Journal of Alloys and Compounds 455 (2008) 164–167

Response to thermal exposure of Al/K2TiF6/C powder blends

Yücel Birol ∗
Materials Institute, Marmara Research Center, TUBITAK, Gebze, Kocaeli, Turkey
Received 8 December 2006; received in revised form 8 January 2007; accepted 8 January 2007
Available online 12 January 2007

Abstract
Al–TiCp composites have been extensively studied in recent years owing to their attributes as wear-resistant structural materials and to their
potential as efficient grain refiners. In the present work, Al–TiCp composites were synthesized in situ by the powder metallurgy route, by heat
treating Al/K2 TiF6 /graphite powder blends without the benefit of mechanical milling/alloying. TiC particles formed in aluminium after a series
of reactions when Al/K2 TiF6 /C powder blend was heated at 1000 ◦ C. First, the K2 TiF6 salt was reduced by aluminium at approximately 560 ◦ C
generating Al3 Ti particles and K–Al–F salts which make up additional consitutents in the powder blend. Further increase in the temperature led to
the melting of the aluminium powder which wet and engulfed the Al3 Ti particles thus produced. K–Al–F salts are believed to have played a key
role in the sintering process by cleaning and stripping the surface oxides of the aluminium powders. The Al3 Ti particles were gradually replaced
by TiC particles when the powder blend was heated above 800 ◦ C. One-hour heating at 1000 ◦ C yielded a composite sample with predominantly
TiC particles.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Composite materials; Aluminium alloys

1. Introduction situ metal matrix composites [19–24]. TiC particles generated

Among several reinforcements identified for aluminium
alloys, TiC is particularly attractive as it offers high hardness
and elastic modulus, low density, good wettability yet low chem-
ical reactivity with aluminium melts [1–4]. Al–TiCp composites
combine the attractive features of TiC particles with the ductil-
ity and toughness of the aluminium matrix, leading to a unique
combination of properties [5–11]. They have been extensively
studied in recent years not only because of their attributes
as wear-resistant structural materials but also on account of
their potential as very efficient grain refiners [12–17]. Sev-
eral Al–Ti–C alloys have already been commercialized as grain
refining master alloys and have long been in use in aluminium
foundries world wide [18].
A variety of processes have been employed to produce
Al–TiCp composites. Solidification processing involves direct
addition of TiC powders into molten aluminium, often by
mechanical means [9–11], and is thus economical and practi-
cal. Al–Ti–C system, however, is well suited for fabricating in
by in situ reactions between Al–Ti melts and various carbon
sources [5,6,25–30] are thermodynamically stable, have clean
interfaces with the matrix and are thus much stronger. Some
in situ techniques to synthesize Al–TiCp composites employ
powder metallurgy (PM) methods [31,32]. PM-processed com-
posites are superior to their cast counterparts which suffer poor
mechanical properties due to the clustering of reinforcing parti-
cles during solidification processing [33]. PM processing often
involves sintering of powder blends prepared by mechanical
milling/alloying of individual elements which assures better dis-
tribution of the particles in the consolidated material [34,35]. The
present work was undertaken to synthesize Al–TiCp composites
in situ, via PM route, by heat treating Al/K2 TiF6 /graphite pow-
der blends without the benefit of mechanical milling/alloying.
The reactions involved in the synthesis were investigated by
thermal and metallograhic analysis of samples taken during the
process.
2. Experimental

A mixture of 5 g aluminium powder (99.7 wt.% Al, maximum particle size:

350 ␮m), 1.23 g K2 TiF6 and 0.066 g graphite powder (Ti:C ratio was 4) was
∗ Tel.: +90 262 6773084; fax: +90 262 6412309. dry-milled for several minutes to obtain a blended mixture. The powder blend
E-mail address: yucel.birol@mam.gov.tr. thus obtained was heated in the differential thermal analyzer (DTA) cell until

0925-8388/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jallcom.2007.01.021
 Y. Birol / Journal of Alloys and Compounds 455 (2008) 164–167 165

1100 ◦ C to investigate its response to thermal exposure. The DTA experiment

was performed under flowing argon at a heating rate of 10 ◦ C/min. Larger vol-
umes of Al/K2 TiF6 /C powder blends were additionally heated in a tube furnace
in the same manner as that employed in the DTA experiment, to temperatures
which mark the end of the major thermal signals displayed in the DTA curve.
They were held at these temperatures for 1 h and then quenched to room temper-
ature to retain the microstructural features introduced by these heat treatments.
The heat treated powder blends were subsequently analyzed with X-ray diffrac-
tion (XRD) and metallographic techniques, in order to identify the reactions
responsible for the DTA signals. XRD was conducted with Cu K␣ radiation at a
scan rate of 0.5◦ min−1 in order to improve the counting frequency. Samples for
metallographic analysis were prepared using conventional practices and were
examined with an optical microscope.

3. Results and discussion

The DTA spectrum of the Al/K2 TiF6 /C powder blend exhibits

a total of four signals two of which are endothermic (Fig. 1). The
first endothermic signal is a very small one at approximately
385 ◦ C, and is linked with the removal of moisture from the
halide salt while the second one at 660 ◦ C is produced by the
melting of aluminium powders. Of the two exothermic peaks,
the second one which follows melting of aluminium powders
implies a long lasting reaction which occurs between 800 and
1000 ◦ C. The XRD spectrum of the as-blended mixture reveals,
in addition to those of aluminium, reflections of K2 TiF6 and
carbon, the intensities of which scale with their approximate vol-
ume fractions (Fig. 2a). The XRD spectrum of the powder blend
heated at 400 ◦ C for 1 h was almost identical to that of the as-
blended mixture, confirming that no change in the constituents
has occurred after the first, small endothermic signal.
The second sample from the powder blend was heated at
580 ◦ C for 1 h, in order to establish in the powder blend the
reaction that produced the first exothermic signal in the DTA
scan. The XRD pattern of this sample, which was still in powder
form after the heat treatment, is strikingly different from that of
the as-blended mixture (Fig. 2b). Al3 Ti, K3 AlF6 and KAlF4
reflections are noted for the first time while those of K2 TiF6 in
the as-blended mixture are almost completely missing. Such a
change in the constituents of the powder blend upon heating at
580 ◦ C is best accounted for by a reaction between the K2 TiF6
salt and aluminium powders,
Fig. 2. X-ray diffraction patterns of Al/K2 TiF6 /C powder blend samples (a) in
3K2 TiF6 + 13Al → 3Al3 Ti + 3KAlF4 + K3 AlF6 (1) the as-blended state, and after heating isothermally for 1 h at (b) 580 ◦ C, (c)
750 ◦ C, (d) 900 ◦ C and (e) 1000 ◦ C. () Al, (䊉) K2 TiF6 , () C, () Al3 Ti, (♦)
So, it is fair to conclude that reaction (1) is responsible for the KAlF4 , () K3 AlF6 and () TiC.
first exothermic peak in Fig. 1. While Al3 Ti lines can be readily
identified in the XRD spectrum (Fig. 2b), the optical micro-
graphs of aluminium powder sections provides no evidence for
Al3 Ti phase inside aluminium powder grains (Fig. 3a). Al3 Ti is
apparently present in the powder blend but not inside aluminium
powders. This may also imply that the aluminides which have
precipitated out are yet too small to be resolved at optical micro-
scope resolutions. Carbon lines, on the other hand, persist in
the XRD spectrum after heating at 580 ◦ C, suggesting that car-
bon does not engage in any reaction at this temperature. This
is further evidenced by the lack of carbides carbon might have
produced with Al and/or Ti.
Fig. 1. DTA spectrum of the Al/K2 TiF6 /C powder blend (recorded at a heating The Al/K2 TiF6 /C powder blend heated at 750 ◦ C for 1 h was
rate of 10 ◦ C/min). no longer in powder form but has largely densified after melting
166 Y. Birol / Journal of Alloys and Compounds 455 (2008) 164–167
Fig. 3. Optical micrographs of Al/K2 TiF6 /C powder blend samples heated
isothermally for 1 h at (a) 580 ◦ C, (b) 750 ◦ C and (c) 1000 ◦ C.
of the major constituent, via liquid phase sintering. KAlF4 and
K3 AlF6 salts generated by reaction (1) are claimed to have
played a key role in the sintering process by cleaning the surface
oxide films of the aluminium powders, leading to the fusion
of individual aluminium powder grains. The XRD pattern
of the alloy thus obtained is dominated by Al3 Ti reflections
while reflections of K–Al–F salts and carbon have almost
vanished (Fig. 2c). The microstructure of this sample shows
small, blocky Al3 Ti particles only (Fig. 3b), and thus confirm
the XRD results. It is then fair to claim that the aluminium
melt has penetrated between the powder constituents and have
eventually engulfed the Al3 Ti particles which have formed
earlier. Graphite particles, on the other hand, were not wet by the
molten Al–Ti alloy and have floated to the top together with the
spent salt. This claim is further evidenced by the XRD spectrum.
Metallographic and XRD analysis both show that carbon is not
incorporated in, what appears to be a binary Al–Ti alloy at this
stage.
Al3 Ti lines were reduced while TiC lines were noted for the
first time when the powder blend was heated at 900 ◦ C, before
the end of the second exothermic peak (Fig. 2d). TiC lines have
grown larger after isothermal heating at 1000 ◦ C (Fig. 2e). The
XRD results are further supported by metallographic investi-
gations. Al3 Ti particles inside aluminium powders are largely
replaced by a fine dispersion of TiC particles (Fig. 3c). This
change in microstructural features seems to imply a reaction
between Al3 Ti and carbon,
Al3 Ti + C → TiC + 3Al (2)
which is favored thermodynamically, as TiC is more stable with
respect to Al3 Ti [36]. However, reaction (2) was shown recently
not to occur in a temperature range where Al3 Ti coexisted in the
aluminium melt with graphite, possibly due to the failure of the
aluminium melt to wet the latter [36]. When particulate graphite
was introduced into an Al–Ti melt, TiC formed only when Al3 Ti
dissolved in the melt with increasing temperatures but not unless
the halide salt is involved in the process [36]. The same mecha-
nism is believed to be operating in the present case. The features
of the second exothermic peak seem to imply that TiC forms over
a range of temperatures, as soon and as long as solute Ti is made
available via the solutionizing of Al3 Ti particles in the melt with
increasing temperatures. A notable fraction of the solute Ti then
reacts with graphite particles to generate TiC particles while
the rest crystallizes in the form of coarse aluminide plates upon
quenching (Fig. 3c). The conversion of Al3 Ti into TiC improves
with increasing temperatures as inferred from the XRD analysis
of samples heat treated within this temperature range (Fig. 2d
and e).
The formation of TiC particles is thus claimed to rely on the
reaction between solute Ti and carbon,
Ti + C → TiC (3)
The mechanism of TiC generation upon thermal exposure of the
Al/K2 TiF6 /C powder blend is very similar to that observed when
pre-mixed K2 TiF6 salt and particulate graphite are added into
molten aluminium in the liquid metallurgy route [36]. The use
of K2 TiF6 , and the K–Al–F salts produced through its reduction
by aluminium, once again, play a key role. The present mecha-
nism, however, is evidently different with respect to that which
involves a reaction between Al4 C3 and Al3 Ti when Al–Ti alloy
powder, mechanically alloyed with carbon, is heated at temper-
atures similar to those employed in the present work [37]. The
latter route fails to generate TiC particles without the benefit of
mechanical alloying.
 Y. Birol / Journal of Alloys and Compounds 455 (2008) 164–167
4. Summary
TiC particles form in the aluminium matrix after a series of
reactions when Al/K2 TiF6 /C powder blend is heated at 1000 ◦ C.
First, the K2 TiF6 salt is reduced by aluminium at approximately
560 ◦ C. Al3 Ti particles thus form, become another constituent
of the powder blend and are wet and penetrated by the alu-
minium melt above 660 ◦ C. K–Al–F salts generated during the
formation of Al3 Ti particles help to clean the surface oxides of
the aluminium powders and play a key role in the liquid phase
sintering process. The graphite particles, on the other hand, are
rejected by the melt and float together with the K–Al–F salts.
The sample which has largely sintered at 750 ◦ C is dominated
by blocky Al3 Ti particles uniformly distributed inside the alu-
minium matrix. Al3 Ti particles are gradually replaced by a fine
dispersion of TiC particles as soon and as long as solute Ti is
made available via the solutionizing of Al3 Ti particles over a
range of temperatures starting at 800 ◦ C. One-hour isothermal
heating at 1000 ◦ C yields a composite sample with predomi-
nantly TiC particles.
Acknowledgements
It is a pleasure to thank F. Alageyik, O. Çakır and E.
Karabeyoğlu for their help in the experimental part of this work.
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