Titanium dioxide preparation

Suzuki A, Tukuda R (1969) Kinetics of the transition of titanium dioxide prepared by sulfate process and chloride process. Bull Chem Soc Japan 42 1853-1957... 

Eremenko, B.V. et al., Stability of aqueous dispersions of the hydrated titanium dioxide prepared by titanium tetrachloride hydrolysis, Colloid J., 63, 173, 2001. 

Commercial titanium dioxide preparations were added, at constant temperature and with stirring, to aqueous solutions of iron III nitrate containing the required amounts of iron ions in the minimum volume of doubly-distilled water. Subsequent to separation and diying, the solid specimens were calcined in air at fixed temperatures in the range 773K to 1273K for a period of 24 hours. Experimental methods detailing the preparations of ii and iii above have been reported previously [5,71. 

Barium Chrome See Barium Yellow. Barium-Extended Titanium Dioxide n Analogous to calcium-extended titanium dioxide, prepared by... 

This occurs naturally as a white solid in various crystalline forms, in all of which six oxygen atoms surround each titanium atom. Titanium dioxide is important as a white pigment, because it is nontoxic. chemically inert and highly opaque, and can be finely ground for paint purposes it is often prepared pure by dissolving the natural form in sulphuric acid, hydrolysing to the hydrated dioxide and heating the latter to make the anhydrous form. 

Although white lead was the oldest white hiding pigment ia paints, it has been totally replaced by titanium dioxide, which has better covering power and is nontoxic (see Pigments). Nevertheless, basic lead carbonate has many other uses, including as a catalyst for the preparation of polyesters from... 

The sol—gel technique has been used mosdy to prepare alumina membranes. Figure 18 shows a cross section of a composite alumina membrane made by sHp coating successive sols with different particle sizes onto a porous ceramic support. SiUca or titanium membranes could also be made by the same principles. Unsupported titanium dioxide membranes with pore sizes of 5 nm or less have been made by the sol—gel process (57). 

To produce the mtile titanium dioxide pigment, hydrolysis of the mother Hquor has to be carried out in the presence of a specially prepared hydrosol as a seeding agent. This hydrosol is made by the neutralization of a portion of the mother Hquor in the presence of hydrochloric or some other monohydric acid. Because of the large amount of the hydrosol that must be added to the mixture (about 6% concentration), the hydrolysis reaction takes only about 1 hr. 

Production. Commercial production of Hthopone started in the first half of the nineteenth century, and continued to grow until the middle of the twentieth century when titanium dioxide started to dominate the white, inorganic pigment market. Lithopone is prepared by combining barium sulfide and 2inc sulfate solutions at 50—60°C ... 

Research-grade material may be prepared by reaction of pelleted mixtures of titanium dioxide and boron at 1700°C in a vacuum furnace. Under these conditions, the oxygen is eliminated as a volatile boron oxide (17). Technical grade (purity > 98%) material may be made by the carbothermal reduction of titanium dioxide in the presence of boron or boron carbide. The endothermic reaction is carried out by heating briquettes made from a mixture of the reactants in electric furnaces at 2000°C (11,18,19). 

Precipitation of a hydrated titanium oxide by mixing aqueous solutions of titanium chloride with alkaU forms the precipitation seeds, which are used to initiate precipitation in the Mecklenburg (50) variant of the sulfate process for the production of pigmentary titanium dioxide. Hydrolysis of aqueous solutions of titanium chloride is also used for the preparation of high purity (>99.999%) titanium dioxide for electroceramic appHcations (see Ceramics). In addition, hydrated titanium dioxide is used as a pure starting material for the manufacture of other titanium compounds. 

Anatase and mtile are produced commercially, whereas brookite has been produced by heating amorphous titanium dioxide, which is prepared from an alkyl titanate or sodium titanate [12034-34-3] with sodium or potassium hydroxide in. an autoclave at 200—600°C for several days. Only mtile has been synthesized from melts in the form of large single crystals. More recentiy (57), a new polymorph of titanium dioxide, Ti02(B), has been demonstrated, which is formed by hydrolysis of K Ti O to form 20, followed by subsequent calcination/dehydration at 500°C. The relatively open stmcture... 

Ferrous orthotitanate [12160-20-2] Fe2Ti04, is orthorhombic and opaque. It has been prepared by heating a mixture of ferrous oxide and titanium dioxide. Ferrous dititanate [12160-10-0] FeTi20, is orthorhombic and has been prepared by reducing ilmenite with carbon at 1000°C. The metallic ion formed in the reaction is removed, leaving a composition that is essentially the dititanate. Ferric titanate [1310-39-0] (pseudobrookite), Fe2TiO, is orthorhombic and occurs to a limited state in nature. It has been prepared by heating a mixture of ferric oxide and titanium dioxide in a sealed quartz tube at 1000°C. 

A patent (122) for the production of pigment-grade titanium dioxide describes preparation of titanium tetrafluoride by the reaction of SiF and ilmenite. 

Titanium oxide dichloride [13780-39-8] TiOCl2, is a yellow hygroscopic soHd that may be prepared by bubbling ozone or chlorine monoxide through titanium tetrachloride. It is insoluble in nonpolar solvents but forms a large number of adducts with oxygen donors, eg, ether. It decomposes to titanium tetrachloride and titanium dioxide at temperatures of ca 180°C (136). 

Titanium Silicides. The titanium—silicon system includes Ti Si, Ti Si, TiSi, and TiSi (154). Physical properties are summarized in Table 18. Direct synthesis by heating the elements in vacuo or in a protective atmosphere is possible. In the latter case, it is convenient to use titanium hydride instead of titanium metal. Other preparative methods include high temperature electrolysis of molten salt baths containing titanium dioxide and alkalifluorosiUcate (155) reaction of TiCl, SiCl, and H2 at ca 1150°C, using appropriate reactant quantities for both TiSi and TiSi2 (156) and, for Ti Si, reaction between titanium dioxide and calcium siUcide at ca 1200°C, followed by dissolution of excess lime and calcium siUcate in acetic acid. 

Titanium trisulfide [12423-80-2], TiS, a black crystalline soHd having a monoclinic stmcture and a theoretical density of 3230 kg/m, can be prepared by reaction between titanium tetrachloride vapor and H2S at 480—540°C. The reaction product is then mixed with sulfur and heated to 600°C ia a sealed tube to remove residual chlorine. Sublimatioa may be used to separate the trisulfide (390°C) from the disulfide (500°C). Titanium trisulfide, iasoluble ia hydrochloric acid but soluble ia both hot and cold sulfuric acid, reacts with concentrated nitric acid to form titanium dioxide. 

Titanium Dioxide Hollow Fibers. HoUow fibers of titanium dioxide can be manufactured by preparing a solution of a tetraalkyl titanate, an acid such as HCl, and an alcohol such as isopropyl alcohol, followed by spinning and drying the resultant fiber (573). 

Other Rea.ctlons, The anhydride of neopentanoic acid, neopentanoyl anhydride [1538-75-6] can be made by the reaction of neopentanoic acid with acetic anhydride (25). The reaction of neopentanoic acid with acetone using various catalysts, such as titanium dioxide (26) or 2irconium oxide (27), gives 3,3-dimethyl-2-butanone [75-97-8] commonly referred to as pinacolone. Other routes to pinacolone include the reaction of pivaloyl chloride [3282-30-2] with Grignard reagents (28) and the condensation of neopentanoic acid with acetic acid using a rare-earth oxide catalyst (29). Amides of neopentanoic acid can be prepared direcdy from the acid, from the acid chloride, or from esters, using primary or secondary amines. 

Lakes. Lakes are a special kind of color additive prepared by precipitating a soluble dye onto an approved iasoluble base or substratum. In the case of D C and Ext. D C lakes, this substratum may be alumina, blanc fixe, gloss white, clay, titanium dioxide, 2iac oxide, talc, rosia, aluminum ben2oate, calcium carbonate, or any combination of two or more of these materials. Currentiy, alumina is the only substratum approved for manufactuting FD C lakes. 

Chemical vapour deposition Example. The preparation of films of titanium dioxide. 

Tacconi NR, Chenthamarakshan CR, Rajeshwar K, Tacconi El (2005) Selenium-modified titanium dioxide photochemical diode/electrolyte junctions Photocatalytic and electrochemical preparation, characterization, and model simulations. 1 Phys Chem B 109 11953-11960... 

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