Non-isothermal crystallization and nanostructuring in potassium niobium silicate glasses

Potassium niobium silicate (KNS) glasses the composition of which is characterized by the K₂O/Nb₂O₅ molar ratio ranging from 0.85 to 1.2 and SiO₂ 50-54 mol% were examined in order to clarify the influence of chemical composition on formation of transparent nanostructured state of glasses. Differential thermal analysis, X-ray diffraction and scanning electron microscopy were used to study the non-isothermal crystallization of the KNS glasses as well as their morphological features. It was found that all glasses devitrify in three steps forming unidentified phases at the first two ones while at higher temperature (1000-1100 °C) the crystallization of K₃Nb₃O₆Si₂O₇ takes place. For prolonged heat treatment time (more than 5 h) at high temperature (1050-1100 °C) the transformation of this phase into the KNbSi₂O₇ ferroelectric one occurs in some extent. Nanostructuring occurs at the first stage of the devitrification process. It results from two partially overlapped processes: amorphous phase separation and subsequent crystallization. It was shown that only for the glass with the K₂O/Nb₂O₅ molar ratio equal to 0.85 and SiO₂ 50 mol% it is possible to separate the above processes by isothermal heat treatments at 680 °C obtaining fully transparent nanostructured samples. These samples contain nanocrystals 10 times smaller than the amorphous inhomogeneities of the phase separated matrix in which are dispersed.     

Pressure-induced crystallization in a bulk amorphous Zr-based alloy

Crystallization of multi-component on amorphous Zr-based alloy (Zr₄₁Ti₁₄Cu_12.5Ni₉Be_22.5C₁) is investigated at different pressures and temperatures. We have previously found that the primary crystallization temperature decreases with increasing pressure below 6 GPa, and the crystallization follows a different process under high pressure when compared to that at ambient pressure. In this work, pressure-induced crystallization is observed by in situ X-ray diffraction (XRD) using synchrotron radiation in a diamond anvil cell at ∼25 GPa and room temperature. This phase transition between amorphous and crystalline is reversible and the crystallized sample returns to the amorphous state during decompression. The mechanism for pressure-induced crystallization is discussed. We suggest that the crystallized phases under high pressure are interstitial solid solution phases formed from the amorphous matrix without long-range atomic rearrangements.     

Non-isothermal crystallization of PVDF/PMMA blends processed in low and high shear mixers

The morphological, thermal and non-isothermal crystallization behavior of poly(vinylidene fluoride) (PVDF) and its blends with poly(methyl methacrylate) (PMMA) processed in low (LSM) and high (HSM) shear mixers were studied by differential scanning calorimetry (DSC). The processing effect on the PVDF melt and crystallization kinetics was described and the effect of PMMA on the PVDF crystallization was also investigated. The addition of PMMA into PVDF increases of relative B phase content independent of the processing conditions. The validity of the modified Avrami and Kolmogorov–Johnson–Mehl–Avrami (KJMA) models for the non-isothermal crystallization of PVDF/PMMA blends are discussed. The KJMA method described accurately the non-isothermal crystallization behavior. The results showed a shift in the PVDF crystallization/fusion peak to lower temperatures. The activation energies for crystallization of PVDF and its blends evaluated through the isoconversional method using Friedman's approximation were higher for samples processed in the LSM. Differences in the activation energies were related to the ability of the molecular segments to crystallize when reaching the growing crystallization front, confirming that the mixing process has some effect on the interaction between the polymers. On the other hand, the isoconversional methods in combination with the KJMA equation provide better understanding of the kinetics of the crystallization process demonstrated by a strongly dependence of activation energy (Ea), relative crystalline fraction (XT), and global and local Avrami exponents (n and n (XT)).     

Complex primary crystallization kinetics of amorphous Finemet alloy

The complex primary crystallization kinetics of the amorphous Finemet soft magnetic alloys has been analyzed by non-isothermal DSC measurements. The local activation energies E_c(α) were determined by an isoconversional method without assuming the kinetic model function and its average value was about 383 kJ/mol. The nucleation activation energy E_n and growth activation energy E_g were 425 and 333 kJ/mol, respectively. And the apparent local activation energies E_c can be expressed by E_n and E_g as follows: E_c = aE_n + bE_g. The local Avrami exponents lies between 1 and 2 in a wide range of 0.2 < α < 0.9, and it indicates that dominating crystallization mechanism in the non-isothermal primary crystallization of amorphous Finemet alloy is one dimensional growth at a near-zero nucleation rate for surface crystallization. The significant variation of local Avrami exponent and local activation energy for primary crystallization with crystallized volume fraction demonstrates that the primary crystallization kinetics of amorphous Finemet alloy varies at different stages. In addition, the variable local activation energies E_c(α) and local Avrami exponents n(α) are applicable and correct in describing the primary crystallization process of the amorphous Finemet alloy according to the theoretical DSC curve simulation.     

A possible new approach to the better understanding of crystallization kinetics

Literature data dealing with the structure of solutions, solubility of tiny particles, and the organization of small colloidal particles in solutions were summarized to support the evidence that the growth units in the crystallization by precipitation are identical with clusters or primary particles. These growth units may self-organize themselves in a kind of a three-dimensional network surrounding the growing crystals or secondary particles. This colloidal concept was used to explain qualitatively some experimental facts observed in the controlled double jet precipitation of sparingly soluble salts.     

Aluminum-induced crystallization: Nucleation and growth process

The formation of polycrystalline silicon (poly-Si) films by Al-induced crystallization (ALILE process) was studied in situ by optical microscopy. The characteristic feature of this process is that nucleation is strongly suppressed after an initial nucleation period. The use of cooling periods in the course of annealing leads to enhanced nucleation and reveals that the formation of Si depleted regions around the growing grains prevents further nucleation. The growth mechanism is discussed starting from the phase diagram of the Al/Si system. It turns out that the critical parameter is the actual concentration of Si in Al and the value of supersaturation.     

Non-isothermal crystallization kinetics of ZnO-BaO-B2O3-SiO2 glass

Glass of composition 40SiO₂-30BaO-20ZnO-10B₂O₃ (mol%) was made by conventional melting and casting process. Crystallization kinetics of above glass has been investigated under non-isothermal conditions, using the formal theory of transformations for heterogeneous nucleation. The procedure is applied to the experimental data obtained by differential thermal analysis (DTA), using continuous-heating techniques. The crystallization results are analyzed, and both the activation energy of crystallization process as well as the crystallization mechanism is characterized. Dilatometric measurement of this glass was also done and data obtained was used to calculate the viscosity of the formed glass. Development of crystalline phases on thermal treatments of the glass at various temperatures has been analyzed by X-ray diffraction. Microstructure of the crystalline phases was investigated by scanning electron microscopy (SEM) and the development of various structural features with variation in heat treatment cycle was observed. The nucleation and growth of these phases in the matrix of glass has been described and discussed.     

Formation of amorphous Mn-Bi films and their crystallization process

Mn-Bi alloy films were prepared by simultaneous vacuum deposition at liquid N₂ temperature and their structures were investigated by transmission electron microscopy and electron diffraction. Films with compositions in the range of 34 to 63 at% Mn have the Bi lattice structure at room temperature. Films with composition in the range of 68 to 95 at% Mn show diffuse haloes at room temperature. When they are heated above room temperature, those in the range of 70 to 85 at% Mn show nucleation and grain growth crystallization, whereas the films of 68 and 95 at% Mn show only grain growth crystallization. The films in the range of 70 to 85 at% Mn are concluded to be amorphous at low and at room temperature. Some of the crystals obtained by nucleation and the grain growth crystallization grow as large as 10 μm in length. Their diffraction patterns are not ascribable to reported crystals in this alloy system.     

Non-isothermal crystallization kinetic studies on MgO–Al2O3–SiO2–TiO2 glass

Thermal stability and crystallization kinetics of the glass 21% MgO, 21.36% Al₂O₃, 53.32% SiO₂ and 4.11% TiO₂ (mol%) has been studied using differential thermal analysis (DTA), dilatometry and X-ray diffraction (XRD). Glass in both bulk and frit forms were produced by melting in platinum crucible at 1600 °C for 1–2 h. From variation of DTA peak maximum temperature with heating rate, the activation energies of crystallization were calculated to be 340 kJ mol⁻¹ and 498 kJ mol⁻¹ for first and second crystallization exotherms, respectively. Crystallization of bulk glass was carried out at various temperatures and for different time durations in the range of 850–1000 °C. The influence of the addition of TiO₂ on the crystallization sequence of the glass was experimentally determined and discussed.     

Non-isothermal crystallization kinetics of La2CaB10O19 from glass

The non-isothermal crystallization kinetics of La₂CaB₁₀O₁₉ (LCB) from a La₂O₃-CaO-B₂O₃ glass was studied. Differential thermal analysis methods were performed on three glass powders to obtain the kinetic parameters of LCB crystallization mechanism. The activation energies for overall crystallization (E), obtained by the methods of Kissinger and Ozawa, were in the range of 479-569 kJ/mol. Multiple (five) analysis methods were used to estimate the Avrami exponent (n), which could consequently be reduced into the single value of n = 3.1 ± 0.3. The growth morphology index (m) of LCB was corroborated by microscopy (optical and electron) images, which revealed a three dimensional growth. Energy dispersive spectroscopy confirmed that LCB is the crystallizing phase from the glass by an interface controlled mechanism. The parameters of the Johnson-Mehl-Avrami kinetic model for the analysis of LCB crystallization from glass were found to be n = m = 3.     

Peculiarities of the initial transient process of binary melt crystallization

The time dependence of the crystallization rate V(t) in the transient process that occurs during crystal pulling into a cold zone at a constant rate W has been investigated within the one-dimensional time-dependent model of binary melt solidification using numerical and analytical approaches. It is shown that the character of the dependence V(t) in this process is mainly determined by the parameter B _w = V _c /W, where V _c is the crystallization rate at which the constitutional supercooling zone is formed in the melt. At B _w ≥ 1, the function V(t) monotonically approaches its steady-state value W, while at B _w < 1 V(t) is generally nonmonotonic. The nonmonotonic character of V(t) can manifest itself both as aperiodic damping and in the form of damping oscillations. At B _w ∼ 0.1, the vibrational amplitude of the crystallization rate in the initial transient process may reach several tens of a percent of W.     

Spontaneous crystallization of sodium chloride from aqueous‐ethanol solutions; Part 3: Examination of a model of the crystallization process

In the present work the examination of the proposed earlier model of spontaneous crystallization process was done. The model describes kinetics of the crystallization process after the end of the induction period. To test the model the published data on crystallization and aggregation kinetics of sodium chloride at its spontaneous crystallization from supersaturated aqueous‐ethanol solutions were used. It was found an excellent coincidence of the experimental and theoretical data on concentration of the salt and the total number of crystals in solution at crystallization. The model allows predicting with satisfactory accuracy kinetics of crystallization using such general parameters of sodium chloride as the specific surface energy and the height of the nucleus‐bridges between crystals at coalescence. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Phase separation and crystallization in a melt-spun Ti45Zr35Ni17Cu3 alloy

Structure and crystallization behavior of amorphous and quasicrystalline Ti₄₅Zr₃₅Ni₁₇Cu₃ alloy have been studied. DSC trace of the amorphous alloy obtained during continuous heating to 1300 K shows distinctly an exothermic peak and two endothermic peaks. The amorphous alloy has different structures depending on annealing temperature. The first exothermic reaction at low temperature region from 400 K to 900 K is due to the precipitation of an icosahedral quasicrystalline phase, and the second endothermic reaction at higher temperature region from 950 K to 990 K results from the transformation of the I-phase to C14 Laves and α-(Ti, Zr) phases.     

Part 1: Kinetics and mechanism of the crystallization process

The kinetics of spontaneous crystallization of sodium chloride from aqueous‐ethanol solutions were studied. During the crystallization the electrical conductance and optical transmission of the supersaturated solutions were measured automatically. For monitoring of the total surface of growing potassium chloride crystals at the crystallization the turbidimetric method was used. The growth rate and activation energy were determined. The crystal growth rate was proportional to supersaturation. When the volume fraction of ethanol in solution increased from 14.85 to 29.72%, the activation energy of the growth process did not change and was about 50 kJ· mol^‐1. Aggregation of the crystals was found. The aggregation kinetics of the crystals may be described approximately by the famous Smoluchowski equation for coagulation of colloidal particles. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Metastable zone of sodium hydrogen carbonate crystallization in ammonia-soda process

Experimental results of an investigation of metastable zone and sodium hydrogen carbonate nucleation from the included supersaturated solutions are presented. In order to attain a better crystal size distribution some temperature patterns along the cooling part of the carbonating column have been suggested. It has been shown that high crystal growth rates might be carried on smaller size carbonating columns.     

Impact of agglomeration on crystalline product quality within the crystallization process chain

The quality of crystalline products, defined by e.g. purity or crystal size distribution (CSD), is primarily dominated by crystallization conditions but influenced by further downstream processes like solid‐liquid separation and drying also. Through uncontrolled agglomeration within the crystallization process chain the purity or CSD can be negatively affected. Therefore, in context of process optimization, missing knowledge of the impacts on the final product can lead to product batches out of specification. To increase the understanding of agglomeration and to provide insight into the relevance of holistic process optimization the agglomeration behavior of L‐alanine crystals is exemplarily quantified over the crystalline process chain. For the quantification the agglomeration degree (Ag) and the agglomeration degree distribution (AgD) are determined. The results show that the product quality achieved after crystallization is significantly affected by agglomeration during drying. Especially if washing after solid‐liquid separation is omitted, a broadening of the CSD is observed. Moreover, the evaluation by the AgD indicates that the final product can be ‐ despite similar characteristics of the CSD ‐ highly different. Consequently, it can be concluded that the characterization of the product quality by the CSD alone is insufficient and the quantification of agglomeration is essential for process optimization.     

Angular dependence of low-field microwave absorption in Co-rich amorphous alloys

Microwave power absorption measurements at 9.4 GHz (X-band) were carried out on as-cast amorphous ribbons of nominal composition Co₆₆Fe₄B₁₂Si₁₃Nb₄Cu, prepared by melt spinning. The angular dependence of low-field absorption (LFA) was investigated from θ = 0° to 180° in two orientations. In both cases the ribbon axis was orientated parallel to the DC magnetic field. In orientation 1, the ribbon plane was parallel to the AC microwave field. In orientation 2, it was perpendicular to the AC field. LFA spectra showed an antisymmetric shape (a minimum and a maximum), whose separation increased as a function of the angle between the DC field and the ribbon axis. A similar angular behavior was observed for the resonance field of the ferromagnetic resonance (FMR). For the orientation 1, the resonance field increased as a function of the angle, which can be explained in terms of the contribution of the shape anisotropy to the total anisotropy field. A similar behavior was observed in LFA, which suggests that the shape anisotropy field can be observed in the angular dependence of LFA. In the orientation 2, the observed changes occur within the plane associated with the induced anisotropy due to the rapid solidification process. The LFA signal is capable therefore to detect different contributions to the total anisotropy.