J. Phys. Chm.

Solids

Pergamon

Press 1965. Vol. 26, pp. 1727-1745.

Printed in Great Britain.

MAGNETIC

PROPERTIES OF Cr RICH Fe-Cr ALLOYS AT LOW TEMPERATURES

Y. ISHIKAWA of Tokyo, Tokyo, Japan

Institute for Solid State Physics, University

and
R. TOURNIBR Laboratoire dElectrostatique and J. FILIPPI Grenoble, France

et de Physique du Metal, C.N.R.S. (Received 14 May 1965)

Abstract--Magnetic properties of F+Cr alloys containing less than 20 at. % Fe were investigated in the temperature range 0.05-600K. The results confirmed that the iron atom has a localized moment of 2 pg at high temperatures. The magnetic moment of iron remains paramagnetic down to 2K for 1 at. $O Fe-Q, while for the specimen containingmore than 3 at. y0 Fe, the moment of iron is suggested to be arranged in an antiferromagnetic order at helium temperature. The analysis of the susceptibility as well as the isothermal magnetization curve suggest that the magnetic moment of iron at low temperature is about l-4 ps or smaller. Neutron diffraction measurements showed the existence of a long range pure antiferromagnetic order in 4.7 at. y0 Fe-Cr below about 260K with the magnetic moment of O-62 + 0.02 PB at helium temperature. It is shown that the magnetic properties of the 4.7 at. % Fe-0 alloy at low temperatures can be interpreted in terms of superantiferromagnetism and those of 10 and 15 at. o/0 Fe-Cr alloys by a combination of superparamagnetism and superantiferromagnetism. The magnetic contribution to the specific heat at low temperatures was estimated by using the proposed model.

1. INTRODUCTION THE PURPOSE of this article is to discuss the mag-

netic behaviour of iron in the Cr rich Fe-Cr alloys where the ferromagnetic order does not exist. The Fe-Cr alloy is a typical ferromagnetic alloy system which has been studied by many investigators.(l-6) One of the characteristics of this alloy system is that magnetic properties as well as other physical properties are very sensitive to heat treatment.@--5) Both magnetic moment and Curie temperature are found to increase by ageing at 500C and it is suggested that this may be due to the fact that the alloy is segregated into ironrich phase and chromium-rich phase by this heat treatment.t3*5) The alloys containing less than 18 at. y. Fe are not ferromagnetic down to 4*2K, when quenched from high temperatures,@*s) Although the isothermal magnetization curves at 4K showed
1727

a tendency to saturate in a magnetic field of 20,000 Oe, no remanence was observed; the magnetization curve has a characteristic of a temperature well above the Curie point of the bulk specimen. Two models have been proposed to interpret this phenomenon. According to the localized model which attributes the ferromagnetism of this system to the nearest neighbor ferromagnetic interaction between iron atoms, the phenomenon can be interpreted in terms of superparamagnetism of the magnetic cluster formed by incomplete linkage of the magnetic interaction. The phenomenon was also explained from the stand point of the collective electron model.@) Since the alloy has a composition close to the onset of ferromagnetism, the exchange interaction is large but not large enough to displace the band of one spin. The alloy is therefore paramagnetic, but the external magnetic field induces a magnetization much larger than

1725

Y. ISMIKAWA,

R. TOURNIER

and

J. FILIPPI

in the case without ferromagnetic interaction. A saturation effect of the magnetization curve may thus be observed at low temperature. The two models give different results at extremely low temperatures where thermal agitation of magnetic moments does not exist. In the former case, the alloy has a remanent magnetization below the blocking temperature of superparamagnetic clustering, while in the latter case, it can remain paramagnetic even at absolute zero temperature. It is therefore of interest to study carefully the magnetic properties of alloys in this composition range at very low temperatures, because it gives some information on the origin of the ferromagnetism of the alloy system. The investigation of the magnetic properties of the Fe-Cr system containing less than 20 at. /bFe is also important to the understanding of the anomalous behaviors of the specific heat at low temperatures found in the Fe-Cr alloys of this composition range. CHENG, WEI and BECK found that the Fe-Cr alloys of about 20 at. y& Fe-Cr have a large electronic specific heat and they suggested that the d band has a sharp maximum in this composition range. Since such a maximum is rather difficult to explain theoretically, some authorsuz) suggested that it might be due to the magnetic contribution. They observed also that C/T vs. T2 curves of 2, 5 and 20 at. y!b Fe-Cr increase with decreasing temperatures, a fact that suggests the existence of magnetic clusters,(ls3l4) in the alloys. For alloys containing 10 and 15 at. 96 Fe-Cr, C/T vs. T2 curves are straight lines with a positive slope which is anomalously high, suggesting again the existence of a magnetic contribution to the term proportional to Ta. The magnetic behavior of iron in the very diluted Fe-Cr alloys has also been investigated by several authors who wanted to understand the magnetic properties of chromium. Neutron diffraction studies revealed that pure chromium is antiferromagnetic below 38C with sinusoidally modulated magnetic moments.@s-17) Newman and Stevens found from susceptibility measurements that iron atoms have a localized moment of 2 FB in chromium.us) The magnetic interaction between the magnetic moments of iron and chromium is expected to be very weak because the Mossbauer spectra of Fe57 in chromium does not split into six lines even at liquid helium temperature.@@ The

magnetic structure of chromium is sensitively modified by impurities of transition metals.@*~21) The NCel temperature of chromium decreases with an addition of iron impurities.(ls,2*~22,23) The anomaly of physical properties such as susceptibility, dilatation and resistivity found at the NCel temperature is more intensified in the chromium containing small amounts of iron than in pure chromium. In order to understand these magnetic behaviours of iron in the Fe-Cr alloy particularly at low temperatures, the alloys containing less than 20 at. ,$ Fe were investigated in the temperature range 0.05-600K. The results have been published in short forms in Comptes Rendus.@-2s) 2. EXPERIMENTAL DETAILS

The specimens were prepared by melting pure chromium and electrolytic iron of 99.95% purity in an argon arc furnace at Atomic Energy Center of Grenoble. Two kinds of chromium were used as the original material. One was Johnson Matthey extra pure chromium (Cr I) and another which contains no impurities (< 10 ppm.) other than oxygen was supplied from the National Research Institute for Metal in Japan (Cr II). The alloys were annealed at 1180C for three days in evacuated silica tubes and were then water quenched. The concentration determined by chemical analysis is shown in Table 1. The magnetic properties were measured by three methods; magnetic susceptibilities of chromium containing less than 6 at. y0 Fe were measured in a magnetic field of 9000 Oe by means of a magnetic balance of the horizontal displacement type, field dependences of the magnetization in the temperature range between 4.2K and room temperature were measured by an extraction type magnetometer and the magnetizations below 4K were measured with another type of magnetometer designed by one of authors (R.T.) and L. WEIIL,@~) the essential features of which are described in Fig. 1. The magnetic field of about 25000 Oe is produced by a coil J which is forcedly cooled by pure water. The specimen is connected with a paramagnetic salt of iron alum % through a bundle of copper wires G about 40 cm in length. The whole system 13 is pulled up with a mechanical system driven by an electric motor SO that the specimen is displaced between the centres of two opposite pick-up coils H. The response of a

MAGNETIC

PROPERTIES

OF

Cr

RICH

Fe-Cr

ALLOYS

AT

LOW

TEMPERATURES

1729

Table 1. Composition of specimens

Analysis (at. %) No. 1 2 3 4 5 6 Norminal composition
Feo.01 Feo.035

Original chromium Cr II Cr I Cr I Cr I CrII Cr I

Fe 1.02 3.46 4.65 6.05 9.05 15.20

Cr 98.98 96.54 95.35 93.95 90.95 84.80

(30.99
Cro.005

Feo.05 Cro.95 Feo.065 Cro.935 Feo.10 Cro.90

Feo.15 Cr0.85

t
-to He dewarNn dewar-

_,@ @ ~~ 0 ---@

connected with extraction system vacuum pump radiation shield soldering supporter air tight by wood metal of tube inductance salt coil nyron tube

__a mutual 3
,_a ,,@ ,/,a / @

paramagnetic copper pick up specimen magnetic coil wires coils

FIG. 1. Low temperature connected to the pick-up coils is then proportional to the magnetization. The temperature below O.lK is attained by adiabatic demagnetization of the paramagnetic salt using the coil J. Temperatures between O.lK and 1K were obtained by natural warming of the paramagnetic salt. The temperatures below 1.2K were estimated by measuring the susceptibilities of paramagnetic salt which was originally calibrated fluxmeter

magnetometer.

against the vapour pressure of liquid helium. The thermal contact between the salt and the specimen is sufficiently good, so that the specimen attains the same temperature as that of the salt within a few min. Since the magnetic field applied on the specimen by the coil J has negligible small effect on the paramagnetic salt, we can measure cycles of hysteresis of the specimen even at a temperature below O*lK if hysteresis losses are small.

1730

Y. 3. EXPERIMENTAL

ISHIKAWA, RESULTS

R.

TOURNIER

and

J.

FILIPPI

3.1 Initial susceptibility Figure 2 shows magnetic susceptibility of pure chromium (Cr II). The susceptibility at 300K is 3.42 e.m.u./g, which is slightly smaller than the value obtained by NEWMAN and STEVENS.@) The susceptibility seems to depend strongly on the oxygen content. Even if the specimen was annealed in the same condition, it varied approximately ten per cent ranging from 3.40 x 10-s e.m.u./g to 3 *80 x 10-s e.m.u./g. The rapid increase of the susceptibility at low temperatures may be due to the effect of the impurities. In Fig. 3 the initial susceptibilities xi of the alloys are plotted against temperature. The ordinate is the inverse of the specific susceptibility XFe of iron defined by 1 -=XFe

about 1 or 2 per cent error to XFe, because the temperature dependent part of xm, which is expected to be of the same order of magnitude as that of pure chromium is only a few per cent of xm. In the case of 1 at. oh Fe-Cr alloy, xna was determined so that the susceptibility xz fit a following relation

c
Xi=Xrn+T-O

(2)

over a range of temperature as wide as possible. The best fit was achieved by putting xm = 3.65 x10-s e.m.u./g. For other specimens, xm was tentatively evaluated from a relation
Xm = (ICW)XO (3)

Cw
xr--Xm

(1)

where xm and CW are the susceptibility of the matrix and the weight fraction of iron respectively. xna is very difficult to evaluate, because it depends not only on temperature but also on the concentration of iron dissolved in the alloy. We assumed as a first approximation that xm does not vary with temperature. This approximation gives

where Cw is weight fraction of iron and xs was assumed to be 3 *6 x 10-s e.m.u./g. As the initial susceptibility xg at low temperature is an order of magnitude greater than xm, this approximation does not give appreciable errors for XFe in these specimens. Figure 3 indicates that the susceptibility has an anomaly below room temperature, in accordance with the result of NEWMAN and STEVENS.@) The

e.m U./g X Cr

II

IO6
35

3.2

50

100

150
Temperature

200
II.

250
T 1K

300 1

FIG. 2. Magnetic susceptibility of chromium

MAGNETIC

PRUPERTfES

OF C1- RICH

Fe-Cr

ALLOYS

AT

LOW

TEMPERATURES

1731

IQQ

200 Temperature

300 r

(K3

FIG, 3. Inverse of specific susceptibility of ima in F&r vs. lxm~pera~ure. The ordinate in the left hand
side is that for 1 at. 0h Fe-G, while that in the right hand side is for other specimens.

~orn$~~ could sot be- detected for specim~s containing more than 9 at. % Fe_ The anomaly occnrs at the Mel temperature of chromium3 which has been confirmed by a neutron diffraction study.(ss) The specific susceptibilities obey the Curie-Weiss law at low temperatures as well as above the Nt!el temperature. The effective magnetic moments pen determined from the Curie constants are plot&d agamst compositions tog&her with the pammagnetic Curie temperatures @ in Fig. 4. p&h)@ and 0 (h)@ are the values determined from the susceptibi&y above the N&X temperatuxe, while ~~~~~~~ and ~~)~ are those determ&cd at low temperatures. ~~t~rn~~c variations are foxmd for both the ef%ctive moments and the

pa~~e~~ curiepoints. ~st~) t3kes a unset value of 383 PB over the composition range between I and 10 at. /o Fe, which suggests that iron has a localized moment of about 2 ,UBat high temperatures. The result is in good agreement with that of %~MA~ and STEVENS.W On the other hand, pert(I) is smaller than p&h) for the specimen containing less than 5 at. o/o Fe, and it increases rapidly when the concentration of Fe exceeds 5 at. Oh. This is closely related with the observation that the magnetic proper&s of specimens in this ~rn~~~~on range change* although on& sfightiy, by the age&g. F#r example once the specimen is warmed up to 7&3X to measure the susceptibility* the susceptibility at room

1732

Y.

ISHIKAWA,

R.

TOURNIER

and J.

FILIPPI

temperature increases appreciably compared with the value measured before heating. In other words the iron atoms in the specimen show the tendency to agglomerate. The atoms therefore do not distribute at random and the number of iron atoms

law at low temperature, a fact which suggests that the moments of the iron atoms arrange themselves in some sort of ordered structure. The transition temperature is about 4K for 3.5 at. y. Fe-Cr, but it is not clear for the other specimens.

O(K)
200

I
i
tion. A-A

Fe in C:

FIG. 4. Dependences of effective magnetic moments 0, @ and paramagnetic Curie points 0, @ on composiAfter NEWMAN and STINENS.@~) @ Effective moments estimated theoretically.

which have other iron atoms as nearest neighbors increases even if the specimen is quenched from high temperatures. In the figure, the calculated effective moments at low temperatures peff (Cal) are also plotted against composition. Their moments were evaluated by a method discussed in a later section by assuming the random distribution of iron atoms. The experimental values deviate from the calculated ones for the specimen containing more than 5 at. oh Fe. The inverse of magnetic susceptibility varies almost linearly with temperature down to 2K for suggesting the magnetic 1 at. y. Fe-Cr alloy, moment of the irons is paramagnetic down to this temperature. For other specimens, the susceptibilities deviate downward from the Curie-Weiss

3.2 Field dependence of the magnetization and the remanfmce The field dependence of the magnetization, which is shown in Figs. 5, 6, 7 and 8, is not Iinear at low temperatures for the specimens containing more than 5 at. o/O Fe, in accordance with the result of A.RRoTT.(~) In the case of the 4.7 at. o/o Fe-Cr, no remanence (less than 0.01 e.m.u./g) appears down to O-05K. The specimen containing 6 at. y. Fe has a slight remanence at liquid helium temperature but it does not vary appreciably with decreasing temperature, suggesting that the remnance is due to the ferromagnetic impurities. Contrary to the former cases, the 10 at. o/0Fe--G and the 15 at. y. Fe-Cr show a remanence below 4K which increases almost Iinearly down to O*OSK as

MAGNETIC

PROPERTIES

OF

Cr

RICH

Fe-Cr

ALLOYS

AT

LOW

TEMPERATURES

1733

e.m.u./g M 1-5 47 at % Fe-Cr

5000
FIG. 5. Field dependence

l0000
of magnetization

15000

20000 t-l

25000

(Oe)

at low temperature for 4.7 at. y0 Fe-Cr,

M emu/g
6 at % Fe-G

3.0

.z 20 0 .v z &I s I.0

5000
FIG. 6. Field dependence

10000
of magnetization

15000

20000 H

(Oe)

at low temperatures for 6.0 at. y0 Fe-C%

1734

Y. em&q ,

LSHIKAWA,

R. TOURNIER

and

J.

FILIPPI

15 at % Fe-Cr

005K 4.2K 138K 204K 26K 34K 40K 46K 55K 75K I I25K

, --5000 10000 15000 20000 H

FIG. 7. Field dependence of magnetization

25000

(Oe)

at low temperatures for 9.0 at. y0 Fe-Cr.

e.m

u/g

9 at %

e-J-----

15000

20000

(Oe)

FIG. 8. Field dependence

of magnetization

at low temperatures for 15.2 at. % Fe-Cr.

MAGNETIC shown

PROPERTIES

OF

Cr

RICH

Fe-Cr

ALLOYS

AT

LOW

TEMPERATURES

1735

in Fig. 9. The hysteresis of the remanence of the 15 at. o/oFe-Cr measured at 1*2K and 0.06K is presented in Fig. 10. Each point in the figure corresponds to the remanent magnetization observed after applying the magnetic field indicated on the abscissa in the opposite direction to the remanent magnetization originally produced by a magnetic field of 25000 Oe. This figure indicates that at both temperatures, 1*2K and 0*06K, the remanent magnetization is saturated e.m.u./g Mr 4

The specimens with 6 at. y0 Fe and 9 at. y0 Fe were cooled from room temperature to 1~2K in a magnetic field of 12000 Oe in order to examine the effect of cooling in field, but no effect was observed for both the specimens.(Q) 3.3 Neutron diflraction study of the 4.7 at. oh Fe-Cr(Qs) Neutron diffraction measurements were made for a polycrystal of the 4.7 at. y. Fe-Cr at Centre

15 at % Fe-Cr

I
FIG. 9. Temperature

2
Temperature dependence

4 T (K) below 4K.

of remanent magnetization

by a magnetic field of 10000 Oe. Therefore the remanent magnetization 4.138 e.m.u./g acquired by a magnetic field of 25000 Oe at 0~04K is considered to be the maximum remanent magnetization of the 15 at. o/oFe-Cr. It is interesting to note that the reversal of the remanent magnetization at 0.06K takes place discontinuously by three steps. This discontinuity was also found in the hysteresis curve of the magnetization of 15 at. y. Fe-Cr taken at 0*04K, as shown in Fig. 11. The remanent magnetization is stable with respect to time at 0*04K, but time decay was observed between 1*2K and 4K. The decrease of the remanent magnetization was found to be proportional to the logarithm of time as indicated in Fig. 12.

dEtudes Nucleaires de Grenoble using a spectrometer installed in the pile SILOE. Soiler slits with the collimator angle of 8 was used to increase resolution. As is shown in Fig. 13, at the position of (100) of the chemical unit cell, a magnetic peak was observed at 4*2K. No satellite was detected around the peak. This result indicates that pure antiferromagnetic order exists in the crystal. The magnetic intensity is normalized by a nuclear peak (200). The magnetic moment estimated by using the form factor of MnQf is 0.62 f 0.02 PB at 4*2K, which is slightly larger than the magnetic moment of pure chromium of 0.59 ~LBobtained by SHIRANE and TAKEI. It must be noticed that the magnetic peak is much narrower than the nuclear peak, which is favourable to the collective electron model

1736

Y.

ISHIKAWA,

R.

TOURNIER

and

J.

FILIPPI

Mt e.mu/g
15 at % Fe-Cr

(Oe) -6000 H

-5000 - -1-o I.ZK

I
d

I / /

- -20 -30

__I

O06K<T<009K -40

FIG. 10. Hysteresis of remanent magnetization

of 1.5 at. 9; Fe-Cr

measured at 1*2K and 0.06OK.

M 15

e.m.u./g

IO

0 ._ 05 .N -z & 2 0 H

-5
Fro. 11. Hysteresis of 15 at. % Fe-Cr at 0*04K.

MAGNETIC for &he mmged

PRUPERTZES cftronium.

OF

Cr RICH

Fe-Cr

ALLOYS

AT

LOW

TEMPERATURES

IX%?

%3x in@msity rtf mag-

p&t!f

~~~~~~~~~~~~. They

are teading to a mn-

net& peak decrees

temperature 2nd it does not exist at room temperature. This result supports the fact that the anomaiy of the susceptibility found at 255% is thought to occur at the NCel temperature of chromium. e.m.u./g Mr I

with increasing

stant value and zero respective@ at OK* His theory explains qua&atiye%y the decrease of the susceptibility at the NCef point Axf Tp) ~1s W& as the deviation of XFe from the Curie law below a temperature corresponding to kT = AE. Ax(XIV)

15 at % Fe-0

Frcl. 12. Time

decay of remaxxent mrrgnetisation of 15 at. yO Fe-Cr.

4.1 The magnetic behlrsiar of &&ted alloys of iron in chwmium The magnetic susceptibilities of the impurities of iron in chromium was discussed theoretically by &MER,@9) Assuming that the. ~~~e~omagne~c structure of chro~um is not disturbed by the external field, he showed that the susceptibiity X& of the poiycrysti is given at few temperature by X,+ = ~(NM~JAE)ET)tanhAE/kT +b(NM~~/kT)st3chzaE/kT. (4)

is given by

where MF~ is the localized moment of iron and AE is the interaction energy between iron and chromium atoms. The first term in the second member corresponds to the p~~~endicn~ar snsceptiMity, while the second term corresponds to the

Fm the specim~ cont2~~g 33 at. y& Fe, AE be&g an order of magnitude of 4+K, then ~~T~~~~~T~~ calculated from the above r&tion is an order of IO-4 which would not be detected with QW apparatus. Therefore the anomaly of the susceptibility actually found cannot simply be explained by such a mechanism. Another possibility is that the magnetic moment of iron diminishes below the N&e1 point as is expected from tbe susceptibility data. This possibility cannot be excluded, because the magnitude of the magnetic moment depends on the state density at

1738

Y.

ISHIKAWA, c1001

R.

TOURNIER
r2qo1 4.2K

and J.

FILIPPI

ii*

118 12012~2

124

24.0

244

24-8-F-tI

xro!

CiOOl Cl001 7i 147K

293K

zz
s

II.8

120

12.2 I24

II6

118 12.0 12.2 124 126 --28

FIG. 13. Neutron diffraction patterns of (100) and (200) for 4.7 at. y0 Fe-G.

the Fermi surface of the band of the matrix in which the impurity is imbedded,(s@ which may change when the antiferromagnetic structure is established. The investigation of the isomer shift of Fe57 by the Mijssbauer effect is one of the best ways to examine this possibility. Our preliminary study, however, did not detect any appreciable change of the isomer shift at the NCel point for a 3 at. oh Fe-Cr. BLUM et aZ.@l) studied the M&sbauer effect of Fe57 in chromium under high field at low temperatures and found that their results are consistent with the existence of a small localized moment of the Fe atoms ( < 0-S PB). Since our experimental results of susceptibility suggest the existence of a localized moment of about 1.4~~ at low temperatures in this system, it is also possible that chromium atoms surrounding iron atoms have an induced localized moment which may be different between the paramagnetic state and the antiferromagnetic state.

We have assumed a priori in the above consideration that the magnetic interaction between the iron and the chromium plays a main role in the deviation of the susceptibility from the CurieWeiss law at 4K. If it is really the case, the susceptibility of 1 at. oh Fe-Cr may also deviate from the Curie-Weiss law at the same temperature, which is contrary to the observation. We suppose at the present stage that the difference in the magnetic interaction is due to the difference in the magnetic structure between 1 at. y. Fe-Cr and 3.5 at. % Fe-Cr.(23) The former is expected to have a sinusoidally modulated antiferromagnetic structure, while the latter specimen is confirmed to have a pure antiferromagnetic structure.@2) Further experimental investigations are necessary to obtain a definitive interpretation of the origin of the localized moment as well as the magnetic coupling between the localized moment and that of chromium.

MAGNETIC

PROPERTIES

OF

Cr

RICH

Fe-Cr

ALLOYS

AT

LOW

TEMPERATURES

1739

4.2 Initial susceptibility of alloys with more thun 5 at. y0 Fe

It has been shown in Fig. 4 that the effective moment at low temperature pen(l) becomes greater than 2.83 PB for alloys containing more than 5 at. y0 Fe. The susceptibility of magnetically dilute alloys was discussed in general by SATO, ARROTT and KIKUCHI in the Bethe approximation.(7) They showed that the apparent effective moment of dilute alloys estimated from the slope of the inverse susceptibility increases owing to the formation of the magnetic short range order. One of the authors (Y.I.) showed in a previous paper(s) that the effective moment of the dilute systems at sufficiently low temperature can be approximately evaluated by considering the system as an assembly of magnetic clusters formed by the nearest neighbor exchange interaction between magnetic ions. In the Fe-Cr system, the ferromagnetic interaction between the nearest neighboring iron atoms is much stronger than the interaction between iron and chromium, the coupled moments of iron atoms in the clusters composed of nearest neighboring iron atoms remain appreciably constant over a certain temperature range below 100K and they might be agitated thermally as a giant moment just like the superparamagnetic particle. The initial susceptibility per mole of the system at sufficiently low temperatures is, then, given by(s)

He showed that the expression (6) is practically the same as the result of the rigorous calculation by the Bethe approximation.(s) If the distribution of atoms is at random, G(n) which is the probability of finding n irons in the nearest neighbor position in the body-centred cubic structure can be evaluated using following approximate relations G(l) = PO G(2) = P~(Po+P~) G(3) = P~(Po+P~)~+P~Pz(Po+P~) G(4) = PS(PO+P~)~+P~P;(PO+P~)+~P;(PO+P~
G(5) + (1 - XjG(i)) pi = SC&l -#-

(7)

xmoz =

P&NSoW(n)(&+ 1)
3K( T- 0)

Pleff2N = 3/q-@)

(6)

where p is the concentration of iron atoms. Thevalues of G(n) as well as the effective moments calculated for the alloys studied are presented in Table 2. The results are also plotted in Fig. 3. The results of the calculation indicate that the effective moment increases by the effect of the magnetic short range order, but it is not sufficient to explain the sharp increase of the moment for the composition higher than 5 at. o/0 Fe. One of the reasons of the anomaly is probably that the distribution of irons starts to deviate from the random distribution from this composition as was suggested in a previous paragraph. The effective moments of the alloy containing less than 5 at. oh Fe can well be interpreted if we put SO = 0.7 and g = 2*. * Strictly speaking, if the spin quantum number So is not half integers, the susceptibility cannot be expressed in a simple form such as equation (6).

where g, N, SO, S, and G(n) are the g-factor, the Avogadro number, the spin of an iron atom, total spin of the cluster composed of n irons (Sn = nSs) and the volume fraction of the cluster respectively.

Table 2. Calculated distribution functions and effective moments

Composition (at. 96) 1.02 3.46 4.65 6.05 9.05 15.20 -

G(1) 0.9212 0.7545 0.6829 0.6071 0.4683 0.2674

G(2) 0.0756 0.2097 0.2531 02871 0.3134 0.2494

G(3) 0.0028 0.0312 0.0525 0.0791 0.1386 0.1618

G(4) 0.0004 0.0032 0.0080 0.0168 0.0460 0.0870

G(5) 0~0000 0*0014 0.003 5 0.0099 0.0337 0.2344

/w(So

= 1)

/&So

= 0.7) 2.234 2.358 2.422 2.500 2.678 3.118

2.887 3.024 3.096 3.184 3,384 3.884

1740

Y.

ISHIKAWA,

R.

TOURNIER

and

J.

FILIPPI

function type magnetization curves observed for 4.7 at. y0 Fe-Cr alloy cannot be interpreted in terms of superparamagnetism, because no remanence is observed down to O*O.YK. Moreover, the temperature variation of magnetization is rather small between 4-0.05K (cf. Fig. 6), which suggests that the magnetic moment is not completely paramagnetic at 4K. Since we detected the antiferromagnetic order of the chromium in the alloy, it is reasonable to suppose that the magnetic moments of irons arrange themselves in the antiferromagnetic order through the magnetic interaction between iron and chromium at low temperatures. The magnetic behavior is quite similar to the superantiferromagnetism found for antiferromagnetic fine particles.(ss) The theory of the superantiferromagnetism was developed by NCel,(s@ in which he showed that the magnetic moments on the surface of the fine particle are placed under the influence of the molecular field one half of that acting on the inner moments and that they tend to orient themselves in the direction of the applied field, while the inner moments orient themselves in a direction perpendicular to the applied field, if magnetic anisotropy can be neglected. Owing to the different orientation of the magnetic moments, the magnetization curve of the antiferromagnetic fine particle shows a concavity toward the field axis. In our system, the effective molecular field acting on the resultant moments of the group composed of two or three iron atoms is much smaller than that acting on an isolated iron atom. The magnetic moment of the group behaves just like the moment on the surface of the fine particle, while the moments of the isolated atom arrange themselves antiferromagnetically. The rigorous calculation of the magnetization process of this system can be done in the same way as NCel did.(sJ) However if

4.3 Field dependence of magnetization@s) (i) 4.7 at. % Fe-Cr. The Langevin

we assume that the antiferromagnetic structure of the chromium is not disturbed by the external field, which is practically the case in our system, the field dependence of magnetization at absolute zero temperature can be estimated in the simple way shown below. When we apply an external field H in a direction perpendicular to the antiferromagnetic axis, the resultant magnetic moment il&. of the group composed of n irons tends to orient itself towards the direction of the applied field. The equilibrium angle & of the moment with the field direction at 0K is given by

M&H sin 4% = anM&&

cos &

(8)

where an is an effective coupling constant of MF, with chromium atoms and MFn, = nlM~,+ The induced magnetization per gram M(H) in the direction of the applied field is then

M(H) = $NMF, 2 G(n)cos &

G(n)&

= -$Mo

%TF(h,)2

(9)

where N, MO and G(n) are the number of iron atoms per gram, the saturation magnetization of iron per gram and the volume fraction of the group composed of n iron atoms respectively. We take into account the situation that only two-thirds of itron atoms contribute to the perpendicular susceptibility at 0K. h, is given by

h, = H/anMcr

= HjnHe,

(10)

The interaction coefficients an calculated by the molecular field approximation are presented in Table 3. As this table shows, the group composed of the even number of iron atoms does not interact with the matrix, if we only take into account the

Table 3. Calculated aa ?l
nearest neighbor an

1
1 ~J/&$LB~

16J,3&+

J: exchange integral.

MAGNETIC

PROPERTIES

OF

Cr

RICH

Fe-Cr

ALLOYS

AT

LOW

TEMPERATURES

1741

(Oe)

H
FIG. 14. Calculated magnetization curve of 4.7 at. y0 Fe at absolute zero temperature for three different values of a2 and comparison with experimental results.

short range interaction. Therefore, a2 is left as a parameter in the calculation. The induced magnetization M(H)/Me were, then, evaluated for three different values of a2 by using the distribution function for 4.7 at. y0 Fe presented in Table 2. The results are shown in Fig. 14, where the experimental results normalized by Me are also plotted versus the magnetic field. Me is evaluated by assuming that the moment of iron is 1.4 pJ3, which is the value estimated from the susceptibility data. He1 is an order of magnitude of kT,/MF,, where T, is a temperature below which the moments of the isolated iron atoms align themselves antiferromagnetically through the interaction with the moments of chromium. Since the initial susceptibility deviates from the Curie-Weiss law at about lSK, we put Tc = 15K. The figure shows that the best agreement between the experimental result and the calculation was achieved for a2 = &al(Hez = SHeI). Although the quantitative agreement is not satisfactory even in this case, our simple calculation explains fairly well the tendency to saturate of the magnetization curve of the antiferromagnetic dilute alloy. If we adopt different values for G(n), the calculated curve can

be approached more closely to the experimental result. The magnetic properties of the 6 at. o/0 Fe-Cr are expected to be almost the same as those of the 4.7 at. o/o Fe-Cr. (z?) 15 at. % Fe-Cr. It has been found that the magnetic properties of the 15 at. o/o Fe-Cr have the characteristics of superparamagnetism. The magnetization curve has a concavity toward the field axis, while the remanent magnetization appears below 4K, increases almost linearly down to 0*04K, and decays with the logarithm of time. According to the theory of ferromagnetic fine particles developed by NCel(35) and STREET and WOOLEY,@~) the variation of the remanence of fine particles with respect to temperature and time is given by

AM,=

M,kT - cu H I (@577+bgt+Q) m cm0

(11)

where v~, Hem, 10 and Mr are the maximum volume, the maximum coercive force, the intensity of magnetization of the particle and the maximum remanent magnetization of the system respectively. Q is a constant of the order of 22.

1742

Y.

ISHIKAWA,

R.

TOURNIER

and

J.

FILIPPI

This formula gives rise to a following relation

AMJAT
AMr/A(log t) =

logt+Q T

Q
N r

(12)

This relation actually holds in our case with Q = 17. This fact suggests the existence of the superparamagnetic clusters or regions in the alloy whose maximum blocking temperature is about 4K. The magnetic moment of the largest cluster Mmax can be estimated from the blocking temperature TB by the following relation@)

netism and superantiferromagnetism. The situation is almost the same for 10 at. oh Fe-Cr. The existence of the antiferromagnetic coupling between the isolated iron atoms was never expected for the Fe-Cr alloys of this composition range. It is possible that the antiferromagnetic structure of chromium is retained even in 15 at. //o Fe-Cr. The antiferromagnetic character found in this alloy is quite different from those found in usual magnetically dilute alloys such as Cu-Mn@*) and Au-Fe.@) The antiferromagnetic order does not seem to occur cooperatively and no field cooling effect was observed. 4.4 The speci$c heat at low temperatures Our experimental results suggest that in the Fe-Cr alloys the paramagnetic atoms or superparamagnetic clusters exist down to liquid helium temperature. Therefore these paramagnetic moments contribute to the specific heat at low temperatures. The magnetic contribution is given by a following relation
CM =

$MmaxHcm = 25 kTB.

(13)

is 300~~ if we adopt 10000 Oe for Hcnz cf?cig. 10). If the superparamagnetic cluster is composed only of the iron atoms with the moment of 2 jL& the volume of the cluster corresponds to about 150 atoms of iron. In reality it is more reasonable to suppose that the cluster consists of the ferromagnetic iron rich Fe-Cr alloys segregated in the alloy. Our preliminary study indicates that the remanent magnetization increases by ageing at 600C. It is noted, however, that all magnetic properties cannot be interpretated in terms of superparamagnetism. The superaparamagnetic cluster must be saturated at absolute zero temperature, if the applied field exceeds the magnetic anisotropy field. Moreover the saturated magnetization must be at most twice as large as that of the maximum remanent magnetization. In reality, the magnetization at 0*04K does not saturate even in a magnetic field of 25000 Oe and the magnetization in the magnetic field of 25000 Oe is three times as large as the maximum remanent magnetization. We must therefore conclude that there exist iron atoms which dp not belong to the superparamagnetic cluster. Their magnetic moments might be almost quenched thermally at 4K, because the reversible part of magnetization does not vary appreciably between 4K and 0*04K. The interaction between the magnetic moments is presumably antiferromagnetic, because the magnetization is not saturated even at absolute zero temperature. This behavior is quite similar to that found for 4.7 at. y/, Fe-Cr. The magnetic properties of 15 at. y0 Fe-Cr is therefore explained by the combination of two phenomena; superparamag-

ZNk{f(gpBHe/kT) -f([2S+llgwHe/kT)), (14)

where Z, N, S and He are respectively the number of degrees of freedom of the thermal agitation, the number of magnetic atoms or clusters, the total spin of atom or cluster and the effective magnetic field around which the magnetic moments are agitated. f(x) a function defined by is

f(*) =

x2ex
(e_1)2

(15)

The equation (14) gives rise to the Shottky type specific heat for the paramagnetic spins, while in the case of the superparamagnetic cluster, S being practically infinity, CM is temperature independent at a temperature T > gpBH/k, which is of a magnetic cluster type. The magnetic contribution CM was calculated for 4.7 at. y. Fe-Cr by using the effective field He and the distribution function G(n) defined in the previous section. Z and as are assumed to be 1 and $6al respectively. The CM/T calculated is plotted versus Ts in Fig. 15, together with the experimental results.(la) It was found that the magnetic contribution mainly comes from the

MAGNETIC

PROPERTIES

OF

Cr

RICH

Fe-Cr

ALLOYS

AT

LOW

TEMPERATURES

1743

47

at

Fe-Cr

;m 5 Tf

6-

4 _

itl!e+ical

wz vt=I

325 . at % Fe-Cr Experimental (Cheng et aI I,

I
2 4 6 8 IO 12 14 16

FIG. 15. Calculated magnetic contribution to specific heat CM/T vs. Ts for 4.7 at. y0 Fe-Cr with u2 = +l and comparison with experimental results of CHnvG et ~21.(~~)

of two iron atoms and it is fairly large. The disagreement between the calculation and the observation can be improved if the number of the group of two iron atoms is smaller than that expected from the random distribution. In the case of the 10 at. y. and the 15 at. y0 Fe-Cr, the superparamagnetic clusters really exist. The results do not conflict with the experimental observation that the specific heat does not show the magnetic cluster type anomaly.(lO) The number of the superparamagnetic clusters decreases with decreasing temperature, so that the specific heat due to the magnetic cluster is not independent of temperature. It is noted that the isolated iron atoms and the group of two iron atoms in these alloys may also contribute in some ways to low temperature specific heat, because they are expected to be weakly coupled with the matrix and become aligned in some magnetic order below 4K. Such isolated iron atoms and the groups of iron atoms inevitably exist even in the alloys with more than 20 at. O/.Fe where the long range ferromagnetic order exists. Therefore one must be careful in the interpretation of the specific heat results of Fe-Cr alloys in the 20 at. y0 Fe composition range. group

4.5 The discontinuous change of the magnetization at 0*06K(zs) It has been shown in the previous section that the magnetization process at 0.06K of 15 at. y0 Fe-Cr is quite different from that at 1.2K (cf. Fig. 10). The reversal of the remanent magnetization at 0.06K takes place in three discontinuous steps contrary to the case at 1~2K where the remanent magnetization decreases continuously with increasing the magnetic field applied in the opposite direction to the remanent magnetization. The difference in the magnetization process between in two cases may be attributed to the difference in the experimental condition; the specimen was in the helium atmosphere at 1*2K, while it was in the adiabatic state at 0*06K. When we apply a weak magnetic field h in the opposite direction to the remanent magnetization, the magnetic moment AMI of the ferromagnetic clusters with a coercive force Hc smaller than h reverse in direction. The magnetic energy corresponding to 2AMlh is released in this process. As the specimen is in the adiabatic state at 0*06K and the specific heat at such a low temperature is sufficiently small, the released energy raises the local temperature of the surrounding region with

1744

Y.

ISHIKAWA,

R.

TOURNIER

and J.

FILIPPI

a volume AVr by ATl. The local increase of the temperature induces the reversal of the magnetic moments AMs of clusters having the coercive force A slightly higher than h at OK, which results in increasing further the temperature of the surrounding region with a volume AV, by ATs. The temperature variation of the irreversible magnetization in AVl in a weak magnetic field, AMsIAVlATl is approximately the same with the decrease of the remanent magnetization with temperature which is given by AMr(e.m.u./g) = -AT with A = 1.3 (e.m.u./deg.g) (cf. Fig. 10). ATs is then given by

AT2 = 2AM2h/CpAV2
In order magnetic than ATl. to induce

= ( zi:)ATl

(16)

that the avalanche of the reversal of the moments occurs, ATs must be greater The minimum magnetic field h required the first avalanche is, therefore, defined by

ha-----2AAV1

c,A

V2

(17)

Using the value C, = O-3 x 10-s cal/mol deg (the electric specific heat at O~lK(ls)), we obtain h > 93 AVgjAVl Oe. As AV2jAVj > 1 and the value of C, adopted may be underestimated, the minimum field estimated is considered to be in good agreement with the experimental observation. This model explains also the facts that the first jump of the hysteresis of remanent magnetization occurs after a small continuous decrease of the remanent magnetization and that the avalanche stops for the clusters having the coercive force greater than 1500 Oe (cf. Fig. 10). Since A decreases and AV2/AVl increases for such clusters, equation (17) does not hold for them. The second avalanche may be induced by the same mechanism when the applied field exceeds the minimum coercive force of the clusters which remain unreversed. The explanation given here suggests that the ferromagnetic clusters do not magnetically couple with each other or with the matrix even at 0*06K. 5. Conclusion We have found that, in dilute Fe-Cr alloys, the iron atoms have a localized moment and that they

behave paramagnetically in the antiferromagnetitally ordered chromium. The magnitude of the moment is different between at high temperature and below the NCel temperature of chromium. The analysis of the susceptibility at high temperatures in a customary way suggests the existence of a constant magnetic moment of 2 PB on the iron atoms in the specimen with the iron less than 10 at. $6. Low temperature susceptibility as well as the isothermal magnetization curve, however, can be better interpreted if we assume that the moment of iron is about 1.4 pi. The magnetic interaction between the localized moment and the antiferromagnetic matrix is of the order of magnitude of 4K. It seems that the magnitude of the interaction depends on the concentration of the iron in the alloy; the interaction may be smaller than 2K for the 1 at. o/0 Fe-Cr, but it is expected to be about 15K for the 4.7 at. $6 Fe-Cr. Neutron diffraction studies demonstrated that the pure antiferromagnetic structure exists below about 260K in 4.7 at. /A Fe-Cr. The antiferromagnetic structure of chromium is expected to be retained even in the 15 at. o/0Fe-Cr. The magnetic properties of the Fe-Cr alloy with less than 20 at. o/0Fe can be interpreted on the basis of the localized model if we take into account two facts; (1) that the nearest neighboring iron atoms form the short range magnetic order at low temperatures and (2) that the iron atoms have the tendency to agglomerate in the alloys containing more than 5 at. o/0Fe. The magnetic properties of the 5 at. y0 Fe-Cr alloy present a typical example that the Langevin function type magnetization curve is not necessarily explained in terms of superparamagnetism.(s) By a simple calculation we showed that if a magnetically dilute system contains ferromagnetic clusters composed of two or three magnetic atoms, the magnetization curve can show a tendency to saturate even if the magnetic interaction between the clusters is antiferromagnetic. This phenomenon is fundamentally the same with that of the superantiferromagnetism found in the antiferromagnetic fine particles. The magnetic contribution to the specific heat at low temperatures was estimated by using the model proposed for this alloy and is found to be fairly large. In the case of 10 at. % Fe and 15 at. % Fe-Cr,

MAGNETIC

PROPERTIES

OF Cr RICH

Fe-Cr

ALLOYS

AT

LOW

TEMPERATURES

1745

the superparamagnetic clusters really exist in the alloys with the maximum blocking temperature below 4K. The analysis of the hysteresis of the remanent magnetization at 0.06K suggests that magnetic coupling between the clusters can be neglected even at 0.06K. The magnetic properties of the alloys can be interpreted by a combination of superparamagnetism and superantiferromagnetism. Finally we must remark that the similar consideration is necessary to interpret the magnetic properties of the magnetically dilute alloys such as Cu-Co(40~41) and Au-Fe(@) for which the Langevin function type magnetization curve as well as the remanent magnetization have been observed at low temperatures. Acknowledgements-The main parts of this work had

11. WOOD J. H., Pkys. Rev. 126, 517 (1962). 12. MARSHALLW.. Phvs. Rev. 118. 1519 (19601. 13. SCHRGDBR K.,J. 2ppI. Pkys. i2, 880 il96i). 14. LIVINGSTON J. D. and BEAN C. P., J. Appl. Phys. 32, 1964 (1961). 15. CORLISS L., HASTING J. and WEISS R., Phys. Rev. Lett. 3, 211 (1959). 16. BACON G. E., Acta. Cryst. 14, 823 (1961). 17. SHIRANE G. and TAKBI W. J., J. Phys. Sot. Japan 17, Sup. B-III 35 (1962). 18. NEWMAN M. M. and STEVENS K. W. H.. Proc.

Phys. Sac. 74,290 (1959). 19. ~~ERTHHEI~ G. K., J. Appt. Phys. 32, 110 (1961). 20. DE VRIES G., J. Phys. Radium 20,438 (1959). 21. HA~MAGUCHI WOLLAN E. 0. and KOEHLERW. C., Y., Phys. Rev., 138, A737 (1965). 22. RATAN N. S.. WATERSTRATR. M. and BECK P. A.. j. Appl. P&s. 31, 731 (1960). 23. SUZUKI T. and TAKAGI H., J. Phys. Sot. Japan 19,
1241 (1964).

24. ISHIKA~A Y., FILIPPI P. and PAUTHENET Compt. R., Rend. 259, 3466 (1964). been accomplished during one of the authors stay in 25. ISHIKAWAY. and TOURNIER R., Compt. Rend. 259, Grenoble. He expresses his cordial thanks to Professor 3713 (1964). L. N&L, Professor L. WEIL and Professor R. PAUTHENET 26. TOURNIER R. and ISHIKAWAY., Compt. Rend. 259, for their hospitality in their laboratories. The authors 3947 (1964). thanks are a&o d;e to Professor BRISSONEAIJ and Dr. 27. TOURNIERR. and WEIL L., to be published. ALEONAR~for their advice and assistance in the prepara28. ISHIKAWAY. and ROULT G., unpublished. tion of specimens, to Dr. QUEZEL for measurements of 29. LOMER W. M., Altstralian J. Phys. 13, 451 (1960). the susceptibility at high temperatures, to Dr. TACHI30. ANDERSON W., Pkys. Rev. 124,41 (1961). P. KAWA of the National Research Institute for Metal in 31. BLUM N., FREEMANA. J., GRODZINS L., WERNICK Japan for supplying pure chromium and to Prof. J. H. and WERTHHEIM G. K., Bull. Amer. Phys. CHIKAZUMI for reading the manuscript. They are Sot. 8, 43 (1963) ; BLUM N. and GRODZINS L., indebted to Professor BERTAUT and Dr. ROULT for the Pkys. Rev. 136, A133 (1964). neutron diffraction studies. REFERENCES Constitution of Binary
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40. JACOBSI. S. and SCI~MITT R. W., Phys. Rev. 113, 459 (1959). 41. TOURNIER R. and WEIL L., J. Phys. Radium 23, 522 (1962). 42. HENRY N. E., Phys. Rev. Lett. 11,468 (1963).