Borates, metallic

Like many late transition metals, nickel has featured, albeit briefly, in the pursuit of poly(pyrazolyl)borate-metal-carbollide complexes. Thus, [c/oso-3-(r 2-Ph2Bp)-3,l,2-NiC2B9H11] (90 ) has been obtained as the tet-ramethylammonium salt,39 via the reaction of [Me4N][Ph2Bp] with the neutral bisphosphine nickel dicarbollide [doso-3,3-(PhEt2P)2-3,l,2-... 

Tungstated, Molybdated, and Borated Metal Oxides 1 7.2.2.1 Preparation of WOj/ZrOj and MoOj/ZrOj [30]... 

There appear to be neither short nor comprehensive Gmehn-type reviews devoted entirely to rare earth borates. Metal borates have been treated in some recent reviews emphasizing d-block elements, however (Farmers, 1982). The nomenclature of borates, as well as that of many other oxoanion compounds capable of different stoichiometries, is confusing and partially contradictory. For instance, R2O3 3B2O3 is called metaborate because the formula can be written R(B02)3, yet the structural data available indicate it to be hexaborate. In the present review, in order to facilitate comparisons between different compounds, empirical formulae based on stoichiometry are preferred to names the generally accepted name orthoborate, which is not contradictory to the structural formula, is used, however. 

Boron III) oxide, B2O3, is obtained by ignition of boric acid. Combines with water to reform B(0H)3. The fused oxide dissolves metal oxides to give borates. 

Boron trioxide is not particularly soluble in water but it slowly dissolves to form both dioxo(HB02)(meta) and trioxo(H3B03) (ortho) boric acids. It is a dimorphous oxide and exists as either a glassy or a crystalline solid. Boron trioxide is an acidic oxide and combines with metal oxides and hydroxides to form borates, some of which have characteristic colours—a fact utilised in analysis as the "borax bead test , cf alumina p. 150. Boric acid. H3BO3. properly called trioxoboric acid, may be prepared by adding excess hydrochloric or sulphuric acid to a hot saturated solution of borax, sodium heptaoxotetraborate, Na2B407, when the only moderately soluble boric acid separates as white flaky crystals on cooling. Boric acid is a very weak monobasic acid it is, in fact, a Lewis acid since its acidity is due to an initial acceptance of a lone pair of electrons from water rather than direct proton donation as in the case of Lowry-Bronsted acids, i.e. 

Uses. Lithium fluoride is used primarily in the ceramic industry to reduce firing temperatures and improve resistance to thermal shock, abrasion, and acid attack (see Ceramics). Another use of LiF is in flux compositions with other fluorides, chlorides, and borates for metal joining (17) (see Solders). 

The composition of the builders in an alkaline cleaner is dependent on the metal substrate from which the soil is to be removed. For steel (qv) or stainless steel aggressive, ie, high pH, alkaline salts such as sodium or potassium hydroxide can be used as the main alkaline builder. For aluminum, zinc, brass, or tin plate, less aggressive (lower pH) builders such as sodium or potassium siUcates, mono- and diphosphates, borates, and bicarbonates are used. 

Occurrence. Niobium and tantalum usually occur together. Niobium never occurs as the metal, ie, ia the free state. Sometimes it occurs as a hydroxide, siUcate, or borate most often it is combiaed with oxygen and another metal, forming a niobate or tantalate ia which the niobium and tantalum isomorphously replace one another with Htde change ia physical properties except density. Ore concentrations of niobium usually occur as carbonatites and are associated with tantalum ia pegmatites and alluvial deposits. Principal niobium-beariag minerals can be divided iato two groups, the titano- and tantalo-niobates. 

Tetraalkyl titanates react with organic borates, B(OR )2, to give complexes of the general formula Ti(OR)4 B(OR )2, which are useful as catalysts and cross-linking agents (562). Mixtures of chelated organic titanates such as TYZOR TE and TYZOR LA with alkaU metal borates, such as borax, or boric acid can be used to produce shear-stable fracturing fluids (563). 

The oxides and oxyacids of boron as well as a variety of hydrated and anhydrous metal borates are discussed hereia. An alphabetical Hst of compounds referred to ia the text is given ia Table 1. 

Boric oxide is an excellent Lewis acid. It coordinates even weak bases to form four-coordinate borate species. Reaction with sulfuric acid produces H[B(HSO 4] (18). At high (>1000° C) temperatures molten boric oxide dissolves most metal oxides and is thus very corrosive to metals in the presence of oxygen. 

Alcohols react with boric acid with elimination of water to form borate esters, B(OR)3. A wide variety of borate salts and complexes have been prepared by the reaction of boric acid and inorganic bases, amines, and heavy-metal cations or oxyanions (44,45). Fusion with metal oxides yields... 

The principal impurities ia technical-grade bode acid are the by-product sulfates, <0.1 wt %, and vadous minor metallic impurities present in the borate ores. A bode acid titer is not an effective measure of purity because overdrying may result in partial conversion to metabotic acid and lead to B(0H)2 assays above 100%. High putity bode acid is prepared by recrystallization of technical-grade matedal. 

A number of boron chemicals are prepared directly from boric acid. These include synthetic inorganic borate salts, boron phosphate, fluoborates, boron ttihaHdes, borate esters, boron carbide, and metal aHoys such as ferroboron [11108-67-1]. 

Polyborates and pH Behavior. Whereas bode acid is essentiaHy monomeric ia dilute aqueous solutions, polymeric species may form at concentrations above 0.1 M. The conjugate base of bode acid in aqueous systems is the tetrahydroxyborate [15390-83-7] anion sometimes caHed the metaborate anion, B(OH) 4. This species is also the principal anion in solutions of alkaH metal (1 1) borates such as sodium metaborate,... 

The polyions postulated in solution all have known structural analogues in crystalline borate salts. Investigations of the Raman (66) and B nmr (67) spectra of borate solutions have confirmed the presence of three of these species the triborate (3), B202(0H) 4, tetraborate (4), [B40 (0H) 4], and pentaborate (5) B O (OH) 4, polyanions. Skeletal stmctures were assigned based on coincidences between the solution spectra and those soHd borates for which definitive stmctural data are available (52). These same ions have been postulated to be present in alkah metal borate glasses as well. 

Table 9. Aqueous Solubilities of Alkali Metal and Ammonium Borates at Various Temperatures...

Approximately 5% of the U.S. consumption of is in agriculture. Boron is a necessary trace nutrient for plants and is added in small quantities to a number of fertilizers. Borates are also used in crop sprays for fast rehef of boron deficiency. Borates, when apphed at relatively high concentration, act as nonselective herbicides. Small quantities of borates are used in the manufacture of alloys and refractories (qv). Molten borates readily dissolve other metal oxides usage as a flux in metallurgy is an important apphcation. Other important small volume apphcations for borates are in fire retardants for both plastics and ceUulosic materials, in hydrocarbon fuels for fungus control, and in automotive antifreeze for corrosion control (see Corrosion and corrosion inhibitors). Borates are used as neutron absorbers in nuclear reactors. Several borates, which are registered with the Environmental Protection Agency (EPA) can be used for insecticidal purposes, eg, TIM-BOR. 

A number of reviews have appeared covering the various aspects of borate glasses. The stmcture, physical properties, thermochemistry, reactions, phase equihbria, and electrical properties of alkah borate melts and glasses have been presented (73). The apphcation of x-ray diffraction, nmr, Raman scattering, in spectroscopy, and esr to stmctural analysis is available (26). Phase-equihbrium diagrams for a large number of anhydrous borate systems are included in a compilation (145), and thermochemical data on the anhydrous alkah metal borates have been compiled (17). 

Borate salts or complexes of virtually every metal have been prepared. For most metals, a series of hydrated and anhydrous compounds maybe obtained by varying the starting materials and/or reaction conditions. Some have achieved commercial importance. 

In general, hydrated borates of heavy metals ate prepared by mixing aqueous solutions or suspensions of the metal oxides, sulfates, or halides and boric acid or alkali metal borates such as borax. The precipitates formed from basic solutions are often sparingly-soluble amorphous soHds having variable compositions. Crystalline products are generally obtained from slightly acidic solutions. 

Anhydrous metal borates may be prepared by heating the hydrated salts to 300—500°C, or by direct fusion of the metal oxide with boric acid or B2O2. Many binary and tertiary anhydrous systems containing B2O2 form vitreous phases over certain ranges of composition (145). 

Copper, Manganese, and Cobalt Borates. Borate salts of copper, manganese, and cobalt ate precipitated when borax is added to aqueous solutions of the metal(Il) sulfates or chlorides (152). However, these materials are no longer produced commercially. 

N. P. Nies, "Alkah-Metal Borates Physical and Chemical Properties," in Ref. 3, section A9, p. 343. 

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