Effect of boron addition on microstructure,mechanical properties and oxidation resistance of TaC ceramics

TaC ceramics with 0.03–0.60?wt% of boron additions were prepared by hot pressing at 2100?°C for 1?h under a pressure of 40?MPa. Effects of boron content on densification, phase composition, microstructure, mechanical properties and oxidation resistance of the TaC ceramics were investigated. When the boron content was 0.12?wt% and above, full density was obtained due to reactions between boron and oxygen impurity at presence of TaC. Minor phases of TaB₂ and C were formed in the 0.24 and 0.60?wt% B compositions after gas-out of the oxygen impurity. Microstructure of the TaC ceramics was refined with increasing in boron content. The TaC ceramic with 0.24?wt% of boron showed the best mechanical properties with a Vickers hardness, flexural strength and fracture toughness of 17.7?GPa, 534?MPa and 4.6?MPa?m^1/2, respectively. When more boron was added, interfacial bonding of the TaC grains was strengthened causing a decrease in fracture toughness. Oxidation resistance of the TaC ceramics increased with boron content. Particularly, the 0.60?wt% B composition showed a weight gain of 0.0018?g/cm² after oxidization at 800?°C in air for 3?h.     

Boron-modified phenol formaldehyde resin-based self-healing matrix for Cf/SiBOC composites

C_f/SiBOC was fabricated from 2D carbon fabric as reinforcement and slurry-containing boron-modified phenol formaldehyde (BPF) resin with silicon as matrix resin using reaction-bonded silicon carbide method. The processing involves synthesis of (BPF) resin by reacting various amount of boric acid with phenol formaldehyde resin, polymer to ceramic transformation at 1450°C under argon atmosphere, with and without silicon, thermal transformation of the polymer matrix composite into a ceramic matrix composite and evaluation of isothermal oxidation for ceramics and its composites at 1000, 1250 and 1500°C. The ceramic studies, confirmed the formation of B₄C, SiC and SiB₄ (SiBOC) mixed phase and the role of boron as a catalyst for graphitisation of free carbon present in the ceramic. Oxidation of C_f/SiBOC composite at various temperatures leads to the formation of borosilicate glass which heals the cracks, hindering the inwards diffusion of oxygen.     

A simple and efficient method for the synthesis of SiBNC ceramics with different Si/B atomic ratios

The high-temperature durability of SiBNC ceramics is significantly influenced by Si/B ratios and the synthetic procedures. Single-source synthetic routes can yield homogeneous ceramics at the atomic level, but the Si/B ratio cannot be efficiently adjusted. In this paper, a simple and efficient method for the synthesis of SiBNC precursor polyborosilazanes (PBSZs) with different Si/B ratios has been established via a one-pot reaction involving boron trichloride, dichloromethylsilane and hexamethyldisilazane in different molar ratios. The Si/B ratios of the derived SiBNC ceramics were consistent with that of the precursor PBSZs. When pyrolysed at 1000 °C, PBSZs with 0.52, 0.94 and 2.12 Si/B ratios transformed into SiB_2.6N₅C_2.2, SiB_0.9N_2.7C_1.3 and Si₂BN₃C_1.4 ceramics respectively. The polymer-to-ceramic process was also studied and featured ceramic yields of 43.2 wt%, 50.1 wt% and 62.2 wt%, respectively. The derived ceramic SiB_0.9N_2.7C_1.3 resisted crystallization up until 1700 °C, whereas the SiB_2.6N₅C_2.2 and Si₂BN₃C_1.4 could remain amorphous up to 1600 °C only. Using the precursor with 0.94 Si/B ratio, the SiBNC ceramic fibres were also obtained.     

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.     

Spark plasma sintering of boron nitride micron tubes reinforced boron carbide ceramics with excellent mechanical property

In this paper, the novel boron nitride micron tubes (BNMTs) were used to reinforce commercial boron carbide (B₄C) ceramics prepared via spark plasma sintering technology. The effects of the sintering parameters, sintering temperature, the holding time, and the BNMTs content on the microstructure and mechanical properties of B₄C/BNMTs composite ceramics were studied. The results indicated that adding a proper amount of BNMTs could inhibit the grain growth of B₄C and improve the fracture toughness of the B₄C/BNMTs composite ceramics. The prepared composite ceramic sample with 5 wt% BNMTs at 1850°C, 8 min and 30 MPa displayed the best mechanical properties. The relative density, hardness, fracture toughness, and bending strength of the samples were 99.7% ± .1%, 35.62 ± .43 GPa, 6.23 ± .2 MPa m^1/2, and 517 ± 7.8 MPa, respectively. Therein, the corresponding value of hardness, fracture toughness, and bending strength was increased by 10.3%, 43.59%, and 61.5%, respectively, than that of the B₄C/BNMTs composite ceramic without BNMTs. It was proved that the high interface binding energy and bridging effect between boron carbide and BNMTs were the toughening principle of BNMTs.     

Effects of B4C addition on the microstructure and properties of porous alumina ceramics fabricated by direct selective laser sintering

Direct selective laser sintering (dSLS) is a promising method for the fabrication of complex-shaped ceramic parts. In this paper, boron carbide (B₄C) was used as an inorganic additive to improve the laser sintering behavior of alumina. The effects of B₄C addition on the microstructure and mechanical properties of porous alumina ceramics were investigated. Mixture of alumina powders and different amount of B₄C were directly sintered using different SLS parameters. Results indicated that the process window of alumina could be expanded by the addition of B₄C. Furthermore, the amount of B₄C played an important role in surface morphologies of alumina ceramics. It could be explained by the increase of mass transfer due to the addition of B₄C, which enhanced the densification process. The compressive strength of sintered samples increased with the increase of B₄C, which reached its maximum value when the content of B₄C was 7?wt% and the density of the samples after post treatment could reach 1.4?g/cm³. In addition, a size expansion phenomenon was observed. The size expansion could reach 5% after SLS, which could be attributed to the pin effects and oxidation behavior of B₄C particles.     

Preparation and high-temperature performance of HfC-based nanocomposites derived from precursor with Hf-(O,N) bonds

A novel precursor was synthesized by reacting hafnium chloride with dicyandiamide and dimethylformamide. The precursor was characterized via FT-IR and NMR, as well as TG. Subsequently, the precursor was annealed in Ar over a range of temperatures from 1000 °C to 2000 °C, and the microstructural evolution of the ceramics was investigated by XRD, XPS, and TEM. The results show that the carbothermal reduction of the precursor starts at 1150 °C and the ceramic yields at 1500 °C reach 44.6 wt%. The obtained powders exhibit a uniform distribution and are composed of N-doped HfC and graphite. The N-doped structure postponed the oxidation of the HfC(N) ceramics. The HfC(N) ceramics were first oxidized to yield HfO₂, carbon, and nitrogen, and then the carbon was oxidized with the evolution of CO₂. The presented synthesis method is believed to be applicable to the preparation of other high-performance ceramics.     

Novel class of precursor-derived Zr–La–B–C(O) based ceramics containing nano-crystalline ultra-high temperature phases stable beyond 1600 °C

In this work, a novel ultra-high temperature resistant precursor-derived ceramic containing Zr, La, B, and C was synthesized through precursor modification of phenol formaldehyde resin. The thermal stability and resistance to crystallization of the ceramic at a temperature of 1600 °C was investigated and was found to be profoundly influenced by the boron content in the starting precursors. The ceramics remained amorphous at 1600 °C for 2 h in argon and upon sustained heat-treatment for up to 16 h resulted in nano-crystalline ultra-high temperature phases such as ZrB₂, ZrC, LaB₆ and La₂Zr₂O₇. Thermodynamic equilibrium phase calculations show that even longer durations of heat treatment may be required to achieve thermodynamic equilibrium. High-resolution transmission electron microscopy revealed encapsulation of nanocrystals (<5 nm) in an amorphous matrix surrounded by turbostratic layers of carbon inhibiting its growth. Spectrochemical techniques confirmed the presence of boron substituted carbon in the amorphous matrix of the ceramic. The unique nature of the amorphous matrix lends the ceramic resistance to crystallization and chemical degradation that can surpass the likes of classical silicon-based precursor-derived ceramics.     

Novel processable precursor for BN by the polymer-derived ceramics route

Novel precursors polymerized from (alkylamino)borazines (AAB) were synthesized and transformation of processable poly-AAB to boron nitride (BN) was researched. The AAB monomers of the type (BNH)₃(NHR)₃ were synthesized via ammolysis of 2,4,6-trichloroborazine (TCB) with different propylamines under mild conditions. The specially designed monomers served as molecular precursors for BN by the polymer-derived ceramics route. The processability of the polymeric precursors varied with propylamino-groups of AAB linked with boron atoms on (BNH)₃. The good processability of the poly[2,4,6-tris(iso-propylamino)borazine] (PTPⁱAB) was proven by melt-spinning it into polymer fiber. Furthermore, the PTPⁱAB gave a ceramic yield of about 53 wt% in Ar at 1200 °C by TGA. Based on FTIR, Raman, XRD, XPS and elemental analysis, the pyrolytic product of PTPⁱAB showed a composition of BN_1.07. In addition, the BN illustrated excellent oxygen resistance in air.     

Preparation and properties of high-porosity ZrB2-SiC ceramics by water-based freeze casting

The development of novel cermet composites based on porous ceramics with high porosity, interconnected pore structure and good mechanical property has attracted considerable attention in engineering application. In this work, water-based freeze casting process was employed to fabricate ZrB₂-SiC porous ceramic with aligned lamellar-channels structure using PAA-NH₄ as the dispersant. The results revealed that the well-dispersed suspension with best rheological behavior was obtained using 1.0 wt% PAA-NH₄ at pH 9. The crack-free porous ceramic exhibited small volume shrinkage ranging from 2.59 % to 1.87 %. By varying the solid loading, the fabricated samples displayed a tailored porosity ranging from 76.12% to 59.37% and an excellent compressive strength of 7 MPa to 78 MPa. After oxidation, the samples displayed a decreased porosity and an increased compressive strength. The ZrB₂­SiC porous ceramic fabricated in this work will be a promising candidate for the framework of cermet composite.     

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.     

Electrical conductivity and infrared radiation performance of SiC-CNT composite ceramics

SiC ceramic is an excellent infrared source material that can be used in a wide range of fields, like infrared heating, night vision and communication, but its poor electrical properties limit it. In this work, carbon nanotubes (CNTs) were selected as conductive phase filler, and SiC-CNT composite ceramics were prepared by SPS method. The effects of CNT content on the microstructures, electrical properties and infrared radiation performance of the composites were studied. The introduction of CNT effectively reduced the height of Schottky barrier at grain boundary, thus weakening the grain boundary effect, reducing the grain boundary resistance, further weakening the nonlinear characteristics and bulk resistivity of the composite ceramics. When the content of CNT was 1 wt%, electrical percolation was achieved, and the bulk resistivity of SiC ceramics dropped by nearly 3 orders of magnitude. The preferred orientation distribution of CNT made the bulk resistivity perpendicular to the pressure direction R_⊥ always lower than that parallel to the pressure direction R_//. The sample with 5 wt% CNT assumed linear conductivity characteristics, with bulk resistivity in different direction of 16.5 Ω cm (R_//) and 11.8 Ω cm (R_⊥), respectively. CNT addition slightly increased the infrared radiation performance of SiC ceramics, and the sample with 5 wt% CNT possessed the highest total emissivity of 0.675. The excellent electrical conductivity and infrared radiation performance of SiC-CNT composite ceramic confirmed this class as a promising infrared source material.     

Synthesis and pyrolysis of single-source precursor for HfCxN1-x-SiC ceramic with different SiC contents

A novel single-source precursor was synthesized to prepare HfC_xN_1-x/SiC multiphase ceramics by using hafnium chloride (HfCl₄), diallylamine (DAA) and polycarbosilane (PCS). We conducted an investigation of the synthesis process, polymer-to-ceramic conversion, as well as the microstructure and phase evolution of HfC_xN_1-x/SiC multiphase ceramics with different levels of SiC content. The results showed that the core-shell particles of HfC_xN_1-x-carbon were embedded homogeneously in the β-SiC matrix which is beneficial for preventing grain growth and improving oxidation resistance. Based on data from oxidation tests, the ceramics improved the oxidation temperature and remained stable at a high temperature (1500 °C) with oxidation layer formation on the surface. Due to the highly cross-linked structure without oxygen, high ceramic yield, homogeneous composition and excellent oxidation resistance of the pyrolysis product, the as-prepared precursor is a promising material for making high-performance composite ceramics.     

Boron nitride by pyrolysis of the melt-processable poly[tris(methylamino)borane]: Structure, composition and oxidation resistance

Evolution of structure and composition of the melt-processable poly[tris(methylamino)borane] (PTMB) during its conversion to ceramics was studied by TGA, FTIR, Raman, XRD, XPS and elemental analysis (EA). The results show that the ceramic yield was greatly improved from 60.22 to 74.4 wt% at 900 °C by curing in NH₃ prior to pyrolysis. The carbon impurity in the precursor can be removed effectively in NH₃ whereas no similar result occurred in N₂. In NH₃, 93 wt% of carbon was removed at 600 °C and the carbon content in the pyrolyzed product at 900 °C was only 0.37 wt%. At the same time, the conversion from polymer to ceramics was almost completed at 900 °C. Moreover, the sample acquired at 900 °C was amorphous boron nitride (BN), while that of further annealing at 1600 °C showed characteristic of turbostratic BN (t-BN). Additionally, the BN with nearly stoichiometric composition exhibited good oxidation resistance even up to 900 °C in air.     

Influence of Yb and Si on the fabrication of Yb:YAG transparent ceramics using spherical Y2O3 powders

Yb:YAG (yttrium aluminum garnet) transparent ceramics were fabricated by the solid-state method using monodispersed spherical Y₂O₃ powders as well as commercial Al₂O₃ and Yb₂O₃ powders. Pure YAG phase was obtained at low temperature due to homogeneous mixing of powders. Under the same sintering conditions, the Yb:YAG ceramics with different doping contents of Yb³⁺ had similar morphologies and densification rates. After being sintered at 1700 °C in vacuum, the ceramic samples had high transparencies. The Yb:YAG ceramics doped with 0.5 wt% SiO₂ formed Y–Si–O liquid phase and nonstoichiometric point defects that enhanced sintering. Compared with Nd doping, Yb doping hardly affected the YAG grain growth, sintering densification or optical transmittance, probably because Yb³⁺ easily entered the YAG lattice and had a high segregation coefficient.     

Effect of boron content on the microstructure and electromagnetic properties of SiBCN ceramics

Electromagnetic wave (EMW) absorbing materials have excellent potential for various applications in civil engineering and the military. In this study, siliconboron carbonitride (SiBCN) ceramics with excellent EMW absorption capability and oxidation resistance were obtained by adjusting the boron content. The results revealed that the graphite crystallite size in the SiBCN ceramics increased from 3.42 to 3.78 nm, whereas the thickness of the oxide layer decreased from 16.6 to 8.2 μm. The highest electrical conductivity and permittivity for the SiBCN ceramics were obtained when the boron content was 5%. The minimum reflection loss was ?35.25 dB at 10.57 GHz and a ceramic thickness of 2.0 mm. At a temperature of 600 °C, the SiBCN ceramic exhibited excellent EMW attenuation ability; particularly, the minimum reflection loss reached ?29.18 dB at 9.65 GHz and a ceramic thickness of 2.5 mm. The superior EMW absorption properties of the SiBCN ceramics at high temperatures can be ascribed to the synergistic effect of relaxation and conductivity. The results suggest that boron could enhance the transformation of amorphous carbon into crystalline graphite and increase the number of heterointerfaces and conductive paths. This work provides a method for obtaining SiBCN ceramics with excellent EMW absorption properties.     

Influence of Li2O–B2O3–SiO2 glass on the sintering behavior and microwave dielectric properties of BaO–0.15ZnO–4TiO2 ceramics

This paper reports the investigation of the performance of Li₂O–B₂O₃–SiO₂ (LBS) glass as a sintering aid to lower the sintering temperature of BaO–0.15ZnO–4TiO₂ (BZT) ceramics, as well as the detailed study on the sintering behavior, phase evolution, microstructure and microwave dielectric properties of the resulting BZT ceramics. The addition of LBS glass significantly lowers the sintering temperature of the BZT ceramics from 1150 °C to 875–925 °C. Small amount of LBS glass promotes the densification of BZT ceramic and improves the dielectric properties. However, excessive LBS addition leads to the precipitation of glass phase and growth of abnormal grain, deteriorating the dielectric properties of the BZT ceramic. The BZT ceramic with 5 wt% LBS addition sintered at 900 °C shows excellent microwave dielectric properties: ε_r=27.88, Q×f=14,795 GHz.     

Effects of porosity on electrical and thermal conductivities of porous SiC ceramics

The effects of porosity on the electrical and thermal conductivities of porous SiC ceramics, containing Y₂O₃–AlN additives, were investigated. The porosity of the porous SiC ceramic could be controlled in the range of 28–64 % by adjusting the sacrificial template (polymer microbead) content (0–30 wt%) and sintering temperature (1800–2000 °C). Both electrical and thermal conductivities of the porous SiC ceramics decreased, from 7.7 to 1.7 Ω⁻¹ cm⁻¹ and from 37.9 to 5.8 W/(m·K), respectively, with the increase in porosity from 30 to 63 %. The porous SiC ceramic with a coarser microstructure exhibited higher electrical and thermal conductivities than those of the ceramic with a finer microstructure at the equivalent porosity because of the smaller number of grain boundaries per unit volume. The decoupling of the electrical conductivity from the thermal conductivity was possible to some extent by adjusting the sintering temperature, i.e., microstructure, of the porous SiC ceramic.     

Oxygen Interaction with Hexagonal OsB2 at High Temperature

The stability of ReB₂‐type hexagonal OsB₂ powder at high temperature with oxygen presence has been studied by thermogravimetric analysis, differential scanning calorimetry, SEM, EDS, and high‐temperature scanning transmission electron microscopy and XRD. Results of the study revealed that OsB₂ ceramics interact readily with oxygen present in reducing atmosphere, especially at high temperature and produces boric acid, which decomposes on the surface of the powder resulting in the formation of boron vacancies in the hexagonal OsB₂ lattice as well as changes in the stoichiometry of the compound. It was also found that under low oxygen partial pressure, sintering of OsB₂ powders occurred at a relatively low temperature (900°C). Hexagonal OsB₂ ceramic is prone to oxidation and it is very sensitive to oxygen partial pressures, especially at high temperatures.     

Pore structure and thermal oxidation curing behavior of porous polymer derived ceramics with superhigh porosity fabricated by freeze casting

Porous ceramics with porosity up to 92.5 % have been successfully fabricated by freeze casting of polycarbosilane (PCS) solution. The effect of PCS concentration and thermal oxidation curing on the pore structure and compressive properties was investigated. Curing mechanism and thermodynamics were illuminated through analyzing the molecular structure, curing activation energy, and curing degree. Porous ceramics, mainly composed of SiC and a small amount of SiO₂, have dendritic pore structure which well replicates the solidification morphology of camphene solvent. Results of FT-IR and Gaussian computation of PCS electron density show that Si–H and Si–CH₃ bonds play a dominant role in thermal oxidation curing reaction. Both curing degree and ceramic yield increase with the increase in curing temperature and time. The curing degree of Si–H bond is close to 52 % and the corresponding ceramic yield is about 83 % when the porous PCS was cured at 200 °C for 90 min. Both polymer concentration and curing time have influences on the compressive strength of porous ceramics.