Journal of Materials Research and Technology 31 (2024) 372–387

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Journal of Materials Research and Technology

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

Effect of β-spodumene additions on the phase composition, thermal,

mechanical, and fracture behavior of zirconia toughened
alumina composites
S.M. Naga a, M. Sayed a, Khaled A. Omran b, M.A.H. El-Meniawi b, Hossam El-Din M. Sallam b,
O. Hanzel c, A.M. Hassan b, *
a
Refractories, Ceramics and Building Materials Department, National Research Centre, El Buhouth Str., 12622, Cairo, Egypt
b
Materials Engineering Department, Zagazig University, Zagazig, 44519, Egypt
c
Institute of Inorganic Chemistry, Slovak Academy of Sciences, Dúbravska Cesta 9, 845 36, Bratislava, Slovak Republic

A R T I C L E I N F O A B S T R A C T

Keywords: The fabrication of ceramic composites with low thermal expansion and excellent mechanical properties is
Zirconia-toughened-alumina essential for thermal barrier coating (TBC) applications. For this purpose, using the sol-gel process, novel ceramic
β-Spodumene composites were developed by combining varying weight percentages of β-spodumene (0–20 wt%) with zirconia
Microstructure
toughened alumina (ZTA). The influence of β-spodumene addition on the densification, phase composition,
Thermal diffusivity
microstructure, and mechanical, thermal, and fracture behavior of the studied composites was investigated
Fracture toughness
experimentally and numerically. Increasing the β-spodumene content reduces the sintering temperature of the
formed composites by 75 ◦ C. Introducing 5 wt% β-spodumene to ZTA composite improves the densification
process by serving as a mineralizer. X-ray diffraction (XRD) revealed that the t-m ZrO2 transformation was
enhanced by increasing the β-spodumene content. The results demonstrated that composites with β-spodumene
content of 5 wt% exhibited the best mechanical performance. The numerical prediction of fracture toughness
agreed well with the experimental results for different composites.

1. Introduction acceptable mechanical properties, reasonable melting points and ther­

mal expansions, high dimensional stability, resistance to corrosion and
Over the last few decades, the gas turbine industry has made great chemical attack, and excellent thermal resistivity [11,12].
strides in employing ceramic coatings in order to protect metal com­ One of the essential properties of thermal barrier coatings is their low
ponents such as combustion chambers, blades, and vanes from thermal diffusivity and low conductivity. It was reported that applying
extremely hot turbine conditions. These ceramic coatings are known as nanosized coatings decreased the thermal diffusivity by 60–90%
thermal barrier coatings (TBCs) [1–4]. TBCs are utilized to reduce heat compared to traditional thermal barrier coating. Additionally, nano­
transfer from hot gases to the metal surface in order to improve the sized coatings have a 40% lower thermal conductivity analogized to
durability, efficiency, operating temperature, and lifetime of gas turbine micro sized coatings [13,14]. The microstructure features of the nano­
components by using a multilayer structure [5–8]. sized thermal barrier coating greatly enhanced the thermal conductiv­
The choice of TBC materials is limited by several fundamental ity, thermal diffusivity, and thermal cycle life of the coat [14]. The
criteria such as a) elevated melting points, b) alteration in phases from uniform distribution of the nanoparticles and the uniform distribution of
room temperature to operational temperatures, c) minimal thermal the microcracks enhanced the reduction of the thermal conductivity and
conductivity, d) resistance to chemical reactions, e) alignment of ther­ improved the thermal cycle life [15].
mal expansion and strong bonding with the metallic base, and f) slow Recently, the need for turbines operating at higher temperatures
consolidation rate of the porous microstructure [9,10]. Accordingly, activated the search for novel TBC materials having ultra-low thermal
ceramics are considered an important choice to be selected for achieving conductivity. Applying such TBCs will permit the reduction in the coat
the previous requirements due to their excellent properties, such as layer thickness and operation of the engine at a higher temperature

* Corresponding author.
E-mail address: [email protected] (A.M. Hassan).

https://doi.org/10.1016/j.jmrt.2024.06.054
Received 25 March 2024; Received in revised form 6 June 2024; Accepted 8 June 2024
Available online 12 June 2024
2238-7854/© 2024 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
S.M. Naga et al. Journal of Materials Research and Technology 31 (2024) 372–387

while upholding the metallic substrate at a lower temperature, which from 5 to 15 mass%, while the thermal expansion coefficient changed
improves the turbine efficiency. from 1.05 to 2.67 10− 6 ◦ C− 1. On the other hand, prepared 5–20 mass%
To reduce the thermal conductivity, lattice waves have to be scat­ β-spodumene/mullite composites exhibited an excellent enhancement
tered. Many routes adapted for the scattering of lattice waves as the in both sintering temperatures and bending strength, while a reduction
creation of lattice defects like grain boundaries, solute cations, oxygen in both hardness and thermal expansion coefficients was observed
vacancies, porosity, and inclusions [16,17]. To achieve the required compared to pure mullite [32].
needs, the doping of YSZ with rare earth elements ions was intensively Beta-eucryptite (β-LiAlSiO4) is regarded as a negative thermal
studied [18–20]. Nowadays, continuous research is going on to reduce expansion (NTE) material that has a lot of research interest for the
the thermal conductivity of the coating layer of the TBC. development of low CTE ceramic composites in many industrial appli­
Many researchers proved that the porosity is inversely proportional cations, its linear coefficient thermal expansions (CTEs) ranging from
to the thermal conductivity, i.e., decreasing porosity increases the ma­ ambient temperature to 800 ◦ C are αa = 8.21 × 10− 6/◦ C and αc = − 17.6
terial’s thermal conductivity [21–23]. However, it was noted that for × 10− 6/◦ C [41].
materials with identical porosity, the material’s structure possesses the Furthermore, Coutinho et al. [42] simulated numerically
upper hand in determining the thermal conductivity behaviors [21]. disk-shaped bio ceramics specimens of (CeY)-TZP/Al2O3/H6A compos­
Accordingly, it is possible to modify the thermal conductivity and ite using the 3D finite element method (FEM) through ABAQUS soft­
thermal expansion coefficient by choosing the top coat ceramic material, ware. Only the elastic characteristics described by the Poisson ratio and
dopants, and additives which will be used [24–26]. Young’s modulus are used in their analysis. They showed a difference of
Zirconia toughened alumina (ZTA) has many advantages, such as up to 10.5% between the experimental and the predicted numerical
high strength, hardness, toughness, high abrasion and wear resistance, values of flexural strength. This difference may be attributed to the
chemical inertness at room temperature, and moderate heat resistance complicated microstructure of the (CeY)-TZP/Al2O3/H6A ceramic,
[27]. These advantages candidate promote ZTAs to be used as coating which comprises many phases and microstructures after sintering.
materials in the industry of combustion engines. In order to improve the Elghazel et al. [43] found numerically that the fracture toughness values
properties of ZTAs, some additive materials have been utilized, such as of tricalcium phosphate–fluorapatite composites increased with
ceramic-hexa-aluminates, pentavalent oxides, etc. …. It was reported increased fluorapatite addition. They found a good agreement between
that additions of various amounts of Nb+5, Gd3+, Dy3+, or La+3 have the experimental and numerical results. Zaiemyekeh et al. [44] con­
noticeable influences on enhancing the mechanical properties [28,29] structed a constitutive material model to predict the mechanical
and reducing the sintering temperatures of ZTA ceramics [30]. behavior of Al2O3-ceramic at different loading rates. They found a good
Partially stabilized zirconia (PSZ) is one of the best composite ma­ agreement between numerical and experimental work. Cui et al. [45]
terials. It is prepared by incorporating ZrO2 with oxides such as yttria studied the effect of V-notch and groove tip angles on the fracture
(Y2O3), ceria (CeO2), and magnesia (MgO). The transformation of the toughness of different ceramic materials. They found a good agreement
tetragonal (t) to monoclinic zirconia (m-ZrO2) has been widely used to between numerical and experimental work.
increase the toughness of ceramic materials [31]. Up to now, it has been noticed that the influence of β-spodumene on
Lithium aluminosilicate (LAS) is regarded as one of the most signif­ the properties of ZTA composites has not been studied. The present
icant glass-ceramic systems. It is suitable for many applications due to its research employs the β-spodumene phase, characterized by its low
extra low and sometimes negative thermal expansion, which permits thermal expansion coefficient, for preparing β-spodumene/ZTA com­
high thermal stability and increased chemical resistance. Ceramics posites with low thermal conductivity, which is suitable for thermal
composed of lithium aluminosilicate (LAS) can maintain the body’s di­ barrier coating (TBC) applications. A numerical simulation study was
mensions throughout a broad range of temperatures. The lithium also conducted to predict the effect of β-spodumene percentage on the
aluminosilicate system consists of three essential crystalline phases: fracture toughness of β-spodumene/ZTA composites.
Spodumene Li2O–Al2O3–4SiO2, Eucryptite Li2O–Al2O3–2SiO2, and Pet­
alite Li2O–Al2O3–8SiO2 [32]. β-spodumene Li2O–Al2O3–4SiO2 is 2. Experimental procedure
frequently utilized to increase the strength of ceramics, glasses, and glass
ceramics and to enhance their chemical and thermal shock resistance. 2.1. Materials
Both traditional and advanced methods are used for preparing β-spod­
umene. The sol-gel technique has been utilized to create Aluminum tri-isopropoxide, Al(C3H7O)3 Wessex Hous, Shaftesbury,
multi-component β-spodumene composites that are ultrafine, high pu­ Dorset, SP7 9PX, UK Molekula, was used as a precursor of Al2O3. Zir­
rity, and yield. The Sol-gel process provides uniform, environmentally conium tetra-n-butoxide Zr(OC4H9)4 STREM CHEMICALS was used as a
safe products while lowering the sintering temperature and precursor of ZrO2. Yttrium oxide, Y2O3, (99.9%-Y) STREM CHEMICALS.
manufacturing time [33,34]. Tetraethyl orthosilicate TEOS, Si (OC2H5)4 (98% Aldrich). (Fluka,
Several authors studied the effect of β-Spodumene addition on the Sigma- Aldrich ChemieGmbh, Germany). Lithium Carbonate Li2CO3 98
mechanical, thermal, and densification characteristics of alumina % (Extra pure). Nitric acid (HNO3) and absolute ethanol (purity 99.8%)
[35–38], mullite, and cordierite [39,40] ceramics. Production of provided by (Fisher Scientific, UK) were used as starting materials in this
alumina-spodumene ceramics via the addition of varying proportions of study.
β-spodumene, ranging from 15 to 45 wt%, to calcined Al2O3 powders
was investigated [38]. The attained results suggest a satisfactory per­ 2.2. Preparation of zirconia toughened alumina (ZTA) by sol-gel
formance for structural uses, particularly considering the advantageous method
correlation between improved mechanical behavior and reduced ther­
mal expansion. A low thermal expansion of approximately about (5 × Zirconia toughened alumina (ZTA) was produced by combining 15
10− 6 ◦ C− 1) was identified. The composition of the resulting glass had mol% ZrO2 and 85 mol% Al2O3, as described in our previous study [46].
different lithium concentrations, which had an impact on the produced Briefly, according to the required composition, an alumina sol was
materials’ ability to expand thermally. The influence of β-spodumene created by hydrolyzing aluminum tri-isopropoxide in distilled water
mass% on the sintering behavior, densification, and mechanical char­ with a few drops of strong HNO3. The mixture was then homogenized for
acteristics of β-spodumene/alumina composites sintered between 1400 2 h using a magnetic stirrer. Zirconium tetra-n-butoxide was quickly
and 1600 ◦ C was studied [36]. It was observed that the densification dissolved in pure ethanol in a separate beaker, and once a clear zirconia
improved by increasing the amount of β-spodumene. The bending sol was achieved. Nitric acid was used to dissolve a calculated amount of
strength improved by 43% when the amount of β-spodumene increased yttrium oxide (3 mol %) in hot water, which was then added to the

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Table 1 2.4. Preparation and sintering of β-spodumene/ZTA composites

Different batch compositions of ZTA/β-spodumene composites.
Specimens′ code ZTA, wt.% Spodumene, wt.% Various amounts of ZTA powder were combined with the synthe­
sized spodumene, as illustrated in Table 1. The different batch compo­
ZTA 100 –
5S-ZTA 95 5 sitions were ground in an automated ball mill for 2 h at a constant speed
10S-ZTA 90 10 of 300 rpm. To obtain a homogenized powder, the powder mixtures
15S-ZTA 85 15 were sieved using a 90 μm stainless steel sieve. The designated batches
20S-ZTA 80 20 were uniaxially pressed at room temperature into discs with a diameter
of 15 mm and a thickness of 6.0 mm for physical and microstructural
zirconia sol. Eventually, a transparent sol of ZTA was obtained by adding evaluation and into 60 × 10 × 5 mm3 rectangular bars at 60 KN to
the 3 mol. % yttria-stabilized zirconia (YSZ) sol to the aluminum examine the mechanical characteristics of the batches under study. The
tri-isopropoxide solution. To produce the gel, the resulting sol was produced samples were sintered in a static air electric oven at various
stored for a whole night. After that, they were dried at 100 ◦ C and temperatures 1400◦ , 1500◦ , 1600◦ , 1650◦ , and 1675 ◦ C at a heating rate
calcined for 2 h at 1200 ◦ C with a heating rate of 10 ◦ C per minute. The of 5 ◦ C/min and soaked for an hour, as illustrated in Fig. 1.
phase composition of the residual powder was investigated using an
X-ray diffractometer (XRD). 2.5. Characterization

2.3. Preparation of β-spodumene by sol-gel method The Archimedes method (ASTM C-20) was used to determine the
fired specimens’ bulk density and apparent porosity [47]. In order to
In order to fully dissolve aluminum isopropoxide (AIP), it was pro­ calculate the relative density of the sintered composites, the measured
gressively dissolved in hot distilled water and agitated for 2 h. In another bulk densities of five sintered samples from each mentioned composition
beaker, nitric acid and Li2CO3 were combined until Li2CO3 was were compared to their theoretical values (theoretical densities for ZTA
completely dissolved. Then, it was added to the AIP solution and and β-spodumene are 4.29 g/cm3 and 2.406 g/cm3, respectively). The
continuously stirred until the mixture turned clear. Complete hydrolysis phase composition of the prepared materials and studied samples were
was achieved to TEOS by adding 1 mL HNO3 to 500 mL of distilled water investigated by X-ray diffraction (XRD) with CuK radiation (D 500,
and stirring at 80 ◦ C. This was done at 80 ◦ C. It was subsequently added Siemens, Mannheim, Germany), using a Philips PW 1730 X-ray
to Li-AIP solution and was allowed to gel at 80 ◦ C. The resulting gel was diffractometer equipped with a Cu target and Ni filter. The equation of
left to dry overnight at 100 ◦ C before being calcined for 1 h at 1200 ◦ C the Debye-Scherrer method [48] was applied to calculate the average of
with a firing rate of 10 ◦ C/min. the β-spodumene particle size based on the XRD data by using the
following equation (1):
D = kλ/(βCos θ) (1)

Fig. 1. Processing scheme for pure ZTA and β-spodumene/ZTA composites’ fabrication and characterization.

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Table 2 where K1pb is the fracture toughness, Pmax is the max load, So is the
The mean value of the experimental specimen dimensions used in numerical
specimen span, a is the crack length, W is the specimen width, and B is
simulations. (All dimensions in mm).
the specimen thickness.
Specimens′ Smooth Pre-Cracked Using a dilatometer (NETZSCH DIL 402 PC), Thermal expansion
code
Specimen’s Geometry Specimen’s Geometry Crack measurements were performed on bars sized (25 × 5 × 5) mm in the
Geometry temperature range of ambient temperature to 1100 ◦ C at a heating and
L B W L B W a cooling rate of 5 ◦ C/min. The average values of five samples of each
ZTA 44.5 9.59 4.5 44.38 4.5 9.51 4.25
composition were used for the evaluation of the thermal expansion co­
5 S-ZTA 43.58 9.05 4.4 43.58 4.42 9.1 4.1 efficient of the studied composites.
10 S-ZTA 46.48 9.29 4.69 46.52 4.69 9.38 4.34 The thermal diffusivity was determined using a laser flash analyzer
15 S-ZTA 45.54 8.82 4.6 45.63 4.6 8.7 3.84 (Linseis LFA 1000, Germany). Five disks of each composition (diameter
20 S-ZTA 45.84 9.16 4.66 45.84 4.66 9.22 4.3
of 10 mm) of the sintered samples were prepared for thermal diffusivity
measurements. Thin gold layer was deposited on the surface of the
where D: the crystalline size of nanoparticles (nm), k: Scherrer constant samples to spread the heat impulses homogeneously on the surface of
= 0.9, λ: the wavelength of x-ray source = 1.542 Å, β: the full width at the samples. Additionally, a thin graphite layer was sprayed onto both
half maximum (FWHM) (radians), θ: peak position (radians). Trans­ sides of the samples before measurements to hinder any reflection of the
mission electron microscopy (TEM) at 200 kV was performed using laser beam or the sensitivity of the IR sensor on the back side of the
JEOL, Japan’s JEM-2100-HR Electron probe micro-analyzer, to assess samples. One side of the sample was heated by a short laser pulse and the
the prepared spodumene’s particle size. temperature rise on the opposite side was measured using an infrared
Scanning Electron Microscopy (SEM; Model XL 30, Philips, Eind­ detector. α(T) was thus determined by the following equation (6), ac­
hoven, Netherlands with an attached EDX unit) was used to study the cording to the standard ASTM E1461-01 [52].
samples’ microstructure. The samples were thermally etched at 1500 ◦ C
d2
for 15 min. The grain size has been measured using ImageJ software α(T) = 0.1388 × (6)
t1/2
program (https://imagej.net).
The Vickers hardness of the sintered samples was measured with a
where d is the thickness of sample, t½is the time needed for the back of
hardness tester (Omnimet automatic MHK system Model Micro Met
the specimen to reach half of the maximum temperature after pulse
5114, Buehler USA). 30 indents were indicated, and the mean hardness
heating. The measurements were carried out from room temperature up
was determined. According to the following equation (2) [49]:
to 1000 ◦ C (with a step of 100 ◦ C) in a vacuum. At least three mea­
P surements were taken at each temperature, and the data was averaged.
H = 1.8544 (2)
d2
3. Numerical work
where P is the load and d is the length of the diagonal s impression.
A three-point bending test was adopted to measure the flexural The two-dimensional finite element method (2D-FEM) was imple­
strength and fracture toughness of the present compositions using a mented using ABAQUS software to simulate the progressive damage
universal testing machine (Tinius Olsen 25 ST), according to ASTM process of smooth and pre-cracked ceramic matrix composite specimens
C1161-13 [50] and ASTM C1421-18 [51], respectively. The measure of [53]. In this study, the extended finite element method (XFEM) was
bending strength was obtained by a crosshead speed of 0.5 mm/min. adopted to obtain crack initiation and propagation and load-deflection
Ten rectangular specimens with dimensions of 5 mm × 10 mm × 50 mm curves of smooth and pre-cracked specimens. XFEM is an extension of
were polished and then ground for each composition; five replicas were the conventional FEM. This makes it possible for discontinuities to occur
used to measure the flexural strength, and the other five were used to in an element by using enrichment functions. Additional nodes are given
measure the fracture toughness of each composition. The failure load enrichment functions to understand the discontinuity and singularity
obtained from the 3-point bending test is used to calculate the bending surrounding the crack. These two functions follow the discontinuity that
strength using the following equation (3): occurs when the crack opens and is sensitive to singularities [53–55].
3Pf L To get the stress intensity factor (SIF) for the pre-cracked specimens,
σ= (3) the Contour Integral Technique (CIT) was used [53,54]. The beginning
2BW2
of the material failure was investigated using the CIT. The J-integral is
where σ is the bending strength, Pf is the failure load, L is the specimen often used to characterize the energy release associated with the growth
length, W is the specimen width, and B is the specimen thickness. of cracks in rate-independent quasi-static fracture analysis. If the ma­
The fracture toughness was obtained by notches that were made on terial response is linear, the J-integral can be related to the stress in­
the surface (10 mm × 50 mm) using a diamond-charged cutting wheel tensity factor. The energy release rate connected to crack advance
perpendicular to the rectangle bar’s length. The depth of the notches defines the J-integral. To describe the strength of the crack tip singu­
was approximately up to 50% of the height of the specimen, and the larity, Rice developed the J-integral. The stress intensity factor can be
fracture toughness was determined by applying the following equations determined using the following Equation (7) for mode I since the J-in­
(4) and (5): tegral equals the energy release rate [56].
⎡ ⎤ √̅̅̅̅̅̅̅
[ ]1 ʹ
a 2 K= J.E (7)
Pmax So 10− 6 ⎢ 3 w
[ ]⎢ ⎥
⎥
KIpb = g ⎢ [ (4)
3 ⎣ ] ⎥
1 ⎦
BW2 2 1− a 2
ʹ ʹ
w Where K is SIF, E = E for plane stress, and E=1−EѴ for the plane strain.

[ ][ ][ [ ] [ ]2 ]
1.99 − a
1 − a 2.15 − 3.93 a
+ 2.72 a 3.1. Specimen geometry and mechanical properties
(a) w /w w w
g=g = [ ] (5)
w 1 + 2 wa In this investigation, there are five groups, each group containing
three to five replicas, as listed in Table 2. Specimen’s geometry, such as
length, width, and height, varied for each specimen whether it is smooth

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Table 3 3.2. Boundary conditions

Specimen’s groups of mechanical properties for numerical simulation.
Specimens′ code E (GPa) ν G (N/mm) σmax (MPa) Contact between surfaces is utilized according to the master and
slave approach. In the current FE model, the contact surfaces of the
ZTA 109.787 0.124 0.144 132.35
5 S-ZTA 147.627 0.174 0.154 207.25
specimen are denoted as the slave surfaces, while the more rigid ele­
10 S-ZTA 75.714 0.099 0.082 93.9 ments, such as the loading components and the supporting structures,
15 S-ZTA 902.51 0.114 0.118 104.03 are designated as the master surfaces [53]. Furthermore, these contact
20 S-ZTA 75 0.176 0.113 83.66 characteristics are simulated using the penalty friction formulation.
Since the coefficient of friction between advanced ceramics and steel can
or pre-cracked, but the value of span (So) is 40 mm, which is constant for range from 0.3 to 0.7 but is typically 0.4 for ZTA ceramics in dry sliding,
all specimens, and the crack width is constant for all pre-cracked spec­ the friction coefficient between the specimen and the other parts is
imens which are about 0.45 mm, but the crack length varies from group considered 0.4 according to these references [58–62]. Two support el­
to another. It is worth noting that the orientation of the 3-BP specimens, ements are responsible for providing the necessary structural support to
according to ASTM C1161-13 [50], i.e., their widths are greater than the specimen, as shown in Fig. 2.
their heights. Each one of the support elements has its degrees of freedom (DOF) to
Mechanical properties such as Modulus of Elasticity (E) have been achieve equilibrium conditions in the model, as the right one acts as
obtained using two different methods; the first one is computed roller support that allows moving in the (X-direction) and prevents
analytically using Equation (2), and the other one was obtained through moving in the (Y-direction). On the other hand, the left support acts as
sonic Resonance (sound wave technique) according to ASTM C1198-20 hinged support with zero DOF in all directions. The specimen experi­
[57]. In the current study, the Modulus of Elasticity that has been used ences loading through a central loading part located at its mid-span.
was obtained analytically according to the following equation (8): Additionally, the loading part is constrained to have only one DOF in
(Y-direction). The loading part is subjected to load using a displacement
P × L3 control method.
E= (8)
48 × δ × I

where P is the applied load (N), L is the specimen’s span (mm), δ is the 3.3. Meshing and mesh sensitivity
deflection (mm), and I is the moment of inertia (mm4).
The mechanical properties of each group in the current models, such A mesh sensitivity analysis and model verification were performed
as Modulus of Elasticity (E), Poisson ratio (ν), Maximum Bending Stress before comparing the results of the numerical model for the Flexural
(σmax ), and Fracture energy (G), are listed in Table 3. Strength test with the experimental results. The effect of element size is
assessed to determine the ideal element size to simulate the current
experimental work. This is accomplished with group specimens of 5 S-

Fig. 2. The boundary condition for loading parts and supports.

Fig. 3. The details of a simulated beam sample with mesh arrangement.

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S.M. Naga et al. Journal of Materials Research and Technology 31 (2024) 372–387

( )
(a) g a
w
f = (9)
w √̅̅̅ ( )3
a 2
π× 1− w

As shown in Fig. 4, when the element size decreases, the error be­
tween the analytical geometry correction factor values and numerical
simulation diminishes until it reaches 0.2 mm element size; the error is
found to be the same even if it is down than 0.2 mm. Therefore, the more
suitable element size for the present numerical work is 0.2 mm, as it
gives the most minor error. According to the mesh element size of 0.2
mm that has been selected, the numbers of nodes and elements of each
model were tabulated in Table 4.

4. Results and discussion

4.1. Experimental results

4.1.1. Characterization of the β-spodumene

Fig. 5a shows the phase composition of the β-spodumene powder
Fig. 4. The effect of mesh size on the geometry correction factor.
calcined at 1200 ◦ C using X-ray diffraction analysis (XRD). The figure
illustrated that β-spodumene (β-LiAlSi2O6) is the only phase detected
with high crystallinity and sharpness peaks, where no other secondary
Table 4 phases were detected. The developed β-spodumene matches the JCPDS
The numbers of nodes and elements of each model. (76–0921) tetragonal crystal system. Ferraz et al. [63] demonstrated
Specimens′ code Smooth Pre-Cracked that β-LiAlSi2O6 phase starts to develop from around 700 ◦ C. However,
Abdallah et al. [64] concluded that β-quartz tends to appear intermit­
Elements Nodes Elements Nodes
tently at temperatures above 1075 ◦ C, possibly as a consequence of the
ZTA 2439 2592 4873 5074 complete disappearance of α-spodumene at 1125 ◦ C and then again due
5 S-ZTA 2293 2443 4669 4867
to the complete conversion of γ to β-spodumene at 1200 ◦ C. Accordingly,
10 S-ZTA 2637 2795 5055 5261
15 S-ZTA 2485 2640 4678 4878 we selected 1200 ◦ C to obtain pure and well-crystalline β-spodumene.
20 S-ZTA 2589 2745 4955 5159 Furthermore, the Debye-Scherrer method was utilized to calculate the
average particle size of the produced β-spodumene powder based on
XRD data. The results indicate that the average particle size is = 38.39
ZTA, which give higher results in all experimental investigations. The ± 10.50 nm.
mesh refinement focused on the crack region where the crack begins to The crystalline shape and size of the synthesized β-spodumene are
propagate due to the high-stress gradients. Around the crack of about 2 investigated using a transmission electron microscope (TEM), Fig. 5b.
mm on both sides of the crack, the mish size was minimal, and it The results indicate that β-spodumene particles possess semi-hexagonal
gradually became larger as it moved outward to both ends of the spec­ forms. Highly agglomerated particles with size ranges between 24.22
imen. The meshing process was accomplished to the numerical model as and 43.78 nm were observed in the sample. Moreover, the results of
shown in Fig. 3 using element type CPS4R (A 4-node bilinear plane stress β-spodumene powder particle size distribution estimated by TEM are
quadrilateral, reduced integration, hourglass control) for both specimen illustrated in Fig. 5c. The data showed that the mean diameter of
and supports. β-spodumene nanoparticles calculated from TEM images (DTEM) is 36.23
Different mesh sizes were used,i.e., 0.1, 0.2, 0.4, 0.8, 1, 1.3, and 1.5 ± 2.03 nm, which agrees with the results obtained from the XRD anal­
mm. Fig. 4 displays the relationship between the crack length-to-depth ysis. All the results prove that β-spodumene powder is in the nano-scale
ratio and the geometry correction factors for various mesh sizes. SIF with a particle size ranging between 24.22 and 43.78 nm.
was calculated according to Equations (4) and (5), as mentioned before
[51]. As known, Y is the geometric correction factor for bending speci­ 4.1.2. Characterization of the sintered β-spodumene/ZTA composites
mens, which is equal to f (a/w), which is calculated by the following
equation (9) based on the previous equations (4) and (5):
4.1.2.1. Sintering behavior. Fig. 6 illustrates the effect of sintering

Fig. 5. The synthesized nano spodumene powder’s (a) XRD pattern, (b) TEM image, and (c) particle size distribution diagram obtained by TEM image.

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Fig. 6. The effect of sintering temperatures and β-spodumene wt.% on both (a) the bulk density and (b) the apparent porosity of the studied samples.

temperatures and β-spodumene wt.% additions on both (a) the bulk

density and (b) the apparent porosity of the studied pure ZTA and
β-spodumene/ZTA composite samples. It could be noticed that, at a high
sintering temperature of 1675 ◦ C, the 5 S-ZTA sample exhibited the
highest density value of 3.68 g/cm3, accompanied by an apparent
porosity of 4.45%. In contrast, the pure ZTA sample revealed a slight
reduction in density of 3.49 g/cm3, accompanied by a 14.25% measured
apparent porosity. The introduction of 5 wt% β-spodumene plays the
mineralizer role in enhancing the densification process [36].
On the other hand, samples containing 10–20 wt% β-spodumene
showed a reduced apparent porosity and an increased bulk density when
the sintering temperature was increased from 1400◦ up to 1600 ◦ C, this
behavior could be attributed to the polarization ability of Li+ ions for the
Al ions to form the lithium aluminum silicate phase. The formation of
the new phase led to a decrease in the viscosity of the formed liquid
phases. The formed low viscose liquid phase fills the pores and grain
boundaries, enhancing the densification of the sintered samples [65,66].
Also, it could be noticed that increasing the β-spodumene wt.% to more
than 5% reduced the sintering temperatures of the sintered samples by
75 ◦ C. This behavior is due to the formation of the lithium aluminum
silicate liquid phase, which serves as a sintering aid by its
intra-agglomeration effect [36]. At the same time, increasing the
Fig. 7. X-ray diffraction patterns for pure ZTA (3 mol% YSZ) and 5 wt% β-spodumene wt.% from 15 to 20% reduced the bulk density of the
β-spodumene-ZTA composite samples fired at 1675 ◦ C. samples at higher sintering temperatures. This behavior was explained
by some researchers [67,68], who claimed that raising the β-spodumene
wt.% could enhance the liquid phase formation, which enables the

Table 5
Thermal and mechanical behaviors of different studied samples at their optimal sintering temperatures.
Thermal Behavior Mechanical Behavior
6
Specimens’ code Coefficient of Thermal Expansion x(10− Thermal Diffusivity Bending Strength Fracture Toughness (MPa. Vicker’s Hardness
◦ − 1
C ) (mm2/s) (MPa) m0.5) Number
(1000 ◦ C)

ZTA 7.98 þ0.012 1.31 þ0.02 132.35 þ5.8 4.05 þ0.4 966.28 þ24.7
¡0.024 ¡0.02 ¡4.1 ¡0.15 ¡7.3
5 S-ZTA 7.52 þ0.02 0.95 þ0.03 207.25 þ9.6 5.04 þ0.17 1749.40 þ28.2
¡0.021 ¡0.04 ¡7.8 ¡0.6 ¡21
10 S-ZTA 6.50 þ0.013 0.91 þ0.02 93.91 þ11 2.50 þ0.3 1410.20 þ17.5
¡0.024 ¡0.013 ¡3.9 ¡0.23 ¡25.2
15 S-ZTA 5.62 þ0.016 0.84 þ0.02 104.03 þ2.1 3.89 þ0.2 1015.08 þ9.6
¡0.021 ¡0.014 ¡2.7 ¡0.25 ¡21.4
20 S-ZTA 5.33 þ0.017 0.70 þ0.02 83.66 þ2.9 2.71 þ0.16 654.90 þ16.3
¡0.019 ¡0.01 ¡4.6 ¡0.11 ¡11.2

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Table 6
Maximum applied load and deflection of experimental and numerical results for smooth specimens.
Specimens′ Specimens Load Deflection Experimental Numerical Error %b
Code (N) (mm) a
Average S.D. CoV % +++
Load Deflection Load Deflection
(N) (mm)
Load Deflection Load Deflection Load Deflection
(N) (mm) (N) (mm)

ZTA Z1 428 0.074686 428.25 0.07 14.6 0.005 3.4 6.6 449.23 0.073 4.9 2.9
Z4 424 0.067087
Z7 448 0.0759
Z10 413 0.0673
5 S-ZTA A1 612 0.08455 635.5 0.0891 48.7 0.005 7.7 5.6 680.4 0.0892 7.1 0.1
A4 579 0.08531
A8 685 0.09482
A10 666 0.09156
10 S-ZTA B1 313 0.0657 320 0.07 33.4 0.006 10.4 8 346.7 0.073 8.3 3.54
B2 364 0.07252
B5 283 0.065401
B8 320 0.07689
15 S-ZTA C2 338 0.068361 322.8 0.067 20.9 0.007 6.5 10.3 349.7 0.069 8.3 4.1
C4 319 0.06462
C5 288 0.05571
C9 338 0.07234
C10 331 0.072184
20 S-ZTA D3 258 0.062932 265.78 0.063 12.2 0.004 4.6 6.6 288.7 0.064 8.6 0.88
D4 285 0.063853
D7 267 0.05968
D8 253 0.05974
D10 265.92 0.06981

• S.D.
+++
= coefficient of variation × 100. Error %.
a
= standard deviation. CoV%.
b
= Error between numerical values and average of experimental values ((Num - Exp)/Exp) × 100.

Table 7
Experimental and numerical results of load and deflection of pre-cracked specimens.
Specimens′ Specimens Load Deflection Experimental Numerical Error %
Code (N) (mm)
Average S.D. CoV % Load Deflection Load Deflection
(N) (mm)
Load Deflection Load Deflection Load Deflection
(N) (mm) (N) (mm)

ZTA Z3 185 0.0252 185.5 0.0286 13.3 0.003 7.2 9.7 203.05 0.029 9.5 2.8
Z5 197 0.03024
Z6 193 0.03142
Z9 167 0.0276
5 S-ZTA A2 239 0.03882 211.5 0.0386 21.5 0.003 10.1 7.3 217.61 0.0406 2.9 5.1
A3 217 0.04215
A5 190 0.03526
A9 200 0.0381
10 S-ZTA B3 123 0.03045 111.8 0.0347 10.2 0.004 9.1 11.8 121.02 0.0353 8.2 1.75
B4 100 0.0411
B6 122 0.03255
B7 106 0.03333
B9 108 0.03618
15 S-ZTA C1 135 0.0415 147 0.0381 19.9 0.003 13.6 8 134.01 0.0366 − 8.8 − 4.1
C3 136 0.03558
C6 170 0.0373
20 S-ZTA D1 100 0.0322 118.3 0.0394 12.8 0.006 10.9 16.3 129.26 0.0412 9.3 4.47
D5 119 0.03625
D6 125 0.04252
D9 129 0.0466

appearance of the pores. It is well known that pores hinder the densi­ Concerning the pure ZTA sample, the resulting patterns indicate the
fication of the ceramic bodies. Also, the low density of the β-spodumene presence of alumina as a corundum phase (α-Al2O3; rhombohedra-
phase (2.38 g/cm3) compared to ZTA density (4.29 g/cm3) can auto­ structured ICDD card standard data No. 75–1865). While two ZrO2
matically decrease the net bulk density of the produced composite phases were identified: the tetragonal phase (t-ZrO2; ICDD card standard
specimens. Therefore, in this study, sintering temperatures of 1675 ◦ C data No. 88–1007) and the monoclinic phase (m-ZrO2; ICDD card
for ZTA and 5 S-ZTA samples and 1600 ◦ C for 10 S-ZTA, 15 S-ZTA and standard data No. 88–2390). It is noticed that the t-ZrO2 phase is present
20 S-ZTA samples are considered the optimal sintering temperatures. as the main phase with the highest intensity while a few minor peaks of
the m-ZrO2 phase are observed.
4.1.2.2. Phase composition. Fig. 7 displays the XRD diffraction patterns Addition of 5 wt% β-spodumene slightly decreased the peak intensity
of pure ZTA and the 5 S-ZTA composite samples sintered at 1675 ◦ C. of the t-ZrO2 in the sample sintered at 1675 ◦ C. No secondary phases

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thermally etched pure ZTA composite. The dominant phase present is α-

Al2O3 (grey grains) with grains of different sizes and morphology of
equiaxed or hexagonal. It is worth noting that the grain size of α- Al2O3
has been measured using ImageJ software program. ZrO2 particles
(white grains) displayed up through the Al2O3 matrix in a homogeneous
distribution, which were either small particles located inside the Al2O3
particles (intragranular) or as agglomerate batches at the triple junctions
of the α-Al2O3 particles (intergranular). The ZTA sample micrographs
indicate the high porosity of the samples even at the sintering temper­
ature of 1675 ◦ C and the complete absence of the liquid phase. On the
other hand, adding 5 wt% β-spodumene to ZTA (5 S-ZTA specimens)
enhanced the coalescence of the α-Al2O3 grains via the presence of the
liquid phase created by the dissociation of β-spodumene at the high
sintering temperature of 1675 ◦ C. The presence of the liquid phase
enhanced the densification process due to the mineralizing role played
by the 5% β-spodumene addition Fig. 9 (b and g).
The micrographs for the 10 S-ZTA samples shown in Fig. 9 (c and h)
indicated that the α-Al2O3 grains have nearly the same structure as 5 S-
ZTA composites with nearly equiaxed grain structure. However, more
intergranular ZrO2 and twinned ZrO2 grains in the matrix suggest an
increased t-m ZrO2 transformation. Some previous studies revealed that
the intragranular particles are tetragonal ZrO2, while the intergranular
is mainly monoclinic ZrO2 [70].
Fig. 8. XRD patterns for the sintered composite samples containing 10–20 wt% Increasing the β-spodumene content to 15 wt %, Fig. 9 (d and i)
β-spodumene compared to the pure ZTA sample at 1600 ◦ C. shows an alumina elongated grain structure with a more homogeneous
network arrangement than the previous presented samples. This may be
were observed, which may be an indication of the effect of raising the assigned to some silica glassy phase production mainly associated with
sintering temperature to 1675 ◦ C on the dissolving of β-spodumene and the decomposition of the zircon phase [71]. Generally, the glassy phase
the improvement in the densification of the produced sample Fig. 5a. formation causes the alumina grains to transform from deficient
This emphasizes that the 5 wt% spodumene’ content in the 5 S-ZTA boundaries to homogeneous and connected networks, as shown in Fig. 9
composite sample acts as a mineralizer [36]. (d and i) [72]. We believe that the developed homogenous and
Fig. 8 illustrates the phase compositions of the pure ZTA and sintered well-distributed alumina grains created by the presence of a small
samples containing 10, 15, and 20 wt% β-spodumene (entitled as 10 S- amount of the generated glassy phase improved the mechanical
ZTA, 15 S-ZTA, and 20 S-ZTA) at their optimal sintering temperature of behavior. It worth mentioning that the glassy phase cannot be detected
(1600 ◦ C). It is clear that the most observed phase is the corundum phase by the XRD analysis due to its small amounts.
(α-Al2O3; ICDD card standard data No. 43–1484). Moreover, small- The micrographs of composites containing 20 wt% β-spodumene,
intensity zircon’s peaks (ZrSiO4; ICDD card standard data No. Fig. 9 (e and j) revealed a less crystallized grain structure with the
83–1374) were detected in samples containing 10 wt% and 15 wt% appearance of elongated-grained alumina grains. The existence of a
β-spodumene. The formation of the zircon (ZrSiO4) phase is related to minor quantity of small grains may be referred to as the formation of the
the reaction between ZrO2 and β-spodumene. eucryptite phase.
It was noticed that by the increase in the β-spodumene content up to Fig. 9 (k-o) illustrates the energy dispersion X-ray spectroscopy
20 wt% (20 S-ZTA sample), ZrSiO4 peaks were predominantly dis­ (EDX) analysis for the studied pure ZTA and β-spodumene/ZTA com­
appeared, while marked new eucryptite phase peaks (LiAlSiO4; ICDD posite samples. The result shows that, as the β-spodumene content in the
card standard data No. 13–0378), and small peaks of lithium silicate ZTA matrix material increased from 5 to 20 wt%, an increasing Si
(Li2Si2O5; ICDD card standard data No. 04–0436) was observed. element peak was observed, which could be attributed to the formation
It is to be mentioned that t-ZrO2 peak intensity decreased with a of lithium aluminum silicate phases, such as LiAlSiO4, and Li2Si2O5. This
marked increase in the m-ZrO2 peak intensity as the β-spodumene result has been confirmed by XRD analysis. In contrast, the Zr element
content increased. The previous behavior could be attributed to two peak was more intense in the pure ZTA sample and became less intense
main factors: 1) the interaction between yttria and several oxides such as when β-spodumene was added.
SiO2 hinders its stabilization effect on ZrO2, leading to the promotion in
the formation of m-ZrO2 and directing to the reduction in the stabili­ 4.1.2.4. Thermal behavior
zation of the t-ZrO2 phase [31]. 2) The decomposition of zircon (ZrSiO4), 4.1.2.4.1. Thermal expansion coefficient. It is well known that
which starts to form at about 1600 ◦ C and significantly increases at α-Al2O3, t-ZrO2, and m-ZrO2 exhibit high thermal expansion coefficients
1650 ◦ C into both amorphous SiO2 phase and t-ZrO2, which is sponta­ of 7.5 × 10− 6, 11.60 × 10− 6, and 10.31 × 10− 6 ◦ C− 1, respectively.
neously transformed into a monoclinic structure (m-ZrO2) during the Whereas zircon has a low thermal expansion of 4.1 × 10− 6 ◦ C− 1, and
whole cooling process [69]. It is to be stated that with the increase in the eucryptite has a negative thermal expansion of − 4.93 × 10− 6 ◦ C− 1 [73].
β-spodumene content (from 15 to 20 wt%) and formation of the LiAl­ It will be difficult to predict the value of the final coefficient thermal
SiO4phase, the α-Al2O3 peak was shifted from 2θ = 25.70◦ to 2θ = expansion of the sintered composites as a result of the newly developed
25.36◦ with an increase in its intensity due to the overlapping with the phases generated during the composites’ sintering illustrated in XRD
LiAlSiO4 phase present at 2θ = 25.36◦ . results (Fig. 7) and the thermal expansion mismatch between the pro­
duced phases in the studied samples.
4.1.2.3. Microstructure. Fig. 9 illustrates the scanning electron micro­ Table 5 displays the coefficient of thermal expansion (CTE) for pure
scopy (SEM) micrographs at various magnification ranges and the en­ ZTA and various β-spodumene/ZTA composite samples fired at the
ergy dispersion X-ray spectroscopy (EDX) of pure ZTA and optimal sintering temperature. The table shows that the thermal
β-spodumene/ZTA composite samples at the optimum sintering tem­ expansion coefficient decreases with increasing β-spodumene content up
peratures. Fig. 9 (a and f) shows the SEM micrographs of polished and

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Fig. 9. The scanning electron microscopy (SEM) micrographs at various magnification ranges (a–j) and their energy dispersion X-ray spectroscopy (EDX) analysis
(k–o) of pure ZTA and β-spodumene/ZTA composites at their optimum sintering temperature.

to 20 wt%. The reduction in the CTE of the studied composites with the transformation of β-spodumene into eucryptite.
increase in the β-spodumene content is probable due to the formation of 4.1.2.4.2. Thermal diffusivity. Thermal diffusivity results of ZTA/
low CTE phase (eucryptite) and the decrease of high CTE phases (like β-spodumene (0–20 wt%) measured at 1000 ◦ C are presented in Table 5.
ZrO2 and Al2O3). It is observed that the thermal expansion coefficient It is observed that increasing the β-spodumene’s weight percentages
values were significantly influenced by the increasement in β-spodu­ decreases the thermal diffusivity of the formed composite. This behavior
mene amounts, the sintering temperature and the phases formed as a could be attributed to the fact that β-spodumene possesses a lower
result of the interaction between the β-spodumene and zirconia or the thermal conductivity (2 W/m.K) compared to both alumina (30 W/m.K)

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Fig. 10. The experimental and numerical load–deflection curves for different groups of smooth specimens.

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Fig. 11. The experimental and numerical load–deflection curves for different groups of pre-cracked specimens.

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which could be attributed to the increase in the amount of glassy phase

that might hinder complete sintering, and as a result, the bending
strength is reduced. In addition, the thermal expansion coefficient
mismatch between the crystalline phases and the glass phase present in
composites can reduce the bending strength of produced composites
[79]. On the other hand, adding 15 wt% β-spodumene noticeably
enhanced the bending strength of the samples by about 10.8% compared
to that containing 10 wt% β-spodumene. The enhancement in the
bending strength may be due to the change in the alumina grains’ shape
to an elongated one, which affected the bending strength positively.
Further increase in the β-spodumene wt.% to 20% caused a pronounced
decrease in the bending strength. The destabilization of t-ZrO2 (as
mentioned in XRD results) and the increase in SiO2 % content led to a
deterioration of the bending strength [31]. Furthermore, Table 6 illus­
trates the maximum applied load and the corresponding deflection of
smooth specimens of each group. The coefficient of variance percentage
(CoV%) between each of all grouped specimens’ maximum applied load
and deflection is also illustrated in the table. The CoV% of maximum
applied load for both groups (ZTA and 20 S-ZTA) was lower than 5%,
and for groups (5 S-ZTA and 15 S-ZTA) ranged between 6% and 8%, but
the group (10 S-ZTA) was higher than 10%, at about 10.4%. However,
Fig. 12. Comparison between the Experimental and Numerical Fracture
the CoV% of deflection was less than 10% for all groups except for group
Toughness for each group specimen.
(15 S-ZTA), which was higher than 10% at about 10.3%.
4.1.2.5.2. Fracture toughness. Table 7 illustrates the maximum
and nearly close to stabilized zirconia (2 W/m.K) [74,75]. Also, it was
applied load and the corresponding deflection of cracked specimens of
mentioned by Ahmed and Pan [76] that increasing the percentages of
each group. The coefficient of variance percentage (CoV%) between
secondary phases reduces the mean free path of phonons, thus
each of all grouped specimens’ maximum applied load and deflection is
decreasing the thermal diffusivity of ceramic composites, which is in
also illustrated in the table. The CoV% of the maximum applied load for
agreement with our results when the β-spodumene percentages were
both groups (ZTA and 10 S-ZTA) was less than 10%, but the rest of the
increased up to 20 wt%. on the other hand, Porosity is a crucial factor
groups didn’t exceed 15%. On the other hand, the CoV% of deflection for
that influences the thermal conductivity of ceramics, which means that
groups (ZTA, 5 S-ZTA, and 15 S-ZTA) doesn’t exceed 10%, but it was
it could control the thermal diffusivity. Some researchers indicated that
higher than 10% for group (10 S-ZTA) as it was about 11.8%; only group
the thermal conductivity of porous silicate ceramics commonly de­
(20 S-ZTA) exceeded 15% as it was about 16.3%.
creases with increasing the porosity [77,78]. Based on the previous data,
Table 5 shows that the fracture toughness for the 5 S-ZTA samples is
we believe that increasing the percentage of β-spodumene added has a
higher than that for pure ZTA samples by about 20%. It is known that the
vital effect in decreasing the thermal diffusivity of the composites.
addition of lithium disilicate ceramics improves the fracture toughness
of ceramic composites via the interlocking of microstructure and crys­
4.1.2.5. Mechanical behavior talline shapes [80]. It is noticed from Fig. 9 (f) and (g) that the aspect
4.1.2.5.1. Bending strength. Table 5 illustrates the three-point ratio of the 5 S-ZTA sample’s grain is higher than the pure ZTA samples,
bending strength of ZTA and ZTA/β-spodumene composites. β-spodu­ i.e., 5 S-ZTA grain size’s (ranged between 5.04 and 7.04 μm) > pure ZTA
mene addition of 5 wt% increased the bending strength of the com­ grain size’s (ranged between 1.98 and 3.12 μm), Such a situation can
posites from 132.35 MPa for pure ZTA samples to 207.24 MPa for 5 S- promote bridging and hinder crack propagation, thus enhancing the
ZTA composites. This behavior could be attributed to the denser struc­ fracture toughness [81]. Also, the addition of β-spodumene to
ture obtained by 5 wt% β-spodumene addition, Fig. 6b. The β-spodu­ alumina-ceramics closes connected pores; therefore, the microstructure
mene content of 10 wt% reduced the bending strength to ≈94 MPa becomes more compact, corresponding with water absorption’s

Fig. 13. Comparison of the failure of specimens between the experimental and numerical for both (a) Smooth Specimens and (b) Pre-Cracked Specimens.

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reduction and open porosity, resulting in improved fracture toughness until it reaches the top edge, and the specimens fail. There is a good
[65]. The reduction in fracture toughness from 5.04 MPa m0.5–2.5 MPa agreement between the numerical prediction and the experimental
m0.5 by increasing the β-spodumene wt.% to 10% may be due to the high measurements, revealing that the FEA is a good candidate for predicting
increase in the porosity% (compared to all studied samples) [82]. the flexural and failure behaviors of ceramic composites.
Increasing the β-spodumene wt.% to 15% raised the fracture toughness
by 55% (3.89 MPa m0.5), Table 5. It could be because of the rod-like 5. Conclusion
morphology of the α-Al2O3 particles compared to specimens with low
β-spodumene percentages. Despite the slight increase in the porosity of Ceramic composites candidated for thermal barrier coating (TBC)
these specimens, the rod-like grains could improve fracture toughness applications were developed by combining various weight percentages
results to a higher degree [83]. Raising the spodumene wt.% to 20% of β-spodumene (0–20 wt%) with partially stabilized zirconia toughened
reduced the fracture toughness to 2.71 MPa m0.5. Fig. 9d clarifies that alumina (ZTA). The results outlined the followings:
the samples’ degree of crystallization at this concentration is lower than
all other studied samples. The lower mismatch between the grains and • The interaction between Y2O3 and SiO2 oxides, plus the decompo­
the glassy phase is an additional factor leading to lower residual stresses sition of ZrSiO4, affected the stabilization process of ZrO2. It pro­
and lower energy required during crack deflection, resulting in lower moted the formation of m-ZrO2 and reduced the percentage of the
fracture toughness values [81]. Also, the increase in the m-ZrO2 per­ stabilized t-ZrO2 phase.
centages is an essential factor in reducing the fracture toughness results • Increasing the β-spodumene wt.% in the samples led to the formation
of the samples containing higher β-spodumene wt.%. of β-eucryptite and tiny amounts of zircon, which affected reducing
4.1.2.5.3. Hardness. The results of Vickers’s hardness of the studied the CTE of the formed composites.
composites shown in Table 5 indicated that the HV values agree with the • The addition of 5 wt% β-spodumene to ZTA composites enhanced the
porosity results. The abovementioned determinations are cited by many densification process through β-spodumene role as a mineralizer.
authors who claimed that hardness values greatly depend on the Further, an increase in β-spodumene wt.% up to 20% showed a slight
porosity % present. Also, it is noticed that 5 S-ZTA samples showed more improvement in both bulk density and apparent porosity % due to
than double the HV values obtained by the 20 wt% β-spodumene sam­ the filling of both pores and grain boundaries with the low viscous
ples. This behavior may be due to the inability of the enhanced low liquid phase.
porosity of the other composites to counterbalance the effect of the • The introduction of β-spodumene as a secondary phase and the for­
relative softness of the β-spodumene on the HV values [32,84]. From mation of new phases such as Li2Si2O5 and ZrSiO4 during sintering
another point of view, the increase in monoclinic-ZrO2 % (XRD Fig. 8) had a significant effect on reducing both the thermal expansion co­
and the higher grain sizes of β-eucryptite [85] could cause cracks for­ efficient and the thermal diffusivity of the studied composites with
mation and, thus, reduce the hardness results for such composites [86]. the increasement in β-spodumene wt.%.
• The increase in the m-ZrO2 percentages, the softness of β-spodumene
4.2. Numerical simulation and its dissociation into amorphous phases, in addition to the effect
of the increased amount of glassy phase with the increase in
4.2.1. Model verification β-spodumene wt.% than 5%, had a significant influence on the sin­
This simulation aims to determine the applied load at which the tering temperatures and the mechanical properties of the specimens.
specimens exhibit failure and its related deflection. The results of the • There is good agreement between the experimental results and the
current FE model were validated by comparing them with the experi­ numerical predictions of the flexural and fracture behavior of
mental results to ensure that the current FE model accurately represents different composites.
the test. As illustrated in Figs. 10 and 11, the validity of the FE model
was verified by comparing the experimental and the simulated load-
deflection curves of five groups of smooth and pre-cracked specimens. Declaration of competing interest
Comparisons between the relative error for each group, expressed as the
error% of maximum applied load and the deflection for the simulated The authors declare that they have no known competing financial
specimens. The average load and deflection results for each group are interests or personal relationships that could have appeared to influence
shown in Tables 6 and 7 There is a good agreement between the the work reported in this paper.
experimental and numerical results for smooth and pre-cracked group
specimens that error% doesn’t exceed 10%, as shown in Tables 6 and 7
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