Amorphization and crystallization characteristics of TiNi shape memory alloys by severe plastic deformation

Differential scanning calorimetry (DSC) was used to determine the crystallization fraction and rate in TiNi alloys by severe plastic deformation. Results showed that the reverse martensitic transformation peak was not observed during the first heating at the rate of 40 K/min in the as-rolled samples, but one exothermic peak was observed at 620 K, which was associated with the amorphous crystallization process. During the second heating, reverse martensitic transformation was recovered. The onset crystallization temperature was low in the initial stage of crystallization with lower heating rates, but the crystallization fraction was found to increase with increasing temperature. However, the crystallization fraction was almost constant in the initial stage of crystallization with a relatively high heating rate. In all heating rates, the amorphous crystallization rates almost always reached maximum as the volumetric fraction of amorphous crystallization rose to 50%.     

A study of the crystallization kinetics of some Cu-As-Te glasses

The crystallization kinetics of two amorphous alloys in the Cu-As-Te system was studied by differential scanning calorimetry, using continuous heating methods, and applying a new analysis procedure in order to calculate the kinetic parameters which define the crystallization reactions, in the Johnson-Mehl-Avrami model. In this analysis, the crystallized fraction interval at which the characteristic function of said model is constant was taken into account. The values obtained for these parameters made it possible to discuss the glass-forming ability of the compounds under study, and the types of crystalline growths in the alloys.     

Curie temperature of METGLAS magnetic alloys measured by different techniques

A series of experiments was performed to determine the Curie temperature Tcof six METGLAS® magnetic alloys using three different techniques: thermogravimetry with magnetic field, differential scanning calorimetry (DSC), and magnetic susceptibility. The purpose of the work was to assess the sensitivity of the three methods, to establish the relationships between magnetic properties and enthalpy in the vicinity of Tc, and finally, to determine physically valid criteria for Tcwhen using the susceptibility method. The full matrix of data is given for the following METGLAS alloys: 2605S-2, 2605SC, 2605S-3A, 2705M, 2826MB, and 2605CO. Good accord between the temperature-dependence of magnetic moment, susceptibility, and enthalpy of the first five alloys is shown. A feature which can be identified with Tcis defined for each of the measurement methods. Interesting behavior was observed in the case of the METGLAS alloy 2605CO which has so small an enthalpy of the magnetic transition that DSC cannot be used. Both magnetic methods used, thermogravimetry with magnetic field and susceptibility, reveal a steplike temperature-dependence of magnetic moment and susceptibility. A strong dependence of Tcon the heating rate during measurement was observed, indicating superposition of the magnetic disordering and relaxation processes in the amorphous state. Extrapolation of the data shows that the virtual Tcfor METGLAS 2605CO in the completely amorphous state should be as high as 547°C (820 K).     

Fe45Co7Cr15Mo10Y2B6C15大块非晶合金的晶化动力学研究

为了明确Fe基块体非晶材料的晶化过程,通过铜模吸铸法制备了Fe45Co7Cr15Mo10Y2B6C15块体非晶合金,采用连续和等温差热扫描量热法对非晶合金在1 000 K以下的晶化动力过程进行了研究.研究表明:在973 K时效后的晶化产物为铁的碳化物;晶化过程的激活能达到了555.9 kJ/mol,非晶热稳定性良好;Avrami常数n值接近2,随着退火温度的变化,n值没有明显的变化,非晶晶化机理没有发生改变,而放热峰宽随着退火温度的降低明显宽化,说明非晶晶化过程是一个二维扩散控制的形核与长大过程.     

Controllable phase transformation and improved thermal stability of nickel on tungsten substrate by electrodeposition

Present study reports a controllable phase transformation of nickel(Ni) from amorphous to cubic crystal structures on tungsten(W) substrate by electrodeposition. X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy and energy dispersive spectroscopy were used to characterize the microstructure, micro-constituents and surface morphology of as-prepared Ni. The microstructure of Ni was strongly affected by the applied overpotential and deposition time. It is demonstrated that by controlling these two parameters either amorphous or cubic crystal structure of Ni on the W substrate could be obtained. The crystallization mechanism is discussed based on Gibbs crystal growth theory and Ostwald's rule. It is concluded that W substrate, acting as a heat sink, can effectively promote the thermal stability of amorphous Ni, based on the data from differential scanning calorimetry and Kissinger's model. This work contributes to the elucidation of the crystallization mechanism of Ni on W powder substrates, and proves that, better than alloying with other elements, incorporating powder substrates will significantly improve the crystallization temperature, hence the thermostability of amorphous Ni.     

用热分析技术研究非晶态合金的退火转变动力学

论述了示差扫描热分析（ＤＳＣ）和热重分析（ＴＧ）在研究非晶态合金退火转变动力学方面的应用。利用多速率示差扫描热分析技术和热重分析技术,辅之以其它性能参量的测定和Ｘ射线衍射分析,可对反映非晶态合金退火转变动力学特征的重要参数－－－激活能进行测定,并借此分析退火转变动力学以及各个不同过程之间的联系。     

Crystallization of (Fe, Co)78Si9B13 alloys: influence of relaxation processes

Crystallization of Fe78-xCoxSi9B13 amorphous alloys has been studied by differential scanning calorimetry (DSC), thermomagnetic gravimetry and X-ray diffraction techniques. Thermal stability of the amorphous alloy monotonically decreases with increasing cobalt content. The devitrification process as detected by DSC occurs in two main stages partially overlapping in temperature, but magnetic characterization reveals a third stage for cobalt-rich alloys. Primary precipitation of -(Fe, Co) is followed by a polymorphic reaction to give (Fe, Co)2B phase. Fe3B-type phase is also detected at the end of the first crystallization stage for iron-rich alloys and -Co(Si) and Co2B phases are found in fully crystallized samples for x=60. The influence of relaxation processes on the crystallization was investigated, but no significant effects of pre-annealing on the crystallization parameters resulted. © 1998 Chapman & Hall     

Kinetics of crystallization of a Fe-based multicomponent amorphous alloy

The Fe-based multicomponent amorphous alloys (also referred to as metallic glasses) are known to exhibit soft magnetic properties and, it makes them important for many technological applications. However, metallic glasses are in a thermodynamically metastable state and in case of high temperature operating conditions, the thermally activated crystallization would be detrimental to their magnetic properties. The study of crystallization kinetics of metallic glasses gives useful insight about its thermal stability. In the present work, crystallization study of Fe₆₇Co₁₈B₁₄Si₁ (2605CO) metallic glass has been carried out using differential scanning calorimetry (DSC) technique. Mössbauer study has also been undertaken to know the phases formed during the crystallization process. The alloy shows two-stage crystallization. The activation energy has been derived using the Kissinger method. It is found to be equal to 220 kJ/mol and 349 kJ/mol for the first and second crystallization peaks, respectively. The Mössbauer study indicates the formation of α-(Fe, Co) and (Fe, Co)₃B phases in the alloy.     

Isochronal crystallization kinetics of Fe40Ni40B20 amorphous alloy

The kinetics of crystallization of amorphous Fe₄₀Ni₄₀B₂₀ alloy upon isochronal annealing was investigated applying power-compensating differential scanning calorimetry with heating rates of (5, 10, 20, 30, 40) K/min. The corresponding microstructural evolution was studied by means of X-ray diffraction, focused ion beam and scanning electron microscopy, and transmission electron microscopy. Crystallization of Fe₄₀Ni₄₀B₂₀ alloy upon isochronal annealing takes place by formation of nano-scaled grains consisting of a face-centered cubic solid solution phase (Fe,Ni) and an orthorhombic compound phase (Fe,Ni)₃B. Kinetic analysis was performed by application of a modular model of phase transformation kinetics, fitted to all experimental transformation-rate curves simultaneously. The crystallization reaction can be described by nucleation with a continuous nucleation rate incorporating a nucleation index a and by growth in three dimensions according to a linear growth law. The kinetics of transformation and the resulting microstructure observed upon isochronal annealing clearly differ from those upon isothermal annealing investigated in a previous study, reflecting different mechanisms operating upon isochronal and isothermal crystallization.     

Crystallization kinetics of mechanically alloyed amorphous Fe-Ti alloys during annealing

The crystallization behaviors of mechanically alloyed amorphous Fe-Ti alloys were studied. The α-Fe phase formed during annealing as a result of the devitrification of the amorphous phase. According to the Kissinger plot, the crystallization activation energy (E) was obtained as 171 kJ/mol, which is close to the activation energy for the diffusion of Fe in α-Ti. According to the non-isothermal Johnson–Mehl–Avrami (JMA) analysis and obtaining the volume fraction of the crystalline phase from the differential scanning calorimetry (DSC) plots, the average Avrami exponent (n) was determined as 1.61 and 5.67 for low and high heating rates, respectively. Moreover, a method for obtaining the value of E based on the non-isothermal JMA analysis was proposed. The value of E was determined as ~185 and 191 kJ/mol respectively for low and high heating rates, which are consistent with the value determined from the Kissinger plot for all heating rates.     

Crystallization kinetics of Zr-33 at % Ni amorphous alloy

The amorphous to crystalline transition in Zr-33 at% Ni amorphous alloy has been found to occur by polymorphic crystallization. The product of the cyrstallization process has been identified as the equilibrium Zr₂Ni intermetallic phase. The kinetics of crystallization have been studied independently using differential scanning calorimetry (DSC) and transmission electron microscopy. The activation energy of crystallization has been evaluated by isothermal and continuous heating in DSC. The isothermal anneals have revealed that the crystallization follows the Johnson-Mehl-Avrami kinetics with an Avrami exponent close to 4. The microstructural changes accompanying crystallization have been studied for an interpretation of the Avrami exponent. The nucleation and growth rates of crystals have been estimated at different temperatures in order to determine the activation energies of the two processes. It has been found that nucleation is thermally activated and growth is interface controlled.     

Crystallization and phase transformation behaviour of electroless nickel-phosphorus deposits with low and medium phosphorus contents under continuous heating

Electroless nickel-phosphorus deposits with 5–8 wt% P and 3–5 wt% P were analysed for the effects of continuous heating on the crystallization kinetics and phase transformation behaviour of the deposits. The as-deposited coatings consist of a mixture of amorphous and microcrystalline nickel phases, featuring in their X-ray diffraction patterns. Continuous heating processes to 300°C–800°C at 20°C/min were carried out on the deposits in a differential scanning calorimetric apparatus. The subsequent X-ray diffraction analyses show that the sequence of phase transformation process was: amorphous phase + microcrystalline nickel f.c.c. nickel + Ni₃P stable phases. Preferred orientation of nickel (200) plane developed in the deposits after the heating processes. Differential scanning calorimetry of the deposits indicates that the crystallization temperatures increased with decreasing phosphorus content, and increasing heating rate. Crystallization activation energies of the deposits (230 and 322 kJ/mol, respectively) were calculated using the peak temperatures of crystallization process, from the differential scanning calorimetric curves at the heating rates ranging from 5 to 50°C/min. It was found that the deposit with lower phosphorus content has higher activation energy.     

Determination of the activation energies for nucleation and growth of crystal nuclei in metallic glasses

A mathematical procedure is proposed in order to determine separately the activation energy for nucleation,E _n, and for growth,E _g, from isothermal crystallization experiments on metallic glasses. Differential scanning calorimetry (DSC) is used in the isothermal mode to estimate the crystalline fraction as a function of time. The model deals only with polymorphic and eutectic growth. Cu₆₀Zr₄₀ amorphous alloys produced with different quenching rates are taken as an example for demonstrating the ability of the proposed method. It is shown that the number of pre-nuclei can be related to the conditions of the initial quench.     

Effect of irradiation particle mass on crystallization of amorphous alloys

The crystallization temperature of amorphous alloys was found to be significantly lowered by heavy ion or electron irradiation during annealing. However, only heavy ion irradiation altered the mode of crystallization. Both a binary and multi-element amorphous alloy showed this type of response to irradiation. Radiation-enhanced diffusion processes in the amorphous state can explain the increased crystallization kinetics during irradiation. Heavy ion irradiation alters the crystallization mode by causing direct transformation to the final equilibrium phase as opposed to intermediate metastable phase formation during thermal annealing or electron irradiation. The equilibrium phase is believed to nucleate directly in the displacement cascades, which only form during heavy ion bombardment.     

铁基非晶合金退火脆化与防脆技术

综述了铁基非晶合金退火脆化的影响因素，分析了各种防止退火脆化的方法，认为在电脉冲快速加热的同时外加磁场退火，则是改善铁基非晶合金磁性能、防止其退火脆化的一种较好的方法。     

Transformation behavior and thermal stability of Al-based systems prepared by ball milling

Transmission electron microscopy, X-ray diffraction, scanning electron microscopy, differential thermal analysis, and differential scanning calorimetry were used to investigate the transformation behavior of (Al_0.88Ni_0.08Co_0.04)_100−x,Zr_x, (wherex = 0 to 5 at. %) alloys during ball milling, and the thermal stability during the reverse process of return to equilibrium. The results have shown that the crystalline to amorphous transformation occurs only in compositions containing Zr. Mechanical grinding is shown to easily amorphize the Al₃Zr compound which enters in equilibrium with the fcc-Al and (Co, Ni)₂Al₉ phases for the compositions studied. The formation of an amorphous phase at the fcc-Al and Co₂Al₉ grain boundaries leads to a wetting transition, and with decreasing grain size the initially nanostructured Al₈₈Ni₈Co₄ alloy was found to progressively transform to an amorphous alloy. The crystallization temperature, the activation energy, and the crystallization enthalpy increase, while the melting temperature of the quaternary alloys decrease with increasing Zr substitution up to 5 at. %.     

新型Zr-Nb基大块非晶合金的形成及性能

本文用水淬法制备 Zr-Nb基大块非晶合金 ;并采用 DSC热分析法测定了该种合金的玻璃转变温度和热稳定性 ;采用超声检测方法精确测定了材料的声学性能 ,由此计算得到一组大块非晶合金的弹性性能参数。     

Kinetic Characteristic of Hydrogenation Zr-Ti-Cu-Ni-Be Bulk

The relationship between the hydrogen content and the microhardness and the charging period, the effect of hydrogen on the activation energy, the kinetics of glass transition and crystallization of Zr-Ti-Cu-Ni-Be bulk amorphous alloy were studied by differential scanning calorimetry (DSC) and the Kissinger equation. It shows that both of the hydrogen content and the microhardness are related to the charging period, and that the glass transition and crystallization behavior are associated with the heating rate, and possess the kinetic effect. Hydrogen increases the glass transition temperature and the crystallization temperature, decreasing the enthalpies in the different stages of crystallization. Hydrogen increases the activation energies of the glass transition and the crystallization and changes the kinetic effect. The dependent extent between the glass transition, the crystallization and heating rate decreases after hydrogen charging.     

Kinetic Characteristic of Hydrogenation Zr-Ti-Cu-Ni-Be Bulk Amorphous Alloys

The relationship between the hydrogen content and the microhardness and the charging period, the effect of hydrogen on the activation energy, the kinetics of glass transition and crystallization of Zr-Ti-Cu-Ni-Be bulk amorphous alloy were studied by differential scanning calorimetry (DSC) and the Kissinger equation. It shows that both of the hydrogen content and the microhardness are related to the charging period, and that the glass transition and crystallization behavior are associated with the heating rate, and possess the kinetic effect. Hydrogen increases the glass transition temperature and the crystallization temperature, decreasing the enthalpies in the different stages of crystallization. Hydrogen increases the activation energies of the glass transition and the crystallization and changes the kinetic effect. The dependent extent between the glass transition, the crystallization and heating rate decreases after hydrogen charging.     

Effects of Nb Alloying on Nano-Crystallization Kinetics of Fe55-x Cr18Mo7B16C4Nbx(x=0, 3) Bulk Amorphous Alloys

Crystallization kinetics of Fe55-xCr18Mo7B16C4Nbx(x= 0, 3) bulk amorphous alloys were analyzed using X-ray diffraction and differential scanning calorimetric (DSC) tests. In practice, crystallization and growth mechanism were evaluated using DSC tests at four different heating rates (10, 20, 30, and 40 K/min) and kinetic models. Two-step crystallization behavior was observed when Fe55Cr18Mo7B16C4 and Fe52Cr18Mo7B16C4Nb3 bulk amorphous alloys were annealed, where Fe36Cr12Mo10 phase was crystallized in the first step of crystallization. Results show that Fe36Cr12Mo10 and Fe3C phases were crystallized in the structures of the alloys after further annealing process. Activation energy for the crystallization of Fe36Cr12Mo10 phase was measured to be 543 kJ/mol in Fe52Cr18Mo7B16C4Nb3 alloy and 375 kJ/mol for Fe55Cr18Mo7B16C4 alloy according to Kissinger-Starink model. Moreover, a two-dimensional diffusion controlled growth mechanism with decreasing nucleation rate was found in Fe52Cr18Mo7B16C4Nb3 alloy whereas a three-dimensional diffusion controlled growth mechanism with decreasing nucleation rate was found in crystallization of Fe36Cr12Mo10 phase dur- ing annealing of Fe55Cr18Mo7B16C4 alloy. TEM (transmission electron microscopy) observations reveal that crystalline Fe36Cr12Mo10 phase nucleated in the structures of the alloys in an average size of 10 nm with completely mottled morphology.