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Course Packet 02course Packet 02: Learning Module 02: Chemistry of Materials
Course Packet 02course Packet 02: Learning Module 02: Chemistry of Materials
Packet
LM01-FCHE
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Course Packet 02
This course packet is about metals, their occurrence, their physical properties, chemical properties
extractions, structure and corrosion.
Objectives
Describe how the properties of a metal are related to its structure
Explain how delocalized electrons are involved in metallic bonding
Explain factors affecting the corrosion of metals and the rusting of iron and steel
Analyze how the method used to extract metals relates to the reactivity series
Describe the composition and uses of steel and other alloys how the properties of steel are
related to its structure
Know the advantages and disadvantages of recycling metals
Develop awareness and concern towards the environment by understanding how mining and
extraction can damage the environment.
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METALS
Gold (Ag) Gold is unreactive and malleable. It does not tarnish or change its
appearance in the air, and is very soft. Gold is mixed with other metals to
make jewellery. Pure gold is used in electronics.
Copper (Cu) Copper is a good electrical conductor and is ductile. It is used for electric
and telephone wires. It can also be used in plumbing because it is not
corroded by water.
Iron (Fe) Iron is hard, strong, abundant and not too expensive. These properties
make it useful in building and engineering. However, iron rusts easily.
Rusting changes the appearance of the metal and can make structures
unsafe.
Titanium (Ti) Titanium is a strong metal but it is also light and very resistant to
corrosion. It is mixed with other metal and is used in the aerospace
industry, watchmaking, and in artificial bones and joints, such as those
made for hips and knees.
It is easy to find products made from metals, but there are other uses of metals that
are less obvious. Metals are used as catalysts to speed up reactions. Nickel is used as a
catalyst to make margarine. Platinum is used in catalytic converters in car exhausts to clean
up fumes and reduce pollution. Compounds containing metals have many uses. For example,
metal compounds are used to colour materials including stained glass and even make-up.
Cost. A metal may have the best properties for a job but it might be too expensive.
For example, silver is a better conductor than copper but it is too expensive to be used
for electric wires.
Extraction method. This can greatly affect the price and availability of a metal.
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For example, aluminium only became a commonly used metal in the late 19 th century
as better extraction methods made it cheaper.
PROPERTIES OF METALS
The properties of metals are related to their structure. Metals often have high melting
points and boiling points. Gold, for example, has a melting point of 1064 °C and a boiling
point of 2807 °C.
This property is due to the strong attraction between the positively-charged metal
ions and the sea of electrons. In metal extraction and other industrial processes, furnaces
often run continuously to maintain the high temperatures needed to work with molten
metals.
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These electrons then move faster and so transfer the gained energy throughout the
metal. This makes heat transfer in metals very efficient. Delocalized electrons also conduct
electricity through metals in a similar way.
Metals are usually strong, not brittle. When a metal is hit, the layers of metal ions are
able to slide over each other, and so the structure does not shatter.
Figure 3
The metallic bonds do not break because the delocalized electrons are free to move
throughout the structure. This also explains why metals are malleable (easy to shape) and
ductile (can be drawn into wires).
CLASSIFICATION OF METALS
Metals can be classified into three groups: ferrous metals, non-ferrous metals and
alloys.
Ferrous Metals
Ferrous metals are metals which contain iron. They will corrode if unprotected.
Ferrous metals will be attracted by a magnet.
Iron forms the basis of all ferrous metals but it is of little use because of its limited
properties. However, when combined with extremely small amount of carbon, it become
more useful.
The more carbon added to steel, the harder the alloyed steel. Unfortunately, when we
add carbon to steel, this reduces the ductility and malleability of the material. There will
always be a trade-off between hardness and brittleness when combining carbon with steel.
However, there are several processes such as case-hardening, hardening, tempering,
normalising and annealing which can be employed to counteract some of these properties.
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Non-ferrous Metals
Non-ferrous are metals which do not contain iron. Pure metals such as aluminium,
copper, tin and lead are non-ferrous, and do not rust.
ALLOYS
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An alloy is a mixture of a metal with at least one other element. Steel is a common
example of an alloy. It contains iron mixed with carbon and other elements. Adding other
elements to a metal changes its structure and so changes its properties.
brass: an alloy of copper and zinc. It does not tarnish and is used for door knobs,
buttons and musical instruments.
amalgam: an alloy of mercury and silver or tin. It is used for dental fillings because it
can be shaped when warm and resists corrosion.
Although pure gold is sometimes used in electronics, gold jewellery is always a mixture of
gold and other metals. Pure gold is actually quite soft. Adding small amounts of other metals
makes the gold hard enough to use in jewellery. Alloying gold with different metals also
affects its colour.
The familiar yellow gold is an alloy of gold with copper and silver. Adding more copper
than silver gives redder shades. White gold is an alloy of gold with nickel, platinum or
palladium. Around 12% of people may be allergic to the nickel in white gold.
Copper coins used to be made from pure copper but most ‘copper’ coins used around the
world are now made from copper alloys. Previously, as the value of copper increased, the
metal used to make the coin became worth more than the actual coins. A melted-down, pure
copper coin could have been sold for more than the face value of the coin. Nowadays, copper
coins have been made from copper-plated steel and are magnetic. A magnet can be used to
separate copper coins by age.
Steel is an alloy of iron and other elements, including carbon, nickel and chromium. Steel
is stronger than pure iron and can be used for everything from sauce pans to suspension
bridges.
The atoms in pure iron are arranged in densely-packed layers. These layers can slide over
each other. This makes pure iron a very soft material.
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The atoms of other elements are different sizes. When other elements are added to iron,
their atoms distort the regular structure of the iron atoms. It is more difficult for the layers of
iron atoms in steel to slide over each other and so this alloy is stronger than pure iron.
Steel can contain up to 2% carbon. Varying the amount of carbon gives steel different
properties. For example, a higher carbon content makes a hard steel.
Table 3. Different types of steel are classified by how much carbon they contain.
Smart Alloys
A smart material can change one or more of its physical characteristics under the
influence of an external stimulus.
Shape memory alloy is a type of smart material made from metals that returns to its
original shape after being deformed.
Nitinol is a type of shape memory alloy made from nickel and titanium. This
material can be used to make a pair of glasses that ‘remembers’ its shape and does not break
when crushed. Nitinol has also been used to hold badly broken bones in place while they
heal.
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The reactivity series is the list of metals placed in order of their reactivity. It can be
used to make predictions about the reactions of metals.
Predictions can be made about simple reactions of metals with oxygen, water and
acids.
Predictions can also be made about more complex reactions where one metal is
competing with another.
Hydrogen is included in the series as it is useful in identifying metals, below it, that
do not react with acids to produce hydrogen gas. Carbon is also added for comparison.
Sodium Na
Calcium Ca
Magnesium Mg
Aluminium Al
[Carbon] C
Zinc Zn
Iron Fe
Tin Sn
Lead Pb
[Hydrogen] [H]
Copper Cu
Mercury Hg
Silver Ag
Gold Au
DISPLACEMENT REACTIONS
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The reactivity series can be used to predict if a metal will react with a metal
compound (e.g. chloride, nitrate or sulfate).
If the metal is less reactive than the metal in the compound, it will not compete and
so there is no reaction.
copper(II)
magnesium magnesium chloride Copper
+ chloride +
Mg MgCl2 Cu
CuCl2
Magnesium is a more reactive metal than copper, so magnesium displaces the copper from its
compound.
Silver is a less reactive metal than magnesium, so silver does not displace the magnesium
from its compound.
The words “plumber” and “plumbing” come from plumbum (the Latin word for lead)
because the ancient Romans used lead for their water pipes. Lead reacts very slowly with
water making it poisonous, so this metal is no longer used in plumbing. Copper is a much
better metal for water pipes because it does not react at all with water.
Some metals react vigorously with water, some metals react slowly and some do not
react at all. When a metal reacts with water, the products are a metal hydroxide and
hydrogen gas.
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Lithium Bubbles of gas are given off quite 2Li(s) + 2H2O(l) 2LiOH(aq) +
quickly. When tested with universal H2(g)
indicator the water is now alkaline.
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Most metals will react with oxygen. Some metals react faster than others and some
may react very slowly or not at all. When a metal does react with oxygen, the product is a
metal oxide.
Gold is an unreactive metal that does not react with acid. Other metals, such as
magnesium and zinc, react with acid producing bubbles of gas. The “squeaky pop” test
shows that this gas is hydrogen.
When a metal reacts with acid, the products are a metal salt and hydrogen.
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Silver
Most metal carbonates decompose when heated strongly. The ease of decomposition
of metal carbonates depends on the position of the metal in the activity series. The less
reactive the metal, the less stable is its carbonate. Thus, ease of thermal decomposition of
metal carbonates increase down the activity series.
The products of thermal decomposition are the metal oxide and carbon dioxide.
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Zinc
Iron
Most metals are found in the Earth’s crust combined with other elements in rocks
known as ores. Due to the general reactive nature of metals, they are normally found
combined with non-metals such as oxygen, sulfur, and the halogens. For example, iron is
found combined with oxygen in ores called haematite and magnetite.
Metals need to be extracted from ores before they can be turned into useful products.
Extraction methods vary for different metals. Gold and other unreactive metals occur native.
Metals that are found in the ground as uncombined elements do not require further
extraction. Metals are extracted from their ores by redox reactions. An ore is a rock that
contains enough of a metal compound to make it economically viable to quarry the rock and
extract the metal. Ores are usually metal oxides or sulfides, which are reduced to extract the
metal. Sulfide ores are often roasted in air to give the oxide, which is then reduced.
After a metal has been extracted from its ore, it often needs to be purified before use.
There are two main ways of extracting metals from their ores:
reduction (burning ores with carbon)
electrolysis
The method of extraction which is most appropriate depends on the reactivity of the
metal being extracted. This can be discovered using the reactivity series. The table below
summarizes the methods for the extraction of metals from their ore.
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Metals are often found combined with oxygen as oxides. To obtain the metal, the
oxygen must be removed. The removal of oxygen from a substance is called reduction.
Carbon can be used to extract metals by reduction. In this reaction, the carbon
removes oxygen from lead oxide. This occurs because carbon is more reactive than lead. The
addition of oxygen to a substance is called oxidation.
A metal can be reduced by carbon if it is less reactive than carbon and so appears
below carbon in the reactivity series. Certain metals, such as iron, can be only be reduced
using carbon if they are heated to very high temperatures. If a metal is more reactive than
carbon, other chemical reactions and processes must be used in its extraction.
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6. Limestone reacts with sand and other impurities in the iron ore to form slag. This
floats on the top of the iron. It is drained off and can be used to build roads.
7. The reactions inside the blast furnace produce carbon dioxide and nitrogen. These
b) Removing impurities
In electrolysis, the ionic substance must be dissolved in water or melted so that the
ions are free to move. The substance that the current passes through and splits up is called
the electrolyte. The electrolyte contains positive and negative ions.
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Figure 6
Electrolytic cells are type of electrochemical cell that works on a chemical system by
applying electric current through the system.
Electrolysis cells can be divided into two categories based on the electrodes used:
a) Passive Electrolysis – the electrodes are chemically inert materials that simply provide a
path for electrons. This is used in industry to purify metals that corrode easily.
b) Active Electrolysis – the electrodes are part of the electrolytic reaction. This is used to
plate materials (electroplating) to provide resistance to corrosion.
Extracting Aluminium
Aluminium is one of the most useful metals in the world. It is a reactive metal that is
found in the ore bauxite combined with oxygen as aluminium oxide (Al2O3). Electrolysis
breaks down the Al2O3 into aluminium and oxygen. As the aluminium loses oxygen,
reduction takes place.
1. The electrolysis of aluminium oxide takes place in steel tanks lined with graphite. The
lining is the negative electrode (cathode). Graphite blocks, which hang over the tank
are the positive electrodes (anode). (See Figure 7)
2. Aluminium oxide is dissolved in molten cryolite. The Al3+ and O2- ions become free to
move. (See Figure 8)
3. When the current is switched on, molten aluminium forms at the negative electrode
(cathode) at the bottom of the tank. Oxygen gas forms at the positive electrodes
(anode). (See Figure 9)
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4. The positive Al3+ ions are attracted to negative electrode (cathode). They gain
electrons and become aluminium atoms, forming liquid metal at the bottom of the
tank. This is reduction.
5. The negative O2- ions are attracted to positive electrode (anode). They lose electrons
and become oxygen atoms, which form oxygen molecules and are given off as a gas.
This is oxidation.
6. In these hot conditions, the oxygen formed at the positive electrodes reacts with
graphite to form carbon dioxide. The graphite gradually wears away and these
electrodes eventually have to be replaced. (See Figure 10)
Figure 10 Figure 11
7. The surface is the coolest part of the hot molten electrolyte and a crust of aluminium
oxide forms here. The pure molten aluminium formed at the bottom of the tank is run
off at intervals. (See Figure 11)
Al3+ + 3e- Al
2O2- O2 + 4e-
Overall reaction:
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Copper is an excellent conductor and does not corrode quickly which makes it a good
material for wiring and plumbing. Only pure copper can be used for electric wires because
even very low levels of impurities will reduce the conductivity.
Copper can occur as a native metal, but more often it is found combined with other
elements, such as in the ore malachite. The copper extracted from compounds by reduction
with carbon is impure. Electrolysis can be used after reduction to remove the impurities and
obtain pure copper.
Figure 12
1. The positive electrode (anode) is impure copper; the negative electrode (cathode) is
pure copper; the electrolyte is copper sulfate solution. (See Figure 12)
2. Copper ions (Cu2+) in the electrolyte are attracted to the negative electrode (cathode).
Each Cu2+ ions gains two electrons to form a copper atom, which sticks to the
electrode. This is reduction. The cathode gets thicker as it is coated with copper.
3. Copper atoms in the positive electrode (anode) can lose two electrons to form
copper ions (Cu2+) which dissolve into the electrolyte. This is oxidation. By losing
electrons these atoms become copper ions and so the anode slowly dissolves away.
4. As the copper ions (Cu2+) are released at the cathode, atoms of impurities in impure
copper also become free and just sink to the bottom as “anode mud”. The mud they
form is collected as it may contain silver and gold.
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Cu2+ + 2e- Cu
Cu Cu2+ + 2e-
This process is carried out on a huge scale in industry. The copper formed on the
cathode is 99.99% pure. The precious metals recovered from the impurities are also sold off
and help to make this industrial process profitable.
Extraction of copper
Copper can also be extracted from chalcopyrite ore (CuFeS2). The first step in the
extraction is to heat the ore with silicon oxide to form copper(I) sulfide, Cu 2S. The second step
is to roast the copper(I) sulfide in air.
The copper is reduced from oxidation state +1 to 0 and the oxygen is reduced from
oxidation state 0 to -2. The sulfur is oxidized from oxidation state -2 to +4. The reducing agent
is the sulfide ion.
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CuSO4 + Fe Cu + FeSO4
Copper is reduced from oxidation state +2 to 0. Iron is oxidized from oxidation state 0
to +2.
Advantages of the displacement reaction include making use of scrap iron that would
otherwise have to be dumped, and the lower temperatures used. Lower temperatures mean
lower energy costs, which is both cheaper and less environmentally harmful.
Extraction of titanium
Titanium is extracted from its ore rutile, TiO2. It is first converted from titanium(IV)
oxide to titanium(IV) chloride at 900 °C:
Fan blades for the Rolls Royce RB211 engine, which is used to power jumbo jet
aircraft such as the Boeing 747, are made of titanium. They are stacked ready for use during
aircraft maintenance. The Rolls Royce RB211 was developed during the 1960s. Its large fan
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drives slow-moving air around the core engine, increasing engine efficiency and reducing
noise.
The first step is the conversion of the ore to tungsten oxide, WO3. The next step is to
reduce the ore by reacting it with hydrogen:
Tungsten has the highest melting point of all the metals (3422°C) and is therefore
used in conventional light bulb filaments.
Like titanium, tungsten cannot be extracted using reduction of the ore with carbon
because tungsten carbide is formed. However, tungsten carbides (WC and W 2C) are very
hard substances with many applications, from drill tips and ammunition to ball point pens.
Using hydrogen as the reducing agent raises safety problems because mixtures of
hydrogen and air are highly flammable. Tungsten has the highest melting point of all the
metals when they are considered in their pure form.
CORROSION OF METALS
Corrosion is the gradual destruction of a metal due to reactions with other chemicals
in its environment. Over time, corrosion changes the appearance of the metal as it breaks
down and it becomes weaker. Corrosion can seriously damage metallic objects and
structures. Coating the surface of a metal with paint and certain chemicals can protect it from
corrosion.
Only a few metals exist in nature as uncombined elements, such as gold and silver.
Such noble metals do not corrode. An active metal is a reactive metal that forms a non-
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adherent and porous oxide layer. The oxide layer of active metals can flake off, allowing
continued corrosion. Most metals are active metals and exist in nature as compounds.
Aluminium is a very reactive metal. However, it does not corrode in the presence of
oxygen.
Figure 14
The outer aluminium atoms react with oxygen in the atmosphere. This forms a thin
layer of aluminium oxide on the metal’s surface, which protects the metal from corrosion.
Rusting is the specific name given to the corrosion of iron. The two main condition
for rusting of iron to take place are the presence of water and air (oxygen). Rusting will not
take place if either one of the components is missing. It is a chemical reaction between iron,
oxygen and water.
The chemical name for rust is hydrated iron oxide. Rust can form on cars and
buildings, making them unsafe. It is an expensive problem.
Impure.
In contact with a less active metal.
Under mechanical stress.
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When iron rusts, iron (Fe) atoms form Fe 3+ ions. This is oxidation, because the iron
atoms have lost electrons. We say that the oxidation state of the iron is 3, because the ions
have a charge of 3+. This is why rust is called iron (III) oxide.
Fe Fe3+ + 3e–
O2 + 4e– 2O2–
Stainless steel is an alloy of iron which contains around 12% chromium and smaller
amounts of nickel and carbon.
Figure 15
Chromium is more reactive than iron. It reacts quickly with oxygen from the air to
form a very thin layer of chromium oxide on the surface of the steel. This protects the iron
atoms from reacting with the oxygen in the air and prevents rust forming. If the steel is
scratched or cut, more chromium atoms quickly form a new protective layer.
Rusting Prevention
Rusting can be prevented by preventing either/both oxygen and water from coming
in contact with iron. The table below illustrates some measures that can be taken to prevent
rusting.
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Coating the iron surface with oil, grease, Prevents air and water from reaching the
paint or plastic. iron.
Electroplating is used to coat one metal onto another to make it look better or to
prevent corrosion. To electroplate an object, the object must have a negative charge. Then the
object is immersed into a solution that contains salt of the metal to be deposited. The metallic
ions of the salt carry a positive charge and are attracted to the negative part. When they
reach it, the negatively charged part provides the electrons to reduce the positively charged
ions to metallic form.
Details of the electrolysis of copper(II) sulfate solution with two different electrodes
(a) graphite (carbon) electrodes and (b) copper electrodes are as follows:
The negative cathode electrode attracts Cu 2+ ions (from copper sulfate) and H + ions
(from water). Only the copper ion is discharged, being reduced to copper metal. The less
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reactive a metal, the more readily its ion is reduced on the electrode surface. A copper deposit
forms as the positive copper ions are attracted to the negative electrode (cathode).
Figure 16
Oxygen gas is formed at the positive electrode, an oxidation reaction (electron loss).
The negative sulfate ions (SO42-) or the traces of hydroxide ions (OH –) are attracted to the
positive electrode. But the sulfate ion is too stable and nothing happens. Instead either
hydroxide ions or water molecules are discharged and oxidised to form oxygen.
Oxidation (anode): 4 OH–(aq) – 4e- 2 H2O(l) + O2(g) (negative ion oxidation by electron
loss)
When Copper(II) sulfate is electrolysed with a copper anode electrode (the cathode can be
carbon or copper), the copper deposit on the cathode (–) equals the copper dissolves at the
anode (+). Therefore the blue colour of the Cu2+ ions stays constant because Cu deposited = Cu
dissolved. Both involve a two electron transfer so it means mass of Cu deposited = mass of Cu
dissolving for the same quantity of current flowing (flow of electrons). You can check this out
by weighing the dry electrodes before and after the electrolysis has taken place. The
electrolysis also works with a carbon anode and you see the blackness of the graphite change
to the orange-brown colour of the copper deposit.
Reduction (cathode): Cu2+(aq) + 2e- Cu(s) (copper deposit, reduction by 2e- gained)
It’s the copper anode that is the crucial difference than electrolysing copper sulfate
solution with an inert carbon/graphite/platinum electrode. The negative sulfate ions SO 42-
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(from copper(II) sulfate) or the traces of hydroxide ions OH – (from water) are attracted to the
positive electrode. But both the sulfate ion and hydroxide ion are too stable and nothing
happens to them because the copper anode is preferentially oxidised to discharge Cu 2+ copper
Oxidation (anode): Cu(s) – 2e- Cu2+(aq) (copper dissolves, oxidation by 2e- lost)
Balancing Act
Copper atoms oxidised to copper(II) ions: dissolving of copper in its electrolytic purification
or electroplating (must have positive copper anode). The change involves two electrons per
copper atom.
Copper(II) ion reduced to copper atoms: deposition of copper in its electrolytic purification or
electroplating using copper(II) sulfate solution, so the electrode can be copper or other metal
to be plated or any other conducting material. The change involves two electrons per copper
ion.
This means for every copper atom that gets oxidised, one copper ion is reduced.
Thus, when copper electrodes are used in the electrolysis of copper sulfate solution, the mass
loss of copper from the positive anode electrode should equal the mass of copper gained and
deposited on the negative cathode electrode.
Figure 17
Summary
As described already, the use of a copper positive anode electrode is the basis of the
method of electroplating any conducting solid with a layer of copper which can be
reproduced by electroplating other conducting materials with zinc (a way of galvanising
steel), nickel, silver or chromium ('chromium plating').
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The electrolyte solution must contain ions of the metal that will form the
electroplated deposit; and the ions come from an appropriate salt solution e.g. copper sulfate
for copper, silver nitrate for silver, zinc sulfate for zinc or chromium chloride for chromium
coatings.
The anode must be made of the metal that will form the electroplated coating on the
positive anode object e.g. copper or silver. As the metal is coated on the -ve cathode object,
simultaneously the metal of the +ve anode is oxidised to refresh the solution of metal ions. So
there is no depletion of the crucial ion concentration. These positive ions will migrate towards
the negative electrode object to be coated.
The purification of copper by electrolysis amounts to copper plating so all you have
to do is swap the pure negative copper cathode with the metal you want to coat. Swap the
impure positive copper anode with any pure block of the metal you want to form the coating
layer on the negative electrode object.
RECYCLING OF METALS
When metal is extracted from the ground, it creates a lot of negative impact to the
environment. Open-cast mining removes ores using explosives. It produces dust and can
scar the landscape. Extracting metals causes huge amounts of waste. Copper production
discards 99.5% of the extracted ore. Harmful waste gases, including sulfur dioxide, carbon
dioxide and carbon monoxide, are produced by extraction. Extraction, especially electrolysis,
also uses lots of electricity.
New mining techniques can decrease the effects of metal extraction on the
environment.
Leaching uses less electricity than traditional mining and does not produce waste
gases. Copper ores are treated with and dissolved in dilute sulfuric acid, producing
copper sulfate. Electrolysis is then used to extract the copper. Certain bacteria can
also be used to dissolve ores and form copper sulfate.
Phytomining uses plants to absorb metals from the soil. The process can be used to
clean contaminated land. Treating the plants with certain chemicals increases their
ability to accumulate minerals in their cells.
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One problem is that metallic materials in recycled objects are often mixtures of
different metals. This can mean that obtaining pure metals from recycling is more expensive,
as it may use more electricity than extracting metals from ores.
The social, economic and environmental issues associated with recycling metals
include:
The lack of awareness regarding the benefits of recycling metals may hinder people
from taking an active role in such programs.
Metals are only recycled if they are economically beneficial. It is cheaper to extract
iron from its core than recycling it which discourages recycling.
The cost of separating metal from other wastes can be high.
Alloys may not always be recycled as it can be difficult to separate the different
metals.
Recycling certain metals can lead to the production of pollutants. For example,
extracting lead produces a lot of fumes which pollutes the atmosphere.
Learning Module 02
Chemistry of Materials
Course Packet 03
Polymers
This is a property of
Bataan Peninsula State University
Knowledge Area Code : SCIE
Course Code : FCHE0114
NOT FOR SALE
Learning Module Code : LM02-FCHE0114
Course Packet Code : LM02- FCHE0114-03
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Course Packet 03
Polymers
Introduction
Polymers are ubiquitous materials used in construction, engineering, and countless commercial
products. These applications can be as varied as the polymeric materials used in medical devices,
pharmaceuticals, food and beverage packaging, and personal care cosmetics. They are made from
repeating chains of bonded molecules that are typically organic but, in some cases, may even be
inorganic in nature.
This course packet explains the use of polymers and demonstrates how their properties are controlled
by their molecular structure. You will learn how this structure determines which polymer to use for a
particular product. You will also explore the manufacturing techniques used and the how the use of
polymerization can be used to control the structure of polymers.
Objectives
Identify alkenes as a common raw material for polymers
Classify the different types of polymer
Name common addition polymers and condensation polymers
Explain the formation of addition polymers such as LDPE
Explain the formation of condensation polymers such as polyesters
Describe the factors that affect the properties of a plastic, including the arrangement of
polymer chains
Explain the structure, properties and uses of thermosoftening and thermosetting plastics
Identify the different methods for disposing of waste plastic.
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POLYMERS
The word ‘polymer’ comes from the Greek words poly (meaning ‘many’) and meros
(meaning ‘parts’). Many polymers are formed from alkenes, which are a family of
hydrocarbon molecules with the general formula CnH2n. Alkenes contain at least one double
covalent bond between carbon atoms. The double bond makes them very reactive.
Polymerization
The process by which polyethene and other polymers is made is called addition
polymerization. This is because many alkenes are added together.
The ‘n’ means that the polymer contains a very large number of the
repeating unit shown in the brackets.
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1. Draw two C atoms that were in the double bond with a single
covalent bond.
2. Draw the brackets and the ‘n’.
3. Add the links outside the brackets.
4. Add the atoms that were attached to each C atom of the double bond.
CLASSIFICATION OF POLYMERS
Polymers can be classified into a number of ways which are described below.
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I. Linear polymers:
In linear polymers, the repeat units are just joined end to end in a straight line. The
molecules themselves are fairly strong, since all the atoms within the molecule are covalently
bonded. There is also hydrogen bonding and van der Waals bonded between the chains.
These polymers have high melting points and are of higher density. A common example of
this is PVC (Poly-vinyl chloride). This polymer is largely used for making electric cables and
pipes.
Figure 1
They are of low density having low melting points. Low-density polyethene (LDPE)
used in plastic bags and general purpose containers is a common example.
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I. THERMOPLASTIC Figure 5
Thermoplastics are made of long chains of polymers which don’t cross over very
often. When heated, the molecules slip easily over one another. They do not contain any cross
bond and can easily be shaped by heating and using moulds.
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Unplasticised PVC, usually called uPVC, is hard. It is used for pipes and window
frames. Plasticised PVC is soft. It is used for clothing and flooring.
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1. Injection moulding
2. Extrusion
3. Blow moulding
Injection Moulding
Figure 10
Extrusion
Figure 11
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Blow Moulding
Figure 12
III. ELASTOMER
Figure 13
Stretchy polymers like rubber and spandex are elastomers. They demonstrate the
property of elastic deformation: when force is applied the fiber stretches, but when the force
is removed the fiber returns to its original shape and size. The molecular structure includes
chains that prefer being tangled. If they are stretched and straightened, a restoring force pulls
them back into the shorter, tangled position.
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Vulcanizing Rubber
Figure 14
It's relatively easy to pull them apart—and that's why latex rubber is so stretchy and
elastic.
IV. FIBERS
Fibers are a class of polymers which are a thread like in nature, and can easily be
woven. They have strong inter-molecules forces between the chains giving them less elasticity
and high tensile strength. The intermolecular forces may be hydrogen bonds or dipole-dipole
interaction. Fibres have sharp and high melting points. A common example is that of Nylon-
66, which is used in carpets and apparels.
At the molecular level, fibers are composed of long carbon chains with few or no
branches. In a fiber strand, multiple polymer molecules line up in parallel. Their
intermolecular forces encourage an ordered, rather crystalline, arrangement. If you pull on
both ends of a strand, it will not stretch very much since the chains are already aligned. Wool
is an exception to this; sulfur atoms in adjacent chains find each other and form sulfur bonds,
crosslinking the chains. This gives wool its crinkly texture.
Generally, fibers can be divided into two broad groups depending on the source,
either natural or synthetic.
Natural fibers come from plants, animals and minerals. They usually have short
fibers, called staple fibers. The exception to this rule is silk, a natural fiber whose continuous
filaments are up to one kilometre in length.
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Synthetic fibers are man-made, usually from chemical sources. They are continuous
filament fibers, which means the fibers are long and do not always have to be spun into yarn.
Blending different fibers together produces yarns that have the combined properties
of each component fiber. Using fibre blends improves the appearance, performance, comfort
and aftercare of fabric. Blending can also reduce the cost of an expensive fiber.
Polyester/ Cotton blend: shirts are more easy-care and crease-resistant than shirts
made from 100 percent cotton.
Cotton/ Lycra blend: jeans are more comfortable, stretchy and fit better than cotton
jeans.
Acrylic/ Wool blend: trousers are less expensive than 100 percent wool trousers.
Polyester or nylon microfibers are 60 to 100 times finer than a human hair. They can
be blended with synthetic or natural fibers and are used for clothing for outdoor pursuits and
active sportswear.
Elastane (Lycra) is always used in a blend with other fibers. It is used to make
sportswear, body-hugging clothes and bandages. It has good handle and drape, is durable,
crease resistant, stretchy (more comfortable) and is easy care. It has low warmth and is
absorbent.
I. NATURAL POLYMERS
Natural polymers are polymers which occur in nature and are existing in natural
sources like plants and animals. Some common examples are Proteins (which are found in
humans and animals alike), Cellulose and Starch (which are found in plants) or Rubber
(which we harvest from the latex of a tropical plant).
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1. Polysaccharides:
Polysaccharides are important class of biopolymers which are made up of long chains
of monosaccharide units bound together by glycosidic bonds. Polysaccharides contain more
than ten monosaccharide units. Starch and glycogen are very common examples for storage
polysaccharides. Similarly, cellulose and chitin are examples for structural polysaccharides
Figure 16
2. Nucleic Acids:
Nucleic acids, such as DNA (deoxyribonucleic acid) and RNA (ribonucleic acid), are
made from nucleotide monomers. Nucleic acids are found in all living things, where they
function in encoding, transmitting and expressing genetic information.
Figure 17
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3. Proteins:
Proteins are large biological molecules, made up of the smallest units called α-amino
acids. They are building blocks of plant and animal cells. Many proteins are enzymes that
catalyze biochemical reactions and are essential to metabolic functions.
Figure 18
4. Natural Rubber:
Natural rubber is the polymer of isoprene. This is mainly harvested as a sticky milky
colloidal form called latex from the bark of the rubber tree.
Figure 19
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A. Addition polymers:
Addition polymers are formed by the repeated addition of monomer molecules. The
polymer is formed by polymerization of monomers with double or triple bonds (unsaturated
compounds). The addition polymerization generally involves three steps called initiation,
propagation and termination.
1. The reaction is a free radical reaction, involving free radicals (Ra•) produced by
oxygen initiators.
2. Initiation step: The free radical reacts with an ethane molecule, breaking the pi bond.
One electron goes to form a bond between one carbon and the free radical. The
second electron moves to the other carbon. The end result is a new free radical:
RaCH2CH2•
3. Chain propagation: The new free radical can react with another ethane molecule, to
create a longer free radical: RaCH2CH2CH2CH2•. The process continues, with ethane
molecules reacting with either the initial free radical (Ra•) or a lengthened free
radical (Ra(CH2)n•).
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4. Chain termination: The chain continues to grow until two free radicals react with
each other. Because this can occur at any time, polyethene consists of chains of
different lengths.
The reaction conditions under which ethene polymerizes affect the structure and
properties of the poly(e)thene.
Low-density polythene (LDPE) is formed under a high pressure (1400 atm) and a
temperature of about 170°C. These conditions cause a high level of branching,
meaning that the polymer chains cannot pack tightly together.
High-density polythene (HDPE) is formed with a catalyst, a pressure of 2 atm and a
temperature of about 70°C. Little branching occurs under these conditions, resulting
in chains that can pack tightly together to create a denser material.
The properties of a plastics depend greatly on how the polymer chains are arranged:
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The unreactivity of addition polymers, which makes them useful for storing food and
chemicals, means they are not biodegradable and persist in the environment for many years.
B. Condensation Polymers:
a dicarboxylic acid (a carboxylic acid with two –COOH groups) and a diol (an
alcohol with two –OH groups)
substances containing both –COOH and –OH groups.
a dicarboxylic acid and a diamine (an amine with two NH2 groups)
amino acids, which contain both –COOH and –NH2 groups.
Formation of polyesters
1. A carboxylic acid and an alcohol can react to form esters. This is an example of
condensation reaction because water molecule is formed during the reaction.
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2. If a dicarboxylic acid and a diol are used and a water molecule is removed, the
polymer formed is called polyester.
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Formation of polyamides
2. If a dicarboxylic acid and diamine are used and a water molecule is removed,
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Unlike addition polymers, which don’t readily degrade, condensation polymers can
be designed that biodegrade, photodegrade or which can be recycled. Condensation
polymers biodegrade by hydrolysis, which is the reverse of the condensation reactions that
form them.
Some condensation polymers, such as nylon, degrade very slowly, which is necessary
for them to be useful. Condensation polymers such as poly(lactic acid) have been designed to
biodegrade more quickly and are used in disposable plastic items such as packaging.
Table 2. Summary
CHARACTERISTICS OF POLYMERS
Every polymer has very distinct characteristics, but most polymers have the
following general attributes.
1. Polymers can be very resistant to chemicals. Consider all the cleaning fluids in your
home that are packaged in plastic. Reading the warning labels that describe what
happens when the chemical comes in contact with skin or eyes or is ingested will
emphasize the need for chemical resistance in the plastic packaging. While solvents
easily dissolve some plastics, other plastics provide safe, non-breakable packages for
aggressive solvents.
2. Polymers can be both thermal and electrical insulators. A walk through your house
will reinforce this concept, as you consider all the appliances, cords, electrical outlets
and wiring that are made or covered with polymeric materials. Thermal resistance is
evident in the kitchen with pot and pan handles made of polymers, the coffee pot
handles, the foam core of refrigerators and freezers, insulated cups, coolers, and
microwave cookware. The thermal underwear that many skiers wear is made of
polypropylene and the fiberfill in winter jackets is acrylic and polyester.
3. Generally, polymers are very light in weight with significant degrees of strength.
Consider the range of applications, from toys to the frame structure of space stations,
or from delicate nylon fiber in pantyhose to Kevlar, which is used in bulletproof
vests. Some polymers float in water while others sink. But, compared to the density
of stone, concrete, steel, copper, or aluminum, all plastics are lightweight materials.
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4. Polymers can be processed in various ways. Extrusion produces thin fibers or heavy
pipes or films or food bottles. Injection molding can produce very intricate parts or
large car body panels. Plastics can be molded into drums or be mixed with solvents
to become adhesives or paints. Elastomers and some plastics stretch and are very
flexible. Some plastics are stretched in processing to hold their shape, such as soft
drink bottles. Other polymers can be foamed like polystyrene (Styrofoam™),
polyurethane and polyethylene.
6. Polymers are usually made of petroleum, but not always. Many polymers are made
of repeat units derived from natural gas or coal or crude oil. But building block
repeat units can sometimes be made from renewable materials such as polylactic acid
from corn or cellulosics from cotton linters. Some plastics have always been made
from renewable materials such as cellulose acetate used for screwdriver handles and
gift ribbon. When the building blocks can be made more economically from
renewable materials than from fossil fuels, either old plastics find new raw materials
or new plastics are introduced.
7. Polymers can be used to make items that have no alternatives from other materials.
Polymers can be made into clear, waterproof films. PVC is used to make medical
tubing and blood bags that extend the shelf life of blood and blood products. PVC
safely delivers flammable oxygen in non-burning flexible tubing. And anti-
thrombogenic material, such as heparin, can be incorporated into flexible PVC
catheters for open heart surgery, dialysis, and blood collection. Many medical devices
rely on polymers to permit effective functioning.
Polymers can actually exist in a crystalline state. When we think of a crystal structure
of a metal or ceramic, we think at the atomic level. But with polymers, we need to think at the
molecular level. All of those chains need to come together in an ordered way. Because of this
complexity, rarely would you have a polymer material that is completely crystalline. It is
much more common to have regions of crystallinity, scattered throughout the amorphous.
Remember how much the chains twist and kink. Any chain misalignment will result in a
non-order, amorphous region.
Whereas metals are almost completely crystalline, polymers range from completely
amorphous to about 95% crystalline. The density of the material can tell us to what extent it
has been crystallized. It makes sense that a polymer that is highly crystalline will be denser
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than an equivalent polymer that is amorphous. How much crystallinity will be ending up for
a given polymer depends of how quickly the polymer cooled while it was forming, and what
the chain configuration is. If you want a more highly crystalline structure you need to give
the polymer sufficient time to cool – so that all those polymer chains can find a nice, ordered
place to be. If you cool it quickly upon forming, the chains won’t have a chance to align and
bond nicely to other chains. They’ll be frozen in place in whatever position they began in.
Figure 20
The complexity of the repeat unit plays a big role. If you’ve got a very complex repeat
unit or lots of bonds and atoms, it will be tough for them to crystallize in an ordered way,
when the polymer is forming. Some crystallinity will occur, but it definitely won’t be
dominate. But take a very simple repeat unit – polyethylene is a good example, and it will
crystallize pretty nicely, even if it was to be rapidly cooled. So some of this is out of our
control: it depends on the repeat unit. This is partly why there’s such a big range in polymeric
materials between totally amorphous and almost completely crystalline.
Structure is also important. Linear molecules will more easily align – there is no
awkward chains sticking out that prevents alignment. With branched structures, there are
indeed branches sticking out awkwardly. This makes it difficult for branched polymers to
crystallize. In fact, they may never crystallize. They might be completely amorphous. And
cross-linked and highly networked polymers are even more unlikely to crystallize. You can
safely assume that those polymers are amorphous.
COPOLYMER
If the polymer chain is formed from only one type of monomer units are called
homopolymers. Alternatively, two of more different monomer units can combine to form a
polymer chain is called copolymers.
AAAAAAAAAAAAAA or
Homopolymer
BBBBBBBBBBBBBBB
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The characteristics that make polymers so attractive and useful, lightweight and
almost limitless physical forms of many polymers designed to deliver specific appearance
and functionality, make post-consumer recycling challenging. When enough used plastic
items can be gathered together, companies develop technology to recycle those used plastics.
The recycling rate for all plastics is not as high as any would want. But, the recycling rate for
the 1,170,000,000 pounds of polyester bottles, 23.1%, recycled in 2005 and the 953,000,000
pounds of high density polyethylene bottles, 28.8%, recycled in 2005 show that when critical
mass of defined material is available, recycling can be a commercial success.
Applications for recycled plastics are growing every day. Recycled plastics can be
blended with virgin plastic (plastic that has not been processed before) without sacrificing
properties in many applications. Recycled plastics are used to make polymeric timbers for use
in picnic tables, fences and outdoor playgrounds, thus providing low maintenance, no
splinters products and saving natural lumber. Plastic from soft drink and water bottles can be
spun into fiber for the production of carpet or made into new food bottles. Closed loop
recycling does occur, but sometimes the most valuable use for a recycled plastic is into an
application different than the original use.
An option for plastics that are not recycled, especially those that are soiled, such as
used food wrap or diapers, can be a waste-to-energy system (WTE). When localities decide to
use waste-to-energy systems to manage solid waste, plastics can be a useful component.
The controlled combustion of polymers produces heat energy. The heat energy
produced by the burning plastic municipal waste not only can be converted to electrical
energy but also helps burn the wet trash that is present. Paper also produces heat when
burned, but not as much as do plastics. On the other hand, glass, aluminium and other metals
do not release any energy when burned.
To better understand the incineration process, consider the smoke coming off a
burning item. If one were to ignite the smoke with a lit propane torch, one would observe
that the smoke disappears. This exercise illustrates that the by-products of incomplete
burning are still flammable. Proper incineration burns the material and the by-products of the
initial burning and also takes care of air and solid emissions to insure public safety.
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Some plastics can be composted either because of special additives or because of the
construction of the polymers. Compostable plastics frequently require more intense
conditions to decompose than are available in backyard compost piles. Commercial
composters are suggested for compostable plastics.
Plastics can also be safely land filled, although the valuable energy resource of the
plastics would then be lost for recycling or energy capture. Plastics are used to line landfills
so that leachate is captured and groundwater is not polluted. Non-degrading plastics help
stabilize the ground so that after the landfill is closed, the land can be stable enough for useful
futures.
Polymers affect every day of our life. These materials have so many varied
characteristics and applications that their usefulness can only be measured by our
imagination. Polymers are the materials of past, present and future generations.
PET is one of the most commonly used plastics in consumer products, and is found in
most water and pop bottles, and some packaging. It is intended for single use applications;
repeated use increases the risk of leaching and bacterial growth. PET plastic is difficult to
decontaminate, and proper cleaning requires harmful chemicals. Polyethylene terephthalates
may leach carcinogens.
PET plastic is recyclable. The plastic is crushed and then shredded into small flakes
which are then reprocessed to make new PET bottles, or spun into polyester fiber. This
recycled fiber is used to make textiles such as fleece garments, carpets, stuffing for pillows
and life jackets, and similar products.
Products made of #1 (PET) plastic should be recycled but not reused. To use less PET
plastic, consider switching to reusable beverage containers and replacing disposable food
packaging with reusable alternatives.
HDPE plastic is the stiff plastic used to make milk jugs, detergent and oil bottles,
toys, and some plastic bags. HDPE is the most commonly recycled plastic and is considered
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one of the safest forms of plastic. It is a relatively simple and cost-effective process to recycle
HDPE plastic for secondary use.
HDPE plastic is very hard-wearing and does not break down under exposure to
sunlight or extremes of heating or freezing. For this reason, HDPE is used to make picnic
tables, plastic lumber, waste bins, park benches, bed liners for trucks and other products
which require durability and weather-resistance. It is also a popular material for recycled
plastic raised garden beds.
Products made of HDPE are reusable and recyclable. However, since only small
percent of HDPE gets recycled each year, it’s wise to use as little as possible. To cut down,
consider replacing your disposable produce bags with reusable alternatives.
PVC is a soft, flexible plastic used to make clear plastic food wrapping, cooking oil
bottles, teething rings, children’s and pets’ toys, and blister packaging for myriad consumer
products. It is commonly used as the sheathing material for computer cables, to make plastic
pipes and parts for plumbing, and in garden hoses. Because PVC is relatively impervious to
sunlight and weather, it is used to make window frames, garden hoses, arbors, raised beds
and trellises.
PVC is dubbed the “poison plastic” because it contains numerous toxins which it can
leach throughout its entire life cycle. Almost all products using PVC require virgin material
for their construction; less than 1% of PVC material is recycled.
Products made using PVC plastic are not recyclable. While some PCV products can
be repurposed, PVC products should not be reused for applications with food or for
children’s use. To avoid items made with PVC plastic, consider replacing plastic food wrap
with reusable beeswax wraps; plastic toys with reclaimed wool stuffed animals; and your
PVC garden hose with a drinking water safe garden hose.
LDPE is often found in shrink wraps, dry cleaner garment bags, squeezable bottles,
and the type of plastic bags used to package bread. The plastic grocery bags used in most
stores today are made using LDPE plastic. Some clothing and furniture also uses this type of
plastic.
LDPE is considered less toxic than other plastics, and relatively safe for use. It is not
commonly recycled, however, although this is changing in many communities today as more
plastic recycling programs gear up to handle this material. When recycled, LDPE plastic is
used for plastic lumber, landscaping boards, garbage can liners and floor tiles. Products made
using recycled LDPE are not as hard or rigid as those made using recycled HDPE plastic.
Products made using LDPE plastic are reusable, but not always recyclable. To cut
down on the amount of LDPE that you consume, try replacing your plastic grocery bags with
fabric alternatives and taking a cloth bag to your local bakery the next time you buy a loaf of
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bread. You can also replace plastic sandwich bags with platinum silicone alternatives, which
are heat safe.
PP is considered safe for reuse. To recycle products made from PP, check with your
local curbside program to see if they are now accepting this material. To cut down on how
much PP you consume, opt for reusable straws instead of plastic ones, reusable water bottles,
and cloth diapers.
Polystyrene may leach styrene, a possible human carcinogen, into food products
(especially when heated in a microwave). Chemicals present in polystyrene have been linked
with human health and reproductive system dysfunction.
Recycling is not widely available for polystyrene products. While the technology for
recycling polystyrene is available, the market for recycling is small. Awareness among
consumers has grown, however, and polystyrene is being reused more often.
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The #7 category was designed as a catch-all for polycarbonate (PC) and “other”
plastics, so reuse and recycling protocols are not standardized within this category. Of
primary concern with #7 plastics, however, is the potential for chemical leaching into food or
drink products packaged in polycarbonate containers made using BPA (Bisphenol A). BPA is
a xenoestrogen, a known endocrine disruptor.
Number 7 plastics are used to make baby bottles, sippy cups, water cooler bottles and
car parts. BPA is found in polycarbonate plastic food containers often marked on the bottom
with the letters “PC” by the recycling label #7. Some polycarbonate water bottles are
marketed as ‘non-leaching’ for minimizing plastic taste or odor, however there is still a
possibility that trace amounts of BPA will migrate from these containers, particularly if used
to heat liquids.
A new generation of compostable plastics, made from bio-based polymers like corn
starch, is being developed to replace polycarbonates. These are also included in category #7,
which can be confusing to the consumer. These compostable plastics have the initials “PLA”
on the bottom near the recycling symbol. Some may also say “Compostable.”
Number plastics are not for reuse, unless they have the PLA compostable coding.
When possible it is best to avoid #7 plastics, especially for children’s food. Plastics with the
recycling labels #1, #2 and #4 on the bottom are safer choices and do not contain BPA. PLA
coded plastics should be thrown in the compost and not the recycle bin since PLA
compostable plastics are not recyclable. To avoid chemicals leaking into your foods from food
packaging, try going homemade and storing your leftovers (or your lunches) in platinum
silicone or stainless steel.
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Course Packet 04
Nanoscale science and technology, often referred to as "nanoscience" or "nanotechnology," are science
and engineering enabled by our relatively new ability to manipulate and characterize matter at the
level of single atoms and small groups of atoms. This capability is the result of many developments in
the last two decades of the 20th century, including inventions of scientific instruments like the
scanning tunneling microscope. Using such tools, scientists and engineers have begun controlling the
structure and properties of materials and systems at the scale of 10 -9 meters, or 1/100,000 the width of
a human hair. Scientists and engineers anticipate that nanoscale work will enable the development of
materials and systems with dramatic new properties relevant to virtually every sector of the economy,
such as medicine, telecommunications, and computers, and to areas of national interest such as
homeland security. Indeed, early products based on nanoscale technology have already found their way
into the marketplace and into defense applications.
Objectives
Understand what nanotechnology is about and how to use it
Describe fabrication methods in nanotechnology (top down & bottom up) and
characterization methods in nanotechnology
Gain knowledge of structure, properties, manufacturing, and applications of fullerenes and
carbon nanotubes.
Discuss applications of nanomaterial and implication of health and safety related to
nanomaterial.
Develop awareness and concern towards the environment.
Appreciate the significance of nanomaterial in improving the quality of life.
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NANOTECHNOLOGY
A nanometre (nm) is 0.000 000 001 meter (or 10 -9 m). That’s one millionth of a
millimeter. Nanoparticles are very small, less than 100 nm across.
Figure 1
Nanotechnology is not a new idea. Nanoparticles have in fact been used by people
for thousands of years. The Egyptians used ink containing nanoparticles of black pigment.
Nanoparticles of lead sulfide were used by the Romans to dye their hair black. Nanoparticles
of gold and silver have also been used since the 10th century to colour ceramics and stained
glass.
Insects and lizards are able to stick to walls because of the nanostructures on their
feet.
Spiders’ webs are made of super-strong nanofibers.
Butterflies’ wings contain shiny reflective nanocrystals.
Chloroplasts in plant cells are nanofactories that harness the Sun’s energy to make
glucose.
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Development of Nanotechnology
Figure 2
CLASSIFICATION OF NANOMATERIALS
Nanomaterials or the nanoparticles are the set of particles or the substances where
atlas one dimension is less than approximately 100nm.
Nanomaterial is an object that has atleast one dimension in the nanometer scale
approximately 1-100nm.
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PROPERTIES OF NANOPARTICLES
Nanoparticles have more atoms or molecules nearer the surface than larger particles.
In reactions, nanoparticles are able to react more quickly. This is because more atoms in a
nanoparticle can be in contact with the reactant, than in a larger particle.
Figure 3
Nanoparticles have a much bigger surface area to volume ratio than larger particles.
This is very useful for substances such as catalysts.
Magnetic Properties
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3. Bulk gold and platinum are non-magnetic but at the nano size they act as magnetic
particles. Au nanoparticles become ferromagnetic when they are capped with the
appropriate molecules such as thiol.
Optical Properties
1. In small nano clusters the effect of reduced dimensionality on electronic structure has
the most profound effect on the energies of highest occupied molecular orbital
(HOMO) which is valence band and the lowest unoccupied molecular orbital
(LUMO),essentially the conduction band.
2. The optical emission and adsorption occurs when the transition of the electrons occur
between these two states.
3. Semiconductors and many metals show large changes in optical properties such as
color, as a function of particle size.
4. Colloidal suspensions of gold nanoparticles have a deep red color which becomes
progressively more yellow as the particle size increases.
Gold spheres of 10-20nm exhibit red color, 2-5nm exhibit yellow color and >20nm
exhibit purple color. Similarly, silver particles of 40nm exhibit blue color and 100nm exhibit
yellow color. Prism shaped Silver particles red color.
Electronic Properties
1. The changes which occur in electronic properties as the system length scale is
reduced are related mainly to the increasing influence of the wave-like property of
the electrons (quantum mechanical effects) and the scarcity of scattering centres.
2. As the size of the system becomes comparable with the de Broglie wavelength of the
electrons, the discrete nature of the energy states becomes apparent once again,
although a fully discrete energy spectrum is only observed in systems that are
confined in all three dimensions.
3. In certain cases, conducting materials become insulators below a critical length scale,
as the energy bands cease to overlap. Owing to their intrinsic wave-like nature,
electrons can tunnel quantum mechanically between two closely adjacent
nanostructures, and if a voltage is applied between two nanostructures which aligns
the discrete energy levels in the DOS, resonant tunnelling occurs, which abruptly
increases the tunnelling current.
4. Conduction in highly confined structures, such as quantum dots, is very sensitive to
the presence of other charge carriers and hence the charge state of the dot.
5. These Coulomb blockade effects result in conduction processes involving single
electrons and as a result they require only a small amount of energy to operate a
switch, transistor or memory element.
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Two basic strategies are used to produce nanoparticles: 'top-down' and 'bottom-up'.
The term 'top-down' refers here to the mechanical crushing of source material using a milling
process. In the 'bottom-up' strategy, structures are built up by chemical processes. The
selection of the respective process depends on the chemical composition and the desired
features specified for the nanoparticles.
Figure 4
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1.
Course Packet 04Course Pa
Top-Down (Mechanical-physical production processes)
Figure 5
This involves using small-scale versions of normal machines to cut and shape
structures into nano-sized pieces. The micro-etching process is already being used to make
microchips that are even smaller and hold more components.
Milling processes
Milling involves thermal stress and is energy intensive. Lengthier processing can
potentially abrade the grinding media, contaminating the particles. Purely mechanical milling
can be accompanied by reactive milling: here, a chemical or chemo-physical reaction
accompanies the milling process.
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2.
Course Packet 04Course Pa
allow full control of particle shape.
This involves building up nanoparticles atom by atom. This can be carried out using
machines such as the scanning tunnelling microscope, which can pick up and move atoms
and molecules around.
Figure 6
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Gas phase processes are among the most common industrial-scale technologies for
producing nanomaterials in powder or film form.
Particles can also be produced from droplets using centrifugal forces, compressed air,
sonic waves, ultrasound, vibrations, electrostatics and other methods. The droplets are
transformed into a powder either through direct pyrolysis (thermal cleavage of chemical
compounds) or via direct reactions with another gas. In spray pyrolysis, droplets of the
source material are transported through a high-temperature field (flame, oven), which
rapidly vaporizes the readily volatile components or leads to decomposition reactions. The
formed particles are collected on filters.
Precipitation processes
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The precipitation of solids from a metal ion-containing solution is one of the most
frequently employed production processes for nanomaterials. Metal oxides as well as non-
oxides or metallic nanoparticles can be produced by this approach. The process is based on
Sol-gel processes
Figure 8
Self-assembly
This involves atoms and molecules putting themselves together. It occurs in every
human being. Molecules are assembled in cells to form very complicated structures.
Molecules such as DNA, can replicate themselves.
Learning Module 02: Chemistry of Materials 112
Course
Packet
LM02-FCHE
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The key to using self-assembly as a controlled and directed fabrication process lies in
designing the components that are required to self-assemble into desired patterns and
On a very small scale you wouldn't even use the term 'self-assembly' but rather
'chemical synthesis' – the processes chemists have refined over many years. However, the
stability of covalent bonds enables the synthesis of almost arbitrary configurations of only up
to 1000 atoms. Larger molecules, molecular aggregates, and forms of organized matter more
extensive than molecules cannot be synthesized bond-by-bond. Self-assembly is one strategy
for organizing matter on these larger scales.
Fullerenes
The element carbon can exist in different structural forms, which are known as
allotropes. Diamond and graphite are the two most common allotropes of carbon. Carbon
can also exist in other forms, collectively called fullerenes.
The first of these, buckminsterfullerene, was discovered by accident, in 1985, and its
discovery opened up a whole new area of chemistry. It was named after an American
architect Richard Buckminster Fuller who had designed buildings made of dome-shaped
structures.
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Figure 9
The molecules can be used as cages to trap atoms and smaller molecules inside them.
The surface of C60 molecules can be coated with other atoms. For example, coating
with hydrogen makes a smooth substance that is even more slippery than Teflon.
The molecules can be joined together to make bigger fullerene structures.
C60 molecules are also known as ‘buckyballs’. Since the discovery of this first
fullerene, other types of fullerenes that have been made include:
Some of the uses of fullerenes that scientists are currently working on include:
Non-stick slippery coatings for machinery, which act like miniature ball bearings.
Cages to hold drug molecules that can be delivered directly into the body.
Molecular sieves, which traps large particles like viruses while allowing smaller,
healthy particles to pass through.
Chemical sponges to soak up toxic substances in the body.
Carbon Nanotubes
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The bonding between the carbon atoms being the same as between carbon atoms in
graphite. The ends are capped with a buckyball. The nanotubes are 1 nm in diameter
Multi-walled nanotubes exist. In these, several tubes can rotate and slide within in
each other, almost without friction. As well as single walled nanotubes, double and multi-
walled carbon nanotubes can be produced in a similar way. These materials have been
demonstrated to be the stiffest and strongest fibres known and have exceptional electrical
conducting properties.
The properties of nanotubes make them useful in many ways. Some examples include:
USES OF NANOPARTICLES
Catalysis
Heterogeneous catalysis takes place when reactions occur on the surface of a solid
catalyst. One catalytic application already developed is the use of cerium(IV) oxide
nanoparticles which are added to diesel and bio-diesel fuels in very small amounts (5-10
ppm). When diesel fuel is combusted in an engine, it is not completely oxidized and fine
particles of carbon, carbon monoxide as well as unreacted fuel are emitted. The additive,
cerium(IV) oxide acts as a heterogeneous catalyst and ensures that the fuel is combusted
completely to carbon dioxide and water, thus leading to an improvement in fuel efficiency by
as much as 4-11% and much less pollution (about 18% less particulate matter is emitted).
Because of their size, the cerium(IV) oxide nanoparticles forms a homogeneous solution in the
fuel and are thus easily premixed with the fuel, which then requires no special delivery
equipment and does not require any modification to the vehicle engine. The catalysts in
catalytic converters for cars are nanoparticles of alloys of palladium and rhodium.
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Carbon nanotubes are not only very strong but are also flexible. They can be twisted
and bent without breaking. Thus they are used in polymers and composites to strengthen a
structure, to increase the electrical conductivity of the material and to increase heat transfer.
A 'fleece' fabric has been produced that contains nanoparticles of carbon, derived
from bamboo, infused into a range of fibres (rayon, polyesters and polyamides). Through the
highly absorbent, high surface areas and surface modifications of the nanoparticles, they can
be used in such products to provide properties, including anti-bacterial, anti-fungal,
deodorizing, thermal-regulating and static-free, yet soft and comfortable to wear. The
nanoparticles are embedded in the fibres rather than present as a coating, and are not
removed from the fabric when washed.
Nanotechnology will have an enormous impact in the healthcare and personal care
industries, because of the extremely small dimensions of nanoparticles and their mobility.
The chemical reactivity rate, the location of effect, and the timing of a treatment are all
affected by particle size. Efficient drug delivery is being tested already. Biological
microelectromechanical devices (bioMEMS) implanted into the body to deliver doses of
drugs or carry new cells to damaged tissues bring the concept of nanosurgery into being.
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Carbon nanotubes produce composites with epoxy resins with a tensile strength 5 -10
times higher than comparable carbon fibre reinforced materials. Yacht masts have been
produced commercially, which are up to 30 times stiffer without adding any extra weight.
Other applications of carbon nanotube reinforced composites include tennis rackets,
fishing rods, and car body panels used in racing cars for strength and lightness, thereby
enhancing performance. The cushioning properties of trainer shoe soles have been improved
by incorporating nanoparticles thereby changing the structure of the polymeric soles, whilst
at the same time extending durability because of the hardness enhanced by the presence of
the nanoparticles.
A recent concern regarding nanoparticles is whether their small sizes and novel
properties may pose significant health or environmental risks. There is much debate over the
safety and environmental impact of nanotechnology. One particular concern is the potential
cancer-causing risks from inhaled particles similar to those that were posed by asbestos
fibres.
As many of the applications described above involve nanoparticles being locked into
polymeric composites, film and fibres, it is not expected that such nanomaterials will pose a
threat to the health and safety of users. More important however, is the exposure of plant
operators handling 'raw' nanoparticles in making these materials. Before universal
application of nanotechnology can really be advanced much further, definitive studies of the
effect of nanoparticles on the body and the environment must be completed.
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On the other hand, some global environmental issues might well be resolved using
nanomaterials. One of the greatest potential impacts of nanotechnology on the lives of the
majority of people on Earth could be desalination and purification of water, providing fresh
The future of nanotechnology has been a subject of many scientific and nonscientific
speculations, including several doomsday visions in popular culture that predicted self-
replicating nano particles taking part in massive assaults on humanity and the environment.
An example of such scenario is given in Michael Crichton popular novel Prey, where "grey
goo" self-replicates and overwhelms the world... Dire predictions have accompanied many
new technologies at their infancy (for example robotics in the 1940s and 1950s). The more
futuristic visions of nanotechnology include on one hand the envisioned use of nano-particles
inside the body and the blood stream (for diagnostic and therapeutic purposes), and on the
other hand – potential development of new weapons of mass destruction enabled by
nanotechnology.
As was the case with many new technologies, solid predictions of their course of
developments are difficult to make. If nanotechnology were to follow the paths of other new
technologies (digital communications, the Internet) the early predictions – for the first ten
years – would tend to overestimate the impact of the technology (much less is achieved
compared to predictions); the long-term prediction – for the first 50-75 years – would tend to
underestimate that impact (much more is achieved compared to predictions).
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