Ion-exchange selectivities of amorphous and anatase-types hydrous titanium dioxides and the possible separation of bivalent transition metal ions

Summary Amorphous and anatase-type hydrous titanium dioxides showed typical amphoteric ion-exchange properties. The ion-exchange selectivity for bivalent transition metal ions was studied as a function of both pH and metal ion concentration in ammonium nitrate media. The selectivity series was Co<Ni<Mn<Zn<Cd<Cu for the amorphous and Ni<Co<Mn<Zn<Cd<Cu for the anatase-type material. The separation factor on the anatase-type material is larger than on the amorphous material. Effective group separation of Co–Ni and Zn–Cd–Cu could be achieved on an ion-exchange column containing the anatase-type hydrous titanium dioxide.Part XXIV in a series on synthetic inorganic ion-exchange materials.     

Effect of Precipitation pH and Heat Treatment on the Properties of Hydrous Zirconium Dioxide

The effect of the precipitation pH and subsequent heat treatment is studied on the properties of hydrous zirconium dioxide precipitated by ammonia from nitrate solutions. Precipitation at pH ≤ 6 generates hydrous zirconium dioxide, which contains excess sorbate nitrate ions; the product precipitated at pH ≥ 7 contains excess ammonium ions. This distinction considerably affects the course of thermolysis and the morphology of products. The exotherm associated with the formation of the crystal structure of zirconia becomes more pronounced with rising precipitation pH. In addition, the samples prepared at pH ≥ 7 have a more developed surface. The morphologic and microstructural evolution of hydrous zirconium dioxide samples during thermolysis is described.     

Calculation of kinetic parameters from TG curve on the base of dehydration process of hydrous titanium dioxide

A direct method of evaluating of kinetic equation parameters based on TG curve is proposed. The method was applied to calculate kinetic parameters of the process of dehydration of hydrous titanium dioxide.

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Zusammenfassung Es wird ein direktes Verfahren zur Bestimmung der Parameter der kinetischen Gleichung auf der Basis von TG-Kurven gegeben. Das Verfahren wurde zur Berechnung der kinetischen Parameter des Dehydratationsprozesses von wasserhaltigem Titandioxid benutzt.

     

A radiochemical study of the kinetics of ion exchange on hydrous titanium dioxide

This paper reports a radiochemical study of the kinetics of ion exchange of Na⁺ and Cs⁺ with H⁺ on hydrous titanium dioxide. The experimental conditions are set to favor the particle diffusion mechanism only, and this is confirmed by the Bt versus t plots. On the basis of these studies the various physical parameters such as the effective diffusion coefficients, activation energies and entropies of activation have been evaluated. Tentative explanations are given for these results, from which some conclusions are drawn.     

Distribution coefficients of lanthanide elements and some separations on layered hydrous titanium dioxide

Distribution coefficients /K_d/ of lanthanide elements on layered hydrous titanium dioxide, H₂Ti₄O₉.nH₂O /where n=1.2–1.3/, have been determined as a function of the pH of the aqueous phase. The plots of 1g K_d vs. pH gave straight lines with slopes equal to +3 except for the data for heavier lanthanides, suggesting ideal ion-exchange equilibria between tervalent cations in the aqueous phase and hydrogen ions in the hydrous oxide. Mutual separations of La–Cs and La–Ba have been achieved on a column of this material on the basis of large differences in affinities between the metal ion pairs.     

Synthesis of rutile titanium dioxide from Russian raw materials

The conditions of the structure formation of rutile titanium dioxide from titanium dioxide (anatase) and titanium hydroxide isolated by thermolysis from the titanium compound (NH₄)₂TiO(SO₄)₂ · H₂O and by thermal hydrolysis of a titanium sulfate(IV) solution, respectively, were studied. It was shown that the mechanical activation of the studied powders causes, in addition to a decrease in the initial grain size, deep destructuring with the formation of the transition phase, which, in the process of the subsequent high-temperature treatment, functions as a matrix for the formation of rutile. The research results will be used for the development of a new variant of the technology for the synthesis of titanium dioxide, which is an important component of compositions for polymeric materials—in particular, the K-300-61 and K-153 adhesives.     

Thermal and sorption behavior of polyacrylonitrile supported hydrous titanium dioxide

Summary Modification of the physico-chemical properties of hydrous titanium dioxide (TiO₂) was conducted by using binding polyacrylonitrile (PAN) for the preparation of larger size particles having higher granular strength. The thermal behavior of the obtained composite has been studied by thermogravimetric and differential thermal analysis (TG/DTA). Sorption behavior of the TiO₂-PAN composite for removal of some hazardous radionuclides has been studied at different conditions such as, pH, contact time, ion concentrations and reaction temperature as well as the drying temperature. The effects of interfering ions as well as some complexing agents on the distribution ratio of the sorption process have been determined. As a result of the obtained data the optimum conditions for the removal of the studied radionuclides were recommended.     

Formation of the structure of cerium oxide-modified titanium dioxide

The formation of the structure of titanium dioxide containing 3–15 wt % CeO₂ in a wide temperature range (300–850°C) has been investigated by X-ray powder diffraction, electron microscopy, and adsorption methods. Modification of titanium dioxide with cerium oxide causes the formation of nanostructured Ce-Ti-O compounds consisting of incoherently intergrown fine anatase crystallites. The crystallites are separated by interblock boundaries in which cerium ions are stabilized. The nanostructure formed in the Ce-TiO₂ oxide system stabilizes the anatase phase, prevents the sintering of anatase particles at high temperatures, and allows modified anatase to retain a larger specific surface area and a higher porosity upon heat treatment than pure titanium dioxide does.     

Silicon Dioxide Coating of Titanium Dioxide Nanoparticles from Dielectric Barrier Discharge in a Gaseous Mixture of Silane and Nitrogen

The coating of titanium dioxide nanoparticles with silicon dioxide has been carried out by dielectric barrier discharge (DBD) plasma treatments to enhance the thermostability of Titania for applications at high temperature processes. During the first coating processing step, a closed film of silicon nitride was produced via plasma treatment in a gaseous mixture of silane and nitrogen, while atmospheric surface contaminations got mainly removed. In the second processing step, the DBD plasma treatment in oxygen or air was used to convert the silicon nitride mainly into silicon dioxide. Remaining carbon impurities at the interfaces between titanium dioxide and silicon nitride after the nitrogen/silane plasma treatment were subsequently removed simultaneously. Atomic force microscopy and X-ray photoelectron spectroscopy were employed to study the DBD plasma treatments of the TiO₂ nanoparticles.     

Ion-exchangers in radioactive waste management Part XIV: Removal behavior of hydrous titanium oxide and sodium titanate for Cs(I)

The removal behavior of hydrous titanium oxide and sodium titanate for Cs(I) from aqueous solutions by radiotracers was studied. Batch experiments revealed that an increase in Cs concentration (10^–8 to 10^–2 mol·dm^–3), temperature (298 to 328 K) and pH (2.50 to 10.20) apparently enhanced the uptake of Cs(I) on hydrous titanium oxide whereas a high degree of uptake of Cs(I) on sodium titanate was almost unaffected by a change in adsorption temperature (298 to 328 K) and pH (2.50 to 10.20). Both systems follow Freundlich adsorption isotherm. Uptake of Cs(I) on hydrous titanium oxide obeys first order rate law. According to thermodynamic data the uptake is endothermic and apparently irreversible in nature.This revised version was published online in November 2005 with corrections to the Cover Date.     

Determination of tungsten in silicates and natural waters

Coprecipitation with hydrous manganese dioxide is used for the concentration of tungsten from natural waters (including sea water) and from solutions prepared from silicate rocks and sediments by hydrofluoric acid attack. After dissolution of the hydrous manganese dioxide precipitate in acidified sulphur dioxide solution, cation excliange is used to separate tungsten and molybdenum from other coprecipitated elements, hydrogen peroxide being used as eluant. Molybdenum is separated from tungsten by extraction of its dithiol complex from 24 N hydrochloric acid medium containing citric acid and can be determined photometrically. After destruction of citric acid, tungsten is determined photometrically with dithiol. The overall cliemical yield of th analytical process is 94±1%. The standard deviation of the method is ±0.010 μg for sea water (0.116 μg W/l) and ca 0.05 μg/g for siliceous sediments containing 0.5–1.0 μg W/g.     

二氧化钛纳米晶溶胶内渗透电极对染料敏化太阳能电池的光伏性能的提高

以自制的过氧钛酸(PTA)水溶液为前驱体,用水热法制备了透明锐钛矿相二氧化钛溶胶.无需有机添加剂可得到直径小于7 nm的棒状二氧化钛纳米晶溶胶.通过将溶胶内渗透到染料敏化太阳能电池(DSSCs)的多孔二氧化钛电极后,消除了多孔电极内的大孔并改善了电极内纳米晶之间的连通性.用扫描电子显微镜(SEM)和光学轮廓仪对溶胶内渗透后的光阳极进行了表征.结果表明:小颗粒棒状二氧化钛纳米晶附着在多孔的二氧化钛表面,填充了电极由于烧结产生的大孔,并在多孔的二氧化钛内部形成了有利于电子传输的网络结构.与未经处理的多孔电极相比,改性后的光阳极组装成染料敏化太阳能电池后光电转化效率提高了64%.     

Effect of Light on the Electrokinetic Behavior of TiO(2) Particles in Contact with Cr(VI) Aqueous Solutions

The electrokinetic behavior of titanium dioxide particles (Degussa P25, mainly composed of anatase) put in contact with chromium(VI) aqueous solutions is highly sensitive to light exposure under normal laboratory conditions. In the dark, adsorption of Cr(VI) gives rise to substantial decrements in the mobilities, especially in the acidic branch, and, at higher concentrations, to shifts in the isoelectric point (pH(piep)) to lower values, as expected for anionic chemisorption. A two-mode adsorption model accounts qualitatively for the results. Under light, pH(piep) shifts in the opposite direction as the Cr(VI) concentration increases. A maximum value is attained at [Cr(VI)] approximately 10(-3) mol dm(-3), pH(piep) 8.2, which coincides with values reported for hydrous chromium(III) oxides. At higher concentrations, Cr(VI) adsorption defines a shift of pH(piep) to lower values. It is concluded that light absorption by titanium dioxide promotes the reduction of Cr(VI) and the surface precipitation of the hydrous Cr(III) oxide. The values of pH(piep) for partially covered surfaces are well described by a simple model of surface ionization derived earlier. FTIR/ATR analysis of the surfaces supports this interpretation, and further suggests that one of the modes of Cr(VI) adsorption implies surface dimerization to yield adsorbed dichromate. Copyright 2000 Academic Press.     

Effect of Heat Treatment Temperature on Surface Topography and Hydrophobicity of Polydimethylsiloxane/Titanium Oxide Hybrid Films

Hydrophobic thin films of polydimethylsiloxane (PDMS) - titamium (hydrous) oxide hybrid material were deposited on glass substrate by dip coating from the precursor containing hydroxyl-terminated PDMS and titanium tetraisopropoxide (TIP), as well as small amounts of water and ethyl acetoacetate. Film's hydrophobicity was evaluated by performing contact angle measurement, while surface topography was analyzed by using an atomic force microscope (AFM). Effects of heat treatment temperature and TIP:PDMS ratio on film's hydrophobicity are described.     

The effect of titanium dioxide exposure on the thermal properties of Zebrafish (<Emphasis Type="Italic">Danio rerio</Emphasis>) bones

This article presents the changes in the thermal properties of the control and titanium dioxide (TiO₂), both nano and bulk exposed Zebrafish bones by using thermo analytical techniques. The result shows that the mass loss due to the thermal decomposition occurs in three distinct steps due to loss of water, organic and inorganic materials. The titanium dioxide exposed bones present a different thermal behaviour compared to the control bones. The residue masses are found to be increased due to titanium dioxide exposure. In particular, nano titanium dioxide exposure increases the residue mass level significantly (three fold) when compared to titanium dioxide bulk exposure. These thermal characteristics can be used as a qualitative method to check the metal oxide intoxication in biological samples.     

Particle size characterization of titanium dioxide in sunscreen products using sedimentation field-flow fractionation–inductively coupled plasma–mass spectrometry

Sedimentation field-flow fractionation–inductively coupled plasma–mass spectrometry (SdFFF-ICP-MS) was successfully applied to investigate particle size distribution of titanium dioxide (TiO₂) in sunscreen samples after hexane extraction to remove organic components from the samples. Three brands of sunscreen products of various sun protection factor (SPF) value were used as samples. Different particle size distribution profiles were observed for sunscreen samples of various brands and SPF values; however, the particle size distributions of titanium dioxide in most sunscreen samples investigated in this work were larger than 100 nm. The titanium dioxide concentrations were higher for the products of higher SPF values. By comparing the results obtained from online SdFFF-ICP-MS and those from the off-line ICP-MS determination of titanium after acid digestion, ICP-MS was found to effectively atomize and ionize the titanium dioxide particle without the need for acid digestion of the samples. Therefore, the online coupling between SdFFF and ICP-MS could be effectively used to provide quantitative information of titanium dioxide concentrations across particle size distribution profiles.     

Ion exchange/adsorption properties of crystalline compound of anatase and rutile

The crystallinely hydrous titanium dioxide, H₄Ti₃O₈, was synthesized by heating amorphous titanium hydroxide at 80°C for 12 hours. XRD, TGA and pH titration were employed to characterize the prepared crystal. The studies on acid, base and radiation stabilities of the crystal demonstrate the reliability of this type of ion exchange material for treating radioactive nuclear wastes. The uranyl ions are so much preferred by the crystal that the complexation of uranyl and chloride ions in solution phase is completely destructed. The uptake of uranium on the crystal is remarkably sensitive to the solution pH. Plot of log/K_D of the uranium on the crystal vs. equilibrium pH generates a series of lines with the mean slope of 0.40, which is the verification of sophisticated loading mechanisms in H/UO ₂ ²⁺ reaction.     

Transformations of hydrated titanium dioxide in hydrothermal treatment

X-ray diffraction analysis, transmission electron microscopy, IR spectroscopy, mass spectrometry, chemical analysis, and thermogravimetry were used to study transformations in the course of a hydrothermal treatment (150–240°C of samples of hydrated titanium dioxide produced by thermal hydrolysis of sulfuric acid solutions of titanium(IV) compounds), in water. The dependences of the dispersion and chemical composition of the samples obtained on the thermal treatment temperature were determined.     

Matrix isolation spectroscopic and theoretical study of carbon dioxide activation by titanium oxide molecules

The reactions of titanium monoxide and dioxide molecules with carbon dioxide were investigated by matrix isolation infrared spectroscopy. It was found that the titanium monoxide molecule is able to activate carbon dioxide to form the titanium dioxide-carbon monoxide complex upon visible light excitation via a weakly bound TiO(η(1)-OCO) intermediate in solid neon. In contrast, the titanium dioxide molecule reacted with carbon dioxide to form the titanium monoxide-carbonate complex spontaneously on annealing. Theoretical calculations predicted that both activation processes are thermodynamically exothermic and kinetically facile.     

Photoinduced dissolution of titanium dioxide by oxalic acid

The photoinduced dissolution of titanium dioxide is observed upon the UV irradiation of aqueous solutions of degassed suspensions of this semiconductor in the presence of oxalic acid. A mechanism is proposed involving the photoinduced and dark dissolution of titanium dioxide with the formation of titanium(III) and titanium(IV) oxalates, respectively.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 29, No. 6, pp. 545–547, November–December, 1994.