Reaction of calcium and phosphate ions with titanium,zirconium, niobium,and tantalum

To understand the bone formation ability of constituent metal elements of new titanium alloys, titanium, zirconium, niobium, and tantalum, these metals were immersed in various electrolytes containing calcium and/or phosphate ions and characterized using X‐ray photoelectron spectroscopy. In addition, cathodic polarization of the metals in the electrolytes was performed to evaluate the stability of the surface oxide films on the metals in the electrolyte. The calcium phosphate layer formed on Ti in electrolytes containing calcium and phosphate ions is relatively protective against mass transfer throughout the layer. However, the zirconium phosphate layer formed on Zr is much more protective and stable than that on Ti. Therefore, calcium ions were not incorporated. Nb and Ta formed calcium phosphate, but the amount was smaller than that in Ti, because phosphates formed on Nb and Ta are somewhat protective and the incorporation of the calcium ion is inhibited. Titanium played the most important role in forming calcium phosphate, while zirconium inhibited the formation of calcium phosphate on titanium alloys. The control of bone formation is feasible by the design of titanium alloys. Copyright © 2015 John Wiley & Sons, Ltd.     

Adsorption of organic substances on broken clay surfaces: a quantum chemical study

Hydrogen-bonded interactions between local defect structures on broken clay surfaces modeled as molecular clusters and the organic molecules acetic acid, acetate, and N-methylacetamide (NMA) have been investigated. Density functional theory and polarized basis sets have been used for the computation of optimized interaction complexes and formation energies. The activity of the defect structures has been characterized as physical or chemical in terms of the strength of the hydrogen bonds formed. Chemical defects lead to significantly enhanced interactions with stronger hydrogen bonds and larger elongation of OH bonds in comparison to the physical defects. The type of interaction with the defect structure significantly influences the planarity of the model peptide bond in NMA. Both cases, enhancement of the planarity by increase of the CN double bond character and strong deviations from planarity, are observed.     

Adsorption of trimethylamine on zirconium silicate and polyethylene powder surfaces

Sorptive interactions of volatile organic compounds (VOCs) with indoor surfaces play a major role in inhalation exposure to these species. Using ZrSiO₄ and polyethylene (PE) to model mineral surfaces and carpeting, respectively, the adsorption behavior of gaseous trimethylamine (TMA) was examined under conditions of 80% relative humidity (RH) in N₂ and in the presence of 1000 ppm CO₂ or NH₃. TMA adsorption and desorption behavior were studied using attenuated total reflection infrared (ATR-IR) and X-ray photoelectron (XPS) spectroscopies. Spectral data revealed that TMA adsorbed on both surfaces in a protonated state. Stronger adsorption was observed to occur on ZrSiO₄. XPS scans indicate that the “dry” ZrSiO₄ surface maintains OH groups available for bonding, supporting earlier research showing that partition coefficients increase as RH decreases.     

Adsorption of fibrinogen on tantalum oxide, titanium oxide and gold studied by the QCM-D technique

The adsorption of human fibrinogen on tantalum oxide, titanium oxide and gold surfaces has been studied by quartz crystal microbalance with dissipation (QCM-D) at 37 degrees C. Two different protein concentrations have been used, one close to physiological concentration (1 mg/ml) and one significantly lower (0.033 mg/ml). To further characterize the adsorbed fibrinogen layer, the subsequent binding of both polyclonal and monoclonal antibodies of fibrinogen is studied. We found that the viscoelastic properties of the fibrinogen layer depends strongly on the initial protein concentration. The trend is generally seen for all three surfaces. The fibrinogen layer on gold and tantalum oxide is found to have the same viscoelastic properties, which are different from those found for the fibrinogen layer adsorbed on titanium oxide. The dependency of the surface chemistry on the viscoelastic properties of the fibrinogen layer is observed directly for the 0.033 mg/ml solution, and indirectly through the antibody response for the 1 mg/ml solution. From this we conclude that the orientation and/or denaturation of fibrinogen on a surface depends on the surface chemistry and the protein concentration in the solution, and that the binding of antibodies is a useful way to detect this difference.     

Adsorption behavior of carboxymethyl starch on titanium dioxide surfaces

The adsorption of carboxymethyl starch (CMS) on titanium dioxide surface from aqueous solution of electrolyte was investigated by adsorption and electrokinetics mobility measurements. Zeta potential measurements showed that the addition of CMS resulted in a shift of isoelectric point to the more acidic region, indicating the adsorption of CMS from the aqueous solution onto titanium dioxide surface. The positively charged and hydrophilic surface sites of titanium dioxide favor the adsorption of CMS molecules. The adsorption capacity of CMS on titanium dioxide surface was found to be controlled by the number of functional group on CMS that promotes surface charge CMS adsorption in agreement with Langmuir isotherm. For the adsorption of CMS, the pseudo-second-order kinetics of chemical reaction provides the best correlation of the experimental data.     

Triazamethylenemethane complexes of zirconium and tantalum

Addition of [Li₂(THF)₄][C(NPh)₃] (2) to a THF solution of Cp^*ZrCl₃ (Cp^*=C₅Me₅) yields, after recrystallization in Et₂O, the zwitterionic species Cp^*[C(NPh)₃]ZrCl₂Li(Et₂O)(THF) (3). Treating 3 with excess methylaluminoxane (MAO) affords a homogeneous Ziegler–Natta catalyst for ethylene polymerization. Addition of LiNPh₂ to 3 allows for Cl substitution to give the new product Cp^*[C(NPh)₃]Zr(NPh₂)ClLi(THF)₂ (4). A single crystal diffraction study of 4 reveals that the [C(NPh)₃] ligand is η²-bound. The group 5 complex Cp^*[C(NPh)₃]TaMe₂ (5) was prepared by addition of 2 to Cp^*TaMe₂Cl(OSO₃CF₃). The X-ray diffraction structure of 5 shows that the [C(NPh)₃] ligand is η²-bound to tantalum and that, when compared to 4, there is less electron delocalization across the inner core of [C(NPh)₃].     

Niobium,tantalum, and titanium fluoride solutions

Parameters for the preparation of concentrated tantalum, niobium, and titanium fluoride solutions by dissolution of their oxides or hydroxides in hydrofluoric acid were studied. Anatase titania, niobium oxide, and tantalum oxide calcined to 900°C were found to have high dissolution rates. Solid phases separated upon the dissolution of niobium, tantalum, and titanium oxides in hydrofluoric acid were identified as NbO₂F, TaO₂F, Ta₃O₇F, and TiOF₂. Niobium hydroxide dissolution in an autoclave at the atmospheric pressure gave various complex salts: NH₄NbOF₄ and (NH₄)₃Nb₂OF₁₁.     

Adsorption of organic substances with different physicochemical properties

The linear regions of the adsorption isotherms of freon 13B1 (CF₃Br) on active carbons with different porous structures were studied by gas chromatography at 343–573 K. The Henry's constants were determined, and the isosteric heats of adsorption (Q) were calculated in the region of zero filling. It was established that theQ values for active carbons with different pore size distributions are almost the same and vary within 38–41 kJ mol^–1. This coincidence can be explained assuming that the interaction between the adsorbed molecules and the active carbons occurs in the pores whose sizes are comparable with those of the adsorbed molecules.For part 1, see Ref. 1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 439–441, March, 1995.     

Adsorption characteristics of traces of silver on selected surfaces

A study of materials used for the storage of dilute aqueous solutions of silver established the adsorption characteristics of Teflon, Vycor, polypropylene, polystyrene and coatings of paraffin, acrylic spray, and Tygon paint. None of these materials or coatings was found satisfactory for prolonged storage of water samples containing trace quantities of silver. As in an earlier study, it was necessary to complex the silver in the sample with sufficient sodium thiosulfate to insure less than 1 % adsorption to containers over a 30-day contact period.     

Effect of preparative conditions on the surface characteristics of mixed zirconium and titanium oxides

The surface characteristics of mixed zirconium and titanium oxides prepared from different starting materials are investigated. One mode of preparation entailed the use of zirconium sulfate and titanium oxysulfate as starting materials and ammonium hydroxide as precipitating agent. The produced oxides were washed to different extents to obtain samples with different sulfate content. A second preparative mode used zirconium oxychloride and titanous chloride as starting materials also with ammonium hydroxide as precipitating agent. The oxidation of the titanous to the titanic form for these oxides was carried out by means of oxygen gas. Resulting samples were heat treated at 400 °C and 600 °C, and textural characteristics determined from the adsorption of N₂ at 77 K, complemented by infrared and thermal studies. The samples precipitated from the oxychloride and chloride salts of zirconium and titanium, as well as those precipitated from the sulfate and oxysulfate salts and washed free of the sulfate ions displayed quite similar textural characteristics. The unheated samples and those heat-treated at 400 °C were mesoporous, with some microporosity, and relatively large surface areas in the order of 200–300 m²/g. Heat treatment to 600 °C led to a relative decrease in surface area, in the order of 100 m²/g, and to the disappearance of microporosity. The mixed zirconium and titanium oxides with a sulfate content of ≈17% displayed significantly lower surface areas, smaller than 10 m²/g, with a prevalence of micro and mesoporosity. Infrared and thermal studies indicated the presence of differently bounded sulfato groups, which seem to have a blocking effect on the pores, resulting in the observed smaller surface areas.     

The adsorptivity of organic substances with various physico-chemical properties

The adsorption isotherms of benzene,n-hexane, cyclohexane, and 1,2-dibromo-1,1,2,2-tetrafluoroethane on a nonporous carbon adsorbent, carbon black, were calculated from the results of a gas-chromatographic experiment at 373 K. A general equation of adsorption isotherm for vapors of organic substances on nonporous sorbents that was proposed earlier is shown to be valid in the range of relative pressures,p/p _s, of 10^–7–1 and temperatures of 293–373 K.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1381–1383, August, 1993.     

Adsorption of anions to zirconium(IV) and titanium(IV) chemically immobilized on gel-phase

Adsorption behaviors of 25 anions to zirconium(IV) and titanium(IV) chemically immobilized on a gel-phase were studied by ion chromatography and by batch adsorption experiments. The affinities of Zr(IV) to iminodiacetate as an anchoring group and to anions as a sample are much stronger than those of Ti(IV). On a Zr(IV) column, fourteen anions showed no retention, four anions showed pH-dependent retention in a low pH region, and seven anions were irreversibly adsorbed at pH <7. In the last group, fluoride was adsorbed both by the ligand exchange mechanism and the addition mechanism, while phosphate, arsenate and selenite were only by the ligand exchange mechanism. The structures of the adsorbed species are discussed.     

Synthesis of zirconium, hafnium, and tantalum complexes with sterically demanding hydrazide ligands

The bulky hydrazine t-BuN(H)NMe2 was synthesized via hydrazone and t-BuN(H)N(H)Me intermediates as the major component in a 90:5:5 mixture consisting of t-BuN(H)NMe2, t-BuN(Me)N(H)Me, and t-BuN(Me)NMe2. Reacting the mixture with n-BuLi followed by distillation and fractional crystallization led to the isolation of the ligand precursor LiN(t-Bu)NMe2. Lithium hydrazides, LiN(R)NMe2, were reacted with metal chlorides to afford the hydrazide complexes M(N(Et)NMe2)4 (M = Zr or Hf), MCl(N(R)NMe2)3 (M = Zr, R = i-Pr or t-Bu; M = Hf, R = t-Bu), and TaCl3(N(i-Pr)NMe2)2. The X-ray crystal structures of [LiN(i-Pr)NMe2]4, [LiN(t-Bu)NMe2.THF]2, ZrCl(N(R)NMe2)3 (R = i-Pr or t-Bu), and TaCl3(N(i-Pr)NMe2)2 were determined. The structural analyses revealed that the hydrazide ligands in ZrCl(N(R)NMe2)3 (R = i-Pr or t-Bu) and TaCl3(N(i-Pr)NMe2)2 are eta2 coordinated.     

Low-temperature synthesis of nanodispersed titanium,zirconium, and hafnium carbides

Nanosized refractory titanium, zirconium, and hafnium carbides were manufactured from highly dispersed metal dioxide-carbon starting mixtures at moderate temperatures of 1200°C or lower. The products were characterized by powder X-ray diffraction, elemental analysis, and transmission electron microscopy. The average size of particles (in nanometers) manufactured at 1200°C was as follows: for TiC, 13 ± 4; for ZrC, 17 ± 3; and for HfC, 16 ± 3; the average crystallite size (in nanometers) was as follows: for TiC, 8 ± 2; for ZrC, 5 ± 2; and for HfC, 8 ± 3. Thermodynamic modeling was performed for the synthesis of Group IVB carbides via carbothermal reduction of the corresponding oxides. The results show that in the titanium dioxide-carbon system, for example, titanium monocarbide formation is possible at a temperature as low as 850°C (p = 10⁻⁴ MPa). Highly dispersed metal dioxide-carbon starting mixtures were prepared using solgel technology from metal alkoxyacetylacetonates in the presence of a polymeric carbon source.     

High-temperature oxidation of titanium, zirconium, and hafniyum in steam

The influence exerted by the nature of titanium, zirconium, and hafnium on the kinetic parameters of oxidation and on the diffusion mechanism of scale formation in steam at 973–1473 K is analyzed. The results obtained are compared with the data for the air medium.     

Ethylene oligomerization on heterogenized titanium and zirconium complexes

Besides other products, linear middle-range olefins were obtained in the low temperature oligomerization of ethylene with a selectivity of 30–58% and a linearity up to 85%. Activated ticanium and zirconium complexes as catalysts were attached to SiO₂ through surface bounded bidentate S- and N-containing ligands, the former being superior to the latter with respect to product quality.

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