Short range ordering in rapidly quenched Fe83P17 amorphous alloys

Mössbauer spectroscopy, X-ray diffractometry and differential scanning calorimetry were used to study the effect of the preparation parameters on the short range ordering of Fe₈₃P₁₇ amorphous alloys. The samples were quenched with different quenching rates from the melt which was kept either at 1100°C or 1250°C for 20 min. The short range order of the amorphous samples was found to depend on the quenching rate due to the relaxation taking place during rapid quenching of the melt. In one case, in the sample quenched with the lowest quenching rate from the melt of 1250°C, crystalline phases identified as Fe₃P and -Fe were also found. This phase separation can be understood by taking into consideration the effect of both the melt temperature and the quenching rate. In this case, the cooling time can be long enough for separation of the phases which can be expected within the range of 1040–1250°C according to the phase diagram.     

Glass-forming ability and crystallization kinetics of amorphous palladium-boron alloys

Palladium-boron alloys have been prepared to check their ability to produce metallic glasses when spun from the melt.An amorphous alloy with 31.5 at.% boron obtained in the form of ribbon has been submitted to both isothermal and non-isothermal DSC tests. The isothermal crystallization kinetics have been analyzed according to the Avrami law for phase transformations in solids.The n exponent of the law has been determined to obtain information on the geometrical features of the growing crystals. A confirmation of the calculated n value has been sought through an analysis of non-isothermal DSC peaks     

Effect of amorphous seeds on the crystallization kinetics of Na-A zeolite

The formation of crystal nuclei occurs when alkaline aluminosilicate gels are treated at temperatures below the crystallization temperature or during crystallization of gels rather than during precipitation of the gels. The linear growth rate of the crystals of Na-A zeolites yielded by alkaline aluminosilicate gels in the presence of amorphous seeds is a function of the product of the concentrations of the silicate and aluminate ions in the intermicellar liquid.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 799–804, May, 1994.     

Crystallization kinetics of amorphous Fe75-xCuxSi9B16

In this work the influence of Cu admixtures on the crystallization process of amorphous Fe-Si-B alloys is studied, based on measurements of differential thermal calorimetry of the series Fe_75-xCu_xSi₉B₁₆ (x=0, 1, 2, 2.8 and 3.5) during their heating with different heating rates. The first crystallization stage can not be traced for any of the amounts of Cu content examined, while the second stage is observed only when the Cu content is 1 at%. The activation energy as estimated with Kissinger's method for the third crystallization stage has a mean value of 326 kJ mol^-1 and with the isoconversional Flynn, Wall and Ozawa method is almost constant when 0.05<a<0.6 and exhibits a small monotical decrease when a>0.6. The main crystallization peak can not be described by means of a single JMA-type function. This revised version was published online in August 2006 with corrections to the Cover Date.     

Trace tritium recovery from the residue of liquid Li17Pb83 alloy

The liquid Li₁₇Pb₈₃ alloy is a prominent breeder material for use in a fusion reactor. In the design of an effective tritium extraction system for the liquid lithium lead bubbler of the test blanket module of such a reactor, finding ways to strictly limit the losses of tritium and to minimize radioactive risks is very important. For this purpose, the isotope exchange process has been investigated as a means of trace tritium recovery from a model of the residue from Li₁₇Pb₈₃ alloy. The results indicate that the isotope exchange process is an effective means of tritium recovery from the residue of Li₁₇Pb₈₃ alloy, and the optimum composition of the exchange carrier gas is He + 0.1% D₂. The exchange temperature and number of exchange steps are the main factors influencing the efficiency of tritium recovery from the residue. Trace tritium recovery efficiency increases with increasing exchange temperature and number of times of exchange. Tritium recovery efficiency can approach 80% when the residue is treated six times at 823 K. A gas-liquid two-phase contact model to describe the proceeding of tritium release from the liquid Li₁₇Pb₈₃ alloy has been derived on the basis of this experiment.     

Phase formation and controlled nanostructuring in amorphous Fe80B20 alloy

The temperature dependence of the volume fraction of the crystalline phase in Fe₈₀B₂₀ amorphous alloy is calculated using equations from the homogeneous nucleation theory of binary systems. It is shown that the crystallization of Fe₈₀B₂₀ alloy is two-stage, as is confirmed by the experimental data obtained by means of highly sensitive dilatometry and X-ray diffractometry. On the basis of results of calculations performed within the theory of the high-temperature stability of amorphous alloys, two areas of its practical application are proposed: (i) enhancing the thermal stability of amorphous alloys by isothermal annealing in the range of temperatures where crystalline nuclei can transition to the amorphous phase; (ii) controlled nanostructuring of the amorphous state with different modes of treatment. Methods are proposed for obtaining the nanostructured state from the initial amorphous state. Alloys in the nanocrystalline state are obtained, as is confirmed by the results from electron microscope investigations.     

Study of crystallization kinetics of trans-1,4-polyisoprene

The concentrations and the growth rates of high- and low-melting type spherulites of trans-1,4-polyisoprene were measured in the temperature range 39–49°C. It was shown that above about 40°C., the crystallization rate of trans-1,4-polyisoprene is determined primarily by the radial growth rate of high-melting form (HMF) spherulites, whereas the predominance of the low-melting form (LMF) crystals below 40°C. can be attributed to the high rate of formation of LMF primary nuclei at lower crystallization temperatures. Temperature-independent rate parameters were calculated from optical and dilatometric measurements and were found to be in good agreement. Both the change in nucleation habit and spherulite growth rate with temperature can be explained on the basis of a lower end surface free energy of LMF crystals of trans-1,4-polyisoprene compared to that of the HMF crystals.     

Study of hydrogen evolution reaction on Ni–P amorphous alloy in the light of experimental and quantum chemistry

The hydrogen evolution reaction (HER) on Ni–P alloys was investigated experimentally and theoretically. First Ni–P alloys with P content in the range from 5.8 to 10.0 wt% were prepared by electrodeposition. The best catalysis to the HER was found on the Ni–P alloys with P content of 6.0 wt% (10.8 at%). In order to understand the function of P element in Ni–P amorphous alloys for the HER, the density-functional theory (DFT) method and front molecular orbital (FMO) theory were used to analyze the function of P element in Ni–P amorphous alloys for the HER. The research shows: it is easier for water molecule to get the first electron and form Ni_n+1–H and Ni_nP–H on Ni_n+1 clusters than on Ni_nP clusters, but it is more difficult for water molecule to get the second electron from Ni_n+1–H than Ni_nP–H. The strength of Ni_n+1–H bond is always greater than that of Ni_nP–H. It means it is more difficult for hydrogen evolutes from Ni_n+1 clusters than Ni_nP clusters. Regardless of which step among all steps of the HER is the rate-control step, the Ni–P alloys with P contents being in a range of 9.1–14.3 at% would be always good to the whole HER.     

Non-isothermal crystallization in amorphous selenium films

The usual determination of kinetic parameters of crystallization of amorphous products is based on isothermal measurements. In general the crystallization of amorphous selenium thin films is studied by non-isothermal experiments (DTA). The adaptation to non-isothermal crystallization of the Avrami transformation rate equation allows us to determine different types of crystallization. These different regions enable one to determine the variations of the growth rate and of the nucleation rate versus temperature. The influence of the wavelength of illumination during the crystallization time on these parameters is also investigated.

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Zusammenfassung Die übliche Bestimmung kinetischer Parameter der Kristallisation amorpher Produkte basiert auf isothermen Messungen. Die Kristallisation von amorphem Selen in dünnen Schichten wird im allgemeinen in nicht-isothermen Experimenten (DTA) untersucht. Die Adaptation der Transformationsgeschwindigkeitsgleichung nach Avrami an die nicht-isotherme Kristallisation ermöglicht die Bestimmung verschiedener Kristallisationtypen. Dadurch wird es möglich, die Veränderungen der Wachstumsgeschwindigkeit und der Geschwindigkeit der Nukleation in Abhängigkeit von der Temperatur zu bestimmen. Der Einfluß der Wellenlänge bei der Bestrahlung während der Kristallisation auf diese Parameter wird ebenfalls untersucht.

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Ni-P非晶态合金中电子转移问题的DFT研究

根据Ni-P非晶态合金结构的短程有序、Ni和P之间具较强化学作用和结构中不存在P-P直接相连的实验事实,选择了Ni~nP(n=1-6)原子簇模型,用密度泛函理论方法对其进行计算。结果表明,在模型体系中,随着P含量的减少,电子转移方向发生变化,P原子由得电子变为失电子。这与Ni-P非晶态合金的实验结果一致,说明Ni~nP(n=1-6)原子簇模型能反映Ni-P非晶态合金的结构特点。     

Investigation of structural relaxation of Fe85B15 amorphous metallic alloy by thermomagnetization

Thermomagnetometry was used to determine the Curie temperature of Fe₈₅B₁₅ amorphous alloy. Measurements were made with a TGS-1 Perkin-Elmer thermobalance in a permanent magnetic field. Armosphous material with a thickness of 25 m was prepared by melt spinning.In the temperature region 300 to 800 K the sample is characterized by one Curie transformation in the amorphous matrix atT _c570 K. A broad region of primary crystallization of -Fe begins at approximately 660 K, followed closely by the rapid crystallization of Fe₃B phase with maximum atT _cr2 750 K. Amorphous material which is unstable due to quenching is relaxed by annealing. The structural relaxation causes ageing of the Curie temperature in the metallic glass.The observed phenomena might be explained in terms of certain changes in local atomic arrangement.

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Zusammenfassung Die thermomagnetometrische Methode wurde zur Bestimmung der Curie-Temperatur der amorphen Legierung Fe₈₅B₁₅ herangezogen. Die Messungen wurden mit einer Perkin-Elmer-Thermowaage des Typs TGS-1 unter Anwendung eines permanenten Magnetfeldes ausgeführt. Das 25 m dicke amorphe Material wurde nach dem Schmelzspinnverfahren dargestellt. Im Temperaturbereich von 300 bis 800 K ist für die Probe eine Curie-Transformation in der amorphen Matrix beiT _c570 K charakteristisch. Ein breiter Bereich der primÄren Kristallisation von -Fe beginnt bei etwa 660 K, dem sofort eine schnelle Kristallisation der Fe₃B-Phase mit maximaler Geschwindigkeit beiT _cr2 750 K folgt. Die durch Abschrecken eintretende InstabilitÄt des amorphen Materials wird durch Tempern aufgehoben. Die strukturelle Relaxation verursacht eine Alterung der Curie-Temperatur im metallischen Glas. Die beobachteten PhÄnomene können durch VerÄnderungen der lokalen Anordnung der Atome erklÄrt werden

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Fe₈₅B₁₅. -1 -, . 25 . 300–800 . -Fe 660 , Fe₃B T _cr2750 . , , . . .

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We wish to thank P. Duhaj for the preparation of glassy ribbons.     

Crystallization kinetics of amorphous

The active sites of hydrogen-exchanged Y zeolite (HY) and dealuminated (HDY) zeolites are investigated by TPD of carbon monoxide. Only the high temperature TPD spectra of CO (TM»620-690°C) were observed, meaning that CO molecules interact with very strong acid sites. The amounts of CO bonded on these sites are small (less than 1 molecule per unit cell). The strong influence of dealumination on the coverage degree is found. The calculated values for kinetic parameters indicate chemisorption of CO in the investigated systems (Edes»240 kJ mol^-1, A»1011 s^-1).     

Morphology and crystallization kinetics of compact (HGW) and porous (ASW) amorphous water ice

An investigation of porosity and isothermal crystallization kinetics of amorphous ice produced either by background water vapour deposition (ASW) or by hyperquenching of liquid droplets (HGW) is presented. These two types of ice are relevant for astronomical ice research (Gálvez et al., Astrophys. J., 2010, 724, 539) and are studied here for the first time under comparable experimental conditions. From CH(4) isothermal adsorption experiments at 40 K, surface areas of 280 ± 30 m(2) g(-1) for the ASW deposits and of 40 ± 12 m(2) g(-1) for comparable HGW samples were obtained. The crystallization kinetics was studied at 150 K by following the evolution of the band shape of the OD stretching vibration in HDO doped ASW and HGW samples generated at 14 K, 40 K and 90 K. Comparable rate constants of ～7 × 10(-4) s(-1) were obtained in all cases. However a significant difference was found between the n Avrami parameter of the samples generated at 14 K (n～ 1) and that of the rest (n > 2). This result hints at the possible existence of a structurally different form of amorphous ice for very low generation temperatures, already suggested in previous literature works.     

Crystallization kinetics study of melt-spun Zr66.7Ni33.3 amorphous alloy by electrical resistivity measurements

In this paper, the electronic transport properties of as-spun Zr_66.7Ni_33.3 alloys were studied in detail by a combination of electrical resistivity and absolute thermoelectric power measurements over a temperature range from 25 up to 400 °C. Moreover, the isochronal and isothermal crystallization kinetics of Zr_66.7Ni_33.3 glassy alloy has been investigated based on the electrical resistivity measurements. The comparative study of the crystallization kinetics of these binary amorphous alloys was carried out, for the first time to our knowledge, using an accurate method for electrical resistivity measurements. In the isochronal heating process, the apparent activation energy for crystallization was determined to be, respectively, 371.4 kJ mol⁻¹ and 382.2 kJ mol⁻¹, by means of Kissinger and Ozawa methods. The Johnson–Mehl–Avrami model was used to describe the isothermal transformation kinetics, and the local Avrami exponent has been determined in the range from 2.97 to 3.23 with an average value of 3.1, implying a mainly diffusion-controlled three-dimensional growth with an increasing nucleation rate. Based on an Arrhenius relationship, the local activation energy was analyzed, which yields an average value E_x = 376.2 kJ mol⁻¹.

     

Crystallization kinetics of amorphous Se

Differential scanning calorimetry was used to study crystallization behavior in selenium glass under non-isothermal conditions. The crystallization kinetics were described in terms of the Johnson–Mehl–Avrami nucleation-growth model; activation energies and kinetic parameter m _JMA were determined. The study was performed in dependence with particle size, so that a novel approach to the evaluation of crystallization kinetics—the advanced interpretation of characteristic kinetic functions—could be employed. Extensive discussion of all aspects of a full-scale kinetic study for a complex crystallization process was performed within the framework of the introduced conception. The complexity of the crystallization process was found to be 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 a changing amount of volume nuclei originating from the combination of the pre-nucleation period and the actual glass preparation phase. The main objective of the study is to demonstrate the extent of so-far neglected information hidden in the characteristic kinetic functions and introduce a convenient tool for its acquisition.     

Nonisothermal crystallization kinetics of amorphous Te51.3As45.7Cu3

The structure and kinetics of the crystallization reaction of amorphous Te_51.3As_45.7Cu₃ were studied under nonisothermal conditions using scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). Two exothermic changes were reported. Five isoconversional methods, of Kissinger–Akahira–Sunose (KAS), Flynn–Wall–Ozawa (FWO), Tang, Starink, and Vyazovkin, were used to determine the variation of the activation energy for crystallization with temperature, E(T). The results show that the activation energy for crystallization associated with the first peak first decreases with increasing temperature and then increases. Different behaviour was observed for the second peak, where an increase of E with temperature followed by a decrease. The effect of heating rate on the reaction model, g(), was also different for the two crystallization peaks.     

The crystallization kinetics of polyamide-12

The crystallization kinetics of polyamide-12 has been investigated using a combination of differential scanning calorimetry (DSC) and hot-stage optical microscopy. The DSC data for isothermal crystallization were consistent with a simple two-parameter Avrami model for isothermal crystallization and optical measurements of the spherulite growth rates and nucleation density. On the basis of semiempirical expressions for these quantities, it is shown that with small adjustments the model can also account for DSC data for nonisothermal crystallization, provided that corrections are made for the dynamic heat balance between the sample and the DSC oven. Received: 9 March 2000 Accepted: 28 September 2000     

诱导自催化法制备Ni-P超细非晶合金的动力学研究

加入诱导剂(如KBH~4)可使Ni^2+与H~2PO~2^-反应在常温下进行, 便于测量反应中放出的H~2体积, 有利于研究反应的动力学过程及其与反应条件下关系。反应为二级自催化反应, 反应活化能约60kj.mol^-1, pH值不影响反应速率常数, 但pH值越大, 反应诱导期越长, 一般可在40min内完成。由于加入诱导剂能一次成核,生成的Ni-P非晶合金为均匀的球形颗粒。     

Improved experimental characterization of crystallization kinetics

Polymer solidification occurring in many processes, like for instance injection molding, compression molding and extrusion, is a complex phenomenon, strongly influenced by the thermo-mechanical history experienced by the material during processing. From this point of view, characterization of polymer crystallization in the range of processing conditions, i.e. including high cooling rate, is of great technological and academic interest. Quiescent, non-isothermal crystallization kinetics of two polypropylene resins were investigated using a new method, based on fast cooling of thin samples with air/water sprays and optical detection of the crystallization phenomenon. The range of cooling rates attained in this experimental study is considerably larger than that achieved by traditional methods. Quiescent crystallization kinetics of the resins is also investigated by the means of DSC, operated under isothermal conditions with a limited degree of under-cooling and for constant cooling rates up to about 1 K s⁻¹. The results demonstrate the importance of performing fast cooling experiments to gather reliable crystallization kinetics data.