Course 1 Materials Science
Chapter 1. The Properties of Materials
The properties expressed in a quantitative manner are the tools the engineer uses to
design a device made of different materials (such as an electrical transformer, a car, a bridge, a
plane). The properties also provide a basis for predicting the behaviour of the material under
various conditions, and they decide upon the best technological operations the materials are acted
on in order to transform them in useful products – by casting, working, machining, welding a.s.o.
Some of the most important properties of engineering materials are:
Mechanical: strength, stiffness (rigiditate), hardness, toughness, ductility.
Thermal: specific heat, thermal expansion, conductivity
Chemical: chemical composition, corrosion resistance
Electrical: conductivity, dielectric permitivity
Magnetic: permeability, coercive force, hysteresis
Physical: density, dimensions (size and shape), structure
Fundamentally the properties of a material depend on the nature of that particular
material (steel, bronze, glass) but also on the state of the material and on its structure (a
quenched steel has different mechanical properties as compared to the properties of the same
steel in cast condition). On the other hand the properties of a material are inseparably tied to the
conditions of use and environment. Mechanical strength, for instance, differs for various forms
of loading, and is expressed by such terms as tensile strength, compressive strength or fatigue
strength. Dielectric permitivity and magnetic permeability vary with the frequency of the
alternating field. Corrosion resistance is strongly dependent on the chemical environment. Many
properties vary with the temperature.
Experiments for determining properties are usually called tests. Tests may provide
properties for use in design or information on the quality of a material (control testing). Because
properties depend on so many internal and external factors, the test procedures are standardized,
in order to obtain comparable results. Much of the standardization of tests is done by ASTM
(American Society for Testing of Materials).
As far as the mechanical properties are concerned, the tests can be carried out under
tension, compression, bending and shear, either under static or dynamic loads. Tension and
compression tests under static loads are the most commonly used. The tension test is always used
for ductile materials with a certain degree of plasticity, such as ferrous and nonferrous metals,
rubbers and fibers. The compression test is mostly used for brittle materials such concrete,
engineering bricks, and cast irons, which are characterized by a low tensile strength as compared
to compressive strength.
On the basis of the properties involved in their application, materials can be divided in
two important groups:
I -structural materials whose applications is based mainly on their mechanical
properties, but sometimes also on their corrosion resistance to the chemical environment (a car
engine, a bridge, a ship).
II -functional materials whose application is based mainly on their physical, electrical or
magnetic properties (copper wire for carrying an electrical current, soft magnetic materials to
build the core of an electrical transformer, semiconductor materials to make an integrated circuit
or a solar battery).
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1.1. Mechanical properties
The main property involved in making such large structures as a ship, a bridge, a
building, is strength. Other mechanical properties are: elasticity, hardness, toughness and creep.
Each of these properties is associated with the ability of the material to resist mechanical forces.
But resistance to deformation is not always the rule. A spring, for example, is intended to change
its shape under load (of course no permanent deformation should persist after the load is
removed). Other items are fabricated in the desired shape by applying a permanent deformation
(the fender of a car is obtained by cold pressing).
To define the mechanical properties of materials some basic terms such as stress and
strain are needed.
Stress is defined as force per unit area and so we may also call it the unit force. Stress is
expressed in MPa or in daN/mm2 (the latter unit is ten times larger than the first one). Because a
force may be decomposed into a normal component F σ and a tangential component Fτ (Fig. 1),
the unit force (or stress) may be either a normal stress denoted σ (that is perpendicular to the area
on which it is acting), or a tangential stress denoted τ (that is parallel to the area on which it is
acting).
Strain is the deformation of a material and it is usually expressed as a percentage of the
original length. Strain may be elastic ot plastic.
Elastic strain disappears after the load is removed.
Fig.1. The components of the force against the area on which they
are acting: Fσ = normal component, Fτ = tangential component.
According to the Hooke's law, the elastic strain is proportional to
the amount of applied stress: σ = E . ε ; τ = G . γ
The proportionality constants E and G are called elastic moduli (E
= the longitudinal elastic modulus or Young's modulus and G = the transverse elastic modulus).
The elastic moduli depend mainly on the nature of the material, being related to the intensity of
the interatomic bonding, and they are little affected by the environment or material conditions.
Because the strain is a dimensionless quantity, the elastic modulus is expressed in the same units
as the stress.
Rigidity or stiffness is the reciprocal of the elastic strain: 1/ε = E . 1/σ
Plastic strain is the strain which is permanently given to a material by stress which
exceed the elastic limit. Plastic strain is the result of a permanent displacement of the atoms
inside the material.
Ductility is the amount of plastic deformation εF at the fracture point. Another way to
measure ductility is reduction in area at the point of fracture; this index is expressed in percent
and is calculated as:
(A0 – AF)/A0 x 100, [%].
where A0 is the original area and A F is the final area. Because there is no volume change during
plastic deformation, the two ways to express ductility are equivalent (elongation at fracture and
reduction in area).
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Stress-strain curves give more information about the effect of stress upon strain. Figure 2
shows the stress-strain relationship for different types of materials. All materials have a range of
elastic strain but the amount of plastic strain is not the same. Generally speaking, in the elastic
range the strain increases proportionally with stress, but in the plastic range the strain increases
more rapidly than stress.
A non-ductile (or brittle) material will not deform plastically before breaking (Fig.2a). A
ductile material has an elastic limit (or proportional limit) beyond which yield or plastic
deformation occurs. The yield strength of a ductile material (almost equal to the elastic limit) is
computed by dividing the force initiating the yield (or the plastic deformation) by the cross-
sectional area. In materials such as some soft steels (Fig.2b) the yield stress is marked by a
definite yield point. In other ductile materials, where the proportional limit is less obvious, the
yield strength is defined as the unit force required to give 0.2% plastic deformation (Fig.2c).
The tensile strength (also called ultimate strength σU) is calculated by dividing the
maximum load by the original cross-sectional area A 0. Because of area reduction during plastic
deformation the breaking (or fracture) strength may be less than ultimate tensile strength. This
apparent anomaly occurs because the conventional or engineering calculated stress has been
based on the original cross-sectional area and gauge length (distanţa între capetele de prindere)
of the specimen. Doing so is more convenient for the engineer, but the true values of stress and
strain should be based on the instantaneous area and length of the specimen. As seen in Fig.2d
the true stress will noticeably differ from the conventional (or engineering) stress especially
close to the breaking point because of the strong reduction in cross-section.
Fig.2 Stress-strain diagrams, (a) Nonductile material with no plastic deformation (example: cast
iron), (b) Ductile material with yield point (example: low-carbon steel), (c) Ductile material without
noticeable yield point (example: aluminium), (d) True stress-curve vs. engineering stress-curve. B.S.
= breaking strength, T.S. = tensile strength, Y.S. = yield strength, Elong. =. elongation, x - rupture.
To conclude, the strength is a measure of the stress required to deform or break a material
(the yield stress σy or Rp0,2, the ultimate tensile strength σU or Rm).
Toughness has a different meaning as it is a measure of the energy required to break a
material. Energy may be approximated to the area under the stress-strain curve (this is called the
static toughness). A ductile material with the same strength as a non-ductile (brittle) material will
require more energy for breaking and be tougher.
Charpy tests are used to measure toughness in conditions of impact load; this is
denominated KCU (dynamic toughness).
It is to be noticed that dynamic toughness is very sensitive to temperature, showing a
more or less sharp decrease at a sufficiently low temperature (the ductile-brittle transition
temperature). Dynamic toughness is also very sensitive to the presence of surface scratches and
internal microcracks.
Hardness is defined as the resistance of a material to penetration of the surface. As might
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be expected, the hardness and the strength of a material are closely related.
The Brinell hardness (HB) is calculated by dividing the pressing force F by the area A of
the imprint left on the material surface by a large indenter (a very hard steel or tungsten carbide
ball). So Brinell hardness is expressed in the same units (MPa or daN/mm2) as strength.
The Rockwell hardness (HR) is measured by the depth of penetration by a small
standardized indenter. Several Rockwell scales for materials of different hardness ranges have
been established by selecting various indenter shapes and materials. The most commonly used is
the Rockwell C scale for which the indenter is a diamond cone.
1.2. Nature of the Engineering Materials (Metallic, Ceramic, Polymeric)
Materials may be defined as the solids used by man for fabricating the objects that make
up the support of his life framework. So the consumable chemical substances or the energetic
fuels are not included in this definition.
Both structural and functional materials may belong to one of the following three main
groups, each of a different nature:
I. metallic materials
II. ceramic materials
III. organic polymeric materials
This classification is based on rational criteria such as the atomic and structural
characteristics as well as on the specific properties of each group of materials, but it cannot be
perfect. So the diamond may be considered a three dimensional organic polymer because it
consists of carbon atoms. But according to its mechanical properties (especially its extremely
high hardness) it might be classified among ceramic materials. On the other hand diamond and
graphite range themselves among the best thermal conductors, though the thermal conductivity is
considered to be a metallic property. Neither the electrical conductivity is nowadays an exclusive
property of metals because some oxides (VO 2, a ceramic material) and some organic polymers
are known to conduct electricity.
The metallic materials group comprises pure metals and alloys. An alloy is a metallic
material usually obtained by melting together several metals called constituents. The main
constituent is the base metal (ferrous alloys, Al based alloys, Cu based alloys). Sometimes even a
non-metallic element may be a constituent of an alloy (carbon in steels and cast irons, silicon in
some aluminium alloys).
Metals and alloys are extremely good electrical and thermal conductors, they are opaque
for the visible light, some of them are ferromagnetic materials. These special physical properties
make metals and alloys very valuable functional materials.
But the main application of metals and alloys is based on their mechanical properties.
Metallic materials are strong (they can sustain important loads at room temperature and also at
high temperature), they are ductile (they can be formed in the desired shape by plastic
deformation operations such as rolling, forging, extrusion, stamping (matriţare), wire-drawing
(trefilare)), they can be joined by welding and, the most important of all, they are tough.
Toughness is the opposite of brittleness and it enables metallic machine parts to sustain
loads in excess of their elastic limit without failure, by a local plastic yield. A completely brittle
body can deform only elastically; if the load exceeds the elastic limit fracture is imminent.
Metallic alloys largely used in engineering (steels, aluminium alloys, copper alloys, nickel
alloys, titanium alloys) are tough because they have a high ductility. Brittle materials (such as
most ceramics and organic polymers) have low toughness because they have no ductility (they
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show only a very small plastic deformation before fracture). This is the chief superiority of
metallic materials in contrast with ceramic or polymeric materials.
But metals have also their drawbacks. They are not available in the desired quantity,
some of them are strategic materials (Ni, Co, radioactive U and Th). This is because they are not
abundant in the earth crust and because their stable natural form is that of compounds (oxides,
sulphides). Only a few metals are sometimes found in nature in native form (gold, copper), the
others must be obtained by chemical reduction from their ores (minereuri). In addition metals are
subjected to corrosion in service and for special applications they are not sufficiently refractory
or not sufficiently strong.
Alternative materials (ceramics and organic polymers) are based on more abundant raw
materials, they are more corrosion resistant, they are less heavy than metals, some of them are
highly refractory. Unfortunately these are brittle materials, their toughness is low, parts made of
them are not reliable in service.
Efforts are being done to obtain advanced ceramic materials with improved toughness
and reliability in service.
The most intelligent way to benefit of the qualities of the brittle materials is to use them
as strong and hard reinforcing fibers in composite materials, by incorporating them in a ductile
matrix.
Generally speaking, the ceramics are inorganic materials resulting from the combination
of some metallic elements (Mg, Al, Fe, a.s.o.) with a few metalloids (such as oxygen, carbon,
nitrogen, silicon) giving rise to refractory compounds such as oxides, silicates, carbides, nitrides.
Ceramic materials are good electrical and thermal insulators, they have high melting
points, they have high strength at elevated temperature, they are hard but unfortunately they are
brittle.
Organic polymers consist of molecules that make up long chains of carbon atoms to
which atoms such as chlorine, hydrogen, nitrogen, silicon, sulphur can be attached. Organic
polymers have various mechanical properties (organic glasses, plastics, rubbers) but generally
they are not tough and not stiff. Organic polymers are light materials, they are easy to shape, they
are good thermal and electrical insulators. Unfortunately organic polymers cannot be used, as a
rule, at temperatures higher than 200°C.
Chapter 2. Structure Of Materials
2.1 The Levels of Structure and the Scales of Examination
The structure of a material or its internal organization can be considered at different
levels:
1-subatomic,
2-atomic or molecular,
3-crystalline,
4-microscopic,
5-macroscopic.
1. The subatomic level is concerned with the degree of interaction of electrons and nuclei
within individual atoms.
2. The atomic level is concerned with the interactions between atoms or molecules which
determine cohesion in different states of aggregation of the material. Various types of bonds are
operating: metallic bonds in metals and alloys, covalent bonds and ionic bonds in ceramic
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materials, covalent bonds and weak van der Waals bonds in organic polymers.
3. The crystalline level is concerned with the ordered arrangement in space of the
constitutive particles of the material -atoms, ions, molecules- and also with the imperfections of
different kinds existing in this ideal arrangement.
4. The microscopic level is concerned with the morphological characteristics of the
crystalline grains in polycrystalline materials and also with the substructure of the grains.
5. The macroscopic level is concerned with the various kinds of non-uniformities
(chemical, crystalline, mechanical) existing throughout the whole body of the product made of a
specific material.
The usual examination of the structure of a product proceeds in the reverse order, namely
from the macroscopic level down to the crystalline level. In doing so one has to go over nine
orders of magnitude in the scale of examination, from the level of one meter down to the level of
one nanometer (10-9 m).
These successive levels are examined by optical microscopy (a few mm down to 1μm),
by electron microscopy (100 μm down to a few nm) and by X-ray diffraction (to analyse the
atomic arrangement). A short characterization of each of these methods of examination will be
given here.
2.2. The Crystalline Level of Structure and its Examination by Diffraction Techniques
Metals and alloys are crystalline materials, many ceramic materials and some organic
polymers are also crystalline. Some ceramic and polymeric materials are amorphous (inorganic
glasses).
The difference between a crystalline material and an amorphous solid (a glass) lies in the
type of atomic arrangement. The atoms positions are disordered in a glass, except for the first or
second sphere of coordination containing the nearest neighbours of a specific atom (short range
order).
The constitutive particles in crystals may be of various kinds:
1. neutral molecules bonded by weak van der Waals forces in molecular crystals (for
instance naphthalene crystals)
2. positive ions in metallic crystals
3. alternating positive ions and negative ions in ionic crystals;
4. neutral atoms bonded by covalent bonds in covalent crystals.
It is instructive to see how such a covalently bonded crystal is built. The simplest
example to be examined is the diamond crystal. Each carbon atom in the diamond crystal is
bonded by four covalent bonds to four carbon atom neighbours that form a tetrahedron. One can
see (Fig. 3) that the needed number of covalent bonds according to the 8-N rule (where N is the
group number in the periodic table) is established not in a closed system like in oxygen molecule
O=O, but in an open system. That means that a crystal can be considered as a giant molecule
which can grow indefinitely.
++++ +-+- I Fig.3. Constitutive particles in various types of
++++ +-+- - C - crystals having different atomic bondings.
metallic ionic covalent
The crystalline structure is studied by diffraction techniques: X-ray diffraction, electron
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diffraction, neutron diffraction.
Consider a series of parallel planes of atoms spaced by an interplanar distance d on which
a beam of monochromatic X-ray radiation is falling (Fig.4). The planes with a relatively large
number of atoms on them usually give rise to strong reflection of the incident X-rays. The path
difference for rays DEF and ABC is GEH, which is equal to twice the distance GE. But
GE = EH = [Link]θ.
If this path difference is equal to an integral number of wavelengths, then the amplitudes
will be reinforced and an intensity peak will be observed. The conditions for this are described
by the Bragg equation: nλ = 2dsinθ
where n are integers 1,2,3,4,..., representing a multiple wavelength, X. Physically, the Bragg
equation implies that λ, d and θ have such values so as to give integral values of n for an
intensity peak observed.
Atomic planes
Fig.4. Diffraction from
planes of atoms;
( α = θ)
2.3. The Microscopic Level of Structure and its Examination by Optical and Electron
Microscopy
Engineering materials are, with very few exceptions, polycrystalline bodies. Such
materials consist of a multitude of small microscopic crystals in contact, named crystalline
grains. The microstructural features that can be revealed by microscopic analysis are: nature,
shape, size and association of the crystalline grains. At higher magnification, in an electron
microscope, finer microstructural features can be observed: subgrains, mosaic blocks or
crystalline imperfections (dislocations, stacking faults) that represent the substructure of the
material.
The magnification of a microscope is important in order to reveal the finest details of the
structure.
The useful magnification Mu is given by the following relationship: Mu=d’/d
where d’ is the resolution or the power of separation of the human eye ≈ 0.2 mm (that
means the minimum distance between two points that can be seen as distinct); d is the resolution
or the separation power of the microscope which is given by the following relationships:
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d = λ/([Link]α) (for oblique illumination) or d = λ/([Link]α) (for perpendicular illumination)
where X is the wavelength of the incident beam, n is the refraction index of the medium existing
between sample and objective lens (n=l for air, n=1.5 for cedar oil), α is half the opening angle of
the objective lens (α ≤ 72°).
Then one can express the magnification as follows:
Mu =0.2x2 ([Link]α)/λ = 0.4 ([Link]α)/λ
To obtain higher magnification and to observe finer details either n can be enhanced (immersion
microscope) or λ has to be diminished (electron microscope).
For an optical microscope (a reflexion microscope must be used because metals and most
of ceramic materials are not transparent) the maximum magnification is M u = 800 (λ= 500 nm
for visible light) or Mu = 1200 (immersion in cedar oil).
In electron microscopy a far shorter wavelength is used, namely the de Broglie wave
associated to fast moving electrons. In an electron microscope electrons are emitted in vacuum
from a hot tungsten filament. They are accelerated by a potential difference U, and finally they
are focused by electromagnetic lenses on the surface of the sample. The wavelength of the de
Broglie wave can be calculated as follows:
For U= 15000V, λÅ = 0,01 nm
This value is four orders of magnitude shorter then the wavelength of the visible light
Hence magnifications of hundred thousand up to one million are possible with electron
microscopy.
• Scanning electron microscopy gives reflexion images of the microrelief of the sample
surface (largely used for studying fracture aspects); advantages: massive samples may be used
(the same as in optical microscopy) and disadvantages: limited magnification (< 100.000).
• Transmission electron microscopy in two variants:
a) replica examination: a collodion replica is taken of the microrelief of the massive
sample surface; after shadowing with a thin film of chromium (vacuum deposited) the replica is
then examined by transmission.
b) thin foil examination: electrolytic thinning is used to obtain a 50-100 nm thin foil
transparent for electrons. The sample having a sheet shape is the anode in an electrolytic cell; it
is dissolved progressively until it gets perforated in some points. Magnification of hundred
thousand, up to 1 million times are possible with transmission electron microscopy, if high
enough accelerating voltages are used.
• Analytical electron microscopy makes use of that fraction of the incident electrons
which are absorbed in the sample. These absorbed electrons cause electronic transitions between
the inner quantic levels of the atoms in the sample. These quantic transitions are accompanied by
X-ray emission whose wavelength is characteristic for each atomic species present within the
microvolume (~l μm3) of the sample in which the finely focused electron beam has penetrated.
The characteristic X-rays emitted by the analyzed microvolume of the sample are separated
according to their wavelength by means of a diffracting crystal. The intensity of each wavelength
is measured by means of radiation counter (a Geiger-Muller, or better a proportional counter).
On a monitor screen one sees a map of the concentration of the analyzed chemical element
within the microvolume which is under examination.
5) The macroscopic level of structure is concerned with the whole part or semiproduct in
which different kinds of inhomogeneities are present: crystalline, chemical, mechanical.
For instance in a cast ingot or metallic part the shape and size of the crystalline grains differ from
the outer layer to the core; the same difference is seen in the distribution of the component
chemical elements (chemical segregation). In addition internal discontinuities may be present;
these can be put in evidence by techniques of non-destructive defectoscopy (X-ray, γ-ray,
ultrasonic defectoscopy).
Chapter 3. Crystalline Structure And Crystal Lattices
3.1. Crystallographic Systems and Crystal Lattices
The long-range order in crystals is characterized by a periodic arrangement of atoms in
the three dimensional space. This order is expressed by the crystal lattice (a system of points
representing the centers of the atoms which make up the crystal). In usual crystals the lattice
points are equivalent because they are subject to a translational repetition in space. Recently, a
new type of long-range ordered materials have been produced, namely the quasi-crystals whose
lattices are aperiodic being characterized by a lack of translational symmetry; such quasi-crystals
have been first obtained in 1984 by rapid solidification of certain aluminium alloy melts.
A translational crystal lattice is completely defined by the unit cell; this is the minimum
arrangement of lattice point whos translation in three directions in space gives rise to the whole
infinite lattice. An unit cell, as seen in Fig. 5, is a parallelepiped characterized by six geometrical
features:
a,b,c = lattice parameters (or lattice constants) that are the edges of the unit cell
α, β, γ = angles between the edges of the unit cell
Fig. 5 Translational crystal lattice and its unit cell
These six geometrical features define the shape and size of the unit cell and they
determine the position of the diffraction rings on the diffractogram.
According to the relations existing between these six geometrical features of the unit cell,
the crystal lattices may belong to the following seven possible crystallographic systems:
1) cubic a=b=c, α = β = γ = 90°
2) tetragonal a = b ≠ c α = β = γ = 90°
3) orthorhombic a ≠b ≠c α = β = γ = 90°
4) rhombohedral (trigonal) a = b = c α = β = γ ≠ 90°
5) hexagonal a = b ≠ c α = β = 90°; γ =120°
6) monoclinic a ≠b ≠c α = β = 90° ≠ γ
7) triclinic a ≠b ≠c α ≠ β ≠ γ ≠ 90°
Metallic lattices belong only to cubic and hexagonal systems. But intermetallic
compounds in alloys or ceramic compounds used in engineering may possess crystal lattices
belonging to whatever crystallographic system. For instance iron carbide (Fe 3C) which imparts
hardness and strength to steel and cast iron has an orthorhombic lattice while special carbides in
alloy steels may have a trigonal lattice.
To characterize completely a crystal lattice, the arrangement of the lattice points within
the unit cell must also be specified. This arrangement of points determines the intensity of the
diffraction rings of the diffractogram. The number n of lattice points belonging to an unit cell
can be computed by means of the following relationship:
n = 1/8 nc + ½ nf + ni
where nC represents points located in the corners of the unit cell, nf represents points located on
the faces of the unit cell and ni represents points within the body of the unit cell.
A crystal lattice comprising only nC lattice points is a primitive lattice (n =1 point/unit
cell). A crystal lattice comprising additional nf and ni lattice points is a non-primitive lattice (n>l
point/unit cell). Increasing n means a more compact lattice.
Only fourteen Bravais lattices are possible with the seven crystallographic systems and
they are illustrated in Fig. 6
Fig.6. The seven crystal systems and
14 Bravais lattices
The limited number of Bravais lattices
is a natural consequence since all
points in a crystal lattice must be
equivalent (they should result one
from another by a translation
operation).
