Effect of molybdenum addition on the thermal properties of silicate–phosphate glasses

Aim of the study was analysis of two groups of glasses: silicate?Cphosphate (41?mol.% SiO₂?C6?mol.% P₂O₅) and with inverse phosphate?Csilicate matrix (41?mol.% P₂O₅?C6?mol.% SiO₂) modified by the addition of molybdenum ions. Their effect on glass forming ability, glass transition effect, crystallization process, and kind of crystallizing phases was examined using such methods as DSC, XRD, and SEM. It was found that the solubility limit of MoO₃ in silicate?Cphosphate glasses is 4.4?<?[MoO₃]?<?5.7?mol.%, whereas in phosphate?Csilicate glasses MoO₃ is fully dissolved. It was found that in the case of both matrixes addition of molybdenum ions decreases the glass transition temperature (T _g), as well as the value of specific heat change (?c _p ) accompanying the glass transformation. The presence of molybdenum caused reduced the thermal stability of the studied glasses and a multi-step crystallization of silicate?Cphosphate glasses. It was found that the crystallizing phases were silicates and phosphates in both groups of glasses. Only in the case of silicate?Cphosphate glasses containing MoO₃ in an amount ??3.3?mol.% one of the crystallization product was powellite (CaMoO₄). The nature of transitions taking place during heating of the analyzed glasses was in accordance with crystallochemical factors (strengths of bonds) and chemical affinity of the glass components (?G formation).     

Structure and properties of glasses in the system Li2O–SnO–B2O3

Glasses in the system Li₂O–SnO–B₂O₃ system were prepared by a melt-quenching method. Thermal and viscous properties and local structure of these glasses were investigated. The SnO–B₂O₃ glasses exhibited relatively low glass-transition temperatures (T_g) around 350 °C and excellent thermal stability against crystallization. Viscosity measurements in the vicinity of T_g indicated that the glasses were considerably fragile compared to alkali borate glasses. Fraction of four-coordinated boron was maximized at the composition with 50 mol% SnO and that of nonbridging oxygen, which is not purely ionic in alkali borate systems but partially covalent, augmented with an increase in the SnO content. Correlation between glass properties and structure was discussed in the SnO–B₂O₃ binary system.     

Influence of modifiers and glass-forming ions on the crystallization of glasses of the NaCaPO4–SiO2 system

Silicate?Cphosphate glasses of the XYPO₄?CSiO₂ and XYPO₄?CSiO₂?CAlPO₄ (where X?=?Na⁺ and/or K⁺ and Y?=?Ca²⁺ and/or Mg²⁺) systems have been the subject of the presented investigations. Bioactive glasses from these systems are the base for obtaining glass-crystalline biomaterials through a direct crystallization. However, growth of crystalline phases very adversely affects the bioactivity of the glasses. Uncontrolled growth of crystalline phases can be reduced by means of a glass phase separation phenomenon in the silicate?Cphosphate glasses because boundaries of inclusion-matrix phase may be a barrier limiting the growth of crystalline phases. Microscopic and EDX investigations which have been carried out have shown that glass phase separation occurs in glasses belonging to XYPO₄?CSiO₂ and XYPO₄?CSiO₂?CAlPO₄ systems. Introduction of aluminum ions into the glass structure leads to a rapid homogenization of its texture. Based on DSC examinations it has been found out that crystallization of the glasses of XYPO₄?CSiO₂ systems is a multistep process. The presence of several (the number depends on the type of modifiers and glass-forming ions) clearly separated exothermic peaks in DSC curves of investigated glasses makes it possible to crystallize only the inclusions with the matrix remaining amorphous or vice versa. It has been shown that, crystallization of glasses of XYPO₄?CSiO₂?CAlPO₄ system is single-stage process, which is the consequence of the homogenizing effect of aluminum ions on their texture.     

Thermal properties and structure of zinc–manganese metaphosphate glasses

Journal of Thermal Analysis and Calorimetry - The thermal properties and some physical characteristics of the metaphosphate glassy system xMnO–(50?x)ZnO–50P2O5 were studied....     

Modeling of the thermodynamic properties of lead–tellurium liquid alloys

Application of the Redlich–Kister polynomial with varied number of parameters for describing the concentration dependence of thermodynamic systems of liquid metallic systems with a strong interaction between their components is considered for the example of the lead–tellurium system. Particular attention is given to the range of dilute solutions of tellurium in liquid lead.     

Gamma-ray shielding and structural properties of barium–bismuth–borosilicate glasses

The attenuation coefficients of barium–bismuth–borosilicate glasses have been measured for gamma-ray photon energies of 662, 1173 and 1332 keV using a narrow beam transmission geometry. These coefficients were then used to obtain the values of mass attenuation coefficients, effective atomic number, effective electron density and mean free path. Good agreement has been observed between experimental and theoretical values of these parameters. From the obtained results it is reported here that from the barium–bismuth–borosilicate glasses are better shields to gamma-radiations in comparison to the standard radiation shielding concretes from the shielding point of view. The molar volume, FTIR and acoustic investigations have been used to study the structural properties of the prepared glass system. The obtained results reveal that the formation of non-bridging oxygens occurs at higher concentration of Bi₂O₃.     

Effect of preparation conditions on the composition,structure, and properties of iron–molybdenum catalyst

X-ray phase analysis, synchronous thermal analysis, and IR spectroscopy were used to study the process in which an iron-molybdenum catalyst for partial oxidation of methanol to formaldehyde is prepared. The influence exerted by the pH of the medium on the composition, structure, and properties of the oxide Fe–Mo catalyst was examined. It was found that the amount of the active component in a sample obtained at pH 2 is the largest, and the sample exhibits the best activity in the reaction of methanol oxidation to formaldehyde. The possibility was examined of the occurrence of side reactions in which carbon monoxide is converted. It was found that the conversion occurs only on samples obtained at pH > 2.     

Synthesis and photoreaction mechanism of a novel bifunctional photochromic compound

New functionalized spiroxazine containing azo group has been prepared and its photochromic mechanism has been investigated by laser induced time-resolved techniques.     

Trace measurement of lead and cadmium ions in wastewater samples using a novel dithizone immobilized metal–organic framework-based μ-dispersive solid-phase extraction

A low-cost, reliable, easy-to-perform, sensitive and environmentally friendly metal–organic framework (MOF)-based μ-dispersivesolid-phase extraction (μ-dSPE) method for extraction and graphite furnace atomic absorption spectrometry (GF-AAS) determination of lead and cadmium ions in several wastewater samples was successfully developed. Initially, a zinc-based MOF nanosorbent was prepared, immobilized with appropriate complexing agent dithizone (DTZ), characterized and eventually applied for the simultaneous extraction of the target ions. In practice, the application of the DTZ-based MOF nanosorbent led to improvements in the extraction efficiency. After the extraction of the target ions, the desorption process, which was facilitated with vigorous agitation, was performed by applying a small amount of a desorption solvent (inorganic acid, HNO₃). In the next step, concentrations of the desorbed heavy metal ions were measured using GF-AAS. The parameters influencing the adsorption and desorption efficiencies were thoroughly evaluated followed by the establishment of optimal conditions. Under the optimum conditions, the calibration curves for respective Pb(II) and Cd(II) ions were linear over the concentration ranges 0.5–5.0 and 0.05–2.0 μg l⁻¹. Relative recovery tests on spiked wastewater samples were performed with the results varying between 96% and 103%, whilst the analogous precisions were located in the range 1.8–3.1%. Finally, the μ-dSPE method in conjunction with GF-AAS was demonstrated to be fast, sensitive and cost-effective, and could be potentially used in environmental laboratories for the surveillance of lead and cadmium ions in various wastewater samples.     

Optical and electrochemical properties of novel fused tricyclic thiophene–15-crown-5 systems and their complexes with Mg and Ba ions

New polycyclic aromatic derivatives annulated both with thiophene and with 15-crown-5 ether moieties, crown naphthothiophenes, were synthesized via the Mallory photocyclization with the use of iodine as the mild oxidizer, while two isomeric products were readily separated by column chromatography. Their complexation with Ba²⁺ and Mg²⁺ cations was examined by both optical and electrochemical methods. Spectroelectrochemical studies indicate that the obtained compounds, depending on their structure, can be chemically stable in the oxidized state     

Textural and surface chemistry of activated bagasse and its role in the removal of chromium ions from solution

The role of the surface chemical and physical properties of activated carbon in the removal of chromium was investigated. This was conducted by fitting the chromium removal by adsorption and reduction to Cr(III) to the physical properties including total surface and pore size of the carbon and its chemical property globally measured using carbon pH. The role of heteroatoms—sulfur, nitrogen, hydrogen and oxygen, to chromium removal was also investigated. This study showed that the structural and chemical properties displayed dual and conflicting properties in removing chromium. As such efficiencies gained in controlling the structure of the carbon are minimal. Optimal carbon properties which exhibited high chromium adsorption included high surface area, large pore size, high quantities of sulfur and nitrogen and minimal hydrogen and oxygen contents.     

Kinetic analysis of the crystallization processes in the glasses of the Bi–As–S system

Kinetic analysis of the crystallization process in Bi₄(As₂S₃)₉₆ and Bi₆(As₂S₃)₉₄ glasses was performed based on DSC curves recorded under non-isothermal measurement conditions. Samples were thermally treated at different heating rates in the temperature range 300?C770?K. The activation energy of crystallization E and the pre-exponential factor K ₀ are determined by the Kissinger method and the characteristic crystallization parameters m and n of investigated glasses by the Matusita method. For both crystallization processes the glass with 4 at.% of Bi is characterized by the mechanism of volume nucleation, which is manifested in the form of two-dimensional growth at the first crystallization process, and as three-dimensional at the second one. On the other hand, in the sample with 6 at.% Bi, the average value of the parameter m is close to one, which indicates one-dimensional crystal growth. Compatibility of the values of the parameters m and n suggests that this sample has a large number of crystallization centers, which do not increase significantly during the thermal treatment.     

Thermodynamic properties of lead–sodium–antimony liquid alloys

The thermodynamic properties of lead–sodium–antimony liquid alloys were determined by the emf method. The thermodynamic properties of the edge binary systems, sodium–lead, sodium–antimony, and lead–antimony, were analyzed. The possibility of approximately estimating the thermodynamic properties of the ternary system on the basis of data on the edge binary systems using the simplest geometric models was demonstrated. The sodium-containing alloys show significant negative deviations from the ideal behavior. All the data are given for 900 K.     

Complexation of metal ions with the novel azathia crown ethers carrying anthracene pendant in acetonitrile–dichloromethane

A series of crown ethers carrying an anthracene group with nitrogen–sulfur donor atom, which differ in having three, four and five sulfur atoms in the macrocycle was designed and synthesized by the reaction of the corresponding macrocyclic compound and 9-chloromethyl-anthracene. The influence of metal cations such as Al³⁺, Zn²⁺, Fe²⁺, Fe³⁺, Co²⁺, Ni²⁺, Mn²⁺, Cu²⁺, Cd²⁺, Hg²⁺ and Pb²⁺ on the spectroscopic properties of the ligands was investigated in acetonitrile–dichloromethane (1:1) by means of absorption and emission spectrometry. Absorption spectra show isosbestic points in the spectrophotometric titration of Al³⁺, Zn²⁺, Fe²⁺, Fe³⁺, Cu²⁺, Hg²⁺ and Pb²⁺ the results of which disclosed the complexation compositions and complex stability constants of the novel ligands with these cations. The monoazapentathia crown ether showed sensitivity for Al³⁺ with linear range and detection limit of 2.6 × 10⁻⁶ M–2.6 × 10⁻⁵ M and 8.1 × 10⁻⁷ M, respectively.     

Thermal,mechanical, electrical and thermoelectric properties of Bi–As–Se glasses

Journal of Thermal Analysis and Calorimetry - The effects of natural polyphenol-based thermal stabilizer synthesized from tannin, a flavonoid-type natural polyphenol, on the processing, rheological...     

Thermal properties and crystallization of BaO–MoO3–P2O5 glasses

Journal of Thermal Analysis and Calorimetry - The thermal behavior and crystallization of barium molybdate-phosphate glasses were studied in two compositional series, namely A:...     

Synthesis and photochromic properties of new nonsymmetric dihetarylethenes ?? indole and thiophene derivatives

New nonsymmetric dihetarylethenes were synthesized: 3-(5-methoxy-1,2-dimethyl-1H-indol-3-yl)-4-(3-thienyl)furan-2,5-dione and photochromic 1-alkyl-(1-aryl)-3-(5-methoxy-1,2-dimethyl-1H-indol-3-yl)-4-(3-thienyl)-1(H)-pyrrole-2,5-diones. The absence of benzoannulation in the indole moiety results in the enhancement of the efficiencies of fluorescence and photocyclization of noncyclic isomers compared to the benzoindole derivatives.     

Complexation of metal ions with the novel diazadithia crown ether carrying two anthryl pendants in acetonitrile–tetrahydrofuran

A new crown ether carrying two anthryl groups with nitrogen–sulfur donor atom was designed and synthesized by the reaction of the corresponding macrocyclic compound and 9-chloromethyl anthracene. The influence of metal cations such as Al³⁺, Zn²⁺, Fe²⁺, Fe³⁺, Co²⁺, Ni²⁺, Mn²⁺, Cu²⁺, Cd²⁺, Hg²⁺ and Pb²⁺ on the spectroscopic properties of the ligand was investigated in acetonitrile–tetrahydofuran solution (1/1) by means of absorption and emission spectrometry. Absorption spectra show isosbestic points in the spectrophotometric titration of Fe²⁺, Fe³⁺, Al³⁺, Cu²⁺ and Hg²⁺. The results of spectrophotometric titration experiments disclosed the complexation stoichiometry and complex stability constant of the novel ligand with Fe²⁺, Fe³⁺, Al³⁺, Cu²⁺and Hg²⁺cations. The presence of excess amounts of Al³⁺, Zn²⁺, Fe²⁺, Fe³⁺, Co²⁺, Ni²⁺, Mn²⁺, Cu²⁺, Cd²⁺, Hg²⁺ and Pb²⁺ cations caused an enhancement of anthryl fluorescence. The ligand showed good sensitivity for Zn²⁺ with respect to other metal cations with linear range and detection limit of 1.4 × 10^?7 to 4.1 × 10^?6 M and 1.0 × 10^?8 M respectively.