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DSpace at VNU: Influence of Ti and V substitution for Al on the properties of Nd60Fe30Al10 alloys

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At increasing the Ti or V content, the crystalline fraction in the samples increases and for x ¼ 10; the alloys are fully crystalline.. All samples, some of them in a partly crystalline

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Influence of Ti and V substitution for Al on the properties of

N Chau*, N.H Luong, C.X Huu, N.T Thep, H.D Anh

Center for Materials Science, National University of Hanoi, 334 Nguyen Trai, Thanh Xuan, Hanoi, Viet Nam

Abstract

Systems with compositions Nd60Fe30Al10xTixand Nd60Fe30Al10xVx(x ¼ 2; 4, 6, 8, and 10) have been prepared by arc melting and copper mold suction-casting The cast surface of the samples is partially crystalline At increasing the Ti

or V content, the crystalline fraction in the samples increases and for x ¼ 10; the alloys are fully crystalline Melting temperatures also increase with increasing Ti or V content in the samples All samples, some of them in a partly crystalline state, exhibit good hard magnetic properties at room temperature With increasing Ti or V content, the magnetization continuously decreases, whereas both the coercivity and the Curie temperature increase

Thermomagnetic curves measured for all samples at low field exhibit an interesting shape The temperature dependence of the coercivity of the samples has been determined

r2003 Published by Elsevier Science B.V

PACS: 75.50.Bb; 75.50 Lk; 75.50.Vv

Keywords: Magnetization; Hard magnetic materials; Crystallization–amorphous systems; Rare-earth alloys

Recently, Inoue et al [1–3] prepared bulk

amorphous alloys of the type Ln–Fe–Al (Ln=Nd,

Pr) by a copper mold casting technique These

alloys have generated considerable interest in both

fundamental research and applications because

they exhibit a large coercivity at room

tempera-ture Unlike the magnetic ribbons, in which the

amorphous state can be only obtained by cooling

from the melt with very high cooling rates of about

106K/s, the amorphous state in the bulk alloys

occurs at cooling rates as low as 1–102K/s

However, the authors of Refs [4–8] pointed out

that it is difficult to prepare samples with a fully

amorphous state from these alloys According to

Inoue et al [2,3], the hard magnetic properties occur in the alloys Ln–Fe–Al only when they are in the bulk amorphous state The same authors of Refs [4–8] have shown that the hard magnetic properties also persist in partially crystalline bulk samples The effects of B substitution for Al [7]

and Co substitution for Al[8]have been studied This work presents the influence of Ti and V substitutions for Al in the alloy Nd60Fe30Al10, on its structure and magnetic properties

Two alloy systems with compositions

Nd60Fe30Al10xTix (x ¼ 2; 4, 6, 8 and 10) and

Nd60Fe30Al10xVx (x ¼ 2; 4, 6, 8 and 10) have been prepared by arc-melting a mixture of high-purity elements in an argon atmosphere After melting all elements together, the samples were prepared by suction-casting of the molten alloy

*Corresponding author Tel./fax: +84-4-858-9496.

E-mail address: chau@cms.edu.vn (N Chau).

0304-8853/03/$ - see front matter r 2003 Published by Elsevier Science B.V.

doi:10.1016/S0304-8853(03)00075-1

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into a water-cooled copper mold The structure of

the as-cast samples was examined with X-ray

diffraction using a Bruker D5005 apparatus The

composition was checked by EDS included in the

JEOL 5410 LV SEM The thermal stability of the

alloys has been determined by DSC using a TA

Instruments SDT 2960 Magnetization and

hyster-esis loops were measured using a Digital

Measure-ment Systems VSM model DMS 880

X-ray diffraction patterns of samples of both

alloy systems show that the cast surfaces of all

samples are crystalline, probably due to

crystal-lization originating from the copper mold wall

To study the variation of crystallinity with

respect to the position in the sample, we have

taken X-ray diffraction patterns at depths of

d ¼ 0:2 and 0.4 mm beneath the surface of the

samples The results show that with increasing

depth the samples essentially remain crystalline,

although the crystallinity fraction somewhat

decreases Quantitative analysis by EDS

reveals that the alloys have the intended nominal

compositions

The DSC curves of all samples have been

determined The samples with lower Ti content

show an exothermic peak associated with

crystal-lization With increasing Ti concentration the

crystallization transition becomes less clear and

the sample with x ¼ 10 does not show any

crystallization transition It indicates that the

sample Nd60Fe30Ti10 is fully crystalline In the

samples with lower V content a supercooled,

partially amorphous state exists Nd60Fe30V10 is

also fully crystalline We find that the melting

temperature of the studied samples clearly

in-creases with increasing Ti or V content The

authors of Ref [9]pointed out that the addition

of Co significantly enhances the glass-forming

ability of Nd70xFe20Al10Coxalloys Our

observa-tion here is in agreement with the results obtained

in Ref [7] for Nd60Fe30Al10xBx alloys in which

the glass-forming ability decreases with increasing

B content

Nd60Fe30Al10xTix (Fig 1a) and Nd60Fe30

Al10xVx (Fig 1b) samples at room temperature

We see that with increasing Ti or V content, both

the magnetization measured at maximum field and

the remanence decrease whereas the coercivity increases

Thermomagnetic curves of the samples were measured at temperatures up to 620 K At low fields, the Hopkinson effect is clearly seen Fig 2

-20 -10 0 10

20

x = 2

x = 4

x = 6

x = 8

x = 10

H (kOe)

14.0 10.5 7.0 3.5 0 -3.5 -7.0 -10.5 -14.0

-20 -10 0 10 20

x = 2

x = 4

x = 6

x = 8

x = 10

H (kOe)

(a)

(b) Fig 1 Hysteresis loops of the Nd 60 Fe 30 Al 10x Ti x (a) and

Nd 60 Fe 30 Al 10x V x (b) samples at room temperature for different x-values.

0 2 4 6 8 10 12 14 16

300 350 400 450 500 550 600

10000 Oe

5000 Oe

2500 Oe

1000 Oe

500 Oe

100 Oe

T (K) Fig 2 Thermomagnetic curves of Nd 60 Fe 30 Al 6 V 4 measured at different applied fields.

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presents a representative series of thermomagnetic

curves for Nd60Fe30Al6V4 Note that crystalline

fraction in this V substituted sample is rather high

The occurrence of a Hopkinson effect here

indicates that the magnetic anisotropy decreases

rapidly with increasing temperature and the

magnetic saturation can be easily reached at low

magnetic fields due to a rotation of domain

moments

measurements at low field we derived the

composi-tion dependence of the magnetic characteristics of

the samples as presented in Table 1 One can see

fromTable 1that in both systems of samples, the

Curie temperature increases with increasing Ti or

V content substituted for Al

Hysteresis loops are measured from low to high

temperatures The available maximum field is not

enough to saturate the samples, i.e the hysteresis

loops are minor loops However, the coercivity

increases rapidly with decreasing temperature For

example, HC of Nd60Fe30Al8Ti2 is 8.5 kOe at

201 K and 0.5 kOe at 390 K whereas HC of

Nd60Fe30Al8V2is 8.35 kOe at 240 K and 0.46 kOe

at 390 K

Field-cooled (FC) and zero-field-cooled (ZFC)

curves have been assessed for all samples Fig 3

shows representative data, for Nd60Fe30Al6Ti4

(Fig 3a) and Nd60Fe30Al6V4(Fig 3b) It is

inter-esting to note that these curves are clearly

separated from each other at low temperatures

This remarkable feature of magnetic properties in

two series of samples indicates the appearance of

short-range ferromagnetic interactions This is

confirmed by observing spin-glass-like behavior

at low temperature and in low field ranges In low

applied fields, both the ZFC and FC

magnetiza-tion curves split at a temperature below the

so-called irreversibility temperature, Tr (oTC) Both the ZFC and FC MðTÞ curves resemble each other substantially in the range of TXTr; implying the irreversibility of magnetization In addition, the low field ZFC MðTÞ curves clearly show a cusp at

a so-called spin freezing (or spin–glass transition) temperature, Tg; where a maximum magnetization

is attained, as demonstrated inFig 3 This research is performed within the project

420101 of the Vietnam National Program for Fundamental Sciences and the Vietnamese—US

Table 1

Composition dependence of magnetic characteristics

X Nd 60 Fe 30 Al 10x Ti x Nd 60 Fe 30 Al 10x V x

Z F C

0.0 1.2 2.4 3.6

T (K)

(a)

(b)

0 1 2 3 4 5

F C

T (K)

Z F C

F C

Fig 3 FC and ZFC curves measured in a field of 20 Oe for

Nd 60 Fe 30 Al 6 Ti 4 (a) and Nd 60 Fe 30 Al 6 V 4 (b).

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Cooperation project supported in part by the US

National Science Foundation

References

[1] A Inoue, T Zhang, A Takeuchi, IEEE Trans Mag 33

(1997) 3814.

[2] A Inoue, T Zhang, W Zhang, A Takeuchi, J Inst Met.

37 (1996) 99.

[3] A Inoue, T Zang, A Takeuchi, Sci Rep., RITU A 44

(1997) 261.

[4] Y Li, J Ding, S.C Ng, X.Z Wang, J Magn Magn Mater.

187 (1998) 273.

[5] J Ding, Y Li, X.Z Wang, J Phys D 32 (1999) 713 [6] N Chau, N.H Luong, D.T.K Anh, C.X Huu, Proceedings

of the Third Vietnamese-German Seminar on Physics and Engineering, Ho Chi Minh City, 3–8 April 2000, p 133 [7] N Chau, N.H Luong, C.X Huu, N.X Phuc, N.H Dan, J Magn Magn Mater 242–245 (2002) 1314.

[8] N.H Dan, N.X Phuc, V.H Ky, N.M Hong, N Chau, N.H Luong, C.X Huu, R.W McCallum, L.H Lewis, L.D Tung, MRS Symp Proc 674 (2001) U.2.6.1.

[9] G.J Fan, W Loser, S Roth, J Eckert, L Schuetz, J Mater Res 15 (2000) 1556.

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