Nanoscale materials

Nanoscale materials are defined as a set of substances where at least one dimension is less than
approximately 100 nanometers. A nanometer is one millionth of a millimeter - approximately
100,000 times smaller than the diameter of a human hair. Nanomaterials are of interest because at
this scale unique optical, magnetic, electrical, and other properties emerge. These emergent
properties have the potential for great impacts in electronics, medicine, and other fields.

Classification of Nanomaterials

Nanomaterials have extremely small size which having at least one dimension 100 nm or less.
Nanomaterials can be nanoscale in one dimension (eg. surface films), two dimensions (eg. strands
or fibres), or three dimensions (eg. particles). They can exist in single, fused, aggregated or
agglomerated forms with spherical, tubular, and irregular shapes.

Common types of nanomaterials include nanotubes, dendrimers, quantum dots and

fullerenes. Nanomaterials have applications in the field of nano technology, and displays different
physical chemical characteristics from normal chemicals (i.e., silver nano, carbon nanotube,
fullerene, photocatalyst, carbon nano, silica). According to Siegel, Nanostructured materials are
classified as Zero dimensional, one dimensional, two dimensional, three dimensional
nanostructures.

Fig. 1. Classification of Nanomaterials (a) 0D spheres and clusters, (b) 1D nanofibers, wires, and
rods, (c) 2D films, plates, and networks, (d) 3D nanomaterials.
Important of nanomaterials

These materials have created a high interest in recent years by virtue of their unusual mechanical,
electrical, optical and magnetic properties. Some examples are given below:

(i) Nanophase ceramics are of particular interest because they are more ductile at elevated
temperatures as compared to the coarse-grained ceramics.

(ii) Nanostructured semiconductors are known to show various non-linear optical properties
Nanostructured semiconductors are used as window layers in solar cells.

(iii) Nanosized metallic powders have been used for the production of gas tight materials, dense
parts and porous coatings.

(iv) Single nanosized magnetic particles are mono-domains and one expects that also in magnetic
nanophase materials the grains correspond with domains, while boundaries on the contrary to
disordered walls.

(v) Nanostructured metal clusters and colloids of mono- or plurimetallic composition have a
special impact in catalytic applications.

(vi) Nanostructured metal-oxide thin films are receiving a growing attention for the realization of
gas sensors (NOx, CO, CO2, CH4 and aromatic hydrocarbons) with enhanced sensitivity and
selectivity. Nanostructured metal-oxide (MnO2) finds application for rechargeable batteries for
cars or consumer goods.

(vii) Polymer based composites with a high content of inorganic particles leading to a high
dielectric constant are interesting materials for photonic band gap structure.

Nanomaterial - synthesis

Nanomaterial - synthesis and processing 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. 5) 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.

Fig. 2. Schematic illustration of the preparative methods of nanoparticles.

Properties of Nanomaterials

Nanomaterials have the structural features in between of those of atoms and the bulk materials.
While most microstructured materials have similar properties to the corresponding bulk materials,
the properties of materials with nanometer dimensions are significantly different from those of
atoms and bulks materials. This is mainly due to the nanometer size of the materials which render
them:

(i) Large fraction of surface atoms;

(ii) High surface energy;

(iii) Spatial confinement;

(iv) Reduced imperfections, which do not exist in the corresponding bulk materials.
Optical properties

One of the most fascinating and useful aspects of nanomaterials is their optical properties.
Applications based on optical properties of nanomaterials include optical detector, laser, sensor,
imaging, phosphor, display, solar cell, photocatalysis, photoelectrochemistry and biomedicine.

Electrical properties

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.

Mechanical properties

“Mechanical Properties of Nanoparticles” deals with bulk metallic and ceramic materials,
influence of porosity, influence of grain size, super plasticity, filled polymer composites, particle-
filled polymers, polymer-based nanocomposites filled with platelets, carbon nanotube-based
composites.

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.

Disadvantages of Nanomaterials

(i) Instability of the particles - Retaining the active metal nanoparticles is highly challenging, as
the kinetics associated with nanomaterials is rapid.

(ii) Fine metal particles act as strong explosives owing to their high surface area coming in direct
contact with oxygen.

(iii) Impurity - Because nanoparticles are highly reactive, they inherently interact with impurities
as well.
(iv) Biologically harmful - Nanomaterials are usually considered harmful as they become
transparent to the cell-dermis.

(v) Difficulty in synthesis, isolation and application.(vi) Recycling and disposal - There are no
hard-and-fast safe disposal policies evolved for nanomaterials.

STRUCTURE OF GRAPHITE
It is also a crystalline form of carbon.
In graphite each carbon atom is covalently bonded to three
carbon atoms to give trigonal geometry.
Bond angle in graphite is 120oC. Each carbon atom in
graphite is sp2 hybridized.
Three out of four valence electrons of each carbon atom
are used in bond formation with three other carbon atoms
while the fourth electron is free to move in the structure of
graphite. Basic trigonal units unite together to give basic
hexagonal ring. In hexagonal ring C-C bond length is
1.42Ao.
In graphite these rings form flat layers.
These layers are arranged in parallel, one above the other.
These layers are 3.35Ao apart and are held together by
weak van der waals forces only.
These layers can slide over one another. Thus it is very
soft.
Fourth electron of each carbon atom forms delocalized p-
bonds which spread uniformly over all carbon atoms. Due
to this reason graphite conducts electricity parallel to its
plane.
Uses. Solid lubricants Moderator in nuclear
reactorsElectrodes Pencil lead.

Fullerenes
The new form was found to have the structure of a
truncatedicosahedron, and was named Buckminster
fullerene, after the architect Buckminster Fuller who
designed geodesic domes in the 1960s.
In 1990 physicists W. Krätschmer and D.R. Huffman for
the first time produce dissoluble quantities of C60 by
causing an arc between two graphite rods to burn in a
helium atmosphere and extracting the carbon condensate.
Fullerenes are closed hollow cages consisting of carbon
atoms interconnected in pentagonal and hexagonal rings.
Each carbon atom on the cage surface is bonded to three
carbon neighbors therefore is sp2 hybridized.
The most famous fullerene is C60, known also by “
buckyball ".
Other relatively common clusters are C70, C72, C74, C76,
C80, C82 and C84 (plenty of others, higher or lower than
C60, exist too but less abundant in the experimentally
produced mixture fullerene soot).
Fullerenes can be made by vaporizing carbon within a gas
medium(they could form spontaneously in a condensing
carbon vapor).
Buckyballs are relatively cheap; carbon is everywhere!
Even though each carbon atom is only bonded with three
other carbons (they are most comfortable with four bonds)
in a fullerene molecule, dangling a single carbon atom next
to the structure is not strong enough to break the structure
of the fullerene molecule.
In fullerenes, 12 pentagonal rings are necessary and
sufficient to effect the cage closure.
Fullerenes contain carbon atoms arranged as a
combination of 12 pentagonal rings and n hexagonal rings.
The chemical formula is C20+2n.
Fullerene cages are about 7-15 Å in diameter, and are one
carbon atom thick.
Quite stable from chemical and physical points of view
(breaking the balls requires temperatures of about 1000 °C.

Appliations
The fullerenes have synthetic pharmaceutical and
industrial applications.
Degenerative diseases and ordinary aging processes are
caused by intracellular Oxygen free radicals with unpaired
electrons.
C60 fullerenes can react with radicals. Thus halting the
process of aging.
It acts as good MRI contrast agent.
They can also Be used in light emitting diodes in different
electronic equipments and computingdivices.

Carbon nanotubes (CNTs) are allotropes of carbon with

acylindrical nanostructure. Nanotubes have been
constructed with length-to-diameter ratio of up to
132,000,000:1, significantly larger than for any other
material.
These cylindrical carbon molecules have unusual
properties, Which are valuable for nanotechnology,
electronics, optics and other fields of materials science and
technology.
In particular, owing to their extraordinary thermal
conductivity and mechanical and electrical properties,
carbon nanotubes may find applications as additives to
various structural materials.
Nanotubes are members of the fullerene structural family,
which also includes the spherical buckyballs, and the ends
of a nanotube may be capped with a hemisphere of the
buckyball structure.
Their name is derived from their long, hollow structure
with the walls formed by one-atom-thick sheets of carbon,
called graphene.
These sheets are rolled at specific and discrete ("chiral")
angles, and the combination of the rolling angle and radius
decides the nanotube properties; for example, whether the
individual nanotube shell is a metal or semiconductor.
Nanotubes are categorized as single-walled nanotubes
(SWNTs) and multi-walled nanotubes (MWNTs).
Individual nanotubes naturally align themselves
into"ropes" held together by van der Waals forces.
(a) Armchair, (b,c) zig-zag and (d) chiraltube; (a) metallic,
(b) small gapsemiconductor, and (c,d)semiconductor.
Properties and Applications:
The nanotubes are extremely strong and stiff and relatively
ductile. For singlewalled nanotubes tensile strengths range
between 50 and 200 Gpa more than carbon fibres.
This is strongest known material. Elastic modulus values
are ofthe order of one tera pascal with fracture strains
between 5% to 20%. They have very low densities.
Because of these properties carbon nano tube has been
termed as ultimate fibre.
It has been regarded as 100 times stronger than steel at the
same time six times lighter (weight wise).
They find applications in filling material in composite
material. They can act as either conductors or
semiconductors depending on their chirality so they find
their applications in molecular electronics and computers
they are used as ultra sensitive electrochemical sensors.
They are used in batteries and fuel cells. Field emission
results from the tunnelling of electrons from a metal tip in
to vacuum under application of strong electric field.
Small diameter and high aspect ratio(lower loading of
CNTs is needed compare to other conductive additives to
achieve same electrical conductivity.
CNTs are very favorable for field emission.)Even for
moderate voltages a strong electric field develops at free
end of supported CNTs because of their sharpness.
The large surface area and high absorbency of CNTs make
them ideal candidates for use in air gas and water filtration.

Graphene
Graphene is the strongest, thinnest material known to exist.
Graphene is an atomic-scale honeycomb lattice made of
carbon atoms.
It is the basic structural element of other allotropes,
including graphite, charcoal, carbon nanotubes and
fullerenes.
Graphene can be described as a one- atom thick layer of
graphite.
Graphene is a 2D crystal of carbon atoms, arranged in a
honeycomb lattice Each carbon atom is sp2 hybridized and
it is bound to its three neighbors.
Structure of Graphene
Graphene is commonly modified with oxygen- and
nitrogen- containing functional groups.
Graphene has the highest ratio of edgy carbons (in
comparison with similar materials such as carbon
nanotubes).
Graphene burns at very low temperature (e.g., 350 °C).
Carbon atoms at the edge of graphene sheets have special
chemical reactivity.
Only form of carbon (and generally all solid materials) in
which each single atom is in exposure for chemical
reaction from two sides (due to the 2D structure).
Graphene is chemically the most reactive form of carbon.
Chemical Properties
High charge carrier mobility, for which values of 10,000
cm2/Vs, in some cases even 200,000 cm2/Vs were
reported. It is a zero-overlap semimetal (with both holes
and electrons as charge carriers) with very high electrical
conductivity.
Electronic Properties
In an insulator or semiconductor, an electron bound to an
atom can break free only if it gets enough energy from heat
or passing photon to jump the ‘band gap’.
Mechanical Properties
It is expected that graphene’s mechanical properties will
find applications into making a new generation of super
strong composite materials and along combined with its
optical properties, making flexible displays.
Thermal Properties
Its thermal conductivity is much higher than all the other
carbon structures as carbon nanotubes, graphite and
diamond
Applications
While as of 2014, graphene is not used in commercial
applications, many have been proposed and/or are under
active development, in areas including electronics,
biological engineering, filtration, lightweight/strong
composite materials, photovoltaics and energy storage.
Biomedical
Graphene could soon be used to analyze DNA at a record-
breaking pace.
Integrated circuits
Graphene has a high carrier mobility, as well as low noise,
allowing it to be used as the channel in a field-effect
transistor.
Filters Desalination:
By very precise control over the size of the holes in the
graphene sheet, graphene oxide filters could outperform
other techniques of desalination by a significant margin.
Ethanol distillation:
Graphene oxide membranes allow water vapor to pass
through, but are impermeable to other liquids and gases.
Solar cells
Graphene turned to be a promising material for
photoelectrochemical energy conversion in dye sensitized
solar cells.

Anti- Bacterial
In 2010, the Chinese Academy of Sciences has found that
sheets of graphene oxide are highly effective at killing
bacteria such as Escherichia coli.
Other Applications
 Chemical sensors, Optical Modulators, Thermal
management materials, Liquid Cells for Electron
Microscopy, Composite Materials, Energy Harvesting,
Piezoelectric materials, Single-molecule gas detection, IR
detectors, Graphene nanoribbons.

Composites

The word “composite” means “made of two or more different parts.” or “A composite is a
combination of two or more different materials that are mixed in an effort to blend the best
properties of both.”

“ A Nanocomposite is a composite material, in which one of the components has at least one
dimension that is around 10-9 m. or“ A Nanocomposite is a multiphase solid material where one
of the phases has one, two or three dimensions of less than 100 nm, or structure having nano-
scale repeat distance between the different phases that make up the material.

Mechanically the term nanocomposites are differ from conventional composites due to the
exceptionally high surface to volume ratio of the reinforcing and/or its exceptionally high aspect
ratio. Continuous phase is called “matrix”, whereas discontinuous phase is called reinforcement"
or “reinforcing material” consist of one or more discontinuous phases of distributed in one
continuous phase.

Polymer based Nanocomposites

Non polymer based

Metal/Metal nanocomposites (either in the form of alloy or core-shell structure).

Metal/Ceramic nanocomposites Eg. Pt-Ru (either in the form of nanotube or complicated
nanostructure)
Ceramic/Ceramic nanocomposites Eg. Polysilazane/polysiloxane (alloy or ceramic) Eg.
Zirconia-toughened alumina

Polymer/Ceramic Nanocomposites

Inorganic/Organic Polymer nanocomposites (Layer structure) Eg. Barium-titanate with

polymers

Inorganic/Organic Hybrid Nanocomposites (clusters) Eg. Polymer nanofiber with zero valent
nanoparticles. (Nanocrystal) Eg. CdS nanocrystals, Poly N- vinyl carbozole- photorefractivity.

Polymer/ layered silicate nanocomposites Eg. Nylon-6 (N6)/ montmorillonite(MMT) with

Polymer/Polymer nanocomposites

silicate Biocomposites (fillers) Eg. Poly(p- phinylene oxide )- plastic scrap recycling Eg.
Elastin- collagen

POLYMERIC COMPOSITES

All the engineering materials (high polymers, metals and ceramics) possess their outstanding
characteristics as well as limitations.

Classification

Reinforcement: Particles (dispersion strengthened or large particles)

Fibres (discontinuous - short or continuous - aligned )

Structural (laminates and sandwich structures)

Matrix: Metal matrix composites (MMC)

Ceramic matrix composites (CMC)

Polymer matrix composites (PMC)

PARTICLE-REINFORCED COMPOSITE MATERIALS:

Factors that have an influence in physical and mechanical properties: size, distribution and
particle content.

TYPES OF PARTICLE-REINFORCED COMPOSITE MATERIALS:

 Structural

High modulus

Low density

Particle shape (avoid corners)

Thermal:

Expansion coefficient and conductivity

Lubricants

Lubricants are those substances, which are Used to reduce the force of Friction between two
sliding surfaces.

Lubrication

Lubrication is the process, or technique employed to reduce wear on surfaces in close

proximity, and moving relative to each another.

Composition of lubricants

Typically contains 90% base oil (petroleum-mineral oils) and less than 10% additives.

Non liquid lubricants contain Grease, powder (dry graphite, Molibdenum disulphite), Teflon
tape used in plumbing etc.

Those non liquid lubricants provide lubrication at higher temp.(up to 350 °C).

Additives

The properties of a lubricant can be improved by adding certain chemicals detergent dispersers
corrosion inhibitors, foam depressants , anti oxidants, Oiliness improvers.

Different Lubricating conditions

Dry Lubrication- No lubricant present between the surfaces. No oil film Thin oil film.

Boundary lubrication (Thin film) -This condition is found on machine slide ways (Lathe cross
slide, milling machine table).
Objectives of Lubrication

To reduce noise from the moving components of the machine.

To carry away heat from the bearing.

To protect the bearing surfaces from corrosion.

To reduce wear on the bearing surfaces.

To reduce frictional resistance.

Lubricating Methods

Circulation (pressure)

Bath type (Splash)

Wick type

Grease packing

Oil gun

Oil can

Types of Lubricant

Animal oils - From animal fats

Vegetable oils - From plant seeds

Mineral oils - Hydrocarbons obtained from minerals

Synthetic oils - From various chemicals

Grease - Semi-fluid lubricant

Dry - Molybdenum disulphide, Graphite

 Synthetic lubricants e.g. Polyglycols, Silicones, Organic amines, Imines, Amides.

Liquid Lubricants e.g. Mineral oils, Vegetable oils, Animal oils

Semi solid lubricants e.g. Grease and Vaseline

Solid lubricants e.g Wax, Talc, Mica, Molibdenum disulphide

Properties of Lubricant

A lubricant is a substance introduced to reduce frictional force and heat generation between the
surfaces in mutual contact, when the surfaces move.
A good lubricating oil generally possess the following characteristics:

Oilness: It ensures the adherence to the bearings and spread over the surface. This property makes
oil smooth and very important in boundary lubrication.

Strength: The lubricant must have high strength to avoid metal contact and seizure under heavy
loads.

Chemical Stability: The lubricant should not react with surfaces and any deposit in the cylinder.

Pour Point: It should be low to allow the flow of lubricant at low temperature to the oil pump.

Flash Point and Fire Point: The lubricating oil should not burn inside the cylinder, otherwise it
will leave heavy deposit and poisonous exhaust. Therefore, the flash point and fire point of the
lubricating oil must be high.

Neutralization: The oil should not have a tendency to form deposits by reacting with air, water,
fuel or the products of combustion.

Stability –Retention of properties as long as possible (Oxidization, Biological degradation,

Dilution).

Oiliness- Ability of the lubricant to stay in place between the bearing surfaces.

Viscosity - Resistance of a liquid to flow. The viscosity of oil should not change with rise in
temperature.

Emulsification: It is the property of a lubricant due to which the lubricating oil mixed with water
to form an emulsion. A good lubricant should have low emulsion number.
Volatility: It shows the evaporation behavior of lubricant at high temperature. A good lubricant
should have low volatility.

Corrosion Stability: It should not decompose during operation at high temperature. A good
lubricant must be stable towards heat.

Thermal Stability: A good lubricant should not take part in corrosion. It is properties of lubricant
which represents its resistance toward the metals.

Functions of Lubricants

Carry away contaminants

Transfer heat

Reduce friction

Keep moving parts apart

Prevent corrosion

Protect against wear

Transmit power

Debris.

MoS2

It is widely used as a solid lubricant because of its low friction properties and robustness.

 In appearance and feel, molybdenum disulphide is similar to graphite.

MoS2 is classified as a metal dichalcogenide. It is a silvery black solid that occurs as the
mineral molybdenite, the principal ore for molybdenum.

MoS2 belongs to the group of TMDs with the common formula MX2, wherein M represents a
transition metal.

Within a single X-M-X layer, the M and X atoms form a 2D hexagonal sub-lattice. The
Young’s modulus of MoS2 can be enhanced by a factor of five by sandwiching it between two
Grapheme layers.
MoS2 also has the advantage that it is as stiff as stainless steel but is also capable of being
flexible.

It has a key advantage over graphene- it can amplify electronic signals at room temperature,
while graphene must be cooled to 70 Kelvin- cold enough for nitrogen to turn into liquid.

Along with the other group-VI layered compounds, MoS2 exhibits semiconducting behavior.

The fundamental indirect band gap of bulk MoS2 is 1.22 to 1.23 eV, while the direct band gap
ranges from 1.74 to 1.77 eV. The hole mobility (96.62 cm2 V−1 s−1) in monolayer sheets of
MoS2 is about twice that of the electron mobility (43.96 cm2 V−1 s−1).