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.     

Carbon Doping in Boron Suboxide: Structure,Energetics, and Elastic Properties

The structural, electronic, and elastic properties of pristine and carbon‐doped boron suboxide (B₆O) are calculated using density functional theory. The results indicate that it is energetically preferable for a single carbon atom to substitute into an oxygen site rather than a boron site. The lattice parameters and cell volume increase to relieve the residual stress created by the carbon substitution. The interstitial position is not favorable for a single atom substitution. However, if two carbon atoms substitute for two neighboring oxygen atoms, then it becomes energetically favorable to dope an interstitial oxygen, boron, or carbon atom along the C–C chain. If the interstitial dopant is either boron or carbon, a local B₄C‐like structure with either a C–B–C or C–C–C chain is created within the boron suboxide unit cell. The resulting structure shows improvements in the bulk modulus at the expense of the shear and Young's moduli. The moduli further improve if an additional carbon is substituted within a polar or equatorial site of the neighboring B₁₂ icosahedron. Based on these calculations, we conclude that carbon doping can either harden or soften B₆O depending on the manner in which the substitutions are populated. Furthermore, as B₆O samples are often oxygen deficient, C doping can occupy such sites and improve the elastic properties.     

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.     

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.     

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.     

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.     

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.     

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).     

Bioengineering functional copolymers: V. Synthesis,LCST, and thermal behavior of poly(N‐isopropyl acrylamide‐co‐p‐vinylphenylboronic acid)

New boron‐containing stimuli‐responsive (pH‐ and temperature‐sensitive) copolymers were synthesized and characterized. Structure and composition of copolymers were determined by FTIR and ¹H‐NMR spectroscopy, and elemental analysis and titration (N and B contents for NIPA and VPBA unit, respectively). By DSC and XRD measurements, it is established that the synthesized copolymers have a semicrystalline structure due to formation of intra‐ and/or intermolecular H‐bonded supramolecular architecture. The copolymer composition–structure–property relationship indicates semicrystalline structure of copolymers with different compositions, degrees of crystallinity, and thermal and stimuli‐responsive behaviors depends on the content of boron‐containing monomer linkage. Results of DSC, DTA, and TGA analyses indicated that copolymers have T_g and T_m and high thermal stability. These water‐soluble and temperature‐ and pH‐sensitive amphiphilic copolymers can be used as polymeric carries for delivery of biological entities for diverse biomedical use, including boron neutron capture therapy. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 573–582, 2005     

Rate‐Dependent Mechanical Behavior and Amorphization of Ultrafine‐Grained Boron Carbide

An investigation into mechanical properties and amorphization behavior of ultrafine‐grained (0.3 μm) boron carbide (B₄C) is conducted and compared to a baseline coarse‐grained (10 μm) boron carbide. Static and dynamic uniaxial compressive strength, and static and dynamic Vickers indentation hardness were determined, and Raman spectroscopy was then conducted on indented regions to quantify and compare the intensity of amorphization. In relation to coarse‐grained B₄C the ultrafine‐grained material exhibited, on average, a 33% higher static compressive strength, 20% higher dynamic compressive strength, 10% higher static Vickers hardness, and 23% higher dynamic Vickers hardness. In addition, there was an 18% reduction in indentation‐induced radial crack length in ultrafine‐grained B₄C, which corresponded to an increase in estimated fracture toughness. Although traditional coarse‐grained B₄C exhibits an 8.6% decrease in hardness from the static to dynamic regimes, ultrafine‐grained B₄C showed only negligible change under similar conditions, suggesting a reduced propensity for amorphization. Raman spectroscopic analysis confirmed this result by revealing significantly lower amorphization intensity in ultrafine‐B₄C compared to coarse‐grained B₄C. These results may have significant positive implications in the implementation of ultrafine‐grained boron carbide as a material for improved performance in impact and other high‐pressure applications.     

2D‐ and 3D Observation and Mechanism of Self‐Healing in Glass–Boron Composites

The self‐healing of a crack in a glass–boron composite has been observed by X‐ray nanotomography. It shows the occurrence of a healing effect within the bulk of the composite, despite of a limited oxygen access in the crack. This 3D tomographic observation offers new insights in the mechanism of healing, complementary to in situ high‐temperature environmental scanning electron microscopy. In addition, nano‐X‐ray fluorescence imaging, electron microprobe and solid‐state NMR gave evidence that the molten B₂O₃, produced by the oxidation of boron particles at 700°C, reacts with the glass matrix to form borosilicate compounds that also contribute to heal the crack. The high viscosity of B₂O₃ at 700°C leads to the formation of bridges between the walls of the crack, which limit oxygen diffusion. Thus, the B particle oxidation is not completed after a single healing cycle, meaning that several healing cycles can be obtained in a composite.     

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.     

Efficient Synthesis of 9‐Tosylaminofluorene Derivatives by Boron Trifluoride Etherate‐Catalyzed Aza‐Friedel–Crafts Reaction of in situ Generated N‐Tosylbenzaldimines

An efficient and expeditious boron trifluoride etherate (BF₃⋅Et₂O) catalyzed one‐pot reaction for the synthesis of N‐tosyl‐9‐aminofluorenes and anthracene derivatives from in situ generated N‐tosylbenzaldimines via an aza‐Friedal–Crafts reaction has been developed. The catalytic reaction shows high substrate tolerance with excellent yields.     

Low‐Temperature Synthesis of Calcium Hexaboride Powder via Transient Boron Carbide Formation

Calcium hexaboride (CaB₆) powder was synthesized by carbothermal reduction using a low‐temperature synthesis method for boron carbide (B₄C) powder. A B₄C precursor consisting of boron oxide (B₂O₃) and carbon components was prepared from a condensed boric acid (H₃BO₃)‐poly(vinyl alcohol) (PVA) product by thermal decomposition in air, which was then mixed with calcium carbonate (CaCO₃) powder. CaB₆ was formed via the transient formation of calcium borate (Ca₃B₂O₆) and B₄C, which were in close contact owing to the finely dispersed B₂O₃/carbon structure of the B₄C precursor. CaB₆ powder with fine particles was synthesized by heat treatment at 1400°C for 10 h in an Ar flow.     

Comparison of micelles formed by amphiphilic poly(ethylene glycol)‐b‐poly(trimethylene carbonate) star block copolymers

In this article, we describe the synthesis and solution properties of PEG‐b‐PTMC star block copolymers via ring‐opening polymerization (ROP) of trimethylene carbonate (TMC) monomer initiated at the hydroxyl end group of the core PEG using HCl Et₂O as a monomer activator. The ROP of TMC was performed to synthesize PEG‐b‐PTMC star block copolymers with one, two, four, and eight arms. The PEG‐b‐PTMC star block copolymers with same ratio of between hydrophobic PTMC and hydrophilic PEG segments were obtained in quantitative yield and exhibited monomodal GPC curves. The amphiphilic PEG‐b‐PTMC star block copolymers formed spherical micelles with a core–shell structure in an aqueous phase. The mean hydrodynamic diameters of the micelles increased from 17 to 194 nm with increasing arm number. As arm number increased, the critical micelle concentration (CMC) of the PEG‐b‐PTMC star block copolymers increased from 3.1 × 10^?3 to 21.1 × 10^?3 mg/mL but the partition equilibrium constant, which is an indicator of the hydrophobicity of the micelles of the PEG‐b‐PTMC star block copolymers in aqueous media, decreased from 4.44 × 10⁴ to 1.34 × 10⁴. In conclusion, we confirmed that the PEG‐b‐PTMC star block copolymers form micelles and, hence, may be potential hydrophobic drug delivery vehicles. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Adenosine and 2′‐Deoxyadenosine Modified with Boron Cluster Pharmacophores as New Classes of Human Blood Platelet Function Modulators

Novel types of adenosine and 2′‐deoxyadenosine derivatives containing boron clusters at positions C2′, N6, or C8 were synthesized. The effect of these modified compounds on platelet function was studied. Modification of adenosine at the C2′ position with a para‐carborane cluster (C₂B₁₀H₁₁) results in efficient inhibition of platelet function, including aggregation, protein secretion, and P‐selectin expression induced by thrombin or ADP. These preliminary findings and the new chemistry proposed form the basis for the development of a new class of adenosine analogues that modulate human blood platelet activities.     

Synthesis of PMMA‐PTHF‐PMMA and PMMA‐PTHF‐PST linear and star block copolymers

Combination of cationic, redox free radical, and thermal free radical polymerizations was performed to obtain linear and star polytetramethylene oxide (poly‐THF)‐polymethyl methacrylate (PMMA)/polystyrene (PSt) multiblock copolymers. Cationic polymerization of THF was initiated by the mixture of AgSbF₆ and bis(4,4′ bromo‐methyl benzoyl) peroxide (BBP) or bis (3,5,3′,5′ dibromomethyl benzoyl) peroxide (BDBP) at 20°C to obtain linear and star poly‐THF initiators with M_w varying from 7,500 to 59,000 Da. Poly‐THF samples with hydroxyl ends were used in the methyl methacrylate (MMA) polymerization in the presence of Ce(IV) salt at 40°C to obtain poly(THF‐b‐MMA) block copolymers containing the peroxide group in the middle. Poly(MMA‐b‐THF) linear and star block copolymers having the peroxide group in the chain were used in the polymerization of methyl methacrylate (MMA) and styrene (St) at 80°C to obtain PMMA‐b‐PTHF‐b‐PMMA and PMMA‐b‐PTHF‐b‐PSt linear and star multiblock copolymers. Polymers obtained were characterizated by GPC, FT‐IR, DSC, TGA, ¹H‐NMR, and ¹³C‐NMR techniques and the fractional precipitation method. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 219–226, 2004     

Electrical characterization of the boron trifluoride doped poly(3‐aminoacetophenone)/p‐Si junction

Electrical and interface state properties of the borontrifluoride doped poly(3‐aminoacetophenone)/p‐Si junction have been investigated by current‐voltage and impedance spectroscopy methods. Al/p‐Si/P₃APBF₃/Aldiode indicates a nonideal behavior with electrical parameters (n = 3.53, ?_B = 0.82 eV, and R_s = 1.48 kΩ), which result from the interfacial layer, series resistance, and resistance of the organic semiconductor. The obtained barrier height value of the Al/p‐Si/P₃APBF₃/Aldiode is higher than that of the conventional Al/p‐Si (?_B = 0.58 eV) Schottky diode. The interface state density of the diode was of the order of 1.05× 10¹² eV^?1 cm^?2. It is evaluated that the barrier height and interface state density values of the diode are modified using the boron trifluoride doped poly (3‐aminoacetophenone) organic semiconductor. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Energetics and Structure of Polymer‐Derived Si–(B–)O–C Glasses: Effect of the Boron Content and Pyrolysis Temperature

The structure and properties of polymer‐derived Si–(B–)O–C glasses have been shown to be significantly influenced by the boron content and pyrolysis temperature. This work determined the impact of these two parameters on the thermodynamic stability of these glasses. High‐temperature oxide melt solution calorimetry was performed on a series of amorphous samples, with varying boron contents (0–7.7 at.%), obtained by pyrolysis of precursors made by a sol–gel technique. Thermodynamic analysis of the calorimetric results demonstrated that at a constant pyrolysis temperature, adding boron makes the materials energetically less stable. While the B‐containing glasses pyrolyzed at 1000°C were energetically less stable than the competitive crystalline components, increasing the pyrolysis temperature to 1200°C led to their enthalpic stability. ²⁹Si and ¹¹B MAS nuclear magnetic resonance (NMR) spectroscopy measurements on selected samples confirmed a decrease in the concentrations of mixed Si‐centered SO_iC_4?i and B‐centered BO_jC_3?j bonds at the expense of formation of SiO₄ and B(OSi)₃ species (indicating a tendency toward phase separation) when the boron content and pyrolysis temperature increased. In light of the findings from calorimetry and NMR spectroscopy, we propose a structure–energetic relationship in Si–(B–)O–C glasses.