High‐Temperature Strength of Boron Suboxide Ceramic Consolidated by Spark Plasma Sintering

The spark plasma sintering (SPS) of B₆O ceramics using a highly crystalline boron suboxide powder with a low oxygen deficiency level is reported. The monolithic boron suboxide ceramic exhibited a room‐temperature strength of 300 ± 20 MPa, which is comparable to the strength of monolithic boron carbide. With increasing flexural test temperature, the strength of the boron suboxide ceramics increased to 450 MPa at 1400°C. The increase in strength with the temperature is associated with the unique microstructure of boron suboxide grains, which allows intergranular “brittle” fracture along subgrains even at 1400°C. This suggests that even higher strengths can be achieved.     

Amorphous boron suboxide

We study the atomic structure and the electronic and mechanical properties of amorphous boron suboxide (B₆O) using an ab initio molecular dynamic technique. The amorphous network is attained from the rapid solidification of the melt and found to consist of boron and oxygen-rich regions. In the boron-rich regions, boron atoms form mostly perfect or imperfect pentagonal pyramid-like configurations that normally yield the construction of ideal and incomplete B₁₂ molecules in the model. In addition to the B₁₂ molecules, we also observe the development of a pentagonal bipyramid (B₇) molecule in the noncrystalline structure. In the oxygen-rich regions, on the other hand, boron and oxygen atoms form threefold and twofold coordinated motifs, respectively. The boron-rich and oxygen-rich regions indeed represent structurally the characteristic of amorphous boron and boron trioxide (B₂O₃). The amorphous phase possesses a small band gap energy with respect to the crystal. On the bases of the localization of the tail states, we suggest that the p-type doping might be more convenient than the n-type doping in amorphous B₆O. Bulk modulus and Vickers hardness of the noncrystalline configuration is estimated are be 106 and 13-18 GPa, respectively, which are noticeably less than those of the crystalline structure. Such a noticeable decrease in the mechanical properties is attributed to the presence of open structured B₂O₃ glassy domains in the amorphous model.     

Spark plasma sintering and high-temperature strength of B6O–TaB2 ceramics

Tantalum diboride – boron suboxide ceramic composites were densified by spark plasma sintering at 1900 °C. Strength and fracture toughness of these bulk composites at room temperature were 490 MPa and 4 MPa m^1/2, respectively. Flexural strength of B₆O–TaB₂ ceramics increased up to 800 °C and remained unchanged up to 1600 °C. At 1800 °C a rapid decrease in strength down to 300 MPa was observed and was accompanied by change in fracture mechanisms suggestive of decomposition of boron suboxide grains. Fracture toughness of B₆O–TaB₂ composites showed a minimum at 800 °C, suggestive a relaxation of thermal stresses generated from the mismatch in coefficients of thermal expansion.Flexural strength at elevated temperatures for bulk TaB₂ reference sample was also investigated.Results suggest that formation of composite provides additional strengthening/toughening as in all cases flexural strength and fracture toughness of the B₆O–TaB₂ ceramic composite was higher than that reported for B₆O monoliths.     

Synthesis of Multilayered Star‐Shaped B6O Particles Using the Seed‐Mediated Growth Method

In this study, we introduce a simple and effective seed‐mediated growth method (SMGM) for the controlled synthesis of boron suboxide powder. By employing starting powders with different concentrations and adding boron suboxide seeds with a star‐like morphology, we demonstrate that B₆O ceramics that exhibit high‐level crystallinity can be synthesized using SMGM at ambient pressure conditions. The formation of multilayered star‐shaped B₆O particles via SMGM is reported for the first time.     

Microstructure and interfacial reactions between B6O and (Ni,Co) couples

The search for suitable additives for boron suboxide (B₆O) materials which could improve densification, reduce sintering temperature and tailor the microstructure has been of great importance. In an earlier study it was shown that transition metal borides qualify as sintering aids for B₆O, but partial segregations of the boride secondary phases were found. In this work, efforts have been made to understand the chemical interaction between the B₆O and boride phase. A reaction couple of sintered B₆O, nickel and green compact B₆O were assembled and heat-treated at 1850 °C for 20 min. XRD and SEM examinations of the reaction zone show the formation of nickel boride, diffusing into the B₆O matrix and a substantial grain growth of B₆O at the interface.     

High pressure modifications in amorphous boron suboxide: An ab initio study

Using constant pressure ab initio calculations, we probe the high-pressure modifications in amorphous boron suboxide (B₆O) consisting of glassy boron trioxide (B₂O₃) and boron (B) domains up to a theoretical pressure of 100 GPa. At this pressure, the structure remains amorphous. We find a steady increase in the average coordination of both B and oxygen (O) atoms. O atoms mostly attain threefold coordination as in B₂O₃ glass at high pressures. On the other hand, the mean coordination number of B-atoms reaches six at high pressures and the structural changes in B-rich regions are perceived to be quite analogous to those of amorphous B. B₁₂ clusters are found to persevere during the pressurizing process and the high-pressure modifications occur predominantly around O-atoms and the regions that connect the pentagonal pyramid-like motifs to each other. Upon pressure release, some high-pressure configurations persist in the model and another noncrystalline structure being about 10% denser than the original state is recovered, suggesting a permanent densification and a possible irreversible amorphous-to-amorphous phase transformation in B₆O. The recovered network shows slightly better mechanical properties than the uncompressed model. During the compression and decompression processes, amorphous B₆O remains semiconducting. The delocalization of some band tail states is seen at high pressures.     

Densification and properties of superhard B6O materials with cobalt additions

The search for suitable additives for boron suboxide (B₆O) materials which could improve densification, reduce sintering temperature and tailor the microstructure has been productive. B₆O materials doped with 0–5 vol% cobalt addition were sintered at temperatures up to 1850 °C and pressure of 50 MPa for 20 min. Relationships between the formed phases, microstructures and mechanical properties of the sintered materials were investigated as a function of sintering conditions and added cobalt content. The hardness of the sintered B₆O materials increases with sintering temperature, while the fracture toughness increases with increasing cobalt content and reduces with increasing sintering temperature.     

Effects of B4C and BN additions on formation of NbB2–Al2O3 composites from reduction-based combustion synthesis

Formation of NbB₂–Al₂O₃ composites was investigated by reduction-based combustion synthesis in the SHS mode. Amorphous boron, B₄C, and BN were adopted as the source of boron in three reaction systems composed of Nb₂O₅–Al–B, Nb₂O₅–Al–B–B₄C and Nb₂O₅–Al–B–BN. In addition, the effect of excess boron up to 30 at% was examined. For the B- and B/BN-based reaction schemes, the synthesis process involved not only aluminothermal but borothermal reduction of Nb₂O₅. The latter caused a significant loss of boron in the form of gaseous oxides, and therefore, their resulting products contained NbB, Nb₃B₄, and NbB₂ even if the samples were formulated with boron of 30 atom.% in excess. Besides acting as a boron precursor, B₄C was showed to effectively suppress the borothermal reaction for the B/B₄C-adopted sample. Consequently, a small amount of excess boron of 10 atom.% was sufficient for the B/B₄C-adopted sample to produce the NbB₂–Al₂O₃ composite with trivial minor phases.     

Hard and tough boron suboxide based composites

Boron suboxide (B₆O) powder was synthesized at temperatures of about 1400 °C from the reaction of amorphous boron powder with boric acid. The synthesized B₆O powders were hot pressed at temperatures up to 1900 °C and at pressures of 50 MPa. Additionally to pure B₆O materials, composites with aluminium were prepared. The microstructure and properties of the sintered compacts were investigated. The addition of aluminium in the composites results in the formation of an additional aluminium borate phase. The composites showed a similar hardness (∼30 GPa) as the pure B₆O samples but increased fracture toughness (∼3.5 MPa m^1/2).     

Effect of Carbon and Oxygen on the Densification and Microstructure of Hot Pressed Zirconium Diboride

The role of carbon additions and oxygen content on the densification of zirconium diboride (ZrB₂) was studied. ZrB₂ with up to 1 wt% added carbon was hot pressed at temperatures of 2000°C and 2100°C. Nominally pure ZrB₂ hot pressed at 2100°C achieved relative densities >95.5%. Carbon and oxygen analysis indicate that oxygen removal was facilitated by the reduction of oxides with carbon or the removal of boria (B₂O₃) as a vapor. Therefore, by removing oxides from the particle surfaces, carbon additions of ≥0.5 wt% enabled densification to proceed to >96.5% of theoretical at 2000°C. Raman spectroscopy revealed the formation of boron carbide (B_4.3C) in specimens with carbon additions of ≥0.75 wt%. The formation of B_4.3C was eliminated via a 1 wt% addition of zirconium hydride (ZrH₂), as a source of zirconium, resulting in the formation of carbon as the only residual second phase. Grain sizes were in the range of 7–10 μm (2000°C) and 12–16 μm (2100°C) and only appeared to be controlled by temperature, as no trends due to the evaluated carbon or oxygen contents were observed.     

Interaction of boron suboxide with compacted graphite cast iron

The chemical interaction of boron suboxide (B₆O) with compacted graphite cast iron (CGI) was investigated using static interaction diffusion couples between B₆O and CGI at 700 °C, 900 °C and 1100 °C for 1 h. This interaction offers the possibility to evaluate the potential of B₆O as a cutting tool. The microstructures and phase compositions of the interaction zones were investigated. At 700 °C and 900 °C the chemical interaction was minimal. However, at 1100 °C, Fe₂B and SiO₂ were formed at the interface. Hence, machining at 1100 °C is likely to result in chemical wear.     

Densification behavior of flash sintered boron suboxide

A study to quantify the flash sintering kinetics of boron suboxide (B₆O) under various electric field strengths and cut‐off amperages is presented. B₆O is conventionally sintered at a prolonged temperature above 1800°C, near its thermal decomposition temperature, with an overpressure >3 atm. By applying a direct current (DC) electric field across a green powder compact, B₆O can be sintered at 1000°C at atmospheric pressure. During the flash sintering process, an intensive radiation was emitted (electroluminescence), which is distinct from the thermal radiation (thermoluminescence) that is expected in conventional sintering. It was observed that the degree of sintering of the large B₆O specimen was heterogeneous due to apparent localization of electrically conducting paths. The material near the surface was sintered, but the core of the specimen was not. It was found that the flash event occurred at a critical temperature, which was obtained by combining external heating via ambient furnace conditions and internal Joule heating. The progressive densification behaviors of the B₆O are also presented.     

Optical characterization of boron carbide powders synthesized with varying B-to-C ratios

Boron carbide powders were synthesized from elemental powders and studied using X-ray diffraction (XRD) and UV–visible diffuse reflectance, Raman, and diffuse reflectance IR spectroscopies. Following reaction at 1400°C for 6 h, synthesized powders exhibited possible faulting as suggested by XRD patterns. B₃C, B_4.3C, and B₅C powders contained graphitic carbon whereas the boron carbides with higher B/C ratios contained no residual carbon, suggesting that the carbon rich phase boundary is likely temperature dependent. Analysis by Raman and IR spectroscopy suggested that Raman spectra are influenced by excitation frequency due to resonance. We suggest that measurement of boron carbides with resonant Raman lifts the selection rules to allow measurement of Raman silent modes that are present in the IR spectra. Optical reflectance of the boron carbide powders revealed that the B/C ratio governed the indirect and direct optical band gaps of the faulted powders. B₃C and B_4.3C powders were light gray in spite of the presence of the carbon, whereas B₅C, B_6.5C, B₁₀C, and B₁₂C were gray, green, brown, and dark brown, respectively. Increasing carbon content increased the optical indirect band gap from 1.3 eV for B₁₂C to 3.2 eV for B₃C, causing the observed color changes.     

Polymer‐Derived SiC/B4C/C Nanocomposites: Structural Evolution and Crystallization Behavior

Structural evolution and crystallization behavior between 600°C and 1450°C during the preparation of bulk SiC/B₄C/C nanocomposites by the pyrolysis of CB‐PSA preceramic were investigated. The CB‐PSA preceramic converts into carbon‐rich Si–B–C ceramics up to 800°C. Structural evolution and crystallization of Si–B–C materials could be controlled by adjusting the pyrolytic temperature. The Si–B–C ceramics are amorphous between 800°C and 1000°C. Phase separation and crystallization begin at 1100°C. The crystallization of β‐SiC takes place at 1100°C and B₄C nanocrystallites generate at 1300°C. The sizes of β‐SiC and B₄C nanocrystals increase with the pyrolytic temperature rising. In addition, the boron‐doping effect on structural evolution was studied by comparing the crystallization and graphitization behavior of Si–B–C ceramics and the corresponding Si–C materials. Boron is helpful for the growth of β‐SiC nanocrystals and the graphitization, but harmful for the nucleation of β‐SiC crystallites.     

EFFECT OF COMPOSITION AND THERMAL HISTORY ON DIELECTRIC CONSTANTS OF SODA-BOROSILICATE GLASSES*

The dielectric constants, densities, and refractive indices of two series of soda-boro-silicate glasses were measured at 25° C. on some quenched specimens and on other specimens that were stabilized at different temperatures. The compositions of the two series were Na₂O-4.69 SiO₂-B₂O, (0 to 45%) and Na₂O B₂O₃-SiO₂ (30 to 100%), respectively. The structure of the glasses was found to depend on the ratio of oxygen atoms to the sum of the boron and silicon atoms and also on the concentration of the sodium ions. If the ratio of O to B + Si is greater than 2.0 or if the ratio of oxygen to sodium ions is less than 6.0, some of the oxygens are bonded only to one boron or to one silicon atom. The presence of “single-bonded” oxygen atoms in the glass structure leads to a lower density and a higher dielectric constant and refractive index. The dielectric constant decreases and the density increases continuously as the temperature of heat treatment is lowered. The effect of heat treatment is greater for the glasses which contain the larger number of “single-bonded” oxygen atoms and the higher concentration of sodium ions.     

Effects of boron oxide composition,structure, and morphology on B4C formation via the SHS process in the B2O3–Mg – C ternary system

This study investigates the formation of B₄C in the B₂O₃–Mg–C ternary system via a magnesiothermic reduction process using two kinds of boron oxide (B₂O₃) ‒ the commercial B₂O₃ and that synthesized from boric acid via the coupled chemical-thermal process. In addition to the raw materials, the products were subjected to XRD, FTIR, SEM, and FESEM analyses to determine the effects of microstructural and morphological properties of boron oxide as an important raw material, on B₄C formation in the combustion synthesis process. For this purpose, powder mixtures of B₂O₃:Mg:C were prepared at a stoichiometric molar ratio of 2:6:1 and compacted into pellets using a uniaxial hydraulic press, which were subsequently subjected to the combustion synthesis process based on the self-propagating high-temperature synthesis (SHS). Finally, the samples thus obtained were leached in an aqueous hydrochloric acid solution. Analysis of the commercial B₂O₃ revealed the presence of large amounts of such by-products as magnesium borate (Mg₃B₂O₆) and magnesium oxide (MgO) along with relatively small amounts of boron carbide after the leaching process, while those obtained for the chemically-thermally synthesized B₂O₃ showed a relatively large amount of B₄C (from micron-sized particles to nanoparticles) together with a remaining carbon phase and very small amounts of magnesium borate as by-products. It can be, therefore, concluded that the changes in chemical composition and introduction of a hydrous HBO₂ phase in the boron oxide in the B₂O₃–Mg–C mixture as well as its varied microstructure, morphology, and particle size have significant effects on the efficiency of B₄C production through the SHS process.     

Composition-dependent intrinsic defect structures in pyroclore RE2B2O7 (RE = La,Nd, Gd; B = Sn,Hf, Zr)

Point defects are closely correlated with various properties of pyrochlore oxides and therefore play a key role on their engineering applications. Here, the native point defect complexes in RE₂B₂O₇ (RE = La, Nd, Gd; B = Sn, Hf, Zr) under stoichiometric and nonstoichiometric compositions are studied by first-principles calculations. The O Frenkel defect complex is predicted to be the predominant defect structure in stoichiometric zirconates and hafnates, whereas the cation antisite defect complex is the predominant one in stannates. In the case of BO₂ excess, the formation of the B-RE antisite defect together with the RE vacancy and the oxygen interstitial is energetically favorable, whereas the RE-B antisite defect together with the oxygen vacancy and the RE interstitial is preferable under the RE₂O₃ excess environments. Additionally, the formation energies of the native defect complexes are greatly affected by the B-site and/or RE-site cations. The strategy on tailoring the intrinsic defect structures of these pyrochlore oxides is proposed. It is expected to guide the experiments on the defect-related property optimization through stoichiometric and nonstoichiometric compositions, so as to meet the specific engineering requirements and promote their commercial applications.     

Effect of BN or B4C content on physical and tribological properties of copper-clad laminates reinforced with carbon fiber and epoxy resin

Plasma treatment was used to improve the surface roughness of copper foil. The copper-clad laminates reinforced with carbon fiber, boron nitride (BN), or boron carbide (B₄C), and epoxy resin were prepared by hot pressing. The effect of BN or B₄C content on the physical properties and tribological properties of copper-clad laminates reinforced with carbon fiber and epoxy resin were studied. The resulting copper-clad laminate exhibited desirable properties, such as dielectric constant, peel strength, oxygen index, and arc resistance, which were influenced by the concentration of BN or B₄C particles. Additionally, the wear and friction properties of the laminate were evaluated, revealing the effects of load, sliding speed, and particle content on weight loss, specific wear rate, and coefficient of friction. SEM analysis of worn surfaces provided insight into the stages of wear, highlighting the importance of an oxide layer in reducing wear and protecting the copper surface.     

Microstructural evolution during the infiltration of boron carbide with molten silicon

The previously reported model that accounts for the formation of the core-rim structure in reaction-bonded boron carbide composites (RBBC) is expanded and validated by additional experimental observations and by a thermodynamic analysis of the ternary B–C–Si system. The microstructure of the RBBC composites consists of boron carbide particles with a core-rim structure, β-SiC and some residual silicon. The SiC carbide particles have a polygonal shape in composites fabricated in the presence of free carbon, in contrast to the plate-like morphology when the initial boron carbide is the sole source of carbon. In the course of the infiltration process, the original B₄C particles dissolve partly or fully in molten silicon, and a local equilibrium is established between boron carbide, molten silicon and SiC. Overall equilibrium in the system is achieved as a result of the precipitation of the ternary boron carbide phase B₁₂(B,C,Si)₃ at the surface of the original boron carbide particles and leads to the formation of the rim regions. This feature is well accounted for by the “stoichiometric saturation” approach, which takes into account the congruent dissolution of B₄C particles. The SiC phase, which precipitates form the silicon melt adopts the β-allotropic structure and grows preferably as single plate-like particles with an {1 1 1}_β habit plane. The morphology of the SiC particles is determined by the amount of carbon available for their formation.     

First-principles study of phase-transition temperature and optical properties of alkaline earth metal (Be,Mg, Ca,Sr or Ba)-doped VO2

Vanadium dioxide (VO₂) is an attractive material for energy-saving smart windows due to its metal-to-insulator reversible phase transition near ambient temperature, accompanied by large changes in its optical properties. We conducted first-principles calculations to study the phase-transition temperature and optical properties of alkaline earth metal (Be, Mg, Ca, Sr or Ba)-doped VO₂. The results show that the Be atom prefers to locate at the octahedral interstitial site, while Mg, Ca, Sr and Ba atoms prefer to substitute for the V atom in VO₂. Be, Mg, Ca, Sr and Ba doping reduces the phase-transition temperature of VO₂ 0by 51.4, 59.7, 61.5, 58.4 and 58.3?K, respectively, when the doping concentration is set at one atomic percentage. In addition, the introduction of alkaline earth metal scales the band structures of VO₂, which enhances the ability to block the infrared light (in the order of Be > Mg > Ca > Sr > Ba) and promotes the transmission of visible light (in the order of Be > Mg ≈ Ca > Sr > Ba).