First-principles studies of boron nanostructures

Boron is an 'electron deficient' element which has a rather fascinating chemical versatility. In the solid state, the elemental boron has neither a pure covalent nor a pure metallic character. As a result, its vast structural dimensionally and peculiar bonding features hold a unique place among other elements in the periodic table. In order to understand and properly describe these unusual bonding features, a detailed and systematic theoretical study is needed. In this work, I will show that some of the qualitative features of boron nanostructures, including clusters, sheets and nanotubes can easily be extracted from the results of first principles calculations based on density functional theory. Specifically, the size-dependent evolution of topological structures and bonding characteristics of boron clusters, Bn will be discussed. Based on the scenario observed in the boron clusters, the unique properties of boron sheets and boron nanotubes will be described. Moreover, the ballistic electron transport in single-walled carbon nanotubes will be considered. It is expected that the theoretical results obtained in the present thesis will initiate further studies on boron nanostructures, which will be helpful in understanding, designing and realizing boron-based nanoscale devices.

Boron nitride nanotubes : synthesis, characterization, functionalization, and potential applications

Boron nitride nanotubes (BNNTs) are structurally similar to carbon nanotubes (CNTs), but exhibit completely different physical and chemical properties. Thus, BNNTs with various interesting properties may be complementary to CNTs and provide an alternative perspective to be useful in different applications. However, synthesis of high quality of BNNTs is still challenging. Hence, the major goals of this research work focus on the fundamental study of synthesis, characterizations, functionalization, and explorations of potential applications. In this work, we have established a new growth vapor trapping (GVT) approach to produce high quality and quantity BNNTs on a Si substrate, by using a conventional tube furnace. This chemical vapor deposition (CVD) approach was conducted at a growth temperature of 1200 °C. As compared to other known approaches, our GVT technique is much simpler in experimental setup and requires relatively lower growth temperatures. The as-grown BNNTs are fully characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), electron energy loss spectroscopy (EELS), Energy Filtered Mapping, Raman spectroscopy, Fourier Transform Infra Red spectroscopy (FTIR), UV-Visible (UV-vis) absorption spectroscopy, etc. Following this success, the growth of BNNTs is now as convenient as growing CNTs and ZnO nanowires. Some important parameters have been identified to produce high-quality BNNTs on Si substrates. Furthermore, we have identified a series of effective catalysts for patterned growth of BNNTs at desirable or pre-defined locations. This catalytic CVD technique is achieved based on our finding that MgO, Ni or Fe are the good catalysts for the growth of BNNTs. The success of patterned growth not only explains the role of catalysts in the formation of BNNTs, this technique will also become technologically important for future device fabrication of BNNTs. Following our success in controlled growth of BNNTs on substrates, we have discovered the superhydrophobic behavior of these partially vertically aligned BNNTs. Since BNNTs are chemically inert, resistive to oxidation up to ~1000°C, and transparent to UV-visible light, our discovery suggests that BNNTs could be useful as self-cleaning, insulating and protective coatings under rigorous chemical and thermal conditions. We have also established various approaches to functionalize BNNTs with polymeric molecules and carbon coatings. First, we showed that BNNTs can be functionalized by mPEG-DSPE (Polyethylene glycol-1,2-distearoyl-sn-glycero-3-phosphoethanolamine), a bio-compatible polymer that helps disperse and dissolve BNNTs in water solution. Furthermore, well-dispersed BNNTs in water can be cut from its original length of >10µm to(>20hrs). This success is an essential step to implement BNNTs in biomedical applications. On the other hand, we have also succeeded to functionalize BNNTs with various conjugated polymers. This success enables the dispersion of BNNTs in organic solvents instead of water. Our approaches are useful for applications of BNNTs in high-strength composites. In addition, we have also functionalized BNNTs with carbon decoration. This was performed by introducing methane (CH4) gas into the growth process of BNNT. Graphitic carbon coatings can be deposited on the side wall of BNNTs with thicknesses ranging from 2 to 5 nm. This success can modulate the conductivity of pure BNNTs from insulating to weakly electrically conductive. Finally, efforts were devoted to explore the application of the wide bandgap BNNTs in solar-blind deep UV (DUV) photo-detectors. We found that photoelectric current generated by the DUV light was dominated in the microelectrodes of our devices. The contribution of photocurrent from BNNTs is not significant if there is any. Implication from these preliminary experiments and potential future work are discussed.

An Experimental Investigation of the Age Hardening of Nickel with Boron

Since 1911, at which time, the age hardening phenomenon of duralumin was discovered by Film, much re­search has been carried on investigating the various alloy systems. The successful application of age hardening to the copper aluminum system (duralumin) has indicated the possibility of hardening practically all the metals in the same way.

An Investigation of the Age-Hardening of Copper with Nickel-Boron Compounds

Boron is an element whose metallurgical possibil­ities have never been fully investigated. The principal reason for this fact seems to lie in the difficulties encountered in preparing elemental boron and its various intermetallic compounds.

The Effect of Boron on the Hardenability of Steel

Many attempts have been made to improve iron and steel and their alloys by the addition of boron. The re­sults obtained were not encouraging for the reason that the amount of boron used, generally from 0.2 to 2.0 per cent is altogether too high. This percentage of boron ren­ders the product hard and brittle and of late the experiments with boron in this connection have been practically abandoned.

The Solubility of Zinc Ethyl Xanthate in Water

A determination of the solubility of zinc ethyl xanthate was attempted by measuring the refractive index of a saturated solution of that salt. The small increment in refractive index effected by adding zinc ethyl xanthate to water in saturation quantities rendered measurements difficult and of dubious accuracy.

Increasing the dynamic range for the analysis of boron in PGAA

Prompt gamma activation analysis (PGAA) is especially sensitive for elements with high neutron-capture cross sections, like boron, which can be detected down to a level of ng/g. However, if it is a major component, the high count rate from its signal will distort the spectra, making the evaluation difficult. A lead attenuator was introduced in front of the HPGe-detector to reduce low-energy gamma radiation and specifically the boron gamma rays reaching the detector, whose thickness was found to be optimal at 10 mm. Detection efficiencies with and without the lead attenuator were compared, and it was shown that the dynamic range of the PGAA technique was significantly increased. The method was verified with the analyses of stoichiometric compounds: TiB2, NiB, PVC, Alborex, and Alborite.

Screening of gap junction antagonists on dye coupling in the rabbit retina.

Many cell types in the retina are coupled via gap junctions and so there is a pressing need for a potent and reversible gap junction antagonist. We screened a series of potential gap junction antagonists by evaluating their effects on dye coupling in the network of A-type horizontal cells. We evaluated the following compounds: meclofenamic acid (MFA), mefloquine, 2-aminoethyldiphenyl borate (2-APB), 18-alpha-glycyrrhetinic acid, 18-beta-glycyrrhetinic acid (18-beta-GA), retinoic acid, flufenamic acid, niflumic acid, and carbenoxolone. The efficacy of each drug was determined by measuring the diffusion coefficient for Neurobiotin (Mills & Massey, 1998). MFA, 18-beta-GA, 2-APB and mefloquine were the most effective antagonists, completely eliminating A-type horizontal cell coupling at a concentration of 200 muM. Niflumic acid, flufenamic acid, and carbenoxolone were less potent. Additionally, carbenoxolone was difficult to wash out and also may be harmful, as the retina became opaque and swollen. MFA, 18-beta-GA, 2-APB and mefloquine also blocked coupling in B-type horizontal cells and AII amacrine cells. Because these cell types express different connexins, this suggests that the antagonists were relatively non-selective across several different types of gap junction. It should be emphasized that MFA was water-soluble and its effects on dye coupling were easily reversible. In contrast, the other gap junction antagonists, except carbenoxolone, required DMSO to make stock solutions and were difficult to wash out of the preparation at the doses required to block coupling in A-type HCs. The combination of potency, water solubility and reversibility suggest that MFA may be a useful compound to manipulate gap junction coupling.

Boron-Bearing Kornerupine from Fiskenaesset, West Greenland: A Reexamination of Specimens from the Type Locality

In 1884, Lorenzen proposed the formula MgAI2SiO6 for his new mineral kornerupine from Fiskenæsset and did not suspect it to contain boron. Lacroix and de Gramont (1919) reported boron in Fiskenæsset kornerupine, while Herd (1973) found none. New analyses (ion microprobe mass analyser and spectrophotometric) of kornerupine in three specimens from the type locality, including the specimens analysed by Lorenzen and Herd, indicate the presence of boron in all three, in amounts ranging from 0.50 to 1.44 wt.% B203, e.g. (Li0.04 Na0.01 Ca0.01) (Mg3.49 Mn0.01 Fe0.17 Ti0.01 Al5.64)Σ9.30 (Si3.67 Al1.02 B0.31)Σ5 O21 (OH0.99 F0.01) for Lorenzen's specimen. Textures and chemical compositions suggest that kornerupine crystallized in equilibrium in the following assemblages, all with anorthite (An 92-95) and phlogopite (XFe = atomic Fe/(Fe + Mg) = 0.028-0.035): (1) kornerupine (0.045)-gedrite (0.067); (2) kornerupine (0.038-0.050)-sapphirine (0.032-0.035); and (3) kornerupine (0.050)-hornblende. Fluorine contents of kornerupine range from 0.01 to 0.06%, of phlogopite, from 0.09 to 0.10%. In the first assemblage, sapphirine (0.040) and corundum are enclosed in radiating bundles of kornerupine; additionally sapphirine, corundum, and/or gedrite occur with chlorite and pinite (cordierite?) as breakdown products of kornerupine. Kornerupine may have formed by reactions such as: gedrite + sapphirine + corundum + B203 (in solution) + H20 = kornerupine + anorthite + Na-phlogopite under conditions of the granulite facies. Boron for kornerupine formation was most likely remobilized by hydrous fluids from metasedimentary rocks occurring along the upper contact of the Fiskenæsset gabbro-anorthosite complex with amphibolite.