Development of AI-Ti-C Grain Refiners Containing TiC

ABINASH BANERJI and WINFRIED REIF

Cast A1-Ti-C grain refiners were synthesized by reacting up to 2 pct graphite particles of 20 micron
average size with stirred AI-(5 to 10) pct Ti alloy melts, which generated submicron-sized TiC particles
within the melts, and their solidified structures showed preferential segregation of the carbide phase
in the grain or cell boundary regions and occasional presence of free carbon whose amount exceeded
equilibrium values. At the usual melt temperatures of below 1273 K, though, TiC formed first, but
was subsequently found to react with the melt forming a sheathing of A14C3 and Ti3A1C which resulted
into poisoning of the TiC particles. However, it was possible to reverse these reactions in order to
regain the virgin TiC particles by superheating the melts in the temperature region where TiC particles
are thermodynamically stable. Grain refining tests using the TiC master alloys produced fine equiaxed
grains of cast aluminum whose sizes were comparable to that obtainable with the standard TiB2
commercial grain refiner. TiC particles introduced vi a the master alloys were found to occur in the
grain centers, thereby confirming that they nucleated aluminum crystals.
I. I NTRODUCTI ON
GRAI N refinement of aluminum and its alloy castings
through additions of grain refiners has been a common in-
dustrial practice. It has been known that some of the transi-
tion metals, v i z . , Ti, Zr, and Nb, can grain-refine aluminum.
Several authors ~2'3 have asserted that refinement by these
elements, which form peritectic systems with aluminum, is
due to nucleation of solid solution grains by crystals of
aluminides of these elements vi a the peritectic reaction. As
a contrast, it was also found that marked reduction in the
grain size could occur at concentrations of these elements
which are too small to produce their respective compounds
with aluminum. Cibula 4 attributed this grain refinement ob-
tainable through additions of transition elements in hypo-
peritectic concentrations, to their interstitial carbides which
could possibly arise as a result of reaction of transition
elements with the traces of carbon which is almost always
present in the melts, since aluminum is usually melted in
graphite crucibles. The so-called "carbide theory" has been
generally accepted in spite of a few contradictory results. 1.5.6
Cibula 4 made various trials to add carbon to aluminum
melts in the form of graphite powder or rod, carbon tet-
rachloride, carbon monoxide, acetylene, or high carbon
steel. Carbon was also added together with potassium halide
flux or the same picked up by melting aluminum in carbo-
naceous crucibles. The work was further extended 7 to syn-
thesize hardeners by reacting potassium titanofluoride with
graphite. TiC powder was also mixed with aluminum pow-
der and pressed into pellets which were subsequently stirred
into aluminum melts, or alternately carbide powder was
stirred into small pellets of molten flux. But all the above
trials virtually failed to introduce any appreciable amount of
carbon, and Cibula finally concluded that very little success
was achieved in attempts to increase carbon of aIloys con-
taining titanium and no useful results were obtained owing
to the difficulties in forming and dispersing the carbides.
In the subsequent era, from time to time, though, there
were some attempts directed toward introducing carbon or
ABINASH BANERJI, Scientist on leave from Regional Research Labo-
ratory (CSIR), Bhopal, is Research Associate, and WINFRIED REIF is
Professor, both with the Institut fiir Metallforschung-Metallkunde, Tech-
nische Universit~it Berlin, Strasse des 17 Juni 135, D-1000 Berlin 12.
Manuscript submitted January 2, 1986.
TiC in A1-Ti alloys, but they either did not succeed at all or
could at the best generate only too little carbide to provide
any scope for practical use. These included mainly the
works of Mondolfo and co-workers, 1,6 Lihl et al . ,8 Nakao
et al. , 5 , 9 and Thury. ~o The latter reacted graphite with potas-
sium titanofluoride salt in molten aluminum melt similar to
that of Cibula and briefly outlined the possible chemical
reactions, but failed to bring forward any new ideas other
than what Cibula had already conveyed. Morimune et al . "
reported that TiC particles are fairly stable in aluminum
melts but decompose gradually during isothermal holding.
Now, examining the state of art prevailing over the last
three to four decades as well as based on our own experience
to increase the carbon content of A1-Ti alloy melts, we felt
that there are two essential problems encountered in syn-
thesizing these alloys, v i z . , poor wettability of carbon with
molten aluminum, and the other problem which will be dis-
cussed later in the paper, that even if carbon is successfully
reacted with titanium to form TiC particles in the melt at
the usual melt temperatures, then also they would fail to
grain-refine aluminum due to their thennodynamical in-
stability at the usual melt temperatures. Therefore, by look-
ing into the above problems with the help of energetics
prevailing at the carbon/melt interface and relevant thermo-
chemistry applied to the formation of carbides in the melt,
we have now succeeded in generating substantial and con-
trolled volume fractions of submicron sized TiC particles in
A1-Ti alloys, which could in turn successfully grain-refine
aluminum and its alloy castings. ~2 After briefly reporting the
initial results, ~3 we now proceed further to demonstrate that
these master alloys containing TiC particles could be viable
potential additives to aluminum and its alloy melts for the
nucleation of multiple grains in the cast products, thereby
posing a strong contention for the existing A1-Ti-B and
A1-Ti commercial grain refiners.
II. EXPERI MENTAL
A1-Ti-C grain refiners were prepared from commercial
A1-Ti binary alloys containing 5 to 10 pct Ti (compositions
in weight pct throughout unless otherwise specified) and
graphite powder of 20/.tm average particle size. Typical
compositions of some A1-Ti alloys and that of graphite are
given in Table I.
METALLURGICAL TRANSACTIONS A VOLUME 17A, DECEMBER 1986--2127
Table I. l ~pi c al Composi t i ons of Materials Used
Elements Ti Fe Si V Ca S Others AI C
pct
AI-6 pct Ti alloy 5.81 0.14 0.07 0.26 - - - - 0.20 balance
AI-10 pct Ti alloy 9.62 0.15 0.11 0.48 - - - - 0.30 balance
ppm
Graphite 25 160 130 - - 45 60 40 - - balance
A1-Ti alloys were melted using either electrical resistance
or a medi um frequency induction furnace. In the case of the
former, 100 to 400 g batches of alloys were melted, and
each batch was superheated to a temperature between 1023
and 1273 K and stirred by a mechanical stirrer, so that a
deep vortex was generated. A similar stirrer was earlier
empl oyed by Banerji and Rohatgi 14'~5 to prepare cast alumi-
num mat ri x part i cul at e composi t es. Details about the
mechanical stirrer and a comprehensi ve review on cast com-
posites can be found in Reference 14. Now the graphite
powder, which was suitably preheated to expel the adsorbed
moisture, was added to the vortex in small batches and
stirred into the melt in succession. After complete additions,
the stirring was further continued at a reduced speed till the
reaction of graphite with the melt was completed. This was
ascertained by stopping the stirring action so that if any
graphite particles did not react, then they were found to be
rejected by the melt. However, experience showed that, to
obtain desired results, the entire process of incorporation
and reaction of the graphite particles with the melt must be
compl et ed rapidly within an opt i mum time which depended
somewhat upon such factors as the melt chemistry, size of
the graphite particles, temperature of the melt, and the in-
tensity and mode of stirring. Further details about t hem can
be found elsewhere. ~2 Holding the melts longer than this
opt i mum reaction time was found to "poi son" the melts, and
the resultant master alloys no longer possessed good grain
refining quality for al umi num castings. Now, after the
graphite/melt reaction was compl et ed, the stirrer was with-
drawn and melt poured into permanent molds.
In case of induction melting, in situ electromagnetic stir-
ring was utilized to incorporate the graphite particles into the
melt and also to activate reaction at the graphite/melt inter-
face. Batches of 500 to 1000 g of AI-Ti alloys were melted
and the rest of the process was quite similar to the mechan-
ical stirring process, except that in the case of induction
melting, incorporation of graphite into the melt and the
subsequent reaction for the format i on of TiC apparently
needed more t i me than that in the case of mechanical stir-
ring, because of the absence of any vortex which delayed the
transfer of carbon particles across the melt/oxide interface.
This resulted in occurrence of certain undesirable reactions
in the melts due to prol onged holding, which was, however,
necessary to get all the graphite particles incorporated and
reacted with the melts.
Therefore, these melts as well as those prepared by me-
chanical stirring which were held longer than the opt i mum
reaction time, e. g. , due to lack of an exact optimization
and/or control of this time, were further superheated to
higher temperatures (preferably between 1573 and 1673 K)
and held there for about 5 to 10 minutes for the rejuvenation
of active nucleants, and the melts subsequently cast.
Chemical analysis (except for carbon) of the mast er alloys
was done with an at omi c absorption spectrometer. Total
carbon was determined by an automatic combust i on appara-
tus, wherein the sample is combusted in a stream of oxygen
and the carbon of the specimen is convert ed into CO2,
which is then fed into a measuring chamber, where the
concentration peak is detected with a non-dispersive spec-
trometer. The linear signal is integrated and displayed digi-
tally after weight compensation and bl ank value correction.
The free carbon was estimated by wet chemical analysis.
The master alloys prepared as above were subsequently
tested for grain refi nement of commerci al l y pure aluminum
(99.7 pct). To each 100 g mel t of al umi num, different
amounts (0.05 to 0. 2 pct) of grain refiners were added at a
melt temperature of 998 K, and the melts poured at various
holding times into a water cooled steel mold. For com-
parison, similar castings were also prepared with additions
of A1-5 pct Ti-1 pct B and A1-6 pct Ti commerci al grain
refiners. The cast structures were microscopically studied
and grain size determined using a line intercept method. J6 The
average grain size was comput ed from a large number of
non-overlapping measurement s using a comput er program.
I I I . RE S UL T S
A. On the Metallography of Grain Refiners
Table II summari zes the different compositions of A1-
Ti-C master alloys prepared and their respective typical
microstructures are shown in Figures l (a) through (e). They
Table II. Typical Ti and C Analyses of Master Al l oys
Master Alloy Total
Ti Pct
Carbide Excess Total Carbide
C Pct
Free Free (Calculated)
xl 0 -3 X10 -6
AI-5 pct Ti-0,5 pct C 4.91
AI-6 pct Ti-l.0 pct C 5.64
A1-7 pct Ti-l.5 pct C 7.25
A1-8 pct Ti-2.0 pct C 7.88
1.632 3.278 0.41 0.408
3.244 2.396 0.82 0.811
5.712 1.538 1.44 1.428
7.204 0.676 1.82 1.801
2.0 1.43
9.0 1.96
12.0 3.06
19.0 6.95
2128--VOLUME 17A, DECEMBER 1986 METALLURGICAL TRANSACTIONS A
(a)
(d)
(b) (e)
Fig. 1--Typical microstructures of master alloys having compositions:
(a) A1-5 pct Ti-0.2 pct C, (b) AI-5 pct Ti-0.5 pet C, (c) A1-6 pct Ti-
1.0 pet C, (d) AI-7pct Ti-l.5 pct C, and (e) AI-8 pct Ti-2.0 pct C. Mag-
nification 166 times.
(c)
contained about 5 to 8 pct Ti, up to 2 pct C, and the
rest aluminum. The usual impurities including mainly V,
Si, and Fe did not exceed 0.7 pct.
The microstractures of master alloys exhibited primary
A13Ti particles and another particulate phase which segre-
gated generally at the cell or grain boundaries. The latter
phase consisted of fine particles usually of submicron size as
shown in the secondary electron image (SEI) of a selected
region of segregation (Figure 2(a)). Figures 2(b) and (c)
show typical X-ray mappings of Ti and C, respectively, in
the region of Figure 2(a). Enrichment of both Ti and C in
these particles confirmed that they are TiC. The volume
fraction of TiC increased with increasing carbon content of
the alloy (Figures l(a) through (e)) and though the micro-
structure of the alloy showed very high concentration of TiC
METALLURGICAL TRANSACTIONS A VOLUME 17A, DECEMBER 1986--2129
(a)
(b)
at a composition of 1.8 pct C and 8 pct Ti, presence of
some A13Ti needles could be still observed. Further, no
systematic estimation of the volume fraction of TiC could
be made as the particles were too fine to be observed indi-
vidually in an optical microscope and hence the inter-
particle spacings could not be sufficiently resolved for
their estimation.
The master alloys which were cast before all carbon reac-
ted completely with the melt, exhibited frequently unreacted
or partly reacted graphite particles as shown in Figure 3. In
general also, as evident from the chemical analysis of free
carbon (Table II), the microstructures of sufficiently well-
reacted alloys, too, showed the presence of some graphite.
The amount of free graphite eventually increased with
decreasing time of processing after graphite additions. A
theoretical calculation of unreacted carbon which should
be in equilibrium with the excess titanium of the melt
(see Appendix) yielded considerably smaller values than the
actual free carbon analyses (Table II). This discrepancy
might be attributed to (a) possibly much lower activity of
titanium in the melt than its wt pct used in the calculation,
because its actual concentrations may not strictly conform to
dilute concentration, (b) insufficient holding time of the
melts for attaining equilibrium conditions.
Figure 4(a) shows a reaction zone along the periphery of
such a carbon particle, indicating that the carbon particle
had just begun to react with titanium when the melt solidi-
fied, preventing any further reaction to proceed. On the
other hand, Figure 4(b) shows that a similar carbon particle
has now been penetrated by the melt and reaction proceeds
further via diffusion, and in Figure 4(c) it can be seen that
yet another carbon particle has completely reacted gener-
ating fine TiC particles which, however, still did not disin-
tegrate and disperse into the melt. From these micrographs
it is evident that carbon particles of about 20/ zm aver-
age size would generate a large number of TiC particles
which on disintegration from the mother compact, disperse
as fine particles of submicron size. This is well illustrated
in the electron micrographs showing individual TiC par-
ticles (Figures 5(a) and (b)). Figure 5(a) shows a Scanning
(c)
Fig. 2--Electron probe microanalysis of master alloy: (a) SE1 of TiC
segregated region, (b) Ti-X-ray image, and (c) C-X-ray image. Mag-
nification 1660 times.
Fig. 3--Optical micrograph of A1-Ti-C master alloy showing unreacted
graphite particles. Magnification 166 times.
2130--VOLUME 17A, DECEMBER 1986 METALLURGICAL TRANSACTIONS A
(a) (a)
(b)
Fig. 5- Electron micrographs of TiC particles: (a) SEM picture. (b) TEM
picture. Magnification of (a) 2120 times and of (b) 5300 times.
(b)
(c)
Fig. 4--Optical micrographs of master alloy showing reaction sequence
of the melt with graphite particle: (a) onset of reaction at the particle
periphery, (b) penetration by the melt, and (c) completion of reaction.
Magnification 830 times.
Electron Microscopic (SEM) picture of the alloy exhibit-
ing a group of TiC particles which have well-developed
crystalline morphology and angular to polygonal shapes.
In the Transmission Electron Microscopic (TEM) picture
(Figure 5(b)), these particles as well as the interparticle
spacings could be further resolved, and the particles were
found to range generally in the sizes of 300 to 1500 nm.
Their interparticle spacings, however, varied considerably
and could not be generalized.
B. On the Grain Refinement of Aluminum
Figure 6 shows a macrograph of commercially pure alu-
minum castings before and after grain refinement with ad-
ditions of increasing amounts of AI-6 pct Ti rod and A1-6
pct Ti-1 pct C ingot alloys each. It can he seen that the
amount of the columnar grains decreased with increasing
additions of both the grain refiners; however, in the case of
the TiC additions, the columnar zone diminished more rap-
idly with increasing additions and the size of the equiaxed
grains became relatively more fine. At an addition of 0.2 pct
of the carbide grain refiner, the columnar zone virtually
disappeared, whereas this zone could still be observed in the
case of similar binary alloy addition.
Figure 7 shows the variation of average grain size with
increasing holding time of commercially pure aluminum
METALLURGICAL TRANSACTIONS A VOLUME 17A, DECEMBER 1986--2131
300-
A!-6%Ti
AI - 6%T i - 15~C
O~Z O. 05~f 0.19' 0 ,.2% Additions
Fig. 6- - Macr ogr aphs of cast aluminum after grain refinement with dif-
ferent additions of A1-6 pct Ti and A1-6 pct Ti-1 pct C master alloys,
respectively. Holding time = 5 min. Magnification 0.24 times.
castings through 0,2 pct additions of A1-6 pct Ti-1 pct C
and A1-7 pct Ti-l.5 pct C as-cast alloys and A1-5 pct Ti-
1 pct B standard rod alloy each. The castings without any
additions showed predominantly columnar grains whose av-
erage size exceeded 1200/~m, whereas the inoculated cast-
ings showed fine equiaxed grains. The above two A1-Ti-C
Qc.
200
- 1
I
1
100 I I I I [
2 5 10 30 60
Log f , min.
Fig. 7 - - Ef f ect of holding time (t) of Al-melts on the average grain size of
castings made after 0.2 pct additions of (1) A1-5 pct Ti-1 pct B rod,
(2) AI-7 pet Ti-l. 5 pct C ingot, (3) AI-6 pct Ti-1 pct C ingot.
(a) (b)
(c) (d)
Fig. 8- - EPMA of crystallization center showing (a) SEI of the subgrain structure, (b) SEI of the nucleant, (c) Ti-X-ray image of the nucleant, and
(d) C-X-ray image of the nucleant. Magnification of (a) 364 times and of (b) through (d) 7280 times.
2132--VOLUME 17A, DECEMBER 1986 METALLURGICAL TRANSACTIONS A
grain refiners produced excellent grain refinement in the
one-hour test, and average grain sizes of 221 and 210/xm
were, respectively, obtained in the castings which compared
well with the 201 /~m average grain size obtained with the
A1-Ti-B rod, which is today regarded as the most efficient
grain refiner.
Figures 8(a) through (d) show a typical result of Electron
Probe Microanalysis (EPMA) of crystallization center in an
inoculated casting. Figure 8(a) shows SEI of a subgrain
structure, followed by magni fi ed SEI of the nucleant
(Figure 8(b)). Typical X-ray mappings in the region of
Figure 8(b) showing enrichment of Ti (Figure 8(c)) and C
(Figure 8(d)) confirmed that the nucleants are TiC particles,
which were observed frequently in such other crystalliza-
tion centers.
IV. DISCUSSION
It has been ext ensi vel y observed that liquid alumi-
num does not wet carbon up to a temperature of about
1273 K. t7,~8,19 Above 1273 K, the contact angle was found to
decrease with increasing temperatures and attained values
below 90 deg at temperatures exceeding 1373 K. This was
accompanied by an interfacial reaction resulting in the for-
mation of ALC3 at the carbon/melt interface. Further, ac-
cording to the chemical theory of wetting, the work of
adhesion at interracial boundary is determined by the free
energy loss (AG) through the liquid metal/wetted body
interaction. Therefore, it should he possible to determine the
wettability of carbon with a liquid metal by AG of formation
of the metal carbide. In view of this, it was suggested 2~ that
aluminum should wet carbon at temperatures beginning at
its melting point, since free energy change of aluminum
carbide formation is negative at the melting point of alumi-
num as follows:
4AI + 3C = A14C3, AG9~ = - 191 kJ " mol -~
[ 1 ]
However, this does not actually occur, presumably because
of the presence of aluminum oxide film in the melt which
does exist even in a vacuum of 10 -3 Pa. The oxide film is
believed to break only above 1273 K. Considering this the-
ory, Naidich et a1.2~ employed a capillary method to remove
the oxide film in order to wet carbon, but their results also
showed that only in some cases they could at the best lower
contact angle below 90 deg at a temperature of over 1223 K.
It might be noted that using a similar technique earlier
Kostikov et al . ~8 had reported a contact angle of 75 deg for
aluminum on vitreous carbon at a temperature of 973 K;
however, their results have not yet been confirmed by oth-
ers. 2~ Moreover, the same authors have also reported large
contact angles of aluminum on graphite up to temperatures
of 1373 K.
Therefore, considering the various reports available on
the wetting of carbon by aluminum, it could well be pre-
sumed that graphite would not react with aluminum below
1273 K in the usual melting conditions. Further, the pres-
ence of titanium, though it increases the viscosity sharply,
has no effect on the surface tension of liquid aluminum. 22
When all other conditions remain the same, the wettability
is a function of the surface tension of liquid phase. There-
fore, graphite, either, is not likely to get wetted by AI-Ti
alloy melts below 1273 K, unless some chemical reaction
takes place. In this work, hence, the temperature for the
addition of graphite was chosen below 1273 K in order to
prevent any direct reaction of carbon with aluminum. At the
same time, graphite particles were preheated to expel the
adsorbed moisture in order to increase their surface energies
so that a reaction between carbon and titanium could be
promoted as follows:
T i + C = TiC [2]
A13Ti + C = TiC + 3A1 [3]
In addition, removal of moisture releases the hydrogen
bonds, thereby causing debonding of the clusters of carbon
particles and at the same time minimizing any gas pick-up
of the melts.
Titanium has been found to react with carbon below
1273 K forming TiC, 23 and this is the only titanium carbide
known with variable composition due to carbon depletion.
For the formation of TiC, of course, it is necessary to agitate
the melts sufficiently to get the carbon particles inside the
melt surface for the above reactions to take place. Once
the TiC particles form in the melt, they will be wetted by
the melt as the contact angle of liquid aluminum with TiC
above 973 K has been found to be below 90 deg and de-
crease rapidly with increasing temperatures. ~.24 Moreover, the
above reported studies on wettability, even though carried
under high vacuum or inert atmosphere, were performed on
extemal blocks of the solid phase, whose surface energies
and purity are likely to be much lower than the freshly
formed TiC particles of this study which were generated
i ns i t u in the melt and eventually in submicron sizes possess-
ing very high specific surfaces. This would even cause
much better wetting of the TiC particles than could be ex-
pected from the earlier reports. Therefore, these fine TiC
particles would get thoroughly dispersed into the melt owing
now to a low solid-liquid interfacial energy (y sl) and
mixed uniformly throughout the melt due to the stirring
provided. However, stirring must be continued at least inter-
mittently until the melt is cast, because both TiC and the
remaining primary A13Ti precipitates tend to settle to the
bottom of a static melt owing to their higher densities than
the melt.
Wetting of the TiC particles with the melt is, however,
desirable for their stable dispersion; on the other hand, this
also has quite a disadvantage, because now the liquid alumi-
num being able to wet TiC should induce the following
reactions at the particle/melt interface:
3TiC + 4A1 = A14C3 + 3Ti [4]
9Ti + A14C3 --- 3Ti3A1C + A1 [5]
thereby forming A14C3 and Ti3A1C compounds at the TiC
particulate surfaces. However thin might be the presence of
these phases, they would now change altogether the surface
chemistry of TiC particles, rendering them unsuitable for the
nucleation of aluminum crystals.
Now, the relative stabilities of A14C3 and TiC in Al-melt
would depend upon their repective AG of formation. There-
fore, in order to make any further prediction, first of all AG
should be determined as a function of temperature for
Eqs. [1] and [2], respectively.
METALLURGICAL TRANSACTIONS A VOLUME 17A, DECEMBER 1986--2133
Calculation of Free Energy Changes
The st andard free ener gy change of a chemi cal react i on is
gi ven by:
t "
T
A G ~ = ( ~/ - / ~98 K+298J AC e dT)
c
T
- - z ( ms ~ 9 8 K+298 I ACp / T d T ) {61
where AH~98 K = st andard ent hal py change at 298 K
AS~98 K = st andard ent r opy change at 298 K
AC e = change in the mol ar heat capaci t y
For the f or mat i on of Ti C, vide react i on [2], the free en-
ergy change (cal 9 mo1-1) is gi ven by: 25
AG~- =
- 4 5 1 0 0 - 2. 48T In T + 1. 37 10- 3T 2
+ 0. 74 x 10ST -~ + 19. 4T [7]
for the t emperat ure range of 298 to 1150 K, and
AG~. = - 4 5 2 0 0 - 0 . 23T In T + 0. 11 10- 3T 2
+ 0. 74 x 10ST -1 + 4 . 9 6 T [8]
for the t emperat ure range of 1150 t o 1800 K.
The free ener gy change of react i on [1] for the f or ma-
tion of A14C3 wa s cal cul at ed f r om the standard t hermo-
chemi cal properties of the react ant s and product (Table III)
as fol l ows:
Changi ng Joul es t o cal ori es, changes in the ent ropy, en-
thalpy, and heat capaci t y f or f or mat i on of A14C3 after sim-
plification are, respect i vel y,
AS~98K = - 6 . 1 6 cal 9 K - l . mol -l
AH~98 K = - 5 3 4 4 0 cal 9 mol -~
and,
ace
= 7. 292 - 21. 055 x 1 0 - 3 T - 8. 958 x 10ST -2
+ 12. 465 x 10 -6 T: cal 9 K -1 9 t ool -1 [9]
Subst i t ut i ng t he val ues in Eq. [6] and i nt egr at i ng t he
funct i ons:
AG} = - 5 7 7 9 4 - 7. 29T In T - 2. 08 1 0 - 6 T 3
+ 10. 53 x 10- 3T 2 + 4. 48 x 10ST -j
+ 54. 33T c a l " mo1-1 [10]
The above Eq. [10] coul d be used t o cal cul at e the free en-
ergy change of A14C3 f or mat i on, vide Eq. [1], in t he t em-
perature range of 298 to 1800 K.
Figure 9 shows the st andard free ener gy changes of the
format i ons of Ti C and A14C3 f r om their respect i ve el ement s
as functions of t emper at ur e in the range o f 298 t o 1800 K.
It can be seen t hat Ti C is unstable in al umi num mel t bel ow
about 1450 K whi ch woul d f avor react i on [4] f ol l owed by
reaction [5] at t he Ti C/ Al - me l t interface. Thi s woul d lead to
the format i ons of A14C 3 and Ti3A1C compounds envel opi ng
the Ti C particles.
What we call "poi soni ng" of the Ti C part i cl es was cl earl y
evi denced in the studies carri ed out on the ext ract ed particles
with the help of EPMA and electron di ffract i on. The extrac-
t i on process consi st ed of initially ext ract i ng t he carbide
particles on cel l ul ose triacetate, f ol l owed by sputtering the
replica face wi t h car bon fi l m of about 200 t o 300 A and
subsequently di ssol vi ng the plastic in acet one whi ch, in
turn, left a secondar y car bon replica. Fi gures 10(a) t hrough
(c) provi de some t ypi cal results of EPMA per f or med on the
poi soned Ti C particles whi ch show in Fi gure 10(a), el ect ron
i mage of the carbi de particles, fol l owed by X- r ay mappi ngs
of Ti and A1 in Fi gures 10(b) and 10(c), respect i vel y. Distri-
bution of car bon in these particles coul d not be det ermi ned
because the preparat i on of extraction repl i cas was possible
/30
/50
,.. 170
~. 190
. L
~ 210
I
2 3 0 -
25O
0
I I I I I I I I
4 0 0 8 0 0 1200 1600 2000
TEMPERATURE, K
Fig. 9- - Va r i a t i on of st andard free energy changes for t he Ti C and A14C3
formations with t emperat ure.
T a b l e l l I . T h e r m o c h e m i c a i P r o p e r t i e s
- AH%8 K S~98 K
Substance kJ 9 mol - ' J 9 K- ' ' mol 1
Cp = 4.1868(a + 10 -3 bT + 105 cT 2 + 10-6dT2)
J 9 K ~ 9 mol -~ (Temp. Range 298 to 1800 K)
b c d
A14C3 223.6 104.67 36.97 6.866 - 10.02 - -
A1 0 28.34 7.4 - - - - - -
C g r a p h i t e 0 5.69 0.026 9.307 -- 0.354 --4. 155
2134--VOLUME 17A, DECEMBER 1986 METALLURGICAL TRANSACTIONS A
(a)
(b)
(c)
Fig. 10--EPMA micrographs of extracted TiC particles showing (a) SEI
picture, (b) Ti-X-ray image, and (c) AI-X-ray image. Magnification
3320 times.
only on carbon substrates. Presence of A1 in the extracted
particles (Figure 10(c)) suggested chemical reactions of the
type given in Eqs. [4] and [5], and the subsequent electron
diffraction studies 26 confirmed the presence of phases, vi z. ,
A14C3 and Ti3A1C in addition to TiC. Formation of A14C3 at
the graphite/aluminum interface is well known and was also
reported earlier by Cisse et al. 27 while studying the nuclea-
tion of aluminum crystals on TiC blocks. However, its
poisoning effect on the TiC nucleants was not known earlier.
Further, the perovskite phase Ti3A1C was known to exist in
the titanium-rich side of A1-Ti-C system, 2s which has now
been found to develop also in the Al-rich side.
Now, let us go back to the disputed report of Crossley and
Mondolfo, ~ who found that low carbon additions did not
affect the grain size of aluminum castings and higher
amounts increased the same, particularly at hyperperitectic
Ti-levels. This was attributed to the eventual reduction in
number of active AI3Ti particles available in the melt as a
result of TiC formation. Now, based on our findings of the
poisoning of TiC particles, their results could possibly be
explained. If they had obtained TiC dispersions, it was most
likely that these particles became poisoned during prepara-
tion of the grain refiners, because unless deliberate pre-
caution is taken, they are atmost sure to get contaminated at
least on the particulate surfaces, and prolonged holding
might even cause the above-mentioned reactions to proceed
further across the bulk of the particles through diffusion. For
example, the latter could be the reason for the observed
decrease in the number of TiC particles during isothermal
holding of Al-melt containing TiC dispersions. II Similarly,
here it may also be mentioned that, hitherto all previous
attempts to disperse or generate TiC particles in A1-Ti melts
didn' t succeed in obtaining substantial amounts of the same
in the solidified alloys, yet whatever amounts of this phase
could be obtained, they were prone to poisoning below
1450 K as a result of the above-mentioned superficial reac-
tions. Of course, this does not dispute the hitherto believed
carbide theory forwarded by Cibula, according to which the
TiC particles develop in the melt after the A1-Ti grain refiner
has been added. Since the holding of the melts after the grain
refiner additions is usually quite short, this would not pro-
vide enough time for the damaging reactions to occur, there-
by preventing the TiC particles from getting poisoned.
The initial results of the grain refinement test (Figure 6)
confirmed that the additions of TiC via the A1-Ti-C grain
refiners caused substantially greater refinement than that
obtainable through the additions of identical amounts of the
AI-Ti binary commercial alloy, thereby removing any in-
hibitions about the effectiveness of TiC as a grain refiner for
aluminum. Further, frequent identification of TiC in the
grain centers also confirmed that the above grain refinement
was due to nucleation of aluminum by the TiC particles. It
may be noted that the A1-Ti binary alloy was used in the rod
form which showed block-like A13Ti particles. This form of
the alloy is very effective at short holding periods, like the
one used in this test. Whereas, in case of similar additions
of an AI-Ti ingot, which showed A13Ti needles, a five-
minute holding test produced practically no grain refinement.
In the case of the A1-Ti-B master alloy also the use of rod
form was made for similar reason. On the other hand, all the
A1-Ti-C grain refiners were used in the as-cast ingot form,
which generally showed the needle-like morphology of
AI3Ti (Figure 1). In spite of that, these master alloys pro-
METALLURGICAL TRANSACTIONS A VOLUME 17A, DECEMBER 1986--2135
duced excellent grain refinements in the short holding peri-
ods (Figure 7). The average grain sizes obtained through
them were comparable with those through TiB2 additions.
However, this report provides only the introductory results
of grain refinement and more comprehensive work is on the
way to characterize these master alloys containing TiC in
varying industrial conditions in cooperation with London &
Scandinavian Metallurgical Co. , before they could be suit-
ably inducted into useful practical applications.
V. CONCLUSI ONS
1. AI-Ti-C master alloys were produced by reacting carbon
particles of 20/ ~m average size with Al-(5 to 10) pct Ti
alloy melts, while the melt was stirred.
2. Typical master alloys contained 5 to 8 pct Ti and 0.4 to
2.0 pct C, and their microstructures showed TiC par-
ticles of average size < 1 /zm in addition to the AI3Ti
phase. Amounts of free carbon were usually quite neg-
ligible, but exceeded theoretically calculated equilib-
rium values.
3. TiC particles were found to become poisoned in the usual
melting temperatures of < 1273 K, possibly due to their
higher free energy of formation than that of A14C3, which
led to the formation of A14C 3 and Ti3AIC compounds on
the TiC particulate surfaces. Theoretical calculations
showed that TiC is more stable than A14C3 above 1450 K
and the experiments showed that the poisoned TiC par-
ticles could be rejuvenated by heat-treating the melts
sufficiently above 1500 K.
4. All A1-Ti-C master alloys produced much better grain
refinement of Al-castings than AI-Ti master alloys,
and some of them produced grain sizes close to that
obtainable through A1-5 pct Ti-1 pct B commercial rod
additions.
5. TiC particles which became poisoned due to formations
of A14C3 and Ti3AIC produced poor grain refinement.
6. TiC particles introduced via master alloys were found in
the grain centers of Al-castings, thereby confirming that
they are active nucleants.
AP P ENDI X
Calculation of unreacted carbon in
equilibrium with titanium of the melt
The free energy change of a chemical reaction is given by:
s [A1] AG~ = - RT In aR x a '

where a denotes activity of the respective component shown
by the subscript and the power stands for the number of
moles each of the reactants A, B and products R, S.
For the formation of TiC from Ti and C present in A1-
melts, the free energy change may be given by:
AG~ = - RT I n ( aTic / [A2]
\ aTi X a c /
Assuming the activity of TiC to be unity as it is in the pure
state, and the activities of Ti and C equal to their weight
percentages, the above Eq. [A2] becomes:
1
AG~ = - RT In
(wt pct Ti) x (wt pct C)
[A3]
provided the concentrations are low.
Since In K = -AG~ where K = equilibrium con-
stant, R = 8.31434 J 9 K -1 9 mol -~, and AG ~ = - 165. 6
kJ 9 mol -~ (for the TiC formation at 1623 K), K becomes
equal to 2.137 l0 s. Since the usual superheatings of the
melts were in the range of 1573 to 1673 K, the average
temperature of 1623 K was used to calculate AG ~
Now, substituting the value of K in Eq. [A3],
(wt pct C) = 4.7 10-6/(wt pct Ti)
IA4]
Percentage of carbon which should be in equilibrium with
the excess titanium of melt was calculated from Eq. [A4],
and typical values for different master alloy compositions
are provided in Table III as C pct (calculated).
ACKNOWLEDGMENTS
The authors wish to acknowledge a recent grant from
London & Scandinavian Metallurgical Co. for further work
in this area and thank RRL(CSIR) Bhopal for granting study
leave to A. Banerji. This work is a part of Abinash Banerji's
Ph.D. Thesis at the Technische Universit~it Berlin.
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2136-- VOLUME 17A, DECEMBER t986 METALLURGICAL TRANSACTIONS A
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METALLURGICAL TRANSACTIONS A VOLUME 17A, DECEMBER 1986--2137