Materials Science & Engineering A 758 (2019) 103–111

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Materials Science & Engineering A

journal homepage: www.elsevier.com/locate/msea

An investigation of equibiaxial flexural strength and hardness properties of T

Al2O3–Ni nanocomposites based microstructures with ZrO2 and Cr2O3
additives
Betül Kafkaslıoğlu Yıldız∗, Yahya Kemal Tür
Department of Materials Science and Engineering, Gebze Technical University, Gebze, Turkey

ARTICLE INFO ABSTRACT

Keywords: The investigation of new ceramics and ceramic composites to overcome the inadequacies of monolithic ceramics
Al2O3 without using costly techniques and equipment is essential for developing ceramic armor components. The aim
Composites of the research was analyzing the mechanical properties (elastic modulus, flexural strength, and hardness) of
Ceramic armor Al2O3/1 vol% Ni nanocomposites with 5 vol% ZrO2 or 1 vol% Cr2O3 additives and estimating their performance
Flexural strength
by comparing with the pure Al2O3, Al2O3/ZrO2 composite, and Al2O3/Cr2O3 ceramic system for armor appli-
Hardness
Stored energy
cations. The heterogeneous precipitation method was used to obtain nano-sized metal particles in the ceramic
matrix for the Ni-containing compositions. Equibiaxial flexural tests were conducted for strength measurements
and stored energy at failure was estimated by using the theoretical deflection of the cylindrical plate; also, post-
failure total crack lengths were measured. Simultaneous addition of Ni and ZrO2 on Al2O3 matrix resulted in the
highest hardness (25.5 ± 1.0 GPa) and flexural strength (367 ± 34 MPa) compared to other compositions
because of the hardening effect of Ni and the grain boundary strengthening mechanism. Moreover, this com-
position showed the highest resistance to fragmentation as evidenced by the shortest crack length per stored
energy at failure. Cr2O3 addition also provided remarkable results related to the solid solution formation for both
the pure Al2O3 and Al2O3/Ni composites. By this comparative study, different compositions with high me-
chanical properties have been introduced as the potential candidates to be used in armor applications with static
tests giving an indication about ballistic performance.

1. Introduction considered to overcome the disadvantages of Al2O3 for armor applica-

Advanced ceramics are commonly used as a constituent of armor
systems [1,2]. Alumina (Al2O3), silicon carbide (SiC) and boron carbide
(B4C) are the most preferred armor ceramics among the oxides and
carbides [3,4]. The ceramic component is determined by considering
both cost and performance. SiC and B4C are generally densified via hot
pressing with its high cost or reaction bonding. Al2O3 enables relatively
cheap manufacturing and provides high physical properties (hardness,
elastic modulus, compressive strength) [5]. However, Al2O3 has a lower
hardness (1800 HV) and flexural strength (∼400 MPa) compared with
SiC (2300 HV and ∼634 MPa) and B4C (2700 HV and ∼450 MPa) and
that hinders its ballistic performance [6,7]. Al2O3 matrix composites
that consist of whiskers, particulates or fibers are studied and produced
to increase the mechanical properties of matrix material for most of the
applications [1,9]. Ceramic composite production using relatively in-
expensive starting materials and consolidation techniques can be
tions. Pressureless sintering is a low cost technique when it is used at
lower temperatures for oxide ceramics and ceramic composites; it is
also easier to apply to mass production. Pressureless sintered Al2O3 has
a cost ∼4.5 times lower than the pressureless sintered SiC at 2000 °C
and ∼9 times lower than the hot pressed SiC [8]. Therefore, choosing
additives that allow to densification of Al2O3 with pressureless sintering
and without increasing its sintering temperature (1450–1600 °C) would
help to maintain the cost advantage of Al2O3.
The toughness, the flexural strength and the hardness of ceramic
matrix can be improved by the addition of metallic micro- or nano-
particles into the ceramic matrix [10–13]. Al2O3/nickel (Ni) system has
been widely studied because of the advantageous properties of Ni (high
oxidation resistance, high melting temperature) and controlled pro-
cessing with the possibility of using different Ni precursors (metal salt,
oxides) [14–16]. An increase in the hardness of Al2O3–Ni nanocompo-
sites is observed and it is attributed to nano-sized Ni particles with

∗
Corresponding author.
E-mail address: bkafkaslioglu@gtu.edu.tr (B.K. Yıldız).

https://doi.org/10.1016/j.msea.2019.05.014
Received 21 February 2019; Received in revised form 18 April 2019; Accepted 6 May 2019
Available online 07 May 2019
0921-5093/ © 2019 Elsevier B.V. All rights reserved.
B.K. Yıldız and Y.K. Tür
Fig. 1. Flow diagram of the heterogeneous precipitation method for the Ni-containing nanocomposite powders.
blocked or nonexistent dislocations results in hardening effect known as
Hall-Petch [13,17,18]. In the absence of dislocation motion, hardness is
controlled by higher shear modulus (G) for nanometals as in ceramic
materials [18]. The toughness improvement is attributed to the change
in the crack propagation direction and the strength improvement is
mainly a result of the microstructural refinement [12,19,20]. It is al-
ready known and studied that addition of yttria (Y2O3) - stabilized
zirconia (ZrO2) in Al2O3 improves its toughness and strength [21–23].
In this regard, second-phase reinforcement of Al2O3 with ZrO2 and Ni
was studied by Tuan et al. [20] and a significant increase in strength
values could be obtained by using pressureless sintering.
As another additive, chromia (Cr2O3) was added to Al2O3 in many
studies to increase its physical properties [24–26]. Different from most
of the other additives, Cr2O3 forms a substitutional solid solution with
Al2O3 over the full range of compositions at high temperatures. Dif-
ferent Cr2O3 ratios have different effects on the microstructure and
mechanical properties of Al2O3. The source of Cr2O3 (chromium nitrate
or powder) also influences the properties of the ceramic material [26].
In this work, Cr2O3 powder and Ni precursor were used to investigate
the synergic effect of different mechanisms on the microstructure and
the mechanical properties.
The ceramic armor component must be sufficiently robust for de-
feating the projectile by reducing its kinetic energy and breaking it into
pieces. High hardness plays an important role in the performance of the
ceramic armor. The projectile can be deformed, broken or shattered
owing to the high hardness of the ceramic and the high hardness will
also lead to further damage during the rest of the penetration process
[27]. While the hardness is of great importance in terms of damaging
the projectile, the strength comes into prominence when it is desired to
maintain the structural integrity of the ceramic so high strength is re-
quired especially for the multi-hit performance [28]. The duration that
the projectile interacts with the surface of the ceramic and does not
penetrate is expressed as ‘‘dwell time’‘. The high elastic modulus of
ceramic has a strong effect on ballistic resistance by extending the dwell
interaction. Also, high elastic modulus allows for wider crack spacings
and larger fragments that are exposed to higher inertial forces. Larger
fragments cause more damage to the projectile for the hard ceramic
component [29]. Therefore, a combination of these mechanical prop-
erties (hardness, strength, and elastic modulus) is essential for the
performance of armor ceramic.
High-velocity impact behavior of ceramic armor components is a
complicated mechanism for interpretation [30]. The cost of ballistic
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Materials Science & Engineering A 758 (2019) 103–111
testing is expensive and the results obtained cannot be generalized to
many cases [31]. But ballistic behavior could be associated with static
mechanical tests in some cases, especially when equibiaxial flexural
strength test was used. The equibiaxial flexural strength test can gen-
erate large fracture surface area and could have a similar fracture
pattern at the center with the ceramic components that are ballistically
tested [3,30]. Based on this thought, the equibiaxial flexural strength
test was preferred to evaluate the strength behavior and crack patterns
of different compositions for the current study. The mechanical prop-
erties (elastic modulus, flexural strength, and hardness) of Al2O3-1 vol%
Ni nanocomposites prepared by the heterogeneous precipitation
method with ZrO2 or Cr2O3 additives were investigated. Micro-
structural effect of different oxides and Ni particles addition on me-
chanical properties of Al2O3 was discussed to estimate these composites
performance at ambient temperature as an armor component. Using
elastic solutions, deflection of the specimens were estimated and used
for evaluation of the stored energy at failure. Measured crack length-
stored energy relations for each composition were compared and pos-
sible fragmentation behavior under impact was discussed.
2. Experimental procedure
For the fabrication of the compositions, α-Al2O3 powder (Alfa Aesar,
99.95% purity, 0.25–0.45 μm), Y2O3 stabilized ZrO2 (YSZ) powder
(3 mol% Y2O3, Inframat Advanced Materials, average particle
size < 0.5 μm), Cr2O3 powder (Alfa Aesar, 99% metals basis), nickel
nitrate hexahydrate (Ni(NO3)2·6H2O) (BDH Chemicals Ltd., Poole,
England, 98% purity), ammonium bicarbonate as precipitant
(NH4HCO3) (Sigma Aldrich, 99% purity), polyacrylic acid as dispersant
(Darvan 821A, MSE Tech Co. Ltd., Turkey) were used. Before dry
pressing of the prepared powders, polypropylene carbonate (PPC)
(QPAC 40, Empower Materials, USA) was used as a binder. The amount
of Ni(NO3)2·6H2O was adjusted to 1 vol% Ni ratio in the final compo-
sites. The volume ratios of ZrO2 and Cr2O3 were 5% and 1% in Al2O3/Ni
nanocomposites, respectively. The fabrication procedure is presented in
Fig. 1. The heterogeneous precipitation method was used to produce
nano-Ni particles on the ceramic matrix. The details of the fabrication
method can be found in the literature [15,16,32]. The pure Al2O3,
Al2O3/1 vol% Ni nanocomposite, Al2O3/1 vol% Cr2O3 ceramic system
and Al2O3/5 vol% ZrO2 composite were also prepared for comparison
reason by ball milling the powder mixtures and then drying process
except for the Ni-containing nanocomposites that were produced by the
B.K. Yıldız and Y.K. Tür
Fig. 2. Schematic and photo of the equibiaxial flexural strength test equipment
for disc specimens.
heterogeneous precipitation method. All the prepared powders were
exposed to the heat treatment at 500 ᵒC for 2 h in air to eliminate the
dispersant and to obtain nano NiO particles for the Ni-containing
compositions. An appropriate amount of (five times the amount of
nickel by moles) precipitant addition dropwise as 1 M aqueous solution
to the Ni(NO3)2·6H2O containing slurry provided an amorphous coating
layer (NiCO3·2Ni(OH)2·2H2O) on the surface of the ceramic powder.
The amorphous coating layer was crystallized to discrete nano-sized
NiO particles after the calcination at 500 ᵒC for 2 h in air. Heat treat-
ment at 700 ᵒC for 4 h in H2/Ar atmosphere was carried out so that
nano NiO particles were reduced to nano-sized Ni particles. The para-
meters of calcination and reduction (temperature, atmosphere, and
duration) were selected according to the previous studies by Li et al.
[32,33] and Kafkaslıoğlu and Tür [15,16]. It is stated that the removal
of the dispersant and decomposition of the amorphous precipitate oc-
curs nearly at 450 ᵒC according to the thermogravimetric analysis
(TGA) and differential thermal analysis (DTA) results [33].
An appropriate amount of PPC – acetone solution was added to the
prepared powder mixtures under stirring. Then, acetone was evapo-
rated, and the powder mixtures were crushed and sieved to 90 μm be-
fore compaction. Green pellets were formed using a hydraulic hand
press at a pressure of 40 MPa with 35 mm diameter steel mold and cold
isostatic pressing (CIP) was applied to the pellets under 200 MPa to
increase the green density and the green strength. The green density
was calculated in the range of 56–60% for all the compositions.
The samples were subjected to pressureless sintering at 1550 ᵒC for
2 h to densification. The pure Al2O3 and Al2O3/5 vol% ZrO2 composites
were sintered in air; all the other samples were sintered in H2/Ar at-
mosphere to prevent oxidation of Ni and evaporation of Cr2O3. The
heating rate was set at 2 ᵒC/min from 25 ᵒC to 250 ᵒC with 30 min dwell
time and 1 ᵒC/min from 250 ᵒC to 350 ᵒC with 60 min dwell time during
which the binder burn out was carried out. Finally, 5 ᵒC/min from 350
ᵒC to 1550 ᵒC with 2 h dwell time and cooled down to room tempera-
ture in the furnace. The binder burn out temperature was selected ac-
cording to the technical data given by the manufacturer. PPC could be
burned out both in air and reducing atmosphere, on account of this, it
was chosen as an appropriate binder for the systems used in this study.
The sintering parameters were tested earlier with the prepared smaller
sized pellets for each composition and determined by depending on
these results and the literature [15,16,24]. The dimensions of the sin-
tered specimens were around 28 mm in diameter and 2.5 mm in
thickness with slight variations in the diameters and thicknesses due to
densification differences.
The crystal structure and phase composition of the sintered samples
were identified by means of X-ray diffraction analysis (XRD) at a
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Materials Science & Engineering A 758 (2019) 103–111
scanning rate of 3ᵒ/min over the 2θ range from 20 ⁰ to 80 ⁰. All the
sintered samples were grinded by a single-sided lapping machine with
an average particle size of 30 μm SiC powder (F320) to equalize
thickness of the pellets with ± 0.03 mm tolerance for the mechanical
tests. Direct measurements of mass and macroscopic dimensions were
used to measure the bulk densities of the sintered samples; this method
was preferred to Archimedes’ method because it was observed that its
standard deviation was lower, and repeatability was better. Theoretical
densities of the composites were calculated by the rule of mixtures for
all the compositions to estimate the relative densities from the theo-
retical densities of Al2O3, ZrO2, Cr2O3, and Ni which are 3.98, 6.10,
5.22 and 8.91 g/cm3, respectively. The elastic modulus of the sintered
samples was measured with 10 specimens for each composition using
an impulse excitation technique (GrindoSonic® Mk5) in accordance
with ASTM E 1876 standard to disc-shaped specimens. Theoretical
values of the elastic modulus of Cr2O3 containing ceramic systems, ZrO2
and Ni particulate composites were calculated by averaging the Voigt
(Rule of mixtures) and Reuss (Inverse rule of mixtures) bounds for the
materials, also called VRH average [34].
Microstructural analysis of the samples and the fracture surface
characterization were carried out by a scanning electron microscope
(SEM) (Philips XL 30 SFEG). Al2O3 grain size was measured from SEM
micrographs of polished and thermally etched samples (at 1400 ᵒC, 1 h
for Ni-containing samples and 2 h for the others, all in the sintering
atmospheres) with linear intercept method where more than 400 in-
tercepts were counted for each composition. ZrO2 and Ni particle sizes
for the particulate composites were also measured form thermally
etched SEM micrographs by using an image analysis software.
The hardness of the samples was measured by the Vickers in-
dentation technique with an Instron® Wolpert Testor 2100 equipped
with a diamond pyramid indenter. The applied load of the indent was a
5 kg for a period of 10 s with 10 measurements for each composition. To
measure the flexural strength of the samples, the equibiaxial flexural
strength test (ring on ring) was used according to ASTM C 1499–03 for
cylindrical test specimen and conducted with an Instron® 5569 uni-
versal test device as shown in Fig. 2. The surface of the samples was
prepared by grinding and polishing with F320 SiC powder and 1200
grade SiC abrasive paper. Ten specimens of each composition were used
for the strength measurements and a lubricant was applied to the ring
tips to eliminate frictional stresses. The displacement rate was set at
0.3 mm/min and the diameters of the support ring (a) and the load ring
(b) were 23.9 mm and 9.8 mm, respectively. Following the tests, pho-
tographs of the tensile surface of all the samples were taken and the
total crack length was measured using an image analysis software. The
cracks’ lengths were measured piecewise using the distance function of
the software and summed up in order to find the total crack length for
each specimen; measurements repeated twice to ensure consistency.
3. Results and discussion
X-ray diffraction patterns of the pure Al2O3 together with Al2O3/Ni,
Al2O3/ZrO2, Al2O3/Cr2O3, Al2O3/Ni–ZrO2 and Al2O3/Ni–Cr2O3 com-
positions (now on referred as A, AN, AZ, AC, ANZ, and ANC, respec-
tively) pressureless sintered at 1550 ᵒC for 2 h are given in Fig. 3. The
volume ratios of the additives in Al2O3 were 5% for ZrO2 and 1% for
both Ni and Cr2O3, and while preparing the powder mixtures, the used
ratios were chosen according to the literature and the previous studies
for Ni, ZrO2, and Cr2O3 [15,20]. The volume ratio of Ni was kept low in
order to reduce the chance of Ni particle to meet one other so that the
coarsening of Ni could be limited even by using pressureless sintering to
prepare the composite. Also, a series of density-elastic modulus-hard-
ness measurements were carried out for Cr2O3 addition with different
volume ratios (0.5, 1, 5 vol%) and the highest values were obtained for
1 vol% Cr2O3 in the preliminary studies.
The XRD patterns reveal the presence of t-ZrO2 (tetragonal zirconia)
in AZ and ANZ composites; no monoclinic ZrO2 phase was detected.
B.K. Yıldız and Y.K. Tür Materials Science & Engineering A 758 (2019) 103–111

Fig. 3. XRD results of the sintered ceramics and the composites prepared with Al2O3, Ni, ZrO2, and Cr2O3.

Also, Ni phase was present in the XRD patterns for all the Ni-containing ANC have a narrower range of the data points even though all the
composites, namely AN, ANZ, and ANC. The presence of Cr2O3 phase compositions prepared under the same conditions. Homogeneous zir-
both in AC ceramics and ANC composites were not detected because of conia particle dispersion on Al2O3 results in grains with similar sizes,
the solid solution formation of Cr2O3 -Al2O3 with the same corundum and parallel to the highest relative density, the low standard deviation
crystal structure. No new compound of α-Al2O3 with the additives was in Al2O3 grain size compared to A, AN and AC could be obtained. The
found in any of the samples. heterogeneous precipitation method that was used in this study has the
Table 1 lists the relative density, the Al2O3 grain size and the elastic advantage of providing homogeneous metal particle dispersion [9,15].
modulus measurements for all the compositions. During the sintering So, homogeneous metal phase dispersion could be obtained for the Ni-
process, vaporization of Cr2O3 into Cr-containing species (e.g. CrO3) is containing compositions and addition of Ni does not have a negative
inevitable in even H2/Ar if the atmosphere was not purified and it is effect on density distribution if densification is not poor as in ANZ and
hard to determine the exact amount of dissolved Cr2O3 in the sintered ANC compared to AN. Also, Ni addition inhibits the grain growth of
body [35,36]. Yet, Cr2O3 ratio was assumed to be 1 vol% in the relative Al2O3 even in low ratios and Ni particle dispersion decreased Al2O3
density calculations to compare the densification behavior of the sam- grain size for ANC composite compared to AC [10].
ples, neglecting the loss by evaporation. The sintering temperature (1550 ᵒC) is above the melting point of Ni
As seen from Table 1, the addition of Ni particles inhibited the (1453 ᵒC). The wetting of liquid Ni on Al2O3 and ZrO2 is poor (128ᵒ and
densification in AN compared to pure Al2O3, and in ANC compared to 118⁰, respectively) that generates a weak interface and has a negative
AC. The highest relative density was obtained for AZ composites; the effect on densification [32,37–39]. But it is stated in the literature that
relative density of ANZ was lower than AZ even though the difference the addition of stabilized zirconia helps the densification of Al2O3 as a
was not as pronounced as in AN and ANC composites. A similar pattern sintering aid and also inhibits the grain growth [40,41]. Al2O3 powder
can be seen on the grain sizes of the composites: AN has a smaller grain used in this study does not contain any sintering aid (i.e. MgO). YSZ
size compared to pure Al2O3 and ANC has a smaller grain size compared addition showed the highest densification behavior in spite of the
to AC, but ANZ and AZ have similar grain sizes. presence of Ni and helped to the process as a sintering aid. However,
Fig. 4 shows the Al2O3 grain size measurement results which were the grain growth inhibitor effect of ZrO2 was not active because of the
found by using the linear intercept method from six SEM micrographs poor densification of pure Al2O3 with small particle size. Also, Cr2O3
that were taken from different areas of each sample. For A, AN and AC addition showed an increase in densification for both pure Al2O3 and
compositions high standard deviation in grain sizes were observed. The Al2O3/Ni composites and the grain size of Al2O3 increased consequently
wide range of the data points in the y-axis, specifically gathering of data as seen in Table 1. The growth rate of Al2O3 increases in the presence of
points at two grain sizes, indicates the difference in the densification Cr3+ ions because of the coherency strain energy at the grain boundary
locally. This was attributed to the inhomogeneous density distribution [42]. Rapid migration of grain boundaries as a result of coherency
of the pellets prior to sintering. However, it is seen that AZ, ANZ, and strain energy causes changes in the microstructure that a chemically
induced boundary migration takes place generally in all solid solutions
if the temperature is high enough for the boundary mobility [24,43].
Table 1 The relative elastic modulus values were calculated as the ratio of
Relative densities, Al2O3 grain sizes, absolute and relative elastic modulus va-
the measured elastic modulus with respect to the VRH average; taking
lues for the produced ceramic and the composite samples.
the elastic modulus of Al2O3, ZrO2, Cr2O3, and Ni as 420, 210, 280 and
Composition Relative Density, Al2O3 grain size, Elastic Modulus, Relative E, 200 GPa, respectively [12]. Fig. 4 shows the relative elastic modulus (E
% (μm) E, (GPa) % %) with respect to the relative density (ρ%) together with the linear fit
A 95.7 0.85 ± 0.20 362 ± 6 86.2 line; the correlation between the mechanical properties ρ% and E% is
AN 92.8 0.76 ± 0.20 327 ± 18 78.6 very high with R2 = 0.97. The highest E% value was obtained for AZ
AZ 98.5 1.24 ± 0.10 386 ± 3 95.3 composite as expected from its highest density and the lowest E% was
AC 96.7 1.42 ± 0.22 373 ± 4 89.5 obtained for AN composite. Data one more time shows the importance
ANZ 97.7 1.28 ± 0.12 377 ± 3 93.8
of densification in improving the mechanical properties of ceramic
ANC 94.8 1.09 ± 0.11 346 ± 14 83.5
materials: higher the relative density, higher the elastic modulus. An-
other observation is that as the relative density decreases, the standard

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B.K. Yıldız and Y.K. Tür
Fig. 4. a) The Al2O3 grain size measurements from six different SEM images for each composition and b) the relative elastic modulus (%) as a function of the relative
density (%). The solid line is the linear fit line of the data.
deviation increases. Low densification of AN composites not only re-
sults in local variations of the grain sizes at the microscopic scale but
also higher standard deviation of the elastic modulus of the samples at
the macroscopic scale.
Fig. 5 shows SEM micrographs of thermally etched specimens for all
the compositions. Ni and ZrO2 particles are brighter and Al2O3 grains
are the darker in the micrographs. Ni and ZrO2 particles were homo-
geneously distributed in the Al2O3 matrix. Ni particles in AN were lo-
cated at the triple junctions and in the intergranular boundaries with an
average size of 0.33 ± 0.10 μm. It is obvious that the Ni particles that
were obtained in a nanometer scale by the reduction heat treatment
grew after sintering above its melting point. ZrO2 particles for AZ
composition mostly occupied in the intergranular boundaries and in the
triple junctions with an average particle size of 0.47 ± 0.20 μm and a
smaller fraction of them within Al2O3 grains with an average particle
size of 0.21 ± 0.06 μm. It is hard to distinguish ZrO2 and Ni particles in
the micrographs for ANZ composites due to their similar brightness and
close particle sizes; the average particle size of bright phases was
0.52 ± 0.19 μm which indicates that an increase in ZrO2 particle size
was seen in ANZ composites compared to AZ [44]. The distribution
character of Ni in Al2O3 was not changed for ANC composite; however,
the average particle size was increased to 0.40 ± 0.09 μm. It appears
that Cr3+ ion rich active Al2O3 grain surfaces not only effects Al2O3
Fig. 5. Thermally etched SEM-BSE mode micrographs of a) A, b) AZ, c) AC, d) AN, e) ANZ, and f) ANC.
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Materials Science & Engineering A 758 (2019) 103–111
grain growth but also the diffusion of Ni and results in coalescence of Ni
particles.
The flexural strength values for all the compositions are shown in
Fig. 6 and the fracture surfaces of the specimens are shown in Fig. 7.
Mostly grain boundary fracture (intergranular) mode can be seen for
both Al2O3 and AN composite. Ni addition was effective to hinder the
grain growth of Al2O3 with 10% grain size reduction even though the
densification of Al2O3 was low. For dense ceramic materials, the
strength depends on the microstructural flaw size if the surface defects
are eliminated. Thus, higher strength values are the result of micro-
structural refinement in these ceramics. However, in AN composite,
microstructural refinement effect was unlikely because of the low
densification and high porosity. The slight increase in strength of AN
compared to pure Al2O3 may be attributed to an increase in toughness
because of the ductile metal phase addition [45].
The higher density of AZ compared to Al2O3 and AN is the reason
for its higher strength (276 ± 51 MPa) even though mostly inter-
granular fracture mode was dominant in AZ composites similar to Al2O3
and AN. Simultaneous addition of 3 mol% Y2O3 stabilized ZrO2 (5 vol
%) and Ni (1 vol%) to Al2O3 is very effective to increase the strength of
composite (367 ± 34 MPa). The highest strength was obtained for that
composition even though the relative density was slightly lower than
AZ. Also, the relatively small scatter of the strength data indicates the
B.K. Yıldız and Y.K. Tür
Fig. 6. a) The flexural strength and b) the hardness of the compositions as a function of the relative density. The solid line in (b) is the estimated hardness of Al2O3-
based composites as a function of relative density given by Ref. [15].
uniformity of the microstructure compared to the other compositions.
The fracture mode changed from intergranular to transgranular (clea-
vage) in ANZ composite and ∼33% strength increase could be obtained
compared to AZ composite. This increase in strength is mainly due to
the change in fracture mode in relation to the presence of Ni particles in
the intergranular boundaries results in the grain boundary strength-
ening. The energy needed to cause crack propagation through the
grains is higher than the energy needed for crack propagation through
the grain boundaries, so the fracture mode change increases the
strength of the material [11,19].
When 1 vol% Cr2O3 was added to AN composite, fracture mode
changed to a mixture of intergranular and transgranular fracture as
seen in Fig. 7 and the strength increased 28% even though there was a
decrease in the relative density. Also, 19% strength increase was also
obtained by addition Cr2O3 in Al2O3 with the increase in the density
and change in fracture mode from intergranular to the mixture. A ra-
dius difference between Cr3+ and Al3+ ions (0.076 nm and 0.068 nm,
respectively) generates compressive stress while forming a substitu-
tional solid solution. The localized compressive stress induces the
strengthening of the grain boundary and causes an increase in the
strength of ceramic as solid solution strengthening [37]. In here, the
mentioned strengthening effect to some extent was a result of a change
Fig. 7. Fracture surfaces SEM micrographs of a) A, b) AZ, c) AC, d) AN, e) ANZ, and f) ANC.
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Materials Science & Engineering A 758 (2019) 103–111
in fracture mode from intergranular to a mixed mode with Cr2O3 ad-
dition for both in Al2O3 and Al2O3/Ni composites.
Fig. 8 shows the typical crack patterns for each composition after
the equibiaxial flexural strength tests. Arrows on each photograph in-
dicate the possible crack initiation sites. Table 2 gives the average total
crack length for each composition The total crack length for each spe-
cimen increases with increasing branching of the propagating cracks
and the branching of the initial crack is attributed to a critical energy
level [46]. The greater the flexural strength of the part, the more the
stored energy at failure, and on average the more pronounced is the
branching and hence the total crack length. A and AN compositions
have the lowest strength with only a couple of branches and AC, AZ,
and ANC compositions have moderate strength with similar fracture
patterns. Finally, ANZ composition has the highest strength with the
highest number of branching.
The stored elastic energy in a specimen is equal to the work done by
the force and can be evaluated by the area below the load-displacement
(P-Δ) curve. Since the load-displacement relation of ceramic materials
is linear, the work done by the load can be found by:
1
W= P
2 (1)
B.K. Yıldız and Y.K. Tür Materials Science & Engineering A 758 (2019) 103–111

Fig. 8. Disc specimens of all the compositions fractured in the equibiaxial

flexural strength test; a) A, b) AZ, c) AC, d) AN, e) ANZ, and f) ANC. Arrows
indicate the possible crack origins.

Fig. 9. The total crack length as a function of the stored energy and the linear
Table 2
fit line for each composition.
Relative density, flexural strength, average total crack length, the slope of the
stored energy versus the total crack length fit line and hardness values for all
the compositions.
Composition Relative Flexural Total Crack Slope Hardness crack length and accompanying smallest fragment size and ANZ would
Density, Strength, Length, (mm) (m/J) (GPa) have the shortest total crack length with the largest fragment size.
% (MPa) For Ni-containing composites, as the presence of Ni particles in-
creases the grain boundary strength, the stored energy is used for the
A 95.7 199 ± 53 55.1 ± 24 3.0 19.7 ± 1.2
AN 92.8 212 ± 47 68.3 ± 32 3.0 20.7 ± 1.2 transgranular fracture, decreasing the crack driving energy, hence
AZ 98.5 276 ± 51 77.3 ± 38 2.5 22.1 ± 1.0 branching is suppressed. Also, for ZrO2-containing composites, stress-
AC 96.7 237 ± 47 87.1 ± 31 3.5 23.1 ± 0.9 induced phase transformation of ZrO2 from tetragonal to monoclinic
ANZ 97.7 367 ± 34 106.4 ± 19 2.0 25.5 ± 1.0 phase consumes the energy, decreasing the effective crack driving en-
ANC 94.8 272 ± 43 99.1 ± 28 2.8 23.2 ± 0.9
ergy needed for the crack branching. This would result in a reduction of
the total crack length for a given stored energy. The combined effect of
Ni and ZrO2 would explain the smaller slope of ANZ even though it has
where P is the applied load (N) and Δ is the displacement of the load the highest average strength.
(m). The deflection of the cylindrical specimen during a ring on ring For Cr2O3-containing compositions, there is a radius difference be-
test can be evaluated by using the available solutions for the symmetric tween Cr3+ and Al3+ ions and because of this difference, compressive
bending of circular plates. Timoshenko derives the deflection of the stress is generated in the Al2O3 lattice by the substitution of Cr3+ ions
concentrically loaded simply supported circular plate and gives the in place of Al3+ ions as stated before. Therefore, in these compositions
deflection at the radius equal to the loading ring radius (r = b) as fol- there exists residual stored energy that would contribute to the stored
lows [47]: energy during fracture, increasing the effective crack driving energy
which in turn promotes branching of the crack front. In other words, the
P 11 a2 b2 b higher slope of AC ceramic can be attributed to these compressive
= (w )r = b = (a2 b 2) 1 + + 2b2log
8 D 21+ a2 a (2) stresses on the crystal lattice of Al2O3 due to the solid solution forma-
tion.
where w is the deflection of the circular plate (m), a and b are support Fig. 6(b) shows the relation of the Vickers hardness (GPa) and the
ring and loading ring radii (m), ν is the Poisson's ratio, and D is defined relative density (ρ%) of all the compositions and Table 2 gives the
as: measured average hardness values. Kafkaslıoğlu and Tür [15] showed
that the hardness of Al2O3-based composites decreases with the de-
Et 3
D= creasing relative density and proposed an exponential relation to esti-
12(1 2)
(3) mate the hardness:
where E is the elastic modulus (Pa) and t is the thickness of the plate H = H0 e 4.2(1 ) (4)
(m).
For each specimen, the stored energy at fracture was calculated where H0 is the hardness of the fully dense material. By regression
using Eq. (1) together with Eq. (2) for the displacement of the load. analysis, it was found that H0 = 23.6 GPa. The solid curve in Fig. 6(b)
Fig. 9 gives the stored energy at failure versus the total crack length points out this equation.
together with the linear fit line for each composition. Assuming the Even though AN and ANC composites have lower densities than the
crack length should be zero for zero stored energy, the intercept of the pure Al2O3, their hardness values are above the solid line, showing that
linear fit lines is forced to the origin. There is a considerable scatter the Ni addition has a positive effect on the hardness of the ceramic. The
both in the stored energy and the total crack length for all the speci- hardening effect of Ni particles close to 100 nm size scale is demon-
mens, yet it is seen that the crack length increases with the increasing strated and attributed to Hall Petch effect, e.i. Small particle sizes re-
stored energy. Table 2 shows that the slope of the linear fit line for AC is strict dislocation motion increasing the yield strength and the hardness
the greatest (3.5 m/J) and the slope of the linear fit line for ANZ is the of nanometals [18]. The hardness of ZrO2 is lower than Al2O3, so the
smallest (2.0 m/J) while others have slopes close to each other. In other hardness increase of AZ composites can be attributed to the better
words, for a given fracture energy AC would have the longest total densification and the homogeneous grain size distribution of these

109
B.K. Yıldız and Y.K. Tür
composites compared to pure Al2O3. Ni addition to AZ composites re-
sulted in 15% hardness increase demonstrating the hardening effect of
Ni particles in spite of a decrease in the relative density compared to
AZ. It is seen that the average Ni particle size is above 100 nm but there
is still a fraction of particles with sizes near this critical value that
contributes to the hardness [15,19].
In the early studies of Al2O3–Cr2O3 solid solution, a hardness in-
crease was reported but there are other studies that the solid solution
effect was not so active for the hardening of the material [24,48]. In this
study, Cr2O3 addition to the pure Al2O3 increased the hardness of the
material as the relative density was increased; yet, the measured
hardness is above the solid line indicating the hardening effect of Cr2O3
addition besides densification. Solid solution formation not only helped
the densification of Al2O3 as stated before but also resulted in an in-
crease in hardness above expected from densification. The hardness of
AC compared to AZ also demonstrates the hardening effect of Cr2O3
solid solution on Al2O3 based ceramics even though its hardening effect
was less pronounced than Ni addition.
A ceramic ballistic component is expected to have an optimum
combination of high mechanical properties (elastic modulus, tensile
strength, hardness) [29,49]. Also, resistance to fragmentation is ex-
pected for multi-hit applications while fragmentation would be bene-
ficial for abrasion of the penetrator for single hit applications [29]. Ni
addition to Al2O3 has been shown to increase the flexural strength and
the hardness of the material; however, it decreases the relative density
and the homogeneity of the material, decreasing its reliability. In this
study, it is seen that ZrO2 and Cr2O3 additives considerably improved
the properties of the AN composites. Specifically, ANZ composites
possess the highest strength and hardness values even though their
relative density and elastic modulus were slightly lower than the AZ
composites. Moreover, ANZ composites have the lowest slope of the
stored energy-crack length linear fit line indicating their possible ability
to withstand multiple hits by projectiles. On the other hand of the
spectrum is AC ceramic, which has intermediate mechanical properties,
yet the highest slope which would be a good candidate for single hit
conditions.
4. Conclusion
Al2O3/1 vol% Ni nanocomposites were prepared with (5 vol%) ZrO2
and (1 vol%) Cr2O3 additives to investigate the effect of different me-
chanisms on the mechanical properties of the composites to be used as
an armor component. The study was carried out by analyzing the re-
lation of microstructure and the physical properties of all the prepared
compositions. The highest densification and homogeneity were ob-
tained for AZ and ANZ composites accompanied by the highest elastic
modulus values with small standard deviations. 73% and 28% increase
in the flexural strength of AN was measured with ZrO2 and Cr2O3 ad-
ditions, respectively because of better densification and change in
fracture modes from intergranular to transgranular for ANZ and to mix
mode for ANC. The change in fracture mode was attributed to the
strengthening mechanism effects in the presence of additives. Also, Ni
particles addition to all compositions increased the hardness, especially
for ANZ composite with 25.5 ± 1.0 GPa hardness and the hardening
behavior was attributed to the Hall-Petch effect partly provided by the
near 100 nm size particles. The hardening effect of Cr2O3 solid solution
in Al2O3 was verified by the higher hardness of AC compared to Al2O3
and AZ although its hardening effect was less than Ni addition. ANZ
composites have the lowest slope of stored energy-crack length fit line
indicating that branching of this composite is lower than others for
given fracture energy. This would give larger fragments in an impact
situation and may increase the multiple hit capacity. AC ceramic system
with the highest slope would give smaller fragments compared to other
compositions. With its intermediate mechanical properties, this com-
position can be utilized as a ceramic component of an armor system in
different conditions.
110
Materials Science & Engineering A 758 (2019) 103–111
Acknowledgment
The support of Gebze Technical University Scientific Research
Council to project with a grant number 2018-A105-62 is greatly ap-
preciated. Authors also thank Ahmet NAZIM and Adem ŞEN for their
assistance in SEM and XRD analysis of this study, respectively.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.msea.2019.05.014.
Data availability
The raw/processed data required to reproduce these findings cannot
be shared at this time as the data also forms part of an ongoing study.
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