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Acta Materialia 50 (2002) 1113–1123 www.actamat-journals.com Cyclic phase transformations of mechanically alloyed Co 7

Acta Materialia 50 (2002) 1113–1123

Acta Materialia 50 (2002) 1113–1123 www.actamat-journals.com Cyclic phase transformations of mechanically alloyed Co 7

www.actamat-journals.com

Cyclic phase transformations of mechanically alloyed Co 75 Ti 25 powders

M. Sherif El-Eskandarany a,* , K. Aoki b , K. Sumiyama c , K. Suzuki d

a Mining and Petroleum Engineering Department, Faculty of Engineering, Al-Azhar University, 11371 Nasr City, Cairo, Egypt

b Department of Materials Science, Kitami Institute of Technology, Kitami, Hokkaido 090, Japan c Department of Materials Science and Engineering, Nagoya Institute of Technology, Nagoya 466-8555, Japan

d Advanced Institute of Materials Science, Moniwadai 2-6-8, Taihaku-ku, Sendai 982-0252, Japan

Received 31 January 2001; revised 24 October 2001; accepted 19 November 2001

Abstract

Cyclic crystalline–amorphous–crystalline phase transformations have been investigated during high-energy ball mill- ing of a mixture of elemental Co 75 Ti 25 powder under an argon gas atmosphere. The results have shown that the single amorphous phase, which is obtained after 11 ks of mechanical alloying time, transforms into a new metastable phase of nanocrystalline bcc-Co 3 Ti upon milling for 86 ks. However, it transforms to the same amorphous phase upon further milling (360 ks). The present work shows the effects of the milling time and the milling speed on the structure of the mechanically alloyed powders. 2002 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.

Keywords: Mechanical alloying; X-ray diffraction (XRD); Differential thermal analysis (DTA); Scanning electron microscopy (SEM); Transmission electron microscopy (TEM); Amorphous materials; Metastable phase; Powders; Microstructure; Lattice defects

1. Introduction

Since 1983, the mechanical alloying (MA) [1] method has been successfully employed for the preparation of several amorphous alloy powders [2–10], carbides [11,12], nitrides [13,14] and nano- composite materials [15,16], using the ball milling and/or rod-milling techniques. It has been reported

* Corresponding author. Present address: Inoue Superliquid Glass Project, Exploratory Research for Advanced Technology, Japan Science and Technology Corporation, Yagiyama-Min- ami, 2-1-1, Sendai 982-0807, Japan. Tel.: +81-22-243-0261; fax: +81-22-243-7616. E-mail address: msherif@sendai.jst.go.jp (M. Sherif El- Eskandarany).

that further milling of amorphous Ti 75 Al 25 [17], Al 80 Fe 20 [18], Fe 78 Al 13 Si 9 [19] and Ti 50 Al 25 Nb 25 [20] alloy powders leads to amorphous–crystalline phase transformation (crystallization) and the for- mation of crystalline phases. The present study has been undertaken as part of an investigation into the structural changes that take place upon high-energy ball milling of a mix- ture of elemental Co 75 Ti 25 powders at room tem- perature. For the purpose of the present work, X- ray diffraction, scanning and transmission electron microscopes, and differential thermal analysis have been used to detect the structural changes and the thermal stability of the milled products. In addition, the change of magnetization for the ball- milled powders has also been measured to follow

1359-6454/02/$22.00 2002 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved. PII: S 1359-6454(01)00412-8

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the structural changes at the several stages of mill- ing.

2. Experimental procedure

Pure elemental powders (99.9%) of Co (70 µm)

the milled powders. The gas contamination con- tents (oxygen, nitrogen and hydrogen) were determined by helium carrier fusion–thermal con- ductivity method.

3. Results

and

Ti (50 µm) were mixed to give the nominal

composition of Co 75 Ti 25 (at. %) in a glove box

3.1. Ball-milling the elemental powders at a

under purified argon atmosphere and sealed in a

rotation speed of 4.2 s 1

stainless steel vial (SUS 316, 250 ml in volume) together with 50 stainless steel balls (SUS 316, 10

3.1.1. XRD analyses

mm

in diameter). The ball-to-powder weight ratio

The XRD patterns of as-milled Co 75 Ti 25 pow-

was

maintained as 17:1. The MA process was per-

ders are shown in Fig. 1 after selected mechanical

formed in a high-energy planetary ball mill (Fritsch

alloying times. In contrast to the initial mixture of

P5) at a rotation speed of 4.2 s 1 . However, some samples were obtained after milling at rotation speeds of 1.1, 2.1 and 3.3 s 1 , using the same mill- ing conditions. The MA experiments were perfor-

polycrystalline hcp-Co and hcp-Ti [Fig. 1(a)], a broad diffuse and smooth halo appears after 11 ks of MA time [Fig. 1(b)], suggesting the formation of an amorphous phase. When this sample was

med

under the same experimental conditions three

annealed under argon gas in a DTA system at 1200

times to confirm the reproducibility of the present

investigation and to avoid any accidental results.

In the all milling runs, the ball mill was interrupted when the temperature of the vial reached approx. 320 K (almost every 1.8 ks of continuous milling)

and then resumed when the temperature decreased

to 300 K. The structural changes with the milling

time for the powders were followed by X-ray dif- fraction (XRD) with CuKα radiation and trans- mission electron microscopy (TEM), using a 200 kV microscope. The metallographical and morpho- logical examinations of the milled powders were performed by means of light microscopy and scan- ning electron microscopy, using a 25 kV micro- scope. The samples were thermally analyzed with

a differential thermal analyzer (DTA) at a heating

rate of 0.33 K/s. The DTA measurements were per-

formed at a constant heating rate of 0.33 K/s under

an argon gas atmosphere. All the samples were heated up to 1200 K (first run) and cooled down to about 400 K. Then, second heating runs (dashed

lines) were performed in order to get the base line.

The magnetization of the milled powders was mea-

sured at room temperature in magnetic fields up 16

kOe using a vibrating sample magnetometer (VSM)). An induction coupled plasma emission method was used to analyze the concentration of Co and Ti, and the degree of Fe contamination in

of Co and Ti, and the degree of Fe contamination in Fig. 1. XRD patterns of

Fig. 1. XRD patterns of ball-milled Co 75 Ti 25 powders after (a) 0, (b) 11, (c) 86, (d) 173, (e) 360, (f) 540 and (g) 720 ks of MA time, using a rotation speed of 4.2 s 1 .

M. Sherif El-Eskandarany et al. / Acta Materialia 50 (2002) 11131123

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K, it revealed an fcc structure [Fig. 2(a)] that corre- sponded to the equilibrium phase of Co 3 Ti [21]. Surprisingly, the obtained amorphous phase trans- forms into a new metastable phase of bcc-Co 3 Ti upon milling for 86 ks [Fig. 1(c)]. The lattice para- meter, a 0 , of this new metastable phase was calcu- lated to be 0.2855 nm, being smaller than that for the ordered phase of equiatomic bcc-CoTi (0.2987 nm) [22]. After 173 ks of MA time, the Bragg peaks that corresponding to the bcc-Co 3 Ti became broader [Fig. 1(d)]. When this sample is annealed at 1200 K in a DTA under argon gas ow, it reveals a polycrystalline structure corresponding to bcc-Co 3 Ti (metastable phase) coexisting with the ordered fcc-Co 3 Ti [Fig. 2(b)]. This is attributed to the crystallization of the existing amorphous phase in the ball-milled powders at this stage of milling.

phase in the ball-milled powders at this stage of milling. Fig. 2. XRD patterns of ball-milled

Fig. 2. XRD patterns of ball-milled Co 75 Ti 25 powders that were heated up to 1200 in DTA under Ar gas atmosphere after milling for (a) 11 and 173 ks of MA time. The XRD pattern in (c) is for the sample that was milled for 86 ks and then heated up to 1589 K in DTA under Ar gas atmosphere.

After 360 ks of MA time, this bcc phase transforms completely to an amorphous phase, suggested by the halo that is presented in Fig. 1(e). Increasing the MA time to 540 ks again leads to the formation of a nanocrystalline phase of bcc-Co 3 Ti coexisting with an amorphous phase, as shown in Fig. 1(f). In a cyclic-phase transformation, this metastable

phase returns to the same amorphous phase of Co 75 Ti 25 upon milling for 720 ks [Fig. 1(g)]. It is worth mentioned that such cyclic phase transform- ations have been observed for all the samples which were milled for three (and sometimes four) different milling runs. It is worth noting that this

nonequilibrium phase of bcc-Co 3 Ti transforms

an ordered phase of fcc-Co 3 Ti upon annealing up

to 1589 K, as presented in Fig. 2(c).

into

3.1.2. TEM analyses The bright eld images (BFIs) and the corre- sponding selected area diffraction patterns (SADPs) for the ball-milled Co 75 Ti 25 powders are shown in Fig. 3 after selected MA times. The BFI and the corresponding SADP for the sample taken after 18 ks of MA time are shown together in Fig. 3(a). Overall, the sample appears to have a homo- geneous ne structure with no dominant structure contrast. In addition, the SADP [inset of Fig. 3(a)] shows a typical halo pattern of an amorphous phase. Contrary to this sample, the BFI [Fig. 3(b)] of the powders, which milled for 75 ks of MA time, shows the existence of numerous faults with

ks of MA time, shows the existence of numerous faults with Fig. 3. BFIs and the

Fig. 3. BFIs and the corresponding SADPs of as-ball-milled Co 75 Ti 25 powders after (a) 18, (b) 75 and (c) 86 ks of MA time, using a rotation speed of 4.2 s 1 .

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grain boundary fringes and heavy dislocations in the boundary. Furthermore, some crystalline cells with an average diameter of approx. 55 nm can be seen. Moreover, the SADP shows a halo pattern coexisting with obvious sharp spots, indicating the existence of large crystals in the amorphous matrix of Co 75 Ti 25 . The BFI of the powders that milled for 86 ks of MA time is presented together with the related SADP in Fig. 3(c). The powders consist of nano-size grains (less than 30 nm in diameter) of polycrystalline bcc-Co 3 Ti, as indicated by the DebyeScherrer rings. These nanocrystalline cells are subjected to a continuous shear and impact forces upon further milling for 386 ks so that the powders are heavily dislocated, as shown in Fig. 4(a). Such defects lead to a rise in the free energy

in Fig. 4(a). Such defects lead to a rise in the free energy Fig. 4. BFIs

Fig. 4. BFIs of as-ball-milled Co 75 Ti 25 powders after (a) 386 and (b) 720 ks of MA time, using a rotation speed of 4.2 s 1 .

from the more stable phase (bcc-Co 3 Ti) to a less stable phase (amorphous), as indicated by the homogeneous and ne structure which is presented in Fig. 4(b).

3.1.3. Magnetic measurements Since the magnetization is sensitive to the struc- ture, the magnetic properties of mechanically

alloyed Co 75 Ti 25 powders are

powerful tool to monitor the phase transformations. The magnetizations of the milled powders for the three different milling runs are plotted as a function of the MA time in Fig. 5. The rapid decrease in the value of magnetization during the rst few kilo- seconds (3.67.2 ks) indicates a drastic decrease in pure Co particles in the mixture of Co 75 Ti 25 pow- ders and the formation of an amorphous phase. After 11 ks of MA time, it decreases down to a range of 6570 emu/g. During the next stage of milling (14.422 ks), it is almost constant, suggest- ing the completion of the solid-state amorphization reaction. After 43 ks of MA time, the magnetiz- ation tends to increase slightly to a higher value, ranging from 79 to 87 emu/g, suggesting the pre- cipitation of bcc-Co 3 Ti (a ferromagnetic phase) in the amorphous matrix of Co 75 Ti 25 alloy powders. After 86 ks of the MA time, the amorphous phase

considered as a

86 ks of the MA time, the amorphous phase considered as a Fig. 5. Magnetization measured

Fig. 5. Magnetization measured at room temperature of as- mixed and ball-milled Co 75 Ti 25 powders as a function of the MA time. The rotation speed of MA is 4.1 s 1 for sample prep- aration. The closed symbols display the results for the samples prepared through three independent milling runs. The solid, dot- ted and broken lines are drawn for eye guides.

M. Sherif El-Eskandarany et al. / Acta Materialia 50 (2002) 11131123

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transforms completely into bcc-Co 3 Ti [Fig. 1(c)] where the magnetization increases drastically to have higher values, ranging from 121 to 127 emu/g. It is worth noting that these values are about twice as large as that of fcc-Co 3 Ti (approx. 56 emu/g), which was obtained by isothermal annealing the amorphous Co 75 Ti 25 alloy powders. This indicates that the mechanically alloyed bcc- Co 3 Ti phase has higher magnetization at room tem- perature. After 173 ks of MA time, the magnetiz- ation of bcc-Co 3 Ti slightly decreases due to the partial formation of the amorphous phase. After milling for 259360 ks, the magnetization of the samples attains the same values (6570 emu/g) as the amorphous samples. After 540 ks of MA time, nanocrystalline bcc-Co 3 Ti phase is formed where the magnetization increases again to a higher value, ranging from 110 to 118 emu/g. This value is slightly lower than that one of the bcc-Co 3 Ti samples, which obtained after 86 ks of MA time, probably due to the existence of amorphous Co 75 Ti 25 phase [Fig. 1 (f)]. The amorphous phase that was obtained after 720 ks of MA time [Fig. 1(g)] has almost the same magnetization value of the mechanically alloyed 18 and 360 ks amorph- ous alloys.

3.1.4. Thermal stability The DTA curves of mechanically alloyed Co 75 Ti 25 powders are presented in Fig. 6 after selected MA times. After 11 ks of MA time [Fig. 6(a)], a single sharp exothermic peak appears at 874 K. The low temperature broad exothermic reaction, which appears in the scan, is might be attributed to the relaxation of the obtained amorph- ous phase. This exothermic reaction is attributed to crystallization of the obtained amorphous phase into an ordered phase of fcc-Co 3 Ti [Fig. 2(a)]. No remarkable changes on the crystallization tempera- ture can be detected in the sample that was milled for 22 ks [Fig. 6(b)]. After 86 ks of MA time, the exothermic reaction disappears and no further reac- tions can be detected, as illustrated in Fig. 6(c). This suggests the amorphouscrystalline (bcc- Co 3 Ti) phase transformation of the as-milled sam- ple. This bcc-crystalline phase is thermally stable and does not change to any other phase(s) even at high temperatures, as high as 1500 K. It however,

even at high temperatures, as high as 1500 K. It however, Fig. 6. DTA curves of

Fig. 6. DTA curves of ball-milled Co 75 Ti 25 powders that milled for (a) 11, (b) 22, (c) 86, (d) 173, (e) 360, (f) 540 and (g) 720 ks of MA time, using a rotation speed of 4.2 s 1 .

transforms to the ordered phase of fcc-Co 3 Ti upon annealing at 1589 K [Fig. 2(c)]. A broad exother- mic peak that is centered at about 880 K is observed for the sample, which is milled for 173 ks [Fig. 6(d)]. This exothermic reaction takes place due to the crystallization of the small mole fraction of the amorphous phase in the milled powders. The XRD pattern of the sample that was heated up to

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1200 K [Fig. 2(b)] shows the co-existence of an fcc-Co 3 Ti with the bcc-Co 3 Ti phase that had already been formed during the ball milling pro- cess. This bcc-Co 3 Ti phase transforms to a single amorphous phase after 360 ks of the MA time, sug- gested by the sharp exothermic reaction which appears at 880 K in Fig. 6(e). The broad exother-

mic peak of the sample, which was milled for 540 ks, indicates the existence of a small amount of the amorphous phase [Fig. 6(f)]. After 720 ks of MA time, the bcc-Co 3 Ti phase transformed to an

upon milling for 720

amorphous Co 75 Ti 25 powders

ks which crystallizes through a single sharp exo-

thermic peak [Fig. 6(g)].

3.2. Ball-milling the elemental powders at several rotation speeds

In order to understand the effect of the milling rotation speed on the cyclic phase transformations, several samples of mechanically alloyed Co 75 Ti 25 were prepared using rotation milling speeds of 1.1,

2.1 and 3.3 s 1 .

Fig. 7(a) shows the XRD patterns of the milled

powders at a rotation speed of 1.1 s 1 . After 4386 ks of MA time, the milled powders are still a mixture of elemental Co and Ti without the exist- ence of any reacted phases [Fig. 7(a) (1) and(2)]. No remarkable changes in the total structure can be observed for the powders that were milled for milling times as long as 173 ks [Fig. 7(a)(3)]. The powders at this stage of milling (173 ks) are heav- ily defected [Fig. 8(a)] and contain large grains of polycrystalline Co and Ti, as indicated by the sharp spot pattern in Fig. 8(b). The metallographical examination of the powders at this stage of milling shows that the particles are still have a layered structure morphology with an average particle size of approx. 500 µm in diameter [Fig. 9(a)]. Some broadening can however be seen, indicating the formation of an amorphous phase coexisting with the starting reactant materials of Co and Ti. As the milling time increases (360720 ks), the intensities of the Bragg peaks for the unprocessed powders decreased [Fig. 7(a)(46)], suggesting a progress of the solid state amorphization reaction. The broad diffuse halo becomes more marked for the sample that was milled for 720 ks, indicating an

for the sample that was milled for 720 ks, indicating an Fig. 7. samples were taken

Fig. 7.

samples were taken after (1) 43, (2) 86, (3) 173, (4) 360, (5) 540 and (6) 720 ks of MA time.

XRD patterns of ball-milled Co 75 Ti 25 powders that were milled at a rotation speed of (a) 1.1, (b) 2.1 and (c) 3.3 s 1 . The

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et al. / Acta Materialia 50 (2002) 1113 – 1123 1119 Fig. 8. BFIs and the

Fig. 8. BFIs and the corresponding SADPs of ball-milled Co 75 Ti 25 powders that were milled for 173 ks at three different rotation speeds, (a, b) 1.1, (c, d) 2.1 and (e, f) 3.3 s 1 .

speeds, (a, b) 1.1, (c, d) 2.1 and (e, f) 3.3 s 1 . Fig. 9.

Fig. 9.

milled Co 75 Ti 25 powders that were milled for 173 ks at three

different rotation speeds, (a) 1.1, (b) 2.1 and (c) 3.3 s 1 .

SEM micrographs of the cross sectional view of ball-

increase in the mole fraction of an amorphous phase [Fig. 7(a)(6)]. Fig. 7(b) shows the XRD patterns of the milled powders at rotation speeds of 2.1 s 1 . When the powders are mechanically alloyed at this milling speed, the intensities of the Bragg peaks for the elemental starting materials have decreased during the rst stage of milling (4386 ks), whereas a halo pattern overlapped with the Bragg peaks of the starting materials is detectable for the sample that milled for 86 ks [Fig. 7(b)(2)], indicating the for- mation of an amorphous phase coexisting with the nano-size starting materials. The BFI and the cor- responding SADP of the powders that milled for 173 ks are shown in Fig. 8(c,d), respectively. The overall matrix which has a ne structure is an

amorphous Co 75 Ti 25 alloy with clear visible halo diffraction pattern [Fig. 8 (d)]. Those small nano- size cells that are embedded into the amorphous matrix correspond to the unprocessed powders of Co and Ti. The SEM micrograph of the cross-sec- tional view for the powder which was milled for 173 ks is shown in Fig. 9(b). The powders have a lamellar structure, indicating the existence of a large mole fraction of the unreacted Co and Ti powders. An amorphous phase is formed after 360 ks of milling, characterized by a broad diffuse halo, as displayed in Fig. 7(b)(4). Increasing the milling time (540720 ks) does not lead to any crystalliz- ation and/or phase transformations, as displayed in Fig. 7(b)(5) and (6). The XRD patterns of the milled powders at rotation speeds of 3.3 s 1 are displayed in Fig. 7(c). An amorphous phase is formed with small mole fraction of the starting powders after 43 ks of milling [Fig. 7c(1)]. Increasing the MA time (86 ks) leads to enhancement of the solid state amor- phization reaction and a single amorphous phase is obtained, characterized by a broad diffuse and smooth halo, as displayed in Fig. 7(b)(2). This amorphous phase is suddenly crystallized into bcc- Co 3 Ti [Fig. 7(c)(3)]. The obtained metastable phase consists of nanocrystalline grains (less than 50 nm in diameter, [Fig. 8(e)] with a sharp diffrac- tion ring pattern [Fig. 8(f)]. The cross-sectional view of the powders that milled for 173 ks have mirror-like metallography without precipitation of any other phase(s), indicating the formation of a single phase [Fig. 9(c)]. After 360540 ks of MA time, this metastable phase have started to trans- form to an amorphous phase, characterized by the broadening in the Bragg peaks [Fig. 7(c)(4) and (5)]. A single amorphous phase is obtained after 720 ks, suggested by the smooth halo [Fig.

7(c)(6)].

The XRD patterns in Fig. 10 present the effect of the rotation speed of the mill on the cyclic phase transformations for mechanically alloyed Co 75 Ti 25 powders. The powders of the starting materials [Fig. 10(a)] which had been already milled for 720 ks at a rotation speed of 1.1 s 1 [Fig. 7(a)(6)] were then milled at a higher rotation speed (4.2 s 1 ). In contrast to the starting materials (720 ks) that con- tain a small mole fraction of an amorphous phase

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et al. / Acta Materialia 50 (2002) 1113 – 1123 Fig. 10. XRD patterns of ball

Fig. 10. XRD patterns of ball milled Co 75 Ti 25 powders that were milled rst for 720 ks of MA time at a rotation speed of 1.1 s 1 (a), and then milled at a rotation speed of 4.2 s 1 for (b) 10, (c) 90 and (d) 170 ks of MA time.

with elemental Co and Ti phases, an amorphous phase is predominant upon milling the powders for just 10 ks [Fig. 10(b)]. Increasing the milling time to 90 ks leads to crystallization of the amorphous phase into a metastable bcc-Co 3 Ti phase [Fig. 10(c)] which has the same lattice constant as the one which is obtained after 86 ks by milling the elemental powders at a rotation speed of 4.2 s 1 for 86 ks [Fig. 1(c)]. On an expected amorphouscrystallineamorphous cyclic phase transform- ation, this metastable phase is retained to an amorphous phase after further milling (170 ks), as suggested by the clear halo in Fig. 10(d).

3.3. Chemical analysis

The iron and gas (oxygen, nitrogen and hydrogen) contamination contents of the powders that were milled at a rotation speed of 4.2 s 1 are

plotted in Fig. 11 as a function of the milling time. During the rst stage of MA, the iron which comes from the stainless steel milling tool increases dras- tically to about 0.75 at.%. The gas contamination content that may be introduced to the milled pow- der during the ball-milling process and/or handling the sample outside the glove box increases during this stage of milling. This is attributed to the for- mation of active-fresh surfaces of the elemental powders (especially Ti) which are able to react with the surrounding atmosphere. As the MA time increases the milling tools are coated with the milled powder that works as iron-resistance wear. These coated balls play an important role to pre- vent introducing a further iron contamination to the milled powder. The iron contamination content of the end product is about 0.80 at.%, as illustrated in Fig. 12. In addition, no remarkable changes in the gas content can be detected for the samples that milled for longer times.

4. Discussion

The present results conrm that the cyclic amor- phization reaction takes place upon high-energy ball milling elemental powders of Co 75 Ti 25 under an argon gas atmosphere at room temperature. Fig. 12 summarizes the results obtained by milling the powders at a rotation speed of 4.2 s 1 . Obviously, a homogeneous amorphous phase is formed after

. Obviously, a homogeneous amorphous phase is formed after Fig. 11. Dependence of the contamination content

Fig. 11. Dependence of the contamination content of ball- milled Co 75 Ti 25 powders on the MA time, using a rotation speed of 4.2 s 1 .

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et al. / Acta Materialia 50 (2002) 1113 – 1123 1121 Fig. 12. Schematic illustration of

Fig. 12. Schematic illustration of amorphouscrystallineamorphous cyclic phase transformations that are took place dur- ing ball-milling elemental powders of Co 75 Ti 25 , using a rotation speed of 4.2 s 1 .

only a few kiloseconds of milling [Fig. 1(b)]. The amorphous phase formed at this stage is not stable against the impact and shear forces, which are gen- erated by the milling media (balls) and surprisingly transforms into a new nonequilibrium phase of nanocrystalline bcc-Co 3 Ti upon further milling [Fig. 1(c)]. Such a room temperature transform- ation between the amorphous and crystalline phases can be repeated upon longer milling (see Figs. 1 and 5), using a high rotation speed of mill- ing, as high as 4.2 s 1 . The obtained metastable phase transforms to an ordered fcc-Co 3 Ti upon annealing at 1589 K [Fig. 2(c)]. This amorphous phase transforms into an ordered fcc-Co 3 Ti upon annealing at 1200 K [Fig. 2(a)]. Whilst the pow- ders are milled at a lower rotation speed of milling (1.1 and 2.1 s 1 ) such cyclic transformations could

not be observed [Fig. 7(a,b)]. When the powders previously milled at a low rotation speed are re- milled at a higher rotation speed (4.2 s 1 ), the cyc- lic amorphization is detected (Fig. 10). It is worth

noting that the cyclic amorphization is not unique for Co 75 Ti 25 alloy. It has been commonly observed for some mechanically alloyed powders such as, Al 50 Zr 50 [10] and Co 50 Ti 50 [23] so that the reversi- bility of phase transformations is not unique to a particular system. It has been reported [24] that hcp-Co transforms to fcc-Co phase by high-energy ball milling an elemental Co at room temperature. The obtained fcc phase was again transformed to hcp-Co by further milling. One possible factor, which leads to such cyclic

Co 75 Ti 25 ,

crystallineamorphous transformation of

is the introduction of contamination in the ball- milled powders. The total impurity concentration measured at various MA times is less than 1.50 at. % for the milled powders (Fig. 11). It has been suggested by the chemical analyses, that there was no oscillation in the impurities values while the cyclic transformation took place (Figs. 5 and 12). These low values of the contamination contents plus the fact that they do not oscillate during the

milling time [25] can make us neglect their effects for such cyclic amorphization. They therefore do not play any role in such reported cyclic phase transformations of Co 75 Ti 25 . Another possible factor, which can lead to the cyclic phase transformations, is the temperature rise during the milling. In order to examine the effect of temperature increase on the structure of the powder during milling, the samples that milled

for

11 ks (amorphous phase of Co 75 Ti 25 alloy) and

86 ks (bcc-Co 3 Ti) were heated separately in the

DTA to 700 K (well above the measured tempera- ture of the vial). The XRD patterns of these samples prove that no phase transformation has

taken place even at this relatively high temperature, having the same XRD patterns displayed in Fig.

1(b,c). In contrast, the amorphous Co 75 Ti 25

alloy is

transformed to an ordered fcc-Co 3 Ti upon

heating

to about 880 K, as shown by the DTA measure- ments (see Fig. 6). In addition, the bcc-Co 3 Ti phase transforms into fcc-Co 3 Ti when it is annealed at 1589 K [Fig. 2(c)]. In this context, the temperature recorded during the ball-milling process is far

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below the temperatures required for structural changes in the milled powder. The TEM/EDX analyses for the obtained amorphous and bcc- Co 3 Ti phases [Fig. 3(a,c)] have not shown any con- centration gradient or compositional uctuation, indicating that both the amorphous and metastable phases are homogeneous. Since mechanical milling introduces many vac- ancies, lattice defects, grain boundaries and sur- faces, milled powders store a large amount of mechanical-strain energy [2631]. In the initial milling stage, crystalline elemental powders are mechanically crushed and fresh surfaces are highly created. Kneading of such ground powders enhances atomic diffusion of elemental atoms and to step-by-step local alloying (mechanical alloying). When the long-range periodic structure is destroyed by introduction of defects, an amorph- ous phase is obtained as a metastable state. In the milling process, friction between balls, balls and the surface of a vial also generate frictional heat. Such heat not only accelerates diffusion of consti- tutional atoms of powder mixture, but also contrib- utes to thermal annealing of the amorphous phase. Without interruption of the milling process, the amorphous phase is transformed to the equilibrium crystalline fcc phase (over-milling). Hence the milling process was interrupted every 1.8 ks to reduce the vial temperature down to 300 K, the amorphous phase is moderately annealed, being transformed to another metastable bcc phase under mechanical shear and impact forces. Since further mechanical milling again introduces many defects in the crystalline phase and destroys the periodical structure, the bcc phase is transformed to the amorphous phase (mechanical disordering). These sequential transformations are observed as the cyc- lic transformation in the moderate milling process. Moreover, the present result suggests that the for- mation enthalpy of the metastable bcc phase is comparable to the amorphous phase and the energy barrier between these two phases is rather low to allow such transformation.

5. Conclusion

In conclusion, we have demonstrated cyclic amorphous-to-crystalline phase transformations

during ball milling of elemental Co 75 Ti 25 powder. After a few kiloseconds of milling, a solid-state reaction takes place at the fresh interfaces of Co/Ti layers and an amorphous phase of Co 75 Ti 25 is for- med after 11 ks. This amorphous phase transforms into an ordered fcc-Co 3 Ti upon heating to 880 K (crystallization). Further milling (86 ks) also leads to an amorphouscrystalline transformation (crystallization) and the formed phase is metastable bcc-Co 3 Ti nanocrystalline powders. We have attri- buted this transformation, which took place in the ball mill to the inability of the formed amorphous phase to withstand the impact and shear forces that are generated by the milling media (balls). When the milling time is increased (360 ks), the crystal- line phase is subjected to several defects (points and lattice defects) that raise the free energy from the stable phase of bcc-Co 3 Ti to a less stable phase (amorphous). Here, the crystallineamorphous transformation which takes place is similar to the mechanical grinding method [28] in which the amorphization occurs by relaxing the short-range order without any compositional changes. Further milling leads to the formation of crystalline and/or amorphous phases depending on the milling time.

References

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