Recent progress in boron nanomaterials

Abstract

Various types of zero, one, and two-dimensional boron nanomaterials such as nanoclusters, nanowires, nanotubes, nanobelts, nanoribbons, nanosheets, and monolayer crystalline sheets named borophene have been experimentally synthesized and identified in the last 20 years. Owing to their low dimensionality, boron nanomaterials have different bonding configurations from those of three-dimensional bulk boron crystals composed of icosahedra or icosahedral fragments. The resulting intriguing physical and chemical properties of boron nanomaterials are fascinating from the viewpoint of material science. Moreover, the wide variety of boron nanomaterials themselves could be the building blocks for combining with other existing nanomaterials, molecules, atoms, and/or ions to design and create materials with new functionalities and properties. Here, the progress of the boron nanomaterials is reviewed and perspectives and future directions are described.     

Modelling of boron nitride: Atomic scale simulations on thin film growth

Molecular-dynamics simulations on ion-beam deposition of boron nitride are presented. A realistic Tersoff-like potential energy functional for boron nitride, which was specially fitted to ab initio-data, has been used. The impact of energetic boron and nitrogen atoms on a c-BN target is simulated with energies ranging from 10 to 600 eV. The structural analysis of the grown films shows that a loose, dominantly sp²-bonded structure arises at high ion flux. In no case the formation of a sp³-bonded phase is observed, but the obtained films partially reveal textured basal planes as found in experiment. Two different growth regimes are identified for ion energies above and below 100 eV.     

Structural characterization of electrodeposited boron

Structural characterization of electrodeposited boron was carried out by using transmission electron microscopy and Raman spectroscopy. Electron diffraction and phase contrast imaging were carried out by using transmission electron microscopy. Phase identification was done based on the analysis of electron diffraction patterns and the power spectrum calculated from the lattice images from thin regions of the sample. Raman spectroscopic examination was carried out to study the nature of bonding and the allotropic form of boron obtained after electrodeposition. The results obtained from transmission electron microscopy showed the presence of nanocrystallites embedded in an amorphous mass of boron. Raman microscopic studies showed that amorphous boron could be converted to its crystalline form at high temperatures.     

Microtexture and structure of boron nitride fibres by transmission electron microscopy, X-ray diffraction, photoelectron spectroscopy and Raman scattering

Continuous boron nitride fibres have been fabricated by melt spinning and pyrolysis of poly[2,4,6-tris(methylamino)borazine]. The longitudinal mechanical properties depend on mechanical stress and temperature applied during the conversion process. High-performance and low-performance fibres were characterized in order to find relationship between structure and physical properties. In all the cases, photoelectron spectroscopy (XPS) analysis proves that the chemical composition of the fibre is close to stoichiometric BN. The crystallite sizes were measured by means of X-ray diffraction (XRD) and Raman techniques. Cross-sections of separated fibres were investigated by high-resolution electron microscopy (HREM) and transmission electron microscopy (TEM). All the BN fibres have a hexagonal turbostratic structure. With increasing stress and temperature, the tensile strength and the elastic modulus increase. In the high-performance fibres, the 002 layers with an increased distance (about 0.35 nm) showed a mean stacking sequence near to graphite and a preferred orientation of the 002 layers parallel to the fibre axis.     

Atomic structure and vibrational properties of icosahedral α-boron and B4C boron carbide

The Raman and infrared spectra of α-rhombohedral boron B₁₂ and of B₄C boron carbide have been determined by accurate first-principles calculations based on density-functional perturbation theory. Our results account for all the features observed experimentally, including the characteristic Raman-active mode around 530 cm⁻¹, which is attributed to the libration of the icosahedra. A comparison of the calculated vibrational spectra with experimental data allows the first unambiguous determination of the atomic structure of B₄C. Analysis of our data shows that the high bulk moduli of α-rhombohedral boron and of B₄C boron carbide – 220 and 240 GPa, respectively – are mainly determined by the stiff intramolecular bonding within each icosahedron. This finding is at variance with the current interpretation of recent neutron diffraction data on B₄C in terms of a postulated larger stiffness of the intermolecular bonds in icosahedral solids (inverted molecular compressibility). Our results show that icosahedral boron-rich solids should be considered as members of a new class of covalently bonded materials.     

New insight in boron chemistry: Application in two-photon absorption

Two groups of one-dimensional (1D) boron containing two-photon absorbing fluorophores have been prepared and characterized. One group includes boron atoms incorporated in the conjugated or pseudo conjugated central core and the other contain a boron cluster as an acceptor group at one end of the fluorophores. Two boron containing central cores (with two boron atoms) have been explored: the cyclodiborazane and the pyrazabole moieties. The chosen boron cluster, p-carborane, contains 10 boron atoms. All the prepared fluorophores present high two-photon absorption cross-sections. Some water-soluble as well as lipophylic dyes have been prepared and used in bio-imaging.     

Synthesis of an orthorhombic high pressure boron phase

The densest boron phase (2.52 g cm^-3) was produced as a result of the synthesis under pressures above 9 GPa and temperatures up to ∼1800 °C. The x-ray powder diffraction pattern and the Raman spectra of the new material do not correspond to those of any known boron phases. A new high-pressure high-temperature boron phase was defined to have an orthorhombic symmetry (Pnnm (No. 58)) and 28 atoms per unit cell.     

Synthesis of an orthorhombic high pressure boron phase

Abstract

The densest boron phase (2.52 g cm^-3) was produced as a result of the synthesis under pressures above 9 GPa and temperatures up to ～1800 °C. The x-ray powder diffraction pattern and the Raman spectra of the new material do not correspond to those of any known boron phases. A new high-pressure high-temperature boron phase was defined to have an orthorhombic symmetry (Pnnm (No. 58)) and 28 atoms per unit cell.     

Effects of boron and heat treatment on structure of dual-phase Ti-TiC

Anin situ method was developed to fabricate a two-phase mixture of titanium carbide in a titanium matrix by solidification from a titanium-carbon melt. The solidified morphology consisted of three-dimensional TiC dendrites in a titanium matrix. The secondary dendrite arm spacing was found to be influenced by the presence of boron. The structure and microhardness of the components as a function of boron content and heat-treatment procedure were determined. Heat treatment plays a major role in the structure while the effect of boron is minimal. Results from X-ray diffraction analysis indicate that the solidified carbide is very rich in vacancies in the carbon sublattice. Annealing leads to a redistribution of the titanium atoms to occupy some of the vacant carbon sites. This thermal redistribution effect results in a dramatic decrease in the hardness of the carbides. The lattice parameter measurement supports the above structure evolution.     

Fatigue crack growth in hybrid boron/glass/aluminium fibre metal laminates

The crack growth behaviour of hybrid boron/glass/aluminium fibre metal laminates (FMLs) under constant‐amplitude fatigue loading was investigated. The hybrid FMLs consist of Al 2024‐T3 alloy as the metal layers and a mixture of boron fibres and glass fibres as the fibre layers. Two types of boron/glass/aluminium laminates were fabricated and tested. In the first type, the glass fibre/prepreg and the boron fibre/prepreg were used separately in the fibre layers, and in the second type, the boron fibres and the glass fibres were uniformly mingled together to form a hybrid boron fibre/glass fibre prepreg. An analytical model was also proposed to predict the fatigue crack growth behaviour of hybrid boron/glass/aluminium FMLs. The effective stress intensity factor at a crack tip was formulated as a function of the remote stress intensity factor, crack opening stress intensity factor, and the bridging stress intensity factor. The bridging stress acting on the delamination boundary along the crack length was also calculated based on the crack opening relations. Then, the empirical Paris‐type fatigue crack growth law was used for predicting the crack growth rates. A good correlation between the predicted and experimental crack growth rates has been obtained.     

Transmission electron microscopic investigations on SiC- and BN-coated carbon fibres

Carbon fibres were coated with layers of silicon carbide (SiC) and boron nitride (BN) by conventional chemical vapour deposition. The SiC films were deposited by thermal decomposition of methyltrichlorosilane, whereas the BN films were deposited using the stepwise disproportion reaction of boron chloride with ammonia. Samples for electron microscopic investigations were prepared by separating film from fibre or by conventional mechanical thinning and subsequent ion milling of cross sections of coated fibres. Bright- and dark-field images of both planar and cross-sectional electron microscopic investigations on the fibre coatings gave detailed information on film thickness and morphology. High-resolution images improved the structural information of electron diffraction patterns. Crystal dimensions in the SiC film vary between 10 and 40 nm. Electron diffraction revealed the crystal structure to be a mixture of disordered hexagonal 2H-SiC and cubic -SiC. High-resolution images showed the (1 1 1)-planes to be preferred for deposition. In BN films, a hexagonal turbostratic structure similar to turbostratic carbon was observed. Apart from amorphous regions, nanocrystalline parts were detected, which have a higher structural perfection in the stacking sequence of their (0 0 2)-planes compared to the (0 0 2)-planes of the turbostratic carbon fibre. High-resolution images located the film-fibre interface that was confirmed by electron energy loss spectroscopy.     

Effect of boron on hot ductility oflow carbon low alloyed steel

Abstract

The influence of boron on the hot ductility of C-Mn-Al-Cr steel has been investigated. At <980°C M(CB)₃ precipitated out and about half of the boron content was in solution in austenite at >900°C. It was found that solute boron atoms segregate to austenite grain boundaries and occupy the vacancies induced by deformation. This prevents the formation and propagation of microcracks at boundaries and results in improved hot ductility and a reduced dynamic recrystallisation temperature.     

Hydrogen adsorption on boron doped graphene: an ab initio study

(i)?The electronic and structural properties of boron doped graphene sheets, and (ii)?the chemisorption processes of hydrogen adatoms on the boron doped graphene sheets have been examined by ab initio total energy calculations. In (i)?we find that the structural deformations are very localized around the boron substitutional sites, and in accordance with previous studies (Endo et al 2001 J.?Appl.?Phys. 90 5670) there is an increase of the electronic density of states near the Fermi level. Our simulated scanning tunneling microscope (STM) images, for occupied states, indicate the formation of bright (triangular) spots lying on the substitutional boron (center) and nearest-neighbor carbon (edge) sites. Those STM images are attributed to the increase of the density of states within an energy interval of 0.5?eV below the Fermi level. For a boron concentration of ～2.4%, we find that two boron atoms lying on the opposite sites of the same hexagonal ring (B1-B2 configuration) represents the energetically most stable configuration, which is in contrast with previous theoretical findings. Having determined the energetically most stable configuration for substitutional boron atoms on graphene sheets, we next considered the hydrogen adsorption process as a function of the boron concentration, (ii). Our calculated binding energies indicate that the C-H bonds are strengthened near boron substitutional sites. Indeed, the binding energy of hydrogen adatoms forming a dimer-like structure on the boron doped B1-B2 graphene sheet is higher than the binding energy of an isolated H(2) molecule. Since the formation of the H dimer-like structure may represent the initial stage of the hydrogen clustering process on graphene sheets, we can infer that the formation of H clusters is quite likely not only on clean graphene sheets, which is in consonance with previous studies (Hornek?r et al 2006 Phys.?Rev.?Lett. 97 186102), but also on B1-B2 boron doped graphene sheets. However, for a low concentration of boron atoms, the formation of H dimer structures is not expected to occur near a single substitutional boron site. That is, the formation (or not) of H clusters on graphene sheets can be tuned by the concentration of substitutional boron atoms.     

Influence of different boron precursors on superconducting and mechanical properties of MgB2

The superconducting, structural and mechanical properties of MgB₂ bulk samples have been studied as a function of precursor B powder particle size by means of AC susceptibility, XRD and microhardness measurements, respectively. The in situ processed MgB₂ samples have been prepared by means of conventional solid state reaction method with magnesium powder (99.8 %, 325 mesh) and four different types of boron powders (95.2, >95, 91.9 and 86.7 %) from two sources, Pavezyum and Sigma Aldrich. The XRD measurements showed that the diffraction peaks for our samples belong to the main phase of the MgB₂ diffraction patterns. The highest critical temperature T _c = 37.7 K was achieved for the MgB₂ sample which was fabricated by using >95 % purity amorphous boron. Microhardness measurements were performed to investigate the mechanical properties. Load independent hardness, Vickers microhardness, Young’s modulus, fracture toughness, and yield strength values were calculated separately for all samples. The results were analyzed by using the Meyer’s law, proportional sample resistance model, elastic–plastic deformation model, Hays Kendall approach, and indentation induced cracking (IIC) model. It was found that the IIC model is the most successful model to describe the mechanical properties of our samples.     

Deformation-driven electrical transport of individual boron nitride nanotubes

In contrast to standard metallic or semiconducting graphitic carbon nanotubes, for years their structural analogs, boron nitride nanotubes, in which alternating boron and nitrogen atoms substitute for carbon atoms in a graphitic network, have been considered to be truly electrically insulating due to a wide band gap of layered BN. Alternatively, here, we show that under in situ elastic bending deformation at room temperature inside a 300 kV high-resolution transmission electron microscope, a normally electrically insulating multiwalled BN nanotube may surprisingly transform to a semiconductor. The semiconducting parameters of bent multiwalled BN nanotubes squeezed between two approaching gold contacts inside the pole piece of the microscope have been retrieved based on the experimentally recorded I-V curves. In addition, the first experimental signs suggestive of piezoelectric behavior in deformed BN nanotubes have been observed.     

High-pressure high-temperature synthesis and structure of α-tetragonal boron

Abstract

Microcrystals of α-tetragonal (α-t) boron with unit cell parameters a=9.05077(6) and c=5.13409(6) Å and measured density 2.16–2.22 g cm^?3 were obtained by pyrolysis of decaborane B₁₀H₁₄ at pressures of 8–9 GPa and temperatures of 1100–1600 ^○C. The crystal structure is in good agreement with the model proposed by Hoard et al (1958 J. Am. Chem. Soc. 80 4507). However, compared to the original model, we found small deformations of icosahedra and changes in the interatomic distances within the unit cell of the synthesized α-t boron.     

AFM observation of surface topography of fibre Bragg gratings fabricated in germanium–boron codoped fibres and hydrogen-loaded fibres

This paper reports the measurement of the surface topology of optical fibres containing a fibre Bragg grating (FBG) using an atomic force microscope (AFM). The AFM observation was made on FBGs fabricated via the phase mask technique in germanium–boron codoped optical fibres, in hydrogen-loaded germanium–boron codoped fibres and in standard telecommunications optical fibres. The surface images reveal that a spatial corrugation pattern was induced by the UV-irradiation, with a period that is half of the period of the phase mask. This UV-induced surface structure was found only on the side of the fibre facing towards the incident UV-irradiation and did not appear on the rear surface. The AFM probe scanned a 10×10 μm² surface area at seven sites along the 6.0 mm length of fibre that was exposed to the UV-irradiation. The amplitude of the spatial corrugation pattern observed on the AFM image was quantified for each site. It was found that the amplitude in a range of 0.7–3.2 nm was a function of UV-laser intensity distribution and the type of fibre. Hydrogen loaded optical fibres exhibited a corrugation with an amplitude twice as large as that observed in the Ge–B doped fibres that were not hydrogen-loaded. This correlates with the increase in photosensitivity produced by the hydrogen loading. A similar UV-induced spatial corrugation was also observed on standard telecom fibres, but without inducing the refractive index change in the fibre core. The observation of surface topology provides an insight into the structural changes induced during FBG fabrication. UV-induced densification and laser ablation could account for the formation of the surface troughs.     

The morphologies of boron fibres in the temperature range 1000 to 1500° C and the relationship between mechanical properties and morphology

The main surface morphologies of boron fibres in the temperature range 1000 to 1500° C and the relevant experimental conditions for obtaining them have been investigated. After tensile testing of boron fibres with the various main morphologies, an approximate value for the tensile fracture stress could be assigned to each morphology. A method for identifyingin situ the morphologies formed during the deposition process is described. Finally, the maximum preparation times for obtaining high-strength boron fibres at various temperatures have been calculated.