UNIVERSIDAD CARLOS III DE MADRID

ESCUELA POLITÉCNICA SUPERIOR

DEPARTMENT OF MATERIALS SCIENCE AND ENGINEERING

LABORATORY SESSIONS

MATERIALS SCIENCE AND ENGINEERING

Course 2020-2021
Coordinating teachers: Maria Eugenia Rabanal
 Materials science and engineering
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RULES OF USE AND WORK IN THE LABORATORY

GENERAL RULES OF SECURITY

SAFETY IN LABORATORIES. GENERAL MEASURES

Habits:
Do not eat food, drink beverages, chew gum, apply any cosmetics or lick anything.
Wash your hands after performing all experiments.
Order and cleanliness:
 Work areas should be kept clean and tidy and free from coats, bags and books.
Health:
 If the student has any incompatibility with some chemical product, a pacemaker or any
pathology which could be relevant to the proper course of the practice she/he should inform
the teacher before performing it.
Clothing:
 The use of rings, bracelets, wristwatches, necklaces, ties and clothes with tassels, which
could difficult the equipment use, must be avoided. Long hair must be tied in a ponytail.
 The footwear must be closed (avoid using sandals) and the use of short-sleeved clothes or
shorts is not advisable.
In general:
 Behaviour in the laboratory must be correct. In no case, the students can make run or play.
Misbehaviour in the laboratory is an expulsion motive. It is essential to read and understand
the laboratory outline before entering the laboratory. The students must follow the
teacher’s instructions during the entire laboratory lesson.
 It is not permitted to perform experiments which are not authorised by the teacher. Nor
touch any equipment or laboratory material which do not belong to the current practice.
In the case of an accident:
 Any incident, even small, will be considered as an accident.
 Students must immediately notify any incidents to the laboratory teacher.
 It is indispensable to know the location and functioning of showers and extinguishers,
as well as the escape routes.
 In the case of evacuation, it shall be done by any of the two doors with anti-panic lock.
Exit from the building will be performed by the escape routes.
 The area located on the exterior of the building (next to the flags) is set as a mandatory
meeting point.

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SPECIFIC SECURITY RULES

RISK IN THE USE OF MACHINES

In some occasions, the risk cannot be eliminated, being necessary to use mutual protection
means guards and safety devices.

1. A guard is the component of a machine used as a physical barrier to protect.

2. A protective device is one that prevents starting or holding a dangerous machine stage
as it is detected or the possible human presence in the danger zone.
 Do not turn off existing security devices.
 Use the security means correctly.
 Do not use equipment or machinery without knowing how it works.
 Before performing any task on a machine, the students must follow carefully the instructions
that are given. In the case of doubt, please ask the teacher.
 Unplug tools and equipment before its setting.
 In the case of danger or unforeseen event, immediately click the emergency stop (the red
push-button).
 It is not allowed the use by students of presses, blending machines, thread grinders, drills,
millers, lathes or any machine tool.
 It is forbidden to repair, clear or clean any equipment by students. Notify the anomaly so
that trained personnel perform the necessary task.
USE OF FURNACES:
 Be extremely cautious when operating furnaces, if it is observed any anomaly immediately
notify the teacher. Use protective gloves and goggles at all times. Make use of clamps when
handling test pieces. Do not leave gloves, coats or any material that may be combustible
close to ovens.
USE OF THE METAL ROLLING MACHINE:
 Be extremely cautious when operating the rolling machine. The test pieces must be placed
when the system is turned off. For the extraction of the pieces from the feeding area, turn
direction must be inverted and, once the system is turned off, the piece can be removed.
USE OF THE CHARPY IMPACT TEST MACHINE:
 To place the piece, raise the hammer (5 cm), after settling it, lift the hammer to the desired
height.
 Do not access the pendulum cell unit until the hammer has completely stopped its
movement.

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OPERATING LABORATORY RULES

a) The attendance at ALL sessions is mandatory to pass the laboratory sessions.

b) It is required strict PUNCTUALITY at the entrance of the laboratory.
c) Students must read the practice outline BEFORE entering the laboratory.
d) At the end of each practice, all the material and the working place must be organised and tidy,
the teacher will revise it and will stamp the corresponding card of each student.
e) It is not possible to change the laboratory group.
f) Mobile phones must be silent during the laboratory sessions. In exceptional cases, the teacher
must be consulted previously.
g) Students must attend to the laboratory with the laboratory coat. If the student does not have
it before entering the lab, he/she will NOT perform the session. Under no circumstances, the
teacher will supply laboratory coats. If necessary, the teacher will supply other protection facilities.

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SESSION I: COLD WORKING OF METALS

1. OBJECTIVE

To study the effect of cold working and recrystallisation process on the hardness and electrical
conductivity of brass.

2. MATERIAL

Brass samples
Metal rolling machine
Oven
Hardness tester
Optical microscope
Conductivity meter

3. INTRODUCTION

Metallic materials can present different values of elastic limit (Young’s modulus), hardness and
strength, based on the opposition of the structure to the movement of dislocations. There are
different hardness mechanisms for crystalline materials: cold working also referred to as strain
hardening, solid solution strengthening, precipitation hardening or grain size reduction. What
all these mechanisms have in common is that they alter the properties of the material by
blocking dislocation movement.
The goal of this practice is to study the changes in the properties of a crystalline material after
performing a cold working. It is important to note that material is only considered to work at
low temperature or "cold working" when at that temperature there is insufficient energy to
produce thermally activated processes in which diffusion takes place. Normally, a material is
considered to cold work when the temperature is below to 0.3Tf. There are two types of cold
working processes: Mass deformation processes (rolling, forging, extrusion and drawing) and
deformation processes on the sheet (inlaying, cutting). In this case, the deformation will be done
by rolling and will produce hardening by cold work (work hardening).
Plastic deformation of metal at low temperature mainly takes place by movement of
dislocations. As deformation progresses, the dislocations interact, slow down and multiply. The
higher the level of deformation achieved, the higher number of dislocations, and therefore there
is also an increase in dislocation density. So, this will cause difficulty moving them, and higher
stress values will be needed to achieve plastic deformation, which will lead to progressive
hardening by cold working. Hardening is observed as an increase in hardness values but also as
an increase in the yield strength.
If a metallic material is subjected to a certain stress above its yield strength, once the load is
removed the material will present a permanent deformation which causes a change in its
dimensions. Also, its yield strength will also change, as when the load is applied again, the new
tensile curve will follow the unloading line of the first test, and the tension at which the plastic
deformation occurs will be greater than that of the initial test. (Figure 1)

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Stress (Mpa)
Unloading

Loading

Strain

Figure 1. The stress-strain curve in a tensile test.

After cold working of a metallic material, it remains in a metastable point due to the increased
free energy caused by the creation of large amounts of dislocations. The material needs to
minimise its free energy so that it can achieve its equilibrium state. To reduce dislocation
density, a heat treatment is carried out, known as annealing. Annealing is a process that consists
of increasing the temperature and maintaining it for a period. Then, the material is slowly cooled
down, usually inside the oven. During this time, changes in microstructure will be produced as
well as other modifications in the material properties. There are three stages during annealing:
recovery, recrystallisation and grain growth.
During cold working, the grains are elongated in the rolling direction, and this shape is kept
during the recovery stage. In this first stage, only changes in the number and positions of
dislocations occur. The temperature allows the dislocations to move as well as to change plane,
which further helps them to rearrange in positions of less energy.
In the recrystallisation stage, nucleation and growth processes occur, which allow the obtaining
of a microstructure with equiaxed grains, formed from the elongated starting grains. Finally, in
the third stage, new equiaxed grains increase their size, reducing the grain boundary surface and
thus decreasing the free energy of the material.

4. EXPERIMENTAL PROCEDURE

Use of conductivity meter

1. Deformed samples will be selected to carry out the measurements in those areas that
allow the best metal-probe contact.
2. Place the conductivity meter probe over the sample and read the conductivity value
(MS/m).
3. At least three measurements will be done to calculate the average.
DANGER: the conductivity meter probe is very delicate; the students must put extreme care in
NOT HITTING IT.

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Measurement of the variation of properties

The steps to follow are:
- Measure the hardness and conductivity in the initial state of the specimen 1 (without
cold working).
- After, the samples 2, 3 and 4 are cold rolled, reducing its section by 10, 30 and 50 %,
respectively, measuring the hardness and conductivity in each case.
- Sample 5 is already prepared. It has been rolled to 50% and annealed in the oven at 650
ºC for 10 min. and slowly cooling in the oven. Measure its hardness and conductivity.

Metallographic inspection
In the optical microscope, brass samples already prepared with different rolling degrees will be
observed.

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SESSION II: CRYSTALLINE STRUCTURES

1. OBJECTIVES

 Construction of compact and non-compact crystalline structures

 Identification of interstitial sites
 Determination of crystalline structures using x-ray diffraction
 Determination of lattice parameters of crystalline structures

2. MATERIALS

31 expanded polystyrene spheres

Several diffraction patterns
Millimetre ruler

3. INTRODUCTION

Crystalline lattices
Metallic solids, semiconductor materials, many ceramic materials and even some polymers have
a crystalline structure where atoms display both a short and a long-range order, being the
particles (atoms, ions or molecules) arranged along the material forming a lattice.
Crystalline structures can be easily described by the so-called unit cell, which is the simplest unit
that, by indefinite repetition in the three spatial directions, generates the crystal. If the exact
arrangement of atoms within a unit cell is known, then the arrangement of the whole crystal
can also be known. The unit cell is a parallelepiped (Figure 2), which is entirely defined regarding
their lattice parameters or constants: the three edges lengths (a, b and c) and the three lattice
angles (α, β and ).

Figure 2. Unit cell and lattice parameters

The three-dimensional crystalline lattice is generating by stacking or translation of the unit cell,
and there are only seven different possible combinations of the lattice parameters that meet
this requirement, that is, there are only seven combinations of parallelepipeds to reproduce the
three-dimensional space completely without holes or superposing them. These systems are
those shown in the table in Figure 3, where the lattice parameters which define them are also
shown.
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Figure 3. Crystalline systems

The crystalline structure is formed when the atoms are identically distributed along the crystalline
lattice. Thus, there are four basic types of atomic distribution in the unit cell: atoms located at each
of the vertices (lattice type P), atoms at each of the vertices and the centres of all the faces (lattice
type F), atoms located at each of the vertices and the centres of two opposed faces (lattice type
C) and atoms at each of the vertices and in the centre of the unit cell (lattice type I). The different
combinations of crystalline systems and lattices types results in the 14 Bravais lattices (Figure 4).

Figure 4. Bravais lattices

The crystalline structures come from the different ways in which atoms, ions or molecules are
arranged or “packed” along the space. The atomic packing in the plane can be done compactly,
forming a compact plane (Figure 5 right), or in a non-compact way, forming a non-compact plane
(Figure 5 left). The compact or non-compact stacking of these planes results in the different
crystalline lattices.

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Figure 5. Non-compact (left) and compact (right) planes.

Stacking up non-compact planes in a non-compact way creates a simple cubic structures (Figure
6 left). Stacking up non-compact planes in a compact way results in a body-centred cubic
structure (Figure 6 right).

Figure 6. Non-compact (left) and compact (right) stacking up of non-compact planes.

The non-compact stacking up of compact planes results in a simple hexagonal structure. The
compact stacking up of compact planes can be done following two stacking sequences: ABABAB,
leading to the compact hexagonal structure (Figure 7 left) or ABCABCABC, which results in the
face-centred cubic structure (Figure 7 right).

Figure 7. ABABAB (left) and ABCABC (right) stacking sequences.

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In any of the crystalline structures previously described, there are holes between the atoms in
the lattice, in which, smaller atoms can be placed. These holes are known as interstitial sites or
holes. The types of holes that are going to be studied in this course are the tetrahedral and
octahedral holes (Figure 8). In compact structures, there are 2n tetrahedral holes and n
octahedral holes (being n the number of atoms in the unit cell).

Figure 8. Tetrahedral and octahedral holes

X-ray diffraction. Analysis of crystalline structures
One way for studying the crystalline solids structure is the x-ray diffraction technique. This is
possible because the x-ray wavelength is in the order of magnitude of the interplanar spacing in
crystalline solids.
In general, diffraction occurs when a wave encounters a series of regularly spaced obstacles that
are capable of scattering the wave so that the diffracted waves give as a result a diffraction pattern
that informs about the order of those obstacles that scattered the waves.
The basis of the diffraction can be resumed as follows: when the x-ray diffraction takes place in a
crystalline structure, therefore an ordered structure, the obstacles or scattering centres are the
atoms that form the planes. As the distance between adjacent and parallel planes of atoms
(interplanar spacing) is in the order of the x-radiation wavelength when a monochromatic x-ray
beam is an incident on a crystalline material the scattering would take place due to their atoms.
The register of these interferences is known as x-rays diffraction.
When an x-rays beam, of known wavelength, impinges on a sample, a scattering of the x-radiation
takes place by the electronic clouds associated with the atoms of the crystal. As there are a lot of
parallel planes involved in the scattering, the scattered waves coming from these planes will
interfere with each other. The interference will be constructive if the difference in the path length
of scattered waves coming from adjacent planes is equal to an integer number of wavelengths.
This is illustrated in Figure 9, where a beam with a wavelength, λ, is incident on a group of planes
at an angle θ. This group of planes have the same h, k and l Miller indices and are separated by the
interplanar spacing dhkl. The x-rays beam is scattered at an angle equal to that of the incident beam,
following the Bragg’s law (Equation 1).
2dhkl sinθ = n λ where n may be any integer (1, 2, 3, …) Equation 1

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Figure 9. Schematic representation of the diffraction phenomenon.

In an x-ray diffraction experiment, a set of reflections is obtained, resulting from the constructive
interferences, which provides information about the crystallographic planes of the material. Thus,
it is possible to characterise the way in which the constituents of a crystalline material are ordered.
The intensity of the beam scattered by a given set of planes depends on the nature of the atoms
defining the planes. Therefore, from the measurement of the reflections intensities, it is possible
to identify the different atoms of the crystal.
The result of an x-ray diffraction experiment consists of a graph where the intensity of the
diffracted ray (ordinate) is plotted as a function of diffraction angle θ (usually 2θ) (abscissa). This
representation is known as diffraction pattern or diffraction diagram. Thus, knowing the
wavelength of the x-radiation and measuring the diffraction angles θ, the characteristic interplanar
spacings of a crystal can be calculated. The information that can be obtained from the diffraction
pattern is extensive; we are going to limit us to the calculation of lattice parameters and the
identification of substances using already known diffraction patterns.
Reading a diffraction pattern
Using a millimetre ruler, the 2θ angle (abscissa) of each reflexion (peak), as well as their absolute
intensity (height) are measured, writing down both values in a 5-column table. The relative
intensities, calculated as a percentage of the most intense reflexion, is noted down in the third
column. The values of the interplanar spacing dhkl are obtained using the 2θ values and applying
the Bragg’s law (2dhkl sinθ = n λ, being n=1), knowing that in the x-ray diffraction experiment a
radiation Kα of Cu (λ = 1,5405 Å) has been used.
Taking into account the interplanar spacing values dhkl of the three more intense reflections, the
ASTM cards are checked, selecting the one that fits better our substance problem; confirming with
all the other measured reflections. The ASTM cards have the information about interplanar
spacing, the relative intensity of the reflections and the Miller indices related, which are the
characteristic parameters of the crystalline solid.
Once the substance problem and its ASTM card are known, the properties of the metal are known,
and the cell volume, atomic packing factor and volumetric density can be calculated. To do so, the
lattice parameters of the unit cell must be known beforehand. As the three metal of the ASTM
cards has a cubic structure, the three edges lengths are equal, a=b=c, and the lattice parameter a
can be related with the interplanar spacing dhkl using the following expression.

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= Equation 2

The atomic packing factor is obtained as follows:

∑
= Equation 3
The volumetric density is calculated:
∑ ×
= ×
Equation 4

Where M is the atomic weight of the atom.

4. EXPERIMENTAL METHOD

a) Crystalline structures using rigid spheres

- Build the following structures:
i) Simple cubic and face-centred cubic (FCC)
ii) Simple hexagonal and hexagonal close-packed (HCP).
- Draw the unit cell of each built structure.
- Identify and draw the octahedral and tetrahedral holes of the compact or close-packed
structures.
b) From the corresponding diffraction pattern:
-Identification of the metal
Index the diffraction pattern peaks and identify the metal using the ASTM cards given below. Note
down in the diffraction pattern the crystallographic planes corresponding to the indexed
reflections.
Calculate the lattice parameters of the unit cell and, once its symmetry is known, obtain the atomic
radius, cell volume, atomic packing factor and volumetric density. Draw in the unit cell the three
families of planes whose intensities are maximum.

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JCPDS Cards

04-0836
Cu
d, Å int h k l
Copper
Rad: CuKa1=1.5405 Filter: Ni Beta 2.0880 100 1 1 1
Cut-off: Int: Diffract. I/Icor.: 1.8080 46 2 0 0
Ref: Swanson, Tatge, etc. (1953) 1.2780 20 2 2 0
Sys.: Cubic (FCC) SG.: Fm3m (225) 1.0900 17 3 1 1
a: b: c: A: C: 1.0436 5 2 2 2
: : : Z: 4 mp: 1083 0.9038 3 4 0 0
Dx: 8.935 Dm: 8.950 SS/FOM 0.8293 9 3 3 1
Colour: red 0.8083 8 4 2 0

04-0787
Al
d, Å int h k l
Aluminium
Rad: CuKa1=1.5405 Filter: Ni Beta 2.3380 100 1 1 1
Cut off: Int: Diffract. I/Icor.: 2.0240 47 2 0 0
Ref: Swanson, et al., Natl. Bur. Stand. (U.S.), Cir. (1953) 1.4310 22 2 2 0
Sys.: Cubic (FCC) SG.: Fm3m (225) 1.2210 24 3 1 1
a: b: c: A: 4 C: 1.1690 7 2 2 2
: : : Z: mp: 1.0124 2 4 0 0
Dx: 2.699 Dm: SS/FOM 0.9289 8 3 3 1
Colour: metallic grey 0.9055 8 4 2 0
0.8266 8 4 2 0
06-0696
Fe
d, Å int h k l
Iron
Rad: CuKa1=1.5405 Filter: Ni Beta 2.0268 100 1 1 0
Cut off: Int: Diffract. I/Icor.: 1.4332 20 2 0 0
Ref: Swanson, et al., Natl. Bur. Stand. (U.S.), Cir. (1955) 1.1702 30 2 1 1
Sys.: Cubic (BCC) SG.: Im3m (229) 1.0134 10 2 2 0
a: b: c: A: C: 0.9064 12 3 1 0
: : : Z: 2 mp: 0.8275 6 2 2 2
Dx: 7.875 Dm: SS/FOM
Colour: metallic grey

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SESSION III: POLYMER IDENTIFICATION

1. OBJECTIVES

The realisation of preliminary analytical tests to identify industrial use polymers.

2. MATERIALS

Several polymer samples (pellets and plates)

Cutter
Test tube
Tweezers
Universal indicator (paper)
Goggles
Bunsen burner
Pure copper wire
Polymer samples to identify in vials with different dissolvents

3. INTRODUCTION

The term plastic encompasses all materials based on macromolecules in a chain configuration
which is composed by the high repetition of monomers. These monomers are low weight molecules
which are bonded by covalent bonds. Each monomer has a different physical and chemical
property, the polymers formed keep part of those properties and also, by its own structure, adds
new ones. Combining two or more monomers can be obtained very different polymeric materials
properties, depending on the relative amount of each. The polymer chains can be linear or
branched, be united to form a crosslinked structure or not. The possibilities in the composition and
structure, make the polymers have a range of critical applications.
Due to its intern structure, which is based on directional covalent bonds, so no free electrons are
available, they are bad heat and electricity conductors. This intern configuration it is also
responsible for their low-density values in comparison with metals and ceramic materials.
Most of the polymer materials have a high specific mechanical resistance and specific rigidity (ratio
between the mechanical property and its density), great corrosion resistance, low-cost of
production and a big number of functionalities in continuous development. Those characteristics
make polymers a better choice than conventional materials in applications as spring joints, hinges
film, structural foams, non-lubricated bearings, special sliding, etc.
The plastic as an industrial product is a combination of polymers and a variable number of other
substances, fillers, additives, which are added to give the final material characteristics or specific
features. In some cases, it is necessary to subject the plastic to treatment before analysis, in which
separate polymer additives and its low molecular weight impurities.
The identification process consists of submitting the material to a series of preliminary tests such
as solubility, density, melting and smell of the flame. In some cases, it is necessary to specific tests
such as testing for the presence of heteroatoms (any atom different from carbon or hydrogen).

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POLYMERS STRUCTURE AND MOLECULAR WEIGHT

These materials have very different characteristics compared to organic substances of low
molecular weight. They usually are solids at room temperature, present viscous behaviour and they
can have large elastic deformation or break as a brittle solid. They can be found as films, powder,
pellets, fibres, etc. Their properties are related to several aspects as their intern structure, molecular
weight, symmetry, chemical nature.
Polymers structure
Polymers structure can be, as is showed in Figure 10, linear, branched, reticulated and lattice.

a) Linear
b) Branched
c) Reticulated/Crosslinked
d) Lattice (high reticulation
degree)

Figure 1. Polymers structure classification.

Molecular weight
A polymer is formed by a set of macromolecules whose size is irregular. The size of the
macromolecules is determined by their molecular weight. These materials cannot speak of a
specific molecular weight but rather of a molecular weight distribution. The determination of the
molecular weight distribution should be done according to statistical averages:
Average number or first moment of distribution

Mn 
N M i i

N i

Weight average and second statistical moment

Mw 
W M i i

Wi
The width of the molecular size distribution can be calculated from the polydispersity index, defined
by:

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Tacticity
The spatial arrangement of groups and substituent concerning the skeleton of the macromolecule
is important because they influence the intermolecular cohesive forces and hence the crystallinity
and physical properties. Depending on the spatial arrangement of groups of polymers can be
classified into isotactic, syndiotactic and atactic, Figure 10.

Figure 10. Polymer chain spatial configurations.

SOLID STATE PROPERTIES

Crystallinity

Under certain conditions, some polymers can form crystalline structures when they are cooled
from melted state. For that purpose, polymer chains must acquire an extended conformation
which allows them to pack and to form a tridimensional crystalline order. Crystallization capacity
of polymers depends on chain regularity and its interactions with each other. The usual crystalline
polymers are those who present a regular chemical and geometrical structure. Polyethylene is the
simplest and most conventional polymer which also makes it the most crystalline one (90 %).
However, branched polyethylene (lower regularity) presents a lower crystallinity (50 %).
In general, we speak about semicrystalline polymers because a complete crystalline polymer is not
possible. In polymers, there is a coexistence between crystalline regions and amorphous ones.
Crystalline regions are named as spherulites (Figure 11). Polymers crystalline regions are smaller
than conventional crystals (like in metals), contain imperfections, and they are connected to
amorphous regions through shared chains.

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Crystalline lamella

Crystalline lamella

Figure 11. Polymer amorphous and crystalline regions.

Crystallinity factors can be summed up in:

- Kinetic factors: Cooling procedure.
- Structural factors: symmetry, tacticity, grade of branches, molecular weight,
copolymerization and polarity.

Thermal transitions: Glass transition temperature and melting temperature

The temperature increases will produce changes in the polymer state at the glass transition
temperature or at the melting temperature. Complete amorphous materials present a glass
transition temperature meanwhile crystalline ones present a melting temperature. The change of
volume against temperature for three different polymers (amorphous, semi-crystalline and
crystalline) is plotted in Figure 12.
Specific volume

Tg Tm
Temperature

Figure 12. Specific volume against temperature. Amorphous polymer (A), semi-crystalline polymer (B) and crystalline
polymer (C).

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POLYMERS CLASSIFICATION ATTENDING THEIR BEHAVIOUR AGAINST TEMPERATURE

a) Thermoplastics polymers
They are composed by linear or low-branched macromolecules, and they behave as plastic
and ductile material. At high temperatures, thermoplastics become soft, and they are shaped by
viscous flux, keeping their shape after cooling. Moreover, these polymers have a reversible
behaviour against temperature; they can be reheated and reshaped without losing significant
properties. Some examples of thermoplastics polymers, among their properties, applications and
formulation, are summarised in Table 1.

Table 1. Properties of some thermoplastics polymers

Name Registered name Properties Applications Formula
Household
Polythene, Cheap, easy processing, good
utensils,
Alkathene, chemical resistance, poor
Polyethylene (PE) packaging, -(CH2-CH2)-
Hostalen, resistance under severe
containers
Lupolen, Alathon environmental conditions
Packaging,
-(CH2-CH-)
Cheap, easy processing, good containers,
Propathene,
Polypropylene (PP) chemical resistance, poor UV furniture,
Appryl, Novelen CH3
resistance pipes

Packaging,
Inexpensive, rigid, good -(CH2-CH-)
Darvic, Corvic, cable
Polyvinyl- chloride chemical resistance, limited
Geon, Evipol, insulation,
(PVC) thermal stability, additives Cl
Vinnolit, Hostalit pipes, toys
required for processing
Suitable . H2 C .
containers,
Styron, Cheap, transparent, rigid, packaging,
Polystyrene (PS) Polystyrol, excellent insulating properties, appliances
Novacor low water absorption, brittle

Transparent, excellent Transparent CH3

Polymethyl- Perspex, environmental properties, sheets,
OCH3
methacrylate Plexiglas, Lucite, tough, stiff, poor insulating airplane . H 2C
(PMMA) Acrylate properties, poor resistance to windows,
organic solvents lamps, displays O
Nylon, Ultramid, Textile,
Zytel, Caprolan, Tough, flexible, abrasion brushes,
(CH 2) 5
Polyamide (PA) Stanyl, Capron, resistance, good friction and surgical HN CO
Akulon, Rilsan, wear properties, absorbs water appliances,
Vestamid clothes, ropes.
Nonstick
Low friction, good electrical
surfaces, duct
Polytetrafluoro- Teflón, Fluon, insulation, excellent chemical
tape, -(CF2-CF2)-
ethylene (PTFE) Halon, Hostaflon resistance, insoluble, relatively
engineering
expensive
applications

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b) Thermosets polymers
Thermosets polymers have a crosslinked structure which can be formed by heating, the
addition of crosslinkers or a combination of both. They present an excellent thermal stability and
rigidity. They do not melt, and they can only be shaped during their synthesis procedure. Some
examples of thermosets polymers, among their properties, applications and formulation, are
summarised in Table 2.

Table 2. Properties of some thermosets polymers

Registered
Name Properties Applications Formula
name
Electrical
Good chemical appliances,
Bakelite,
Phenolic resistance, fixtures and
Plenco,
resins thermal and furniture,
Durite
flame adhesives,
laminates
Tough, good Adhesives,
adhesion, coatings,
Araldite, excellent laminates,
Epoxy
Epon, chemical construction,
resins
Epikote resistance, good electrical and
electrical electronic
properties components
Automotive
Laminac, Low viscosity,
Polyester engineering,
Aripo, cheap
Resins construición,
Baygal
boats

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Elastomers
Elastomers are polymers which deform easily against the application of stress maintaining the
capacity of recovering their original shape after the load is retired. This property is a consequence
of their weak crosslinked structure that it is formed by a reticule with a low cross-links density. The
number of crosslinking points depend on the number of polyfunctional groups of the base
monomers and have a direct consequence in their elasticity. Some examples of elastomers, among
their properties, applications and formulation, are summarised in Table 3.

Table 3. Properties of some thermosets polymers

Registered
Name Properties Applications Formula
name
Good abrasion
Poly (cis-
resistance, poor
isoprene) Natsyn, Gaskets, shoe soles,
heat resistance,
(natural Amenpol. condoms
excellent electrical
rubber)
properties

Medical implants,
Silactic,Rim Thermally stable,
sealants, flexible
Silicone plast, resistant to water,
moulds, electrical
Sinale expensive
boards

Good abrasion Tires, Climbing

Poly (cis-
resistance, poor shoe soles, door
isoprene)
heat resistance, and
(syntetic
excellent electrical windowprofiles,
rubber)
properties hoses, belts,
matting,

CHARACTERISTICS PROPERTIES USED IN POLYMER IDENTIFICATION

Solubility
The polymers have a dissolution process different from that observed in low molecular weight
compounds. The reason for this behaviour is directly related to the size and structure of the
polymer. A dissolution process involves the step of solvent molecules between the molecules of
solute occurring intermolecular interactions solute-solvent and weakening interactions solute-
solute or solvent-solvent.
For a polymer, this process is hampered by the entanglement between the chains that form the
material. The increase of branching (crosslinking) in the polymer makes difficult the solvent
molecules penetration. A first stage is needed in which the solvent embed the polymer so that to
unravel the tangle; then there is swelling of the polymer. Once this stage is finished, common to
all polymers, more solvent molecules could solvate the polymer chains to solubilise the whole
polymer forming a single phase. The solubility of some polymers is presented in table 4.

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Table 4. Polymers solubility

POLYMER
Polyethylene, polypropylene
atactic and isotactic
Polycarbonate
Polystyrene cyclohexanone, THF, methyl ketone,
THF, cyclohexanone, methyl ketone,
Polyvinyl chloride
Polytetrafluoroethylene
Polyacrylates and
polymethacrylates
Aliphatic polyesters
Formic acid, concentrated sulfuric
Polyamides
Epoxy resins
Phenolic resins
Natural and syntetic Rubber
Silicones
Polycarbonate
Solvent No solvent
Acetone, diethyl ether, methanol,
p-Xylene, trichlorobenzene
ethanol, ethyl acetate, NaOH, HCl,
Hydrocarbons (> 80 º C)
toluene, THF
THF, chloroform NaOH, HCl, diethyl ether ethanol, toluene
Benzene, toluene, chloroform,
Ethanol, methanol, diethyl ether
(swollen), NaOH, HCl
DMF
Methanol, acetone, heptane, NaOH, HCl,
DMF toluene, THF, chloroform
Insoluble
Chloroform, acetone, THF, DMF, Methanol, diethyl ether, ethanol, toluene,
toluene, ethyl acetate NaOH, HCl
Chloroform, formic acid and Methanol, diethyl ether, aliphatic
benzene hydrocarbons
Methanol, diethyl ether, hydrocarbons
acid, DMF
p-Xylene, trichlorobenzene Methanol, diethyl ether, ethanol, toluene,
Hydrocarbons (> 80 º C) NaOH, HCl
Insoluble
Insoluble (swollen)
Insoluble (swollen)
Insoluble (swollen)

Density

The density of a material (ρ) is the ratio between the mass (m) and volume (V):   m V . A simple
method to determine the density of the polymer is by flotation. This approach implies that the
sample of the polymer floats or sinks in the liquid of known density. For example, samples can be
dipped in methanol (ρ = 0.79 gcm-3), water (ρ = 1.00 g cm-3), etc. The behaviour of the sample is
then observed, in other words, if the sample remains on the surface of the liquid, the liquid floats
or sinks. Behaviour determines whether the polymer has lower or higher density than the liquid in
which it is immersed. The density of several polymers can be found in Table 5.

Table 5. Average density of some polymers

Polymer Density (g cm-3) Polymer Density (g cm-3)
Silicone 0.80 PP 0.85-0.92
LDPE 0.89-0.93 natural rubber 0.94
HDPE 0.94-0.98 Nylon 12 1.01-1.04
PS 1.04-1.06 ABS 1.04-108
Nylon 6 1.07-1.09 Polyester resin 1.10-1.40
PAN 1.14-1.17 PVA 1.17-1.20
PMMA 1.16-1.20 PC (polycarbonate) 1.20-1.22
PU (polyurethane) 1.20-1.26 PEEK (polietercetona) 1.26-1.32
PEI (polyetherimide) 1.27 PET (polietilentere phthalate) 1.38-1.41
PVC 1.38-1.41 PTFE 2.10-2.30

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Heat behavior
Heating a polymer sample may provide relevant information about the nature of the polymer. The
tests performed are two:
a) Flame behaviour: a small sample is maintained with a spatula or metal tweezers, in the
lower part of the flame of a Bunsen burner. The appearance of the flame and the
production of odour are characteristic for each type of polymer. In Table 6 a list of polymers
with their thermal behaviour is given to help to identify each material.

b) Pyrolysis test: with this test, we can study the behaviour of polymer degradation. Thermal
degradation produces low molecular weight fragments that are often flammable or have
distinctive odours. The polymer sample is introduced into a pyrolysis tube and held with
tweezers to the Bunsen burner flame. At the top stands a pH indicator paper to determine
the nature of the smoke. The polymer can be distinguished as acidic, basic or neutral. The
pH interval of each polymer can be consulted in Table 7.

Table 6. Behaviour of polymers to the flame and characteristic odour

Polymer Inflammability /Combustion Flame appearance
PTFE Burn very little, virtually fireproof Yellow
PE It moderately burns, readily combustible, easily Yellow, blue base
PP ignited droplets merge Yellow, blue base
PVC Yellow, green base
Nylon(s) It is hard ignited,self-extinguishing by removing Yellow, blue smoke
the flame, moderately combustible
Bright yellow, black
PC
smoke
Yellow, blue base, light,
PS
black smoke
It is easily ignited, continues to remove the
PMMA Yellow, blue base, bright
flame burning
Yellow/orange, dark,
Rubber
black smoke
Epoxy resin Hard to ignite Orange/yellow, grey
Polyester Yellow, blue base,
Burn moderately
resin medium, black smoke
Silicone self-extinguishing No flame, white smoke
Phenolic
Hard to ignite Yellow
resin
Table 7 pH range of slowly heated polymer vapor tube
pH 0.5-4.0 pH 5.0-5.5 pH 8.0-9.5
Polyester resin Silicone Nylon(s)
PU elastomer PP PAN
Cellulose acetate PE Amino resin
Cellulose nitrate PS Phenolic resin

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PET Epoxy resin ABS

PVC PVA
PTFE PMMA
PC
PU crosslinked

The main properties of the three types of polymers to identify are shown in table 8.

Table 8. Properties of thermoplastics, thermosets and elastomers.

Thermoplastics Thermosets Elastomers

Heat They melt No melting No melting

Solubility They can be dissolved Insoluble Insoluble, they swell

Low cross-linking
Structure Linear Crosslinked
degree

Amorphous or
Crystallinity Amorphous Amorphous
semicrystalline

Stiffness a T<Tg Stiffness,   4%   100-1000%

Mech. Prop. 4
3
E  10 MPa E  10 MPa E low  1 MPa

With chemical
Process No chemical reaction With chemical reaction
reaction

Natural rubber,
PE, PP, PVC, Polyamides, Epoxy resins, Phenolic resins,
Examples Polybutadiene,
Polyesters Formaldehyde-Phenolic resins.
Polyisoprene.

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4. EXPERIMENTAL PROCEDURE

The practice will take place in groups of two or three people, and each group will have several
samples of polymers. By performing all identification tests described below groups will be able to
identify the polymer.

PRELIMINARY TESTS

The following traits to be observed are a function of material thickness and the type and
percentage of filler loading.
Visually one can distinguish amorphous thermoplastics, because, in general, are transparent or
translucent as glass. The assessment is always easier in a natural state and without load. The semi-
crystalline thermoplastics are opaque (milky turbidity).
As for the surface appearance, it should be noted that parts made with amorphous and
semicrystalline thermoplastics have a surface partially shining, observed in the samples in sheet
form. In this section of the practice, it is only necessary to observe and record the external aspects
present in the samples, without any manipulation.

MECHANICAL BEHAVIOUR

Thermosets are basically more brittle than thermoplastics, the experimental part of this section is
to observe the mechanical behaviour when its surface is cut with a cutter. It can easily distinguish
between thermoplastics and thermosets. The procedure is as follows:
Procedure: With a very sharp razor is made a cut and slides beneath the surface trying to start
shaving. Thermoplastic polymers are chipped including those that are brittle and reinforced with
fibreglass. Thermosets are not chipped; sometimes they are just shredded fragments or powder.

THERMAL BEHAVIOUR

The test should be performed with high conscientiousness and, if necessary, be repeated.

Burning behaviour
For the test, the students need: a test tube, clamp, beaker, wash bottle with distilled water,
universal indicator (paper) and goggles.
Procedure: the sample, cut into fragments, is introduced into a test tube again and it remains for
1 minute in the flame. Bunsen burner must be regulated for a small and blue flame. To analyse the
vapours, a strip of indicator paper moistened with distilled water is introduced into the tube. If
necessary, on further heating until vapours formed can reach the top of the test tube. This test
must be done under supervision and always inside of a fume extractor.

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Comments
a. Melting behaviour: the substance melts, it does not melt; becomes fluid, it is viscous; the
melt mass becomes dark coloured; bubbles appear, it decomposes.
b. The colouration of paper indicator: if it remains colourless, the reaction will be neutral;
if turns red, the reaction is acidic, and if it is blue, alkaline; should always be considered the
intensity of staining.
c. Vapors smell: after heating the sample and see how the vapours come out of the test
tube, the vapours will be smelled wearing your protective goggles and taking all the care as
possible.
Observe and record all changes in the polymer and the colour of the indicator paper. Using
the tables presented above to identify the type of polymer with which we work.

Evaluation of the combustion behaviour

For the test, a Bunsen burner with small flame and tweezers will be used. It is useful to have dishes
of porcelain or metal, even aluminium foil or sheet steel, to collect the drops of molten substances.
This test must be done under supervision and always inside of a fume extractor.
Procedure: the sample is held with tweezers, and it is heated with a small flame, in this manner is
possible to observe the behaviour of combustion. When it starts to burn, the sample is removed
from the flame, and we can see their post-combustion.
Comments
a. Inflammability: plastic can be easy or difficult to ignite.
b. Combustibility: plastic burns, not burn, show dense smoke, it becomes incandescent.
c. Color flame: bright or black; may splash or drop.
d. Residue on the spatula: if the plastic is completely reduced to ashes, the calcining residue
permits inferred if the plastic was reinforced with fibreglass, glass balls, ground mineral
fillers etc., by inorganic fillers. Sediment on the spatula is due to pigments, and other
additives are not noticeably affecting the density.
Observe and record all changes in the polymer and the colour of the indicator paper. Using the
tables presented above to identify the type of polymer with which we are working.

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CHLORINE TEST (Beilstein test)

This essay is based on the green colour of the flame in the presence of chlorine or bromine
(halogens substances).
For testing is needed: Bunsen burner of adjustable flame, a pure copper wire with a thickness of 2
mm and 20 mm in length.
Procedure: the copper wire is subjected to the flame until it ceases to give colour, then the
polymer is touched with glow-wire and comes back to the flame. If the material traces of the flame
burns green, indicating the presence of chlorine (or bromine).
The reaction takes place can be represented as follows:
(--X--) + CuO CuX (colored complex)
This test is not specific because compounds with nitrogen obtained a flame of the same colour,
due to the formation of (CN2) Cu.
The green colour of the flame is produced in PVC and derivatives (including PVC plastic), in
chlorinated PE and chlorinated rubber, but also in the fireproof plastic (fire protected) with
chlorinated or brominated additives, although it contains no chlorine in its basic polymeric
structure.
If the flame is green, in some cases is necessary to see if the chlorine (or bromine) is in the same
molecular structure of the polymer or only in the additives. If vapour reaction is very acidic, then
it is likely that chlorine is part of the same basic molecule.
Perform the test on the polymer samples to identify which of them has halogen atoms in its
structure.

SOLUBILITY
For the test are required vials of 100 ml glass-stoppered, 1 litre of the following solvents: toluene,
chloroform (ClCH3), ethyl ether, ethanol, tetrahydrofuran (THF), NaOH and HCl aqueous solution.
We must be very cautious in handling solvents of the low boiling point; no smoking, no subjecting
them to direct flame, no sparks and no discharge into the piles to flow to drain.
Procedure: For a better comparison, practice tests will be under identical conditions of
temperature and time. A few pieces of the polymer will be placed in a vial with 50 ml of solvent;
the bottle will be closed with a cap and left at room temperature at least 10 h. After the time are
made the following observations: DISSOLVED, INFLATION, NOT DISSOLVED. Table 1 shows the
solubility of some polymers in different solvents.

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SESSION IV: THERMAL TREATMENTS

1. OBJECTIVE

To know the effect of cooling steel processes on different physical and mechanical properties,
as well as on the metallographic structures.

2. MATERIAL
Steel probes with 0.45% C for Jominy and Charpy tests.
Gloves, tweezers and protection elements against heat.
Metal bucket with water.
Broaching machine to notch the probes.
Ovens at 850 ºC.
Charpy pendulum.
Jominy equipment.
Polishing machine with sandpaper 180 grade.
Hardness tester with slide table.
Optical microscope.

3. INTRODUCTION
Thermal treatment is a term given to a heating and cooling process at adequate temperatures
to change the granular structure of metals or alloys, modifying their properties and behaviour.
Austenitizing is transforming a steel structure to austenite (Fe-γ). It consists on heating a steel
above the critical temperature (A3 in hypoeutectoid steels and Acm in hypereutectoid steels) and
holding it for a period of time long enough for transformation to occur.
The austenitizing temperature of each steel results from Fe-C phase diagram as it is shown in
Figure 13. Once austenite is obtained, it will be transformed to other phases while cooling,
depending on the cooling rate.

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Figure 13. Fe-C Phase Diagram

If austenite is slowly cooled down (e.g. the oven is turned off, and the sample is cooled down
inside the oven), it will be transformed to different microconstituents according to phase
diagram. This means: hypoeutectoid steels: perlite and ferrite, hypereutectoid steels: perlite and
proeutectoid cementite, eutectoid steels: perlite.
On the other hand, if it is quickly cooled down, the transformation is not seen on the phase
diagram. If the cooling rate is increased, it will be a non-equilibrium phase transformation.
Therefore, it should be analysed according to TTT diagrams (transformation-temperature-time),
where time is a variable to take into consideration.
In case it is cooled down with a high cooling rate, austenite will be transformed to another phase
called martensite instead. This transformation is produced by diffusion, due to the high cooling rate
which is responsible for its properties.
The absence of diffusion during the transformation hampers that carbon atoms located at the FCC
structure of austenite keep their BCT structure of martensite, distorting the lattice and hampering
the movement of dislocations. Consequently, it increases the hardness of this phase. As a result,
the hardness of martensite is determined by the carbon content. This transformation is shown in
Figure 14.

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Austenite (FC) Martensite (tetragonal BC)

Figure 14: Transformation from austenite to martensite.

There are some cooling rates which are too high to form equilibrium phases, but the martensitic
transformation still occurs. In this case, a new microconstituent called bainite is obtained,
meaning a ferrite matrix with cementite dispersed in the matrix.
TTT diagrams are plots of temperature versus time (usually on a logarithmic scale). There are
two kinds of TTT diagrams: Isothermal Transformation (ITT) and Continuous Cooling
Transformation (CCT). Both types of diagrams are shown in Figure 15 for an eutectoid steel.

Figure 15: TTT diagram of a eutectoid steel.

There are several steel thermal treatments: Continuous Cooling Transformation treatments:
annealing, normalising and quenching; and Isothermal Transformation treatments:
martempering and austempering. Only Continuous Cooling Transformation treatments are
studied in this laboratory session.

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Annealing
The aim of this treatment is obtaining an equilibrium structure with low hardness, tensile
strength and yield strength, together with a good ductility and tenacity. Once steel has been
heated up, it is slowly cooled down. It is usually carried out leaving the steel to cool down inside
the oven at very low cooling rates. A structure of big grains of ferrite and pearlite is usually
obtained.

Normalizing
The aim of this treatment is obtaining an equilibrium structure but thinner. Therefore, it is slowly
cooled down but with cooling rates higher than annealing cooling rates. It is often cooled down
in the air.

Quenching
Quenching is a process of cooling a metal at a rapid rate where martensite is obtained which is
a non-equilibrium phase with a hard, brittle crystalline structure. To ensure the complete
quenching and so, the formation of martensite, it must be cooled down in a proper cooling
system. It is usually done by immersion in cooling liquids.
Hardenability is the ability of steels to harden by quenching. It results from its composition
(content of carbon and alloy elements) and grain size.

JOMINY TEST
It is used to evaluate the suitability of steel to harden by quenching and to calculate the critical
quenching rate and the critical diameter of an ingot.
Critical quenching rate is the minimum cooling rate needed to achieve a complete quenching and
to obtain a fully martensitic structure after cooling down from austenitizing temperature.
Critical diameter of an ingot is the diameter that a steel bar must have to reach a given hardness
inside and to be cooled at the certain critical rate. It can be obtained by using tables or graphs
such as the graph shown in Figure 16.

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Figure 16. The graph to calculate the critical diameter of an ingot.

This test is used to measure and compare the hardenability of different steels. A 100 mm length
cylindrical bar with 25 mm diameter is used. It is heated up above the austenitizing temperature,
and it is rapidly cooled down with water from one end (Figure 17). After that, the hardness is
measured from the end which has been quenched to the opposite end.

T > A3 o Acm

Figure 17. Scheme of the Jominy test.

CHARPY TEST
It is an impact test to determinate the tenacity of the samples. It consists of a pendulum of
known mass and length that is dropped from a known height to impact a notched specimen of
material. The energy transferred to the material can be inferred by comparing the difference in
the height of the hammer before and after the fracture (energy absorbed by the fracture event).

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It has an important application in the determination of the ductile-brittle transition due to

changes in temperature. Some materials (mainly with BCC crystalline structure) show a high
decrease of the energy absorbed during the impact by reducing the temperature of the test.
These materials have a ductile-brittle transition. Above that temperature, the material is ductile,
but below it, the material is brittle.
Ductile-brittle transition curves of some steels are shown in Figure 2.

Figure 18. Ductile-brittle transition curves of some steels.

4. EXPERIMENTAL PROCEDURE

Jominy test
A standardised steel probe is used and put it in the oven designed specifically for this test,
which is at the austenitizing temperature as it is shown in Figure 19. After the required time,
the probe is removed and situated in support to put it in contact with a vertical water jet at
a constant rate for 10 minutes. Once this time is over, it must be cooled down completely
in water.

Figure 19. Drawing of the equipment used for Jominy test.

After cooling the probe, the two existing planes are sandblasted measuring the hardness in
one of them (Rockwell C scale). The position of the measurement points should be made in

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a way that allows the construction of a representative curve of hardness variations vs the
equivalent length.
 Charpy test
To perform the test on the pendulum, the probe must be notched first using the broaching
machine, taking care in not leaving chippings in the brush before and after the process, so
that the notch is perfect.
The probe is put on the supports so that the notch is perpendicular to the ground and on
the opposite side to that in which the pendulum will impact as it is shown in Error! Reference
source not found.
Then, the pendulum is raised through the steering wheel, and the needle dial is placed in 30
kpm. The pendulum is dropped releasing the pawl on the rear side, taking the utmost care
and standing out of the trajectory of the pendulum to avoid shocks and braking the
pendulum.

Figure 20. Escheme of a Charpy test

This test will be done with three different samples. One of them is tested at temperature room,
another one is tested right after taking it out of the oven, and the last one is tested after
quenching. The notches are done before the thermal treatments in each sample.
The absorbed energy value is the tenacity. It is also important to see, the aspect and shape of
the samples after fracture to determinate the different properties of samples.

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