Unit 2.

Engineering Materials
Syllabus
Composite materials: Introduction; different types and applications. Photovoltaic materials:
solar cells and dye sensitized solar cells- principle and applications. Nanomaterials: Synthesis,
characterization and applications of nano materials (fullerene, graphene, carbon nanotubes and
quantum dots) in electronic and nano devices.

Composite materials

Composite materials are multiphase materials obtained through the artificial combination of
different materials in order to attain properties that the individual components by themselves
cannot attain. They are not multiphase materials in which the different phases are formed
naturally by reactions, phase transformations, or other phenomena. An example is carbon fiber
reinforced polymer. Composite materials should be distinguished from alloys, which can
comprise two more components but are formed naturally through processes such as casting.
Composite materials can be tailored for various properties by appropriately choosing their
components, their proportions, their distributions, their morphologies, their degrees of
crystallinity, their crystallographic textures, as well as the structure and composition of the
interface between components. Due to this strong tailorability, composite materials can be
designed to satisfy the needs of technologies relating to the aerospace, automobile, electronics,
construction, energy, biomedical and other industries. As a result, composite materials constitute
most commercial engineering materials.

Wood is a fibrous composite: cellulose fibers in a lignin matrix. The cellulose fibers have high
tensile strength but are very flexible (i.e., low stiffness), while the lignin matrix joins the fibers
and furnishes the stiffness. Bone is yet another example of a natural composite that supports the
weight of various members of the body. It consists of short and soft collagen fibers embedded in
a mineral matrix called apatite.
Since the early 1960s, there has been an increasing demand for materials that are stiffer and
stronger yet lighter in fields as diverse as aerospace, energy, and civil construction. The demands
made on materials for better overall performance are so great and diverse that no one material
can satisfy them. This naturally led to a resurgence of the ancient concept of combining different
materials in an integral-composite material to satisfy the user requirements. Such composite
material systems result in a performance unattainable by the individual constituents, and they
offer the great advantage of a flexible design; that is, one can, in principle, tailor-make the
material as per specifications of an optimum design.

An example of a composite material is a lightweight structural composite that is obtained by

embedding continuous carbon fibers in one or more orientations in a polymer matrix. The fibers
provide the strength and stiffness, while the polymer serves as the binder. In particular, carbon
fiber polymer-matrix composites have the following attractive properties:

Low density (lower than aluminum)

High strength (as strong as high-strength steels)

High stiffness (stiffer than titanium, yet much lower in density)

Good fatigue resistance

Good creep resistance

Low friction coefficient and good wear resistance

Toughness and damage tolerance (as enabled by using appropriate fiber orientations)

Chemical resistance (chemical resistance controlled by the polymer matrix)

Corrosion resistance

Dimensional stability (can be designed for zero CTE)

Vibration damping ability

Low electrical resistivity

High electromagnetic interference (EMI) shielding effectiveness

High thermal conductivity

Another example of a composite is concrete, which is a structural composite obtained by

combining (through mixing) cement (the matrix, i.e., the binder, obtained by a reaction – known
as hydration – between cement and water), sand (fine aggregate), gravel (coarse aggregate), and
optionally other ingredients that are known as admixtures. Short fibers and silica fume (a fine
SiO2 particulate) are examples of admixtures. In general, composites are classified according to
their matrix material.

Above figure makes a comparison, admittedly for illustrative purposes, between conventional
monolithic materials, such as aluminum and steel, and composite materials. This figure indicates
the possibilities of improvements that one can obtain over conventional materials by the use of
composite materials.

Practically everything in this world is a composite material. Such a definition would make things
quite unwieldy. Therefore, we shall call a material that satisfies the following conditions a
composite material:
1. It is manufactured (i.e., naturally occurring composites, such as wood, are excluded).

2. It consists of two or more physically and/or chemically distinct, suitably arranged or

distributed phases with an interface separating them.

3. It has characteristics that are not depicted by any of the components in isolation.

The main classes of composites are polymer-matrix, cement matrix, metal-matrix, carbon-matrix
and ceramic-matrix composites.

The structure of a composite is commonly such that one of the components is the matrix while
the other components are fillers bound by the matrix, which is often called the binder. For
example, in carbon fiber reinforced polymer, which is important for lightweight structures, the
polymer is the matrix, while the carbon fiber is the filler. In case of a structural composite, the
filler usually serves as a reinforcement (reinforcement is the action or process of reinforcing or
strengthening). For example, carbon fiber is a reinforcement in the polymermatrix composite.

Composites can be classified according to the matrix material, which can be a polymer, a metal,
a carbon, a ceramic or a cement.

The technology and cost of composite materials depend largely on the processability; i.e., how
the components are combined to form a composite material. The processability depends largely
on the ability of the components to join, thereby forming a cohesive material. The processing
often involves elevated temperatures and/or pressures. The required temperature and pressure, as
well as the processing time, are typically dictated by the matrix material. The bonding of the
filler with the matrix at an elevated temperature has a disadvantage in that bond weakening or
even debonding may occur during the subsequent cooling, due to the difference in the thermal
contraction (related to the coefficient of thermal expansion, or CTE) between filler and matrix.

1. Polymer-Matrix Composites

Polymer matrix composites (PMCs) have established themselves as engineering structural

materials, not just as laboratory curiosities or cheap stuff for making chairs and tables. This came
about not only because of the introduction of high-performance fibers such as carbon, boron, and
aramid but also because of some new and improved matrix materials.

e.g.

Boron Fibers: Boron is an inherently brittle material. It is commercially made by chemical vapor
deposition (CVD) of boron on a substrate, that is, boron fiber as produced is itself a composite
fiber. Interest in the use of strong but light boron fibers as a possible structural component in
aerospace and other structures has been continuous, although it must be admitted that this
interest has periodically waxed and waned in the face of rather stiff competition from other
advanced fibers, in particular, carbon fibers.
Fabrication method: Hydrogen gas is used to reduce boron trihalide, where X denotes a halogen:
Cl, Br, or I.

In this process of halide reduction, the temperatures involved are very high (Boron melting point:
2,076 °C), and, thus, one needs a refractory material, for example, a high-melting-point metal
such as tungsten (Melting point: 3,422 °C), as a substrate.
Boron fiber composites are in use in a number of US military aircraft, notably the F-14 and F-15,
and in the US space shuttle. They are also used for stiffening golf shafts, tennis rackets, bicycle
frames, and in making repair patches for polymer-matrix composites. One big obstacle to the
widespread use of boron fiber is its high cost compared to that of other fibers.
Carbon Fibers: Carbon is a very light element with a density equal to 2.268 g/cm3. Carbon can
exist in a variety of crystalline forms. Our interest here is in the so-called graphitic structure
wherein the carbon atoms are arranged in the form of hexagonal layers. The other well-known
form of carbon is the covalent diamond structure wherein the carbon atoms are arranged in a
three-dimensional configuration with little structural flexibility. Another form of carbon is
Buckminster Fullerene (or Bucky ball), with a molecular composition of C60 or C70. One can
also have carbon nanotubes, which are nothing but drawn out version of Buckyballs. Carbon in
the graphitic form is highly anisotropic, with a theoretical Young’s modulus in the layer plane
being equal to about 1,000 GPa, while that along the c-axis is equal to about 35 GPa.

As we know, the bond strength determines the modulus of a material. Thus, the high-strength
bond between carbon atoms in the layer plane results in an extremely high modulus while the
weak van der Waals-type bond between the neighbouring layers results in a lower modulus in
that direction. Consequently, almost all processing techniques of carbon fiber have the goal of
obtaining a very high degree of preferred orientation of hexagonal planes along the fiber axis.

Carbon fibers of extremely high modulus can be made by carbonization of organic precursor
fibers followed by graphitization at high temperatures. The organic precursor fiber, that is, the
raw material for carbon fiber, is generally a special textile polymeric fiber that can be carbonized
without melting.

Carbon fibers made from

a. PAN (polyacrylonitrile) are known as ex-PAN carbon fibers.
 b. Cellulose (natural polymer that is frequently found in a fibrous form. In fact, cotton fiber,
which is cellulosic, was one of the first to be carbonized. As mentioned above, Thomas
Edison did that to obtain carbon filament for incandescent lamp) are known as ex-
Cellulose Carbon Fibers.
c. Polyvinyl chloride (PVC), petroleum asphalt, and coal tar based fibres are also known as
ex-Pitch Carbon Fibers.

Carbon fibers are used in a variety of applications in the aerospace and sporting goods industries.
Cargo bay doors and booster rocket casings in the US space shuttle are made of carbon fiber
reinforced epoxy composites. Modern commercial aircraft such as Boeing 787 (Dreamliner) has
fuselage and wings made of carbon fiber/epoxy composites. With the ever decreasing price of
carbon fibers, applications of carbon fibers in other areas have also increased, for example,
various machinery items such as turbine, compressor, and windmill blades and flywheels; in the
field of medicine the applications include both equipment and implant materials (e.g., ligament
replacement in knees and hip joint replacement).

Polymer-matrix composites (abbreviated PMC) can be classified according to whether the matrix
is a thermoset or a thermoplastic polymer. Thermoset matrix composites are traditionally far
more common, but thermoplastic-matrix composites are currently the focus of rapid
development. The advantages of thermoplastic-matrix composites compared to thermoset-matrix
composites include the following:

1. Lower manufacturing cost

2. No cure (no treatment)
3. Unlimited shelf-life
4. Reprocessing possible (for repair and recycling)
5. Fewer health risks due to chemicals during processing
6. Low moisture content
7. Thermal shaping possible
8. Weldability (fusion bonding possible).
9. Better performance
10. High toughness (damage tolerance)
11. High environmental tolerance.

The disadvantages of thermoplastic-matrix composites include the following:

1. Limitations in relation to processing methods

2. High processing temperatures
3. High viscosities

Polymer-matrix composites are much easier to fabricate than metal-matrix, carbon-matrix, and
ceramic-matrix composites, whether the polymer is a thermoset or a thermoplastic. This is
because of the relatively low processing temperatures required to fabricate polymer-matrix
composites. For thermosets, such as epoxy, phenolic, and furfuryl resin, the processing
temperature typically ranges from room temperature to about 200°C; for thermoplastic polymers,
such as polyimide (PI), polyethersulfone (PES), polyetheretherketone (PEEK), polyetherimide
(PEI), and polyphenyl sulfide (PPS), the processing temperature typically ranges from 300 to
400°C.

Thermosets (especially epoxy) have long been used as polymer matrices for carbon fiber
composites. During treatment, usually performed in the presence of heat and pressure, a
thermoset resin hardens gradually due to the completion of polymerization and the associated
crosslinking of the polymer molecules. Thermoplastic polymers have recently become important
because of their greater ductility and processing speed compared to thermosets, and the recent
availability of thermoplastics that can withstand high temperatures. The higher processing speed
of thermoplastics arises from the fact that amorphous thermoplastics soften immediately upon
heating above the glass transition temperature, and so the softened material can be shaped easily.
Subsequent cooling completes the processing.

The processing of polymer-matrix composites typically requires heating. In the case of a

thermosetting resin, the heating is to cause the completion of polymerization (cross-linking) of
the resin. In the case of a thermoplastic matrix, the heating is done to soften or melt the
thermoplastic matrix. (The melting temperature is higher than the softening temperature but it
allows more extensive flow.) As the polymerization process is a reaction, it takes time. In
contrast, the softening or melting is a phase transition that occurs once the appropriate
temperature is reached. As a result, the processing time tends to be considerably longer for a
thermoset-matrix composite than a thermoplastic-matrix composite.

Applications of Polymer-matrix composites (PMC)

1. Aerospace and Military Aircraft. The aerospace industry is estimated to consume about
50 percent of advanced composites production in the United States. The primary matrix
materials used in aerospace applications are epoxies, and the most common
reinforcements are carbon/graphite, aramid (e.g. Kevlar), and high-stiffness glass fibers.
Compared with metals, the principal advantages of advanced composites in aerospace
applications are their superior specific strength and stiffness, resulting in weight savings
of 10 to 60 percent over metal designs (in Boing 787 body). Additional advantages of
advanced composites are their superior fatigue and corrosion resistance, and vibration-
damping properties. Advanced composites have become essential to the superior
performance of a large number of fighter and attack aircraft
2. Automotive Industry. Because of greatly improved corrosion resistance PMC
automobiles could last 20 or more years compared to the current average vehicle lifetime.
3. Construction purpose. PMCs are widely used in construction of Buildings, Bridges,
Housing, Lampposts, Smokestacks, Highway culverts.
4. Medical Devices. The impact of PMCs on orthopaedic and biomaterial devices such as
Hips joint replacement, Knee/knee joint replacement, bone plates, intramedullary nails is
 expected to be especially significant. PMC materials are currently being developed for
medical prostheses and implants.
5. Marine industry. The innovations in the area of composite materials have a great impact
on the development of the modern ships built for the marine industry. The small weight
of marine constructions is important for the lower fuel consumption and polymer based
composite materials show water and corrosion resistance.
6. In the field of sport. Formula One sector is developing polymer composite materials in
manufacturing structures of bicycles. PMCs frames ensure lightness, good mechanical
properties and stiffness. An Australian manufacturer of sustainable surfboards, Samsara
Surfboards (Melbourne, Australia) is currently producing ultra-high performance eco
surfboards.

7. PMC materials have considerable potential for use in many different kinds of high-speed
industrial machinery. Current applications include such components as centrifuge rotors,
weaving machinery, hand-held tools, and robot arms. All of these applications take
advantage of the low inertial mass, but they also benefit to varying degrees from the
tailorable an isotropic stiffness, superior strength, low thermal expansion, and fatigue-life
and vibration-damping characteristics of PMCs. In robotic applications, increasing both
the
8. In robotics Speed and the endpoint accuracy of the robot are desired improvements.
Stiffness is the key mechanical property in that the endpoint accuracy is limited by
bending deflections in the beam-shaped robot members. With metal designs, stiffness is
obtained at the cost of higher mass, which limits the robot’s response time. Because of
their superior stiffness per unit weight, PMCs are a promising solution to this problem.
2. Metal-Matrix Composites (MMC)

The processing of a metal-matrix composite (abbreviated MMC) tends to be much more

expensive than that of a polymer-matrix composite due to the high processing temperature
required. The fabrication of metal-matrix composites often involves the use of an intermediate,
called a preform, in the form of sheets, wires, cylinders, or near-net shapes. The size and shape
of the preform are the same as those of the composite article to be made. The preform contains
the reinforcement, which is usually held together by a binder that can be a polymer (e.g., acrylic,
styrene), a ceramic (e.g., silica, aluminum metaphosphate), or the matrix metal itself.

The most popular method of fabricating metal-matrix composites is the infiltration of a preform
by a liquid metal, typically under pressure, as illustrated in above Figure. The temperature needs
to be above the solidus temperature (i.e., the temperature above which liquid metal exists, such
that the liquid metal coexists with the solid metal unless the temperature is above the liquidus).
In order to use a liquid metal infiltration temperature that is not too high, a metal (e.g.,
aluminum) with a relatively low melting temperature is usually chosen for the matrix. The low
viscosities of liquid metals compared to resins or glasses make infiltration very appropriate for
metal-matrix composites. Nevertheless, pressure is usually required because it is difficult for the
liquid metal to wet the reinforcement. The pressure can be provided by a gas (e.g., argon) or a
piston, as illustrated in above Figure. When a piston is used, the process can be quite fast.
A variety of metals and their alloys can be used as matrix materials. We describe briefly the
important characteristics of some of the more common ones.

1. Aluminum Alloys

Aluminum alloys, because of their low density and excellent strength, toughness, and resistance
to corrosion, find important applications in the aerospace field. Of special mention in this regard
are the Al–Cu–Mg and Al–Zn–Mg–Cu alloys, very important precipitation-hardenable alloys.
Aluminum-lithium alloys form one of the most important precipitation-hardenable aluminum
alloys. Lithium, when added to aluminum as a primary alloying element, has the unique
characteristic of increasing the elastic modulus and decreasing the density of the alloy.

2. Titanium Alloys

Titanium is one of the important aerospace materials. It has a density of 4.5 g/cm3 and a Young’s
modulus of 115 GPa. For titanium alloys, the density can vary between 4.3 and 5.1 g/cm3, while
the modulus can have a range of 80–130 GPa. High strength/weight and modulus/weight ratios
are important. Titanium has a relatively high melting point (1,672 ˚C) and retains strength to
high temperatures with good oxidation and corrosion resistance. All these factors make it an
ideal material for aerospace applications. Titanium alloys are used in jet engines (turbine and
compressor blades), fuselage parts, etc. It is, however, an expensive material.

Applications of Metal-Matrix Composites (MMC):

1. Reduction in the weight of a component is a major driving force for any application in the
aerospace field. Aluminium MMcs are widely used in aerospace applications and in
missiles due to its light weight and high elastic modulus.
2. One of the important applications of MMCs in the automotive area is in diesel piston
crowns. This application involves incorporation of short fibers of alumina or alumina +
silica in the crown of the piston. The conventional diesel engine piston made of a nickel
cast iron. The replacement of the nickel cast iron by aluminum matrix composite resulted
in a lighter, more abrasion-resistant, and cheaper product.
3. High performance tungsten carbide is used in making cutting tools.
4. Some tank armors may be made from metal matrix composites, probably steel reinforced
with boron nitride, which is a good reinforcement for steel because it is very stiff and it
does not dissolve in molten steel.
5. Some automotive disc brakes use MMCs. Modern high-performance sport cars, such as
those built by Porsche, use rotors made of carbon fiber within a silicon carbide matrix
because of its high specific heat and thermal conductivity.
6. Ford offers a Metal Matrix Composite (MMC) driveshaft upgrade. The MMC driveshaft
is made of an aluminum matrix reinforced with boron carbide, allowing the critical speed
of the driveshaft to be raised by reducing inertia. The MMC driveshaft has become a
common modification for racers, allowing the top speed to be increased far beyond the
safe operating speeds of a standard aluminum driveshaft.
7. Honda has used aluminum metal matrix composite cylinder liners in some of their
engines, including the B21A1, H22A and H23A, F20C and F22C, and the C32B used in
the NSX.
8. Toyota has used metal matrix composites in the Yamaha-designed 2ZZ-GE engine which
is used in the later Toyota car models.
9. The F-16 Fighting Falcon uses monofilament silicon carbide fibers in a titanium matrix
for a structural component of the jet's landing gear.
10. Specialized Bicycles has used aluminum MMC compounds for its top of the range
bicycle frames for several years. Griffen Bicycles also made boron carbide-aluminum
MMC bike frames.
11. Some equipment in particle accelerators such as Radio Frequency Quadrupoles (RFQs)
or electron targets use copper MMC compounds such as Glidcop to retain the material
properties of copper at high temperatures and radiation levels.
12. Copper-silver alloy matrix containing 55% by volume diamond particles, known as
Dymalloy, is used as a substrate for high-power, high-density multi-chip modules in
electronics for its very high thermal conductivity.
13. Aluminium-Graphite composites are used in power electronic modules because of their
high thermal conductivity, the adjustable coefficient of thermal expansion and the low
density.
3. Carbon–Carbon Composites

Carbon is a very versatile material. It can exist in a variety of forms; amorphous, graphite,
diamond, fullerenes, graphene, nanotubes, etc.

Diamond. Carbon in the diamond form has an FCC structure; it is also called diamond cubic.
Each C atom is covalently bonded to four carbon atoms at the vertices of a tetrahedron and the
interatomic distance = 0.154 nm. Carbon in the diamond form has isotropic properties (physical
property which has the same value when measured in different directions.). It is one of the
hardest materials.

Graphite. Graphitic form of carbon has a hexagonal structure. Carbon atoms are arranged in
layers. The bonding between atoms in the plane of the layer is covalent but the bonding between
layers is weak, van der Waals type.

Carbon black. A generic term for carbon powder of extremely fine size (nm range) and very high
surface area. It is essentially elemental carbon (>97 %), electrically conductive, and finds
extensive use in tires and other rubber products as well as in printing inks and paints.

Carbon nanotubes. These are hollow, cylindrical tubes of carbon atoms with diameter in the
range of 5–20 nm. They are frequently referred to as CNTs. They show some very unusual
properties, such as extremely high stiffness and strength.

Carbon is an excellent high temperature material when used in an inert or nonoxidizing

atmosphere. The major drawback of carbon is that it reacts with oxygen, forming gaseous oxides
of carbon.

The carbon fibers used for carbon–carbon composites are usually continuous and woven. Both
two-dimensional and higher-dimensional weaves are used, though the latter has the advantage of
enhanced interlaminar shear strength.

The carbon matrix in a carbon fiber/carbon matrix composite is generally obtained by chemical
vapor deposition (CVD) of carbon or thermal decomposition of a source of carbon such as pitch
or phenolic resin. Generally, many pores form during this conversion of a hydrocarbon to
carbon. Thus, a dense and strong pore-free carbon/carbon composite is not easy to fabricate.

Carbon/carbon composites were originally developed for the space program, they have now
become high performance engineering materials, with special high temperature applications.
More specifically, these high temperature applications involve brakes for aircraft and
automobiles, dies for use in hot-pressing, high temperature fasteners, heating elements in
furnaces, liners and protection tubes, etc. Carbon/carbon composites are expensive mainly
because of the long processing times involved.

Carbon-matrix composites are made by the carbonization of the matrix of a polymer-matrix

composite. The process of carbonization (also known as pyrolysis) is similar to charring
(burning), which involves a chemical reaction that removes essentially all atoms that are not
carbon from the polymer (the carbon precursor).

The carbon yield (or char yield) from carbonization is around 50wt.% for ordinary pitch and 80–
88wt.% for mesophase pitch (pitch of higher molecular weight) at atmospheric pressure.

The carbonization process is typically conducted in an inert atmosphere at around 650–1,200°C.

The atmosphere is usually nitrogen at temperatures up to 1,000°C and is argon at temperatures
above 1,000°C. Argon at high temperatures is used because carbon tends to react with nitrogen
to form poisonous cyanide compounds above 1,000°C. One common carbon precursor is pitch (a
polyaromatic hydrocarbon material derived from petroleum or coal), which is a mixture of
thermoplastic polymers. Pitch is attractive because of its relatively high char yield (i.e., the mass
of the resulting carbon divided by the mass of the carbon precursor). A high char yield means a
smaller amount of porosity in the resulting carbon-matrix composite. Significant increases in the
carbon yield of pitch can be obtained through the use of high pressure during carbonization.
A thermoplastic polymer such as pitch melts upon heating. The melting of the matrix is
undesirable for the conversion of a polymer-matrix composite to a carbon-matrix composite.
Furthermore, during carbonization, pitch tends to bloat (swell/ expand) due to the evolution of
gases generated by pyrolysis. The bloating can cause the expulsion of pitch from the carbon fiber
preform during carbonization. Thus, the carbonization process is usually preceded by a process
known as stabilization, which involves heating at 200–300°C in the presence of oxygen. In
stabilization, oxygen diffuses into the carbon precursor and reacts with it, thus converting it
chemically to a form that does not melt. Hence, the stabilization process is also known as
infusibilization.

The main disadvantages of carbon–carbon composites are their high fabrication cost, poor
oxidation resistance, poor inter-laminar properties (especially for two dimensionally woven
fibers), the difficulty involved in making joints, and the insufficient engineering database.

Applications of Carbon/Carbon Composites

Major applications of carbon/carbon composites involve uses at high temperatures, for example,
as heat shields for reentry vehicles, aircraft brakes, hot-pressing dies, and high-temperature parts
such as nozzles. Brakes for racing cars and some high end luxury cars are the latest entry. Heat
shields and nozzles are made of multidirectionally reinforced carbon/carbon composites.

As pointed out, carbon/carbon composites can withstand high temperatures in an inert

atmosphere. Lack of oxidation resistance is a major problem, and a great deal of effort has been
put into the development of oxidation-resistant coatings for carbon fibers, with SiC coating being
the primary coating material.

Other applications of carbon/carbon composites include their use as implants and internal repair
of bone fractures because of their excellent biocompatibility. They are also used to make molds
for hot pressing. Carbon/carbon molds can withstand higher pressures and offer a longer use life
than polycrystalline graphite.

4. Cement-Matrix Composites
Cement-matrix composites include concrete, which is a cement-matrix composite with a fine
aggregate (sand), a coarse aggregate (gravel) and optionally other additives (called admixtures).
Concrete is the most widely used civil structural material. When the coarse aggregate is absent,
the composite is known as a mortar, which is used in masonry (for joining bricks) and for filling
cracks. When both coarse and fine aggregates are absent, the material is known as cement paste.
Cement paste is rigid after curing (the hydration reaction involving cement –a silicate – and
water to form a rigid gel).

The admixtures can be a fine particulate such as silica (SiO2) fume to decrease the porosity in
the composite. It can be a polymer (used in either a liquid solution form or a solid dispersion
form) such as latex, again to decrease the porosity. It can be short fibers (such as carbon fibers,
glass fibers, polymer fibers and steel fibers) to increase the toughness and decrease the drying
shrinkage (shrinkage during curing – undesirable, as it can cause cracks to form). Continuous
fibers are seldom used because of their high cost and the impossibility of incorporating
continuous fibers into a cement mix. Due to the bidding system used for many construction
projects, low cost is essential.

Fibrous cement-matrix composites are structural materials that are gaining in importance quite
rapidly due to the increasing demand for superior structural and functional properties.
Discontinuous fibers used in concrete include steel, glass, polymer and carbon fibers. Among
these fibers, carbon and glass fibers are micrometer scale (e.g., 10μm) in diameter, whereas steel
and polymer fibers are usually much larger in diameter (e.g., 100μm). For the microfibers, the
fiber length is typically around 5mm, as fiber dispersion becomes more difficult as the fiber
length increases. Due to the weak bond between fiber and the cement matrix, continuous fibers
are much more effective than short fibers at reinforcing concrete. However, continuous fibers
cannot be incorporated into a concrete mix, and it is difficult for the concrete mix to penetrate
into the space between adjacent fibers, even in the absence of aggregates. The alignment of the
continuous fibers in concrete also adds to the implementation difficulty. Therefore, short fibers
are typically used.

The effect of short fiber addition on the properties of cement increases with increasing fiber
volume fraction unless the fiber volume fraction is so high that the air void content becomes
excessively high. (The air void content increases with fiber content, and air voids tend to have a
negative effect on many properties, such as the compressive strength.) In addition, the
workability of the mix decreases with increasing fiber content. Moreover, the cost increases with
increasing fiber content. Therefore, a rather low volume fraction of fibers is desirable. A fiber
content as low as 0.2vol% is effective, although fiber contents exceeding 1vol% are common.
The required fiber volume fraction increases with increasing fiber diameter and increases with
increasing particle size of the aggregate.

The improvement in the structural properties due to the addition of discontinuous fibers to
cement includes increases in the tensile ductility and toughness and a decrease in the drying
shrinkage. A low drying shrinkage is particularly valuable for large structures, as cracks can
form due to the shrinkage and the cracks are wide for the same fractional shrinkage if the
structure is large. In the case of the fiber being carbon fiber, improvements in the tensile strength
and the flexural strength also occur. Carbon fibers (made from isotropic pitch) are advantageous
in their superior ability to increase the tensile strength of cement, even though the tensile
strength, modulus and ductility of the isotropic pitch based carbon fibers are low compared to
most other fibers. Carbon fibers are also advantageous because of their relative chemical
inertness.

[**Carbon fibers or carbon fibres are fibers about 5–10 micrometres in diameter and composed
mostly of carbon atoms. Carbon fibers have several advantages including high stiffness, high
tensile strength, low weight, high chemical resistance, high temperature tolerance and low
thermal expansion.]

5. Ceramic-Matrix Composites (CMC)

Ceramic materials are very hard and brittle.

Ceramic materials in general have a very attractive package of properties: high strength and high
stiffness at very high temperatures, chemical inertness, low density, and so on. This attractive
package is marred by one deadly flaw, namely, an utter lack of toughness.
Generally, they consist of one or more metals combined with a nonmetal such as oxygen, carbon,
or nitrogen. They have strong covalent and ionic bonds and very few slip systems available
compared to metals. Thus, characteristically, ceramics have low failure strains and low
toughness or fracture energies. In addition to being brittle, they lack uniformity in properties,
have low thermal and mechanical shock resistance, and have low tensile strength. On the other
hand, ceramic materials have very high elastic moduli, low densities, and can withstand very
high temperatures. The last item is very important and is the real driving force behind the effort
to produce tough ceramics. Consider the fact that metallic superalloys, used in jet engines, can
easily withstand temperatures up to 800 ˚C and can go up to 1,100 ˚C with oxidation-resistant
coatings. Beyond this temperature, one must use ceramic materials if they are available with the
requisite toughness.

By far, the major disadvantage of ceramics is their extreme brittleness. Even the minutest of
surface flaws (scratches or nicks) or internal flaws (inclusions, pores, or microcracks) can have
disastrous (terrible) results.

Ceramic materials, with the exception of glasses, are crystalline, as are metals. Unlike metals,
however, ceramic materials have mostly ionic bonding and some covalent bonding. Ionic
bonding involves electron transfer between atomic species constituting the ceramic compound;
that is, one atom gives up an electron(s) while another accepts an electron(s). Electrical neutrality
is maintained; that is, positively charged ions (cations) balance the negatively charged ions
(anions). Generally, ceramic compounds are stoichiometric; that is, there exists a fixed ratio of
cations to anions. Examples are alumina (Al2O3), beryllia (BeO), spinels (MgAl2O4), silicon
carbide (SiC), and silicon nitride (Si3N4).

Glass-ceramic materials form yet another important category of ceramics. They form a sort of
composite material because they consist of 95–98 % by volume of crystalline phase and the rest
glassy phase. Important examples of glass-ceramic systems include the following:

1. Li2O-Al2O3-SiO2: This has a very low thermal expansion and is therefore very resistant to
thermal shock. Corningware is a well-known trade name of this class of glass-ceramic.

2. MgO-Al2O3-SiO2: This has high electrical resistance coupled with high mechanical strength.
Glasses, the traditional silicate ceramic materials, are inorganic solid like materials that do not
crystallize when cooled from the liquid state. Their structure is not crystalline but that of a
supercooled liquid.

Applications of CMCs

Ceramic matrix composites find applications in many areas. A convenient classification of the
applications of CMCs is aerospace and nonaerospace.

1. Materials-related drivers for applications of CMCs in the aerospace field are:

• High specific stiffness and strength leading to a weight reduction, and, consequently,
decreased fuel consumption.
• Reduction in fabrication and maintenance cost.
• Higher operating temperatures leading to a greater thermal efficiency.
• Longer service life.
• Signature reduction, which is valuable in stealth technology (reduce the distance at which
a vehicle can be detected).

CMCs can lead to improvements in aerospace vehicles including aircraft, helicopters, missiles,
and reentry vehicles. Projected skin temperatures in future hypersonic aircraft are higher than
1,600 ˚C.

2. In cutting tools: An important area of CMC applications is that of cutting tool inserts.
Silicon carbide whisker reinforced alumina (SiC/Al2O3) composites are used as cutting
tool inserts for high-speed cutting of superalloys. Among the characteristics that make
CMCs good candidates for cutting tool inserts are: Abrasion resistance, Thermal shock,
resistance, Strength, Fracture toughness, and Thermal conductivity.
3. Candle-type filters consisting of ceramic fibers in a silicon carbide matrix can be used to
remove particulate matter from high-temperature gas streams up to 1,000 ˚C. The high-
temperature capability of such filters can eliminate the need to cool the gas stream prior
to filtration, which may increase process efficiency and eliminate the cost and complexity
of gas dilution, air scrubbers, or heat exchangers.
4. An interesting application is a radiant burner tube made of CMCs. Heat transfer between
two objects can occur by conduction when the two objects are in contact, by convection
such as by mixing of hot and cold fluids, or by radiation which involves transmission of
electromagnetic waves through space (even vacuum). In a radiant burner tube, heat is
transferred from combustion gases to the radiant tube and then by radiation that energy is
transferred to the load (the material to be heated). Radiant tube burners are useful in
situations where combustion products must not come in contact with the material to be
heated, i.e., they are an indirect heating burning meaning the heat is transferred without
any direct flame or combustion exhaust. Radiant tube burner systems are designed to
reduce nitrous oxide in the burning process.
 Photovoltaic materials

The term photovoltaic is derived from photo meaning “light” and voltaic meaning “electricity”;

thus, photovoltaic cells are cells that convert sunlight directly into electricity at the atomic level.

Photovoltaic cells are made of special materials called semiconductors, such as silicon, that

exhibit a property known as the photoelectric effect. Basically, when light energy strikes the cell,

loosely bound electrons are knocked out from the atoms in the semiconductor material. When

these free electrons are captured, the result is an electric current that can be used as electricity.

In order to produce electricity, sunlight has to be captured and converted into thermal or electric

energy suitable for human consumption. Sun energy races toward the Earth at very high speed,

and if its path was not obstructed by space junk or clouds and dust in the atmosphere, it would

arrive to us at full power. Sunlight travels from the sun to Earth in approximately 8 minutes, and

while it loses some of its energy during this journey, most of it arrives here safe and sound and

ready to serve us. We call this “beam” or “direct” radiation. Measured at the top of the

atmosphere, we find the highest power density reaching up to 1,367 W/m2. Its power drops after

crossing the atmosphere to approximately 900-1,100 W/m2 as measured at noon in the deserts

during the summer months, and much less than that in other parts of the globe and during

different seasons of the year. When the sunlight hits clouds, dust, or man-made gasses in the air,

it gets scattered and we call that “diffused” radiation. Diffused radiation has properties very

different from direct radiation. It contains less energy, and thus PV modules will produce less

power under diffused radiation, in some cases much less.

Solar electricity, also known as photovoltaics (PV), has shown since the 1970s that the human

race can get a substantial portion of its electrical power without burning fossil fuels (coal, oil or

natural gas) or creating nuclear fission reactions. Photovoltaics helps us avoid most of the threats

associated with our present techniques of electricity production and also has many other benefits.

Photovoltaics is the technology that generates direct current (DC) electrical power measured in

Watts (W) or kiloWatts (kW) from semiconductors when they are illuminated by photons. As

long as light is shining on the solar cell (the name for the individual PV element), it generates

electrical power. When the light stops, the electricity stops. Solar cells never need recharging

like a battery. Solar cells are made of materials called semiconductors, which have weakly

bonded electrons occupying a band of energy called the valence band. When energy exceeding a

certain threshold, called the band gap energy, is applied to a valence electron, the bonds are

broken and the electron is somewhat “free” to move around in a new energy band called the

conduction band where it can “conduct” electricity through the material. Thus, the free electrons

in the conduction band are separated from the valence band by the band gap (measured in units

of electron volts or eV). This energy needed to free the electron can be supplied by photons,

which are particles of light. When the solar cell is exposed to sunlight, photons hit valence

electrons, breaking the bonds and pumping them to the conduction band. There, a specially made

selective contact that collects conduction-band electrons drives such electrons to the external

circuit. The electrons lose their energy by doing work in the external circuit such as pumping

water, spinning a fan, powering a sewing machine motor, a light bulb, or a computer. They are

restored to the solar cell by the return loop of the circuit via a second selective contact, which

returns them to the valence band with the same energy that they started with. The movement of

these electrons in the external circuit and contacts is called the electric current.
Solar heat Collector Images
Solar water heater images
Solar cooker images
Dye sensitized solar cells

Several semiconductor materials, including single-crystal and polycrystal forms of n- and p-Si,
n- and p-GaAs, n- and p-InP, and n-CdS, have been used as photoelectrodes. These materials,
when used with a suitable redox electrolyte, can produce solar light-to-current conversion
efficiency of approximately 10%. However, under irradiation, photocorrosion of the electrode in
the electrolyte solution frequently occurs, resulting in poor stability of the cell.

Oxide semiconductor materials have good stability under irradiation in solution. However, stable
oxide semiconductors cannot absorb visible light because they have relatively wide band gaps.
Sensitization of wide band gap oxide semiconductor materials, such as TiO2, ZnO, and SnO2,
with photosensitizers, such as organic dyes, that can absorb visible light has been extensively
studied in relation to the development of photography technology since the late nineteenth
century. In the sensitization process, photosensitizers adsorbed onto the semiconductor surface
absorb visible light and excited electrons are injected into the conduction band of the
semiconductor electrodes. Dye-sensitized oxide semiconductor photoelectrodes have been used
for Photoelectrochemical solar cells. The spectral response of the dye-sensitized solar cell
depends on the absorption properties of the dye.

Photoelectrodes made of such materials as Si, GaAs, InP, and CdS decompose under irradiation
in solution owing to photocorrosion. In contrast, oxide semiconductor materials, especially TiO2,
have good chemical stability under visible irradiation in solution; additionally, they are nontoxic
and inexpensive.

Examples: Molecular structures of typical Ru complex photosensitizers. The Ru(II) complex

dyes have shown the best results in dye-sensitized solar cells, but these are very costly because
of ruthenium, which may increase the overall cost of the cell.
Exposure of this solar-cell assembly to visible light leads to a sequence of reactions. Following
figure shows schematically these processes. We first consider the reactions that take place at the
anode, where the absorption of the light by the dye (S) leads to formation of its electronically
excited state S*:

The molecule in the excited state can decay back to the ground state or undergo oxidative
quenching, injecting electrons into the conduction band of TiO2.

Injected electrons in the conduction band of TiO2 are transported between TiO2 nanoparticles
and consequently reach the counter electrode through the external load and wiring.

The oxidized dye is reduced rapidly to the ground state by the donor (iodide, I- ion is redox
mediator) present in the electrolyte. I- is oxidized to the oxidized state, I3-:
In the absence of a redox mediator to intercept and rapidly reduce the oxidized dye (S+),
recombination with the electrons of the titania layer takes place, without any measurable
photocurrent:

The electrons reaching the counter-electrode through the external circuit reduce in turn the
oxidized iodide (I-) so that the entire sequence of electron transfer reactions involving the dye
and the redox mediator is rendered cyclic:

The performance of a dye-sensitized solar cells is predominantly based on four energy levels of
the component: the excited state (approximately LUMO) and the ground state (HOMO) of the
photosensitizer, the Fermi level of the TiO2 electrode, which is located near the conduction-band
level, and the redox potential of the mediator (I-/I3-) in the electrolyte.

The photocurrent obtained from a dye-sensitized solar cells is determined by the energy
difference between the HOMO and the LUMO of the photosensitizer, analogous to the band gap.
The smaller the HOMO–LUMO energy gap, the larger the photocurrent will be because of the
utilization of the long-wavelength region in the solar spectrum.
 Schematic drawing of a dye-sensitized solar cell showing the principles of operation.

Characteristics of dye-sensitized solar cells

As described above, the photovoltaic (PV) mechanism of dye-sensitized solar cells is different
from that of conventional p-n-type solar cells. The dye-sensitized solar cell has other unique
characteristics such as the following:

1. High energy conversion efficiency: A dye-sensitized solar cells efficiency equal to that of the
amorphous Si solar cell has been obtained during laboratory development and efficiencies
greater than 10% may be possible.
2. Low-cost fabrication: The dye-sensitized solar cells is very simple to construct and is made of
low-cost materials. Fabrication costs will therefore be less than that for conventional solar cells.

3. Abundant supply of component materials: Oxide semiconductors such as TiO2, dye, and
iodine are abundantly available. Although metal deposits of Ru are limited, the amount of Ru
complex used in the dye-sensitized solar cells is very less.

4. Good potential for colorful, adaptable consumer products: Colorful and transparent solar cells
can be made using various kinds of dyes, depending on the use of the cell.

5. Low potential for environmental pollution: The TiO2, dyes, and iodine used in the dye-
sensitized solar cells are nontoxic. The only component that could potentially cause harm is the
organic solvents used in the electrolyte solution. Future research should be directed toward
developing a solid-state electrolyte.

6. Good recyclability: The organic dye photosensitizers adsorbed on the electrode can be
removed by washing the electrode with alkali solutions or combustion, providing recyclability of
the dye-sensitized solar cells.
Nanomaterials
Properties

High electrical conductivity

Semi metal/zero gap semiconductor

High electron mobility • Mechanical properties

One of the strongest material – Ultimate tensile strength is 130GPa (0.4 GPa-Steel)
Very light – High surface area to volume ratio.

High elastic properties too (Young’s modulus – 0.5TPa)

Applications of Graphene

Graphene is a one-atom-thick sheet of carbon atoms arranged in a honeycomb-like pattern.

Graphene is considered to be the world's thinnest, strongest and most conductive material - to

both electricity and heat. All this properties are exciting researchers and businesses around the

world - as graphene has the potential the revolutionize entire industries - in the fields of

electricity, conductivity, energy generation, batteries, sensors and more.

1. Mechanical strength: Graphene is the world's strongest material, and so can be used to

enhance the strength of other materials. Researchers have demonstrated that adding even a trade

amount of graphene to plastics, metals or other materials can make these materials much

stronger. Such graphene-enhanced composite materials can find uses in aerospace, building

materials, mobile devices, and many other applications.

2. Thermal applications: Graphene is the world's most conductive material to heat. As graphene

is also strong and light, it means that it is a great material to make heat-spreading solutions, such

as heat sinks. This could be useful in both microelectronics (for example to make LED lighting

more efficient and longer lasting) and also in larger applications - for example thermal foils for

mobile devices.

3. Energy storage: Because graphene is the world's thinnest material, it is also the material with

the highest surface-area to volume ratio. This makes graphene a very promising material to be

used in batteries and supercapacitors. Graphene may enable devices that can store more energy -

and charge faster, too. Graphene can also be used to enhance fuel-cells. Graphene can be
incorporated into both the anode or the cathode in various battery systems to increase the

efficiency of the battery and improve the charge/discharge cycle rate. The excellent electrical

conductivity, surface area and dispersibility of graphene enhances the beneficial properties

present in many traditional inorganic-based electrodes, whilst simultaneously relieving the

electrodes of their limitations. Due to its versatile nature, graphene has been incorporated into

lithium-ion batteries, lithium-sulphur batteries, supercapacitors and fuel cells, of which there are

multiple variations of each available on the market today.

4. Sensors: The ideal sensor is able to detect minute changes in its surrounding environment.

Because of the planar and consitent arrangement of atoms in a graphene sheet, every atom within

the sheet is exposed to the surrounding environment. This allows graphene to effectively detect

changes in its surroundings at micrometer dimensions, providing a high degree of sensitivity.

Graphene is also able to detect individual events on a molecular level. Many of graphenes

properties are beneficial in sensor applications; as such, graphene could be used in sensors in

various fields including bio-sensors, diagnostics, field effect transistors, DNA sensors and gas

sensors, to name a few.

5. Catalyst support: Even though the surface of graphene is planar and uniform, like any other

material in existence it is subject to intrinsic defects. Catalysts in the form of metal ions can sit in

these cavities and be supported. In addition to providing mechanical support, the excellent

charge carrier ability of graphene assists the charge transfer reactions involving the catalyst.

Graphene is also inert and does not interfere (in a negative way) with the interaction between the

catalyst and the substrate materials. Graphene also provides an even disperision of catalyst

particles, so the catalyst-substate reaction is consistent across the whole support.

6. Graphene-polymer composite materials: Graphene can be incorporated into polymeric

materials to form graphene-polymer composite materials. As many polymeric materials suffer

from strength-related problems, the incorporaton of graphene can help to increase the tensile

strength of the polymers, increasing the shelf life of the polymeric material in commercial

applications. Incorporating graphene into polymers can also give polymers electrical

conductivity properties.

7. Functional inks: Graphene can be used in functional inks for electronic, heat resistant and

anti-corrosion purposes. By incorporating graphene into ink formulations, the conductivity

properties associated with graphene influence the ink, causing it to become conductive. The inks

can then be used to coat electronics. Compared to other conducting inks, graphene is non-toxic,

environmentally friendly, cheaper, quick-drying and recyclable. Graphene also has a high

thermal stability, making it an ideal for heat resistant ink coating in electronic applications that

produce large amounts of heat. It is also an ink of choice when processing temperatures need to

be high, as the graphene won’t break down during the manufacturing process. Graphene also

exhibits excellent chemical stability and is inert. For applications where environmental factors

are an issue, graphene inks can provide a stable barrier to protect materials from chemicals and

corrosion.

8. Graphene filtration: Graphene oxide membranes are capable of forming a perfect barrier

when dealing with liquids and gasses. They can effectively separate organic solvent from water

and remove water from a gas mixture to an exceptional level. They have even been proved to

stop helium, the hardest gas to block.

9. Biomedical applications: Graphene applications in biomedicine are numerous and can be

classified into several main areas: transport (delivery) systems, sensors, tissue engineering and

biological agents (for example antimicrobials).

10. Coatings: By combining graphene with paint, a unique graphene coating is formed which

could signal the end of the deterioration of ships and cars through rust. The same technique could

also by applied to brick and stone to weatherproof houses, or even to food packaging to stop the

transfer of water and oxygen molecules which causes food to go off.

Synthesis of Graphene:

In recent years, various techniques have been established for graphene

synthesis. However, mechanical cleaving (exfoliation), chemical exfoliation,
thermal chemical vapour deposition (CVD), and Epitaxial Growth of Graphene
on SiC are the most commonly used methods today.

Mechanical cleaving (exfoliation)

Mechanical exfoliation is may be the rarest and eminent process for extracting single layer

graphene flakes on preferred substrates. It is the first recognized method of graphene synthesis.

This is a top-down technique in nanotechnology, by which a longitudinal or transverse stress is

created on the surface of the layered structure materials. Graphite is formed when mono-atomic

graphene layers are stacked together by weak van der Waals forces. The interlayer distance is

3.34 Å. For mechanical cleaving, approx. 300 nN/μm2 external force is required to separate one

mono-atomic layer from graphite. Stacking of sheets in graphite is the result of overlap of
partially filled p orbital perpendicular to the plane of the sheet (involving van der Waals forces).

Exfoliation is the reverse of stacking; owing to the weak bonding and large lattice spacing in the

perpendicular direction compared to the small lattice spacing and stronger bonding in the

hexagonal lattice plane. Graphene sheets of different thickness can indeed be obtained through

mechanical exfoliation or by peeling off layers from graphitic materials such as highly ordered

pyrolytic graphite (HOPG), single-crystal graphite, or natural graphite.

Process:

A fresh piece of Scotch tape is taken (about six inches long).

The adhesive side is pressed onto the HOPG (Highly Ordered Pyrolytic Graphite) for about ten

seconds.

The tape is gently peeled away with thick shiny layers of graphite attached to it.

The part of the tape with layers from the HOPG was refolded upon a clean adhesive section of

the same piece of the tape and then the tape is unfolded.

This process is repeated several times until the end of the tape is no longer shiny but becomes

dark/dull and grey.

These graphite layers on the tape are transferred onto the surface of the Si/SiO2 wafers by gently

pressing them onto the tape for some time and then peeling off.
Figure: Mechanical Exfoliation (a) Adhesive tape is pressed onto the HOPG. (b) The tape is
peeled off when some layers stick to the surface. (c) This tape is pressed onto the surface of the
target substrate. (d) The tape is peeled off when the layers stick to the target surface.

Mechanical Exfoliation Advantages: • Safe and simple process. • Few layer graphene
can be easily obtained. • The chances of impurity in the graphene so obtained are less. •
Sample preparation is simplified.

Limitations: • Yield obtained may not meet the requirements. • Requires skilled manual
labour. • Despite the fact that tape residue does not seriously affect the quality of the
graphene flake samples, it does make those samples more difficult to find on the
substrate.

Chemical vapour deposition (CVD)

Chemical vapour deposition comprises chemical reaction on which process

molecules are heated and changed to a gaseous state and that is called
precursor. In this CVD process a substrate is diffused on thermally disintegrated
precursors in high temperature. It deposits on thin films, crystalline, solid,
liquid or gaseous precursors on the surface of the substrate. The deposition of
high-quality graphene from CVD process is usually done onto various
transition-metal substrates like as Ni, Pd, Ru, Ir, and Cu. CVD growth of
graphene has been mainly practiced on copper and nickel substrates. Nickel was
the first substrate on which CVD growth of large area graphene was attempted.
In 1966, Ni exposed to methane at T = 900 °C to form thin graphite.

Chemical exfoliation (e.g. Hummers method)

Among all the other methods reported for the preparation of graphite oxide, the Hummers' method is

the most popular one in which KMnO4 and NaNO3 are used as oxidizing agents for the oxidation of

graphite in the presence of concentrated H2SO4, depending on the requirement of the extent of oxygen

functionalities. Graphite is composed of stacked graphene sheets with an interlayer spacing of 3.4 Å

and in the same way, graphite oxide is composed of graphene oxide (GO) sheets stacked with an

interlayer spacing of 8.4 Å. The structure of graphene oxide contains a number of oxygen

functionalities such as hydroxyl, carboxyl, epoxide and carbonyl groups.

Graphene oxide (GO) is electrically insulating and thermally unstable; therefore, to restore its

electrical and thermal properties, its reduction is necessary. The term “reduced graphene” is used

because the complete reduction of graphene oxide to graphene does not occur. Thermal exfoliation

and reduction of graphite oxide to thermally reduced graphene oxide (TRG) can be achieved by the

rapid heating of dry graphite oxide for a very short period (30 s) at high temperature (∼1000 °C)

under inert atmosphere. Exfoliation of graphite oxide to GO takes place due to the pressure generated

by the evolved CO2, which occurs due to the decomposition of epoxy, carboxyl and hydroxyl groups

of GO that exceeds van der Waals forces holding GO sheets to each other.
Epitaxial Growth of Graphene on SiC

Epitaxial means upper ordered layer

Sublimation of SiC (Silicon carbide) in comparison with other methods is a technique that has
been developed for the simple fabrication of large-area, low-defect-density graphene films
directly on a semiconducting substrate. The growth of epitaxial graphene on SiC is based on
thermal decomposition of the SiC substrate.

When SiC substrates are annealed at high temperatures, Si atoms selectively desorb from the
surface and the C atoms left behind naturally form few-layer graphene. Because SiC is a wide-
band-gap semiconductor, few-layer graphene on SiC can serve as a graphene substrate for
electronics applications. SiC wafer technology is advancing rapidly in terms of production cost
and scale, and our results to date indicate that the thermal decomposition method is indeed
suitable for large-scale few-layer graphene fabrication. Thermal treatment of SiC at 1300 ℃
under vacuum, sublimation of the silicon atoms occurred, carbon-enriched surface
reorganization and graphitization takes place.

Advantages: • High quality graphene. • Easy method for growing single crystals of
graphene. • The layers of graphene can be controlled conveniently. • Higher
temperatures ensure reproducible, clean and ordered graphene. • Patterning of
graphene is easier due to the use of insulating SiC substrate. • Further advantage is
that SiC is already a large bandgap semiconductor already used in electronic
applications.
Quantum dots

Nanoscience is the study of novel phenomena and properties of materials that occur at

extremely small length scales, typically on the nanoscale that is the size of atoms and

molecules. Nanotechnology is the application of nanoscience and engineering to produce novel

materials and devices

Quantum dots (QDs) are tiny semiconductor particles a few nanometres in size, having optical

and electronic properties that differ from larger light-emitting diode (LED: a semiconductor

light source that emits light when current flows through it) particles. They are a central theme

in nanotechnology. Many types of quantum dot, when excited by electricity or light, emit light

at frequencies that can be precisely tuned by changing the dots' size, shape and material,

enabling numerous applications.

An important parameter of a semiconductor material is the width of the energy gap that

separates the conduction from the valence energy bands (Figure 1, left). In semiconductors of

macroscopic sizes, the width of this gap is a fixed parameter, which is determined by the

material’s identity. However, the situation changes in the case of nanoscale semiconductor

particles with sizes less than ~10 nm (Figure 1, right). This size range corresponds to the

regime of quantum confinement for which electronic excitations “feel” the presence of the

particle boundaries and respond to changes in the particle size by adjusting their energy

spectra. This phenomenon is known as the quantum size effect, whereas nanoscale particles

that exhibit it are often referred to as quantum dots (QDs). In addition to increasing energy

gap, quantum confinement leads to a collapse of the continuous energy bands of the bulk
material into discrete, “atomic” energy levels. These well-separated QD states can be labelled

using atomic-like notations (1S, 1P, 1D, etc.), as illustrated in Figure 1.

Figure 1
In any case, as a result of quantization, for decreasing QD sizes, the HOMO level shifts

downward in the potential energy scale, while the LUMO level shifts upward. Obviously, this

leads not only to an increase in the band gap but also to an increase in the driving force for

electron and hole injection into the surrounding phases.

Since their discovery (or one might rather call “first synthesis”) approximately 10 years ago,

carbon quantum dots (first identified as “carbon nanoparticles”, but later adopted the term

“Carbon-Dots”, evoking similarities to the widely studied inorganic “quantum dots”) and their

structurally related cousins graphene quantum dots (abbreviated “GQDs”) have attracted

significant and growing interest in both scientific and technology circles.

The first report on the production of Carbon-Dots, quite tellingly, featured an almost

“accidental” discovery of fluorescent carbon nanoparticles through an unrelated synthetic

pathway—a byproduct in arc-discharged soot generated for the synthesis of carbon nanotubes.

Analysis of the “fluorescent carbon” as these particles were initially termed indicated that they

comprised of very small, nanometer scale, particulates of carbonaceous material, concluded to

be small carbon nanotube fragments. Fluorescent “carbon nanocrystals” were produced, in fact,

as side products in other carbon nanotube preparations, and also upon further chemical

processing of nanotube samples—both multiwall carbon nanotubes (MWCNTs) as well as

single-wall nanotubes (SWNTs) (see Fig. 2).

While those studies detected Carbon-Dots as a side-product of carbon nanotubes, the

realization that the “fluorescent carbon” contained new carbon nanostructures has attracted

growing interest and led to research aimed at specific synthesis of the new carbon
nanoparticles, later termed “carbon quantum dots.” Early synthesis procedures mostly used

“brute-force” experimental schemes, using high energy impact upon a carbon source thereby

generating the fluorescent carbon nanoparticles. Later studies laid the groundwork for more

broadly applicable strategies of Carbon-Dot synthesis.

Synthesis 1. A representative early example of a brute force approach to construct Carbon-Dots

was through laser ablation. Laser ablation has been routinely used to produce inorganic

nanoparticles from solid substrates; the high energy delivered by the laser beam causes

ablation, or removal, of particulates from the target solid substrate, and the substances thus

removed have been often found to exhibit nanoscale dimensionalities. This phenomenon was

also the case in one of the first direct demonstrations of Carbon-Dots. The high-temperature

treatment of a graphite powder/cement mixture and then applied laser ablation (using the

widely employed Nd:YAG laser) resulted in carbon target. High temperature (900 °C) was also

required to generate the carbon nanoparticles.

Synthesis 2. Numerous carbon-containing substrates have been successfully utilized as

building blocks for construction of Carbon-Dots, including organic solvents, various

saccharides, amino acids, proteins, and others. Notably, the underlying feature in most Carbon-

Dot preparation schemes is the proposition that formation of the graphitic nanoparticles is

thermodynamically (and/or kinetically) favored, regardless of carbon precursor used.

Following Figure depicts a laser-based scheme for production of Carbon-Dots using toluene—

a common organic solvent—as the carbon precursor. The preparation scheme relied on

irradiating the toluene sample with non-focused pulsed laser—different than the high power

laser irradiation employed in ablation process. Irradiation by the non-focused laser beam
appeared to have induced transformation of toluene into graphene sheaths, which subsequently

produced fluorescent Carbon-Dots. The researchers also achieved certain tuning of the Carbon-

Dots sizes through modulating the laser power.

Synthesis 3. Electrochemical methodologies have been also demonstrated for Carbon-Dot

synthesis, for example, utilized graphite electrodes as carbon source. Specifically, the

researchers employed graphite rods as both cathode and anode in an electrochemical cell setup,

with NaOH/ethanol as the electrolyte solution. Passage of current through the electrochemical

circuit resulted in “chipping” of the graphite rods, producing Carbon-Dots exhibiting different

colors (i.e., luminescence wavelengths). While the Carbon-Dots generated in this experiment

did not possess uniform spherical morphologies.

In following figure, the preparation of graphene quantum dots (GQDs) by an easy

electrochemical exfoliation method is shown, in which two graphite rods are used as

electrodes.

Synthesis 4: A typical solution-based strategy (wet chemistry) was utilized for the synthesis of

Carbon-Dots. The process was based upon inserting the carbon source (phenol/formaldehyde

resin) within porous silica colloids acting as host matrix. A high-temperature carbonization
process (e.g., pyrolysis) generated Carbon-Dots which were subsequently released through

dissolution of the silica scaffold (support or platform); further surface passivation of the dots

gave rise to the typical luminescence properties. While pyrolysis was the main driving force

for Carbon-Dot production, the porous silica carriers were instrumental in preventing

aggregation of the nanoparticles.

Synthesis 5: Carbon soot, generated in numerous carbon-processing reactions, has been found

to be a useful precursor substance for Carbon-Dots. For example, soot produced by candle

burning could be a source of Carbon-Dots, generated simply through refluxing the soot in a

strong acid (such as nitric acid), followed by size separation of the smaller nanoparticles. The

strong oxidation properties of the acid were crucial for dissolution of large carbon aggregates

in the soot; the acid further reacted with the carbon colloids to produce the oxygen- and
nitrogen-containing surface defects associated with the fluorescence emission of the particles.

Such soot-based techniques, however, yielded Carbon-Dots exhibiting relatively low

brightness (e.g., low quantum yield), likely because of the large particles produced and the

broad size distribution.

Potential applications of quantum dots

Tuning the size of quantum dots is attractive for many potential applications. For instance,

larger quantum dots have a greater spectrum-shift towards red compared to smaller dots, and

exhibit less pronounced quantum properties. Conversely, the smaller particles allow one to

take advantage of more subtle quantum effects.

1. In modern biological analysis, various kinds of organic dyes are used. However, as

technology advances, greater flexibility in these dyes is sought. To this end, quantum dots have

quickly filled in the role, being found to be superior to traditional organic dyes on several

counts, one of the most immediately obvious being brightness (owing to the high extinction

coefficient combined with a comparable quantum yield to fluorescent dyes) as well as their

stability (allowing much less photobleaching). It has been estimated that quantum dots are 20

times brighter and 100 times more stable than traditional fluorescent reporters. Quantum dots

can have antibacterial properties similar to nanoparticles and can kill bacteria in a dose-

dependent manner. The use of quantum dots for highly sensitive cellular imaging has seen

major advances.

The use of quantum dots for tumor targeting under in vivo conditions employ two targeting

schemes: active targeting and passive targeting. In the case of active targeting, quantum dots

are functionalized with tumor-specific binding sites to selectively bind to tumor cells. Passive

targeting uses the enhanced permeation and retention of tumor cells for the delivery of

quantum dot probes. Fast-growing tumor cells typically have more permeable membranes than

healthy cells, allowing the leakage of small nanoparticles into the cell body.
2. The tunable absorption spectrum and high extinction coefficients of quantum dots make

them attractive for light harvesting technologies such as photovoltaics. Quantum dots may be

able to increase the efficiency and reduce the cost of today's typical silicon photovoltaic cells.

3. Several methods are proposed for using quantum dots to improve existing light-emitting

diode (LED) design, including "Quantum Dot Light Emitting Diode" (QD-LED or QLED)

displays and "Quantum Dot White Light Emitting Diode" (QD-WLED) displays. Because

Quantum dots naturally produce monochromatic light, they can be more efficient than light

sources which must be color filtered.

4. Quantum dots are valued for displays because they emit light in very specific gaussian

distributions. This can result in a display with visibly more accurate colors. A conventional

color liquid crystal display (LCD) is usually backlit by fluorescent lamps (CCFLs) or

conventional white LEDs that are color filtered to produce red, green, and blue pixels.

Quantum dot displays use blue-emitting LEDs rather than white LEDs as the light sources. The

converting part of the emitted light is converted into pure green and red light by the

corresponding color quantum dots placed in front of the blue LED or using a quantum dot

infused diffuser sheet in the backlight optical stack.

5. Quantum dot photodetectors (QDPs) have potential applications in surveillance, machine

vision, industrial inspection, spectroscopy, and fluorescent biomedical imaging.

6. Quantum dots also function as photocatalysts for the light driven chemical conversion of

water into hydrogen as a pathway to solar fuel.