Microstructural characterization of as-cast hf-b alloys

An accurate knowledge of several metal-boron phase diagrams is important to evaluation of higher order systems such as metal-silicon-boron ternaries. The refinement and reassessment of phase diagram data is a continuous work, thus the reevaluation of metal-boron systems provides the possibility to confirm previous data from an investigation using higher purity materials and better analytical techniques. This work presents results of rigorous microstructural characterization of as-cast hafnium-boron alloys which are significant to assess the liquid composition associated to most of the invariant reactions of this system. Alloys were prepared by arc melting high purity hafnium (minimum 99.8%) and boron (minimum 99.5%) slices under argon atmosphere in water-cooled copper crucible with non consumable tungsten electrode and titanium getter. The phases were identified by scanning electron microscopy, using back-scattered electron image mode and X-ray diffraction. In general, a good agreement was found between our data and those from the currently accepted Hafnium-Boron phase diagram. The phases identified are αHfSS and B-RhomSS, the intermediate compounds HfB and HfB2 and the liquide L. The reactions are the eutectic L ⇔ αHfSS + HfB and L ⇔ HfB2 + B-Rhom, the peritectic L + HfB2 ⇔ HfB and the congruent formation of HfB2.

Chemical and boron isotopic compositions of volcanics from ODP Sites 135-834 to 135-840

The influence of fluid flux on petrogenesis in the Tonga-Kermadec Arc was investigated using ion microprobe measurements of B/Be and boron isotope ratios (11B/10B) to document the source and relative volumes of the fluids released from the subducting oceanic plate. We analyzed young lavas from eight different islands along the Tonga-Kermadec Arc, as well as glass shards in volcanic sediments from Ocean Drilling Program (ODP) Site 840, which record the variations in the chemistry of Tonga magmatism since 7 Ma. B/Be is variable (5.8-122), in young Tonga-Kermadec Arc lavas. In contrast, glass shards from around 3 to 4 Ma old volcanic sediments at Site 840 have the highest B/Be values yet reported for arc lavas (18-607). These values are too high to be related simply to a sediment influence on petrogenesis. Together with very high d11B values (-11.6 to +37.5) for the same shards and lavas these data indicate that most of the B is derived from fluid escaped from the subducting altered Pacific oceanic crust, rather than from sediment. High d11B values also reflect large degrees of isotopic fractionation in this cold fast subduction zone. Lower d11B values noted in the Kermadec Arc (17 to -4.4) are related to the influence of sediment eroded from New Zealand and slower convergence. High fluid flux (B/Be) is synchronous in Tonga and the Marianas at 3 to 4 Ma and may be related to acceleration of the Pacific Plate just prior to this time. The timing of maximum B/Be at 3 to 4 Ma correlates with maximum light rare earth (LREE) and high field strength element depletion. This suggests maximum degrees of partial melting at this time. Although thinning of the arc lithosphere during rifting to form the Lau Basin is expected to influence the arc geochemistry, variable aqueous fluid flux from the subducting plate alone appears capable of explaining boron and other trace element systematics in the Tonga-Kermadec Arc with no indication of slab melting.

Chemistry and boron isotope ratios of Izu arc front volcanic rocks

The process of fluid release from the subducting slab beneath the Izu arc volcanic front (Izu VF) was examined by measuring B concentrations and B isotope ratios in the Neogene fallout tephra (ODP Site 782A). Both were measured by secondary ion mass spectrometry, in a subset of matrix glasses and glassy plagioclase-hosted melt inclusions selected from material previously analyzed for major and trace elements (glasses) and radiogenic isotopes (Sr, Nd, Pb; bulk tephra). These tephra glasses have high B abundances (~10-60 ppm) and heavy delta11B values (+4.5? to +12.0?), extending the previously reported range for Izu VF rocks (delta11B, +7.0? to +7.3?). The glasses show striking negative correlations of delta11B with large ion lithophile element (LILE)/Nb ratios. These correlations cannot be explained by mixing two separate slab fluids, originating from the subducting sediment and the subducting basaltic crust, respectively (model A). Two alternative models (models B and C) are proposed. Model B proposes that the inverse correlations are inherited from altered oceanic crust (AOC), which shows a systematic decrease of B and LILE with increasing depth (from basaltic layer 2A to layer 3), paralleled by an increase in delta11B (from ~ +1? to +10? to +24?). In this model, the contribution of sedimentary B is insignificant (<4% of B in the Izu VF rocks). Model C explains the correlation as a mixture of a low-delta11B (~ +1?) 'composite' slab fluid (a mixture of metasediment- and metabasalt-derived fluids) with a metasomatized mantle wedge containing elevated B (~1-2 ppm) and heavy delta11B (~ +14?). The mantle wedge was likely metasomatized by 11B-rich fluids beneath the outer forearc, and subsequently down dragged to arc front depths by the descending slab. Pb-B isotope systematics indicate that, at arc front depths, ~ 53% of the B in the Izu VF is derived from the wedge. This implies that the heavy delta11B values of Izu VF rocks are largely a result of fluid fractionation, and do not reflect variations in slab source provenance (i.e. subducting sediment vs. basaltic crust). Since the B content of the peridotite at the outer forearc (7-58 ppm B, mean 24 +/- 16 ppm) is much higher than beneath the arc front (~1-2 ppm B), the hydrated mantle wedge must have released a B-rich fluid on its downward path. This 'wedge flux' can explain (1) the across-arc decrease in B and delta11B (e.g. Izu, Kuriles), without requiring a progressive decrease in fluid flux from the subducting slab, and (2) the thermal structure of volcanic arcs, as reflected in the B and delta11B variations of volcanic arc rocks.

Catalytic enantioselective arylations: boron to zinc exchange as a powerful tool for the generation of transferable aryl groups

The transmetalation between boron and zinc is of great importance for application in organic synthesis, since it allows the formation of new carbon-carbon bonds between organometallic units and electrophiles. The direct arylation of aldehydes or more scarcely ketones, in a catalytic, enantioselective manner using chiral catalysts has been described recently. The enantiomerically enriched diarylmethanols obtained in these reactions are valuable precursors for important bioactive molecules. This review provides a synopsis of this ever-growing field and highlights some of the challenges that still remain.

Synthesis of diaryl selenides using electrophilic selenium species and nucleophilic boron reagents in ionic liquids

We described herein the use of imidazolium ionic liquids [bmim]PF(6) and [bmim]BF(4) in the selective, metal and catalyst-free synthesis of unsymmetrical diaryl selenides by electrophilic substitution in arylboron reagents with arylselenium halides (Cl and Br) at room temperature. This is a general substitution reaction and it was performed with arylboronic acids or potassium aryltrifluoroborates bearing electron-withdrawing or electron-donating groups, affording the corresponding diaryl selenides in good to excellent yields. The ionic liquid [bmim][PF(6)] was easily recovered and utilized for further substitution reactions.

Barrier-free substitutional doping of graphene sheets with boron atoms: Ab initio calculations

Using ab initio methods, we propose a simple and effective way to substitutionally dope graphene sheets with boron. The method consists of selectively exposing each side of the graphene sheet to different elements. We first expose one side of the membrane to boron while the other side is exposed to nitrogen. Proceeding this way, the B atoms will be spontaneously incorporated into the graphene membrane without any activation barrier. In a second step, the system should be exposed to a H-rich environment, which will remove the CN radical from the layer and form HCN, leading to a perfect substitutional doping.

BORON UPTAKE AND DISTRIBUTION IN FIELD GROWN CITRUS TREES

In low fertility tropical soils, boron (B) deficiency impairs fruit production. However, little information is available on the efficiency of nutrient application and use by trees. Therefore, this work verified the effects of soil and foliar applications of boron in a commercial citrus orchard. An experiment was conducted with fertigated 4-year-old `Valencia` sweet orange trees on `Swingle` citrumelo rootstock. Boron (isotopically-enriched 10B) was supplied to trees once or twice in the growing season, either dripped in the soil or sprayed on the leaves. Trees were sampled at different periods and separated into different parts for total B contents and 10B/11B isotope ratios analyses. Soil B applied via fertigation was more efficient than foliar application for the organs grown after the B fertilization. Recovery of labeled B by fruits was 21% for fertigation and 7% for foliar application. Residual effects of nutrient application in the grove were observed in the year after labeled fertilizer application, which greater proportions derived from the soil supply.

Absorption and Mobility of Boron in Young Citrus Plants

Boron (B) deficiency is widespread in Brazilian citrus orchards and has been considered an important soil constraint to citrus yield. The aim of this work was to study B uptake and its mobility in young citrus trees, under different B statuses, in two rootstocks. The experiment was carried out in a greenhouse, with `Valencia` sweet orange trees budded on Rangpur lime or Swingle citrumelo. The plants were grown in pots containing nutrient solutions under either adequate or deficient B supply. Plants with different B levels were transplanted into solution with adequate level of B, enriched in 10 B in different stages of development ( vegetative growth and fruiting). About 20 to 35% of B content in the new parts of orange tree came from plant reserves. Boron mobility within the plant was influenced by its nutritional status; that is, the longer the period was that the plants were grown under deficient supply, the smaller was the mobility. Boron concentration in the sweet orange trees on Swingle was higher than that on Rangpur, suggesting higher demand of swingle Citrumelo for B.

Electrochemical oxidation of acid black 210 dye on the boron-doped diamond electrode in the presence of phosphate ions: Effect of current density, pH, and chloride ions

The electrochemical oxidation of acid black 210 dye (AB-210) on the boron-doped diamond (BDD) was investigated under different pH conditions. The best performance for the AB-210 oxidation occurred in alkaline phosphate solution. This is probably due to oxidizing agents such as phosphate radicals and peroxodiphosphate ions, which can be electrochemically produced with good yields on the BDD anode, mainly in alkaline solution. Under this condition, the COD (chemical oxygen demand) removal was higher than that obtained from the model proposed by Comninellis. Electrolyses performed in phosphate buffer and in the presence of chloride ions resulted in faster COD and color removals in acid and neutral solutions, but in alkaline phosphate solution, a better performance in terms of TOC removal was obtained in the absence of chloride. Moreover, organochloride compounds were detected in all electrolyses performed in the presence of chloride. The AB-210 electrooxidation on BDD using phosphate as supporting electrolyte proved to be interesting since oxidizing species generated from phosphate ions were able to completely degrade the dye without producing organochloride compounds. (C) 2009 Elsevier Ltd. All rights reserved.

A critical comparison of the external and internal boron requirements for contrasting species in boron-buffered solution culture

Despite reports that boron (B) requirements differ among plant species there is a shortage of critical evidence to demonstrate unequivocally whether species differ in internal or external B requirements or both. The present research was conducted to establish the external and internal B requirements of three contrasting species, a woody dicot (marri), an herbaceous dicot (sunflower) and a monocot (wheat) using B-buffered solution culture. Boron-buffered solution culture provided satisfactory control of external B concentrations ranging from 0.04 to 30 muM throughout the 20- (sunflower and wheat) or 40-day (marri) growth period. At low external B concentrations (less than or equal to 0.13 muM), the growth of marri and sunflower was severely depressed but by contrast the vegetative growth of wheat plants was satisfactory and free of B deficiency symptoms. Marri and sunflower plants achieved total maximum shoot growth at greater than or equal to1.2 muM B in solutions while wheat plants did so at greater than or equal to 0.6 muM B. The critical B concentrations (mg kg(-1) dry matter) in the youngest open leaf blades of marri, sunflower and wheat plants were 17.9, 19.7 and 1.2 on 20, 10 and 10 days after transplanting (DAT), respectively. Lower internal and external B requirements of wheat were matched by a lower uptake rate of B compared to marri and sunflower.

Dry matter production and boron concentrations of vegetative and reproductive tissues of canola and sunflower plants grown in nutrient solution

Canola (Brassica napus L.) and sunflower (Helianthus annuus L.), two important oilseed crops, are sensitive to low boron (B) supply. Symptoms of B deficiency are often more severe during the reproductive stage, but it is not known if this is due to a decreased external B supply with time or an increased sensitivity to low B during this stage. Canola and sunflower were grown for 75 days after transplanting (DAT) in two solution culture experiments using Amberlite (IRA-743) B-specific resin to maintain constant B concentration in solution over the range 0.6 - 53 muM. Initially, the vegetative growth of both crops was good in all treatments. With the onset of the reproductive stage, however, severe B deficiency symptoms developed and growth of canola and sunflower was reduced with less than or equal to 0.9 and less than or equal to 0.7 muM B, respectively. At these concentrations, reproductive parts failed to develop. The critical B concentration (i.e. 90% of maximum shoot dry matter yield) in the youngest opened leaf was 18 mg kg(-1) in canola and 25 mg kg(-1) in sunflower at 75 DAT. The results of this study indicate that the reproductive stage of these two oilseed crops is more sensitive than the vegetative stage to low B supply.

Boron-doped nanocrystalline silicon thin films for solar cells

This article reports on the structural, electronic, and optical properties of boron-doped hydrogenated nanocrystalline silicon (nc-Si: H) thin films. The films were deposited by plasma-enhanced chemical vapour deposition (PECVD) at a substrate temperature of 150 degrees C. Crystalline volume fraction and dark conductivity of the films were determined as a function of trimethylboron-to-silane flow ratio. Optical constants of doped and undoped nc-Si: H were obtained from transmission and reflection spectra. By employing p(+) nc-Si: H as a window layer combined with a p' a-SiC buffer layer, a-Si: H-based p-p'-i-n solar cells on ZnO:Al-coated glass substrates were fabricated. Device characteristics were obtained from current-voltage and spectral-response measurements. (C) 2011 Elsevier B. V. All rights reserved.

Consolidating preservative-treated wood: Combined mechanical performance of boron and polymeric products in wood degraded by Coniophora puteana

When timber elements in heritage buildings are moderately degraded by fungi and assuming underlying moisture problems have been solved, two actions can be taken: i) use a biocide to stop fungal activity; ii) consolidate the degraded elements so that the timber keeps on fulfilling its structural and decorative functions. The aim of this work is to investigate the mechanical performance of maritime pine wood degraded by fungi after being treated with a biocide followed by impregnation with a polymer product. Three commercially available products were used: a boron water-based biocide, an acrylic consolidant and an epoxy-based consolidant. Treated and consolidated specimens were subjected to mechanical tests: axial compression test (NP 618), static surface hardness (ISO 3350) and bending test (NP 619). Sets of replicates were subjected to an evaporation ageing test (EN 73) after application of the products and also tested for mechanical behaviour. An increase in mechanical strength was observed for both consolidants with no significant influence from the previous use of biocide product. The specimens subjected to ageing showed a slightly better general mechanical performance.

Large-area homogeneous periodic surface structures generated on the surface sputtered boron carbide thin films by femtosecond laser processing

Amorphous and crystalline sputtered boron carbide thin films have a very high hardness even surpassing that of bulk crystalline boron carbide (≈41 GPa). However, magnetron sputtered B-C films have high friction coefficients (C.o.F) which limit their industrial application. Nanopatterning of materials surfaces has been proposed as a solution to decrease the C.o.F. The contact area of the nanopatterned surfaces is decreased due to the nanometre size of the asperities which results in a significant reduction of adhesion and friction. In the present work, the surface of amorphous and polycrystalline B-C thin films deposited by magnetron sputtering was nanopatterned using infrared femtosecond laser radiation. Successive parallel laser tracks 10 μm apart were overlapped in order to obtain a processed area of about 3 mm2. Sinusoidal-like undulations with the same spatial period as the laser tracks were formed on the surface of the amorphous boron carbide films after laser processing. The undulations amplitude increases with increasing laser fluence. The formation of undulations with a 10 μm period was also observed on the surface of the crystalline boron carbide film processed with a pulse energy of 72 μJ. The amplitude of the undulations is about 10 times higher than in the amorphous films processed at the same pulse energy due to the higher roughness of the films and consequent increase in laser radiation absorption. LIPSS formation on the surface of the films was achieved for the three B-C films under study. However, LIPSS are formed under different circumstances. Processing of the amorphous films at low fluence (72 μJ) results in LIPSS formation only on localized spots on the film surface. LIPSS formation was also observed on the top of the undulations formed after laser processing with 78 μJ of the amorphous film deposited at 800 °C. Finally, large-area homogeneous LIPSS coverage of the boron carbide crystalline films surface was achieved within a large range of laser fluences although holes are also formed at higher laser fluences.

Responses of higher plants to boron deficiency

Dissertation presented to obtain the degree of Doctorate in Biochemistry by Instituto de Tecnologia Química e Biológica of Universidade Nova de Lisboa