The changes in electronic structure related to transport processes occurring during the alloying of he alloy Ni3Mn with iron and cobalt, and the ordering of the ternary alloys thus formed are presented. The Hall effect, the absolute thermal emf, the internal saturation induction, the Nernst-Ettingshausen constant, and the electrical resistivity were measured. Results show a decrease in the contribution of hole sections of the Fermi surface to the transport process occurs together with a considerable increase in the contribution of electron sections. In this case, the mobility of 3 dimensional holes decreases and the mobility of 4s electrons increases considerably

Fadin, V. P.

Zhukova, V. M.

English

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NASA TECHNICAL MEMORANDUM NASA TM-76620
N A^^S pE.Pt• -, f
STUDY OF CERTAIN FEATURES OF THE ELECTRONIC STRUCTURE OF THE TERNARY
ALLOYS Ni 3 (Mn, Fe) and Ni 3 (Mn, Co)
V. M. Zhukova and V. P. Fadin
(NASA-TH-76620) STUDY OF CERTAIN FEATURES
OF THE ELECTRONIC STRUCTURE OF THE TERNARY
ALLOYS Ni2 (fin, Fe) AND Ni3 (fin, Co) (National
Aeronautics and Space Administration) 11 p
HC A02/AF A01
	 CSCL 11F G3/26
V82-11180
Uaclas
01217
Translation of "Issledovanie nekotorykh osobennostey elektronnoy
struktury troynykh splavov Ni 3 (Mn, Fe) and Ni 3 (Mn, Co)", Metallo-
fizika, No. 37, 1971, pp. 18-22
NATIONAL AERONAUTICS AND SPACE ADMINISTRATION
WASHINGTON, D.C. 20546	 SEPTEMBER 1981
STANDARD TITLE PAGE
1. Row No. L Oovemmem Aneselon No. It R6elplenl'6 C6hleg No.
S	 T-66 .
4. Title mW SobM/lo STUDY OF CERTAIN FEATURES OF S. R6paI Ooh
THE ELECTRONIC STRUCTURE OF THE T RNARY
1984. P6rsrnoleq apnl 	 Co46ALLOYS N13 (Mn, Fe)	 and Ni3 (Mn, Co
P. Awthet(e) e. Pulennlq Og6nl40ll6n Rep6e1 No.
V. M. Zhukova and V. Pi Fadin
•	 1e. rr«A UnII N..
T. Potle Heg Og6wlesa6n Neme and A4b6ee 11. f o~t w Oe6M No.
NASw- 19Leo-Kanner Associates M TM of NOW ono 1116064 Covereof
Translation
Redwood 'City, California 940.63
12. Spensetlq Apeey Home 6n4 A46se6'
National Aeronautics and Space Admini•-
stration a	 Washington, DC	 20546 IA. 11"W660ne*90"yC040
IL Sopplomenhey Notes
Translation of• "tssledovanie nekotorykh osobennostey elek-
tronnoy struktury'troynykh splavov Ni,(Mn, Fe) and Ni 3 (Mn, Co)"
etallofizika, No. 37, 1971 9 pp. 18-22.
16. Ae....a
Study of-the changes in electronic structure related to trans-
port phenomena occurring during-the alloying of the alloy
N13Mn with iron and.cobalt and during the ordering of the
ternary alloys thus formed. 	 This study is performed by
measuring the Hall effect, - the absolute-thermal emf', the in-
ternal saturation induction, the Nernst-Ettingshausen constant,
and the electrical resistivity.	 It is shown that, when the
alloy Ni 3Mn is alloyed with iron and cobalt and the ternary
alloys thus formed become.ordered, a decrease in the contri-
bution of hole sections of.the Fermi surface to transport 	 -
henomena occurs togetherlwith a'consider lable increase in the
contribution • of electron se0,ion5.
	 In this case, the mobility
of 3d holes decreases and the mobility or 4s electrons
increases considerably.
17. Key woe!• 111616oted by AWhoriN) le. Olehl►ot16n Shlement
Unclassified-Unlimited
It. S6ewdly clesel41ot M1e #.peel) 20. secomr cleself. (of this pegs) 21. No. of Pegse 22.
Unclassified Unclassified
R • 1
HASA•110
STUDY OF CERTAIN FEATURES OF THE ELECTRONIC STRUCTURE OF THE TERNARY
ALLOYS N13 (Mn, Fe) and Ni3 (Mn, Co)
V. M. Zhukova and V. P. Fadin
Tomsk State University, Tomsk
18*1. The alloy N13 Mn is
metals. It is shown in
of the alloy Ni3Mn with
properties differently,
tronic structure, which
[2-41. The nature of V
• typical ordered alloy of transition
• series of studies [1-5j that alloying
iron and cobalt affects many of its
specifically the parameters of the elec-
are associated with transport phenomena
Ze indicated effect is not clear.
►RIGf Pf^,L PAGE 1$
OF POOR QUALITY
Table 1
No. of
Alloys) \i I	 Ali] I	 Fe I	 (;u
I	 2.1 0 — —1 71, 11
2 74.8 20,4 4,8 --
3 75,0 16,0 9.0 —
4 74,3 12,4 13,3 --
5 74.:) 9.4 16,1 --
G 7 4,5 6,3 19,2 —
7 75,0 -- 25,0
ri 75,0 21.0 — 4.0
9 75,0 16,0 — 9,11
10 75,0 12,5 — 12,5
\O
eo
l
0
.-r
O
a_
3U	
X2.5
Fe or Co, atomics %
Figure 1
One may obtain the most complete information on the elec-
tronic structure of the metals by using the anomalous skin effect
method, the cle G aas-Van Alfen effect method, the magnetic acoustic
effect method, and others. However, the enumerated methods are
applicable for materials for which large times of relaxation of
the electrons of conductivity are characteristic. Therefore, they
are unsuitab2o for the study of the electronic structure of alloys
(especially alloys of transition metals). The methods of measure-
ment of the Hall effect, the absolute thermoelectromotive force S,
*Numbers in the margin indicate pagination in the foreign text.
1
the internal saturation induction Bs , the Nernst-Ettingshausen
constant Qo and the specific resistivity a are very sensitive to
changes in the electronic structure of the alloys (6].
In the current study, the indicated methods were used to
study the change in certain parameters of the electronic structure•
associated with transport phenomena, for alloying of the alloy
Ni An with iron and cobalt and for ordering of the ternary alloys
which form in this case.
i
2. The composition of the studied alloys, in atomic %, is
given in table 1. The alloys were smelted in an induction furnace
from initial materials of technical purity (alloys with iron), and
a purity of 99.996 ( alloys with cobalt) . The ingots of the alloys
were forged into bars after homogenization (at 1200 0
 C for three
days), and then rolled out into a strip 0.12 to 0.10 mm thick.
Utilized as the characteristics of state of the alloys were
the magnitudes of S, p, and Q 0 listed above, and the normal Hall
constant Ro .
The Hall and Nernst-Ettingshausen electromotive forces were
measured on three-lobed samp.Les according to the procedure in 17,8;.
The procedure of measurements for S and p is described in (4].
The disordered state of the alloys was achieved by their
heating to 1000° C, holding at the given temperature for two
hours, and subsequent water quenching. Ordering nf the alloys
was carried out according; to the conditions described in [3].
3. According to the four-band model of metals and alloys
(9), in the case of negligibly small conductivity of the 3d band,
the relationship
is fulfilled, where n s
 is the number of s-electrons, and n* is the
2
effective number of charge carriers in the metal or alloy.
Consequently, relationship (1) may serve as the criterion of the
relative contribution of the holes to the transport phenomena of
the metals and alloys. In the case where relationship (1) is not
fulfilled for the studied metal or alloy, then holes make a sub-
stantial contribution to the transport phenomena. The effective
number of charge carriers may be calculated according to the
relationship [10 1
where a is the electron charge, and n is the number of atoms per
unit of volume of metal or alloy.
Presented in figure 1 are the concentration dependences of
Ro for the disordered alloys of quasibinary section Ni3Mn—Ni3Fe
(curve 1) and Ni3Mn—Ni 3Co (curve 2). It is evident that alloying
of the alloy Ni 3Mn with iron and cobalt has a substantially
different effect on the nature of the change in the normal Hall
constant R oe If the concentration dependence of R o of the alloys
with iron has a monotonously diminishing nature, then, in the case
of alloys with cobalt, it drops to Cszs4 atomic % Co, increases with
4 atomic % Co < C < 9 atomic %# and then decreases again.
Given in table 2 are the values of Roo n*, ns and 4. for the
studied alloys.
2
i .a
(,^ Id tb
O >^ 1+	 td .-+ .^
.-0
d NO \^
Q r1 U w w
x a
oe° 0
0.11 1.74 0,..2
1,21 o.58 0,5,'
4 1,1 v5 11,43 Il,ax
5 LN's o'37 wAl
41 22,11.{ 0.:15 0.61
7 2,13 11,,11 0,63
8 1,71; (ball 11,.'2
!1 L:Ii II,;i2 0,:^4
Ill 1,!1'J 0,311 0,36
"d C14 \ \
•4 r" r-4 LO d 0 O\ \
•p
O?
N
N
V
CC
w
^y
p
N
O' on
4^^ —1.x!1 0,: ► 7 u.. 2.1
2,11 ! 11,.1'2 0,7 12.8
4.2
-	 1,29 ll'35 U,' 11,0
12.0 1,77 0,40 0.- 21,3
148 11,,1:4 0.7 45.3
2.8 1,x; 11,:1'4
--- --
2.7 Ors 0,32 J
I,1 —2, l:i O,30
According to the data in [11].
3
n .
The very small positive value of R D (see table 2 and figure 1)
for the disordered alloy N1 3Mn indicates the slightly differing
contributions of the hole and electron sections of the Fermi
surface (PF) in it. In this case, it is necessEry to note that
the sign of RO , in the general case, depends oa the tensor of the
inverse effective mass 1/m*. If the Fermi surface differs con-
siderably from a sphere, then %he components of the tensor may
have different signs in different (or even in the same) sections
of the Fermi surface. Therefore, individual sections of the
electron Fermi surface may give a positive contribution to Rot
while individual sections of the hole Fermi surface may give a
negative contribution. However, a large portion of the electron
Fermi surface gives a negative contributiGn, and the hole Fermi
Lurface gives a positive contribution, to R 0 . Consequently,	 20
hole Od-holes) sections of the Fermi surface make a substantial
contribution to the transport phenomena of the disordered alloy
Ni3Mn.
The replacement of a relatively small amount (Cs 4.8 atomic
%) of manganese in the alloy Ni 3Mn with iron disrupts the
approximate equality of the contributions of the electron and hole
sections of the Fermi surface to R 0 . Therefore, in spite of the
slight changes in the structure of the 3d-band in this case [2-41,
there occurs a considerable change in R 0 (see figure 1 and table
2). Similar effects were observed in a number of other alloys
(during their alloying), and in metals as well (with a change in
temperature) [9, 12, 131.
It is evident from analysis of the data in table 2 that, for
the ternary alloys Ni3(Mn, Fe) with a relatively small iron con-
centration, condition (1) is not fulfilled. Consequently, in the
indicated alloys (in spite of the negative values of R 0 ), the hole
sections of the Fermi surface make a substantial contribution to
the transport phenomena. With a subsequent increase in the iron
concentration (C> 4.8 atomic %) in the alloys N1 3 (Mn, Fe), the
contribution of the hole sections of the Fermi surface to R0 de-
creases (and the contribution of the electron sections increases
M.
4
accordingly), and with C=9 atomic %* Fe becomes negligibly small.
As is evident from table 2 9 for the latter alloy, n*mn3 . Conse-
quently, only the s-electrons are charge carriers in the given
alloy, and, according to [91, the relaxation times of the 9-
electrone g in both directions of spin, should be roughly equal
(T s f^Ts+). The following relationships are obtained in [14]:
1/T•f (Ev) — Na f (Er) + 0,
Orr (Ep) N.,+ (Eh) + P.	 (3)
where N d +(E F) and N d +(E F) are the densities of electron states
in the dT- and d +-bands, respectively, E F is the Fermi energy,
and B is the contribution to s-electron scattering because of the
s— s-transitions, which is usually equal for both directions of
spin.
It follows from (3) that, for the alloy Ni + 16 atomic % Mn
+ 9 atomic % Fe, N d t(E F ) ;--N d +(E F ) , which agrees with the nature
of the concentration dependence of the internal saturation in-
duction of Ni3(Mn, Fe) alloys 131. Evidently, the Fermi level
of the given alloy in the 3d+ -band is located to the right of the
highest maximum on the curve Nd=f (E) [14, 2-41.
A further decrease in R 0 , with an increase in the iron
concentration in the N13(Mn, Fe) alloys, is evidently brought
about basically by a decrease in Nd +.( EF ), since N dt (EF ) changes
weakly in this case [2-41•
The value n*f- nS/2 (see table 2) for the alloy N1 3 Fe indicates
that the 3d+-band is filled, and N d +(E F)=0. Therefore, the 4s+-
electrons of the given alloy may be scattered only into the 4s-
band with a low density cf state, as a result of which they have
a high mobility and give a basic contribution to Ro o by lowering it.
C-
	
	
The monotonous and smooth nature of the concentration dependence
of the R Q of the N13Mn--Ni3Fe alloys of quasibinary cross section
5
6I.
CO
-4 u
ol^d(( N
(b w
^' o
w
O rv1
N
V
w
.r
o 
ue ^,
it M 4d s
^ u
a
v
A
oCp
it
m u
i u
V) H
W ^
N u 6
^r
^ w
•rl	 N
i >
0
indicates the presence of a closed Fermi surface in the indicated
alloys. Actually, if the Fermi surface in the alloy Ni3Mn were
opens thenp witih its alloying with iron. the Fermi surface contact
with the boundary of the zone (and therefore the contribution of
the holes to RO ) should increase. Therefore, R0 2-O should also
increase. The experimental data show a sharp decrease in R 0
 and
the contribution of the holes to R 0 . The conclusion on a closed
Fermi surface in the given alloys agrees with the results in (4).
obtained on the basis of analysis of the experimental values of S
and P 9 and for the alloy N13Fe—with the results in (16) . The
comparison of the results, obtained by two ( and for the alloy
N13Fe—by three) independent experimental methods # indicates
their sufficient reliability.
The sharp reduction in R 0 with alloying of the alloy N13Mn 	 21
with small cobalt additives ( curve 2 in figure 1) is evidently
brought about by the sharp increase in the contribution of the
electron sections of the Fermi surface to the transport phenomena,
which is associated with the introduction of two additional 3d-
electrons by each cobalt atom ( instead of the one introduced by
an iron atom) into the 3d -band of the N13 Mn alloy. The nature of
the subsequent nonmonotonous course of the concentration depen-
dence of RD ( just as that of a number of other characteristics
(3, 51) still remains somewhat unclear.
The changes in the contributions of the electron and hole
Fermi sk.:•fpces to the transport phenomena may be brought about
by a change in both the number of charge carriers t and their
6
	
Fe or Co, atomic $ 	 Fe, atomic $
Fig. 2	 Fig. 3
mobilities. In this case, the Fermi levels in the d- and s-bands
should also change. In order to determine the indicated magnitudes,
it is necessary to know the values of S, 
P'O P % and the specific
electrical conductivity o for the studied alloys. The values of
S are taken from [4] 9 the values of o are calculated according to
the values of p [ 4) , and RO and Q 0 are measured in t',, -,e given study,
and given in table 2. By utilizing the experimentally meaeured
values of the indicated magnitudes, one can use the relationships
in [17-20] to determine the values of the mobilities of the 4s-
electrons and the 3d-holes in the studied alloys. The results of the
calculations are given in .figure 2. It is evident that a decrease.
in the contribution of the hole sections of the Fermi surface, and
an increase in the contribution of the electron sections of the
Fermi surface, to the transport phenomena during alloying of the
alloy Ni 3Mn with iron is brought about basically by a decrease in
the mobility of the 3d-holes (curve 1). and by an intensive in-
crease in the mobility of the 4s-electrons (curve c). The still
more intensive mobility of the s-electrons v s increases with
alloying of the Ni3Mn alloy with cobalt (curve )), although the
concentration dependence of us is not monotonous here. The mobility
of the d-holes in the latter case also falls considerably more
intensively than in alloys with iron.
Given in figure 3 are the concentration dependences of the
mobility us ( curve 1) and the time of relaxation T s ( curve 2) of
the s-electrons of the N13 (Mn, Fe) ordered alloys of quasibinary
cross-section. It is evident from comparison of the curves of us
(see figures 2 and 3) that, with ordering of the given alloys, there
occurs a considerable increase in the mobility of the s-electrons.
It is evident from the data in table 2 that, even with Cm4.8
atomic % Fe, the value of n* approximately satisfies condition (1) .
This indicates the negligibly small contribution of the hole
sections of the Fermi surface to the transport phenomena of the
given alloy.
The trend of the curves us =f(C) and Ts (C) (see figure 3)
agrees satisfactorily with the trend of the curve of the density
7
-	 -j
of states Ndof(..') for the given alloys 1159 5t 41. With alloying
of the alloy Ni 3Mn with iron, the Fermi level displaces towards
the top of the 3d-band 15, 41, and, in this case, up to C=9 atomic
% Fe, there occurs a decrease in both N d+ and N d+. Therefore, the
scattering of s-electrons into the d-band decreases, while u s and
Ts increase accordingly. With C >9 atomic % Fe, the Fermi level in
the 3d+-band passes through a deep minimum of the curve Nd of(E)
115, 5, 41= therefore, NO begins to increase, while N d+ continues
to decrease, which leads to a considerable decrease in us , and to
a slight (very small) decrease in T S (in this case, a nearly
horizontal area is observed on curve 2 in figure 3). As the Fermi
surface approaches the top of the 3d+-band, Nd + rapidly decreases
to zeros therefore, the scattering of s-electrons into the 3d+-band
decreases rapidly (also to zero), and u g and Ts increase, reaching
maximum values in the alloy Ni3Fe.
Thus, with alloying of the alloy N13 Mn with iron and cobalt,
and with ordering of the product ternary alloys in this case,
there occurs a decrease in the contribution of hole section,
and a considerable increase in the contribution of electron sections,
of the Fermi surface to the transport phenomena. In this caset
the mobility of the 3d-holes decreases, and the mobility of the
4s-electrons increases considerably. Clearly manifested on the
concentration dependences of u s and TS of the ordered alloys
N13 (Mn, Fe) is disruption of the monotonous nature, associated
with the passage of the Fermi level through the point of the deep
energetic minimum of the curve of density of statea N d=f(E),
obtained theoretically in 115). The given results may serve as
indirect experimental corroboration of the correctness of the
calculations carried out in 1151.
8
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1. Minaeva, G. G., Panin, V. Ye., Fading V. P., Ryabyshkina, G. A.,
Zhukova, V. M., in the books
	 if
h Diffusion Processes n Metals
	 a tova umka
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&,l
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 Zavodskav
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9


Study of certain features of the electronic structure of the ternary alloys Ni2(Mn, Fe) and Ni3(Mn, Co)

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