Structural Changes of Structural Changes of CoCo7070FeFe55SiSi1010BB1515 Amorphous Alloy Amorphous Alloy

Induced During HeatingInduced During Heating

Professor Professor Dragica M. MinićDragica M. MinićFaculty of Physical Chemistry, University BelgradeFaculty of Physical Chemistry, University Belgrade

E-mail: E-mail: drminic@gmail.comdrminic@gmail.com or or dminic2003@yahoo.comdminic2003@yahoo.com

Telephon: 1-512-250-2088Telephon: 1-512-250-2088

or 1-512-507-2822or 1-512-507-2822

IntroductionIntroduction

The amorphous metallic alloys represent a class of materials The amorphous metallic alloys represent a class of materials characterized by structure with absence of the long range order. For characterized by structure with absence of the long range order. For multi-component alloys this is more universal feature. multi-component alloys this is more universal feature.

As the first approach, amorphous alloys can be considered as two or As the first approach, amorphous alloys can be considered as two or multi-components solid solutions, like a liquid solutions. However, multi-components solid solutions, like a liquid solutions. However, they posses the typical properties of solids. they posses the typical properties of solids.

According to intensive experimental investigations, the amorphous According to intensive experimental investigations, the amorphous alloys can be obtained practically in any multi-component system, by alloys can be obtained practically in any multi-component system, by rapid cooling of liquid metals, alloys or their vapors condensing on a rapid cooling of liquid metals, alloys or their vapors condensing on a cold support, but the other methods used for achieving strong non-cold support, but the other methods used for achieving strong non-equilibrium conditions can be use too.equilibrium conditions can be use too.

Synthesized alloys in forms of ribbon or wire represent a new Synthesized alloys in forms of ribbon or wire represent a new materials with an interesting combination of physical properties that materials with an interesting combination of physical properties that make them very attractive from the technical point of view. make them very attractive from the technical point of view.

The amorphous state of matter is, however, structurally and The amorphous state of matter is, however, structurally and thermodynamically unstable and very susceptible to partial or thermodynamically unstable and very susceptible to partial or complete crystallization during thermal treatment or nonisothermal complete crystallization during thermal treatment or nonisothermal compacting. The latter imposes the knowledge of alloys stability in a compacting. The latter imposes the knowledge of alloys stability in a broad temperature range due to different crystallization processes broad temperature range due to different crystallization processes which appears during heating. which appears during heating.

By annealing below the crystallization temperature this material By annealing below the crystallization temperature this material undergoes structural relaxation processes including two competitive undergoes structural relaxation processes including two competitive processes: free volume decrease, which lowers the rate of diffusion processes: free volume decrease, which lowers the rate of diffusion mass transport, and arranging process which brings the alloy closer mass transport, and arranging process which brings the alloy closer to the crystalline state by increasing its readiness for crystallization. to the crystalline state by increasing its readiness for crystallization.

Physical features of amorphous metal alloys are irreversibly changed Physical features of amorphous metal alloys are irreversibly changed in the process of structural relaxation occurring slightly below the in the process of structural relaxation occurring slightly below the crystallization temperature. crystallization temperature.

Kinetic properties of amorphous alloys show a correlation between Kinetic properties of amorphous alloys show a correlation between the physical nature of anomalous behavior of electronic states density the physical nature of anomalous behavior of electronic states density at the Fermi level, thermal conductivity, heat capacitance and at the Fermi level, thermal conductivity, heat capacitance and electrical resistivity and structural inhomogeneities in these materials. electrical resistivity and structural inhomogeneities in these materials.

Recently, a giant magnetoimpedance (GMI) effect, discovered in the Recently, a giant magnetoimpedance (GMI) effect, discovered in the amorphous alloys, has generated growing interest among amorphous alloys, has generated growing interest among researchers and manufacturers because of their practical use for researchers and manufacturers because of their practical use for magnetic sensing and recording applications. Among these alloys, magnetic sensing and recording applications. Among these alloys, those from the quaternary Co-Fe-Si-B system have attracted those from the quaternary Co-Fe-Si-B system have attracted considerable attention in recent years. However, the physical considerable attention in recent years. However, the physical properties of this amorphous alloy systems are strongly dependent properties of this amorphous alloy systems are strongly dependent on composition, the cooling rate, oblique of alloy, subsequent on composition, the cooling rate, oblique of alloy, subsequent thermal treatment etc.thermal treatment etc.

Our recent published results on CoOur recent published results on Co8484FeFe55SiSi8.58.5BB2.52.5 amorphous alloy amorphous alloy shows that crystallization occurs via three steps. shows that crystallization occurs via three steps.

The first two steps, nucleation and formation of microcrystallites The first two steps, nucleation and formation of microcrystallites between 530 and 540 between 530 and 540 C are insufficient to give measurable XRD C are insufficient to give measurable XRD changes. changes.

The real crystallization process takes place during the last step at The real crystallization process takes place during the last step at temperatures above 800 temperatures above 800 C. C.

Our results obtained on CoOur results obtained on Co7070FeFe55SiSi1010BB1515 amorphous alloy by amorphous alloy by measuring the thermo-electromotive force during isothermal measuring the thermo-electromotive force during isothermal annealing at temperatures under crystallization point shows annealing at temperatures under crystallization point shows influence of the change free electron state density at the Fermi level influence of the change free electron state density at the Fermi level on electrical an magnetic properties of investigated alloy.on electrical an magnetic properties of investigated alloy.

To explain the mentioned influences, in this study, we investigated To explain the mentioned influences, in this study, we investigated the thermal stability and structural transformations of the thermal stability and structural transformations of CoCo7070FeFe55SiSi1010BB1515 amorphous alloy in broad interval from ambient amorphous alloy in broad interval from ambient temperature to 1000 temperature to 1000 C.C.

Experimental procedureExperimental procedure

A thirty-micrometer-thick ribbon of the CoA thirty-micrometer-thick ribbon of the Co7070FeFe55SiSi1010BB1515 amorphous amorphous alloy, prepared in the Baykov Institute of Metallurgy in Moscow by alloy, prepared in the Baykov Institute of Metallurgy in Moscow by the melt spinning method, was used as a sample in our research.the melt spinning method, was used as a sample in our research.

The thermal stability was investigated by non-isothermal analysis The thermal stability was investigated by non-isothermal analysis

(DSC) using a Du Pont Thermal Analyzer (model 1090). In this case, (DSC) using a Du Pont Thermal Analyzer (model 1090). In this case, samples of about several milligrams were heated in the DSC cell samples of about several milligrams were heated in the DSC cell from room temperature to 700 °C, at heating rates of 5, 10, 15, 20 from room temperature to 700 °C, at heating rates of 5, 10, 15, 20 and 40 and 40 C/min, in a stream of nitrogen at ambient pressure.C/min, in a stream of nitrogen at ambient pressure.

The X-ray powder diffraction patterns were recorded on a Philips The X-ray powder diffraction patterns were recorded on a Philips PW-1710 automated diffractometer using a Cu tube operated at 40 PW-1710 automated diffractometer using a Cu tube operated at 40 kV and 30 mA. kV and 30 mA.

The instrument was equipped with a diffracted beam curved graphite The instrument was equipped with a diffracted beam curved graphite monochromator and Xe-filled proportional counter. monochromator and Xe-filled proportional counter.

For routine characterization diffraction data were collected in the 4-For routine characterization diffraction data were collected in the 4-100100 2 2 range of Bragg angles, counting for 1 second. range of Bragg angles, counting for 1 second.

Diffraction data for a crystallite size measurements between 40 to Diffraction data for a crystallite size measurements between 40 to 5050 Bragg angles were collected using a 4 seconds scan at 0,02 Bragg angles were collected using a 4 seconds scan at 0,02 steps. A fixed 1steps. A fixed 1 divergence and 0.1 mm receiving slits were used. divergence and 0.1 mm receiving slits were used. Silicon powder was used as an external standard for calibration of Silicon powder was used as an external standard for calibration of diffractometer. diffractometer.

All XRD measurements were recorded on a solid samples in a form All XRD measurements were recorded on a solid samples in a form of ribbon at ambient temperature. Prior to XRD experiment the of ribbon at ambient temperature. Prior to XRD experiment the samples were heated to the elevated temperatures for 20 minutes in samples were heated to the elevated temperatures for 20 minutes in the nitrogen atmosphere.the nitrogen atmosphere.

The unit cell dimensions of alloys formed at 1000The unit cell dimensions of alloys formed at 1000C were calculated C were calculated from powder data by least square refinement procedure using from powder data by least square refinement procedure using program Lsucripc. program Lsucripc.

The face centered cubic unit cell dimensions and Fm3m space The face centered cubic unit cell dimensions and Fm3m space group for Co found in JCPDF data base (file card 15-0806), were group for Co found in JCPDF data base (file card 15-0806), were applied as a starting parameters for least square procedure. applied as a starting parameters for least square procedure.

Crystallite size dimensions i.e. the length of coherent ordered Crystallite size dimensions i.e. the length of coherent ordered structure (structure (DHKLDHKLÅ), were determined by using an interactive Å), were determined by using an interactive Windows program for profile fitting and size analysis Winfit. Windows program for profile fitting and size analysis Winfit.

Full-width at half-maximum (FWHM) values of the (111) peaks at Full-width at half-maximum (FWHM) values of the (111) peaks at Bragg angle 2Bragg angle 2=44.9=44.9, were fitted assuming a Pearson VII function , were fitted assuming a Pearson VII function for a profile.for a profile.

Results and discussionResults and discussion

Thermal investigationsThermal investigations

To estimate the ability of alloys to form amorphous phases and to define To estimate the ability of alloys to form amorphous phases and to define their thermal stability the kinetics of crystallization during heating is their thermal stability the kinetics of crystallization during heating is usually investigated. usually investigated.

For this purpose thermal analysis is the most frequently used methods. For this purpose thermal analysis is the most frequently used methods. Using different heating rates and measuring one property, proportionally Using different heating rates and measuring one property, proportionally connected with the degree of conversion, the dependence of connected with the degree of conversion, the dependence of conversion rate on temperature and time can be determined. conversion rate on temperature and time can be determined.

The general equation enabling the analysis of conversion kinetics for The general equation enabling the analysis of conversion kinetics for nucleation and growth of particles of new phase was proposed by nucleation and growth of particles of new phase was proposed by AvramiAvrami

Where Where ((), n and are degree of transformed, Avrami ), n and are degree of transformed, Avrami constant volume, frequency factor and activation energy, respectively. constant volume, frequency factor and activation energy, respectively.

( ) 1 exp[ ( ) ]nk

0 exp( / )ak k E RT

From this equation by using various approaches for the transition to From this equation by using various approaches for the transition to constant rates of heating and by checking the characteristic constant rates of heating and by checking the characteristic temperatures corresponding to the definite part of conversion (temperatures corresponding to the definite part of conversion (), ), we can obtain expressions for calculation of activation energy of we can obtain expressions for calculation of activation energy of processes known as Ozawa’s equation:processes known as Ozawa’s equation:

and Kissinger’s equation :and Kissinger’s equation :

where where C1C1 and and C2 C2 are constants. are constants.

The linearity criterion of the experimental data plotted in the The linearity criterion of the experimental data plotted in the corresponding coordinates is usually taken as a proof of reliability corresponding coordinates is usually taken as a proof of reliability of one or another equation.of one or another equation.

1ln a

i

EC

RT

2

2ln i a

i i

T EC

RT

According to DSC measurements, the alloy crystallizes step by step According to DSC measurements, the alloy crystallizes step by step with two well formed exothermal maxima at temperatures at about with two well formed exothermal maxima at temperatures at about T1=460T1=460C and T2=540C and T2=540C, respectively.C, respectively.

DSC curve of initial amorphous CoDSC curve of initial amorphous Co7070FeFe55SiSi1010BB1515 alloy; heating rate10 alloy; heating rate10 C/min.C/min.

The thermal and kinetic values of the crystallization process were The thermal and kinetic values of the crystallization process were determined by analyzing the shifts of exothermal maxima in DSC determined by analyzing the shifts of exothermal maxima in DSC thermograms depending on the heating rate. thermograms depending on the heating rate.

0.00118 0.00120 0.00122 0.00124 0.00126

1.5

2.0

2.5

3.0

3.5

R = - 0,99859B = - 66745,30041Ea = 554920,4276

T2

T1

R = -0,99933B = - 53581,02102Ea = 445472,6088

ln

1/T The Activation energy plots, for both steps of crystallization according Ozawa

0.00118 0.00120 0.00122 0.00124 0.001269.5

10.0

10.5

11.0

11.5

12.0

R = 0,99786B = 65370,43863Ea =543489,8268

R = 0,9994B = 52096,13749Ea = 433127,2871

T1

T2

ln(T

2 /)

1/T

The Activation energy plots, for both steps of crystallization according Kissinger:

The thermal and kinetic parameters process of crystallization The thermal and kinetic parameters process of crystallization

It is interesting to note the high values of the calculated activation It is interesting to note the high values of the calculated activation energies of amorphous alloy crystallization processes. energies of amorphous alloy crystallization processes.

StepStep EaEa

[kJ/mol][kJ/mol]

OzawaOzawa

EaEa

[kJ/mol][kJ/mol]

KissingerKissinger

kk

[1/s][1/s]

tt1/21/2

[1/s][1/s]

11 445.5445.51111 433.1433.11111 0.0190.019 36.536.5

22 554.9554.91111 543.5543.51111 0.0230.023 30.130.1

The activation energy of solid state reactions proceeding through formation of nuclei and The activation energy of solid state reactions proceeding through formation of nuclei and their growth, according to opinion of some researches, has no physical meaning but only their growth, according to opinion of some researches, has no physical meaning but only empirical character and practically establishes only the dependence of the rate of empirical character and practically establishes only the dependence of the rate of conversion on temperature. conversion on temperature.

This energy can be spent, not only for overcoming the activation barrier but, mainly for its This energy can be spent, not only for overcoming the activation barrier but, mainly for its downturn due to cooperative displacement of atoms. downturn due to cooperative displacement of atoms.

Thus in experiments, the total value of energy spent both, for down-turning the potential Thus in experiments, the total value of energy spent both, for down-turning the potential activation barrier and for its overcoming is determined. The opinion that the elementary activation barrier and for its overcoming is determined. The opinion that the elementary act of solid state conversion is accompanied by simultaneous correlated displacement of act of solid state conversion is accompanied by simultaneous correlated displacement of groups of atoms is especially relevant to the process of crystallization of amorphous groups of atoms is especially relevant to the process of crystallization of amorphous alloys, which is well described by the kinetics of viscous flow characterized by the alloys, which is well described by the kinetics of viscous flow characterized by the simultaneous movement of atom collectives. simultaneous movement of atom collectives.

Finely, the crystallization of amorphous alloys is a very complicated process accompanied Finely, the crystallization of amorphous alloys is a very complicated process accompanied by nucleation and growth of various crystal phases under continuously varied conditions by nucleation and growth of various crystal phases under continuously varied conditions of chemicals surroundings in a zone of conversion. Obviously, such a process occurs not of chemicals surroundings in a zone of conversion. Obviously, such a process occurs not only with the single value of activation energy and not by formation of a single only with the single value of activation energy and not by formation of a single configuration of activated complex. In practice, with the multitude of probable ways of configuration of activated complex. In practice, with the multitude of probable ways of conversions, only those mechanisms and activated complexes of the crystallization conversions, only those mechanisms and activated complexes of the crystallization process will be realized that are the most probable at a given temperature. Any change of process will be realized that are the most probable at a given temperature. Any change of crystallization conditions, such as heating rate, can result in a change of the mechanism crystallization conditions, such as heating rate, can result in a change of the mechanism and main activation complex of the crystallization process. Thus high values of activation and main activation complex of the crystallization process. Thus high values of activation energy of crystallization of amorphous alloys, first of all, indicates that a lot of atoms energy of crystallization of amorphous alloys, first of all, indicates that a lot of atoms participate in an elementary act of structure reorganization, as well as high complexity of participate in an elementary act of structure reorganization, as well as high complexity of these processes.these processes.

X-ray powder diffraction investigationsX-ray powder diffraction investigations

It is obvious that initial sample, a, pass through successive phase It is obvious that initial sample, a, pass through successive phase transformations during heating treatment. Between ambient transformations during heating treatment. Between ambient temperature and 300temperature and 300C, initial alloy retains amorphous properties C, initial alloy retains amorphous properties what is consistent with SEM investigations. what is consistent with SEM investigations.

Prolonged heating between 400 and 500Prolonged heating between 400 and 500C induces amorphous C induces amorphous alloy crystallization to, at least, two unidentified intermediary alloy crystallization to, at least, two unidentified intermediary crystalline phases, (curves b and c). One of these two phases with crystalline phases, (curves b and c). One of these two phases with characteristic peak at 2characteristic peak at 2=44.20=44.20, is more abundant and represent , is more abundant and represent the (111) inter-planar distance of Co-rich FCC cubic crystal lattice. the (111) inter-planar distance of Co-rich FCC cubic crystal lattice. The phase is always present at 400The phase is always present at 400C, b, which means that its C, b, which means that its crystallization from amorphous matrix started earlier between 300 crystallization from amorphous matrix started earlier between 300 and 400and 400. In other words, thermally induced elemental segregation . In other words, thermally induced elemental segregation in amorphous ribbon always starts in aforementioned temperature in amorphous ribbon always starts in aforementioned temperature region. The alloy segregation/crystallization processes induced by region. The alloy segregation/crystallization processes induced by heating are monitored also by appearance of dendritic forms in heating are monitored also by appearance of dendritic forms in SEM micrographs taken between 400 and 500 SEM micrographs taken between 400 and 500 C. C.