NONFERROUS METALS AND ALLOYS

SCANDIUM-ALLOYED ALUMINUM ALLOYS

V. I. Elagin, V. V. Zakharov,
and T. D. Rostova
DDC 669.715'793
Alloying with scandium has a strong and varied influence on the structure and properties
of aluminum and aluminum alloys [1-12]. The character of influence of addition of Sc is
close to that of widely used additions of such transition metals as Mn, Cr, and particularly
Zr [13]. However, the action of Sc additions isstronger and appears more effective.
Scandium is a strong modifier of the as-cast grain structure and with addition of it
to aluminum alloys in an amount exceeding a certain eriticai content the maximum possible
refinement of the as-cast grains for the specific casting conditions occurs. Addition of
scandium makes it possible to obtain continuously cast billets of aluminum alloys with a
nondendritic temperature [8].
In comparison with other antirecrystallization additions scandium increases to the
maximum degree the recrystallization temperature of worked aluminum alloy semifinished pro-
ducts. With correct selection of the alloy composition, especially the Sc content, and
also of the production parameters for production of semifinished products their recrystalliza-
tion temperature becomes higher than the solidus temperature. During heating of such semi-
finished products above the solidus temperature the aluminum matrix changes from the solid
unrecrystallized state to the liquid without the recrystallization stage. As the result
of the strong antirecrystallization action of Sc production of thin sheet (less than 1 mm
thick) in cold rolling with high degrees of deformation (up to 85% total reduction) becomes
possible. Such sheets have a completely unrecrystallized structure after heating for harden-
ing or annealing.
The nature of the influence of Sc on the structure and properties of aluminum alloys
has been discussed in sufficient detail in the literature [4-8]. The essence of it is that
the AI3Sc phase formed in AI-Sc alloys has a crystalline lattice possessing practically
complete dimensional and structural agreement with the crystalline lattice of AI. This
feature provides the strongest modifying action of the primary AI3Sc particles in crystal-
lization of the molten metal and ease in homogeneous origin of secondary particles in de-
composition of the supersaturated solid solution of Sc in AI. The latter promotes the fact
that secondary AI3Sc particles originate simultaneously in many areas of the aluminum matrix
at once without passing through metastable stages and, what is most important, in very dis-
persed form. The degree of dispersion of the particles also causes increased resistance
of the alloys to recrystallization and significant strengthening of the aluminum matrix.
The basic practical value of addition of Sc to aluminum alloys is the possibility of
an additional increase in the strength properties of wrought semifinished products as the
result of preservation of the unrecrystallized structure, refinement of the subgrain struc-
ture in the unrecrystallized matrix, and the direct hardening action of the dispersed
particles containing Sc. An analysis of the data of [i] and of the results of our investi-
gations showed that with addition of up to %0.4% Sc to aluminum and aluminum alloys each
0.1% Sc causes an average increase in o t of 50 N/mm 2. This significantly exceeds the
strengthening action of all alloy element additions (Mg, Cu, Zn, Si, Mn, Cr, etc.) to com-
mercial aluminum alloys known and used in practice.
The purpose of this work was determination of the basic metallurgical principles of
alloying of aluminum alloys with scandium. The article summarizes the results of our many
years' of investigations in this area and the literature data of other authors has also
been used.
Translated from Metallovedenie i Termicheskaya Obrabotka Metallov, No. i, pp. 24-28,
January, 1992.
0026-0673/92/0102-0037512.50 1992 Plenum Publishing Corporation 37
TABLE i
Scandium
content, %
0
0,1
0,2
0,3
0,4
0,6
t
90
lO0
180
240
270
300
I
NI~ 2
o0.2
70
80
160
220
255
285
~,%
41,3
39,3
17,8
15,3.
16,0
14,8
t,C
~00
500
ooo
300:
200,
~0
550
O50
550
2501
Fig. i.
b
%.
z l
\ i \ ' I
\
~0 z I03 10 ~ I05 fO6T, sec
a
x i
i
0 102 ~03 lO* ~c, see
b
C-curves of the start of decom-
position of the supersaturated solid solu-
tions in 92 mm diam. billets of binary
aluminum alloys drawn on the basis of a 5%
change in electrical conductivity (a~)
a: ,) 0.4% Sc; A) 0.6% Mn; ,) 0.3% Zr: b:
o) 0.1% Sc; A) 0.2% So; a) 0.3% Sc; +) 0.~%
Sc; x) 0.6% Sc.
Selection of the Limits of Scandium Content in Aluminum Alloys
One of the basic question related to alloying of aluminum alloys with scandium is its
optimum content. The Sc content must be selected so that under conditions of crystalliza-
tion corresponding to continuous casting of aluminum alloy ingots a large portion of the
Sc is found in solid solution. In subsequent production heatings the solid solution contain-
ing Sc decomposes with formation of secondary particles of AI3Sc of the optimum degree of
dispersion providing a sharp increase in recrystallization temperature and strengthening
of the alloy. The other, smaller portion of Sc must be precipitated in crystallization
in the form of primary AI3Sc particles and modify the as-cast grain structure in the ingot
or in the weld joint.
To solve this question let us consider the AI-Sc phase diagram. With aluminum scandium
forms a eutetic-type diagram with limited solubility [4-6]. The maximum equilibrium solu-
bility of Sc in AI is 0.35-0.40%. With cooling rates in solidification corresponding to
continuous casting of ingots an anomalously supersaturated solid solution of Sc (up to 0.6%)
in AI is formed. In connection with this the maximum or close to maximum hardening effect
in wrought semifinished products obtained from continuously cast billets of binary aluminum
alloys may be obtained with a content of about 0.6% Sc (Table i).
With an increase in Sc content from 0 to 0.6% the strength properties increase signi-
ficantly. It should be noted that the increase in strength properties occurs with damping.
In connection with this with a content of >0.6% Sc the increase in strength properties will
probably be insignificant.
38
T i.p~ sec v, d , s e c -I
fO 5 v ~ lO -Z
r~.n / fO -J
I0 2 , ~ i / fO -
\
10 " " - ~ fO -5
OJ 0,2 0,3 0,~ 0,~ O,6So,/o
The r e l a t i o n s h i p o f t h e i n - Fig. 2.
cubation period ~i.p preceding de-
composition of the solid solution
and of the rate of decomposition v d
at 450C in binary AI-Sc alloys to
scandium content.
H
100
80
60
4,0
fO
/
~0
/k
~ - - ~ - - + ~ ~,+
. x ~ X " " E - - " ~--x
fO 2 fO 3 I 0 ~' f05 106 t', sec
Fig 3. Change in microhardness of 92-mm-diameter
ingots of binary AI-Sc alloys with different
scandium contents during an isothermal hold at
300C: ) 0.1% Sc; +) 0.2% Sc; o) 0.3% Sc; o) 0.4%
Sc; A) 0.6% Sc.
An increase in strength properties with an increase in Sc content all the way up to 0.6%
is possible only with obsevation of certain conditions. It is necessary to strictly control
the temperature-time parameters of homogenization and heating for working by pressure and
heat treatment. This is necessary to provide the optimum degree of decomposition of the
supersaturated solid solution of Sc in AI, which is unstable in comparison w i t h the solid
solutions of other transition metals in aluminum. As may be seen from Fig. la, the incuba-
tion period preceding decomposition of the solid solution is three to four orders of magni-
tude shorter in AI-Sc alloys than i n A I - M n and AI-Zr system alloys and the rate of decomposi-
tion characterizing the reduction in solid solution content in aluminum is five to six orders
of magnitude higher in AI-Sc alloys than in AI-Mn and AI-Zr alloys [ 7 ] . in this case the
stability of the solid solution of Sc in A1 drops sharply w i t h an increase in Sc content
(Fig. ib). The incubation period preceding decomposition of the solid solution decreases
and the rate of decomposition increases (Fig. 2).
The rate of coagulation of the decomposition of the solid solution of Sc in A1 (second-
ary particles of AI3Sc) is also very high, several orders of m a g n i t u d e higher than for
the other transition metals. The rate of coagulation of secondary particles increases with
an increase in original Sc content in the solid solution. It is possible to determine the
rate of coagulation of the particles from the rate of softening of binary AI-Sc alloys
during an isothermal hold at increased temperature. Figure 3 shows curves of the change
39
t , 96'
65o % 1
/
A
350 " "---.........
25O
10 102 103 t O * 105 10 s ~, sec
F i g . 4- C- c u r v e s o f t h e s t a r t a n d f i n i s h o f d e -
c o mp o s i t i o n o f t h e s o l i d s o l u t i o n i n 92 ram d i a m.
b i l l e t s o f A 1 - 0 . 4 % Sc ( o , , ) a n d A 1 - 0 . 4 % S c - 0 . 1 5 %
Ar (&, A) alloys drawn on the basis of the change
in electrical conductivity: white symbols) start
of decomposition (A--I=5%], black symbols) finish
, i p
I
of decomposition ( A - - = 6 O % )
p
H
100
50
fO 10 2
c - ~ J
10 3 lO ~ /0 5 z', sec
Fig. 5. Relationship of the microhardness
of billets of AI-0.4% Sc (D) and A1-0.4%
Sc-0.15% Zr (o) alloys to annealing time at
350C.
in microhardness of AI-Sc alloy ingots during isothermal annealing at 300C. The character
of change in microhardness of AI-Sc alloy ingots is determined by decomposition of the
solid solution and the degree of dispersion of the decomposition products, secondary parti-
cles of AI3Sc. The descending branches of the curves of change in microhardness are deter-
mined by the rate of coagulation of the secondary particles of AI3Sc. The higher the Sc
content, the faster the rate of softening and, consequently, the more intensely the process
of coagulation of the particles occurs. After a long hold even at 300C the advantage
in hardness of alloys with a higher Sc content is partially lost.
Therefore in selection of the optimum Sc content it is necessary to take the following
factors into consideration: i) in complex alloys the limiting solubility of Sc in A1 de-
creases; 2) the solid solution of scandium in aluminum is unstable; 3) AI3Sc particles
are prone t o w a r d c o a g u l a t i o n . In addition, it must be taken into consideration that under
production conditions billets and semifinished products are subjected to long high-tempera-
ture heatings, as the result of which practically complete decomposition of the supersatu-
rated solid solution of Sc in A1 and significant coagulation of the decomposition products
occur. In connection with the above for commercial aluminum alloys on 0.6% Sc content is
not the optimum. The desirable Sc content limits in various aluminum alloys may be assumed
to be 0.1-0.5%.
Alloying of A l u m i n u m Alloys Containing Scandium with Zirconium. As accumulated ex-
perience shows, Sc must be added to aluminum alloys together with Zr. The necessity of
addition of Zr is related to the fact that it significantly (up to 50%) dissolves in AI3Sc
phase [12, 14]. The Al3(Scl-xZrx) phase formed preserves all of the positive qualities
of AI3Sc mentioned above and acquires new useful properties.
40
Fig. 6. Microstructure of AI-0.4% Sc (a) and AI-0.4% Sc-0.15% Zr
(b) alloy billets after an isothermal hold at 450C for 17.5 h.
22,000x
The same as particles of AIjSc phase, primary particles of Al3(Sc1_xZr x) are active
centers of crystallization of grains of the aluminum solid solution and are capable of
significantly refining the grain structure of aluminum alloys. In the presence of Zr a
nondendritic structure is formed in continuously cast billets with a content of 0.2% Sc
and more while in alloys without Zr a nondendritic structure is observed only with hyper-
eutectic contents of Sc, that is, with more than 0.5% Sc.
During decomposition of the supersaturated solid solution of Sc and Zr in A1 formed
in crystallization of the molten metal secondary particles of Al3(Sc~_xZr x) phase are pre-
cipitated. These particles, as for particles of AI3Sc phase, are dispersed and cause a
strong antirecrystallization and strengthening effect. However, together with this, in
contrast to AI3Sc phase particles, Al3(Sc1_xZr x) intermetallide particles are significantly
less prone to coagulation in high temperature heating and therefore the antirecrystalliza-
tion and strengthening effect is preserved in formation of them to a greater degree.
Figure 4 shows C-curves of the start and finish of decomposition of the supersatu-
rated solid solution in billets of AI-0.4% Sc and AI-0.4% Sc-0.15 Zr Alloys. Addition
of Zr has little influence on the initial stages of the change in concentration of the
aluminum solid solution but significantly accelerates this process subsequently. The curves
of the change in microhardness of billets of these alloys during an isothermal hold at
350C also indicates that softening of the alloy with addition of Zr occurs significantly
more slowly (Fig. 5). This is related to the lower rate of coagulation of the A l 3 ( S c 1 _ x Z r x )
phase particles than of AI3Sc phase particles (Fig. 6). It should be noted that in billets
of AI-0.4% Sc-0.15% Zr together with fine Al3(Scl_xZr x) phase particles coarser particles
identified as AI3Sc were observed at the boundaries of the dendritic cells. Formation of
them is apparently the result of enrichment of the billet dendritic cell boundaries with
scandium and depletion of them of zirconium as the result of the different character of
dendritic segregation of these elements during crystallization.
Therefore addition of Zr to aluminum alloys containing Sc makes it possible to use
the very strong modifying action of Sc with lower contents of it (starting with about 0.2%)
while without Zr the modifying effect of Sc appears only with hypereutectic contents (more
than ~0.5%). In addition Zr makes it possible to increase the temperature of production
heating and the time of it without decreasing the positive action of Sc.
A p p a r e n t l y Al3(Scl_xZrx) is an Al~Sc-base substitutional solid solution in which Sc
is replaced by Zr, which is close to it in nature. In this case the type of lattice is
preserved and the lattice parameter changes little. Zr may replace up to 50 wt.% of the
Sc. Therefore Al3(Sc1_xZrx ) is a phase of variable composition and depending upon the quantity
of Zr dissolved in it the properties of this phase change, particularly the thermal sta-
bility of the particles of the phase and their tendency toward coagulation in high-tempera-
ture heating. In this case, as experiments show, Al3(Sc1_xZrx ) phase particles with a
maximum quantity of zirconium dissolved in them possess the m a x i m u m tendency toward coagu-
lation. An analysis of the curves of the relationship of the microhardness of AI-Sc-Zr
alloy ingots to the legnth of hold at 400C shows (Fig. 7) that the optimum composition
is the alloy with the same ratio of scandium to zirconium (AI-0.75% Sc-0.75% Zr). From
the AI--Sc--Zr phase diagram[14] it has been established that this alloy is located in the
+ Al3(Sc1_xZrx) phase area at the boundary with the ~ + Al3(Scl_xZr x) + AI3Zr ternary
phase area. In this case 50% of the Sc atoms in Al3(Scl_xZrx) phase must be replaced with
Zr atoms.
41
H
5O
30 !
+
0
i i
" b - - .
" . . ~
. +- - +- -
1 0 # ~ 0 5 " ,, s e c
Fig. 7. Microhardness of AI-Sc-Zr system
alloy billets with different ratios of
the scandium and zirconium contents with
the same total of them in relation to
annealing time at 400C: x) 1.5 Sc; o)
1.0% Sc + 0.5% Zr; 4) 0.75% Sc + 0.75%
Zr; ,) 0.5% Sc + 1.0% Zr; A) 0.25% Sc +
1.25% Zr; +) 1.5% Zr.
H
70
55
60
55
50
#5
~0
50
Z5
0 10
I02 ~0 ~ fO ~" ~05 10 ~ "C , s e c
Fig. 8. Relationship of the microhardness of AI-
0.2% Sc alloy billets with additions of transition
metals to hold time at 450C: 4) without addi-
tions; o) 0.25% Zr; ~ 0.15% Hf; ,) 0.08 Zr + 0.08%
Hf; D) 0.05% Ti; [] 0.03% V; m) 0.025% Ti + 0.015%
V; A) 0.15% Zr 0.03% Ti + 0.02% V; +) 0.015%
Zr + 0.15% Co.
C o n s e q u e n t l y to preserve and even strengthen the positive qualities of'Sc the ratio
between the Sc and Zr contents in commercial aluminum alloys must be i:i.
As experience shows, with a content of more than 0.10-0.15% Zr in high- and medium-
alloy a l u m i n u m alloys coarse AIsSc primary intermetallides are formed, especially in cast-
ing large billets. Taking this into consideration, the Sc content must be the same as
of Zr, 0.10-0.15%. However, p r o b a b l y in this case not all of the potential possibilities
of scandium as an alloying component will be used. Taking this into consideration the Sc
content may be increased to 0.15-0.30%.
W i t h decrease in Sc content from 0.4 to 0.2% its role as a strengthener decreases
significantly (Fig. 8). In this case the Zr addition plays the role not only of a sta-
bilizer (Fig. 6) but also of a strengthener. It more than doubles the strengthening effect
as the result of increasing the supersaturation of the original solid solution and of the
corresponding increase in the degree of dispersion of the products of its decomposition.
42
TABLE 2
Recrystallization temperature T r (C)
Silicon of sheet with a thickness of,
content, %
I
0
0,2
0,3
0,4
3 2
610/620 610/620
580/620 570/590
420/600 450/575
400/540 400/450
61o/620
560/580
480/560
400/450
Explanation. The first figure is the tem-
perature of the start of recrystallization
and the second of the finish of recrystal-
iization.
Consequently in alloying of alloys with comparatively small quantity of scandium (~0.2%)
the role of Zr increases significantly. In this case alloying of aluminum alloys with
only scandium without zirconium loses practical sense as the result of the small positive
effect.
Alloyin~ of A l u m i n u m Alloys Containing Scandium with the Transition
Metals Mn, Ti, Cr, V, and Hf
Manganese does not react with scandium and does not form intermetallic compounds with
it. As in other i n d u s t r i a l aluminum alloys, addition of Mn to aluminum alloys alloyed
with Sc promotes an increase in strength properties and an improvement of the corrosion
resistance of the alloys. For this purpose 0.2-0.5% Mn must be added to aluminum alloys
containing Sc. Alloying with manganese in larger quantities is undesirable as the result
of the reduction in solubility of Sc and formation of intermetallides.
In some cases the manganese content is specified such as if it is n e c e s s a r y to obtain
high superplastic properties, thermal conductivity, etc.
Titanium, as for zirconium, is capable of dissolving in AI~Sc phase, replacing Sc
atoms. However, in contrast to Zr the solubility of Ti in AI3Sc phase is significantly
less. Like Zr Ti does not strengthen the modifying effect of Sc but decreases the critical
Sc content starting with which its modifying action appears. Ti may be added to aluminum
alloys alloyed with Sc as a complex modifier together with Zr in a quantity of 0.02-0.06%.
In addition, addition of Ti has a detremental effect on strengthening indices in de-
composition of the supersaturated solid solution of Sc in AI, accelerating somewhat the
softening processes (Fig. 8).
Chromium. Addition of Cr to aluminum alloys decreases somewhat the strengthening
and antirecrystallization effects from addition of Sc. This was established in investigation
of binary AI-Sc alloys and of AI-Zn-Mg-Sc system commercial alloys. In addition, addition
of Cr to AI-Zn-Mg-Sc system alloys decreases their plasticity and fracture toughness~
strengthens their tendency toward exfoliation corrosion, and has a detremental effect on
weldability.
Vanadium. A small addition of V to AI-Sc alloys decreases the strengthening effect
in decomposition of the supersaturated solid solution (Fig. 8) and reduces the antire-
crystallization effect related to allying with scandium. The presence of Zr neutralizes
the negative action of V.
Hafnium. Addition of 0.15% Hf to AI-0.2% Sc alloy strengthens the strengthening effect
in decomposition of the supersaturated solid solution (Fig. 8) and increases somewhat the
recrystallization temperature of this alloy. A p p a r e n t l y Hf is a positive addition to
aluminum alloys containing Sc but to obtain a significant effect it must be added in a
larger quantity than was done in the experiments conducted.
43
Interaction of Scandium with the Primary Alloying Elements Used in Commercial
A l u m i n u m Alloys
Of all the primary alloying elements normally used in commercial aluminum alloys (Mg,
Zn, Cu, Sc, Li) Mg, Zn, and Li do not form chemical compounds with Sc. In connection with
this it is desirable to add scandium primarily to aluminum alloys in which the primary
alloy elements are Mg, Zn, and Li. The question of the desirability of addition of Sc to
wrought aluminum alloys in which Cu and Si are used as primary alloy elements requires
additional study.
With Sc copper forms W phase (AI, Cu, Sc) [15]. This phase is formed in crystallization
of the molten metal and does not dissolve in subsequent heating. As lhe result of this
SC and Cu in the composition of W phase do not participate in strengthening the alloy and
thereby reduce the strength properties of the alloys. In addition W phase particles increase
the volume share of excess phases in the structure of the alloys, as the result of which
their plasticity, impact strength, and fracture toughness decrease. For example, an attempt
to improve DI6 (Al-~u-Mg system) and type 1201 (AI-Cu system) alloys by addition to them
of 0.4% Sc was not crowned with success. The strength properties, the relative elongation,
and the fracture toughness of the alloys dropped as the result of formation of W phase
particles.
However, as an analysis of the AI-Cu-Sc diagram shows [15], with contents of less
than 1.5% Cu and 0.2% Sc W phase is not formed. In connection with this if in the alloy
the Cu content does not exceed this level a positive effect may be expected from addition
of Sc.
Silicon decreases the strengthening effect in decomposition of the supersaturated
solid solution of Sc in A1 formed in crystallization of the molten metal and also sharply
reduces the recrystallization temperature of aluminum alloy semifinished products contain-
ing Sc (Table 2). This occurs for two reasons. First, with addition and an increase in
the Si content there is a change in the character of decomposition of the solid solution
from continuous to interrupted. The products of interrupted decomposition are coarser
and the density of their distribution in a unit of volume of the alloy is significantly
less. Second, Si forms with S c a chemical compound [16].
The Si content in aluminum alloys alloyed with Sc must not exceed 0.15%.
Iron. Fe impurity does not form chemical compounds with Sc, does not change the
character of decomposition of the solid solution of Sc in AI, and therefore does not de-
crease the positive action of Sc on the structure and properties of aluminum alloys. The
Fe content in aluminum alloys alloyed with Sc must be limited guided by recommendations
for commercial aluminum alloys without scandium.
Conclusion. The basic principles of alloying of aluminum alloys with scandium are:
it is desirable to add scandium to aluminum alloys in a quantity from 0.i to 0.3%
together with zirconium (0.05-0.15%), which strengthens the positive influence of scandium
on the structure and properties of alloys;
the greatest effect (that is, the positive influence on mechanical properties and
other characteristics) from addition of scandium together with zirconium is observed for
alloys not containing alloy elements combining scandium in insoluble phases, specifically
the AI-Mg, AI-Zn-Mg, and AI-Mg-Li systems;
with a limited copper content alloying with scandium together with zirconium of A I -
Zn-Mg-Cu and AI-Cu-Li system alloys is possible.
At present on the basis of or taking into c o n s i d e r a t i o n t h e principles developed of
alloying of aluminum alloys with scandium commercial aluminum alloys based on the A I - M g -
Sc-Sr (01570, 01571, 01523, 01505), AI-Zn-Mg-Sc-Zr (01970, 01975), and AI-Li--Mg-Sc-Zr
(10421, 01423) systems have been developed.
1.
2.
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