Materials Today: Proceedings xxx (xxxx) xxx

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Materials Today: Proceedings

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Impacts of inclusion of additives on physical, microstructural, and

mechanical properties of Alumina and Zirconia toughened alumina (ZTA)
ceramic composite: A review
Saugata Sarker a, Homayra Tabassum Mumu a, Md. Al-Amin b,c, Md. Zahangir Alam c, M.A. Gafur b,⇑
a
Department of Materials and Metallurgical Engineering, Bangladesh University of Engineering and Technology, Dhaka 1000, Bangladesh
b
Pilot Plant and Process Development Centre, Bangladesh Council of Scientific and Industrial Research, Dhaka 1205, Bangladesh
c
Department of Applied Chemistry and Chemical Engineering, University of Dhaka, Dhaka 1000, Bangladesh

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

Article history: Zirconia toughened alumina (ZTA) is one of the widely discussed advanced ceramic in recent times. ZTA
Available online xxxx boasts excellent mechanically properties such as high hardness, high strength. Additionally, the material
is chemically inert and possess greater compressive strength. Despite having such versatility, lack of frac-
Keywords: ture toughness and shock resistance prevent its utilization in broad scale. To improve the fracture tough-
Zirconia toughened alumina ness and other mechanical properties, metals, metallic oxides additives such as MgO, CaO, CeO2, Cr2O3,
Ceramic composites strontium hexa-alumina, Ag, Ni, FeO were commonly added to ZTA in the academic research. The purpose
Mechanical properties
of this review paper is to provide a wholistic perspective on the trend of mechanical property alteration
Scanning electron microscope (SEM)
Crystallinity
upon addition of different additives. Trend of mechanical property alteration such as density, fracture
toughness, microhardness, strength provide a comparative analysis to solve this critical research and
industrial problems.
Copyright Ó 2022 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the International Confer-
ence on Materials, Processing & Characterization.

1. Introduction highest mechanical properties. But, t-ZrO2 is not stable at room

Zirconia toughened Alumina (ZTA) ceramics have become a
widely discussed and investigated material due to its excellent
mechanical properties like high strength, dimensional stability,
high temperature strength, hardness and many more. Although
the major drawbacks of alumina (Al2O3) based ceramics are the
low fracture toughness. Although the vast application of ZTA
ranges from structural, mechanical to biomedical applications,
the lack of fracture toughness causes an intriguing design problem
that were solved through modulation of sintering, oxide addition,
synthesis route alteration etc.[1]. Through proper engineering
and modulation, the properties of ZTA can be modified to be a high
performance ceramic [2].
ZTA matrix mostly consist of alumina with zirconia grains
resided in between the matrix. Zirconia phase is added to the
matrix to improve its fracture toughness and other mechanical
properties. Cubic, tetragonal and monoclinic are three possible
phases for zirconia. Among them, tetragonal zirconia boasts the
⇑ Corresponding author.
temperature. Stabilizers are added to increase tetragonal zirconia
volume fraction on ZTA matrix. Most common stabilizer for ZTA
is Yttria-stabilized-zirconia (YSZ). Stabilization can also be done
by CaO or CeO2 which is illustrated using Kroger-Vink notations.
Certain material inclusion may have an impact on lattice parame-
ter or thermal properties which was discussed extensively. Anion
vacancy or cation vacancy is induced by the addition of certain
material at their ionic state that can impact the properties of ZTA.
A variety of toughening mechanisms is induced by the addition
of certain inclusions. Zirconia can do transformation toughening
and microcrack toughening that helps to improve the toughness
of ZTA. Strontium Hexa-aluminate and Calcium Hexa-aluminate
have a platelet-like morphology. By the addition of such material
can induce crack bridging and crack deflection mechanisms. Other
toughening mechanisms are also discussed in this journal. Certain
material can also improve the hardness of the ZTA matrix-like
Cr2O3.
Another prominent impact of adding inclusion is its ability to
engineer the grain boundary. Some oxides such as ZrO2, MgO has
grain refinement properties. On the contrary, some oxide may

https://doi.org/10.1016/j.matpr.2022.02.481
2214-7853/Copyright Ó 2022 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the International Conference on Materials, Processing & Characterization.

Please cite this article as: S. Sarker, Homayra Tabassum Mumu, Md. Al-Amin et al., Impacts of inclusion of additives on physical, microstructural, and
mechanical properties of Alumina and Zirconia toughened alumina (ZTA) ceramic composite: A review, Materials Today: Proceedings, https://doi.org/
10.1016/j.matpr.2022.02.481
S. Sarker, Homayra Tabassum Mumu, Md. Al-Amin et al. Materials Today: Proceedings xxx (xxxx) xxx

cause disruptions in the grain boundaries initiating cracks in the
matrix. To illustrate the impact on grain boundary, the thesis of
this work focused on SEM images from different experimental
papers to investigate the generic changes in the matrix. Addition-
ally, the grain boundary effect is associated with the particle size
and porosity as well. Certain additives may hinder the pore propa-
gation and some may contain unique morphology to allow clog-
ging of the cracks.
The surface hardness of ZTA can be engineered by additives as
well. The pinning effect helps to increase the value and might be
aided by the addition of certain materials. XRD and Rietveld anal-
ysis helps to identify the phases present due to the inclusions.
Phases have a serious impact on the mechanical and thermal
behavior of the ZTA. Some inclusion while added in a certain por-
tion may increase certain mechanical properties while others may
just decrease it.
Zirconia Toughened Alumina (ZTA) ceramics boast immense
potential due to its excellent mechanical properties in contrast to
other ceramics. Considering the cost of manufacturing, ZTA can
be considered to be an excellent engineering choice. ZTA ceramics
contain high amount of alumina which is extremely cheap and
most manufacturing routes utilized in ZTA like Ball milling, Sol-
gel, Co-precipitation is relatively less expensive than the highly
sophisticated processing methods utilized in other advanced
ceramics. In terms of the mechanical properties, ZTA boasts com-
petitive fracture toughness in comparison with other advanced
ceramics. Although, ZTA has inherently low Vickers Microhardness
in comparison to other ceramics but it is still high enough to boast
a diverse set of applications. The comparison of mechanical prop-
erties and their relative cost is listed in the Table 1.
Zirconia toughened alumina (ZTA) is particularly interesting
research topic due to its diverse application. It can be utilized as
traditional applications like structural ceramic and cutting tools.
Alongside it has immense potential as a biomedical implant. ZTA
ceramics are mostly bioinert but addition of different oxides may
change this behavior. The motivation of selecting this material is
the lack of comprehensive analysis on the impact of different addi-
tives and their subsequent property enhancements. Addition of dif-
ferent oxides can improve the mechanical properties significantly.
One of the major drawbacks of the advanced ceramics is its low
toughness. The toughness of the ZTA can be enriched significantly
by the proper choice of additives. But in most design problem,
wholistically analyzed literature is required to judge the perspec-
tive of different additives. This review paper aims to solve this
issue by providing in depth analysis of different additives utilized
in ZTA.
This review will focus on the alteration and the trend of change
of mechanical properties of ZTA upon various oxide or metal inclu-
sions. Impact of additives such as MgO, Y2O3, TiO2, CeO2, CaO, Ag,
SrO. 6Al2O3, Cr2O3, Fe2O3, CuO, Ta2O5, Nb2O5, CuO, Er2O3 are exten-
sively discussed. The journal aims to identify the impact of inclu-
properties. Along with it, a comparative study is done to under-
stand which inclusion can help to get the best mechanical proper-
ties in certain conditions. An understanding of why certain
inclusions behave in the ZTA matrix in a certain way has also been
discussed.
2. Impact of oxide inclusions
2.1. Inclusion of magnesium oxide (MgO)
2.1.1. Introduction
MgO exhibits a low fracture toughness of 2.8 MPa.m1/2, with
density analogous to Al2O3 with a value of 3.58 gm/cm3 and a
low hardness value of around 5–7 GPa. Despite such handicaps,
the addition of MgO up to a certain threshold can lead to enhance-
ment of certain mechanical properties. Mahmood et al. [3] showed
a microhardness and fracture toughness improvement of the ZTA
ceramic after adding MgO of less than 0.3 wt%. From the literature
analysis in Table 2, it can be pointed out that the MgO addition is
limited to about 1.5 wt%. Although it has certain benefits that can
boast the mechanical properties, higher than 1.5 wt% addition can
have negative impact on the mechanical property of the ceramic.
High MgO addition can cause the formation of spinel as indicated
from the phase diagram of MgO-Al2O3. So, in most applications it
is limited to around 1.5 wt% addition.
2.1.2. Crystallinity
MgO may have strong dehydrative and dehydrogenative activ-
ity. Mg2+ is slightly higher in radius than Al3+ and has one less
charge. Due to this, they can generate P-semiconductor that leads
to dehydrogenative properties. Mg2+ is expected to embody leaving
intact basic structure [12]. In the case of MgO is doped in the alu-
mina matrix, the Kroger-Vink equation is as follows, [13].
0
ðMg x ÞAl $ ðMg 0 ÞAl þ h
Mg2+ represents a relatively negative charge when added to Al3+
matrix. This kind of doping may lead to dipole formation. It can
have high surface mobility that may lead to change of diffusion
co-efficient that can explain certain mechanical property change
with MgO addition. For Al3+ doping on MgO, cation vacancy forma-
tion and Al3+ ion replacing Mg2+ ion is described in the following
doping reaction by the ionic version of Kroger-Vink notation for
the ionic defect [14].
x  00
Al2 O3 þ 3ðMg 2þ
3þ
Þ $ 2ðAlMg 2þ Þ þ ðV Mg2þ Þ þ 3MgOðsrgÞ
Mg 2þ
where ‘srg’ defines a site of repeatable grain growth site like grain
boundary [9,10].
The formation of the lattice defect in the MgO-ZrO2 system has
been explained by the following Kroger-Vink equation[17]:
00

sions on ZTA so that it can be engineered to get the best MgO $ Mg Zr þ V ::o þ Oxo

Table 1
Comparison of mechanical properties of different advanced ceramics.

Ceramics Name Mechanical Properties Cost of References

Manufacturing
Density (g/ Vickers Hardness Elastic Modulus Fracture Toughness
cm3) (GPa) (GPa) (MPam0.5)
Zirconia Toughened 3.7–4.1 10–18 350–450 4–10 Moderate [3,4]
Alumina
Zirconia 6.1 12 201 6–15 High [5]
Silicon Carbide 3.1 26–30 300–330 4–5 High [6]
Silicon Nitride 2.2–3.4 15–40 140–310 4–9.5 High [7-9]
Alumina 3.9–3.95 17.65 380 3.3–5 Low [10,11]

2
S. Sarker, Homayra Tabassum Mumu, Md. Al-Amin et al. Materials Today: Proceedings xxx (xxxx) xxx

Table 2
Data showing impact of MgO addition on alumina and ZTA ceramic.

Phase system Composition Sintering Densification/density) Properties Additional comments Reference

temperature
(0C)
Al2O3-MgO Al2O3-0.03% MgO 1100–1550 98–99.9% Grain size: 0.2–3.5 mm Grain size increases with sintering [40]
temperature as porosity decreases
Al2O3-0.05% MgO 1100–1550 98.1–99.9% Grain size: 0.2–3.0 Grain size increases with sintering
micro-meter temperature as porosity decreases
Al2O3-MgO Al2O3-0.25% MgO 1600 89.83% – Densification is good for smaller [46]
(25 mm) particle size
Al2O3-0.25% MgO 80.804% Densification is poor for bigger particle
(90 mm) size
Al2O3-MgB2 Al2O3-5% MgB2 1450 3.58 Fracture toughness: 4 Density decreases but fracture [44]
Vickers microhardness: toughness increases with addition of
2.09 GPa MgB2
Al2O3-MgO Al2O3-0.1% MgO 1650 3.44 Vickers microhardness: Densification and fracture toughness [43]
2.07 slightly increase with MgO addition
Al2O3-0.3% MgO 3.48 Vickers microhardness: but Grain size decreases significantly.
2.08
Al2O3-0.7% MgO 3.76 Vickers microhardness:
2.275
Al2O3-MgO-SiC Al2O3- 1650 1.83% for 0 ppm MgO Vickers microhardness Both Vickers microhardness and [47]
(1–1000 ppm) 2. 94.3% for 1000 ppm increases from 10.5 to densification increases for small
MgO-5% SiC of MgO 15.5 for MgO addition addition of MgO
of 0 to 1000 ppm
Al2O3-MgO-YSZ Al2O3- 0.5MgO-20 1600 4.39 Vickers microhardness: Densification increases to more than [45]
wt.%YSZ 1680 Hv that of the ZTA upon minor addition.
Al2O3- 1 MgO-20 4.35 Vickers microhardness: But slowly decreases with increasing
wt.%YSZ 1680 Hv MgO. Vickers hardness gradually
Al2O3- 1.5MgO-20 4.28 Vickers microhardness: decreases as well.
wt.%YSZ 1645 Hv
Al2O3- 2MgO-20 4.2 Vickers microhardness:
wt.%YSZ 1650 Hv
Al2O3-MgO-YSZ-TiO2 Al2O3-0.5MgO-15Y 1520 4.00 Fracture toughness: 8.3 Mechanical property improves for [3]
SZ-0.5TiO2 Vickers Microhardness: addition up to 1 wt% MgO addition
1350 Hv then decreases slightly
Al2O3-0.5MgO-15Y 4.02 Fracture toughness: 9.2
SZ-0.5TiO2 Vickers Microhardness:
1375 Hv
Al2O3-0.5MgO-15Y 4.01 Fracture toughness: 9
SZ-0.5TiO2 Vickers Microhardness:
1340 Hv

Zirconia has a face-centered-cubic fluorite structure that is
stable at high temperatures. Replacing Zr4+ ion with the divalent
stabilizer of Mg2+ leads to defect structure. The defect structure
consists of disordered cation and randomly distributed oxygen
vacancies. As there are other structures than cubic zirconia, the
dopant may segregate at the grain boundary [18]. Also, with the
decline of temperature, as the cubic zirconia phase change to the
tetragonal phase, an oxygen vacancy is decreased resulting in
low oxygen diffusivity. If the Mg2+ concentration is more than
1 wt% then the divalent cations and the oxygen vacancies may
likely form neutral vacancy-dopant defect pairs [19]. It can be writ-
ten as,.
00 00
Mg Zr þ V ::0 $ ðMg Zr V ::0 Þ
This causes a reduction of high mobility oxygen ion through
free vacancy. However, if the inclusion is lower than 1 wt% then
the impact would not be prominent. Mainly, MgO doping or inclu-
sion can generate a solid solution and increase stability of fluorite
phase of ZrO2[10]. Hence, It can be used to stabilise the zirconia to
its high temperature phases. At high temperature(2400 °C) the lat-
tice parameter for cubic phase is around 5.272 Å [11]. The value
decreases with the decrease in temperature and is not stable at
room temperature. But extrapolating by considering temperature
dependence of thermal expansion co-efficient the value gets
around 5.090 Å[12]. A higher ionic radius in a lower ionic crystal
usually increases the lattice parameter. Mg2+ has a radius of
3
0.089 nm for co-ordination number 8 where Zr4+ has a radius of
0.084 nm with co-ordination number 8[13]. But, substituting Zr4+
by Mg2+ in the cation sublattice leads to loss of oxygen ions in
anion sublattice and that helps to decrease the lattice parameter
by a really small margin [14]. Although as the solid solution formed
by addition with c-ZrO2 decomposes at room temperature and lat-
tice constant dependency of cubic symmetry on dopant level is
complicated by MgO solubility in t, m-ZrO2 [19]. Still, lower MgO
usually means higher lattice parameter.
2.1.3. Phase diagram of MgO-Al2O3 system
Fig. 1 illustrated the phase diagram between the MgO and alu-
mina system. Here we can see that they have almost minimal sol-
ubility at the operating temperature range. In most cases, Minor
amount of MgO is added to the alumina phase. So, corundum is a
phase that is most likely to be present in the matrix. The solubility
limit is around 0.04 mol% for the addition of MgO. In terms of
higher addition of MgO, spinel can be found in the matrix. Since,
spinel is a glassy phase, that will degrade mechanical properties
such as fracture toughness, Vickers microhardness and flexural
strength. That explains why upon high degree of addition of MgO
leads to a poor mechanical property. That basic reason is the for-
mation of spinel. But for small degree addition, only corundum is
the possible phase that can be found and that leads to enhance-
ment of certain mechanical properties. For MgO rich spinel we
can also get periclase. However, that will not be common in the
minor addition of MgO on ZTA.
S. Sarker, Homayra Tabassum Mumu, Md. Al-Amin et al.
Fig. 1. Phase diagram of the MgO-alumina system[20].
2.1.4. Density
Coble [21] first showed that adding MgO can lead to near theo-
retical density for ZTA. The addition of MgO up to 1 wt% in the ZTA
matrix can increase densification significantly. However, for higher
MgO percentage, the microstructure contains both inter and intra-
granular voids that lead to lower density. There was a total of 4 dif-
ferent sets of theories regarding the mechanism that dictates den-
sity alteration upon MgO addition,.
1. MgO raises the diffusion co-efficient, lattice diameter, or bound-
ary area [15-21]. Consequently, smaller pore mobility increases
avoiding pore breakaway and abnormal grain growth.
2. The surface diffusion coefficient is increased upon MgO addition
that leads to higher pore mobility, Mp. The surface diffusion
mechanism enables the pore movement. Consequently, a larger
grain and larger pore at a given density are obtained [18,22,23].
3. MgO decreases the grain growth upon sintering as it decreases
the surface diffusion co-efficient. This theory investigates a
model where control of grain growth is done by pore drag [30].
4. MgO lowers the mobility of grain boundary and allows for pores
to stay stagnant to moving grain boundaries during sintering
[18,25-27].
If the first hypothesis is correct then that explains why MgO can
increase the density of ZTA. The high pore mobility will not only
generate a more homogenous matrix but also prevents large pore
formation. In ZTA especially, the volume expansion occurs due to
the phase transformation of zirconia, and small dispersed pores
can be filled or nullified more easily resulting in a dense ceramic.
If the densification is uniform, thus the mass transfer is isotro-
pic then local densification will happen at a similar rate to an
extent that there will be no difference between it and macroscopic
density. But in a practical scenario, it is nowhere near uniform. But
this uniform attribute can correspond with the kinetic theory.
However, MgO doping always provides a higher value according
to this theory than practice. The cause of this might be a slow
migration of pores that leads to a slow increase in distance
between pores. This explains the final stage densification and also
the statistical impact of kinetic theory leading to the inconsistency
described earlier. Ikegami et al. [26] further investigated that the
impact of magnesia mostly favours density enhancement than
4
Materials Today: Proceedings xxx (xxxx) xxx
grain refinement at 1400 °C. But for a sintering temperature below
that, the effect opposes..
Pore concentration is an essential parameter in this mechanism.
Provided the matrix is free of pore, it can be said that MgO will def-
initely help to form finer grain. On the other hand, this idea is con-
tradicted by Monty et al. [20,28] who concluded that in single
crystal, MgO helps to decrease surface diffusion co-efficient by
the factor of 10. So, it appears both density and rate of grain growth
increases for MgO addition. However, Berry et al. [25] found that
change in densification rate/grain growth is minimal and only
increase the fraction by 1.2.
Pore-boundary separation is another impact of the MgO. Har-
mer et al. [35] concluded that MgO causes rapid pore removal dur-
ing sintering. It also enhances pore mobility and reduces pore size
hence making it attached to the grain boundary.
MgO may also increases the oxygen diffusion coefficient in alu-
mina. One contributing factor might be that, as the impurity segre-
gation causes lowering of the surface tension, similar thing can
occur due to MgO as it causes decrease in surface tension. Since
segregation of any impurity decreases the surface tension of solid
in general, segregation of MgO causes a significant reduction of
surface tension. Also, MgO decreased the disparity between surface
tension and grain boundary tension of alumina [36] that MgO nar-
rowed the dispersion of surface and grain boundary dihedral
angles of alumina [22,31] that helps to remove pores from the sin-
tered sample at the final stage [26].
2.1.5. Grain boundary refinement
The most prominent impact of MgO is grain growth inhibition
of ZTA, precisely of alumina matrix. In pure alumina, grain growth
is not homogenous. Mostly high grain growth can initiate in high-
density regions. MgO suppresses inhomogeneous densification and
prevents alumina grain growth [38]. That can happen due to sev-
eral complex reasons that are handicapped by the problem of char-
acterization in the grain growth chemistry [39]. Kim et al. [40]
concluded that MgO doping has a minimum impact on resultant
densification and makes microstructure less sensitive to sintering
temperature through suppressing grain growth. Bennison et al.
[33] suggested that in a single phase with MgO, a concept called
the solute drag model becomes prominent. In this mechanism,
MgO seemed to cause segregation and create hindrance in solute
S. Sarker, Homayra Tabassum Mumu, Md. Al-Amin et al.
motion. The liquid phase transformation is even more complex
[24] and a total of 4 mechanisms are described. According to the
first mechanism, MgO acts as a scavenger and drags impurity ions
generating solid ions that in turn impose solute drag force on the
moving grain boundary. The second mechanism suggested that
magnesium oxide alters in interfacial energy that results in equal
wetting condition. The third mechanism said that addition of
MgO results in a partial crystallization of the liquid phase that
decreases intergranular matter transfer [39]. The fourth mecha-
nism suggests the same restraint of matter transfer through disso-
lution precipitation at grain boundary or by increasing viscosity.
Bennison et al. [41] suggested that MgO acts as a microstructural
stabilizer leading to a finer grain. It was also concluded that MgO
functions by reducing the mobility difference between un-wet
grain boundaries through pinning mechanism and grain bound-
aries wet by the intergranular liquid film. So many theories also
shed light on the behaviour of MgO. MgO, in general, has 2 sorts
of impacts, one is the impact that corresponds to high sensitivity
to experimental procedures. This leads to a high degree of variance
in the mechanism that leads to such inconsistency. The other form
of impact is insensitive to experimental procedures. Brook et al.
[42] described this phenomenon and further analysed by Ikegami
et al. [26]. It was mainly based on the migration of a grain bound-
ary between two grains with pores and has the following premise,.
1. The phenomena regarding mobility and migration of pore is
independent of that dictates grain-boundary migration. How-
ever, the total driving force for these migrations equals the total
force determined by its microstructure.
2. If the migration rate of a grain boundary exceeds that of the
pores, pore-grain-boundary separation will occur, leaving such
pores in the grain.
Fig. 2 illustrated two micrographs containing varying amount of
MgO in the alumina matrix [26]. From the microstructure, we can
see that upon addition of further MgO results in an average grain
size that is much shorter than the regular alumina grain. The
MgO addition leads to a much finer grain size and a significant
grain refinement for the alumina ceramics.
2.1.6. Hardness
Rittidech et al. [43] analysed a comparison between the hard-
ness of ZTA for MgO addition. The hardness value tends to increase
with the addition of magnesia up to 0.7 wt%. Further analysis by
Abdullah et al. [3] showed a similar trend as a result, only hardness
Fig. 2. (1) SEM image of Alumina containing 50 ppm MgO and (2) SEM micrograph of Alumina containing 1000 ppm MgO[26].
5
Materials Today: Proceedings xxx (xxxx) xxx
tends to drop after 1 wt% addition. Since MgO helps to create fine
grain boundary and dense ceramic and generates a low concentra-
tion of pore that enable the hardness value to increase initially. It
decreases after a certain value due to pore concentration and spinel
formation.
2.1.7. Phase analysis
XRD analysis by Abdullah et al. [3] confirmed the existence of
spinel for a sample containing more than 0.5 wt% MgO. The solubil-
ity of MgO in alumina is 75 and 175 ppm at temperatures of
1720 °C and 1880 °C [31]. So, the formation of spinel is evident.
Spinel can be of two types; one is stoichiometric spinel and
another is non-stoichiometric spinel. Non-stoichiometric spinel
can consist of magnesia rich or alumina rich constituents. Among
the two types alumina rich constituents are relatively denser
[20]. Also, microstructural studies showed well developed com-
pacted structure for stoichiometric and magnesia rich composi-
tions, but less developed small grains for an alumina rich one.
Hong et al. [44] suggested that strong vaporization of Mg allow a
columnar grain growth of MgO. Spinel may grow around Al2O3
and can be enhanced by adding MgB2.
2.1.8. Data analysis
Considerations: 1. percentages are taken in weight%. 2. Missing
data were not considered 3. Referenced journals may also contain
additional information that were disregarded due to the ease of
explanation. 4. Unitless parameters for density is in gram/cm3,
fracture toughness MPam0.5 and Vickers microhardness in MPa
unit.
The increase of fracture toughness may increase for a smaller
percentage of MgO due to its impact on creating more compact
composite and significant size reduction of grain. However, Azar
et al. [45] concluded for pure alumina that, although the initial
increase in fracture toughness is noticeable, it starts to decrease
after as low as 0.5 wt% for pure Al2O3-MgO system, and the
decrease is sharp since smaller grain can bear low load due small
grain bridges lower load-bearing ability. Beyond 1 wt% addition
it doesn’t depend on any microstructural phenomena, rather the
rule of the mixture itself. Since according to the rule of mixture,
more addition of MgO decreases the fracture toughness, the graph
of Fig. 3 follows accordingly. Different literatures were holistically
analysed in the Table 2 arranging all the different property com-
parison at different additivee levels.
A comparative study by Abdullah et al. [37] of mechanical prop-
erties at 1450 °C has been illustrated in the Fig. 3.
S. Sarker, Homayra Tabassum Mumu, Md. Al-Amin et al.
Fig. 3. Alteration of mechanical property upon addition of MgO on ZTA[37].
2.1.9. Fracture toughness
The increase of fracture toughness may increase for a smaller
percentage of MgO due to its impact on creating more compact
composite and significant size reduction of grain. However, Azhar
et al. [45] concluded for pure alumina that, although the initial
increase in fracture toughness is noticeable, it starts to decrease
after as low as 0.5 wt% for pure Al2O3-MgO system, and the
decrease is sharp since smaller grain can bear low load due small
grain bridges lower load-bearing ability. Beyond 1 wt% addition
it doesn’t depend on any microstructural phenomena, rather the
rule of the mixture itself. Since according to the rule of mixture,
more addition of MgO decreases the fracture toughness, the graph
follows accordingly.
2.1.10. Miscellaneous
Other properties like diametral tensile strength increase up the
addition of 1 wt% MgO since the reduction of pore and better den-
sification makes it hard for the crack to propagate. Also, as the den-
sity decreases after 1 wt% so does this property.
2.2. Inclusion of yttrium oxide(Y2O3)
2.2.1. Introduction
Y2O3 is used as a stabilizer for Zirconia. Its main use is for phase
modification and through that process helping to get better
mechanical properties in ZTA. Y2O3 has no direct impact on the
mechanical properties of ZTA. Rittidech et al. [48] found the best
mechanical properties for 4 mol% Y2O3 addition. The impacts of
Y2O3 addition closely correspond with the metamorphosis of zirco-
nia and that needs to be discussed first. Zirconia has three phases,
monoclinic, tetragonal, and cubic among them only monoclinic is
stable at room temperature. The tetragonal phase is stable at
around 1100–1900 °C and during its transition to the monoclinic
phase causes volume expansion that is detrimental for most
mechanical properties. Y2O3 addition in general helps with the sta-
bilization of higher temperature phases like the tetragonal and
cubic phase of zirconia[43-47]. Tetragonal to monoclinic transfor-
mation might be martensitic in nature and occur due to a lack of
6
Materials Today: Proceedings xxx (xxxx) xxx
surface relief and habit plane [47-49]. The transformation also
causes a deformation twin to occur [55]. Becher [56] analysed that
crack growth of alumina ceramic can be significantly reduced by
dispersed partially stabilized zirconia and its impact is mainly on
the degree of stabilization. In general, the stabilization of zirconia
refers to the higher stability of the tetragonal phase of room tem-
perature. The higher percentage of tetragonal zirconia leads to bet-
ter transformation toughening. The monoclinic phase of zirconia
can lead to a higher concentration of microcrack in the ZTA matrix.
There is a critical value for the grain size of zirconia over which
transformation toughening could occur. But, a higher percentage
of zirconia leads to a higher percentage of monoclinic zirconia.
When zirconia is present in a low percentage, the matrix mostly
consists of tetragonal zirconia. This impact creates a portrait of
why the stabilization of zirconia is a priority. Claussen et al. [57]
showed that un-stabilized zirconia provides a poor fracture tough-
ness while added to pure alumina since adding more zirconia in
ZTA will generate more monoclinic fraction. (After addition of
around 15 wt% zirconia).
2.2.2. Phase analysis
Rittidech et al. [48] illustrated a trend of monoclinic and tetrag-
onal zirconia fraction with changing Y2O3. It can be analysed that,
adding Y2O3 up to 4 vol% provides the highest stability of tetrago-
nal zirconia, and then decreases significantly after that. Over stabi-
lized zirconia may still degrade mechanical properties.
For analysing why Yttrium oxide helps to generate a high-
temperature phase of zirconia, the phase diagram illustrated at
the Fig. 4 needs to be analysed [58].
Lefevre et al. [59] has found the existence of the tetragonal
phase in zirconia rich element at room temperature. Further
refinement of peritectic points and other parameters have been
found throughout various works [54-58].
According to the phase diagram around 3 mol% addition of Y2O3,
which is around 4–7 wt% can increase the stability of tetragonal
zirconia at a temperature much lower than its equilibrium temper-
ature. Hence, if the cooling rate is fast enough, ZTA will have a
higher percentage of tetragonal zirconia than anticipated. The free
S. Sarker, Homayra Tabassum Mumu, Md. Al-Amin et al.
Fig. 4. Phase diagram of Yttria- zirconia phase system [58].
energy also reduces through this process. The cooling rate is
another determining factor. If the cooling rate is slow, then more
monoclinic fraction will generate by transformation and is highly
undesirable [64].
2.2.3. Ionic solubility
Stabilization by Y2O3 involves the displacement of an oxygen
atom in the fluorite structure that affects stability [65]. The pres-
ence of anion such as chloride, sulphate, phosphate can lead to sta-
bilization of the tetragonal zirconia phase at room temperature
[66]. Hence, Oxygen vacancy is significant in this mechanism of
Y2O3 [67]. Basu et al. [68] adopted Kroger-Vink notation to write
the defect reaction for zirconia doped by Y2O3 as,
Y2 O3 ! 2Y0 Zr + 3Oo x + Vo ::
Where, Y0Zr = yttria atom in zirconia lattice site, Oxo = oxygen atom in
normal lattice site, and V..o = a vacancy at an oxygen lattice site. The
disorder is induced in a zirconia-yttria system by increasing oxygen
vacancy concentration and thus stabilizing tetragonal zirconia at
room temperature.
Sakuma et al. [69] interpreted the transformation as second-
order and suggested that the t0 -t + c decomposition involves a spin-
odal, where the anion vacancies are important in stabilizing the c
phase. The t0 doesn’t undergo the stress-induced t-m transforma-
tion [53,65]. The cubic phase of zirconia added with 3 mol% yttria
and being subjected to a faster cooling rate can do a diffusion-less
transformation to form t0 . Meanwhile, c-t transformation involves
long-range diffusion [71]. Hayakawa et al. [72] concluded that this
transformation leads to surface relief. Notably, the tetragonal zir-
conia obtained has a herringbone structure. Fig. 5 illustrated the
individual structure of the zirconia and yttria individually and
the change of the microstructure upon their addition. The Yttria
stabilised zirconia can take a cubic fluorite structure.
2.2.4. Low temperature degradation of zirconia
ZTA with yttria exhibits a really poor mechanical property when
subjected to moist air or hot water in around 230 °C. The water
vapor induces a tetragonal to monoclinic phase transformation of
zirconia that helps to degrade strength significantly. In efforts to
investigating its mechanism, Schmauder et al. [73] suggested that
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Materials Today: Proceedings xxx (xxxx) xxx
Fig. 5. Crystal structure of zirconia, yttria and combined.
stress corrosion of the tetragonal zirconia phase causes this and
further microcrack helps for water to migrate on the surface.
Meanwhile, at that temperature range, Yttrium hydroxide is more
stable than yttria [74]. Lange et al. [75] suggested that, since
yttrium has low activity in zirconia structure, it will be leached
out and form hydroxide. Due to this, there will be regions depleted
of yttrium which enables the transformation. But that must be con-
trolled by slow diffusion of Y3+ because diffusion of water molecule
inside the matrix will take approx. 1021 years for 1 nm depth only
which is impossible [76]. So, this model cannot explain the phe-
nomena. Among the other possible theories, Sato suggested that
the transformation is first-order concerning tetragonal zirconia
and non-aqueous solvents containing a lone-pair electron orbital
opposite a proton donor site also accelerated the tetragonal-to-
monoclinic phase transformation. It was also concluded that a
higher percentage of yttria in the matrix helps to keep the transfor-
mation to a minimum. In short, it provides the idea of anion diffu-
sion being responsible for the transformation. Analogous to this
concept, Yoshimura et al. [77] observed –OH formed at the surface
of the material and further theorized that migration of –OH at the
surface accumulates stresses to prepare nucleating defects. This
enables the nucleating of the monoclinic phase at tetragonal grain.
To solve this issue, Sato et al. [78] aged the sample for 168 h at
100 °C to suppress the degradation of strength. Watanabe tried
to age Y-TZP at 300 °C for 1000 h. Such a mechanism can stabilize
the tetragonal [48] zirconia, slowing degradation of property.
Nitriding the surface of the ceramic also seems to work. However,
the t0 phase is not sensitive to water-related damage at high
temperatures.
2.2.5. Conclusion
In conclusion, the main impact of yttria in ZTA is its impact on
the stabilization of zirconia. It also leads to a better toughness of
ZTA and minor grain boundary refinement. Microcrack size during
S. Sarker, Homayra Tabassum Mumu, Md. Al-Amin et al.
the transformation toughening can also depend on both the parti-
cle size and stabilizing agent yttria. In the sample 3 wt% yttria has
been used which is the optimum value of grain growth and phase
transformation.
2.3. Inclusion of Titanium oxide (TiO2)
High hardness from alumina and high toughness from zirconia
is combined in ZTA ceramics that are used as biomaterials and den-
tal ceramics. But to decrease the sintering temperature of ZTA,
additives are used. TiO2 is the most commonly used and the most
effective additive for enhancing the sintering and mechanical
behaviour of ZTA [74,75]. The effect of TiO2 addition on the
microstructure and mechanical properties depend on the composi-
tion of the ZrO2 /Al2O3 system, the mole fraction of TiO2, sintering
conditions like sintering temperature (TS) and dwell time, solubil-
ity of TiO2 in that system at TS.
A. Khaskhoussi et al. demonstrates the effect of TiO2 addition in
different systems containing varying amounts of both ZrO2 and
Al2O3. It has been observed that composites containing high
Al2O3, an equal amount of ZrO2 and Al2O3, and high ZrO2, form dif-
ferent phases and hence affected differently due to the addition of
TiO2 [81].
Doping in alumina within solubility limit:
Values of the ionic radius of the ions present in the system are
Ti4+ is 0.0745 nm, Ti3+ is 0.064 nm, Zr4+ is 0.086 nm, Al3+ is
0.057 nm, Y3+ is 0.102 nm for and O2 is 0.138 nm [75-77]. While
doping in alumina, since Ti4+ ions are larger than Al3+ ions, they dif-
fuse in Al2O3 lattice by substituting Al3+ ions and the Kröger-Vink
notation is as follows [83]:
 000
3TiO2 $ 3TiAl þ V Al þ 6OXO
When Ti4+ substitutes Al3+, 1 mol positive charge generates. To
balance the change in crystal, 1 mol of Al vacancy is generated for
3 mol Ti4+ substitution. Thus, TiO2 addition enhances the vacancy
concentration of Al.
The Kröger-Vink notation for substitution of Al3+ ions by Ti3+
ions are:
X
TiO2 $ TiAl þ 2OXO
Titanium ions are larger than Al3+, and thus their substitution
distorts the lattice. The lattice parameters ‘a’ and ‘c’ increase,
resulting in an increment of unit cell volume of Al2O3 with increas-
ing TiO2 content [84].
But when TiO2 is added in ZTA systems or YSZ, CeO2-ZrO2 smal-
ler ions of Ti4+ substitute Zr4+ forming a solid solution[85]:
X significantly smaller than ZrO2, a solid solution of (Zr, Ti)O2 forms.
TiO2 $ TiZr þ 2OXO
Since Ti4+ ions are smaller than Zr4+ ions, this substitution dis-
torts the lattice, the lattice parameter a and c decreases. The vol-
ume of a unit cell also decreases with higher TiO2 content [85].
TiO2 enhances t-ZrO2 retention [76,81]. As TiO2 reduces the par-
ticle size of ZrO2, some become smaller than the critical size
required for tetragonal to monoclinic transformation. Higher TiO2
content reduces transformability and thus gradually increasing t-
ZrO2 retention [113,118].
TiO2 addition in alumina rich system within solubility limit
enhances densification [74,81-83]. TiO2 addition increases density
of Al3+ vacancy in the structure resulting in enhanced diffusivity of
Al3+ [82-84]. Thus, densification improves, and bulk density
increases. The grain size of Al2O3 decreased gradually due to the
pinning effect of TiO2 as the concentration of TiO2 approaches its
solubility limit [85,86].
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Materials Today: Proceedings xxx (xxxx) xxx
2.3.1. Solubility
Solubility of TiO2 depends on zirconia, phase of zirconia, and
temperature. Solubility increases with increasing sintering tem-
perature. For a fixed temperature solubility in zirconia depends
on the stabilizer and its concentration. At 1600 °C solubility in
3YSZ is 14–16 mol% whereas in 6YSZ solubility is 18 mol%. In zir-
conia stabilized by 12 mol% CeO2 solubility limit is 10 mol% at
1400 °C [83]. Solubility of TiO2 in Al2O3 is 0.27 wt% at 1300–
1700 °C [84,87]. According to Abdullah Al Mahmood et al, the
range of solubility limit is 0.15–0.35 mol% [80].
TiO2 has limited solubility in ZrO2 thus when added in ZTA
beyond that limit Ti diffuses out of solid solution (Zr, Ti)O2 or pre-
cipitate as a transitory phase ZrTiO4 and reacts with Al2O3 forming
a secondary phase at the grain boundary according to the following
reaction at temperatures above 1280 °C [74,75,85]:
ZrTiO4 + Al2 O3 ! Al2 TiO5 + ZrO2
TiO2 + Al2 O3 ! Al2 TiO5
Al2TiO5 has larger and elongated grains that elongates further
with increasing TiO2 content. Thus, the grain size increases gradu-
ally. Bulk density increases while adding TiO2 up to the solubility
limit and then decreases as Al2TiO5 has a lower density than both
Al2O3 and TiO2 [91]. Relative density increases rapidly up to 100%
with TiO2 addition approaching its solubility limit [75,76]. Hard-
ness and bending strength increase and reach maximum value
for TiO2 content equal to solubility limit then decreases gradually
with increasing TiO2 amount as these properties depend mainly
on grain size for ZTA [91].
Fracture toughness increases with increasing TiO2 content up to
solubility due to the increasing phase amount of t-ZrO2. But it has
been observed that higher TiO2 content decreases transformability
drastically [81]. This means transformation toughening decreases.
But doping beyond solubility results in the formation of Al2TiO5
which is of elongated shape. Thus, Al2TiO5 deflects crack and
changes its path to multiplane. It, changes crack mode from trans
granular to intergranular and hence increasing fracture toughness
with increasing TiO2 content [93].
Modulus of elasticity of TiO2 are around 110 GPa [89], Al2O3
360–400 GPa [94], ZrO2 200–220 GPa [94], Al2TiO5 around 105
GPa [95].
With increasing TiO2 addition in ZTA, elasticity reduces linearly
according to the rule of mixture. Modulus of elasticity also
degrades due to larger grain size formed with higher TiO2 content.
At higher temperatures, TiO2 behaves in a more inelastic way thus
reducing elastic modulus further.
When TiO2 is added in YSZ or ZTA where the Al2O3 fraction is
ZrTiO4 of Orthorhombic structure (ICDD data 00–034-0415 [81])
forms at a temperature above 1300 °C when doped beyond its sol-
ubility limit [79]. With higher addition of TiO2 content, the fraction
of ZrTiO4 phase increases [81]. This ZrTiO4 phase enhances the
grain growth of ZrO2 [86] and reduces densification [96] during
sintering by increasing sintering temperature. Since the grain size
of ZrO2 increases progressively, density decreases with the addi-
tion of higher TiO2 in zirconia rich systems. Fracture strength and
hardness increase slightly when doped within the solubility limit
and decreases gradually with further addition due to larger grains
[74,76,80]. The slight increase is due to intergranular nano disper-
sion with a small addition of TiO2 [85]. Ti3+ reduces the t-m trans-
formability of ZrO2 by reducing lattice parameters below the
critical size required for transformation. Elastic modulus decreases
with the addition of TiO2 due to the solid solution of (Zr, Ti)O2 that
forms in the lattice [85].
S. Sarker, Homayra Tabassum Mumu, Md. Al-Amin et al.
2.3.2. Microstructural analysis
It can be concluded that the content of TiO2 influenced the
Al2O3 and YSZ grains. In TiO2 undoped ZTA samples, the crack
propagates through the grains in trans-granular mode by following
an almost straight path. But in TiO2 added ZTA, the crack was
deflected by the elongated Al2TiO5 phase and followed a longer
path along the grain boundaries which is known as intergranular
mode. Thus, Al2TiO5 deflects crack and changes its path to multi-
plane. It, changes crack mode from trans-granular to intergranular
and hence increasing fracture toughness with increasing TiO2 con-
tent [93].
2.4. Inclusion of CeO2
TZP ceramics are widely used for medical purposes because of
its high strength and bio-inertness. But TZP undergoes slow phase
transformation from tetragonal to monoclinic ZrO2 in the presence
of water or steam at a wide temperature range of 60–500 °C. This
phenomenon is known as low-temperature degradation (LTD) or
hydrothermal degradation. The t-m martensitic transformation is
accompanied by 4–5% volume expansion which generates stress
and microcracks resulting in a drastic decline in mechanical prop-
erties [97]. Stabilizers and additives are introduced to prevent LTD
and CeO2 is the most common choice for biomedical grade TZP and
ZTA.
The advantage CeO2 has over other stabilizers (mainly Y) is
that it has good aging (hydrothermal degradation) resistance
in moist environment and has better fracture toughness
[76,92]. It has a very stable structure, high thermal stability,
high hardness, and corrosion resistance [85,93-95]. The transi-
tion zone for CeO2 stabilization is the largest [101]. CeO2 is
better than Y as Ce-TZP has higher fracture toughness than
Y-TZP. CeO2 is cheaper but Ce-TZP has lower hardness than
Y-TZP[102].
CeO2 has high reactivity than most other rare earth elements
found in nature [85,93] due to its high Oxygen storage capacity
resulting from ample oxygen vacancies and low redox potential
between Ce3+ and Ce4+ [93-95]. Thus, when ZTA is doped with
CeO2 exceeding the limit of solid solution the following reactions
occur [93,95]:
CeO2 + Al2 O3 ! CeAlO3
Ce4+ is completely reduced by Al2O3 at high temperatures. Ce3+
ions substitute Al3+ ions.
Fig. 6. Crack propagation behaviour for ZTA sample containing (1) 0 wt% Titanium oxide (2) 7 wt% Titanium oxide[93].
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Materials Today: Proceedings xxx (xxxx) xxx
Ce2 O3 + 11Al2 O3 ! Ce2 O3 . Al2 O3 + 10 Al2 O3
! Ce2 O3 .11Al2 O3 ! 2CeAl11 O18
This reaction occurs at 1200–1400 °C [103]. Both reactions are
reversible. CeO2 reactions are highly dependent on atmosphere
[93,99,100].
CeAl11O18 has elongated grains consisting of 4 oxygen layers
stacked in HCP, 1 layer of Ce2O3 whereas Al2O3 has oxygen layers
stacked in HCP [93,101]. The elongated grain size could be the
result of distortion generated in the lattice layers resulting in lat-
tice expansion because of Ce4+ (0.097 nm) ion reduction into larger
sized Ce3+ (0.114 nm) ion [93,101]. Grain size of CeAl11O18
increases with increasing CeO2 content [98].
According to the equilibrium phase diagram of CeO2-ZrO2, (il-
lustrated on Fig. 6) monoclinic solid solution of ZrO2 and CeO2 exist
up to 10 mol% CeO2 addition below 1000 °C. Tetragonal ZrO2 and
CeO2 solid solution is stable above 1000 °C up to 20 mol% CeO2
addition. For higher CeO2 addition (>20 mol%), solid solution of
cubic ZrO2 along with tetragonal phase exist [96,102]. Optimum
CeO2 content is 12 mol% for stabilizing TZP [102].
When CeO2 is added to the ZTA system, larger-sized Ce4+ ion
substitutes Zr4+ in the lattice creating large distortion. Thus lattice
parameters increase with the progressive addition of CeO2
[98,103].. If CeO2 is added to the YSZ system, Ce4+ ion substitutes
Y3+ because it has similar valance like Zr4+ ion. Addition of
5–10 mol% CeO2 in CeO2 stabilized ZTA results in formation of
Ce0.5Zr0.5O2. With further addition 15–20 mol% Ce0.6Zr0.4O2 and
Ce0.7Zr0.3O2 phase form [103]. Excess CeO2 also reacts with ZrO2
and forms compounds like (in Al2O3-YSZ-TiO2), Ce2Zr3O10 (in ZTA).
When the optimum level of CeO2 is added to ZTA, Ce3+ ion
increases the grain boundary mobility of Al2O3 by forming a glassy
phase boundary (knows as fluxing). The mobility of the grain
boundary of Al2O3 is more than that of intergranular ZrO2 particles.
Thus, the Al2O3 grain boundary breaks away from the particles
[92,104,105]. The addition of CeO2 enhances the grain growth of
both Al2O3 and ZrO2.
Porosity decreases reaches its minimum as the concentration of
CeO2 approaches its solubility limit. When added beyond solubil-
ity, CeO2 forms the CeAl11O18 phase of elongated shape. With more
CeO2 content CeAl11O18 phase content rises too, resulting in more
heterogeneous grain size and distribution. The spherical grains of
Al2O3, ZrO2, and elongated grains of CeAl11O18 phase cannot pack
closely and remove pores. Thus, porosity increases when CeO2 is
added beyond its solubility.
S. Sarker, Homayra Tabassum Mumu, Md. Al-Amin et al.
The bulk density increases up to the solubility of CeO2 is attrib-
uted to the following factors:
 True density of CeO2 is 7.65 g/cm3 which is higher than both
Al2O3 and ZrO2 [98].
 CeO2 addition stabilizes ZrO2 into the tetragonal phase which
has a higher density than the monoclinic phase. Increasing
CeO2 content increases the tetragonal ZrO2 phase fraction and
decreases m-ZrO2.
 Decreasing porosity.
Density then declines with further addition due to increasing
pores and larger grains of CeAl11O18 [96,100]. A similar trend has
been observed in hardness values as it depends on bulk density
and porosity. Due to the refractory behaviour of CeO2 being a rare
earth oxide, its addition decreases shrinkage [111]. Densification
decreases as a result of decreased grain boundary diffusion with
increasing CeO2 [111]. Salma M. Naga et al. showed in his work
that of CeO2 improves densification and lowers sintering tempera-
ture [103]. Fig. 7 shows the change of mechanical properties upon
addition of CeO2 to ZTA. We can see that, almost all the mechanical
property improved up to 5 wt% in this particular case.
The addition of CeO2 up to the solubility limit increases fracture
toughness of ZTA as CeO2 increases tetragonal phase percentage
which enhances stress-induced transformation toughening. But
addition beyond solubility forms elongated CeAl11O18 phase.
Although elongated shaped, CeAl11O18 grains cannot deflect crack.
Instead, it allows propagation straight though it via a trans granu-
lar mechanism [93,100]. Thus fracture toughness degrade gradu-
ally with further addition of CeO2 [93,100]. However, Rajeb et al.
explained the initial increment in fracture toughness in his work
by claiming that the CeAl11O18 phase deflects crack too many
planes around the grain, increases crack path, and leads to inter-
granular crack propagation mechanism [105]. Fig. 8 showed the
Fig. 7. Phase diagram of zirconia-ceria system[101107].
10
Materials Today: Proceedings xxx (xxxx) xxx
crack propagation through ceria-stabilised ZTA. The crack deflec-
tion however is not apparent from this particular image. However,
the propagation crack may different with the interfaces. Like in this
figure an intra-granular crack propagation is observed. But Akin
et al. showed a micrograph of fracture surface of CeO2 doped
ZTA, where crack propagated in trans-granular mode through the
CeAl11O18 grain [98]. Fig. 9 illustrates the scanning electron micro-
scope imaging of the cerium oxide stabilised ZTA.
2.5. Inclusion of silver (Ag)
2.5.1. Introduction
ZTA is highly regarded as a material to have potential as bio
ceramic. Among all the additional mechanical properties a bio
ceramic should have, bioactivity, anti-bacterial, and the anti-
inflammatory property is considered to be significant. The inclu-
sion of silver leads to minimal mechanical property improvements.
But, its property regarding its cellular response is something worth
considering. Silver doped ZTA also has potential on dental implants
[112].
2.5.2. Biological application
Silver has good biocompatibility and contains no toxicity espe-
cially on mammalian cells [108,109]. Shih-fu et al. [115] experi-
mented with the antibacterial properties of Ag while added with
ZTA. For the experiment, a gram-positive bacteria Staphylococcus
Aureus and a gram-negative virus E. coli is considered. Silver in
the ionic form gets absorbed into the surface of the negatively
charged bacterial cell and destroy its cell wall and membrane. Sil-
ver also stopped cell division from occurring while creating hin-
drances on cell integration [116]. Silver has good anti-bacterial
property against gram-positive Staphylococcus Aureus but has less
impact on E. coli. At that work 4 wt% silver inclusion resulted in a
98.6% antibacterial rate of S. aureus and 87.9 wt% E. coli.
S. Sarker, Homayra Tabassum Mumu, Md. Al-Amin et al.
Fig. 8. Graph showing impact of CeO2 addition on the mechanical properties of ZTA[103].
Fig. 9. A Scanning electron microscope image of crack surface containing Cerium
oxide stabilised ZTA[105].
2.5.3. Densification
Including silver to the ZTA matrix prohibits the densification of
the alumina matrix. Silver has a melting point 960 °C which a lot
lower than the average sintering temperature. Consequently, Silver
is mostly present in grain boundary prohibiting grain growth of
alumina. Also, Silver has more tendency to wet zirconia than alu-
mina [105,112]. Due to that, zirconia particles get attached to silver
particles and increases the inclusion size for silver. Due to this
mobility, grains containing silver are replaced by pore thus
decreasing density. Also, a significant portion of silver gets evapo-
rated during the sintering operation and creates a vacancy in the
form of a pore [119]. Taking the rated density value of 3.95 gm/
cm3 for Al2O3, 6.1 gm/cm3 for YSZ, 10.49 gm/cm3 for silver the den-
sity can be assumed to be 4.31 g/cm3 for 5 wt% YSZ, 5 wt% Silver
and 90 percent alumina and 4.74 g/cm3 for 10 wt% silver, 10 wt%
YSZ and 80 wt% Al2O3. These data was collected for a sample that
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Materials Today: Proceedings xxx (xxxx) xxx
is subjected to a sintering temperature of 1600 °C(considering
the obtained densification of 98.3% for the initial and 98.5% for
the latter) [113,114].
2.5.4. Microstructure
Silver is highly visible in the microstructure of the ZTA ceramic.
In the Fig. 10, we can see different microstructures of ZTA contain-
ing silver particles. Mostly they are well dispersed in the matrix
due to the process route of the system. Silver due to its highly
dense nature can generate a proper dispersion and wetting condi-
tion with the ZTA ceramic. In the figure we can see the nano-
particles being dispersed as an agglomerate or dispersed in
between the particles of the alumina and zirconia [107,113,114].
Along with it, the crack surface morphology shows a significant
bit of crack deflection due to the second phase addition of the sil-
ver. The silver nano particles seem to be deflecting the crack along
the interfacial separation between alumina and silver. Along with
it, the length increase of the crack path should contribute towards
the toughness increase of the matrix. The fracture surface of the
microstructure containing silver and ZTA shows a semi-brittle frac-
ture. The particle separation of single silver particle is not notice-
able. That leads to the conclusion that the crack propagation
path another the separation between foreign silver particle and
ZTA requires less energy than the general intragranular crack prop-
agation path. So, crack bridging, crack deflection will be the more
prominent toughening mechanism other than toughening due to
the silver material bulk itself.
2.5.5. Fracture toughness
Silver, much like Zirconia, has been used as an additive to alu-
mina for improving toughness. The toughness in this ceramic
matrix depends strongly on the grain size. As the increase of grain
size will effectively create more flaws in the matrix [115,116]. Due
to this fact, silver and zirconia’s ability to prohibit grain growth in
the matrix should consequently enhance toughness. When silver is
added to ZTA, it can create a synergy impact. The synergy impact is
observed when elements like SiC whiskers or Zirconia is added to
S. Sarker, Homayra Tabassum Mumu, Md. Al-Amin et al.
Fig. 10. (1) Silver nanoparticle in the YSZ-Ag9.5 grain [107] (2) Polished and thermally etched sample of ZTA with 15 wt% silver [113] (3) Fracture surface of ZTA containing
10 wt% silver [113] (4) Polished surface containing crack propagation in ZTA containing 15 vol% silver [114].
mullite or alumina. This theory concludes the increment of the
toughness of a matrix will be almost equal to the sum of the indi-
vidual toughening agent [117,118]. So, if A and B are two toughen-
ing agents then,
DK ICðAþBÞ ¼ DK ICðAÞ þ DK ICðBÞ
Silver has obvious toughening properties as previously men-
tioned. But, the toughness increment for silver addition in ZTA is
lower than the sum of their individual toughness increment when
subjected to ZTA. Silver is a soft metal and much of its toughening
property for ZTA is done through the transformation toughening as
previously discussed. The soft silver matrix absorbs a lot of the
impact of fracture stress through plastic deformation. Which is
why the synergy effect is not prominent [125]. But the highest
toughness can be found in 7.5% zirconia and silver.
2.5.6. Elastic modulus
However, the inclusion of silver also decreases the elastic mod-
ulus of the matrix. The elastic modulus of ZTA follows a linear rule
of mixture. The elastic modulus of silver is only 76 GPa. Also, as
previously mentioned, silver nullifies the impact of transformation
toughening that can lead to a more consolidated grain which is also
a reason for poor elastic modulus. Due to the inhibition of grain
growth, the flexural strength also increases with silver addition.
2.5.7. Miscellaneous
Increasing silver will coarsen the matrix of silver. Hence as the
amount of inclusion increases the more it is likely to contact each.
The particle size of the zirconia and silver in alumina–zirconia-
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silver composites in larger than alumina–zirconia and alumina-
silver composites.
The toughness of composite, however, does not enhance lin-
early with the increase of the inclusion because,
1. The increase of inclusion percentage, increase the chance of
inclusions to interact with the crack.
2. Coarsening due to relatively better wetting between zirconia
and silver reduces the number of dispersed inclusions [126].
This dual impact shows such a contradictory result. It was pre-
viously mentioned that the inclusion of silver reduces the elastic
modulus of the matrix. That eases up the matrix and helps for
the transformation of zirconia (tetragonal to monoclinic) that
reduces transformability. Here the percentage of toughness
increase is higher than the elastic modulus decrease making the
inclusion of silver beneficial overall.
2.6. Inclusion of chromium oxide (Cr2O3)
2.6.1. Introduction
Chromium oxide is used in ZTA for the enhancement of several
mechanical properties like wear resistance, hardness, and tough-
ness. For application regarding ZTA cutting tools, chromium oxide
can have significant benefits [127].
2.6.2. Crystallinity
The solid solution of alumina and chromium oxide follows
Vegard’s Law [128]. Alumina and chromium oxide thus form an
S. Sarker, Homayra Tabassum Mumu, Md. Al-Amin et al.
iso-valent solid solution where an atom or ion can interchange as
they are a similar entity of the same charge in the parent structure.
Both alumina and chromium oxides are sesqui-oxide and have a
similar corundum crystal structure. Here Al3+ and Cr3+ ions occupy
two-third of the available octahedral site in the closed pack hexag-
onal structure [129]. This can be confirmed further by the fact that
the inclusion of chromium oxide in ZTA increases the lattice
parameter as predicted. At higher temperatures (above 1000 °C),
a range of solid solutions can be obtained. Roy et al. [130] investi-
gated the sub-solidus phase equilibrium(in temperature range
370–950 °C) and found a miscibility gap. Two phases were in the
form of (Al, Cr)2O3 (pink ruby) and (Cr, Al)2O3. Among the two crys-
talline phases, one is alumina rich and another one is chromium
oxide rich.
2.6.3. Stabilization impact
Chromium oxide can stabilize zirconia to its high-temperature
phases. After adding a significant amount of chromium oxide in
the ZTA, the tetragonal and cubic phase gets relatively stabilized.
The retention of the tetragonal phase at room temperature has
nothing to do with the formation of a solid solution. Stabilization
occurs due to strong surface interaction between zirconia and
chromium oxide [131]. The tetragonal to monoclinic phase trans-
formation of zirconia can be inhibited by altering oxygen vacancies
associated with Zr ion [132]. Stephanic et al. [131] suggested that
Cr2O3 adsorbed on the surface of Zirconia and prevent it from
accessing oxygen. The mechanism is similar to the adsorption of
sulphate ion on zirconia [133]. Since the mechanism involves
adsorption, at low chromium oxide content, the impact would be
insignificant due to low shielding but after the addition of around
5 wt% chromium oxides, it would be noticeable. Ray et al. [134]
showed that the presence of chromium ion can stabilize the cubic
zirconia phase at as low as 950 °C in the polymer precursor solu-
tion. However, at a solid-state synthesis scenario of ZTA, stabiliza-
tion of cubic zirconia by chromium oxide is yet to be confirmed.
Though in a system with alumina, Tadahisa et al. [135] showed
that chromium oxide addition increases monoclinic fraction and
lattice parameters. So, the impact of chromium oxide on zirconia,
in the ZTA matrix is still unclear. Since the lattice parameter of zir-
conia in ZTA increases with chromium oxide addition and mono-
clinic zirconia has 5% more volume than the rest, it’s easy to
assume that the impact mentioned earlier only occurs when
Cr2O3 is added with zirconia only. But, other aspects like fracture
toughness increased with chromium oxide addition and that can
be attributed with a finer grain refining caused by tetragonal zirco-
nia. Ahmad et al. [136] showed that this theory can be right. Fur-
ther research has to be done in this remark to confirm this
conflicting phenomenon.
2.6.4. Densification
The addition of chromium oxide will decrease the densification
of ZTA. It also reduces the sinterability of the matrix [137]. In the
presence of air, chromium oxide is subjected to vaporization and
condensation that leads to significant weight loss [138]. Addition-
ally, pore formation is accelerated and the impact of condensation
is more severe if the percentage of chromium present is higher.
Pore formation leads to significant mechanical property degrada-
tion and leads to poor densification. Thus in ZTA composite, for
the better mechanical property, the percentage of chromium is
kept low [139]. This problem can be partially solved by hot press-
ing the sample that leads to the more dense and homogenous grain
[140]. Also, in the alumina-chromium oxide system, chromium is
the only mobile cation. The preferred mode of transport of chro-
mium ion is as vapor. The diffusion coefficient of that is signifi-
cantly higher than that in the solid-state. The vaporization of
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Materials Today: Proceedings xxx (xxxx) xxx
excess chromium controls the diffusion process, hence full densifi-
cation is not generally observed.
2.6.5. Grain size distribution
Riu et. al [141] investigated the aspect of isostatically hot
pressed alumina-chromium oxide composite. The grain of isostat-
ically hot pressed alumina-chromium oxide composite has little
chromium on the core region. But the surrounding cell is rich in
chromium. This behaviour occurs due to the fact that diffusion of
chromium is high at the grain boundary than in the bulk of alu-
mina. The activity of chromium with alumina is minimal. Ionic
motion is mainly prevalent in the diffusivity layer. Between 650
and 1250 °C, ionic motion is the overriding mechanism of transport
of high diffusivity layer [142]. The impact of Cr2O3 is dependent on
the migration of the grain boundary that occurs due to the coher-
ency of strain energy [143]. In the composite having higher chro-
mium than 2 mol% exhibits a bimodal grain size distribution.
Bimodal grain distribution implies that there will be an equally
high percentage of large and small grains and a low percentage
of grains of in-between sizes. At this composition large plate-like
grain form due to heterogeneously distributed Cr2O3. As long as
the concentration of Cr2O3 stays low, only a fraction of large
plate-like grain can form creating bimodal grain size distribution.
But at higher concentrations, the grain growth occurs significantly
faster and leads to a high percentage of smaller grain. Fig. 11 shows
the grain size reduction of alumina and zirconia upon addition of
chromium oxide.
2.6.6. Fracture toughness
Fracture toughness increases with the addition of Cr2O3 com-
paring to pure alumina. But it then decreases to as low as pure alu-
mina due to the formation of the pore as previously discussed. The
increase of toughness may be due to the formation of large plate-
like grain since it increases crack bridging. It may also increase the
flaw tolerance of alumina [141]. But after a certain percentage of
chromium addition, fracture toughness drops and it goes even
lower than pure alumina. Lack of densification and pore leads to
this problem. Azhar et al. [6] found the maximum value of both
toughness and hardness for 0.6 wt% addition of chromium.
Fig. 12 illustrated the change of fracture toughness upon addition
of chromium oxide from two different derivative routes.
2.6.7. Microhardness
The most positive and highly used impact of Cr2O3 is on micro-
hardness improvement. The addition of chromium significantly
increases the hardness of the ZTA matrix [121,140]. The hardness
is even higher if the sample is hot pressed. As we know, the solid
solution between two metals always generates a harder composite.
Since the interaction between alumina and chromium oxide gener-
ates a solid solution, the hardness of the sample is higher than the
hardness of pure alumina at times. However, the hardness drops
after a certain composition since a higher composition of chro-
mium oxide leads to higher vaporization that leads to higher
porosity. Singh et al. [147] found the maximum hardness for
0.6 wt% chromium addition at ZTA and decreases afterward. Han-
ishah et al. [148] showed that the decrease of ZTA after certain
chromium addition can be prevented by adding TiO2 that leads
to grain boundary refinement to compensate for the formation of
the pore.
2.6.8. Miscellaneous
Chromium oxide addition also improves the wear resistance
behaviour of the ZTA. Flexural strength is also expected to increase
though it hasn’t been shown in any literature. The origin of chro-
mium oxide can vary also. Most of it can be found in mineral form
in Eskolaite that is hexagonal. Also, in a few experiments Cr (NO3)3-
S. Sarker, Homayra Tabassum Mumu, Md. Al-Amin et al.
Fig. 11. Grain size alteration upon addition of chromium oxide to alumina and zirconia [144].
Fig. 12. Change of fracture toughness for two different derivative of chromium
oxide addition to ZTA[144].
9H2O precursor was used. Jin et al. [149] compared the mechanical
properties between these two geneses of chromium oxide. The
chromium of the precursor route is more likely to dissolve in alu-
mina and zirconia. Since solid solution formation can be enhanced
by dissolution, chromium of the precursor route is more likely to
form a solid solution increasing the density of the material. Also,
another reason, it promotes densification is by inhibiting alumina
grain growth that prevents the porosity concentration to increase.
For a similar reason, the precursor route leads to better toughness
and hardness than the conventional one.
2.6.9. Inclusion of ferric oxide (Fe2O3)
Fe2O3 is a very common dopant used for achieving the biocom-
patibility and aesthetic properties in bio-ceramics like Y-TZP
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Materials Today: Proceedings xxx (xxxx) xxx
(Yttria doped Tetragonal polycrystal zirconia) dental materials.
Although Fe2O3 is used as a stabilizer in the zirconia system, its
effect in ZTA has not been experimented yet. Since the doping of
Fe2O3 in ZTA is yet unexplored, the interaction between Fe2O3
and Al2O3 in a ZTA system is not discussed in this paper. But the
interaction between Fe2O3 and ZrO2 in the zirconia system inter-
preted by extensive experimentations could be useful for predict-
ing the doping effect in the ZTA system.
The radius of Fe3+ ion is about 0.55–0.78 Å whereas that of Al3+,
Zr , O2,Y3+ ions are respectively 0.54 Å, 0.84 Å, 1.38 Å and 1.019 Å
4+
[144-146]. Since Fe3+ ion is very small compared to Zr4+, Y3+, and
O2 ions, when incorporated in Y-TZP, it occupies the substitu-
tional and interstitial sites depending on its concentration
[144,147-149]. This distorts the perfect fluorite structure of S-
ZrO2 and more distortion in the already distorted fluorite structure
of t-ZrO2 [151]. The Kröger-Vink notation for substitution of Zr4+ by
Fe3+ is as follows [152].
0
2Fe2 O3 $ 4FeZr þ 2V O þ 6OXO
The defect equation for Fe3+ ion occupying the interstitial site is
[152]:
0
2Fe2 O3 $ 3FeZr þ Fe X
i þ 6OO
As shown in equation 1, when ZrO2 is doped with 2 mol of
Fe2O3, 4 mol of Fe3+ ion substitute 4 mol of Zr4+ ions creating
4 mol of negative charge. For the purpose of charge balancing in
the crystal, 2 mol of O2 ion vacancies form. And the volume of
the unit cell decreases due to the substitution of smaller motif
[146,147]. But in equation 2, 3 mol of Fe3+ ion substitute 3 Zr4+ ions
creating 3 negative charge which is nullified by 1 mol of Fe3+ ion
occupying an interstitial site. As a result, the volume of the unit cell
increases [145,146,150]. C.L. Wang et al. showed in his work that
the unit cell volume increases slightly with the addition of Fe2O3
up to its solubility limit (0.5 mol% in the work) and then decreases.
So, it can be inferred that in tetragonal zirconia, Fe3+ ion occupies
S. Sarker, Homayra Tabassum Mumu, Md. Al-Amin et al.
interstitial sites when added up to its solubility limit in zirconia,
and further doping of Fe3+ ion results in the substitution of Zr4+
ions [152]. And since interstitial sites in cubic crystals are smaller
than sites in tetragonal ones, Fe3+ ions incorporated in cubic ZrO2,
only substitute Zr4+ ions. Thus, effect of Fe2O3 is more pronounced
in cubic phase than in tetragonal phase [152].
The phase formation depends on the concentration of Fe2O3,
stabilizers, and additives. When doped in a small amount within
the solubility limit of Fe3+ in ZrO2 (around 1–1.5 mol% depending
on composition), mainly t- ZrO2 phase along with a very small
amount of cubic phases forms in 3Y-TZP and only S-ZrO2 forms
in 8Y-TZP. With an increasing amount of Fe2O3, cubic phase frac-
tion increases [151]. Figueroa et al [155]showed that in the case
of un-stabilized ZrO2, doping up to 12 mol% Fe2O3 results in t-
ZrO2 phase. The addition of Fe2O3 beyond 12 mol% would result
in a substitutional cubic structure of ZrO2.
Fe2O3 being a transitional metal oxide, effectively enhances the
sintering of ceramics [151]. Lower sintering temperature and
higher relative density can be achieved by Fe2O3 addition [151].
Fe2O3 enhances the densification progressively during sintering
at any temperature with increasing Fe2O3 content. Doping Fe2O3
in the zirconia system introduces more defects in the structure.
Fe3+ ion increases the rate of diffusion by increasing the jump fre-
quency of Zr4+ ions, which in turn, increases the densification rate
[145,150]. The increase in the jump frequency is attributed to two
factors. Fe3+ ion migrates by interstitial diffusion when present in
low concentration i.e., below solubility limit and diffuses by
vacancy mechanism beyond solubility. When Fe3+ ions diffuse
from the substitutional site to the interstitial site, the cation charge
density drops in that region leaving a vacant site for Zr4+ ions to
jump to. Also, undersized Fe3+ ions form a weaker bond with O
which weakens the Zr-O bond too. As a result, the activation
energy of Zr4+ ions decreases while increasing diffusion coefficient
[151].
Fe2O3 adds colour to Y-TZP sintered products by grain boundary
segregation of Fe3+ ion. Colour becomes darker with higher Fe2O3
content. For a fixed concentration of Fe2O3, colour change is more
drastic for lower mol% of yttria. When yttria content is low, both
tetragonal and minor amounts of cubic phase forms whereas
higher yttria content results in the formation of only the cubic
phase. Tetragonal to monoclinic phase transformation induces
Fe3+ to behave like Y3+ and segregate severely at the grain bound-
ary. With increasing Fe2O3 content, more Fe3+ segregate which
gives a darker shade to the solids [145,146].
Grain growth depends on grain boundary migration which
depends on solid solution transport mechanism [151,152]. When
impurities segregate at triple point junctions along the grain
boundary, they obstruct its mobility resulting in an increased triple
point junction drag. This hinders grain growth during sintering and
increases densification. As mentioned earlier, grain boundary seg-
regation is a transformation induced phenomenon. Since the
tetragonal ZrO2 phase can transform into a monoclinic phase, grain
boundary segregation of Fe3+ ion takes place in microstructures
containing t- ZrO2. Grain growth of cubic phase is 30–250 times
faster than tetragonal phase [145,153,154]. Thus, partially stabi-
lized zirconia has lower grain growth rate. Stabilized zirconia
doped with Fe2O3 has larger grains than that of partially stabilized
zirconia doped with Fe2O3. It can be inferred that Fe2O3 can effec-
tively suppress grain growth in the t-ZrO2 phase. F. Guo et al
showed in his work that with increasing Fe2O3 content up to
0.5 mol%, grain size increases rapidly in cubic zirconia structure
and then reaches a constant value. Increasing the concentration
in the tetragonal zirconia system has no significant change in grain
growth rate [151].
The hardness of a material is higher for smaller grain size and
homogenous phase distribution. The Vickers hardness increase
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Materials Today: Proceedings xxx (xxxx) xxx
slightly with increasing Fe2O3 content up to its solubility limit
and then decrease gradually in Fe2O3 doped tetragonal zirconia
[152]. This is due to the fine grains and the increasing density of
the solids with the addition of Fe2O3. But in cubic zirconia, doping
enhances grain growth and thus hardness decreases drastically.
2.7. Inclusion of strontium hexa-aluminate
2.7.1. Introduction
ZTA consists mostly of the alumina matrix (almost 80–95%)
which has a high hardness value. However, alumina has poor frac-
ture toughness performance that is compensated by the stabilized
zirconia addition. In the ZTA matrix, other toughening agents are
also frequently added for a significantly enhanced property and
among them, Hexa-aluminates especially of strontium, lanthanum,
or calcium are widely used. Strontium Hexa-aluminate addition
can enhance toughness significantly but may also lead to poor den-
sification and higher porosity.
2.7.2. Grain morphology
Strontium Hexa-aluminate has a platelet-like shape. Dispersed
stabilized zirconia particles in the ZTA helps to enhance the tough-
ness by mechanisms such as microcrack toughening or transforma-
tion toughening. Strontium Hexa-aluminate’s platelet-like
structure can encourage better fracture resistance by mechanisms
such as crack deflection, crack branching, trans granular fissure
toughening [161]. These mechanisms can increase the fracture
resistance by 1.5–2.5 MPam1/2 [162]. The planar structure may
coarsen the matrix and while added at a significant amount, can
submerge the grain with whisker-like secondary phases. Strontium
Hexa-aluminate generally orients as lamellae like formation and it
can prevent crack propagation. As a crack propagates through the
matrix and meets the lamellae, it can either go through it and gen-
erates an intragranular crack or can avoid it to form an intergran-
ular crack. Either mechanism wastes a significant portion of the
indentation force and hence increases the fracture resistance of
the matrix. Becher et al. [163] suggested that adding a second
phase can significantly increase the toughness of ZTA. However,
the increment of toughness depends on the toughness of the sec-
ond phase rather than the strength.
2.7.3. Fracture toughness
In the ZTA and Strontium Hexa-aluminate matrix, a crack is ini-
tially deflected by the Partially stabilized zirconia, then after meet-
ing the interface between ZTA and strontium Hexa-aluminate and
deflects for a certain length at the boundary. Then the crack tends
to break through the platelet like structure and exits through to the
matrix and stops momentarily [164]. This was both a crack bridg-
ing and deflection mechanism that wastes a lot of applied stress.
The importance of these mechanisms on the fracture toughness
can be proved by the following few equations by song [159,160]:
K r ¼ K m þ DK s þ DK b þ DK d
Where, K r is the fracture resistance, K m is the fracture toughness of
the matrix, DK s are impacts of transformation (most likely of tetrag-
onal to the monoclinic transformation of zirconia), DK b is the contri-
bution by the crack bridging and DK d is the contribution due to the
crack deflection.
Z p=2 
1 pffiffiffi p
yd =ym ¼ 2
d2 þ Ls Lp ½1 þ 2 cos u þ du
d 0 4
Where, Ls is the maximum deflection length and Lp is the average
diameter of the platelet. The first equation illustrated that provided
other parameters are equal, strontium Hexa-aluminate can increase
the fracture resistance if it can do crack deflection and crack bridg-
S. Sarker, Homayra Tabassum Mumu, Md. Al-Amin et al.
ing. The platelet-like grain of the subject inclusion makes the crack
tip to take a more elongated path around the grain boundary which
in turn, according to the second equation consumes a lot of fracture
energy [167]. Also, as previously discussed, the coarsening of the
ZTA grain with a secondary particle can lead to higher flaw toler-
ance that leads to a better toughness. Another parameter that dic-
tates the toughening of ZTA is transformability. The increase of
Strontium Hexa-aluminate increases the monoclinic fraction of zir-
conia which is associated with a volume expansion that leads to an
increase of fracture resistance [168]. Naga et al. [161] found the
highest value of toughness for 30 wt% addition and Raymond
et al. [169] suggested that the best toughness value can be obtained
for SrO/Al2O3 = 0.33. At higher inclusion percentage, the impact of
zirconia toughening decreases, and that may lead to an overall
reduction of fracture resistance.
2.7.4. Densification
The addition of strontium hexa-aluminate decreases the density
significantly. It also increases porosity. The formation of a platelet-
like structure helps to trap a high concentration of closed pores.
This leads to high porosity at higher inclusion percentages
[164,165]. Grain boundary separation between the interfaces of
alumina and strontium hexa-aluminate is weak and has high cohe-
sion [168]. The majority of the pore is present in the grain bound-
ary and pore-boundary separation does occur but not within large
grains. Also, At high-temperature SrO can form a liquid phase that
upon enough soaking time gets evaporated and generate pores
[172]. These lead to higher porosity and poor density performance.
The inclusion of strontium hexa-aluminate doesn’t have any signif-
icant impact on the sinter ability of the ZTA.
2.7.5. Microhardness
Additionally, the hardness also decreases with higher inclusion
[165,167]. The hardest material in the ZTA matrix is the alumina.
With increasing strontium hexa-aluminate, the indentation resis-
tance decreases due to previously mentioned poor grain boundary
separation or alumina being less dormant in the matrix.
2.7.6. Miscellaneous
Flexural strength also increases with increasing second phase
inclusion. This is rare since most second phase particle decreases
the flexural strength of the ZTA. The slight increase of flexural
strength is some cases can be attributed to the elongated grain
morphology but the change is not significant. However, the maxi-
mum value of strength is dependent on the critical stress to initiate
the transformation of zirconia [174]. The highest value can be
obtained at 10 wt% addition of strontium hexa-aluminate [161].
During different processing techniques, other phases like
SrO.2Al2O3 and SrO.Al2O3 can be found. However, most of them
are not practically useful as they lead to poor mechanical proper-
ties [175].
2.8. Inclusion of calcium oxide (CaO)
2.8.1. Introduction
Calcium oxide has been widely used in the alumina-based
ceramics for the better mechanical property, grain growth engi-
neering, porosity enhancement, or some biomedical applications.
In the ZTA matrix, calcium oxide can react with alumina and form
a list of compounds. Some of them are (considering, C for Calcium
oxide and A for alumina) C3A, CA6, CA2, C12A7, CA. Among them CA2
is monoclinic and CA6 is hexagonal [176].
2.8.2. Phase analysis
Among the phases, the activation energy of sintered CA and CA2
is more when there are in a mix than their sum [177]. CA and CA2
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Materials Today: Proceedings xxx (xxxx) xxx
are reaction intermediates and will dissolve to form the CA6. The
lime-rich C3A and C12A7 is highly reactive and hence also dissolves
into CA6. [178] Among the phases, CA6 has the highest melting
point and has the highest alumina percentage. Their formation
can follow these steps:
1. Low-temperature dissolution reaction by CaO(C) and Al2O3(A)
CaO þ 6Al2 O3 ! CaO:6Al2 O3
2. the reaction between CaO and Al2O3
CaO:Al2 O3 þ 5Al2 O3 ! CaO:6Al2 O3
3. the reaction between CaO.2Al2O3 and Al2O3
CaO.2Al2O3 + 4Al2O3?.CaO:6Al2 O3
4. the reaction among CaO.Al2O3, CaO.Al2O3, and Al2O3
CaO.2Al2O3 +CaO:Al2 O3 + 9Al2O3?.2CaO:6Al2 O3
The phase diagram of the CaO and Alumina system are illus-
trated in the Fig. 13.
The stages of reaction can occur that ultimately leads to the for-
mation of CA6. Its mineral name is hibonite. Hibonite is the most
alumina rich phase among the others and has the highest melting
point [179]. It is a gem mineral that has a specific gravity of 3.84
and Mohs hardness of 7.5–8 [180]. It has similar properties to
the alumina. It has also the same thermal expansion coefficient
as the alumina. But since its anisotropic, the expansion is not uni-
form and hence the thermal shock can disintegrate the matrix of
the ceramic [181].
Most Hexa-aluminates (as previously discussed in the stron-
tium Hexa-aluminates) have a platelike structure. Similarly, CA6
has a magneto plumbite platelet like structure [181]. CA6 grain
morphology indicates a preferential grain growth along the basal
plane. The diffusion of Ca2+ and O2 to the alumina rich grain is
the rate-determining parameter. This leads to a certain anisotropy
that leads to the orientation of the basal plane perpendicular to the
reaction front. The resultant microstructure has platelet-like mor-
phology [170,176]. Apart from this, equiaxed morphology is also
observed. Christina et al. [183] suggested that platelet like grain
are obtained only from low density, large pore samples that are
poorly dispersed, and form an agglomerate. On the other hand,
equiaxed samples are mainly the outcome of well-dispersed pro-
cess routes with high sintering temperatures. The process route
induced homogeneity leads to this. At the latter stage of grain
growth, neighbouring grains that are disposed parallel to the basal
planes get welded together. This is the main mechanism for grain
growth and the two different morphologies have significance in
defining the mechanical properties. The activation energy required
for the CA6 formation is 40 kj/mole [184].
2.9. Lattice parameter and stabilization
Ca2+ ion while added to the Zr4+ ion of ZTA can alter lattice
parameter and phase stability. The ionic radius of Ca2+ is 1.12 A°
where for Zr4+ it is 0.84 A°. Hence Ca2+ should increase the lattice
parameter significantly [185]. In reality, however, the increase is
somewhat compensated by oxygen vacancy substitution to main-
tain charge neutrality. Although the increase is around 0.11%. Add-
ing Ca2+ in the Zr4+ can induce oxygen vacancy as it is an n-type
semiconductor [186]. For small percentage inclusion of the oxygen,
vacancy appears small but with higher inclusion, it gets agglomer-
ated and larger vacancy is observed [187]. Charge with smaller
valency is less likely to get dissolved in higher valency and that’s
S. Sarker, Homayra Tabassum Mumu, Md. Al-Amin et al.
Fig. 13. Phase diagram of CaO-Al2O3 phase system[176].
the case for Ca2+. The replacement of Zr4+ in the lattice by Ca2+ is
illustrated by the following Kroger-Vink notation:
00
Zr xZr þ Oxo $ CaZr þ V ::o
00
CaZr represents that, Ca2+ occupies the site normally occupied
by a Zr4+ ion; V ::o represents an oxygen vacancy.
Along with the lattice parameter, the tetrahedral bond length is
also increased [185]. Aliovalent cation ions dopants such as Ca2+
may replace the Zr4+ in the cation network that generates oxygen
vacancy for charge compensation. Lower charge state, larger ionic
size, and ionicity favour the stabilization of Zr4+ [126,182]. Ca2+
having all these characteristics can help stabilize the high-
temperature phases of zirconia.
2.9.1. Microstructural analysis
The microstructure of the calcium hexa-aluminate is shown are
shown in the Fig. 14. Mostly hexa-aluminates are discussed since
they are most likely to be found upon CaO addition to ZTA system
or any alumina ceramic system. The micrographs show a platelet-
like morphology around the matrix [183,184]. This specific mor-
phology leads to a series of crack bridging and crack deflection in
the matrix. Upon addition of such platelet-like grains in the ZTA
matrix, it leads to an increase of the crack path preferably leading
to a higher fracture toughness value. It can however be assumed
that the grain separation between the hexa-aluminate grain and
alumina grain is the preferential direction for crack propagation.
However, in a system where intragranular crack propagation is
dormant, the fracture toughness increment will not be as signifi-
cant. In terms of this particular case though, the increment of
toughness in highly visible and that is well documented in several
journals.
2.9.2. Fracture toughness
The inclusion of CA6 on ZTA can increase toughness. Due to its
platelet-like structure, it generally exhibits crack bridging(this
mechanism is similar to the one described for strontium Hexa-
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Materials Today: Proceedings xxx (xxxx) xxx
aluminate) [191]. Another mechanism is observed called crack dis-
position. This occurs while the crack is propagating along the basal
plane [192]. When the movement of the crack is trans-granular and
planes perpendicular to the flat boundaries, a morphology called
sub-boundaries is observed. Crack deflection at the sub-grain
boundary is hard as it crosses more length between the cleavage
step than between the basal plane. However, the trans-granular
fracture is observed in the microstructure of CA6 which indicates
weak structural integrity of sub-grain boundaries, and it’s easier
for the crack to propagate through the grains than through the
grain boundary. Along with the toughness improvement, CA6 can
improve the R curve behaviour due to its platelet-like morphology
[193]. More round-shaped morphology doesn’t increment the
toughness since it doesn’t favour crack-bridging as much. Although
for a higher percentage inclusion of CA6 may decrease the tough-
ness due to the gradual increase of pore. At low CaO content, CA6
has platelet-like morphology that leads to better crack bridging.
At higher CaO content, CA6 grains are equiaxed and hence it has
also no impact on the mechanical property [194].
2.9.3. Densification
In the alumina system, CA6 addition will initially increase the
densification and will peak at 10 wt% inclusion. Subsequently,
porosity decreases up to that point [184,189]. After that composi-
tion, densification decreases significantly. Asmi et al. [196] and
Nagaoka et al. [197] suggested that densification doesn’t increase
up to 15 wt% addition and rather stay stagnant or decrease at a
higher percentage. Such disparity cannot be traced back to its pro-
cessing routes. However, a well-dispersed matrix is less likely to
trap closed pores especially if the grain growth rate is high [198].
Despite being a Hexa-aluminate, the grain morphology substan-
tially differentiates the impact of strontium Hexa-aluminate from
the Calcium Hexa-aluminate on ZTA. For CA6 much higher densifi-
cation can be obtained [199]. For a high percentage of addition, the
amount of porosity increment is so high that, CA6 or CaO addition
is used in ZTA to form porous ceramics [200]. Since high porosity
leads to poor thermal conductivity [179], it can lead to certain
S. Sarker, Homayra Tabassum Mumu, Md. Al-Amin et al.
Fig. 14. (1) & (2) are grain morphology of the calcium hexa-aluminate [190] and (3) & (4) are optical micrographs containing Alumina-15 wt% CaO system[189].
applications. The initial increase of densification is not observed in
similar Hexa-aluminates. Since CA6 is similar to alumina in terms
of its physical, thermal property and initial nucleation of CA6 (at
similar sintering condition) involves relatively rounded grain that
is less likely to trap pores in the matrix, the densification may
increase slightly [201]. Also, CA6 is less dense than zirconia and
subjected to a volume expansion that generates pore filling. The
sintering temperature required for proper densification is as high
as 1750 °C. Upon cooling from temperature that high a lot of mon-
oclinic zirconia phase may form that degrades the mechanical
property further. In addition to the high temperature, higher soak-
ing time is also necessary as the solid-state diffusion in the con-
stituents is sluggish which leads to high porosity [194]. Also,
decreasing the sintering period may help with the compaction
since higher grain growth may lead to more entrapment of closed
pore that leads to better mechanical property.
2.9.4. Grain growth
CaO can cause minor grain growth inhibition in the ZTA by
reduction of the pore as the grains touch each other. Also, the ani-
sotropic grain growth of CA6 can lead to poor thermal shock resis-
tance despite having a similar thermal expansion coefficient as
alumina [181].
2.9.5. Synthesis problem
Synthesis of an alumina-based ceramic having CA6 in the matrix
is harder due to its certain reaction conditions. The reaction is
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Materials Today: Proceedings xxx (xxxx) xxx
diffusion-controlled and the simple addition of CaO may not gener-
ate CA6 in the matrix. However, the absence of sharp exotherm is
the reason why the formation of CA2 or CA6 is slow and explains
why it is diffusion controlled. Diffusion exotherm is present by a
certain decomposition of CaCO3 [196]. So, a certain mixture of
CaCO3 and CaO is used to form CA6. In the ZTA ceramic, the CaCO3
sites start nucleating as the platelet-like/equiaxed CA6 grain unidi-
rectionally. Gradually all calcium carbonate present either form
CA6 and gaseous carbon-dioxide (that also increases pores). To
compensate for the pores, more CaO is added [177,194]. However,
a detailed description of this mechanism is not relevant to this
journal.
2.9.6. Miscellaneous
CaO addition can increase the cold modulus of rupture [202].
Hardness is also low for the region having a high concentration
of CA6. The hardness of CaO is low comparing to alumina (Mohs
scale 7.5 vs 9). So, according to the linear rule of mixture, the addi-
tion of CaO will decrease the hardness. But if CA6 clusters are
formed in the grain then only the region surrounding it will exhibit
low hardness [190]. However, how different grain morphology
may influence hardness is a topic up for further investigation.
The flexural strength of the ZTA with CA6 addition is dependent
on the porosity of the matrix. As flexural strength is not an intrinsic
property and is strongly dependent on the amount of critical flaw
present, it can be attributed to the porosity change. With high
porosity, strength will decrease, and vice versa [192].
S. Sarker, Homayra Tabassum Mumu, Md. Al-Amin et al.
2.9.7. Inclusion of tantalum pentoxide (Ta2O5)
When ZTA is doped with Ta2O5, it forms a solid solution by sub-
stituting Zr4+ ions:
0
2Ta2 O5 $ 4TaZr þ V Zr þ 10OXO
When Ta5+ ions substitute Zr4+ ion, to conserve charge balance,
1 mol of Zr4+ vacancy is generated for every 4 mol of substitution.
The increasing Zr4+ vacancy increases diffusion and jump rate of
Zr4+ ion [151]. Ta5+ ions diffuse by vacancy diffusion mechanism
thus the vitrification rate improves resulting in better sintering
[203]. Ta5+ ions diffuse by interstitial diffusion mechanism too
which partially enhances diffusion rate of Zr4+ ions. Bulk density
and relative density increase with increasing Ta2O5 due to
improved densification. When Ta2O5 is added more than its solu-
bility, about 2 mol% in ZrO2, a new phase TaZr2.75O8 emerges at alu-
mina grain boundaries [204]..
Ta5+ ions increase grain boundary mobility, thus increasing
grain growth. Alumina grains become elongated and both alumina
and zirconia grains grow with increasing Ta2O5 content [199,200].
TaZr2.75O8 phase forms when solubility limit is exceeded.
Hardness increases when doped with Ta2O5 since higher densi-
fication is achieved. Ta5+ ion also enhances cohesion between
grains which is also a contributing factor for achieving higher hard-
ness. The thermal expansion coefficient of ZrO2 (10.8x106/°C) and
Al2O3 (8.8x106/°C) is larger than that of Ta2O5(3.6x106/°C) below
1000 °C [204]. The difference in thermal coefficient among differ-
ent phases produce internal stress that enhances the hardness of
the material.
Oxygen vacancies are responsible for the stabilization of tetrag-
onal and cubic structures. Since doping with Ta5+ ions decrease the
vacancy concentration of oxygen ions, Ta5+ ions reduces stability of
tetragonal and cubic zirconia high temperature polymorphs
[199,201,202].
Doping with Ta5+ ions improve the anisotropy of the tetragonal
layered structure because of following factors.
 Decrease in oxygen vacancies reduce disruption
 Distortion generated due to substitution of Zr4+(0.79 nm) by
smaller ions of Ta5+ (0.69 nm)[204][208]
 Zr—OI and Zr—OII bifurcation
 Smaller Ta—O bond length than Zr—OI
Stronger anisotropy results in higher tetragonality which
enhances t-m transformability and thus increasing fracture tough-
ness [199,202]. Adding Ta2O5 beyond solubility would no longer
improve transformability. The elongated grains of alumina also
increases fracture toughness with increasing Ta2O5 content
[199,203].
2.10. Inclusion of niobium pentoxide (Nb2O5)
Nb2O5 is used to enhance the sinterability and mechanical prop-
erties of YSZ [209]. Nb metal is used to form metal matrix hybrid
composite with high toughness, R curve behaviour and high toler-
ance [205,206].
When Nb2O5 is added to ZTA within its solubility limit, the Nb5+
ions substitute the Zr4+ ions according to the following equation
[199,207]:
 0
2Nb2 O5 $ 4NbZr þ V Zr þ 10OXO
Since the size of Nb5+ (0.68 Å) is smaller than Zr4+ ions (0.79 Å),
lattice distortion is generated. With increasing Nb2O5, the lattice
parameter of ZrO2 decreases [209]. Incorporation of Nb5+ ions cre-
ate cation vacancy, which improves the diffusion coefficient of Zr4+
ions [204]. Nb5+ ions migrate by vacancy diffusion which increases
19
Materials Today: Proceedings xxx (xxxx) xxx
diffusion rate and sintering. Thus, density increases gradually with
increasing Nb2O5 content [212]. However, when addition of Nb2O5
exceeds its solubility limit, which is 1 mol%, CeNbO4 forms [209].
Effect of Nb2O5 addition in alumina matrix has been proven to
significantly enhance densification, sintering. Density increases
due to grain size refinement [213]. Grain size of both alumina
and zirconia decreases due to improved densification and low
grain growth when Nb2O5 is added to ZTA. Enhancement of hard-
ness while doping with Nb2O5, is due to increased cohesion
between grains and finer grains [199,204].
The toughness also increases due to finer grain size achieved
with Nb2O5 doping. Smaller particle size means higher surface
energy, which means better stability of tetragonal phase [209-
211]. Thus, Nb2O5 addition increases tetragonal zirconia phase
fraction in the structure by improving its stability. This leads to
higher toughening by transformation toughening mechanism.
2.10.1. Inclusion of Erbium oxide (Er2O3)
Erbium being a rare earth element, can stabilize ZrO2 [217].
However, it is not commonly used as a dopant to enhance mechan-
ical and microstructural properties of zirconia toughened alumina.
Er3+ effects ZTA in a similar way like Fe3+ does because of tri-
valency [218].
when Er2O3 is added within its solubility limit, it forms a solid
solution with ZrO2 by substituting Zr4+ ion according to the follow-
ing Kröger-Vink notation:
0
Er2 O3 $ 2ErZr þ V O þ 3OXO
Since Er3+ ions(0.088 nm) and Zr4+ ions (0.072 nm) are similar in
size, the substitution causes distortion in lattice [218]. The lattice
parameters increase with increasing Er2O3 [219]. According to this
equation, to maintain charge balance, oxygen vacancies are
formed. This enhances the bulk and lattice diffusivity of both Al3+
and Zr4+ ion. When Er2O3 concentration exceeds its solubility in
ZrO2, Er2O3 reacts with t-ZrO2 to form Zr3Er4O12 (Erbium zirconium
oxide), a new phase [212,213].
Er3+ stabilizes t-ZrO2 and c-ZrO2 phases [214,215]. As a result,
when Er2O3 content approaches its solubility limit, the volume
fraction of the m-ZrO2 phase decreases gradually. Zr3Er4O12 influ-
ences the transformation of ZrO2 from tetragonal to monoclinic.
Thus, with increasing Er2O3 beyond 5 wt%, the Zr3Er4O12 phase
increases while the t-ZrO2 phase decreases [218]. Addition of
increasing Er3+ content reduces the martensitic transformation
temperature (t-m ZrO2) gradually [217].
Er2O3 addition affects the microstructure of ZTA. Sui Y et el.
Showed in his work that grain size of both Al2O3 and ZrO2
decreases as Er2O3 (addition up to 5 wt%) hinders diffusion of
Al3+ and Zr4+ ions across the grain boundary [218]. Adding more
than 5 wt% of Er2O3 resulted in the granulate Zr3Er4O12 phase that
covers the grains. But when 15 wt% Er2O3 is added, the Zr3Er4O12
phase assumes a block-like shape.
Density increases due to the pinning effect up to solubility and
then decreases as Zr3Er4O12 phase forms. Er3+ ion enhances the
jump frequency of Zr4+ ion by lowering the activation energy. Thus,
up to the solubility limit, increasing Er2O3 increases the densifica-
tion rate. But beyond that, densification declines.
Since a decrease in grain size, increase in density, and increasing
cohesion in grains occur due to an increase in Er3+ ions, Vickers
hardness and bending strength increase with increasing Er2O3 con-
tent up to solid solubility limit and then decrease as the formation
of Zr3Er4O12 phase consumes Er3+.
Fracture toughness of ZTA doped with increasing Er3+ ion
increases with as it enhances tetragonal to monoclinic transforma-
tion of ZrO2 and thus enhancing stress-induced transformation
toughening. But beyond solubility, the t- ZrO2 to m- ZrO2 transfor-
S. Sarker, Homayra Tabassum Mumu, Md. Al-Amin et al.
mation decreases as Er3+ ion decreases to form a secondary Zr3Er4-
O12 phase. Thus fracture toughness decreases with Er2O3 exceeding
the solubility limit [218].
2.11. Inclusion of copper oxide (CuO)
When CuO is added to ZTA, it increases the contact area of par-
ticles and enhances the diffusivity of Zr4+. Doping with CuO
enhances sintering by forming a liquid phase which is due to the
high melting point of CuO [216,217]. When added within the sol-
ubility limit, density increases with increasing CuO content. Grain
size decreases due to the pinning effect of CuO. Thus, hardness and
elasticity improve with increasing CuO content. Fracture toughness
doesn’t vary much with CuO doping and variation of CuO content
[223].
But when doped beyond the solubility limit, pores form due to
difference in thermal expansion coefficient and rate of grain
boundary migration of CuO, Alumina, and zirconia. Density
decreases too with no pinning effect. Thus, the progressive addi-
tion of CuO beyond its solubility results in degradation in mechan-
ical properties such as hardness and elastic modulus [223].
However, fracture toughness increases significantly when
doped beyond solubility due to the formation of a new phase
[223]. When CuO reacts with Yttria, some tetragonal zirconia
grains transform into monoclinic when stress is induced due to
the lack of surrounding the Yttria phase. Thus fracture toughness
is improved by enhanced transformability [224].
CuO addition also decreases friction and improves wear resis-
tance which is independent of CuO content [225].
2.12. Inclusion of Nickel (Ni)
Nickel is a widely used metal with a variety of application.
Nickel is mostly used as a structural material due to its good frac-
ture toughness and strength. However, in terms of its addition
with ZTA, it has certain limitations since it has a low melting
and boiling temperature. Since, ZTA ceramics are also considered
to withstand high temperature, nickel addition will simply dim-
mish that property. However, few researches were conducted
for judging its properties upon addition to ZTA. Chen et al.
[226] shows the effect of adding both Ni and ZrO2 in alumina.
Fig. 13 contains information about the variation of density, grain
size and modulus of strength with Nickel addition. Ni vaporizes
above 1600 C leading to a greater pore formation. So, high
amount of Ni addition will simply result in a decrease of
densification.
Ni grains are larger in size than ZrO2 grains. As mentioned pre-
viously, ZrO2 has pinning effect on alumina grain and thus the
grain size of alumina decreases as ZrO2 increases. This is particu-
larly apparent in this particular case since Nickel was added
simultaneously with zirconia. Hence, despite the pinning effect,
the grain size of zirconia increases. However, Ni segregates in
the grain boundaries, thus hinders the grain growth of alumina.
Ni being a soft metal, bridges the crack surfaces. The crack surface
bridging, as previously discussed will lead to a significant absorp-
tion of fracture energy leading to an increase of fracture
toughness.
3. Comparative discussion on mechanical properties
3.1. On density
Density is largely dependent on grain size. Lower grain size
produces higher density. H. Manshor et al. [227] showed that
the closely packed and smaller grains tended to have a higher
20
Materials Today: Proceedings xxx (xxxx) xxx
density. The density of ceramics composite can also be improved
by the addition of different additives. Having microstructure pin-
ning effect, MgO and TiO2 resist the unusual grain growth of
Al2O3 [223,224].
It is noticed from Manshor et al. [148] that at 3 wt% TiO2, the
bulk density was maximum and began reducing from the addition
of 5 wt% onward. The main reason is that after 5 wt%, TiO2 has no
longer ability to resist the grain growth of Al2O3 and forms a sec-
ondary phase. The coarser grain size has a reverse effect on densi-
fication and the secondary phase has a lower density than Al2O3
and TiO2 [225,226].
According to S.A. Dhar et al. [231] with the increasing of TiO2
content from 0 wt% to 4 wt%, the density of the ceramics composite
increased and the highest density value was 4.18 g/cm3 at 4 wt% of
TiO2. Further addition of TiO2 decreased the density due to the
presence of the secondary phase i.e. Al2TiO5 as indicated by Man-
shor et al. [232].
Sktani et al. [201] reported that 5 wt% CaO added with ZTA
showed the highest density of 4.23 g/cm3 and lowest porosity of
1.05%. Naga et al. [204] studied that effect of Ta2O5 on physical
mechanical properties of ZTA. With the addition of 3 wt% Ta2O5,
the highest bulk density was increased to 4.13 g/cm3.
Rejab et al. [228] showed that 0.5 wt% MgO added with ZTA-
CeO2 increased the density about 7.31% compared with 0 wt%
MgO but MgO with more than 0.5 wt% decreased the density
because a secondary phase is generated instead of pinning effect.
A. A. Mahmood et al. [3] observed the highest density and that
was for 1 wt% MgO added with ZTA-TiO2 achieved about 94% of
the theoretical density.
According to H. Manshor et al. [227] with the increasing of
Cr2O3 content from 0 wt% to 0.6 wt%, the density of the ceramics
composite increased up to 4.063 g/cm3 and further addition of
Cr2O3 decreased the density due to the formation of pores and
developments of various crystalline phases in the sintered com-
pacts [42]. In case of microwave sintering(MW), H. Manshor
et al. [88,228] showed that, with the increasing of Cr2O3 content
from 0 wt% to 0.6 wt%, the density of the ceramics composite
increased up to 4.063 g/cm3 and further addition of Cr2O3
decreased the density [138].
Rejab et al. [233] was found that ZTA with 1.0 wt% of CeO2 gave
the maximum bulk density obtained (4.28 g/cm3). However, fur-
ther addition of CeO2 caused the bulk density to decrease due to
the presence of secondary phase CeAl11O18. It is observed that
the addition of 5 wt% CeO2 with ZTA have the maximum bulk den-
sity of 4.41gm/cm3.
Due to the low melting temperature of only 960 °C and high
rate of vaporization, the densification decreases for higher percent-
age (above 12 wt%) addition of silver. But silver being heavily
dense metal, the total density increases especially at low additions.
The densification is around 98.3 percent for 5 wt% addition of silver
to 5 wt% zirconia and rest of alumina which by calculating gives a
density of 4.31 gm/cm3. For similar parameter with 10 wt% zirco-
nia and 10 wt% silver and rest of alumina the densification is
around 98.5 percent and a provide a density of 4.74 gm/cm3 at sin-
tering temperature of 1600 °C [113,114].
Addition of Strontium Hexa-aluminate decreases the density
slightly. Addition of Strontium Hexa-aluminate to pure alumina
also provides a similar impact. For 5 wt% addition density comes
around 3.71 gm/cm3 and for 10 wt% addition density comes around
3.70 gm/cm3 for a sintering temperature of 1600 °C. [234] But
addition of 10 wt% with rest of ZTA at sintering temperature
1650 °C provides a density of 4.14 gm/cm3 for CIP sample. Also
for 30 wt% addition with rest of ZTA at same sintering temperature
provides a density of 3.94 gm/cm3 thus showing a downward trend
due to entrapment of the pores and its unique grain morphology as
previously discussed [171].
S. Sarker, Homayra Tabassum Mumu, Md. Al-Amin et al.
3.2. On Vickers hardness
Hardness depends on the density [3], the higher the density the
higher the hardness. As density depends on grain size, smaller
grains result in a homogeneous and dense ceramics which in turn
increases the Vickers hardness and reduces the porosity. In ceram-
ics, the effect of grain size on strength has been studied over past
60 years [230-238]. The reduced grain size has two prominent
effects. Firstly, the flaw sizes are reduced and secondly, the stresses
produced from anisotropic thermal expansion are reduced in case
of ceramic with anisotropic crystal structure [231,233]. The poros-
ity also affects the hardness. The increase in porosity led to a
reduction in hardness [228]. Porosity affects the strength in two
ways. First, porosity creates stress concentration points and crack
will form and propagate when stress reaches a critical level subse-
quently reduce strength. Second, pores reduce the cross-sectional
areas over which load can be applied and consequently lowers
the strength of materials [108]. H. Manshor et al. [227] showed
that the increase in hardness was consistent with the density of
the composite and hence the addition of Cr2O3 from 0 to 0.6 wt%
increased the hardness of ZTA-TiO2 composite. However, the fur-
ther addition dropped the hardness of the composite due to the
decrease in weight of the composite as a result of volatilization
of Cr2O3 to CrO3. Rejab, Nik Akmar, et al. [108] shows that highest
Vickers hardness is achieved with 5 wt% of CeO2 due to the higher
densification of ZTA-CeO2 samples but the hardness is dropped
with the further addition of CeO2 due to the lower density caused
by the presence of new phase, Ce2Zr3O10.
Fig. 15. Dental and arthroplasty uses of Zirconia Toughened alumina [245-247].
21
Materials Today: Proceedings xxx (xxxx) xxx
Vickers microhardness obtained for silver addition to ZTA is still
up for further research. For Strontium Hexa-aluminate addition
with 90 wt% ZTA and 10 wt% SA6 at sintering temperature
1650 °C, a hardness of 1790 HV is obtained for uniaxially pressed
sample and a hardness of 1910 HV is obtained for a CIP (cold iso-
statically pressed) sample. Again for 70 wt% ZTA and 30 wt% SA6
a hardness of 1290 HV is obtained for CIP sample and for uniaxially
pressed sample the obtained value is 1250 HV [155,165]. The
downward trend of hardness is due to the decreasing amount of
alumina with increasing SA6 and the entrapment of pore at grain
as previously discussed.
Fig. 15 shows the effects of various ceramic oxides on the hard-
ness of ZTA. In this figure, the individual additives were used for
optimum wt.% added with ZTA at which the hardness was maxi-
mum. From this figure, it is observed that the addition of 5 wt%
CeO2 with ZTA have the maximum hardness of 1688 HV for con-
ventional method and of 1803.4 HV for microwave sintering with
the addition of 0.6 wt% Cr2O3 on ZTA-TiO2 composite. With the
addition of 3 wt% Ta2O5 on ZTA showed the highest Vickers hard-
ness of 1867 HV for ZTA was prepared by sol–gel method.
3.3. On fracture toughness
Fracture toughness is improved by the method known as trans-
formation toughening. Fracture toughness is a function of elon-
gated grains, i.e. highest amount of elongated grains results in
the highest fracture toughness value [148]. As indicated by Kruzic
et al. [244] elongated grains in the microstructure force a crack to
S. Sarker, Homayra Tabassum Mumu, Md. Al-Amin et al. Materials Today: Proceedings xxx (xxxx) xxx

deflect in more than one plane to get around the grain. Subse- lated. Choice of proper addition may provide a new path towards
quently, more energy is required to round through prolonged building a highly fracture resistance ZTA ceramic. The final
grains contrasted to flat platelets in the microstructure. A Larger mechanical properties of ZTA are strongly dependent on the types
number of crack deflections are also responsible to strengthen of additives utilized. Certain application may demand unique prop-
the ceramic composites [22,54,55]. Fracture toughness is also erties that can be engineered through the choice of additives and
influenced by the porosity. The lower the porosity the greater the this review article is likely to provide the researches with a set of
fracture toughness. Manshor [24] demonstrated that the fracture general guidelines on that regard.
toughness of ZTA-TiO2 composites was increased up to 7.15
MPam1/2 by the addition of Cr2O3 up to 0.6 wt% but further
5. Applications and subsequent enhancement of properties
increase in Cr2O3 reduced the toughness as a result of vaporization
through additives
and condensation of Cr2O3, which made the composites more por-
ous [103,133,134]. According to Rejab et al. [108] with the addition
Zirconia toughened alumina (ZTA) has a diverse set of applica-
of 5 wt% CeO2 the fracture toughness reached a maximum value of
tions. Mostly it is utilized in the sectors where the strength of
8.38 MPam1/2 but with the further addition of CeO2 the fracture
the material required is very high. Additionally, as a structural
toughness decreased.
ceramic it is utilized as wear sleeves, spraying nozzles, steering
Strontium Hexa-aluminate addition to ZTA can increase the
nozzles, and valve control discs. Among the diverse set of applica-
fracture toughness significantly. It was explained earlier as how
tion in which it is utilized, biomechanical implants are one of them.
crack deflection and crack bridging due to its platelet-like mor-
It has certain applications in the hip implants and hip arthroplasty
phology aids the mechanical properties such as toughness. For
[245-247]. Some of those illustrations were shown at Fig. 15.
10 wt% addition of SA6 at sintering temperature 1650 °C the frac-
One of the prominent applications of ZTA is its utilization as a
ture toughness is around 6.7 MPam1/2 and for 30 wt% addition at
liner in the COC implants. Most of the COC implants have bilayer
same sintering temperature the toughness is 7.89 MPam1/2
of ceramic and ZTA can be utilized by an inert internal layer. Those
[155,165]. CaO has a similar impact as it generates Calcium
ceramics are utilized to enhance the stability of the hips. Due to the
Hexa-aluminate in the matrix with similar morphology that leads
inert nature of the ZTA ceramics, it is less likely to cause any detri-
to toughness increment. Silver addition for Al2O3-Ag-ZrO2 system,
mental reactions with the tissue and have the potentially to be uti-
with 5 wt% addition of silver at sintering temperature 1600 °C,
lized more prominently.
toughness is 5.95 MPam1/2 and for 10 wt% addition at same sinter-
Another prominent utilization of the ZTA ceramic lies as beads
ing temperature it increases to around 7.05 MPam1/2.
and balls of grinding media. ZTA boasts high hardness and strength
that enables it to be utilized as beads and balls for different sets of
griding media. Due to the relative ease of manufacturing, such ZTA
4. Research gap and future scope
beads are widely utilized in research and lab environment.
Although its utilization in the industries is however limited, it
Zirconia toughened alumina (ZTA) is widely investigated in the
shows immense potential for that application.
recent years for its diverse application. From this review paper, it
The market potential for the additives is excellent. For example,
was pointed out that the property enhancement through addition
commonly Yttria is utilized to stabilise the zirconia polycrystals in
of different metals and oxides can yield excellent property
the ZTA matrix. But it can also be done by additives like CaO and
enhancement. However, there are certain areas that can still
MgO. From the economic standpoint, CaO and MgO is relatively
improve through further research on the topic.
cheaper and may aid other beneficial properties as well. Also, com-
Firstly, the synergistic effect of adding multiple oxides is yet to
monly utilized bio ceramics are expensive as well. The utilisation
be widely investigated. In most literature, single oxide addition
of ZTA with proper additive like silver can replace it easily. Espe-
and its subsequent property enhancement is considered. However,
cially in the field of biomedical implants ZTA has significant poten-
further improvement can be done through investigating the bene-
tial for application. In terms of the additive, small amount of
ficial properties of multiple oxides simultaneously. One prime
addition should be sufficient to enhance the mechanical properties
example of it is the addition of MgO and TiO2 simultaneously in
significantly. Some of the oxides are incredibly expensive and high
the matrix of ZTA. It can yield better mechanical properties as well
amount of addition does not justify the cost at all. For example,
as decrease the sintering temperature for which maximum
TiO2 despite having property enhancement ability is not an eco-
mechanical property is achieved. Other similar combinations can
nomically viable option if not utilized in highly sophisticated appli-
be obtained through rigorous investigation that may yield even
cations. The beauty of analysing different additives is that different
better mechanical properties with minimal cost.
alternatives can easily be tested and it may replace the more
Moreover, the biomedical application of ZTA is yet to be fully
expensive one. But it goes without saying up to 50–100% improve-
explored. ZTA shows bioinert behaviour and does not contain
ment of fracture toughness can be attained by certain oxide addi-
and carcinogenic effect on the cell of the body. It can be utilized
tion of only 1–1.5 wt% and on those circumstances it may make
as a perfect bio ceramic provided it is subjected to property
economic sense.
enhancements. Commonly used bio ceramics like hydroxy-
apatite yield far lower mechanical properties than ZTA and more
expensive to make. ZTA has the potential to replace those bio 6. Conclusion
ceramics especially in hip joint and dental parts. Also, as indicated
in the review paper, addition of small amount of silver will This paper reviews the effects of various ceramic oxides such as
enhance the antibacterial properties of ZTA. More investigations MgO, Cr2O3, TiO2, Ta2O5, CaO and CeO2 on grain size, density, hard-
of that nature can take place where certain bioactive properties ness and fracture toughness of ZTA based ceramic composites. The
can be obtained from the ZTA. It is without doubt that most future study focuses the role of grain size on density and porosity. The
applications of the ZTA ceramic will evolve around its application optimum wt.% of different ceramic oxides at which the ZTA com-
in the field of bio medical implantations. posite shows better properties is also presented. From the litera-
One of the prominent problems of ZTA, like other advanced ture review a set of observations can be made regarding the
ceramics, is the lack of fracture toughness. To improve the fracture mechanical property enhancements. The observations are as
toughness, the phase transformation of zirconia is highly regu- following,
22
S. Sarker, Homayra Tabassum Mumu, Md. Al-Amin et al.
1. Additives such as MgO, CaO and CeO2 improves the stability of
tetragonal zirconia polycrystals in the ZTA matrix. Due to that,
it is expected to enhance the transformation toughening poten-
tial for the residual zirconia. Yttria is most widely utilized for
stabilising the zirconia. But there is significant potential for
the mentioned oxides for replacing yttria especially since some
of them are less costly.
2. Although ZTA ceramics have a high hardness in general, hard-
ness enhancement can be done by adding certain additives like
Cr2O3 or Ta2O5. While materials like silver and MgO have the
opposite effect. In certain cutting tool applications hardness
improvement might be required but otherwise hardness rang-
ing from 10 to 15 GPa is sufficient.
3. For the biomedical application, certain additives can boast
excellent enhancement of property. Addition of additive like sil-
ver can boast mild antibacterial resistance. More investigation
is required to understand the impact of other additives on
mechanical property.
4. Grain boundary modification can be done to the base alumina
through addition of certain oxides. MgO addition can decrease
the grain size of the alumina. Addition of CaO can cause the for-
mation of phases like hibonite which have a different tubular
morphology in contrast to the spherical one of alumina.
So, it can be concluded that ZTA has diverse application in the
field of structural and biomedical field. Addition of different addi-
tives can help to improve the mechanical, biomedical properties as
discussed elaborately in this paper. The properties of ZTA can be
more increased by the combination of two or more ceramic oxides.
Certain compositional addition can lead to a desirable property
that may have vast application. The other aspect of application like
biomedical is not widely discussed in this journal. However, there
are a lot of potential on that regard as well. This journal should
help the reader to co-relate different properties of ZTA upon addi-
tion of a lot of inclusions and select their desired material
accordingly.
CRediT authorship contribution statement
Saugata Sarker: Data curation, Methodology, Writing – original
draft, Visualization, Investigation. Homayra Tabassum Mumu:
Methodology, Data curation, Validation. Md. Al-Amin: Methodol-
ogy, Writing – original draft, Formal analysis, Data curation, Inves-
tigation. Md. Zahangir Alam: Project administration, Supervision,
Validation. M.A. Gafur: Conceptualization, Supervision, Writing –
review & editing, Formal analysis, Project administration,
Validation.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgement
The journal was aided by the kind help of pilot plant and pro-
cess development centre (PP & PDC) of Bangladesh council of scien-
tific and industrial research (BCSIR) and Department of Applied
Chemistry and Chemical Engineering, University of Dhaka.
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