Joining of ultra-refractory carbides

Transient-liquid-phase (TLP) bonding enables joining at reduced temperatures relative to those required by more traditional joining routes while preserving the potential for high-temperature applications of ultrarefractory carbides. Pure ZrC, HfC and TaC ultra-high temperature ceramics (UHTCs) were joined using a multilayer Ni/Nb/Ni interlayer by executing a 30-min bonding cycle under low load (<1.3 kPA) at 1400 °C in a high-vacuum furnace. Microstructural and microchemical analyses of the resulting joints were conducted using scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS). The SEM/EDS analysis suggests that the (Ni,Nb)-containing liquid formed during bonding wets the carbide matrices properly, resulting in well-bonded crack-free interfaces between the UHTCs and the Nb-rich interlayer. Although there were many similarities between the resulting joints, the microstructures in the interlayer-carbide transition regions also exhibited considerable diversity.     

Bond characteristics,mechanical properties,and high-temperature thermal conductivity of (Hf1−xTax)C composites

Bond characteristics, mechanical properties, and high-temperature thermal conductivity of ultrahigh-temperature ceramics (UHTCs), hafnium carbide (HfC), tantalum carbide (TaC), and their solid solution composites, were investigated using first-principles calculations. Mulliken analyses revealed that Ta formed stronger covalent bonds with C than did Hf. Bond overlap analyses indicated that the Hf–C bond possessed mixed covalent and ionic bond characteristics, compared with the more covalent character of the Ta–C bond. Consequently, the overall elastic properties were enhanced with increasing number of Ta–C bonds in the composites. The overall metallicity of the composites also increased with increasing TaC content; thus, the mechanical properties did not improve monotonically. Our results indicate that adding a small amount of TaC to HfC or vice versa to produce a composite would create a new UHTC with greatly improved elastic and mechanical properties as well as high-temperature thermal conductivity.     

Consolidation and characterization of highly dense single-phase Ta–Hf–C solid solution ceramics

Herein, Ta–Hf–C solid solution ceramics were consolidated from nano-scale Ta–Hf–C solid solution powders for the first time. Four different compositions (4TaC–1HfC, 1TaC–1HfC, 1TaC–3HfC, and 1TaC–4HfC) were prepared by hot-pressed sintering at 2100°C, 70 MPa pressure and a holding time of 30 minutes. The densification, formation of single-phase solid solution and mechanical properties of the samples were systemically investigated. Relative density >95% was achieved for all four compositions with some improvement when TaC content was increased. And the formation of single-phase Ta–Hf–C solid solution was strongly demonstrated by phase analysis and crystal measurement using XRD and TEM. A significant improvement of hardness up to ~30 GPa was achieved, which was much higher than that of pure TaC (18.9 GPa) and HfC (22.1 GPa), due to the high densification and solid solution strengthening mechanism.     

Fabrication and characterisation of high-performance joints made of ZrB2-SiC ultra-high temperature ceramics

Joining is crucial for ultra-high temperature ceramics (UHTCs) to be used in demanding environments due to the difficulty in manufacturing large and complex ceramic components. In this study, ZrB₂-SiC composite UHTCs parts were joined via Ni foil as filler, and the mechanical properties and oxidation behaviour of the fabricated ZrB₂-SiC/Ni/ZrB₂-SiC (ZS/Ni/ZS) joint were investigated. Firstly, dense ZrB₂-SiC composites were prepared from nano-sized powders by spark plasma sintering (SPS). The ZrB₂-SiC parts were then joined using SPS. Furthermore, the elastic modulus, hardness, shear strength and high temperature oxidation behaviour of the ZS/Ni/ZS joint were examined to evaluate its properties and performance. The experimental results showed that the ZrB₂-SiC parts were effectively joined via Ni foil using SPS and the resultant microstructures were free from any marked defects or residual metallic layers in the joint. Although the elastic modulus and hardness in the joining zone were lower than those in the base ZrB₂-SiC ceramics, the shear strength of the joint reached ∼161 MPa, demonstrating satisfactory mechanical properties. Oxidation tests revealed that the ZS/Ni/ZS joint possesses good oxidation resistance for a wide range of elevated temperatures (800–1600 ^oC), paving the way for its employment in extreme environments.     

Wettability and interfacial phenomena in the liquid-phase bonding of refractory diboride ceramics: Recent developments

Joining and integration technologies are integral to manufacturing of components based on ultrahigh-temperature ceramics (UHTCs) such as transition metal diborides. Brazing is a particularly attractive joining technique because of its simplicity and versatility, but its use to join the UHTCs demands knowledge of the complex interplay among high-temperature wettability, interfacial reactions, and chemical and thermoelastic compatibilities. This paper summarizes the research and development activities carried out over the last two decades to characterize the wettability and interfacial phenomena in brazing of refractory diboride ceramics. The contact angle data of various metal alloys on diboride-based ceramics have been collected and critically evaluated in conjunction with an analysis of the chemistry and structure of the interface to understand the underlying mechanisms and phenomena that govern interface formation. It explores how solid–liquid interactions impact and are impacted by physical, chemical, and mechanical properties of joined materials. It also describes how this knowledge has been successfully utilized to create liquid-phase bonded diboride-based joints. The paper concludes with a summary of the current state of the art and highlights integration challenges and future research and technology development needs in the area.     

Unveiling enhanced oxidation resistance and mechanical integrity of multicomponent ultra-high temperature carbides

The development of a new class of multicomponent ultra-high temperature ceramics (MC-UHTCs), often referred to as high-entropy UHTCs, has gained increased interest due to the possibility of improved thermomechanical and oxidation properties. In this study, a systematic approach by gradual addition in the UHTC components ranging from a binary to a dense quaternary (Ta,Nb,Hf,Ti)C is synthesized using spark plasma sintering (SPS). The solid solutioning was the critical factor in homogenizing the composition in the multicomponent system. The segregation of NbC and HfC was seen in binary and ternary UHTC systems, while a single-phase homogeneity was observed in the quaternary UHTC improving its hardness up to 34.8 GPa. The presence of closely spaced slip lines in the MC-UHTCs enhances resistance to indentation damage up to 72% at an applied load of 200 N. The formation of complex mixed oxide phase of Hf₆Ta₂O₁₇ ensued in the lower to negligible oxidation even up to 3 min of plasma exposure with temperature exceeding 2800°C. In sum, though the entropy remains medium (0.96R) for the selected system, the quaternary UHTC system undoubtedly has significantly better thermomechanical performance when compared to established baseline UHTCs. This raises the debate on the justification for calling a multicomponent system a “high entropy” to be seen in a new light. The developed MC-UHTCs elicits the paradigm of this new class of UHTCs expanding their potential in thermal protection systems for hypersonic applications.     

Polymer precursor‐derived HfC–SiC ultrahigh‐temperature ceramic nanocomposites

Due to poor mechanical properties and antioxidation properties, etc of single phase ultrahigh‐temperature ceramics (UHTCs), the second phase such as SiC was usually introduced for improving those properties. Herein, a novel stratagem for synthesis of binary HfC–SiC ceramics has been presented. A Hf–O–Hf polymer as a HfO₂ precursor has been synthesized for preparing soluble HfC–SiC precursors with high solid content and low viscosity solutions without additional organic solvents. The structure of PHO was characterized by FTIR and ¹H‐NMR, the crystalline behavior and morphologies of polymer‐derived ceramics were identified by XRD, SEM‐EDS, and TEM. It was shown that PHO firstly transformed into HfO₂, and then reacted with in situ carbon derived from DVB and PCS thus producing cubic HfC through carbothermal reduction. In addition, the obtained HfC–SiC nanopowders exhibited spherical morphology with a diameter less than 100 nm, while the Hf, Si, and C are homogeneously distributed.     

Ultrafast joining of zirconia ceramics using electric field at low temperatures

This work describes an electric-field assisted joining technique that is capable of joining 3 mol.% yttria stabilized zirconia (3YSZ) ceramics within 1 min at furnace temperature of 400 °C. The joint with 94–99% of the parent material’s three-point bending strength (638 ± 21 MPa) was achieved at furnace temperature of 600–900 °C by optimizing the key joining parameters, including the applied electric current, joining time and furnace temperature. Increase in current and joining time promoted the formation of dense joint, but they also led to degradation of the strength of parent material via defect accumulation. The furnace temperature enhanced the defect annihilation, which lowered the extent of strength degradation of the parent material. Therefore, the joint formed at high furnace temperature with threshold current and appropriate joining time displayed high strength. It was experimentally demonstrated that the electric field enabled the ultrafast joining, rather than the Joule heating.     

Solid solution synthesis of tantalum carbide‐hafnium carbide by spark plasma sintering

Solid solutions of Tantalum carbide (TaC) and Hafnium carbide (HfC) were synthesized by spark plasma sintering. Five different compositions (pure HfC, HfC‐20 vol% TaC, HfC‐ 50 vol% TaC, HfC‐ 80 vol% TaC, and pure TaC) were sintered at 1850°C, 60 MPa pressure and a holding time of 10 min without any sintering aids. Near‐full density was achieved for all samples, especially in the HfC‐contained samples. The porosity in pure TaC samples was caused by the oxygen contamination (Ta₂O₅) on the starting powder surface. The addition of HfC increased the overall densification by transferring the oxygen contamination from TaC surface and forming ultrafine HfO₂ and Hf‐O‐C grains. With the increasing HfC concentration, the overall grain size was reduced by 50% from HfC‐ 80 vol% TaC to HfC‐20 vol% TaC sample. The solid solution formation required extra energy, which restricted the grain growth. The lattice parameters for the solid solution samples were obtained using X‐ray diffraction which had an excellent match with the theoretical values computed using Vegard's Law. The mechanical properties of the solid solution samples outperformed the pure TaC and HfC carbides samples due to the increased densification and smaller grain size.     

Ultra-high temperature deformation in TaC and HfC

TaC and HfC bars were thermo-mechanically tested up to 2900?°C using a non-contact loading method based on the Lorentz force. It was observed that HfC deflected more than TaC up to 2300?°C, which has been contributed to a difference in grain size facilitating diffusional creep, either Nabarro-Herring or Coble creep. Above 2500?°C, TaC continued to deflect more with temperature whereas HfC showed a reduced deflection. This reduced deflection was found to be an artifact of a preload plastic deformation response. Though both sets of samples were identified to have a prevalence of <110>{110} slip, at elevated temperatures, it appears that mass transport and diffusional creep mechanisms dominate evident by porosity in the grain boundaries. The activation energies of TaC were found to be 946?±?157?kJ/mol (between 2500–2700?°C) and HfC to be 685?±?54?kJ/mol (between 2100–2300?°C).     

Joining partially-sintered alumina ceramics using a mixture slurry of alumina sol and suspension

The joining of advanced ceramics allows the manufacture of components with a range of complex shapes that cannot be achieved in a cost-effective manner using existing techniques, i.e. green state shaping and/or machining. A new technique for joining partially-sintered alumina ceramics was developed by simply using a mixed slurry of Al₂O₃ sol and suspension. The interlayer of the joints had the same composition as the parent bodies, and the mechanical and chemical properties of the joint were comparable to those of the bulk material. This process can be applied to the joining of a variety of advanced ceramics.     

Microstructure and mechanical properties of TaC ceramics with 1–7.5 mol% Si as sintering aid

Metallic Si as sintering aid was effective in densifying tantalum carbide ceramic (TaC) by spark plasma sintering (SPS) at 1700°C. Full density was reached at 5.0 mol% Si addition (equivalent to 1.088% Si in weight) and above. Enhanced densification of TaC ceramic with Si was associated with decrease in oxygen content from ~0.24 wt% in TaC powder to ~0.03 wt% in consolidated specimen. Rest of the oxygen species was collected at multigrain conjunctions to form SiO₂‐based liquid at high temperatures. Upon cooling, Ta, Si, O, and C dissolving in the liquid precipitated minor phases of TaSi_x and SiC of low concentrations. Microstructure of TaC ceramics was refined by the Si addition, with average grain size decreasing from 11±8 μm at 1.0 mol% Si to 3±2 μm at 7.5 mol% Si addition. Ta solute in SiC and Si solute in TaC were evidenced. TaC ceramic containing 7.5 mol% Si had a relatively good flexural strength and fracture toughness of 646±51 MPa and 5.0 MPa·m^1/2, respectively.     

Crystal-size dependence of the spark-plasma-sintering kinetics of ZrB2 ultra-high-temperature ceramics

The crystal-size dependence of the spark-plasma-sintering (SPS) kinetics of ZrB₂ ultra-high-temperature ceramics (UHTCs) was investigated. It was found that refining the starting powder enhances the SPS kinetics, reducing the onset temperatures of sintering and of the intermediate and final sintering regimes, as well as promoting a greater maximum shrinkage rate at lower temperatures. This enhancement was only relevant with reduction in crystal size to the nanoscale. Finally, the implications for low-temperature sintering of ZrB₂ UHTCs are discussed.     

Low‐Temperature Sintering of HfC/SiC Nanocomposites Using HfSi2‐C Additives

HfC/SiC nanocomposites were fabricated via the reactive spark plasma sintering (R‐SPS) of a nano‐HfC powder and HfSi₂‐C sintering additives. The densification temperature decreased to 1750°C as the additive content increased. XRD analysis indicated the formation of pure HfC–(19.3–33.8 vol%) SiC within the sintered composites without residual silicide or oxide phases or secondary nonoxide phases. Ultrafine and homogeneously distributed HfC (470 nm) and SiC (300 nm) grains were obtained in the dense composites using nano‐HfC powder through the high‐energy ball‐milling of the raw powders and R‐SPS. Grain growth was further suppressed by the low‐temperature sintering using R‐SPS. No amorphous phase was identified at the grain boundary. The maximum Vickers hardness, Young's modulus, and fracture toughness values of the HfC/SiC nanocomposites were 22 GPa, 292 GPa, and 2.44 MPa·m^1/2, respectively.     

Micro-welding of sapphire and metal by femtosecond laser

A direct joining of sapphire and Fe–36Ni alloy was successfully realized via femtosecond laser micro-welding for the first time. A sound joint without any voids or microcracks was obtained with a narrow interface width less than 1 μm. There was no obvious element diffusion or metallurgical reactions at the interface. Sapphire and Fe–36Ni alloy were found chemically bonded and mechanically interlocked evidenced by jagged feature at the interface due to “cold” machining of femtosecond laser ablation. The highly localized femtosecond laser irradiation and smaller heat-affected zone contributed to the shear strength of the joint as high as 108.35 MPa. A higher laser scanning speed corresponded with less jagged feature and thermal stress due to the reduced thermal deposition at the interface. Proper micro-welding parameters were obtained for sapphire/Fe–36Ni alloy, and was verified in the direct joining of sapphire/steel and sapphire/silicon. It appears the femtosecond laser micro-welding technique is promising for direct joining of materials with large physical property disparities, and beneficial for manufacturing of optomechanical components at high precision, efficiency and performance.     

Sintering highly dense ultra-high temperature ceramics with suppressed grain growth

Grain coarsening normally occurs at the final stage of sintering, resulting in trapped pores within grains, which deteriorates the density and the performance of ceramics, especially for ultra-high temperature ceramics (UHTCs). Here, we propose to sinter this class of ceramics in a specific temperature range and coupled with a relatively high pressure. The retarded grain boundary migration and pressure-enhanced diffusion ensure the proceeding of densification even at final stage. A highly dense TaC ceramic (98.6 %) with the average grain size of 1.48 μm was prepared under 250 MPa via high pressure spark plasma sintering using a C_f/C die at 1850 °C. It was suggested that the final-stage densification is mainly attributed to grain boundary plastic deformation-involved mechanisms. Compared to the usual sintering route using a high temperature (>2000 °C) and normal pressure (<100 MPa), this work provides a useful strategy to acquire highly dense and fine-grained UHTCs.     

Strengthening and toughening of TiN-based and TiB2-based ceramic tool materials with HfC additive

Effects of HfC addition on the microstructures and mechanical properties of TiN-based and TiB₂-based ceramic tool materials have been investigated. Their pore number decreased gradually and relative densities increased progressively when the HfC content increased from 15 wt% to 25 wt%. The achieved high relative densities to some extent derived from the high sintering pressure and the metal phases. HfC grains of about 1 µm evenly dispersed in these materials. Both TiN and TiB₂ grains become smaller with increasing HfC content from 15 wt% to 25 wt%, which indicated that HfC additive can inhibit TiN grain and TiB₂ grain growth, leading to the formation of a fine microstructure advantageous to improve flexural strength. Especially, TiB₂-HfC ceramics exhibited the typical core-rim structure that can enhance flexural strength and fracture toughness. The toughening mechanisms of TiB₂-HfC ceramics mainly included the pullout of HfC grain, crack deflection, crack bridging, transgranular fracture and the core-rim structure, while the toughening mechanisms of TiN-HfC ceramics mainly included pullout of HfC grain, fine grain, crack deflection and crack bridging. Besides, HfC hardness had an important influence on the hardness of these materials. Higher HfC content increased Vickers hardness of TiN-HfC composite, but lowered Vickers hardness of TiB₂-HfC composite, being HfC hardness higher than for TiN while HfC hardness is lower than for TiB₂. The decrease of fracture toughness of TiN-HfC ceramic tool materials with the increase of HfC content was attributed to the formation of a weaker interface strength.     

Mechanical Behavior and Applications of Plasma Arc Welded Ceramics

Zirconium diboride and zirconium carbide‐based ceramics were joined by plasma arc welding to demonstrate the versatility of this technique. A parent material composition consisting of ZrB₂ with 20 vol% ZrC was hot pressed to near full density, sectioned to produce specimens for welding, and welded together to produce billets for mechanical property studies. The four‐point flexure strength of the parent material was ~660 MPa, while the strength of the welded specimens ranged from ~140 to ~250 MPa. Microstructural analysis revealed that decreased strength in the welded specimens was caused by volume flaws, microcracking of large ZrB₂ grains (up to 1 mm in length), and residual tensile stresses that developed at the surface of weld pools during cooling. The versatility of plasma arc welding was demonstrated by joining of ZrC‐based ceramics and fabricating three ZrB₂–ZrC components for potential applications, including a high‐temperature electrical contact, an ultra‐high‐temperature thermocouple, and a wedge that was a notional wing leading edge. These three applications demonstrated the ability to join ceramics to a refractory metal, fabricate a chemically inert high‐temperature thermocouple, and produce complex shapes for aerospace applications.     

Pressure-less joining of alumina ceramics by the reaction-bonded aluminum oxide (RBAO) method

The present work demonstrates a pressure-less and reliable joining technique for alumina ceramics through a reaction-bonded aluminum oxide (RBAO) method. Effective joining relies on the RBAO mechanism, in which Al particles are converted to alumina through oxidation and bond with alumina particles from the parts to be joined upon sintering. Alumina ceramics in a green state were successfully joined with the use of an Al/Al₂O₃ powder mixture as an interlayer. The oxidation behavior of the Al particles was confirmed by thermogravimetry and X-ray diffraction analyses. Joining was performed in ambient air at 1650 °C for 2 h without applying any external pressure. Microstructural observations at the joining interfaces indicated a compact joining. The joining strengths were assessed by determining the biaxial strengths at room temperature, and the joined samples exhibited no fractures at the joining interfaces. Moreover, the joints had a strength of almost 100 % when compared with those of the parent alumina ceramics.     

Joining of zirconia ceramics in green state using a paste of zirconia slurry

A new technique for the green state joining of zirconia ceramics has been developed simply by using a paste of zirconia slurry. The interlayer of the joints has the same composition as the parent green bodies and, therefore, the mechanical properties of the joint are comparable to those of the bulk materials. Using this method, large and/or complex ceramic components could be produced cost effectively, because it minimizes the machining of the sintered body and eliminates the need for special equipment. This process can be applied to the joining of various other advanced ceramics.