Basic Concepts of Crystal Structures

Structure of Metals
 • An alloy is a material that contains more than
one element and has the characteristic
properties of a metal.
❑Alloying of metals is a ways of modifying
the properties of pure metallic elements.
For example,
❑Iron involves alloy compositions (for
Alloys example, stainless steel).
❑Bronze is formed by alloying copper and
tin,
❑Brass is an alloy of copper and zinc.
❑Pure gold is too soft to be used in jewelry,
but alloys of gold are much harder
Some Common Alloys
• Recall: Solids that form homogeneous mixtures are called solid solutions.
• Substitutional alloy
❑classification of an alloy when atoms of the solute in a solid solution occupy
positions normally occupied by a solvent atom.
❑the two metallic components have similar atomic radii and chemical-bonding
characteristics
• Interstitial alloy
❑classification of an alloy when the solute atoms occupy interstitial positions in
the “holes” between solvent atoms.
Figure 1. The distribution of solute and solvent atoms in a
substitutional alloy and an interstitial alloy. Both types of
alloys are solid solutions and, therefore, homogeneous
mixtures.
Question:
 Face-Centered Cubic (FCC):
• Aluminum (Al)
• Copper (Cu)
• Gold (Au)
Examples of • Silver (Ag)
Metals with • Lead (Pb)

Crystalline Body-Centered Cubic (BCC):

Structures: • Iron (Fe)

• Chromium (Cr)
• Tungsten (W)

Hexagonal Close-Packed (HCP):

• Magnesium (Mg)
• Titanium (Ti)
• Zinc (Zn)
Solid Solutions Crystalline Structures:

• Gold-copper alloy, molecular model.

• Gold atoms are gold, copper atoms are red.

• The crystal lattice of this alloy has a face

centred cubic (FCC) structure, similar to that
adopted by both copper and gold in their
pure state.

• This can be seen in the unit cell of the

crystal, outlined in blue at lower left.

• A gold atom is found at each vertex of a

cube, with a copper atom in the centre of
each of the cube's faces.
Brass (Copper-Zinc Alloy):

• Brass is a solid solution alloy of copper (Cu)

and zinc (Zn).
• It typically exhibits a face-centered cubic
(FCC) crystal structure.
• The atoms of copper and zinc are randomly
distributed in the crystal lattice, forming a
homogeneous mixture.
• Brass with a high percentage of copper has
a FCC crystal structure, while brass with
more zinc has a BCC crystal structure.
• The FCC crystal structure of brass is like that
of copper with copper atoms on the
corners and center of each face of the unit
cell with zinc atoms between the copper
atoms.
Bronze (Copper-Tin Alloy):

• Bronze is a solid solution alloy of copper (Cu) and tin (Sn).

• The crystal structure of bronze depends on the composition. At
lower tin concentrations, it may have an FCC structure, while at
higher tin concentrations, it may have a body-centered tetragonal
(BCC) structure.
• The solid solution nature of bronze contributes to its desirable
properties, including strength and corrosion resistance.
Stainless Steel (Iron-Chromium-Nickel Alloy):

• Stainless steel is a solid solution alloy primarily composed of iron (Fe),

chromium (Cr), and nickel (Ni), with other elements in smaller amounts.
• The crystal structure of stainless steel depends on the specific composition,
but it often exhibits an FCC structure.
• The addition of chromium enhances corrosion resistance, and nickel
contributes to the stability of the austenitic phase.
Nitinol (Nickel-Titanium Alloy):

• Nitinol is a shape memory alloy composed of nickel (Ni) and titanium

(Ti).
• It typically exhibits a body-centered tetragonal (BCC) structure at low
temperatures and transforms to an austenitic structure at higher
temperatures.
• Nitinol is known for its ability to "remember" its original shape and
return to it when heated.
Polymers
 Polymers • Denoted by molecular substances of high
molecular weight formed by the polymerization
(from the (joining together) of monomers, molecules with
low molecular weight.
Greek polys, • have hundreds to hundreds of thousands of
“many,” and repeat units
meros, • Natural polymers (or biopolymers) created within
organisms
“parts”) ❑Example: wool, leather, silk, and natural
rubber
• Synthetic polymers created in the laboratory
❑many of these synthetic polymers have a
backbone of carbon–carbon bonds because
carbon atoms have an exceptional ability to
form strong stable bonds with one another.
Plastics:
• Plastics are
polymeric solids that
can be formed into
various shapes,
usually by the
application of heat
and pressure.
Several types of
plastics:
Thermoplastics
• can be reshaped.
• For example, plastic milk
containers are made from
the thermoplastic
polymer polyethylene.
• These containers can be
melted down and the
polymer recycled for
some other use.
Thermosetting plastic (also called a
thermoset)
• is shaped through irreversible
chemical processes and,
therefore, cannot be reshaped
readily.
• nylon and polyesters - can be
formed into fibers
‒These fibers can be woven
into fabrics and cords and
fashioned into clothing, tire
cord, and other useful
objects.
Elastomer
•rubbery or elastic behavior.
•regains its original shape upon removal of the
distorting force, if it has not been distorted
beyond some elastic limit
•Example: Rubber
Polymers of
Commercial
Importance
 • depends on various factors, including
the type of polymer, the
Crystallographic arrangement of polymer chains, and
Structure of the processing conditions
Polymers
• The crystallographic structure is
influenced by the arrangement of
polymer chains.
Two Main Types Crystalline Structure:

of • In some polymers, especially those with a regular

Crystallographic and ordered arrangement of polymer chains,
crystalline regions can form.
Structures • The basic repeating unit in the crystalline regions
Associated with is often referred to as a lamella. Lamella consist
of densely packed and ordered polymer chains.
Polymers: • The packing of chains in crystalline regions can be
influenced by factors such as the size and shape
of polymer chains, as well as intermolecular
forces like van der Waals forces and hydrogen
bonding.
• Polyethylene and polypropylene are examples of
polymers that can exhibit crystalline regions.
Amorphous Structure:

• Many polymers also have amorphous

regions, where the polymer chains lack long-
range order. In amorphous regions, the
polymer chains are randomly arranged.
• Amorphous regions contribute to the overall
flexibility and transparency of the polymer.
• The amorphous nature of polymers is
influenced by factors such as molecular
weight, branching, and the presence of side
groups.
• Examples of amorphous polymers include
polystyrene and poly(methyl methacrylate).
Semicrystalline Polymers:
• Some polymers exhibit a combination of
crystalline and amorphous regions, and
they are termed semicrystalline polymers.
• The degree of crystallinity in these
polymers can be controlled by factors
such as processing conditions (cooling
rate, pressure), molecular weight, and the
presence of additives.
• Polyethylene and polypropylene are
common examples of semicrystalline
polymers.
 Polymer Structure:

• Chain Regularity:
Factors that ❑Polymers with more regular and ordered
affect polymer repeating units are more likely to form crystalline
regions.
crystallinity ❑In contrast, polymers with irregular or random
structures tend to have lower crystallinity.
include: • Chain Flexibility: The flexibility of polymer chains also
plays a role.
❑Flexible chains are more likely to adopt a random
coil conformation, reducing the tendency to form
crystalline structures.
❑Rigid or semi-rigid chains, on the other hand, can
more readily align and stack, promoting
crystallinity.
Polymer Structure:

• Molecular Weight:
❑Higher molecular weight polymers often have
a higher tendency to form crystalline regions.
❑Longer chains provide more opportunities for
ordered packing and intermolecular
interactions.

• Branching and Side Groups:

❑The presence of branching or side groups can
disrupt the regular packing of polymer chains,
reducing crystallinity.
❑Linear polymers with minimal branching are
more likely to form crystalline structures.
Intermolecular Forces:

• Van der Waals Forces:

❑ These weak attractive forces between adjacent polymer chains
play a crucial role in polymer crystallinity.
❑ The closer the packing of polymer chains, the stronger the van
der Waals forces.
❑ Polymers with stronger van der Waals forces are more likely to
form crystalline structures.

• Hydrogen Bonding:
❑ If the polymer chains contain functional groups that can form
hydrogen bonds, this can enhance crystallinity.
❑ Hydrogen bonding promotes the alignment of polymer chains,
leading to the formation of crystalline regions.

• Dipole-Dipole Interactions:
❑ Polymers with polar groups can exhibit dipole-dipole
interactions, which contribute to crystallinity.
❑ The alignment of polar groups enhances the regular packing of
chains.
 Examples of 1. Polyethylene (PE):
• Structure: Polyethylene can have a linear or
Crystalline branched structure, and it is composed of
Polymers with repeating ethylene monomer units.
their • Crystalline Structure: Polyethylene often
Structures and exhibits both crystalline and amorphous
regions. The crystalline structure can be
Uses: either low-density polyethylene (LDPE) or
high-density polyethylene (HDPE), depending
on the degree of branching and packing.

• Uses: HDPE is used for containers, pipes, and

packaging materials. LDPE is commonly used
for films, coatings, and flexible containers.
2. Polypropylene (PP):

• Structure: Polypropylene is composed of

repeating propylene monomer units, and it
can have a tactic or isotactic structure.

• Crystalline Structure: Polypropylene is a semi-

crystalline polymer with a predominantly
crystalline structure. Isotactic polypropylene
has a higher degree of crystallinity.

• Uses: Polypropylene is used in packaging

materials, fibers, automotive components,
and medical devices.
3. Polyethylene Terephthalate (PET):

• Structure: Polyethylene terephthalate is

composed of repeating ethylene glycol and
terephthalic acid units.

• Crystalline Structure: PET is a semi-crystalline

polymer with a highly ordered crystalline
structure.

• Uses: PET is commonly used in the

production of beverage bottles, food
containers, and synthetic fibers (e.g.,
polyester).
4. Polyoxymethylene (POM):

• Structure: Polyoxymethylene, also known

as acetal or polyformaldehyde, is
composed of repeating formaldehyde
units.

• Crystalline Structure: POM is a crystalline

polymer with a high degree of
crystallinity.

• Uses: POM is used in engineering

applications, such as gears, bearings, and
other precision components, due to its
high strength, stiffness, and low friction.
5. Polyamide (Nylon):

• Structure: Polyamides, commonly known

as nylon, are composed of repeating
amide (NH-CO) units.

• Crystalline Structure: Nylon is a semi-

crystalline polymer with a combination of
crystalline and amorphous regions.

• Uses: Nylons are used in the production of

fibers, fabrics, and engineering plastics,
known for their strength, abrasion
resistance, and low friction.
Nanomaterials
Crystalline Structures of Engineered Nanomaterials

Nanotechnology

• the science and engineering of nanoscale system, whose

sizes range from 1 to 100 nm
• behave neither like atoms, which are smaller (1x101 nm) , nor
like crystals which are at least 1x105 nm
• For example:
‒5-nm particle has about half of its atoms on its surface
Engineered Nanomaterials:

• Engineered nanomaterials are deliberately designed and

fabricated materials at the nanoscale, often exhibiting
unique properties tailored for specific applications.

• The crystalline structure of engineered nanomaterials is

crucial in determining their properties and
performance.
 Chemical Properties of Nanomaterials

Surface Chemistry:
• High Surface Area: Nanomaterials often have a high surface area-to-volume ratio
due to their small size. This increased surface area can lead to enhanced
reactivity and interactions with surrounding environments.
• Surface Functionalization: The surface of nanomaterials can be modified or
functionalized to introduce specific chemical groups, making them more
compatible with certain applications or enhancing their stability.
Reactivity:
• Enhanced Reactivity: The reactivity of nanomaterials can be higher than that of
bulk materials due to their increased surface reactivity and the presence of
unsaturated surface atoms.
• Catalytic Properties: Some nanomaterials, such as nanoparticles or nanocatalysts,
exhibit catalytic properties, enabling them to accelerate chemical reactions.
Chemical Stability:
• Stability in Different Environments: Nanomaterials may exhibit
different levels of stability in various environments. Some may be
prone to oxidation or degradation, while others can be designed to
be stable under specific conditions.
Electrochemical Properties:
• Electrochemical Reactivity: Nanomaterials, especially those with
high electrical conductivity, such as carbon-based nanomaterials
(e.g., graphene, carbon nanotubes), can display unique
electrochemical properties. This makes them valuable in energy
storage devices, sensors, and electronic applications.
Photophysical Properties:
• Photoactivity: Nanomaterials, like quantum dots and metal
nanoparticles, may exhibit photoactivity, absorbing and emitting
light. This property is employed in applications such as
photovoltaics, sensors, and imaging.

Interaction with Biomolecules:

• Biocompatibility: Nanomaterials designed for biomedical
applications need to be biocompatible. The surface chemistry
influences their interaction with biomolecules, cells, and tissues,
impacting their biocompatibility.
Surface Charge:
• Zeta Potential: The zeta potential, or surface charge, of nanomaterials can affect their
stability and interaction with other particles, surfaces, or biological entities. Charged
nanoparticles may be attracted or repelled by surfaces with opposite or similar charges.

Solubility:
• Solubility Characteristics: Some nanomaterials, particularly nanoparticles, may exhibit
different solubility characteristics compared to their bulk counterparts. This can
influence their dispersion in liquids and biological fluids.

Selective Adsorption:
• Selective Adsorption: Certain nanomaterials can selectively adsorb specific molecules or
ions onto their surfaces, making them useful in purification processes and environmental
remediation.
Examples of Crystalline Structures of Engineered
Nanomaterials

1. Quantum Dots:
• Crystalline Structure: Quantum dots are semiconductor nanocrystals with a crystalline
structure. The most common types include cadmium selenide (CdSe), cadmium sulfide
(CdS), and indium phosphide (InP).
• Applications: Quantum dots are widely used in optoelectronics and bioimaging due to
their size-dependent optical properties, such as tunable fluorescence.

2. Carbon Nanotubes (CNTs):

• Crystalline Structure: Carbon nanotubes have a tubular structure composed of carbon
atoms arranged in a hexagonal lattice. They can have single-walled (SWCNT) or multi-
walled (MWCNT) configurations.
• Applications: CNTs are used in various fields, including nanoelectronics, composite
materials, and nanomedicine, due to their exceptional mechanical, electrical, and
thermal properties.
3. Graphene:
• Crystalline Structure: Graphene is a single layer of carbon atoms arranged in a hexagonal
lattice. It forms the basic structural element of other carbon allotropes like graphite.
• Applications: Graphene has applications in electronics, energy storage, sensors, and
composite materials due to its high electrical conductivity, thermal conductivity, and
mechanical strength.

4. Metal Nanoparticles:
• Crystalline Structure: Metal nanoparticles, such as gold (Au) and silver (Ag)
nanoparticles, typically have a crystalline structure. The size and shape of these
nanoparticles can influence their properties.
• Applications: Metal nanoparticles are used in catalysis, imaging, drug delivery, and
sensing applications due to their unique optical, catalytic, and surface plasmon
resonance properties.
Metal-Organic Frameworks (MOFs):

• Crystalline Structure: MOFs are hybrid materials composed

of metal ions or clusters connected by organic ligands. They
exhibit a highly ordered crystalline structure with pores.

• Applications: MOFs have applications in gas storage,

separation, catalysis, and drug delivery, leveraging their
tunable porosity and surface functionality.
Silica Nanoparticles:

• Crystalline Structure: Silica nanoparticles, often used in

nanomedicine and sensing, can have a crystalline structure
depending on their synthesis method. Mesoporous silica
nanoparticles (MSNs) are an example.

• Applications: Silica nanoparticles find applications in drug

delivery, imaging, and as carriers for biomolecules due to
their biocompatibility and tunable surface properties.
Titanium Dioxide Nanoparticles (TiO2):

• Crystalline Structure: Titanium dioxide nanoparticles commonly

exist in crystalline forms such as anatase or rutile. (Red or Blue)

• Applications: TiO2 nanoparticles are widely used in

photocatalysis, sunscreens, and as a white pigment in paints
due to their photocatalytic and UV-absorbing properties.