Nucleation and crystallisation kinetics of a Na-fluorrichterite based glass by differential scanning calorimetry (DSC)

The present paper shows the results of a nucleation and crystallisation study of a Na-fluorrichterite glass carried out by dynamic scanning calorimetry (DSC). The kinetic study was performed using different procedures (Kissinger, Matusita–Sakka and Kissinger–Akahira–Sunose (KAS) methods), and the Avrami parameter was determined from the Ozawa and Malek approximations and the Malek equation. The results have indicated the coexistence of surface and bulk crystallisation in the devitrification process of the studied glass. The kinetic study has shown that the activation energy of the crystallisation process is over 400 kJ/mol and that the mechanism proposed is a Johnson–Mehl–Avrami mechanism with n equal to 3, which implies that the crystallisation develops through the three-dimensional growth of crystals. The study of the variation of the activation energy with crystallisation using the KAS method has shown that the crystallisation process undergoes a multiple step mechanism, where the main part of the whole process corresponds to the three-dimensional growth of crystals. The mechanism proposed was confirmed by applying the Pérez-Maqueda et al. criterion.     

Effects of LiPO3 glass crystallisation

The LiPO₃ glass crystallisation has been investigated with calorimetry, scanning electron microscopy, optical microscopy and X-ray powder diffraction. It was discovered that the crystallisation at a given temperature depends on the thermal prehistory of the sample. It is shown that the cooled samples can change over the course of several hours. From the microphotographs, it is clear that the surface crystallisation mechanism is predominant for this glass. The velocities of the crystallisation front expansion for 425, 440, 460 °C are 4.9, 18.6 and 34.5 μm/min, respectively.     

Synthesis of celsian ceramics from zeolite precursors

A novel low temperature technique has been developed for the synthesis of celsian glass-ceramics. The technique involves ion exchange of zeolites, their subsequent heat treatment to form a glassy phase from which celsian is crystallized. Monoclinic celsian was produced at temperatures as low as 1000°C at heat treatment times of 6 h.     

Fluoride-containing bioactive glass-ceramics

Fluorapatite glass-ceramics are osteoconductive, and glass-ceramics containing fluorapatite crystals in a bioactive silicate glass matrix can combine the benefits of fluorapatite with the bone-regenerative properties of bioactive glasses. High phosphate content (around 6 mol% P₂O₅) bioactive glasses (SiO₂–P₂O₅–CaO–Na₂O–CaF₂) were prepared by a melt-quench route. Structural investigation using density measurements and calculations confirmed the presence of phosphorus as orthophosphate. Upon heat treatment, the glasses crystallised to mixed sodium calcium fluoride orthophosphates (sodium-containing compositions) and fluorapatite (sodium-free composition). Fluoride suppressed spontaneous crystallisation, allowing formation of glass-ceramics by controlled crystallisation. A notable feature is that silicate network polymerisation and network connectivity did not change during crystallisation, resulting in orthophosphate and fluorapatite crystals embedded within a bioactive glass matrix. By keeping the phosphate content high and the sodium content low, fluorapatite glass-ceramics can be obtained, while not affecting the structure of the bioactive silicate glass phase.     

The annealing of alkaline-earth metal polymetaphosphate powders (I). Crystallisation and sintering processes

Amorphous barium, strontium, calcium and magnesium polymetaphosphate powders (MP₂O₆)_n, n = 20 were prepared by dehydration of the corresponding polymetaphosphate hydrate precipitates. These powders were annealed by different continuous and isothermal heat treatments over the temperature range 450° to 700 °C, the glass transition temperatures T_g to above (T_g + 120) °C. The morphologies at different degrees of crystallisation were studied by scanning electron microscopy. For the main crystallisation process (ten to sixty-seventy percent crystallisation), the powder particles retained their original pea-pod form; then after seventy percent crystallisation, these crystallised particles sintered laterally to lozenge-shaped twin-hexagonal crystals of lengths 0.5 to 3 μm. Differential thermal analysis confirmed that a markedly exothermic crystallisation process (overall enthalpy changes from about 30 to 45 kJ mol⁻¹) was occurring within the powder particles. Crystallisation rates varied from < 0.005 min⁻¹ at temperatures near T_g to > 0.5 min⁻¹ at higher temperatures; the activation energies for this process varied from 360 to 560 kJ mol⁻¹. The completely annealed crystals were studied by scanning electron microscopy, X-ray diffraction and further differential thermal analysis to 1000 °C. The X-ray diffraction d value patterns, the fusion temperatures and the enthalpies of fusion were all in close agreement with the literature values for the corresponding beta alkaline-earth metal polymetaphosphates prepared by melt crystallisation.     

Crystallisation kinetics,glass forming ability and thermal stability in glassy Se100 − xInx chalcogenide alloys

Differential scanning calorimetry (DSC) studies have been done under non-isothermal conditions at different heating rates for glassy Se_100 ? xIn_x (5 ≤ x ≤ 20) alloys. DSC traces with well-defined endothermic and exothermic troughs and peaks at glass transition (T_g), crystallisation (T_c) and melting (T_m) temperatures were observed. The crystallisation kinetics parameters, Avrami index (n), activation energy for crystallisation (E_c) and frequency factor (K_o), have been calculated on the basis of the classical Johnson–Mehl–Avrami (JMA) model and related methods derived by Kissinger, Augis–Bennett and Mahedevan. Activation energy for glass transformation (E_t) has been evaluated on the usual two different non-isothermal methods developed by Moynihan and Kissinger. An extension of the Augis–Bennett method well known for evaluating E_c to calculate E_t has been explored with satisfactory results. Results obtained from these methods are in close agreement with each other. Close correlation between E_t, E_c and heating rate (β) was observed. The glass forming ability (GFA) and thermal stability parameters have been calculated for each glass system. It was found that the proportion of indium additive changed significantly the values of glass/crystal transformation, GFA and thermal stability of the studied system.     

X-ray scattering studies of the short and medium range ordering in AsxTe1−x glasses

The structures of As_xTe_1−x(x = 0.2, 0.4, and 0.5) glasses are studied using the differential X-ray anomalous scattering technique. The partial distribution functions have also been obtained for the stoichiometric As₂Te₃ glass, giving information on the medium range ordering. All the glasses show chemical disorder to differing extents, the As₂Te₃ glass being the most disordered. The Te coordination number undergoes a change at x=0.4 where it is 2.5 compared with 2 for AsTe. This change indicates the existence of about 50% of threefold Te sites in the stoichiometric glass, as well as in the Te-rich glasses. Some of the physical properties of the glasses may be explained based on these results.     

Effect of V2O5 addition on the crystallisation of glasses belonging to the CaO–ZrO2–SiO2 system

The crystallisation of CaO–ZrO₂–SiO₂ glasses doped with V₂O₅ (0.1–5 mol%) has been investigated in terms of microstructure and thermal parameters. Results indicate that crystallisation is predominantly controlled by a surface nucleation mechanism, even though a partial bulk nucleation has been encountered in compositions containing more than 2 mol% of doping oxide. As detected from differential thermal analysis curves, glass transition temperature and crystallisation temperature, are strongly dependent upon V₂O₅ content varying from 0.0 to 2.0 mol%, while the crystallisation activation energy values decrease with a parabolic trend from B-glass (0.0 mol% V₂O₅ content, 495±7) to V-0.7 (0.7 mol% V₂O₅ content, 420±6) composition, increasing again to 442±5 kJ/mol K with higher amount of V₂O₅. The microstructure of the glass-ceramic materials clearly showed a marked dependence upon the amount of V₂O₅, also due to the presence of phase separation for content higher than 0.7 mol%. Wollastonite, CaO·SiO₂, and a calcia–zirconia–silicate, 2CaO·4SiO₂·ZrO₂, are the main crystalline phases whose ratio slightly varies with vanadium oxide content. The glass ceramics obtained from the studied materials are greenish and bluish coloured, so it is possible to use the studied glasses as coloured frits for tile glazes.     

Molecular dynamics simulation for the rapid solidification process of MgO–Al2O3–SiO2 glass–ceramics

A molecular dynamics simulation method was used to study the effects of the microstructure on the solidification process of different cooling rates in the MgO–Al₂O₃–SiO₂ glass–ceramics with cordierite as the main crystalline phase. The reasons for changes in the microstructure during the solidification process were analysed by the radial distribution function curve, the bond angular distribution, the coordination number and the volume changes. The results showed that the cooling rate greatly affected the crystallisation process and the glass transition process. When the cooling rate was too fast, the atoms could not undergo a massive displacement before they were “frozen”, and the ability of atoms to achieve an equilibrium position was limited. Some amorphous phases were formed as a result of the disorder of the atomic arrangement, then some crystalline phase precipitated from the vitreous, and a glass–ceramic material was eventually formed.     

Mechanisms controlling primary crystallisation of Ga20Te80 glasses

The kinetic study of the crystallisation process of Ga₂₀Te₈₀ glass from isothermal and continuous heating calorimetric data have been performed applying a recently developed procedure. The kinetic information was complemented with X-ray diffraction measurements. With this scope, three crystallisation patterns, with three-dimensional isotropic growth have been analysed: (i) site saturation and interface controlled growth. (ii) homogeneous nucleation with interface controlled growth and (iii) homogeneous nucleation with two simultaneous modes of crystal growth (interface- and diffusion-controlled). A complex model with two simultaneous modes of three-dimensional isotropic crystal growth with decreasing homogeneous nucleation and soft impingement has been applied for modelling primary crystallisation of the Ga₂₀Te₈₀ glass. The model goes beyond the isokinetic hypothesis when coupling isothermal and continuous heating kinetic data. The apparent activation energy E_a = (2.06 ± 0.03) eV/at obtained for the primary crystallisation of the phase Te is shown to correspond to an activation energy for nucleation E_I = (2.85 ± 0.03) eV/at and an interface controlled activation energy for growth E_u = (1.90 ± 0.03) eV/at at the crystallisation onset.     

TEM Investigation of Stacking Faults in the Superconducting Compound YNi2B2C

To evaluate the influence of composition and high-temperature heat treatment on the occurrence of stacking faults and intergrowths in the layered superconducting compound YNi₂B₂C a series of polycrystalline samples and a single crystal were investigated by TEM. Stacking faults were found in the most inhomogeneous sample only, which was annealed at 1100°C. Homogenisation at temperatures of 1450°C and higher results in a recovery of stacking faults. The observed faults should develop during crystallisation by formation of extra planes of YC or Ni₂B, resulting in a local deviation from the stoichiometric composition. In highly faulted areas the distance of stacking faults was about 50nm. These faults have apparently no influence on the superconduction transition temperature T_c.     

Bulk crystallisation of (00l) oriented fresnoite Sr2TiSi2O8 in glass-ceramics of the Sr-Ti-Si-K-B-O system

This paper shows that glass-ceramics containing highly surface and bulk preferentially oriented fresnoite Sr₂TiSi₂O₈ crystals can be synthesised by a simple isothermal heat treatment of suitable glass compositions in the Sr-Ti-Si-K-B-O system. For all tested compositions, crystallisation starts from the free surfaces of the specimens and propagates to bulk with time. If most of these compositions lead to (00l) preferential orientation at the specimens' surfaces, bulk crystal texture is very composition dependent. The effects of variation in K₂O and B₂O₃ contents on the crystallisation have been studied. It is shown that low K₂O and high B₂O₃ contents are required to keep the (00l) orientation from the surface into the bulk. This result seems to be explained by the viscosities of the initial and residual glasses at the temperature of crystallisation: a low viscosity leads to a fine and homogeneous microstructure with small and strongly (00l) bulk oriented crystals.     

New AlDy(Ni,Co) glasses - the influence of pre-aging on decomposition and modelling of the crystallisation

The decomposition of AlDy₆Ni₁₀ and AlDy₈Ni₆Co₂ glasses prepared by melt spinning after different pre-aging regimes was investigated. The modelling of the transformation at the glass transition and the crystallisation was tested by a more general Johnson-Mehl-Avrami-Kolmogorov model and by the determination of the local kinetic parameter. The relaxation was tested with an lnt kinetic model after Gibbs.     

Untersuchung der Ausscheidungsverhältnisse von schmelzgegossenen hochaluminiumoxidhaltigen feuerfesten Materialien

The relation between the conditions of crystallisation and grain texture of fused refractory bricks with high contents of aluminium oxide ist investigated. The results make clear that bricks with small contents of a glass phase have to becooled down slowly, thus avoiding a strongly disturbed growth of the corundum crystals in larger areas of the brick. A fast solidification process caused by rapid cooling does not result in a defined growth of dendrites and in the formation of a stable equilibrium state.     

Study on local structure in amorphous SbS films by Raman scattering

A stoichiometric Sb₄₀S₆₀ film contains SbSb and SS bonds in addition to SbS bonds in an SbS₃ unit. The amount of the SbSb bond rapidly decreases with an increase in the S content beyond the stoichiometric value. On the other hand, as the S content decrease beyond the stoichiometric value, the SbS bond decreases and the SbSb bond increases. Annealing at temperatures near the glass transition decreases the fraction of the SbSb bond in the Sb₄₀S₆₀ film.     

Sintering process of glasses in the system Na2O-B2O3-SiO2

In this work, the sintering process of different glasses in the system Na₂O-B₂O₃-SiO₂ has been studied. The studied compositions are suitable for sealing the gas manifolds of molten carbonate fuel cells. Sealing glasses are usually applied on the surfaces to be sealed using powder glass mixed with an organic medium. The agglomerant elimination and the sintering of the glass powder take place during the thermal treatment. Three different particle sizes of glass powder and different sintering temperatures and times have been used to reveal the influence of the specific surface area and viscosity on sintering. The control of these parameters allows optimization of the sealing conditions of the glasses. Dense materials have been characterized as well as the sintering mechanism. Two processes take place during the thermal treatment: the sintering process and the quartz crystallisation. Both processes act in opposite directions on the glass densification. Crystallisation is the dominant process at long times and high temperatures. The viscous flow Scherer model has been adequately applied to the experimental data.     

Effect of heat treatment on the optical absorption of tin diselenide thin films

Optical absorption measurements were made on tin diselenide thin films grown on glass substrates by thermal evaporation of stoichiometric bulk compound. In the as-deposited films, optical absorption was dominated by an indirect transition at lower photon energies with a band gap of 1.4 eV. The direct allowed transition with a band gap of 1.62 eV was predominant at higher energies. Annealing the film at elevated temperatures resulted in the decrease of both the direct and indirect transition band gaps.     

Effect of temperature programmes on protein crystallisation

Varying the temperature has been proven to be beneficial for improving the screening efficiency of protein crystallisation, and thus a crystallisation screening strategy based on this phenomenon can be developed. Such a temperature varying strategy can be applied in practical crystallisation screening, however, there are no guidelines for determining what temperature programme should be utilised. It is therefore necessary to investigate how the temperature programme affects the crystallisation process, so as to help people design a suitable temperature programme. For this purpose, we investigated the effect of temperature programmes on the protein crystallisation (lysozyme, proteinase K, and concanavalin A) that are characterised by different solubility behaviours with respect to temperature. Judging from the reproducibility studies of protein crystallisation with different temperature programmes, we recommend using linear temperature programmes for a moderate time period (24 to 48 h) and a large temperature range according to the properties of the proteins. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

连续离子层吸附反应(SILAR)法制备AgGaS2纳米薄膜及性能表征

采用连续离子层吸附反应(SILAR)法,通过500℃退火在玻璃衬底上制备出AgGaS2纳米薄膜.使用X射线衍射(XRD)、扫描电镜(SEM)、X射线能谱(EDS)、紫外可见(UV-Vis)谱和光致发光(PL)谱等对纳米薄膜的物相、形貌、化学配比和光学性能进行了定性和定量表征.XRD测试结果表明,实验获得产物为黄铜矿结构AgGaS2,并观测到(112)面和(224)面.使用Scherrer公式估算了AgGaS2产物的晶粒平均粒度大小约为30 nm.SEM观测到的AgGaS2纳米薄膜外形均匀一致,沉积紧密,薄膜沉积的纳米平均颗粒直径约为18～ 26 nm.EDS测试结果显示AgGaS2纳米薄膜中Ag、Ga和S三元素的原子相对百分含量为25.12;,26.66;和49.93;,其化学计量比几近于1∶1∶2物质的量比.通过紫外可见透过光谱得到截止波长为470.1 nm,禁带宽度为2.64 eV.室温PL测试发现发光中心在456 nm,与AgGaS2晶体发光中心相比产生了约40nm的蓝移.以上结果充分表明SILAR法是一种制备AgGaS2纳米薄膜的有效方式.     

大气开放式MOCVD氧化镁薄膜的生长及表征

以2,4-乙酰丙酮化镁为前驱体,衬底温度为480℃,采用MOCVD工艺,分别在玻璃、氧化铝陶瓷、单晶Si(111)和Si(100)衬底上生长了取向生长的氧化镁薄膜。X射线衍射结果表明,无论是采用玻璃、氧化铝、单晶Si(111)和Si(100)衬底,氧化镁薄膜都是沿着(100)晶面取向生长。通过扫描电镜观察得到,在单晶Si(100)衬底上生长的氧化镁薄膜表面平整致密。模拟卢瑟福背散射结果显示,沉积时间超过70min时,界面处发生硅向氧化镁层少量扩散现象。