Fabrication of ZrB2 ceramics by reactive hot pressing of ZrB and B

Zirconium diboride (ZrB₂) ceramics were prepared by reactive hot pressing of ZrB+B powder mixture. Formation of a transient liquid due to eutectic reaction of ZrB₂+Zr→L_eu(ZrB2+Zr) at 1661°C following peritectic decomposition of 2ZrB=ZrB₂+Zr at 1250°C during heating up of the ZrB+B mixture facilitated densification. The liquid phase was subsequently eliminated via reaction of B with Zr in the eutectic liquid L_eu(ZrB2+Zr) to result in a dense ZrB₂ ceramic. Full density was reached after reactive hot pressing at 1900°C under 30 MPa for 1 h. The ZrB₂ ceramic had a refined microstructure consisting of grains of <1.5 μm in size and relatively good Vickers hardness (21 ± 2 GPa) and flexural strength (595 ± 63 MPa).     

High-strength ZrB2-based ceramics prepared by reactive pulsed electric current sintering of ZrB2–ZrH2 powders

Fully densified ZrB₂-based ceramic composites were produced by reactive pulsed electric current sintering (PECS) of ZrB₂–ZrH₂ powders within a total thermal cycle time of only 35 min. The composition of the final composite was directly influenced by the initial ZrH₂ content in the starting powder batch. With increasing ZrH₂ content, ZrB₂–ZrO₂, ZrB₂–ZrB–ZrO₂ and ZrB₂–ZrB–Zr₃O composites were obtained. The ZrB₂–ZrB–ZrO₂ composite derived from a 9.8 wt% ZrH₂ starting powder exhibited an excellent flexural strength of 1382 MPa combined with a Vickers hardness of 17.1 GPa and a fracture toughness of 5.0 MPa m^1/2. The high strength was attributed to a fine grain size and the removal of B₂O₃ through reaction with Zr. Higher ZrH₂ content starting powders were densified through solution-reprecipitation resulting in the formation of coarser angular ZrB₂–ZrB composites with a Zr₃O grain boundary phase with a fracture toughness of 5.0 MPa m^1/2 and an acceptable strength in the 852–939 MPa range.     

ZrB2-based solid solution ceramics and their mechanical and thermal properties

Zirconium diboride ceramics as one of the main members of ultrahigh-temperature ceramics are capable of being used as structural components at ultrahigh temperatures. Entropy adjusting is a newly developed approach to improving the properties of ceramics. In this work, a series of ZrB₂-based solid solution ceramics with different mixing entropies, formulated (Zr_xTi_yNb_yTa_y)B₂ (x = .25, .85, .925, .9625, 1; x + 3y = 1), were prepared by adjusting the content of other diborides. Diboride solid solution powders were synthesized by boro/carbothermal reduction process and then densified by spark plasma sintering. The results show that the formation of a single-phase solid solution is independent of the mixing entropy in (Zr_xTi_yNb_yTa_y)B₂ system. The addition of other diborides into ZrB₂ is beneficial to reduce the particle size of the synthesized powder and promote the densification process. The dense sintered samples with higher mixing entropy have finer grain size, higher hardness, and modulus. The (Zr_0.25Ti_0.25Nb_0.25Ta_0.25)B₂ ceramic has the highest hardness of 31 GPa and a modulus of 682 GPa. Severe lattice distortion in samples with higher mixing entropy will result in increased phonon scattering and lower thermal conductivity.     

Fabrication and properties of reactively hot pressed ZrB2–SiC ceramics

ZrB₂–SiC ceramics with relative densities >99% were fabricated by ‘in situ’ reactive hot pressing from ZrH₂, B₄C and Si. The reaction was studied using two processes, (1) powder reactions at temperatures from 1150 to 1400 °C and (2) reactive hot pressing between 1600 and 1900 °C. The products from the reaction of a 2ZrH₂:1B₄C:1Si molar mixture were ZrB₂, SiC, ZrO₂ and ZrC. Modification of the composition to 2ZrH₂:1.07B₄C:1.16Si resulted in the elimination of the undesired ZrO₂ and ZrC phases. The final composition was approximately ZrB₂–27 vol% SiC with no undesired phases detected by X-ray diffraction, and only low concentrations of B₄C detected by scanning electron microscopy. Elimination of the undesired phases was accomplished by removing surface oxides through chemical reactions at elevated temperatures. Reactively hot pressed samples consisting of ZrB₂ with 27 vol% SiC had a Young's modulus of 508 GPa, a flexure strength of 720 MPa, a fracture toughness of 3.5 MPa m^1/2 and a Vickers’ hardness of 22.8 GPa.     

Toughened ZrB2-based ceramics through SiC whisker or SiC chopped fiber additions

In order to improve the fracture toughness, SiC whiskers or SiC chopped fibers were added to a ZrB₂ matrix in volumetric fraction of 10 and 20 vol.%. The composites were hot-pressed between 1650 and 1730 °C and their final relative densities were higher than 95%. Even at the lowest sintering temperature, the whiskers showed an evident degradation. On the other hand, the fibers maintained their initial shape and a strong interface formed between matrix and reinforcement. The fracture toughness of the composites increased from 30 to 50% compared to the baseline material, with the fibers showing a slightly higher toughening effect. In the whiskers-reinforced composites, the room-temperature strength increased when 10 vol.% whiskers were added. In the fibers-reinforced composites, the room-temperature strength decreased regardless the amount of fibers added. The high-temperature strength of the composites was higher than that of the baseline material for both types of reinforcement.     

Tribological behavior of carbon fiber reinforced ZrB2 based ultra high temperature ceramics

The tribological behavior of ultra-high temperature ceramic matrix composites (UHTCMCs) was investigated to understand these materials in friction applications. Samples consisting of pitch-based randomly orientated chopped carbon fiber (CF) reinforced ZrB₂-10 vol% SiC were prepared (ZS). The tribological behavior was tested on a self-designed dynamometer, coupling the UHTCMC pads with either carbon fiber reinforced carbon−silicon carbide (C/C-SiC) or steel disks, with two applied contact pressures (1 and 3 MPa) and the surface microstructures were analyzed to unravel the wear mechanisms. Even at high mechanical stresses, tests against the C/C-SiC disk showed stable braking performance and wear. The abraded material from a steel disk formed a stable friction film by fusing together harder pad particles with abraded steel, which reduced wear and stabilized the braking performance. The high values of coefficient of friction obtained (0.5–0.7), their stability during the braking and the acceptable wear rate make these materials appealing for automotive brake applications.     

Method to improve the oxidation resistance of ZrB2-based ceramics for reusable space systems

UHTCs are the most suitable materials for space and hypersonic, however in service they lose their properties owing to oxidation damages. Tailoring composition and microstructure on a multiscale level may maintain structural stability in the sub-layers. Sintering of ZrB₂-MoSi₂ ceramics at 1900–2150?°C results in microstructures characterized by partial or complete (Zr,Mo)B₂ solid solutions. This has notable impacts on the performance of the composites subjected to cyclic oxidation at 1650?°C. Coupled XRD, SEM and TEM analyses pointed out the formation of a unique interpenetrating microstructure, where ZrO₂ micro-grains encase stable nano-sized MoB particles. This architecture manifested its suitability during repeated oxidation limiting the effect of oxygen attack to some microns thickness, due to diffused Mo which prevented turbulence and bursting phenomena on the outer glass.This study elucidates the processing conditions that lead to the development of prominent materials for application in new generation thermal protection systems for reusable space components.     

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.     

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.     

Toughening and ablation mechanism of Si3N4 short fiber toughened ZrB2-based ceramics

ZrB₂-based ceramics with Si₃N₄ short fiber (ZSN) were prepared by wet-spinning extrusion and hot pressing. The toughness of ZSN was 5.6 MPa·m^1/2, which was 20% higher than that of monolithic ceramic (4.7 MPa·m^1/2). The ablation performance of ZSN was evaluated by air discharge plasma ablation platform with a heat flux of 8.04 MW/m² for 120 s. The mass and linear ablation rates of ZSN were − 0.19 mg/s and − 0.25 µm/s, respectively. The specimens of ZSN remained intact while monolithic ceramics exhibited destructive fracture. The better ablation performance of ZSN is attributed to the addition of Si₃N₄ short fiber which increased the fracture toughness, reduced the elastic modulus, and improved the thermal conductivity at high temperature.     

Dry sliding wear behaviour of ZrB2-based ceramics: Self-mated and cross coupling with alumina

Systematic dry sliding wear tests with monolithic ZrB₂ and Al₂O₃ pins coupled to ZrB₂, ZrB₂-20 vol% SiC and Al₂O₃ discs were carried out in a disc-on-pin configuration. The steady state friction of ZrB₂ self-mated or cross coupled with Al₂O₃ was about 1.1. Self-mated monolithic ZrB₂ discs worn about three orders of magnitude more than self-mated Al₂O₃ discs. ZrB₂ pin wear rate was almost double when coupled to ZrB₂ or ZrB₂-20 vol% SiC discs than when coupled to Al₂O₃ discs. The wear track of ZrB₂-based materials showed an oxygen increment due to humidity-driven tribo-reaction. In all the systems, the main wear mechanisms observed were microfracture and abrasion. Numerical calculations and fracture models were employed to describe the wear mechanisms. By nanoindentation tests on worn and unworn areas, a significant lower hardness of the debris layer formed when ZrB₂ materials were involved.     

Mechanical properties of ZrB2- and HfB2-based ultra-high temperature ceramics fabricated by spark plasma sintering

Flexural strengths at room temperature, at 1400 °C in air and at room temperature after 1 h oxidation at 1400 °C were determined for ZrB₂- and HfB₂-based ultra-high temperature ceramics (UHTCs). Defects caused by electrical discharge machining (EDM) lowered measured strengths significantly and were used to calculate fracture toughness via a fracture mechanics approach. ZrB₂ with 20 vol.% SiC had room temperature strength of 700 ± 90 MPa, fracture toughness of 6.4 ± 0.6 MPa, Vickers hardness at 9.8 N load of 21.1 ± 0.6 GPa, 1400 °C strength of 400 ± 30 MPa and room temperature strength after 1 h oxidation at 1400 °C of 678 ± 15 MPa with an oxide layer thickness of 45 ± 5 μm. HfB₂ with 20 vol.% SiC showed room temperature strength of 620 ± 50 MPa, fracture toughness of 5.0 ± 0.4 MPa, Vickers hardness at 9.8 N load of 27.0 ± 0.6 GPa, 1400 °C strength of 590 ± 150 MPa and room temperature strength after 1 h oxidation at 1400 °C of 660 ± 25 MPa with an oxide layer thickness of 12 ± 1 μm. 2 wt.% La₂O₃ addition to UHTCs slightly reduced mechanical performance while increasing tolerance to property degradation after oxidation and effectively aided internal stress relaxation during spark plasma sintering (SPS) cooling, as quantified by X-ray diffraction (XRD). Slow crack growth was suggested as the failure mechanism at high temperatures as a consequence of sharp cracks formation during oxidation.     

Prevention of SiC-fiber decomposition via integration of a buffer layer in ZrB2-based ultra-high temperature ceramics

A ZrB₂-based ceramic, containing short Hi-Nicalon SiC fibers, was fabricated with a Mo-impermeable buffer layer sandwiched between bulk and the outermost oxidation resistant ZrB₂–MoSi₂ layer, in order to prevent inward Mo diffusion and associated fiber degradation reactions. This additional layer consisted of ZrB₂ doped with either Si₃N₄ or with the polymer-derived ceramics (PDCs) SiCN and SiHfBCN. Scanning electron microscopy imaging and elemental mapping via energy-dispersive X-ray spectroscopy showed that this tailored sample geometry provides an effective diffusion barrier to prevent the SiC fibers from deterioration due to reactions with Mo or Mo-compounds. In contrast, the structure of the SiC fibers in a reference sample without buffer layer is strongly degraded by MoSi₂ diffusion into the fiber core. The comparison of the three buffer-layer systems showed a moderate alteration of the fiber structure in the case of Si₃N₄ addition, whereas in the PDC-doped samples hardly any structural change within the fibers was observed. A stepwise reaction mechanism is deduced, based on the continuous progression of a reaction zone that propagates toward the ZrB₂–MoSi₂ top layer. The progression of such a reaction zone as a consequence of the different eutectic melts forming in the different layers, that is, first in the SiC-fiber-containing bulk, then in the buffer layer itself, and finally in the top layer at high temperature, allows for an effective separation of the ZrB₂–MoSi₂ top layer from the SiC fibers. Subsequent oxidation at 1500°C and 1650°C for 15 min did not affect the efficiency of all three buffer layers, since no structural changes regarding buffer layer and fibers were observed, as compared to the non-oxidized samples.     

Microstructure,mechanical behavior and oxidation resistance of disorderly assembled ZrB2-based short fibrous monolithic ceramics

Axially aligned fibrous monolithic ceramics present non-catastrophic fracture behavior via crack deflection and delamination along cell boundaries. However, severe in-plane anisotropy and time-consuming preparation procedures prevent their extensive promotion. The introduction of high content of weak phase components with poor oxidation resistance in weak interface destroys the excellent oxidation resistance of ceramic matrix. In this work, ZrB₂-based short fibrous monolithic (SFM) ceramics with in-plane isotropic mechanical properties and excellent oxidation resistance were easily prepared by hot pressing randomly assembled short ceramic fibers. The microstructure and mechanical behavior of ZrB₂-based SFM ceramics densified at various temperatures were systematically investigated. The mechanical properties of ZrB₂-based SFM ceramics slightly improved with the increase of sintering temperature. ZrB₂-based SFM ceramics exhibited excellent oxidation resistance and remained intact without macroscopic cracks after ablation for 615 s in oxyacetylene flame with maximum temperatures exceeding 2150 °C. The oxidation behavior was analyzed in detail.     

Fabrication and properties of CNT/Ni/Y/ZrB2 nanocomposites reinforced in situ

Carbon nanotubes (CNTs) were synthesized in situ by chemical vapor deposition of methane over nano‐ZrB₂ matrix using Ni/Y catalysts. Well‐grown CNTs with tangled and long bodies and mainly composed of well‐crystallized graphite were obtained when the Ni content reaches 10 wt%. The CNT/ZrB₂ nanocomposites obtained by spark plasma sintering at 1400°C exhibited full density and optimal mechanical properties. The flexural strength and fracture toughness of the nanocomposites were 1184 ± 52 MPa and 10.8 ± 0.3 MPa·m^1/2, respectively. Results indicated that the dispersion of CNTs in situ can improve composite performance, rendering the mechanical properties of the CNT/ZrB₂ nanocomposites synthesized in situ considerably superior to those of monolithic ZrB₂ nanoceramics and CNT/ZrB₂ nanocomposites synthesized using the traditional method. The toughening mechanisms included crack deflection, crack bridging, CNT debonding, pull‐out, and fracture.     

Combustion synthesis of high-temperature ZrB2-SiC ceramics

The work is dedicated to researching into combustion kinetics and mechanism as well as the stages of the chemical transformations during self-propagating high-temperature synthesis of ZrB₂-SiC based ceramics. Dependences of the combustion temperature and rate on the initial temperature (T₀) have been studied. It has been shown that the stages of the chemical reactions of ZrB₂ diboride and SiC carbide formation do not change within the range of T_0?=?298–700?К. The effective activation energy of the combustion process amounted to 170–270?kJ/mol, from which it has been concluded that chemical interaction through the melt plays a leading role. The stages of the chemical transformations in the combustion wave have been studied by dynamic X-ray diffraction. First, ZrB₂ phase forms from Zr-Si melt saturated with boron, and SiC phase is registered later. The SHS method has successfully been used in order to obtain ZrB₂-SiC composite powders and compact ceramics with a silicon carbide content of 25–75%. The ceramics are characterized by a residual porosity of 1.5%, hardness up to 25?GPa, the elastic modulus of 318?±?21?GPa, elastic recovery of 36% and thermal conductivity of 54.9?W/(m?×?K) at T_room.     

Densification,microstructure and mechanical properties of ZrB2–SiCw ceramic composites

ZrB₂–SiCw composites were prepared through hot-pressing at a low temperature of 1800 °C, and Al₂O₃ plus Y₂O₃ were added as sintering aids. Analysis revealed that additives may react with impurities (i.e. surface oxygen impurities and residual metallic impurities) to form a transient liquid phase, thus promote the sintering and densification of ZrB₂–SiCw composites. The content of additives was found to have a significant influence on the sinterability, microstructure and mechanical properties of ZrB₂–SiCw composites. ZrB₂–SiCw composite prepared with a small amount of additives (3 vol.%) provided the optimal combination of microstructure (relative density of 98.3%) and excellent properties, including flexural strength of 783 MPa and fracture toughness of 6.7 MPa m^1/2. With further addition of additives, SiC whiskers were inclined to gather together and be enveloped by excessive liquids to form core-rim-like structures, which lead to little decrease in mechanical properties.     

Anisotropy oxidation of textured ZrB2–MoSi2 ceramics

Oxidation behavior of hot forged textured ZrB₂–20 vol% MoSi₂ ceramics with platelet ZrB₂ grains was investigated at 1500 °C for exposure time from 0.5 to 12 h. Compared to untextured ceramics, the textured ceramics showed obvious anisotropic oxidation behavior and the surface normal to the hot forging pressure demonstrated better oxidation resistance. Such improvement in the oxidation resistance is primarily considered as a higher intrinsic ZrB₂ atomic density on the orientated {0 0 l} planes in the textured ceramics. It is expectable that the anisotropic textured ZrB₂–MoSi₂ ceramics can offer better oxidation resistance when a certain surface with higher oxidation resistance is exposed to air at elevated temperature.     

Fabrication and optical properties of Y2O3-based ceramics with broad emission bandwidth

In this article, we report on the fabrication and optical properties of highly transparent yttria ceramics for lasers active media with broadband gain profile. Laser synthesis method was used to produce Y₂O₃-based nanopowders doped with 1 mol.% Nd³⁺ or Yb³⁺ for these transparent ceramics. The additives of sesquioxides Lu₂O₃ and Sc₂O₃ were used along with ZrO₂ to disorder the crystalline structure. The porosity and average grain size decrease with these additives and the emission bandwidths of Nd³⁺ (⁴F_3/2 → ⁴I_11/2) and Yb³⁺ (²F_5/2 → ²F_7/2) transitions widen to 40 and 60 nm, respectively. Laser operation with the slope efficiency of 29% was obtained in [(Yb_0.01Lu_0.24Y_0.75)₂O₃]_0.88(ZrO₂)_0.12 ceramic sample.     

Nanoindentation and tribology of ZrB2 based luminescent ceramics

Nano-mechanical and wear characteristics of ZrB₂ + Al₂O₃:Cr³⁺,Nd³⁺ (Al₂O₃ co-doped with Cr³⁺ and Nd³⁺ ions) luminescent ceramic composites have been investigated using nanoindentation and tribological tests. Nanoindentation was carried out using a Berkovich diamond tip applying continuous stiffness measuring (CSM) mode with a maximum depth of 200 nm. The wear behaviour was studied during dry sliding in the air with a SiC counter body at applied loads of 5 and 50 N, and sliding speed of 0.1 m/s. The nanohardness of the ZrB₂ and Al₂O₃ are very similar with mean values of 34.2 GPa and 32.6 GPa, respectively The Young modulus for ZrB₂ is higher with a mean value of 555.6 GPa in comparison to the Young modulus of alumina with mean value of 473.8 GPa. Pop – in effect was found during the indentation of ZrB₂ grains at indentation loads from 0.2–8.0 mN. The lowest coefficient of friction was measured for ZrB₂ + 8%Al₂O₃:Cr³⁺,Nd³⁺ at 5 N load with value of approximately 0.5. The wear rate of the system ZrB₂ + 32 % Al₂O₃:Cr³⁺,Nd³⁺ at 5 N is significantly lower in comparison to the wear rate of ZrB₂ + 8% Al₂O₃:Cr³⁺,Nd³⁺ but at a load of 50 N the wear of the systems is very similar approximately 1. 10⁻⁵ mm³/N.m. Tribolayer formation connected with debris origin, oxidation and tribochemical reactions were characteristic for both composites with similar chemical composition but different size and thickness of tribolayers.