Preparation and microstructure of 3D framework TiC–TiB2 ceramics and their reinforced steel matrix composites

An efficient method for in-situ fabrication of a three-dimensional framework based on heterogeneous TiC–TiB₂ materials with different B₄C content has been reported in the present study. Interpenetrating TiC–TiB₂/steel composites were subsequently prepared by infiltrating molten steel into TiC–TiB₂ framework. The XRD and SEM analyses confirmed that three-dimensional ceramics framework mainly consisted of heterogeneous TiC–TiB₂ phases with the ceramic particles closely connected with each other. TiC–TiB₂ ceramics framework exhibited a high porosity in the range 87.11%–95.95% and low bulk density of 0.17–0.22 g/cm³. The sample with ceramic framework containing 20 wt% B₄C exhibited the strongly continuous microstructure, whereas the sample with ceramic framework containing 25 wt% B₄C had the weakly continuous framework. The Vickers hardness and fracture toughness in the composites reached 284.5 HV and 23.7 MPa m^1/2, respectively. An optimal TiC: TiB₂ mass ratio of 37:55 could effectively inhibit the decomposition of TiB₂ in the molten steel. Inspecting the fracture surface, the dominated fracture modes was noted to be the quasi-cleavage and trans-granular dimple fracture, which could be attributed to novel three-dimensional bi-continuous structure formed between ceramic framework and steel substrate.     

High-strength TiB2-B4C composite ceramics sintered by spark plasma sintering

Spark plasma sintering (SPS) is an advanced sintering technique because of its fast sintering speed and short dwelling time. In this study, TiB₂, Y₂O₃, Al₂O₃, and different contents of B₄C were used as the raw materials to synthesize TiB₂-B₄C composites ceramics at 1850°C under a uniaxial loading of 48 MPa for 10 min via SPS in vacuum. The influence of different B₄C content on the microstructure and mechanical properties of TiB₂-B₄C composites ceramics are explored. The experimental results show that TiB₂-B₄C composite ceramic achieves relatively good comprehensive properties and exceptionally excellent flexural strength when the addition amount of B₄C reaches 10 wt.%. Its relative density, Vickers hardness, fracture toughness, and flexural strength reach to 99.20%, 24.65 ± .66 GPa, 3.16 MPa·m^1/2, 730.65 ± 74.11 MPa, respectively.     

Development of spark plasma sintered conductive SiC–TiB2 composites for electrical discharge machining applications

Highly dense electrically conductive silicon carbide (SiC)–(0, 10, 20, and 30 vol%) titanium boride (TiB₂) composites with 10 vol% of Y₂O₃–AlN additives were fabricated at a relatively low temperature of 1800°C by spark plasma sintering in nitrogen atmosphere. Phase analysis of sintered composites reveals suppressed β→α phase transformation due to low sintering temperature, nitride additives, and nitrogen sintering atmosphere. With increase in TiB₂ content, hardness increased from 20.6 to 23.7 GPa and fracture toughness increased from 3.6 to 5.5 MPa m^1/2. The electrical conductivity increased to a remarkable 2.72 × 10³ (Ω cm)^–1 for SiC–30 vol% TiB₂ composites due to large amount of conductive reinforcement, additive composition, and sintering in nitrogen atmosphere. The successful electrical discharge machining illustrates potential of the sintered SiC–TiB₂ composites toward extending the application regime of conventional SiC-based ceramics.     

Synergistic effects of TiB2 and graphene nanoplatelets on the mechanical and electrical properties of B4C ceramic

Monolithic B₄C, B₄C–TiB₂, and B₄C–TiB₂–graphene nanoplatelets (GNPs) were fabricated by hot pressing (HP) at 1900 °C for 1 h under an axial pressure of 30 MPa. The microstructures and mechanical and electrical properties of the B₄C composites were investigated. The results show that the GNPs are distributed homogeneously in B₄C-based ceramic composites. Compared with monolithic B₄C, the TiB₂–GNPs-containing B₄C composite exhibits an approximately 68 % increase in flexural strength and a 169 % increase in fracture toughness due to the synergistic effects of TiB₂ particles and GNPs. The toughening mechanisms mainly include TiB₂ crack deflection, crack branching, transgranular fracture and GNPs crack deflection, crack bridging, and GNPs pull-out. Additionally, the electrical conductivity of the B₄C composite reinforced with dual fillers is three orders of magnitude higher than that of monolithic B₄C due to the establishment of a conductive network. The addition of GNPs can efficiently connect the isolated conductive TiB₂ particles in the B₄C matrix and provides an additional channel for electron migration.     

Microstructure and mechanical properties of TiB2–B4C ceramics fabricated by hot-pressing

In this study, TiB₂–B₄C composite ceramics were prepared using Y₂O₃ and Al₂O₃ as the sintering aids. Different contents of B₄C were added to seek promoted comprehensive mechanical properties of the composites. The mixed powders were sintered at 1850 °C under a uniaxial loading of 30 MPa for 2 h via hot-pressing. Through the measurement of XRD, SEM and related mechanical properties, the influence of B₄C content on the microstructure and mechanical properties of TiB₂–B₄C composites ceramics was discussed. The experimental results show that TiB₂–B₄C composite ceramics exhibit excellent mechanical properties, which can be attributed to the dense microstructure and fine grain size. In addition, TiB₂–B₄C composite ceramic shows a relatively high comprehensive properties when the addition amount of B₄C is 20 wt%. The relative density, Vickers hardness, fracture toughness and flexural strength are measured to be 99.61%, 27.63 ± 1.73 GPa, 4.77 ± 0.06 MPa m^1/2, 612.5 ± 28.78 MPa, respectively.     

Fabrication of toughened B4C composites with high electrical conductivity using MAX phase as a novel sintering aid

MAX phase Ti₃AlC₂ was chosen as a novel sintering aid to prepare electrically conductive B₄C composites with high strength and toughness. Dense B₄C composites can be obtained at a hot-pressing temperature as low as 1850 °C with 15 vol% Ti₃AlC₂. The enhanced sinterability was mainly ascribed to the in situ reactions between B₄C and Ti₃AlC₂ as well as the liquid phase decomposed from Ti₃AlC₂. Both the Vickers hardness and fracture toughness increase with increasing Ti₃AlC₂ amount, and high hardness and toughness values of 28.5 GPa and 7.02 MPa m^−1/2 respectively were achieved for B₄C composites sintered with 20 vol% Ti₃AlC₂ at 1900 °C. Crack deflection by homogenously distributed TiB₂ particles was identified as the main toughening mechanism. Besides, B₄C composites sintered with Ti₃AlC₂ show significantly improved electrical conductivity due to the percolation of highly conductive TiB₂ phase, which could enhance the machinability of B₄C composites largely by allowing electrical discharge machining.     

Synthesis and performance of TiB2–B4C composites by high pressure of TiC–B mixture

TiB₂–B₄C composites were in situ synthesized and consolidated by high pressure synthesis method from a mixture of TiC and B powders at the pressure and temperature of 5.0 GPa and 1500℃-1900℃. The phase composition, microstructure, density, hardness, thermal conductivity, and electrical resistivity of TiB₂–B₄C composites were analyzed. As the increase in the synthesis temperature, the products were TiB₂ and B₄C phases and that crystallinity improved. TiB₂–B₄C composites were dense without obvious pores. TiB₂–B₄C composites synthesized at 1800℃ obtained the optimized performance, including the relative density of 98.2%, the Vickers hardness of 31.7 ± 1.2 GPa with the load of 9.8 N, the thermal conductivity of 30.3 ± 0.7 W/(m K), and the electrical resistivity of 3.3 × 10⁻³ Ω cm, respectively. The grain size of the TiB₂–B₄C composites changed with the increase in synthesis temperature, leading to the changes in hardness, thermal conductivity, and electrical resistivity.     

Mechanical,Tribological, and Thermal Properties of Hot‐Pressed ZrB2‐B4C Composite

The effect of addition of submicrometer‐sized B₄C (5,10 and 15 wt%) on microstructure, phase composition, hardness, fracture toughness, scratch resistance, wear resistance, and thermal behavior of hot‐pressed ZrB₂‐B₄C composites is reported. ZrB₂‐B₄C (10 wt%) composite has V_H1 of 20.81 GPa and fracture toughness of 3.93 at 1 kgf, scratch resistance coefficient of 0.40, wear resistance coefficient of 0.01, and ware rate of 0.49 × 10^?3 mm³/Nm at 10N. Crack deflection by homogeneously dispersed submicrometer‐sized B₄C in ZrB₂ matrix can improve the mechanical and tribological properties. Thermal conductivity of ZrB₂‐B₄C composites varied from 70.13 to 45.30 W/m K between 100°C and 1000°C which is encouraging for making ultra‐high temperature ceramics (UHTC) component.     

Transition metal diboride-silicon carbide-boron carbide ceramics with super-high hardness and strength

Three phase boride and carbide ceramics were found to have remarkably high hardness values. Six different compositions were produced by hot pressing ternary mixtures of Group IVB transition metal diborides, SiC, and B₄C. Vickers’ hardness at 9.8 N was ~31 GPa for a ceramic containing 70 vol% TiB₂, 15 vol% SiC, and 15 vol% B₄C, increasing to ~33 GPa for a ceramic containing equal volume fractions of the three constituents. Hardness values for the ceramics containing ZrB₂ and HfB₂ were ~30% and 20% lower than the corresponding TiB₂ containing ceramics, respectively. Hardness values also increased as indentation load decreased due to the indentation size effect. At an indentation load of 0.49 N, the hardness of the previously reported ceramic containing equal volume fractions of TiB₂, SiC and B₄C was ~54 GPa, the highest of the ceramics in the present study and higher than the hardness values reported for so-called “superhard” ceramics at comparable indentation loads. The previously reported ceramic containing 70 vol% TiB₂, 15 vol% SiC, and 15 vol% B₄C also displayed the highest flexural strength of ~1.3 GPa and fracture toughness of 5.7 MPa·m^1/2, decreasing to ~0.9 GPa and 4.5 MPa·m^1/2 for a ceramic containing equal volume fractions of the constituents.     

Preparation of B4C composites toughened by TiB2-SiC agglomerates

High-performance B₄C composites toughened by TiB₂-SiC agglomerates were fabricated via reactive hot pressing with B₄C, TiC and Si as raw materials. The TiB₂-SiC composite serves as a composite toughening phase formed in the B₄C matrix through an in situ reaction; its agglomerates are composed of interlocked TiB₂ and SiC, which can remarkably improve the toughness of the B₄C composites. The Vickers hardness, flexural strength and fracture toughness of the B₄C-TiB₂-SiC composite reached 35.18 ± 0.45 GPa, 567 ± 14 MPa, and 6.38 ± 0.18 MPa m^1/2 respectively. The special toughening structure of the TiB₂-SiC composite introduced into B₄C ceramics was evaluated for the first time in this study.     

B4C‒TiB2 composite with modified microstructure and enhanced properties from optimal size coupling of raw powders

B₄C‒15 vol% TiB₂ composites were fabricated by in situ reactive spark plasma sintering with B₄C, TiC, and amorphous B powders as the raw materials. The size coupling of initial B₄C and TiC particles was optimized based on the reaction mechanism to derive B₄C‒TiB₂ composites with enhanced microstructure and properties. During the reactive sintering, fine B₄C–TiB₂ particles were firstly formed by an in situ reaction between TiC and B. Then, large B₄C particles tended to grow at the cost of small B₄C particles. The in situ TiB₂ grains gradually grew up and interconnect, distributing around the large B₄C grains to form an intergranular TiB₂ network. The results showed that the B₄C‒15 vol% TiB₂ composite prepared from 3.12 μm B₄C powder and 0.80 μm TiC powder had the optimal comprehensive properties, with a relative density of 99.50%, a Vickers hardness of 31.84 GPa, a flexural strength of 780 MPa, a fracture toughness of 5.77 MPa·m^1/2, as well as an electrical resistivity of 3.01 × 10⁻² Ω·cm.     

High toughness TiB2–Al2O3 composite ceramics produced by reactive hot pressing with fusible components

A manufacturing method of high toughness TiB₂–Al₂O₃ ceramic composites by reactive hot pressing via exothermic reactions with Al, B₂O₃, C and TiB₂ has been developed. The usage of fusible initial components (Al and B₂O₃) in the hot pressing procedure allowed forming dense ceramics with homogeneous fine structure at 1900°C and 20 MPa (after 8 min exposure) without any grinding of the initial powders. The hot pressed TiB₂–Al₂O₃ composites exhibit the fracture toughness of 9 MPa m^1/2, which is much higher than that of both single phase TiB₂ (6 MPa m^1/2) and Al₂O₃ (4 MPa m^1/2) ceramics.     

Microstructure and mechanical properties of B4C–TiB2–SiC composites toughened by composite structural toughening phases

B₄C–TiB₂–SiC composites toughened by composite structural toughening phases, which are the units of (TiB₂–SiC) composite, were fabricated through reactive hot pressing with B₄C, TiC, and Si as raw materials. The units of (TiB₂–SiC) composite with the size of 10‐20 μm are composed of interlocking TiB₂ and SiC with the size of 1‐5 μm. The addition of TiC and Si can effectively promote the sintering of B₄C ceramics. The relative densities of all the B₄C composites with different contents of TiB₂ and SiC are close to completely dense (98.9%‐99.4%), thereby resulting in superior hardness (33.1‐36.2 GPa). With the increase in the content of TiB₂ and SiC, the already improved fracture toughness of the B₄C composite continuously increases (5.3‐6.5 MPa·m^1/2), but the flexure strength initially increases and then decreases. When cracks cross the units of the (TiB₂–SiC) composite, the cracks deflect along the interior boundary of TiB₂ and SiC inside the units. As the crack growth path is lengthened, the crack propagation direction is changed, thereby consuming more crack extension energy. The cumulative contributions improve the fracture toughness of the B₄C composite. Therefore, the composite structural toughening units of the (TiB₂–SiC) composite play an important role in reinforcing the fracture toughness of the composites.     

Preparation and mechanical properties of laminated B4C–TiB2/BN ceramics

Laminated B₄C–TiB₂ ceramics with h-BN interface layers were successfully prepared by roll forming and tape casting, and samples with different numbers of stacked layers were obtained. Scanning electron microscopy and X-ray diffraction were used to analyze the microstructure and interlayer crystal phases of the composites, and the bending strength, fracture toughness, and work of fracture were measured. As the number of h-BN layers increased, the fracture toughness increased from 7.38 ± 0.5 MPa m^1/2 to 9.01 ± 0.61 MPa m^1/2, which is 2–3 times higher than that of monolithic B₄C ceramics. As the fracture toughness increased, the hardness remained at a high level (31.67 GPa). Bending tests showed that cracks deflected when they encountered the h-BN interfacial layers. The toughening mechanisms included the deflection and branching of cracks and generation of new microcracks, which increased the length of the propagation path and work of fracture.     

Microstructures and mechanical properties of B4C–SiC and B4C–SiC–TiB2 ceramic composites fabricated by hot pressing

Boron carbide (B₄C) ceramic composites with excellent mechanical properties were fabricated by hot-pressing using B₄C, silicon carbide (SiC), titanium boride (TiB₂), and magnesium aluminum silicate (MAS) as raw materials. The influences of SiC and TiB₂ content on the microstructural evolution and mechanical properties of the composites were systematically investigated. The mechanism by which MAS promotes the sintering process of composites was also investigated. MAS exists in composites in the form of amorphous phase. It can effectively remove the oxide layer from the surface of ceramic particles during the high temperature sintering process. The typical values of relative density, hardness, bending strength, and fracture toughness of B₄C–SiC–TiB₂ composites are 99.6%, 32.61 GPa, 434 MPa, and 6.20 MPa m^1/2, respectively. Based on the microstructure observations and finite element modeling, the operative toughening mechanism is mainly attributed to the crack deflection along the grain boundary, which results from the residual stress field generated by the thermal expansion mismatch between B₄C and TiB₂ phase.     

Microstructure and mechanical properties of hot-pressed B4C/TiC/Mo ceramic composites

Boron carbide (B₄C)/TiC/Mo ceramic composites with different content of TiC were produced by hot pressing. The effect of TiC content on the microstructure and mechanical properties of the composites has been studied. Results showed that chemical reaction took place for this system during hot pressing sintering, and resulted in a B₄C/TiB₂/Mo composite with high density and improved mechanical properties compared to monolithic B₄C ceramic. Densification rates of the B₄C/TiC/Mo composites were found to be affected by additions of TiC. Increasing TiC content led to increase in the densification rates of the composites. The sintering temperature was lowered from 2150 °C for monolithic B₄C to 1950 °C for the B₄C/TiC/Mo composites. The fracture toughness, flexural strength, and hardness of the composites increased with increasing TiC content up to 10 wt.%. The maximum values of fracture toughness, flexural strength, and hardness are 4.3 MPa m^1/2, 695 MPa, and 25.0 GPa, respectively.     

Microstructure and mechanical properties of B4C–TiB2 ceramic composites prepared via a two-step method

B₄C–TiB₂ ceramic composites were fabricated by a two-step method. First, B₄C–TiB₂ composite powders were synthesized from TiC–B powder mixtures at 1400 ℃, then mixed with commercial B₄C powders by ball milling and the B₄C–TiB₂ ceramic composites were prepared by hot pressing at 1950 ℃. This two-step method not only effectively refined TiB₂ grains, but also allowed the composition of the composites to be freely designed. The microstructure and mechanical properties of the composites were investigated. The results showed that the B₄C–TiB₂ ceramic composite with a 10 wt% TiB₂ content obtained the ideal comprehensive performance, with a volume density, Vickers hardness, bending strength, and fracture toughness of 2.61 g/cm³, 35.3 GPa, 708 MPa, and 5.82 MPa m^1/2, respectively. The advantages of the in-situ reaction process were fully exerted by the two-step method, which made a remarkable contribution to the excellent properties of B₄C–TiB₂ ceramic composites.     

Microstructural Effects on the Mechanical Properties of SiC‐15 vol% TiB2 Particulate‐Reinforced Ceramic Composites

The microstructures and mechanical properties were studied for two different SiC ceramics containing 15 vol% of TiB₂ particulates. The first was prepared from commercially available spray‐dried granules and the second by blending individual SiC and TiB₂ powders. The average TiB₂ particle sizes were 2.7 μm for the ceramic prepared from blended powders, which had a uniform distribution of TiB₂, and 2.3 μm for the ceramic prepared from spray‐dried granules, which had a nonuniform distribution of TiB₂ agglomerates. Although the two ceramics had hardness values of 26 GPa, the other properties were different. For example, the fracture toughness was 4.3 MPa·m^1/2 for the ceramic prepared from blended powders compared to 3.1 MPa·m^1/2 for the ceramic prepared from spray‐dried granules. In contrast, the Weibull modulus for the ceramic prepared from spray‐dried granules was 21 compared to 12 for the other. Calculations predicted spontaneous microcracking in the ceramic prepared from spray‐dried granules, which was confirmed by analysis of the microstructure. The presence of microcracks accounted for the higher Weibull modulus, but lower flexural strength, Young's modulus and fracture toughness for the ceramic prepared from spray‐dried granules.     

Fracture toughness in some hetero-modulus composite carbides: carbon inclusions and voids

Structure and mechanical characteristics of dense ceramic composites synthesised by reactive hot pressing of TiC–B₄C powder mixtures at 1800–1950°C under 30?MPa were investigated by X-ray diffraction, scanning electron microscopy and energy dispersive X-ray spectroscopy (SEM and EDX). The results show that during hot pressing solid-phase chemical reaction 2TiC?+?B₄C?=?2TiB₂?+?3C has occurred with final products like TiB₂–TiC–C, TiB₂–C or TiB₂–B₄C–C hetero-modulus composite formation with around one micrometer size carbon precipitates. The fracture toughness depends on the amount of graphite precipitation and has a distinct maximum K1C?=?10?MPa?m^1/2 at nearly 7?vol.-% of carbon precipitate. The fracture toughness behaviour is explained by the developed model of crack propagation. Within the model, it is shown that pores (voids) and low-modulus carbon inclusions blunt the cracks and can increase ceramic toughness in some cases.     

Microstructure and mechanical property of (TiB2-SiC) agglomerate-toughened B4C-TiB2-SiC composites

B₄C-TiB₂-SiC composites toughened by (TiB₂-SiC) agglomerates were prepared via reactive hot pressing with B₄C and TiSi₂ as raw materials. Phase composition, microstructure, and mechanical properties of the fabricated composites were investigated. The function of (TiB₂-SiC) agglomerates was analyzed, and the strengthening and toughening mechanism were also discussed. Results indicated that some of the in situ formed TiB₂ and SiC were interlocked to form special (TiB₂-SiC) agglomerates in the matrix. The good comprehensive performances of 510 MPa flexural strength, 5.84 MPa·m^1/2 fracture toughness, and 31.93 GPa hardness were obtained in the composites fabricated with 30 wt% TiSi₂. The in situ introduced fine TiB₂ and SiC grains refined the grains of B₄C due to the pinning effect, which enhanced the strength. The special (TiB₂-SiC) agglomerates and the existing toughening phenomena such as crack deflection, branching, and microcrack regions induced by the mismatch of thermal expansion coefficients, had cumulative effects on improving the fracture toughness.