Engineering Materials
Engineering Materials
Engineering Materials
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The stronger the materials the greater the load it can withstand
Toughness
It is the ability of a material to absorb the energy and gets plastically
deformed without fracturing. Its numerical value is determined by the
amount of energy per unit volume. Its unit is Joule/ m3. Value of toughness
of a material can be determined by stress-strain characteristics of a material.
For good toughness, materials should have good strength as well as ductility.
For example: brittle materials, having good strength but limited ductility are
not tough enough. Conversely, materials having good ductility but low
strength are also not tough enough. Therefore, to be tough, a material should
be capable to withstand both high stress and strain.
Hardness
It is the ability of a material to resist to permanent shape change due to
external stress. There are various measure of hardness – Scratch Hardness,
Indentation Hardness and Rebound Hardness.
1. Scratch Hardness
Scratch Hardness is the ability of materials to the oppose the
scratches to outer surface layer due to external force.
2. Indentation Hardness
It is the ability of materials to oppose the dent due to punch of
external hard and sharp objects.
3. Rebound Hardness
Rebound hardness is also called as dynamic hardness. It is
determined by the height of “bounce” of a diamond tipped
hammer dropped from a fixed height on the material.
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Hardenability
It is the ability of a material to attain the hardness by heat treatment
processing. It is determined by the depth up to which the material becomes
hard. The SI unit of hardenability is meter (similar to length). Hardenability
of material is inversely proportional to the weldability of material.
Brittleness
Brittleness of a material indicates that how easily it gets fractured when it is
subjected to a force or load. When a brittle material is subjected to a stress it
observes very less energy and gets fractures without significant strain.
Brittleness is converse to ductility of material. Brittleness of material is
temperature dependent. Some metals which are ductile at normal
temperature become brittle at low temperature.
Malleability
Malleability is a property of solid materials which indicates that how easily a
material gets deformed under compressive stress. Malleability is often
categorized by the ability of material to be formed in the form of a thin sheet
by hammering or rolling. This mechanical property is an aspect of plasticity
of material. Malleability of material is temperature dependent. With rise in
temperature, the malleability of material increases.
Ductility
Ductility is a property of a solid material which indicates that how easily a
material gets deformed under tensile stress. Ductility is often categorized by
the ability of material to get stretched into a wire by pulling or drawing. This
mechanical property is also an aspect of plasticity of material and is
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temperature dependent. With rise in temperature, the ductility of material
increases.
Resilience
Resilience is the ability of material to absorb the energy when it is deformed
elastically by applying stress and release the energy when stress is removed.
Proof resilience is defined as the maximum energy that can be absorbed
without permanent deformation. The modulus of resilience is defined as the
maximum energy that can be absorbed per unit volume without permanent
deformation. It can be determined by integrating the stress-strain cure from
zero to elastic limit. Its unit is joule/m3.
Fatigue
Fatigue is the weakening of material caused by the repeated loading of the
material. When a material is subjected to cyclic loading, and loading greater
than certain threshold value but much below the strength of material
(ultimate tensile strength limit or yield stress limit), microscopic cracks
begin to form at grain boundaries and interfaces. Eventually the crack
reaches to a critical size. This crack propagates suddenly and the structure
gets fractured. The shape of structure affects the fatigue very much. Square
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holes and sharp corners lead to elevated stresses where the fatigue crack
initiates.
Heat Conductivity:
Heat conductivity, also known as thermal conductivity, is the ability of a
material to conduct heat. It is the rate at which heat flows through a unit area
of a material when there is a temperature gradient. Heat conductivity is
crucial in various applications, such as thermal insulation, heat sinks, and
heat exchangers.
Variations in Heat Conductivity:
Heat conductivity can vary significantly among different materials due to
factors such as atomic structure, crystal arrangement, and density. Some key
points to consider include:
• Atomic Structure: Materials with a regular, closely-packed atomic
structure, such as metals, tend to have high heat conductivity. This is
because vibrations (phonons) can propagate easily through the lattice.
• Crystal Orientation: Heat conductivity can vary with the crystallographic
orientation of the material. Anisotropic materials, like wood or layered
composites, can have significantly different heat conductivities in different
directions.
• Temperature: Heat conductivity often decreases with increasing
temperature due to increased phonon scattering, especially in non-metals
and alloys.
• Porosity and Density: Materials with high porosity or low density generally
have lower heat conductivity since air or voids impede heat transfer.
Electrical Conductivity:
Electrical conductivity is the measure of a material's ability to conduct
electric current. It is determined by the movement of charge carriers
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(electrons or ions) in response to an applied electric field. Electrical
conductivity is a crucial property in applications such as electronic
components, wires, and conductive coatings.
Variations in Electrical Conductivity:
Electrical conductivity varies widely among materials due to factors like the
availability of free charge carriers and their mobility. Key factors include:
• Electron Mobility: Metals generally have high electrical conductivity due to
the presence of free electrons that can move easily through the lattice.
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• Alloying and Impurities: The presence of impurities or alloying elements
can significantly affect resistivity in both metals and semiconductors.
Certain impurities can enhance or reduce conductivity.
• Crystal Defects: Crystal defects, such as vacancies or dislocations, can
contribute to higher resistivity by impeding the movement of charge
carriers.
What is corrosion?
Corrosion is the surface wastage that occurs when metals are
exposed toreactive environments.
Corrosion is the result of interaction between a metal and an
environment which resultsin its gradual destruction.
Corrosion is the deterioration of materials as a result of a
reaction with its environment.
Corrosion is the destructive attack of a metal by a chemical or
electrochemicalreaction with the environment.
Classification of Corrosion:
There Are Three Primary Reasons For Concern About And Study
Of Corrosion:
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• Economic Losses: Economic losses can be divided into direct and
indirect losses.
• Direct losses: are those losses associated with the direct replacement
of corroded equipment, components, and structures. Also included are
those costs, both of Labour and material, to maintain equipment and
structures to prevent corrosion from taking place or to control the rate
of corrosion. Falling into this category are such items as painting,
application of protective coatings or linings, operating costs for
catholically protected pipelines and structures.
Indirect Losses: Typical of these indirect losses are the following examples.
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• Loss of Efficiency: Corrosion in a piping system can
result in the buildup of a scale. This scale can cause a
reduction in heat transfer as well as an increase in the
power required to pump the fluid through the system.
The efficient operation of other mechanical equipment
can also be reduced by corrosion. This reduction in
efficiency can cause an increase in operating costs as
well as result in increased fuel consumption, lubricant
loss, and reduced work output. extra cost is involved.
In some instances, the actual corrosive effect Is not
known and consequently, for safety reasons, a much
thicker shell results.
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3) Crevice corrosion is a highly penetrative type of localized
corrosion that occurs in or directly adjacent to gaps or crevices on
the surface of a metal. These crevices can be the result of a
connection between two surfaces (metal to metal or metal to non-
metal), or by an accumulation of deposits (dirt, mud, biofouling,
etc.). This type of corrosion is characterized by deterioration in
the area of the crevice while the surrounding areas of the metal
substrate remain unaffected. One of the main criteria for the
development of crevice corrosion is the presence of stagnant
water within the crevice. This lack of fluid movement gives rise
to the depletion of dissolved oxygen and an abundance of
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difficult. The grain boundaries now represent a path of high
corrosion vulnerability.
6) Selective Leaching
• Corrosion Fatigue
Biological Corrosion
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5. As far as possible, crevices (gap or crack) should be
avoided betweenadjacent parts of a structure.
6. Bolts and rivets should be replaced by proper welding
7. Metal washers should be replaced by rubber or plastic
washers as they do not adsorb water. They also act as
insulation.
8. Corrosion in pipelines can be prevented by using smooth bends.
9. Heat treatment like annealing minimizes the stress corrosion.
10. A good design of water storage container is the one
from which water can be drained and cleaned easily. Such a
design avoids accumulation of dirt etc.
Cathodic Protection:
The reduction or prevention of corrosion by making metallic
structure as cathode in the electrolytic cell is called cathodic
protection. Since there will not be any anodic area on the metal,
corrosion does not occur. There are two methods of applying
cathodic protection to metallic structures.
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employed is called sacrificial anode. The corroded sacrificial anode
block is replaced by a fresh one. Metals commonly employed as
sacrificial anodes are magnesium, zinc, aluminium and their alloys.
Magnesium has the most negative potential and can provide highest
current output and hence is widely used in high resistivity
electrolytes like soil.
Applications:
Advantages:
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Limitations:
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to nullify the corrosion current and convert the corroding metal from
anode to cathode. Usually the impressed current is derived from a
direct current sources (like battery or rectifier on AC line) with an
insoluble, inert anode (like graphite, scrap iron, stainless steel,
platinum or high silica iron).
A sufficient DC current is applied to an inert anode, buried in the
soil (or immersed in the corroding medium) and connected to the
metallic structure to be protected. The anode is, usually, a back fill,
composed of coke breeze or gypsum, so as to increase the
electrical contact with the surrounding soil. Impressed current
cathodic protection has been applied to open water box coolers,
water tanks, buried oil or water pipes, condensers, transmission line
towers, marine piers, laid up ships etc. This kind of protection
technique is particularly useful for large structures for long
term operations.
i) DE aeration:
Fresh water contains dissolved oxygen. The presence of increased
amount of oxygen is harmful and increases the corrosion rate.
Deaeration involves the removal of dissolved oxygen by increase
of temperature together with mechanical agitation. It also
removes dissolved carbon dioxide in water.
Cathodic Inhibitors:
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Depending on the nature of the cathodic reaction in an electrochemical
corrosion,cathodic inhibitors are classified into
salts.
Vapour phase inhibitors:
These are organic inhibitors which are readily vapourised and form a
protective layeron the metal surface. These are conveniently used to
prevent corrosion in closed spaces, storage containers, packing
materials, sophisticated equipments etc.
E) Anodic Protection
This is an electrochemical method of corrosion control in which
an external potential control system, called potentiostat, is used to
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produce and maintain a thin non corroding, passive film on a metal
or an alloy. The use of potentiostat is to shift corrosion potential into
passive potential so that the corrosion of the metal is stopped. The
potential of the object (say acid storage tank) to be protected is
controlled by potential controller (potentiostat) so that under
certain potential range, the object becomes passive and prevents
further corrosion. This potential range depends upon the
relationship between the metal and the environment.
Applications:
F) Protective Coatings
Introduction:
In order to protect metals from corrosion, it is necessary to cover
the surface by means of protective coatings. These coatings act as a
physical barrier between the coated metal surface and the
environment. They afford decorative appeal and impart special
properties like hardness, oxidation resistance and thermal
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insulation.
Classification:
Protective coatings can be broadly classified into two types. They are
1. Inorganic coatings 2. Organic coatings
Inorganic coatings are further classified into two types. They are
i) Metallic coating:
1. Hot dipping- Galvanising, Tinning
2. Metal cladding
3. Cementation-Sherardising, Chromising, Calorising
4. Electroplating.
ii) Non-metallic coating:
1. Surface coating or chemical conversion coating – Chrom
2. Anodising
3. Enamel coating or Vitreous or Porcelain coating.
Organic coatings consists of Paints, Varnishes, Lacquers and Enamels.
Protective Coatings
a) Paints:
1) Hot dipping:
It is used for producing a coating of low-melting metals such as Zn, Sn
, Pb, Al etc., on iron, steel and copper which have relatively higher melting
points. The process in immersing the base metal in a bath of the molten
coating-metal, covered by a molten flux layer (usually zinc chloride).
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2) Galvanizing:
It is the process of coating iron or steel sheets with a thin coat of zinc to
prevent them from rusting. The process is iron or steel article is first
cleaned with dil. Sulphuric acid and washed with distilled water and
dried. The dried metal is dipped in bath of molten zinc, now the thin
layer of zinc is coated on the iron or steel article.
3) Metal cladding:
It is the process by which a dense, homogeneous layer of coating
metal is bonded firmly and permanently to the base metal on one or
both sides. Corrosion resistant metals like nickel, copper, lead, and
alloys like SS, nickel alloys, copper alloys, lead alloys can be
used as cladding materials.
4) Tinning:
It is a method of coating tin over the iron or steel articles. The process is
first treating steel sheet in dilute sulphuric acid and it is passed through
a flux (ZnCl2), next steel passes through a tank of molten tin and finally
through a series of rollers from underneath (bottom of) the surface of
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a layer of palm oil.
5) Electroplating Or Electrodeposition
The base metal to be plated is made cathode whereas the anode is either
made of the coating metal itself or an inert material of good electrical
conductivity (like graphite).
Objectives: Electroplating is carried out for
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Procedure:
The article to be plated is first treated with organic solvent like carbon
tetrachloride, acetone, tetrachloro ethylene to remove oils, greases etc.
Then it is made free from surface scale, oxides, etc. by treating with dil.
HCl or H2SO4 (acid pickling). The cleaned article is then made as the
cathode of the electrolytic cell. The anode is either the coating metal
itself or an inert materialof good electrical conductivity.
• Optimum temperature
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coating.
Metal ions + reducing agents Metal (deposited) + Oxidised
product
• Electroless Nickel Plating:
Pretreatment and activation of the surface: The surface to be plated
is first degreased by using organic solvents or alkali, followed by
acid treatment.
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Sub-module 2:
FEROUS METALS AND ALLOYS
INTRODUCTION
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produce the desired chemical composition.
This process takes place in a ladle treatment station or ladle furnace
where the steel is maintained at a particular temperature by external
heat from electrodes in the lid placed on the ladle.
After the desired chemical composition is achieved, the ladle can be
placed in a vacuum chamber to remove undesirable gases such as
hydrogen and oxygen.
This process is called degassing and is used for higher quality steel
products such as railroad rail, sheet, plate, bar, and forged products.
Stainless steel grades are usually produced in an induction or electric arc
furnace, sometimes under vacuum.
To refine stainless steel, the argon–oxygen decarburization (AOD)
process is used.
In the AOD, an argon–oxygen gas mixture is injected through the molten
steel to remove carbon without a substantial loss of chromium (the main
element in stainless steel).
Continuous Casting.
Today, most steel is cast into solid form in a continuous-casting (also
called strand casting) machine.
Here, the liquid begins solidification in a water-cooled copper mold while
the steel billet, slab, or bloom is withdrawn from the bottom of the mold.
The partially solidified shape is continuously withdrawn from the machine
and cut to length for further processing.
The continuous-casting process can proceed for days or weeks as ladle
after ladle of molten steel feeds the casting machine. Some steels are not
continuously cast but are poured into individual cast-iron molds to form an
ingot that is later reduced in size by forging or a rolling process to some
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other shape. Since the continuous-casting process offers substantial
economic and quality advantages over ingot casting most steel in the
world is produced by continuous casting.
Rolling/ Forging.
Once cast into billet, slab, or bloom form, the steel is hot rolled through a
series of rolling mills or squeezed/ hammered by forging to produce the
final shape.
To form hot-rolled sheet, a 50- to 300-mm-thick slab is reduced to final
thickness, e.g., 2 mm, in one or more roughing stands followed by a series
of six or seven finishing stands. To obtain thinner steel sheet, e.g.,0.5
mm, the hot-rolled sheet must be pickled in acid to remove the iron
oxide scale and further cold rolled in a series of rolling stands called a
tandem mill.
Because the cold-rolling process produces a hard sheet with little ductility,
it is annealed either by batch annealing or continuous annealing. New
casting technology is emerging where thin sheet (under 1 mm) can be
directly cast from the liquid through water-cooled, rotating rolls that act as
a mold as in continuous casting. This new process eliminates many of the
steps in conventional hot-rolled sheet processing. Plate steels are produced
by hot rolling a slab in a reversing roughing mill and a reversing finishing
mill. Steel for railway rails is hot rolled from a bloom in a blooming
mill, a roughing mill, and one or more finishing mills. Steel bars are
produced from a heated billet that is hot rolled in a series of roughing
and finishing mills. Forged steels are produced from an ingot that is
heated to forging temperature and squeezed or hammered in a hydraulic
press or drop forge. The processing sequence in all these deformation
processes can vary depending on the design, layout, and age of the steel
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plant.
STEEL ALLOYS
Each particular alloying element has an influence on the structure and
prop- erties of steel. The following elements are important alloying
elements in steel:
Carbon.
It is inexpensive and has a strong influence on hardness and strength.
It is the basic and essential alloying element in all plain-carbon, low-
alloy, and tool steels. Carbon is an interstitial element that occupies sites
between the larger iron atoms in the bcc and fcc lattices.
Carbon can increase yield strength of pure iron (0% C) with a strength
of about 28 to 190 MPa at 0.005% C, the maximum solubility of carbon
at room temperature.
Manganese.
Manganese is also an essential element in all carbon, low-alloy, and alloy
steels. Manganese has several roles as an alloying element. One role is
to assure that all residual sulfur is combined to form manganese sulfide
(MnS).
Manganese is generally added to steel with a minimum manganese:
sulfur ratio of 20:1. Without manganese the sulfur would combine with
iron and form iron sulfide (FeS), which is a brittle compound that
lowers toughness and ductility and causes a phenomenon called hot
shortness.
Hot shortness is a condition where a compound (such as FeS) or
insoluble element (such as copper) in steel has a low melting point and
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thus forms an unacceptable cracklike surface con- dition during hot
rolling. Another role of manganese is in strengthening steel.
Silicon.
Silicon is added to many carbon and low-alloy steels as a deoxi-dizer, i.e.,
it removes dissolved oxygen from molten steel during the steel-refining
process. Oxygen is an undesirable element in steel because it forms oxide
inclusions, which can degrade ductility, toughness, and fatigue resistance.
Silicon has a moderate effect on strengthening steel but is usually not added
for strengthening.
Phosphorus.
Phosphorus is considered a tramp or residual element in steel and is
carefully restricted to levels generally below 0.02%. However, like carbon,
phosphorus is an interstitial element that can substantially strengthen iron.
For this reason, phosphorus is added to a special class of steels called
rephosphorized steels for strength. Rephosphorized steels also have
enhanced machinability.
Sulfur.
Sulfur is also considered a tramp element in steel and is usually restricted to
below about 0.02%. Although an element with a small atomic diameter,
sulfur is not considered an interstitial alloying element because it is
insoluble in iron. However, as in the case of phosphorus, sulfur is added to
a special class of steels called resulfurized steels that have improved
machinability. These steels are called free-machining steels.
Copper.
These copper particles increase strength and hardness. Copper is also added
to low-alloy steels for atmospheric corrosion protection (these steels are
called weathering steels). One problem with copper in steel is that it cannot
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be oxidized and removed during steel refining. Thus, over time, the copper
level of steel produced from steel scrap is slowly increasing.
Nickel.
Nickel is an important element because of its positive effect on
hardenability. Many important low-alloy steels contain nickel for this
reason. Nickel, being a substitutional element in the iron lattice has a small
effect on increasing yield strength. Nickel, being an austenite stabilizer,
is also a vital
Chromium.
Like nickel, chromium has a positive effect on hardenability and is an
important alloying element in many low-alloy steels. For corrosion
resistance, chromium is present in all stainless steels as a solid solution
element. In addition to hardenability and solid solution effects, chromium
forms several important chromium carbides that are necessary for wear
resistance in many tool steels and steels used for rolls in hot- and cold-
rolling mills.
Molybdenum.
Molybdenum is a potent hardenability element and is found in many
low-alloy steels.
Vanadium.
Although vanadium is a potent hardenability element, its most useful role
is in the formation of a vanadium nitride and vanadium carbide (it can
also be in a combined form of vanadium carbonitride). A very
important role of vanadium is in microalloyed steels, also called high-
strength, low-alloy (HSLA) steels. These steels are strengthened by
precipitation of vanadium nitrides and vanadium carbides (vanadium
carbonitrides). The formation of vanadium carbide is important for wear
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resistance. Vanadium carbide is much harder than iron carbide,
chromium carbide, and molybdenum carbide. Vana- dium is thus
important in high-speed tool steels, which are used as drill bits that retain
their hardness as the tool heats by friction.
Tungsten.
Tungsten is not an addition to low-alloy steels but is a vital al- loying
element in high-speed tool steels where it forms hard tungsten carbide
particles.
Aluminum.
Aluminum is employed as a deoxidizer in steel and is generally used in
conjunction with silicon (also a deoxidizer).
A deoxidizer removes undesirable oxygen from molten steel. Titanium.
Titanium is a strong deoxidizer but is usually not used solely for that
purpose. Titanium is important in microalloyed steels (HSLA steels)
because of the formation of titanium nitride (TiN) precipitates. Titanium
nitrides pin grain boundary movement in austenite and thus provides
grain refinement. Another role of titanium is in steels containing boron
where a titanium addition extracts nitrogen from liquid steel so that
boron, a strong nitride former, remains in elemental form to enhance
hardenability.
Niobium (Columbium). Niobium is also important in microalloyed
(HSLA) steels for its precipitation strengthening through the formation of
niobium car- bonitrides. Some microalloyed steels employ both vanadium
and niobium. Be- cause of its affinity for both carbon and nitrogen,
niobium is an element found in some IF steels. Niobium is also added
as a carbide stabilizer (prevents car- bides from dissolving and reforming
in undesirable locations) in some austenitic stainless steels (AISI type 347,
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348, and 384), ferritic stainless steels (AISI type 436 and 444), and
precipitation hardening stainless steels (AISI type 630).
Tantalum. Because of its affinity for carbon, tantalum, like niobium, is
added as a carbide stabilizer to some austenitic stainless steels (AISI
type 347 and 348).
Boron. On a weight percent basis, boron is the most powerful hardenability
element in steel. A minute quantity of boron, e.g., 0.003%, is sufficient
to pro- vide ample hardenability in a low-alloy steel. However, boron is a
strong nitride former and can only achieve its hardenability capability if
in elemental form. Thus, boron must be protected from forming nitrides by
adding a sufficient amount of titanium to first combine with the nitrogen
in the steel.
Calcium. Calcium is a strong deoxidizer in steel but is not used for that
purpose. In a aluminum-deoxidized (killed) steel, calcium combines with
sulfur to form calcium sulfide particles. This form of sulfide remains as
spherical par- ticles as compared with manganese sulfide, which is soft and
elongates into stringers upon hot rolling. Thus, steels properly treated with
calcium do not have the characteristics associated with MnS stringers, i.e.,
property directionality or anisotropy.
Zirconium. Although expensive and rarely added to steel, zirconium acts
like titanium in forming zirconium nitride participates.
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SUBMODULE 5
HEAT TREATMENT OF STEEL
Heat treatment is a controlled heating and cooling process applied to metals
and alloys to alter their physical and mechanical properties. This process can
significantly impact the hardness, strength, toughness, and other essential
characteristics of materials.
Importance of Heat Treatment Furnaces
Heat treatment furnaces provide a controlled environment to perform
specific heat treatment processes precisely and consistently. They enable
uniform heating, precise temperature control, and controlled cooling rates,
ensuring that desired material properties are achieved.
Types of Heat Treatment Furnaces
Salt bath furnaces, also known as salt pot furnaces, use molten salt as the
heating medium. Salt bath furnaces are a specialized type of heat treatment
equipment used to enhance the properties of metals and alloys. The process
involves immersing the workpiece into a bath of molten salt at high
temperatures, creating a controlled environment for various heat treatment
processes.
They are particularly suitable for processes like carburizing, carbonitriding,
and nitrocarburizing. A typical salt bath furnace consists of several essential
components. The heating element provides the necessary heat to melt the salt
and maintain the desired temperature, the insulated Chamber encloses the
salt bath to ensure heat retention and safety, and the temperature Control
System: Allows precise temperature adjustments for different heat treatment
processes.
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• The direct contact between the molten salt and the workpiece enables rapid
and uniform heating, leading to consistent and predictable heat treatment
results.
• Salt bath furnaces have reduced oxidation, as the salt creates a protective
atmosphere.
• They are also suitable for small and intricate parts due to easy immersion.
Salt bath furnaces ensure even temperature distribution throughout the bath,
ensuring uniform heat treatment across all parts of the workpiece.
• Salt bath furnaces have a limited temperature range based on the type of
salt used.
• After heat treatment, the workpiece may retain salt residue, necessitating
thorough cleaning to avoid any adverse effects on subsequent processes or
end products.
• They also require high maintenance to prevent salt leakage and corrosion.
2. Box Furnaces
Box furnaces, also called batch furnaces, are versatile and widely used for
various heat treatment processes. They consist of an insulated chamber to
accommodate the workload and provide controlled heating. The box
furnace's main purpose is to provide a controlled heating environment for
various heat treatment processes.
In the batch furnace, the workpieces are loaded into the insulated chamber
and subjected to controlled heating at specific temperatures. The furnace's
heating elements generate the required heat, and the insulation helps
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maintain uniform temperature distribution throughout the chamber. Once the
heat treatment process is complete, the workpieces are removed from the
furnace.
Advantages of Box Furnaces
• Box furnaces require longer heating and cooling times due to the batch
processing nature.
• They have less uniformity due to potential temperature variation within the
chamber.
• They also have limited automation capabilities compared to continuous
furnaces.
• The initial investment for purchasing a box furnace can be higher,
especially for advanced models with additional features.
3. Continuous Furnaces
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Continuous furnaces offer a continuous flow of workpieces through the
heating chamber on a conveyor or roller system. The furnace's heating
elements generate the required heat, and the conveyor system ensures a
steady flow of workpieces through the heating chamber. As the workpieces
move through the furnace, they undergo the specified heat treatment process.
Continuous furnaces have high production rates and efficiency due to
continuous processing. Continuous furnaces ensure uniform heating of
workpieces throughout the entire process. The consistent heat distribution
leads to uniform material properties and improved product quality. They also
have reduced labor requirements.
However, continuous furnaces have limited flexibility in handling small
batches or complex geometries. They require higher energy consumption
during continuous operation. Continuous furnaces are complex systems, and
their maintenance requires specialized knowledge and resources.
4. Vacuum Furnaces
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through radiation, which provides more uniform and efficient heating
compared to conduction or convection. Vacuum furnaces can achieve high
temperatures and pressures, making them suitable for advanced heat
treatment processes.
However, vacuum furnaces require a significant initial investment due to
their advanced technology and sophisticated construction. They have slower
heating rates compared to other furnace types. Vacuum furnaces are more
suitable for batch processing, which may limit their production volume
compared to continuous furnaces.
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Induction heating furnaces require a significant initial investment, including
the cost of specialized equipment and power supplies. Operating induction
heating furnaces requires skilled personnel with expertise in induction
heating principles and safety procedures. Induction heating is most effective
for surface heating, which may limit its application in certain heat treatment
processes.
The process of heat treatment is among the highly effective processes
utilized in the materials science industry for obtaining the desired
physiochemical properties of the materials. These furnaces carefully monitor
the treatment process and enable precise and controlled modification of
material properties. The selection of a furnace depends on the material,
temperature requirements, and production volume. Keeping in view all the
parameters, selecting the most viable heat treatment furnace results in
obtaining the most viable results.
Processes.
Annealing (Full Annealing).
It is used to soften steel and to improve ductility.
In this process, the steel is heated into the lower regions of the
austenite phase field and slow cooled to room temperature. The resulting
microstructure consists of coarse ferrite or coarse ferrite plus pearlite,
depending upon carbon and alloy content of the steel.
Normalizing.
Steel is normalized by heating into the austenite phase field at
temperatures somewhat higher than those used by annealing followed by air
cooling. Many steels are normalized to establish a uniform ferrite plus
pearlite microstructure and a uniform grain size.
Spheriodizing.
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To produce a steel in its softest possible condition, it is usually
spheriodized by heating just above or just below the eutectoid
temperature of 727°C and holding at that temperature for an extended time.
This process breaks down lamellar pearlite into small spheroids of
cementite in a continuous matrix of ferrite.
To obtain a very uniform dispersion of cementite spheroids, the starting
microstructure is usually martensite. This is because carbon is more
uniformly distributed in martensite than in lamellar pearlite. The cementite
lamella must first dissolve and then redistribute the carbon as spheroids
whereas the cementite spheroids can form directly from mar- tensite.
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Tempering.
When quenched steels (martensitic steel) are tempered by heat- ing to
temperatures approaching the eutectoid temperature of 727°C, the dis-
solved carbon in the martensite forms cementite particles, and the steels
become more ductile. Quenching and tempering are used in a variety
of steel products to obtain desired combinations of strength and
toughness.
EQUILIBRIUM DIAGRAM
The Iron-Carbon Phase Diagram
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The phase diagrams are very important tools in the study of alloys for
solutions of many practical problems in metallurgy. These diagrams define
the regions of the stability of a phase which can exist in an alloy system
under the condition of constant atmospheric pressure. For a binary system,
the coordinates of these diagrams are temperature and composition. The
inter-relationships between the phases, the temperature and the composition
in an alloy system are normally presented by phase diagram only under
equilibrium conditions. Such conditions occur during slow heating and
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cooling rates of the alloys, when the kinetics of transformations do not play
an important role.
In their simplest form, iron and steels are alloys of iron (Fe) and carbon (C).
There are three types of ferrous alloys.
These alloys consist of
The study of the constitution and structure of iron and steels starts with the
iron-carbon (Fe-C) phase diagram (Fig 1). Fe-C phase diagram is also used
as the basis for the understanding of the heat treatment processes.
C is an interstitial impurity in Fe. It forms a solid solution with alpha,
gamma and delta phases of iron. Maximum solubility of C in alpha iron is
0.025 % at 727 deg C. Body centred cubic (BCC) iron has relatively small
interstitial positions. Maximum solubility of C in the face centred cubic
(FCC) gamma iron is 2.14 % at 1148 deg C. FCC iron has larger interstitial
positions. Mechanical properties of iron-carbon alloys (iron and steels)
depend on their microstructure, that is, how the different phases are mixed.
Main phases of iron and steels in equilibrium are the following phases.
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tetragonal structure without the loss of its contained carbon atoms into
cementite and ferrite. It is super saturated solution of C atoms in ferrite. It is
a hard metastable phase. It has lath morphology when C is less than 0.6 %,
plate morphology when C is more than 1 %, and mixture of those in
between. It is having high strength and hardness and low toughness.
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CLASSIFICATION OF STEELS
Carbon Steels
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normally surrounded by a α-ferrite or pearlite matrix. Because of these
graphite flakes, a fractured surface takes on a gray appearance, hence its
name.
Mechanically, gray iron is comparatively weak and brittle in tension as a
consequence of its microstructure; the tips of the graphite flakes are sharp
and pointed, and may serve as points of stress concentration when
an external tensile stress is applied. Strength and ductility are much higher
under compressive loads. Gray irons do have some desirable characteristics
and, in fact, are utilized extensively. They are very effective in damping
vibrational energy; which compares the relative damping capacities
of steel and gray iron. Base structures for machines and heavy equipment
that are exposed to vibrations are frequently constructed of this material. In
addition, gray irons exhibit a high resistance to wear. Furthermore, in the
molten state they have a high fluidity at casting temperature, which permits
casting pieces having intricate shapes; also, casting shrinkage is low.
Finally, and perhaps most important, gray cast irons are among the least
expensive of all metallic materials.
Ductile (or Nodular) Iron
When the microstructure of cast iron consists of nodules or spheroids of
graphite in pearlitic or ferritic matrix, the resulting material is called
nodular cast iron. It consists of the product advantages of steel and process
advantages of cast iron. Adding a small amount of magnesium and/or
cerium to the gray iron before casting produces a distinctly different
microstructure and set of mechanical properties.
Alloy Cast Iron
We have seen the properties of the different cast irons but many of the irons
lack:
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• Shock and impact resistance
• Corrosion and heat resistance at high temperatures
So alloying elements such as Ni, Cr, Mo, V, etc. can give additional
properties for cast irons. The most common alloying elements are Nickel
and Chromium. Thus depending on the composition of Nickel and
Chromium, alloy cast irons can be classified in to two:
• Ni- Hard and
• Ni- resist
Effect of alloying Elements on Cast Irons:
Alloying elements in cast irons have similar effect like that of steels. They
can be used to improve mechanical properties, refine grain, increase the
hardness by stabilizing cementite and forming other hard carbides,
stabilizing marten site and austenite structures, and improve corrosion
resistance.
Nickel
• Nickel improves graphitization.
• It has grain refining effect.
• Prevent chilling in thin sections
• Prevent coarse grain in thick section
• Reduce crack in thin section.
Chromium
• Chromium is a strong carbide stabilize which inhibits graphitization
• It will give the cast iron less grain growth
• Using both Ni and Cr can overcome the disadvantage of using them
in separate.
Molybdenum
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• If molybdenum is added in cast iron small amount of it will dissolve
in ferrite
• Whereas large amount of molybdenum forms double carbides
• Increase hardness of thick sections
• Promotes uniformity of microstructures
Vanadium
• It promotes heat resistance due to stable carbide formation
• Strength and hardness can also be increased by vanadium
Copper
• It has very slight graphitization effect.
• It has little influence on the mechanical properties.
• The main effect of copper on cast irons is that it improves resistance
to corrosion.
Additionally, the properties of cast iron can be improved by applying heat
treatment. The method of heat treatment of cast iron is the same as that of
steel. The most common types of heat treatment works are:
• Stress relieving
• Annealing
• Quenching and tempering
• Surface hardening
Types of carbon steel and their properties
Carbon steel is a versatile and widely used material that comes in a variety
of types, each with its own unique properties. Some of the most common
types of carbon steel include:
Low Carbon Steel:
Also known as mild steel, this type of carbon steel contains a low amount of
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carbon (up to 0.3%) and is easy to shape and weld. It’s commonly used for
structural applications, such as buildings and bridges.
Medium Carbon Steel:
With a carbon content of 0.3% to 0.6%, medium carbon steel is stronger than
low carbon steel but still easy to machine and weld. It’s often used for gears,
axles, and other machine parts.
High Carbon Steel:
This type of carbon steel contains a carbon content of 0.6% to 1.4%, making
it strong and hard but also less ductile and difficult to weld. It’s commonly
used for cutting tools, knives, and springs.
Ultra-High Carbon Steel:
With a carbon content of more than 1.4%, ultra-high carbon steel is
extremely strong and hard but also brittle and difficult to work with. It’s
used in applications that require extreme hardness, such as drill bits and saw
blades.
Understanding the properties of each type of carbon steel is important in
selecting the right material for a particular application.
Carbon steel production
Low-carbon steel is the most commonly used form of carbon steel due to its
affordability and versatility.
These steels typically contain less than 0.25 wt.% carbon and cannot be
hardened by heat treatment to form martensite. Instead, they are
strengthened through cold work or through the addition of other elements.
Carbon steels are generally soft and have low strength, but they exhibit high
ductility, making them excellent for machining, welding, and other
applications where formability is important.
High-strength, low-alloy (HSLA) steels are a type of low-carbon steel that
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contain small amounts of other elements, such as copper, nickel, vanadium,
and molybdenum. These elements, which can make up to 10 wt.% of the
steel content, help to increase the strength and hardness of the material while
retaining ductility.
HSLA steels are often heat-treated to achieve their high strength and are
more resistant to corrosion than plain low-carbon steels. They are easily
formable and machinable, making them ideal for use in a range of industries,
including construction, automotive, and aerospace.
Medium Carbon Steel
Medium-carbon steel contains between 0.25 and 0.60 wt.% carbon and 0.60
to 1.65 wt.% manganese. The addition of manganese improves the strength
and hardenability of the steel. Heat treatment, which involves austenitizing
followed by quenching and tempering, can improve the mechanical
properties of medium-carbon steels, giving them a martensitic
microstructure.
However, heat treatment can only be performed on thin sections of the steel.
To improve the ability of medium-carbon steel to be heat treated and
hardened, additional alloying elements such as chromium, molybdenum, and
nickel may be added.
Hardened medium-carbon steels have greater strength than low-carbon
steels, but this comes at the expense of ductility and toughness. Medium-
carbon steels are often used in applications that require a balance of strength
and ductility, such as shafts, gears, and axles in automotive and machinery
industries. Understanding the properties of medium-carbon steel is important
in selecting the right material for a particular application.
High-carbon steel
High-carbon steel contains between 0.60 and 1.25 wt.% carbon and 0.30 to
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0.90 wt.% manganese. It is the hardest and toughest of the carbon steels but
has the lowest ductility. Due to its high carbon content, high-carbon steel is
typically hardened and tempered, making it very wear-resistant.
Tool steels and die steels are specific types of high-carbon steels that are
used in applications where high wear resistance and toughness are critical.
These steels contain additional alloying elements such as chromium,
vanadium, molybdenum, and tungsten, which contribute to the formation of
carbide compounds such as tungsten carbide (WC). This results in a very
hard and wear-resistant steel that is well-suited for cutting tools, dies, and
molds.
Despite their excellent wear resistance, high-carbon steels have limited use
in applications where toughness and ductility are important. The brittleness
of these steels makes them prone to fracture and failure under certain
conditions. As with all steels, selecting the appropriate high-carbon steel for
a given application requires careful consideration of the desired properties
and the operating environment.
Ultra-high carbon steel
Ultra-high carbon steel is a type of steel that contains a very high percentage
of carbon, typically between 1.25% and 2.0%. This high carbon content
gives the steel exceptional hardness and wear resistance, making it ideal for
use in cutting tools, knives, and other applications that require sharpness and
durability. Ultra-high carbon steel also has high strength, making it well-
suited for applications that require high levels of strength and durability.
One of the key characteristics of ultra-high carbon steel is its hardness. With
a hardness typically above 60 HRC, ultra-high carbon steel is one of the
hardest materials available. This makes it ideal for use in cutting tools and
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other applications where hardness and wear resistance are important.
However, this high hardness also makes ultra-high carbon steel more brittle
and less ductile than other types of steel, which can make it more difficult to
work with.
Another important characteristic of ultra-high carbon steel is its wear
resistance. Ultra-high carbon steel has excellent wear resistance, which
makes it well-suited for applications that involve high levels of abrasion or
impact. This makes it an excellent choice for use in machine parts, gears,
and other industrial applications where wear resistance is important.
However, it is important to note that ultra-high carbon steel may not be
suitable for all applications, particularly those that require high levels of
ductility or machinability.
Applications of Carbon Steel
Low-Carbon steel
SUS304 vs SS304 Stainless Steel Low-carbon steel is widely used in various
applications due to its ductility, toughness, and affordability. Some common
uses of low carbon steel include:
Construction: Low carbon steel is often used in the construction industry to
make structural components such as beams, columns, and girders.
Automotive: It is used to manufacture car bodies, chassis, and other
components due to its high strength and malleability.
Pipes: Low carbon steel is used to make pipes for various applications,
including water supply, gas transmission, and oil pipelines.
Furniture: It is also used to manufacture furniture due to its strength and
durability.
Appliances: Low carbon steel is used in the production of various household
appliances such as washing machines, refrigerators, and dishwashers.
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Manufacturing: It is used in the manufacturing of a wide range of products,
including tools, machinery, and equipment, due to its excellent machinability
and weldability.
Medium-carbon steel
Medium-carbon steel has good strength and toughness and is often used in
applications where high strength and wear resistance are required.
Some common uses of medium-carbon steel include:
• Automotive: Medium-carbon steel is used to manufacture parts such
as gears, crankshafts, and axles due to its high strength and wear
resistance.
• Machinery: It is used in the production of machinery and equipment
components such as shafts, couplings, and sprockets.
• Construction: Medium-carbon steel is used in the construction of
bridges, buildings, and other structures due to its strength and
durability.
• Railway tracks: It is used to manufacture railway tracks and other rail
components due to its wear resistance and strength.
• Tools: Medium-carbon steel is used to manufacture various types of
cutting tools, including knives, saw blades, and drill bits, due to its
hardness and toughness.
• Springs: It is also used to make springs and other components that
require high strength and toughness.
High-carbon steel
• Cutting tools: High-carbon steel is used to make cutting tools such as
knives, saw blades, and drill bits due to its hardness and wear
resistance.
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• Springs: It is used to make springs and other components that require
high strength and durability, such as in automotive suspension
systems.
• Automotive: High-carbon steel is used in the manufacture of various
automotive components such as crankshafts, axles, and gears.
• Rails: It is used to manufacture railway tracks and other rail
components due to its high strength and wear resistance.
• Wire ropes: High-carbon steel is used to make wire ropes and other
cables that require high strength and durability.
• Construction: It is used in construction applications such as
reinforcement bars and cables for bridges and high-rise buildings.
Ultra-high carbon steel
Ultra-high carbon steel is primarily used in applications that require high
levels of hardness, wear resistance, and strength. Some common applications
of ultra-high carbon steel include:
• Cutting tools: Ultra-high carbon steel is commonly used to make
cutting tools such as knives, saw blades, and drill bits. Its high
hardness and wear resistance make it well-suited for cutting and
drilling applications that require sharpness and durability.
• Industrial machine parts: Ultra-high carbon steel is often used to
make machine parts such as gears, bearings, and shafts. Its high
strength and wear resistance make it ideal for use in industrial
settings where parts are subjected to high levels of stress and wear.
• Automotive parts: Ultra-high carbon steel can also be used to make
automotive parts such as springs and suspension components. Its
high strength and toughness make it well-suited for these
applications, where durability and reliability are key.
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• Mining equipment: Ultra-high carbon steel is often used in mining
equipment such as drills and cutting tools. Its high hardness and wear
resistance make it ideal for use in harsh mining environments where
equipment is subjected to high levels of abrasion and impact.
• Musical instruments: Ultra-high carbon steel is sometimes used in the
production of musical instruments such as guitars and cymbals. Its
high density and unique acoustic properties make it well-suited for
these applications, where tone and resonance are important.
Sub-module 3:
NONFERROUS METALS
What is Non-Ferrous Metal?
Non-ferrous metals are those which do not contain iron as main constituent
or base metal.
Non-ferrous metals have industrial applications because of their case of
fabrication (like rolling, forging, casting, welding, and machining), electrical
and thermal conductivity, resistance to corrosion, light-weight, etc.
However, at high temperatures, their strength is lowered, and shrinkage is
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more than ferrous metals. The principal non-ferrous metals used in
engineering applications are Copper, Aluminum, Zinc, Tin, Lead, Cobalt,
Nickel, Chromium, Magnesium, and their alloys.
Ferrous Metals like steel and iron is used commonly in buildings and
engineering industries. However, many non-ferrous metals and their alloys
have also been used to great advantage in both buildings and engineering
industries.
In fact, in some cases, they form far better materials than iron and steel and
have replaced them to a great extent.
However, the non-ferrous metals are comparatively costlier and are selected
for use only when they satisfy certain specific requirements and possess
some definite properties.
Following are the special advantages of non-ferrous metals over ferrous
metals in some selected areas.
In Civil Engineering Construction, Aluminum and some of its alloys offer a
very suitable alternative material to steel in some special engineering
construction. Thus, wrought aluminum alloys are:
• Economical;
• Resistant to Corrosion;
• Light in weight;
• Compared to steels, they have been used in, i.e., construction of
bridges and roofs in situations where not much strength is required.
In these situations, they have been found to save 50% of extra weight.
In Engineering Industries, Copper, zinc, nickel, and chromium in their pure
and alloyed forms have been used as materials in situations where:
• High tensile strength is required at elevated temperatures.
• High ductility and malleability are required.
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• High resistance to heat is required.
• High electrical conductivity is required.
• In the above fields and situations, mostly non-ferrous metals are
used.
Non-Ferrous Metals List; Its Types, Properties, Uses.
1. Aluminum:
Aluminum is mainly obtained from bauxite ore.
Aluminum is a very common component (about 8 percent) of the earth crust,
the most common ore of aluminum is Bauxite (Al2O3. n H2O). As a metal,
aluminum was first discovered in 1825.
Aluminum is highly resistant to corrosion. When exposed to moist air,
aluminum forms a thin film of oxide at the top, which is impervious to
air/moisture, and thus saves the metal from further corrosion.
Properties of Aluminum.
Following are some important properties of this metal.
• It is silvery-white metal and shows brilliant luster when fresh.
• It is an excellent conductor of heat and electricity.
• It is light in weight with a specific gravity of about 2.7.
• It is a good reflector of light.
• It is non-magnetic and has high resistance to corrosion.
• It is soft, tough, malleable, and ductile.
• It is very ductile and can be transformed into any shape by rolling,
stamping, extruding, forging, drawing, and spinning.
• 8. Its melting temperature is about 658°C.
• 9. It has high tensile strength.
• It can also be cast into any shape by any method of casting, i.e., die
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casting, chill casting, and sand casting.
• It is resistant to organic acids, salt solutions, etc.
• It has a tensile strength of about 900kg/cm2 in the annealed
condition. It can be improved to 1600kg/cm2 by the hard-rolling
method.
Uses of Aluminum:
1. It is used in the manufacturing of equipment for chemical and food
industries, cooking utensils, cookers, steam-jacketed kettles, etc.
2. Due to its lightweight and high tensile strength, it is used in structural
work of airplanes, ships, trains, buses, trucks, etc. And also used for roofing,
sheathing, window frames, foils, posts, etc.
3. It is used for manufacturing of electric cables.
4. Used for manufacturing of reflectors and mirrors.
5. Aluminum powder is used for preparing paints.
6. It is used in iron and steel making as a de-oxidizer.
Aluminum Alloys:
Following are alloys of aluminum.
• Wrought aluminum alloys.
• Casting aluminum alloys.
2. Copper:
Copper is extracted from copper ores such as copper pyrites, etc.
Metallic copper and its various alloys have been used in engineering
industries and for many other activities from 100 of years.
This is due to some of the useful properties of copper.
Properties of Copper:
Some of the most important properties of copper are as under:
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• It is soft, strong, tough, malleable, and ductile.
• It is very malleable and ductile so that it can be converted into any
desired shape.
• It has excellent joining properties, i.e., it can be joined by almost all
the common methods: welding, soldering, brazing, and riveting.
• It becomes brittle just before melting.
• It can be forged, soldered, rolled and drawn into wires.
• It has good resistance to corrosion.
• It is a good conductor of both heat and electricity next to silver.
• It forms excellent alloys.
• It is reddish-brown in color.
• Its specific gravity is 8.93.
• It has a melting point of 1083°C.
Uses of Copper.
• It is used for making cables and wires for electric applications.
• It is used for electroplating.
• Used for manufacturing of utensils and making of copper alloys.
• It is used for making of munitions and tubes in engineering
applications.
Copper Alloys:
Following are the alloys of copper:
• Brasses.
• Bronzes.
3. Lead:
Lead has been used for centuries in buildings and other engineering
industries. Lead is extracted from three chief ore minerals.
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• Galena
• Cerrussite
• Anglesite
Properties of Lead:
The metallic lead has the following properties.
• It has bluish Grey color.
• It has typically brilliant luster.
• It has a high density – 11.35 g/cm3.
• It has a low melting point of 327 centigrade.
• It has a high boiling point of 1744 centigrade.
• It is very good at resisting corrosion.
Lead Alloys:
In general, lead doesn’t form many alloys. Its alloying capacity is limited
because of its low melting point. Following are the important alloys of lead.
• Solder
• Terne plate
• Type metal
• Bearing metal
4. Zinc:
Zinc is another non-ferrous metal. It is obtained from zinc ores like zinc
blends and calamine. The chief ore mineral of zinc is sulfide called
sphalerite.
Smithsonite, Zincite (ZnO) and Calamine (ZnCO3) are other common zinc
minerals.
Zinc Properties:
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Following are some important properties of Zinc.
• It is bluish-white in color and has bright luster.
• It resists corrosion.
• It is brittle at normal temperature.
• It becomes malleable and ductile when heated to a temperature of
100 to 150°C. Hence, at this temperature, it can be rolled into sheets
and drawn into wires.
• It has a density of 7.14 g/ml.
• It has a melting point of 419 centigrade and boiling point of 907
centigrade.
• It has a tensile strength of 700-1400 kg/cm2.
• Commercial zinc (spelter) is easily attacked by acids.
• Zinc surface is covered by a dull basic zinc carbonate in moist air.
5. Nickel:
Nickel was first discovered in 1750. It is manufactured from its sulfide ore
named pentlandite [NiFe(S)].
The ore is first concentrated by froth flotation process and then roasted and
smelted like other non-ferrous metals.
Nickel Properties:
Following are some important properties of nickel.
• It is the strongest metal in all the non-ferrous metals, having tensile
strength ranges from 4200-8400 kg/cm2.
• It is highly resistant to many types of corrosion. Thus it can
withstand in water, moisture, atmospheric gases, etc.
• Its modulus of elasticity, thermal and electrical conductivity is the
same as steel.
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• It is highly malleable and ductile.
• Its density is 8.9 g/cm3.
• It has a melting point of 1455 centigrade.
6. Magnesium:
Magnesium forms the lightest materials used in structural engineering. It has
a set of properties that make it suitable as an engineering material.
Magnesium Properties and uses:
Magnesium is a very useful metal both as a pure metal and in alloys its main
properties are as follows:
• It is very light with a specific gravity of 1.74.
• It has a melting point of 650 centigrade, which is similar to that of
aluminum.
• It has poor corrosion resistance.
• It has quite a high thermal conductivity and a high coefficient of
thermal expansion.
• It forms very useful alloys with some metals like aluminum, thorium,
zinc, zirconium, and tin, etc.
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chemistry of industrial polymers, is extraordinary, ranging in the thousands
and even millions of atomic mass units (as opposed to the tens of atomic
mass units commonly found in other chemical compounds). The size of the
molecules, together with their physical state and the structures that they
adopt, are the principal causes of the unique properties associated with
plastics—including the ability to be molded and shaped.
Thermoplastic and thermosetting
As mentioned above, polymers that are classified as plastics can be divided
into two major categories: thermoplastics and thermosets.
Thermoplastics such as polyethylene and polystyrene are capable of being
molded and remolded repeatedly. Thus, a foamed-polystyrene cup can be
heated and reshaped into a new form—for instance, a dish.
The polymer structure associated with thermoplastics is that of individual
molecules that are separate from one another and flow past one another. The
molecules may have low or extremely high molecular weight, and they may
be branched or linear in structure, but the essential feature is that of
separability and consequent mobility.
Thermosets, on the other hand, cannot be reprocessed upon reheating.
During their initial processing, thermosetting resins undergo a chemical
reaction that results in an infusible, insoluble network. Essentially, the entire
heated, finished article becomes one large molecule. For example, the epoxy
polymer used in making a fibre-reinforced laminate for a golf club
undergoes a cross-linking reaction when it is molded at a high temperature.
Subsequent application of heat does not soften the material to the point
where it can be reworked and indeed may serve only to break it down.
Property Thermoplastics Thermosetting plastics
Molecular Structure Linear or branched Cross-linked three-
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polymer chains dimensional network
Response to Heat Soften when heated and Irreversibly harden
harden when cooled when heated and cannot
(reversible) be softened upon
cooling
Chemical Reactivity Typically chemically May undergo chemical
inert changes when heated,
often curing or cross-
linking
Melting Point Have a specific melting Do not have a distinct
point melting point;
decompose when
heated
Processability Can be melted and
reshaped multiple times Can only be
molded once; subsequent
without significant heating leads to
degradation degradation
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polypropylene, PVC resin, melamine-
formaldehyde resin
Typical Applications Packaging, consumer Aerospace components,
goods, automotive parts electrical insulators,
composite materials
Properties
• Versatility: Plastics can be engineered to have a broad range of
properties, making them suitable for various applications, from
flexible packaging to rigid structural components.
• Low Density: Most plastics have low densities, making them
lightweight materials compared to metals and ceramics. This
property is advantageous in applications where weight reduction is
essential.
• High Strength-to-Weight Ratio: Certain plastics, such as reinforced
or composite plastics, can exhibit a high strength-to-weight ratio,
making them suitable for structural applications.
• Durability: Plastics are often durable and resistant to environmental
factors, such as moisture, chemicals, and UV radiation. This
durability makes them suitable for outdoor and long-term
applications.
• Flexibility: Many plastics are flexible and can be easily molded into
various shapes and forms. This property is advantageous in
applications like packaging and consumer goods.
• Transparency: Some plastics are transparent or translucent, allowing
for optical applications, such as lenses, windows, and display
screens.
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• Electrical Insulation: Plastics are excellent electrical insulators,
making them suitable for applications where electrical conductivity
needs to be minimized.
• Thermal Insulation: Plastics have low thermal conductivity, which
makes them effective insulators against heat and cold. This property
is valuable in construction and insulation materials.
• Chemical Resistance: Plastics can resist damage from a wide range
of chemicals, making them suitable for use in corrosive
environments.
• Low Cost: Plastics are often cost-effective materials to manufacture,
which contributes to their widespread use in consumer products and
industrial applications.
• Recyclability: Many plastics can be recycled, which is important for
reducing environmental waste and conserving resources.
• Biocompatibility: Some plastics are biocompatible and safe for use in
medical and healthcare applications, such as surgical implants and
medical devices.
• Colorability: Plastics can be easily colored during manufacturing,
allowing for a wide range of color options in products.
• Moldability: Plastics can be molded into complex shapes using
various manufacturing processes, including injection molding,
extrusion, and thermoforming.
• Low Friction: Certain plastics have low coefficients of friction,
making them suitable for applications where reduced friction and
wear are critical.
Additives
In many plastic products, the polymer is only one constituent. In order to
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arrive at a set of properties appropriate to the product, the polymer is almost
always combined with other ingredients, or additives, which are mixed in
during processing and fabrication. Among these additives are plasticizers,
colorants, reinforcements, and stabilizers. These are described in turn below.
Plasticizers
Plasticizers are used to change the Tg of a polymer. Polyvinyl chloride
(PVC), for instance, is often mixed with nonvolatile liquids for this reason.
Colorants
For most consumer applications, plastics are coloured. The ease with which
colour is incorporated throughout a molded article is an advantage of plastics
over metals and ceramics, which depend on coatings for colour.
Popular pigments for colouring plastics include titanium dioxide and zinc
oxide (white), carbon (black), and various other inorganic oxides such as
iron and chromium. Organic compounds can be used to add colour either as
pigments (insoluble) or as dyes (soluble).
Reinforcements
Reinforcements, as the name suggests, are used to enhance the mechanical
properties of a plastic. Finely divided silica, carbon black, talc, mica, and
calcium carbonate, as well as short fibres of a variety of materials, can be
incorporated as particulate fillers. (The use of long or even continuous fibres
as reinforcement, especially with thermosets, is described below in Fibre
reinforcement.) Incorporating large amounts of particulate filler during the
making of plastics such as polypropylene and polyethylene can increase their
stiffness. The effect is less dramatic when temperature is below the
polymer’s Tg.
Stabilizers
In order for a plastic to have a long and useful life in any application, the
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properties of that plastic should change as little as possible with time.
Stabilizers are added, usually in small quantities, to counter the effects of
aging.
Because all carbon-based polymers are subject to oxidation, the most
common stabilizers are antioxidants. Hindered phenols and tertiary amines
are used in plastics in concentrations as low as a few parts per million.
The processing and fabrication of plastics
The processing of raw materials into usable forms is termed fabrication or
conversion. An example from the plastics industry would be the conversion
of plastic pellets into films or the conversion of films into food containers. In
this section the mixing, forming, finishing, and fibre reinforcing of plastics
are described in turn.
Compounding
The first step in most plastic fabrication procedures is compounding, the
mixing together of various raw materials in proportions according to a
specific recipe. Most often the plastic resins are supplied to the fabricator as
cylindrical pellets (several millimetres in diameter and length) or as flakes
and powders. Other forms include viscous liquids, solutions, and
suspensions.
Forming
The process of forming plastics into various shapes typically involves the
steps of melting, shaping, and solidifying. As an example, polyethylene
pellets can be heated above Tm, placed in a mold under pressure, and cooled
to below Tm in order to make the final product dimensionally stable.
Thermoplastics in general are solidified by cooling below Tg or Tm.
Thermosets are solidified by heating in order to carry out the chemical
reactions necessary for network formation.
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Extrusion
In extrusion, a melted polymer is forced through an orifice with a particular
cross section (the die), and a continuous shape is formed with a constant
cross section similar to that of the orifice.
Although thermosets can be extruded and cross-linked by heating the
extrudate, thermoplastics that are extruded and solidified by cooling are
much more common. Among the products that can be produced by extrusion
are film, sheet, tubing, pipes, insulation, and home siding.
In each case the profile is determined by the die geometry, and solidification
is by cooling.
Blow extrusion of thermoplastic polymers
Most plastic grocery bags and similar items are made by the continuous
extrusion of tubing.
In blow extrusion, the tube is expanded before being cooled by being made
to flow around a massive air bubble.
Air is prevented from escaping from the bubble by collapsing the film on the
other side of the bubble. For some applications, laminated structures may be
made by extruding more than one material at the same time through the same
die or through multiple dies.
Multilayer films are useful since the outer layers may contribute strength and
moisture resistance while an inner layer may control oxygen permeability—
an important factor in food packaging. The layered films may be formed
through blow extrusion, or extrudates from three machines may be pressed
together in a die block to form a three-layer flat sheet that is subsequently
cooled by contact with a chilled roll.
The flow through a die in extrusion always results in some orientation of the
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polymer molecules. Orientation may be increased by drawing—that is,
pulling on the extrudate in the direction of polymer flow or in some other
direction either before or after partial solidification. In the blow extrusion
process, polymer molecules are oriented around the circumference of the bag
as well as along its length, resulting in a biaxially oriented structure that
often has superior mechanical properties over the unoriented material.
Compression molding
In the simplest form of compression molding, a molding powder (or pellets,
which are also sometimes called molding powder) is heated and at the same
time compressed into a specific shape. In the case of a thermoset, the melting
must be rapid, since a network starts to form immediately, and it is essential
for the melt to fill the mold completely before solidification progresses to the
point where flow stops.
The molded article is pushed out of the cavity by the action of ejector pins,
which operate automatically when the mold is opened.
In some cases, pushing the resin into the mold before it has liquefied may
cause undue stress on other parts. For example, metal inserts to be molded
into a plastic electrical connector may be bent out of position. This problem
is solved by transfer molding, in which the resin is liquefied in one chamber
and then transferred to the mold cavity.
In one form of compression molding, a layer of reinforcing material may be
laid down before the resin is introduced. The heat and pressure not only form
the mass into the desired shape but also combine the reinforcement and resin
into an intimately bound form. When flat plates are used as the mold, sheets
of various materials can be molded together to form a laminated sheet.
Ordinary plywood is an example of a thermoset-bound laminate. In
plywood, layers of wood are both adhered to one another and impregnated
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by a thermoset such as urea-formaldehyde, which forms a network on
heating.
Injection molding
It is usually slow and inefficient to mold thermoplastics using the
compression molding techniques described above. In particular, it is
necessary to cool a thermoplastic part before removing it from the mold, and
this requires that the mass of metal making up the mold also be cooled and
then reheated for each part. Injection molding is a method of overcoming
this inefficiency. Injection molding resembles transfer molding in that the
liquefying of the resin and the regulating of its flow is carried out in a part of
the apparatus that remains hot, while the shaping and cooling is carried out
in a part that remains cool. In a reciprocating screw injection molding
machine, material flows under gravity from the hopper onto a turning screw.
The mechanical energy supplied by the screw, together with auxiliary
heaters, converts the resin into a molten state. At the same time the screw
retracts toward the hopper end. When a sufficient amount of resin is melted,
the screw moves forward, acting as a ram and forcing the polymer melt
through a gate into the cooled mold. Once the plastic has solidified in the
mold, the mold is unclamped and opened, and the part is pushed from the
mold by automatic ejector pins. The mold is then closed and clamped, and
the screw turns and retracts again to repeat the cycle of liquefying a new
increment of resin. For small parts, cycles can be as rapid as several
injections per minute.
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such as automobile bumpers and inside panels through a process known as
reaction injection molding, or RIM. The two liquid precursors of
polyurethane are a multifunctional isocyanate and a prepolymer, a low-
molecular-weight polyether or polyester bearing a multiplicity of reactive
end-groups such as hydroxyl, amine, or amide. In the presence of a catalyst
such as a tin soap, the two reactants rapidly form a network joined mainly by
urethane groups. The reaction takes place so rapidly that the two precursors
have to be combined in a special mixing head and immediately introduced
into the mold. However, once in the mold, the product requires very little
pressure to fill and conform to the mold—especially since a small amount of
gas is evolved in the injection process, expanding the polymer volume and
reducing resistance to flow. The low molding pressures allow relatively
lightweight and inexpensive molds to be used, even when large items such as
bumper assemblies or refrigerator doors are formed.
Blow molding
The popularity of thermoplastic containers for products previously marketed
in glass is due in no small part to the development of blow molding. In this
technique, a thermoplastic hollow tube, the parison, is formed by injection
molding or extrusion. In heated form, the tube is sealed at one end and then
blown up like a balloon. The expansion is carried out in a split mold with a
cold surface; as the thermoplastic encounters the surface, it cools and
becomes dimensionally stable. The parison itself can be programmed as it is
formed with varying wall thickness along its length, so that, when it is
expanded in the mold, the final wall thickness will be controlled at corners
and other critical locations. In the process of expansion both in diameter and
length (stretch blow molding), the polymer is biaxially oriented, resulting in
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enhanced strength and, in the case of polyethylene terephthalate (PET)
particularly, enhanced crystallinity.
Blow molding has been employed to produce bottles of polyethylene,
polypropylene, polystyrene, polycarbonate, PVC, and PET for domestic
consumer products. It also has been used to produce fuel tanks for
automobiles.
In the case of a high-density-polyethylene tank, the blown article may be
further treated with sulfur trioxide in order to improve the resistance to
swelling or permeation by gasoline.
• International Space Station
• More From Britannica
• history of technology: Plastics
• Casting and dipping
Not every forming process requires high pressures. If the material to be
molded is already a stable liquid, simply pouring (casting) the liquid into a
mold may suffice. Since the mold need not be massive, even the cyclical
heating and cooling for a thermoplastic is efficiently done.
One example of a cast thermoplastic is a suspension of finely divided, low-
porosity PVC particles in a plasticizer such as dioctyl phthalate (DOP). This
suspension forms a free-flowing liquid (a plastisol) that is stable for months.
However, if the suspension (for instance, 60 parts PVC and 40 parts
plasticizer) is heated to 180 °C (356 °F) for five minutes, the PVC and
plasticizer will form a homogeneous gel that will not separate into its
components when cooled back to room temperature. A very realistic insect
or fishing worm can be cast from a plastisol using inexpensive molds and a
cycle requiring only minutes. In addition, when a mold in the shape of a
hand is dipped into a plastisol and then removed, subsequent heating will
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produce a glove that can be stripped from the mold after cooling.
Thermoset materials can also be cast. For example, a mixture of polymer and
multifunctional monomers with initiators can be poured into a heated mold.
When polymerization is complete, the article can be removed from the mold.
A transparent lens can be formed in this way using a diallyl diglycol
carbonate monomer and a free-radical initiator.
Rotational molding
In order to make a hollow article, a split mold can be partially filled with a
plastisol or a finely divided polymer powder. Rotation of the mold while
heating converts the liquid or fuses the powder into a continuous film on the
interior surface of the mold. When the mold is cooled and opened, the
hollow part can be removed. Among the articles produced in this manner are
many toys such as balls and dolls.
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molding, has been used to make margarine cups and other refrigerated food
containers from sheets of acrylonitrile-butadiene-styrene copolymer.
• Foaming
• polystyrene
• polystyrene
Foams, also called expanded plastics, possess inherent features that make
them suitable for certain applications. For instance, the thermal conductivity
of a foam is lower than that of the solid polymer. Also, a foamed polymer is
more rigid than the solid polymer for any given weight of the material.
Finally, compressive stresses usually cause foams to collapse while
absorbing much energy, an obvious advantage in protective packaging.
Properties such as these can be tailored to fit various applications by the
choice of polymer and by the manner of foam formation or fabrication. The
largest markets for foamed plastics are in home insulation (polystyrene,
polyurethane, phenol formaldehyde) and in packaging, including various
disposable food and drink containers.
Foamed thermoplastics
Polystyrene pellets can be impregnated with isopentane at room temperature
and modest pressure. When the pellets are heated, they can be made to fuse
together at the same time that the isopentane evaporates, foaming the
polystyrene and cooling the assembly at the same time.
Usually the pellets are prefoamed to some extent before being put into a
mold to form a cup or some form of rigid packaging. The isopentane-
impregnated pellets may also be heated under pressure and extruded, in
which case a continuous sheet of foamed polystyrene is obtained that can be
shaped into packaging, dishes, or egg cartons while it is still warm.
Structural foams can also be produced by injecting nitrogen or some other
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gas into a molten thermoplastic such as polystyrene or polypropylene under
pressure in an extruder. Foams produced in this manner are more dense than
the ones described above, but they have excellent strength and rigidity,
making them suitable for furniture and other architectural uses.
One way of making foams of a variety of thermoplastics is to incorporate a
material that will decompose to generate a gas when heated. To be an
effective blowing agent, the material should decompose at about the molding
temperature of the plastic, decompose over a narrow temperature range,
evolve a large volume of gas, and, of course, be safe to use. One commercial
agent is azodicarbonamide, usually compounded with some other ingredients
in order to modify the decomposition temperature and to aid in dispersion of
the agent in the resin. One mole (116 grams) of azodicarbonamide generates
about 39,000 cubic cm of nitrogen and other gases at 200 °C. Thus, 1 gram
added to 100 grams of polyethylene can result in foam with a volume of
more than 800 cubic cm. Polymers that can be foamed with blowing agents
include polyethylene, polypropylene, polystyrene, polyamides, and
plasticized PVC.
Foamed thermosets
The rapid reaction of isocyanates with hydroxyl-bearing prepolymers to
make polyurethanes is mentioned above in Reaction injection molding.
These materials also can be foamed by incorporating a volatile liquid, which
evaporates under the heat of reaction and foams the reactive mixture to a
high degree. The rigidity of the network depends on the components chosen,
especially the prepolymer.
Hydroxyl-terminated polyethers are often used to prepare flexible foams,
which are used in furniture cushioning. Hydroxyl-terminated polyesters, on
the other hand, are popular for making rigid foams such as those used in
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custom packaging of appliances. The good adhesion of polyurethanes to
metallic surfaces has brought about some novel uses, such as filling and
making rigid certain aircraft components (rudders and elevators, for
example).
Another rigid thermoset that can be foamed in place is based on phenol-
formaldehyde resins. The final stage of network formation is brought about
by addition of an acid catalyst in the presence of a volatile liquid.
• Finishing
• Joining
Some plastics can be joined by welding, in the same manner as metals—
PVC and polyethylene tanks and ductwork being prime examples. More
commonly, surfaces are joined by being brought into contact with one
another and heated by conduction or by dielectric heating. Heat sealing of
bags made from tubes of blow-extruded polyolefins such as polyethylene
and polypropylene usually requires contact with a hot sealing bar. PVC has a
high enough dielectric loss that heat can be generated throughout the
material by exposure to a high-frequency, high-voltage electric field.
Machining
Rigid thermoplastics and thermosets can be machined by conventional
processes such as drilling, sawing, turning on a lathe, sanding, and other
operations. Glass-reinforced thermosets are machined into gears, pulleys,
and other shapes, especially when the number of parts does not justify
construction of a metal mold. Various forms can be stamped out (die-cut)
from sheets of thermoplastics and thermosets. The cups made by vacuum
forming, for instance, are cut out of the mother sheet using a sharp die. In the
case of a thermoplastic such as polystyrene, the scrap sheet left over can be
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reground and remolded.
Coating
Although colour may be added in the form of a pigment or dye throughout a
plastic article, there are many applications where a surface coating is
valuable for protective or decorative purposes. The automobile bumpers
produced by reaction injection molding can be painted to match the rest of
the body. It is important in applying coatings to plastics that the solvent used
does not cause swelling of the underlying substrate. For this reason, latex
dispersion paints have found favour, although surface treatment is necessary
to provide good bonding with these materials.
Fibre reinforcement
The term polymer-matrix composite is applied to a number of plastic-based
materials in which several phases are present. It is often used to describe
systems in which a continuous phase (the matrix) is polymeric and another
phase (the reinforcement) has at least one long dimension. The major classes
of composites include those made up of discrete layers (sandwich laminates)
and those reinforced by fibrous mats, woven cloth, or long, continuous
filaments of glass or other materials.
Sandwich laminates
Plywood is a form of sandwich construction of natural wood fibres with
plastics. The layers are easily distinguished and are both held together and
impregnated with a thermosetting resin, usually urea formaldehyde. A
decorative laminate can consist of a half-dozen layers of fibrous kraft paper
(similar to paper used for grocery bags) together with a surface layer of
paper with a printed design—the entire assembly being impregnated with a
melamine-formaldehyde resin. For both plywood and the paper laminate, the
cross-linking reaction is carried out with sheets of the material pressed and
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heated in large laminating presses.
Fibreglass
Fibrous reinforcement in popular usage is almost synonymous with
fiberglass, although other fibrous materials (carbon, boron, metals, aramid
polymers) are also used. Glass fiber is supplied as mats of randomly oriented
microfibrils, as woven cloth, and as continuous or discontinuous filaments.
Hand lay-up is a versatile method employed in the construction of large
structures such as tanks, pools, and boat hulls. In hand, lay-up mats of glass
fibers are arranged over a mold and sprayed with a matrix-forming resin,
such as a solution of unsaturated polyester (60 parts) in styrene monomer (40
parts) together with free-radical polymerization initiators. The mat can be
supplied already impregnated with resin. Polymerization and network
formation may require heating, although free-radical “redox” systems can
initiate polymerization at room temperature. The molding may be compacted
by covering the mold with a blanket and applying a vacuum between the
blanket and the surface or, when the volume of production justifies it, by use
of a matching metal mold.
Continuous multifilament yarns consist of strands with several hundred
filaments, each of which is 5 to 20 micrometres in diameter. These are
incorporated into a plastic matrix through a process known as filament
winding, in which resin-impregnated strands are wound around a form called
a mandrel and then coated with the matrix resin. When the matrix resin is
converted into a network, the strength in the hoop direction is very great
(being essentially that of the glass fibres). Epoxies are most often used as
matrix resins, because of their good adhesion to glass fibres, although water
resistance may not be as good as with the unsaturated polyesters.
A method for producing profiles (cross-sectional shapes) with continuous
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fibre reinforcement is pultrusion. As the name suggests, pultrusion resembles
extrusion, except that the impregnated fibres are pulled through a die that
defines the profile while being heated to form a dimensionally stable
network.
Recycling and resource recovery
In many municipalities, the favoured method of disposing of solid waste is in
sanitary landfills, in which layers of refuse alternate with layers of soil.
However, concerns over the wisdom of such land use have encouraged
efforts to dispose of various materials by recycling them for re-use or to
derive some positive benefits. Paper as well as glass and aluminum
containers have been recycled to some degree for many years, and in more
recent years plastic recycling has become common. There are several
technical and economic problems in the recycling of plastics; they fall into
two general categories: (1) identification, segregation (or sorting), and
gathering into central stations and (2) the economics of recovering value.
Identification, segregation, gathering
Since plastics used in packaging form a highly visible part (approximately
20 percent by volume but less than 10 percent by weight) of the waste
stream, most recycling efforts have focused on containers. Almost all bottles,
food trays, cups, and dishes made of the major commodity plastics now bear
an identifying number enclosed in a triangle together with an abbreviation.
In addition to such labeling, in many localities consumers are encouraged to
return empty beverage containers to the place of purchase by being required
to pay a deposit on each unit at the time of purchase. This system helps to
solve two of the major problems associated with economical recycling, since
the consumer seeking return of the deposit does the sorting and the stores
gather the plastics into central locations. An added attraction of deposit laws
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is a notable decrease in roadside litter. However, while such measures have
helped to raise dramatically the recycling rate of plastic bottles—especially
those made of polyethylene terephthalate (PET) and high-density
polyethylene (HDPE)—less than 10 percent of all plastic products are
recycled after first use. (On the other hand, most plastics are used in long-
term applications such as construction, appliances, and home furnishings, for
which efficient recycling is difficult.)
Economic recovery of value
In general, thermoplastic materials can be recycled more readily than
thermosets. Still, there are inherent limitations on the recycling of even these
materials. First, a recyclable plastic may be contaminated by nonplastics or
by different polymers making up the original product. Even within a single
polymer type, there are differences in molecular weight. For instance, a
supplier of polystyrene may produce a material of high molecular weight for
sheet-formed food trays, since that forming process favours a high melt
viscosity and elasticity. At the same time, the supplier may offer a low-
molecular-weight polystyrene for the injection molding of disposable
dinnerware, since injection molding works best with a melt of low viscosity
and very little elasticity. If the polymers from both types of product are
mixed in a recycling operation, the mixed material will not be very suitable
for either of the original applications.
Another complication to the recycling of plastics is the mixing together of
pigments or dyes of different colours, and yet another is the problem of
quality control. Almost all plastics change either slightly or greatly as a
result of initial fabrication and use. Some, for instance, undergo changes in
molecular weight due to cross-linking or chain scission (breaking of the
chemical bonds that hold a polymer chain together). Others undergo
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oxidation, another common reaction that can also change the properties of a
plastic.
For all the foregoing reasons, recycled plastics will almost always have
certain disadvantages in comparison to unrecycled plastics. Most
thermoplastics are therefore recycled into somewhat less-demanding
applications. HDPE from thin-walled grocery bags, for example, may be
converted into thick-walled flowerpots; polyvinyl chloride (PVC) recovered
from bottles may be used in traffic cones; and PET recovered from beverage
bottles may be washed, dried, and melt-spun into fibrous filling for pillows
and clothing. Waste plastics that cannot be separated by polymer type can be
made into plastic “lumber,” extruded slabs that are suitable for applications
such as industrial flooring and park benches. Owing to its heterogeneous
composition, plastic lumber is inherently weaker than the original polymers.
Other recycling processes that make use of mixed plastics are pyrolysis,
which converts the solids into a petroleum-like substance, and direct
incineration, which can provide energy for power plants or industrial
furnaces.
Despite the difficulties in making the recycling of plastics economically
attractive on a large scale, many successful processes have been developed
for more narrowly defined “niche” applications. Automotive suppliers have
found it feasible to recycle polyurethanes from the insides of panels and
dashboards if proper attention is paid to the design of the original materials.
The polycarbonates widely used in compact discs have been recovered and
effectively reused. The polypropylene casings of automobile batteries can be
recovered economically during lead-recycling operations and then remolded
for the same application. Some manufacturers depolymerize PET by
hydrolysis or methanolysis; the resulting materials can be purified by
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distillation and then repolymerized.
In most plastic recycling operations, the first step after sorting is to chop and
grind the plastic into chips, which are easier to clean and handle in
subsequent steps. The chips commonly are first washed in order to remove
nonplastic items such as labels, caps, and adhesives. If the material comes
from a narrowly defined source, it may be possible to dry the washed chips
and immediately extrude them into molding pellets or even to extrude them
directly into fibres. For “mixed-waste” polymers, automatic separation
processes based on differences in density or solubility have been used to
some extent.
Recycling and resource recovery
In many municipalities, the favoured method of disposing of solid waste is in
sanitary landfills, in which layers of refuse alternate with layers of soil.
However, concerns over the wisdom of such land use has encouraged efforts
to dispose of various materials by recycling them for re-use or to derive
some positive benefits. Paper as well as glass and aluminum containers have
been recycled to some degree for many years, and in more recent years
plastic recycling has become common. There are several technical and
economic problems in the recycling of plastics; they fall into two general
categories: (1) identification, segregation (or sorting), and gathering into
central stations and (2) the economics of recovering value.
Identification, segregation, gathering
plastic items being sorted at a recycling centre
Since plastics used in packaging form a highly visible part (approximately
20 percent by volume but less than 10 percent by weight) of the waste
stream, most recycling efforts have focused on containers. Almost all bottles,
food trays, cups, and dishes made of the major commodity plastics now bear
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an identifying number enclosed in a triangle together with an abbreviation.
In addition to such labeling, in many localities consumers are encouraged to
return empty beverage containers to the place of purchase by being required
to pay a deposit on each unit at the time of purchase. This system helps to
solve two of the major problems associated with economical recycling, since
the consumer seeking return of the deposit does the sorting and the stores
gather the plastics into central locations. An added attraction of deposit laws
is a notable decrease in roadside litter. However, while such measures have
helped to raise dramatically the recycling rate of plastic bottles—especially
those made of polyethylene terephthalate (PET) and high-density
polyethylene (HDPE)—less than 10 percent of all plastic products are
recycled after first use. (On the other hand, most plastics are used in long-
term applications such as construction, appliances, and home furnishings, for
which efficient recycling is difficult.)
Economic recovery of value
In general, thermoplastic materials can be recycled more readily than
thermosets. Still, there are inherent limitations on the recycling of even these
materials. First, a recyclable plastic may be contaminated by nonplastics or
by different polymers making up the original product. Even within a single
polymer type, there are differences in molecular weight. For instance, a
supplier of polystyrene may produce a material of high molecular weight for
sheet-formed food trays, since that forming process favours a high melt
viscosity and elasticity. At the same time, the supplier may offer a low-
molecular-weight polystyrene for the injection molding of disposable
dinnerware, since injection molding works best with a melt of low viscosity
and very little elasticity. If the polymers from both types of product are
mixed in a recycling operation, the mixed material will not be very suitable
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for either of the original applications.
Another complication to the recycling of plastics is the mixing together of
pigments or dyes of different colours, and yet another is the problem of
quality control. Almost all plastics change either slightly or greatly as a
result of initial fabrication and use. Some, for instance, undergo changes in
molecular weight due to cross-linking or chain scission (breaking of the
chemical bonds that hold a polymer chain together). Others undergo
oxidation, another common reaction that can also change the properties of a
plastic.
For all the foregoing reasons, recycled plastics will almost always have
certain disadvantages in comparison to unrecycled plastics. Most
thermoplastics are therefore recycled into somewhat less-demanding
applications. HDPE from thin-walled grocery bags, for example, may be
converted into thick-walled flowerpots; polyvinyl chloride (PVC) recovered
from bottles may be used in traffic cones; and PET recovered from beverage
bottles may be washed, dried, and melt-spun into fibrous filling for pillows
and clothing. Waste plastics that cannot be separated by polymer type can be
made into plastic “lumber,” extruded slabs that are suitable for applications
such as industrial flooring and park benches. Owing to its heterogeneous
composition, plastic lumber is inherently weaker than the original polymers.
Other recycling processes that make use of mixed plastics are pyrolysis,
which converts the solids into a petroleum-like substance, and direct
incineration, which can provide energy for power plants or industrial
furnaces.
Despite the difficulties in making the recycling of plastics economically
attractive on a large scale, many successful processes have been developed
for more narrowly defined “niche” applications. Automotive suppliers have
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found it feasible to recycle polyurethanes from the insides of panels and
dashboards if proper attention is paid to the design of the original materials.
The polycarbonates widely used in compact discs have been recovered and
effectively reused. The polypropylene casings of automobile batteries can be
recovered economically during lead-recycling operations and then remolded
for the same application. Some manufacturers depolymerize PET by
hydrolysis or methanolysis; the resulting materials can be purified by
distillation and then repolymerized.
In most plastic recycling operations, the first step after sorting is to chop and
grind the plastic into chips, which are easier to clean and handle in
subsequent steps. The chips commonly are first washed in order to remove
nonplastic items such as labels, caps, and adhesives. If the material comes
from a narrowly defined source, it may be possible to dry the washed chips
and immediately extrude them into molding pellets or even to extrude them
directly into fibres. For “mixed-waste” polymers, automatic separation
processes based on differences in density or solubility have been used to
some extent.
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OVERVIEW OF CERAMIC PROCESSING
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well as nonoxides. The greatest use of microwaves in ceramics processing
is in drying, but the use of microwaves in sintering is promising in cases
where volumetric heating and small grain size are desirable.
Self-Propagating Synthesis
Mechanochemical Synthesis
Reaction Bonding
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purity achievable and the control over stoichiometry. In some cases, there
are fewer steps involved with a preceramic polymer than with powder
processing. For example, the pyrolysis can lead to a porous perform
that requires infiltration by reaction bonding (as in RBSN, reaction
bonded silicon nitride), chemical vapor deposition (CVD), or chemical
vapor infiltration (CVI).
Sol–Gel Processing
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resulting in a material with nanometer features. The concept behind the
sol–gel process is that a combination of chemical reactions turns a
homogeneous solution of reactants into an infinite molecular weight
oxide polymer. This polymer is a three-dimensional skeleton
surrounding interconnected pores. Ideally, the polymer is isotropic,
homogene- ous, uniform in nanostructure, and it replicates its mold
exactly and miniaturizes all features without distortion. The
nanostructure and the nanophase porosity in gels are, in fact, the
features of interest, both scientifically and technologically. The sol–gel
process involves initially a homogeneous solution of one or more
selected alkoxides. Alkoxides are the organometallic precursors for
silica, alumina, titania, zirconia, among others. By far the most
common system is one composed of tetraethyl orthosilicate [TEOS–
Si(OC2H5)4]–water–alcohol. Eventually, the solution reacts to a point
where the molecular structure is no longer reversible. This point is
known as the sol–gel transition. The gel is an elastic solid filling the
same volume as the solution. Alkoxides react at different rates
according to the electronegativity of the cation.
A catalyst is used to start reactions and control pH. The reactions are
first hydrolysis to make the solution active (reaction 1), followed by
condensation polymerization (reaction 2) along with further hydrolysis.
These reactions in- crease the molecular weight of the oxide polymer
(reactions 3 and 4) resulting in either the monohydroxide AlOOH
(boehmite) or the trihydroxide Al(OH)3 (bayerite). Nonaqueous sol–gel
processes have been used to prepare most tran- sition-metal oxides. In
systems with multiple valence, the intermediate species are oligomers that
exist on the nanometer scale.
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Aqueous colloidal sols also are used for sol–gel processing, recognizing
that the mechanism for accomplishing the sol–gel transition is quite
different. In sols such as Ludox, changing the pH or changing the
concentration causes the ag- gregation of sol particles. The sols can be
gelled in such a way that the oxide skeleton is a continuous linking of sol
particles. These are discrete features that make up the skeleton
corresponding to the dimensions of the sol. The other features are pores
within secondary particles and pores between secondary par- ticles. The
chemical and structural differences between nonaqueous alkoxide
precursors and aqueous sol precursors become blurred at later stages of
the sol– gel process.
Mixing as a first step applies to the single alkoxide, multiple alkoxide, and
colloidal sol processes. Absence of light scattering is a good indication of
uni- form mixing. Since the building blocks are nanometer in size, and
smaller than the wavelength of visible light, it is easy to follow, in a
qualitative way, the progress of the linking of building blocks. Gelling is
often determined empiri- cally as the time when the solution shows no
flow. This is referred to as the time to gel. For this step, viscosity is a
good diagnostic for the transition from a viscous liquid to a rigid
structure.
Table 2 summarizes the shapes available by the sol–gel process. All of the
options are more or less porous materials. In all cases, it is important that
the porosity remain interconnected, whether the form of the material is
essentially one-dimensional such as a fiber, two-dimensional such as a
film, or three- dimensional such as bulk monoliths. These shapes can be
divided into those that show isotropic shrinkage from the preform to the
final form and those that show anisotropic shrinkage. Bulk materials fall
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into the isotropic category. Thin films on substrates fall into the
anisotropic category. High aspect ratio fibers also show anisotropic
shrinkage. Sol–gel thin films are exceedingly simple to prepare. A solution
containing the desired oxide precursors is applied to a substrate by
spinning, dipping, or draining. The process is able to apply a coating to
inside and outside of complex shapes simultaneously. The time to gel is
short, indi- cating film formation, drying and creation of pores must be
rapid. When it comes to dip coatings, 50 to 500 nm coatings are easy
to make but thicker coatings
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are more difficult. Similarly, fibers can be drawn out of low-water-
content so- lutions. The sol–gel process allows one to bait and draw
a string of gel about the same diameter as the desired fiber directly
from the solution.
The sol–gel process based on casting and molding can make
bulk objects. The process can be used to make a microporous preform
that is near-net shape. This preform is called a monolith to refer to its
continuity. Monolithic gels can be formed from a colloidal sol or from
an alkoxide solution. The main difference between colloidal gels and
alkoxide gels is their pore structures. Alkoxide gels have small pores
(<10 nm), while colloidal gels have bigger pores or voids between
particles. Monolith fabrication is arguably the most challenging dem-
onstration of the sol–gel process.
Having selected geometry and designed the formulations
accordingly, there are several further steps common to monoliths, films,
and fibers. First of all, the gels must be dried. For monoliths, drying is
more difficult because of the thicker dimensions. Keeping in mind the
nanostructured character of the material, sev- eral drying treatments
have been developed. One possibility is aerogels that are dried in an
autoclave by hypercritical techniques. That is, the solvent is removed
above its critical point. The resulting gel is about 10% dense and shows
no shrinkage. The more common case is xerogels that are dried by
natural evapo- ration. Xerogels are 60% dense and have reductions
40–70% in volume.
Following reacting, gelling, and drying, gel materials have many of
the char- acteristics of the corresponding ceramic oxide, but they are
more or less porous. Interconnected pores, which remain open at the
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surface until the gels are fired to temperatures well above 600°C,
allow the water and solvent to escape.
When the goal of the sol–gel process is a pore-free dense oxide, the
final stage of processing is sintering. The high surface area of gels is
looked at as a high driving force for sintering, so sintering is likely to
occur at lower temper- atures than in conventional powder compacts.
This drive to remove porosity in the end produces a material similar
to conventionally processed materials.
Remember that high purity and uniform nanostructure are trademarks of
the sol–gel process. The challenge of the sol–gel process is to
exploit the nano- structure aspects of the process to derive real benefits.
In single-component, single-phase materials, by far the most important
nanophase property is the po- rosity. Porosity also means that there is
surface area. Sol–gel processing has a special contribution to multiphase
material design and fabrication, in that the porosity provides access to
the nanoscale for processes such as liquid or vapor infiltrations, physical
or chemical depositions, and chemical reactions such as pyrolysis or
oxidation/ reduction.
Because the sol–gel process is a low-temperature process, it is possible
to incorporate organic material. This is accomplished by infiltrating a
previously formed oxide gel with monomer, creating an organic–
inorganic copolymer with a metal alkoxide, or simultaneously
polymerizing monomer and metal alkoxide. Because of the scale of
mixing of the organic and inorganic phases, these ma- terials are
nanocomposites. The products of some of these syntheses can be
classified as sequential interpenetrating networks or simultaneous
interpenetrat- ing networks.
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Among the features of sol–gel processing, the one that should stand
out at this point is its nanometer scale. In the long run, the advantages
for the sol–gel
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