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 study of Mn-containing silicate–phosphate glasses

Silicate-phosphate glasses of SiO₂–P₂O₅–K₂O–MgO–CaO system containing manganese cations were investigated to obtain information about the influence of manganese ions on the thermal behavior of such glasses. Amorphous state of glasses and the course of phase transformation and crystallization taking place during their heating were investigated by DSC, XRD, and FTIR methods. It was shown that an increasing content of manganese replacing calcium and magnesium in the structure of analyzed glasses causes decrease of glass transition temperature (T _g) and heat capacity change (Δc _p) accompanying the glass transformation. Simultaneously, thermal stability of the glasses increased. Products of multistage crystallization of glasses containing up to 8 mol% of MnO₂ were: marokite (CaMn₂O₄), phosphate of Ca₉MgK(PO₄)₇ type, and diopside (CaMgSi₂O₆). Product of crystallization of glasses containing higher amount of manganese was braunite (Mn₇O₈SiO₄). This was accompanied by change of structure of magnesium calcium silicates from diopside-type structure to akermanite-type silicates (Ca₂MgSi₂O₇). The data interpretation was based on bonds and chemical interactions of the individual components forming the glass structure.     

Thermal behaviour of Fe-doped silicate–phosphate glasses

Thermal behaviour and structure of glasses from the SiO₂–P₂O₅–K₂O–MgO–CaO system modified by Fe₂O₃ addition were studied by DSC, XRD and FTIR methods. It has been found that the replacement of MgO and CaO modifiers by Fe₂O₃ in the structural network of silicate–phosphate glass results in decrease of the glass transition temperature (T _g) and heat capacity change (ΔC _p) accompanying the glass transformation. Simultaneously, the ability for crystallization, its course and the type of the forming phases depend on the relative proportions between iron and phosphorus as components forming the silicate–phosphate structure. The type of the crystal phases forming in the course of heating the considered glass has been found to be in agreement with the character of the domains occurring in this glass, confirmed by FTIR examinations.     

Effect of copper addition on glass transition of silicate–phosphate glasses

Glass transformation effect of mixed SiO₂?CP₂O₅?CK₂O?CMgO?CCaO?CCuO glasses was studied by DSC, XRD, SEM, and Raman spectroscopy methods. The relationship between the parameters characterizing glass transformation effect and an amount of phosphorous and copper forming the glassy structure was discussed. It was shown that an increasing content of phosphorous increased solubility of copper in the structure of the studied glasses which was the result of P?CO?CCu bonds formation. Degree of changes of T _g, ?c _p, and time of relaxation values were higher in glasses with higher content of P₂O₅ and CuO. The observed relations were explained on the basis of the local atomic interactions in the structure of glass.     

Characterization of thermally induced of crystalline phases in CuO-containing silicate–phosphate glasses

The DSC, XRD, FTIR, and ³¹P MAS-NMR methods were applied to study complex crystallization processes occurring during the thermal treatment of multicomponent SiO₂–P₂O₅–K₂O–CaO–MgO glasses modified by the addition of variable amount of copper. The crystallization temperatures were found to decrease with the increasing copper content. The products of multistage crystallization identified by XRD and characterized by FTIR and NMR are the Ca₉KMg(PO₄)₇ and Ca₁₉Cu₂(PO₄)₁₄ phosphates of whitlockite-type, and the CaMgSi₂O₆ and Cu_0.69Mg_1.31Si₂O₆ silicates of diopside type.     

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).     

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.     

Effect of glass composition on the interactions between structural elements in Cu-containing silicate–phosphate glasses

The structure of silicate–phosphate glasses from the SiO₂–P₂O₅–K₂O–CaO–MgO–CuO system acting as slow release fertilizers, containing different amounts of copper ions replacing magnesium or calcium ions, was examined by DSC, XRD, ³¹P, and ²⁹Si MAS–NMR techniques. The chemical activity of the glasses in the 2 mass% citric acid solution was measured by the ICP-AES method. The studies showed that regardless of the kind of replaced components, the Cu ions prefer to associate with the phosphorous Q¹ units, forming the domains composed of orthophosphate with P–O–Cu bonds. The formation of domains with chemically stable P–O–Cu bonds resulted in poorer glass solubility under conditions simulating the natural soil environment.     

The devitrification of glasses in the binary system SiO2TiO2

The solid solutions series in the system SiO₂TiOP₂ in the vitreous as well as in the devitrified state were investigated by various methods up to 10% by weight TiO₂. The relative intensities of the characteristics infrared absorption bands and of the respective Raman scattering bands about 950 cm⁻¹ reach their maximum at about 4% TiO₂ (by weight).These and other effects observed at this concentration of TiO₂ are discussed in connection with the linking of [SiO₄] and [TiO₄] tetrahedra and with the observed separation of rutile and anatase in small quantities in the devitrification process. A possible sequence of events during the devitrification process in this system is suggested.     

Structural studies of copper-containing multicomponent glasses from the SiO2–P2O5–K2O–CaO–MgO system

Multicomponent glasses from the SiO₂–P₂O₅–K₂O–MgO–CaO–CuO system acting as slow release fertilizers were synthesized by the melt-quenching technique. The influence of CuO and P₂O₅ addition on the structure of glasses was evaluated by FTIR, Raman, ³¹P, and ²⁹Si MAS NMR spectroscopies. The studies showed that the Cu²⁺ ions displacing Ca²⁺ ions and Mg²⁺ ions in the structure of glass prefer to associate with the phosphorus Q¹ species, forming the Q⁰ species with chemically stable POCu bonds. This is accompanied by the reduction of the degree of polymerization of the phospho-oxygen sub-network, with a simultaneous increased degree of polymerization of the silico-oxygen sub-network of the silicate–phosphate glasses.     

Kinetics of nonisothermal crystallization of Cs2O–Fe2O3–P2O5 glasses

The crystallization kinetics of Cs₂O–Fe₂O₃–P₂O₅ glasses containing 12.5–27 mol% Cs₂O were studied by using differential scanning calorimetry under nonisothermal conditions. Strong dependence of activation energy with temperature was observed, indicating the complex nature of the crystallization process. The various crystallization products were identified by X-ray diffraction technique. CsFeP₂O₇ was found to be the major crystalline phase in all cases. The overall activation energy obtained by classical model-free kinetic method was compared with that of isoconversional method; and from the results, the dependence of activation energy on extent of reaction and average temperature was delineated.     

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:...     

Extended study of crystallization kinetics for Se–Te glasses

Crystallization kinetics of chosen compositions from Se–Te glassy system were studied under non-isothermal conditions depending on particle size using differential scanning calorimetry. The purpose of this article is to demonstrate the extent of information accessible by the modern kinetic analysis provided by the differential scanning calorimetry, and to suggest its importance and merit for the development of new, high-tech PCM materials. The crystallization kinetics was described in terms of the nucleation-growth Johnson–Mehl–Avrami model. Complexity of the crystallization process was in this case represented by very closely overlapping consecutive competing surface and bulk nucleation-growth mechanisms. Mutual interactions of both mechanisms as well as all other observed effects were explained in terms of thermal gradients, surface crystallization centers arising from the sample preparation treatments, and changing amount of volume nuclei originating from the combination of pre-nucleation period, and the very glass preparation phase. Accent was laid on the merits resulting from interpretations of characteristic kinetic functions. A new criterion for quick determination of the dominating crystallization mechanism—surface or bulk—was introduced.     

Influence of SrO content on microstructure and crystallization of glazes in the SiO2–Al2O3–CaO–MgO–K2O system

The effect of the SrO addition on the microstructure and structure of the glazes from the SiO₂–Al₂O₃–CaO–MgO–K₂O system was investigated in this study. The results were obtained by testing the ability of the frits crystallization, the stability of the crystallizing phases during the single-step fast-firing cycle depending on their chemical composition and the effect of addition of strontium oxide. Differential scanning calorimetry (DSC) curves showed that all glazes crystallized, and diopside and anorthite were mainly identified as dominant phases in the obtained glazes, while the size and amount of each depended on the amount of SrO introduced. The thermal characteristic of the frits was carried out using DSC, and crystalline phases were determined by X-ray diffractometry. The glaze microstructure was investigated by scanning electron microscopy and transmission electron microscopy. Additional information on the microstructure of frits was derived from spectroscopic studies in the mid-infrared range.

     

Thermal stability of Li2O–SiO2–TiO2 gels evaluated by the induction period of crystallization

To evaluate the thermal stability of materials, various criteria have been used. Not only the simple parameters, as characteristic temperatures, but also the combined criteria E/RT _p , k _f (T) and criterion based on the length of induction period of crystallization have been taken into account. Four gels with the composition Li₂O–2SiO₂–nTiO₂ (n = 0.00, 0.03, 0.062, and 0.1) were prepared and the validity of the criteria was tested by applying them to these gels. The results indicate that thermal stability of the studied gels decrease with amount of TiO₂.     

Melt crystallization of CuFe2S3 in the Cu–Fe–S system

The possibility of melt crystallization of the compound with CuFe₂S₃ composition was established by carrying out quasiequilibrium directional crystallization. The initial liquid had the following composition: Fe 33.3, Cu 16.7, and S 50.0 at.%. The produced sample consisted of three zones with different chemical compositions. The volume fraction of the first zone was 6 %, the second zone was 77 % and the third zone was 17 %. The composition of the first zone corresponded to pyrrhotite solid solution (poss). The second zone had the constant composition CuFe₂S₃. The third zone had variable composition. In the article this zone is not described. We constructed the curves describing the variations in the composition of solid ingot and melt during poss and CuFe₂S₃ crystallization, calculated the distribution coefficients of components, and determined the equation of phase reaction while transferring from the first to the second zone. A polythermal cross-section of phase diagram of the Cu–Fe–S system was built using the directional crystallization and thermal analysis of specially synthesized samples along the crystallization path. It is shown that stoichiometric CuFe₂S₃ compound crystallized from melt and the cross-section of phase diagram along the crystallization path is quasibinary. Thus, liquidus surface of the Fe–Cu–S system contains the region of primary crystallization of CuFe₂S₃, which is located between the crystallization fields of poss and intermediate solid solution.     

The crystallization kinetics of the Bi2O3-added MgO–Al2O3–SiO2–TiO2 glass ceramics system produced from industrial waste

Journal of Thermal Analysis and Calorimetry - Carbon nanotubes (CNTs) with different content of carboxylated groups on their surface (depending on the duration of their treatment with nitric acid)...     

Glass transition and crystallization kinetics analysis of Sb–Se–Ge chalcogenide glasses

Differential thermal analysis (DTA) has been employed to investigate the effect of Ge addition on the glass transition behavior and crystallization kinetics of Sb₁₀Se_90?xGe_x (x = 0, 19, 21, 23, 25, 27) alloys. The three characteristic temperatures viz. glass transition (T _g), crystallization (T _c), and melting (T _m) have been determined and found to vary with the heating rates and Ge content. Thermal stability and glass forming tendency have been evaluated in terms of ΔT (= T _c ? T _g) and reduced glass transition temperature. The activation energies for glass transition and crystallization have been used to analyze the nucleation and growth process. The activation energy analysis also determines the suitability of alloys to be used in switching applications. Results have been interpreted in terms of bond energies and structural transformations in the investigated alloys.