Final Dissertation Report

Microstructure and mechanical

properties of Alumina Zirconia
ceramic composites
Ambarish Maji
Reg. No.: 120503430
M Tech.
(Manufacturing Engg. & Technology)
Under the guidance of
Dr. H.S. Tripathi (Guide)
Mr. Ankur Srivastava

Dr. Anoop Mukherjee (Co Guide)

INTRODUCTION
Ceramics - A ceramic is an inorganic, nonmetallic solid
prepared by the action of heat and subsequent cooling.
The word "ceramic" comes from the Greek word keramikos
or keramos means potters clay.
Ceramic materials may have a crystalline or partly
crystalline structure, or may be amorphous (e.g. Glass).
Ceramic products are usually divided into four sectors
a. Structural
b. Refractories
c. White wares
d. Advanced ceramics

REFRACTORIES

Refractories are high temperature resistant materials

which retain their strength at high temperatures.

They are used to make bricks, cements, crucibles and to

make refractory linings, which line furnaces, kilns and
incinerators.

Properties of refractories
(I) Refractory materials must be chemically and physically
stable at high temperatures.
(II) They are resistant to thermal shock and chemically inert.

The oxides of Aluminium (Alumina), Silicon (Silica) and

Magnesium (Magnesia) are the most important materials

Alumina Zirconia ceramics

In todays world Alumina Zirconia composite plays a big
role in medical and mechanical industries. There are two
types of alumina zirconia composites.
(i) Alumina Toughened Zirconia (ATZ)
(ii) Zirconia Toughened Alumina (ZTA)
Alumina Toughened Zirconia (ATZ) ceramics are
attractive materials for biomedical implants and other
engineering applications requiring high strength and
abrasion resistance at ambient temperature.
It is a composite ceramic material consisting of small
(order of magnitude 1 m after firing) alumina particles
in a very fine matrix of (nanosized) zirconia particles.

ATZ
ATZ consists of two different ceramic
materials.
(i) Alumina (Al2O3)
(ii) Zirconia (ZrO2)

Alumina

Aluminium oxide is a chemical compound of Aluminium

and Oxygen with the chemical formula Al2O3. It is the
most commonly occurring of several oxides of
Aluminium, and specifically identified as Aluminium
Oxide (Alumina).

Properties of Alumina

Formula: Al2O3
Melting point: 2,072C
Molar mass: 101.96 g/mol
Density: 3.95 g/cm
Boiling point: 2,977C

Zirconia
Zirconium Dioxide (Zirconia), is a white crystalline oxide
of Zirconium. The word Zirconium comes from Arabic
word Zargon which means golden in color. Its most
naturally occurring form, Its most naturally occurring
form, with a monoclinic crystalline structure, is the
mineral Baddeleyite. Zirconium dioxide is one of the
most studied ceramic materials.

Properties of Zirconia

Formula: ZrO2
Melting point: 2715C
Density: 5.68 g/cm
Molar mass: 123.218 g/mol
Boiling point: 4300C
Soluble in: Water

Zirconia (Continued)
Zirconia consists of three different phases.
1. Monoclinic < 1170C
2. Tetragonal =1170C - 2370C
3. Cubic > 2370C
Zirconia is used in this research is not pure Zirconia but it is
Yttria stabilized Zirconia (3Y-TZP) [3 mol% Yttria stabilized
Tetragonal Zirconia Polycrystal].
ZrO2 adopts a monoclinic crystal structure at room temperature
and transitions to tetragonal and cubic at higher temperatures.
The volume expansion caused by the cubic to tetragonal to
monoclinic transformation induces large stresses, and these
stresses cause ZrO2 to crack upon cooling from high
temperatures.
When the zirconia is blended with some other oxides, the
tetragonal and/or cubic phases are stabilized.

OBJECTIVE

The main objectives of the work are

1. To develop Alumina Toughened Zirconia (ATZ) by different sintering

route.
2. To evaluate mechanical properties like hardness, fracture
toughness, and calculate the same.
3. Microstructures can be evaluated to observe grains and grain
boundaries in FESEM (Field Emission Scanning Electron Microscope).
4. AP (Apparent Porosity) and BD (Bulk Density) test can also be done
to visualize how AP and BD of ATZ changes through various
sintering routes.
5. Specific Gravity of Alumina and Zirconia are to be found out through
specific gravity test.
6. To analyze the phases of alumina, zirconia and sintered ATZ through
X Ray diffraction.

Tools and Methodologies

The project is divided into 4 categories such as

1. Product preparation: Alumina and Zirconia powders are

mixed with each other.
2. Fabrication of shapes: Bars and Discs are made of this
ceramic composite by
mixing binders
and processed through uniaxial pressing and
isopressing.
3. Sintering: Sintering is done though different sintering
route.
4. Evaluation: Evaluate the physical and mechanical
properties and microstructures of ATZ.

Product preparation
XRD (X Ray Diffraction) Analysis

Alumina and Zirconia powders are collected and sent them to

XRD (X Ray Diffraction) analysis to know the phase of
Alumina and Zirconia. Pure Alumina in room temp. is at
monoclinic phase and stabilized zirconia in tetragonal phase.

Alumina: The most common form of crystalline aluminum

oxide is known as Corundum. Generally Alumina exists in
Al2O3 phase ( monoclinic phase).

Zirconia: In Zirconia three phases are shown: Monoclinic <

1170 C, Tetragonal 1170C - 2370C, and Cubic > 2370 C. A
few percentages of the oxides of calcium or yttrium stabilize
the cubic phase. In this experiment Yttria Stabilized Zirconia
powder is in Tetragonal phase at room temperature.

ATZ: Zirconia in ATZ posses tetragonal and alumina posses

monoclinic phase.

XRD (Continued)

XRD (Continued)

It has been observed that alumina posses all monoclinic

(Corundum) phase

Yttria stabilized zirconia posses 86% of tetragonal (Zirconium

oxide) phase, 13% of monoclinic (Zirconium oxide) phase and
1% of cubic (Yttrium zirconium oxide) phase.

ATZ posses 64% of tetragonal (Zirconium oxide) phase, 19% of

monoclinic (Aluminum oxide) phase, 14% of monoclinic
(Baddeleyite) phase and 2% of cubic (Yttrium zirconium oxide)
phase.

XRD Machine
XRD Machine: X ray is a highly energized electromagnetic
radiation. All electromagnetic waves undergo diffraction or
scattering.
X-rays have a similar nature to visible light rays, but have a
much shorter wavelength.
X-ray wavelengths are comparable to the distances between
atoms in molecules, rays scattered by different atoms
interfere with each other.
If they are out of step, they cancel each other out and if
they are in step, they reinforce each other.
In this Experiment X-ray pass through ceramic powder at
desired angle. The interference of X-ray passing through the
powder shows the graph and the peak.

XRD Machine (Continued)

XRD
machine

Working process
of XRD

XRD machine working process

XRD works following Braggs law

n =2dsin

When a monochromatic x-ray beam with wavelength

is incident on the lattice planes in a crystal planes in a
crystal at an angle , diffraction occurs only when the
distance traveled by the rays reflected from successive
planes differs by a complete number n of wavelengths.

is kept constant by using filtered X- ray

radiation that is approximately monochromatic.

d may have value consistent with

the crystal structure.

is the variable parameters, in terms of

which the diffraction peaks are measured.

Chemical Analysis

Alumina: The most common form of crystalline

aluminum oxide is known as corundum. The oxygen ions
nearly form a hexagonal close-packed structure with
aluminum ions at the centre.
O

Its grain size is

0.2 m

Al

Chemical
Compositi
on

Al2O3

SiO2

Fe2O3

Na2O

Amount

99.0%

100 ppm

100 ppm

0.5%

Chemical Analysis (Continued)

Zirconia: Pure zirconium dioxide undergoes a phase

transformations like
Monoclinic (1173C)Tetragonal (2370C)Cubic
(2690C)melt
Materials related to YSZ (Yttria Stabilized Zirconia) include
Calcia, Magnesia, Ceria, Hafnia or alumina as stabilization
factor.
Its grain size is 0.15 to 0.2m

Chemical
ZrO2
Composit
ion

Y2O3

HfO2

Al2O3

Other
Oxides

93%

4.9%

2%

0.1%

< 0.1%

Amount

Fabrication of shapes
Attrition Milling
Alumina and Zirconia powders are mixed with each other at
different proportion and make 6 different batches where
alumina proportion increases from 0 to 30.
Six different batches are ZA0, ZA10, ZA15, ZA20, ZA25,
ZA30 [Z stands for zirconia and A stands for alumina].
It means in 1st batch alumina is 0%, in 2nd batch 10% and so
on.
Then each batch is grinded and mixed in attrition mill in
which both powders are mixed properly and powder
particles are grinded by zirconia balls inside attrition mill.
As a result particle size of the powder is reduced and it
becomes fine.

Attrition Mill Machine

Attrition Mill: It is a machine where powders are mixed and
grinded into smaller particle size with the help of rotating
zirconia balls.
There is a cylindrical case in which a huge numbers of tiny
zirconia balls are placed. A shaft with multiple arms is
inserted inside the case and the shaft is driven by the motor.
As the shaft rotates, zirconia balls around the shaft also
rotate and powders inside the case are grinded and mixed.
In this project Ethyl Alcohol (CH3CH2OH)is poured inside the
case to mix with powder and make a solution, because Ethyl
Alcohol does not react with Zirconia.
Motor rotates at 400 rpm for 2hrs. After this process solution
is taken out and collected in a container. While drying
Alcohol evaporates and fine powder is collected.

Attrition Mill Machine

Inside of Attrition Mill

cylinder case
Attrition Mill
Machine

Uniaxial pressing and Isopressing

Powders mixture of each batch is mixed with PVA (Poly

Vinyl Alcohol) which acts as a binder and pour it in
different geometrical mould.

when pressure is applied in the mould from one direction

they are bonded and take the shape of the mould.

Particular numbers of bars and palettes of suitable

geometrical shape are made by pressing machine.

These bars and palettes are wrapped with rubber caps and
put it in a big mould. Fill the mould with the oil and apply
pressure from one side for isopressing operation.

Better bonding is provided in bars and palettes.

Pressing and Isopressing

(Continued)

ATZ Bars and Palettes made

by pressing
1

1. Bar pressing
mould
2. Palette pressing
mould

Uniaxial Pressing Machine

Pressing machine is a machine ceramic powder mixed with

binder is inserted into the mould of a particular shape.

Pressure is applied from one direction and material comes

out from that mould in its shape when pressure is released.

In this experiment 2 tons of pressure is applied.

Pressing
Machine

Isopressing Machine

A particular geometrical shaped material wrapped up by rubber

cap is inserted into the mould of Isopressing machine. The
remaining of mould is filled up with viscous oil. Around the mould
lid two rubber bands are attached.

Then a huge amount of pressure (80 tons) is applied from one

direction to the mould and the pressure is equally spread in the
oil in all direction and through that oil equilibrium pressure
applied on the material. As a result bonding of the material gets
firm.

Iso Pressing
Machine

Sintering
Sintering is a method for creating objects from powders, including
metal and ceramic powders.
It is based on atomic diffusion. Diffusion occurs in any material above
absolute zero, but it occurs much faster at higher temperatures. In
most sintering processes, the powdered material is held in a mold
and then heated to a temperature below the melting point.
The atoms in the powder particles diffuse across the boundaries of
the particles, fusing the particles together and creating one solid
piece.
In this experiment ceramic bars and palettes are sintered at different
temp. like (1350, 1450, 1500, 1550, 1600, 1650)C for AP and BD
test.
In each sintering furnace is programmed as up to 1000C temp. rises
at 5C /min and after 1000C to final temp. it increases at 3C /min.
Then dwelling is for 2hrs. At this time furnace temp. is constant at
highest programmed point. Then it goes down gradually.

Sintering Furnace

Sintering Furnace with

Control Board

Heating coils
inside furnace
chamber

Evaluation
There are four tests are done and their
results are observed and evaluated.
1.AP (Apparent Porosity) & BD (Bulk Density)
test
2.Specific gravity test
3.Hardness and fracture toughness test
4.Observation of microstructure in FESEM

Apparent Porosity (AP) & Bulk

Density (BD) Test

Sintered materials from different temperatures are examined for

AP and BD test.
AP and BD are measured in 4 steps.
1. Dry weight (D) of sintered material is calculated.
2. These materials are wrapped in a cloth and put in water. Water
is boiling for 2 hours. As a result the pours of the materials are
filled with water.
3. Then suspended weight (S) of the material is calculated under
water. Its value is less than dry weight value.
4. At last surface water these wet materials are soaked by wet
cloth one by one. Then soaked weight (W) of those materials are
measured one by one. Which is greater than dry weight because
its pours are filled with water.

AP & BD Test

AP and BD are calculated from three weight values and

using two different formulas. Those two formulas are:

Porosity decreases and Density increases in a ceramic

material as sintered temperature increases.

AP & BD Result

AP & BD Result (Continued)

Specific Gravity Test

Specific Gravity of Alumina and Zirconia are measured.

Kerosene is used for this experiment because zirconia
reacts with water and form zirconia hydroxide.

It is tested in 4 steps:

1. Dry bottle weight (W1) is measured.

2. A few amount of powder is poured in bottle and again
bottle with powder weight (W2) is measured.
3. Then kerosene is poured in bottle fully and bottle with
powder and kerosene weight (W3) is measured.
4. After this bottle is cleaned properly and dried in hot drier
totally. Then bottle is filled with kerosene only and weight
(W4) of bottle with kerosene is measured.

Specific Gravity Result

Specific gravity is calculated using following formula:

Density of Yttria Stablized Zirconia is 5.9 gm/cc. and

density of Alumina is 3.95 gm/cc. theoretically.

Hardness and Fracture toughness

test
Hardness is a measure of how resistant solid matter
is to various kinds of permanent shape change when
a force is applied. In this experiment Vickers
hardness test is done through micro indentation
process.

Fracture toughness is a property which describes the

ability of material containing a crack to resist
fracture, and is one of the most important properties
of any material for many design applications.
The linear-elastic fracture toughness of a material is
determined from the stress intensity factor (K) at
which a thin crack in the material begins to grow. It
is denoted by KIc and has units of

Hardness and Fracture toughness

test
(continued.)
The Vickers test is often easier to use than other hardness
tests since the required calculations are independent of the
size of the indenter, loads of various magnitudes are applied
to a flat surface through indenter depending on the
hardness of the material to be measured.
The HV number is then determined by the ratio F/A, where F
is the force applied to the diamond in kilograms- force and A
is the surface area of the resulting indentation in square
millimeters. A can be determined by the formula.
or

where d is the

average length of
the diagonal left by the indenter in millimeters.

So
and its unit

, where HV is Vickers hardness no.

is kgf /mm2.

Hardness and fracture toughness

result
ZA0

ZA10

ZA15

ZA20

ZA25

ZA30

Sampl
e

Load
(Kgf)

Time
(sec.)

Hardness
(Gpa)

Fracture toughness
(Mpa.m0.5)

ZA0

10

5.80.6

8.60.3

ZA10

10

6.40.9

8.370.92

ZA15

10

7.30.2

8.110.95

ZA20

10

7.430.31

7.90.9

ZA25

10

7.660.45

6.530.17

Hardness and fracture toughness

result
(continued.)

Hardness graph

Fracture toughness graph

Microstructure observation through

FESEM
Field emission microscopy (FEM) is an analytical technique
used in materials science to investigate molecular surface
structures and their electronic properties. Microscopy
techniques are used to produce real space magnified images
of a surface showing what it looks like.

A Field Emission Microscope

consists of a metallic sample in
the form of a sharp tip and a
conducting fluorescent screen
enclosed in ultrahigh vacuum.
The tip radius used is typically of the
order of 100 nm. It is composed of a metal with a high melting
point.
The sample is held at a large negative potential (1-10 kV)
relative to the fluorescent screen. This gives the electric field
near the tip apex to be the order of 1010 V/m which is high
enough for field emission of electrons to take place.

Microstructure observation result

Field emission scanning electron microscopy (FESEM)

provides topographical and elemental information at
magnifications of 10x to 300,000x, with virtually
unlimited depth of field.

Compared with convention scanning electron

microscopy (SEM), field emission SEM (FESEM)
produces clearer, less electro statically distorted
images with spatial resolution down to 1 and 1/2
nanometers three to six times better.

Here are microscopic structures of different samples.

ZA0

ZA10

ZA20

 Grain size of alumina and zirconia are measured for

each image and calculated results are displayed in a
table
Sample
Grain size (m)
Alumina

Zirconia

ZA0

0.36

ZA10

0.67

0.31

ZA20

0.78

0.26

Parameters effecting the change of

properties of ceramic composites

Parameters those effect in the change of the properties

of ceramic composites are

1. Sintering temperature: As sintering temperature rises,

porosity of the material reduces and bulk density
increases.

2. Alumina-Zirconia mixing Ratio: As alumina percentage

increases in alumina-zirconia mixing ratio, porosity
decreases and bulk density increases.

Flow Chart of Project Work

All mechanical properties and microstructures

are yet to be tested.

Upcoming Expected Results

Mechanical properties characterization: Mechanical

properties like hardness, bending strength and fracture
toughness should increase with increasing of alumina
percentage in ATZ.

Microstructure observation: The number of alumina

grains within zirconia grains should increase with
increasing of alumina zirconia proportion in ATZ.

Applications
Alumina-Zirconia ceramic composite is used mostly in
biomedical application and orthopedic field.

This composite offers several advantages allowing the

coupling of good properties of alumina, and the hardness,
chemical inertia, biocompatibility and toughness of zirconia.

Recently CeramTec (Plochingen, Germany) has

commercialized BIOLOX delta, a composite material
consisting of 80 vol.% Al2O3, approximately 18.5 vol.% ZrO 2,
and 1.5 vol.% of mixed oxides (CrO 2 & Y2O3) characterized by
strength higher than 1150 MPa and toughness of 8.5
MPa/m1/2. It is made by alumina-zirconia ceramic composites.

Conclusion

In this project alumina and zirconia powders are characterized

through XRD and chemical analysis.

They are mixed with each other in 6 different ratios to make 6

different batches.

This ATZ composite is isopressed and sintered in different route

to calculate AP and BD.

The crystal structure of grains and chemical composition can be

known from above work.

The sp. gravity of the materials and the change of porosity and
density with temperature change can be observed from the
above work.

In future mechanical properties and microstructures of ATZ will

be tested to find out what the behavior of this ceramic is and
what will be its application.

Reference

[1]. N.P. Bansal, Dongming Zhu, Thermal Conductivity of Alumina

Toughened Zirconia Composites, NASA/TM, 2003, 1-8.

[2]. Yong-Qi Zaho, Li Jiang et al., Shear bond strengths between

alumina toughened zirconia cores and veneering ceramics and their
susceptibility to aging, Asia Pacific Journal of Tropical Medicine, 2012,
402-405.

[3]. E. Camposilvan, F.G. Marro et al., Mechanical properties of

alumina infiltrated zirconia nanocomposites, XIII National Congress of
Mechanical Properties of Solids, Institute of Materials Technology of
the UPV, Spain, 2012, 203-207.

[4]. Willi Pabst, Eva Gregorova et al., Alumina Toughened Zirconia

made by room temperature extrusion o f ceramic pastes, Dept. of
Glass and Ceramics, Institute of Chemical Technology, Czech Republic,
2000, 41-46.

[5]. Jyoti Prakash et al., Mechanical Behavior of Alumina- Zirconia

composite by slurry method, International Journal o f Engineering
Science and Technology, 2011, 1359 -1367.