GE1717

Introduction to Materials

MATERIALS
Material – [lat. "matter"] any form of matter that constitutes an object

Kinds of Materials
1. Natural material – material made by nature, whether organic or inorganic in nature
2. Synthetic material – material made by man, using both organic and inorganic substances

Synthesis – [grc. "place together"] chemical reaction where two (2) or more substances combine to form
a new complex substance
Catalyst – [grc. "dissolve"] any substance that substantially affects the rate of reaction of materials

Types of Catalysis
1. Positive – catalysts capable of increasing the rate of reaction of materials by lowering the activation
energy required

Figure 1. Positive catalysis graph

Source: http://www.sciencehq.com/wp-content/uploads/positive-catalyst.jpg
2. Negative – a.k.a. inhibitors; catalysts capable of decreasing the rate of reactions by increasing the
required activation energy

Figure 2. Negative catalysis graph

Source: http://www.sciencehq.com/wp-content/uploads/Negative-Catalysts.jpg

Kinds of Catalysts
1. Heterogeneous – a catalyst that exists as a separate material, in a different phase from the reactants,
in the reaction process (e.g. a solid catalyst in a liquid material mixture)
a. Adsorptive – molecules in fluids (adsorbate) bind to a solid or liquid surface (adsorbent)
i. The catalyst is the adsorbent
ii. The reactants are the adsorbates

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b. Surface – the adsorbate's molecules diffuse on the adsorbent's surface initiating reaction, then
desorb (i.e. split away) from the adsorbent
2. Homogeneous – a catalyst that exists as a separate material, in the same phase as the reactants, in
the reaction process (e.g. a liquid catalyst in a liquid material mixture)
a. Acid-base catalysis – material is catalyzed either by an acid (𝐻 + ) or a base (𝑂𝐻 − )
i. Specific acid catalysis – catalysis performed by a specific acid or base
ii. General acid catalysis – catalysis performed by any acid or base
b. Organometallic – material is catalyzed by organometallic compounds
3. Photocatalyst – a catalyst that uses light to activate its catalytic properties
4. Enzymes and biocatalysts – catalysts used for biological processes
5. Nanocatalysts – nanomaterials capable of being catalysts
6. Autocatalyst – a catalyst that is the product of a reaction

Characterizations
1. Metal – [grc. "mine, quarry"] any material that has high thermal and electric conductivity, as well as
forming bonds and cations with nonmetals (Thomas Net, n.d.)
2. Alloy – [fro. "assemble, join", from lat. "bind"] a combination of at least two (2) materials, with one (1)
of these as a metal, whose properties are vastly different from its original form (Chegg Study, n.d.)
3. Ceramic – [grc. "pottery"] any inorganic nonmetallic solid made up of either metal or nonmetal
compounds, primarily used in pottery (Science Learning Hub, n.d.)
4. Nanomaterial – [grc. "dwarf" + material] any chemical substance or material that is manufactured and
used in small-scale settings (European Commission, n.d.)
– a material with any external dimension in the nanoscale (i.e. 1–100 nm) or having an
internal structure or surface structure in the nanoscale (ISO Online Browsing Platform, 2015)
5. Biomedical material – [grc. "life" + lat. "physician"] non-viable materials used in different medicinal
devices proposed to act together with biological systems (Murphy, 2016)
6. Optical material – [grc. "seen"] non-viable materials used in different optical devices
7. Composites – [lat. "put together"] combination of two (2) or more materials whose chemical properties
are different from its constituents' properties
8. Polymer – [grc. "having many parts"] any substance made up of various network formations of
repeating units of compounds

Characterization Techniques
1. Microscopy – probes and maps the surface (and subsurface) structures of a material using photons,
electrons, ions, or any other physical
probes

Scanning Electron Microscopy (SEM) is a

form of microscopy where a focused beam
of electrons scans the surface of an object,
creating a detailed three-dimensional image
(NanoScience Instruments, n.d.).

Parts of the SE Microscope

1. Electron gun – a machine where
thermoelectrons are fired as a beam
by inducing voltage between the
filament and the anode within
2. Electron column – focuses and
illuminates the specimen using the
generated electron beam
Figure 3. Parts of a scanning electron microscope (SEM).
Source: https://www.slideshare.net/gurya87/scanning-electron-microscope-sem

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3. Vacuum pumps – keeps the electron column free of particles that may otherwise disrupt the electron
beam
4. Specimen chamber – highly vacuumed part of the SEM where the specimen is placed for examination
where detectors are located
5. Operation panel – main control unit of the SEM
6. Operation unit – display area for specimen examination
7. Cryo-unit – an add-on part where frozen specimens are prepared before insertion in the specimen
chamber (applicable if the SEM has a cryo mode)

Applications
 Image morphology of the samples (e.g. bulk material, coatings, foils, sectioned material)
 Image analyses on its compositional and/or bonding differences (i.e. contrasting and backscattering of
electrons)
 Image molecular probes (e.g. metal and fluorescent probes)
 Undertake micro- and nano-lithography (i.e. debride materials from the sample)
 Study optoelectronic behavior of semiconductors using cathodoluminescence
 View/Map grain (or crystallographic) orientation
 View wet, dry, and/or frozen materials
 Heat or cool materials during observation
 Generate X-rays from samples for microanalysis to determine chemical composition (MyScope, 2014)

Requirements
 Material must be electrically conductive;
 Material must be electrically grounded

Transmission Electron Microscopy

(TEM) is a form of microscopy where a
high-energy beam of electrons is shone
on a very thin sample of an object,
creating a detailed two-dimensional
image (Warwick, n.d.).

Parts of the TE Microscope

The TEM also has the same parts as the
SEM, with a few notable citations:
1. Electromagnetic lens system –
lens where a solenoid focuses
the spiraling electron beam
2. The electron column contains
both the specimen chamber as
well as apertures for further Figure 4. Parts of a transmission electron microscope (TEM).
precision Source: https://www.nobelprize.org/educational/physics/microscopes/tem/index.html
3. The detectors have a cooling
system.

Applications
 Image morphology of the samples (e.g. viewing material's section, fine powders suspended on a thin
film, microorganisms and virus analyses, frozen solutions)
 3D image construction (using tilt method)
 Image analyses on its compositional and/or bonding differences (i.e. contrasting and using
spectroscopy techniques, microanalysis, and electron energy loss)
 Physically manipulate samples while viewing them, such as indent or compress them, to measure
mechanical properties (only when holders specialized for these techniques are available)

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 View frozen materials (in a TEM with a cryostage setup)

 Acquire electron diffraction patterns (using the physics of Bragg Diffraction)
 Perform electron energy loss spectroscopy of the beam passing through a sample to determine sample
composition or the bonding states of atoms in the sample
 Generate X-rays from samples for microanalysis to determine chemical composition (MyScope, 2014)

Requirements
 Material must be electrically conductive;
 Material must be electrically grounded;
 Material must be prepared thin

2. Macroscopy – uses various principles to test the material's quantifiable properties

3. Spectroscopy – uses various principles to reveal details about a material's properties, such as chemical
composition, crystal structure, photoelectric properties, and variations of a material's composition, using
optical radiation and X-rays

POLYMERS
 These were developed during the 1920s, when certain materials such as wood, gelatin, and cotton
among others were found to have puzzling properties.
 Hermann Staudinger (1920) clearly showed that the long-held misconception of small aggregates (held
together by intermolecular forces) were in fact enormously large molecules made up of various similar
particulates held together by covalent bonds (Chang & Goldsby, 2016).
 Monomers with double bonds are represented in two (2) forms (i.e. isomerism) which are the following:
o cis- Configuration – the form where radicals exist on the same side of the configuration
o trans- Configuration – the form where radicals exist on opposite sides of the configuration.
 The following types of polymers exist depending on the monomer (i.e. repeating subunit) present:
o Homopolymers are polymers that comprise of only one (1) type of monomer
o Copolymers are polymers with two (2) monomers
o Terpolymers are polymers with three (3) monomers
 Complex asymmetric substances form complex polymeric structures (i.e. tacticity), such as the
following:
o Atactic polymers form monomer chains in a random fashion

o Syndiotactic polymers form monomer chains in a neat, alternating fashion

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o Isotactic polymers form monomer chains where the radical is found in a similar setup as the
previous (i.e. ordered formation)

Properties
1. High strength - low weight ratio
2. High resistance to other chemicals
3. High thermal and electrical resistance (i.e. good insulators)
4. Multiple ways of processing
5. Nigh-limitless range of characteristics and colors
6. Mostly non-biodegradable (i.e. degrading for a very long time)

Processes
1. Addition reaction – involves unsaturated compounds containing double (or triple) bonds (i.e. 𝐶 = 𝐶 or
𝐶 ≡ 𝐶 bonds)
Examples:
 Hydrogenation – treatment of substances with molecular hydrogen (𝐻2 ), with the treated
substances usually unsaturated before the process
– reduces double or triple bonds in hydrocarbons
– requires three (3) components, namely: molecular hydrogen, the substance,
and a catalyst
 Catalyst can be nickel, palladium, or platinum
 Substances that are saturated are mostly alkenes

Mechanism:
As an example, polypropylene, with the chemical formula (𝐶3 𝐻6 )𝑛 , is a stable polymer used in
hydronic heating and cooling systems, particularly for computer systems. It is made up of
multiple propene monomers. It involves a Ziegler-Natta catalyst (𝑅2 ) that is heated to form two
(2) radicals,
𝑅2 → 2𝑅 ⋅
The reactive radical attacks a propene molecule to generate a new radical,
𝑅 ⋅ + 𝐶𝐻2 = 𝐶𝐻 − 𝐶𝐻3 → 𝑅 − 𝐶𝐻2 − 𝐶𝐻 = 𝐶𝐻2 ⋅ ,
The initial reaction sets off a chain reaction with another available propene molecule, and so
on;
𝑅 − 𝐶𝐻2 − 𝐶𝐻 = 𝐶𝐻2 ⋅ + 𝐶𝐻2 = 𝐶𝐻 − 𝐶𝐻3 → 𝑅 − 𝐶𝐻2 − 𝐶𝐻 = 𝐶𝐻2 − 𝐶𝐻2 − 𝐶𝐻
= 𝐶𝐻2 ⋅
Very quickly, a long chain of 𝐶𝐻2 groups is built. Eventually, this process ends with the
combination of two (2) long-chain radicals that forms polyethylene. The expanded formula is
𝑅 − (−𝐶𝐻2 − 𝐶𝐻 = 𝐶𝐻2 −)𝑛 − 𝐶𝐻2 − 𝐶𝐻
= 𝐶𝐻2 ⋅ + 𝑅 − (−𝐶𝐻2 − 𝐶𝐻 = 𝐶𝐻2 −)𝑛 − 𝐶𝐻2 − 𝐶𝐻 = 𝐶𝐻2 ⋅
→ 𝑅 − (−𝐶𝐻2 − 𝐶𝐻 = 𝐶𝐻2 −)𝑛 − 𝐶𝐻2 − 𝐶𝐻 = 𝐶𝐻 − 𝐶𝐻
= 𝐶𝐻 − 𝐶𝐻2 − (−𝐶𝐻2 = 𝐶𝐻 − 𝐶𝐻2 −)𝑛 − 𝑅
where −(−𝐶𝐻2 − 𝐶𝐻 = 𝐶𝐻2 −)𝑛 − is a shorthand for long repeating units of the polymer. The
subscript 𝑛 represents a large value (in the hundreds value) (Chang & Goldsby, 2016).

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 Hydrohalogenation – Hydrogen halides are any compound that has both hydrogen and a
halogen, which become acids in aqueous phase; thus, these take place if hydrogen halides
interact with organic compounds.

Mechanism:
As an example, ethylene, with the chemical formula 𝐶2 𝐻4 , is a stable alkene used in making
polyethylene. If hydrogen chloride (𝐻𝐶𝑙) is added to it, it forms a chloroethane, as shown below:
𝐻𝐶𝑙 + 𝐶𝐻2 = 𝐶𝐻2 → 𝐶𝐻3 − 𝐶𝐻2 − 𝐶𝑙

 Halogenation – similar with hydrohalogenation, but only involves the halogens

2. Condensation reaction – a reaction where two (2) or more molecules combine to form a larger
molecule, at the expense of losing some smaller molecules simultaneous to the reaction (usually water
or methanol)

Mechanism:
An example is the production of polyester ([𝐶8 𝐻8 (𝐶𝑂2 𝐻)2 ]𝑛 ). It uses terephthalic acid, an organic
compound with the chemical formula 𝐶6 𝐻4 (𝐶𝑂2 𝐻)2 . The terephthalic acid's configuration is shown
below:

Polyester is also made from ethylene (𝐶2 𝐻4 ). It is a stable organic compound used to make plastic. It
also exists in an aqueous form (called ethylene glycol, 𝐶2 𝐻4 (𝑂𝐻)2 ), which is primarily used in this
process,

In the given scenario, ethylene glycol is added to the terephthalic acid, creating a monomer shown
below. Water (𝐻2 𝑂) is also one (1) of its by-products.

As the process continues, polyester is made. Model-wise, the polyethylene can look like the diagram
below (with the extra ethylene chains represented by the hanging hydroxide molecule 𝑂𝐻 − ),

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METALS
 Refer to Pages 6–11 of 04 Handout 2 for the timeline of metals and metallurgy.
 Ore – any naturally-occurring solid material that contains extractable metal or any valuable mineral
 Scale – residual flaky material made from oxidized metal, usually from iron
 Metallurgy – study of the physical and chemical behavior of metallic elements, its compounds and
mixtures (i.e. alloys)
Metallurgical Process
1. Ore Enrichment
a. Levigation – a.k.a. hydraulic washing; the process of washing away the impurities from
powdered ore, leaving the required metals to precipitate
b. Froth Flotation – the process of mixing powdered ore with water and a small amount of oil within
a tank, with the air blown inside the tank, creating a froth that carries the important metals to
the surface
c. Liquation – the process of heating the ore, allowing the metal with the lower melting point to
collect at the bottom, leaving the impurities
d. Magnetic Separation – the process of separating the ore from the impurities by means of
magnetic manipulation
e. Leaching – a.k.a. chemical separation; the process of adding chemicals that can effectively
dissolve the required metals in a powdered ore, leaving the impurities behind
2. Conversion of enriched ores to metal oxides
a. Calcination – the process of converting oxide and carbonate ores into metal oxides by heating
the enriched ores in the absence of air
b. Roasting – the process of converting sulfide ores into metal oxides by heating the enriched ores
in the presence of air
3. Metal extraction from metal oxides
a. Heat reduction – the process of extracting the required, albeit impure, metal from the metal
oxide using heat
b. Chemical reduction – the process of extracting the required, albeit impure, metal from the metal
oxide using a reducing agent
i. Smelting [ger. "melt"] – chemical reduction using 𝐶
ii. Alumino-thermic process – a.k.a. thermite process; a chemical reduction using
aluminum (aluminium, 𝐴𝑙)
4. Metal Refinement
a. Liquation – extracts tin (𝑆𝑛) and lead (𝑃𝑏)
b. Cupellation – extraction of silver (𝐴𝑔) from lead ore using a heated cupel (a vessel made of
bone-ash) in the presence of air
c. Poling – extraction of copper (𝐶𝑢) by stirring the molten impure 𝐶𝑢 using green wood poles
d. Electrolytic refining – metal extraction by means of redox reactions in a setup similar to
electroplating
e. Crystal bar process – a process developed by Anton Eduard van Arkel and Jan Hendrik de
Boer that allows the refinement of ultra-pure metals, such as titanium (𝑇𝑖), vanadium (𝑉), and
zirconium (𝑇𝑖) among others
 Metalworking - process of working with metals to create various formations and structures that suits a
particular need or assemblage

Properties
1. Mostly lustrous (i.e. shiny)
2. Mostly solid
Exemptions: 𝑅𝑏, 𝐶𝑠, 𝐹𝑟, 𝐺𝑎, and 𝐻𝑔
3. Most are highly dense
4. Most can be easily deformed (i.e. malleability, ductility)

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5. Easily form positive ions

6. High density
7. High thermal and electrical conductivity
8. Strength depends on crystal structure arrangement

Processes
 Hot Working – process of working (i.e. manipulating plastic deformation) on a material well beyond its
recrystallization temperature

ADVANTAGES DISADVANTAGES
Hardness and ductility remain the same Metal loss by scale formation
Metal loss may cause weakening on the
Porosity is eliminated
material itself
Improves a metal's physical properties and
Fatigue failures may significantly appear
refines its grain structure
Large shape changes can be made without
ruptures
Impurities are broken up and redistributed
High cost of labor (e.g. high energy
evenly throughout the material
consumption)
Machines used for working are smaller and
faster
A material's surfaces need not to be clean

 Cold Working – process of working on a material below its recrystallization temperature

ADVANTAGES DISADVANTAGES
Good dimensional control Only ductile materials can be shaped
The material has good surface finish Metal may be overworked
Improves a metal's strength and hardness
Applicable to metals that can't handle heat Heat treatment is eventually needed
treatment

Common Hot Working Processes

1. Casting – a method where solid materials are dissolved and heated (at the temperature required to
alter its chemical structure), which are then poured in molds to generate the required shape after
solidifying
2. Forging – process of hammering a metal billet into shape, usually incorporating heat to reduce
workload
3. Heat Treatment – process of altering the metal's molecular structure by introducing heat
a. Annealing – process of heat treatment that allows the metal to be more ductile by heating the
material above its recrystallization temperature
b. Quenching – process of rapidly cooling the material, forcing it to "recrystallize" itself, improving the
metal's hardness (i.e. strength), but lowering its toughness (i.e. impact resistance)
c. Tempering – process of alleviating stresses on the worked material, trying to balance out the metal's
hardness and toughness
4. Rolling – process of passing a billet through successively narrow rollers for sheet-making
5. Extrusion – process of forcing a hot metal into a pressurized casting die which is shaped upon cooling
6. Work Hardening – process of toughening up metals by means of plastic deformation
7. Electroplating – process of bonding a thin layer of metal on another metal's surface through redox
reaction
8. Thermal spraying – process of coating a metal with a melted material by spraying the melted material
on the worked material

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Common Cold Working Processes

Squeezing Bending Shearing Drawing
Rolling Angling / Angle Shearing Bar and Tube Drawing
Swaging Rolling Slitting Wire Drawing
Cold Forging Roll Forming Blanking Spinning
Sizing Sheet Drawing Piercing Embossing
Extrusion Seaming / Hemming Lancing Stretch Forming
Riveting Flanging Perforating Shell Drawing
Staking Straightening Notching Ironing
Coining Nibbling High-Energy Rate Forming
Peening / Shot Peening Shaving
Burnishing Trimming
Die Hobbing Cutoff
Thread Rolling Dinking

 Swaging – forces the material to change its shape using a molding die
 Cold forging – forging using little to no heat, reducing scale production
 Sizing – process of minimizing the metal's thickness via squeezing
 Riveting – widely-used joining process using metal rivets to join two (2) metals
 Staking – joining process where one (1) has a hole cut through and the other has a boss that
symmetrically fits in the hole
 Coining – process of inducing plastic flow by subjecting the metal to a sufficiently high-stress work,
similar to coin-making
 Peening – process of repeatedly delivering blows to a material, which improves the material's
compressive stress, relieves it of tensile stress, and encourages strain hardening
 Burnishing – plastic deformation of a material's surface through repeated sliding with another object,
making a rough surface smoother
 Die Hobbing – a deformation process where a hardened hob continuously presses on a metal
supported by a mold, creating a dent on, or reshaping, the material
 Thread Rolling – a rolling process that allows threads to form (i.e. screws, nuts and bolts)
 Roll Forming – a rolling process where a strip of sheet metal is shaped and bent by multiple rollers
 Drawing – process of pulling the metal into a desired shape
 Hemming and Seaming
o Hemming – a folding process used to improve a metal's finish, hide imperfections, or reinforce its
edges
o Seaming – a folding process used for tight sealing (i.e. tin cans) and in both amusement park cars
and automotive industry
 Flanging – a deformation process where a sheet metal is bent at 90°
 Shearing – process of fracturing the metal using two (2) cutting edges
o Slitting – a shearing process of cutting a material through a series of slits
o Blanking and Piercing – a shearing process where a metal is punched out using a punch and die
 Blanking requires the punched-out material (i.e. a blank)
 Piercing requires the material where the blank came from
 Dinking – a specialized piercing process, developed for softer metals, where a beveled
hollow punch is used to pierce the metal
o Lancing – a shearing process where the cut material is not completely cut out, allowing it to be
bent and shaped while still attached
 Nibbling – process of repeated hole-punching on a metal that allows for cutting contours
 Perforating – a punching process where multiple small holes are simultaneously punched out
 Embossing – a stamping process where a raised or sunken relief is produced onto a material

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 Shell Drawing – a drawing process where a material is drawn out really long and narrow, and is used
for making containers and covers
 High-Energy Rate Forming – a drawing process where a material is forced into shape by high energy
discharges, such as explosion shockwaves, electrode, and electromagnetic manipulations

NANOMATERIALS
 First nanomaterials were formed after the primordial burst (i.e. Big Bang), found in early meteorites
 Nature evolved the development of nanostructures, evident in seashells, smoke particles, and bones
 Michael Faraday first synthesized colloidal gold particles in 1857
 Precipitated and fumed silica nanoparticles, as substitutes for ultrafine carbon black for rubber, were
manufactured and sold in the US and Germany in the 1940s
 Metallic nanopowders for magnetic tapes were developed in the 1960s and 1970s
 Granqvist and Buhrmn first created nanocrystals using the popular inert-evaporation technique in 1976
 Nanophase engineering today rapidly expands in various structural and functional materials (inorganic
and organic) for various mechanical, catalytic, electric, magnetic, optical, and electronic functions
(Alagarasi, 2011)

Properties
 Incredibly small
 Used widely in optoelectronics
 Various forms lend various applications

Classifications
According to Dimension
1. Three-dimensional – nanomaterials whose three (3) dimensions exceed the nanoparticle range (i.e.
1–50 nm)
Examples: bulk materials
2. Two-dimensional – nanomaterials which have two (2) dimensions exceeding the nanoparticle range
Examples: nanofilms or thin-film multilayers and nanosheets
3. One-dimensional – nanomaterials which have one (1) dimension exceeding the nanoparticle range
Examples: nanowires, nanorods and nanotubes
4. Zero-dimensional – nanomaterials whose three (3) dimensions never exceed the nanoparticle range
Examples: nanoparticles (spherical, cuboid, polygonal)

According to Origin
1. Natural – nanomaterials made from organic compounds
Examples: protein molecules, viruses, natural colloids, and mineral clay and materials
2. Artificial – nanomaterials which are deliberately prepared through a well-defined mechanical and
fabrication process (Bose, n.d.)
Examples: quantum dots and carbon nanotubes

According to Structural Configuration

1. Carbon-based – nanomaterials whose carbon base allows to form hollow spherical, ellipsoid, or
tubular configurations
2. Metal-based – nanomaterials which have metal ions in the composition, creating tightly-packed
conductive nanoparticles, such as quantum dots
3. Dendrimers – nanomaterials which have highly-branched macromolecules, but its measurements are
still restricted at a nanolevel
4. Composites – multiphase solid materials which have nanoparticles in its makeup

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04 Handout 1 *Property of STI

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