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Chapter

10
Nano and Biomaterials
Intended Learning Outcomes

After studying this chapter, you should be able to do the following:

1. Determine the various type of biomaterials, its properties and applications

2. Determine the materials to be used as a nanomaterial
3. Cite the other application for nanomaterials
4. Differentiate the method used in producing nanomaterial

This chapter is divided into two topics, the biomaterial and nanomaterials. The first part of this
chapter will discuss all about the biomaterials, the materials to be used in biomedical application, their
properties that make use as biomaterial and its applications. The second part is all about the
nanomaterials. The different types of nanomaterials will be discussed, its properties and application.
The synthesis of the material also included in the last part of the chapter.

Biomaterials

Biomaterials is a material that is intended to interface with the biological system to treat,
evaluate, treat, enhance and replace any organ, tissue or function of the body. They are implanted to
the human body as a replacement of damaged or diseased body parts. These materials should not
produce toxic substances and should be compatible with the body tissues. The materials such as
metals, polymers, ceramics, composites and semiconductors can be used as a biomaterial.

Metallic Biomaterials

Metals are widely used as a material for biomedical implants. They are many devices and
surgical tool that are made of metal. Some of the example of the applications of metal as a biomaterial
can be shown in shown in Figure 5.1. For instance, metals can be used for the reconstruction of the
bone damage such as artificial hip, shoulder, knee and elbow joints. Metals can also be used for
fracture fixation such as plates, screws, pins, nails and rod. It can also be used as an oral and
maxillofacial reconstructions such as dental implants and miniplates. It can also use for cardiovascular
intervention such as stents, pacemaker and heart valves. Metals that are used as a biomaterial should
exhibit the following properties:
• Metals should have a high resistance to corrosion
• Metals should be compatible to the body tissue
• Metals should have high resistance to wear.
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• Metals should have outstanding mechanical properties.

Figure 1. Example of the application of metals as a biomaterials.

Most metallic material that are used as a biomaterial have a stable surface oxide layer that
improves their resistance to corrosion. The materials should satisfy the needed mechanical properties
for their application. For example, when a metal is utilized to augment a bone, the modulus of elasticity
of the metal should be preferably equivalent to that of the bone. It can cause the loss of bone quality if
the modulus of elasticity of the metal is greater than that of the bone. The bone will be remodel to adjust
to the lower load.
Table 1.0 shows the list of metallic biomaterials, their properties and applications

Table 1.0
Mettalic Biomaterials

Metals Properties Applications

Titanium and its alloys • Light weight • pacemaker case
• Pure Ti (cp-Ti) • excellent resistance to • housing for ventricular assist
Titanium– corrosion devices
6Aluminum– • enhanced • total joint replacements
4Vanadium biocompatibility maxillofacial
• craniofacial and dental implants

Stainless Steel • low recoil martensitic stainless steel:

• good radial strength • Surgical and dental instruments
• good expandability • surgical and dental instruments
• sufficient flexibility (pliers, forceps, curettes,
for Austenitic Stainless Steel scalpels, dental burs, explorer
• high temperature and root elevators
strength ferritic stainless steel:
• excellent cryogenic • medical guide pins
properties, • handles for instruments
• formability austenitic stainless steel
• high oxidation resistance • medical implant and
devices

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• Austenitic stainless
steels possess excellent
cryogenic properties,
high-temperature
strength, oxidation
resistance, and
formability.
Cobalt–chromium • Possess superior • Used for dental, orthopedic, and
alloys mechanical properties cardiovascular implants and
1. ASTM F75 (Co– such as high corrosion devices
28Cr–6Mo casting resistance, high wear
alloy) resistance and high
2. ASTM F799 (Co– fatigue resistance.
28Cr–6Mo • Well demonstrated the
thermodynamically biocompatibility and
processed alloy) blood compatibility of
3. ASTM F90 (Co– these alloys
20Cr–15W–10Ni • The yield and tensile
wrought alloy) strength of ASTM F799
4. ASTM F562 (Co– alloys are two times as
35Ni–20Cr–10Mo high as those for cast
wrought alloy) ASTM F75 alloys
• excellent strength, high
ductility, and corrosion
resistance,
• ASTM F562 has the
highest tensile strength
among the metals that
are used in biomedical
application
Nitinol (Ni–Ti) • At low temperature it is • Orthodontic wires
plastically deformed but • blood clot filters
if exposed at high • self-expanding vascular stents
temperature it returns • medical staples
back to its original pre-
deformed shape
Tantalum • biocompatibility • dental implants
• excellent resistance to • cerebral covering for cranial
corrosion defects
• coronary stents
• vascular clips
• fracture fixation
Magnesium and its light weight and biodegradability orthopedic applications
Alloys making biodegradable coronary stents

Polymers
The most used polymer for total joint prostheses is the ultra-high molecular weight
polyethylene. It is chemically identical to the material used for plastic bags. Same with the bone

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cement which is used with bone surgery and Plexiglass which is used for windows panes. They
used polymethylmethacrylate (PMMA). The polymer to be used as an implant should meet the
strict safety standards that is required by the government and other agencies and should be
contaminant free.
The polymer-based implants are quite inexpensive to manufacture and made reactive so
that different chemical molecules can attached to the surface of the implants to make more
compatible with the surrounding environment in the body. Some of the polymer used for implant
is biodegradable in the body. This is one of the advantages of using the polymers as biomaterial.
But the polymer is not stiff as metals or ceramics, so this material cannot be used or not advisable
to use if the implant is requiring to carry large loads.

In table 2.0 shows the list of common polymeric biomaterials, properties and its application

Table 2.0
Common Polymeric Materials

Polymeric Biomaterials Properties Application

Polyethylene • ductile • used extensively in
• ultrahigh molecular • superior wear properties orthopedic total joint
weight polyethylene compared to other implants such as bearing
(UHMWPE) polymers material in total hip,
• tough shoulder and knee
prostheses
Polymethylmethacrylate (PMMA) • Lightweight • it is used for bone
• Easier to process, less cement to stabilize total
expensive and easy to joint prostheses
handle than • It is also used to
polycarbonate eliminate scars and
• It has a great mechanical wrinkles on the skin
properties and low tissue permanently
toxicity • It is also used for dental
• slow degradation implant (substitute for
missing roots)
•
Polylactic Acid (PLA) and • biodegradable • it is widely used for
polyglycolic acid (PGA) implants in medical
applications
• it is widely used in the
field of orthopedics such
as fixation devices for
bone and soft tissue
• It is also used for dental
and controlled drug-
delivery applications
Polycaprolactone (PCL) • biodegradable • Mostly used in tissue
engineering application
• Also used for drug
delivery devices
Polyanhydrides • possess high hydrolytic • used primarily for drug
instability delivery

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• it is highly reactive
materials which degrade
by surface tension
• by surface erosion
Polyurethanes • good mechanical • used as lead for
properties and blood pacemakers, heart
biocompatibility valve, catheters and
ligament reconstruction
Silicones • have good blood • used for catheters
biocompatibility • used for prostheses for
the replacement of
carpal bones, toes and
finger joints
• widely used in breast
reconstruction and
augmentations
• used for jaw and chin
augmentation and nasal
supports
Hydrogels • provide comfort to the • used extensively for soft
user and have better contact lenses
oxygen permeability • used for drug delivery
compare to the hard • used for tissue
lenses made from engineering
PMMA • wound healing

Nanopolymers • particles are small • Drug delivery vehicles

• they can deliver their especially in the area of
payload of drug in a very cancer therapy
efficient manner leading
to a high efficacy
Source: Agrawal,2014

Ceramics

Bio-ceramics refers to ceramics that are used in medical applications. Different ceramics
and glass materials are being used for this application from bone implants to biomedical pumps.
Ceramics are used in structural functions as tissue and joints replacement and also used as a
coating to improve the biocompatibility of the metal implants. These ceramics also used to provide
temporary structures for tissue regenerations.
The main advantage of the ceramics are their mechanical integrity and their chemical and
physical compatibility in the presence of host or biological environments. Bioceramics used for
implant should have the following properties:
• Non- toxic
• Non-carcinogenic
• Do not induce allergic reactions and inflammatory response
• Induce tissue regeneration (if needed)
• Induce tissue integration (If needed)

Some of the commonly used bioceramics today in medicine and dentistry are shown I
table 3.0.
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Table 3.0
List of Commonly Used Bioceramics

Bioceramics Properties Application

Alumina (Al2O3) • inertness, • commonly used in
biocompatibility and orthopedics and
excellent wear dentistry
resistance • used in hip and knees
prostheses
• used for fabrication of
crowns
Carbon • excellent strength • commonly used for
• excellent durability implant fabrication amd
• excellent wear surface coatings
resistance and thrombo • used for fabrication of
resistance small joints

Calcium phosphates (CaP) • Can be found in human • fabrication of medical

body devices
• can be synthetically
produced in laboratory
• very brittle but is strong
• Hydroxyapatite (HA) in compression,
• its solubility is also
dependent on the
biological environment,
such as the pH and the
ionic concentration of
the solutions, as well as
the protonation state of
the phosphate ions
when immersed in a
solution
• slows the degradation of
the structure
• Tricalcium phosphate • used for healing tissue
(TCP) and acts as a template
for the cell to use and
grow
Calcium sulfate • complete and rapid • bone regeneration
(CaSO4·H2O) resorption, and
(Plaster of Paris) biocompatibility.
Bioactive glass • These glasses bond to • used in dentistry
the tissue and are
biocompatible
Nanoceramics • greater surface area • used for imaging and
• greater porosity diagnoses
• increased surface • implantology
reactivity • drug delivery
• increased surfaced • anti-cancer therapy
roughness • gene therapy
• gene therapy
Source: Agrawal,2014

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Natural biomaterials

Like synthetic materials, natural materials can also be used as biomaterials. This material
should satisfy the following requirements:
• non-toxic
• non-allergic
• non-inflammatory
• having excellent mechanical properties
• capable of inducing cell attachment and differentiation (if needed)
• low cost
Advantageous characteristics of natural material include facilitating cell attachment,
enhance the mechanical properties of synthetic materials and ability to bind and deliver
macromolecules. These characteristics are the reasons why natural materials are widely used in
several biomedical applications. devices.
In table 4.0 shows some of the commonly used natural biomaterials for the fabrication of
medical devices,

Table 4.0
List of Commonly Used Natural Biomaterials

Natural Biomaterials Properties Application

Collagen • has unique structural • used for tissue
properties regeneration and wound
• can be resorbed into the healing
body • has a potential for
• non-toxic stabilizing encapsulated
• produces minimal and transplanted cells
immune response, even
between different
species
Elastin • it has an ability to stretch • used vascular stents
and relax • repairing skin, bladder,
• high stability with a half - fallopian tubes, intestine,
life of 70 years stomach, colon, lung
• and heart
• breast implants
Silk • biocompatibility, slow • used for fabrication of
degradability, and medical and non-
excellent mechanical medical products
properties • medical sutures
Chitosan • produces minimal forein • repair focal cartilage
body reaction lesions resulting from
trauma
• wound dressing
• tissue engineering

Cellulose • insoluble in water • used in pharmaceutical

• its properties are formulations for various
dependent on its length, purposes
• used as tablet binders

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chain and other • used as artificial skin in

properties burn therapy and ulcers
• tasteless
• odorless
• hydrophilic
• possess exceptional
strength
Alginate • non-toxic • Used in dental prosthetic
• non-inflammatory applications
• has an ability to absorb • Used in bandages
water • wound dressings
• biodegradable applications
• controllable porosity
• good mucoadhesive
• easily processed in
water
Hyaluronan • it has an ability to swell in • tissue regeneration
water • embryonic development
• highly viscoelastic ability • extracellular matrix
• highly hydrophilic hemostasis
• wound healing
• orthopedic
• cardiovascular
• dermatology

Chondroitin sulfate • it has ability to bind and • polymer for tissue

modulate growth factors engineering applications
and cytokines, • used as a surgical aid
• inhibition of proteases,
• involvement in cell
adhesion,
• migration,
• proliferation, and
differentiation,
• non-immunogenic,
• degrade to non-toxic
oligosaccharides
Coral • biocompatible • used as as filling for
• osteoconductive defects
• mechanical properties • onlay graft in
are comparable to orthopedics and
cancellous bone traumatology
• craniofacial
• dental
• neurosurgery
• spinal fusion

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Example of Biomaterials

Intraocular Lenses

It is made of PMM, silicone elastomer and other materials. After lens is inserted, good
vision is restored immediately.

Figure 2. Intraocular Lenses

Source: Khandelwal, 2013
Heart Valve

It is made from carbons, elastomers, metals, fabrics and natural valves. It is attached by
polyester mesh. The tissue growth facilitated by Polar Oxygen-Containing Groups. After the valve
implanted, cardiac function is restored to near normal. The most widely used is the bileaflet tilting
disk heart valve.

Figure 3. Heart Valve

Source: Khandelwal, 2013

Dental Implants
Titanium are the common materials used as a replacement for the root portion of the
missing natural tooth. It is placed in the bone of the lower and upper jaw.
Most dental implants are: pure titanium screw-shaped cylinders that act as roots for
crowns and bridges, or as supports for dentures. It should be bio-inert, there is no reaction in
tissue and no rejection or allergic reactions.

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Figure 4. Dental Implants

Source: Khandelwal, 2013

Vascular Grafts

Vascular graft should be good structure retention, flexible, high fatigue resistance,
adequate burst strength , good handling properties and biostable. It is designed with open porous
structure. It is made of Poly (ethylene terephthalate)—PET or Dacron

Figure 5. Vascular Grafts

Source: Khandelwal, 2013

Hip-Replacements
It is made of corrosion resistant high-strength metal alloys or very high molecular weight
polymers.

Figure 6. Hip Replacements

Source: Khandelwal, 2013

Knee Implants
This material replaces the joint/ ligaments and allowing the movement of the knee and
mobility of the leg. Common materials used for knee implants are metal and plastic.

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Figure 7. Knee Implants

https://medlineplus.gov/ency/article/002974.htm

Kidney Implants

Artificial kidney is a device works like a normal kidney. This unit is divided into several
parts, where it enters the blood is filtered after absorbing nutrients and discarding waste
susbtancies.

Figure 8. Artificial Kidney

Source: Singularityhub.com
Artificial Hearts

It is a mechanical device used in order to bridge the time for heart transplantation or to
replace permanently the heart if transplantation is impossible. The heart consists is formed using
synthetic material and has power supplies.

Figure 9. Artificial heart

Source: https://science.howstuffworks.com/innovation/everyday-innovations/artificial-heart.htm

PACEMAKER
It is a device which uses electrical impulses contacting the heart muscles. It consists of a
pager-sized housing device that contains a battery and the electronic circuitry that runs the device,
along with one or two long thin electrical wires that travel from the pacemaker housing device to
the heart, its implanted below the skin in the shoulder area.

Figure 10. Pacemaker

Source: https://www.mayoclinic.org/tests-procedures/pacemaker/about/pac-20384689

CONTACT LENS

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It is a corrective lens placed on the cornea of the eye. Designed to improve vision because
some people have a mismatch between the refractive power of the eye and the length of the eye
leading to a refraction error. A contact lens neutralizes this mismatch and allows for correct
focusing of light to the retina. It is made of pliable hydrophilic plastics called hydrogels that absorb
significant amount of water to keep the lenses soft and supple.

Figure 11. Contact lense

Source: Healthline.com
Artificial Tissue
It should be biodegradable. It is the polymer result of condensation of lactic acid and
glycolyic acid.

Figure 12. Artificial Tissue

Source: Hussain, 2014
Bone Cement
Used to anchor artificial joints such as hip joints, shoulder, knee and elbow joints.

Figure 13. Total Hip Replacement

Source: Almurshidimed.com

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Nanomaterial
Nanomaterials defined as a material where the sized of the individual blocks are less than
100nm. Nanomaterial has the properties that depend on inherently on small grain size and it is
quite expensive.

Nanomaterials may be zero-dimensional (e.g., nanoparticles), one-dimensional (e.g.,

nanorods or nanotubes), or two-dimensional (usually realized as thin films or stacks of thin films).

Figure 1. Examples of Nanomaterials

Source: Alagarasi, 2011

Types of NanoMaterials

1. Carbon Based Materials

Carbon based nanomaterials are composed mostly of carbon. It is in the form of hollow
spheres, tubes or ellipsoids. Fullerenes refers to spherical and ellipsoidal carbon nanomaterial
while nanotubes refer to the cylindrical ones. It has many potentials uses such as improved films
and coatings and a greater potential in electronic application. This materials are stronger and
lighter.

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Figure 2. Examples of Carbon-based Material

Source: George, 2013

2. Metal Based Materials

The example of these materials are quantum dots, nanogold, metal oxide and nanosilver.
A quantum dot is a closely packed semiconductor crystal comprised of hundreds or thousands of
atoms, and whose size is on the order of a few nanometers to a few hundred nanometers.
Changing the size of quantum dots changes their optical properties.

Figure 3. Metal Based Nanomaterials

Source: Richards, 2017

3. Dendrimers
Dendrimers are nanosized polymers built from branched units. It has a numerous chain
ends, and can be tailored to perform specific chemical functions. This materials can be useful for
drug delivery.

4. Composites
Composites is a combination of nanoparticles with the other nanoparticles or a
combination of nanoparticle with lager materials. Sample of these materials are the nanoclays
that are added to products to enhance mechanical, thermal, barrier and flame-retardant
properties. They are three basic types of Nanocomposite:

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• Zero-dimensional particles in a matrix, ideally the individual particles do not touch

each other (Fig. 4a)
• One-dimensional nanocomposites consisting of nanotubes or nanorods
distributed in a matrix (Fig 4b)
• Two-dimensional nanocomposites built from stacks of thin films made of two or
more different materials
Figure 4. shows the three basic types of nanocomposites (a) Zero-dimensional particles
in a matrix, (b) One-dimensional nanocomposites and (c) Two-dimensional nanocomposites

Figure 4. Basic Types of Nanocomposites

Source: Vollath, 2013

Properties of Nanomaterials

Optical properties
Optical property of the nanomaterial is one of the most fascinating and useful aspects of
nanomaterials. Nanomaterials can be used for optical detector, sensor, laser, imaging, phosphor,
display, photocatalysis, solar cell, photoelctrochemistry and biomedicine. The optical properties
of nanomaterials depend on parameters such as feature size, surface characteristics, shapes
and other variables including doping and interaction with the surrounding environment or other
nanostructures.

Figure 5. Fluorescence emission of (CdSe) ZnS Quantum dots of various sizes and absorption
spectra of various sizes and shapes of gold nanoparticles
Source: Chem. Soc. Rev., 2006, 35, 209–217
Electrical properties

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Electrical Properties of Nanoparticles” discuss about fundamentals of electrical

conductivity in nanotubes and nanorods, carbon nanotubes, photoconductivity of nanorods,
electrical conductivity of nanocomposites. One interesting method which can be used to
demonstrate the steps in conductance is the mechanical thinning of a nanowire and measurement
of the electrical current at a constant applied voltage. The important point here is that, with
decreasing diameter of the wire, the number of electron wave modes contributing to the electrical
conductivity is becoming increasingly smaller by well-defined quantized steps.

Figure 6. Electrical Behavior of nanotubes

Source: P. G. Collins and Ph. Avouris, Scientific American, 62, 2000, 283

Mechanical properties
“Mechanical Properties of Nanoparticles” deals with bulk metallic and ceramic materials,
influence of porosity, influence of grain size, superplasticity, filled polymer composites, particle-
filled polymers, polymer-based nanocomposites filled with platelets, carbon nanotube-based
composites. However, two materials, neither of which is produced by pressing and sintering, have
attracted much greater interest as they will undoubtedly achieve industrial importance. These
materials are polymers which contain nanoparticles or nanotubes to improve their mechanical
behaviors, and severely plastic-deformed metals, which exhibit astonishing properties. However,
because of their larger grain size, the latter are generally not accepted as nanomaterials.

Magnetic properties
Bulk gold and Pt are non-magnetic, but at the nano size they are magnetic. Surface atoms
are not only different to bulk atoms, but they can also be modified by interaction with other
chemical species, that is, by capping the nanoparticles. This phenomenon opens the possibility
to modify the physical properties of the nanoparticles by capping them with appropriate molecules.
Actually, it should be possible that non-ferromagnetic bulk materials exhibit ferromagnetic-like
behavior when prepared in nano range.

Selected Application of nanomaterials

Fuel cells

Carbon nanotubes - Microbial fuel cell

Microbial fuel cell is a device in which bacteria consume water-soluble waste such as
sugar, starch and alcohols and produces electricity plus clean water. This technology will make it
possible to generate electricity while treating domestic or industrial wastewater.

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Figure 7. Microbial Fuel Cell

Source: Alagarasi, 2011

Catalysis
Higher surface area available with the nanomaterial counterparts, nano-catalysts tend to
have exceptional surface activity. For example, reaction rate at nano-aluminum can go so high,
that it is utilized as a solid-fuel in rocket propulsion, whereas the bulk aluminum is widely used in
utensils. Nano-aluminum becomes highly reactive and supplies the required thrust to send off pay
loads in space. Similarly, catalysts assisting or retarding the reaction rates are dependent on the
surface activity, and can very well be utilized in manipulating the rate-controlling step.

Phosphors for High-Definition TV

The resolution of a television, or a monitor, depends greatly on the size of the pixel. These
pixels are essentially made of materials called "phosphors," which glow when struck by a stream
of electrons inside the cathode ray tube (CRT). The resolution improves with a reduction in the
size of the pixel, or the phosphors. Nanocrystalline zinc selenide, zinc sulfide, cadmium sulfide,
and lead telluride synthesized by the sol-gel techniques are candidates for improving the
resolution of monitors.

Next-Generation Computer Chips

Nanomaterials help the industry break these barriers down by providing the manufacturers
with nanocrystalline starting materials, ultra-high purity materials, materials with better thermal
conductivity, and longer-lasting, durable interconnections (connections between various
components in the microprocessors) The example application is the nanowires for junctionless
transistors.

Elimination of Pollutants
Nanomaterials possess extremely large grain boundaries relative to their grain size.
Hence, they are very active in terms of their chemical, physical, and mechanical properties. Due
to their enhanced chemical activity, nanomaterials can be used as catalysts to react with such
noxious and toxic gases as carbon monoxide and nitrogen oxide in automobile catalytic
converters and power generation equipment to prevent environmental pollution arising from
burning gasoline and coal.

Sun-screen lotion

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Sun-screen lotions containing nano-TiO2 provide enhanced sun protection factor (SPF)
while eliminating stickiness. The added advantage of nano skin blocks (ZnO and TiO2) arises as
they protect the skin by sitting onto it rather than penetrating into the skin. Thus they block UV
radiation effectively for prolonged duration. Additionally, they are transparent, thus retain natural
skin color while working better than conventional skin-lotions.

Sensors
Sensors rely on the highly active surface to initiate a response with minute change in the
concentration of the species to be detected. Engineered monolayers (few Angstroms thick) on
the sensor surface are exposed to the environment and the peculiar functionality (such as change
in potential as the CO/anthrax level is detected) is utilized in sensing

Disadvantages of Nanomaterials
• Instability of the particles
• Fine metal particles act as strong explosives owing to their high surface area coming in
direct contact with oxygen
• Impurity
• Biologically harmful
• Difficulty in synthesis, isolation and application
• Recycling and disposal

Synthesis and Processing of Nanomaterials

Nanomaterials deal with very fine structures: a nanometer is a billionth of a meter. This
indeed allows us to think in both the ‘bottom up’ or the ‘top down’ approaches (Fig. 8) to synthesize
nanomaterials, i.e. either to assemble atoms together or to dis-assemble (break, or dissociate)
bulk solids into finer pieces until they are constituted of only a few atoms. This domain is a pure
example of interdisciplinary work encompassing physics, chemistry, and engineering up to
medicine.

Figure 8. Shematic illustration of the Preparative Methods of Nanoparticles

Source: Alagarasi,2011

Methods for creating nanostructures

There are many different ways of creating nanostructures: of course, macromolecules or
nanoparticles or buckyballs or nanotubes and so on can be synthesized artificially for certain
specific materials. They can also be arranged by methods based on equilibrium or near-
equilibrium thermodynamics such as methods of self-organization and self-assembly (sometimes
also called bio-mimetic processes). Using these methods, synthesized materials can be arranged
into useful shapes so that finally the material can be applied to a certain application.

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Mechanical grinding
Mechanical attrition is a typical example of ‘top down’ method of synthesis of
nanomaterials, where the material is prepared not by cluster assembly but by the structural
decomposition of coarser-grained structures as the result of severe plastic deformation. This has
become a popular method to make nanocrystalline materials because of its simplicity, the
relatively inexpensive equipment needed, and the applicability to essentially the synthesis of all
classes of materials.

Figure 9. Schematic Diagram of the principle of Mechanical Milling

Source: Alagarasi, 2011

Mechanical milling is typically achieved using high energy shaker, planetary ball, or
tumbler mills. The energy transferred to the powder from refractory or steel balls depends on the
rotational (vibrational) speed, size and number of the balls, ratio of the ball to powder mass, the
time of milling and the milling atmosphere. Nanoparticles are produced by the shear action during
grinding.

Wet Chemical Synthesis of Nanomaterials

In principle we can classify the wet chemical synthesis of nanomaterials into two broad
groups: 1. The top down method: where single crystals are etched in an aqueous solution for
producing nanomaterials, For example, the synthesis of porous silicon by electrochemical etching.
2. The bottom up method: consisting of sol-gel method, precipitation etc. where materials
containing the desired precursors are mixed in a controlled fashion to form a colloidal solution.

Sol-gel process
The sol-gel process, involves the evolution of inorganic networks through the formation of
a colloidal suspension (sol) and gelation of the sol to form a network in a continuous liquid phase
(gel). The precursors for synthesizing these colloids consist usually of a metal or metalloid
element surrounded by various reactive ligands.
Sol-gel method of synthesizing nanomaterials is very popular amongst chemists and is
widely employed to prepare oxide materials. The sol-gel process can be characterized by a series
of distinct steps.

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Figure 10. Sol-gel Process of Synthesis Nanomaterials

Source: Alagarasi, 2011
Gas Phase synthesis of nanomaterials
The gas-phase synthesis methods are of increasing interest because they allow elegant
way to control process parameters in order to be able to produce size, shape and chemical
composition controlled nanostructures. In conventional chemical vapour deposition (CVD)
synthesis, gaseous products either are allowed to react homogeneously or heterogeneously
depending on a particular application.

Furnace
The simplest fashion to produce nanoparticles is by heating the desired material in a heat
resistant crucible containing the desired material. This method is appropriate only for materials
that have a high vapour pressure at the heated temperatures that can be as high as 2000°C.

Figure 11. Synthesis of single-phase nanomaterials from a heated crucible

Source: Alagarasi, 2011

Flame assisted ultrasonic spray pyrolysis

In this process, precursors are nebulized and then unwanted components are burnt in a
flame to get the required material, eg. ZrO2 has been obtained by this method from a precursor
of Zr(CH3 CH2 CH2O)4. Flame hydrolysis that is a variant of this process is used for the
manufacture of fused silica.

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Figure 12. Flame assisted ultrasonic spray pyrolysis

Source: Alagarasi, 2011

Gas Condensation Processing (GPC)

In this technique, a metallic or inorganic material, e.g. a suboxide, is vaporised using
thermal evaporation sources such as crucibles, electron beam evaporation devices or sputtering
sources in an atmosphere of 1-50 mbar He (or another inert gas like Ar, Ne, Kr). Cluster form in
the vicinity of the source by homogenous nucleation in the gas phase and grow by coalescence
and incorporation of atoms from the gas phase.

Figure 13. Typical set-up for gas condensation synthesis of nanomaterials

Source: Alagarasi, 2011

Chemical Vapour Condensation (CVC)

The evaporative source used in GPC is replaced by a hot wall reactor in the Chemical
Vapour Condensation or the CVC process. Depending on the processing parameters nucleation
of nanoparticles is observed during chemical vapour deposition (CVC) of thin films and poses a
major problem in obtaining good film qualities.

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Figure 14. Schematic of a Typical CVC reactor

Source: Alagarasi, 2011

Sputtered Plasma Processing

In this method is yet again a variation of the gas-condensation method excepting the fact
that the source material is a sputtering target and this target is sputtered using rare gases and
the constituents are allowed to agglomerate to produce nanomaterial. Both dc (direct current) and
rf (radio-frequency) sputtering has been used to synthesize nanoparticles. This method is
specifically suitable for the preparation of ultrapure and non-agglomerated nanoparticles of metal.

Microwave Plasma Processing

This technique is similar to the previously discussed CVC method but employs plasma
instead of high temperature for decomposition of the metal organic precursors. The method uses
microwave plasma in a 50 mm diameter reaction vessel made of quartz placed in a cavity
connected to a microwave generator. A precursor such as a chloride compound is introduced into
the front end of the reactor. Generally, the microwave cavity is designed as a single mode cavity
using the TE10 mode in a WR975 waveguide with a frequency of 0.915 GHz. T

Particle precipitation aided CVD

In another variation of this process, colloidal clusters of materials are used to prepare
nanoparticles. The CVD reaction conditions are so set that particles form by condensation in the
gas phase and collect onto a substrate, which is kept under a different condition that allows
heterogeneous nucleation. By this method both nanoparticles and particulate films can be
prepared.

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Figure 15. Schematic Representation of (1) Nanoparticle and (2) Particulate film Formation
Source: Alagarasi, 2011

Laser ablation
Laser ablation has been extensively used for the preparation of nanoparticles and
particulate films. In this process a laser beam is used as the primary excitation source of ablation
for generating clusters directly from a solid sample in a wide variety of applications.

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CHAPTER TEST

Directions: Answer the following question comprehensively. Write your answer on the space
provided.

Questions

1. What are the importance of biomaterials?

2. Based on your experience, cite an example where biomaterials are used.

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3. Discuss the different types of nanomaterials.

4. Discuss at least three methods in producing nanomaterials.

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References:

1. Introduction to Biomaterials: Basic Theory With Engineering Applications by C. M. Agrawal, J.

L. Ong, M. R. Appleford and G. Mani, 2014
2. Nanomaterials: An Introduction to Synthesis, Properties, and Applications by Dieter Vollath,
2nd Edition, 2013
3. Mani G. (2016) Chapter 1b Metallic Biomaterials: Cobalt-Chromium Alloys. In: Murphy W.,
Black J., Hastings G. (eds) Handbook of Biomaterial Properties. Springer, New York, NY.
https://doi.org/10.1007/978-1-4939-3305-1_15
4.Alagarasi, A. (2011) “Introduction to Nanomaterials” Available at:
https://maken.wikiwijs.nl/bestanden/427519/Lesson_7_APPENDIX-2_Article2.pdf
5.Justin George, 2013 “Carbon Nano materials” University of Antwerpen 1, available at:
https://www.slideshare.net/JustinGeorge3/carbon-nano-marerials
6. U.S. Environmental Protection Agency. 2017. Classification of Nanomaterials, The Four Main Types
of Intentionally Produced Nanomaterials. AZoNano,
https://www.azonano.com/article.aspx?ArticleID=1872.
7. Khandelwal, Saransh (2013) “Biomaterials and its Application” Availavle at:
https://www.slideshare.net/khsaransh/biomaterial-and-its-applications
8. Hussain, Gulfam (2014) “Biomaterials” Available at:
https://www.slideshare.net/e_gulfam/biomaterials-36179632

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