Materials and Design 32 (2011) 3554–3559

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Materials and Design

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Short Communication

Grain refinement and wear properties evaluation of aluminum alloy 2014

matrix-TiB2 in-situ composites
C. Mallikarjuna a,⇑, S.M. Shashidhara b, U.S. Mallik c, K.I. Parashivamurthy c
a
Al Jabal Al Garbhi University, Faculty of Engineering, Gharyan, India
b
Kalpataru Institute of Technology, Tiptur, Karnataka, India
c
Siddaganga Institute of Technology, Tumkur, Karnataka, India

a r t i c l e i n f o a b s t r a c t

Article history: A salt base exothermic reaction process has been employed to produce aluminum alloy 2014 matrix-TiB2
Received 21 October 2010 composites using an exothermic reaction process at 850 °C using K2TiF6 and KBF4 salts. The period of
Accepted 20 January 2011 exothermic reaction was varied from a minimum of 15 min to a maximum of 45 min to investigate
Available online 24 January 2011
the relationship between the degree of reaction and the growth behavior of TiB2 formed. These have been
compared with commercially available aluminum alloy 2014 material. Structural and wear properties
have been measured. These show that TiB2 is extremely effective in enhancing wear properties in addi-
tion to significantly reducing the coefficient of friction. The microstructure and phase composition of the
materials obtained were studied using X-ray diffraction and scanning electron microscopy (SEM). Very
fine ceramic particles were obtained in the aluminum alloy matrix.
Crown Copyright Ó 2011 Published by Elsevier Ltd. All rights reserved.

1. Introduction
It is now widely recognized that aluminum base metal matrix
composites have a high potential for advanced structural applica-
tions when high specific strength and modulus as well as good
wear resistance are important [1]. Traditionally, metal matrix com-
posites have been produced by powder metallurgy, pre-form infil-
tration, spray deposition and various casting technologies [2–7]. In
all the above techniques the reinforcing powder size is in the order
of microns to tens of microns and very rarely below one micron. In
the last decade new in-situ fabrication technologies for processing
metal and ceramic composites have emerged [8–11]. There is con-
siderable interest in the properties of aluminum base metal matrix
composites, especially for wear resistant components in automo-
biles. There are several reports of Al Si alloys that have been pro-
duced by powder metallurgical routes for this purpose. Air
atomisation followed by consolidation and extrusion allows light-
weight, wear resistant materials to be designed with a fine scale
dispersion of silicon in an aluminum alloy matrix. Descriptions of
demonstrator connecting rods etc. have been published and cur-
rently air conditioner vanes are manufactured by this route. The
costs of this production method and the restrictions on shape have
resulted in a lack of market penetration. There is a need for a low
cost dispersion strengthened lightweight alloy that can be handled
by traditional methods (e.g. casting) and yet can withstand the
wear requirements. The literature is saturated with papers on
⇑ Corresponding author. Tel.: +91 9448166621; fax: +91 8162282994.
E-mail addresses: cm.bilwa@gmail.com, ajag.uni@gmail.com (C. Mallikarjuna).
metal matrix composites although the majority of these are fo-
cused on the advanced regions of the market, example aerospace.
Continuous and discontinuous whisker and particulate dispersions
have all been employed, based on infiltration, spraying, and pow-
der metallurgical routes. Typical among all of these is the use of in-
ert gas atomised powders that are blended with SiC particles and
consolidated by die pressing, and extrusion. Given the high cost
of fiber reinforcement and the need to design with a non-isotropic
material, great interest has focused on composites, which are dis-
persion strengthened. A balance of properties depending upon
mean particle size and volume fraction can be most easily achieved
by the powder metallurgical route although for a low cost process
a casting route is preferable. A compromise is to use the osprey
process and several companies are exploring this method on a pilot
scale. Specific reinforcements like SiC, TiB2, and Al2O3 can be em-
ployed to enhance modulus, tensile strength and creep resistance
while having an adverse effect on ductility, fracture toughness,
etc. The reports on wear properties are surprisingly varied and
have recently been summarized by many researchers [12,13].
The majority of the work concentrated on SiC and Al2O3 reinforce-
ment introduced during casting. Many of the recent reports have
concentrated on samples produced by the Duralcan process
[14,15] in which the alloys have to contain silicon if SiC particles
are to be used in order to prevent adverse particle reactions. The
consensus of these reports is that the wear rate decreases with
increasing particle volume fraction, assuming the particles are of
constant size. Likewise, despite some earlier work to the contrary,
most workers reported [16,17] similar results. Their results dem-
onstrate that, particle size and volume fraction have little effect

0261-3069/$ - see front matter Crown Copyright Ó 2011 Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.matdes.2011.01.036
 C. Mallikarjuna et al. / Materials and Design 32 (2011) 3554–3559 3555

on wear rate but particulate reinforcement increases the load nec-
essary to change from mild to severe wear. In all the above in-
stances, the particles were introduced deliberately and
systematically, either in a powder blend or by additions to a melt.
Problems can occur with dispersoid distribution and settling out
during casting. In this paper a cast aluminum alloy is described
in which the dispersoid (TiB2) has been created by an in-situ reac-
tion so that the particles are formed within a melt. The aim of the
present paper is to describe the wear properties of the aluminum
alloy 2014 matrix-TiB2 in-situ composites and these have been
compared with commercially available aluminum alloy 2014
material.
3. Results and discussion
3.1. Grain refinement
3.1.1. Microstructural examination for grain structure
Fig. 1 shows the microstructure images of the in-situ processed
TiB2-2014 aluminum alloy composite specimens. As observed from
the microstructures, the grain sizes were refined. The closed ring
structure indicates the formation of the fine grain structure during
in-situ processing. Similar work was carried out by many research-
ers [19–21] and they also found the grain refinement by in-situ
processed TiB2 – aluminum composites.

2. Experimental procedure 3.1.2. Grain size

The grain sizes of in-situ processed samples are shown in Fig. 2,
Two types of salts, namely K2TiF6 and KBF4 were used to synthe- as a function of the reaction holding time. Grain size of the in-situ
size the TiB2 reinforcement in Aluminum alloy 2014 matrix mate- processed material has reduced to 7.7%, therefore reduction was
rial. Aluminum was first melted at 850 °C, after which the two up to 92.3%. Micro structural observation showed a decreasing
types of salts were added to the molten aluminum alloy in the trend in grain size of the composites as the reaction holding time
atomic ratio in accordance with Ti/2B using the stirring method. increases. Results of in-situ processed TiB2-2014 aluminum alloy
The stirrer used being mild steel stirrer coated with zirconia. Coat- composite indicate that the drastic decrease in grain size up to a
ing is applied to the mild steel stirrer to avoid possible contamina-
tion of the molten metal. Chemical reaction between the two salts
and the molten aluminum alloy took place to form in-situ TiB2 par-
ticulates in aluminum alloy. The period of chemical reaction was
varied in steps of 15 min up to 45 min at 850 °C to investigate
the relationship between the degree of reaction and the growth
behavior of TiB2. After the reaction, the composite was cast into
rods of 25 mm diameter.
After polishing and etching, the specimens are examined for
grain structures using computerized optical microscope. Wear test
was carried out using computerized wear testing machine as per
ASTM G-99 standard [18]. X-ray diffraction analysis was made to
confirm the presence of TiB2 in the TiB2-2014 aluminum alloy com-
posite. Microstructure images are taken using scanning electron
microscope to study the distribution of TiB2 particles in 2014 Fig. 2. The grain size of in-situ processed samples as a function of reaction holding
aluminum alloy. time of allied salts in aluminum alloy 2014.

Fig. 1. Grain structure of in-situ processed TiB2-2014 aluminum alloy composite specimens: (a) before in-situ process, (b) after in-situ process for reaction holding time of
15 min, (c) after in-situ process for reaction holding time of 30 min and (d) after in-situ process for reaction holding time of 45 min.
3556 C. Mallikarjuna et al. / Materials and Design 32 (2011) 3554–3559

Fig. 3. XRD pattern of in-situ processed 2014 aluminum alloy–TiB2 composite specimen for reaction holding time of: (a) 15 min, (b) 30 min and (c) 45 min.
 C. Mallikarjuna et al. / Materials and Design 32 (2011) 3554–3559 3557

reaction holding time of 30 min, followed by a smaller decrease up process of TiB2 from Ti and B, they are believed to be caused by the
to a reaction holding time of 45 min as shown in Fig. 2. This can be presence of TiAl3 in the MMC.
related to the coupled effect of the particulate size and weight per-
centage of TiB2 in aluminum alloy matrix. Generally for a given
3.3. Microstructural analysis using scanning electron microscope
particulate size, an increase in weight percentage will increase
the number of particulates and similarly, for a given weight per-
Scanning electron microscope (SEM) microstructures, showing
centage, decrease in particulate size will increase the number of
the general micro structural features of 2014 aluminum alloy–
particulates. Thus, in our research it is related to the decrease in
TiB2 composite samples prepared with reaction holding times of
grain size up to a reaction holding time of 30 min is due to the cou-
15, 30 and 45 min are shown in Fig. 4.
pled effects of increase in the weight percentage of TiB2 particu-
It was observed that hexagonal shape TiB2 particulates were
lates in the aluminum alloy matrix and the decrease in the size
formed even for 15 min of chemical reaction holding time in
of the TiB2 particulates. It is evident that the grain refinement of
Fig. 4a, even though they were hardly detectable by XRD. Because
aluminum alloy 2014 by addition of titanium and boron via re-
of short reaction time, complete reaction was not achieved. There-
agent salts K2TiF6 and KBF4 has been studied extensively by many
fore residual salts could still be found after casting. Consequently,
researchers [22,23]. Mohanty and Gruzleski [22] studied the com-
only a small amount of TiB2 particles has been observed. Also it
mercial grain refining practice of aluminum has been experimen-
was observed that with more reaction holding time of 45 min, hex-
tally simulated by introducing synthetic TiB2 crystallites into
agonal shape TiB2 particulates were formed in more numbers in
melts and they found that in grain refining practice, TiB2 plays an
Fig. 4c. The clear edges of the TiB2 particles can also be seen from
indirect role in grain nucleation. Yucel Birol [23] studied that the
Fig. 4c. More detailed studies have shown that for the aluminum
ball-milled Al/K2TiF6/KBF4 powder blends heat treated at approxi-
copper alloy, the segregate appears to be the Al2Cu phase, which
mately 525 °C are compacted to produce Al–Ti–B pellets with in-
exhibits a strong tendency to wet the TiB2 particles. Hence, the re-
situ formed Al3Ti and TiB2 particles. These pellets are shown to
shaped TiB2 particle is most likely due to the formation of thin
be adequate grain refiners for aluminum alloys.
Al2Cu layers surrounding the TiB2. Since the chemical reactions
took place entirely in the molten aluminum, no oxidation layer
on the surfaces of the TiB2 particles could be formed. The TiB2 par-
3.2. X-ray diffraction analysis
ticles were observed that homogeneously distributed. No large
agglomerations of TiB2 particles or porosity could be noticed. From
X-ray diffraction (XRD) patterns of metal metrix composites
microstructural observation, a significant fraction of very tiny par-
formed in-situ after a reaction holding time of 15, 30 and 45 min
ticles was observed. According to a study [22] on grain refinement,
respectively, are shown in Fig. 3. The formation of TiB2 has been
when excess Ti is present, most of the TiB2 tiny particles will be
confirmed by the presence of titanium boron peaks. Similar result
located.
was found by Lakshmi et al. [19].
For a short reaction holding time, TiB2 peaks are difficult to ob-
serve since the volume fraction of in-situ TiB2 is very low. With the 3.4. Wear behavior
increase in reaction holding time duration, more TiB2 particles are
formed in-situ. Therefore, the relative intensity of the TiB2 peaks Wear testing was performed on a computerized pin on disc
increased. Some weak peaks are observed near the aluminum peak, wear testing machine under controlled conditions. The samples
according to the diffraction angles of the peaks and the formation were unlubricated. For comparisons, wear tests were performed

Fig. 4. SEM microstructures of 2014 aluminum alloy–TiB2 composite produced in-situ with reaction holding time of: (a) 15 min, (b) 30 min and (c) 45 min.
3558 C. Mallikarjuna et al. / Materials and Design 32 (2011) 3554–3559

on 2014 aluminum alloy – TiB2 composite before and after in-situ 3

WEAR RATE
processes.
Load 10N
2
Load 20N
3.4.1. Effect of load on wear displacement Load 30N
1
The wear displacement of in-situ processed 2014 aluminum al- Load 40N
loy – TiB2 composite as a function of load is presented in Fig. 5. The 0
incorporation of in-situ process into the 2014 aluminum alloy sig- 0 15 30 45 60
nificantly improves the wear resistance. From the graph, we can REACTION HOLDING TIME (min)
observe that the wear displacement is rapidly increasing from
20 N load for the unprocessed aluminum alloy and wear displace- Fig. 7. Graph of wear rate vs. reaction holding time of allied salts in 2014 aluminum
alloy.
ment is gradually increasing from 10 N to 40 N for processed alu-
minum alloy, because of grain boundary sliding during the
processes, wear displacement is reduced for processed aluminum
4
alloy.

It was observed that as the reaction holding time increased the
wear displacement decreases because of the decrease in grain size,
but more significantly the transition load from mild to severe wear
increases, as illustrated by the change in slopes of the curves.
3.4.2. Effect of in-situ process on coefficient of friction
In Fig. 6 results of in-situ processed 2014 aluminum alloy – TiB2
composite specimens are obtained for coefficient of friction when
plotted against reaction holding time of allied salts in aluminum
alloy 2014. From the limited data, it can be seen that the coefficient
of friction increases with reaction holding time. Before in-situ pro-
cess, the material had a lower friction coefficient than the pro-
cessed material.
It was observed that at the lower load, the friction coefficient in-
creased with reaction holding time because of decrease in grain
size and also at low surface pressure, the friction is directly propor-
tional to the pressure between the surfaces. At the higher load,
behavior was erratic owing to the opposing effects of material
fracture.
3.4.3. Effect of in-situ process on wear rate
For in-situ processed 2014 aluminum alloy – TiB2 composite
specimens, results are obtained in Fig. 7 for wear rate when plotted
WEAR DISPLACEMENT
WEAR RATE
3 RHT 0 min
2
RHT 15 min
RHT 30 min
1 RHT 45 min
0
0 10 20 30 40 50
LOAD (N)
Fig. 8. Graph of wear rate vs. load applied for in-situ processed samples.
against reaction holding time of allied salts in aluminum alloy
2014. From the limited data it can be seen that the wear rate de-
creases with reaction holding time. Wear testing at room temper-
ature revealed a significant reduction in the wear after in-situ
process. A comparison between processed and unprocessed 2014
aluminum alloy suggested that the former was a slightly more
wear resistant material. Improvements were due to the effect of
grain boundary sliding during process.
3.4.4. Effect of load on wear rate
The wear rate of in-situ processed 2014 aluminum alloy – TiB2
composite as a function of load is presented in Fig. 8. The incorpo-
ration of in-situ process into the 2014 aluminum alloy significantly
improves the wear resistance. From the graph, we can observe that
the wear rate is rapidly increasing from 30 N load for the unpro-
cessed aluminum alloy and wear rate is gradually increasing from

350 10 N to 40 N for processed aluminum alloy, because of grain

300 boundary sliding during the processes, wear rate is reduced for
250 RHT 0f 0 min processed aluminum alloy.
(microns)

200 RHT 0f 15 min In in-situ process, increase in the reaction holding time of allied
150 RHT 0f 30 min salts in 2014 aluminum alloy give rise to decrease in wear on the
100 RHT 0f 45 min pin material. The incorporation of in-situ process into the 2014
50 Al alloy significantly improves the wear resistance. The improve-
0
ment in the wear behavior of the processed alloy is attributed to
0 10 20 30 40 50 the changes in the wear mechanisms brought about by the pres-
LOAD (N) ence of in-situ process. These results are in good agreement with
the observations made by other researchers [16,17,24–27].
Fig. 5. Graph of wear displacement vs. load applied for in-situ processed samples.
4. Conclusions

0.5 (1) In-situ aluminum alloy–TiB2 composites were synthesized

CO EFFICIENT OF

0.4 successfully by exothermic reaction between K2TiF6 and

Load 10N
FRICTION

KBF4 salts in aluminum alloy 2014.

0.3 Load 20N
(2) Formation of TiB2 particulates are conformed by the XRD
0.2 Load 30N studies.
0.1 Load 40N (3) For longer reaction holding time, number of TiB2 particulates
decreases due to more formation of cryolite slag.
0
0 15 30 45 60 (4) The grain size of the in-situ processed aluminum alloy–TiB2
composites decreased significantly up to 30 min, followed
REACTION HOLDING TIME (min) by a very less decrease up to 45 min.
Fig. 6. Graph of coefficient of friction vs. reaction holding time of allied salts in
(5) The coefficient of friction decreases with increasing period of
aluminum alloy 2014. reaction holding time.
 C. Mallikarjuna et al. / Materials and Design 32 (2011) 3554–3559
(6) As the applied load increases the wear displacement also
increases.
(7) The incorporation of fine TiB2 into cast aluminum alloy by a
reactive casting route is a viable and practical method for
making structural and wear resistant parts.
(8) The effect of TiB2 on the as cast properties of aluminum alloy
2014 is significantly greater.
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