International Journal of Refractory Metals & Hard Materials 74 (2018) 78–86

Contents lists available at ScienceDirect

International Journal of Refractory Metals

& Hard Materials
journal homepage: www.elsevier.com/locate/IJRMHM

Fabrication of tougher ZTA ceramics with sustainable high hardness through T

(RSM) optimisation
⁎
Zhwan Dilshad Ibrahim Sktania, Nik Akmar Rejaba, Mani Maran Ratnamb, Zainal Arifin Ahmada,
a
Structural Materials Niche Area, School of Materials and Mineral Resources Engineering, Engineering Campus, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang,
Malaysia
b
School of Mechanical Engineering, Engineering Campus, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang, Malaysia

A R T I C LE I N FO A B S T R A C T

Keywords: The requirement of attainment hard and simultaneously tough materials is a crucial matter for industrial sectors.
ZTA However, the toughness and hardness are mutually exclusive. Enhancing one result in the other being sacrificed.
RSM Hence, the strategy of compromise between formations of elongated CaAl12O19 grains with minimum porosity
ANOVA inside ZTA is implemented to overcome this challenge. To accomplish this target, the Design of Experiment
CaAl12O19, indentation fracture resistance
(DOE) is employed through Response Surface methodology (RSM) involving Central Composite Design (CCD) to
(KIFR)
optimise three variables of combination addition between CaO and CaCO3, sintering temperature and soaking
Vickers hardness
time. The optimised variables resulted to accomplish the optimum responses of the indentation fracture re-
sistance and hardness of ZTA ceramics. Empirical models are found for responses and their quality are checked
using Analysis of Variance (ANOVA) and other parameters. The results show that the sintering temperature is the
most influential variable on the responses while combination addition between CaO and CaCO3 is significant in
improvement of mechanical properties.

1. Introduction engineering applications due to their combination excellent mechanical

The attainment of both toughness and hardness for engineering
applications such as structural materials, cutting inserts, biomedical
implants, bushings, valve seats, dies, bearings, insulators, refractory
uses, high temperature filtering and armours is essential but it is not a
trivial task [1–4]. Unfortunately, these properties are generally mu-
tually exclusive [5]. The reason is attributed to the inverse relationship
between brittleness (especially in ceramics) and plasticity. Therefore, a
compromise is always reached in these applications where either one of
the properties is set aside. Despite of the continuous development of
producing harder materials, these have little to no use in some en-
gineering applications such as structural materials and cutting inserts
without appropriate fracture resistance [6]. For these reasons, it is es-
sential to develop composite materials that are simultaneously tough
and hard for up-to-date industrial applications. Despite of their lower
fracture toughness, ceramics are the best material choices for these
applications due to their light weight, excellent high hardness, high
strength, good mechanical strength at high temperatures and good
thermal shock resistance [5,7].
Zirconia Toughened Alumina (ZTA) is a composite of oxide ceramics
α-Al2O3 and tetragonal t-ZrO2 which is promising ceramic candidate for
properties compared to the pure Al2O3 and ZrO2 [8,9]. However, the
efforts have been exercised for fracture toughness enhancement faced
the hardness reduction [10]. Therefore, a new strategy was examined to
deal with this problematic behaviour. The interplay between amount of
elongated hexaaluminate grains and porosity inside ZTA ceramics that
individually contribute to indentation fracture resistance (KIFR) and
hardness, respectively. This strategy can play a vital role to defeat the
conflict of toughness versus hardness and achieve unprecedented levels
of damage tolerance within their respective ceramics [11]. In-situ for-
mation of elongated CaAl12O19 (calcium hexaaluminate) grains inside
ZTA microstructure during sintering process is a successful solution to
overcome this drawback due to its excellent thermal expansion and
formation less porosity compared to other hexaaluminates [12]. It
highly contributes to KIFR improvement through crack deflection me-
chanism or crack bridging mechanism or both [13,14]. The combina-
tion addition of CaCO3 and CaO was proven as an effective method to
enhance the KIFR while maintaining high hardness through formation of
elongated CaAl12O19 grains with minimum porosity [15].
In spite of precursor materials, sintering temperature and soaking
time have their great impacts on the mechanical properties of ceramics
[16]. To optimise each parameter individually, i.e. one factor at a time

⁎
Corresponding author.
E-mail address: srzainal@usm.my (Z.A. Ahmad).

https://doi.org/10.1016/j.ijrmhm.2018.03.006
Received 29 November 2017; Received in revised form 22 February 2018; Accepted 7 March 2018
Available online 10 March 2018
0263-4368/ © 2018 Elsevier Ltd. All rights reserved.
Z.D.I. Sktani et al.
is time consuming, cumbersome, requires more experimental data sets
and do not provide information about the mutual interactions of the
variables. Therefore, the Design of Experiment (DOE) is necessary to
reduce the number of experiments needed to identify an optimal set of
conditions. Consequently, save considerable time and cost. The DOE is a
mathematical technique that can be used to determine the optimal set
of conditions across many different changeable variables. It develop
process by providing systematic, simple and efficient methodology for
the optimisation of the near optimum design parameters with only a
few well defined experimental sets, resulting in valid and objective
conclusions [17–19]. The current work has three variables (combina-
tion addition of CaCO3 and CaO, sintering temperature and soaking
time). Their individual and interaction effects were discussed on the
two responses (KIFR and Vickers hardness). Hence, the Response Surface
Methodology (RSM) was implemented to optimise responses due to its
significance when evaluation of the influence of several variables on a
group of responses are required [20,21]. With the standard RSM, a
design called a Central Composite Design (CCD) was used to design the
experiment.
2. Materials and methods
2.1. Materials and preparation
The starting raw materials were Al2O3 (Martinswerk, 99% purity),
yttrium-stabilized zirconia (YSZ) (Goodfellow, Y2O3 5.4% as stabilizer),
CaCO3 (Fluka, ≥99% purity) and CaO (Sigma-Aldrich, ≥99.9%
purity). The powders were weighed by the digital balance Presica XT
220. The sample compositions are shown in Table 1. The CaO/CaCO3
ratio is set 4/1 based on the results from the previous work [15]. The
mixtures were wet mixed using ABB-mixer ZrO2 balls for 24 h at
50 rpm. The ratio of ZrO2 ball to the powder was 10:1. The mixed
slurries were dried for 24 h at 100 °C in an oven (Memmert-CU9760)
and the dried cakes were crushed and sieved to pass 40 μm. Then, the
powders pressed by uniaxial pressing at 330 MPa for 120 s into pellets
of 13 mm in diameter and 4 mm in thickness by using MTI pressing
machine. The pellets were sintered in Yudian furnace (Model KHt-
16,000×) under normal atmosphere in three stages. During the first
stage, the samples were sintered from room temperature to 550 °C at
heating rate of 5 °C/min and 2 h soaking time. This stage was necessary
to ensure evaporation of any possible water that previously reacted
with CaO due to the reactivity of CaO [22]. In the second stage, the
pellets were sintered from 550 °C to 800 °C with the same heating rate
and soaking time to remove CO2 and to produce CaO from CaCO3. Fi-
nally, during the third stage; pellets were heated to the range of 1400 °C
to 1600 °C while the soaking time was specified within the range of 2 h
to 4 h.
2.2. Characterisation
Vickers hardness and KIFR of the sintered samples were obtained
using Vickers indentation technique. The hardness tester (Mitutoyo-
model HV-114) was used to measure the Vickers hardness and KIFR by
taking the average of five different readings for each sample. The in-
dentation fracture method (IF method) is an acceptable method for
estimation of indentation fracture resistance of small ceramic products
and components due to its simplicity and applicability to small test
Table 1
Sample codes based on the ZTA added with combination of CaO & CaCO3.
Sample code Al2O3 (g) YSZ (g) CaO (g) CaCO3 (g) Total weight (g)
ZTA-0 24 6 0 0 30
ZTA-1 23.76 5.94 0.24 0.06 30
ZTA-2 23.52 5.88 0.48 0.12 30
79
International Journal of Refractory Metals & Hard Materials 74 (2018) 78–86
samples. IF method does not represent the true fracture toughness
therefore the fracture toughness produced from IF method is termed as
indentation fracture resistance (KIFR) [23–25]. The polished sintered
samples were subjected to HV 30 kgf for 15 s. To determine the crack
mode, there were many proposed methods based on different criteria as
following:
i. Many works stated that the Palmqvist crack can be distinguished
with half-penny crack after polishing the surface layers away. The
radial-median crack system exhibits radial and median cracks and
remains connected to the inverted pyramid of the indentation after
polishing, while the Palmqvist cracks remain radial in nature and
the cracks become detached from the tips of the Vickers indentation
[26].
ii. Others stated that the Palmqvist and median cracks are usually
known to occur at low and high loads, respectively [27]. However,
there are many works shows Palmqvist crack at 30 kgf (HV30)
(294 N) [10,28–30]. Moreover, Quin [31] stated that the loading up
to 490 N still shows the c/a ratio of 2.3 and therefore, the fracture
indentation shows Palmqvist cracks.
iii. The ratio of c/a is another indicator which it is considered by most
of researchers to evaluate the fracture toughness mode. Where c is
the crack length from the centre of the indentation to the crack tip
and a is a half of the indentation diagonal. Some works mentioned
to the ratio of c/a = 2.5 for separation between Palmqvist and
median cracks [32]. Despite of this fact, there are others who
mentioned that the ratio c/a = 3 as the distinguish point between
Palmqvist and median cracks [33]. While some others have pro-
posed different values for l/a ratio, the l/a = 2.5 as distinction be-
tween Palmqvist and median cracks is most widely accepted for ZTA
ceramics [34,35].
As a very important evident for our work, the experimental in-
dentation crack on Fig. 1 shows the Palmqvist crack mode. Fig. 1 was
further enriched with the measurements of crack lengths (l) and half
length of the Vickers indentation diagonal (a) through Field Emission
Scanning Electron Microscopy (FESEM, Zeiss Supra 35) based on the
straight line method. This measurement proved that the crack mode is
identified as Palmqvist cracks according to l/a ratio (0.25 ≤ l/a ≤ 2.5)
which is 1.87 and 1.59, respectively. KIFR was calculated according to
the formula of Palmqvist crack proposed by Niihara [36]:
3(KIc) = 0.035 (H × a1/2) (3E/H)0.4 (c/a)−0.5 (1)
(KIc) is the fracture toughness, H is Vickers hardness, a is the half
length of Vickers diagonal (μm), E is equal to the Young modulus of the
sample, and c is the length of the radial crack size (μm). The Niihara
equation measures the fracture toughness (KIc). Nonetheless, Miyazaki
and Yoshizawa [23,25] works the stated that the KIFR value for most
ceramics is roughly proportional to KIc, which implies that the crack
model is not overly incorrect.
2.3. Design of experiment and analysis
Before designing of experiment (DOE), the suitable values for the
three variables i.e. combinations between CaO and CaCO3 (A), sintering
temperature (B) and soaking time (C) were chosen based on the pre-
vious works. The amount and ratio of combination addition between
CaO and CaCO3 were selected based on the previous finding [37] while
the sintering temperature range based on the preliminary studies. The
sintering temperature range (1400 °C to 1600 °C) was found beneficial
for CaAl12O19 formation [38,39]. Therefore, the sintering temperature
for the current work was set between 1400 °C to 1600 °C. In spite of the
fact that there were no any literature related the direct effect of the
soaking time in the formation of CaAl12O19 inside ZTA matrix, the
soaking time range was selected based on the previous studies on var-
ious ZTA ceramics [9,37,39–42]. They revealed the soaking time was
Z.D.I. Sktani et al.
Fig. 1. Geometries and image of (a) Palmqvist crack, (b) median cracks around Vickers indentation [33] and (c) determination of mode of crack for ZTA ceramic from FESEM image.
effective for ZTA ceramics between 2 h to 4 h to densify ZTA ceramics.
The objective of this study is to find the optimum settings of the
individual effects and simultaneously interaction effects for these
variables (combinations between CaO and CaCO3 (A), sintering tem-
perature (B) and soaking time (C)) that result in maximum responses
(KIFR and hardness). Therefore, RSM was selected for the current study
because it is the best adequate design of multi-variable statistical
methods [20,43]. In addition, the second-order model is the most sui-
table, highly structured, flexible, and diversified in order to locate the
optimum point(s) and when the interaction effects between variables
are required [44]. Therefore, it is required model for the current design.
Central Composite Design (CCD) is a kind of RSM and most commonly
utilised design for fitting second order models was developed using the
design-Expert 6.0 software. A useful variation in the CCD is Face-
Centred Central Composite Design or Face-Centred Cube (FCC) was
suitable to design the experiment due to inadequate percentages of
Combination addition between CaO and CaCO3 < 0% [45]. Therefore,
there are only three levels for each factor in this design which: the high
level (+1), the low level (−1) and the centre points (coded 0) as shown
in Table 2. Furthermore, the FCC does not require as many as centre
points as the spherical CCD. In practice, 2 or 3 centre points are suffi-
cient to provide a good variance of prediction throughout the experi-
mental region [21]. Analysis of Variance (ANOVA) is conducted on the
suggested and modified models. The statistical significance of these
Table 2
Independent variables and their levels in the experimental design.
Symbol sFactors Level
−1 0 1
A Composition of CaO & CaCO3 (wt.%) 0.0 1 2.0
B Sintering Temperature (°C) 1400 1500
C Soaking Time (C):hr 2 3
International Journal of Refractory Metals & Hard Materials 74 (2018) 78–86
models equations were evaluated by the F-values for analysis of var-
iance (ANOVA). ANOVA is based on partitioning the variation in the
data into components. For all terms of a model equation, values char-
acteristic of a so-called ANOVA table are calculated individually [45].
There are many parameters used to measure the quality of the sug-
gested models and how well they fit the experimental data such as:
coefficient of determination (R2), adjusted coefficient of determination
(Adj. R2), adequate precision, coefficient of variation (C.V.) and lack of
fit (LOF) [20]. In statistics, a model with a large F-value (greater than
unity) and a small p-value (< 0.05) is considered to be significant [46].
Furthermore, R2 and (Adj. R2) values are two main indicators for model
significance. The R2 values which were found to be close to 1 illustrated
good agreement between the calculated and observed results within the
range of experiment. Moreover, adequate precision measures the signal
to noise ratio and a ratio > 4 is desirable [20]. The Coefficient of
Variant (C.V.) measures the unexpected or residual variability in the
data as a percentage of the mean of the response variable. The Lack of
Fit LOF compares the residual error to the “Pure Error” from replicated
experimental design points. Furthermore, 3D mapping is a useful tool to
predict the effect of each variable independently and their interactions
on the responses. The two horizontal axes represented any two in the
three independent variables, and the remaining independent variable
was kept at zero level, simultaneously.
3. Results
Table 3 presents the full detail of the design experiment of ZTA
samples. Utilising FCC ensures that all selected values for the variables
were within the specified range. Accordingly, 16 tests were performed
to optimise the three variables and study their effects on the two re-
sponses (KIFR and hardness). These responses are in growth with the
sintering temperature in the given range while they reach plateau in the
1600
4 centre of combination addition between CaO and CaCO3 range. On the
other hand, the soaking time is insignificant when sintering
80
Z.D.I. Sktani et al. International Journal of Refractory Metals & Hard Materials 74 (2018) 78–86

Table 3 The low C.V. values predicts that these experiments have a satisfactory
Process data layout using FCC and test results. reliability and precision. As the p-values of LOF for KIFR and Vickers
hardness > 0.05, they indicate that LOF for these models are insignif-
Run composition of Sintering Soaking Hardness HV KIFR
CaO & CaCO3 temperature Time MPa.m1/2 icant and they are suitable for predicting KIFR and Vickers hardness
(A): wt.% (B): °C (C):hr within the range of variables.
The ANOVA tests from Table 4 and Table 5 observed the first order
1 1 1400 3 796 3.5
effects. A (compositions of CaCO3 and CaO addition wt%) and B (sin-
2 0 1500 3 1312 3.9
3 2 1500 3 1189 3.1 tering temperature) are more highly significant than C (soaking time) as
4 1 1500 3 1371 4.2 the prob > F values are < 0.05. Also prob > F value for B is very
5 1 1500 2 1368 4.3 minimal (< 0.0001), so it is considered to be the most influential
6 0 1600 2 1608 6 parameter among others on the KIFR and Vickers hardness responses.
7 2 1400 2 741 2.1
Similarly, for the second-order main effects on the KIFR, A2 and B2 are
8 2 1600 4 1483 5.8
9 2 1600 2 1470 5.9 significant while C2 is not significant. As the prob > F values of A2 and
10 0 1400 4 904 3.31 B2 were very minimal (< 0.0001), so they were considered to be the
11 1 1500 3 1347 4.1 most influential parameter among them. The second-order main affects
12 1 1500 4 1361 4.25
had less influence on the Vickers hardness as the prob > F values of A2
13 0 1600 4 1603 5.95
14 2 1400 4 723 2.1 and B2 are 0.0090 and 0.0006, respectively while the C2 is not sig-
15 0 1400 2 764 3.2 nificant. In terms of interactive effects, AB has an influence on the KIFR
16 1 1600 3 1590 7 response. In contrast, the other interaction effects are negligible. While,
none of the interactive effects are significant regarding to the Vickers
hardness.
temperature reaches 1600 °C. Usually it is essential to ensure that selected model is providing an
The empirical relationships of KIFR and Vickers hardness are ob- adequate approximation to the real system. By applying the diagnostic
tained from the analysis of Table 3 and are fitted with 2 sec order plots such as the predicted versus actual value plot, the model adequacy
polynomial equations of KIFR and Vickers hardness (VH): can be judged. The Fig. 2 (a) and (b) observed the comparison between
KIFR = 188.47283 − 2.48664 × A − 0.26178 × B − 0.82793 × A2 the experimentally measured values versus the predicted values for KIFR
and Vickers hardness, respectively. The values were distributed rela-
+ 9.22069 × 10−5 × B2 + 2.57 × 10−3 × A × B (2)
tively near to the straight line for both responses. These plots were
V = −35576.235 + 251.81207 × A + 45.17606 × B − 78.68103 × A2 supported by the (Adj. R2) values for KIFR and Vickers hardness were
0.9925 and 0.9895, respectively. These values were close to 1 which
− 0.013618 × B2 (3)
indicated a good agreement between the observed and predicted re-
The ANOVA statistics for KIFR and Vickers hardness are shown in sults.
Table 4 and Table 5, respectively. They indicate that the quadratic The (3D mapping) Fig. 3 plots the response surfaces for both re-
model could be used to navigate the design space. The F-values are sponses and depicted the effect for the three pairs of the variables on
222.01 and 158.37 for KIFR and Vickers hardness, respectively. The p- these responses. The sintering temperature has the positive impact on
values for both models are (< 0.05). Therefore, both models are con- the responses. The higher the sintering temperature, the higher the
sidered significant. The values (R2 = 0.9970) and (R2 = 0.9958) in- responses. The maximum values for KIFR and Vickers hardness were
dicate that 99.70% and 99.58% of the variability in the responses could recorded for the sintering temperature 1600 °C as shown in Fig. 3 (a, c,
be explained by the models of KIFR and Vickers hardness, respectively. d, f). This is in agreement with the p-values obtained for each para-
Meanwhile, the adjusted coefficient of determination (Adj. R2) are meter from ANOVA (Table 4 and Table 5).
0.9925 and 0.9895 for KIFR and Vickers hardness, respectively. These The combination addition of CaO and CaCO3 has relatively varied
very high values advocate a high significance of these models. The influences on the responses. The Vickers hardness gradually decreased
adequate precisions are 47.802 and 34.109 for KIFR and Vickers hard- with more addition of precursors. In contrast, the KIFR doesn't have a
ness, respectively. These high values of adequate precision demon- linear relationship with the additions. It steadily improves with more
strated that these models were significant for the process. The recorded addition, reaching optimum at around 1.0 wt.%, then it declines. The
C.V. are 2.94% and 2.74% for KIFR and Vickers hardness, respectively. porosity accompanied in-situ formation of CaAl12O19 and the amount
and size of CaAl12O19 affect the responses [37]. On the other hand,
Table 4 soaking time effect is negligible on the responses variation.
ANOVA for response surface quadratic models for KIFR. Understanding the interaction between two factors gives a better
insight into the overall process analysis. A variable may interact with
Source Sum of DF Mean F value Prob > F
squares square any or all of the other variables creating the possibility of presence of a
large number of interactions [47]. As shown in Fig. 3, the effects of the
Model 31.78 9 3.53 222.01 < 0.0001 Significant interaction between variables on the Vickers hardness were insignif-
A 1.13 1 1.13 70.98 0.0002 Significant
icant. Contrarily, the interaction effects between the sintering tem-
B 27.03 1 27.03 1699.35 < 0.0001 Significant
C 8.100E-004 1 8.100E-004 0.051 0.8289 perature (B) and the addition of precursors (A) was significant on the
A2 1.81 1 1.81 113.63 < 0.0001 Significant KIFR, this is in agreement with the p-value (0.0012) obtained for AB
B2 2.24 1 2.24 140.93 < 0.0001 Significant from ANOVA (Table 4).
C2 7.386E-003 1 7.386E-003 0.46 0.5210
AB 0.53 1 0.53 33.35 0.0012 Significant
AC 3.200E-003 1 3.200E-003 0.20 0.6695
3.1. Conformation studies
BC 8.450E-003 1 8.450E-003 0.53 0.4935
Residual 0.095 6 0.016 – – In order to verify the adequacy of the mathematical models and 3D
Lack of fit 0.090 5 0.018 3.62 0.3785 response surfaces generated during RSM implementation, duplicate
Pure error 5.000E-003 1 5.000E-003 – –
verification experiments were carried out on the given optimal medium
Cor total 31.87 15 – – –
settings. At the optimised parameters, implied that the predicted values
Std. Dev.: 0.13, Mean: 4.29, C.V.: 2.94, R2: 0.9970, Adj. R2: 0.9925, Pred. R2: 0.9833 and were in good agreement with experimental values. The optimised
Adequate Precision: 47.802. process parameters were 1.05 wt.% of combination addition between

81
Z.D.I. Sktani et al. International Journal of Refractory Metals & Hard Materials 74 (2018) 78–86

Table 5
ANOVA for response surface quadratic models for Vickers hardnesss.

Source Sum of squares DF Mean square F value Prob > F

Model 1.612E + 006 9 1.791E + 005 158.37 < 0.0001 Significant

A 34,281.03 1 34,281.03 30.31 0.0015 Significant
B 1.463E + 006 1 1.463E + 006 1293.86 < 0.0001 Significant
C 1525.23 1 1525.23 1.35 0.2896
A2 16,320.95 1 16,320.95 14.43 0.0090 Significant
B2 48,892.09 1 48,892.09 43.23 0.0006 Significant
C2 3288.68 1 3288.68 2.91 0.1390
AB 357.78 1 357.78 0.32 0.5942
AC 2467.53 1 2467.53 2.18 0.1901
BC 1638.78 1 1638.78 1.45 0.2740
Residual 6786.40 6 1131.07 – –
Lack of fit 6498.40 5 1299.68 4.51 0.3424
Pure error 288.00 1 288.00 – –
Cor total 1.619E + 006 15 – – –

Std. Dev.: 33.63, Mean: 1226.91, C.V.: 2.74, R2: 0.9958, Adj. R2: 0.9895, Pred. R2: 0.9328, and Adequate Precision: 34.109.

CaO and CaCO3 into ZTA samples and sintering temperature of 1600 °C
for a maximum response of 7.1 MPa.m1/2 (KIFR) and 1584 HV (Vickers
hardness).
4. Discussion
The mechanical properties of ZTA ceramics are considerably rely on
the microstructure and phase compositions. The combination addition
between CaO and CaCO3 leads to in-situ formation of CaAl12O19 having
varying grain sizes and creating porosity in the ZTA microstructure.
Therefore, it has its own influence on the KIFR and hardness of ZTA.
Fig. 3 (d and e) show KIFR is steadily enhances with more substances
additions up to around 1.0 wt.% of additions, then it declines. This is
attributable to the elongated CaAl12O19 which effectively deflects
cracks through grain boundaries and act as crack bridging sites. How-
ever, with more substances additions into ZTA ceramics, the produced
CaAl12O19 grains tend to more equiaxed shape. Hence, in spite of more
CaAl12O19 formation through > 1.0 wt.% additions of CaO and CaCO3;
they are not effectively perform the required crack deflection and crack
bridging mechanisms for the KIFR. The details of this mechanism were
explained elsewhere [37]. Additionally, it gradually and slightly re-
duced the hardness of ZTA ceramics due to lower density of produced
CaAl12O19 compared to the ZTA and the volume expansion which al-
ways accompanied with the formation of CaAl12O19 due to mismatch of
density between CaAl12O19, Al2O3 and YSZ [15,48]. In spite of this fact
the Vickers hardness reduction rate is slow due to larger ratio of CaO
compared to CaCO3 addition which avoid decarbonisation and conse-
quently avoiding excess creation of porosity. Therefore, the hardness is
comparable with that of the ZTA without any additions. The statistical
data of ANOVA (Tables 4 and 5) showed the significance of the
combination additions between CaO and CaCO3. The p-values were
0.0002 and 0.0015 for KIFR and Vickers hardness, respectively. These
values suggested that the combination additions of substances were
more influential on the KIFR rather than that for the hardness of ZTA
composites.
The ANOVA (Tables 4 and 5) stated that the sintering temperature
was the most influential variable on the mechanical properties of ZTA.
The p-values were very minimal (< 0.0001) which indicated that it was
significance to control the KIFR and Vickers hardness. The 3D responses
in Fig. 3 depict that the sintering temperature has the positive effect on
the mechanical properties of ZTA. The higher the sintering tempera-
ture, the higher Vickers hardness and KIFR of ZTA. This can be attrib-
uted to the fact that the sintering temperature has a great impact on the
microstructure and phase compositions of ZTA ceramics.
The sintering temperature's influence is observed on the grain
growth of CaAl12O19, Al2O3 and ZrO2, phase transitions of ZrO2 and
porosity of the ZTA structure. It was postulated that the porosity and
grain growth can greatly affect the materials' mechanical properties
[49]. The sintering temperature obviously controls the porosity and
grain growth of ZTA components. The FESEM micrographs in Fig. 4 (a-
c) depicted the microstructure of the optimised ZTA sample (added
with 1.05 wt.% of CaO and CaCO3) at different sintering temperatures
(1400 °C, 1500 °C,1600 °C), respectively. The ZTA samples at 1400 °C
(Fig. 4 a) has small size of grains scattered inside a porous micro-
structure. Few elongated sheet-like grains are observed belongs to
CaAl12O19. When the sintering temperature raised to 1500 °C (Fig. 4 b),
the porosity is decreased, grains sizes are increased and grains' ar-
rangement are closer to each other. These phenomena are more obvious
when the sintering temperature increased to 1600 °C (Fig. 4 c). The
grains are grown bigger compared to those grown at 1500 °C and they

Fig. 2. Predicted response vs actual response of (a) indentation fracture resistance (KIFR) and (b) Vickers hardness.

82
Z.D.I. Sktani et al.
Fig. 3. 3D surface response plots to observed the effect of sintering temperature, soaking time, addition composition of CaO and CaCO3 and their interaction on the KIFR and Vickers
hardness of ZTA.
are arranged closer to each other, simultaneously. This resulted in ob-
vious decrease of porosity. Therefore, the capacity to resist local com-
pression deformation of ZTA structures is increased which it is reflected
at higher hardness of ZTA at 1600 °C despite of addition any amount of
precursor compositions and/or duration of sintering (Fig. 3 a, c). In
addition, the CaAl12O19 grains inside ZTA are considerably affected by
the sintering temperature. They tend to be thicker and lose their sheet-
like platelet shape to more curvature boundary grains when the sin-
tering temperature reaches 1600 °C. The reason is attributable to the
decrease of porosity. Reduction of pore sizes allows the CaAl12O19
grains touch each other which causes inhibition of their growth along
basal plane direction [48]. Therefore, the CaAl12O19 grains at 1600 °C
83
International Journal of Refractory Metals & Hard Materials 74 (2018) 78–86
show more elongated trend. Nonetheless, the CaAl12O19 grains are
perfectly grown and elongated enough to deflect the fracture path,
strong enough to show crack bridging behaviour [50,51]. This explains
the reason of attaining the highest KIFR of ZTA ceramics at 1600 °C.
In spite of this fact, CaAl12O19 was produced at higher sintering
temperatures than 1600 °C inside Al2O3 matrix [52]. Nonetheless, it
was demonstrated that it is difficult to reach full density in reaction-
sintered CaAl12O19 even after increasing sintering temperature up to
1750 °C [53]. Besides that, in-situ formation of CaAl12O19 inside ZTA at
higher temperatures than 1600 °C concerned with the transformation of
ZrO2 grains from tetragonal to monoclinic which it causes the density
reduction and possibility to obtain lower hardness [16,49]. This was the
Z.D.I. Sktani et al.
Fig. 4. FESEM micrographs for ZTA 1.05 wt.% (CaO + CaCO3) at (a) 1400 °C, (b) 1500 °C and (c) 1600 °C; ZTA 1.05 wt.% (CaO + CaCO3) and 1600 °C; at (d) 2 h, (e) 3 h and (f) 4 h.
main reason that the sintering temperature range was restricted to a
reasonable upper limit although higher temperatures were found ben-
eficial for the KIFR enhancement [54]. Accordingly, the sintering tem-
perature 1600 °C was selected as the optimum temperature to attain the
highest hardness and meanwhile improve the KIFR of ZTA composites.
The effect of soaking time on the microstructure of the optimised
ZTA composite of 1.05 wt.% addition at 1600 °C for 2 h, 3 h, 4 h was
shown in Fig. 4 (d, e, f), respectively. The soaking time has a limited
influence on the microstructure, phase compositions and grain growth
of ceramics within the studied range of the current work. It was known
that the porosity also decreases with the increase in time at a fixed
temperature because diffusion is also time dependent phenomenon. The
soaking time at the final sintering temperature has an important role in
the densification process. Matter transport during sintering can be
viewed in terms of the flux of atoms (ions) or, equivalently in terms of
the counter flow of vacancies. As any type of diffusion (lattice or grain
boundary diffusion) requires time to transport matters, sufficient time is
required to achieve a good density. If the pores are trapped inside the
grain, the diffusion path is then higher and sufficient time must be al-
lowed for diffusion to get good densification [16]. The denser micro-
structure enhances the hardness of ceramics. However, abnormal grain
growth is likely to take place when samples are over sintered. Conse-
quently, fewer grains occupy the same area which leads to decrease of
crack deflection mechanism. Furthermore, it causes the ZrO2 grains to
undergo spontaneous phase transformation due to increase their sizes
[55,56]. Meanwhile, the abnormal enlargement of CaAl12O19 grains
should be prevented by shortening the sintering period because it led to
poor compactness [57]. Therefore, longer firing than 4 h was not pro-
cessed to avoid further undesirable hardness reduction of ZTA.
The interactive effects between the sintering temperature and
compositions additions had an influence on the KIFR of ZTA. This was
based on the 3D response surface in Fig. 3 (d) and ANOVA data for AB
(p-value 0.0012) in Table 4. The Fig. 3 (d) shows that the maximum
Vickers hardness and KIFR are obtained at 1600 °C while the KIFR is the
highest in the midrange of compositions addition (around 1.0%wt.)
meanwhile hardness is declined gradually. These findings are supported
by FESEM micrographs (Fig. 5 a, b, c) which shows the of crack paths
for ZTA samples at 1400 °C, 1500 °C and 1600 °C, respectively. The
crack of ZTA 1.05 wt.% of combinations is shown at different sintering
temperatures. It is clear that the sintering temperature affects the grains
arrangement inside ZTA samples, CaAl12O19 shape, porosity and grain
growth of ZTA. It was previously investigated that the excess porosity
84
International Journal of Refractory Metals & Hard Materials 74 (2018) 78–86
reduces the fracture toughness Al2O3-based ceramics [11,58]. On the
other hand, the grains are fine in the ZTA microstructure at tempera-
tures 1400 °C and 1500 °C (Fig. 5 a, b). Although the CaAl12O19 sheet-
like grains are deflect or obstacle the crack path, but they are not ef-
fective enough to improve the KIFR of ZTA samples due to their ex-
istence in the porous microstructure. Nonetheless, the sintering tem-
perature of 1600 °C (Fig. 5c) is effective to decrease porosity, arranges
grains closer to each other and achieve fully grown grains. Therefore,
sustainable high hardness is achieved concurrently with tougher ZTA
ceramics.
5. Conclusion
Tougher ZTA ceramics was successfully attained with sustainable
high hardness through implementing a systematic procedures of
Response Surface Methodology (RSM) standard from the Design of
Experiment (DOE) utilising the strategy of compromising between the
formation of elongated CaAl12O19 grains and porosity inside ZTA
ceramics. To achieve this target, a design called a Central Composite
Design (CCD) from a standard RSM was used successfully implemented
to optimise operational conditions (sintering temperature, combination
addition between CaO and CaCO3 and soaking time) for the mechanical
properties (indentation fracture resistance (KIFR) and Vickers hardness)
of ZTA ceramics. The statistical analysis of the results shows that in the
range studied, sintering temperature is the most influential variable
while the amount of combination addition between CaO and CaCO3 has
its vital role on the responses due to its control of pore formation and
in-situ formation of CaAl12O19 grains. The interactive effect of sintering
temperature and combination addition of CaO and CaCO3 was in-
vestigated in terms of formation enough elongated CaAl12O19 grains
parallel to the porosity reduction. Consequently, the KIFR of ZTA cera-
mics was improved while hardness maintained with reasonable values.
The optimised variables were at 1600 °C, 1.05 wt.% (CaO and CaCO3
combination) to achieve the highest KIFR of 7.1 MPa.m1/2, maintaining
hardness at 1584 HV which it is comparable with the ZTA without any
addition (1603 HV). Meanwhile the soaking time's effect negligible on
the mechanical properties of ZTA ceramics. Two empirical formulas,
developed in terms of the sintering temperature, combination addition
between CaO and CaCO3 and soaking time to represent the KIFR and
Vickers hardness of ZTA and corresponding coefficients of independent
variables were estimated by the application of the Design Expert soft-
ware. The responses evaluated from the empirical formulas show a
Z.D.I. Sktani et al.
Fig. 5. Micrograph of crack propagation of ZTA (1.05 wt.% added with CaO and CaCO3) at sintering temperatures (a) 1400 °C, (b) 1500 °C and (c) 1600 °C.
good agreement with the observed responses.
Acknowledgements
This work is financially supported by research university grant,
Universiti Sains Malaysia RUI 1001/PBAHAN/811212 and teaching
fellow scheme USM. 9/25 Jld. XIII.
References
[1] M.M. Hossen, F.U.Z. Chowdhury, M.A. Gafur, A.K.M.A. Hakim, Investigation of
mechanical properties of Al2O3 - 20 wt.% ZrO2 composites as a function of sintering
temperature, Eur. Sci. J. 10 (9) (2014) 399–411.
[2] V. Ponnilavan, S. Kannan, Structural, morphological and mechanical characteristics
on the role of excess ceria additions in zirconia toughened alumina systems, J.
Alloys Compd. 694 (2017) 1073–1082.
[3] S.R. Elsen, T. Ramesh, Optimization to develop multiple response hardness and
compressive strength of zirconia reinforced alumina by using RSM and GRA, Int. J.
Refract. Met. Hard Mater. 52 (2015) 159–164.
[4] S.R. Elsen, T. Ramesh, Analysis and optimization of dry sliding wear characteristics
of zirconia reinforced alumina composites formed by conventional sintering using
response surface method, Int. J. Refract. Met. Hard Mater. 58 (2016) 92–103.
[5] F. Bouville, E. Maire, S. Meille, B. Van De Moortèle, A.J. Stevenson, Strong, tough,
and stiff bioinspired ceramics from brittleconstituents, Nat. Mat. (2014) 1–7.
[6] R.O. Ritchie, The conflicts between strength and toughness, Nat. Mat. 10 (2011)
817–822.
[7] H. Wu, W. Liu, R. He, Z. Wu, Q. Jiang, X. Song, Y. Chen, L. Cheng,, S. Wu,
Fabrication of dense zirconia-toughened alumina ceramics through a stereo-
lithography-based additive manufacturing, Ceram. Int. 43 (2017) 968–972.
[8] J.F. Bartolomé, A. Smirnov, H. Kurland, J. Grabow, F.A. Müller, New ZrO2/Al2O3
nanocomposite fabricated from hybrid nanoparticles prepared by CO2 laser Co-
vaporization, Sci. Rep. 6 (2016) 1–11.
[9] F. Sommer, R. Landfried, F. Kern, R. Gadow, Mechanical properties of zirconia
toughened alumina with 10–24 vol.% 1.5mol.% Y-TZP reinforcement, J. Eur.
Ceram. Soc. 32 (2012) 3905–3910.
[10] A. Arab, R. Ahmad, Z.A. Ahmad, Effect of SrCO3 Addition on the Dynamic
Compressive Strength of ZTA, Int. J. of Min. Metall. Mater. 23 (4) (2016) 481–489.
[11] T. Oungkulsolmongkol, P. Salee-art, Hardness and fracture toughness of alumina-
based particulate composites with zirconia and strontia additives, J. Met. Mater.
Miner. 20 (2010) 71–78.
[12] C. Schmid, E. Lucchini, O. Sbaizero, S. Maschio, The synthesis of calcium or
strontium hexaluminate added ZTA composite ceramics, J. Eur. Ceram. Soc. 19
(1999) 1741–1746.
[13] R. Guo, D. Guo, Y. Chen, Z. Yang, Q. Yuan, In situ formation of LaAl11O18 rodlike
particles in ZTA ceramics and effect on the mechanical properties, Ceram. Int. 28
(2002) 699–704.
[14] C. Domõânguez, Ã. Chevalier, R. Torrecillas, L. Gremillard, G. Fantozzi,
Thermomechanical properties and fracture mechanisms of calcium hexaluminate, J.
Eur. Ceram. Soc. 21 (2001) 907–917.
[15] Z.D.I. Sktani, A.Z.A. Azhar, M.M. Ratnam, Z.A. Ahmad, The influence of in-situ
formation of hibonite on the properties of zirconia toughened alumina (ZTA)
composites, Ceram. Int. 40 (2014) 6211–6217.
[16] M.M. Hasan, F. Islam, Effect of sintering temperature and time on microstructure
and properties of zirconia toughened alumina (ZTA), Ceram. Trans. 209 (2010)
283–290.
[17] N. Mandal, B. Doloi, B. Mondal, Force prediction model of zirconia toughened
alumina (ZTA) inserts in hard turning of AISI 4340 steel using response surface
methodology, Int. J. Precis. Eng. Manuf. 13 (2012) 1589–1599.
[18] P. Nandal, S.R. Ravella, R.C. Kuhad, Laccase production by coriolopsis capareta
RCK2011: optimization under solid state fermentation by taguchi DOE metho-
dology, Sci. Rep. (2013) 1–7.
[19] P.A. Marinho, T. Chailangkarn, A.R. Muotri, Systematic optimization of human
pluripotent stem cells media using design of experiments, Sci. Rep. 1 (2014) 1–13.
[20] J. Li, J. Peng, S. Guo, L. Zhang, Application of response surface methodology (RSM)
for optimization of sintering process for the preparation of magnesia partially sta-
bilized zirconia (Mg-PSZ) using natural baddeleyite as starting material, Ceram. Int.
85
International Journal of Refractory Metals & Hard Materials 74 (2018) 78–86
39 (2013) 197–202.
[21] D.C. Montgomery, Design and Analysis of Experiments, eighth edition, John Wiley
& Sons, Inc., Arizona, 2013.
[22] M. Giannini, The Crystal Chemistry of Hibonite: An Indicator for Oxygen Fugacity
during Solar Nebula Condensation, Bayrueth, 2014 (Thesis).
[23] H. Miyazaki, Y.I. Yoshizawa, Correlation of the indentation fracture resistance
measured using high-resolution optics and the fracture toughness obtained by the
single edge-notched beam (SEPB) method for typical structural ceramics with
various microstructures, Ceram. Int. 3 (2015) 1–4.
[24] H. Miyazaki, Y.I. Yoshizawa, Refined measurements of indentation fracture re-
sistance of alumina using powerful optical microscopy, Ceram. Int. 40 (2014)
2777–2783.
[25] H. Miyazaki, Y.I. Yoshizawa, A reinvestigation of the validity of the indentation
fracture (IF) method as applied to ceramics, J. Eur. Ceram. Soc. 37 (2017)
4437–4441.
[26] T. Aleksandrov Fabijanić, D. Ćorić, M. Šnajdar Musa, M. Sakoman, Vickers in-
dentation fracture toughness of near-nano and nanostructured WC-Co cemented
carbides, Metals 7 (4) (2017) 1–16.
[27] A. Nastic, A. Merati, M. Bielawski, M. Bolduc, O. Fakolujo, M. Nganbe,
Instrumented and Vickers indentation for the characterization of stiffness, hardness
and toughness of zirconia toughened Al2O3 and SiC armor, J. Mater. Sci. Technol.
31 (2015) 773–783.
[28] A.Z.A. Azhar, H. Mohamad, M.M. Ratnam, Z.A. Ahmad, The effects of MgO addition
on microstructure, mechanical properties and wear performance of zirconia-
toughened alumina cutting inserts, J. Mater. Sci. Technol. 31 (2015) 316–320.
[29] N.A. Rejab, A.Z.A. Azhar, M.M. Ratnam, Z.A. Ahmad, The effects of CeO2 addition
on the physical, microstructural and mechanical properties of yttria stabilized zir-
conia toughened alumina (ZTA), Int. J. Refract. Met. Hard Mater. 36 (2013)
162–166.
[30] N.A. Rejab, W.K. Lee, Z.D.I. Sktani, Z.A. Ahmad, Hardness and toughness en-
hancement of CeO2 addition to ZTA ceramics through HIPping technique, Int.
J.Refract. Met. Hard Mater. 96 (2017) 60–65.
[31] G.D. Quinn, Fracture toughness of ceramics by the Vickers indentation crack length
method: a critical review, Ceramic Engi. Sci. Proceedings 27 (3) (2017) 45–62.
[32] M. Szutkowska, Fracture toughness measurement of WC-Co hardmetals by in-
dentation method, J. Adv. Mat. 31 (3) (1999) 3–7.
[33] M. Kuntz, R. Krüger, The effect of microstructure and chromia content on the
properties of zirconia toughened alumina, Ceram.Int. 44 (2) (2018) 2011–2020.
[34] K. Strecker, S. Ribeiro, M.-J. Hoffmann, Fracture toughness measurements of LPS-
SiC: a comparison of the indentation technique and the SEVNB method, Mater. Res.
8 (2005) 21–124.
[35] A. Moradkhani, H. Baharvandi, M. Tajdari, H. Latifi, J. Martikainen, Determination
of fracture toughness using the area of micro-crack tracks left in brittle materials by
Vickers indentation test, J. Adv. Ceram. 2 (1) (2013) 87–102.
[36] K. Niiharra, A fracture mechanics analysis of indentation-induced Palmqvist crack
in ceramics, J. Mater. Sci. Lett. 2 (1983) 221–223.
[37] Z.D.I. Sktani, M.M. Ratnam, Z.A. Ahmad, Influence of combined CaO and CaCO3
additions on the microstructure and properties of ZTA, J. Australian Ceram. Soc. 52
(2016) 167–176.
[38] L.L. Xueyin, L. Yan-gai, Y. Dexin, Y. Dingyun, H. Zhaohui, F. Minghao, Fabrication
and properties of CaAl12O19-Al2O3 composite ceramics, Key Eng. Mater. 512–515
(2012) 539–542.
[39] C.Y. Zeng, Z.H. Huang, J.T. Huang, Y. Li, Y.G. Xu, S. Yi, M.H. Fang, Y.G. Liu,
Preparation of calcium Hexaluminate using Al2O3 and White Beach sand from
Western Australia, Key Eng. Mater. 512–515 (2012) 940–944.
[40] J.K.M.F. Daguano, C. Santos, R.C. Souza, R.M. Balestra, K. Strecker, C.N. Elias,
Properties of ZrO2–Al2O3 composite as a function of isothermal holding time, Int. J.
Refrac. Met. Hard Mater. 25 (2007) 374–379.
[41] S.M. Kwa, S. Ramesh, L.T. Bang, Y.H. Wong, W.J.K. Chew, C.Y. Tan,
J. Purbolaksono, H. Misran, W.D. Teng, Effect of sintering holding time on the
properties and low-temperature degradation behaviour of manganese oxide-doped
Y-TZP ceramic, J. Ceramic Proc. Res. 16 (2) (2015) 193–198.
[42] H.L. Chu, C.L. Wang, H.E. Lee, Y.Y. Sie, R.S. Chen, W.S. Hwang, M.C. Wang, Effect
of sintering process parameters on the properties of 3Y-PSZ ceramics, IOP Conf. Ser.
Mater. Sci. Eng. 47 (2013) 1–5.
[43] S.G.N. Senthilkumar, T. Tamizharasan, Application of response surface metho-
dology and firefly algorithm for optimizing multiple responses in turning AISI 1045
steel, Arab. J. Sci. Eng. 39 (2014) 8015–8030.
[44] L. Shukla, A. Nishkam, Performance optimization, prediction, and adequacy by
Z.D.I. Sktani et al.
response surfaces methodology with allusion to DRF technique, ISRN Text. 2014
(2014) 1–12.
[45] M. Dutka, M. Ditaranto, T. Løvås, Application of a Central Composite Design for the
Study of NOx Emission Performance of a Low NOx Burner, Energies 8 (2015)
3606–3627.
[46] C. Song, X. Li, L. Wang, W. Shi, Fabrication, characterization and response surface
method (RSM) optimization for tetracycline, Sci. Rep. (2016) 1–12.
[47] N. Mandal, B. Doloi, B. Mondal, Predictive modeling of surface roughness in high
speed machining of AISI 4340 steel using yttria stabilized zirconia toughened alu-
mina turning insert, Int. J. Refract. Met. Hard Mater. 38 (2013) 40–46.
[48] I.R. Oliveira, V.M.C. Leite, G.D. Totti, L.S. Rossatto, R. Salomão, Production of
porous ceramic material using different sources of alumina and calcia, Rev. Mat. 19
(2014) 1–5.
[49] J. Fan, T. Lin, F. Hu, Y. Yu, M. Ibrahim, R. Zheng, S. Huang, J. Ma, Effect of sin-
tering temperature on microstructure and mechanical properties of zirconia-
toughened alumina machinable dental ceramics, Ceram. Int. 43 (2017) 3647–3653.
[50] P. Bai, Y. Chai, Y. Qiu, C. Gong, Y. Tian, The effect of sintering temperature on
prepared and properties of calcium hexaluminate/gehlenite composites, Sci. of
Sintering 46 (2014) 315–321.
[51] J. Liu, H. Yan, M.J. Reece, K. Jiang, Toughening of zirconia/alumina composites by
86
International Journal of Refractory Metals & Hard Materials 74 (2018) 78–86
the addition of graphene platelets, J. Eur. Ceram. Soc. 32 (2012) 4185–4193.
[52] Â. Chevalier, R. Torrecillas, G. Fantozzi, C. Domõânguez, Microstructure develop-
ment in calcium hexaluminate, J. Eur. Ceram. Soc. 21 (2001) 381–387.
[53] L. Xu, M. Chen, L. Jin, X. Yin, N. Wang, L. Liu, Effect of ZrO2 addition on densifi-
cation and mechanical properties of MgAl2O4-CaAl4O7-CaAl12O19 composite, J. Am.
Ceram. Soc. 98 (12) (2015) 4117–4123.
[54] P.G. De La Iglesia, O. García-Moreno, R. Torrecillas, J.L. Menéndez, Influence of
different parameters on calcium hexaluminate reaction sintering by Spark Plasma,
Ceram. Int. 38 (2012) 5325–5332.
[55] J. Zivko-Babic, Andreja Carek, M. Jakovac, Zirconium oxide ceramics in prostho-
dontics, Acta Stomat Croat. (2005) 25–28.
[56] J.K.M.F. Daguano, C. Santos, R.C. Souza, Properties of ZrO2 – Al2O3 composite as a
function of isothermal holding time, Int. J. Refract. Met. Hard Mater. 25 (2007)
374–379.
[57] A. Altun, O.F. Emrullahoglu, T. Çiçek, B. Gurel, H. Yeniflen, S. Akpinar, K. Onel,
B. Onay, Producton and characterization of calcium hexaluminate ceramics, Sci.
Tech. 21 (2007) 118–127.
[58] A.J. Sanchez-Herencia, R. Moreno, C. Baudõân, Fracture behaviour of alumina -
calcium hexaluminate composites obtained by colloidal processing, J. Eur. Ceram.
Soc. 20 (2000) 2575–2583.