Titanium functions

Bradley, C. A. McMurdy, M. J. Tilley, T. D., Selective Catalytic Cyclohexene Oxidation Using Titanium-Functionalized Silicone Nanospheres. J. Phys. 

Hu X, Neoh KG, Shi Z, Kang ET, Poh C, Wang W. An in vitro assessment of titanium functionalized with polysaccharides conjugated with vascular endothelial growth factor for enhanced osseointegration and inhibition of bacterial adhesion. Biomaterials. 2010 31 8854-63. 

Raynor, J. E., Petrie, T. A., Garcia, A. J., Collard, D. M., Controlling Cell Adhesion to Titanium Functionalization of Poly[01igo(Ethylene GlycolJMethacrylate] Brushes with Cell-Adhesive Peptides, Adv. Mater. 2007,19,1724-1728. 

Dialkylaminoethyl acryhc esters are readily prepared by transesterification of the corresponding dialkylaminoethanol (102,103). Catalysts include strong acids and tetraalkyl titanates for higher alkyl esters and titanates, sodium phenoxides, magnesium alkoxides, and dialkyitin oxides, as well as titanium and zirconium chelates, for the preparation of functional esters. Because of loss of catalyst activity during the reaction, incremental or continuous additions may be required to maintain an adequate reaction rate. 

Transesterification of methyl methacrylate with the appropriate alcohol is often the preferred method of preparing higher alkyl and functional methacrylates. The reaction is driven to completion by the use of excess methyl methacrylate and by removal of the methyl methacrylate—methanol a2eotrope. A variety of catalysts have been used, including acids and bases and transition-metal compounds such as dialkjitin oxides (57), titanium(IV) alkoxides (58), and zirconium acetoacetate (59). The use of the transition-metal catalysts allows reaction under nearly neutral conditions and is therefore more tolerant of sensitive functionality in the ester alcohol moiety. In addition, transition-metal catalysts often exhibit higher selectivities than acidic catalysts, particularly with respect to by-product ether formation. 

Though functionally and chemically similar, fillers and pigments ate distinguished from one another in that fillers are added at the wet end of the paper machine, and serve to fill the sheet pigments are added at the size press and serve to alter the surface of the sheet. The most common fillers are mineral pigments, eg, clay, titanium dioxide [13463-67-7] calcium carbonate, siUca [7631-86-9], hydrated alumina [21645-51 -2], and talc [14807-96-6]. 

The materials used in a total joint replacement ate designed to enable the joint to function normally. The artificial components ate generally composed of a metal piece that fits closely into bone tissue. The metals ate varied and include stainless steel or alloys of cobalt, chrome, and titanium. The plastic material used in implants is a polyethylene that is extremely durable and wear-resistant. Also, a bone cement, a methacrylate, is often used to anchor the artificial joint materials into the bone. Cementiess joint replacements have mote tecentiy been developed. In these replacements, the prosthesis and the bone ate made to fit together without the need for bone cement. The implants ate press-fit into the bone. 

Titanium is susceptible to pitting and crevice corrosion in aqueous chloride environments. The area of susceptibiUty for several alloys is shown in Figure 7 as a function of temperature and pH. The susceptibiUty depends on pH. The susceptibiUty temperature increases paraboHcaHy from 65°C as pH is increased from 2ero. After the incorporation of noble-metal additions such as in ASTM Grades 7 or 12, crevice corrosion attack is not observed above pH 2 until ca 270°C. Noble alloying elements shift the equiUbrium potential into the passive region where a protective film is formed and maintained. 

Titanium-cataly2ed ester interchange can be used to prepare polyesters from diester and diols as well as from diacids and diols at considerably higher temperatures. Polymer chains bearing pendant ester and hydroxy functions can be cross-linked with titanates. 

Titanium chelates are formed from tetraalkyl titanates or haUdes and bi- or polydentate ligands. One of the functional groups is usually alcohoHc or enoHc hydroxyl, which interchanges with an alkoxy group, RO, on titanium to Hberate ROH. If the second function is hydroxyl or carboxyl, it may react similarly. Diols and polyols, a-hydroxycarboxyflc acids and oxaUc acid are all examples of this type. P-Keto esters, P-diketones, and alkanolamines are also excellent chelating ligands for titanium. 

The chelated organic titanates also function as adhesion promoters of the ink binder to printed substrates such as plastic films, paper, and aluminum foil (504). The acetylacetone complexes of titanium are the preferred products for promoting adhesion of printing inks to polypropylene films. 

Uses. In spite of unique properties, there are few commercial appUcations for monolithic shapes of borides. They are used for resistance-heated boats (with boron nitride), for aluminum evaporation, and for sliding electrical contacts. There are a number of potential uses ia the control and handling of molten metals and slags where corrosion and erosion resistance are important. Titanium diboride and zirconium diboride are potential cathodes for the aluminum Hall cells (see Aluminum and aluminum alloys). Lanthanum hexaboride and cerium hexaboride are particularly useful as cathodes ia electronic devices because of their high thermal emissivities, low work functions, and resistance to poisoning. 

Gels. Amorphous hydrated silicas of a purity and stmcture typical of those used ia type 1 dentifrices and the liquid portion (humectant system) of type 1 dentifrices both have approximately the same refractive iadex, ie, about 1.47. As a result, the type 1 dentifrices represented ia Table 1 are inherently transparent or translucent. In the marketplace it has become popular to refer to such dentifrices as gels. For marketing reasons some companies have chosen to opacify these products, with titanium dioxide, for example. The opacified products are identical ia functionality, stmcture, and all other ways, except opacity, to their translucent or transparent counterparts. 

The role of antimony oxide is not entirely understood. On its own it is a rather weak fire retardant although it appears to function by all of the mechanisms listed above. It is, however, synergistic with phosphorus and halogen compounds and consequently widely used. Other oxides are sometimes used as alternatives or partial replacements for antimony oxide. These include titanium dioxide, zinc oxide and molybdenic oxide. Zinc borate has also been used. 

Various inorganic esters have been claimed as coupling agents for reinforced plastics, including aminobenzyl phosphonates, dicetylisopropylborate, alkoxy compounds of aluminum, zirconium and titanium, zircoaluminates, and numerous substituted titanates [1]. These metal alkoxides could function in a similar manner to the orthosilicates by reacting with hydroxylated substrates. Like the simple orthosilicates such as tetraethyl orthosilicate (TEOS), it is less evident how an-... 

In primer formulations for adhesive bonding of metals, the coupling agents that are most frequently used are those based on epoxy and amine functionalities. Aqueous solutions of aminosilanes have been successfully used for obtaining stable adhesive bonds between epoxy and steel [10] and epoxy and titanium [11,12], while epoxy functional silanes are preferable for applications involving aluminum substrates [13,14], A simple solution of % epoxy functional silane in water is currently used for field repairs of military aircraft [15] where phosphoric acid anodization would be extremely difficult to carry out, and performance is deemed quite acceptable. 

Under sonication conditions, the reaction of perfluoroalkyl bromides or iodides with zinc can be used to effect a variety of functionalization reactions [39, 40, 41, 42] (equation 30) Interestingly, the ultrasound promoted asymmetric induction with the perfluoroalkyl group on the asymmetric carbon was achieved by the reaction of perfluoroalkyl halides with optically active enamines in the presence of zinc powder and a catalytic amount of dichlorobisftc-cyclopenta-dienyl)titanium [42] (equation 31)... 

Triflates of titanium and tin are effective catalysts for various condensations of carbonyl compounds [I2I, 122, 123, 124, 125] Claisen and Dieckmann type condensations between ester functions proceed under mild conditions in the presence of dichlorobis(trifluoromethanesulfonyloxy)titaiiiuin(rV) and a tertiary amine (equations 59 and 60) These highly regio- and stereoselective condensations were used successfully m the synthesis of carbohydrates [122]... 

Sulfur imides with a single NR functionality, S5NR (6.12), SeNR (6.13) (R = Oct), " SgNH (6.14), ° and S9NH (6.15) ° are obtained by a methodology similar to that which has been used for the preparation of unstable sulfur allotropes, e.g., S9 and Sio. Eor example, the metathesis reaction between the bis(cyclopentadienyl)titanium complexes 6.8-6.10 and the appropriate dichlorosulfane yields 6.14 and 6.15 (Eq. 6.4). °... 

For the construction of oxygen-functionalized Diels-Alder products, Narasaka and coworkers employed the 3-borylpropenoic acid derivative in place of 3-(3-acet-oxypropenoyl)oxazolidinone, which is a poor dienophile in the chiral titanium-catalyzed reaction (Scheme 1.55, Table 1.24). 3-(3-Borylpropenoyl)oxazolidinones react smoothly with acyclic dienes to give the cycloadducts in high optical purity [43]. The boryl group was converted to an hydroxyl group stereospecifically by oxidation, and the alcohol obtained was used as the key intermediate in a total synthesis of (-i-)-paniculide A [44] (Scheme 1.56). 

Finally, the use of the constant pressure minimization algorithm allows searching for phenomena that can be considered as precursors of pressure-induced transitions. For example, the predicted behaviour of the anatase cell constants as a function of pressure shows that the a(P) and c(P) plots are only linear for P<4 GPa, the value that is close to both the theoretical and experimental transition pressures. At higher pressures the a constant starts to grow under compression, indicating inherent structural instability. In the case of ratile there is a different precursor effect, nami y at 11 GPa the distances between the titanium atom and the two different oxygens, axial and equatorial, become equal. Once again, the pressure corresponds closely to the phase transition point. 

Titanium in contact with other metals In most environments the potentials of passive titanium. Monel and stainless steel, are similar, so that galvanic effects are not likely to occur when these metals are connected. On the other hand, titanium usually functions as an efficient cathode, and thus while contact with dissimilar metals is not likely to lead to any significant attack upon titanium, there may well be adverse galvanic effects upon the other metal. The extent and degree of such galvanic attack will depend upon the relative areas of the titanium and the other metal where the area of the second metal is small in relation to that of titanium severe corrosion of the former will occur, while less corrosion will be evident where the proportions are reversedMetals such as stainless steel, which, like titanium, polarise easily, are much less affected in these circumstances than copper-base alloys and mild steel. 

Thus titanium by itself cannot function as an efficient anode for the passage of positive direct current into an electrolyte. The surface film of oxide formed upon the titanium has, however, a most useful property while it will not pass positive direct current into an electrolyte (more correctly, while it will not accept electrons from negatively charged ions in solution), it will accept electrons from, or pass positive current to, another metal pressed on to it. Hence a piece of titanium which has pressed on to its surface a small piece of platinum will pass positive direct current into brine and into many electrolytes, at a high current density, via the platinum, without undue potential rise, and without breakdown of the supporting titanium . ... 

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