Carbon

• Carbon is an element that exists in various polymorphic forms, as

wellll as iin th
the amorphous
h fform
• This group of materials does not really fall within any one of the
traditional metal, ceramic, or polymer classification schemes
• However, one of these materials, graphite, is sometimes classified as
a ceramic, and the crystal structure of diamond, another polymorph, is
ssimilar
a to
o that
a oof zinc
cbblende
e de

Diamond
• Diamond
Di d iis a metastable
t t bl carbon
b polymorph
l h att room ttemperature
t and
d
atmospheric pressure
• The unit cell is shown in the figure
• Each carbon atom bonds to four other carbon atoms, and these
bonds are totally covalent
y
• This is called diamond cubic crystal structure
• This is also found for other Group IVA elements (e.g., germanium,
silicon and gray tin below 13oC)
Diamond (continued…)
• The physical properties of diamond make it an extremely attractive material
• It is extremely hard (one of the hardest materials) and has a very low electrical conductivity
y
• These characteristics are due to its crystal structure and the strong
g interatomic covalent bonds
• Furthermore, it has an unusually high thermal conductivity for a non-metallic material, is
optically transparent in the visible and infrared regions of the electromagnetic spectrum, and has
a high index of refraction
• Relatively large diamond single crystals are used as gemstones
• Industrially diamonds are utilized to grind or cut other softer materials
• Techniques to produce synthetic diamonds have been developed, beginning in the mid-1930s,
g
that have been refined to the degree that today
y a large
g pproportion
p of the industrial-quality
q y
materials are synthetic; in addition, some of those of gem quality
• Over the last several years, diamond in the form of thin films has been produced
• Film growth techniques involve vapor-phase chemical reactions followed by the film deposition
• Maximum film thicknesses are on the order of a millimeter
• Furthermore,
Furthermore none of the films yet produced has the long
long-range
range crystalline regularity of natural
diamond
Diamond (continued…)
• The diamond is polycrystalline and may consist of very small and/or relatively large grains
• In addition, amorphous carbon and graphite may be present
• A scanning electron micrograph of the surface of a diamond thin film is shown in the following
fifigure
Diamond (continued…)
• The mechanical, electrical, and optical properties of diamond films approach those of
the bulk diamond material
• These desirable properties have been and will continue to be exploited so as to
create new and better products
• For example, the surfaces of drills, dies, bearings, knives, and other tools have been
coated with diamond films to increase surface hardness
• Some lenses and radomes have been made stronger while remaining transparent by
the application of diamond coatings
• Coatings have also been applied to loudspeaker tweeters and to high-precision
micrometers
• Potential applications for these films include application to the surface of machine
components such as gears, to optical recording heads and disks, and as substrates
for semiconductor devices
Graphite
• Another polymorph of carbon is graphite
• It has a crystal structure distinctly from that of diamond and is
also more stable than diamond at ambient temperature and
pressure
• The graphite structure is composed of layers of hexagonally
g carbon atoms
arranged
• Within the layers, each carbon atom is bonded to three
coplanar neighbor atoms by strong covalent bonds
• The fourth bonding electron participates in a weak van der
Waals type of bond between the layers
• As a consequence of these weak interplanar bonds
bonds,
interplanar cleavage is facile, which gives rise to the excellent
lubricative p
properties
p of g
graphite
p
Graphite
• Also, the electrical conductivity is relatively high in
crystallographic directions parallel to the hexagonal sheets
Graphite (continued…)
• Other desirable properties of graphite include high strength and good chemical stability at
elevated temperatures and in oxidizing atmospheres, high thermal conductivity, low coefficient of
thermal expansion and high resistance to thermal shock, high adsorption of gases, and good
machinability
hi bilit
• Graphite is commonly used:
g elements for electric furnaces
o as heating
o as electrodes for arc welding
o in metallurgical crucibles
o in casting molds for metal alloys and ceramics
o for high-temperature refractories and insulations
o in rocket nozzles
o in chemical reactor vessels
o for electrical contacts,, brushes and resistors
o as electrodes in batteries
o in air purification devices
Fullerenes
• Another polymorphic form of carbon was discovered in 1985
• It exists in discrete molecular form and consists of a hollow
spherical cluster of sixty carbon atoms, a single molecule denoted
as C60
• Each molecule is composed of groups of carbon atoms that are
g
bonded to one another to form both hexagons ((six-carbon atom))
and pentagons (five-carbon atom) geometrical configurations,
resembling a soccer ball
• One such molecule (shown in the figure) contains 20 hexagons
and 12 pentagons, which are arranged such that no two
pentagons share a common side
• The material composed of C60 molecules is known as
buckminsterfullerene,, named in honor of R. Buckminster Fuller,,
who invented the geodesic dome
• Each C60 is simply a molecular replica of such a dome, which is
often referred to as a buckyball for short Buckminsterfullerene
Fullerenes (continued…)
• The term fullerene is used to denote the class of materials that are composed of this type of
molecule
• Diamond and graphite are what may be termed network solids, in that all of the carbon atoms
f
form primary
i bonds
b d with
ith adjacent
dj t atoms
t throughout
th h t the
th entirety
ti t off the
th solid
lid
• By way of contrast, the carbon atoms in buckminsterfullerene bond together so as to form these
p
spherical molecules
• In the solid state, the C60 units form a crystalline structure and pack together in a face-centered
cubic array
• As a pure crystalline solid, this material is electrically insulating
• However, with proper impurity additions, it can be made highly conductive and semiconductive
Carbon nanotubes
• Another molecular form of carbon has recentlyy been discovered that has some
unique and technologically promising properties
• Its structure consists of a single sheet of graphite, rolled into a tube, both ends are
capped with C60 fullerene hemispheres
• This carbon nanotube is schematically represented in the following figure
• Each nanotube is a single molecule composed of millions of atoms
• The length of this molecule is much greater (on the order of thousands of times
greater) than its diameter
• Multiple-walled carbon nanotubes consisting of concentric cylinders have also been
found to exist.
Carbon nanotubes (continued…)
• Diameter less than 100 nm
• Extremely strong, stiff and ductile
• Single
Single-walled
walled nanotubes have tensile
strength between 50 and 200 GPa. This is
the strongest known material
• Elastic
El ti modulus
d l isi off th
the order
d off 1000 GP
GPa
• Fracture strain is between 5 and 20%
• Low density
• “Ultimate fiber” and suitable for making
composite materials
• Electrical conductivity depends on the
orientation of the hexagonal units of the
graphene plane (i (i.e.,
e tube wall) with the tube
axis
• Can be a metal or a semiconductor
• Can be used to make flat-panel TV and
computer monitors
Crystallinity of polymers

• Polymer crystals are made of packings of molecular

chains to produce an ordered atomic array

• As a consequence of their size and complexity, polymers

are often p
partially
y crystalline
y ((semi-crystalline)
y ) having
g
crystalline regions dispersed within the remaining
amorphous material

• Any chain disorder or misalignment results in an

amorphous region

• Twisting,
g, kinking
g and coiling
g of chains p
prevent strict
ordering of every segment of every chain

• Degree of crystallinity may range from completely

amorphous to up to 95% crystalline

• Metal specimens are almost always crystalline whereas,

manyy ceramics are either totallyy crystalline
y or totally
y
noncrystalline

• Density of a crystalline polymer is greater than an Unit cell of polyethylene

amorphous one of the same material and molecular weight
since the chains are more closely packed together for the
crystalline structure
• The degree
g of crystallinity
y y depends
p on the rate of cooling
g during
g its solidification

• During crystallization upon cooling through the melting temperature, the chains,
g y random and entangled
which are highly g in the viscous liquid,
q , must assume an
ordered configuration

g themselves
• Sufficient time must be allowed for the chains to move and align

• Molecular chemistry and chain configuration also influence the ability of a

polymer
p y to crystallize
y

• Crystallization is not favored in polymers that are composed of chemically

complex
p repeat
p units ((e.g.,
g p polystyrene)
y y )

• Crystallization easily occurs in chemically simple polymers such as polyethylene

even for rapid cooling rates

• Crystallization easily occurs in linear polymers because there are few restrictions
to prevent chain alignment
• Side branches interfere with crystallization such that branched polymers never
are highly crystalline. Excessive branching may prevent crystallization
whatsoever
• Most network and cross-linked polymers are almost totally amorphous
because the cross-links prevent the polymer chains from rearranging and
aligning into a crystalline structure
• Crystalline polymers are usually stronger and more resistant to dissolution and
softening by heat
Polymer crystals

• A semi-crystalline
i t lli polymer
l consists
i t off smallll crystalline
t lli regions
i kknown as crystallites
t llit
• Each crystallite has a precise alignment, which are interspersed with amorphous regions
composed of randomly oriented molecules
• The structure of the crystalline regions may be deduced by examination of polymer single
crystals which may be grown from dilute solutions
y
• These crystals are regular
g shaped,
p , thin p
platelets or lamellae,, approximately
pp y 10 – 20 nm thick
and approximately 10 m long
• Sometimes they form multilayered structure as shown in the figure above
Polymer crystals (continued…)

• The molecular chains within each platelet fold back and forth on
themselves, with folds occurring at the faces. This structure is called chain-
folded model
• Each platelet will consist of a number of molecules
Polymer crystals (continued…)

• Many bulk polymers that are crystallized from

a melt are semicrystalline and form a
spherulite structure
• Each spherulite may grow to be roughly
spherical in shape
• The spherulite consists of an aggregate of
ribbon-like
ibb lik chain-folded
h i f ld d crystallites
t llit (l(lamellae)
ll )
approximately 10 nm thick that radiate outward
from a single n
nucleation
cleation site in the center
• Tie-chain molecules act as connecting links
between adjacent lamellae and they pass
through the amorphous regions
Polymer crystals (continued…)

• As the crystallization of a spherulite structure nears completion, the extremities of adjacent

spherulites
h lit b begin
i tto iimpinge
i on one another
th fforming
i more or lless planar
l b
boundaries
d i
• Prior to this time, they maintain spherical shape
• Spherulites are considered to be the polymer analogue of grains in polycrystalline metals
and ceramics
• Each spherulite is really composed of many different lamellar crystals and some
p
amorphous material
• Polyethylene, polypropylene, poly(vinyl chloride), polytetrafluoroethylene, and nylon form a
spherulite structure when they are crystallized from the melt
Diffraction
• Diffraction occurs when a wave encounters a series of regularly spaced obstacles
that (i) are capable of scattering the wave, and (ii) have spacings that are comparable
in magnitude to the wavelength
• Diffraction is a consequence of specific phase relationships established between
two or more waves that have been scattered by the obstacles
• Two waves are scattered in such a way that they traverse same or different paths
• The phase relationship between the scattered waves depends upon the difference
in path length
• One possibility is that the path length difference is an integral number of
wavelengths
• If the scattered waves mutually reinforce or constructively interfere with one
another, the amplitudes
p are added
• This is a manifestation of diffraction, and we refer to a diffracted beam as one
composed of a large number of scattered waves that mutually reinforce one another
Diffraction (continued…)
Diffraction (continued…)

• Other phase relationships are possible between scattered waves that will not lead
to this mutual reinforcement
• The other extreme is where the path length difference after scattering is some
integral number of half wavelengths
wavelengths. The scattered waves are out of phase
• The corresponding amplitudes cancel one another or destructively interfere
• The resulting wave has zero amplitude
• Phase relationships intermediate between these two extremes exist, resulting in
only partial reinforcement
X-Ray diffraction and Bragg’s law
• X-rays
X rays are a form of electromagnetic radiation that have high energies and short
wavelengths
• The wavelengths are of the order of atomic spacing of the solids
• When a beam of X-rays impinges on a solid material, a portion of this beam will be
scattered in all directions by the electrons associated with each atom that lies within
the beam’s path
X-Ray diffraction and Bragg’s law (continued…)
• Consider two p planes of atoms AA and
parallel p
BB as shown in the figure
• These planes have the same h, k, and l Miller
indices and are separated by the interplanar
spacing dhkl
• Assume
Ass me that a parallel
parallel, monochromatic
monochromatic, and
coherent (in-phase) beam of x-rays of wavelength 
is incident on these two p g 
planes at an angle
• Two rays in this beam, labeled 1 and 2, are
scattered by atoms P and Q
• Constructive interference of the scattered rays 1
and 2 occurs also at an angle  to the planes, if the
path length difference between 1
1P1
P 1 and 2
2Q2
Q 2
(i.e., SQ + QT) is equal to a whole number, n, of
g
wavelengths
X-Ray diffraction and Bragg’s law (continued…)
• The condition for diffraction is,

n  SQ  QT
 d hkl sin   d hkl sin 
 2d hkl sin 

• This equation is known as Bragg’s law

• The order of reflection is n, which can be any integer such as 1, 2, 3, …
• The magnitude of sin  will not exceed unity
• This
Thi iis th
the expression
i relating
l ti ththe wavelength
l th off x-ray to
t interatomic
i t t i spacing
i and
d
the angle of diffracted beam
• For crystal structures that have cubic symmetry
symmetry,

a
d hkl 
h2  k 2  l 2
X-Ray diffraction and Bragg’s law (continued…)

• If the Bragg’s law is not satisfied

satisfied, then the interference will not be constructive in
nature so as to yield a very low-intensity diffracted beam
• Bragg
Bragg’s
s equation is a necessary but not sufficient condition for diffraction by real
crystals
• It specifies when diffraction will occur for unit cells having atoms positioned only at
the cell corners
• However, atoms situated at the other sites, e.g., face and interior unit cell positions
as with BCC and FCC act as extra scattering centers, which can produce out-of-
phase scattering
p g at certain Bragg
gg angles
g
• The net result is the absence of some diffracted beam that, according to Bragg’s
law, should be present
• For BCC structure, (h + k + l) must be even if diffraction is to occur
• For FCC structure, h, k and l must all be either odd or even
Diffraction techniques
• One common diffraction technique employs a powdered or polycrystalline specimen
consisting of many fine and randomly oriented particles that are exposed to
monochromatic x-radiation
x radiation
• Each powder particle or grain is a crystal, and having a large number of them with
random orientations ensures that some p
particles are p
properly
p y oriented such that
every possible set of crystallographic planes will be available for diffraction
• Diffractometer is used to determine the angles at which diffraction occurs for
powdered specimens
• A specimen S in the form of a flat plate is
supported so that rotation about the axis
labeled O is possible
• This axis is perpendicular to the plane of the
slide
• The monochromatic x-ray beam is generated
at point T
• The intensities of diffracted beams are
detected with a counter C
• The specimen, x-ray source, and counter are
p
all coplanar
• The counter is mounted on a movable
carriage that may also be rotated about the O
axis
• Its angular position in terms of 2 is marked
on a graduated scale
• A rotation of the specimen through  is
accompanied by a 2 rotation of the counter
• This ensures that the incident and reflection
angles are maintained equal to one another
• The beam is maintained well-defined and
focused
• As the counter moves at constant angular velocity
velocity, a recorder automatically plots
the diffracted beam intensity as a function of 2, which is known as the diffraction
angle,
g which is measured experimentally
p y
• The high-intensity peaks result when the Bragg diffraction condition is satisfied by
some set of crystallographic planes
• Photographic films are also used instead of the counter
• X-ray diffractometry is used for the determination of crystal structure
• The unit cell size and geometry may be resolved from the angular positions of the
diffraction peaks, whereas arrangement of atoms within the unit cell is associated
with the relative intensities of these peaks
• Electron and neutron beams are also used in other type of material investigations
• Crystallographic orientations of single crystals are possible using x-ray diffraction or
Laue photographs
• Other
Oth uses off x-ray include
i l d qualitative
lit ti and
d quantitative
tit ti chemical
h i l id
identifications
tifi ti and
d
the determination of residual stresses and crystal size