CRYSTAL STRUCTURE

KINDS OF SOLIDS
1. Crystalline
▪ Rigid and has long range order
▪ Atoms, molecules or ions occupy specific
positions forming a “lattice structure”
▪ Have flat faces and distinct angles
2. Amorphous
▪ Lack of well-defined arrangement and long-range
molecular order. (e.g. Rubber)

CRYSTALLINE
Crystalline Lattice – arrangement of the particles in Types of Cubic Cells
a crystalline solid o Simple Cubic Cell (SCC) – basic repeating unit
in the array of atoms. Also known as primitive
Crystal Lattice or Lattice Structure – regular three-
cubic cell.
dimensional arrangement of points in space
Unit Cell
o Unit cell is the basic repeating structural unit of a
crystalline solid (showing the pattern)
o Each sphere is called a “lattice point” that
represents an atom, ion, or molecule
o Repeating unit cells forms the “lattice structure”
of a crystalline solid

Seven Crystal Systems (Bravais Lattices) Packing Spheres

o Coordination Number – number of atoms
surrounding an atom in a crystal lattice. Indicates
how tightly the atoms are packed together. The
larger the CN, the more stable and closer the
atoms are to one another
o Simple/Primitive Cubic Cell – 6 CN
o Body-centered Cubic Cell – 8 CN
o Cubic Close-Packed (or FCC) – 12 CN
o Hexagonal Closed Packed – 12 CN
o Holes/Voids – sites where electrons can move
 TYPES OF CRYSTALS
1. Ionic Crystals Liquid Crystals
▪ held together by Coulombic interaction ▪ has properties of conventional liquids and those
(interaction between a + and - charges) of solid crystals
▪ e.g., table salt ▪ e.g., flowing like a liquid but its molecules may be
2. Covalent Network Crystals oriented in a crystal-like way
▪ held together in an extensive three-
dimensional network entirely by covalent
bond (bond between non-metals)
▪ e.g., diamond and graphite
3. Covalent Molecular Crystals
▪ lattice points are occupied by molecules, so
the attractive forces between them are van der
Waals forces and/or hydrogen bonding
▪ e.g., table sugar
4. Metallic Crystals
▪ held together by metallic bond
▪ every lattice point in a metallic crystal is
occupied by an atom of the same metal
▪ metallic crystals are generally body centered
cubic, face centered cubic, or hexagonal close
packed
Types of Crystal and their General Properties
Example:

Additional:
o Ionic – conductor of electricity in aqueous form
o Covalent Network – insoluble in water
METALS
METALLIC BONDING MODELS
There are two metallic bonding models and both
theories account for properties of metals such as
malleability, ductility, and high thermal and electrical
conductivity.
1. Electron-Sea Model
▪ three-dimensional array of metal cations
immersed in a “sea” of delocalized electrons
that are free to move throughout the crystal
▪ delocalized, mobile valence electrons act as an “
electrostatic glue ” that holds the metal cations
together–metallic bonding
PROPERTIES OF METALS
o Good Conductors of Heat and Electricity
▪ Band theory accounts for the electrical
properties of metals, insulators, and
semiconductors.
❖ Conductors are capable of conducting
an electric current.
❖ Semiconductors are elements that
normally are not conductors, but will
conduct electricity at elevated
temperatures or when combined with a
small amount of certain other elements.
❖ Insulators are ineffective conductors of
electricity
▪ The electrical conductivity of a solid
depends on the spacing of the energy bands
and the extent to which they are occupied.
Metallic Character increases
1. Conductors (Metal) – negligible energy.
Metal’s ability to conduct electricity
decreases with increasing temperature.
2. Semiconductor - much smaller gap that of
insulators, less energy needed
3. Insulator - more energy is needed to excite
an electron into the conduction band
2. Band Theory
▪ aka “molecular orbital theory” for metals
▪ atoms are packed closely together, so the
energy levels of each metal atoms are affected
by the immediate neighbors of the atom as a
result of orbital overlaps.
▪ interaction between two atomic orbitals ⟶
molecular orbitals
▪ molecular orbitals are so closely spaced on the
energy scale that they are more appropriately
described as a “band”.
There are 2 types bands:
a. Valance band (lower) – closely spaced
filled energy levels (full of electrons)
b. Conduction band (higher) – closely space
empty energy levels. Empty, delocalized
molecular orbitals formed by the overlap of
the 3p orbitals.
o Lustrous
▪ due to a large cloud of relatively “free”
electrons
▪ When a beam of light is incident on metal
surface, it polarizes the electron cloud which
creates oscillation of electrons that generates
another electromagnetic wave that opposes
the incident radiation
▪ Incident light rays get reflected
o Malleable and Ductile
▪ Toughness is the property that enables a
material to withstand shock and be deformed
without rupturing
▪ Malleability – withstand extensive permanent
deformation from compression; can be
stamped, hammered or rolled into sheets
▪ Ductility – withstand extensive permanent
deformation from tension, can be stretched or
drawn into wire
Metallic Character decreases
 METALLURGY
Metals exist in nature in either the free or
combined state
Free Metals: Au, Pd, Rh, Ru, Os, Ir, Pt
Metallurgy – The science and technology of
extracting metals from their ores. It also includes
making of alloy, a solid metallic solution composed
of two or more elements.
Metallurgical Process
1. Concentration
▪ Ores are concentrated by separating the
mineral from the gangue.
▪ Separation methods include panning for
gold, magnets, flotation, and chemical
treatment (Bayer process and roasting)
2. Reduction
▪ Once an ore has been concentrated, it is
reduced to free metal, either by chemical
reduction or by electrolysis
▪ Free metals do not need reduction
▪ most active metals have the most negative
reduction potentials so they are the most
difficult to reduce
▪ least active metals have the most positive
reductions potentials so they are the
easiest to reduce

Mineral – a naturally
occurring substance
with a range of chemical
composition.
3. Refining or Purification
Ore – metal-containing ▪ include distillation, chemical purification
mineral and electrofining
▪ Mond process – combination of carbon
monoxide with nickel
POLYMERS
Polymer is a substance composed of large repeating numbers of reactive organic units called monomers.

BASED ON SOURCE
A. Natural Polymers
▪ Polymers found in plant and animal matter.
▪ e.g., starch, natural rubber, resins,
carbohydrates, protein, cellulose
B. Synthetic Polymers
▪ Man-made polymers attained through
laboratory or factory polymerization.
▪ e.g., plastics, synthetic rubber, nylon fibers
1. PET/PETE – Polyethylene Terephthalate
[safe for one time use only]
2. HDPE – High Density Polyethylene [safe]
3. V/ PVC – Vinyl or Polyvinyl Chloride
4. LDPE – Low Density Polyethylene [safe]
5. PP – Polypropylene [safe]
6. PS – Polystyrene
7. OTHER – Others, Miscellaneous

C. Semi-Synthetic Polymers
▪ Polymers synthetically derived from cellulose
▪ e.g., cellulose nitrate, rayon

BASED ON CHAIN BACKBONE

A. Organic Polymer B. Inorganic Polymer
▪ chain generally comprises of carbon atoms ▪ chain is not essentially composed of carbon
▪ mostly synthetic polymers atoms
▪ e.g., Polyamides , Polyesters , Polysulphides ▪ e.g., Glass and silicone rubber
(Polydimethylsiloxane)

BASED ON STRUCTURE
A. Linear Polymer C. Cross-linked Polymer
▪ chains are completely straight ▪ composed of monomers of two or three
▪ building block for thermoplastic polymers functional groups
▪ e.g., PVC, HDPE ▪ e.g., Vulcanized rubber, Phenol formaldehyde
B. Branched Polymer (PF)
▪ contain linear branches off the main chain
▪ e.g., LDPE

BASED ON COMPOSITION
A. Homopolymer c. Random Copolymer - chains composed of
▪ chains composed of same single monomer two monomers that follow no particular
order

d. Graft Copolymer - chains of a single

monomer chain (A) branched with a
B. Copolymer monomer chain of a different species (B)
a. Block Copolymer - chains are composed of
two alternating monomers

b. Alternating Copolymer - chains composed

of two monomers in alternating incorporated
groups
 BASED ON MOLECULAR FORCE
A. Elastomers C. Liquid Resins
▪ Cross-links between chains allow elastomers ▪ Viscous liquid polymers that are capable of
to return to their shape permanent hardening through phase change
▪ e.g., e.g. Buna N, neoprene or wetting.
▪ primarily used as adhesives and sealants
D. Plastics
▪ malleable when heated and can be molded
into shape and hardened into rigid or semi-
elastic materials.
▪ plastic’s IMFA are transition of elastomers
and fibers
B. Fibers
a. Thermoplastics - may be melted down to
▪ Solid polymers that innately form into long
be remolded into another form. Weaker
and thin or thread like material
IMFA
▪ have high tensile strength brought by strong
b. Thermosets - may not be remolded.
IMFA’s, particularly hydrogen bonding
Thermoset possess cross linked structures,
▪ e.g., silk, Nylon 6,6, terylene, polyester and
whose IMFA are strong
cotton
BASED ON MODE OF POLYMERIZATION
A. Addition Polymerization B. Condensation Polymerization
▪ formed by repeatedly adding monomers that ▪ formed through repeated condensation
contain double or triple bonds. reactions of two monomers with two or three
▪ e.g., PFTE, PE functional groups.
▪ Involve unsaturated compounds containing
double or triple bonds particularly C=C and
C≡C that participate in a chain reaction
1. Initiation – active species is generated (free
radical, cation, or anion)
2. Propagation – newly generated “active
species” adds to another monomer in the
same manner as in the initiation step.
3. Termination – terminates through reaction
with another growing chain or by the
spontaneous decomposition of the active site.

CLASSIFICATION OF POLYMERS
Stereoisomers of Polymers
o Isotactic – same side of chain
o Syndiotactic – alternate from side to side
o Atactic – random
 CHARACTERISTIC OF POLYMERS
o Properties of plastics can be changed by
reinforcement with various materials, usually
some fibers (cellulose fibers, fiberglass, carbon
fibers, aramid fibers, and metal filaments)
o Engineering plastics are high strength high
performance materials that can be substituted for
many metal uses. It shows better resistance to
wear, impact, and corrosive chemicals and have
excellent electrical properties

APPLICATIONS OF POLYMERS
Resin Type Applications
Construction, auto-repair putty, laminates, skis, fishing rods, boats and aircraft
Polyester
components, coatings, decorative fixtures, bottles
Replacement for metals, safety helmets, lenses, electrical components, photographic film,
Polycarbonates
die casting, insulators
Polyurethanes Insulation, foam inner liners for clothing, rocket fuel binders, elastomers, adhesives
Laminates, adhesives, flooring, linings, propellers, surface coatings, filament wound
Epoxies
structures (rocket cases)
Packaging films and sheets, containers, wire cable insulation, pipe, linings, coatings, molds,
Polyethylene
toys, housewares
Housewares, medical equipment (can be sterilized), appliances, toys, electronic
Polypropylene
components, tubing and pipe, fibers and filaments, coatings
Pipe and tubing, pipe fittings, adhesives, raincoats and baby pants, building panels,
Polyvinyl Chloride
wastepaper baskets, weather stripping, shoes
Decorative and structural panels, massive glazing domes, automotive lens systems,
Acrylics illuminated translucent floor tiles, windows, and canopies, signs, coatings, adhesives and
elastomers
Insulation, pipe, foams, cooling towers, thin-walled containers, appliances, rubbers,
Polystyrene
automotive instruments and panels
Cellulosic Textile and paper finishes, thickening agents, magnetic tapes, packaging, pipe
NANOMATERIALS
NANOMATERIALS
Nanoscale materials are defined as a set of substances where at least one dimension
is between 1 nm and 100 nm (1 nm = 10-9 m).
Classification of Nanomaterials
1. Nanoscale – one dimension (surface films), two
dimensions (strands or fibres), or three
dimensions (particle)
2. Form – single, fused, aggregated or agglomerated
forms with spherical, tubular, and irregular
shapes
3. Dimensions – number of dimensions not
confined to the nanoscale range (<100 nm)
Zero-dimensional Nanomaterials
o ALL the dimensions are measured within the
nanoscale
o Nanoparticles can:
• be amorphous or crystalline
• be single crystalline or polycrystalline
• be composed of single or multi-chemical
elements
• exhibit various shapes and forms
• exist individually or incorporated in a matrix
• be metallic, ceramic, or polymeric
One-dimensional Nanomaterials
o one dimension is outside the nanoscale
o needle like-shaped nanomaterials
o nanotubes, nanorods, and nanowires
o 1-D nanomaterials can be:
• amorphous or crystalline
• single crystalline or polycrystalline
• stand-alone materials or embedded within
another medium
• be metallic, ceramic, or polymeric
Engineered Nanomaterials
o resources that are designed at molecular
(nanometer) level to take advantage of their small
size and novel properties which are not seen in
their conventional, bulk counterparts
Commercial Products that use nanomaterials
o Stain resistant and wrinkle free textiles
▪ nano-treatments used to enhance garments’
usefulness and durability without degrading
the feel of the fabric
o Cosmetics and sunscreens
▪ nanoscale versions of ingredients to provide
better UV protection, deeper skin
penetration, long lasting effects, increased
color and finish quality etc.
▪ Titanium dioxide and zinc oxide -
nanoparticles as UV filters
▪ Nanospheres or nanoemulsions - increases
their penetration into the skin
Two-dimensional Nanomaterials
o two dimensions are outside the nanoscale
o plate-like shaped nanomaterials
o nanofilms, nanolayers, and nanocoatings
o 2-D nanomaterials can be:
• amorphous or crystalline
• made up of various chemical compositions
• used as a single layer or as multilayer
structures
• deposited on a substrate
• metallic, ceramic, or polymeric
Three-dimensional Nanomaterials
o all dimensions are outside the nanoscale
o bulk nanomaterials
o Materials possess a nanocrystalline structure
o In terms of nanocrystalline structure, bulk
nanomaterials can be composed of a multiple
arrangement of nanosized crystals, most typically
in different orientations.
o dispersions of nanoparticles, bundles of
nanowires, and nanotubes as well as
multinanolayers
Nanotechnology
o science of manipulating atoms and molecules in
the nanoscale
o done by controlling shape and size at the
nanometer scale
o Electronics
▪ Nanoelectronics holds some answers for
how we might increase the capabilities of
electronics devices while we reduce their
weight and power consumption
o Paints and varnishes
▪ Nanoparticles added to paints, for example,
render them corrosion resistant and scratch
proof, and can even make them self cleaning
 NANOPARTICLES
▪ Lower melting point, different colors, and greater reactivity than bulk materials
▪ Because a substantial percentage of the atoms in a nanoparticle are on the surface and are therefore bound less
tightly than those within the bulk solid.
Advantages of Nanoparticles:
1. Much larger relative surface per unit of mass
have discrete, quantized energy
o Nanomaterials have a much greater surface Atoms and
levels so electrons are confined
area to volume ratio than their conventional small molecule
to a very small volume
forms, which can lead to greater chemical Have broads of energy levels so
reactivity and affect their strength Solid metals &
electrons are delocalized
2. New quantum effects semiconductors
throughout the entire crystal
o At the nano scale, it is observed of induced For solid nanoparticles, the
changes in optical (photonic), electrical, solid spacing between energy levels
electronic, mechanical, chemical, biological, nanoparticles increases as the size of the
rheological, structural or magnetic particle decreases
properties.

QUANTUM EFFECTS

an electron is confined in o Color is due to electronic transitions.

3-D space. No electron
0-D nanomaterials
delocalization (freedom to
move) occurs.
electron confinement
occurs in 2-D, whereas
1-D nanomaterials delocalization takes place
along the long axis of the
nanowire/rod/tube
conduction electrons will
be confined across the
2-D nanomaterials
thickness but delocalized in
the plane of the sheet
o When quantum dots is irradiated with UV light,
an electron is excited from the valence band to
an energy level within the conduction band.
o Subsequently, the electron undergoes a transition
from the bottom of the conduction band to the
top of the valence band.
o This transition produces a visible photon having
an energy roughly equal to the band gap.
o The smaller the particle, the larger the band gap
and the greater the shift in the color of the
emitted light from the red to the violet.

A striking electronic effect is seen

in Quantum Dots
o Quantum dots are semiconductor nanoparticles
that are about 1-10 nm in diameter and contain
only hundreds to tens of thousands of atoms.
o When quantum dots is irradiated with UV
light, it emits visible light having a wavelength
that depends on the size of the nanoparticle

o Because of their distinctive optical properties,

quantum dots may have numerous applications.
o As fluorescent probes or labels that allow
simultaneous detection tracking and imaging in
color of a number of biomolecules within a cell.
• The surface of quantum dots is modified
by attaching an organic molecule that
targets and bonds to a specific
biomolecule, such as DNA or a protein.
• The modified quantum dots are thousands
of times smaller than human cells and are
able to penetrate cell membranes.
• When they bond to a biomolecule and are
irradiated with UV light, they serve as
fluorescent probes, or labels, for the
particular biomolecule.
 NANOMATERIAL SYNTHESIS AND PROCESSING
o Design and preparation of nanoparticles with
high functionality, i.e. to fabricate nanomaterials
which have the suitable properties for
applications
o The fabrication of nanomaterials of tailored
properties involves the control of size, shape,
structure, composition and purity of their
constituents
1. Top down approach – to disassemble (break
or dissociate) bulk solids into finer, nano-sized
pieces
2. Bottom up approach – to assemble atoms or
molecules together that leads to formation of
clusters, that further come together to form self
assembled monolayers on the surface of
substrate