A numerical approach to the heat transfer in monolithic and SiC reinforced HfB2, ZrB2 and TiB2 ceramic cutting tools

Cutting tools are widely used in industry and must be hard enough for machining processes, which should work appropriately at low temperatures to improve cutting speed and productivity. In this research, a numerical method was employed to calculate the temperature distribution in the cutting tools made of different diborides. Monolithic and SiC reinforced HfB₂, ZrB₂ and TiB₂ ceramics were selected for investigation and comparison studies. In this regard, 3-dimensional heat conduction equation was solved in a cutting tool with radiative, convective and heat flux boundary conditions by finite element method using COMSOL Multiphysics. This study clarifies that the maximum temperature in the tools made of ZrB₂ and TiB₂ among the monolithic ceramics is lower than that of HfB₂. Moreover, the temperature variation slope versus time is the highest in HfB₂. All composite materials reinforced with SiC showed lower maximum temperature than the monolithic ones. The thermal performance of TiB₂–SiC and ZrB₂–SiC composites was acquired to be better than that of the other investigated materials. The dominant heat transfer mechanism in the cutting tools was conduction.     

Mechanical,Thermal, and Oxidation Properties of Refractory Hafnium and zirconium Compounds

The thermal conductivity, thermal expansion, Youngs Modulus, flexural strength, and brittle–plastic deformation transition temperature were determined for HfB₂, HfC_0·98, HfC_0·67, and HfN_0·92 ceramics. The oxidation resistance of ceramics in the ZrB₂–ZrC–SiC system was characterized as a function of composition and processing technique. The thermal conductivity of HfB₂ exceeded that of the other materials by a factor of 5 at room temperature and by a factor of 2·5 at 820°C. The transition temperature of HfC exhibited a strong stoichiometry dependence, decreasing from 2200°C for HfC_0·98 to 1100°C for HfC_0·67 ceramics. The transition temperature of HfB₂ was 1100°C. The ZrB₂/ZrC/SiC ceramics were prepared from mixtures of Zr (or ZrC), SiB₄, and C using displacement reactions. The ceramics with ZrB₂ as a predominant phase had high oxidation resistance up to 1500°C compared to pure ZrB₂ and ZrC ceramics. The ceramics with ZrB₂/SiC molar ratio of 2 (25 vol% SiC), containing little or no ZrC, were the most oxidation resistant.     

Microstructural characterization of ZrB2–SiC based UHTC tested in the MESOX plasma facility

Microstructures were investigated for ZrB₂–SiC and ZrB₂–HfB₂–SiC ultra high temperature ceramics that were subjected to a high temperature plasma environment. Both materials were tested in the MESOX facility to determine the recombination coefficient for atomic oxygen up to 1750 °C in subsonic air plasma flow. Surfaces were analyzed before and after testing to gain a deeper insight of the surface catalytic properties of these materials. Microstructural analyses highlighted oxidation induced surface modification. Oxide layers were composed of silica with trace amounts of boron oxide and zirconia if the maximum temperature was lower than about 1550 °C and zirconia for higher temperatures. The differences in the oxide layer composition may account for the different catalytic behavior. In particular, the presence of a borosilicate glass layer on the surface of ZrB₂–SiC materials guarantees atomic oxygen recombination coefficients that are relatively lower than the coefficients measured when only zirconia is present. The oxidation processes of ZrB₂–HfB₂–SiC materials, associated with catalytic tests carried out up to 1550 °C, lead to the formation of hafnia as well as silica, and zirconia. The higher recombination coefficients measured in the case of ZrB₂–HfB₂–SiC materials can be correlated with the presence of hafnia which is probably characterized by higher catalytic activity compared to zirconia. In any case, the investigated materials demonstrate a low catalytic activity over the inspected temperature range with maximum values of recombination coefficients close to 0.1.     

Electrical and thermophysical properties of ZrB2 and HfB2 based composites

Electrical resistivities, thermal conductivities and thermal expansion coefficients of hot-pressed ZrB₂–SiC, ZrB₂–SiC–Si₃N₄, ZrB₂–ZrC–SiC–Si₃N₄ and HfB₂–SiC composites have been evaluated. Effects of Si₃N₄ and ZrC additions on electrical and thermophysical properties of ZrB₂–SiC composite have been investigated. Further, properties of ZrB₂–SiC and HfB₂–SiC composites have been compared. Electrical resistivities (at 25 °C), thermal conductivities (between 25 and 1300 °C) and thermal expansion coefficients (over 25–1000 °C) have been determined by four-probe method, laser flash method and thermo-mechanical analyzer, respectively. Experimental results have shown reasonable agreement with theoretical predictions. Electrical resistivities of ZrB₂-based composites are lower than that of HfB₂–SiC composite. Thermal conductivity of ZrB₂ increases with addition of SiC, while it decreases on ZrC addition, which is explained considering relative contributions of electrons and phonons to thermal transport. As expected, thermal expansion coefficient of each composite is reduced by SiC additions in 25–200 °C range, while it exceeds theoretical values at higher temperatures.     

Stress measurements in ZrB2–SiC composites using Raman spectroscopy and neutron diffraction

Raman spectroscopy and neutron diffraction were used to study the stresses generated in zirconium diboride–silicon carbide (ZrB₂–SiC) ceramics. Dense, hot pressed samples were prepared from ZrB₂ containing 30 vol% α-SiC particles. Raman patterns were acquired from the dispersed SiC particulate phase within the composite and stress values were calculated to be 810 MPa. Neutron diffraction patterns were acquired for the ZrB₂–SiC composite, as well as pure ZrB₂ and SiC powders during cooling from ～1800 °C to room temperature. A residual stress of 775 MPa was calculated as a function of temperature by comparing the lattice parameter values for ZrB₂ and SiC within the composite to those of the individual powders. The temperature at which stresses began to accumulate on cooling was found to be ～1400 °C based on observing the deviation in lattice parameters between pure powder samples and those of the composite.     

Shock wave-material interaction in ZrB2–SiC based ultra high temperature ceramics for hypersonic applications

We investigate the thermochemical stability of ZrB₂–SiC based multiphase ceramics to hypersonic aerothermodynamic conditions in free piston shock tube with an objective to understand quantitatively the role of thermal shock and pressure. The developed ceramics sustained impulsive thermomechanical shock, under reflected shock pressure of 6.5 MPa and reflected shock temperature of 4160 K in dissociated oxygen, without structural failure. The conjugate heat transfer analysis predicts the surface temperature of ZrB₂–SiC to reach a maximum of 693 and 865 K, for ZrB₂–SiC–Ti. The transient shock-material response is characterized by surface oxidation of the investigated ceramics, when exposed to high enthalpy gaseous environment, as a consequence of the interaction with ultrafast-heated (10⁶ K/s) gas for ~5 ms. Spectroscopic and structural characterization reveals that addition of Ti improves thermomechanical shock resistance, which is attributed to the assemblage of refractory phases. Taken together, ZrB₂–SiC–Ti based multiphase ceramics exhibit favorable shock-material response under impulse loading.     

Experiment and simulation analysis on thermal shock resistance of laminated ceramics with graphite and boron nitride interfaces

Laminated ZrB₂–SiC ceramics with graphite and BN as the interface layers were fabricated by tape casting and consequent hot pressing. The influences of interface materials on the thermal shock resistance of the laminated ceramics were studied by both experimental and theoretical analyses. Experimental results show that the critical temperature differences of G/LZS (laminated ZrB₂–SiC/G) and BN/LZS (laminated ZrB₂–SiC/BN) were 237 and 99 °C, respectively. The stress gradients of G/LZS and BN/LZS calculated via finite element analysis were 709 and 809 MPa/mm, respectively. Thus, the thermal shock resistance of G/LZS was higher than that of BN/LZS. Such merits of G/LZS can be explained by the following two reasons: one is the thermal conductivity of the graphite interface layer was higher than that of the BN interface layer; the other is the difference of the thermal expansion coefficient for the graphite interface layer and the matrix layer was lower than that for the BN interface layer and the matrix layer.     

ZrB2 – SiC ceramics: Residual stresses and mechanical properties

The stress-strain state of ZrB₂-SiC ultra-high-temperature ceramics, produced using commercial powders with different impurity levels, was investigated by X-ray diffraction. Upon analysis of ZrB₂ and SiC diffraction lines shift, the level of thermal stresses (strains) of the different phases was determined. An increase of internal stresses in ceramics with rising viscous-brittle transition temperatures, T_ve, was attributed to increased grain boundary strength. Ceramics, for which high T_ve and high level of internal stresses were estimated, exhibited high strength, up to 700 MPa at 1400 °C. A field of compressive thermal stresses in the matrix phase resulted to be necessary for achieving high strength at low-temperatures. On the contrary, the presence of low-melting impurities at the grain boundaries negatively impacted on the stress level in ZrB₂ boundaries in the high temperature regime.     

Controllable preparation of porous ZrB2–SiC ceramics via using KCl space holders

In this work, a novel and facile technique based on using KCl as space holders, along with partial sintering (at 1900 °C for 30 min), was explored to prepare porous ZrB₂–SiC ceramics with controllable pore structure, tunable compressive strength and thermal conductivity. The as-prepared porous ZrB₂–SiC samples possess high porosity of 45–67%, low average pore size of 3–7 μm, high compressive strength of 32–106 MPa, and low room temperature thermal conductivity of 13–34 W m⁻¹ K⁻¹. The porosity, pore structure, compressive strength and thermal conductivity of porous ZrB₂–SiC ceramics can be tuned simply by changing KCl content and its particle size. The effect of porosity and pore structure on the thermal conductivity of as-prepared porous ZrB₂–SiC ceramics was examined and found to be consistent with the classical model for porous materials. The poring mechanism of porous ZrB₂–SiC samples via adding pore-forming agent combined with partial sintering was also preliminary illustrated.     

UHTC–carbon fibre composites: Preparation,oxyacetylene torch testing and characterisation

Current generation carbon–carbon (C–C) and carbon–silicon carbide (C–SiC) materials are limited to service temperatures below 1800 °C and materials are sought that can withstand higher temperatures and ablative conditions for aerospace applications. One potential materials solution is carbon fibre-based composites with matrices composed of one or more ultra-high temperature ceramics (UHTCs); the latter are intended to protect the carbon fibres at high temperatures whilst the former provides increased toughness and thermal shock resistance to the system as a whole. Carbon fibre–UHTC powder composites have been prepared via a slurry impregnation and pyrolysis route. Five different UHTC compositions have been used for impregnation, viz. ZrB₂, ZrB₂–20 vol% SiC, ZrB₂–20 vol% SiC–10 vol% LaB₆, HfB₂ and HfC. Their high-temperature oxidation resistance has been studied using a purpose built oxyacetylene torch test facility at temperatures above 2500 °C and the results are compared with that of a C–C benchmark composite.     

Heat conduction mechanisms in hot pressed ZrB2 and ZrB2–SiC composites

Thermal diffusivity and conductivity of hot pressed ZrB₂ with different amounts of B₄C (0–5 wt%) and ZrB₂–SiC composites (10–30 vol% SiC) were investigated experimentally over a wide range of temperature (25–1500 °C). Both thermal diffusivity and thermal conductivity were found to decrease with increase in temperature for all the hot pressed ZrB₂ and ZrB₂–SiC composites. At around 200 °C, thermal conductivity of ZrB₂–SiC composites was found to be composition independent. Thermal conductivity of ZrB₂–SiC composites was also correlated with theoretical predictions of the Maxwell–Eucken relation. The dominated mechanisms of heat transport for all hot pressed ZrB₂ and ZrB₂–SiC composites at room temperature were confirmed by Wiedemann–Franz analysis by using measured electrical conductivity of these materials at room temperature. It was found that electronic thermal conductivity dominated for all monolithic ZrB₂ whereas the phonon contribution to thermal conductivity increased with SiC contents for ZrB₂–SiC composites.     

Pressureless sintering of ZrB2–SiC composite laminates using boron and carbon as sintering aids

Abstract

A processing method common to composite ceramics with very different ZrB₂/SiC ratios was developed in order to exploit ZrB₂–SiC laminates comprising alternate layers with different compositions for thermal protection systems of re-entry vehicles. Ceramic laminates were made using SiC, ZrB₂ and composites with a SiC/ZrB₂ ratio ranging from 100 vol.-%SiC to 100 vol.-%ZrB_2. The preparation was performed by tape casting of a slurry, layer stacking, debinding and pressureless sintering. Boron and carbon proved to be suitable sintering aids for SiC laminates as well as for composite laminates containing SiC. In the case of composites with a ZrB₂ matrix, the second phase of SiC acted as a sintering aid. This process obtains very similar densification for specimens with very different compositions (ranging from 100%SiC to 80ZrB₂–20SiC). The stiffness of ZrB₂–SiC laminates increased with the ZrB₂ content increase, while the bending strength was not affected by the ZrB₂/SiC ratio.     

Thermal Shock Resistance of Laminated ZrB2–SiC Ceramic Evaluated by Indentation Technique

In this work, the thermal shock behavior of laminated ZrB₂–SiC ceramic has been evaluated using indentation‐quench method based on propagation of Vickers cracks and compared with the monolithic ZrB₂–SiC ceramic. The results showed that the laminated ZrB₂–SiC ceramic exhibited better resistance to crack propagation and thermal shock under water quenching condition, and the critical temperature difference (ΔT_c) of laminated ZrB₂–SiC ceramic (ΔT_c ≈ 590°C) was much higher than that of monolithic ceramic (ΔT_c ≈ 290°C). The significant improvement in thermal shock resistance was attributed to residual stresses enhancing the resistance to crack growth during thermal shock loading.     

Qualitative analysis of hafnium diboride based ultra high temperature ceramics under oxyacetylene torch testing at temperatures above 2100 °C

Oxidation tests were carried out on HfB₂–SiC, HfB₂–HfC, HfB₂–WC–SiC, and HfB₂–WSi₂ ceramics using an oxyacetylene torch. The samples were oxidized between 2100 and 2300 °C. From cross-sectional images, scale non-adherence was noted as a limiting factor in oxidation resistance. The sample with the best scale adherence was HfB₂–WSi₂. Factors involving scale non-adherence such as vapor pressure, coefficient of thermal expansion mismatch and phase transformations were considered. In comparing the scale adherence of the samples it was hypothesized that vapor pressure buildup is the principal contributing factor in the scale adherence differences observed among the tested samples. However, the coefficient of thermal expansion mismatch and HfO₂ phase transformation cannot be neglected as contributing factors to scale non-adherence in all samples.     

Improved Green Strength and Green Machinability of ZrB2–SiC Through Gelcasting Based on a Double Gel Network

ZrB₂–SiC green ceramics were fabricated by aqueous gelcasting based on single AM‐MBAM, single Na‐alginate, and double gel network system. ZrB₂–SiC ceramics obtained by aqueous gelcasting based on AM‐MBAM and Na‐alginate double gel network had a dramatically highest green strength of 98.6 ± 5.1 MPa, which was 103% and 61% higher than that of ZrB₂–SiC ceramics based on single AM‐MBAM system and Na‐alginate system, respectively. A “scratch test” was conducted to evaluate the green machinability of as‐prepared ZrB₂–SiC ceramics. The ZrB₂–SiC ceramics based on this double gel network was found to have the best green machinability.     

Mechanical properties of ZrB2–SiC(ZrSi2) ceramics

Mechanical properties of ZrB₂–SiC and ZrB₂–ZrSi₂–SiC ceramics in the temperature range from 20 to 1400 °C were studied. It was found that the introduction of zirconium silicide resulted in pore-free ceramics having bending strengths of 400–500 MPa over a wide range of boride–carbide compositions. Zirconium silicide additive did not lead to significant strength and hardness changes at low temperature, but essentially increased Weibull modulus, and, therefore, the reliability of the ceramics. However, zirconium silicide additions resulted in noticeably reduced bending strength in ZrB₂–SiC based composites at 1400 °C.     

ZrB2–SiC laminated ceramic composites

The oxidation behavior for ZrB₂–20 vol% SiC (ZS20) and ZrB₂–30 vol% SiC (ZS30) ceramics at 1500 °C was evaluated by weight gain measurements and cross-sectional microstructure analysis. Based on the oxidation results, laminated ZrB₂–30 vol% SiC (ZS30)/ZrB₂–25 vol% SiC (ZS25)/ZrB₂–30 vol% SiC (ZS30) symmetric structure with ZS30 as the outer layer were prepared. The influence of thermal residual stress and the layer thickness ratio of outer and inner layer on the mechanical properties of ZS30/ZS25/ZS30 composites were studied. It was found that higher surface compressive stress resulted in higher flexural strength. The fracture toughness of ZS30/ZS25/ZS30 laminates was found to reach to 10.73 MPa m^1/2 at the layer thickness ratio of 0.5, which was almost 2 times that of ZS30 monolithic ceramics.     

Densification of ZrB2-based composites and their mechanical and physical properties: A review

This study reviews densification behaviour, mechanical properties, thermal, and electrical conductivities of the ZrB₂ ceramics and ZrB₂-based composites. Hot-pressing is the most commonly used densification method for the ZrB₂-based ceramics in historic studies. Recently, pressureless sintering, reactive hot pressing, and spark plasma sintering are being developed. Compositions with added carbides and disilicides displayed significant improvement of densification and made pressureless sintering possible at ≤2000 °C. Reactive hot-pressing allows in situ synthesizing and densifying of ZrB₂-based composites. Spark plasma sintering displays a potential and attractive way to densify the ZrB₂ ceramics and ZrB₂-based composites without any additive. Young's modulus can be described by a mixture rule and it decreased with porosity. Fracture toughness displayed in the ZrB₂-based composites is in the range of 2–6 MPa m^1/2. Fine-grained ZrB₂ ceramics had strengths of a few hundred MPa, which increased with the additions of SiC and MoSi₂. The small second phase size and uniform distribution led to higher strengths. The addition of nano-sized SiC particles imparts a better oxidation resistance and improves the strength of post-oxidized ZrB₂-based ceramics. In addition, the ZrB₂-based composites showed high thermal and electrical conductivities, which decreased with temperature. These conductivities are sensitive to composition, microstructure and intergranular phase. The unique combinations of mechanical and physical properties make the ZrB₂-based composites attractive candidates for high-temperature thermomechanical structural applications.     

Toughening of laminated ZrB2-SiC ceramics with residual surface compression

Laminated ZrB₂-SiC ceramics with residual surface compression were prepared by stacking layers with different SiC contents. The maximum apparent fracture toughness of these laminated ZrB₂-SiC ceramics was 10.4 MPam^1/2, which was much higher than that of monolithic ZrB₂-SiC ceramics. The theoretical predictions showed that the apparent fracture toughness was strongly dependent on the position of the notch tip, which was confirmed by the SENB tests. Moreover, laminated ceramics showed a higher fracture load when the notch tip located in the compressive layer, whereas showed a lower fracture load as the notch tip within the tensile layer. The toughening effect of residual compressive stresses was verified by the appearance of crack deflection and pop-in event. The influence of geometrical parameters on the apparent fracture toughness and residual stresses was analyzed. The results of theoretical calculation indicated that the highest residual compressive stress did not correspond to the highest apparent fracture toughness.     

Thermal properties of La2O3-doped ZrB2- and HfB2-based ultra-high temperature ceramics

Thermal properties of La₂O₃-doped ZrB₂- and HfB₂-based ultra high temperature ceramics (UHTCs) have been measured at temperatures from room temperature to 2000 °C and compared with SiC-doped ZrB₂- and HfB₂-based UHTCs and monolithic ZrB₂ and HfB₂. Thermal conductivities of La₂O₃-doped UHTCs remain constant around 55–60 W/mK from 1500 °C to 1900 °C while SiC-doped UHTCs showed a trend to decreasing values over this range.