7 Tiles

SYNTHESIS AND CHARACTERIZATION OF
HYDOXYAPATITE -ZINC OXIDE

NANOCOMPOSITE
Project report submitted in partial fulfilment of the requirement for the

award of the degree of Master of Science in Physics
University of Kerala
By
Reg. No. 1118101
MAR IVANIOS COLLEGE (AUTONOMOUS)

Department of Physics
Mar Ivanios College Road, Bethany Hills, Nalanchira P.O
Thiruvanathapuram, Kerala 695015
2018-2020
HYDOXYAPATITE -ZINC OXIDE
NANOCOMPOSITE
Project report submitted in partial fulfilment of the requirement for the

award of the degree of Master of Science in Physics
University of Kerala
By
ANJU ABRAHAM
Reg No. 1118101
Under the Guidance of
Dr. MATHEW. C.T

Assistant Professor, Department of Physics
Mar Ivanios College, Trivandrum

Department of Physics
Mar Ivanios College Road, Bethany Hills, Nalanchira P.O
Thiruvanathapuram, Kerala 695015

+
(Re-assessed & Re-accredited with ‗A ‘ grade by NAAC)
CPE (College with Potential for Excellence) Status
Conferred by UGC
Mar Ivanios Vidhya Nagar,
Nalanchira P.O., Thiruvananthapuram – 695015, Kerala
CERTIFICATE
This is to certify that the project entitled “SYNTHESIS AND

CHARACTERIZATION OF HYDROXYAPATITE-ZINCOXIDE
NANOCOMPOSITE ” is an authentic record of the work done by Anju Abraham in the
Department of Physics, Mar Ivanios College, Thiruvananthapuram in thepartial
fulfilment for the award of the degree of Master of Science in Physics of the Universityof
Kerala during the period 2018–2020.
Dr. Jijimon K Thomas
Head of the Department

Thiruvananthapuram
Date:
Signature of Examiner
1.
2.
+
(Re-assessed & Re-accredited with ‗A ‘ grade by NAAC)
CPE (College with Potential for Excellence) Status
Conferred by UGC
Mar Ivanios Vidhya Nagar,
Nalanchira P.O., Thiruvananthapuram – 695015, Kerala
CERTIFICATE
This is to certify that the project entitled “SYNTHESIS AND

CHARACTERIZATION OF HYDROXYAPATITE-ZINCOXIDE
NANOCOMPOSITE”submitted to the University of Kerala in partialfulfillment
of the requirement for the award of the degree of Master of Science in Physics is a
record of original research work done by Anju Abraham during the period 2018-
2020, under my guidance at Mar Ivanios College, Thiruvananthapuram.
Dr. MATHEW.C.T
Assistant Professor
Thiruvanathapuram PG and Research Department of Physics
Date: Mar Ivanios College, Trivandrum

DECLARATION
I, Anju Abraham Phereby declare that the project entitled “SYNTHESIS

AND CHARACTERIZATION OF HYDROXYAPATITE-ZINCOXIDE
NANOCOMPOSITE” submitted to the Mar Ivanios College(Autonomous)affiliated
to the University of Kerala in partial fulfillment of the requirements for the award of
the degree of MASTER OF SCIENCE in PHYSICS is an entirely original work
carried out by me independently during the period of 2018-2020 under the
supervision and guidance of Dr.MATHEW.C.T, Assistant Professor, Department Of
Physics, Mar Ivanios College, Trivandrum and the dissertation has not formed the
basis for the award of any Degree/Diploma/Associate ship/Fellowship or other similar
title to any candidate of any university.
Place: Thiruvananthapuram
Date: Anju Abraham P
Acknowledgement
It is with great pleasure that I present my project entitled “SYNTHESIS
AND CHARACTERIZATION OF HYDROXYAPATITE-ZINCOXIDE
NANOCOMPOSITE”. First and foremost, I am thankful to God Almighty for his
Grace and presence all throughout my life, especially during this project.
I would like to extent my deep sense of grateful to Dr. Jijimon K Thomas,

Head of the Department ofPhysics, Mar Ivanios College, Trivandrum who
granted the permission to do the projectwork andfor his constantsupport and
encouragement throughout the course of this work.
I also extent my sincere thanks to Dr.Mathew.C.T, Assistant Professor,

Department of Physics, Mar Ivanios College, Trivandrum for his valuable
guidance throughout my project.
I extend my profound thanks to Dr. K I George, Principal Mar Ivanios
College, for providing necessary facilities to do this project work.
I express my deep sense of gratitude to Mrs.Swapna.Y.V, ResearchScholar,

Electronic Material Research Laboratory, Mar Ivanios College,for valuable help and
support during the progress of the study.
Hope I like to record the encouragement, support and corporation given by my

friends. I extent my sincere thanks to all who helped me directly and indirectly at
various stages of this work.
Anju Abraham P
PREFACE
In this project work entitled ―Synthesis and Characterization of

hydroxyapatite: Zinc oxide nanocomposite‖an exhaustive study of the above said
compound has been carried out and the results have been gently recorded.
The first chapter includes an introduction towards bioceramic materials, their

properties, and applications with brief account of the earlier works.
The second chapter gives an overview of all the experimental techniques used
in this study, their theories and respective instrumentation.
The final chapter concentrates on the results obtained and the analysis and
discussion of these results. Conclusion arrived based on the investigation is also
presented.
A set of references is given at the end of each chapter. Diagrams, photographs,

tables, etc.are attached wherever necessary.
CONTENT
Chapter 1 Bioceramics Page no
1 Introduction 1
1.1 Biomaterial 1
1.1.1 Fields of knowledge to develop biomaterials 2
1.2 Properties of biomaterials 3

1.2.1 Physical properties 3
1.2.2 Chemical properties 7
1.3 Bioceramics 8
1.3.1 Bio-inert 9
1.3.2 Bioactive material 11
1.3.3 Biodegradable materials 12
1.4 Types of bioceramics-tissue attachment 15

1.4.1 Nearly inert crystalline bioceramics 15
1.4.2 Porous ceramics 16
1.4.3 Bioactive glasses and glass ceramics 17
1.4.4 Resorbable ceramics 19
1.5 Composites and coatings 19

1.5.1 Zinc-Hydroxyapatite composite 22
1.5.2 Cationic vicarious ion substitutions 22
1.5.3 Zinc substitution 23
Review of literature 25
Reference 27
Chapter 2 Experimental and characterization techniques
2 Introduction 29
2.1 Synthesis of nanocomposite ceramic powders 29
2.1.1 Co-precipitation method 30
2.1.2 The sol-gel method 31
2.1.3 Hydrothermal method 32
2.1.4 Combustion method 33
2.2 Characterization techniques 35

2.2.1 X-ray diffractin technique 35
2.2.2 UV-visible absorption spectroscopy 37
2.2.3 Vibrational spectroscopy 39
2.2.3.1 Infrared spectroscopy 40
2.2.4 Photoluminous characterization 41

Referances 43
Chapter 3. Synthesis and characterization of

Hydroxyapatite:Zincoxide
composite
3 Introduction 44
3.1 Hydroxyapatite: Zincoxide nanocomposite 45
3.2 Experimental section 46
3.2.1 Preparation of Hydroxyapatite: Zincoxide nanocomposite 46
3.3 Sample characterization 47
3.3.1 X-ray diffraction 47
3.3.2 Fourier transform infrared spectroscopy 48
3.3.3 UV-visible absorption spectroscopy 48
3.3.4 Photoluminous spectroscopy 49
3.3.5 Scanning electron microscopy 49
3.4 result and discussion

3.4.1 X-ray diffraction analysis 50
3.4.2 X-ray analysis of Hydroxyapatite: Zincoxide 52
nanocomposite by W-H plot
3.4.3 FT-IR analysis 53
3.4.4 analysis of UV-visible spectra 54
3.4.5 Photoluminescence analysis 56
3.4.6 FE-SEM analysis 57
Conclusion 61
Reference 62
LIST OF FIGURES
Figure Figure name Page

no no
1.1 Sress-strain curve of traditional engineering materials 4
1.2 Stress-strain curve of biological soft tissue materials 4
1.3 Strain rate dependence 5
1.4 preconditioning 5
1.5 corrosion process 8
2.1 Steps of co-precipitation 30
2.2 Different sol-gel process 31
2.3 Schematic diagram of autoclave 32
2.4 Schematic diagram of hydrothermal method of 33
2.5 synthesis 34
2.6 Three steps of solution combustion method 35
2.7 Bragg‘s diffraction scheme 36
2.8 X-ray diffractometer 38
Perkin Elmer spectrometer
2.9 40
2.10 Schematic diagram of a fourier transform raman 41
spectrometer
Block diagram of a fluorescent spectrophotometer
3.1 50
3.2 51
3.3 XRD pattern of hydroxyapatite nanoparticle 51
3.4 XRD pattern of zincoxide nanoparticle 52
3.5 XRD pattern of hydroxyapatite-zincoxide 53
3.6 nanocomposite 53
3.7 W-H plot for hydroxyapatite-zincoxide 54
FTIR spectrum of hydroxyapatite nanoparticle
3.9 FTIR spectrum of zincoxide nanoparticle 55
3.10 FTIR spectrum of hydroxyapatite-zincoxide 56
3.12 UV-visible absorption spectrum of hydroxyapatite- 58
3.13 zincoxide nanocomposite 59
3.14 Tauc‘s 59
PL spectrum of hydroxyapatite -zincoxide
nanocomposite
FE-SEM micrograph of hydroxyapatite nanoparticle
FE-SEM micrograph of hydroxyapatite-zincoxide
nanocomposite
Grain size distribution in hydroxyapatite nanoparticle
Grain size distribution in hydroxyapatite-zincoxide
nanocomposite
LIST OF TABLES
Table no Table name Page

no
1.1 Use of biomaterials 3
1.2 Thermal conductivity rate of materials 6
1.3 Coefficient of thermal expansion of materials 6
1.4 Properties of bioceramic materials 9
1.5 Composition of apatites and hydroxyapatite 14
1.6 Attachment mechanisms with examples 15
1.7 Bioactive compositions 18
1.8 Characteristics of composite 20
1.9 Lists of bioceramic coatings 21
CHAPTER 1
BIOCERAMICS
1. Introduction
Many millennia ago, the discovery of humankind that fire would irreversibly
transform clay into ceramic pottery led eventually to an agrarian society and an
enormous improvement in the quality and length oflife. Within the last four decades
another revolution has occurred in the use of ceramics to improve the quality of life.
This revolution is the innovative use of specially designed ceramics for the repair and
reconstruction of diseased or damaged parts of the body. Advanced ceramics require
modern processing techniques, and the development of these techniques has led to
advances in medicine and engineering [1] .The development, industrial production,
and clinical implementation of bioceramic materials with improved life time,
reliability, and bioactive functions are high on the agenda of worldwide research and
development [2].
Bioceramics is one of the most active areas of research of materials science in
recent years. It is interesting to note that human body contains several types of
tissues, are possible to be replaced by man-made synthetic materials-ceramics, metals
or polymers. All biomaterials must attain a balance between the physical properties of
the tissues to be replaced together with the biochemical effects they might have on the
surrounding tissues. Bioceramicsis a special kind of biomaterial which are inorganic
compounds that designed to replace a part or function of a human body in a safe,
reliable, economic and physiologically and aesthetically acceptable manner [3].They
must be mechanically and chemically stable in a biological environment but must also
possess biocompatibility. The porcelain was the first bioceramic material that was
using in the 18th century for treatment of dental disorders. Due to technology
improvement, the application of bioceramics increased in the 20th century in the
medical field. the main criteria behind the application of these materials are
biocompatibility, moderate degradation, and high mechanical strength. Additionally,
ceramics are having properties like low conductance, high melting temperatures and
difficult to shear plastically. These characteristics make bioceramics body friendly
substitute. Special process and parameters are required to fabricate a good porous
scaffold [4]. Bioceramics are made in many different phases. They can be single
crystals(sapphire),polycrystalline(aluminaorhydroxyapatite(HA)), glass(bioglass),
glass-ceramics(ceravital or A/W glass- ceramic), or composites(stainless- steel- fiber-
reinforced bioglass or polyethylene-hydroxyapatite(PE-HA))[5] .These materials are
mostly using in biomedical field especially for hard tissue engineering due to their
high mechanical properties. The success of these ceramic materials depends on bio-
functionality and biocompatibility [6]. The biocompatibility of a device or material is
its ability to achieve that particular response throughout the life of implant. The
success of any implants depends on two factors that are tissue response to the implant
and materials behaviour after implantation. After implantation, formation of apatite
on the surface of bioceramics makes better bonding between body tissue and
implants. The bioceramics mainly classified in to three subclasses; bioinert high
strength ceramics, bioactive ceramics which form direct chemical bonds with bone or
even with soft tissue of a living organism; bioresorbable ceramics that actively
participate in the metabolic process of an organism with the predictable results.
Alumina, zircnonia and carbon are termed bioinert. Bioglass and glass ceramics are
bioactive. Calcium phosphate and hydroxyapatite ceramics are categorized as
bioresorbable [7]. Bioceramics including hydroxyapatite, bioglass and calcium
phosphate are using as scaffold, bone filler and coating agent because of their mineral
composition similarity with hard tissue. Bioceramics producing a higher tissue
response as compared to polymers and metals individuals.
Bioceramics are produced in a variety of phases serve many different

functions in the repair of body. In many applications ceramics are used in the form of
bulk materials of a specific shape, called implants, prostheses, or prosthetic device.
Bioceramics are used to fill space while the natural repair process restoresfunction.
The ceramics are also used as a coating on a substrate, or as a second phase in a
composite, combining the characteristics of both into a new material with enhanced
mechanical and biochemical properties. A/W glass-ceramic is used to replace
vertebrae because it has high strength and bonds to bone. Bioactive glasses have low
strength but bond rapidly to bone, so are used to augment the repair of bone defects.
ceramics and glasses have been used for a long time in health-care industry for eye
glasses, diagnostic instruments, chemical ware, thermometers, tissue culture flasks
and fiber optics for endoscopy.[5] Insoluble porous glasses have been used as carriers
for enzymes ,antibodies ,and antigens, since they have several
advantages,notablyresistance to microbial attack, pH changes, solvent conditions
temperature and packing under the high pressure which is required for rapid flow.
Ceramics are widely use in dentistry are restorative materials, gold porcelain crowns,
glass filled ionomer cements. For many decades, bioceramics such as alumina,
zirconia, hydroxyapatite, tricalcium phosphate dental cements have been used
successfully in the clinical practice- dental materials.
1.1 Biomaterial
A biomaterial is a synthetic material that induces specific biological activity
and function satisfactorily in a biological environment without damaging themselves
or the environment [3].These materials are used to make devices to replace a part or a
function of the body in safe, reliably economically, and physiologically acceptable
manner [2]. A variety of devices and materials are used in treatment of disease or
injury. Commonplace examples include suture needles, plates, teeth fillings, etc. The
combination of property requirements of biomaterials are biocompatibility,
pharmacological acceptability (nontoxic, nonallergenic, no immunogenic, no
carcinogenic,) chemically inert and stable(no time dependent degradation), adequate
mechanical strength, adequate fatigue life, sound engineering design, proper weight
and density, relatively inexpensive, reproducible, and easy to fabricate and process
for large scale production. Ceramics are known for their high strength, abrasion
resistant, chemical inertness, and biological activity.
1.1.1 Fields of knowledge to develop biomaterials

1. Science and engineering:(material science) structure-property relationships of
synthetic and biological materials including metals, ceramics, polymers, composites,
tissues (blood and connective tissue), etc
2. Biology and physiology: cell ad molecular biology, anatomy, animal and human
physiology, histopathology, experimental surgery, immunology, etc.
3. Clinical sciences :( all the clinical specialities) density, maxillofacial,
neurosurgery, obstetrics and gynaecology, ophthalmology, orthopaedics, plastic and
reconstructive surgery, thoracic and cardiovascular surgery, veterinary medicine, and
surgery, etc.
Use of biomaterials Example
Replacement of diseased and Artificial hip joint, kidney
damaged part dialysis machine
Assist in healing Sutures, bone plates and screws
Cardiac pacemaker, intra –ocular
Improve Function
lens
Correct functional abnormalities Cardiac pacemaker
Mastectomy augmentation, chin
Correct cosmetic problem
augmentation
Aid to diagnosis Probes and catheters
Aid to treatment Catheters, drains
Table 1.1. Applications of biomaterials
1.2 Properties of biomaterials

1. 2.1Physical properties
(i) Mechanical properties
The tensile test is a common testing procedure used to provide data for
characterization of biomaterials. The discussion below focuses on special
considerations needed for tensile testing biological soft tissue (e.g. ligament and
tendon) compared to traditional engineering materials (e.g. aluminium and steel) [8].
(a) Traditional Engineering Materials
Common assumptions used for testing and analysis of traditional materials are that
they are homogeneous, exhibit small deformations and are linearly elastic. Young's
modulus (E), the slope of the elastic portion of stress-strain curve.[22]
Fig.1.1 Stress-strain curve of traditional engineering materials
(b) Biological soft tissue materials
The assumptions made for the traditional materials are not valid when testing
biological soft tissue samples. These materials are, in general, non-homogeneous due
to the orientation of their collagen and elastin fibers. Hence, care must be taken when
collecting samples and positioning them in testing system to ensure the directions are
consistent with the intended analysis. Biological tissues exhibit large deformation
before failure, therefore, any transducer used to measure strain will need to
accommodate the large movement. Due to the un-crimping of collagen fibers and
elasticity of elastin, the initial portion of a biological sample stress-strain curve has a
high
deformation/low force characteristic known as the toe region.
Fig.1.2 Stress-strain curve of biological soft tissue material

In short, unlike traditional materials, this region is non-linear. A linear region
is typically identified after the toe region and is used for the determination of E. The
mechanical properties of biological tissues are strain or loading rate dependent due to
these tissues, visco-elastic nature. For example, biological tissues typically become
stiffer with increasing strain rate (see figure below).
Fig.1.3 Strain rate dependence
As such, predetermined and tightly controlled strain or loading rates must be

maintained during testing. Furthermore, many biological tissues in their normal state
are preconditioned (e.g. the anterior cruciate ligament) while many are not (e.g.
brain).
For a tissue that has not been preconditioned, its response to load or displacement
from one cycle to the next will not be similar; hence results will not be consistent
(See figure below).
Fig.1.4 Preconditioning
Depending on the type of tissue being tested or response of interest (e.g. sudden
impact or fatigue failure), preconditioning as part of the testing protocol may or may
not be necessary. [22]
(ii) Thermal properties
Wide temperature fluctuations occur in the oral cavity due to the ingestion of
hot or cold food and drink. Thermal Conductivity is the rate of heat flow per unit
temperature gradient. Thus, good conductors have high values of conductivity.
Material Thermal Conductivity

Enmel 0.92 W.m-1.oC-1
Dentine 63 W.m-1.oC-1
Acrylic Resin 0.21 W.m-1.oC-1
Dental Amalgam 23.02 W.m-1.oC-1
Zinc Phosphate Cement 1.17 W.m-1.oC-1
Zinc Oxide Cement 0.46 W.m-1.oC-1
Silicate Materials 0.75 W.m-1.oC-1
Porcelain 1.05 W.m-1.oC-1
Gold 291.70 W.m-1.oC-1
Table.1.2. Thermal conductivity rate of materials
(a) Thermal Diffusivity (D) is defined by the equation: D = K/ Cρ*rWhere, K
is thermal conductivity; C ρ is heat capacity, and ρ is density. Measurements of
thermal diffusivity are often made by embedding a thermocouple in a specimen of
material and plunging the specimen into hot or cold liquid. If the temperature,
recorded by the thermocouple, rapidly reaches that of the liquid, this indicates a high
value of diffusivity. A slow response indicates a lower value of diffusivity is
preferred. In many circumstances, a low value of diffusivity is preferred. There are
occasions on which a high value is beneficial. For example, a denture base material,
ideally, should have a high value of thermal diffusivity in order that the patient retains
a satisfactory response to hot and cold stimuli in the mouth.[22]
(b)Coefficient of thermal expansion is defined as the fractional increase in

length of a body for each degree centigrade increase in temperature.
Material Coefficient thermal expansion

(p.p.m.oC-)
Enamel 11.4
Dentine 8.0
Acrylic Resin 90.0
Porcelain 4.0
Amalgam 25.0
Composite resins 25-60
Silicate Cements 10.0
Table.1.3Coefficient of thermal expansion of material
DL/L0/DT 0c-1 Where DL is the change in length; Lo is the original length; DT

is the temperature change. Because the values of a small numbers. For example, for
amalgam a=0.0000025 °C-1=25 °C-1p.p.m (part per million). This property is
particularly important for filling materials. For filling materials, the most ideal
combination of properties would be low value of diffusivity combined with (a) like
that for tooth substance.
1.2.2 Chemical properties
One of the main factors, which determine the durability of a material, is its chemical
stability. Material should not dissolve, erode or corrode, nor should they leach
important constituents into oral fluids.
(i) Solubility and Erosion
The solubility of a material is a measurement of the extent to which it will
dissolve in each fluid, for example, water or saliva. Erosion is a process which
combines the chemical process of dissolution with a mild mechanical action.
These properties are particularly important for all restorative materials since a high
solubility or poor resistance to erosion will severely limit the effective lifetime of the
restoration. The ph of oral fluids may vary from ph4to ph8.5, representing a range
from mildly acidic to mildly alkaline. Highly acidic soft drinks and the use of chalk-
containing toothpastes extend this range from a lower end of ph2 up to ph11. It is
possible for a material to be stable at near neutral ph7 values but to erode rapidly at
extremes of either acidity or alkalinity. Standard tests of solubility often involve the
storage of disc specimens of materials in water for a period, the results being quoted
as the percentage weight loss of the disc. Such methods, however, often give
misleading results.
When comparing silicate and phosphate cements, for example, silicate

materials appear more soluble in simple laboratory test, but in practice they are more
durable than the phosphates.
(ii) Leaching of constituents
Many materials, when placed in an aqueous environment, absorb water by a

diffusion process. Constituents of the material may be lost into the oral fluids by a
diffusion process commonly referred to as leaching. Some soft acrylic polymers, used
for cushioning, the fitting surfaces of dentures rely on the absence of relatively large
quantities of plasticizer in the acrylic resin for their softness. The slow leaching of
plasticizer causes the resin to become hard and, therefore, ineffective as a cushion.
Occasionally, leaching is used to the benefit of the patient. For example, in some
cements containing calcium hydroxide, slow leaching causes an alkaline environment
in the base of deep cavities. This has the dual benefit of being antibacterial and of
encouraging secondary dentine formation.
(iii) Corrosion
It is a term which specifically characterizes the chemical reactivity of metals and
alloys. Metals and alloys are good electrical conductors and many corrosion processes
involve the setting up of an electrolytic cell as a first stage in the process. The
tendency of a metal to corrode can be predicted from its electrode potential.
It can be seen from the figure below, that materials with large negative electrode
potential values are more reactive whilst those with large positive values are far less
reactive and are often referred to as noble metals.
Fig 1.5 Corrosion process
Chromium has a negative value of electrolytic potential and is at the reactive

end of the series of metals shown. It is, therefore, surprising to learn that chromium is
included as a component of many alloys in order to improve corrosion resistance. The
apparent contradiction can be explained by the passivating effect. Although
chromium is electrochemically active it reacts readily forming a layer of chromic
oxide, which protects the metal or alloy from further decomposition. Other factors,
which can affect the corrosion of metals and alloys, are stress and surface roughness.
Stress in metal components of appliances produces, for example, by excessive or
continued bending can accelerate the rate of corrosion and may lead to failure by
stress corrosion cracking [22]. Pits in rough surfaces can lead to the setting up of
small corrosion cells in which the material at the bottom of the pit acts as the anode
and that at the surface acts as the cathode. The mechanism of this type of corrosion
sometimes referred to as concentration cell corrosion, is complicated but is caused by
the fact that pits tend to become filled with debris, which reduces the oxygen
concentration in the base of the pit compared with the surface. In order to reduce
corrosion by this new mechanism, metals and alloys used in the mouth should be
polished to remove surface irregularities. Ideally, a material placed into a patient's
mouth should be non-toxic, non-irritant, have no carcinogenic or allergic potential
and if used as a filling material, should be harmless to the pulp [8].
1.3 Bio-ceramics
Ceramic is defined as ―synthesized inorganic, solid, crystalline materials,
excluding metals‖. Ceramics used as a biomaterial to fill defects in tooth and bone, to
fix bone grafts, fractures, or prostheses to bone, and to replace diseased tissue are
called bio ceramics. They must be highly biocompatible and antithrombogenic, and
should not be toxic, allergenic, carcinogenic, or teratogenic [9]. Bio ceramics can be
classified in to
four groups
1-Bioinert like Alumina (Al2O3), Zirconia (ZrO2).
2-Resorbable like tri-calcium phosphate (TCP);
3-Bioactive like Hydroxyapatite, bioactive glasses, and glass-ceramics.
4 - Porous for tissue in-growth (hydroxyapatite-coated metals, alumina) of the jawbone.
Artificial
Bioceramics Application Advantages Disadvantages
Implants
Knee, Hip,
Reconstruction High hardness,
Alumina Shoulder, Weak in tension
of fractured part low friction
Elbow, Wrist
Corrosion
Reconstruction Friction
Zirconia Hip, Tooth resistant, hard,
of fractured part problems, costly
less friction
Spinal
Bioglass Protect spinal cord Fragile
fusion
Calcium
Replacement of Sometime
phosphate, Tooth, bone
damaged teeth fragile
Hydroxyapatite
Table.1.4 Properties of bioceramic materials
Applications include: Replacement for hips, knees, teeth, tendons and

ligaments, and repair for disease, maxillofacial reconstruction, augmentation and
stabilization, spinal fusion and bone fillers after tumour surgery. Carbon coatings are
thrombo-resistant and are used for prosthetic heart valves.
1.3.1 Bio-inert
The term bioinert refers to any material that once placed in the human body
has minimal interaction with its surrounding tissue; examples of these are stainless
steel, titanium, alumina, partially stabilized zirconia, and ultrahigh molecular weight
polyethylene. A fibrous capsule might form around bioinert implants; hence its bio
functionality relies on the tissue integration through the implant [10]. These materials
are having stable physiochemical properties and makes good compatibility with the
hard tissues. In other words, when the materials, implant into the body there will not
be a physiological reaction and immunological rejection by body tissue. They keep
their physiochemical and biomechanical properties in the host. Their high hardness,
low friction coefficient and excellent corrosion resistance offer a very low wear rate
at the articulating surfaces in orthopaedic applications. Microstructures are controlled
to inhibit static fatigue and slow crack growth while ceramic under load. Bio-inert
materials are applied as a structural-support implant for example, bone plates and
bone screw [11, 22]. Still no material is completely bio-inert because all materials
produce reactions after implantation in the body.
i. Alumina: The bio inertness of alumina has proven since 1975. An alumina
ceramic has characteristics of high hardness and high abrasion resistance. The
aluminium ions have occupied the interstitial sites in the hexagonal structure. The
reasons for the excellent wear and friction behaviour of Al2O3 are associated with the
surface energy and surface smoothness of this ceramic of Al2O3. The crystalline
nature of alumina makes it insoluble in the regular chemical reagent at room
temperature. Alumina is highly stable oxide because of ionic and covalent bond
present between aluminium and oxygen. These strong bonds avoid alumina from
galvanic reactions. it has excellent properties like good corrosion resistance, low
wear, and friction coefficient. The properties like abrasion resistance, strength, and
chemically inertness of alumina increase its application in hard tissue engineering. it
has been utilized in wear bearing environments such as the total hip arthroplasties
(THA) as the femoral head generating reductions in wear particles fromultra high
molecular weight polyethylene (UHMWPE). Other applications for alumina
encompass porous coatings for femoral stems, porous alumina spacers.[10] If the
alumina implanted in bone marrow, no toxic effect produced in circumferential tissue.
The tensile strength can increase by reducing its grain size and by increasing its
density. The better substitute to surgical metal alloys can produce by generating pure
alumina. Due to the good mechanical behaviour, alumina implants lead to long time
survival predictions [11].
ii. Zirconia (ZrO2): It was firstly recognized by Martin HenrichKlaprothin

1789.
The zirconia exists in three crystalline form i.e. monoclinic at normal temperature
(naturally occurring), cubic and tetragonal at higher temperature. The phase
transformation from tetragonal to monoclinic, enhance the toughness because
monoclinic is a stable phase at low temperature. The mechanical properties can
reduce by doing phase transformation that can lead to cracking. So partially stable
zirconia with normal mechanical strength can used in the medical field for implant
fabrication. The best example of partially stabilize zirconia is yttria stabilized
zirconia. Yttria used to stabilize the phases (tetragonal and cubic) of zirconia and
avoid phase transformation. Yttria also used to stabilize zirconia-based implants
having better static and fatigue strength [12,14]. A single water molecule can induce
the phase transformation from tetragonal to monoclinic that can lead to surface
roughness and micro cracking. Therefore, after several years of implantation, femoral
heads start to degrade slowly in the body. Then on metallic compounds such as MgO,
CaO, and Y2O3 used to improve the stability of zirconia. It has many advantages that
create interest over other ceramic materials because of its phase transformation
mechanisms that enhance the toughness, which manifested in components made from
them. The good mechanical behavior and wear performance of Zirconia makes it a
superior ceramic than alumina. It is a brittle transition metal oxide, which induce the
early bone growth and development. It has good mechanical properties with suitable
biocompatibility. The specialists on Zirconia as biomaterials began since a quarter
century and now Zirconia is in clinical use in complete hip substitution (THR)
however, improvements are in advance for application in other medicinal gadgets
[16].
1.3.2 Bioactive material
A bioactive material is one that elicits a specific biological response at the

interface of the material which results in the formation of a bond between the tissues
and thee material.[13]Bioactive materials having a positive effect on living tissues
and having ability to induce a response that helps in the regeneration, repair and
reconstruction of body tissues. When bioactive material introduced into the body, it
produces a specific biological response that starts to make a chemical bond between
the material interface and the tissue. In tissue engineering, bioactive materials are
specially used to repair orthopedic, craniofacial (skull and face bones) and dental,
chronic osteomyelitis. Examples of bioactive materials are hydroxyapatite, calcium
phosphate. Bioglass dental implants got a significant success in the last few years and
become a promising material. Bioactive materials generate a hydroxyl apatite layer
when immersed in the simulated body fluid (SBF) for some days. The generation of
this artificial apatite layer is like the inorganic phase of natural human bones. Due to
its equivalence, the layer can bond with collagen fibrils and thus to the bone. The
surface reaction is dependent on the material composition and small changes can
totally suppress the bioactive property [9].
i) Bioactive glasses
Bioactive glasses were first developed by Hench (1972), who synthesized

several glasses containing mixtures of silica, phosphate, calcia, and soda [12]. These
materials are used as bulk implants, coatings on metallic or ceramic implants, and
scaffolds for guiding biological therapies. The presence of Ca and P increase the
effectiveness of bioglass because these are the main constituents of the mineral phase
of bone. Some other precursors (MgO or CaF2, and Na2O by K2O) are also
becoming the part of bioactive glass with bioactivity changes. The glass fabrication
process altered by addition of small amount Al2O3 and B2O3 to avoid the inhibition
of the bioactivity, they may substitute SiO2. The bioglass is a system of SiO2-CaO-
NaO2-P2O5, which is widely used as implants. They influence a living organism,
tissue, or cell. Bioglass makes chemically stable bonds and attachments with the
skeletal system of the host body. They form apatite layer when meet body fluid. Thus,
bioactivity is depending upon the apatite formation that shows the compatibility of
bioglass with tissues. This apatite leads to the formation of bone like structure that
demonstrate the osteoconductivity in bioceramic material. The microstructure of
bioglass strengthens the bending strength (215 MPa) and compressive strength (1080
MPa) of whole sections of implant material. Glasses of various compositions (45S5,
58S, 70S30C, S53P4) can obtained and they show very different properties. The silica
and apatite are two significant crystal phases of bioglass. Ca and P rich interface layer
generated in between the material and tissues of bone by solid-state reaction. The
interface reaction understood as a chemical process, which includes a slight solubility
of the glass ceramic. Certain structures of glasses, ceramics, and composites appeared
to frame a mechanically strong bond to bone [15].
1.3.3 Biodegradable materials

These materials are proficient to react and broken down rapidly when meet
body tissue fluid. Biodegradable materials completely degrade into the body tissue
fluid because the tissue fluid breaks down the chemical structure of the materials.
These materials do not require secondary surgery for the removal of implants from
the body. These are completely absorbed by the body tissues and become the part of
hard tissue. The chemicals produced by the ceramic resorption should be able to be
treated by the normal metabolic pathways of the body without producing any toxic
effect. Several polymers, ceramics and metals based biodegradable implants were
synthesized and studied clinically. The controlled degradation of these materials can
be more beneficial for the patients [4].
i. Calcium phosphate ceramics (Ca P)
Calcium phosphate-based materials are using in biomedical field for 20 years.

It is an inorganic phase of bone minerals and helps in the calcification and the
resorption process of bone with improvedbiological affinity and activity. From last
three decades calcium phosphate-based materials used as substitutes for bone tissues.
These used in implants fabrication, coatings, and clinical settings. The scaffold of
calcium phosphate should impeccably design with controlled porosity and structure.
Natural bone contains 25% water, 60% inorganic mineral, and 15 % organic mineral
phases. Bone consists of 70% inorganic mineral phase that can replaced by calcium
phosphate. The 3D plotting helps more in the scaffold fabrication. The 3D designed
scaffolds express better porosity and mechanical properties that enhance cell
attachment and proliferation. The morphology and microstructures of composites and
scaffolds characterized by electron microscopy. Bone mineral gems are extremely
small and have an expansive surface territory. Despite what might expect, calcium
phosphate biomaterials display an insignificant surface area and have solid precious
crystal bonds. Hydroxyapatite and βtricalcium phosphate have shown very good
stability, biocompatibility, and osteoconductivity that increases the scope of these
materials in tissue regeneration. The porous calcium phosphate and composites are
using as a carrier for drugs, ions, biological agents, suitable for the tissue engineering.
Amorphous calcium phosphate and poly (Lactic acid) nano fibrous composites well
applied for sustained release of ions because of its well porosity and biological
characteristics. Different phases of calcium phosphate ceramics are used depending
upon whether a resorbable or bioactive material is desired. These include dicalcium
phosphate (CaHPO4) and hydroxyapatite Ca10(PO4)6(OH)2[HA]. Applications include
dental implants, skin treatments, gum treatment, jawbone reconstruction,
orthopaedics, facial surgery, ear, nose and throat repair, and spinal surgery. The
mechanical behaviour of calcium phosphate ceramics strongly influences their
application as implants. Tensile and compressive strength and fatigue resistance
depend on the total volume of porosity. Because HA implant have low reliability
under tensile load, such calcium phosphate bioceramics can only be used as powders,
or as small, unloaded implants with reinforcing metal posts, coatings on metal
implants, low-bonded porous implants where bone growth acts as a reinforcing phase
and as the bioactive phase in a composite. Calcium phosphate(CaP) biomaterials are
available in various physical forms (particles or blocks; dense or porous). One of their
main characteristics is their porosity. The ideal pore size for bioceramic is like that of
spongy bone. Macroprosity (pore size >501Am) is intentionally introduced into the
material by adding volatile substances or porogens (naphthalene, sugar, hydrogen
peroxide, polymer beads, fibers, etc) before sintering at high temperatures.
Microporosity is formed when the volatile materials are released. Microporosity is
related to pore size <10pm. Microporosity is the result of the sintering process, where
the sintering temperature and time are critical parameters. It has been demonstrated
that microporosity allows body fluid circulation whereas macroporosity provides a
scaffold for bone colonization. Average pore size diameter of 560pm is reported as
the ideal macropore size for bone ingrowth compared to a smaller size (3001.1m).
The main difference between the different commercially available BCP (biphasic
calcium phosphate) are the micro porosities, which are dependent on sintering process
[17]
i) Hydroxyapatite
Synthetic hydroxyapatite Ca10(PO4)6(OH)2 is similar to a natural mineral form

of the apatite in bones and widely used for bone repairs [12]. It is a hexagonal
alloplastic material. It is a biocompatible and crystalline. Henceforth, its structural
composition is same as to natural bone. It has nominal stoichiometric Ca/P atomic
ratio of 1:67. The hydroxyapatite makes similar chemistry with the mineralized phase
of bone. It produces an osteoconductive effect with high biocompatibility that form
bone bonding between material and tissue. Although hydroxyapatite has, high,
constituent similarity to bone but mechanical properties is very low as compared to
natural bone. At nanoscale, hydroxyapatite power has become the main attraction to
improve biological and mechanical properties. To get nano range hydroxyapatite
particles, many methods are investigated e.g. hydrothermal, micro emulsion, sol gel,
co precipitation, combustion and mechanochemical. Hydroxyapatite is an excellent
carrier of growth factors and osteogenic cell, which significantly enhances their
efficacy as a carrier in the future. HA is brittle in nature with lower young modulus
and fracture toughness. Differences in composition of apatite in natural bones and
tooth enamels revealed in table 1.5.
Constituents Apatite In Enamel Hydroxyapatite

(wt%) In bone (wt %)
Ca 36 24.50 39.60
P 17.10 11.50 18.50
Na 0.50 0.70
K 0.08 0.03
Mg 0.44 0.55
F 0.01 0.02
CI 0.30 0.10
CO3^2- 3.20 5.80
Trace Elements
Ca: (Molar ratio) 1.62 1.65 1.67
Table 1.5 Composition of Apetites and hydroxyapatite
The use of HA as an implant material should be, in the first place, recognized for
its good biocompatibility. The biocompatibility of HA was widely examined and stated
by many authors. It has been studied that the presence of HA did not disturb the normal
process of bone tissue maintenance and bone - HA interface. Contamination free HA
fabricated by freeze-drying confirmed by XRD analysis. Lee and co-workers fabricated
crack free six types of HA scaffolds, these scaffolds did not affect the crystallinity of HA.
1.4 Types of bioceramics-tissue attachment

The type of tissue attachment is relatedto the type of tissue response at the
implant interface. No material implanted in living tissues is inert; all materials elicit
a response from living tissues. [5] Four types of response allow different means of
achieving attachment of prostheses to the musculo-skeletal system.
The types of implant-tissue response are:
a- If the material is toxic, the surrounding tissue dies;
b- the material is nontoxic and biologically inactive (nearly inert), a fibrous
tissue of variable thickness forms;
c- If the material is nontoxic and biologically active (bioactive), an interfacial bond
form;
d- If the material is nontoxic and dissolves, the surrounding tissue replaces it.
The attachment mechanisms with examples are summarized below:
Type of Type of Attachment Example

Bio
ceramic
1 Dense, nonporous, nearly insert AI2O3 Single
ceramics attach to bone- growth crystal and
into surface irregularities by polycrystalline)
cementing the device into the
tissues, or by pressing fitting into
a defect (termed Morphology
Fixation)
2. For porous insert implants bone AI2O3 (porous
ingrowth occurs, which polycrystalline)
mechanically attaches the bone hydroxyapetite-
to the material (termed coated porous
Biological Fixation) metals
3. Dense, nonporous, surface- Bioactive glasses
reactive ceramics and glass- Buioactive glass-
ceramics attach directly by ceramics
chemical bonding with the bone Hysdroxyapetite
termed bioactive Fixation)
4. Dense, nonporous (or porous), Calcium sulphate
resorbable ceramics are designed (plaster of Paris)
to be slowly replaced by bone. Tricalcium
phosphate, calcium
Phosphate salts.
Table.1.6 Attachment mechanisms with examples

1.4.1 Nearly inert crystalline bioceramics
Inert refers to materials that are essentially stable with little or no tissue reactivity
when implanted within the living organism. When a biomaterial is nearly inert (type 1)
and the interface is not chemically or biologically bonded, there is relative movement and
progressive development of a non-adherent fibrous capsule in both soft and hard tissues.
Movement at the biomaterial-tissue interface eventually leads to deterioration in function
of the implant or the tissue at the interface or both. Bone at an interface with typel, nearly
inert, implant is very often structurally weak because of disease, localized death of bone,
or stress shielding when higher elastic modules of the implant prevents the bone from
being loaded properly. Most notable among the nearly inert ceramics are alumina and
special forms of carbon and silicon. High density high purity (>99.5%) alumina (a-
Al203) was the first bioceramic widely used clinically. It is used in load-bearing hip
prostheses and dental implants, because of its combination of excellent corrosion
resistance, good biocompatibility, and high wear resistance, and high strength. Although
some dental implants are single-crystal sapphire, most alumina devices are very-fine-
grained polycrystalline a-Al203. A very small amount of magnesia (<0.5%) is used as an
aid to sinter and to limit grain growth during sintering. Strength, fatigue resistance, and
fracture toughness of polycrystalline a-Al203 are a function of grain size and percentage
of sintering aid, i.e. purity. Alumina with an average grain size of <4[1m and >99.7%
purity exhibits good flexural strength and excellent compressive strength[5].
Low wear rates have led to wide-spread use of alumina non-cemented cups, press
fitted into the acetabulum (socket) of the hip. The cups are stabilized by bone growth into
grooves or round pegs. The mating femoral ball surface is also of alumina, which is
bonded to a metallic stem. Though long-term results in general have been excellent, it is
essential that the age of the patient, nature of the disease of the joint, and bioceramics of
the repair be considered carefully before any prosthesis is used. The primary use of
alumina is for the ball of the hip joint, with the socket component being made of
ultrahigh molecular weight polyethylene (PE). Other clinical applications of alumina
implants include knee prostheses, bone screws, jawbone reconstruction, segmental bone
replacement, and blade, screws or post-type dental implants.
1.4.2 Porous ceramics
The concept behind nearly inert, micro-porous bioceramics (type2) is the ingrowths
of tissue into pores on the surface or throughout the implant. The increased interfacial
area between the implant and the tissues result in an increased inertial resistance to
movement of the device in the tissue. The interface is established by the living tissue in
the pores. This method of attachment is often termed biological fixation. It is capable of
withstanding more complex stress states than type 1 implants, which achieve only
morphological fixation. The limitation associated with type2 porous implants is that, for
tissue to remain viable and healthy, it is necessary for the pores to be greater than 100 to
1501.1m in diameter. The large interfacial area required for the porosity is due to the
need to provide a blood supply to the ingrown connective tissue. Vascular tissue does not
appear in pores, which measure less than 1001im. If micro-movement occurs at the
interface of a porous implant, tissue is damaged, the blood supply may be cut off, tissue
dies, inflammation ensues, and the interfacial stability can be destroyed.
The potential advantage offered by a porous ceramic is the inertness combined

with the mechanical stability of the highly convoluted interface developed when bone
grows into the pores of the ceramic. Mechanical requirements of prostheses, however,
severely restrict the use of low strength porous ceramics to low-load or non-load bearing
applications. Studies show that, when load bearing is not a primary requirement, nearly
inert porous ceramics can provide a functional implant. When pore sizes exceed 100g.im,
bone will grow within the interconnecting pore channels near the surface and maintain its
blood supply and long-term health. In this manner, the implant serves as a structural
bridge and model or scaffold for bone formation. The microstructures of certain marine
corals make an almost ideal casting material for obtaining structures with highly
controlled pore sizes. Several types of coral are promising, with pore-size range s of 40-
1601.1m and 200-1000pm. After the coral shape is machined, it is fired to drive offCO2
from the limestone, forming a porous structure of calcia, or transformed directly into
hydroxyapatite ceramic. Porous ceramic surfaces can also be prepared by mixing soluble
metal or salt particles into the surface. The pore size and structure are determined by the
size and shape of the soluble particles that are subsequently removed with a suitable
etchant. The porous surface layer produced by this technique is an integral part of the
underlying dense ceramic phase. Materials, such as alumina, may also be made porous by
using a suitable foaming agent that evolves gases during heating. Porous materials are
weaker than the equivalent bulk form. As the porosity increases, the strength of the
material decreases rapidly. Much surface area is also exposed, so that the effects of the
environment on decreasing the strength become much more important than for dense
nonporous materials [19].
1.4.3 Bioactive glasses and glass-ceramics
Another approach to the solution of the problems of interfacial attachment is the

use of bioactive materials (type3). The concept of bioactive materials is intermediate
between resorbable and bioinert. Certain compositions of glasses, ceramics, glass-
ceramics, and composites have been shown to bond to bone. These materials are also
called bioactive ceramics. Some, even more specialized compositions of bioactive
glasses, will bond to soft tissues as well as bone. A common characteristic of such
bioactive materials is a modification of the surface that occurs upon implantation. The
surface forms a biologically active hydroxycarbonate apatite (HCA) layer, which
provides the bonding interface with tissues. The HCA phase that forms on bioactive
implants has the same chemical structure as the mineral phase in bone and is therefore
responsible for interfacial bonding. The bonding results in an interface that resists
substantial mechanical forces. Bonding to bone was first demonstrated for a range of
bioactive glasses, which contained specific amounts of SiO2, CaO, and P2O5. These
glasses contained less than 60 mol% SiO2, high contents of Na2O, and CaO, and had a
high CaO/ P2O5 ratio. Such a composition produced a surface that was highly reactive
when exposed to an aqueous medium. Many bioactive silica glasses are based upon the
formula (called 45S5), which signifies 45wt% SiO2, S as the network former, and a 5 to 1
molar ratio of Ca to P (in form of CaO and P 2O5 do not bond to bone. 45S5 glass
implants have been used successfully for replacement of ear bones and maintenance of
the jawbone for denture wearers for up to eight years, with nearly 90% retention ratio.
This glass is also used for the restoration of the bone next to teeth that might otherwise be
lost because of gum disease. Several other compositions have developed that are
bioactive, as tabulated below[19]:
Component 45S5 Bioglass KGC A/W Glass
Ceravital ceramic
SIO2 45 46.2 34.2
P2O5 6 - 16.3
CaO 24.5 20.2 44.9
Ca(PO3)2 - 25.5 -
CaF2 - - 0.5
MgO - 2.9 4.6
Na2O 24.5 4.8 -
Structure Glass and Glass ceramic Glass-ceramic

glass-ceramic
Table1.7 Bioactive compositions
Bioactive glass ceramics is biocompatible, osteoconductive, and bonds to bone

without an intervening fibrous connective tissue interface. This material has been widely
used for filling bone defects. When granules of bioactive glass are inserted into bone
defects, ions are released in body fluids and precipitate into a bone-like apatite on the
surface, promoting the adhesion and proliferation of osteogenic cells. After long-term
implantation, this biological apatite layer is partially replaced by bone. Bioactive glass
with macro-porous structure has the properties of layer surface areas, which are
favourable for bone integration. The porosity provides a scaffold on which newly formed
bone can be deposited after vascular ingrowths and osteoblast differentiation. The
porosity of bioglass is also beneficial for resorption and bioactivity.
1.4.4 Resorbable ceramics
They are designed to degrade gradually over a period and be replaced by the natural
host tissue. This leads to a very thin or nonexistent interfacial thickness. This is the
optimal solution to the problem of biomaterials if the requirements of strength and short-
term performance can be met. Natural tissues can repair themselves and are gradually
replaced throughout life by a continual turnover of cell population. As we grow older, the
replacement of cells and tissues is slower and less efficient, which is why parts "wear
out", unfortunately sum faster than others. Thus, resorbable biomaterials are based on the
same principles of repair which have evolved over millions of years.
One of the unique advantages of the resorbable ceramic is that its initial pore-size
can be small, thereby possessing high mechanical strength compared to the strength of
more porous substances. As the ceramic dissolves, it becomes more and more porous
allowing the ingrowth of more supporting tissue to occur. As a result, mechanical
integrity is maintained, and stress concentrations minimized. Complications in
development of resorbable bio-ceramics are:
1) Maintenance of strength and the stability of the interface during the degradation
period and replacement by the natural host tissue.
(2) Matching resorption rates to the repair to the repair rate of body tissues which
themselves vary enormously. Some dissolve too rapidly and some too slowly.
Because large quantities of material may be replaced, it is also essential that a
resorbable biomaterial consist only of metabolically acceptable substances.
This criterion imposes considerable limitations on the compositional design of resorbable

biomaterials.
Resorbable bioceramics have been used to treat maxillofacial defects, for obliterating
periodontal pockets, as artificial tendons and as composite bone plates [5].
1.5 Composites and Coatings
One of the primary restrictions on clinical use of bioceramics is the uncertain

lifetime under the complex stress states, slow crack growth, and cyclic fatigue that arise
in many clinical applications. Two solutions to these limitations are the use of bioactive
ceramics as coatings or in composites. Much of the rapid growth in the field of bioactive
ceramics is due to development of various composite and coating systems. The porosity
of scaffolds varies by changing HA concentration. Current research in tissue engineering
has been constantly seeking for ideal biomaterials to restore loss of tissues andto deliver
cells and growth factors for regenerative medicine. Bio ceramics are one of the most
bioinertand biocompatible biomaterials for hard tissue replacement. Its applications are
limited due to slow resorptionrate (e.g. hydroxyapatite) or weak mechanical
strength(e.g..amorphous calcium – phosphate and bioglass).there is a growing interest in
the development of composite bioceramics, which has combined advantages of
resorbability,strength,andbiocompatibility. Composite materials may be defined as those
materials that consist of two or more fundamentally different components that are able to
act synergistically to give properties superior to those provided by either component
alone. Composites made of bio inert and bioactive ceramics are produced to achieve two
important features, bioactivity and mechanical strength. Such composites were
biologically evaluated by scientist through several animal tests. Alumina ceramic can
form composites with hydroxyapatite that are bioactive. Animal experiments of
HAp/alumina composite reveal that it can form tight osseointegrationwith bone. It is
bioactive with high strength. Tissue reactions of test materials were performed using rats
for two months duration. X-ray diffraction studies showed that alumina exists only in the
form of corundum. As the amount of zirconia increased, mullite formation became
visible on the particle boundaries. Animal studies revealed that these ceramic composites
do not have any adverse effect on the tissue investigated histologically. The influence of
surface properties of ceramics on their biocompatibility was examined in vitro by using
gingival fibroblasts. Al203 - Si02 - Ti02 ceramics with variable composition and sufficient
densities were produced by solgel techniques. Composites have been composed of
plastic, carbon, glass, or ceramic matrices reinforced with various types of fibers,
including carbon, SiC, stainless steel, HA, phosphate glass, and ZrO2. In most cases the
goal is to increase flexural strength and strain to failure and decrease elastic modulus.
The strongest composite achieved to date is A/W glass-ceramic containing a dispersion
of tetragonal Zirconia, which has a bend strength of 700MPa, and fracture to
ughness of
The table below shows the characteristics of those composites:
Matrix Reinforcing Phase
Type1 : Nearly insert Composite
Polyethylene Carbon Fiber
Poly(methacrylate) Carbon fiber
Carbon SiC
Epoxy resin Alumina/stainless steel
Type -2: porous ingrowth composites
Coral HA yoniopora DL polylactic acid
Type-3 : Bioactive Composites
Bioglass Stainless steel fibers
Bioglass Titanium fibers
Collagen HA
polyethylene HA
Poly(methyl -1 methacrylate) Phosphate-silicate –apatite glass fiber
A/W glass-ceramic Trandformation-toughened ZrO2
Polyhydroxybuturate HA
PLA/PGA HA
PLA/PGA PLA/PGA fibers
PLA is poly(lactic acid)
PGA is poly(glycalic acid)
4MPam1/2[7].
Table 1.8 characteristics of composite
Implant materials with similar mechanical properties should be the goal when
bone is to be replaced.Because of the anisotropic deformation and fracture characteristics
of cortical bone, which is itself a composite of compliant collagen fibrils and brittle HCA
crystals, the Young's modulus (E) varies between about 7 to 25GPa. The critical strain
intensity increases from as low as 600Jm-2 to as much as 5000J m2 depending on
orientation, age, and test conditions. Most bioceramics are much stiffer than bone, many
exhibits poor fracture toughness. Consequently, one approach to achieve properties
analogous to bone is to stiffen a compliant biocompatible synthetic polymer, such as PE
with a higher modulus ceramic second phase, such as HA powders. The effect is to
increase Young's modulus froml to 8GPa and to decrease the strain to failure from >90%
to 3% as the volume fraction of HA increases to 0.5. Thus, the mechanical properties of
the PE-HA composite are close to or superior to those of bone. Another promising
approach toward achieving high toughness, ductility and Young's modulus matching that
of bone was developed. This composite use sintered 316 stainless steel of 50-, 100-, 200-
1.1m or Titanium fibers, which provide an interconnected fibrous matrix which then
impregnated with molten 45S5 bioglass. After the composite is cooled and annealed, very
strong and tough material results, with metal to glass volume ratio between -41 to -6.6.
Stress enhancement of up to 340MPa is obtained in bending with substantial ductility of
up to 10% elongation, which bends 90° without fracturing.
A biometric coating, which has reached a significant level of clinical

application, is the use of HA as a coating on porous metal surfaces for fixation of
orthopedic prostheses. This approach combines biological and bioactive fixation. Though
a wide range of methods have been used to apply the coating, plasma spray coating is
usually preferred. The table below lists the bioceramic coatings:
Substrate Coating
316L Stainless steel Pyrolytic carbon
316L Stainless steel 45 S 5 bioglass
316L Stainless steel αAI2O3-HA-TiN
316L Stainless steel HA
Co-Cr alloy 45S5 bioglass
Co-Cr alloy HA
Ti -6AI-4V alloy 45S5 bioglass
Ti-6AI-4V alloy HA
Ti-6AI-4V alloy AI2O3
Ti-6AI-4V alloy HA/ABS glass [ABS is alkali

borosilicate glass]
Table .1.9 lists of bioceramic coatings
1.5.1 Zinc-Hydroxyapatite composite
Hydroxyapatite (HAp, Ca10 (PO4)6(OH)2, Ca/P = 1.67) is widely employed in

biomedical sector, particularly in dentistry and orthopaedics, due to its chemical
similarity to the mineral component of hard tissue. However, the biological apatite,
whose bone and tooth mineral phases are composed, remarkably differs from
stoichiometric HAp, being Ca deficient (Ca/P< 1.67), composed of small crystals and
characterized by poor crystallinityand relatively high solubility. Furthermore, it consists
in carbonated apatite characterized by the presence of various amounts of vicarious ions,
either incorporated
Within the apatite lattice or just adsorbed on the crystal surface, including anionic (e.g.,
F_, Cl_, SiO4
and/or cationic substitutions (e.g., Na+, Mg2+,K+, Sr2+, Zn2+, Ba2+, Al3+).
In fact, calcium phosphates nucleation and growth in biological systems occur in an
environment rich in ions, influencing both the crystallization kinetics and
thermodynamics and, consequently, their stability. the mineral phases of the bone,
enamel, and dentin contains lightly different ionic compositions and lattice parameters
.The current trend is, therefore, to obtain calcium phosphate bio ceramics partially
substituted by these elements in order to mimic the chemical composition of the bone
mineral component, allowing the ability to exchange ions in apatite structure to design,
develop, and characterize new and better calcium phosphates for certain specific
applications. In fact, hydroxyapatite crystal structure can accommodate substitutions by
various other ions for the Ca2+, PO43_, and OH_ groups , these ionic substitutions
affecting the HAp lattice parameters, crystal morphology, crystallinity, solubility, and
thermal stability. In particular, the vicarious ion incorporation within apatite lattice
influences the apatite dissolution rate, remarkably enhancing the proliferation of human
osteoblast-like cells in vitro and consequently encouraging osseointegration. To resemble
the mineral component of the bone, various substitutions, both cationic(substituting for
the calcium) and anionic(substituting for the phosphate or hydroxyl groups), have been
tried and tested, with consequent modifications of the chemical, physical, and biological
properties, as demonstrated in in vitro and in vivo test.
1.5.2 Cationic Vicarious Ions Substitutions
The mechanism of tissue attachment is directly related vicariouscationscan

replace Ca2+ ions, causing a lattice alteration, in terms of contraction or expansion of the
lattice parameters, based on thevicarious ion diameter. Even if it is expected that bigger
cations modify cell volume, leading to a lattice expansion accompanied by higher values
of a-axis parameter, this does not always occur, such as in the case of monovalent
cationsubstitution for bivalent cations. In fact, in the case of substitutions with bivalent
ions (e.g., Mg2+, Zn2+, Sr2+), no charge imbalance occurs within the apatite lattice,
whereas in the case of substitutions with monovalent ions (e.g. Na+, K+), a charge
imbalance is necessary in order to respect the neutrality. As already evidenced, in order
to maintain the neutrality, either the formation of supplementaryvacancies or the
occurrence of simultaneous substitutions ofcations and anions without the formation of
any vacancy or loss of charge balance has been observed. Moreover, the accommodation
of substituting cations either in the site Ca(I) or in the site Ca(II) within the apatite lattice
is strongly correlated to their ionic radiuscation with a larger radius than Ca2+ one tends
to occupy site (II), site Ca(II) being bigger in volume than site Ca(I) .Furthermore, the
anion presence in the channel also influences the cationdistribution between the two sites
Ca(I) and Ca(II), due to the ions‘ charge and the strength of the corresponding bonds. The
synthesis of substituted hydroxyapatite is usually carried out following thetypical
processes employed for that of the undoped material, such as precipitation and titration,
sol–gel process, hydrothermal method, mechanochemical method, etc [20, 21].
1.5.3.1 Zinc Substitution
(a).Biological Role of Zinc
Zinc is an essential microelement present in the active centres of more than300

enzymes involved in the bone metabolism. It can increase enzyme activity and DNA
synthesis and displays antibacterial activity. Zinc can be found in all biological tissues,
being mostly present in the bone. This cation plays pivotal roles in numerous biological
functions, e.g., enzymatic activity, nucleic acid metabolism, protein synthesis,
preservation of the structures and functions of the membranes and hormonal activity, and
the normal growth development of the skeletal system. Indeed, its deficiency is
associated with a decrease in bone density, this ion being able to inhibit osteoclast
differentiation and to promote osteoblast activity. Some experiments with zinc sulphate
were carried out in order to investigate and comprehend the underlying mechanism. On
the basis of these studies, it has been that in the presence of zinc, alkaline phosphatase
(ALP) levels increase. Additionally, the bone metabolism stimulation by Zn has been
also demonstrated by in vivo experiments with zinc sulphate .Concerning the in vitro
action on osteoclasts, Kishi and Yamaguchi reported that Zn hinders the osteoclast-like
cell formation, while Moonga and Dempster evidenced the strong inhibitory action of Zn
on the osteoclastic bone resorption in vitro for zinc amounts as low as 10–14 M. Many
studies have been performed in order to better and more deeply understand the
mechanisms responsible for these inhibitory effects. Owing to the key effect of Zn2+
cations in several metabolic processes, Znincorporation within apatite lattice has been
widely studied [21]
(b) Influence of Zn2+ Substitution on Chemical, Physical, and Micro structuralProperties
of HAp
Significant amounts of Zn can be incorporated within HAp lattice [23, 24] the
substitution limit being 15 mol% according to [23] and 25 mol% according to[24]
However, there is no clear evidence of the maximum level of Zn substitution within
apatite lattice. Generally, considering the level of zinc substitution, it has tobe considered
that the used nominal amount does not always correspond to the actual one[21]. For
instance, starting from a nominal Zn concentration of 5 wt%, Zn-Hap powder with an
actual Zn amount of 0.7 wt% was obtained, on the basis of energy dispersive
spectroscopy (EDS) data [21] Moreover, Li et al. [21] observed that the synthesis
conditions strongly affect the amount of Zn incorporated into HAp structure. In
particular, it is influenced by the kind of base used to maintain constant the synthesis pH.
In fact, synthesizing-HAp starting from an aqueous solutions of calcium nitrate, zinc
nitrate, and ammonium phosphate and using ammonia to maintain constant the pH, the
actual substitution content of zinc was less than half that expected, whereas using sodium
hydroxide to monitor the pH, the actual Zn amount was remarkablyhigher. Analogously
and consequently, the used base also affects the crystallinitydegree, resulting in higher
use of NaOH[21], the crystallinity being also influenced by the Zndopantamount. It has
been alsosuggested that Zn substitution is favoured for Ca(II) site at the HAp (0001)
surface. Concerning the lattice parameters, the lattice parameter c of Zn-
HApprogressively decreases with Zn content [23], owing to the difference in ionic radius
between Zn2+ (0.074 nm) and Ca2+ (0.099 nm). Zn plays an inhibiting effect on HAp
crystallization and favours the β-TCP phase, acting in the same manner magnesium [24]
the thermal stability as well as the crystallinity of the apatite decrease significantly
withincreasing Zn concentration.
(c). Influence of Zn2+ Substitution on Biological Properties of Hap

The biological properties of Zn-HAp have not been deeply and appropriately investigated
yet. However, it has been reported that small amounts of Zn ions within HAplattice are
actively involved in cell growth and differentiation, even if the underlying mechanism
has not been clearly understood and explained yet. The presence of Zn within the apatite
lattice can enhance its biological responsiveness, directly promoting osteoblastic
proliferation and inhibiting the bone resorptionbyosteoclasts.[21] In fact, Zn-HAps with
Zn ion amounts less than 1.2 wt% present effective bioactivity and antibacterial
properties. In detail, Itoet al. demonstrated an increase in osteoblast response, with
enhanced mouseosteoblast-like cell proliferation in vitro, for Zn amounts up to 1.2 wt%,
whereas for higher Zn contents, cytotoxicity was revealed .The inhibitory action of Zn-
HAps on the growth of bacteria and fungi, including. E .coli, S. aureus, Candida albicans
(C. albicans), and Streptococcus mutans (S. mutants), was also demonstrated [21]a zinc
content more than 1000 ppm being necessary to exhibit an antimicrobial effect.
Considering these outstanding properties, Zn-HAps were used as coatings ofdental
implants in order to promote tooth remineralisation, allowing reducing bacterial
adherence and the tartar development, having verified their efficiency toinhibit the
growth of the three most common oral pathogens, i.e.,
Aggregatibacteractinomycetemcomitans, Fusobacteriumnucleatum, and S. mutans.
Moreover, Zn-HAps were used as carriers for the controlled release of ciprofloxacin,
which exhibits antibacterial activity against S. aureus and Pseudomonas (P. aeruginosa),
the most common pathogens causing bone and adjoint diseases. It was demonstrated that
the ciprofloxacin release by the hydroxyapatitetakes place in connection with the zinc ion
release, increasing theantibacterial activity with the drug concentration and the number of
used Zn2+ions. Furthermore, the ciprofloxacin release from Zn-HAp is higher than that
released from the undopedHAp. Thus, Zn HAp based coatings can be seen as a rising
solution in the treatment of bone tissue infections, allowing for the shortening and
increasing of the efficiency of the therapy and for the reduction of the ciprofloxacin dose
with consequent limitation of the resistant strain formation. On the basis of the carried
out studies, it is possible conclude that Zn-HAp can be considered a promising material
for potential applications in the repair of osteoporotic, combining antibacterial effects,
osteoconductivity, and the capability of inhibiting osteoclast activity[21].
Review of literature
Research in bio ceramics continues to advance at arapid pace as new techniques

and materials a reapplied to repair damaged musculoskeletal tissues, large bone defects,
and worn out body parts such as hip and knee joints. Thus, new biomaterials and
improved scaffolds to target major diseases such as impaired fracture healing, soft tissue
repair, osteoporosis, and osteo-arthritis continue to be an important research focus. Some
of the most exciting new materials, porous ceramic scaffolds for bone
repairandbonyingrowth, arenowonthemarket and will soon be common in the orthopaedic
arena, improving the expected lifespan of implants andother surgical procedures. The
target is the development of biomedical devices that last for the remaining life of the
patient. In this case, today‘s routine THR is then bound to become a procedure of the past,
as tissue engineeringandproductssuchas bio ceramic resorbable scaffolds
becomecommonplace. These novel inorganic materials that can augment the body‘s own
ability to regenerate are poised to become significant in future clinical approaches to
restore function in damaged tissue. The possibility of large-scale manufacturing of
engineered tissues seeded with the patient‘s own cells to minimize the risk of rejection is
an innovative alternative to some problems currently associated with prosthetic implants.
If successful, of this approachdramatically improve the quality of life for millions of
people worldwide. In particular, the development of nanostructure alumina and zirconia
ceramics and their composites as well as nanostructured calcium phosphate ceramics and
porous bioactive glasses including silica- based mesoporous materials, possibly as
composites with organic constituents, will provide many desired properties for bone
substitution andtissue engineeringforthenext20years [ 2].
International journal of applied engineering research ISSN 0973-4562 Volume

13, Number 5 (2018) PP. 2744-2752 Published an article, bioceramics for hard tissue
engineering applications. This review article has given the brief explanation of traditional
and current synthetic bio ceramic materials used for the hard tissue engineering. These
materials enhance the compatibility, suitability, and life of the implants. These materials
need further research for the improvement of quality and stability of implants for the
patients. Still, some materials, including, hydroxyapatite, and bioactive glass ceramics
need more research for the improvement of mechanical properties. Bio glass and bio
glass-based materials are highly biocompatible and rapidly degrade in the body.
However, mechanical property of bio glass-based materials is still a major problem. So
metal-bio glass composites can used to get desired mechanical properties in some cases.
The main benefit of bio glass is that it produces apatite layer when it encounter body
fluid. That apatite layer induces the bone regeneration. Other materials as if Alumina is
also producing good mechanical properties, but the use of zirconia with alumina enhance
the mechanical as well as biological characteristics. Hydroxyapatite is naturally similar
with the bone hydroxyapatite therefore it is used for orthopedic as well as dental
applications. These synthetic materials are having some advantages as well as
disadvantages. Therefore, bio ceramics are more favourable material than other materials.
The nano structure based bioceramic materials can be more suitable for the future
applications.
The hand book of bio ceramicsandbio composite gives explanation of

hydroxyapatite crystal structure can accommodate substitutions by variousions for the
Ca2+, PO43_, and OH_ groups , these ionic substitutionsaffecting the HAp lattice
parameters, crystal morphology, crystallinity, solubility, and thermal stability. In
particular, the vicarious ion incorporation within apatitelattice influences the apatite
dissolution rate, remarkably enhancing the proliferationof human osteoblast-like cells in
vitro and consequently encouraging osseointegration. To resemble the mineral
component of the bone, various substitutions, both cationic(substituting for the calcium)
and anionic (substituting for the phosphate or hydroxyl groups), have been tried and
tested, with consequent modifications of the chemical, physical, and biological
properties, as demonstrated in in vitro and in vivo tests. On the basis of the considerations
given above, this chapter reports a review about the majority of the attempted
substitutions within the hydroxyapatite lattice, including both anionic and cationic ions.
In order to achieve this purpose, the manuscript is organized into four sections: in the
first section, a brief introduction about the chemical composition of biological apatites is
reported; in the second section, the structure of stoichiometric hydroxyapatite is shortly
described; in the third section, an overview about the synthesis processes and the
chemical, physical, micro structural, and biological properties of cationicandanionic
substituted hydroxyapatites is reported; and in the fourth section, final considerations and
remarks are summarized.
REFERENCE
[1] Russe Giordano, DMD, CAGS<DMSC&Edward A. McLaren, DDS, MDC,

Ceramics overview; Classificationbymicrostructure andprocessingmethods, VOL
31,2010.
[2] Robert B. Heimann, Ceramics: Bio ceramics, First Published: 15 October 2011,
[3] Park, J & Lakes,R.S, Biomaterials: An Introduction,Third Edition, Springer
science &business media, Newyork,2007.
[4] PawanKumar, Brinjnandan S Dehiya And Anil Sindhu, Bio ceramics For Hard
Tissue Engineering Applications: A Review, Volume 13, Number 5 ,2018.
[5] LarryL. Hench, An Introduction to bio ceramic, Second Edition, imperial college
press ,2013.
[6] Antonio Licciulli, An Introduction to Bio ceramics
[7] Thamaraiselvi, T &. Rajeswari, Sivasankari. Biological Evaluation of Bio ceramic
Materials- A Review: TrendsBiomater.Artif. Organs, 2003.
[8] James F. Shackelford, Biocramics Volume 1 of Advanced Ceramics, 2005.
[9] Dominique G. Poitout(ed.), Biomechanics and biomaterials in orthopaedics,
springer- Verlag London, 2004.
[10] MariaGraziaRaucci, DanielaGiugliano, and Luigi Ambrosio, Fundamental
Properties ofBioceramicsandBio composites, 2015.
[11] Samuel F. Hulbert, Theuse Of Alumina andZircionia In Surgical Implants, World
Scientific, Singapore, 2013.
[12] David H. Kohn, Bioceramics. McGraw Hill, Newyork ,2004.
[13] Larry L. Hench andOrjanAnderson; An introduction to bio ceramics: Bioactive
Glasses. World Scientific, Singapore,1993.
[14] Joon Park; Bioceramics, Properties, Characterizations andApplications, Springer,
2008.
[15] Larry L Hench, Bioactive Glass Bone Grafts: History and Clinical Applications,
Switzerland ,2016.
[16] CorradoPiconi, Alessandro Alan Porporati, Bioinert Ceramics: Zirconia and
Alumina, Switzerland 2016.
[17] Sergey V Dorozhkin, Calcium Phosphate, Switzerland 2016.
[18] Tampieri,Anna& Michele, Lafisco, Sprio, et al. Hydroxyl Apatite: From Nano
Crystals to Hybrid Nanocompositesfor Regenerative Medicine. 2016.
[20] C. Eibekkai, H. Bouyarmane, M. Eikarbane, Smasse, A. Saoiabi, et.al. Zinc
Oxide- Hydroxyapatite NanocompositePhotocatalystsForthe Degradation of
Ciprofloxacin andOfloxacin Antibiotics. Colloids and Surfaces A:
Physiochemical and Engineering Aspects. 2017.
[21] IIariaCacciotti, cationic and anionic substitutions in hydroxyl apatite, Switzerland
,2016.
[22] Larry L. Hench And Julian R. Jones, Biomaterials, Artificial Organs and Tissue
Engineering 2005.
[23] Miyaji F, Kono Y, Suyama Y, Formation and Structure of Zinc –Substituted
Calcium Hydroxy Apatite, Mater Res Bull 40:209-220, 2005
[24] A Bigi, E. Foresti, M. Gandolfi, M. Gazzano,&N. Roveri,Inhibitting Effect of
Zinc On Hydroxyl apatite Crystallization. 1995, 58:49-58,
CHAPTER-2
EXPERIMENTAL AND CHARACTERIZATION
TECHNIQUES
Introduction
This chapter includes the different techniques adopted for the synthesis of ceramic
materials and their characterization. Ceramic powders with different properties can be
produced using different synthesis methods. In the present project work conventional
combustion method is employed. Various techniques for structural analysis and
characterization of the samples include X-ray Diffraction (XRD), UV-Vis spectroscopy,
Raman Spectroscopy, IR Spectroscopy, Neutron Diffraction (ND), SEM etc.The
characterization techniques employed for the present study are X-ray diffraction (XRD),
UVis and Fourier TransformIR and SEM.
2.1 Synthesis of nanocomposite ceramic powders
Traditionally, ceramic nanoparticles are prepared by solid state methods, in which

hydroxide, oxide, carbonate, nitrate, or sulphate raw materials are physically mixed, and
then treated at high temperature for long periods of time to enable the formation of the
nanoparticles. Several modified chemical synthesis techniques have been developed to
obtain nanoscale ceramic particles with a suitable morphology at a low temperature.
There are mainly two approaches for the synthesis of ceramic powders. One is the
mechanical method and the other is the chemical method.
Mechanical methods are mainly of two types:
i. Mixed oxide process
ii. High-energy ball milling
Chemical methods commonly used for the synthesis of the ceramic powder are:
i. Co-precipitation method
ii. Sol-gel methods
iii. Hydrothermal method
iv. Combustion method etc.
2.1.1. Co-precipitation method
Co-precipitation is an easy and reproducible technique that has been widely used in the
preparation of nanoparticles. The nanoprecipitation techniques isotherwise called as
solvent displacement method or interfacial displacement introduced by Fessi and
Coworkers (1989). By using co-precipitation method, it is possible to achieve a high
degree of homogenization together with a small particle size and faster reaction rates.
Commonly used steps involved in the co-precipitation process are:
i. Taking appropriate amounts of starting materials

ii. Making appropriate amount of basic solution having very high Ph
iii. Achieving the reducing state (acidic state) of mixture of all the starting
iv. Maintaining high pH~14 of the precipitation solution
v. Performing decantation to remove excess water, undesired ions and impurities.
Fig 2.1 Steps of Co-precipitation

Co-precipitation requires very low heating treatment, sometimes no need to sinter the
product, onlycalcination is enough. It is preferable when large quantity of powder is
required. In this method, pH is very sensitive parameter which should 17 be carefully
controlled to achieve better product. The co-precipitation method does not work well in
cases where: the two reactants have different solubilities in water, the reactants do not
precipitate at the same rate or supersaturated solutions commonly occur.
2.1.2 The Sol-Gel Method
The sol-gel method for synthesis of glass, ceramics and glass-ceramics has been
receiving much attention over the last few years.
The process involves four stages:
1) Hydrolysis
2) Condensation/Polymerization of monomers
3) Growth of particles
4) Gel formation
Initially the corresponding metal precursor undergoes rapid hydrolysis to produce the
metal hydroxide solution, followed by immediate condensation which leads to the
formation of three-dimensional gels. Later they obtained gel is subjected to drying
process, and the resulting product is readily converted to Xerogel or Aerogel based on the
mode of drying.
Fig.2.2 Different Sol-Gel process steps
Sol-gel process has better control of the structure, including porosity and particle
size. Due to mixing at the molecular level, this process ensures high purity. Besides the
high purity and low sintering temperature, high degree of homogeneity in a molecular
scale of the product can be obtained via sol-gel method. Along with advantages, there are
disadvantages also. Shrinkage of wet gel upon drying, which often leads to fracture due
to the generation of large capillary stresses and, consequently, makes difficult the
attainment of large monolithic pieces. It is difficult to avoid residual porosity and OH
groups. High cost of precursors is another drawback of sol-gel method.[1]
2.1.3 Hydrothermal method

Hydrothermal process is defined as chemical reactions in solvents contained in
sealed vessels in which the temperature of solvents can be brought to around their critical
points via heating simultaneouslywithautogenous pressure. The experimental setup of
hydrothermal synthesis includes a tabular reactor, two piston pumps, syringe pump, back
pressure valve, electric furnace with fluidized sand bed, cooler, flow mixer, manometers
and pressure gauges. The principle of hydrothermal method is that an insoluble material
at ambient temperatures could be made soluble using high temperatures and pressures.
The crystal growth is performed in an apparatus consisting of a steel metal vessel called
autoclave.
Fig 2.3 Schematic diagram of autoclave
The finely divided particles of material to be grown are taken in the bottom of
vessel and suitably oriented single crystal seed plates are suspended in the upper growth
region. A dilute alkaline solution is then poured into the remaining 60 to 80% of free
space of vessel. The vessel is then placed inside a furnace that has been designed to heat
the lower dissolving section isothermally hotter than the upper growth region which is
also maintained isothermal. Under these hightemperatures and pressure the materials in
the lower compartment of the autoclave dissolve in the alkaline solution to become
saturated solution. This saturated solution rises due to the convection caused by the
temperature difference between the upper and lower compartments of the autoclave.
When the solution reaches the upper compartment of the autoclave, it become
supersaturated because of the lower temperature of the compartment, and according to
the degree of the temperature difference it is crystallized on the seed crystal.
Fig 2.4 Schematic diagram of hydrothermal method of synthesis
The products obtained from hydrothermal process is homogeneous in composition. It is

easy to control purity, composition, size and crystal shape of the powder. With this
method it is possible to grow crystals of compounds with high melting points at lower
temperatures. Since the reaction takes place without high-temperature calcinations
process or crushing, much amount of energy saved. The need of expensive autoclaves is a
disadvantage of this method.
2.1.4 Combustion method
Solution combustion method is one of the traditional methods of ceramic synthesis. It is a
worldwide used methodology for the preparation of inorganic ceramic and composite
materials with controlled properties for a wide number of applications, from catalysis to
photo catalysis and electro catalysis, from heavy metal removal to sensoristics and
electronics. Among the soft chemical methods, solution combustion synthesis (SCS) is an
excellent synthesis method in terms of simplicity, cost-efficiency and powder quality of
the product. SCS is based on a fast and self-sustained redox reaction between a fuel and
an oxidant in the presence of metal cations. Usually oxidants are metal precursors
themselves, like for example metal nitrates, and the fuel is any organic material, as for
example citric acid, urea and glycerine, capable of forming complexes with metal ions of
interest.
Combustion synthesis is also known as self-propagating high temperature synthesis. It is
a processing technique by which exothermic reactions are used to produce a variety of
ceramic powders. The process is based on the principle that, once initiated by an external
source, an exothermic reaction occurs, becoming self-sustained and resulting in the
product within a short period of time. Solution combustion synthesis consists of three
main steps such as
i. Formation of the combustion mixture
ii. Formation of the gel
iii. Combustion of the gel.
A schematic description of these three steps is illustrated in Fig 2.5. The desired
metal precursors are mixed in water solution with an organic fuel. A gel network is
formed in the combustion mixture upon dehydration of the solution. The combustion
process between the fuel and the oxidant (i.e.: the nitrates and eventually an additional
oxidant), intimately connected in the gel network, is initiated by a thermal or electric
source. The decomposition of the gel should be preferably in single step, uniform, rapid
and over an arrow temperature range, to ensure that no undesired products are formed. A
fluffy powder is obtained after a few seconds.
Fig 2.5 Three steps of solution combustion method

Modified combustion process is low temperature initiated, self propagating, gas-
producing, exothermic reaction. Combustion technique has attracted much attention in
recent years because it allows for synthesis of ceramic powders in more simple, safe and
fast way. The main potential advantages of combustion synthesis are that the process
requires less energy than in the conventional syntheses and that processing time is
reduced to minutes. Combustion synthesis produce high purity powders with nanophase
particle sizes and narrow size distribution, which are desirable properties for advanced
ceramic materials.[2]
2.2. Characterization Techniques

Characterization techniques involves various methods that give detailed information
about a material; i.e., their chemical composition, morphology, energy in their shells,
their parameters etc. Different types of characterization techniques such as X-ray
diffraction (XRD), UV spectroscopy. Fourier Transform IR spectroscopy, Raman
spectroscopy etc. are used to analyse the characteristic properties [3].
2.2.1. X-Ray Diffraction (XRD) Technique
X-ray diffraction (XRD) is extensively used to characterize the crystalline solids

and to estimate the crystalline sizes. A crystal lattice is made up of regular planes of
atoms equal distance apart. Since the wavelength of X-rays is comparable to the
interatomic distance, laue suggested that it might be possible to diffract X-rays by
crystals. This suggestion came out to be true when Bragg succeeded in diffracting X-rays
from sodium chloride crystal. In 1983 W.L. Bragg and W.H. Bragg worked out a relation
to determine the interatomic distances from X-ray diffraction patterns.
Fig.2.6. Bragg’s diffraction scheme
An integral part of the processes crystal structure determination is an experiment

and the techniques used to collect the experimental data. The experiment consists of
scattering radiation from crystalline lattice, the radiation that usually employed being X-
rays, electrons and neutrons. Although all the three radiation can be employed, most
structure determinations are based on X-ray diffraction technique. The X-rays falling on
these arrays undergo diffraction as shown in the figure 2.6,
2d sinƟ = nA,
Where
d – Interplanardistance
n - Order of diffraction
Ɵ= Angle of diffraction
Wavelength of X-ray radiation
The main parts of an X-ray diffractometer include
i. An X-ray source, because of its high intensity

ii. The sample holder in which the powder sample is placed
iii. The detector
In the X-ray diffract meter, the sample and the detector rotate relative to the X-ray
source, which one moves through 0, the other moves through 20. Alternatively, the
sample can be held fixed and detector and source can be rotated in opposite directions.
The conventional X-ray diffraction geometry and modifications are used for studying
ceramics. A typical X-ray diffract meter is. Shown in the figure 2.7 [4].
Fig.2.7 .x-ray diffractometer
The X-ray spectrum generated by the technique provides the structural fingerprint
of the unknown crystalline materials. In addition, changes in peak position that represent
either, compositional variations or structure-state information's are readily detectable.
The determination of presence of impurities in a pure phase can also be done using X-ray
diffraction study. With modern X-ray optics and detectors, it is possible to detect
impurities below 0.1 wt% which gives information for the optimization of the synthesis
of the material, and for quality control
Lattice Parameter Calculation and theoretical density from XRD pattern
The data of XRD obtained is plotted using Origin software with 20 values along
X-axis and the corresponding intensity along Y-axis. The major peaks are identified and
indexed with the help of JCPDS file.
The relationship between the inter planar spacing (d), the lattice parameters (a, b,
c) and the Miller indices (h, k, l) is given by
1/d2 = (h/a)2+(k/b)2+(l/c)2 [2.7]
The values of d-spacing are available from the XRD data Substituting the values
of 'd' in the above equation we can calculate the lattice parameters.
2.2.2 UV-Visible Absorption Spectroscopy
Ultraviolet-Visible spectroscopy or Ultraviolet Visible spectro photometry (UV-

Vis or UV/Vis) refers to absorption spectroscopy or reflectance spectroscopy in the
ultraviolet-visible spectral region. This means it uses light in the visible and adjacent
(near-UV and near-infrared (NIR)) ranges. The absorption or reflectance in the visible
range directly affects the perceived colour of the chemicals involved. In this region of the
electromagnetic spectrum, molecules undergo electronic transitions. This technique is
complementary to fluorescence spectroscopy. In that fluorescence deals with transitions
from the excited state to the ground state, while absorption measures transitions from the
ground state to the excited state. This technique is applicable to absorption spectroscopy
based upon electromagnetic radiation in the wavelength region of 160nm to 780 nm.
Most transition metal ions absorb in the UV or Visible region of the spectrum. For
the lanthanide and actinide series, the absorption process results from electronic
transitions of 4f and 5felectrons; for elements of the first and second transition-metal
series, the 3d and 4d electrons are responsible.
The instrument used in Ultraviolet-Visible spectroscopy is called a UV-Vis

Spectrophotometer. It measures the intensity of light passing through a sample (/) and
compares it to the intensity of light before it passes through the sample (Is). The
absorbance ratio I/Isis called the transmittance and is usually expressed as a percentage
(%T).
The absorbance A, is based on the transmittance:
A = -log (%T 10%)
Fig.2.8 Perkin Elmer Spectrometer

The UV-Visible spectrophotometer can also be configured to measure reflectance.
In this case, the spectrophotometer measures the intensity of light reflected from a sample
(I), and compares it to the intensity of light reflected from a reference material (4) (such
as a white tile). The ratio I/Isis called the reflectance and is usually expressed as a
percentage (%R).
The diagram of a typical spectrophotometer is shown in the figure 2.8. The basic
parts of a spectrophotometer are a light source, a holder for the sample, a diffraction
grating in a monochromator or a prism to separate the different wavelengths of light, and
a detector. The radiation source is often a Tungsten filament (300-2500 nm),a deuterium
are lamp, which is continuous over the ultraviolet region(190-400 nm), Xenon are lamp,
which is continuous from 160-2.000 nm; or more recently, light emitting diodes (LED)
for the visible wavelengths. The detector is typically a photomukiplier tube, a
photodiode, a photodiode array or a charge-coupled device (CCD). A beam of light from
a visible and or a light source is separated into its component wavelengths by a prism or
diffraction grating. Each monochromatic (single wavelength) beam in turn, is split into
two equal intensity beams by a half-mirrored device. One beam, the sample, beam passes
through a small transparent Container (cuvette) containing the sample. The intensities of
these beams are then measured by electronic detectors and compared. The intensity of
reference beam, which should have suffered no light absorption, is defined as 4. The
intensity of the sample beam is defined as I. Over a short period of time, the
spectrophotometer automatically scans all components wavelengths in the manner
described. The UV region scanned is normally from 200nm to 400 nm and visible portion
is from 400nm to 800 nm. [5]
A band gap, also called an energy gap, is an energy range in a solid where3O
electron states can exist. In graphs of the electronic band structure of solids, the bandgap
generally refers to the energy difference (in electron volts) between the top of the valence
band and the bottom of the conduction band in insulators and semiconductors. Substances
with large band gaps are generally insulators, those with smaller band gaps are
semiconductors, while conductors either have very small band gaps or none, because the
valence and conduction bands overlap.
The Kubelka-Munk theory is generally used for the analysis of diffuse reflectance
spectra obtained from weakly absorbing samples. It provides a correlation between
reflectance and concentration. The concentration of an absorbing species can be
determined using the KubelkaMunk formula:
Where, F(R) = (1-R) 2 /2R = k/ s = Ac/s [2.8]

R=reflectance k =absorption coefficient s = scattering coefficient c =
concentration of the absorbing species A= absorbance
2.2.3 Vibrational Spectroscopy
Transitions between the vibrational levels result in the vibrational spectra which
gives an insight into the discrete motion of the atoms in the molecular system. There are
two types of spectroscopy that involve vibrational transitions. One of them is the Infrared
spectroscopy. During infrared spectroscopy experiments, we observe transitions between
vibrational energy levels of a molecule induced by the absorption of infrared (IR)
radiation. The second type of vibrational spectroscopy is Ramanspectroscopy. In Raman
spectroscopy, vibrational transitions occur during the scatteringof light by molecules.
A molecule can vibrate in many ways, and each way is called a vibrational mode.
For molecules with N atoms in them, linear molecules have 3N-5 degrees of vibrational
modes, whereas nonlinear molecules have 3N-6 degrees of vibrational modes (vibrational
degrees of freedom). As an example H2O, a non-linear molecule, willhave 3 x 3 — 6 = 3
degrees of vibrational freedom, or modes.
Not all fundamental vibrational transitions can be studied by both IR and Raman
spectroscopy because they have different selection rules. Selection rules tell us if
atransition is allowed or forbidden. If a normal mode has an allowed IR transition, we say
that it is IR active. Similarly, if a normal mode has an allowed Raman transition, we say
that it is Raman active. For a vibrational mode in a molecule to be IR active, I must be
associated with changes in the dipole moment. A molecular vibration will be Raman
active only if it causes a change in a component of the polarizability. [6]
The above-mentioned characterization technique, vibrational spectroscopy is not

done for the present project work.
2.2.3.1 Infrared (IR) Spectroscopy
Infrared spectroscopy (IR spectroscopy) is the spectroscopy that deals with the
infrared region of the electromagnetic spectrum that is light with a longer wavelength and
lower frequency than visible light. It covers a. range of techniques, mostly based on
absorption spectroscopy.
As with all spectroscopic techniques, it can be used to identify and study

chemicals. A common laboratory instrument that uses this technique is a Fourier
transform infrared (FTIR) spectrometer.The infrared portion of the electromagnetic
spectrum is usually divided into three regions; the near-, mid- and far- infrared, named
for their relation to the visible spectrum. The higher-energy near-IR, approximately
14000 cm-1- 4000cm-1 (0.8- 2.5 gm wavelength) can excite overtone or harmonic
vibrations. The mid-infrared, approximately 4000cm-1-400cm-1(2.5-25 pm) may be used
to study the fundamental vibrations and associated rotational-vibrational structure. The
far-infrared, approximately 400-10cm-1 (25pm -1000 pm), lying adjacent to the
microwave region, has low energy and may be used for rotational spectroscopy.
Fourier transform infrared (FTIR) spectroscopy is a measurement technique that

allows one to record infrared spectra. Infrared light is guided through an interferometer
and then through the sample (or vice versa). A moving mirror inside the apparatus alters
the distribution of infrared light that passes through the interferometer. The signal
directly recorded, called an "interferogram", represents light output as a function of
mirror position. A data-processing technique called Fourier transform turns this raw data
into the desired result (the sample's spectrum): Light output as a function of infrared
wavelength (or equivalently, wave number). In an FTIR spectrometer, resolutions
increased by increasing optical retardation, that is, by increasing how far the moving
mirror moves.
Fig.2.9 Diagram of a Fourier transform Raman spectrometer and Bruker

DFS/100S Raman spectrometer
An FTIR is typically based on the Michelson Interferometer experimental setup.

The interferometer consists of a beam splitter, a fixed mirror, and a mirror that translates
back and forth, very precisely. The beam splitter is made of a special material that
transmits half of the radiation staking it and reflects the other half. Radiation from the
source strikes the beam splitter and separates into two beams. One beam is transmitted
through the beam splitter to the fixed mirror and the second is reflected off the beam
splitter to the moving mirror. The fixed and moving mirrors reflect the radiation back to
the beam splitter. Again, half of this reflected radiation is transmitted, and half is
reflected at the beam splitter, resulting in one beam passing to the detector and the second
back to and its setup the source. Figure 2.9 shows the basic components of a Fourier
Transform spectrometer and its setup [7].
2.2.4 Photoluminous characterization (PL)
When a material is irradiated with electromagnetic radiation the molecules absorb

it at a definite wavelength and get excited from the ground state to the excited state. The
excess energy is dissipated by either photoluminescence process or by non-radiative
process in the form of heat to the lattice. When photons are absorbed and dissipation of
excess energy takes place by emission of light then it is called photoluminescence. The
measurement of emitted light and its characterization and analysis is photoluminescence
studies. The block diagram of a photoluminescence spectrophotometer is given in
fig.2.11Using photoluminescence spectrophotometer, two types of spectra can be
recorded (i) when the excitation wavelength is fixed while the emission wavelength is
scanned in the region where the emission occurs is called an emission spectrum on the
other hand
fig. 2.10Block diagram of a fluorescent spectrophotometer

(ii) When the emission wavelength is kept fixed while the excitation wavelength
is scanned in the region where the excitation occurs is called an excitation
spectrum [34].
The photoluminescence spectra can be used for the following
(i) From the emission and excitation spectra of the luminescent material it can be
characterized.
(ii) Relative luminescence yield of the synthesized sample can be obtained by
comparing with the luminescence yield of the commercially available
successful lamp phosphors.
(iv) Measurement of color coordinates.
(v) Luminescence of an ion can be used as a probe to characterize the ion itself
and also about its surroundings which is an important application in the field
of research and characterization of the phosphor materials [8].
REFERENCE
[1] Radha Guptha And Ashok Kumar, Bioactive Materials for Biomedical Applications
using Sol Gel Technolog. Biomedical materials (Bristol, England), 2008.
[2] Sung Park and Jae Chun Lee; Nanopowders Synthesized by Solution Combustion
Method and Their Applications, Myongji University, Yongin, Kyunggi .
[3] Koshy et al, US Patent No.6,835,367, Dec 28,2004.
[4] J.J. Kingsley et al, J. Mater, Sci.25, 1305, 1990.
[5] Pathak et al, Nanostructured Materials8, 101, 1997.
[6] S.K. Saha et al, Nanostructured Materials 8, 29,1997.
[7] Raveendranathan et al, J.Am. Ceram.Soc. Bull, 66,688, 1987
[8] H.H Willard, L.L Merrit, F.A Settle, Instrumental Methods of Analysis, VI edn,
CBS Publishers and Distributors,1986.
CHAPTER 3
HYDROXYAPATITE-ZINC OXIDE NANOCOMPOSITE
Introduction
The term apatite was originated from Greek word ‗apate‘which is defined as
deceit because of the various colour represented by different crystals. The changeability
in colour was owned by the crystals because of different elemental configuration with the
basic formula M10(ZO4)6X2, where M represents variety of mineral such as Ca, Mg, Fe
and Cd, Z represents P, As, V, S, C, S and X represents F, Cl, Br and OH.[1] Most
common apatiteis theCalcium hydroxyl apatite, which is a phase of calcium phosphate.
Calcium phosphate is the major constituent of hard tissues such as bone, tooth enamel,
dentine, and calcified parts of tendons. Hydroxyapatite retains the maximum similarity
with the mineral component of these tissues. Also, it owns substantial bioactivity,
biocompatibility, and osteoconductivityfacilitate direct bonding to the natural bone. Pure
HAp (Ca/P molar ratio of 1.67) is thermally stable at pH 4–12. [2] HAp activates the
biomineralisation phenomenon, by its chemical composition and by changing the surface
potential. It makes HAp the most important material to understand the biomineralisation
phenomenon. The HAp has been utilized for various biomedical applications, such as
scaffolds for orthopaedic applications, drug delivery, gene delivery and environmental
remediation. The basic properties of material are crystal shape, size, crystallinity, thermal
stability, morphology, and solubility. It makes the efficient biomedical application. HAp
possesses two basic forms: monoclinic or/ and hexagonal crystal structure. The basic
crystal properties of both hexagonal and monoclinic are space group symmetry, lattice
parameter and sintering temperature. The lattice parameters state various properties ofthe
hydroxyl apatite and changes in these parameters often various physical (crystallinity,
thermal stability, and morphology), chemical (solubility), and other physicochemical and
biological properties.
Zinc is most common mineral element in hard tissues. It has different
physiological roles in immune system and serves in cell division and cell growth.
Deficiency of zinc was found involved in Alzheimer‘s and Parkinson‘s disease. Zinc also
acts as an antidepressant. Zinc oxide (ZnO) is a wide band-gap II–VI binary compound
semiconductor (3.36 eV). It possesses unique optoelectrical and chemical properties. ZnO
is a superlative material for nanoscale optoelectronics and piezoelectric nano generators
[3] ZnO helps in bone regeneration as well asit possesses antimicrobial activity with
enhanced mechanical properties. ZnO nanoparticles (NPs) possess three inherent
mechanisms for antimicrobial action predominantly by Reactive Oxygen Species (ROS)
generation, by attack to nucleus and protein and the disruption of cell wall. These modes
of actions differ from the mechanism of the resistance generation by the microbes like
efflux, drug modification, target modification and enzyme deactivation. Since ZnO NPs
are considered as the best suitable nanoantibiotic for antibiotic resistant bacteria. The
crystal structures ofZnO have three orientations: hexagonal wurtzite, cubic zinc blende
androck salt. Rock salt is also called as Rochelle salt. The main and thermodynamically
stable orientation is wurtzite. In this crystal structure, sp3hybridization governs the whole
structure with each O2− remains fenced by four Zn2+at the junctions of a tetrahedron and
reverse. Cubic substrate nurtures the zinc blende structure at consecutive growth.
Synthesis of ZnO at higher pressure provides the Rochelle salt symmetry. The two major
properties retained by ZnO that is piezoelectricity and impulsive polarization are due to
the hexagonal wurtzite crystal structure [4].
3.1 Hydroxyapatite- Zinc oxide nanocomposite
HAPp has high brittleness and lower fracture toughness. Incorporation of Zn

enhanced the mechanical properties of HAp. The bioapatites are having better biological
and indentation properties than HAp under physiological conditions. It prompts various
researchers to focus on the substitution of HAp with various metal ions, which
subsequently can improve these lags for biomedical applications. Incorporation of Zn
enhanced the mechanical properties of HAp. These substitutions revised the lattice
parameters, which altered the crystallinity and the physical properties of HAp. The
hexagonal crystal structure of HAp allows various metal ions either to replace the
calcium ion from the HAp lattice or to in the void area. The chemical charge imbalance
due to the monovalent and trivalent doped ions causes the changes in the chemical
Properties. The main phase as HAp along with the dopant phase, with a reduction in c
lattice parameter, indicating that only zinc doping does not disperse the HAp into other
phases. However, sintering temperature also plays main role in the Hap phase generation
during synthesis. Integration of zinc not only alters the physical and mechanical
properties of HAp but adds various biological activities to the HAp matrix. These
biological functionalities open a vast area towards the biological applications of HAp.
The incorporation of zinc in HAp matrix enhances the osseointegration and biological
responses of HAp, thus opens the door for various orthopedic as well as other biomedical
applications. ZnO have excellent antimicrobial activity against various pathogens.
Among all these pathogens, zinc shows highest lethal activity against both Gram-positive
and Gram-negativebacteria. The lower concentration of zinc is preferred. Even a lower
concentration of zincis antibacterial when incorporated into the HAp matrix.Inaddition to
the antibacterial activity, Zn incorporated HAp has also shown excellent antifungal
activity. Such antimicrobial activity attracts the biomaterial researchers to explore the all
possible biomedical applications of Zn incorporated HAp. It indicates the potentialuse of
zinc dopedHAp asan antifungal agent.
In this present work, the synthesis of Hydroxyapatite- Zinc oxide nanocomposite

in 60:40 ratio synthezised by combustion method is reported. The powder and pellet
characterization of the sample is done by x-ray diffraction (XRD) technique; UV-visible
spectroscopy and Fourier transform infrared spectroscopy (FTIR), Photo luminous
spectroscopy (PL), and scanning electron microscopy (SEM).
3.2 Experimental Section
3.2.1 Preparation of Hydroxy apatite- Zinc oxide nanocomposite
A single step auto-igniting combustion synthesis is used to prepare nano

structured HAp. Stoichiometric amount of high purity calcium nitrate and diammonium
phosphate are dissolved in distilled water to make a clear solution. Citric acid is then
added to it as a complexing agent and fuel. The oxidant to fuel ratio is adjusted by adding
nitric acid and ammonium hydroxide. The solution containing the precursor mixture is
heated using a hot plate at 2500C in a ventilated fume hood. The solution boils on heating
and undergoes dehydration accompanied by foam. The foam ignites by itself on
persistent heating giving voluminous and fluffy product of combustion.
To prepare nano structured ZnO, a single step auto-igniting combustion synthesis

is used. Stoichiometric amount of high purity zinc nitrate hexahydrate is dissolved in
distilled water to make clear solution. Citric acid is then added to it as a complexing
agent and fuel. The oxidant to fuel ratio is adjusted by adding nitric acid and ammonium
hydroxide. The solution containing the precursor mixture is heated using a hot plate at
2500C in a ventilated fume hood. The solution boils on heating and undergoes
dehydration accompanied by foam. The foam ignites by itself on persistent heating giving
voluminous and fluffy product of combustion.
To prepare 60:40 HAp-ZnO nanocomposite the as prepared nano structured HAp

and ZnO are mixed in the definite proportion and ground well in acetone medium.
The HAp-ZnO nanocomposite powder is uniaxially compacted into pellets in a

12 mm diameter steel die at20 MPa using a hydraulic press.The sintering of the disc
shaped pellets are carried out in a high temperature microwave furnace. In the present
work the susceptor assisted microwave sintering is realised using a microwave furnace
with a pair of 2.45 GHz magnetrons with power 1.1kW each and silicon carbide
susceptor (VBCC/MF/86,VB Ceramics Consultants, India). Its upper limit of temperature
is 1600oC. The heating rate optimised for the present work is 40 oCmin-1 and the soaking
duration is 30 minutes. In this furnace a high quality pyrometer is used to sense the
sample temperature. Considering the variations in the emissivity of ceramic samples the
maximum error possible in the sample chamber as sensed by the pyrometer is 10o C
.The temperature controller is able to maintain the temperature inside the chamber within
a maximum error limits of 1o C .The experimental density of the sintered pellets is
calculated using Archimedes principle
.
3.3 Sample Characterization

3.3.1 X-ray diffraction
Bragg explained x-ray diffraction in crystals by modelling the crystal as a set of

discrete parallel planes separated by a constant parameter d. If λ is the wavelength of X-
rays used and is the angle between the incident ray and the planes of reflection, Bragg‘s
law can be stated as
2d sin   n
Where n=1, 2, 3....stand for first order, second order, third order, maxima
respectively. The position of the peaks in the diffraction pattern depends on the structure,
lattice parameters and symmetry of the crystalline material and the intensities of the
peaks are determined by the scattering power of the atoms. The spacing d between the
crystal planes can be determined from Bragg‘s law and considering the peak position and
radiation source wavelength. The broadening of diffraction peaks associated with small
size of the crystallites can be used to determine crystalline size. The size of
nanocrystallites can be calculated using the Scherrer equation: , whereDis
the average crystallite dimension perpendicular to the reflecting planes , the X-ray
wavelength, K the Scherrer constant, whose value depends on the shape of the crystallite
and is taken as 0.9 for spherical particles.[5]
The as-prepared samples are characterized by X-ray diffractometer (X'pert pro,

PANalytical, the Netherlands) with Cu Kα radiation in the range of 20–60º in steps of
0.0840 for the determination of crystalline structure and phase of the nanomaterials.The
average crystallite size is estimated for all the samples using Scherrer‘s equation. The
Williamson-Hall plot is used for studying lattice strain in the sample.
3.3.2 Fourier Transform Infrared Spectroscopy
Fourier transform infrared spectroscopy plays a vital role in identifying and

characterizing organic, inorganic, polymeric, crystalline and coordination compounds in
solid, liquid, and gaseous forms and is considered as one of the powerful tools in material
science research.
In the present work, FTIR spectra of the samples were recorded at room
temperature using a Perkin Elmer spectrum 2 spectrometer by ATR method in the mid IR
range from 350-4000cm .The instrument has a standard spectral resolution of 0.5 cm-1
and a wavelength precision better than 0.01 cm-1at 3000cm-1.An attenuated total
reflection accessory measures the totally reflected infrared beam when the beam comes in
contact with a sample. Internal reflection spectroscopy passes infrared radiation through
an infrared-transmitting crystal of high refractive index, allowing the radiation to reflect
in the crystal one or more times.The infrared radiation interacts with the sample through a
series of standing waves, called evanescent waves. An evanescent wave is a penetrating
electromagnetic field whose intensity quickly decays as it moves away from its
source.An evanescent wave penetrates into the sample in contact with the crystal,
producing a spectrum of the sample. In ATR mode no sample preparation is required as
in transmittance mode as in KBr Pellet method.Most importantly, the improved spectral
acquisition and reproducibility associated with this technique leads to better quality
database building for more precise material verification and identification. ATR is clearly
an extremely robust and reliable technique for studies involving solids and liquids.
3.3.3 UV-visible absorption spectroscopy
UV visible spectroscopy is an efficient tool to analyze charge confinement in

nanostructured materials. The presence of excitonic features in the case of
nanostructured materials is ascribed to the increase of the exciton binding energy and the
oscillation strength. In strongly confined systems of any dimensionality, many
semiconductors exhibit well resolved excitonic features since the exciton binding energy
can exceed thermal excitation energy Kt. If exciton formation is neglected, the absorption
coefficient can be expressed as a function of photon energy h depends on the types of
the energy bands containing initial and final states. For simple parabolic bands, the
absorption coefficient has the following energy dependence [Nalwa H S 2000]
Where A is proportionality constant and m is another constant for different type

of transition. The values which m can take are , 2, , or 3 for allowed direct, allowed
indirect, forbidden direct and forbidden indirect electronic transitions respectively. If the
conduction band and valence band are close, direct band gap transition occurs, the
spectrum exhibits excitonic absorption peaks. For such cases, band gap is calculated from
excitonic wavelengths.
In the present work, UV- visible spectra of the samples were taken using Perkin-
Elmer spectrophotometer over a range from 200nm to 800nm and the band gap is
calculated by plotting Tauc‘s plot.
3.3.4 Photoluminescence (PL) Spectroscopy
Photoluminescence (PL) is the spontaneous emission of light from a material

under optical excitation. PL spectroscopy is suitable for the characterization of both
organic and inorganic materials of virtually any size. The sample‘s PL emission
properties are characterized by four parameters namely intensity, emission wavelength,
bandwidth of the emission peak, and the emission stability [Qu and peng 2002]. Features
of the emission spectrum can be used to identify surface, interface and impurity levels.
The intensity of the PL signal provides information on the quality of surfaces and
interfaces. PL analysis is non-destructive. Indeed, the technique requires very little
sample manipulation or environmental control. Because the sample is excited optically,
electrical contacts and junctions are unnecessary and high – resistivity materials pose no
practical difficulty. In addition, time-resolved PL can be very fast, making it useful for
characterizing the most rapid processes in a material. Materials with poor radiative
efficiency, such as low-quality indirect band gap semiconductors, are difficult to study
through ordinary PL.
In the present work, PL spectra of the samples were taken using Perkin Elmer
spectrophotometer for an excitation wavelength of 350 nm.
3.3.5 Scanning Electron Microscopy
The field emission scanning electron microscope images a sample surface by

raster scanning over it with a high energy beam of electrons. These electrons are liberated
by a field emission source. The electrons interact with the atoms comprising the sample
to produce signals that contain information about surface topography, composition, and
other properties such as electrical conductivity. The object is scanned by electrons
according to a zigzag pattern.
The size and morphology of the prepared sample analyzed by scanning electron
microscopy (SEM). The SEM images show the shape and size of the particle that are
lying on the surface of the samples[6].In the present work NOVA NANOSEM-450 (FEI,
USA) is used for the surface analysis of the sintered sample. This scanning electron
microscope has a resolution of 1.8 nm in high vacuum mode for non-conducting
materials. The SEM micrographs of the sintered samples are analysed using the softwares
ImageJ version 1.37v. The SEM micrograph give the surface morphology and grain size
distribution which help in the effect of grain size on the optical, thermal and mechanical
properties of the sample.
3.4 Results and Discussion

3.4.1 X-ray Diffraction Analysis
The X-ray diffraction patterns of Hydroxyapatite nanoparticles is shown in figure

3.1.All the peaks including the minor ones are indexed using ICDD PDF No.74-0565.
The d values corresponding to the peaks were determined using Bragg‘s law. These
values are compared with the standard d values and it was found that the experimental d
values agreed closely with the standard d values confirming that the synthesized samples
werephase pureHydroxyapatite.
Fig 3.1 XRD pattern of Hydroxyapatite nanoparticles
The XRD pattern Zinc Oxide nanoparticles is shown 3.2 respectively. All the
peaks are indexed using ICDD PDF No.89-0510 and Zinc Oxide nanoparticles. All the
peaks and the d-spacings calculated match very well with the standard reference data
which indicates that the as prepared sample is phase pure Zinc oxide. These XRD peaks
confirm the efficacy of modified combustion synthesis to prepare phase pure nano
particles in an economic way without using complex experimental set up.
Fig 3.2 XRD pattern of Zinc Oxide nanoparticles
Fig 3.3 XRD pattern of Hydroxyapatite-Zinc Oxide nanocomposite
The XRD pattern of Hydroxyapatite-Zinc Oxide nanocomposite of 60:40 atom%

is shown in fig 3.3. The peaks in the XRD pattern were identified to be resulting from
(200),(002),(210),(211),(130) and (502) reflections of HAp and
(002),(101),(102),(110),(112) and (201) reflections of wurzite phase of ZnO. The sharp
and intense peaks showed the high crystallinity of Hydroxyapatite-Zinc Oxide
nanocomposite. The crystallite size was calculated using Scherrer formula and the
average crystallite size was found to be 17nm.The XRD results in the present project are
in good agreement with reported results [7].
3.4.2 X-ray Analysis of Hydroxyapatite-Zinc Oxide nanocomposite by

Williamson-Hall Method
Fig 3.4W-H plot for Hydroxyapatite-Zinc Oxide nanocomposite
W-H plots is used to estimate the crystallite size and lattice strain of the samples
using following formalism.
k
   D     4    tan 
D cos 
Where <ε> is the rms value of the micro strain in the sample which is assumed to be
same in all crystallographic directions,  D is the particle size broadening,  is strain
broadening, D is the crystallite size, K is the dimensionless shape factor(0.9),λ is the x
ray wavelength for Cu Kα radiation (1.5406A◦) and  the Bragg angle in degree.
k
 cos       4sin  , theseequations are called W-H equations.
D
A plot is drawn with 4sin  along the X axis and  cos  along the Y axis for as
prepared HAp/ZnO nanocomposite is shown in the figure 3.4.From the linear fit to the
data crystallite size can be estimated from the Y intercept and the lattice strain of the
sample can be obtained from the slope of the fit. The above equation represents the
UDM, where the strain was assumed to be uniform in all crystallographic directions, thus
considering isotropic nature of the crystal, where the material properties are independent
of direction along which they are measured [8].
In the present study, the best fit plot is found to be a straight line with positive
slope indicating tensile strain. The particle size obtained from W-H analysis was 21nm.
The micro strain estimated from W-H plot is 0.00131. In the case of samples with
crystallite size less than 20 nm the major cause of line broadening is the small size and
the contribution from the lattice strain can be neglected.
3.4.3 FT-IR Analysis
FTIR spectra were recorded in solid phase using ATR technique in the wave
number region 350-4000cm-1 forHydroxyapatite nanoparticles, Zinc Oxide nanoparticles
and Hydroxyapatite-Zinc Oxide nanocomposite are shown in figure below.
Fig 3.5 FTIR spectrum of Hydroxyapatite nanoparticles in the range 400-4000cm-1

Fig 3.6 FTIR spectrum of Zinc Oxide nanoparticle in the range 350-700cm-1
Fig 3.7 FTIR spectrum of Hydroxyapatite-Zinc Oxide nanocomposite in the range

350-2000cm-1
The FTIR spectrum of HAp-ZnO nanocomposite in the range 350cm-1-4000cm-1

is shown in figure 3.7. For comparing the peaks with the standard peaks of phase pure
HAp and ZnO , the FTIR spectra of HApand ZnO are presented as Fig 3.5, Fig 3.6
respectively. The FTIR spectra supports the formation of Hydroxyapatite-Zinc Oxide
nanocomposite.The absorption peak around570cm-1 confirms the asymmetric bending
vibration PO4 functional group [9].The absorption peak around around 874 cm-1indicate
the out of plane bending mode of functional group of CO3.The peaks that observed
around 415-480 cm-1correspond to the stretching vibration of ZnO [10,11]. The FTIR
analysis confirms the presence of HAp and ZnO in the sample.
3.4.4 Analysis of UV-visible spectra
The optical absorption of Hydroxyapatite-Zinc Oxide nanocomposite was

recorded in the wavelength range from 200-800 nm and the spectrum was shown in
figure below.
Fig3.8 UV-visible absorption spectrum of Hydroxyapatite-Zinc Oxide

nanocomposite
The absorption spectrum of HAp –ZnOnanocomposite is shown in fig. 3.8. The

UV- visible spectrumof HAp-ZnO is recorded in the range 200 – 800nm and observed
that sample shows absorption in the UV region and decreases towards the visible region.
It exhibits a strong absorption peak at 423nm.It confirms the suitability of the material to
be used as potential candidate for UV filters which screen higher energies of the
ultraviolet spectrum from 10 nm to 120 nm which cause biological damage and it also
find application as microwave filters. The properties of poor transmittance in the UV
region but high transmittance in the Vis–NIR regions makes nanophase yttria an
excellent material for screening off the hazardous UV portion of the electromagnetic
spectrum . The optical band gap energy is determined by extrapolating the wavelength of
the onset absorption in the UV region using the intercept in the wavelength axis in the
equation, E=hc/ λ where h is the plank‘s constant, c is the velocity of electromagnetic
radiation and λ is the wavelength corresponding to the absorption. The corresponding
band gap (Eg) for the wavelength 423 nm was 3.4 eV. It matches very well with the
reported values [9,11].
The optical band gap energy is related with the absorbance and photon energy by
the following equation,αhv= β(hv-Eg) mwhere β is an energy independent constant, α is
the optical absorption coefficient, h is the plank‘s constant, v is the frequency of the
incident photon, Egis the optical band gap and m is the constant that characterizes the
nature of transition. A graph is plotted with (αhυ)2 against the energy hυ of the incident
photon and the optical band gap energy obtained from the intercept of the linear region
with the energy axis at (αhυ)2 =0) is found to be 3.4 eV, which is in good agreement the
reported value [11].
Fig 3.9 Tauc’s plot

3.4.5 Photoluminescence (PL) Analysis
Fig 3.10 PL spectrum of Hydroxyapatite-Zinc Oxide nanocomposite
When a material is irradiated with electromagnetic radiation the molecules absorb

it at a definite wavelength and get excited from the ground state to the excited state. The
excess energy is dissipated by either photoluminescence process or by non-radiative
process in the form of heat to the lattice. When photons are absorbed, and dissipation of
excess energy takes place by emission of light then it is called photoluminescence.
Photoluminescence originates from the recombination of surface states. the strong PL
implies that the surface tates remain very shallow as it is reported that quantum yields
of band edge will decrease exponentially with increasing depth of surface state energy
levels. Fig 3.10 shows the photoluminous spectrum of HA –ZnOwhich was obtained by
excitation wavelength of350nm. The spectrum exhibits emission peaks at 405 nm.
Sintering of HAp-ZnO
The HAp-ZnO nanocomposite powder is uniaxially compacted into pellets in a 12

mm diameter steel die at20 MPa using a hydraulic press.The sintering of the disc shaped
pellets are carried out in a high temperature microwave furnace.The pellet is placed in the
microwave chamber in a silicon carbide susceptor and a heating rate of 40 oCmin-1 is used
for sintering the sample. Silicon carbide is a good microwave absorber which readily
absorbs microwaves and gets heated up which in turn heats the sample as in the
conventional sintering. The result is amazing that the pellet achieved a density of 93 % of
the theoretical density at 1250oC for a soaking duration of just 30 minutes without the
application of pressure or sintering additives.
3.4.6 FE-SEM Analysis
SEM was used to study, compare and analyze the effect of sintering additives on
microstructure and mechanical properties of hydroxyapatite and hydroxyapatite-zinc
oxide nanocomposite. In all micrographs, the grain boundaries are clearly visible confirming
the crystallinity of the nano composite. The micrographs also showed no secondary phase or
precipitate formation at the grain boundaries, which also correlates well with the XRD
results, where no secondary phases were recorded in the diffraction patterns. The grain size
was determined by linear intercept method.
Fig3.11 FE-SEM micrograph of Hydroxyapatite

Fig 3.12Grain size distribution in Hydroxyapatite
Figure 3.11 shows the FE-SEM micrographs of HAp.The grains are clearly
distinct and confined with clear grain boundaries. From the figure it is clear that the pellet
is well sintered with minimum porosity. The image analysis using imageJ softwares
shows that the grainsare in the size range 0.1-0.9µm. The grain size distribution is given
in figure 3.12. The average grain size of the entire distribution is 0.33μm.
Fig 3.13 FE-SEM micrograph of Hydroxyapatite-Zinc oxide nanocomposite
Fig 3.14 Grain size distribution in Hydroxyapatite-Zinc oxide nanocomposite
Figure 3.12 shows the FE-SEM micrographs of HAp-ZnO nanocomposite. From

the figure3.12 it is evident that the pellet of HAp-ZnO nanocomposite is well sintered
with minimum number of porous regions. The grains are clearly distinct and confined
with clear grain boundaries.The grain size distribution curve shown in figure 3.14
indicates that the maximum number of grains fall with in the size range 0.1 to 1.8μm for
HAp-ZnO nanocomposite and the average grain size of the entire distribution is 0.43μm.
Conclusions
 The detailed analysis of XRD pattern reveals that HAp and ZnO powders
synthesized by the single step auto-igniting combustion technique are phase
pure.It confirms the efficacy of modified combustion synthesis to prepare phase
pure nano particles in an economic way without using complex experimental set
up.
 The XRD analysis of HAp-ZnO indicates the presence of both HAp and ZnO
phases and the average crystallite size of the HAp-ZnO composite is ~20nm.
 FTIR spectroscopic data also supports the XRD result that the sample is
composed of HAp and ZnO phases and no major impurity peaks are observed in
the spectrum.
 UV-Visible spectrum reveals that the sample absorbs electromagnetic

radiationsbelow 420nm and can be used as an UV filter. The optical band gap
estimated using Tauc‘s plot was 3.3eV.
 The HAP-ZnO composite pellets were sintered to 93 % of the theoretical density

at 1250oC for a soaking duration of just 30 minutes in a microwave furnace
without the application of pressure or sintering additives. This sintering
temperature is found to be lower than the conventional sintering methods and the
reduction in sintering temperature and soaking duration is the reason behind the
reduced grain size observed in the sintered sample.
 The SEM analysis reveals that the samples are well sintered with minimum
porosity and the average grain size of the distribution is 0.43μm. This attributes to
the phase purity of the as prepared powder and the efficacy of microwave
sintering. The samples with reduced grain size may show enhanced hardness and
mechanical properties.
 The results clearly indicate that the HAp-ZnOultra fine nanophase powder
synthesized using single step combustion method followed by microwavesintering
can be used very effectively for the fabrication of bone tissue scaffolds with
improved properties.
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SYNTHESIS AND CHARACTERIZATION OF

HYDOXYAPATITE -ZINC OXIDE

Project report submitted in partial fulfilment of the requirement for the

Reg. No. 1118101

MAR IVANIOS COLLEGE (AUTONOMOUS)

Thiruvanathapuram, Kerala 695015

Project report submitted in partial fulfilment of the requirement for the

Dr. MATHEW. C.T

Mar Ivanios College, Trivandrum

MAR IVANIOS COLLEGE (AUTONOMOUS)

Thiruvanathapuram, Kerala 695015

This is to certify that the project entitled “SYNTHESIS AND

Dr. Jijimon K Thomas

Head of the Department

This is to certify that the project entitled “SYNTHESIS AND

Thiruvanathapuram PG and Research Department of Physics

Date: Mar Ivanios College, Trivandrum

I, Anju Abraham Phereby declare that the project entitled “SYNTHESIS

I would like to extent my deep sense of grateful to Dr. Jijimon K Thomas,

I also extent my sincere thanks to Dr.Mathew.C.T, Assistant Professor,

I express my deep sense of gratitude to Mrs.Swapna.Y.V, ResearchScholar,

Hope I like to record the encouragement, support and corporation given by my

In this project work entitled ―Synthesis and Characterization of

The first chapter includes an introduction towards bioceramic materials, their

A set of references is given at the end of each chapter. Diagrams, photographs,

Chapter 1 Bioceramics Page no

1.2 Properties of biomaterials 3

1.4 Types of bioceramics-tissue attachment 15

1.5 Composites and coatings 19

2.2 Characterization techniques 35

2.2.3.1 Infrared spectroscopy 40

2.2.4 Photoluminous characterization 41

Chapter 3. Synthesis and characterization of

3.4 result and discussion

Figure Figure name Page

Table no Table name Page

Bioceramics are produced in a variety of phases serve many different

1.1.1 Fields of knowledge to develop biomaterials

Table 1.1. Applications of biomaterials

1.2 Properties of biomaterials

deformation/low force characteristic known as the toe region.

Fig.1.2 Stress-strain curve of biological soft tissue material

Fig.1.3 Strain rate dependence

As such, predetermined and tightly controlled strain or loading rates must be

Material Thermal Conductivity

(b)Coefficient of thermal expansion is defined as the fractional increase in

Material Coefficient thermal expansion

Table.1.3Coefficient of thermal expansion of material

DL/L0/DT 0c-1 Where DL is the change in length; Lo is the original length; DT

When comparing silicate and phosphate cements, for example, silicate

(ii) Leaching of constituents

Many materials, when placed in an aqueous environment, absorb water by a

Fig 1.5 Corrosion process

Chromium has a negative value of electrolytic potential and is at the reactive

Table.1.4 Properties of bioceramic materials

Applications include: Replacement for hips, knees, teeth, tendons and

ii. Zirconia (ZrO2): It was firstly recognized by Martin HenrichKlaprothin

1.3.2 Bioactive material

A bioactive material is one that elicits a specific biological response at the

Bioactive glasses were first developed by Hench (1972), who synthesized

1.3.3 Biodegradable materials

i. Calcium phosphate ceramics (Ca P)

Calcium phosphate-based materials are using in biomedical field for 20 years.