Effect of nucleating agents on the crystallization of Li<Subscript>2</Subscript>O-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> system glass

The processes of nucleation of Li₂O-Al₂O₃-SiO₂ glasses with TiO₂ and TiO₂+ZrO₂ as nucleating agents were discussed. The DTA peak temperature and DTA peak height shown a strong dependence on the nucleation temperature in the glass with TiO₂, while in the glass with TiO₂+ZrO₂ this tendency was small. The optimum nucleation temperatures were 745 and 760°C for two glasses. It suggested that with TiO₂+ZrO₂ as nucleating agents, the crystallization had lower sensitivity for nucleation temperature, and the glass had higher nucleation efficiency than with TiO₂.     

CO<Subscript>2</Subscript> adsorption and dehydration behavior of LiNaX,KNaX, CaNaX and CeNaX zeolites

In this study, NaX synthetic zeolite was modified by following the conventional cation exchange method at 70°C. 82, 81, 79 and 48% of sodium were exchanged with Li⁺, K⁺, Ca2⁺ and Ce3⁺, respectively. Thermal analysis data obtained by TG/DSC was used to evaluate the dehydration behavior of the zeolites. The strongest interaction with water and the highest dehydration enthalpy (ΔH) value were found for Li-exchanged form and compared with the other forms. The temperature required for complete dehydration increased with decreasing cation size (cation size: K⁺>Ce³⁺>Ca2⁺>Na⁺>Li⁺). CO₂ adsorption at 5 and 25°C was also studied and the virial model equation was used to analyze the experimental data to calculate the Henry’s law constant, K _o and isosteric heat of adsorption at zero loading Q _st. K _o values decreased with increasing temperature and the highest Qst was obtained for K rich zeolite. It was observed that both dehydration and CO₂ adsorption properties are related to cation introduced into zeolite structure.     

Thermal behaviour and properties of Na<Subscript>2</Subscript>O-TiO<Subscript>2</Subscript>-P<Subscript>2</Subscript>O<Subscript>5</Subscript> glasses

Differential scanning calorimetry (DSC) and thermomechanical analysis (TMA) were used to study the thermal behaviour of (50-x)Na₂O-xTiO₂-50P₂O₅ and 45Na₂O-yTiO₂-(55-y)P₂O₅ glasses. The addition of TiO₂ to the starting glasses (x=0 and y=5 mol% TiO₂) resulted in a nonlinear increase of glass transition temperature and dilatation softening temperature, whereas the thermal expansion coefficient decreased. All prepared glasses crystallize under heating within the temperature range of 300–610°C. The contribution of the surface crystallization mechanism over the internal one increases with increasing TiO₂ content. With increasing TiO₂ content the temperature of maximum nucleation rate is also gradually shifted from a value close to the glass transition temperature towards the crystallization temperature. X-ray diffraction measurements showed that the major compounds formed by glass crystallization were NaPO₃, TiP₂O₇ and NaTi₂(PO₄)₃. The chemical durability of the glasses without titanium oxide is very poor, but with the replacement of Na₂O or P₂O₅ by TiO₂, it increases sharply.     

Influence of B<Subscript>2</Subscript>O<Subscript>3</Subscript> on the structure and crystallization of soil active glasses

Glasses of the SiO₂–P₂O₅–K₂O–MgO–CaO–B₂O₃ system acting as nutrients carriers in the soil environment were synthesised by the melt-quenching technique. Thermal properties were studied using DTA/DSC methods and the influence of B₂O₃ and P₂O₅ content on thermal stability and crystallization process of these glasses was examined. The structure of the glass network was characterized by FTIR, ³¹P, and ¹¹B MAS NMR. The chemical activity of the glasses in the 2 mass% citric acid solution was measured by the ICP-AES method. The analysis indicated that the formation of P–O–B units with chemically stable tetrahedral borate groups decreases the glass solubility in conditions simulating the soil environment.     

pH-sensing properties of PbO<Subscript>2</Subscript> thin film electrodeposited on carbon ceramic electrode

In this paper, a new highly sensitive potentiometric pH electrode is proposed based on the solid-state PbO₂ film electrodeposited on carbon ceramic electrode (CCE). Two different crystal structures of PbO₂, α and β were examined and the similar results were obtained. Moreover, the experimental results obtained for the proposed pH sensor and a conventional glass pH electrode were in good agreement. The electromotive force (emf) signal between the pH-sensitive PbO₂-coated CCE and SCE reference electrode was linear over the pH range of 1.5–12.5. Near-Nernstian slopes of −64.82 and −57.85 mV/pH unit were obtained for α- and β-PbO₂ electrodes, respectively. The interferences of some mono-valence and multi-valence ions on potentiometric response of the sensor were studied. The proposed pH sensor displayed high ion selectivity with respect to K⁺, Na⁺, Ca²⁺, and Li⁺, with log values around −12 and has a working lifetime of about 30 days. Key parameters important for the pH sensor performance, including kind of PbO₂ film, selectivity, response time, stability, and reproducibility, have been characterized. The proposed electrode showed a good efficiency for direct pH-metry after calibration and pH-metric titrations without calibration step. The response time was about 1 s in acidic medium and less than 30 s in alkaline solutions. The pH values of complex matrix samples such as fruit juices measured by the proposed sensor and a conventional glass pH electrode were in good agreement.     

Eu<Superscript>3+</Superscript>-fluorescence properties in nano-crystallized SnO<Subscript>2</Subscript>-SiO<Subscript>2</Subscript> glass-ceramics

Fluorescence and spectral hole burning properties of Eu³⁺ ions were studied in nanocrystals-precipitated SnO₂-SiO₂ glasses. The glasses were prepared to contain various amount of Eu₂O₃ using the sol-gel method, in which SnO₂ nanocrystals were precipitated by heating in air. In the glasses containing Eu₂O₃ less than 1%, the Eu³⁺ ions were preferentially doped in the SnO₂ nanocrystals and their fluorescence intensities were enhanced by the energy transfer due to the recombination of electrons and holes excited in SnO₂ crystals. The SnO₂ nanocrystals-precipitated glasses exhibited the persistent spectral holes with the depth of ∼25% of the total fluorescence intensities of the Eu³⁺ ions. With the increasing Eu₂O₃ concentration, the amount of SnO₂ nanocrystals decreased and the Sn⁴⁺ ions formed the random glass structure together with the silica network. This structure change induced the fluorescence intensities and the hole depth to decrease.     

Local structure and photoluminescent characteristics of Eu<Superscript>3+</Superscript> in ZnO–SiO<Subscript>2</Subscript> glasses

The photoluminescence properties of xZnO–(100−x)SiO₂ (x = 0, 5, 10, 20) containing 1% Eu₂O₃ prepared by a sol–gel method were systematically investigated. The results indicated that the relative proportion of f–f transitions to charge transfer (CT) absorption decreased with the increase of ZnO concentration. The intensity of ⁵D₀–⁷F_J transitions of Eu³⁺ ions was enhanced with the increase of ZnO content due to local structure changes and decreased quantities of Eu³⁺ ions clusters. The results of fluorescence line narrow (FLN) spectra indicated that Eu³⁺ ions occupied one site in SiO₂ glass and two sites in ZnO–SiO₂ glasses. The second-order crystal field parameters were calculated. B₂₀ and B₂₂ for site 1 increased with excitation energy, while ones hardly changed for site 2.     

Interaction energies of histidine with cations (H<Superscript>+</Superscript>, Li<Superscript>+</Superscript>, Na<Superscript>+</Superscript>, K<Superscript>+</Superscript>, Mg<Superscript>2+</Superscript>, Ca<Superscript>2+</Superscript>)

The imidazol side group of histidine has two nitrogen atoms capable of being protonated or participating in metal binding. Hence, histidine can take on various metal-bound and protonated forms in proteins. Because of its variable structural state, histidine often functions as a key amino acid residue in enzymatic reactions. Ab initio (HF and MP2) calculations were done in modeling the cation (H⁺, Li⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺) interaction with side chain of histidine. The region selectivity of metal ion complexation is controlled by the affinity of the side of attack. In the imidazol unite of histidine the ring nitrogen has much higher metal ion (as well as proton) affinity. The complexation energies with the model systems decrease in the following order: Mg²⁺ > Ca²⁺ > Li⁺ > Na⁺ > K⁺. The variation of the bond lengths and the extent of charge transfer upon complexation correlate well with the computed interaction energies.     

Cation binding by 2<Superscript>1</Superscript>,3<Superscript>1</Superscript>-diphenyl-l <Superscript>2</Superscript>,4<Superscript>2</Superscript>-dioxo-7,10,13-trioxa-1,4(3,1)-diquinoxalina-2 (2,3),3(3,2)-diindolizinacyclopentadecaphane and its acyclic analog

The binding of cations Li⁺, Na⁺, K⁺, Cs⁺, Ag⁺, Zn²⁺, Ni²⁺, Co²⁺, NH₄ ⁺ (group I), H⁺, Mg²⁺, Al³⁺, Ga³⁺ (group II), and Ca²⁺, Pb²⁺ (group III) by 2¹,3¹-diphenyl-l ²,4²-dioxo- 7,10,13-trioxa-l,4(3,1)-diquinoxalina-2(2,3),3(3,2)-diindolizinacyclopentadecaphane (1), which contains two indolizine and two quinoxaline fragments and 3,6,9-trioxaundecanes spacer, and by its acyclic analog (2) was studied using cyclic voltammetry in MeCN/0.1 M Bu₄NBF₄. It was concluded that the ions of group I are not bound by these compounds, the ions of group II exhibit the reversible redox-switched binding by the carbamoyl groups of the quinoxaline fragments, whereas the ions of group III are bound not only by the initial compounds and radical cations 1 and 2, but also by dication 1. This binding of the Ca²⁺ and Pb²⁺ ions stabilizes dication 1.     

Influence of the exchangeable cations on SO<Subscript>2</Subscript> adsorption capacities of clinoptilolite-rich natural zeolite

The sulfur dioxide adsorption on clinoptilolite-rich tuff from Bigadiç region of Western of Turkey and its modified forms (Na⁺, K⁺, Ca²⁺ and Mg²⁺) have been studied at 273 K and 293 K up to 100 kPa. The structural properties of clinoptilolites were studied by X-ray diffraction (XRD) and Fourier transform infrared (FT-IR). The quantitative XRD analysis demonstrated that the Natural-B sample is mainly constituted by clinoptilolite (80–85%) with minor contents of quartz (7–8%), feldspar (5–6%) and mica-illit (4–5%). It was found out that the adsorption capacity and the affinity of SO₂ with clinoptilolite samples depended mainly on the type of exchanged cations and decreased as Na-B > K-B > Mg-B > Natural-B > Ca-B for both temperature. These results show that clinoptilolite-rich zeolites are considered potentially good adsorbents for SO₂ removal.     

Chemical durability of MoO<Subscript>3</Subscript>-P<Subscript>2</Subscript>O<Subscript>5</Subscript> and K<Subscript>2</Subscript>O-MoO<Subscript>3</Subscript>-P<Subscript>2</Subscript>O<Subscript>5</Subscript> glasses

Thermal and chemical durability studies of the phosphate glasses belonging to the binary MoO₃-P₂O₅ and the ternary K₂O-MoO₃-P₂O₅ systems are reported. The chemical resistant attack tests carried out on the free alkaline MoO₃-P₂O₅ glasses show that the glass associated with the P/Mo ratio 2 has the high chemical durability. It shows also a high glass transition temperature value. The above findings are interpreted in terms of the cross-link density of the glasses and the strength of the M-O bonds (M=P, Mo). The influence of K₂O addition on the properties (density, T _g, durability) of this binary high water resistant glass is studied. It is found that the chemical durability along with the other physical properties are reduced by the incroporation of K₂O in the glass matrix. The results were explained by assuming the formation of non-bridging oxygens and weak bonds. The mechanism of the dissolution of these glasses is proposed.     

The effect of PO<Subscript>2,5</Subscript> and AlO<Subscript>1,5</Subscript> additions on structural changes and crystallization behavior of SiO<Subscript>2</Subscript>-TiO<Subscript>2</Subscript> sol-gel derived glasses and thin films

SiO₂-TiO₂-PO_2,5 (STP) and SiO₂-TiO₂-AlO_1,5 (STA) glasses were prepared by sol-gel processing. Their infrared absorption spectra (IR), differential thermal analysis curves (DTA) and X-ray diffraction patterns (XRD) have been recorded. In the SiO₂-TiO₂ system, the chemical homogeneity of the sol-gel glass could be evaluated by the relative concentration of Si-O-Ti heterocondensation comparing to Si-O-Si homocondensation. For the STA system, a gradual decrease of the Si-O-Ti/Si-O-Si band ratio (based on IR spectra) with the addition of Al₂O₃ is observed, with the simultaneous formation of Si-O-Al and Ti-O-Al bounds, i.e Al₃ ⁺ ions are dissolved in the SiO₂-TiO₂ glass matrix and do not promote glass-in-glass phase-separation in the composition range of 0–15 mol% AlO_1.5. In the STP system, on the other hand, P=O bond IR stretch in the ternary glasses indicates that P=O free PO₂O_2/2 ⁻ tetrahedra are formed, rather than the double bonded POO_3/2 tetrahedra that usually occur in binary SiO₂-P₂O₅ glasses. It can be concluded that SiO₂-TiO₂-P₂O₅ glass separates into a SiO₂-rich phase and a TiO₂(P₂O₅)-rich phase. During heat-treatment in STA system only anatase precipitates, even at T ~ 1,000 °C, while in for STP, anatase (TiO₂) or (TiO)₂P₂O₇ (TOP) crystals precipitate at ~600 °C, depending on the P₂O₅ concentration. The major crystal phase, cristobalite, precipitated at ~1,000 °C and at ~1,200 °C, the P-containing phase melts.     

Determination of the enthalpy of fusion of Na<Subscript>3</Subscript>FeF<Subscript>6</Subscript>

The areas of the fusion and crystallization peaks of Na₃FeF₆ and of four calibration substances (KCl, NaCl, Na₂SO₄, and K₂SO₄) were measured using the DSC mode of a high-temperature calorimeter. Using the measured quantities and known values of the enthalpy of fusion of the calibration substances, the enthalpy of fusion of Na₃FeF₆ was determined. Its value at the temperature of fusion 1224 K was 70 ± 4 kJ mol⁻¹.     

Physicochemical properties and mixed electronic and ionic conduction of composite ceramics in the system ZrO<Subscript>2</Subscript>-Bi<Subscript>2</Subscript>CuO<Subscript>4</Subscript>-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>

Composites ZrO₂-(Bi₂CuO₄+ 20 wt % Bi₂O₃) (50–80 vol % ZrO₂) are synthesized and their physicochemical properties are studied. It is demonstrated that the composites comprise triple-phase mixtures of ZrO₂ of a monoclinic modification, Bi₂CuO₄, and solid solution Bi_2?x Zr _x O_{3 + x/2} and retain their mechanical strength up to 800°C. Impedance spectroscopy is used to examine their electroconductivity at 700–800°C in the interval of partial oxygen pressures extending from 37 to 2.1 × 10⁴ Pa. Contributions made by electronic and ionic constituents to their overall conductivity are evaluated. The best specimens’ conductivity is ～0.01 S cm^?1, with the electronic and ionic transport numbers nearly equal. The composite consisting of 50 vol % ZrO₂ and 50 vol % (Bi₂CuO₄ + 20 wt % Bi₂CuO₄) is tested in the role of an oxygen-separating membrane. The selective flux of oxygen in the temperature interval 750–800°C amounts to (2.2–6.3) × 10^?8 mol cm^?2 s^?1, testifying that these materials may be used as gas-separating membranes.     

Osmotic Coefficients of the Li<Subscript>2</Subscript>B<Subscript>4</Subscript>O<Subscript>7</Subscript>+LiCl + H<Subscript>2</Subscript>O System at <Emphasis Type="Italic">T</Emphasis>=273.15 K

Osmotic coefficients and water activities for the Li₂B₄O₇+LiCl+H₂O system have been measured at T=273.15 K by the isopiestic method, using an improved apparatus. Two types of osmotic coefficients, φ _S and φ _E, were determined. φ _S is based on the stoichiometric molalities of the solute Li₂B₄O₇(aq), and φ _E is based on equilibrium molalities from consideration of the equilibrium speciation into H₃BO₃,B(OH)₄⁻ and B₃O₃(OH)₄⁻. The stoichiometric equilibrium constants K _m for the aqueous speciation reactions were estimated. Two types of representations of the osmotic coefficients for the Li₂B₄O₇+LiCl+H₂O system are presented with ion-interaction models based on Pitzer’s equations with minor modifications: model (I) represents the φ _S data with six parameters based on considering the ion-interactions between three ionic species of Li⁺, Cl⁻, and B₄O₇²⁻, and model (II) for represents the φ _E data based on considering the equilibrium speciation. The parameters of models (I) and (II) are presented. The standard deviations for the two models are 0.0152 and 0.0298, respectively. Model (I) was more satisfactory than model (II) for representing the isopiestic data.     

Synthesis characterization and catalytic evaluation of Ni/ZrO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> aerogels catalysts

The Ni/ZrO₂/SiO₂ aerogels catalysts were synthesized via three different routes: (i) impregnation ZrO₂–SiO₂ composite aerogels with a aqueous solution of Ni(NO₃)₂, (ii) impregnation SiO₂ aerogels with a mixed aqueous solution of Ni(NO₃)₂ and ZrO(NO₃)₂ · 2H₂O, (iii) one-pot sol–gel procedure from precursors Ni(NO₃)₂/ZrO(NO₃)₂ · 2H₂O/Si(OC₂H₅)₄. These catalysts were characterized by X-ray diffraction (XRD), temperature-programmed reduction (TPR), ammonia temperature-programmed desorption (NH₃-TPD), N₂ adsorption–desorption isotherms and Fourier transform infrared (FT-IR). The Liquid-phase hydrogenation of maleic anhydride (MA) was performed over these catalysts. The results revealed that the different preparation routes result in a difference between the obtained samples, concerning the crystal structure and composition, surface acidity, mixed level of each component, texture, and catalytic selectivity.     

Ion-exchange selectivity of a network calixarene-containing polymer obtained by the template synthesis on Na<Superscript>+</Superscript>, K<Superscript>+</Superscript>, and Ba<Superscript>2+</Superscript> matrices

The ion-exchange equilibrium in network polymers obtained from cis-2,8,14,20-tetraphenyl-4,6,10,12,16,18,22,24-octahydroxycalix[4]arene by template synthesis on cations Na⁺, K⁺, and Ba²⁺ as matrices was studied. The selectivity coefficients of ion exchanges Ba²⁺-H⁺, Na⁺-H⁺, K⁺-H⁺, Na⁺-K⁺, and Na⁺-NH₄ ⁺ were determined. The template synthesis enhanced the affinity of the polymers to matrix-forming cations by 6–8 kJ mol⁻¹. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1919–1922, August, 2005.     

Ultrastructural and Intracellular Chemical Changes of a Novel Halophilic Strain V430 of <Emphasis Type="Italic">Staphylococcus saprophyticus</Emphasis> under CaCl<Subscript>2</Subscript> Stress

Observation of the ultrastructural and intracellular chemical changes of CaCl₂-tolerant strains is important both for understanding their adaptation mechanism under high salt stress and for providing theoretical basis of their application in treating high-CaCl₂ wastewaters. A novel strain V 430 isolated by us has been successfully used to decrease the chemical oxygen demand (COD) concentration of diosgenin wastewater from 20 g l⁻¹ to less than 0.5 g l⁻¹. For this study, strain V430 was incubated in culture media of different CaCl₂ concentrations (up to 9.0%). Strain V430 cells incubated in media of high CaCl₂ concentration excreted extracellular substances and accumulated intracellular Ca²⁺ and K⁺ and free amino acids. The levels of intracellular cations and free amino acids increased with increase in CaCl₂ concentration of the medium. The increase in total free amino acids was mostly due to accumulation of glutamic acid. The strain cells under 9.0% CaCl₂ stress took up K⁺ in a short time, while accumulation of Ca²⁺ proceeded over the whole growth process.     

Ionenselektive Coated Glass-Elektroden

Zusammenfassung Na⁺-, K⁺-, NH ₄ ⁺ - und Ca²⁺ selektive coated glass-Elektroden wurden entwickelt, bei denen eine ionenselektive Carrier-PVC-Membran auf eine ionenselektive Glasschicht aufgebracht wird, die über einen Innenelektrolyten mit der Ableitelektrode in Verbindung steht. Die Selektivität wird durch die aufgebrachte Carrier-PVC-Membran bestimmt, die zusätzlich Weichmacher zur Optimierung der Eigenschaften enthält.

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Ion-selective coated glass electrodes

Summary Na⁺, K⁺, NH ₄ ⁺ and Ca²⁺ selective electrodes have been developed by coating the ion-selective glass layer with a carrier PVC membrane. The glass is in contact with the conducting electrode through an inner electrolyte. The selectivity is determined by the PVC membrane, containing neutral carriers or electrically charged ligands and additionally plasticizers for optimizing the properties.

Dir Arbeit wird vom Bundesministerium für Forschung und Technologie der Bundesrepublik Deutschland gefördert.Prof. Dr. W. Simon stellte freundlicherweise die synthetischen neutralen Carrier für Na⁺ und Ca²⁺ zur Verfügung.     

Viscosity and shrinkage of porous and quartzoid glasses of the Na<Subscript>2</Subscript>O-B<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> system

Shrinkage of porous glasses on heating from 20 to 800°C was studied and temperature dependences of the viscosity in the range of 10¹¹–10¹³ P were determined for quartzoid (sintered) glasses based on five glasses with different compositions in the Na₂O-B₂O₃-SiO₂ system. The shrinkage of porous glasses and the viscosity of quartzoid glasses were analyzed in relation to their composition and temperature of preliminary thermal treatment.