Oxidation behavior of hot pressed ZrB2–SiC and HfB2–SiC composites

Non-isothermal, isothermal and cyclic oxidation behavior of hot pressed ZrB₂–20 (vol.%) SiC (ZS) and HfB₂–20 SiC (HS) composites have been compared. Studies involving heating in thermogravimetric analyzer have shown sharp mass increases at 740 and 1180 °C for ZS, and mass gain till 1100 °C followed by loss for HS. Isothermal oxidation tests for 1, 24 and 100 h durations at 1200 or 1300 °C have shown formation of partially and completely stable oxide scales after ～24 h exposure for ZS and HS, respectively. X-ray diffraction, scanning electron microscopy and energy or wavelength dispersive spectroscopy has confirmed presence of ZrO₂ or HfO₂ in oxide scales of ZS or HS, respectively, besides B₂O₃–SiO₂. Degradation appears more severe in isothermally oxidized ZS due to phase transformations in ZrO₂; and is worse in HS on cyclic oxidation at 1300 °C with air cooling, because of higher thermal residual stresses in its oxide scale.     

Chemical process and solid solution formation in reactive hot pressed ZrB2–SiC ceramics doped with W

ZrB₂–SiC doped with W was prepared from a mixture of Zr, Si, B₄C and W via reactive hot pressing. The fully dense ZrB₂–SiC–WB–ZrC ceramic was obtained at 1900°C for 60 min under 30?MPa in an argon atmosphere. Reaction path and solid solution characteristics of the starting powders were studied through a series of pressureless heat treatment at temperatures between 700 and 1500°C. The solid solution phases of (Zr, W)B₂, (W, Zr)B and (Zr, W)C were formed directly by reactions between the precursors. Homogeneous distribution of solute atoms in solution and the solid solubilities were also studied.     

Investigation of hot pressed ZrB2–SiC–carbon black nanocomposite by scanning and transmission electron microscopy

Hybrid ZrB₂-based composite having 10 vol% nano-sized carbon black and 20 vol% SiC was fabricated by vacuum hot pressing at 1850 °C under 20 MPa for 60 min. The microstructure and sinterability of the as-sintered ceramic was studied by X-ray powder diffraction, scanning electron microscopy, X-ray spectroscopy, scanning transmission electron microscopy and transmission electron microscopy analyses. A fully-dense hybrid composite could be achieved by hot pressing method under the aforementioned conditions. No new in-situ phase formation was detected after sintering process. Although the densification progressed in a non-reactive manner, the addition of carbonaceous material assisted the sinterability acting as the surface oxides cleaner. The precise phase and nanostructural investigations of the prepared ceramic verified the partial graphitization of carbon black and conversion of amorphous nano-additive into crystalline graphite nano-flakes.     

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.     

Mechanical,tribological and thermal properties of hot pressed ZrB2–SiC composite with SiC of different morphology

ZrB₂–SiC composites were prepared by hot pressing with different sources of SiC to study the effect of SiC with different morphology on densification, microstructure, phase composition and mechanical properties like hardness, fracture toughness and tribological properties (namely, scratch resistance, wear parameters) and thermal behaviour of the composites. Three different ZrB₂–SiC composites, i.e. ZrB₂–SiC_P (polycarbosilane derived SiC), ZrB₂–SiC_C (SiC from CUMI, India) and ZrB₂–SiC_H (SiC from H. C. Starck, Germany), were studied. It is found that ZrB₂–SiC_C composite shows highest hardness (19·13 GPa) and fracture toughness (5·30 MPa m^1/2 at 1 kgf load) in comparison with other composites. Interconnected network, better contiguity between grains of ZrB₂–SiC composites and impurity content in starting powders can play significant roles for achieving high mechanical, tribological and thermal properties of the composites. Coefficient of friction and wear parameters of all ZrB₂–SiC composites are very low, and thermal conductivity of ZrB₂–SiC composites varied from 52·71 to 65·53 W (m K)^?1 (ZrB₂–SiC_P), 54·30 to 71·55 W (m K)^?1 (ZrB₂–SiC_C) and 64·25 to 88·02 W (m K)^?1 (ZrB₂–SiC_H), respectively and also calculate the interfacial resistance of all the composites.     

Densification,microstructure and mechanical properties of hot pressed ZrB2–SiC ceramic doped with nano-sized carbon black

The effect of nano-sized carbon black on densification behavior, microstructure, and mechanical properties of zirconium diboride (ZrB₂) – silicon carbide (SiC) ceramic was studied. A ZrB₂-based ceramic matrix composite, reinforced with 20 vol% SiC and doped with 10 vol% nano-sized carbon black, was hot pressed at 1850 °C for 1 h under 20 MPa. For comparison, a monolithic ZrB₂ ceramic and a ZrB₂–20 vol% SiC composite were also fabricated by the same processing conditions. By adding 20 vol% SiC, the sintered density slightly improved to ~93%, compared to the relative density of ~90% of the monolithic one. However, adding 10 vol% nano-sized carbon black to ZrB₂–20 vol% SiC composite meaningfully increased the sinterability, as a relatively fully dense sample was obtained (RD=~100%). The average grain size of sintered ZrB₂ was significantly affected and controlled by adding carbon black together with SiC acting as effective grain growth inhibitors. The Vickers hardness, flexural strength and fracture toughness of SiC reinforced and carbon black doped composites were found to be remarkably higher than those of monolithic ZrB₂ ceramic. Moreover, unreacted carbon black additives in the composite sample resulted in the activation of some toughening mechanisms such as crack deflections.     

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.     

In situ studies of oxidation of ZrB2 and ZrB2–SiC composites at high temperatures

High temperature oxidation of ZrB₂ and the effect of SiC on controlling the oxidation of ZrB₂ in ZrB₂–SiC composites were studied in situ, in air, using X-ray diffraction. Oxidation was studied by quantitatively analyzing the crystalline phase changes in the samples, both non-isothermally, as a function of temperature, up to ～1650 °C, as well as isothermally, as a function of time, at ～1300 °C. During the non-isothermal studies, the formation and transformation of intermediate crystalline phases of ZrO₂ were also observed. The change in SiC content, during isothermal oxidation studies of ZrB₂–SiC composites, was similar in the examined temperature range, regardless of sample microstructure and composition. Higher SiC content, however, markedly retarded the oxidation rate of the ZrB₂ phase in the composites. A novel approach to quantify the extent of oxidation by estimating the thickness of the oxidation layer formed during oxidation of ZrB₂ and ZrB₂–SiC composites, based on fractional conversion of ZrB₂ to ZrO₂ in situ, is presented.     

Room temperature fatigue of ZrB2–SiC ceramic composites

Room temperature time dependent properties of ZrB₂–30 wt%SiC ceramic composite have been studied. Both static slow crack growth and cyclic fatigue deformation have been investigated. While static slow crack growth has been evaluated only in air, three different environments, water, air, and dry air, have been used to study the cyclic fatigue. It was established that under cyclic fatigue the environment plays an important role and humidity significantly facilitate crack growth in ZrB₂–30wt%SiC. The fractography of selected ZrB₂–30wt%SiC samples was performed and it was established that both defects introduced during machining as well as larger defects introduced during the processing served as fracture origins of ceramic composites.     

On the oxidation behavior of ZrB2–SiC–VC composites

In this study, near-fully dense ZrB₂–SiC–VC (75-20-5 vol%) composite was manufactured through hot pressing at 1850°C under the pressure of 40 MPa for 60 min. Then the oxidation examination of the composite was carried out under different durations and temperatures. The microstructure and phase evolution after hot pressing and oxidation processes were examined by scanning electron microscopy, and X-ray diffractometry. The VC addition led to the formation of ZrC and VSi₂ phases, which assisted the densification of the composite by removing ZrO₂ from the particles’ surface. The oxides of ZrO₂, SiO₂, ZrSiO₄, V₂O₅, and VO₂ formed distinct layers on the sample during the oxidation at 1700°C for 4 h with a parabolic regimen and activation energy of 177.5 kJ/mol.     

Microstructure and mechanical properties of in-situ hot pressed (TiB2 + SiC)/Ti3SiC2 composites with tunable TiB2 content

Without impurity phases detected, fully dense (TiB₂?+?SiC)/Ti₃SiC₂ composites have been successfully synthesised by in-situ reaction hot pressing. The effect of TiB₂ content on phase composite, sintering properties, microstructure, and mechanical properties of the composites were thoroughly investigated. With TiB₂ content increasing from 0 to 50?vol.-%, the flexural strength increases first and then decreases, whereas fracture toughness, hardness and modulus show a linear increase. The maximum strength of 826?MPa was obtained at 20?vol.-% TiB₂. On the whole, the (TiB₂?+?SiC)/Ti₃SiC₂ composites exhibit a superior comprehensive mechanical properties superior to other reported Ti₃SiC₂-based composites reinforced by singular reinforcement. The significant strengthening and toughening effect induced by the in-situ incorporated TiB₂ can be ascribed to the unique properties of TiB₂ and the synergistic action of many mechanisms including particle reinforcement, pulling out of grains, crack deflection and grain refinement strengthening.     

Reactive hot pressing of ZrB2–ZrCx ultra-high temperature ceramic composites with the addition of SiC particulate

Starting with non-stoichiometric Zr–B₄C powder mixture ZrB₂–ZrC matrix composites with SiC particulate addition have been made. It was found that variable amounts (5–25 vol%) of SiC could be incorporated and reactively hot pressed (RHPed) to relative densities of 97–99% at 1400–1500 °C. This technique has the potential to fabricate ZrB₂-based matrices at low temperatures with a variety of reinforcements whose composition and volume fraction are not limited by stoichiometric considerations. The hardness of the composites is in the range of 17–22 GPa.     

Spark plasma sintering of quadruplet ZrB2–SiC–ZrC–Cf composites

Spark plasma sintering (SPS) route was employed for preparation of quadruplet ZrB₂–SiC–ZrC–C_f ultrahigh temperature ceramic matrix composites (UHTCMC). Zirconium diboride and silicon carbide powders with a constant ZrB₂:SiC volume ratio of 4:1 were selected as the baseline. Mixtures of ZrB₂–SiC were co-reinforced with zirconium carbide (ZrC: 0–10 vol%) and carbon fiber (C_f: 0–5 vol%), taking into account a constant ratio of 2:1 for ZrC:C_f components. The sintered composite samples, processed at 1800 °C for 5 min and 30 MPa punch press under vacuumed atmosphere, were characterized by densitometry, field emission scanning electron microscopy, energy dispersive spectroscopy, X-ray diffractometry as well as mechanical tests such as hardness and flexural strength measurements. The results verified that the composite co-reinforced with 5 vol% ZrC and 2.5 vol% C_f had the optimal characteristics, i.e., it reached a relative density of 99.6%, a hardness of 18 GPa and a flexural strength of 565 MPa.     

Room temperature R-curve and stable crack growth behaviour of ZrB2–SiC ceramic composites

ABSTRACT

R-curve and controlled stable crack growth behaviour of ZrB₂–17vol.-%SiC and ZrB₂–45vol.-%SiC ceramic composites was studied on V-notched samples using four-point bending at room temperature. The rising K_1R behaviour was determined as a function of the crack extension Δa with a crack bridging mechanism being dominant in such behaviour. Significant differences in crack growth rates were found within the same composition of ceramics simply as the crack length varied during crack growth processes. These differences are indicative of the significant influence of microstructural parameters of the ceramics on crack propagation. The peculiarities of stress intensity factor K₁ and the crack growth-specific behaviour in ZrB₂–SiC particulate ceramic composites are discussed.     

Strength of hot pressed ZrB2–SiC composite after exposure to high temperatures (1000–1700 °C)

Residual strength (room temperature strength after exposure in air at high temperatures) of hot pressed ZrB₂–SiC composites was evaluated as function of SiC contents (10–30 vol%) as well as exposure temperatures for 5 h (1000–1700 °C). Multilayer oxide scale structures were found after exposures. The composition and thickness of these multilayered oxide scale structure was dependent on exposure temperature and SiC contents in composites. After exposure to 1000 °C for 5 h, the residual strength of ZrB₂–SiC composites improved by nearly 60% compared to the as-hot pressed composites with 20 and 30 vol% SiC. On the other hand, the residual strength of these composites remained unchanged after 1500 °C for 5 h. A drastic degradation in residual strength was observed in composites with 20 and 30 vol% SiC after exposure to 1700 °C for 5 h in ZrB₂–SiC. An attempt was made to correlate the microstructural changes and oxide scales with residual strength with respect to variation in SiC content and temperature of expsoure.     

ZrB2–SiC composites prepared by reactive pulsed electric current sintering

Fully densified ZrB₂–20 vol% SiC composites were produced by reactive pulsed electric current sintering (PECS) of a powder mixture containing ZrH₂, B, SiC and B₄C within a total thermal cycle time of only 50 min. During the combined synthesis and sintering process, the ZrH₂ powder decomposed gradually from ZrH₂ into ZrH_m and finally metal Zr that reacted with elemental B to form the ZrB₂ matrix. Reducing the ZrH₂ particle size by attritor milling significantly enhanced densification and allowed initiation of self-propagating high temperature synthesis (SHS) during PECS. The PECS grades exhibited a slightly textured structure, with ≤17% of the ZrB₂ grains oriented with their (0 0 1) planes perpendicular to the direction of pressure and DC current. Because of the ZrB₂ grain orientation, anisotropic mechanical properties were observed. Ceramics prepared from attritor milled powders and PECS with a pressure applied after 5 min upon reaching 1900 °C achieved excellent flexural strengths of 901–937 MPa. The hardness and fracture toughness were respectively 19.7–19.8 GPa and 4.0–4.7 MPa m^1/2 in the direction parallel and 20.2–21.3 GPa and 3.8–3.9 MPa m^1/2 in the direction perpendicular to the applied pressure.     

Microstructure,hardness and fracture toughness of spark plasma sintered ZrB2–SiC–Cf composites

The combined effects of SiC particles and chopped carbon fibers (C_f) as well as sintering conditions on the microstructure and mechanical properties of spark plasma sintered ZrB₂-based composites were investigated by Taguchi methodology. Analysis of variance was used to optimize the spark plasma sintering variables (temperature, time and pressure) and the composition (SiC/C_f ratio) in order to enhance the hardness of ZrB₂–SiC–C_f composites. The sintering temperature was found as the most effective variable, with a significance of 83%, on the hardness. The hardest ZrB₂-based ceramic was achievable by adding 20 vol% SiC and 10 vol% C_f after spark plasma sintering at 1850 °C for 6 min under 30 MPa. Fracture toughness improvement were related to the simultaneous presence of SiC and C_f phases as well as the in-situ formation of nano-sized interfacial ZrC particles. Crack deflection, crack branching and crack bridging were detected as the toughening mechanisms. A Vickers hardness of 14.8 GPa and an indentation fracture toughness of 6.8 MPa m^1/2 were measured for the sample fabricated at optimal processing conditions.     

Oxidation of ZrB2–SiC–ZrSi2 ceramics in oxygen

The oxidation of ZrB₂–SiC and ZrB₂–SiC–ZrSi₂ ceramics of different composition has been studied experimentally at 1500 °C in pure oxygen for up to 50 h. ZrB₂–SiC–ZrSi₂ ceramics proved to be the most oxidation-resistant at ZrSi₂ contents of less then 4 wt%. These ceramics were more oxidation-resistant than ZrB₂–SiC ceramics. An analytical model of growth kinetics for a multilayered scale based on an oxidation–diffusion balance was developed and tested.     

High temperature strength of hot pressed ZrB2–20 vol% SiC ceramics based on ZrB2 starting powders prepared by different carbo/boro-thermal reduction routes

ZrB₂–20 vol% SiC (ZS) ceramics based on ZrB₂ starting powders obtained by different boro/carbo-thermal reductions involving ZrO₂ + B₄C, ZrO₂ + B₄C + C, and ZrO₂ + B, were fully densified by hot pressing at 1900–2000 °C. The flexural strength of these ZS ceramics was measured from room temperature up to 1600 °C. At 1600 °C, the flexural strength of the ceramics is 460 ± 31, 471 ± 32 and 345 ± 11 MPa, respectively. The evolution of the strength as function of temperature is explained in terms of the differences in oxygen content, nature of fracture, grain sizes, grain boundary phases and microstructural defects.     

Effects of TiN content on the properties of hot pressed TiB2–SiC ceramics

This research intended to study the impacts of different contents of the TiN additive on the mechanical properties and microstructural features of the TiB₂–SiC-based composites. Three different samples of TiB₂-15 vol% SiC- x vol% TiN (x = 0, 3.5, and 7) were produced by hot-pressing at 2000 °C under 35 MPa for 120 min. Thanks to advancement of some reactions among the TiB₂ surface oxides and the SiC reinforcement, two in-situ phases of TiC and SiO₂ were produced during the sintering. Nevertheless, the TiN incorporation resulted in generating another in-situ compound (TiC_0.3N_0.7) in the relevant as-sintered ceramics. Moreover, introducing TiN significantly refined the microstructure of the composites, leading to higher mechanical characteristics. Finally, the highest flexural strength (781 MPa) and Vickers hardness (27.1 GPa) values were attained for the sample introduced by 7 vol% TiN.