Journal of Non-Crystalline Solids 345&346 (2004) 178181 www.elsevier.

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Kinetics of crystallization of amorphous Cu50Ti50 alloy

Arun Pratap
a

a,*

, Kirit N. Lad a, T. Lilly Shanker Rao b, Pinal Majmudar a, N.S. Saxena

Applied Physics Department, Faculty of Technology and Engineering, Condensed Matter Physics Laboratory, M.S. University of Baroda, Vadodara 390 001, Gujarat, India b Electronics Department, Narmada College of Science and Commerce, Zadeshwar, Bharuch 392 011, Gujarat, India c Department of Physics, Condensed Matter Physics Laboratory, University of Rajasthan, Jaipur 302 004, Rajasthan, India Available online 12 September 2004

Abstract The kinetics of crystallization of amorphous Cu50Ti50 alloy has been studied with the help of non-isothermal scanning experiments in a dierential scanning calorimeter. The thermograms at dierent scanning rates show a sharp crystallization peak followed by a broad, diuse exothermic event. The method suggested [K. Matusita, S. Sakka, Phys. Chem. Glasses 20 (1979) 77] and the peak shift method given by Kissinger have been utilized to derive important kinetics parameters namely activation energy of crystallization Ec, Avrami exponent, n; and dimensionality of growth m. The derived value of Ec = 303 83 kJ/mol, obtained via the modied Kissinger equation, is in fair agreement with the reported value 280 kJ/mol for Cu50Ti50 [K.H.J. Buschow, Acta Metall. 31 (1983) 155; Scripta Metall. 17 (1983) 1135] and 261.2 kJ/mol for Cu40Ti60 glass reported by Miao et al. The results indicate bulk crystallization in the present amorphous alloy. The dimensionality of growth has been found to decrease with an increase in the heating rate. 2004 Elsevier B.V. All rights reserved.
PACS: 61.43.Fs; 81.10.Jt; 81.70.Pg

1. Introduction Metallic glasses are kinetically metastable materials. It is generally known that high strength and good bending ductility of melt-spun amorphous alloys are lost by annealing-induced crystallization. However, in last decade, a substantial increase in strength has been reported in a number of multiphase nanocrystalline alloys. The bulk amorphous alloys with nanocrystalline dispersoids (nanocrystals dispersed in amorphous matrix) have been reported to have much improved strength than fully amorphous alloys [1,2]. Hence, the kinetics of crystallization of an amorphous system is a key subject for study

Corresponding author. Tel.: +91 265 2782211; fax: +91 265 2423898. E-mail address: apratapmsu@yahoo.com (A. Pratap). 0022-3093/$ - see front matter 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.jnoncrysol.2004.08.018

since it provides new opportunities for structure control by innovative alloy design and processing techniques. Dierential scanning calorimetry (DSC) has become a convenient and widely used tool for studying the kinetics of phase transformations. The kinetic data on the phase transformation can be obtained from this technique in either the isothermal or linear heating (scanning) mode. In isothermal experiments, analysis is performed through the JohnsonMehlAvrami (JMA) formalism to determine the mechanism that governs nucleation and growth [36]. The JMA formalism can also be used for the non-isothermal experiments subject to fulllment of certain conditions [7]. The peak-shift method of Kissinger [8] is a widely used method for the determination of the activation energy. Chen and Spaepen [9] have demonstrated the usefulness of Kissingers method to determine the activation energy of a nucleation-and-growth process in non-isothermal

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experiments. For a linear heating experiment in DSC, Matusita and Sakka [10] have reported a method for determining various growth parameters namely activation energy of crystallization, Avrami exponent or the order parameter, n and the dimensionality of growth, m. Once the crystallization mechanism is known i.e. values of n and m are known, the modied form of the Kissinger equation [11] can be used to determine the Ec. Cu50Ti50 glasses are of special interest [12] due to the fact that CuTi is a congruently melting compound, which should allow static under-cooling experiments. Due to this, it is supposed to be an ideal system to study crystallization of metallic glasses and for comparison of under-cooled melts of the same composition. The study of thermally induced crystallization process in such systems is important to determine their thermal stability. In the present work, the kinetics of crystallization of amorphous Cu50Ti50 alloy is studied using the DSC technique in a linear heating mode. The DSC data is analysed with the help of the Matusita and Sakka method and the Kissinger method to determine the growth mechanism. The activation energy of crystallization (Ec), the order parameter or Avrami exponent (n) and the dimensionality of growth (m) are derived.

Fig. 1. DSC thermograms at linear heating rates 2, 4, 8 and 16 C/min.

2. Experimental The amorphous ribbons of Cu50Ti50 alloy were prepared by a single roller melt-spinning technique in an Argon atmosphere at the Institute of Materials Research, Tohuku University, Sendai, Japan. The amorphicity of the ribbons was conrmed by XRD and TEM investigations. The samples of as-received Cu50Ti50 ribbons were heated in dierential scanning calorimeter (DSC-50, Shimadzu, Japan), in air atmosphere, at four dierent scanning (heating) rates i.e. 2, 4, 8 and 16 C/ min upto a temperature much higher than the glass transition temperature. The DSC scans were recorded by a thermal analyzer (TA-50WSI, Shimadzu, Japan) interfaced to a computer. The heat of transformations and other essential physical quantities were obtained from the thermograms with the help of software, provided with the equipment. In DSC-50, the exothermic events are displayed by the upside shift of the baseline. The equipment has a minimum detection sensitivity of 10 lW.

endothermic glass transition events are clearly seen in the thermograms and, (ii) a small exothermic hump following the rst crystallization event is observed. These two features are absent in the DSC scans at 2 and 16 C/min. The volume fraction (x) of the sample transformed in crystalline phase during the crystallization event has been obtained from the DSC curve as a function of temperature (T). The volume fraction of precipitated crystal can be obtained from the DSC curve by using x S=S 0 ; where S0 is the total area under the crystallization curve i.e. the area under the curve between the temperature at the onset of crystallization Ton and the end-set temperature Tend when the crystallization is completed. S is the area at any temperature T between Ton and Tend at which the fractional crystallization is required to be known. Fig. 2 shows the plot of x vs. T for heating at 4 C/ min. The graphical representation of the volume

1.0

0.8

0.6

x
0.4

b a

3. Results and discussion Fig. 1 shows DSC thermograms for amorphous Cu50Ti50 at dierent heating rates 2, 4, 8 and 16 C/ min. Sharp crystallization peaks are found at 618, 631, 638 and 651 K respectively for the four heating rates. In linear heating experiments at 4 and 8 C/min; (i) the

0.2

0.0 615

620

625

630

635

640

645

650

T (K)
Fig. 2. Plot of volume fraction (x) of crystallized sample as a function of temperature.

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fraction transformed (x) as a function of temperature (T) shows the typical sigmoidal curve and appears quite frequently in the literature [1315]. The sigmoidal plot exhibits the bulk crystallization and excludes the chance of surface crystallization. During the stage a nucleation occurs at various points in the bulk of the sample and bulk crystallization becomes dominant. The stage b shows the growth of nuclei with increased rate of reaction as the surface area of nucleation increases. The decay stage c shows the decrease in surface area as a result of nuclei coalescing. The sigmoidal nature of the increase in x with T has also been conrmed for other heating rates. To determine the mechanism of crystallization from the DSC data the following equation given by Matusita and Sakka [10] has been used to obtain n and m. ln ln1 x n ln a mEc constant; 1 RT where x is the fractional crystallization at any temperature T, and a is the uniform heating rate. To obtain n, ln[ln(1 x)] is plotted against ln a at a xed temperature T. Fig. 3 shows a plot at 629 K with the slope of the straight line t giving the value of n to be 2.67. The values of n for 624 and 619 K are found to be 2.92 and 3.99 respectively. The value of n P 3 shows that the crystallization is interface-controlled. Further, the variable n values indicate that the nucleation and growth takes place by more than one mechanism. The JMA formalism originally prescribed for the study of isothermal crystallization, when applied [16] for continuous heating (non-isothermal crystallization) mode for Cu50Ti50 provides the value of Avrami exponent, n to be around 1.5, indicating that the growth is diusion controlled. Even Miao and Wang [17] obtain n % 2.5 for Cu40Ti60 glass exhibiting three-dimensional growth, constant nucleation rate and diusion control-

led process. Recently, Ruitenberg et al. [18] have compared JMA equation for isothermal and linear heating conditions and have reached at the conclusion that the linear heating exponent is equal to 2n, where n is isothermal Avrami exponent So, based on the value of n obtained here and also on the basis of Ruitenbergs comparison, the crystallization of Cu50Ti50 follows interface controlled growth process. Koster et al. [12] have also pointed out that the assumption of diusioncontrolled nucleation for Cu50Ti50 glass would lead to unrealistic activation energies. Knowing the crystallization mechanism, the activation energy for crystallization Ec can be obtained using the modied Kissinger expression [11]. an ln T2 p ! mEc ln K; RT p 2

where Tp is the peak crystallization temperature. The average value of n = 3.19 is used in Eq. (2) to plot the graph of ln(an =T 2 ) vs. 1000/Tp (Fig. 4). From the p slope of the graph mEc is found to be 665.2 kJ/mol. Using m = 2.19, Ec comes out to be 303 83 kJ/mol which is comparable with the activation energy for crystallization, 280 kJ/mol for Cu50Ti50 obtained by Buschow [19,20] and 261.2 kJ/mol, for Cu40Ti60 glass reported by Miao et al. [21]. The dierence in the two values may be attributed to (i) the slight dierence in the composition; and (ii) to the fact that in the present work the activation energy value has been calculated from modied Kissinger equation whereas Miao et al. [21] have used simple Kissinger equation. It has been reported that the Ec values obtained using modied Kissinger equation come out to be 25% higher than the corresponding result derived through simple Kissinger method [22].

3 2 1 ln( /Tp ) 0 ln[-ln(1-x)] -1 -2 -3 -4 -3.5 -3.0 -2.5 ln

Fig. 3. Plot of ln[ln(1 x)] vs. lna at 629 K.

-17 -18 -19 -20 -21 -22 -23 -24 1.52

2

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-1.5

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1.54

1.56

1.58
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1.62

1000/T p (K )
Fig. 4. Modied Kissingers plot lnan =T 2 vs. 1000/Tp. p

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3 2 1 0 ln[-ln(1-x)] -1 -2 -3 -4 -5 -6 1.52 1.54 1.56 1.58 1.60

-1

4. Conclusion The study of crystallization of amorphous Cu50Ti50 using DSC reveals that the crystallization in this alloy is an interface-controlled process. The dimensionality of growth varies from two-dimensional to three-dimensional with the change in heating rates. The higher the heating rate, the lower is the dimensionality of growth. The activation energy for crystallization found using the modied Kissinger equation is 303 83 kJ/mol. It is physically consistent with the value reported for the Cu50Ti50 alloy by Buschow [19,20] and Cu40Ti60 by Miao et al. [21].
1.62 1.64 1.66

1000/T (K )
Fig. 5. Plot of ln[ln(1 x)] vs. 1000/T at dierent heating rates. (j) 16 C/min, (d) 8 C/min, (m) 4 C/min, (.) 2 C/min.

Acknowledgment The nancial support given by AICTE, New Delhi, under project 8017/RDII/Material/261/98 is gratefully acknowledged.

Table 1 mEc, m values at dierent heating rates Heating rate (a) (C/min) 2 4 8 16 mEc (kJ/mol) 651 32 570 17 635 13 556 6 m 2.14 0.48 1.88 0.46 2.09 0.53 1.83 0.48

References
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To determine mEc at dierent heating rates, using the Matusita and Sakka equation (1), a graph of ln[ln(1 x)] vs. 1000/T is plotted as shown in Fig. 5. The plot should be linear as it has been found for many glasses. In the present case, for all the heating rates, the plot is found to be linear over most of the temperature range. However, in the beginning of the crystallization (i.e. at lower temperature and smaller x values), the relative error in the evaluation of x is large [23]. So, the rst few points at lower T (higher 1/T) in the plot have been left in the linear regression. At high temperatures or in the regions of large crystallized fractions, a break in linearity or rather a lowering of the initial slope is observed for all heating rates [22,24,25]. Generally, the break in the slope is attributed to the saturation of nucleation sites in the later stage of crystallization [22,26] or to the restriction of crystal growth by the small size of particles. In the present case where there is a change in slope, the analysis is conned to the linear region which extends over a large range. The mEc values obtained are listed in Table 1. Using Ec = 303 83 kJ/mol the values of m are also found and are listed in Table 1. The value of m decreases with increasing heating rate. This implies the decrease in the dimensionality of growth with increasing heating rate.