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Energy Procedia 36 (2013) 872 – 880

TerraGreen 13 International Conference 2013 - Advancements in Renewable Energy

and Clean Environment

SEM- Assisted Thermophysical and Mechanical Properties of

Sintered MgO-ZrO2 Composite
Dr.Zeyad S.Ahmeda, Dr.Fadhil A.Chyadb*
a
Ministry of Sciences & Technology, Baghdad, Iraq
b
University of Technology, Department of Materials Engineering, Baghada, Iraq

Abstract

Sintered MgO-ZrO2 Composite were pressed from powders prepared in the range of 2-50 mol.% MgO using direct
mixed reaction. Sintering behaviors were followed in the temperature range of 1200 – 1600ÛC. Microhardness
measurements were determined for as-sintered, thermally-aged and thermally-shocked compacts for different MgO
content. SEM observations were used to identify and observe the phases present and to follow their reflection on the
physicomechanical properties of the sintered compacts at different MgO concentrations. The results obtained may be
allowing for tailoring the microstructure through compromisation between processing method, physical properties
and microstructural relations.

© 2013 The Authors. Published by Elsevier Ltd. Open access under CC BY-NC-ND license.
Selection and/or
Selection and/or peer-review
peer-review underunder responsibility
responsibility of the TerraGreen
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1. Introduction

Zirconium holds a unique place amongst oxide ceramic due its excellent mechanical properties.
This situation ensues from the considerable amount research work that has been carried out since the
discovery of the transformation toughening capabilities of zirconia in the mid 1970 s. Therefore, Zirconia
is one of the most studied ceramic materials [1]. At ambient pressure, usually zirconia can assume three
crystallographic forms depending on the temperature. At room temperature and upon heating up to
1170ÛC, the symmetry is monoclinic, the structure is tetragonal between 1170ÛC and 2370ÛC where cubic
is above 2370ÛC and up to the melting point [2]. Zirconia is often more useful in the phase "stabilized
state" upon heating zirconia undergoes disruptive phase changes. By adding small percentages of Yettria,

* fchyad_2009@yahoo.de

1876-6102 © 2013 The Authors. Published by Elsevier Ltd. Open access under CC BY-NC-ND license.
Selection and/or peer-review under responsibility of the TerraGreen Academy
doi:10.1016/j.egypro.2013.07.100
 Zeyad S. Ahmed and Fadhil A. Chyad / Energy Procedia 36 (2013) 872 – 880 873

the phase changes are eliminated, and the resulting material has superior thermal, mechanical and
electrical properties [3].
Stabilized zirconia is used in oxygen sensors and fuel cell membranes because it has the ability to
allow oxygen ions to move freely through the crystal structure at high temperature. The high ionic
conductivity makes it one of the most useful electroceramic[4] .
Evis et al have studied the composites of hydroxyapatite with partially stabilized zirconia with MgO
and MgF2 were pressure less sintered between 1000ÛC and 1300ÛC. They found that above 1200ÛC,
CaZrO3 was formed [5 ].
Rendtorft et al studied the mullite-zirconia composites were processed and characterized which
presented satisfactory properties for structural applications under severe, chemical and thermomechanical
conditions. Flexural strength, dynamic elastic modulus, toughness and fracture surface energy were
evaluated ,the results were explained by microstructure and the XRD-Rietveld analysis [6].
Maneshain and Banergeo have been prepared a nanocomposite material by adding 15 vol.% alumina to
Zirconia ceramic. It is clear that the sintering temperature and the addition of alumina enhanced the
mechanical properties besides the nanoscale of the particles [7].
Matsumota et al fabricated a composite material that has mechanical properties similar to biocortical
bone and high bioaffinity by compounding hydroxyapatite with the base material zirconia which
possesses high mechanical properties at low toxicity toward living organisms [8].
The study on grapheme platelet / zirconia – toughened alumina (GPL/ZTA ) composite have been done
by liu et al. The results shown that the GPLS are uniformly distributed in the ceramic matrix and survived
high temperature sintering processes .
A 40% increase in facture toughness in the ZTA composite has been achieved by adding graphene
platelet [9].
Li et al have been used ceramic tapes with different sintering behaviors and modified as
Co-sintered to build multilayer devices[10].
This work aimed to prepare compacts specimens from zirconia with 2-50mol% ZrO2 and studying the
densification behavior microstructure developments and hardness.

2. Experimental Methods

The starting powders used are high purity MgO from BDH Ltd, and ZrO2 from (Horkin and Williams
Co.Ltd.). Prior to mixing, these powders were calcined for 5hr at 850 Û and 750 ÛC respectively.
Composites powders ( 2-50 mol % MgO – ZrO2 ) were prepared by mixing and milling as suspension in
methanol using zirconia balls. The mixture was gently dried in oven and then homogenized by blending.
Disc-shaped specimens 10 and 15 mm in dia. By 3 mm thick were prepared by unaxial compaction at 3
tons using WC dies. The green compoacts were sintered in air at 1100 to 1600 ÛC for different sintering
time.
The bulk density was measured by a water displacement method (Archemdes).
The microhardness (Hv) measurements were done for as-sintered, thermally-aged and thermally-shocked
compacts. To investigate the possibility of an aging effect on the mechanical properties and phases
presents, specimens sintered at 1500 ÛC were thermally aged at 1200 ÛC for 2 , 4 and 8 hr. The effect of
thermal shocking on the properties of some sintered compacts was investigated by exposing one group of
these compacts to a temperature of 1650 ÛC ( up thermal shock ) from room temperature. Another group
of the compacts was exposed to air directly
( down thermal shock ) while it was at 1500 ÛC A JEOL – JSM scanning electron microscope was used
for the observations of microstructural changes of sintered, thermally-aged and shocked compacts.
874 Zeyad S. Ahmed and Fadhil A. Chyad / Energy Procedia 36 (2013) 872 – 880

3. Results and Discussion

3.1. Densification behaviors and microstructure

A series of experiments was undertaken to study the behavior of cubical stabilized zirconia (CSZ) in
terms of the dependence of the densifications rate on sintering times, temperatures and MgO content, the
results are shown in figs.1 and 2. It is seen from fig. 1 that the densification rate of CSZ rises and then
saturates as the sintering temperature increased the maximum density occurring around 1550 ÛC. This
could be regarded as an indication that sintering process reaches the final stage as displayed by SEM
micrographs that were shown in Fig.(3). The dependence of the sintered density on the sintering times and
MgO content is shown in Fig.(2). It can be seen that the extent of densification of the compacts is
dependent on the MgO content, being a maximum for 8 mol.% MgO. The basis for such behavior may lie
in the effect of the stabilizer (MgO) on the diffusion coefficient in the material [11]. It may also due to the
presence of different phases at different MgO concentrations. Furthermore, the observation of different
trends exhibited by the densification curves (Fig.2) suggested that the sintering mechanisms change
qualitatively with change in the MgO content.
For example, specimens with 30 mol.% MgO display a linear behavior as compared to the exponential
behavior displayed for 8 mol.% MgO.SEM micrographs shown in Fig.(3-c) and Fig.(4-a, b) clearly assist
the aforementioned differences in that 8 mol.% MgO displayed a microstructural features of single phase
while at 4 mol.% MgO, a two phase material where displayed as shown in Fig.(4-a). For MgO content of
30 mol.% SEM observation in fig.(4-b) reveals a heavily precipitated MgO at the grain boundaries.
Moreover, the density differences among the cubic, tetragonal and monoclinic phases in addition to MgO
( ȡ = 3.38 g/cc ) also be considered as another cause for densification rate variations.

3.2. Mechanical and thermal properties

The variation of Vickers microhardness at different sintering temperatures is shown in Fig.(5) in which
hardness was increased until 1500 ÛC then decline at 1600 ÛC.
Hardness increasing may be closely related to the densification behaviors noticed in Fig.(1), while
hardness decreasing can not. Therefore, other factors must be inquired.
In this category phases present and grain size effect may be regarded. SEM micrographs shown in
Fig.(3) assist the occurrence of a grain growth at 1600 ÛC as compared to the other sintering temperatures,
which may cause this hardness decreasing. Such behavior was noticed by Tsukuma et al [12] in ZrO-
CeO2 system for both of the increasing grain-size and the amount of monoclinic phase formed.
Vickers microhardness indentation was measured for different aging times. The unaged specimens
possess hardness values in around 1000 Hv, whereas aging at 1200ÛC for 30 and 60 min reduce the
hardness values to 700 and 600 Hv respectively, thereafter, the hardness increased slightly to ~ 700 Hv at
120 min and then decreased as shown in Fig.(6).
The effect of thermal shock on the hardness behavior at different MgO content is displayed in Fig.(7),
curve 2 displays the hardness variations for the as-sintered samples sintered at 1500 ÛC for 15hr.
Hardness increases and reaches a maxima at 30 mol.% MgO then decreased until 50 mol.% MgO. This
hardness decreasing may due to the precipitation of increased amounts of MgO at the grain boundaries as
displayed by SEM micrographs shown in Fig. (8 –a & b). The effect sudden up-thermal shocking ( RTĺ
1650ÛC) on the hardness behavior is displayed by curve 1 in Fig.(7). The observed decease in hardness
may be due to the occurrence of phase transformation associated with the decomposition of the cubic
phase to the tetragonal and then to monoclinic lattice.
 Zeyad S. Ahmed and Fadhil A. Chyad / Energy Procedia 36 (2013) 872 – 880 875

The transformed regions noticed in SEM micrographs (Figs. 8 and 9) assist the occurrence of this
decomposition of the cubic phase which is regarded to be the principal cause for hardness behavior
displayed in Fig.(6) [13-14].
The hardness behavior of the as-quenched specimens is displayed in curve 3 of Fig.(7) in which down
thermal shocking ( 1500 ÛC ĺ R.T) appear to enhance the microhardness up to 30 mol.% MgO. This
hardness enhancement may be arise from the retention of cubic (s.s) for the single-phase samples, from
the quenching of the ( cubic s.s + tet s.s ) for the 4 mol.% MgO samples. Also from the the quenching of
the ( cubic s.s + MgO) for 30 and 50 mol.% MgO as indicated by the equilibrium phase diagram for the
system ZrO2- MgO [15].
It is of interest to note that at a 30 mol% MgO similar hardness values are displayed for both as-
sintered and as-quenched specimens. This may be related to the stability of the CZS (s.s) and the moderate
thermal shock resistance of magnesia grains. Similar behavior was noticed for 50 mol% MgO shown in
Fig.(7) in which the MgO content has a pronounced effect which may equalize the expected hardening
resulted from the quenching operations which was clearly observed at 8 mol% MgO. Finally, it is quite
clear from the above discussion that, compromisation between the processing methods, physical
properties and phases relations may be allowing for tailoring the microstructures of ceramic and products
to be suitable for certain applications.

4. Conclusions

A. Physical and mechanical properties in addition to the microstructure were greatly affected by the
preparation methods (wet/dry) used for ZrO2-MgO system.
B. Sintered density and hardness varied with MgO content and possess a maximum at 8 mol%
MgO.
C. MgO play a dual stabilizing effect either in solid solution with ZrO2 or as a precipitate at the
grain boundaries.
D. There was a good correspondence between hardness decrease and the amount of stress-induced
transformation occurred around the indent in ZrO2- MgO system.
E. Linear increase in hardness was noticed for up thermal shock due to the stabilizing effect of
MgO against phase decomposition. Down thermal shock treatment results in a higher hardness
compared with up thermal shock treatment due to the retention of the cubic phase ( C-ZrO2 ) and
( C-s.s ) up to 30 mol% MgO.

5. References

[1] GARVIE,r.,Hannink,R.and Pascoe,R.T. " Ceramic steel ? " Nature,vol. 258,703, 1975.
[2] Kisr, E,Howard,C."Crystal Structure of zirconia phases at their interrelation" Key.Eng.
Material. vol.35,Issu 153, 1998.
[3]Evan,A.G.and Cannon ,R.M. " Toughening of brittle solids by martenstic transformation" Actta,
Mat.1986, 761,34 .
[4] Ralf,N. " Zirconia and zirconia composite in ultimann`s Encyclopedia of industrial chemistry"
Wielly-Vds-Weinhein 2005 .
[5] Evis,Z.,Vsta,M.Kutbay,I. " Improvement in sinterability and phase stability of hydroxyapatite and
partially stabilized zirconia composites" J . of European ceramic society , Vol.20,Issue 4,March
209,P 621-628 .
[6] Rendtorft, N.M,Garrido, L.B. and Agllotti. E.F. " Zirconia toughening of mullite – zirconia –
zircon composities obtained by direct sintering " Ceramics International , Vol.36 , Issu 2, March
2010, P 781 – 788 .
876 Zeyad S. Ahmed and Fadhil A. Chyad / Energy Procedia 36 (2013) 872 – 880

[7] Maneshian, M. and Banergeo M.R. " Effect of sintering on structure and mechanical properties
of alumina – 15 vol% Zirconia nanocomposite compacts " J. of alloy and compounds. Vol. 493 Issue
1 -2 , 18 March 2010 page 613 – 618 .
[8] Matsumota, T.J,An,S-H.,Ishimoto,T,Nakno,T, matsmota .T. and Imazato ,S. "Zirconia-
hydroxapatite composite material with microporous structure" Dental materials, Vol.22 , issue 11 ,
Nov.2011 , P 205 – 211 .
[9] Liu J-Yan ,H,Reece, M. and Jiang .K. " Toughening of zirconia / alumina composites by the
addition of grapheme platelets " J . of the European ceramic society, Vol.32 , issue 16, Dec. 2012 ,
page 4185 – 92.
[10] Li , W. , Feingold ,A.,Palanisamy, P. and Lorenz, G . " Co – Sintering zirconia electrolyte and
Insulator tapes for sensor application " J.American ceramic Soc 11/26/2012 .
[11] S.El-Houte,Interceram, vol.45(4) 249-52,1996.
[12] Tuskuma, K.and Shimada,M.J.Mat.Sci Vol.20 1985,1178-1184.
[13] Wei Chen,L. and Reyes-Morel,P.E.J.Amer.Ceram-Soci vol 69,1986,181-189.
[14] Evans,A.G.and Heuer,A.H,J.Amer.Ceram-Soc. Vol.63, 1980,241-248 .
[15] Grain, C.F, J.Amer. Creamic.Soci, vol.50(6).288-90.1967.
 Zeyad S. Ahmed and Fadhil A. Chyad / Energy Procedia 36 (2013) 872 – 880 877

5.5

D ens ity(g /c m )
3
5

4.5

3.5

3
1000 1100 1200 1300 1400 1500 1600 1700
o
T emperatue C

Figuere (1) Sintered density as a function of sintering temperature for zirconia compact containing 8 mol. % MgO.

Fig. (2) variation of Sintered density with sintering time for compact containing different MgO mol. % and sintered at 1500 ÛC.
878 Zeyad S. Ahmed and Fadhil A. Chyad / Energy Procedia 36 (2013) 872 – 880

a b

c d
Fig. 3 SEM - micrographs show the development of the microstructure for selected sample of Zr02-MgO system containing 8 mol
% MgO and sintered at different temperatures. (a) Sintered at 1300'C for 4 hrs. Particle particle joining characteristics of initial
Sintering stage. (b) Sintered at 1400'C for 4 hrs. Necks development. open and closed porosity existing characteristic of intermediate
sintering stage. (c) Sintered at 1500'C for 4 hrs Neck growth and some pore isolation, characteristics of Intermediate and final
sintering stage. (d) Sintered at 1600'C for 4 1m. Complete pore isolation and rounding characteristics of final stage of densification.

a b
Fig. 4 SEM-micrographs for compacts sintered at 1500°C for 4hrs sintering time. (a) Microstructure of ZrO2-4mol% MgO
compacts showing the presence of two phase structure. (b) Microstructure of ZrO2-30mol% MgO compacts showing the heavily
precipitated MgO (white) at the grain boundaries.
 Zeyad S. Ahmed and Fadhil A. Chyad / Energy Procedia 36 (2013) 872 – 880 879

Vickers Micro hardness (H.V)

1200

1000

800

600

400

200

0
1000 1100 1200 1300 1400 1500 1600 1700
o
Temperature C

Figure (5) Variation of Vickers microhardness with sintering temperature for Zr2O2 compact containing 8 mol. % MgO.

1200

1000
Micro hardness (H.V)

800

600

400

200

0
0 100 200 300 400 500 600 700

Aged time (min.)

Figure (6) Microhardness behavior as a function of aging time for compacts with 8 mol. % MgO aged at 1200 ÛC

1600

1400

1200
Micro hardness (H.V)

up thermal shock from

1000 room temp. to 1650 C

800 as sintering 1500 C for

15 hrs
600
Down thermal shock
from 1500 C to room
400 temp.

200

0
0 10 20 30 40 50 60
Mol. % of MgO

Figure (7) variation of microhardness with MgO mol concentration for a sintered and thermally- shocked compacts of ZrO2 - MgO
system.
880 Zeyad S. Ahmed and Fadhil A. Chyad / Energy Procedia 36 (2013) 872 – 880

a b
Fig. 8 SEM micrographs showing the microstructural features of thermally- shocked compacts from room temperature to 1650°C
for compacts sintered at 1500°C for 15 hrs. (a) ZrO2-30mol%MgO compacts with the presence of limited transformed region. (b)
ZrO2-50mol% MgO compacts with increasing transformed regions.

a b
Fig. 9 SEM micrograph showing the microstructure features of thermally decomposed regions for compacts sintered at 1500°C for
15 hrs and thermally shocked from room temperature to 1650°C. (a) ZrO2-4mol%MgO compacts (b) ZrO2-8mol%MgO compacts.