Influence of fluorine on thermal properties of lead oxyfluoride glass

Oxyfluoride glasses are the basic materials for obtaining transparent glass–ceramic (TGC) which can be used in a wide range of optoelectronics devices such as: amplifiers, up-conversion, telescopes, laser sources. Oxyfluoride TGC is obtained by the control heat treatment of the parent glass due to low phonon nanocrystalline phases. The oxyfluoride glasses from the sodium–lead–silica system were the object of investigation. The influence of fluoride content on the thermal properties of glasses was analyzed. Thermal characteristics of glasses like the transition temperature T _g, the temperature for the crystallization onset T _x, and the maximum crystallization temperature T _c, thermal stability parameter were determined by DTA/DSC method. The linear expansion coefficients of oxyfluoride glasses as a function of temperature were measured using a thermo-mechanical analyzer (TMA 7 Perkin-Elmer). The effect of crystallization on the thermal expansion coefficient and softening temperature T _s was found.     

Effect of reversible structural relaxation on diffusion in bulk metallic glasses

Long time relaxation at temperatures below the calorimetric glass transition causes reversible structural changes in metallic glasses. The resulting enthalpy recovery was measured by means of DSC in Zr_46.8Ti_8.2Cu_7.5Ni₁₀Be_27.5- and Pd₄₀Cu₃₀Ni₁₀P₂₀-bulk glass annealed for different times at 553 K and 542 K, respectively. Relaxation times of about 10⁶ s and 10⁴ s, respectively, were determined. The diffusion coefficients of B, Fe and Co were measured above and below the calorimetric glass transition temperature. Whereas the temperature dependence of these diffusion coefficients in the non-relaxed glasses shows “non-linear” Arrhenius behaviour with a break near the glass transition, the diffusion in the long time relaxed glasses follows a uniform temperature dependence over the entire temperature range with considerably reduced diffusion coefficients below the glass transition. This behaviour can be reversed by annealing the relaxed glasses again at higher temperatures indicating the strong effect of the reversible structural relaxation on the diffusion coefficients.     

Kinetics of non-isothermal crystallization in Cu50Zr43Al7 and (Cu50Zr43Al7)95Be5 metallic glasses

The crystallization kinetics of Cu₅₀Zr₄₃Al₇ and (Cu₅₀Zr₄₃Al₇)₉₅Be₅ metallic glasses was studied using differential scanning calorimetry (DSC) at four different heating rates under non-isothermal condition. The glass transition temperature T _g, the onset temperature of crystallization T _x, and the peak temperature of crystallization T _p of the two metallic glasses were determined from DSC curves. The values of various kinetic parameters such as the activation energy of glass transition E _g, activation energy of crystallization E _p, Avrami exponent n and dimensionality of growth m were evaluated from the dependence of T _g and T _p on the heating rate. The values of E _g and E _p, calculated from many different models, are found to be in good agreement with each other. The average values of the Avrami exponent n are (2.8 ± 0.4) for Cu₅₀Zr₄₃Al₇ metallic glass and (4.2 ± 0.3) for (Cu₅₀Zr₄₃Al₇)₉₅Be₅ metallic glass, which are consistent with the mechanism of two-dimensional growth and three-dimensional growth, respectively. Finally, the parameter H _r, S, and crystallization enthalpy ΔH _c are introduced to estimate the glass-forming ability and thermal stability of metallic glasses. The result shows that the addition of Be improves the glass-forming ability and thermal stability of Cu₅₀Zr₄₃Al₇ metallic glass.     

Differential scanning calorimetry of semiconducting As-Se glasses containing Sb

The compositional dependence of the glass transition temperature (T _g), and the temperature of the maximum rate of crystallization (T _p) of As-Se glasses containing Sb has been measured using non-isothermal DSC. The variation of these characteristic temperatures is found useful in interpreting the structural changes in As-Sb-Se glasses. The role of Sb in these glasses and its effect on the crystallization characteristics is analyzed.     

Sodium and silver phosphate glasses doped with chlorides of Fe,Mn and Zn

A number of samples of sodium and silver phosphate glasses doped with various compositions of some transition metals viz. iron, manganese and zinc chlorides alongwith undoped samples of sodium and silver phosphate glasses were synthesized and characterized by X-ray diffraction, IR spectral, electrical conductivity and differential scanning calorimetry (DSC). The glass transition temperature (T _g) and crystallization temperature (T _c) values obtained from DSC curves were found to increase with increasing concentration of the dopant Fe/Mn/Zn chlorides in both sodium and silver phosphate glasses and the following sequence is observed: T _g(–FeCl₃)>T _g(–MnCl₂)>T _g(–ZnCl₂) T _c(–FeCl₃)>T _c(–MnCl₂)>T _c(–ZnCl₂) The increase in T _g and T _c values indicate enhanced chemical durability of the doped glasses. The electrical conductivity values and the results of FTIR spectral studies have been correlated with the structural changes in the glass matrix by the addition of different transition metal cations as dopants.     

Is the DSC technique capable of determining accurate specific heats of metallic ribbons?

Using the scanning (differential) method and a PE DSC in continuous heating regime as well as the integral (enthalpic) method and a SETARAM DSC in a discontinuous heating regime the specific heats of several metallic glassy ribbons were measured. The linearc _p M(T) dependencies in the as-quenched, relaxed and also the stable crystalline forms of the ribbons in the medium temperature region were found. The room temperature specific heats of these ribbons, the excess contributions due to the relaxed glassy state as well as the non-relaxed glassy state were determined.The sensitivity ofc _p M(T) measurements of metallic ribbons was better than 0.2%, the long term reproducibility in the case of glassy ribbons was 2%. They are related to the errors inc _p M(T) measurements of synthetic sapphire standard or bulk chalcogenide glasses.

---

Zusammenfassung Unter Anwendung des Scanning- (Differential-) Verfahrens und einem PE DSC in kontinuierlichen Heizsystemen sowie des Integral- (Enthalpie-) Verfahrens und einem SETARAM DSC in diskontinuierlichen Heizsystemen wurde die spezifische Wärme diverser metallisch-glasartiger Bänder gemessen. Im abgeschreckten, entspannten Zustand und auch in den kristallinen Formen der Bänder konnte in der mittleren Temperaturregion eine linearec _p M(T) Abhängigkeit gefunden werden. Sowohl die spezifischen Wärmen dieser Bänder bei Raumtemperatur, der zusätzliche Beitrag im entspannten glasartigen Zustand als auch im nichtentspannten glasartigen Zustand wurden bestimmt. Die Empfindlichkeit beic _p M(T)-Messungen metallischer Bänder war besser als 0.2%, die Langzeitreproduzierbarkeit betrug im Falle glasartiger Bänder 2%. Sie wurden auf die Fehlergrö\en vonc _p M(T)-Messungen an einem synthetischen Saphir-Standard oder an massiven Chalkogenidgläsern bezogen.

     

Brillouinspectroscopic investigations of the ferroelectric phase transition in a Polyvinylidenefluoride — Trifluoretylene copolymer

The hypersonic and thermal behaviour of mechanically oriented and electrically poled random copolymers of vinylidenefluoride and trifluoroethylene (70 mol % / 30 mol %) has been investigated by Brillouin spectroscopy and Differential Scanning Calorimetry (DSC) around the glass transition temperatureT _g and the ferroelectric transition temperatureT _c . From the DSC measurements it appears that a further structural transition may exist in the vicinity ofT _c . The influence of poling and annealing the samples on the elastic stiffness constants at room temperature has been studied. Appropriate sound velocity polar plots are compared. Both glass and ferroelectric transtitions are clearly seen in acoustic behaviour and are discussed from the view point of the degree of crystallinity and disorder, respectively.On leave of absence from Institute of Physics, Czech. Acad. Sci., Praha, Czechoslovakia.     

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.     

Non-isothermal crystallisation kinetics study on Se90−xIn10Sbx (x = 0, 1, 2, 4, 5) chalcogenide glasses

The non-isothermal crystallisation kinetics of Se_90?xIn₁₀Sb_x (x = 0, 1, 2, 4, 5) chalcogenide glasses prepared by a conventional melt quenching technique was studied using the differential scanning calorimetry (DSC) measurement at different heating rates 5, 7, 10 and 12 °C min^?1. The values of the glass transition temperature T _g and the crystallisation temperature T _c are found to be composition and heating rate dependent. The activation energy of glass transition E _g, Avrami index n, dimensionality of growth m and activation energy of crystallisation E _c have been determined from different models.     

Excess entropy and thermal behavior of Cu- and Ti-doped bioactive glasses

Bioactive glasses belong to the ceramic family. They are good materials for implantation due to their excellent capacities to create an intimate bond with bones. Copper is known for its anti-inflammatory, antibacterial, and antifungal properties. Titanium is biocompatible and resistant to corrosion. These chemical elements can be introduced in bioactive glasses to provide a wide variety of uses and to enhance the physiological properties of implanted biomaterials. In this work, bioactive glasses doped with different contents of copper and titanium were synthesized by the melting method. The purpose is to study the effect of doping metal element on the thermal characteristics (T _g, T _c, and T _f). The results revealed that the increase of the content of copper and titanium in the glass matrix decreases the melting temperature and induces an increase of the thermal stability. The excess entropies of pure and doped glasses were calculated. Obtained results highlighted the decrease of the excess entropy with the increase of metal elements contents.     

StepScan DSC

StepScan DSC technique was used for the study of the glass transition phenomenon. This method allows relatively good monitoring of reversing and non-reversing processes, and thus is very useful tool for glass transition studies of wide type of glass-forming materials, including inorganic glasses as well as organic polymers. In this work, experience with the StepScan DSC technique is summarized. Some interesting results of its application are presented, such as determination of glass transition temperature independent on thermal history of glass, discovered relationship between the slope of temperature dependence of C _p in T _g, and Angel’s index of fragility and estimation of viscosity glass transition temperature, T _g,η.     

Kinetics of phase transition and thermal stability in Se80?x Te20Zn x (x?=?2, 4, 6, 8, and 10) glasses

Se_80?x Te₂₀Zn _x (x?=?2, 4, 6, 8, and 10) glasses have been prepared using conventional melt quenching technique. The kinetics of phase transformations (glass transition and crystallization) have been studied using differential scanning calorimetry (DSC) under non-isothermal condition at five different heating rates in these glasses. The activation energy of glass transition (E _t), activation energy of crystallization (E _c), Avrami exponent (n), dimensionality of growth (m), and frequency factor (K _o) have been investigated for the better understanding of growth mechanism using different theoretical models. The activation energy is found to be highly dependent on Zn concentration. The rate of crystallization is found to be lowest for Se₇₀Te₂₀Zn₁₀ glassy alloy. The thermal stability of these glasses has been investigated using various stability parameters. The values of these parameters were obtained using characteristic temperatures, such as glass transition temperature T _g, onset crystallization temperature T _c, and peak crystallization temperature T _p. In addition to this, enthalpy-released during crystallization has also been determined. The values of stability parameters show that the thermal stability increases with the increase in Zn concentration in the investigated glassy samples.     

Thermal behaviour and excess entropy of bioactive glasses and Zn-doped glasses

Bioactive glasses prepared in SiO₂–CaO–Na₂O and P₂O₅ system are used as biomaterials in orthopaedic and maxillofacial surgery. Zn presents high physiological interest. It enhances physiological effects of implanted biomaterials. In this work, the thermal characteristics (T _g, T _c and T _f) of pure bioactive glass elaborated with different amounts of CaO, Na₂O in pure glass and with different amounts of introduced Zn in glass (ranging from 0.1 to 10 in mass%), were studied. The excess entropy was calculated for different compounds. Glasses were prepared by the melting process. The thermal behaviour of obtained bioactive glasses was determined using differential thermal analysis. Therefore, the glass transition (T _g), the crystallization (T _c) and the melting temperatures (T _f) were revealed. Moreover, according to Dietzel formula, the thermal stability (TS) of the studied bioactive glasses has been calculated. The first results concerning the impact of different oxides, revealed a decrease of the TS, T _g, T _c and T _f when the SiO₂/CaO increases and revealed an increase of these thermal characteristics when the SiO₂/Na₂O and CaO/Na₂O ratios increase. Introducing Zn into the bioactive glasses induces a decrease of T _f and an increase of TS. Contrary to crystals, prepared glasses have entropy different to zero at T = 0 K and vary versus T _f. The excess entropy of pure glasses and Zn-doped glasses were calculated. The significant variations were registered.     

First-order phase transformation and structural studies in Se<Subscript>85</Subscript>In<Subscript>15−x</Subscript>Zn<Subscript>x</Subscript> chalcogenide glasses

Present research work describes the crystallization kinetics and structural studies in Se₈₅In_15?xZn_x chalcogenide glasses. Bulk alloys of Se₈₅In_15?xZn_x were synthesized by melt-quenching procedure. High resolution X-ray diffraction (HRXRD) was used to confirm the amorphous nature of synthesized samples. Non-isothermal differential scanning calorimetry (DSC) measurements were performed at 5, 10, 15, 20 and 25 K min^?1 heating rates to study kinetics of crystallization in Se₈₅In_15?xZn_x. Various crystallization parameters such as glass transition (T _g), onset crystalline (T _c), peak crystallization (T _p) and melting temperature (T _m) were calculated from DSC curves. The activation energies of structural relaxation (ΔE _t) and crystallization (ΔE _c) were determined by using Kissinger, Moynihan and Ozawa approaches. ΔE _t is found to be the lowest for Se₈₅In₆Zn₉ sample which shows this sample has the highest probability of escape to a state of lower configurational energy and has greater stability. Thermal stability of various compositions was studied and found to vary with Zn content. Further, HRXRD and field emission scanning electron microscope were used for the study of first phase transformation in Se₈₅In_15?xZn_x samples.     

Investigation of structural and thermal characteristics of PVDF/ZnO nanocomposites

The structural and thermal behavior of PVDF/ZnO nanocomposites have been investigated by employing scanning electron microscopy (SEM),TEM, DSC, powder X-ray diffraction (XRD), thermally stimulated discharge current (TSDC), and transient current techniques. SEM/TEM observation indicated the homogeneous dispersion of functionalized ZnO nanoparticles throughout PVDF matrix. DSC shows that the crystallinity is influenced by the presence of ZnO nanoparticles in the PVDF matrix because the filler acts as efficient nucleating agent to facilitate PVDF crystallization. DSC results indicated the enhancement of the glass transition temperature (T _g), melting temperature (T _m) and crystallization temperature (T _c) of nanocomposites compared to pristine PVDF. XRD shows that the full-width at half maximum decreases with increasing ZnO content, which is attributed to the improvement in crystallinity. The incorporation of ZnO nanoparticles influences the modification of polarization process in PVDF as observed by means of TSDC and transient current study.     

Unusual recrystallization and melting behaviour in DSC scans of isotactic polypropylene samples

The unusual dependence of the melting peak temperature of the species recrystallized during DSC scans on the isothermal crystallization temperature (T _c ) is discussed for isotactic polypropylene samples. It is pointed out that such a phenomenon is not due to superheating effects; it is believed to be accounted for by assuming that the rates of the recrystallization phenomena at the same temperature are higher for samples obtained at higherT _c values.     

The glass transition

This work deals with a comparison of data obtained from differential scanning calorimetry (DSC) and thermally stimulated depolarization current (TSDC) investigations. Measurements were performed on various poly(ethylene terephthalate) films: a wholly amorphous, a thermally crystallized and drawn samples. For each specimen, the TSDC complex spectra, resolved into elementary ones, led to the determination of the classical compensation temperature (T _c ). The glass transition temperature (T _g) and the fictive equilibrium temperature (T _f) were determined by means of DSC. It appears thatT _c is different fromT _g and very close toT _f.     

Thermal anomaly in LiKSO4 crystals in the temperature range 300–800 K

Thermal analysis, DTA, TG, TMA and DSC were performed on LiKSO₄ in the temperature range 300 to 800 K, using a Heraeus TA 500 thermal analyser. The thermal expansion coefficients measured along the three fundamental crystallogrpahic axes, together with the specific heatC _p, show anomalous behaviour around the phase transition temperature of these crystals atT _c=705 K. Anisotropy in the thermal expansion coefficient as well as endothermic peaks aroundT _c were also observed, while no loss of weight was detected. The temperature-dependence of the thermal conductivity of LiKSO₄ crystals has been estimated, using the temperature-variation of the thermal diffusivity.     

The kinetics of phase transitions in vitreous chalcogenide semiconductors As10.2Se89.8 and As9Se90Bi in early stage of physical ageing process

The kinetics of glass transition in selenide glasses As_10.2Se_89.8 and As₉Se₉₀Bi in early stage of physical ageing process has been investigated by parallel differential scanning calorimetry (DSC) and exoelectron emission (EEE). It has been found that the glass transition process occurring in investigated glasses is evidenced by peaks on EEE intensity and DSC curves. Admixture of bismuth causes a distinct lowering of the temperature of glass transitions process both in the surface layer and in the volume. The addition of Bi causes a decrease in the value of the activation energy for glass transition process in both the volume and in the surface layer, thus reducing the thermal stability of investigated glasses. Physical ageing in Se-rich chalcogenide glasses leads to a significant increase of endothermic peak area A, temperature of glass transition T _g and decrease of the activation energy value E. All these effects are strongly dependent on glass composition.     

A simple method of evaluating non-isothermal crystallization kinetics in multicomponent polymer systems

A new simple method of evaluating non-isothermal crystallization kinetics is proposed. The procedure based on mathematical treatment of DSC cumulative crystallization curves at their inflection point provides three kinetic parameters: temperature of start of crystallization (T_s), temperature of maximum crystallization rate (T_i) and numerical value of the maximum crystallization rate (s_i), and also final crystallinity after cooling (CR_c). The method is demonstrated on the system poly(ɛ-caprolactone)/poly(lactic acid)/clay C15 and related microfibrillar composite. The method provides the values of T_s and T_i with standard deviation σ = 0.3 and 0.4 °C, respectively. The coefficient of variation v of s_i and CR_c is 5.8 and 1.5%, respectively. The proposed method does not refer to any crystallization model and does not require exact determination of the starting time. It is particularly useful for characterizing a series of samples derived by modification of the neat polymer.