Thermal Decomposition and Crystallization of Aqueous Sol-Gel Derived Zirconium Acetate Gels: Effects of the Additive Anions

Zirconia powders were prepared by forming gels by desiccation of aqueous precursor solutions of zirconium acetate containing nitric or sulfuric acid at pH 2.4 and 1.4 and pyrolyzing the gels to temperatures up to 825°C. The structure development in the gels and solid pyrolysis products was investigated. The crystalline zirconia structures produced monoclinic (m), metastable cubic (c) and tetragonal (t) polymorphs. The structure transition temperatures were strongly dependent on the pH, the anions and the stoichiometry of the zirconium complex in the precursor solution. The monoclinic polymorph fraction in the zirconia formed by pyrolyzing the gel formed from the precursor solution containing sulfuric acid at pH 2.4 to 750°C approaches zero while this ratio in the zirconia formed by pyrolyzing the gel formed from the precursor solution containing nitric acid at pH 1.4 to 825°C is 0.7.     

Tribological behaviors of DLC films in sulfuric acid and sodium hydroxide solutions

Tribological behaviors of three typical kinds of diamond-like carbon (DLC) films (a-C, a-C:Cr, and a-C:H) in sulfuric acid and sodium hydroxide solutions were investigated. The a-C film showed the lowest stable coefficients of friction (COF) in both sulfuric acid and sodium hydroxide solutions but the worst wear resistance in sulfuric acid solution. The a-C:H film showed the highest COF in sulfuric acid solution and the best wear resistance in both sulfuric acid and sodium hydroxide solutions. The a-C:Cr film exhibited superior comprehensive tribological performance in sulfuric acid solution, while in sodium hydroxide solution, high COF and very poor wear resistance was observed. What is more, friction and wear mechanism was revealed by investigating the friction-induced material evolutions on the sliding surface.     

Monochromatized x‐ray photoelectron spectroscopy of the AM60 magnesium alloy surface after treatments in fluoride‐based Ti and Zr solutions

The behaviour of the 6% aluminium–magnesium alloy (AM60) surface in zirconium or titanium fluoride aqueous acid solutions was studied. X‐ray photoelectron spectroscopy was used to investigate modifications in the surface chemistry with respect to the composition of the surface treatment solution. The surface film is composed of magnesium hydroxide and hydroxyfluoride, zirconium oxide, oxyhydroxide or oxyfluoride, titanium oxide and structural and adsorbed water. Optimal parameters leading to the formation of a zirconium‐ or titanium‐rich film were determined. A mechanism is proposed for the formation of zirconium‐ or titanium‐based films. Copyright © 2005 John Wiley & Sons, Ltd.     

Thermal Decomposition and Crystallization of Aqueous Sol-Gel Derived Zirconium Acetate Gels: Effects of the Precursor Solution pH

Crystalline zirconia has previously been formed by desiccation and pyrolysis of a pH 3.4 zirconium acetate precursor solution. In this study, amorphous gels were formed by desiccation of zirconium acetate precursor solutions at pH 0.9 to 3.4 obtained by adding hydrochloric acid and at pH 8.0 by adding ammonium hydroxide to the available pH 3.4 precursor solution. The concentrations of the uncomplexed zirconium ion and the 1 : 1 and 1 : 2 zirconium acetate complexes varied with pH. Decomposition of the amorphous gel and its structure evolution to form crystalline zirconia by pyrolysis were studied. Several decomposition and structure transition temperatures occurring in the pyrolysis and the polymorph distribution in the pyrolysis products were dependent on the pH of the precursor solution. These variations of structure evolution with pH were also related to the relative concentrations of specific zirconium complexes in the precursor solutions. Removal of carbon by pyrolysis was improved by adding hydrochloric acid or ammonium hydroxide to the pH 3.4 precursor solution.     

固体超强酸SO2-4/ZrO2的制备及其催化性能研究

以氧氯化锆为锆原,氨水为沉淀剂,硫酸溶液为浸渍液,通过沉淀-浸渍法制备SO2-4/ZrO2(SZ)酯化催化剂,其结构经BET、X-射线衍射(XRD)、傅立叶变换红外光谱(FT-IR)及扫描电子显微镜(SEM)表征.结果表明:随着焙烧温度升高,催化剂的比表面积依次降低,孔径增大,氧化锆的晶态由无定形态转化为四方晶态再转化为单斜晶态;于600℃焙烧时,催化剂形成的S=O键红外吸收峰最强;于700℃焙烧时,催化剂结构被破坏.在丙烯酸与十八醇的酯化反应中对催化剂进行活性测试.结果表明:600℃焙烧的催化剂产率最高(96.4%).     

Sine-wave polarographic determination of zirconium or niobium in aqueous media

The sine-wave polarographic determination of zirconium in aqueous media was investigated using solutions which were 0.55 – 5.5·10^-3M in zirconyl chloride and 1 M in potassium chloride and had been adjusted to pH 2.0 with hydrochloric acid. It was possible to determine zirconium in the concentration range of 0.05 to 0.4 mg per ml. The sine-wave polarographic behavior of zirconium in aqueous solutions in the pH range 2–3 is discussed. The sine-wave polarographic determination of niobium in aqueous media was investigated using concentrated sulfuric acid containing 5 to 0.1 mg of niobium per ml in a supporting electrolyte of citric acid; the determination of niobium was possible down to 0.1 mg of niobium per ml of concentrated sulfuric acid although the D.C. polarographic method was impractical for the determination of less than 0.5 mg of niobium per ml.     

Extraction of metal ions with a primary amine

This paper describes some experimental results obtained at the extraction of sulfate solutions of U(VI), Mo(VI), V(V), Ce(IV), Zr(IV), Fe(III), Al(III) with a benzene solution of Primene JMT. The aqueous solutions consist of metal sulfates (or other metal salts) in the presence of sulfuric acid with a concentration range of 0–2.1 mol·dm^–3, the concentration of amine in the organic phase being 0.1–0.3 mol·dm^–3. The presence of various species of metal ions in the aqueous phase is considered and the equilibrium concentration of substances extracted in the organic phase is determined. On the basis of the results of chemical analysis (concentration of metals and sulfate ions) the composition of the prevailing complexes in the organic phase is proposed.     

Vinylacetylene chemistry

It is shown that heating vinylacetylenic piperidols I with phosphorus oxychloride in pyridine solution gives dienynes II, the structure of which is determined, in the case of II (R=H), by means of IR spectra and PMR. Hydration of the dienynes II (R=H, Me) in the presence of mercuric sulfate in methanol solution gives -methoxyketones III (R=H, Me). It is also shown that III and aqueous solutions of ammonia or primary amines give the bicyclic piperid-4-ones IV. In the synthesis of IV (R=H, R₁ = i-Pr, Bu) imines V are obtained, which on hydrolysis give piperidones IV (R = H, R₁ = i-Pr, Bu). When the ß-methoxyketone III (R = H) is heated with 5% sulfuric acid in the presence of mercuric sulfate, chroman-4-one is formed.     

Synthesis and properties of noncyclic polyether compounds. Part V : The influence of acid and concentration of cations on the uphill transport rates of cations and selectivities through liquid membranes by synthetic,noncyclic polyether ionophores

The effects of acid and cation concentration on the uphill transport rates of cations and selectivities through chloroform liquid membrane by noncyclic polyether ionophores, which are pentaethylene glycol derivatives containing both 8-quinolyt and o-carboxylphenyl terminal groups, have been demonstrated. Using sulfuric, oxalic, or polyphosphoric acid in aqueous solution, the initial transport rates and the amount of cation transported by the ionophores after two days were larger than those using hydrochloric or nitric acid. Using picric acid, the amount of cation transported decreased greatly. It was confirmed that it decreased where an acid could easily be counter-transported by the ionophore through liquid membranes. On the other hand, it was found that the rates, amounts of cation transported, and selectivities, change with the changing of the cation concentration in the aqueous solutions. When the cation concentration in both aqueous solutions is high enough compared with the pH gradient between the two aqueous solutions, the rate, amount, and selectivity of the ionophore for potassium ion increases compared with when the cation concentration is low.     

Structure of zirconium butoxide complexes in n-butanol solutions

EXAFS and SAXS were used for structure elucidation of zirconium butoxide complexes in n-butanol at concentrations from 0.3 g to 0.015 g ZrO₂ in 1 ml. The basic structural unit of the complex is a tetramer. It has two equal sides with zirconium atoms linked by double oxygen bridges and with zirconium-zirconium distances of 3.5 Å. The other sides in the tetramer are 3.3 Å and 3.9 Å. This difference in bond lengths is explained by the different numbers of double or single ligand bridges between zirconium atoms. The tetramers are apt to undergo oligomerization to form particles with a diameter of 80 Å in solution.     

Colloidal and chemical aspects of nanosized hydrated zirconium dioxide synthesized via a sol-gel process

The processes of coagulation and gelation of sols in zirconium oxychloride aqueous solutions and the properties of hydrated zirconium dioxide sols (pH, particles size, dynamic viscosity) depending on the aging conditions of partially neutralized zirconium oxychloride feedstock solution-zirconyl hydroxychloride used for the synthesis and molar ratio of initial reagents (Zr/NaOH, Zr/CH(3)COO(-)) were first studied in the paper. The concentration and temperature limits of hydrated zirconium dioxide sols stability were determined. The coagulation constant, gelation activation energy, and gelation thermal effect values were found.     

Diffusion in aqueous copper sulfate and copper sulfate-sulfuric acid solutions

Diffusion coefficients of copper sulfate-water and copper sulfate-sulfuric acid-water solutions have been determined at 25°C using conductimetric and diaphragm-cell techniques. The ternary diffusion measurements indicate that diffusion of sulfuric acid can produce large counterflows of copper sulfate and vice versa. If diffusion of copper sulfate in aqueous sulfuric acid solutions is treated as a binary process, the measured apparent diffusivities of copper sulfate can be 1 to 8% lower than the salt's true diffusivity. Equations are developed to predict transport coefficients from the concentrations and mobilities of the diffusing species.     

Esterification of aliphatic hydroxy acids to n-propyl esters in aqueous solutions for their gas chromatographic analysis

Summary Aliphatic hydroxy acids were esterified in aqueous solution in the presence of different amounts of sulfuric acid. Esterification of lactic, tartronic, malic and citric acids in water/n-propanol mixtures with mole ratios between 0.03 and 2.15 can be utilized for the determination of these acids by gas chromatography. Water does not interfere at water/n-propanol mole ratios below 0.03. For mole ratios above 0.03 anhydrous sodium sulfate is used for the binding of water. The mole ratio range was 0.24–2.13 for anhydrous sodium sulfate/water, and 0.16–1.28 for sulfuric acid/anhydrous sodium sulfate.     

Effect of Chemical Modification on Hydrolysis and Condensation Reaction of Zirconium Alkoxide

Chemical modification effect of acetic acid was examined to control the hydrolysis and following condensation reaction of zirconium alkoxide. When acetic acid was added to zirconium alkoxide solution, acetic acid coordinated to a zirconium alkoxide to form a stable bidentate chelating compound if molar ratio of acetic acid to zirconium alkoxide (here after abbreviated as RA) was less than two. In the case of simultaneous addition of acetic acid and water into a zirconium alkoxide solution, acetic acid immediately reacted with alkoxide. Water reacted with residual functional alkoxy groups to proceed the following condensation. Changing the degree of chelating the acetic acid to a zirconium alkoxide led to the control of the hydrolysis and condensation by decreasing the alkoxy groups of zirconium alkoxide. Polymeric transparent monolithic gels could be successfully prepared in the range from RA = 1 to RA = 1.5, and from RW = 1 to RW = 1.5 (here RW means molar ratio of water to zirconium alkoxide), respectively.     

Esterification of aliphatic hydroxy acids to n-butyl esters in aqueous solutions for their gas chromatographic analysis

Summary Aliphatic hydroxy acids were esterified in aqueous solution in the presence of sulfuric acid. Esterification of lactic, tartronic malic and citric acids in water/n-butanol mixtures with mole ratios between 0.02 and 2.53 can be utilized for the determination of these aliphatic hydroxy acids by gas chromatography. Water does not interfere at water/n-butanol mole ratios below 0.02. For mole ratios above 0.02 anhydrous sodium sulfate is used for the binding of water. The mole ratio range was 0.25–2.53 for anhydrous sodium sulfate/water, and 0.32–1.27 for sulfuric acid/anhydrous sodium sulfate.     

The determination of zirconium in its binary alloys with niobium and tantalum

A procedure is presented for the determination of zirconium in the presence of niobium or tantalum. The bulk of the niobium or tantalum is first removed by extracting with hexone from a 10M hyclrofluoric acid, 6M sulphuric acid solution of the sample. The zirconium is then. separated from any unextractcd earth, acid element by precipitation with ammonium hydroxide followed by the addition of hydrogen peroxide. Under these conditions, both the niobium and tantalum form soluble peroxy complexes whereas the zirconium is completely precipitated from solution. After the separation of the precipitate by filtration, it is re-dissolved in hydrochloric acid and the zirconium concentration is finally determined by titration with ethylenediaminetetraacetic acid.     

Sodium sulfate solubilities in high temperature aqueous sodium chloride and sulfuric acid solutions—predictions of solubility,vapor pressure,acidity, and speciation

Experimental measurements of the solubility of sodium sulfate in aqueous solutions containing both sodium chloride and sulfuric acid in the temperature range 250 to 374°C are reported. These measurements have been combined with previous data on the solubility of sodium sulfate in water, in aqueous sodium chloride, and in sulfuric acid solutions to produce a comprehensive model describing the solubility of sodium sulfate in such solutions. Calculations and predictions of solubility, vapor pressure, boiling point elevation, acidity, and speciation are presented. This model is of fundamental interest in itself and also is of importance because the precipitation of sodium sulfate may be a contributing factor in enhancing crevice corrosion in metals exposed to high-temperature water containing chloride and sulfate ions as impurities.     

Aqueous Chemistry of Zirconium(IV) in Carbonate Media

The interactions between carbonate ions and zirconium oxychloride are studied by potentiometry, dialysis, and ¹³C‐ and ¹⁷O‐NMR spectroscopy in aqueous media. The nature of the soluble carbonatohydroxo complexes depends on the proportions of hydrogencarbonate and carbonate ions in solution before the addition of zirconium oxychloride. Carbonate media lead to polynuclear entities containing no more than two complexed carbonate ions per Zr⁴⁺. The presence of hydrogencarbonate favors the formation of less condensed and more carbonated complexes such as [Zr(CO₃)₄]⁴⁻. The polycondensation degree of the species decreases when the number of carbonates linked per Zr⁴⁺ increases. In all complexes, the carbonate is bidentate, and the metal atoms are linked via hydroxo bridges. The complexation of carbonate with Zr⁴⁺ occurs for a total carbonate concentration higher than 0.1M . Consequently, in natural medium, the speciation of this metal is governed only by the formation of hydroxo complexes.     

Esterification of C2−C16 dicarboxylic acids to n-butyl esters in aqueous solutions for their gas chromatographic analysis

Summary C₂–C₁₆ dicarboxylic acids were esterified in aqueous solution in the presence of sulfuric acid. Esterification in water/n-butanol mixtures with mole ratios between 0.02 and 2.53 can be utilized for the quantitative determination of the dicarboxylic acids by gas chromatography. The presence of water does not interfere at water/n-butanol mole ratios below 0.27. For mole ratios above 0.27 anhydrous sodium sulfate has been used for binding the water. The mole ratio range was 0.25–0.75 for anhydrous sodium sulfate/water, and 0.32–1.3 for sulfuric acid/anhydrous sodium sulfate.