composed of B₄C and TiB₂.     

Spark plasma sintering of B4C ceramics: The effects of milling medium and TiB2 addition

Boron carbide (B₄C) ceramics, with a relative density up to 98.4% and limited grain growth, were prepared at 1600-1800 °C by spark plasma sintering (SPS) technique. The effects of powder milling medium (water and 2-propanol) on the powders' surface characteristics and TiB₂ addition on the sintering densification were investigated. The ball milling processing of B₄C powders in water can promote the sintering of B₄C ceramics. A B₂O₃ layer on B₄C particle surface is concluded to promote the densification of the B₄C ceramics at an early sintering stage. This B₂O₃ layer, which normally inhibits the densification process at the final stage of the sintering, can be reduced through reaction with TiB₂ particles, resulting in further densification of the B₄C ceramics.     

Pore formation mechanism and characterization of porous NiTi shape memory alloys synthesized by capsule-free hot isostatic pressing

Porous NiTi alloys with different porosities were fabricated by capsule-free hot isostatic pressing (CF-HIP) with ammonium acid carbonate (NH₄HCO₃) as a space-holder. The microstructure and porosity of porous NiTi produced with different NH₄HCO₃ contents and sintering temperatures were determined. Two different creep expansion models are used to explain the pore expansion mechanism during the sintering process, which involves slow and continuous reduction of the argon pressure at high temperatures. When the NH₄HCO₃ content is 30 wt.% and the sintering temperature is 1050 °C, an ideal porous NiTi alloy with 48 vol.% porosity and circular pores (50–800 μm) is obtained. Compression tests indicate that the porous NiTi alloys with 21–48% porosity possess not only lower Young’s moduli of 6–11 GPa (close to that of human bones) but also higher compression strength and excellent superelasticity. Cell cultures reveal that the porous NiTi prepared here has no apparent cytotoxicity. The porous materials are thus promising biomaterials in hard tissue replacements.     

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.     

Effect of ZrB2 and SiC addition on TiB2-based ceramic composites prepared by spark plasma sintering

TiB₂-based ceramic composites with different amounts of ZrB₂ and SiC were prepared by spark plasma sintering at 1700 °C with an initial pressure of 40 MPa and a holding time of 10 min. The (Ti_xZr_y)B₂ solid solution was found in the sintered TiB₂/ZrB₂/SiC composites by XRD. The microstructural and mechanical properties of the prepared samples were investigated. The composite with the addition of 30 vol.% ZrB₂ shows better comprehensive performances, and the bending strength and the fracture toughness of the composite are 780.5 MPa and 7.34 MPa m^1/2, respectively. The generation of the (Ti_xZr_y)B₂ solid solution makes the microstructures of the composites finer and more homogeneous, which has played a very important role in grain refinement and interface fusion.     

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.     

Investigation the effect of B4C addition on properties of TZM alloy prepared by spark plasma sintering

TZM alloy is one of the most important molybdenum (Mo) based alloy which has a nominal composition containing 0.5–0.8 wt.% titanium (Ti), 0.08–0.1 wt.% zirconium (Zr) and 0.016–0.02 wt.% carbon (C). It is a possible candidate for high temperature applications in a variety of industries. However, the rapid oxidation of TZM alloys at high temperature in air is considered to be one of the drawback. In this study, TZM alloys with additions of 0–5 wt.% B₄C were prepared by spark plasma sintering (SPS) at 1420 °C utilizing 40 MPa pressure for 5 min under vacuum. The effects of B₄C addition on oxidation, densification behavior, microstructure, and mechanical properties were investigated. The TZM alloy with 5 wt.% B₄C have exhibited an approximately 66% reduction in mass loss under normal atmospheric conditions in oxidation tests made at 1000 °C for 60 min. And an increase from 1.9 GPa to 7.8 GPa has been determined in hardness of the alloy.     

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.     

Chemically and mechanically activated combustion synthesis of B4C–TiB2 composites

The self-propagating high-temperature synthesis (SHS) of B₄C–TiB₂ composite powders (1:1 molar ratio) from elemental reactants is performed using polytetrafluoroethylene as reaction promoter. A threshold amount of the polymer has to be added to the mixture for establishing and sustaining the combustion front. However, due to the carburizing role played by Teflon, the resulting product also contains residual C and TiC. When initial graphite is gradually replaced by the polymer, mixture reactivity is enhanced and secondary phases correspondingly decrease, thus leading to the desired composition when all stoichiometric carbon was provided by Teflon. Furthermore, a 3 h ball milling treatment of the reactants mixture allows us to decrease the required amount of Teflon from 30 to 18 wt.%.Therefore, the combination of mechanical and chemical activating methods provides a useful tool to overcome the thermodynamic or kinetic limitations encountered during the fabrication of B₄C–TiB₂ composites by SHS.     

Fabrication and mechanical properties of TiB2/ZrO2 functionally graded ceramics

Five layers were considered for the present TiB₂/ZrO₂ functionally graded ceramics and TiB₂/ZrO₂ functionally graded ceramics were prepared by hot-pressing. The first layer, marked as L₁, was composed of TiB₂–15vol%SiC. The L₂ layer was composed of TiB₂–15vol%SiC–10vol%ZrO₂. The L₃ layer was composed of TiB₂–25vol%ZrO₂ without addition of SiC, because 25vol%ZrO₂ was enough to densify TiB₂. The last two layers, L₄ and L₅, were composed of TiB₂–35vol%ZrO₂ and TiB₂–45vol%ZrO₂, respectively. Denser graded microstructures as well as the stronger interfaces were achieved for TiB₂/ZrO₂ functionally graded ceramics hot-pressed at 1900 °C. Due to the phase transformation of ZrO₂, the toughness of TiB₂/ZrO₂ functionally graded ceramics increased from ~ 4.3 MPa m^1/2 for the TiB₂-rich layer to ~ 8.9 MPa m^1/2 for the ZrO₂-rich layer. The effect of hot-pressing temperature on the toughness of TiB₂/ZrO₂ functionally graded ceramics was further investigated in detail.     

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.     

Effect of Ni content on the compression properties and abrasive wear behavior of the (TiB2–TiCxNy)/Ni composites

The (TiB₂–TiC_xN_y)/Ni composites were fabricated by the method of combustion synthesis and hot press consolidation in a Ni–Ti–B₄C–BN system. The effect of Ni content on the microstructure, hardness, compression properties and abrasive wear behavior of the composites has been investigated. The results indicate that with the increase in Ni content from 30 wt.% to 60 wt.%, the average size of the ceramic particles TiB₂ and TiC_xN_y decreases from 5 μm to ≤ 1 μm, while the hardness and the abrasive wear resistance of the composites decrease. The composite with the Ni content of 30 wt.% Ni possesses the highest hardness (1560.8 Hv) and the best abrasive wear resistance. On another hand, with the increase in the Ni content, the compression strength increases firstly, and then decreases. The composite with 50 wt.% Ni possesses the highest compression strength (3.3 GPa). The hardness and fracture strain of the composite with 50 wt.% Ni are 1251.2 Hv and 3.9%, respectively.     

Mechanical and thermal properties of hot pressed ZrB2 system with TiB2

ZrB₂-TiB₂-based ceramics with varying amount of TiB₂ (up to 30 wt%) were hot pressed at 2200 °C in Ar atmosphere, and the effect of the TiB₂ addition on mechanical properties like hardness, fracture toughness, scratch resistance, wear resistance and thermal conductivity of the system was compared to monolithic ZrB₂ ceramic. It was found from X-ray diffraction that TiB₂ completely entered into the structure and formed solid solution with ZrB₂. Addition of TiB₂ in ZrB₂ system improves the mechanical and wear resistance properties. ZrB₂-TiB₂ (30 wt%) ceramic, for example, showed highest hardness of 22.34 GPa, fracture toughness 3.01 MPa(m)^1/2 and lowest coefficient of friction (0.398 at 10 N load). The addition of TiB₂ in ZrB₂ system showed lower thermal conductivity than monolithic ZrB₂ by increasing grain boundary thermal resistance.     

The Oxidation of TiB2 Ceramics Containing Cr and Fe

The oxidation behavior of TiB₂, TiB₂–0.5 wt.% Cr–0.5 wt.% Fe and TiB₂–1 wt.% Cr–1 wt.% Fe was studied at 800, 900, and 1000°C in static air. These ceramics oxidized rather rapidly and formed thick oxide scales. The oxidation rates of TiB₂-base ceramics were comparable to TiO₂ formation on pure titanium. The scale formed on TiB₂ consisted of TiO₂ and B₂O₃. For TiB–Cr–Fe ceramics, a small amount of Cr- and Fe-oxides was additionally formed. B₂O₃ formed during oxidation tended to evaporate because of its high vapor pressure, making oxide scales porous and fragile. The oxidation of the TiB₂-base ceramics appeared to be governed by the inward transport of oxygen via the highly porous oxide scale. The oxidation resistance of TiB₂–Cr–Fe ceramics was similar to or better than that of TiB₂.     

Effect of reinforcement NbC phase on the mechanical properties of Al2O3-NbC nanocomposites obtained by spark plasma sintering

The sintering behavior of Al₂O₃-NbC nanocomposites fabricated via conventional and spark plasma sintering (SPS) was investigated. The nanometric powders of NbC were prepared by reactive high-energy milling, deagglomerated, leached with acid, added to the Al₂O₃ matrix in the proportion of 5 vol% and dried under airflow. Then, the nanocomposite powders were densified at different temperatures, 1450–1600 °C. Effect of sintering temperature on the microstructure and mechanical properties such as hardness, toughness and bending strength were analyzed. The Al₂O₃-NbC nanocomposites obtained by SPS show full density and maximum hardness value > 25 GPa and bending strength of 532 MPa at 1500 °C. Microstructure observations indicate that NbC nanoparticles are dispersed homogeneously within Al₂O₃ matrix and limit their grain growth. Scanning electron microscopy examination of the fracture surfaces of dense samples obtained at 1600 °C by SPS revealed partial melting of the particle surfaces due to the discharge effect.     

Taguchi analysis on the effect of process parameters on densification during spark plasma sintering of HfB2-20SiC

Field assisted sintering (FAST) has emerged as a useful technique to densify ultra high temperature ceramics like HfB₂-20SiC to a high density at relatively low temperatures and shorter times. The effect of various process variables on the densification during spark plasma sintering of HfB₂-20SiC was studied using Taguchi analysis. The statistical analysis identified sintering temperature as the most significant parameter affecting the densification of HfB₂-20SiC material. A density of 99% was achieved on sintering at 2373 K for 8 min at 30 kN pressure and heating rate of 100 K/min.     

Hardness and toughness enhancement of CeO2 addition to ZTA ceramics through HIPping technique

The aim of this research is to investigate the combined effects of CeO₂ additions and hot-isostatic pressing sintering (HIPping) technique on the hardness and toughness of ZTA ceramics. Addition of CeO₂ to ZTA ceramics leads to formation of a secondary phase (CeAl₁₁O₁₈) which played a vital role in affecting the Vickers hardness and toughness. Microstructure investigations showed that HIPping had a significant role in the removal of pores, and consequently affected both hardness and toughness of the samples. The highest Vickers hardness (1838.3 HV) and toughness (8.92 MPa·√m) were obtained with the 5 wt.% CeO₂ additions that also had the highest bulk density (4.48 g/cm³) and the lowest percentage of porosity (0.37%).