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.     

Investigation of the density and microstructure homogeneity of square-shaped B4C-ZrB2 composites produced by spark plasma sintering method

Square-shaped monolithic B₄C and B₄C-ZrB₂ composites were produced by spark plasma sintering (SPS) method to investigate the effect of 5, 10, 15 vol% ZrB₂ addition on the densification, mechanical and microstructural properties of boron carbide. The relative density of B₄C increased with the increasing volume fraction of ZrB₂ and density differences in different regions of the sample narrowed down. Homogeneous density distribution and microstructure were accomplished with the increasing holding time from 7 to 20 min for the B₄C-15 vol% ZrB₂ composites, and the highest overall relative density was achieved as 99.23%. The hardness and fracture toughness of composites were enhanced with the addition of ZrB₂ compared to monolithic B₄C. The enhancement in fracture toughness was observed due to the crack deflection, crack bridging and crack branching mechanisms. The B₄C-15 vol% ZrB₂ composite exhibited the combination of superior properties (hardness of 33.08 GPa, Vickers indentation fracture toughness of 3.82 MPa.m^1/2).     

Potential-current characteristics in SiC/ZrB2 composite ceramics

ZrB₂/SiC composite ceramics were fabricated to improve the electrical conductive properties of SiC matrix. The debinding and sintering temperatures were determined by computation of Gibbs free energy. As a result, all the samples have the relative density above 99%, and have excellent mechanical and electrical properties. The effects of ZrB₂ content on the microstructure, mechanical and electrical properties were systematically studied. With increasing ZrB₂ content, as-prepared composites show great improvement in their mechanical properties. Importantly, the introduction of ZrB₂ weakened varistor nonlinear characteristic of composite and reduced its resistivity. The reason is the evolution of grain boundary in conductive paths. The sharp decrease of resistivity indicates the formation of percolation paths. The percolation threshold at 1?mA?cm^?2 obtained via percolation model is 10.7963?vol% (19.7098?wt%) ZrB₂. This value is much less than conventional composites, because the percolation path originates from grain boundary breakdown other than continuous conductor chains.     

Friction and wear properties of Si3N4-hBN ceramic composites using different synthetic lubricants

This paper presents a tribological investigation of Si₃N₄-hBN composite ceramics using synthetic lubricants. The friction and wear properties of Si₃N₄-hBN ceramic composites sliding against TC4 titanium alloy (Ti6Al4V) were investigated via pin-on-disc tests. An axial compressive load of 10?N was applied with a sliding speed of 0.73?m/s. Three different lubrication conditions including simulated body fluid (SBF), physiological saline (PS) and bovine serum (BS) were used. For SBF lubrication, the friction coefficients and wear rates of Si₃N₄-hBN/Ti6Al4V pairs were varying with the increase of hBN contents. When using 20?vol% hBN, the average friction coefficient and wear rate of Si₃N₄ (0.28 and 3.5?× 10^?4 mm³ N^?1 m^?1) were as good as that of the pure Si₃N₄ (0.34 and 3.69?× 10^?4 mm³ N^?1 m^?1). Meanwhile, the processability of the Si₃N₄ material would be improved by adding hBN. It was worth to mention that when using 30?vol% hBN, the tribological performance of bearing combination deteriorated with extensive wear from the ceramic pin. This may due to the reduction of mechanical property caused by adding hBN and the occurring of tribochemical reaction. According to the worn surface examination and characterization, the main wear mechanism was abrasive and adhesion wear. Scratch grooves were observed on the metal disc, and metallic transform layers were seen on the ceramic pin. Moreover, surface lubrication film consisting of TiO₂, SiO₂·nH₂O, Mg(OH)₂, and H₃BO₃ were formed on the metal disc when using SBF lubrication and 20?vol% hBN content. Among the three lubrication conditions, SBF generally led to the best tribological performance. No surface lubrication film was found during BS and PS lubrications. This may be resulted from the absence of essential ions to promote the formation of surface lubrication film (PS lubrication) and the formation of a protein barrier on the surface of the metal disc (BS lubrication).     

Comparative study of static and cyclic fatigue of ZrB2-SiC ceramic composites

Room temperature static and cyclic fatigue of ZrB₂-32?vol% SiC and ZrB₂-45?vol% SiC particulate ceramic composites has been studied. It was established that the presence of grain bridging plays an important role in the lifetime and time dependent mechanical performance of ZrB₂-SiC composites. It was also established that the cohesive strength of grain boundaries of the composites was a determining factor if grain bridging would occur during crack growth, as the grain boundaries strength would determine the pathway of the moving crack. Grain bridging was limited in ZrB₂-32?vol% SiC leading to the absence of a cyclic fatigue effect, while grain bridging indeed occurred in ZrB₂-45?vol%SiC contributing to a cyclic fatigue effect which limits the lifetime of the composite. Such differences were responsible for the occurrence of R-curve behavior in ZrB₂-SiC ceramic composites.     

Effect of sintering temperature on the thermal expansion behavior of ZrMgMo3O12p/2024Al composite

A 2024Al metal matrix composite with 10?vol% negative expansion ceramic ZrMgMo₃O₁₂ was fabricated by vacuum hot pressing, and the influence of sintering temperature on the microstructure and thermal expansion coefficient (CTE) of alloys was investigated. Experimental results showed that all ZrMgMo₃O_12p/2024Al composites sintered at 500–530?°C had a similar reticular structure and exhibited different linear expansion coefficients at 40–150?°C and 150–300?°C. The addition of 10?vol% ZrMgMo₃O₁₂ decreased the CTEs of 2024Al by ~ 16% at 40–150?°C and by ~ 7% at 150–300?°C. This addition also increased the hardness of 2024Al by ~ 23%. The density of the composites and the content of Al₂Cu in ZrMgMo₃O_12p/2024Al increased as the sintering temperature increased. The CTEs of the composites decreased, whereas hardness increased. Thermal cycling from 40?°C to 300?°C caused the CTEs of the composites to decrease gradually and reach a stable value after seven cycles. The lowest CTEs of 15.4?×?10^?6 °C^?1 at 40–150?°C and 20.1?×?10^?6 °C^?1 at 150–300?°C were obtained after 10 thermal cycles and were reduced by ~ 32% and ~ 17%, respectively, compared with the CTE of the 2024Al. Among the current reinforcements, ZrMgMo₃O₁₂ negative expansion ceramics showed the highest efficiency to decrease the CTE of Al matrix composites.     

Effect of tantalum addition on microstructure and oxidation of spark plasma sintered ZrB2-20vol% SiC composites

Almost full density (>99% theoretical density (ρ_th)) was achieved for ZrB₂-20vol% SiC-Xwt.% Ta (X = 2,5, 5 and 10) composites after Spark Plasma Sintering (SPS) (Temperature: 1900 °C, Pressure: 50 MPa; Time: 3 min). The microstructure of ZrB₂-based composites exhibited core-rim structure and it consists of major crystalline phases (ZrB₂ core, (Zr, Ta)B₂ rim, SiC), minor amounts of ZrO₂ and (Zr, Ta)C solid solution phases. Both the specific weight (from 22.91 to 18.77 mg/cm²) and oxide layer thickness (401–195 μm) of ZrB₂-20vol% SiC composites decreased with increasing addition of Ta after the isothermal oxidation at 1500 °C for 10 h in air. The cross-sectional microstructure of oxidized samples displayed presence of a stack of three distinctive layers, which includes thick dense SiO₂ top layer, SiC depleted intermediate layer and unreacted bulk. The present work clearly demonstrated the advantage of tantalum addition in improving the oxidation resistance of ZrB₂-20vol% SiC.     

Hard and easy sinterable B4C-TiB2-based composites doped with WC

B₄C-TiB₂ composites were contaminated with WC to study the effect on densification, microstructure and properties. WC was introduced through a mild or a high energy milling with WC-6?wt%Co spheres or directly as sintering aid to 50?vol% B₄C / 50?vol%TiB₂ mixtures. High energy milling was very effective in improving the densification thanks to the synergistic action of WC impurities, acting as sintering aid, and size reduction of the starting TiB₂-B₄C powders. As a result, the sintering temperature necessary for full densification decreased to 1860?°C and both strength and hardness benefited from the microstructure refinement, 860?±?40 MPa and 28.5?±?1.4?GPa respectively. High energy milling was then adopted for producing 75?vol% B₄C/25?vol% TiB₂ and 25?vol% B₄C/ 75vol%TiB₂ mixtures. The B₄C-rich composition showed the highest hardness, 32.2?±?1.8?GPa, whilst the TiB₂-rich composition showed the highest value of toughness, 5.1?±?0.1?MPa?m^0.5.     

Mechanical,tribological and electrical properties of ZrB2 reinforced Cu processed via milling and high-pressure hot pressing

The present work investigates the effect of (0–10 wt%) ZrB₂ reinforcement on densification, mechanical, tribological and electrical properties of Cu. The consolidation of Cu–ZrB₂ samples was carried out using a hot press (temperature: 500 °C, pressure: 500 MPa, time: 30 min, vacuum pressure: 1.3 × 10^-2 mbar). The bulk density of the hot-pressed Cu composites decreased from 8.84 g/cc to 8.16 g/cc and the relative density of samples lowered from 98.6% to 92.1% with the addition of ZrB₂. The incorporation of hard ZrB₂ (up to 10 wt%) improved the hardness of Cu (1.32–2.55 GPa). However, the yield strength and compressive strength of Cu composites increased up to 5 wt% ZrB₂, and further addition of ZrB₂ lowered its strength. The yield strength of Cu samples varied from 602 to 672 MPa and the compressive strength between ~834 and 971 MPa. On the other hand, the coefficient of friction (COF) (from 0.49 to 0.18) and wear rate (from 49.3 × 10^-3 mm³/Nm to 9.1 × 10^-3 mm³/Nm) of Cu–ZrB₂ samples considerably decreased with the addition of ZrB₂. Significantly low wear was observed with Cu-10 wt% ZrB₂ (Cu-10Z) samples, which is 5.41 times less than pure Cu. As far as the wear mechanisms are concerned, in pure Cu, continuous chips (wear debris) were formed during sliding wear by plowing. Whereas the major amount of material loss was occurred due to the plowing mechanism with discontinuous and short chip formation for Cu–ZrB₂ composites. The electrical conductivity of Cu–ZrB₂ samples decreased from 75.7% IACS to 44.1% IACS. In particular, Cu with ZrB₂ (up to 3 wt%) could retain the conductivity of 66.8% IACS. This study reveals that the addition of ZrB₂ (up to 3 wt%) is advantageous to have a good combination of properties for Cu.     

Reactive Hot Pressing and Properties of Zr1−xTixB2–ZrC Composites

Reactive hot pressing was used to prepare Zr_1?xTi_xB₂–ZrC composites with advantageous microstructure and mechanical properties from ZrB₂–TiC powders. The reaction mechanisms and the effects of different levels of TiC on the physical and mechanical properties of the resulting composite were explored in detail and compared to conventionally hot‐pressed ZrB₂ and ZrB₂–ZrC. Incorporation of 10 to 30 vol% TiC enabled full densification and restrained grain growth, reducing the final average grain size from 5.6 μm in pure ZrB₂ to a minimum of 1.4 μm in samples with 30 vol% TiC. The flexural strengths and hardnesses of the composites sintered with TiC were consequently greater than the conventionally processed ZrB₂–ZrC materials, increasing from 440 MPa and 17.4 GPa to a maximum of 670 MPa and 24.2 GPa at 10 vol% TiC. However, despite a decrease in the total average grain size, the flexural strength at higher TiC levels was limited by an increase in ZrC grain growth, which was observed to determine the flexural strength of the reaction sintered composites similar to the case of ZrB₂–SiC.     

Pressureless sintering of Al2O3 containing up to 20 vol% zirconium diboride (ZrB2)

The production of particle composites by means of pressureless sintering provides a cost-effective alternative to production variants such as hot-pressing. However, minimal quantities of additives are sufficient to impede the densification of oxidic matrix components. This paper examines the sintering behaviour of alumina powder as a function of the volume fraction of ZrB₂ (up to 20 vol%). A distinction can be made between two sintering ranges according to the temperature: at T⩽1700° a solid-state process applies. This process is decisively influenced by the boron oxide (B₂O₃) contained in the raw material ZrB₂. The validity of the Lange model, which describes the influence of increasing volumes of inclusions on the densification behaviour of a crystalline matrix phase, is confirmed in this temperature range. At T>1700°C, an aluminium borate melt occurs, accelerating the sintering process substantially. As a result, the composites quickly attain matrix densities greater than 95% of the theoretical density. At higher firing temperatures the ZrB₂ particles coalesce, resulting in the formation of an electrically conductive penetration structure at a content level of 20 vol%.     

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.     

Mechanical,electrical and thermal properties of ZrC-ZrB2-SiC ternary eutectic composites prepared by arc melting

ZrC-ZrB₂-SiC composites were prepared by arc-melting in Ar atmosphere using ZrC, ZrB₂ and SiC as starting materials. The ternary eutectic composition of 20ZrC-30ZrB₂-50SiC (mol%) was first identified. SiC about 7?μm in length and 500?nm in diameter, ZrC about 4 μm in length and 1 μm in diameter, in rod-like microstructure, were uniformly dispersed in ZrB₂ matrix of eutectic composite. The eutectic temperature of ZrC-ZrB₂-SiC composite was approximately 2550?K. The Vickers Hardness and fracture toughness of eutectic composite was 23?GPa and 6.2?MPa?m^1/2, respectively. The electrical conductivity decreased from 7.2?×?10⁷ to 1.75?×?10⁶?S?m^?1 with the temperature increasing from 287 to 800?K. The thermal conductivity decreased from 85 to 61?W?K^?1?m^?1 with increasing temperature from 287 to 973?K.     

Microstructure and mechanical properties of multiwalled carbon nanotube toughened spark plasma sintered ZrB2 composites

ZrB₂ based composites containing 10 vol.-% carbon nanotubes (CNTs) are synthesised by spark plasma sintering at temperatures ranging from 1600 to 18008C and at an applied pressure of 25?MPa. The effects of sintering temperature on densification behaviour, microstructural evolutions and mechanical properties are presented. Results indicate that ZrB₂-CNT composites fabricated at 16508C have the optimal combination of dense microstructure and properties. The fracture toughness is sensitive to the temperature change and reaches 7.2?MPa m^1/2 for the CNT toughened ZrB₂ ceramics, which is higher than the measured result for monolithic ZrB₂ (3.3?MPa m^1/2). The crack deflection and CNT pullout are the dominant toughening mechanisms.     

Synergetic effects of SiC and Csf in ZrB2-based ceramic composites. Part I: Densification behavior

The effects of processing variables on densification behavior of hot pressed ZrB₂-based composites, reinforced with SiC particles and short carbon fibers (C_sf), were studied. A design of experiment approach, Taguchi methodology, was used to investigate the characteristics of ZrB₂–SiC–C_sf composites concentrated upon the hot pressing parameters (sintering temperature, dwell time and applied pressure) as well as the composition (vol% SiC/vol% C_sf). The analysis of variance recognized the sintering temperature and SiC/C_sf ratio as the most effective variables on the relative density of hot pressed composites. The microstructural investigations showed that C_sf can act as a sintering aid and eliminate the oxide impurities (e.g. B₂O₃, ZrO₂ and SiO₂) from the surfaces of raw materials. A fully dense composite was achieved by adding 10 vol% C_sf and 20 vol% SiC to the ZrB₂ matrix via hot pressing at 1850 °C for 30 min under a pressure of 16 MPa. Moreover, the in-situ formation of interfacial ZrC, which also improves the sinterability of ZrB₂-based composites, was studied by energy-dispersive X-ray spectroscopy analysis and verified thermodynamically.     

Factorial design to minimize residual oxygen in reaction hot‐pressed zirconium diboride

Processing parameters to minimize the residual oxygen content of ZrB₂ ceramics prepared by reactive hot‐pressing were selected using statistical analysis. Additions of carbon and excess boron were used to react with oxygen present in the starting ZrH₂ and B powders as an impurity. A 3² full‐factorial experimental design was used to determine the carbon and excess boron contents that minimized residual oxygen content in the final ZrB₂ ceramic while also minimizing formation of any impurity phases. Carbon additions were effective at reducing the oxygen content, but resulted in the formation of residual ZrC. Boron additions were also effective at removing oxygen, but to a lesser extent compared to carbon. In addition to being more effective at removing oxygen, carbon additions also improved the densification behavior, whereas boron additions inhibited densification. The stoichiometric reaction resulted in a ZrB₂ ceramic with a relative density of 99%, but that contained 6.9 vol% of (Zr_1?x,Mg_x)O_2?x as a residual phase following reactive hot‐pressing. The composition with a carbon addition to starting oxygen content having a molar ratio of 1, and a boron to zirconium molar ratio of 2.1, resulted in a 95% dense ceramic with only 0.1 vol% of residual (Zr_1?x,Mg_x)O_2?x and trace amounts of ZrC.     

High temperature oxidation behavior of ZrB2-SiC added MoSi2 ceramics

In this paper, MoSi₂, MoSi₂-20?vol% (ZrB₂-20?vol% SiC) and MoSi₂-40?vol% (ZrB₂-20?vol% SiC) ceramics were prepared using pressureless sintering. The oxidation behaviors of these MoSi₂-(ZrB₂-SiC) ceramics were investigated at 1600?°C for different soaking time of 60, 180 and 300?min, respectively. The oxidation behaviors of the MoSi₂-(ZrB₂-SiC) ceramics were studied through weight change test, oxide layer thickness measurement, and microstructure analysis. Further investigation of the oxidation behaviors of the MoSi₂-(ZrB₂-SiC) ceramics was conducted at a higher temperature of 1800?°C for 10?min. The microstructure evolution of the ceramics was also analyzed. It was finally found that the oxidation resistance of MoSi₂ was improved by adding ZrB₂-SiC additives, and the MoSi₂-20?vol% (ZrB₂-20?vol% SiC) ceramic exhibited the optimal oxidation resistance behavior at elevated temperatures. From this study, it is believe that it can give some fundamental understanding and promote the engineering application of MoSi₂-based ceramics at high temperatures.     

Spark plasma sintering of Al-doped ZrB2–SiC composite

This research presents the influence of Al addition on microstructure and mechanical behavior of ZrB₂–SiC ultra-high temperature ceramic matrix composite (UHTCMC) fabricated by spark plasma sintering (SPS). A 2.5?wt% Al-doped ZrB₂–20?vol% SiC UHTCMC was produced by SPS method at 1900?°C under a pressure of 40?MPa for 7?min. The microstructural and phase analysis of the composite showed that aluminum-containing compounds were formed in-situ during the SPS as a result of chemical reactions between Al and surface oxide films of the raw materials (i.e. ZrO₂ and SiO₂ on the surfaces of ZrB₂ and SiC particles, respectively). The Al dopant was completely consumed and converted to the intermetallic Al₃Zr and Al₄Si compounds as well as Al₂O₃ and Al₂SiO₅. A relative density of 99.8%, a hardness (HV5) of 21.5?GPa and a fracture toughness (indentation method) of 6.3?MPa?m^1/2 were estimated for the Al-doped ZrB₂–SiC composite. Crack bridging, branching, and deflection were identified as the main toughening mechanisms.     

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.     

Fine Ti‐dispersed Al2O3 composites and their mechanical and electrical properties

Al₂O₃/Ti composites containing 0‐30 vol% dispersed fine Ti particles were fabricated using a hot‐press sintering method at 1500°C from mixtures of Al₂O₃ and TiH₂ powders. During sintering, TiH₂ decomposed to form metallic Ti. The effects of the Ti content on the mechanical and electrical properties of the composites were then investigated. No Ti‐Al intermetallic compounds were detected by X‐ray diffraction, and energy‐dispersive X‐ray spectroscopy indicated the presence of Al‐Ti‐O solid solution and Ti‐O phases. The composites showed enhanced densification; the measured densities were higher than the calculated theoretical values. Microstructural observation revealed homogeneously distributed fine Ti particles dispersed in the Al₂O₃ matrix. The Ti particle size ranged from submicrometer to a few micrometers depending on the Ti content. The fracture mode of the composites was primarily transgranular, in contrast to the intergranular fracture mode of monolithic Al₂O₃. Although the flexural strength was decreased with increase in Ti content, the composite containing 20 vol% Ti displayed the maximum fracture toughness of 4.3 MPa·cm^1/2, which was 37% greater than that of monolithic Al₂O₃. The composites containing more than 15 vol% Ti exhibited drastic decreases in resistivity (~10^?1 Ωcm), which were attributed to the formation of interconnected Ti networks at these Ti contents. The percolation threshold volume for electrical conduction in the present system was calculated to be 13.8 vol%. The results indicate that dispersing fine Ti particles into Al₂O₃ increased the fracture toughness and improved the conductivity of Al₂O₃.