Structural and thermal properties of boron nitride nanoparticles

In the present study, our main motivation was to investigate the structural and thermal stability of BN nanoparticles (B_1.0N_0.9-NPs) produced by spray-pyrolysis (SP) of borazine at 1400 °C by thermogravimetric experiments and X-ray diffraction. We observed that B_1.0N_0.9-NPs are relatively stable in air below 850 °C in which only oxidation of the NP surface proceeded. Above 850 °C, the powders started to strongly react with air due to bulk oxidation. Under nitrogen, they appeared to be less stable than plate-like BN synthesized from borazine at 1400 °C through conventional pyrolysis. This is related to the low degree of crystallization of B_1.0N_0.9-NPs that clearly affects their stability. Using a post-pyrolysis treatment at 1400 °C, B_1.0N_0.9-NPs remained stable up to 1600 °C similarly to plate-like BN. However, above 1600 °C, a relatively fast weight loss occurred for B_1.0N_0.9-NPs, whereas plate-like BN remained stable up to 1800 °C. This indicated that their lower size also affects their high temperature thermal behavior.     

Thermal behaviour of a series of poly[B-(methylamino)borazine] for the preparation of boron nitride fibers

The thermal behaviour of a series of poly[B-(methylamino)borazine] prepared at various temperatures ranging from 140 to 200 °C is studied in the present paper as potential BN fiber precursors. It was shown that the softening capability of poly[B-(methylamino)borazine] can be tailored by controlling the temperature at which polymers were prepared to achieve melt-spinning and produce high quality green fibers. Thus as-spun fibers could be next converted into boron nitride fibers using ammonia (25–1000 °C) and nitrogen (25–1800 °C) atmospheres. The quality of boron nitride fibers was shown to depend on the first part of the pyrolysis step (25 and 1000 °C; ammonia atmosphere) in which the great majority of the weight loss necessary for boron nitride production occurs. Ideal poly[B-(methylamino)borazine] as BN fiber precursors are those prepared between 170 and 180 °C. They display appropriate melt-spinnability and ceramic conversion capability.     

Microstructural evolution,mechanical and thermal properties of LaB6 embedded in Si-B-C-N prepared by spark plasma sintering

Si-B-C-N monoliths with 5 wt% LaB₆ additives were prepared by spark plasma sintering at 1250–2000 °C and 50 MPa using a mechanically alloyed mixture of graphite, c-Si, h-BN and LaB₆ powders as the starting materials. Microstructural evolution, mechanical and thermal properties of the as-prepared La/Si-B-C-N monoliths were investigated. The densification of the ceramics starts at 1160° and ends at 1800 °C with the formation of La-containing compounds coupled with SiC and BN(C) phases. La-containing BN(C) grains develop into a lamellar structure at 1900 °C offering improved fracture toughness and decreased Vickers hardness, flexural strength and elastic modulus. The formation of lamellar BN(C) is also responsible for a high thermal expansion coefficient of 4.2×10⁻⁶ /°C.     

Reaction joining of SiC ceramics using TiB2-based composites

SiC ceramics were reaction joined in the temperature range of 1450–1800 °C using TiB₂-based composites starting from four types of joining materials, namely Ti–BN, Ti–B₄C, Ti–BN–Al and Ti–B₄C–Si. XRD analysis and microstructure examination were carried out on SiC joints. It is found that the former two joining materials do not yield good bond for SiC ceramics at temperatures up to 1600 °C. However, Ti–BN–Al system results in the connection of SiC substrates at 1450 °C by the formation of TiB₂–AlN composite. Furthermore, nearly dense SiC joints with crack-free interface have been produced from Ti–BN–Al and Ti–B₄C–Si systems at 1800 °C, i.e. joints TBNA80 and TBCS80, whose average bending strengths are measured to be 65 MPa and 142 MPa, respectively. The joining mechanisms involved are also discussed.     

Low-temperature synthesis of K0.5Na0.5NbO3 ceramics in a wide temperature window via cold-sintering assisted sintering method and enhanced electrical properties

High temperatures (≥ 1100 °C) and narrow temperature window (～ 20 °C) for sintering dense K_0.5Na_0.5NbO₃ ceramics always deteriorate their electrical properties. Here, via cold-sintering assisted sintering method, dense K_0.5Na_0.5NbO₃ ceramics were obtained in a wide temperature span between 800 °C and 1000 °C. An aqueous solution of NaOH and KOH mixture was used as transient liquid. Effects of liquid content (LC), molar concentration (MC) of liquid, cold-sintering temperature (T_CS), and post-annealing temperature (T_AN) on densification and electrical properties of the ceramics were investigated in detail. The ceramics prepared using LC = 10 wt%, MC = 10 mol/L, T_CS = 350 °C, and T_AN = 900 °C exhibit excellent electrical properties with d₃₃ = 123 pC/N, ε_r = 609, tanδ = 0.021, P_r = 28.0 μC/cm², P_m = 39.2 μC/cm², and E_c = 20.3 kV/cm. Compared to the ceramics with same or similar compositions via conventional solid-state sintering, the present K_0.5Na_0.5NbO₃ ceramics exhibit excellent electrical properties. The study endows the cold-sintering assisted sintering the successful method to prepare K_0.5Na_0.5NbO₃ ceramics at low temperatures and in a wide temperature window.     

Effect of the electrode-bulk interface on the dielectric properties of BBZT ceramics

The effects of the electrode-bulk interface on the dielectric properties of Ba_0.9988Bi_0.0008Zr_0.2Ti_0.8O₃ (BBZT) ceramics with a slight change in the thickness (≤15%) were investigated. In BBZT ceramics, the dielectric constant decreases with the increase of thickness, and the interface between electrode and bulk ceramics is considered the main reason. A formula is proposed to calculate the dielectric constant of bulk materials. According to the formula, the electrode-bulk interface has a slight influence on the frequency characteristics of the dielectric constant. However, the ferroelectric to paraelectric phase transition temperature changes from 10 °C to 15 °C for bulk ceramics when the electrode-bulk interface is taken into consideration. In a range of 0 °C–75 °C, obvious differences between ε_B and ε_T are observed due to the electric field induced by removable carriers. The dielectric tunability is degraded by the influence of electrode-bulk interface. BBZT ceramics have considerable tunability (>65% @100 kHz) and a low loss tangent (<0.006 @100 kHz) with an excellent FOM value (>270). This study demonstrates a method of calculating the dielectric constants of bulk ceramic layers and provides a theoretical basis for improving the performance of bulk materials using interfacial layers.     

Preparation and properties of a novel precursor-derived Zr-C-B-N composite ceramic via zirconocene and borazine

A novel preceramic polymer polyzirconocenyborazane (PZCBN) was synthesized by the polymerization of Bis(cyclopentadienyl)zirconium divinyl and borazine, introducing Zr, B, C, N together. The formation and concentration of elements Zr, C, B, N in the precursor and ceramic were detected through FTIR NMR, XRD, SEM and TEM. From the analysis, the Cp₂Zr(CH?CH₂)₂ and borazine linked together via the addition reaction between C?C and B-H. And after pyrolysis at 1200 °C, the precursor turned to ZrC/ZrB₂/BN composite ceramics, with a yield of 52 wt%. EDX resulted showed that the elements were well dispersed in the ceramics. According to SEM and TEM, the ceramic had a relatively dense structure with nano crystalline areas of ZrC embedded in the amorphous Zr-C-B-N matrix. TGA in air demonstrated that the ceramic had a favorable property on oxidation resistance.     

Improved durability of Si/B/N/C random inorganic networks

The inherent high temperature durability as well as the hardness of random inorganic networks composed of Si, B, N and C, can be raised through the incorporation of rigid structural elements (e.g. borazine rings) as well as through an increase of the carbon content. This has been shown by comparison of the high temperature durabilities and micromechanical properties of newly synthesized Si/B/N/C ceramics derived from different acyclic and cyclic single source precursors. Crosslinking of these specially designed monomers with methylamine provides highly homogeneous preceramic polymers, in which the predetermined structural features of the molecular precursors are embedded. Subsequent pyrolysis and calcination up to 1500 °C converts the polymers into all-inorganic amorphous silicon boron carbonitrides. Depending on the constitution of the precursors, the as-obtained materials exhibit a combination of a high carbon content together with borazine rings embedded into the covalent network. Comparing the high temperature stability, hardness and stiffness of the synthesized ceramics, the best performance is achieved when carbon rich borazine derivatives are employed as single source precursors. Thus, the high temperature durability can be raised up to at least 2000 °C, and, at the same time, the microhardness and elastic modulus is maximized up to 14.5 and 127 GPa, respectively. The new materials have been characterized by IR spectroscopy, elemental analysis, XRD, SEM, DTA/TG, and by nanoindentation.     

Phase formation,microstructure development,and mechanical properties of kaolin-based mullite ceramics added with Fe2O3

The effects of Fe₂O₃ on phase evolution, density, microstructural development, and mechanical properties of mullite ceramics from kaolin and alumina were systematically studied. X-ray diffraction results suggested that the ceramics consisted of mullite, sillimanite, and corundum, in the sintering range of 1450°C–1580°C. However, as the sintering was raised to 1580°C, mullite is the main phase with a content of 94%, and the corundum phase content is 5.9%. Simultaneously, high-temperature sintering had a positive effect on the densification of the mullite ceramics, where both the bulk density and flexural strength could be optimized by adjusting the content of Fe₂O₃. It was found that 6 wt% Fe₂O₃ was optimal for the formation of rod-shaped mullite after sintering at 1550°C for 3 h. The sample's maximum bulk density was 2.84 g/cm³, with a flexural strength of 112 MPa. Meanwhile, rod-shaped mullite grains with an aspect ratio of ~9 were formed. As a result, a dense network structure was developed, thus leading to mullite ceramics with excellent mechanical properties. The effect of Fe₂O₃ on the properties might be attributed to the fact that Al³⁺ ions in the [AlO₆] octahedron were replaced by Fe³⁺ ions, resulting in lattice distortion.     

Fabrication and mechanical properties of laminated HfC–SiC/BN ceramics

Laminated HfC–SiC/BN ceramics were successfully fabricated by tape casting and hot pressing. Fully dense HfC–SiC ultra-high temperature ceramics with homogeneous structure were obtained. The introduction of the weak BN layer resulted in a slight decrease of the flexural strength but significantly improved the fracture toughness compared with monolithic HfC–SiC ceramics. The fracture toughness of laminated HfC–SiC/BN ceramics in the parallel direction peaked at 8.06 ± 0.46 MPa m^1/2, which increased by 115% than that of monolithic HfC–SiC ceramics. The composites showed non-catastrophic fracture behaviors in both parallel and perpendicular directions. It indicates that laminated structure design is a promising approach to obtain full density HfC–SiC ceramics with high fracture toughness.     

Non-additive sintering of Si2N2O ceramic with enhanced high-temperature strength,oxidation resistance,and dielectric properties

The high-temperature mechanical and dielectric properties of Si₂N₂O ceramics are often limited by the introduction of a sintering aid. Herein, dense Si₂N₂O was prepared at 1700 °C by hot-pressing oxidized amorphous Si₃N₄ powder without sintering additives. A homogeneous network with short-range order and a SiN₃O structure was formed in the oxidized amorphous Si₃N₄ powder during the hot-pressing process. Si₂N₂O crystals preferentially nucleated at positions within the SiN₃O structure and grew into rod-like and plate-like grains. Fully dense ceramics with mainly crystalline Si₂N₂O and some residual amorphous phases were obtained. The as-prepared Si₂N₂O possessed a good flexural strength of 311 ± 14.9 MPa at 1400 °C, oxidation resistance at 1500 °C, and a low dielectric loss tangent of less than 5 × 10⁻³ at 1000 °C.     

Recycling of coal ash for production of dense β-Sialon/ZrN/ZrON-based ceramics without sintering aids via pressureless sintering

β-Sialon(z = 2, Si₄Al₂O₂N₆)/ZrN composite powders have been synthesized from coal ash, zircon, and active carbon at 1550°C for 6 hours, and β-Sialon(z = 2)/ZrN/ZrON-based composite ceramics (SZZCCS) have been prepared from as-synthesized β-Sialon/ZrN composite powders via pressureless sintering process. The effects of sintering temperatures (1450, 1500, 1550°C) on the phase compositions, microstructures, linear shrinkage ratio, bulk density, and oxidation characteristics of the SZZCCS were investigated in detail, and the oxidation process was also analyzed. It was found that the dense SZZCCS could be prepared at 1550°C for 1 hour, and they mainly consisted of β-Sialon(z = 2), ZrN, and ZrON. The ZrN and ZrON particles were uniformly distributed on the β-Sialon matrix. The sintering properties of the SZZCCS were greatly improved with increasing the sintering temperature. The SZZCCS sintered at 1550°C for 1 hour possessed excellent oxidation resistance at 900°C for 6 hours due to their dense microstructures.     

The new complex high-entropy metal boron carbonitride: Microstructure and mechanical properties

In this contribution, the ternary BCN anion systems of high-entropy ceramics (HEC) are consolidated by hot-pressing sintering and the impacts of sintering temperature and the content of amorphous BCN addition on microstructural evolution and mechanical performance were evaluated. Results confirmed that high-entropy, oxide, and BN(C) phases were precipitated for (Ta_0.2Nb_0.2Zr_0.2Hf_0.2Ti_0.2)(B, C, N) ceramics after sintering at 1900°C. With the decrease of BCN addition, a new phase of MiB₂ (Mi representing the metal atoms) occurred. The Vickers hardness, bending strength, elastic modulus, and fracture toughness of the optimized bulk HECs were investigated, obtained at 24.5 ± 2.3 GPa, 522.0 ± 2.6 MPa, 478.9 ± 11.1 GPa, and 5.36 ± 0.56 MPa m^1/2, respectively.     

Effect of nano aluminum nitride filler on mechanical,thermal, and dielectric properties of the glass/mullite composites for low-temperature co-fired ceramic applications

Mullite/glass/nano aluminum nitride (AlN) filler (1–10 wt% AlN) composites were successfully fabricated for the low-temperature co-fired ceramics applications that require densification temperatures lower than 950°C, high thermal conductivity to dissipate heat and thermal expansion coefficient matched to Si for reliability, and low dielectric constant for high signal transmission speed. Densification temperatures were ≤825°C for all composites due to the viscous sintering of the glass matrix. X-ray diffraction proved that AlN neither chemically reacted with other phases nor decomposed with temperature. The number of closed pores increased with the AlN content, which limited the property improvement expected. A dense mullite/glass/AlN (10 wt%) composite had a thermal expansion coefficient of 4.44 ppm/°C between 25 and 300°C, thermal conductivity of 1.76 W/m.K at 25°C, dielectric constant (loss) of 6.42 (0.0017) at 5 MHz, flexural strength of 88 MPa and elastic modulus of 82 GPa, that are comparable to the commercial low temperature co-fired ceramics products.     

Ti doping and low-temperature sintering of BiFeO3 nanoparticles synthesized by the solvothermal method

In this study, nanoparticles of ferroelectric BiFeO₃ (BFO) doped with 0, 5, and 10 mol% Ti were synthesized by an ethanol-based solvothermal method, and their densification behavior was investigated. The nanoparticles were densified via a normal sintering process at a low temperature of about 600 °C, resulting in dense bulk ceramics of undoped and Ti-doped BFO with a relative density of over 90%. The weight loss due to bismuth evaporation during sintering was suppressed below 0.6% because of the low sintering temperature. The crystal structure analysis of the resulting ceramics confirmed the incorporation of Ti ions into the Fe³⁺ site of BFO. The results of dielectric and X-ray photoelectron spectroscopies showed that Ti doping effectively decreased the concentration of Fe⁴⁺ in the ceramics, leading to suppression of the extrinsic dielectric responses due to the Maxwell–Wagner effect and the hopping motion of the localized holes.     

Mechanical properties of in situ synthesized mullite-based composite ceramics with three-dimensional network structure

Needle-like nanocrystalline mullite powders were prepared through the molten salt process at the temperature of 900°C using coal gangue as raw material. Then, mullite-based composite ceramics were prepared by a conventional solid-state reaction between in situ synthesized mullite and Al₂O₃ powders. Effects of Al₂O₃ content and sintering temperatures on phase compositions, microstructure, and mechanical properties of the mullite-based composite ceramics were also studied. The results show that mullite content productivity increase from 72% to 95%, as the sintering temperature increased from 1480°C to 1580°C, which led to the improvement in the bulk density and flexural strength of the samples. The three-dimensional interlocking structure for mullite-based composite ceramics was obtained by the in situ solid-state reaction process. The maximum bulk density, flexural strength, and fracture toughness for the sample with 15 wt% Al₂O₃ content are 2.48 g/cm³, 139.79 MPa, and 5.62 MPa··m^1/2, respectively, as it was sintered at the temperature of 1560°C for 3 h. The improved mechanical properties of mullite-based composite ceramics maybe ascribed to good densification and increased mullite phase content, as well as to the in situ three-dimensional network structure. Therefore, the results would provide new ideas for high-value utilization of coal gangue.     

Effect of BN content on the structural,mechanical, and dielectric properties of PDCs-SiCN(BN) composite ceramics

Hexagonal boron nitride (h-BN) with low dielectric loss and high temperature resistance opens up new opportunities for the preparation of polymer-derived SiCN ceramics (PDCs-SiCN ceramics) with excellent mechanical and dielectric properties. BN-containing polymer-derived SiCN composite ceramics (PDCs-SiCN(BN) composite ceramics) with different BN content were prepared via a pyrolysis process of ball-milling-blended Polyvinylsilazane/boron nitride (PVSZ/BN) precursors. BN is stably embedded in the SiCN tissue and tightly bound with it. The appropriate content of BN greatly improves the mechanical properties of PDCs-SiCN ceramics, as BN reduces the number of pores and prevents crack expansion. Additionally, BN is also beneficial in lowering the dielectric loss of PDCs-SiCN ceramics because of the weakened polarization relaxation behavior. PDCs-SiCN (BN) composite ceramics have optimal mechanical and dielectric properties when the BN content is 1 wt%. The flexural strength, flexural modulus and compression strength of PDCs-SiCN(BN) composite ceramics with 1 wt% BN doping content were 189.37 MPa, 46.38 GPa, and 399.02 MPa, respectively. Its average dielectric loss (tanδ_ε) at 12.4-18 GHz is 0.0049.     

Dense zircon (ZrSiO4) ceramics by high energy ball milling and spark plasma sintering

The addition of sintering additives has always been detrimental to the mechanical properties of sintered ceramics; therefore, methods to reduce or, as in this case, eliminate sintering additives are usually relevant. In this paper, dense zircon ceramics were obtained starting from mechanically activated powder compacted by spark plasma sintering without employing sintering additives.The high energy ball milling (HEBM) of starting powder was effective to enhance the sintering kinetics. The structural changes of the zircon powder introduced by the HEBM were evaluated. The phase composition and the microstructure of bulk zircon material were analyzed by SEM (EDAX) and XRD. The Vickers hardness and the fracture toughness were evaluated as well.Fully dense materials were obtained at 1400 °C with a heating rate of 100 °C/min, 10 min soaking time and 100 MPa uniaxial pressure. The zircon samples sintered at temperatures above 1400 °C were dissociated in monoclinic zirconia and amorphous silica. The dissociation was detrimental for the mechanical properties. Unlike conventional sintering methods (hot pressing, pressureless sintering) SPS permitted to overcome the dissociation of the zircon material and to obtain additive free, fully dense zircon ceramic with outstanding mechanical properties.     

Low-temperature reactive spark plasma sintering of dense SiC-Ti3SiC2 ceramics

SiC-based ceramics are of great interest for various advanced applications. However, its fabrication requires high-temperature treatment at ～2000 – 2100 °С. In this study, we developed an approach based on low-temperature reactive spark plasma sintering to produce dense SiC-based ceramics with superior mechanical properties. It was found that an SPS temperature of 1600 °C and introduction of 10 – 15 wt% of mechanically activated non-oxide Ti–Si–C additive is required to manufacture ceramics with a theoretical density of higher than 90%. Nonetheless, employing 5 – 15 wt% of the additive mixture and an SPS temperature of 1700 °C, the maximum density of ～ 98% was achieved. The controlled formation and decomposition of the in-situ Ti₃SiC₂ MAX phase enables the fabrication of the engineering ceramics with enhanced compressive strength (550 MPa), elastic modulus (485 GPa), and microhardness (32 GPa), which are comparable to the best-reported SiC ceramics. The study has a significant potential for practical application in the production of advanced SiC-based ceramics for various purposes and could be used for further understanding and development of the high-temperature sintering methods.     

Chemical vapor deposition of pyrolytic boron nitride ceramics from single source precursor

Pyrolytic boron nitride ceramics were prepared on graphite substrates from borazine as the single source precursor by hot-wall chemical vapor deposition in deposition temperature range from 1300 °C to 1600 °C with a total pressure of 200 Pa. The chemical composition and the effect of deposition temperature on the morphology, phase, and structure of the pyrolytic boron nitride were investigated. A high purity product with stoichiometric B/N ratio is obtained. The deposition surface of the product exhibited a pebble-like structure, and the fracture surface showed an apparent laminar structure having a preferential (002) orientation parallel to the surface of the substrate at temperatures above 1400 °C. The product contained some turbostratic and amorphous boron nitride as evidenced from XRD and FTIR examinations. With the increase of deposition temperature, the crystallinity of the pyrolytic boron nitride increased with the turbostratic and amorphous boron nitride turned into hexagonal structure, and the crystallinity of the product became higher.