Abstract

Of
the
Thesis
Development and Characterization of Zirconia-
Graphite Ceramic Carbon Composites.

Submitted to
Chaudhary Charan Singh University Meerut

For the award of the Degree of

Doctor of Philosophy in Physics

By

Ajit Kumar Pandey

under the guidance of

Dr. Sanjay Dhakate and Dr. Anil Govindan

(External Supervisor) (Internal Supervisor)
Scientist EII, National Physical Reader, Department of Physics,
Laboratory MMH College Ghaziabad
New Delhi India Uttar Pradesh, India
February 2011
Introduction

Ceramic materials includes all inorganic and non-metallic materials which can be ionic or
covalently bonded and can be crystalline or amorphous and are produced by the action of heat.
The use of ceramics in electronic components is growing rapidly as a result of their superior
physical properties and new technology development. The markets and material technologies for
ceramics used as insulators, substrates and packages, capacitors, resistors, semiconductors,
piezoelectric devices, and superconductors have shown an outstanding growth during the last
two decades. There is an upward trend in global investments related to advanced ceramics as
seen in the literature. Although research and development in advanced ceramics and related
components has been going on for more than twenty years in India, its requirements towards
competitive commercial needs have neither been systematically studied nor understood. The
onset of globalization and liberalization had put great emphasis on indigenous research and
development which has to gear up to the exacting global standards. Global standards are ever
increasing, therefore to keep up breast with the demands we need substantial inputs in the form
of considerable increase in technical manpower as well as cutting edge infrastructure.

In the present work the emphasis is on ceramic Zirconia and its composites with carbon
(graphitic). Zirconia ceramics also has good properties as catalyst and pigments; it also exhibits
excellent mechanical properties that make it suitable for catalyst support. ZrO 2 was discovered in
Brazil as the naturally occurring mineral, baddeleyite, by Hussak in 1892. This rich mineral
usually contains about 80% ZrO2, but it can be high as 90%. The major impurities in this mineral
are usually TiO2, SiO2, Fe2O3 etc. The other main source of ZrO2 is zircon (ZrSiO4), which occurs
as secondary deposits in India, Australia and U.S. ZrO 2 is not a rare substance and it represents
about 0.02 to 0.03% of the Earth’s crust. Three thermodynamically stable polymorphs of zirconia
exists in different temperatures ranges. The monoclinic phase, stable from room temperature to
about 1100°C, transform to tetragonal phase at 2400°C, and above this temperature transform to
cubic symmetry. The transformations between the different polymorphs are important as far as
the processing and mechanical properties (strength, toughness, etc.) of zirconia ceramics are
concerned. The transformation leads to crumbling of the sintered part made from pure zirconia.
Several dopants such as yttria, ceria, magnesia, calcia, etc. are added to stabilize the high
temperature tetragonal and/or cubic phase in the sintered microstructure.

The reported lattice parameters of the t-ZrO2 at room temperature are 0.5102 nm (a-axis)
and 0.5176 nm (c-axis) for 3mol % yttria stabilized zirconia. “Toughening”, encompasses all
types of mechanical property enhancements that can be achieved by utilizing either the
tetragonal-to-monoclinic phase transformation of ZrO2 particles dispersed in a ceramic matrix or
other effects not directly associated with the transformation.
 The present work was carried out by sintering of zirconia ceramic, but with a non
conventional approach, i.e. without an external mechanical pressure, applying isostatic pressure
while sintering is the general method followed by researchers all over. Sintering commonly
refers to processes of consolidating a body shaped from powder particles which involves heat
treatment at elevated temperatures, usually at T > 0.5Tm [K] (Tm is the melting temperature for
that specific material). Diffusional mass transport is appreciable in this elevated temperature
range. Usually a self-supporting compact is obtained by pressing, casting or other processing
before sintering. All ceramic processing is based on the sintering of powder compacts rather than
melting, forging or other methods. The reasons for that are as follows. First, ceramics usually
melt at high temperatures, which makes melting difficult and inefficient. Second, ceramics are
brittle which is not suitable for processing by thermo-mechanical forming.

The driving force for densification and coarsening during sintering is the decrease in the
surface free energy of power compacts. The numerical value of Γ SV (surface free energy at solid-
vapor interface) is normally greater than ΓSS (surface free energy at solid-solid interface),
therefore the solid-vapor interfaces tend to be replaced by solid-solid interfaces when enough
energy is provided. Classically, the process of sintering is arbitrarily divided into three stages,
the initial, intermediate, and final stages based on physical reasoning so as to arise at simple
geometries for densification by contact flattening.

Composite materials are materials that combine two or more materials (a selected filler or
reinforcing elements and compatible matrix binder) that have quite different properties that when
combined offer properties which are more desirable than the properties of the individual
materials. The different materials work together to give the composite unique properties, but
within the composite we can easily see the different materials; they do not dissolve or blend into
each other.

The key characteristics of composites is

• Specific strength (the strength to weight ratio σ/ρ)

• Specific stiffness or specific modulus (the stiffness-to-weight ratio E/ρ)
• Tailored material (since composites are composed of 2 or more “phases”, they can be
formulated to meet the needs of a specific application with considerable ease)

Composites are not a single material but a family of materials whose stiffness, strength,
density, and thermal and electrical properties can be tailored. The matrix, the reinforcement
material, the volume and shape of the reinforcement, the location of the reinforcement, and the
fabrication method etc. can all be varied to achieve required properties.

Modern applications of composite materials include aerospace, sporting goods,

automotives, military equipments, cutting tools, communication devices, prosthetics, refractories
and building infrastructures, to name a few. Recent research and theories are able to analyze the
behavior of both particulate and fibrous reinforced composites.

Engineered ceramic composite materials must be formed to shape that involves

strategically placing the reinforcements while manipulating the matrix properties to achieve a
melding event at or near the beginning of the component life cycle. Composites are commonly
classified according to their matrix material. Three general classifications of composite materials
are polymer matrix composites (PMCs), metal matrix composites (MMCs), and ceramic matrix
composites (CMCs).

Consider the Mechanical Behavior of a composite. A composite material may be

composed of homogeneous constituents, but it is macroscopically heterogeneous. The material
properties of a homogeneous and isotropic material are independent of both position in the body
and orientation at a point in the body.

The main advantage of using composite materials is that they can be designed to meet
specific design needs. If well-designed, a composite exhibits qualities of each of its constituents
as well as unique qualities neither material possesses alone. Material characteristics that may be
improved by forming a composite are strength, stiffness, corrosion resistance, wear resistance,
strength-to-weight ratios, fatigue life, extreme temperature response, thermal conductivity,
acoustical properties, crack (fracture) resistance, cost, and ease of fabrication. The primary goal
of using ceramic materials in composite form is to retain the attractive qualities while increasing
the fracture toughness.

The objective of the study is to develop a tough and hard ceramic composite material
with a high resistance towards abrasion, using conventional methods. The conventional method
is chosen so that it can be scaled up to be implemented in a manufacturing line. Here it is
planned to bring the best out of two contrasting materials, such that zirconia and carbon, zirconia
(ZrO2) known for its hardness, and tribological properties. Carbon in its graphitic form is tensile
and possesses good lubricating properties. Therefore a combination of these two can lead to
interesting results. The toughness of the composite thus ensued is a case to be elaborately
pursued. There are many theoretical models available in the literature, by which one can predict
the resulting properties based on the values of the participating components. But before we
proceed we can have a quick review of the different parameters, its definitions and comparative
values.

In the study we had adopted an unconventional method, i.e. by forming a composite with
graphitic carbon. A 3-3 composite of zirconia and carbon was thought upon. To achieve the
configuration, initially we had to form a porous zirconia ceramic sample in such a way that the
pores in the ceramic are interconnected by a network of fine ducts, almost like corals, so that the
ceramic part is spongy with a large surface area. This kind of spongy ceramics are able to absorb
a lot of liquid medium, due to this large value of surface area, as well as the cohesive force
between the ceramic and the carbon containing liquid like pitch.

Therefore the developed composite, should be therefore light in weight, but with a
strength and toughness not achievable with plain ceramics whatever the toughening procedure
adopted. The intertwined fibrous carbon can lend tensile strength to the composite, while the
ZrO2 ceramic matrix can withhold large compressive stress. Since bending involves both
compressive as well as tensile strength in tandem, this composite can possess a large flexural
strength. This is the ultimate objective of the work. But we also envisage some combination
properties as a sort of spin off from the main objectives.

Not much work has been done on these lines. So it all the more justified, and the work
shall add to the repertoire of existing composites, so that one may choose at will, or according to
the demands of the situation at any given point of time or need.

Zirconia and its composites has not been tried and tested for these above mentioned
applications although its abundance and properties not only match with that of Alumina, in fact it
is much more superior. Zirconia is much more biocompatible and can be brought to a high
surface finish.

Experimental
a) Materials used for the preparation of the composite.
Zirconia dioxide ( ZrO2) powder Molecular weight 123.22, Pyconometric density 5.7
g/cc, Assay 99.5% was procured from Loba Chemie Pvt., Ltd, India. Polyvinyl alcohol
(PVA) was used as a binder to keep zirconia oxide powder in the stack in the form of
composite at green stage, PVA procured from Titan biotech limited, Bhiwadi, Rajasthan.
MnO2 (molecular weight, molecular 86.93 g/mol, assay 70≥ %) is used as a reaction
accelerator, procured from Merck Specialties Private Limited, Mumbai.
b) Preparation of the Samples.
Porous zirconia monoliths were developed by using different content of zirconia oxide
powder with polyvinyl alcohol (PVA) and sintering the green compact.
c) Characterization Techniques
i) Density Measurement:
Bulk densities of composite samples were measure by ASTM standard (ASTM
C559) Mettler density measurement attachment ME-40290.
ii) Porosity measurement:
Kerosene densities of the composite samples are measured first to measure the
porosity of the samples. The kerosene density of the different porous zirconia
monolith was measured by the kerosene pick-up method as per Archimedes’s
principle.
 iii) Electrical conductivity measurement:
The electrical conductivity was measured by the conventional four probe method
at a constant current supply (100mA). Kiethley 224 programmable current source
was used for providing constant current (i) supply of 100mA while the voltage
drop (V) in between two pin points with a span of 1.2cm was measured by
Keithley 197A autoranging microvolt DMM.
iv) Flexural Strength measurement:
Flexural strength of the composite samples was measured as per ASTM standard
(ASTM D -790) using Instron Universal Testing machine. The determination of
fracture toughness at ambient room temperature followed the pattern ASTM C
1421-9926.
v) X-ray Diffraction:
X ray characterization of the sample, RIGAKU powder X ray diffractometer,
Tokyo, Japan was used which use wavelength for d-spacing 1.5404Ǻ. The 2 theta
value was taken from 5 to 40o.
vi) Optical Microscopy:
In our study we used compound microscope MC 80 from Zeiss.
vii) Scanning Electron Microscopy
In our study latest SEM was used from Carl Zeiss EVO MA10, VPSEM (variable
pressure SEM). This can take images with variable pressure with high resolution
and clarity.

Results From the densities of the samples it can be seen that the apparent density of ZrO 2
ceramic prepared by the conventional solid sintering technique is as close to any commercially
available ZrO2. In pristine form of ZrO2 the density cannot go beyond 5.5 g/cc, therefore the
bulk density implies that the porosity required for the template has been achieved, since even the
densest sample shows a density of 3.45 g/cc, the sintering process was smooth and no
microcracks or faults were visible. The resistivity decreases with temperature showing a
semiconductor type behavior, also the Arrhenius plot as shown in the relevant figures was
helpful in calculating the activation energy (band gap), which shows typical ionic conductivity.
The mechanism of conduction of pristine stabilized ZrO 2 ceramics have been studied in detail,
but here one can see that the conduction is augmented by the presence of graphitic carbon which
is a very good conductor. The composite being a 3-3 connective one is isotropic, and the
resistivities are uniform in all directions. The activation energies are typical of charge carriers
with mobilities resembling ions and oxygen vacancies. The activation energies calculated from
the Arrhenius plots (log ρ vs T-1) are mentioned in the appropriate figures. Ea the activation
energies ranging from 0.8eV to .814 eV, are characteristic of ionic conductivity along with
conductivities due to oxygen vacancies in the bulk.
The Vicker’s hardness as well as modulus of the sample with 1400 oC , high temperature
treated (HTT), is quite high compared to the lower 1200 oC HTT samples. On comparing with
ceramic monolith the flexural strength and modulus shows a remarkable improvement in its
value.
The ceramic monolith is a mixture of two crystal phases of ZrO 2 . From the Debye
Scherer formula the grain size was also calculated and it was found to be between 200 to 300 nm.
Later on it was supported using SEM photographs. The average grain size measured from the
width of the x-ray peaks is considered to be more authentic compared to SEM photographs since
the information highlighted by x-ray diffractogram comes from a deeper level of the lattice as
compared to the information from the surface of the sample in an SEM micrograph. It can be
rightly estimated from the x-ray diffractogram that there is a line broadening effect which is the
result of fine grainsize.
The optical micrograph shows the sample was uniform except for asperities arising due to
leakage of pitch while carbonizing.
The most striking feature which is revealed from the SEM data is that the porosity
it shows is actually a three dimensional network, which is conducive to infiltration of pitch, also
the capillary size roughly calculated from the figure also allows to adjust the vacuum needed to
aid good suction of pitch solution into the monolith. The rest of the micrographs helps in finding
the grain size as well as the extent of infiltration of pitch into the system.
At the end an attempt was made to suck in carbon nano tubes into the system along with
pitch. A SEM micrograph with CNT pulled into the monolith is also given in one of the figure.
That may aid in further research.

Ajit Kumar Pandey