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The binary system Ni-In
Journal of
ALL©YS
ANB~ COMPOUND5 Journal of Alloys and Compeunds 257 (1997) 253-258
ELSEVIER
The binary system Ni-In Ph. D u r u s s e l , G. Burri, E F e s c h o t t e * tnstitut de Chimie Mingrale et Analytique, Universitd de Ix~usanne, BCH, CH-1015 Lausanne-Dorigny, Switzerland
Received 16 December I996; received in revised form 20 January 1997
Abstract The binary system Ni-In has been completely revised by XRD, DTA and EMPA on carefully annealed alloys (from 30 days at 1000 °C to 6 months at lower temperatures (-400 °C)). The solubility of In in Ni varies from 3.3 at.% In at 420 °C, increasing to a maximum of 9.5 at.% In at 908 °C. No solubility of Ni in In has been measured. Only three observed intermetallic compounds are non stoichiometric: Ni2In (high temperature form, stable from 470 °C to 950 °C, with a maximum extent from 3i.2 at.% In (9138°-C) to 42 at.% In (908 °C)), Ni13In9 (peritectok'dic decomposition at 853 °C, with a maximum extent from 38.0 to 42.0 at.% at 200 °C) and NiIn (high temperature form, stable from 779 °C to 930 °C, with a maximum extent from 49.5 at.% in (908 °C) to 58.8 at.% In (865 °C)). All the other observed intermetallic compounds are stoichiometric: Ni3In, Ni2In (low temperature form), NiIn (low temperature form), Ni2In 3 and Ni~In7. © 1997 Elsevier Science S.A. Keywords: Ni alloys; In alloys; Ni-In binary system; DTA; XRD; EMPA; Phase diagram
1. Introduction and previous work The assessed phase diagram [1] (Fig. 1) is based primarily on the compilation of Hultgren [2], with modifications based on the work of Ellner [3], Peretti [4], Best and Goedeke [5] and Livingston [6]. This binary system has not been studied since the compilation presented by Massalski [1] in 1991. According to these earlier works, the proposed intermediate compounds, except NiaIn, show a detectable and more or less wide range of existence. The composition of the compounds is not properly known and their existence is dubious in regard to the observations made in the systems Pd-Sb, Pt-Sb [7], A g - P t [8], P b - P d [9] and Pt-Sn [10], where the large ranges of existence of the intermediate phases given in literature were often due to the absence of equilibrium conditions (annealing time too short to obtain a true equilibrium).
2. Experimental All the alloys (0.6 to 2 g) were synthesised by melting pure metals (Ni 99.998%, Koch-Light and In 99.9995%, Fluka) in an induction furnace in sealed quartz bulbs under an inert atmosphere of argon (Argon (~52~, Carba Gaz). *Corresponding author. 0925-8388/97/$17.00 © 1997 Elsevier Science S.A. All rights reserved. PII S0925-8388(97)00033-9
The composition of our alloys was checked by comparison to the weight of the pure metal mixture before and after the melting in the induction furnace. The measured loss of metal (maximum 0.008 g on 1 g of mixture, for a composition of 90 at.% In) is attributed to In and does not exceed 0.02 at.% In in the region richest in indium. The crude alloys are very stable in air. Each sample was carefully annealed for homogenisation over 7 days. Afterwards, each alloy was fragmented into thin powder, if brittle (25 to 70 at.% In), or into pellets if malleable or very hard. Annealing occurs for a long time in little quartz Ar-filled tubes. In order to obtain equilibrium conditions, checked by permanence of X-ray diffraction (XRD) powder spectra, the annealing times found to be necessary are: - 6 months at 400 °C and ~1 month at r > 9 0 0 °C. XRD measurements were carried out using silicon powder as internal standard for obtaining accurate lattice parameters. In the differential thermal analysis (DTA) measurements, the systematic use of internal standards (Ag, A1, Au, In or Sn), a relatively moderate heating speed (5 °C min -~) and a small amount (<0.1 g) of alloy when the expected liquidus is horizontal, gives a reproducibility of _+2 °C at 950 °C. A good reproducibility (generally _+0.2 at.% In if frequent restandardisations are made with pure metals) of the electron microprobe analysis (EMPA) results is ob-
P. Durussel et al. / Journal of Alloys and Compounds 257 (t997) 253-258
254
Weight 0
]0
1600 t . . . . .
eo
~. . . .
ao
"J . . . . .
40
I., ....
50
PercenL 60
Indium
70
&,-..~._,.,.,.l, ~ , . ~ . , _ r , , . , . J . _ ~ , ~ _ r . , . ~
ao
.l.~.,,.v,.~,
90
~ ,L,~, l . . . .
T' ) ......
10o "-r ~
1455oC
1400
L 1200
C)
o
I000 48.6i ~]00
q)
cD
600
400
200 • 156 834
C
00
20
10
50
40
30
ALomic
Ni
60
Pereeni
80
7d
90
100
[)Ktium
[n
Fig. 1. Ni-In binary system according to the compilation of Massalski [1].
rained by using internal standards (pure Ni and pure In) and Magic IV software [11] for ZAF corrections.
ments are represented. XRD results have always be used to confirm the proposed diagram, even with respect to the stoichiometry of the five compounds producing constant diffraction angles in both sides of the observed phases. Details of the regions around the non-stoichiometric Ni2In and NiIn high temperature forms are shown in Fig. 3. The following points have been more precisely determined:
3. Phase diagram Our completed Ni-In phase diagram is displayed in Fig. 2. Only DTA and electronic microprobe analysis measureNf31n &"
".
\ 25.0.0.T \
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1000
•,
5', ),5" .
~'
'
.
l +
Nil3 In 9 "'"
In
Ni21n 3
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-2j ".oo
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~andA=DTAresuts I
I o" microprob. . . . '~'l I J
2 ,,o;,.c
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8O0
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600
i
iln
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E
#. 400 i i
~
70 ~0.5
t56,
156,6 "c
200
/,.
l/
38.0 ~ 0.5
0 Ni
20
/
!
-
"1
42.0 :E 0,5
40
60
80
at % In Fig. 2. Ni-In phase diagram according to our present work.
1 O0 In
P. Durussel et al. / Journal of Alloys and Compounds 257 (1997) 2 5 3 - 2 5 8
255
1000950 " ~ 25......
~50=~,c
55,0±0,5 ~930 ;~2oo
"°":"-" b"°: ....... =
" /
\
8ooq t 700'
=~,=~0.5
/
~'
~'/
/
I 2°22:
.I/
I
,
- "'2::;::,
I
5
6,o.!
/'=°:
I
\
I'1
,/"
, tt
~
,,o=o°
40 at % In
-J
6o.o,o,5
I ,o.oo
......
30
/
r
;n ??0;, ....
Ni
4
\
! ii .....
t
50
60 In
Fig, 3. Detailed region of the Ni-In system around non-st0ichiometric Ni2In and NiIn high temperature forms.
ILl
660 843 °
/
~
64o O
620
"l-
d 600
I DTAof aiso,81n492annealedfor 3800hoursat 400°C i
t,-
l.u
811
8;0
8~9
&8
8~7
&8
8~
Temperature [°C]
(b) ~
1. The separation of the DTA events occuring at 845_+3 °C (41.8 to 53.3 at.% In) and 853+3 °C (41.5 to 52.7 at.% In) is very difficult because the proximity of both thermal effects. Only the data acquisition software, a very slow heating speed (3 °C/min.) and a very small amount of alloy (0.06 g) allow us to measure the accurate temperatures of these transformations (Fig. 4a). 2. The DTA determination of the range of existence of NiIn high temperature, is also very difficult, because the thermal effects are very small. The amplification of the differential signal (10000 times) and the use of a data acquisition software is necessary to obtain an accurate determination of the NiIn (h.T.) existence region (Fig. 4b). * = Ni3lnphase .
880
Ni74oNi26oannealedat 400°Cfor 4000hours
LU 777 °C
500 ~'
450
o
400
/
03 tO e-
840 °C
32 350 d "o300 LIJ
J
._= 03
Ni31nafter[12]
.-g n,,
DTA of Ni45,91n54.1annealedfor 3500 hours at 400°C i . . . . .
~
. . . . .
738
i
. . . . .
763
i
. . . . .
788
p
. . . . .
813
~ , , , , , i
838
. . . . .
863
20
Temperature [°C] Fig. 4. (a) DTA of Niso.sln,9.2 with slow heating speed (3 °C rain -~) allows the separation of both 845 and 853 °C thermal effects on alloy containing 49.2% of indium; (b) DTA of Ni45,gIn54.t with high amplification (!,0000 times) of the differeatiaIsignal, allows the determination of the range of existence of NiIn (h.T).
40
60
80
100
120
140
Diffraction angle [2®] Fig. (3.= [18] [12]
5. (a) Pattern of Ni74.oIn:~.o annealed at 400°C for 4000 h. Cu Kc~, 1.54060 ,&) and Cu K a : (3.= 1.54438 ,&_);(b) LAZY PULVERIX PC pattern calculated from the parameters and structure reported in Ref. (see Table 1).
256
P. Durussel et al. / Journal of Alloys and Compounds 257 (1997) 253-258
Table 1 Compilation of measured and literature values of lattice parameters Phase
Type of structure
Space group
Calculated parameters (Lazy-pulverix)
Literature parameters [,~]
Ni3In
N i3Sn
P63/mmc
Ni2In (LT.) Ni~In 9
Ni2In
P631mmc (?)
a =5.324 +0.009 c =4.232 ± 0,006 Still uncertain
In~Pt~3
C2/m (?)
Still uncertain
Nitn (I.T.)
CoSn
Pd/mmm (?)
Still uncertain
NiIn (h.T.) Ni~In~
CsC1 A] 13Ni2
Pm-~m P3ml
Ni~In 7
In
Im3m
Not-measured a =4,396-+0.001 c=5.21020.004 a =9.1804+--0.0005
a=5.320 [12] c=4.242 [12] a=4.189 [12] c=5.131 [12] a = 14,646 [12,13] b=8.329 [12,131 c=8.977 [12,13] /3=35,35" [12,13] a=5.2446 [14,15] c=4.3518 [14,15] a=3.06 [20] a=4.387 [12,17] c=5.295 [12,17] a=9.181 [16,17]
3. We checked the crystalline structures proposed for various compounds in the literature (see Table 1) using the <~Lazy-Pulverix PC~ software [18]. The structure proposed for Ni3In (P63/mmc, 25 at.% In) (Fig. 5) is confirmed. 4. The calculated XRD spectra of the stoichiometric low temperature-NiIn (Fig. 6), low temperature-NizIn, Ni2In 3 (Fig. 7) and Ni3In v (Fig. 8) do not exactly fit our observed X-rays data. By contrast the calculated spectra of Ni~3In 9 (38.0 to 42.0 at.% In, structure proposed in literature: C2/m) is very different from the
observed spectrum and indicates that the crystal structure should be completely revised. 5. The EMPA measurements always confirm the stoichiometry of the low temperature forms of Ni2In and NiIn. The extent of both high temperature forms of Ni2In and NiIn is also precisely determined by EMPA (_+0.2 at.% In). The three other compounds Ni3In, NizIn 3 and Ni3In 7 are very narrow at any temperature below their temperature of decomposition and their XRD spectrum reveal constant diffraction lines even at high 2 0 angles (145°).
Ni48.slnsls annealed for 3900 hours at 400°C
Ni~4,e41n~.ls annealed at 700"C for 4200 hours
(a)
tl1 "~
* = Niln phase
1
Nis4.zln45,s a n n e a l e d for 3800 hours at 400"C
t
¢,¢)
I * = Ni21n3 phase
,
Ni4&taNis4,87 annealed at 300"C for 3700 hours
t--
t-
g
(b)
**
*i
**
1~ tY
.,
*
.
*
**"
Phase Niln (low Temperature)after [14] and [18]
II 20
40
=> i1) rr"
Ni2In3 after [12] end [17]
I 60
80
100
120
140
D i f f r a c t i o n a n g l e [219]
Fig. 6. (a) Pattern of Ni4~.sIns~.5 annealed at 400 °C for 3900 h. Cu Kc~ (A= 1.54060 ,~) and Cu Kc% (,~=1.54438 .~); (b) Pattern of Ni54.aIn45.8 annealed at 400 °C for 3800 h. (c) LAZY PULVERIX PC [18] pattern calculated from the parameters and structure reported in Ref. [14,15] (see Table 1 ).
20
40
60
80
100
120
140
Diffraction angle [2(9] Fig. 7. (a) Pattern of Ni3~ ~4In65.~6 annealed at 700 °C for 4200 h. Cu Kct, ( k = 1.54060 A) and Cu Ka 2 (3.= 1.54438 A); (b) Pattern of Ni45 ,'3In54.s7 annealed at 300°C for 3700 h; (c) LAZY PULVERIX PC [18] pattern calculated from the parameters and structure reported in Ref. [12,17] (see Table 1).
P. Durussel et al. / Journal of Alloys and Compounds 257 (1997) 2 5 3 - 2 5 8
* : Ni31n7 phase
. .
4. Discussion and conclusion
Ni~ 841ne&le annealed at 300°C for 3700 hours
03 m m
o3 t03 >
Calculated Ni31n7 after [16] and [17]
r~
(b?
I I, 20
40
/ , I rl
,,,,!
I,IIrl,,,,,,
60 80 100 Diffraction angle [20]
120
,I
257
,I
140
Fig. 8. (a) Pattern of Ni34.84In65.~6 annealed at 300 °C for 3700 h. Cu Ka l (3.= 1.54060 ,~) and Cu Kcq (A= 1,54438 ,~.); (b) LAZY PULVERIX PC [18] pattern calculated from the parameters and structure reported in Ref. [16,17l (see Table 1).
The XRD and EMPA results agree perfectly and underline the presence at low temperature of a larger solubility of In in Ni (3.3+_0.5 at.% In at 420 °C) than previously proposed (-1 at.% In at 400 °C). At higher temperatures the maximum c~-solubility becomes lower (9.5_+0.5 at.% In at 908°C) than previously proposed (14 at.% In at 910 °C [1], after four weeks of annealing). With such sufficiently long annealing times, the Ni-In system becomes much simpler. The two high temperature phases formed congruently at 950 °C (Ni2In (h.T.) and 930°C (NiIn (h.T.) are non-stoichiometric. The Nii3In 9 phase is also non-stoichiometric. All the other intermediate phases are clearly stoichiometric. Such a behaviour was already observed in the Pd-Sb, Pt-Sb [7], Ag-Pt [8], Pb-Pd [9] and Pt-Sn [10]: the establishment of all these equilibrium diagrams required several months of annealing, even at 600 °C.
I v meanatomicvolumina(literature,seetable1) ~ naem atomic ~ volumina A (fromthiswork,seetable1)
28-
26~
25.9
24 -
<_
Vegard'slaw..."
22-
.2 200
.o_ E o
18-[ 16-
....
Niln ' " " ' " " w ~ 7 (iT) ~ ?]21:3. . . . . . . . . . . . . .
18,1
14-[ 12-[
10-' 0
2'0
Ni
4~0
6()
8'0
at % In
100 In
Fig. 9. Variation of the mean atomic volume if" in the intermetallic compounds, according to the composition.
Table 2 The phase transformation present in the Ni-In binary system Phase
Composition [at.% In]
Wide phase
temperature of transformation [ °C]
Pure Ni Ni3In Ni2In (1.T.) Ni2In (h.T.) Ni~3In 9 NiIn (1.T.) NiIn (h.T.) Ni:In 3 Ni3In 7 Pure In
0 25.0---0.5 32.5_+0.5 31.2 to 42.0 (at 908 °C) 38.0 to 42.0 (at 200 °C) 50.0-+0.5 49.5 (908 °C) to 58.8 (865 °C) 60.0_+0.5 70.0_+0.5 I00
Yes No No Yes Yes No Yes No No No
1455 845+2 665*2 470_+2 853+_3 845 +-3 779+_2 865---2 404+_2 156,63
,~
258
P. Durusset et al. / Journal of Alloys and Compounds 257 (1997) 253-258
Table 2 summarizes these main phase transformations in the N i - I n binary system. The deviation from Vegard's law as expressed by the mean atom volume 17"shows an interesting behaviour of In which undergoes an important relative size contraction (Fig. 9). The first part of this graph shows that the mean atomic volumina of the intermetallic compounds Ni3tn, Ni2In (low temperature) and NiIn (h.T.) interpolate linearly between ~7= 10.94 ,i, 3 and 9"14.3 ~3 (for Niln (h.T.). We have not calculated I7 of Ni13In 9, because the spectrum calculated (with Lazy-Pulverix) [18] does not fit the measured spectrum. The second part of this graph shows that mean atomic volume of the other intermetallic compounds (NiIn (h.T.), Ni2In 3 and Ni~In 7) also interpolate linearly between V= 03 = . o3 14.3 A and V=25.9 A . The mean atomic volume, calculated for low temperature-NiIn (17.0 ~3) seems to be too high, which is probably due to its uncertain structure, (see Table t). Also for Nit3In 9, the calculated spectrum based on the structure proposed in the literature [t4,15] indicates that the crystal structure should be revised. Such a description of the contraction o f alloys relative to pure elements has the great advantage of being independent of the crystal structures and allows verification of the number of atoms per unit cell, or better confirms crystallographic data [19].
Acknowledgments The authors express their gratitude to M.G. Troillet, of the Institut de Physique exp~rimentale de l'Universit6 de Lausanne, for the careful EMPA measurements and to J. Pinard for some preparation of alloys and careful D T A measurements.
References [1] T.B. Massalski, Binary Alloys Phase Diagram, 2nd edition, ASM International, Ohio, Vol. 3, 1990, pp. 2267-2268. [2] R. Hultgren, ED. Desai, D.T. Hawkins, M. Gleiser, K.K. Kelley, Selected Values of the Thermodynamic Protx'.rtiesof Binary Alloys, American Society for Metals, Metal Park, Ohio, 1973. [3l E. Ellner, Z. Metallkunde 41 (I950) 401-406. [4] E.A. Peretti, Constitution of Indium Alloys System, The Indium Corporation of America, 1951. [5] K.J. Best, T. Goedeke, Z. Metallkunde 60 f t969) 659-661. [6] J.D. Livingston, Metall. Trans. 3 (1972) 3173-3176. [7l Ph. Durussel, E Feschotte, Les syst~mes binaires Pd-Sb et Pt-Sb, J. Alloys Comp, 176 (1991) 173-181. [8] Ph. Durussel, R Feschotte, A revision of the binary system Ag-Pt, J. Alloys Comp. 239(2) (1996) 226-230. [9] Ph. Dnrussel, E Feschotte, The binary system Pb-Pd, J. Alloys Comp. 236 (I996) 195-202. [I0] Ph. Durussel, R. Massara, R Feschotte, Le syst6me binaire Pt-Sn, J. Alloys Comp. 215 (1994) 175-179. [11] Program Magic IV, J. W. Colby, Bell Telephone Laboratories, Allentown, Pensylvania, 1971. [12] M.F. Singleton, R Nash, The In-Ni system,, Bull. Alloy Phase Diagrams 9 (1988) 592-597. [13] M. Ellner, S. Bhan, K. Schubert, J. Less-Common Met. 19 (1969) 245-252. [14] M. Anderson-S6derberg,Phase Relationship in the Ni-In-P system, J. Less-Common Met. 171 (I991) 179-186. [15] D. Swenson, Y.A. Chang, Phase Equilibria in the Ga-In-Ni System at 600 °C, J. Phase Equilibria 16(6) (1995) 508-515. [16] R.V. Baranova, Z.G. Pinsker, Electron-Diffraction Study of the Structure of the ~ Phase in the Ni-In System, Soy. Phys. Crystallogr. 10 (1966) 614-621. Published in both Russian and English in 1966. [17] E. Hellner, The System Nickel-Indium, Z. Metatlkd 41 (1950) 401--406. In German. [18] Program Lazy-Pulverix PC, Klaus Yvon, Laboratoire de Cristallographie, Universit~ de Gen~ve, 1988. [19] Ph. Dumssel, E Feschotte, Binary alloys classification and control with compared phase diagrams and mean atom volumina, Journal de Chemie Physique, in press. [20] Pearson's Handbook of Crystallographic Data of Intermetallic Phases, 2rid edition, ASM, 1991.
ALL©YS
ANB~ COMPOUND5 Journal of Alloys and Compeunds 257 (1997) 253-258
ELSEVIER
The binary system Ni-In Ph. D u r u s s e l , G. Burri, E F e s c h o t t e * tnstitut de Chimie Mingrale et Analytique, Universitd de Ix~usanne, BCH, CH-1015 Lausanne-Dorigny, Switzerland
Received 16 December I996; received in revised form 20 January 1997
Abstract The binary system Ni-In has been completely revised by XRD, DTA and EMPA on carefully annealed alloys (from 30 days at 1000 °C to 6 months at lower temperatures (-400 °C)). The solubility of In in Ni varies from 3.3 at.% In at 420 °C, increasing to a maximum of 9.5 at.% In at 908 °C. No solubility of Ni in In has been measured. Only three observed intermetallic compounds are non stoichiometric: Ni2In (high temperature form, stable from 470 °C to 950 °C, with a maximum extent from 3i.2 at.% In (9138°-C) to 42 at.% In (908 °C)), Ni13In9 (peritectok'dic decomposition at 853 °C, with a maximum extent from 38.0 to 42.0 at.% at 200 °C) and NiIn (high temperature form, stable from 779 °C to 930 °C, with a maximum extent from 49.5 at.% in (908 °C) to 58.8 at.% In (865 °C)). All the other observed intermetallic compounds are stoichiometric: Ni3In, Ni2In (low temperature form), NiIn (low temperature form), Ni2In 3 and Ni~In7. © 1997 Elsevier Science S.A. Keywords: Ni alloys; In alloys; Ni-In binary system; DTA; XRD; EMPA; Phase diagram
1. Introduction and previous work The assessed phase diagram [1] (Fig. 1) is based primarily on the compilation of Hultgren [2], with modifications based on the work of Ellner [3], Peretti [4], Best and Goedeke [5] and Livingston [6]. This binary system has not been studied since the compilation presented by Massalski [1] in 1991. According to these earlier works, the proposed intermediate compounds, except NiaIn, show a detectable and more or less wide range of existence. The composition of the compounds is not properly known and their existence is dubious in regard to the observations made in the systems Pd-Sb, Pt-Sb [7], A g - P t [8], P b - P d [9] and Pt-Sn [10], where the large ranges of existence of the intermediate phases given in literature were often due to the absence of equilibrium conditions (annealing time too short to obtain a true equilibrium).
2. Experimental All the alloys (0.6 to 2 g) were synthesised by melting pure metals (Ni 99.998%, Koch-Light and In 99.9995%, Fluka) in an induction furnace in sealed quartz bulbs under an inert atmosphere of argon (Argon (~52~, Carba Gaz). *Corresponding author. 0925-8388/97/$17.00 © 1997 Elsevier Science S.A. All rights reserved. PII S0925-8388(97)00033-9
The composition of our alloys was checked by comparison to the weight of the pure metal mixture before and after the melting in the induction furnace. The measured loss of metal (maximum 0.008 g on 1 g of mixture, for a composition of 90 at.% In) is attributed to In and does not exceed 0.02 at.% In in the region richest in indium. The crude alloys are very stable in air. Each sample was carefully annealed for homogenisation over 7 days. Afterwards, each alloy was fragmented into thin powder, if brittle (25 to 70 at.% In), or into pellets if malleable or very hard. Annealing occurs for a long time in little quartz Ar-filled tubes. In order to obtain equilibrium conditions, checked by permanence of X-ray diffraction (XRD) powder spectra, the annealing times found to be necessary are: - 6 months at 400 °C and ~1 month at r > 9 0 0 °C. XRD measurements were carried out using silicon powder as internal standard for obtaining accurate lattice parameters. In the differential thermal analysis (DTA) measurements, the systematic use of internal standards (Ag, A1, Au, In or Sn), a relatively moderate heating speed (5 °C min -~) and a small amount (<0.1 g) of alloy when the expected liquidus is horizontal, gives a reproducibility of _+2 °C at 950 °C. A good reproducibility (generally _+0.2 at.% In if frequent restandardisations are made with pure metals) of the electron microprobe analysis (EMPA) results is ob-
P. Durussel et al. / Journal of Alloys and Compounds 257 (t997) 253-258
254
Weight 0
]0
1600 t . . . . .
eo
~. . . .
ao
"J . . . . .
40
I., ....
50
PercenL 60
Indium
70
&,-..~._,.,.,.l, ~ , . ~ . , _ r , , . , . J . _ ~ , ~ _ r . , . ~
ao
.l.~.,,.v,.~,
90
~ ,L,~, l . . . .
T' ) ......
10o "-r ~
1455oC
1400
L 1200
C)
o
I000 48.6i ~]00
q)
cD
600
400
200 • 156 834
C
00
20
10
50
40
30
ALomic
Ni
60
Pereeni
80
7d
90
100
[)Ktium
[n
Fig. 1. Ni-In binary system according to the compilation of Massalski [1].
rained by using internal standards (pure Ni and pure In) and Magic IV software [11] for ZAF corrections.
ments are represented. XRD results have always be used to confirm the proposed diagram, even with respect to the stoichiometry of the five compounds producing constant diffraction angles in both sides of the observed phases. Details of the regions around the non-stoichiometric Ni2In and NiIn high temperature forms are shown in Fig. 3. The following points have been more precisely determined:
3. Phase diagram Our completed Ni-In phase diagram is displayed in Fig. 2. Only DTA and electronic microprobe analysis measureNf31n &"
".
\ 25.0.0.T \
•,
1000
•,
5', ),5" .
~'
'
.
l +
Nil3 In 9 "'"
In
Ni21n 3
J
I
~ t 5s.o~o.~ l ,~2"C $ ,,.5~0.~ [ +
, o. ,. , . o " ~" ' ~ . ~ ' _, - ~~' r ~.t ~
-2j ".oo
L \ ~
~andA=DTAresuts I
I o" microprob. . . . '~'l I J
2 ,,o;,.c
70±2
°,'°:°°
8O0
.o.
",, ~
600
i
iln
Ni
E
#. 400 i i
~
70 ~0.5
t56,
156,6 "c
200
/,.
l/
38.0 ~ 0.5
0 Ni
20
/
!
-
"1
42.0 :E 0,5
40
60
80
at % In Fig. 2. Ni-In phase diagram according to our present work.
1 O0 In
P. Durussel et al. / Journal of Alloys and Compounds 257 (1997) 2 5 3 - 2 5 8
255
1000950 " ~ 25......
~50=~,c
55,0±0,5 ~930 ;~2oo
"°":"-" b"°: ....... =
" /
\
8ooq t 700'
=~,=~0.5
/
~'
~'/
/
I 2°22:
.I/
I
,
- "'2::;::,
I
5
6,o.!
/'=°:
I
\
I'1
,/"
, tt
~
,,o=o°
40 at % In
-J
6o.o,o,5
I ,o.oo
......
30
/
r
;n ??0;, ....
Ni
4
\
! ii .....
t
50
60 In
Fig, 3. Detailed region of the Ni-In system around non-st0ichiometric Ni2In and NiIn high temperature forms.
ILl
660 843 °
/
~
64o O
620
"l-
d 600
I DTAof aiso,81n492annealedfor 3800hoursat 400°C i
t,-
l.u
811
8;0
8~9
&8
8~7
&8
8~
Temperature [°C]
(b) ~
1. The separation of the DTA events occuring at 845_+3 °C (41.8 to 53.3 at.% In) and 853+3 °C (41.5 to 52.7 at.% In) is very difficult because the proximity of both thermal effects. Only the data acquisition software, a very slow heating speed (3 °C/min.) and a very small amount of alloy (0.06 g) allow us to measure the accurate temperatures of these transformations (Fig. 4a). 2. The DTA determination of the range of existence of NiIn high temperature, is also very difficult, because the thermal effects are very small. The amplification of the differential signal (10000 times) and the use of a data acquisition software is necessary to obtain an accurate determination of the NiIn (h.T.) existence region (Fig. 4b). * = Ni3lnphase .
880
Ni74oNi26oannealedat 400°Cfor 4000hours
LU 777 °C
500 ~'
450
o
400
/
03 tO e-
840 °C
32 350 d "o300 LIJ
J
._= 03
Ni31nafter[12]
.-g n,,
DTA of Ni45,91n54.1annealedfor 3500 hours at 400°C i . . . . .
~
. . . . .
738
i
. . . . .
763
i
. . . . .
788
p
. . . . .
813
~ , , , , , i
838
. . . . .
863
20
Temperature [°C] Fig. 4. (a) DTA of Niso.sln,9.2 with slow heating speed (3 °C rain -~) allows the separation of both 845 and 853 °C thermal effects on alloy containing 49.2% of indium; (b) DTA of Ni45,gIn54.t with high amplification (!,0000 times) of the differeatiaIsignal, allows the determination of the range of existence of NiIn (h.T).
40
60
80
100
120
140
Diffraction angle [2®] Fig. (3.= [18] [12]
5. (a) Pattern of Ni74.oIn:~.o annealed at 400°C for 4000 h. Cu Kc~, 1.54060 ,&) and Cu K a : (3.= 1.54438 ,&_);(b) LAZY PULVERIX PC pattern calculated from the parameters and structure reported in Ref. (see Table 1).
256
P. Durussel et al. / Journal of Alloys and Compounds 257 (1997) 253-258
Table 1 Compilation of measured and literature values of lattice parameters Phase
Type of structure
Space group
Calculated parameters (Lazy-pulverix)
Literature parameters [,~]
Ni3In
N i3Sn
P63/mmc
Ni2In (LT.) Ni~In 9
Ni2In
P631mmc (?)
a =5.324 +0.009 c =4.232 ± 0,006 Still uncertain
In~Pt~3
C2/m (?)
Still uncertain
Nitn (I.T.)
CoSn
Pd/mmm (?)
Still uncertain
NiIn (h.T.) Ni~In~
CsC1 A] 13Ni2
Pm-~m P3ml
Ni~In 7
In
Im3m
Not-measured a =4,396-+0.001 c=5.21020.004 a =9.1804+--0.0005
a=5.320 [12] c=4.242 [12] a=4.189 [12] c=5.131 [12] a = 14,646 [12,13] b=8.329 [12,131 c=8.977 [12,13] /3=35,35" [12,13] a=5.2446 [14,15] c=4.3518 [14,15] a=3.06 [20] a=4.387 [12,17] c=5.295 [12,17] a=9.181 [16,17]
3. We checked the crystalline structures proposed for various compounds in the literature (see Table 1) using the <~Lazy-Pulverix PC~ software [18]. The structure proposed for Ni3In (P63/mmc, 25 at.% In) (Fig. 5) is confirmed. 4. The calculated XRD spectra of the stoichiometric low temperature-NiIn (Fig. 6), low temperature-NizIn, Ni2In 3 (Fig. 7) and Ni3In v (Fig. 8) do not exactly fit our observed X-rays data. By contrast the calculated spectra of Ni~3In 9 (38.0 to 42.0 at.% In, structure proposed in literature: C2/m) is very different from the
observed spectrum and indicates that the crystal structure should be completely revised. 5. The EMPA measurements always confirm the stoichiometry of the low temperature forms of Ni2In and NiIn. The extent of both high temperature forms of Ni2In and NiIn is also precisely determined by EMPA (_+0.2 at.% In). The three other compounds Ni3In, NizIn 3 and Ni3In 7 are very narrow at any temperature below their temperature of decomposition and their XRD spectrum reveal constant diffraction lines even at high 2 0 angles (145°).
Ni48.slnsls annealed for 3900 hours at 400°C
Ni~4,e41n~.ls annealed at 700"C for 4200 hours
(a)
tl1 "~
* = Niln phase
1
Nis4.zln45,s a n n e a l e d for 3800 hours at 400"C
t
¢,¢)
I * = Ni21n3 phase
,
Ni4&taNis4,87 annealed at 300"C for 3700 hours
t--
t-
g
(b)
**
*i
**
1~ tY
.,
*
.
*
**"
Phase Niln (low Temperature)after [14] and [18]
II 20
40
=> i1) rr"
Ni2In3 after [12] end [17]
I 60
80
100
120
140
D i f f r a c t i o n a n g l e [219]
Fig. 6. (a) Pattern of Ni4~.sIns~.5 annealed at 400 °C for 3900 h. Cu Kc~ (A= 1.54060 ,~) and Cu Kc% (,~=1.54438 .~); (b) Pattern of Ni54.aIn45.8 annealed at 400 °C for 3800 h. (c) LAZY PULVERIX PC [18] pattern calculated from the parameters and structure reported in Ref. [14,15] (see Table 1 ).
20
40
60
80
100
120
140
Diffraction angle [2(9] Fig. 7. (a) Pattern of Ni3~ ~4In65.~6 annealed at 700 °C for 4200 h. Cu Kct, ( k = 1.54060 A) and Cu Ka 2 (3.= 1.54438 A); (b) Pattern of Ni45 ,'3In54.s7 annealed at 300°C for 3700 h; (c) LAZY PULVERIX PC [18] pattern calculated from the parameters and structure reported in Ref. [12,17] (see Table 1).
P. Durussel et al. / Journal of Alloys and Compounds 257 (1997) 2 5 3 - 2 5 8
* : Ni31n7 phase
. .
4. Discussion and conclusion
Ni~ 841ne&le annealed at 300°C for 3700 hours
03 m m
o3 t03 >
Calculated Ni31n7 after [16] and [17]
r~
(b?
I I, 20
40
/ , I rl
,,,,!
I,IIrl,,,,,,
60 80 100 Diffraction angle [20]
120
,I
257
,I
140
Fig. 8. (a) Pattern of Ni34.84In65.~6 annealed at 300 °C for 3700 h. Cu Ka l (3.= 1.54060 ,~) and Cu Kcq (A= 1,54438 ,~.); (b) LAZY PULVERIX PC [18] pattern calculated from the parameters and structure reported in Ref. [16,17l (see Table 1).
The XRD and EMPA results agree perfectly and underline the presence at low temperature of a larger solubility of In in Ni (3.3+_0.5 at.% In at 420 °C) than previously proposed (-1 at.% In at 400 °C). At higher temperatures the maximum c~-solubility becomes lower (9.5_+0.5 at.% In at 908°C) than previously proposed (14 at.% In at 910 °C [1], after four weeks of annealing). With such sufficiently long annealing times, the Ni-In system becomes much simpler. The two high temperature phases formed congruently at 950 °C (Ni2In (h.T.) and 930°C (NiIn (h.T.) are non-stoichiometric. The Nii3In 9 phase is also non-stoichiometric. All the other intermediate phases are clearly stoichiometric. Such a behaviour was already observed in the Pd-Sb, Pt-Sb [7], Ag-Pt [8], Pb-Pd [9] and Pt-Sn [10]: the establishment of all these equilibrium diagrams required several months of annealing, even at 600 °C.
I v meanatomicvolumina(literature,seetable1) ~ naem atomic ~ volumina A (fromthiswork,seetable1)
28-
26~
25.9
24 -
<_
Vegard'slaw..."
22-
.2 200
.o_ E o
18-[ 16-
....
Niln ' " " ' " " w ~ 7 (iT) ~ ?]21:3. . . . . . . . . . . . . .
18,1
14-[ 12-[
10-' 0
2'0
Ni
4~0
6()
8'0
at % In
100 In
Fig. 9. Variation of the mean atomic volume if" in the intermetallic compounds, according to the composition.
Table 2 The phase transformation present in the Ni-In binary system Phase
Composition [at.% In]
Wide phase
temperature of transformation [ °C]
Pure Ni Ni3In Ni2In (1.T.) Ni2In (h.T.) Ni~3In 9 NiIn (1.T.) NiIn (h.T.) Ni:In 3 Ni3In 7 Pure In
0 25.0---0.5 32.5_+0.5 31.2 to 42.0 (at 908 °C) 38.0 to 42.0 (at 200 °C) 50.0-+0.5 49.5 (908 °C) to 58.8 (865 °C) 60.0_+0.5 70.0_+0.5 I00
Yes No No Yes Yes No Yes No No No
1455 845+2 665*2 470_+2 853+_3 845 +-3 779+_2 865---2 404+_2 156,63
,~
258
P. Durusset et al. / Journal of Alloys and Compounds 257 (1997) 253-258
Table 2 summarizes these main phase transformations in the N i - I n binary system. The deviation from Vegard's law as expressed by the mean atom volume 17"shows an interesting behaviour of In which undergoes an important relative size contraction (Fig. 9). The first part of this graph shows that the mean atomic volumina of the intermetallic compounds Ni3tn, Ni2In (low temperature) and NiIn (h.T.) interpolate linearly between ~7= 10.94 ,i, 3 and 9"14.3 ~3 (for Niln (h.T.). We have not calculated I7 of Ni13In 9, because the spectrum calculated (with Lazy-Pulverix) [18] does not fit the measured spectrum. The second part of this graph shows that mean atomic volume of the other intermetallic compounds (NiIn (h.T.), Ni2In 3 and Ni~In 7) also interpolate linearly between V= 03 = . o3 14.3 A and V=25.9 A . The mean atomic volume, calculated for low temperature-NiIn (17.0 ~3) seems to be too high, which is probably due to its uncertain structure, (see Table t). Also for Nit3In 9, the calculated spectrum based on the structure proposed in the literature [t4,15] indicates that the crystal structure should be revised. Such a description of the contraction o f alloys relative to pure elements has the great advantage of being independent of the crystal structures and allows verification of the number of atoms per unit cell, or better confirms crystallographic data [19].
Acknowledgments The authors express their gratitude to M.G. Troillet, of the Institut de Physique exp~rimentale de l'Universit6 de Lausanne, for the careful EMPA measurements and to J. Pinard for some preparation of alloys and careful D T A measurements.
References [1] T.B. Massalski, Binary Alloys Phase Diagram, 2nd edition, ASM International, Ohio, Vol. 3, 1990, pp. 2267-2268. [2] R. Hultgren, ED. Desai, D.T. Hawkins, M. Gleiser, K.K. Kelley, Selected Values of the Thermodynamic Protx'.rtiesof Binary Alloys, American Society for Metals, Metal Park, Ohio, 1973. [3l E. Ellner, Z. Metallkunde 41 (I950) 401-406. [4] E.A. Peretti, Constitution of Indium Alloys System, The Indium Corporation of America, 1951. [5] K.J. Best, T. Goedeke, Z. Metallkunde 60 f t969) 659-661. [6] J.D. Livingston, Metall. Trans. 3 (1972) 3173-3176. [7l Ph. Durussel, E Feschotte, Les syst~mes binaires Pd-Sb et Pt-Sb, J. Alloys Comp, 176 (1991) 173-181. [8] Ph. Durussel, R Feschotte, A revision of the binary system Ag-Pt, J. Alloys Comp. 239(2) (1996) 226-230. [9] Ph. Dnrussel, E Feschotte, The binary system Pb-Pd, J. Alloys Comp. 236 (I996) 195-202. [I0] Ph. Durussel, R. Massara, R Feschotte, Le syst6me binaire Pt-Sn, J. Alloys Comp. 215 (1994) 175-179. [11] Program Magic IV, J. W. Colby, Bell Telephone Laboratories, Allentown, Pensylvania, 1971. [12] M.F. Singleton, R Nash, The In-Ni system,, Bull. Alloy Phase Diagrams 9 (1988) 592-597. [13] M. Ellner, S. Bhan, K. Schubert, J. Less-Common Met. 19 (1969) 245-252. [14] M. Anderson-S6derberg,Phase Relationship in the Ni-In-P system, J. Less-Common Met. 171 (I991) 179-186. [15] D. Swenson, Y.A. Chang, Phase Equilibria in the Ga-In-Ni System at 600 °C, J. Phase Equilibria 16(6) (1995) 508-515. [16] R.V. Baranova, Z.G. Pinsker, Electron-Diffraction Study of the Structure of the ~ Phase in the Ni-In System, Soy. Phys. Crystallogr. 10 (1966) 614-621. Published in both Russian and English in 1966. [17] E. Hellner, The System Nickel-Indium, Z. Metatlkd 41 (1950) 401--406. In German. [18] Program Lazy-Pulverix PC, Klaus Yvon, Laboratoire de Cristallographie, Universit~ de Gen~ve, 1988. [19] Ph. Dumssel, E Feschotte, Binary alloys classification and control with compared phase diagrams and mean atom volumina, Journal de Chemie Physique, in press. [20] Pearson's Handbook of Crystallographic Data of Intermetallic Phases, 2rid edition, ASM, 1991.