Materials & Design, Vol. 18, Nos. 4r6, pp.

297301, 1997
1998 Published by Elsevier Science Ltd
Printed in Great Britain. All rights reserved
0261-3069r98 $19.00q0.00
( ) PII: S02613069 97 00068X
The dispersion mechanism of TiB ceramic
2
phase in molten aluminium and its alloys
A. Jha
a,U
, C. Dometakis
b
a
The School of Materials, Clarendon Road, University of Leeds, Leeds LS2 9JT, UK
b
Department of Materials Engineering, Brunel University, Kingston Lane, Uxbridge UB8
3PH, UK
Received 5 August 1997; accepted 18 August 1997
( ) Titanium diboride TiB ceramic particulates are dispersed in molten aluminium and its alloys for grain
2
refining and for making cast metal1matrix composites. For producing cast MMC, the dispersion of the
ceramic phase via in-situ aluminothermic reduction of K TiF and KBF flux mixture with molten
2 6 4
aluminium and, via the addition of exogenously formed TiB with the fluoride flux has been studied at
2
900C. In this article, the aspects of interfacial energy that govern the dispersion and agglomeration of
TiB particulates are examined. The Gibbs-adsorption interface equation is particularly employed to
2
define and to quantify the change in the surface energy as a function of the alloying element
concentration and, consequently the effect of interfacial energy on the nucleation rate of TiB formed
2
via metallothermic reduction reaction and the size of the ceramic phase is also explained. 1998
Published by Elsevier Science Ltd. All rights reserved.
Keywords: aluminium alloys; Al-alloy MMC; TiB and dispersed ceramics
2
Introduction
Aluminium alloy matrix reinforced with the particu-
lates of TiB as a ceramic phase has been identied as
2
a possible alternative to the AlSiC metalmatrix com-
posites
1
. The original article of by Wood et al.
1,2
ex-
amined the microstructural and wear properties of
AlTiB cast metalmatrix composites with less than 8
2
vol.% dispersion of 520 m TiB particulates. The
2
method for ceramic phase dispersion adopted was based
on the extension of the grain-rening master alloy
manufacturing process which was simultaneously stud-
ied by Lee et al.
3
. In the grain-rening master alloy
fabrication, as described by Dometakis et al.
4
, the
complex uorides K TiF and KBF are reduced via
2 6 4
aluminothermic reduction: K TiF q2KBF q10r3 Al
2 6 4
. .
sTiB alloy q3.3 KF AlF q2AlF and yield TiB .
2 3 3 2
The freshly formed TiB at the metalux interface
2
rapidly disperses in metallic aluminium. The mi-
crostructure of the dispersed TiB is dependent on the
2
interfacial energy conditions. In commercial alloys
.
namely A356 Al7Si0.3Mg and Al4.7Cu0.8Mg-
.
0.8Mn segregate at the interdendritic boundaries by a
particle pushing mechanism
1,2
. The dispersion charac-
teristics of TiB in molten aluminium and its alloys
2
have not been studied in the context of surface energy,
which is by far the most important factor governing the
dispersion of TiB in liquid aluminium.
2
In this article, we have studied the importance of
surface tension or the interfacial energy on the disper-
sion of in-situ formed TiB in two different types of
2
alloy matrices: commercial purity aluminium and
U
Correspondence to A. Jha
Al8%Mg1%Zr alloys. For this investigation, the
Gibbs-adsorption equation has been examined for de-
scribing the role of alloying elements on the interfacial
energy of aluminium alloys. We have also explained the
importance of controlling other types of interfaces pre-
sent during the dispersion process. Examples for the
dispersion of exogenously formed TiB particulates in
2
aluminium alloys are also discussed briey.
The control of size and size distribution of the cer-
amic phase dispersed in a light-alloy matrix, e.g. Al-al-
loy is of an engineering importance for fabricating
materials with high specic modulus and strength via
casting technique. The understanding of the mecha-
nism of dispersion of particulates in Al-alloy will en-
able us to design better materials for structural applica-
tions.
Experimental
. .
Commercial purity CP aluminium and AlMg 8% -
1%Zr alloys were selected as matrix materials. Each
matrix composition was rst melted and cooled in a
partially reducing atmosphere of Ar4%H in order to
2
minimize the oxygen contact with molten metal. A
limited number of experiments were also carried out in
an oxidizing atmosphere for making comparison
between the cast microstructures. The melting was
carried out inside a radio frequency coil as described
by Dometakis et al.
4
. After the rst melting and cooling
cycle, a reasonably at metalgas interface was formed
.
inside the alumina crucible, as shown in Figure 1 a .
The masses for K TiF and KBF uxes were calcu-
2 6 4
lated for a selected dispersion volume, e.g. 15% TiB
2
Materials & Design Volume 18 Numbers 4/ 6 1997 297
The dispersion mechanism of TiB ceramic phase in molten aluminium and its alloys: A. Jha and C. Dometakis
2
Figure 1 Schematic diagram of crucible containing aluminium and
. . ux. a Flat surface of frozen aluminium. b Flat surface of Al-metal
. covered with uoride ux. c Fluoride uxqAl ingot after reaction
in Al-alloy and added on the top of the frozen
..
aluminium surface see Figure 1 b . Each ux mixture
was then melted together with the Al-alloys at 900C as
.
shown in Figure 1 c in a partially reducing atmosphere
.
Ar4%H . In the case of exogenous TiB , the ux
2 2
.
mixture was sodium cryolite 3NaF AlF and MgF in
3 2
a proportion of 4:1. The cryoliterMgF mixture was
2
mixed with TiB particulates of average particle size
2
.
25 m . Each ux reaction and ux treatment experi-
ment lasted for 15 min at 900C. After this period, the
ingot was allowed to solidify by switching-off the radio
frequency coil power supply. The ingots weighing
between 15 and 20 g were obtained and these were
prepared for microscopic examination and the results
are discussed below. A limited number of small-scale
casting trials with uniform dispersion of TiB were also
2
melted using 1 kg of aluminium and the microstruc-
tures were reproduced in a Ar4%H atmosphere
2
above 800C.
Results
The microstructures of in-situ dispersed TiB
2
The microstructures of dispersed TiB formed via in-
2
situ reaction of uoride uxes with commercial purity
aluminium are compared in Figure 2. The composition
of uoride ux was the only variant in the ux-assisted
.
TiB dispersion experiments. Figure 2 a shows the
2
back scattered image of the banded structure of TiB
2
in commercial purity aluminium. When the MgF and
2
Li TiF rLiBF mixture partially replaced the
2 6 4
K TiF rKBF mixture, the resulting microstructures
2 6 4
. .
are compared in Figure 2 b and c , respectively. The
absence of the banded TiB structure was conrmed in
2
the latter two cases. The alloy matrix analysis con-
rmed the presence of Mg and Li between 0.25 wt.%
and 0.35 wt.%. These two elements were therefore
transferred during aluminothermic reduction reaction
from the uoride ux mixture to the aluminium matrix
and, consequently the composition of CP aluminium
changed to Mg-rich and Li-rich aluminium alloys, re-
spectively. The particulates of TiB were found to be
2
.
fairly coarse 510 m in the CP aluminium with Mg
..
as an alloying element see Figure 2 b , whereas the
average particle size was below 0.5 m when 0.25 wt.%
Li was present in the CP alloy matrix. In both mi-
crostructures, there is an evidence for coalescence,
however, the extent of coalescence is signicantly higher
Figure 2 Microstructure of commercial purity aluminium containing
. TiB . a Back scattered image of banded layers of TiB in molten
2 2
. aluminium after reaction with K TiF qKBF ux. b Microstruc-
2 6 4
ture of TiB segregating at the grain boundaries in CP aluminium
2
. treated with 90% K TiF qKBF mixed with 10% MgF ux. c
2 6 4 2
Effect of the replacement of 1015% K TiF qKBF ux mixture by
2 6 4
1015% Li TiF qLiBF on the microstructure of TiB in CP
2 6 4 2
aluminium
for CP aluminium with Li. Figure 3 shows a uniformly
dispersed microstructure of 25 m TiB in the
2
AlMgZr alloy matrix. There is neither the presence
of banded structure nor is there any evidence for the
presence of any particleparticle coalescence.
The microstructures of exogenously-formed TiB in CP
2
aluminium
The dispersion of TiB particulates without any ux in
2
the CP aluminium was found to be impossible under
oxidizing conditions. No signicant volume percent of
TiB was observed in the microstructure due to the
2
presence of a tenacious and coherent lm of alumina
Materials & Design Volume 18 Numbers 4/ 6 1997 298
The dispersion mechanism of TiB ceramic phase in molten aluminium and its alloys: A. Jha and C. Dometakis
2
Figure 3 Microstructure of uniformly dispersed TiB facetted par-
2
ticulates in Al-8%Mg-1%Zr alloy. Flux used was K TiF qKBF
2 6 4
at the gasmetal interface. The alumina lm was elimi-
nated by using sodium cryolite mixed with MgF . The
2
microstructure of coarse particulates in Figure 4 can be
compared with the morphological features of TiB in
2
Figures 2 and 3 which varies sharply from the in-situ
microstructure. In Figure 4, the matrixparticulate in-
terfacial regions were also analyzed for Al and Ti by
energy-dispersive X-ray technique and it conrmed that
the matrix consisted of a signicant amount of elemen-
tal Ti which may be present as the Al Ti intermetallic
3
phase. The cavity formed around each particle suggests
that TiB particulates may have reacted with the ma-
2
trix, as it is well known from the grain-rening reac-
tion: 4Al qTiB sAlB qAl Ti. Therefore Ti should
2 2 3
be present in the matrix which is shown in Figure 4.
Discussion
The dispersion of TiB particulates in liquid aluminium
2
and its alloys is greatly inuenced by the surface ten-
sion of the alloy. In other words, the interfacial energy
between the liquid alloy and the ceramic particulates is
one of most important factors whether the particulates
of ceramic phase would coalesce or disperse. Besides
the matrixparticulate interfacial energy, there are
three additional interfaces and each one can have an
effect on the dispersion of the ceramic phase in the
molten aluminium metal. They are the uxatmo-
sphere, uxcrucible and metalux interfaces. We
have not considered the crucibleux boundary for the
in-situ reaction because the TiB particulates form via
2
aluminothermic reduction at the interface and they are
rapidly transferred into the molten matrix. Each of
these factors is discussed in the context of the mi-
crostructural evidences shown above. The ux-crucible
boundary could become signicant in the case of ex-
ogenously formed TiB in view of the low interfacial
2
energy of the graphiteTiB Al interface
5
.
2
The uxatmosphere interface is important from the
point of view of reducing the oxygen contamination of
the metalux interface. The presence of oxygen and
moisture promotes the oxidation of aluminium alloys
and prevents the dispersion of TiB . In a commercial
2
grain-rening master alloy production process, the u-
oride ux is melted in air together with aluminium
metal and cast in air containing moisture. The presence
of moisture in the ux and in air therefore adversely
affects the dispersion of the ceramic phase by forming
an inhibitive layer of alumina; and the extent disper-
sion then becomes inversely dependent on the concen-
tration of moisture in the melting atmosphere and ux
during the melting process. Alumina is thermodynami-
cally more stable than TiB and uoride ux and its
2
removal is only possible by the presence of a cryolite
ux for example. An upper limit for oxygen as alumina
in the ux must be determined from the Al O -cryolite
2 3
phase diagram at a given temperature
6
for avoiding the
saturation condition of Al O at which alumina will
2 3
start forming an inhibitive layer.
The metalux interface is by far the most important
factors for understanding the origin of dispersion of
TiB in molten metal. In the in-situ process, the exclu-
2
sion of TiB particulates by the layer of alumina formed
2
at the surface of liquid aluminium is minimized by
forming cryolite as a by-product of the dispersion reac-
tion shown above. Whereas when the exogenous TiB
2
particles are present, the dispersion condition necessi-
tates the presence of cryolite which helps in reducing
the formation of alumina at the metalux interface.
This is because alumina has a nite solubility in cry-
olite, melts at a given temperature and an example of
the solubility diagram is shown by Dewing et al.
6
.
Besides the molten ux acting as a sink for alumina
formed, it also envelopes molten aluminium and physi-
cally cuts-off the contact between the metal and the
crucible. This can only be explained by considering the
interfacial conditions that satises the energetics:
is smaller than and ,
AlrFlux Alrcrucible uxrcrucible
where is the interfacial energy in J m
y2
.
d d
.
s sy . R.T 1
i
dlnX dlna
i i
The molten ux acts as a reservoir for the surface-ac-
tive elements which greatly modify the uxmetal and
TiB -metal interfacial energies. It is well known from
2
Korolkovs review
7
that the interfacial tension of mol-
ten aluminium drops signicantly with the addition of
solute elements Mg and Li. At a concentration of 0.5
wt.% of the solute elements, the interfacial energy of
pure aluminium at its melting point drops from 0.92 to
0.72 Jm
y2
and 0.58 Jm
y2
, for Mg and Li, respectively
7
.
It is also important to note that when CP aluminium
was used as a reducing agent for uxes containing
MgF and LiF in the forms of Li TiF and LBF , these
2 2 6 4
two uorides are also reduced by Al to their elemental
forms and they rapidly dissolve in molten aluminium by
Materials & Design Volume 18 Numbers 4/ 6 1997 299
The dispersion mechanism of TiB ceramic phase in molten aluminium and its alloys: A. Jha and C. Dometakis
2
Figure 4 Microstructure of exogenously formed TiB added in CP
2
. aluminium with the help of sodium cryoliteqMgF ux. a Low
2
magnication micrograph showing segregation at grain boundaries.
. b Aluminium and Ti-metal energy dispersive X-ray micrograph
lowering its Gibbs free energy and the interfacial en-
ergy between the metal and ceramic phase. The latter
is mathematically described by the Gibbs-adsorption
.
7

Eq. 1 . is called the surface concentration number

i
2
.
of atoms adsorbed per m per g-atom of the solute

y1
atom i, R is the universal gas constant 8.314 J mol
y1
.
K , T is the absolute temperature and a is the
i
thermodynamic activity of the solute atom i in the
aluminium alloy which is expressed by a product of a
constant h and X , i.e. a sh X , where h is the
i i i i i i
Henrian activity coefcient. In this relationship, X is
i
the atomic fraction of the solute in the solvent. Clearly
for a solute i to be surface active, it is essential that
the slope of against ln a must be negative. Other-
i
wise the adsorption of the solute must not occur. Both
Mg and Li satisfy the Gibbs adsorption condition and
lower the value of for molten aluminium and also
promote a high nucleation rate during the process of
ux reaction
4
. This is the reason that the average size
of TiB nucleated is signicantly smaller with the pres-
2
.
ence of Li than when Mg and Mg and Zr are present
as solute elements in the solvent aluminium.
The role of Zr as a minor solute element in the
AlMgZr alloy during the dispersion process is rather
complex. Zirconium atoms serve two important pur-
poses while present in the metal with Mg. It is one of
the strongest boride formers amongst all the solute and
solvent elements present and, therefore, it promotes
.
the formation of Ti,Zr B in preference to other com-
2
plex borides. However, the coexistence of Mg with Zr
.
reduces the surface adsorption of Mg on to Ti,Zr B
2
.
surface compared to Ti,Al B surface. Magnesium as
2
solvent with less 0.2 at.% concentration of Zr promotes
a tendency to demix with -Zr in the MgZr phase
diagram
8
. The behaviour of Ti and Zr as solute atoms
in Al-alloy is similar to those observed in the MgZr
alloy. As a result, the magnesium atoms prefer to be
associated with the aluminium as the solvent atoms and
favour the conditions for surface desorption of Mg on
Zr-rich TiB surface and associative interaction of Mg
2
with aluminium in the matrix to form Mg Al in-
3 2
..
termetallic phases cf. Eq. 1 . This is the main origin
for achieving virtually ideal dispersion condition of
.
Ti,Zr B in the AlMgZr alloys.
2
.
On the basis of Eq. 1 , the ceramic particle coales-
cence arises as a result of the adsorption of the sur-
face-active species on to the surface of TiB -metal
2
interface by lowering the interfacial energy of pure
aluminium. Because the particles of ceramic phase
form an interface with the liquid aluminium, the inter-
facial energy is further reduced by multiple
particleparticle coalescence.
Conclusions
The mechanism of dispersion and coalescence of TiB
2

can be explained by using the Gibbs adsorption Eq.

..
1 which connects the interfacial energy with the bulk
thermodynamic properties of the solute atoms in the
solvent aluminium phase. CP aluminium with Mg and
Li as solute atoms promote the formation of TiB by
2
high nucleation and low growth which is favoured by
the lower surface energy conditions. The ceramic parti-
cles, however, cluster together in order to reduce the
interfacial energy. The presence of zirconium promotes
the dispersion of TiB by allowing Mg atoms to be
2
desorbed from the boride surface which is explained
from the miscibility behaviour of solutes in the MgZr,
Materials & Design Volume 18 Numbers 4/ 6 1997 300
The dispersion mechanism of TiB ceramic phase in molten aluminium and its alloys: A. Jha and C. Dometakis
2
AlZr and AlMg binary phase diagrams and from Eq.
.
1 .
Acknowledgements
The authors acknowledge the support from MERCK,
and the SERC for studentship support.
References
1 Wood, J. V., Davies, P. and Kellie, J. L. F., Materials Science and
Technology, 1993, 9, 830840
2 Wood, J. V. et al., Cast Metals, 1995, 8, 5764
3 Lee, M. S. and Terry, B. S., Materials Science and Technology,
1991, 7, 608612
4 Dometakis, C., Jha, A., Riddle, R. and Smith R., Proceedings of
the 9th International Symposium on Rapid Quenched and
. Metastable Materials RQ9 , 2530 August 1996. eds. P. Duhaj,
P. Mrafko and P. Svec. Elsevier, Amsterdam, 1997, pp. 6067
5 Watson, K. D. and Toguri, J. M., In Proceedings of the Internatio-
nal Symposium on Extraction, Rening and Fabrication of Light
Metals, Ottawa, Ontario, August 1821, 1991. eds. M. Sahoo and
P. Pinfold. Pergamon Press. N.Y., 1991
6 Dewing, E. W., Metallurgical Transactions, 1972, 3, 495
7 Korolkov, A. M., In Casting Properties of Metals and Alloys.
Consultants Bureau, New York, 1960, p. 37
8 Massalski, T. B., In Binary Alloy Phase Diagrams, American Society
for Metals, 1986, 1567, pp. 130, and as in
3
Materials & Design Volume 18 Numbers 4/ 6 1997 301