Ceramics International 46 (2020) 27539–27549

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Effects of sintering additives on the densification and properties of alumina- T

toughened zirconia ceramic composites
M.K.G. Abbasa, S. Ramesha,b,∗, K.Y. Sara Leec, Y.H. Wonga, P. Ganesana, S. Rameshd,
U. Johnson Alengarame, W.D. Tengf, J. Purbolaksonog
a
Center of Advanced Manufacturing and Material Processing, Department of Mechanical Engineering, Faculty of Engineering, University of Malaya, 50603, Kuala Lumpur,
Malaysia
b
Department of Mechanical Engineering, Faculty of Engineering, Universiti Teknologi Brunei, Tungku Highway, Gadong, BE1410, Brunei Darussalam
c
Tunku Abdul Rahman University College, Faculty of Engineering & Technology, Department of Mechanical Engineering, 53300, Kuala Lumpur, Malaysia
d
Centre for Ionics University of Malaya, Department of Physics, Faculty of Science, University of Malaya, 50603, Kuala Lumpur, Malaysia
e
Centre for Innovative Construction Technology (CICT), Department of Civil Engineering, Faculty of Engineering, University of Malaya, 50603, Kuala Lumpur, Malaysia
f
Ceramics Technology Group, SIRIM Berhad, Shah Alam, 40911, Malaysia
g
Department of Mechanical Engineering, Faculty of Industrial Technology, University of Pertamina, Jakarta, 12220, Indonesia

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

Keywords: The effects of manganese oxide, stainless steel and copper oxide doping on the sintering behaviour and me-
Alumina-toughened zirconia chanical properties of alumina-toughened zirconia (ATZ) were investigated. The prepared ceramic composites
Alumina were conventionally sintered at 1250 °C, 1350 °C and 1500 °C, using different holding times (1, 12 and 120 min,
Y-TZP respectively). The tetragonal phase stability, microstructural evolution, relative density, Vickers hardness and
Zirconia
the fracture toughness of the samples were determined. The beneficial effects of sintering additives in aiding the
Sintering additive
Mechanical properties
densification of the ATZ, particularly at low temperatures and short holding times were revealed. In particular,
the addition of copper oxide was the most beneficial in enhancing the properties of ATZ when sintered at 1250 °C
and 1350 °C for short holding times. Sintering at 1500 °C was unnecessary for the copper-doped ATZ to attain the
maximum relative density of > 98%, Vickers hardness of > 12 GPa and fracture toughness of > 5 MPa m1/2. By
contrast, the undoped ATZ required a long holding time and high sintering temperature to achieve similar results
as the doped samples. This research showed the viability of using sintering additives in aiding low temperature
densification and enhancing the mechanical properties of ATZ through conventional sintering.

1. Introduction counterpart, thereby making it a promising composite for many appli-

cations [8–21]. This improvement in the mechanical properties of the
Monolithic oxide ceramics, such as yttria-tetragonal zirconia poly- ATZ has been linked to several mechanisms including crack deflection
crystals (Y-TZP) and alumina (Al2O3), have gained considerable atten- around the hard alumina particles, stress dissipation due to a gradual
tion mainly due to their inherent intrinsic properties, such as high transition in the fracture mode from intergranular to transgranular and
hardness and high stiffness for alumina versus excellent strength and to some extent, crack branching or crack bridging with microcracks that
fracture toughness for Y-TZP, thereby making them viable for a range of are formed during cooling from sintering due to the tetragonal to
applications, including in orthopaedic and dental implant devices monoclinic phase transformation arising from the differential in the
[1–7]. In order to take advantage of the excellent properties offer by coefficient of thermal expansion mismatch between alumina and zir-
these ceramics, researchers developed different composites in which conia [18,22,23].
either alumina is dispersed in a zirconia structure or vice versa. In One of the main challenges in obtaining a highly dense ATZ body
particular, the addition of 20 wt% Al2O3 as a minor phase in the Y-TZP via the conventional sintering method is that the green body should be
matrix, which is subsequently known as alumina-toughened zirconia sintered at high temperatures (≥1500 °C) and/or for long holding times
(ATZ), has been found to be most effective in enhancing the mechanical (≥2 h) or non-conventional sintering techniques, such as hot-pressing
properties of the sintered body when compared to their monolithic and microwave sintering, should be used. Zhang et al. [18] studied the

∗
Corresponding author. Center of Advanced Manufacturing and Material Processing, Department of Mechanical Engineering, Faculty of Engineering, University of
Malaya, 50603, Kuala Lumpur, Malaysia.
E-mail address: [email protected] (S. Ramesh).

https://doi.org/10.1016/j.ceramint.2020.07.246
Received 20 April 2020; Received in revised form 30 June 2020; Accepted 25 July 2020
Available online 29 July 2020
0272-8842/ © 2020 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
M.K.G. Abbas, et al. Ceramics International 46 (2020) 27539–27549

addition of up to 50 vol% Al2O3 in 3Y-TZP and found that the increased as copper oxide, manganese oxide and stainless steel on the low tem-
in the toughness observed in their composites is attributed to the perature sintering of ATZ.
transformation toughening of the tetragonal matrix and partly to the
crack deflection caused by alumina particles in the Y-TZP matrix. The 2. Materials and methods
authors found that the optimum amount of 20 vol% Al2O3/3Y-TZP in a
composite resulted in the highest hardness of 12.6 GPa and flexural The starting powders, 3 mol% yttria-tetragonal zirconia polycrystal
strength of 633.3 MPa when sintered at 1500 °C/2 h. Gil-Flores et al. (Y-TZP) and alumina (99.9% purity, α-Al2O3) were obtained from
[14] compared the sintering behaviour of ATZ (20 wt% Al2O3 + 80 wt Kyoritsu Co. Ltd. (Japan). ATZ was prepared by blending 80 wt% of Y-
% 3Y-TZP) by conventional sintering in air atmosphere at 1400 °C/ TZP with 20 wt% of Al2O3 by attrition milling (Union Process, USA)
120 min to 1500 °C/120 min with that produced by microwave sin- using zirconia milling media (3 mm in diameter) and ethyl alcohol as
tering at 1200 °C and 1400 °C with the holding times of 10 and 30 min, the mixing agent. The mixture was filtered using a sieve, and the slurry
respectively. The authors found that the bulk density and mechanical was placed in an oven (UN 55, Memmert, Germany) for overnight
properties of ATZ could be enhanced by microwave sintering compared drying at 60 °C. The dried cake was crushed and sieved using a 212 μm
with conventional sintering which requires the high temperature of sieve to acquire the undoped ATZ powder. The dopants used in this
1500 °C/120 min to achieve similar properties. work were commercially available high-purity stainless steel powder
Boniecki et al. [22] prepared a variety of composites consisting of grade SS316 (Cr 16–18, Ni 10–14, Mo 2–3, C 0.08, remaining Fe,
20 wt% to 80 wt% Al2O3/3Y-TZP by planetary ball milling. Composites Nanomaterials Inc. USA), manganese oxide (> 99% purity, Reagent
were subsequently sintered at 1480 °C/2 h in air atmosphere. The aim Plus, Sigma-Aldrich, USA) and copper oxide (99.99%, Sigma-Aldrich,
was to investigate the role of zirconia and alumina in governing the USA). To prepare doped ATZ powders, we mixed 0.2 wt% stainless steel
subcritical crack growth of the composites. They showed that high (SS), 0.5 wt% manganese oxide (Mn) and 0.2 wt% copper oxide (Cu)
amounts of zirconia are required to improve the KIc, bending strength powders, respectively to the ATZ by using the same procedure as that of
and resistance to subcritical crack growth in composites. This corre- undoped ATZ powder that was mentioned earlier. Dopant additions
sponds to the transformability of the tetragonal matrix as the X-ray were based on our previous studies with Y-TZP and alumina ceramics
diffraction (XRD) analysis performed on the fracture surfaces of the [2,26–31]. For easy reference, doped powders hereafter were referred
composites indicating that the amount of monoclinic phase that is to as SS-ATZ, Mn-ATZ and Cu-ATZ.
present in 20 wt% Al2O3/3Y-TZP sample (i.e. 20.5%) is closed to that Undoped and doped powders were compacted at 4 MPa into disc
obtained for the monolithic Y-TZP (i.e. 25.2%) which has the highest samples and subsequently cold isostatic pressed at 200 MPa. Green
toughness. However, when the alumina exceeds 20 wt%, a low mono- samples were conventionally sintered in air atmosphere at 1250 °C,
clinic phase and a low KIc were detected in fracture surfaces. The de- 1350 °C and 1500 °C at three different holding times each, that is 1, 12
crease in the transformability of the Y-TZP matrix with increased alu- and 120 min, respectively, using a standard heating and cooling ramp
mina content in the composite was also confirmed by Kern and Gadow rate of 10 °C/min. The bulk density was measured based on
[19]. In this study, ATZ was hot-pressed at 1400 °C/1 h/50 MPa and Archimedes’ principle in water. The relative density of the sintered
1500 °C/1 h/50 MPa. The authors demonstrated that the addition of body was calculated by taking the theoretical density of ATZ (according
alumina produced compressive stresses in the composite matrix coun- to the rule of mixtures) as 5.50 gcm−3 [32,33]. Prior to hardness
teracts the transformation toughening effect of the tetragonal grains i.e. measurement, samples were ground using SiC paper, followed by final
making them stable and unable to respond readily to external applied polishing with 6 μm and 1 μm diamond pastes to acquire a mirror-like
stress. Nevarez-Rascon et al. [24] prepared different amounts of Al2O3 surface. The hardness and KIc were determined using Vickers indenta-
in 3Y-TZP by the powder pressing method. These researchers sintered tion technique. The indentation load used was kept at 10 kgf and ap-
green bodies by burying samples in a powder bed of (ZrO2 + Al2O3), plied for 10 s. Average values were obtained from at least five mea-
and the temperature was initially increased to 1200 °C at a heating rate surements. The KIc was evaluated according to the relationship
of 10 °C/min. followed by final sintering at 1500 °C using a heating rate established by Shetty et al. [34].
of 6 °C/min. and maintained at this temperature for 2 h. The results The phases that were present in the samples were examined by XRD
showed that the ATZ containing 20 wt% Al2O3 has a relative density of (X'Pert Pro, EMPYREAN, PANalytical, Netherlands), using CuKα ra-
~97% compared with ~96.3% and ~88.6% for samples containing diation at 40 kV and 40 mA. The scan was performed from 20° to 80°
30 wt% and 40 wt% Al2O3, respectively. In another research [25], the (2θ) at a step scan of 0.02° and 0.5 s per step. The peaks corresponding
authors sintered ATZ ceramic in a furnace under hydrogen atmosphere to the characteristics of tetragonal zirconia (t), monoclinic zirconia (m)
at 1500 °C for 30 min followed by hot isostatic pressing at 1500 °C with and alumina were identified using JCPDS files no. 48–0224, 37–1484
the pressure of 100 MPa. The samples exhibited the hardness of and 46–1212, respectively. The monoclinic and tetragonal phase con-
14.8 GPa and KIc of 7.4 MPa m1/2. tent were evaluated from Rietveld analysis using the relative intensities
Sequira et al. [20] prepared spray dried ATZ powders (80 wt% Zr – measured over the 2θ range 27°–36° which covers the monoclinic (m)
20 wt% Al2O3) with a controlled particle size distribution and subjected and tetragonal/cubic (t,c) related (111) peaks, according to the formula
the derived powders to conventional sintering at 1400 °C/3 h. The established by Toraya et al. [35]. Since it is common for the t and c
authors showed that the adopted process successfully densifies the peaks to overlap at 2θ = 30.1°, high angle XRD analysis over the 2θ
composite and improves the mechanical properties. Typically, a relative range 72° to 76° which covers the cubic related (400) peaks were
density of 98.4%–98.5% and a KIc of about 4.8–4.9 MPa m1/2 were considered. The volume fraction of the cubic phase was calculated using
obtained for sintered ATZ. The composite also exhibited excellent cy- the relationship established by Miller et al. [36]. The microstructural
tocompatibility and cell viability/proliferation when exposed to evolution of the samples was examined by a field-emission scanning
MG63 cells that were cultured for 1–4 days. electron microscope (SEM). Before imaging, polished samples were
In all these studies involving ATZ, a high sintering temperature and/ subjected to thermal etching at a temperature 50 °C below the sintering
or controlled processing condition couples with the use of non-con- temperature for 30 min. The grain size was measured on SEM micro-
ventional sintering methods would be necessary to obtain a highly graphs according to the linear intercept method [37].
dense body. To the authors’ knowledge, no studies on the use sintering
additives to enhance the densification of ATZ at low temperatures 3. Results and discussion
(< 1400 °C) and use of short holding times (less than 2 h or 120 min)
via the conventional sintering method have conducted to date. In this The XRD phase analysis of the as-received powders revealed that
research, we investigated for the first time the effects of dopants, such powders were composed of the tetragonal (t) zirconia phase (about

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crystalline ceramic, having a two-phase structure comprising of a t

phase (major) and α-Al2O3 (minor phase) as shown in Fig. 2. From
thermodynamic consideration [38], the presences of alumina, having
an elastic modulus almost two-fold that of zirconia, will enhance the
strain free energy (ΔGSE ) of the matrix and hence the t to m phase
transformation on cooling from sintering can be prevented due to the
increased in the transformation barrier (ΔGt − m) . The fact that no
monoclinic phase was detected in the sintered samples support this
view. The Rietveld analysis performed on the samples sintered at
1500 °C also confirmed the absent of any secondary phase resulting
from the reaction between alumina and zirconia. This finding is in good
agreement with the observation of many researchers working with ATZ
having similar composition as in the present work
[10–22,24,32,33,39]. For instance, Bartolomé et al. [39] who prepared
20 wt% Al2O3/Y-TZP nanocomposites and sintered via SPS found that
the samples composed predominantly of the tetragonal phase with
some minor alumina and monoclinic phase detected in the matrix.
Despite the presences of m phase in the sintered samples, the authors
inferred that the presences of Al3+ in the zirconia matrix could have
played a supporting role in the stabilization of the tetragonal structure
in addition to strain effects of the alumina matrix itself. The authors
also believed that some of the Al3+ could have segregated to the zir-
conia grain boundaries and was in part responsible for the enhanced
low-temperature degradation resistant of this ceramic when exposed to
steam environment. The segregation of Y3+ and Al3+ in 0.15 wt%
Fig. 1. The XRD analysis of starting powders.
Al2O3 doped Y-TZP have also been confirmed by Ross et al. [40].
However, their TEM analysis did not show compelling evidence of
glassy phase formation at grain boundaries and triple grain junctions.
From the XRD analysis presented in Fig. 2, the splitting of the cubic
related peaks into two distinct peaks observed particularly at (200)c
plane i.e. at 2θ ~34.9° and the (311)c plane at 2θ ~ 59.8° [41] are clear
indication that tetragonal is the dominant phase in the matrix. This was
also verified by the Rietveld analysis of the ATZs which indicated that
there were only slight changes in the lattice parameters of the tetra-
gonal zirconia between the undoped and doped samples i.e. the varia-
tion in the c/a parameter ratio of the tetragonal lattice varied by about
1%, from 1.4378 (ATZ) to 1.4525 (SS-ATZ). This small changes in the
lattice parameters have also been reported by other authors [42–44].
Nevertheless, the slight increase in the tetragonality observed for the
SS-ATZ samples could be attributed to the development of cubic phase.
This was confirmed by high angle diffraction analysis as shown in Fig. 3
which indicates the present of a distinct peak centered at 2θ of 73.8°
belonging to the cubic (400)c plane [41]. This cubic peak was not ob-
served for other ATZ samples. The measured cubic content for the SS-
ATZ varied from about 3.32% at 1250 °C to about 9.43% at 1500 °C.
The present of cubic phase in ATZ that has been doped with small
amount additives was also reported by Zhang et al. [45]. The authors
calculated that about 7.8% cubic phase was present in their lanthanum
oxide-doped ATZ sintered at 1500 °C for 2 h. In another study, it was
also noted that the cubic phase increases with alumina and dopant
content, with significant abnormal large grains being observed in the
zirconia matrix [44]. This cubic grain normally is of abnormally large in
size than the tetragonal grains and can be easily be seen during SEM
analysis [44–48] as typically shown in Fig. 7 for the SS-ATZ.
The effects of holding time, sintering temperature and dopant ad-
dition on the relative density of the ATZs are shown in Fig. 4. The
beneficial effect of the dopants, particularly for sintering at 1250 °C and
1350 °C, was disclosed. In all cases, copper oxide doping was the most
Fig. 2. Typical XRD signatures of ATZs sintered at 1500 °C for 120 min holding effective in enhancing the densification of ATZ. For example, the re-
time. lative density of Cu-ATZ was much higher (86.5%) than that for the
undoped ATZ sintered at 1250 °C/1 min (76.6%). Similarly, the relative
73 ± 4%) with the remaining being the monoclinic (m) zirconia phase, density of Cu-ATZ was 96.4% when sintered at 1350 °C/1 min. The
and several minor peaks corresponding to the α-Al2O3 phase was also addition of stainless steel and manganese were also effective in pro-
detected, as shown in Fig. 1. As sintering proceeded, all ATZs, regard- moting ATZ densification. According to Fig. 4, regardless of the holding
less of dopant additions and sintering conditions, exhibited highly time, the relative density of all samples increased with increased sin-
tering temperatures in the following order of efficacy: Cu-ATZ > Mn-

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M.K.G. Abbas, et al. Ceramics International 46 (2020) 27539–27549

structure as shown in Fig. 5. The relative density of the ATZ was 92% as
compared to 98% for the Cu-ATZ. Our previous experience working
with transition metal oxides as sintering additives in Y-TZP and alumina
[2,26–31,49] and based on the findings of other workers [50–53], it
was shown that a transient liquid phase involving the dissociation of the
metal oxide and the reaction with yttria at grain boundaries were re-
sponsible for the enhance densification observed at lower temperatures.
This mechanism could be in operative in the present doped ATZs,
however more work is in progress to study the grain boundary mod-
ification caused by the dopants and this will be reported in subsequent
paper. Nevertheless, the present finding is unprecedented when com-
pared with the results of most studies on similar ATZ composition,
where such high densities could only be attained when sintered at ≥
1500 °C or by using non-conventional sintering methods such as mi-
crowave sintering, hot pressing and spark plasma sintering, as shown in
Table 1.
The microstructural evolution of the ATZs sintered at 1350 °C and
1500 °C are shown in Fig. 6 and Fig. 7, respectively. Some interesting
microstructures were observed for doped ATZs. In general, an equiaxed
and a smooth grain texture were observed for tetragonal zirconia grains
(light contrast), whereas a rough texture and exaggerated with occa-
sionally elongated grain morphology were observed for alumina grains
(dark contrast). The holding time had minimal effects on tetragonal
grain and alumina grain sizes when sintered at low temperatures
(≤1350 °C), as shown in Fig. 6. The comparison between the holding
times of 1 min (see Fig. 6a–d). and the 120 min (Fig. 6e–h). showed
minimal differences in the tetragonal grain sizes (Table 2), regardless of
dopant additions. Similarly, there was no significant difference in the
alumina grain size with dopant additions. However, the alumina grain
Fig. 3. High angle XRD signatures of ATZs sintered at 1500 °C revealing the
presence of the cubic (400)c plane in the SS-ATZ. The cubic phase was not size was found to increased monotonically with increasing temperature
detected in all other samples. as shown in Table 3. A typical dual-grained microstructure comprising
of tetragonal and alumina grains which increased in size was observed
with increasing holding time and sintering temperature as shown in
ATZ > SS-ATZ > ATZ. Increasing the holding time promoted den-
Fig. 7. In agreement with the XRD analysis, abnormal large grains be-
sification particularly when sintered at 1250 °C and 1350 °C. The re-
longing to the cubic zirconia phase was observed in the SS-ATZ mi-
lative density of more than 97% can be obtained for ATZ when con-
crostructure, see Fig. 7h.
solidated at 1500 °C/1 min, as shown in Fig. 4.
This formation of cubic grains within tetragonal matrix of zirconia-
The use of manganese oxide, copper oxide and stainless steel as
based ceramics has not been fully understood although many re-
dopants for ATZ that was reported for the first time in this work was
searchers have associated this with the segregation of Y3+ cations at
effective in aiding ATZ densification, particularly at low temperatures
grain boundaries and triple grain junctions [49,54–62]. Duran [57]
(< 1400 °C) and using short holding times (< 120 min or 2 h).
suggested that the development of large cubic grains in their zirconia
Evidence of the beneficial effect of the dopants in promoting densifi-
were due to the interdiffusion of yttrium and zirconium cations which
cation can be seen from the cross-section of the sintered undoped ATZ
promoted fast grain-boundary movement during sintering. Lee and
sample which clearly revealed cluster of particles that have not been
Chen [61] supported this idea and believed that solute segregations
fully consolidated when sintered at 1350 °C/12 min when compared to
could have affected grain boundary energies and diffusivities, thus al-
the doped samples, for example Cu-ATZ, which exhibited a denser
tering grain boundary mobility. Ruhle et al. [54] found that in some

Fig. 4. The variation in relative density for ATZs as a function of sintering temperature, holding time and dopants addition.

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Fig. 5. Cross sectional view of (a) undoped ATZ and (b) Cu-ATZ sintered at 1350 °C/12 min revealing improved densification of the doped sample.

Table 1 tetragonal grains, and from 6.7 wt% to 12 wt% in the cubic grains. A
Comparison of relative density for ATZ reported by other researchers and the similar observation was also confirmed by Tsukuma et al. [56] and
present study. Zhou et al. [59].
Sintering Sintering Dopant Relative Ref. These variations in yttria content in the grains clearly suggests that
methods temperature (°C)/ addition density equilibrium had not been attained during sintering. Based on the TEM
Holding time (%) examination, Ruhle et al. [54] suggested that the presence of yttria-rich
(min.)
large cubic grains was due to the more rapid grain growth by grain
Microwave 1200/30 - 99.0 14 boundary phase diffusion rather than the nucleation of new cubic grains
sintering 1300/30 - 99.8 in the matrix during sintering. Accordingly, the few cubic nuclei that
(MW) were formed, would grow until the system attained its equilibrium
Conventional 1400/120 - 98.3 14 phase content. On the contrary, Matsui et al. [63] believed that as more
sintering (CS) 1500/120 - 99.2
CS 1400/180 (3 h) - 98.5 20
of the Y3+ segregated to the grain boundaries and triple grain junctions
CS 1500/120 - 98.0 18 with increasing temperature, this would create nucleation sites for the
CS 1400/360 (6 h) - 91.0 68 formation of new cubic grains. Similarly, Stoto et al. [62] showed a
1650/240 (4 h) - 96.0 correlation between yttria redistribution and grain growth. The authors
CS 1500/120 - 92.5 17
found that grain growth in 3 mol% Y-TZP ceramics, was inhibited by
1570/120 - 93.2
1610/120 - 91.7 yttria migration but increased drastically once phase equilibrium was
Hot press @ 1400/60 0.02–0.1 wt% 99.7 33 attained. In addition, the authors suggested that yttria segregation
30 MPa graphite flakes would be enhanced by the presence of grain boundary amorphous
CS 1480/120 - 99.1 22 phase and this was supported by Nauer and Carry [64].
Spark Plasma 1400/8 - > 95.0 32
Sintering
The increasing in alumina content has also been suggested to in-
Hot Isostatic 1500 - ~100 25 crease the cubic phase content in the ceramic matrix [44]. The for-
Pressing @ mation of cubic phase in ATZ was also reported by Nevarez-Rascon
100 MPa et al. [24] but the reason for the t to c transformation was not de-
CS 1350/1 0.2 wt% Cu 96.4 Present
liberated. Zhang et al. [65] who investigated the crack behavior in
1350/12 0.5 wt% Mn 96.0 study
1350/12 0.2 wt% SS 98.0 La2O3 and Al2O3 co-doped 3Y-TZP suggested that the segregated dopant
1350/120 0.2 wt% Cu 99.1 cations could bind with the oxygen vacancies at grain boundaries. Since
1350/120 0.5 wt% Mn 98.0 oxygen vacancies play a critical role in the stabilization of the zirconia
1350/120 0.2 wt% SS 98.0 structure, any change in the concentration of these vacancies caused by
the dopants could affect the chemistry and conditions for the cubic
phase formation [66,67]. In the present work, the formation of sec-
commercial yttria-stabilised zirconia, the microstructures were duplex,
ondary phase resulting from the reaction between zirconia and/or
containing mainly of t grains and some large c grains which were ty-
alumina with the dopants was not apparent from the XRD and SEM
pically 3 to 10 times the size of the tetragonal grains. In addition, the
analysis. It is however unclear at this stage on the mechanism involve in
yttria content of the t and c grains, and its spatial distribution within
the cubic phase formation in the SS-ATZ and this would require further
individual grains differed with different commercial materials. They
quantitative studies.
found that the Y2O3 content varied between 1.8 wt% to 4.4 wt% in the
The average Vickers hardness of the undoped and doped ATZ

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Fig. 6. SEM images of undoped ATZ (a, e), Cu-ATZ (b, f), Mn-ATZ (c, g) and SS-ATZ (d, h) sintered at 1350 °C for holding times of 1 min. (a–d) and 120 min. (e–h).
The lighter grain belongs to that of tetragonal zirconia whereas the dark grain is that of alumina.

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M.K.G. Abbas, et al. Ceramics International 46 (2020) 27539–27549

Fig. 7. Microstructure development of undoped ATZ (a, e), Cu-ATZ (b, f), Mn-ATZ (c, g) and SS-ATZ (d, h) sintered at 1500 °C for holding times of 1 min. (a–d) and
120 min. (e–h). The exaggerated grains observed in (h) belongs to the cubic (c) zirconia.

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Table 2
Average tetragonal grain size measured for ATZ.
Holding Time Sample Average grain size (μm) ( ± 0.01 μm)

1250 °C 1350 °C 1500 °C

1 min ATZ 0.14 0.16 0.35

Cu-ATZ 0.16 0.17 0.36
Mn-ATZ 0.15 0.17 0.36
SS-ATZ 0.15 0.17 0.36
120 min ATZ 0.17 0.19 0.52
Cu-ATZ 0.19 0.20 0.56
Mn-ATZ 0.17 0.19 0.63
SS-ATZ 0.17 0.19 0.61

Table 3
Average sizes of the alumina grains. Fig. 9. Vickers hardness variation with relative density for ATZs.
Sintering ATZ Cu-ATZ Mn-ATZ SS-ATZ
temperature (°C)
density as shown in Fig. 4. The graph of Vickers hardness versus relative
1250 0.42 ± 0.27 0.37 ± 0.10 0.48 ± 0.12 0.41 ± 0.11 density as shown in Fig. 9 revealed a linear relationship does exist
1350 0.55 ± 0.20 0.52 ± 0.16 0.61 ± 0.16 0.50 ± 0.18 between both properties. This observation was in good agreement with
1500 0.82 ± 0.22 0.76 ± 0.21 1.14 ± 0.13 0.92 ± 0.15 the results reported by Nevarez-Rascon et al. [24]. These authors re-
ported that the differences in hardness values obtained in their ATZ and
ZTA composites is associated with the residual porosity level in each
composites are shown in Fig. 8. The general trend showed that the
sample. The highest hardness was obtained for 20 wt% Al2O3 compo-
hardness increased with increased holding time for sintering at 1250 °C
sites and undoped alumina, whereas the lowest hardness was recorded
and 1350 °C, regardless of dopant addition. However, the hardness of
for 40 wt% Al2O3-60 wt% Y-TZP composites which correspond to the
the samples sintered at 1500 °C was not influenced by the sintering
lowest relative density (about 89%). These results suggested that the
holding times and remained at approximately 12–12.5 GPa for all
higher porosity in this sample may have resulted in a lower grain
samples. In agreement with the densification trend, copper oxide was
boundary concentration caused by the formation of fewer grains com-
the most beneficial in enhancing the hardness of ATZ at low tempera-
pared with a dense body. Hence, the frequency at which moving dis-
tures, recording values of 9.1 ± 1.2 GPa at 1250 °C/1 min,
location encountered grain boundaries would be low. As a result, the
10.2 ± 1.5 GPa at 1250 °C/12 min and 11.7 ± 1.1 GPa at 1250 °C/
dislocation pileups at grain boundary regions would require less energy
120 min. A Vickers hardness of about 12 GPa can be attained for Mn-
for further deformation, thereby resulting in low hardness.
ATZ and Cu-ATZ samples when sintered at 1350 °C/12 min and for SS-
The KIc of the ATZs increased monotonically with increased tem-
ATZ when sintered at 1350 °C/120 min compared with undoped ATZ
peratures and holding time, as shown in Fig. 10. As shown in the figure,
which can only obtain similar hardness when sintered at 1500 °C. This
Cu-ATZ exhibited the highest KIc (higher than 5 MPa m1/2) when sin-
result was remarkable because such high hardness could only be
tered at 1250 °C and 1350 °C, regardless of the holding time. A high
achieved for most ATZs when sintered at high temperatures [24] or by
toughness of higher than 6 MPa m1/2 can be obtained for Cu-ATZ when
using non-conventional sintering methods [14,25]. For instance, the
sintered at 1350 °C compared with 1500 °C for the undoped ATZ. The
high hardness values of about 12.6 and 14.8 GPa were reported for the
KIc of the ATZs did not change remarkably (i.e. about 5–6 MPa m 1/2)
same ATZ composition as that in the present work when sintered at
when sintered at 1350 °C using 1 min and 12 min holding times. In
1400 °C by spark plasma sintering [32] and hot isostatic pressing at
agreement with the increase in relative density, the undoped ATZ ex-
1500 °C/100 MPa [25], respectively.
hibited high KIc when sintered at 1500 °C. The highest value of
The undoped ATZ could not achieve high hardness at low tem-
6.55 ± 0.02 MPa m1/2 was achieved for samples sintered at 1500 °C/
peratures and holding time owing to the high amounts of porosity re-
120 min. However, this value was higher than those reported by Gil-
maining in the sintered body (see Fig. 5), resulting in lower sintered

Fig. 8. The effect of sintering temperature and holding times on the Vickers hardness of ATZs.

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Fig. 10. Fracture toughness dependence on the sintering temperature and holding time for ATZs.

Flores et al. [14] and Zhang et al. [18], that is 5.5 and 6.2 MPa m1/2, more dominant in the Mn-AZT and Cu-ATZP as can be seen in Fig. 11c
respectively when sintered at 1500 °C/2 h. and d, respectively. This initial observation suggest that these dopants
By contrast, the highest toughness of 6.72 ± 0.04 MPa m1/2 was could have played a role in strengthening the grain boundary of the
obtained for Cu-ATZ when sintered at 1500 °C/120 min. This highest ATZ. This agrees with the work of Zhang et al. [44] on the addition of
toughness value was slightly lower than that (about Al2O3 and La2O3 to Y-TZP. They believed that the segregation of La3+
7.45 ± 0.57 MPa m1/2) reported by Nevarez-Rascon et al. [24] for and Al3+ to the grain boundary played a role in strengthening the grain
similar ATZ composition. The authors attributed the increase in the KIc boundaries by possibly binding with oxygen vacancies. This was also
to a crack deflection mechanism and a mix fracture mode that was evident as the fracture mode transited from intergranular to transgra-
observed in their ATZ. According to these authors, residual stresses nular in the doped ceramics. Besides this, it cannot be over emphasized
would be generated in the composite matrix due to the difference in that any improvement in the sintered density of the ATZ, such as in this
thermal expansion coefficients between zirconia (10.3 × 10−6 K−1) case through the use of dopants, would contribute to increase the ma-
and alumina (8 × 10−6 K−1) resulting from the formation of hoop trix elastic constraint and hence will have a positive effect on the
tensile and radial compressive stresses near the free surface [18]. In the fracture toughness as shown in Fig. 12. This trend is in good agreement
present ATZs, the analysis of the fracture surface (see Fig. 11) indicated with the improved mechanical properties with densification for ATZs as
that the fracture mode changed from mainly intergranular in the un- reported by other researchers [14,24,32,71].
doped ATZ to a mix of intergranular and transgranular fracture in the
doped ATZ. This behavior would cause an increase in the KIc because
the energy needed for crack propagation through the grains would be 4. Conclusions
higher than that required to propagate through grain boundaries
[68–70]. The fraction of the transgranular fracture was found to be The effect of small additions of stainless steel, manganese oxide and
copper oxide as sintering additives on the densification behavior of ATZ

Fig. 11. Fracture surfaces of composites sintered at 1500 °C/120 min: (a) ATZ, (b) SS-ATZ, (c) Mn-ATZ and (d) Cu-ATZ.

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