AI-V

AI-V (Aluminum-Vanadium)
J.L. Murray
Alcoa Technical C e n t e r
Alloy Technology Division
Alcoa Center, PA 15069

Equilibrium Diagram dilute liquidus. Special points of the assessed diagram

are listed in Table 1. Conflicting reports are described
The Al-V intennetallic phases are structurally well below.
characterized, and the solubilityof V in diluteliquidAl is
known, but the phase diagram as a whole stillcontains The equilibrium sofid AI-V phases are:
many uncertainties. On the V-rich side, high melting • The fcc (AI) and bcc (V) solid solutions---the former
temperatures make the liquidus and solidus tempera- with a very narrow homogeneity range (0 to 0.3 at.%
tures difficult to measure and also make equilibrium V) and the latter with a wide ( - 5 0 to 100 at.% V)
difficult to achieve in the solid state. Interest in the pos- range
sibility that "A1V3" would have good superconducting • The Al-rich compounde complex cubic AI21V2 (also
properties has led to numerous investigations around 75 designated AI llV or AI loV), monoclinic A145V7 (also
at.% V, with conflicting results. designated AI7V), hexagonal A123V4 (also designated
On the Al-rich side, the melting reactions are of the AleV), and AI3V with D022 structure
peritectic type and therefore sluggish: it is possible that • AIsV5, with cubic 7 brass structure, which is thought
metastable reactions have been interpreted as stable to have some range of homogeneity at high tempera-
ones, and/or that decomposition of one or more inter- ture. (This range, not being quantitatively known, is
metallics in the solid state has been missed, and that this not indicated in Fig. 1.)
is the reason for conflicting phase diagrams. The as-
sessed AI-V phase diagram (Fig. 1) is based on work by V-Rich Llquldus
Bailey et al. [59Bail for invariant reactions and on work Melting points were determined by Rostoker and
by Willey [53Will and by Eremenko et al. [81Ere] for the Yamamoto [54Ros] and by Carlson et al. [55Carl for al-

Fig. 1 Assessed AI-V Phase Diagram with Experimental Data

Weight Percent Vanadium

0 l0 20 30 40 50 B0 79 ~0 gO 100
~000 .... I....,.I ....... I ..... J. . . 1 I I I i i i I ., i I
......... , ......... , ......... , . . . . . . . . . . . . | ......... i .........

1910°C
leoo, L .........................:::;...:...'-e..........."v............a"'~;;'"'v"~"O°"

lOOK}, ..~ . . . . . r. . . . . V
.."'~1670 i ",
o ,,, : ',
~) 1400. " O '', ' (V)

asoo, ,," > i ~ "

-~ / ~i 2 \ Io 55Cor I

" 738°c I
.... I ........
600 ~" ""'::"" ":::"".

(")[ I GI< I /// B2: ..... ......

4oo~l....... :'lb" ....' i o " ' ~ ........ 4'0 ........ '~ ........ leos.-..... ,~ ........ , ....... :'i~" ...... ioo
Al Atomic Percent Vanadium v
J.L. Murray, 1989.

Bulletin of Alloy Phase Diagrams Vol. 10 No. 4 1989 351

AI-V

Fig. 2 "AI-Rich AIoV Phase Diagram

Weight P e r c e n t V a n a d i u m
0 2 4 6 8 10 12 14 16 IB 20 22
llO0 . . . . . . - . . . . , . . . . . . - . . ,

x 40Rot, XRD
• 55Car. t h e r m a l a n a l y s i s
1000- L ~
o 55EI1, c h e m i c a l a n a l y s i s
~0 0 0 e 59Bai, t h e r m a l a n a l . h e a t i n g

O
1100-
/ ~O •
• 61Geb, t h e r m a l a n a l y s i s
• 61Geb, t w o - p h a s e
÷ 81Ere, chemical analysis
::3 soo- o 53WiI, chemical analysis
•*'J •
<0 736°C
-m a $

¢) ?00- 688.°C , .
iaa
. . . . _
662.1°C
p- ,¢
> > :>
Lt~ ¢q
~" OJ

,oo V-(Al) e-.-4

< < <¢

400
0
......... i ........
2
' " ] ~"- - ~"- . . . . ! . . . . . . . . .
4 6
*
8
.... + xb. . . . . . ~+"
A1 Atomic P e r c e n t V a n a d i u m

J.L. Murray, 1989.

Table I Special Points of the Assessed AI-V Phase Diagram

C o m p o s i t i o n of t h e
r e s p e c t i v e phases, Temperature, Reaction
Reaction at.% v °(2 type

L ~, (A1}........................................... 0 660.452 Melting point

L + AI21V2- (A1) ........................... 0.09 8.7 0.3 662.1 Peritectic
L + A145V7~ A121V2....................... 0.1 13.5 8.7 670 Peritectic
L + A12nV4.~-AJ45V7....................... 0.13 14.8 13.5 688 Peritectic
L + Al:N - AI23V4.......................... 0.22 25 14.8 736 Peritectic
L + AlsV5+-Al:~V............................ 14 38.5 25 - 1360 Peritectic
L + ( V ) - Al~Vr, ..............................
28 46 38.5 - 1670 Peritectic
L--(V) ............................................. 100 1910 Melting point

loys containing more than 5 at.% V (see Fig. 1). Carlson AI-Rich Liquidus
et al. used optical pyrometry with induction or internal The liquidus up to 3 at.% V has been investigated
resistance heating; melting was observed as roundingof [81Ere, 53Wil, 55Ell, 61Geb]. The first three used
a hole or of the edges of irregularly shaped pieces of alloy chenfical analysis of extracted equilibrated liquid and
placed in a graphite crucible. The melting point of pure the last used thermal analysis on cooling. Because of the
V was reported by Carlson e t a l . as 1845 +_. 10 °C (the as- sluggishness of peritectic reactions, substantial (> 100
sessed value is 1910 °C); therefore, a somewhat larger °C) undercoolings were observed in the thermal
uncertainty should be attributed to the melting analysis. Three of the results [53Wil, 55Ell, and 81Ere]
temperatures of V-rich alloys. Incongruent melting of are in reasonable agreement. The Russian liquidus
AlaV.rI and Al3V was reported at 1670 and 1360 °C, points [81Ere] are the lowest, and those of Elliott
respectively. The latter temperature was also deter- [55Ell] are the highest. The assessed liquidus (Fig. 2 and
mined from cooling curves. By determination of in- 3) gives most weight to lower solubilities.
cipient melting via optical pyrometry, Rostoker and
Yanmmoto found the peritectic melting of Al3V at about Four intermetallic compounds have been identified in
1370 °C, in good agreement with the Carlson value of Al-rich alloys--Al21V2, A145V7, A123V4 and Al3V. Al-
1360 °C. though there is reasonable agreement among tempera-

352 Bulletin of Alloy Phase Diagrams Vol. 10 No. 4 1989

 AI-V
Fig. 3 Solubility of V in Liquid AI

Weight Percent Vanadium

I 2 3 4 5 8
|0~0 . . I .... I ...... I ...... i I . . . . I ....
0

IO00,g,~O. 0 0 0 O

L)
o
gO0- + 0 0

850- JO 0

~o
B Z3..s2_c.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

7~. ~ 688~C L+AIs3V4 L+AI45Vv\

"[ /6 70 C
o/662 °c (A1)+AletVe
"°°o ....... o.s' ......... l . . . . . . . . L6'
. . . . . . . . -' ....... ~ ......... ~ ....... -a.,,
Al Atomic Percent Vanadium
J.L.Murray, 1989.

tures of invariant reactions (see Table 2 and Fig. 2), the Metallographic and microprobe analyses [76Lit] were
interpretations of the reactions conflict. Major ex- made on dilute alloys heat treated for short times at
perimental contributions have been made [53Wil, temperatures between 500 and 740 °C. They concluded
55Car, 55EII, 59Bai, 76Lit]. that only AI3V and 'Tk16V" (A123V4) are equilibrium
phases, and that A]21V 2 appears only as a nletastable
Willey [53Wil] used a filtrationtechnique to obtain liq-
transition phase.
uid equilibrated at several temperatures for chemical
analysis. A break in the liquidus curve was found at A two-phase assemblage of (AI) + another phase (not
about 703 °C; the solidphases were identifiedas A121V 2 A121V2), was formed in melt-spun 10 at.% V ribbons held
below 703 °C and AI3V above 703 °C. at 600 °C [86Sch]. However, a fine dispersion ofAl21V2
Bailey et aL [59Bai] performed thermal analysis on was found in a 1.8 at.% V alloy solidified by plasma-jet
heating and establishedthat reactionsoccur at 670, 688, spraying after holding at 600 °C [68Mos].
and 736 °C; they noted that cooling data could not be There is thus some agreement that AI3V, A123V4,and
fused, because large supercooling effects masked the AI21V2 phases predominate, and that AI45V7 is the most
small heats of transfomnation. Although this work es- difficult phase to produce from the liquid. However,
tablished the temperatures of invariant reactions, no there are discrepancies in two major areas: (1) whether
microstructural evidence was presented to show which Al21V2 is a stable phase in equilibrium with (AI) to low
phases were in equilibrium in the invariant reactions. temperature; and (2) whether 736 °C is to be interpreted
Bailey et al. [59Bai] assumed a simple cascade of as the incongruent melting temperature of AI23V4. If
peritectic reactions--that AI21V2, A145V7, and AI23V 4 A123V 4 is in equilibrium with the melt to higher
are the phases melting at 670, 688, and 736 °C, respec- temperatures, then it renmins to determine its peritec-
tively. Gebhardt and Joseph [61Geb] also interpreted tic melting temperature and to correctly interpret the
thermal analysis (cooling) data according to this reac- three invariant reactions at 736, 688, and 670 °C.
tion scheme.
Solubility of V in (AI)
Elliott[55EII] found a peritecticreaction at 727 °C and Based on latticeparameter data, the solubilityof V in
identified the phases in equilibrium with the liquid solid (Al)at 620 °C isabout 0.2 at.% [40Rot]. Varich et al.
above and below 727 °C as Al23V4 and AI21V2 respective- [63Var] used the maximum in paramagnetic suscep-
ly. Elliott found A123V4 to be the equilibrium intermetal- tibility to estimate that the maximum solubility of V in
lic phase up to at least 850 °C, in contradiction with (Al) is 0.3 at.%; the two values are consistent with each
other reports [53Wil, 59Bai]. other and with thermodynamic properties.

Bulletinof Alloy Phase Diagrams Vol. 10 No. 4 1989 353

AI-V
The (AI) solid solution melts by a peritectic reaction, other attempts to synthesize AIV3 were unsuccessful be-
reported to lie a t 1.6 _+ 0.2 °C [55E11] or 1.7 °C [59Bai] cause too high annealing temperatures were chosen.
above the melting point o f pure AI (660.452 °C [Melt]). This view is supported by work [82Sud] with 70.5, 75,
The two values were averaged to give 662.1 °C for the and 90 at.% V alloys using X-ray diffraction (XRD),
peritectic temperature. By extrapolation o f the liquidus electron diffraction,and transmission electron micros-
to 662.1 °C, the composition of the liquid in the peritectic copy (TEM). By XRD, only the bcc phase was found.
equilibrium is less t h a n 0.1 at.% V. Specifically, ther- Howevel; superlatticereflectionsof CsCI structure were
modynandc calculation gives 0.085 and 0.3 at.% V for found in 70.5 and 75 at.% V alloys by electron diffrac-
the compositions o f liquid and (AI) at 662.1 °C. tion, and diffuse scattering corresponding to the A15
structure was also observed.
V-Rich Alloys It can be concluded tentativelythat above 600 and 700
Numerous a t t e m p t s have been made to synthesize an °C, the disordered bcc phase is stable in the binary sys-
A15 compound, AIV3, because of its potential as a super- tem. Small particles,undetected by XRD, of a second
conducting nmterial. Reports [63Hol, 71Kod] have been phase m a y form during quenching. The number of equi-
made of A15 structures formed by annealing a t 100 °C librium phases is not known, nor are the phase boun-
in quartz tubes, with lattice p a r a m e t e r s o f 0.4812 and daries. It is not known how or whether to include the
0.4926 nm, respectively. Kornilov and Matveeva hexagonal [73Leg], tetragonal [73Leg], and pseudo-
[68Kor] tried to duplicate these results, but found that cubic [73Hat] structures in a binary phase diagram at
the only A15 compound present was V3Si; they con- low pressures.
cluded that annealing in quartz tubes causes con-
tamination by Si, and t h a t only the bcc phase is stable in
the binary system. O t h e r s [55Cax; 64Ram, 70Shi] have Table 2 Reported Invariant Reactions for AI-Rich Al-
also reported t h a t only the bcc phase was found in V-rich loys
alloys. Similar findings exist for samples annealed at
700 and 1000 °C [75Hat], but some evidence was Reaction
reported for a martensitic t r a n s f o r m a t i o n to a n un- Postulated temperature
known pseudocubic s t r u c t u r e a f t e r annealing at 1500 Reference reaction ~C
°C. Hexagonal /~ A1V3, with a = 0.7070 and c = [53Wil] .............. L + A13V,~ AI21V2 703
0.9565 nm, was reported to form u n d e r pressures [54Ros] ............. L + AI3V ~, ? < 1210
greater than 30 kbar and above 1500 °C and tetragonal [55Car] ............. L + AI3V,~ A123V4 735
aAIV3, with a = 0.6167 and c ffi 0.9481 nm, appeared at L + AI23V4~ AI21V2 685
lower t e m p e r a t u r e s a n d pressures [73Leg]. No A15 [55Ell] ............... L + A123V4 ~. Al21V2 727
phase was found up to 70 kbar above 1000 °C. L + Al3V ~. A123V4 >850
[59Bai] .............. L + Al3V~ A123V4 736
Hartsough and H a m m o n d [71Har] p e r f o r m e d vacuum L + AI23v4 ~ A]46V7 088
evaporation experiments using substrate t e m p e r a t u r e s L + A145v7- Al2 IV2 670
of 350 to 450 °C and found an A15 phase o f lattice |61Geb] ............. L + AI3V ~* AI23V4 735
p a r a m e t e r 0.4829 nm. With increasing AI content, bcc L + A123V4 ~. A145V7 689
+ A15 and bcc phases were formed. The A15 phase L + A145V7--Al21V2 680
decomposed between 600 and 700 °C. This suggests that

Table 3 AI-V Crystal Structure Data

Struktur-
Composition, Pearson Space bericht
Phase at.% V symbol group designation Prototype Reference
(AI)........................... 0 to 0.3 cF4 Fm~m A1 Cu [Pearson2}
AI21V2....................... -8.7 to 9.1 cF176 Fd~m ... AIIoV [57Bro}
A145V7....................... ~13.5 mC104 C2/m ... AI45V7 [59Brol
AI2:~V4....................... ~ 14.8 hP54 P6~mmc ... AI2.~V4 [60Rayl
AhV .......................... ~25 tI8 I4/mmm D022 AI3Ti 143Bra]
AlsVr) ........................... ci52 I43m D82 CusZn8 [77BraJ
(V) ............................ - 4 6 to 100 ci2 Im3m A2 W [Pearson2]
Other possible phases
AIV:~............................. cP8 Pm'3m A15 Cr3Si [70Sur]
t~AIV:~........................... h** ... . . . . . . [73Leg}
.AIV;j ........................... t** ... . . . . . . [73Leg]

354 Bulletinof Alloy Phase Diagrams Vol. 10 No. 4 1989

 AI-V

Table 4 AI-V Lattice Parameter Data

Composition, Lattice parameters, nm

Phase at.% V a b e Reference
( A l ) ............................................. 0 0.40496 . . . . . . [Ma~alski]
Al21V~......................................... 9.1 1.4492 [57Bro]
Al4~V7......................................... 13.5 2.54 0.759~a) 1.1() [59Bro]
Al2:W4......................................... 14.8 0.76928 ... 1.7040 [578nfi, 60Ray]
Al:W ............................................ 25 0.3780 ... 0.8321 [43Bra]
AlsV5 .......................................... 39.5 0.92345 . . . . . . [77Bra]
( v ) ............................................... 100 0.30240 . . . . . . [Massalski]
Other possible phases
AlV.~............................................ 75 [70Sur]
flAlV:j(b) ..................................... 75 0.7'070 iii 0.956 [73Leg]
.AlV:jib) ..................................... 75 0.6167 ... 0.9481 [73Leg]
(a)/? = 127°. (b) May not be a stable phase at normally ambient temperature and pressure.

parameter and ndcrostructural data [55Carl; however,

Fig. 4 Heats of Formation of Solid AI-V Phases,
quantitative studies were not nmde. Thus, a simple line
Referenced to Solid fcc AI and bcc V
compound is shown in Fig. 1.

Metastable Phases
0 1 ........ ' ...... ' ........ ' ..... ' ....... ' ......... ' ........ ' ......... ' ........ ' ........

The achievement of extended solubility of V in (AI) by

rapid solidification has been reported [63Var, 68Mos,
86Ino, 87Kim], with the maximum value being 2 at.% V
by splat quenching [87Kim].
A145V7 I h~ o A quasicrystalline icosahedral phase has been identified
~-~oo0~_~ooo AIz3V4 ~ o° o [ ° a
in rapidly solidified alloys containing 10 [86Sch], 13.9
[87Kim], and 14.3 at.% V [86Ino]. Kim and Froes
[87Kim] found the icosahedral phase only as a minor
-30000,
~_q

0
constituent, with AI3V predominating, whereas Inoue e t
~ -Sf~O0 0
a/. [86Ino] reported higher volume fractions of the
icosahedral phase, also together with AI3V. Inoue e t a l .
identified the composition of the icesahedral phase as
approximately AI4V by EDXS.
1 o

Crystal Structures and Lattice Parameters

A1 Atomic Percent Vanadium v
Crystal structures of the AI-V phases are listed in Table
3, and lattice parameters are listed in Table 4. The
structures of AI21V2, AI23V4, and A145V7 have an
J.L. Murray, 1989. icosahedron as a basic structural unit [77Bha]. The
structure of AI21V2 is the same as that of AllsMg~Cr2. In
The possibility of the occurrence of stable ordered the binary AI-V system, the structure occurs with vacan-
phases is indicated in Fig. 1 by the boundaries sketched cies on AI sites, hence the common designation AIloV.
within the bcc (V) field. They are not intended to be in- The structure of A]23V4 is closely related to that of
terpreted quantitatively. Al loMn3, AlsCo2, A19SiMn3, and AI loNiFe 3.

The (V) solvus was derived from lattice parameter data Thermodynamics
[55Car]. Enff measurements [67Joh] suggested a some-
what ( - 5 at.%) greater solubility of Al in (V); the lattice [Hnltgren, B] reviewed heat of formation data for solid
parameter data are preferred, because good consistency AI-V alloys (25 to 60 at.% V) from direct reaction
was not found among partial Gibbs energies, heats of calorimetry [60Kub, 69Nec] and partial molal Gibbs
formation, and phase boundary data. That there is some energies, GAb from isopiestic measurements at 1000 °C
homogeneity range of AIsV5 was shown by lattice for 24 to 88 at.% V alloys [67Joh]. More recent inves-

Bulletin of Alloy Phase Diagrams Vol. 10 No. 4 1989 355

AI-V
Table 5 Gibbs Energies of AI-V Phases
Thermodynamic properties of the pure e l e m e n t s
AG{Al,fcc)= 0
AG(AI,L)= 10 708 - 11.4697 T {86Din]
AG(V,L)= 21 500-9.8488 T {86DinJ
AGIV,fcc) = 7500-1.70000 T [88Gui]
Excess properties of solution phases
A(L) = - 6 8 700 + 46.59285 T
B(L) = -19 000 + 7.95275 T
A(fcc) = -40 500
Gibbs energies o f compounds, referenced to fcc AI
and bcc V
^rG(AiSVS) =-22 500 + 5.27736 T
AfG(Al3V) = -26 600 + 8.50273 T
A~G(AI21V2) = -10 140 + 3.5 T
Note: Values in J/g-atom.
tigations are enff measurements of GAI for 40 to 95 at.%
V and 660 to 767 °C [71Sam], and measurements of
AmixH of the liquid at 1534 °C for 0 to 8 at.% V [85Bat].
The two determinations of heats of formation agree well
and were used in the calculation of the phase diagram;
they are shown in Fig. 4. The more recent values of GAI
[71Sam] are very high compared with those reported
earlier [67Joh], and the heats of formation of the bcc
solution derived from these newer results [71Sam] are
inconsistent with the direct calorimetric measure-
ments. Values for GAI at 1000 °C [Hultgren,B] do not
agree with the work [67Joh] upon which they are osten-
siblybased.
Calculation of the Phase Diagram
Gibbs energy functions for the liquid, fcc, A121V2, A13V,
and AIsV5 phases are listed in Table 5. In view of the dis-
agreements about both the phase diagram and ther-
modynamic quantities, these Gibbs energies should be
viewed with skepticism. They allow the Al-rich portion
of the liquidus to be calculated, with a peritectic reac-
tion, L + A121V2 ~ AI3V,,at about 700 °C. A Gibbs energy
function for the bcc phase can also be constructed to
reproduce the V-rich liquidus and solvus, but it is not
tabulated, because it differs from experimental results
[67Joh, 71Sam].
Thermodynamic calculations were done by nonlinear
least-squares optimization of coefficients of Gibbs ener-
gy expansions with respect to selected phase diagram
and thermochemical data. The Gibbs energy of a solu-
tion phase ¢ is expressed as a function of X i n atom frac-
tion V and temperature T in K as:
AmG(¢) = XAfG(AI,¢) (1 -X) AfG(V,¢)
+ R T [XInX +(1 - X ) In (1 -X)]
+ X(1 -X) [A(T) + (1 - 2X) B(T)]
where X is the mole fraction of A1 and the coefficients to
be optimized (A and B) are at most linear formations of
356 Bulletin of Alloy Phase Diagrams Vol. 10 No. 4 1989
T. Sources for the Gibbs energies of the pure elements
are listed with the optimized parameters in Table 5.
Heats of formation of the intermetallic compounds were
constructed, based on the assumptions that all the inter-
metallics are stable phases at 0 K, and that the mini-
m u m heat of formation occurs at the AI3V composition.
It can be seen from Fig. 5 that very small adjustments in
the heats of formation can lead to instabilities of some of
the intermetallic phases.
A feature that occurs in all thermodynamic calculations
of this system is a congruent or near-congruent point in
the bcc liquidus. This feature is a natural result of the
large difference between bcc AI and V melting points,
coupled with the high solubility of AI in (V) and fiat
solidus on the V-rich side of the diagram. Thus the es-
tinmted liquidus (Fig. 1) is drawn somewhat different
from the liquidus shown in previous assessments such
as Hansen.
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357