J. Am. Ceram. Soc.
, 14 (2016)
Journal
Development of Carbon Nanotube Reinforced Bulk Polycrystalline Ceramics
with Intragranular Carbon Nanotube Reinforcement
Mahesh K Satam, Luv Gurnani, Sadavijay Vishwanathe, and Amartya Mukhopadhyay
High Temperature and Energy Materials Laboratory, Department of Metallurgical Engineering and Materials Science, IIT
Bombay, Powai, Mumbai 400076, India
In the bulk polycrystalline ceramiccarbon nanotube (CNT)
composites developed to date, reinforcing CNTs have been pre-
sent just at the matrix grain boundaries, with the grain interi-
ors being nearly completely devoid of CNT; thus severely
limiting the improvements achieved in fracture and wear prop-
erties. Against this backdrop, bulk polycrystalline Al2O3-based
composites, having multi-walled CNTs (MWCNTs) present
within the matrix grain interiors (not just at grain boundaries),
have been developed in this work for the first time. Such
microstructure development has been rendered possible by an
innovative, but facile, wet-chemical synthesis route (sans ball-
milling) involving incorporation of well-dispersed MWCNTs
directly into matrix sol, followed by rapid gelation (within a
few seconds) and sintering (inclusive of crystallization step).
Intragranular MWCNT reinforcements (in solgelled com-
posites) led to significant improvements in indentation-induced
crack propagation resistances and abrasive wear resistances, as
compared to conventionally prepared Al2O3MWCNT com-
posites (i.e., ball-milled counterpart) having the same con-
tents of MWCNT, but present only at grain boundaries. Wear
rates recorded with the solgelled Al2O3-2.5 vol%MWCNT
are lower than those for monolithic Al2O3 and ball-milled
counterpart by ~95% and ~90%, respectively. Such improve-
ments, as never achieved before, are a consequence of reinforc-
ing the matrix grain interiors with MWCNTs.
Keywords: ceramic-MWCNT composite; intragranular rein-
forcements; microstructure; wear resistance; crack propagation
D ESPITE extensive eorts over the last couple of decades
toward improving resistances to fracture/wear damage
of engineering ceramics by reinforcing with carbon nan-
otubes (CNTs), the eects of CNT-reinforcements have not
lived up to the expectations.15 The commonly cited reasons
have been related to challenges associated with dispersing
CNTs.19 However, the authors believe that considerable
progress has now been made in dispersing CNTs correspond-
ing to contents of up to ~5 vol% (sometimes even up
to ~10 vol%3).
One of the aspects that have failed to attract attention is
the usually achieved distribution of the CNTs with respect to
sintered polycrystalline ceramic microstructure. More pre-
cisely, survey of the existing literature base1,2,59 reveals that
in nearly all the cases CNTs end-up being present just at the
matrix grain boundaries, usually in aggregated state, with the
grain interiors being almost completely devoid of reinforcing
CNT. Such inhomogeneous distribution of CNTs (especially,
absence of intragranular reinforcements) is likely to be one
Manuscript No. 38757. Received June 19, 2016; approved July 5, 2016.
Author to whom correspondence should be addressed. e-mail: amartya_mukhopadhyay
@iitb.ac.in
1
DOI: 10.1111/jace.14425
2016 The American Ceramic Society
Rapid Communication
of the more important factors that have severely limited the
improvements achieved.
In this context, the present authors,2 as well as Chu et al.,4
believe that the usually adopted processing route, comprising
of physical mixing of CNTs and ceramic starting powders
(via ball-milling), leads to aggregation of CNTs in the space
between the powder particles. Thus, during subsequent sin-
tering, the CNTs end-up being present only along matrix
grain boundaries. In order to address this yet-to-be resolved
issue, the present work explores the usage of a processing
route which is devoid of physical mixing step. By contrast, it
involves formation of the polycrystalline ceramic matrix itself
in the presence of homogeneously dispersed CNTs, leading
to the development of CNT-reinforced bulk ceramic with the
CNTs present within the matrix grains.
The processing route adopted here is schematically shown
in Fig. 1(a). Pristine MWCNTs (Sigma Aldrich, St. Louis,
MO) of 1015 nm diameter, ~5 lm length and >95% purity
were functionalized, as in our previous publication.3 For the
Al2O3 matrix, aluminum-tri-sec-butoxide was added to etha-
nol (at ~80C) under stirring. The modied alkoxide was
then subjected to partial hydrolysis, using HNO3 and water.
Functionalized MWCNTs (corresponding to 2.5 and 5 vol
%), dispersed in ethanol, were added to the solution under
ultrasonication; followed by very rapid gelation (within a few
seconds) upon adding requisite quantity of water. As per one
of the critical requirements, hydrolysis conditions were opti-
mized to ensure such rapid conversion of sol to gel; so that
the added MWCNTs get trapped/frozen in dispersed state
within the matrix gel. Gel for monolithic Al2O3 was also pre-
pared following the same route.
The dried/ground gels were calcined at 750C in Ar. The
composites prepared via this solgel-based route (sans ball-
milling) will henceforth be referred to as solgelled Al2O3-
MWCNT. For comparison, the as-prepared monolithic Al2O3
powders (after crystalline a-Al2O3 phase formation at 1200C)
were mixed with the functionalized MWCNTs corresponding
to the same compositions by the usual ball-milling approach
(for 24 h in polyethylene bottles). These conventionally
prepared composites will be referred to as ball-milled Al2O3-
MWCNT. Spark plasma sintering in Ar (using 20 mm diame-
ter graphite die; 60 MPa pressure), with holdings for 10 min at
1025C and then at 1450C, resulted in sinter-densities (Archi-
medes method) >99% of theoretical density (qth) (see Table I).
X-ray diraction indicated the presence of a-Al2O3, without
any impurity phase, in all the materials.
Unlike the idealized microstructure for ceramicCNT com-
posites [as depicted in Fig. 1(a)], but similar to nearly all the
microstructures available in literature,1,2,59 the presence of
MWCNTs in aggregated state and only along the matrix grain
boundaries could be seen in TEM (JEOL-2100F; Tokyo,
Japan) for our conventionally prepared (i.e., ball-milled)
Al2O3-MWCNT [Fig. 1(b)]. By contrast, presence of
2 Rapid Communications of the American Ceramic Society

MWCNTs across the matrix grain boundaries and within the the case of our solgelled Al2O3MWCNT composites
matrix grains (accordingly, more uniform distribution; and [Figs. 1(c) and (d)]. High-resolution TEM imaging [see inset in
similar to the idealized microstructure type) could be seen in Fig. 1(c)] indicated good conformity at the interface between

Table I. Sinter-Densities, Grain Sizes, Elastic Modulus, Hardness, Ratios Between Crack (c), and Indent Diagonal (a)
Lengths, Transgranular Fracture Area (as %) and Severity of Grain Pull-Out During Abrasive Wear (as % area) for Monolithic
Al2O3, SolGelled and Ball-Milled Al2O3MWCNT Composites
% area as
transgranular % (area) of grain
Elastic modulus fracture (from pull-outs (from
Sinter-density Grain (Berkovich Vickers fractured worn surface
Materials investigated (%qth) size (lm) nanoindentation) (GPa) hardness (GPa) c/a surface images) images)

Monolithic Al2O3 99.9 1.3
0.04 418
3 19.01
0.43 2.50
0.02 94
Ball-milled Al2O3-2.5 99.7 1.2
0.04 419
12 18.04
1.02 2.43
0.05 22 84
vol%MWCNT
Solgelled Al2O3-2.5 99.8 0.6
0.02 443
5.5 18.11
0.32 2.33
0.02 87 23
vol%MWCNT
Ball milled Al2O3-5 99.4 0.7
0.03 434
8.3 16.05
0.76 2.29
0.05 35 86
vol% MWCNT
Solgelled Al2O3-5 99.6 0.4
0.01 448
8 15.99
0.77 2.06
0.02 98 66
vol% MWCNT

(a)

(b) (c)

(d)

Fig. 1. (a) Schematic representations for the processing route used and the idealized microstructure type having both inter- and intra-granular
MWCNTs. Representative TEM images obtained with as-sintered (b) ball-milled (inset presenting schematic illustration of the non-ideal
microstructure type) and (c, d) solgelled Al2O3-5 vol%MWCNT. Presence of MWCNTs within the matrix grains can be seen in c, d (similar
to the idealized microstructure type). Inset in (c) presents high resolution image across the interface between an intragranular MWCNT and
Al2O3 grain.
 Rapid Communications of the American Ceramic Society
(a)
(b)
(c)
Fig. 2. Eects of MWCNT reinforcements/distributions on the (a)
crack propagation resistances (as evaluated in terms of indentation
toughness); and (b, c) fracture modes (FEG-SEM images).
intragranular MWCNT and Al2O3 matrix. Hence, the pre-
sently adopted route allowed, for the rst time, successful
development of MWCNT-reinforced bulk polycrystalline cera-
mic with the MWCNTs reinforcing the matrix grain interiors,
instead of being present just at grain boundaries.
Incorporation of MWCNTs resulted in reduced matrix
grain sizes (Table I). Interestingly, the solgelled compos-
ites possess still ner grains, as compared to their ball-
milled counterparts. It is believed that the very formation of
crystalline matrix grains in situ (via heterogeneous nucle-
ation) only at the higher temperatures during sintering (i.e.,
lower temperature coarsening regime already being
bypassed) in the presence of MWCNTs resulted in still ner
grains in the case of the solgelled composites.
The hardness (H) data (Table I), as measured using Vick-
ers indentation with 1 kg load (F), show reductions upon
incorporation of 5 vol% MWCNTs, in accordance with the
3
literature.1,3 By contrast, the hardness reductions obtained
upon incorporation of 2.5 vol% MWCNT were almost
insignicant. The relative resistances to crack propagation
under contact loading (Vickers indentation),1,10 have been
evaluated in terms of indentation toughness (Kc; but may
not be considered as bulk fracture toughness), as per the
following equation1,10;
 12
E F
Kc 0:016 ; (1)
H c32
where E is the elastic modulus (Table I) and c is the indenta-
tion-induced crack length. The results, as plotted in Fig. 2(a),
indicate that for both the compositions, the solgelled sam-
ples possess greater crack propagation resistances, as compared
to their ball-milled counterparts. In other words, the inden-
tation toughness is greater for the solgelled Al2O3-5%
MWCNT by ~33% and ~22%, as compared to monolithic
Al2O3 and the ball-milled counterpart, respectively. This indi-
cates that the presence of MWCNTs within the matrix grains
resulted in additional improvements in crack propagation resis-
tances. While the usual mechanisms involving crack bridging
could be observed in both the cases; occurrences of nearly com-
plete transgranular fracture for the solgelled composites
[Fig. 2(b)], as against predominantly and fully intergranular
fracture for the ball-milled composites [Fig. 2(c)] and mono-
lithic Al2O3, respectively, were critically noted (see Table I).
Abrasive wear tests were conducted, using the load-controlled
automated grinding/polishing machine1113 (AUTOMET250;
Buehler, Lake Blu, IL). All the specimens were ground simul-
taneously under normal load of 15 N against a plate impreg-
nated with 45 lm diamond particles and rotating at 250 rpm
for 10 min (t). The wear rates (v) were calculated by measuring
the mass loss (Dm) using the following equation:
Dm
v ; (2)
qAt
where q is the density and A is the surface area. Overall, the
incorporation of MWCNTs resulted in considerable improve-
ments in abrasive wear resistances [see reduced wear rates
compared to monolithic Al2O3 in Fig. 3(a)]. 2.5 vol%
MWCNTs resulted in comparatively greater improvements,
as compared to 5 vol%, which might be due to reductions in
hardness upon incorporation of 5 vol% MWCNTs.
More importantly, similar to the case of resistance to
crack propagation, the solgelled composites showed still
improved wear resistances compared to their ball-milled
counterparts. In this context, possibly the most signicant
result has been that of ~95% reduction in the wear rate for
the solgelled Al2O32.5%MWCNT, as compared to
monolithic Al2O3. To the best of the authors knowledge,
such signicant improvements in abrasive wear resistance
have not been reported before. This may be compared with
lesser reduction (by ~63%) in wear rate obtained with the
ball-milled counterpart (w.r.t. monolithic Al2O3). More
direct comparison indicates that the solgelled Al2O3
2.5%MWCNT exhibited lesser wear rate compared to ball-
milled Al2O32.5%MWCNT by ~90%.
FEG-SEM observations of the worn surfaces of mono-
lithic Al2O3 showed nearly complete brittle fracture-induced
grain pull-outs [Fig. 3(b)]. Even though marginally supressed,
material removal via grain pull-out could be observed even
for the ball-milled Al2O32.5%MWCNT composite
[Fig. 3(c), Table I]. By contrast, the worn surfaces for sol
gelled Al2O32.5%MWCNT appeared relatively undam-
aged, with nearly complete absence of grain pull-out
[Fig. 3(d), Table I]; which agrees with the ~95% reduction in
wear rate. A closer look at the few (and smaller) damaged
regions indicated occurrence of only transgranular fracture
[inset of Fig. 3(d)]. Such observations concerning the modes
of material removal during wear tend to agree fairly well
with the corresponding fracture modes.
4 Rapid Communications of the American Ceramic Society
(a)
(c)
Fig. 3. Eects of MWCNT reinforcements/distributions on the (a) abrasive wear rates; and (b to d) appearances of the worn surfaces depicting
wear mechanisms (FEG-SEM images).
It is usually believed that lubricating properties of CNTs
lead to improvements in wear resistance.14 Without discarding
the same, present observations highlight additional eects of
the distribution of MWCNTs within polycrystalline ceramic
matrix microstructure and the resultant fracture mode. Pres-
ence of intragranular particulate reinforcements in alumina is
known to change the fracture mode to transgranular; which
also improves the wear resistance by suppression of grain pull-
out.11,12 Our observations also highlight similar benecial
eects of the presence of MWCNTs within the matrix grains.
I. Conclusion
Al2O3MWCNT-based bulk polycrystalline ceramic compos-
ites, characterized by the presence of MWCNTs within the
matrix grains (not just at grain boundaries), have been suc-
cessfully developed for the rst time via innovative solgel-
based route. In order to avoid ball-milling of ceramic powder
and MWCNTs (which leads to aggregation of MWCNTs
only at grain boundaries), well-dispersed functionalized
MWCNTs were added directly to the matrix sol, followed by
rapid gelation (within seconds) and sintering (inclusive of
crystallization step) to >99%qth.
The solgelled Al2O3-MWCNTs inter/intragranular
nanocomposites possess considerably improved crack propa-
gation resistance under contact loading w.r.t. monolithic Al2O3
and ball-milled counterpart (containing only intergranular
MWCNTs). More importantly, abrasive wear rates recorded
with the solgelled Al2O32.5vol%MWCNT were lower by
~95% compared to monolithic Al2O3 (as never achieved
before) and also by ~90% compared to the ball-milled coun-
terpart. Presence of MWCNTs within the matrix grains
resulted in nearly complete change in fracture mode to trans-
granular and suppression of brittle fracture-induced grain pull-
out during abrasive wear. Hence, if such near-ideal microstruc-
ture development is successfully achieved by adoption of suit-
able processing routes, the various advantages oered by
MWCNT incorporation within bulk polycrystalline ceramics
may be better utilized.
(b)
(d)
Acknowledgments
The authors thank ISRO-IITB cell and IRCC-IITB for nancial supports;
SAIF, IIT Bombay, for allowing usage of electron microscopes; and IIT Roor-
kee for allowing usage of the SPS facility.
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