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METE 229

Materials Science and Engineering


by Kadri Aydınol (D-103)

any version of the book (W.D. Callister, Materials Science and Engineering an Introduction)
down to the 4th edition will do.

Chapter 1: Introduction
Engineering properties are very much dependent on the structure of matter, although METE is
not directly concerned with the structure

a basic classification system for materials:


● metals and alloys: metallic elements or combinations. Large number of nonlocalized
electrons so good heat-electricity conductors, opaque, strong but deformable
● ceramics: metal-nonmetal compounds, heat and electricity insulators, resistant to high
temperature and harsh environments, hard but brittle
● polymers: C, H and other nonmetallic based organic compounds. Large molecular
structure, low density, extremely flexible
● composites: consists more than one type, displays a combination of best characteristics
● semiconductors: electrical properties intermediate between conductors and insulators
● biomaterials: implanted in human body, must be nontoxic and compatible with body
tissues

Properties depend on structure: ex: hardness vs structure of steel. Examining the


microstructures of steel with different cooling rates, we observe different clusters in the
structure: higher cooling rate (“quenching”) yields greater hardness. So here we have the
processing changing the structure. Electrical resistivity of copper, for example, can be
increased by adding impurities or deforming.

The Materials Selection Process


1. Pick Application, determine required Properties (mechanical, electrical, thermal,
magnetic, optical, deteriorative)
2. From the Properties, identify candidate Material(s) with their structure and
composition
3. Identify the required Processing to change structure and overall shape (casting,
sintering, vapor deposition, doping, forming, joining, annealing)

Thermal properties: thermal expansion, thermal conductivity and thermal shock resistance
Thick glass cup with hot liquid poured into it will actually fracture more easily since the
difference between the inner and outer surfaces is larger
Magnetic properties: variety of applications: electric motors, medical imaging, data storage
etc. Strength also depends on composition, adding 3 atomic % Si makes Fe a better recording
medium!

Optical properties: transmittance of aluminum oxide depends on material structure: higher


porosity yields lower transparency

Deteriorative properties: stress and saltwater causes cracks in metals, heat treatment slows
crack speed in salt water

Chapter 2: Bonding and Properties


Issues to address: What promotes bonding, what types of bonds are there? What properties
are inferred from bonding?

Bohr atom model (discrete orbitals) vs Wave Mechanical Model (probabilistic orbitals)

Electrons in the wave mechanical model tend towards empty orbitals with lowest energy
n: 1, 2, 3, 4 - principal quantum number
l: s, p, d, f - second quantum number
mİ : 1, 3, 5, 7 - number of energy states
ms : magnetic spin

Si (Z = 14) has the configuration 1s2 2s2 2p6 3s2 3p2

Stable electron configurations: noble gases have complete s and p subshells and tend to be
unreactive. Most elements have unstable configurations.

In the periodic table, elements in a column have similar valance structure. On the left we have
the electropositive elements that readily give up electrons to become + ions, and vice versa.

Energy State Diagrams may contain stable (global minimum), unstable and metastable (local
minimum) states. The amount of activation energy needed to carry the system from one state to
another determines the rate of reaction / direction of movement between states

Atomic Bonding: atoms form bonds to lower their energy. for each pair of atoms we have a
certain distance called the equilibrium interatomic spacing, at which the attractive and repulsive
forces between the atoms balance each other. To be able to break the bond (ie pull the atoms
infinitely far away) at least E0 amount of energy will be needed (bond energy).
Ionic Bonding: occurs between + and - ions with large differences in electronegativity, requires
electron transfer. Predominant bonding in ceramics. Between the ions themselves, there will
be coloumbic attraction. As a result, we will have the ions with stable electron configuration.
The specific arrangement of ions (alternating sequence of anions and cations) keeps the
structure from collapsing and imploding. This structure also brings about the brittleness of
ceramic materials.

Covalent Bonding: Requires shared electrons. Electronegativities are comparable. Possible


between nonmetals, as well as metals and nonmetals. A few ceramic materials (carbides and
borides) form covalent bonds. Bond strength can vary (from bismuth to diamond).

Metallic Bonding: Generally strong bonds arising from a sea of donated valance electrons.
Primary bond for metals and their alloys.

Secondary bonding: weak bonds arising from interaction between dipoles (fluctuating
dipoles with asymmetric electron clouds or molecule-induced permanent dipoles), such as Van
der Waals forces. Can occur in liquids or polymers, the weak bonds are why they have low
softening temperatures.

Properties from bonding - Melting Temperature


● stretching the bonds beyond the bonding distance decreases the bonding energy
● lower bonding energy gives lower melting temperature
● liquids and solids are distinguised according to fluidity/viscosity, concerning the
movement of atoms/molecules.
● large for ceramics, moderate for metals, low for polymers
● for polymers we have another defined temperature called “glass transition temperature”
where the material is neither liquid nor solid

Properties from bonding - Elasticity


● elasticity is about the material resuming its original shape when force is removed
● lower elastic modulus means material is easier to deform

● elastic modulus is larger if the bond energy is larger or if the curvature of the energy
curve at the bond length is less steep - to achieve the same amount of seperation
between atoms, we have to provide more energy for a material with less steep energy
curve. (E ~ curvature at r0)
● large elastic modulus for ceramics, moderate for metals, small for polymers

Properties from bonding - Thermal Expansion


● the thermal expansion coefficient alpha is larger if E0 is smaller.

● alpha ~ symmetry at r0
● small for ceramics, moderate for metals, large for polymers

Chapter 3: Crystal Structures and Properties


How do atoms assemble into solid structures? How does density depend on structure? When to
material properties vary with sample/part orientation?

Energy and Packing: dense, regularly packed structures tend to have lower energy. summing
the energies of all pairs in a non-dense random packing would yield a large energy value for the
system, which would be unstable.

Materials and Packing:


● in crystalline materials, we have periodically packed atoms in 3D arrays, which is
typical of metals, many ceramics and some polymers
● in noncrystalline (amorphous) materials we have no period packing, typical of complex
structures and rapid cooling

Crystal Structures
To identify the crystal structure, look for repeating patterns (in terms of repeating surrounding
atoms) by placing imaginary lattice points, then connecting these lattice points to create a 3D
structure. There are six parameters (3 edge lengths, 3 planes) defining this shape. Depending
on these parameters we have 7 different crystal systems.
● cubic - 3 edges same, angles orthogonal
● tetragonal - 2 edges same, angles orthogonal
● orthorombic - arbitrary edges, angles orthogonal
● triclinic - all arbitrary edges with arbitrary angles
● monoclinic
● hexagonal
● rhombohedral

we don’t have, for example, pyramids as a crystal systems, because it lacks the property of
filling space as we repeat it over the axes.

Metallic Crystals
● tend to be densely packed, with simple crystal structures
● reason for dense packing: typically has only one element so all atomic radii is the same,
nearest neighbor distances tend to be small, metal bonding isn’t directional

Atomic Packing Factor (APF)


Simple Cubic Structure (SC) - rare due to poor packing, close packed directions are cube
edges. coordination number = 6 (# nearest neighbors), APF of 0.52

Body Centered Cubic Structure (BCC)- close packed directions are cube diagonals,
coordination number=8, APF of 0.68

Face Centered Cubic Structure (FCC) - close packed directions are face diagonals,
coordination number=12, APF of 0.74, best possible packing for equal-sized atoms, considered
to be a “closely packed” structure

Hexagonal Close-packed Structure (HCP) - coordination number=12, APF of 0.74

Theoretical Density, ro

differs slightly from the actual value

Metals have larger theoretical density due to their close packing (metallic bonding) and large
atomic mass.

Crystals as Building Blocks


As the size of the structure grows, keeping all blocks in the same orientation becomes more
difficult.

During the transformation from liquid to solid, first a few atoms come together to form a nucleus
or seed, then more and more atoms will join it to cause solidification. If several seeds form, they
will almost certainly be at different orientations and thus will grow blocks (grains) with different
orientation (polycrystal). Most engineering materials are polycrystals.
In very few cases it is possible to grow the structure from a single seed with a homogenous
arrangement (single-crystal). Both are advantageous in different scenarios.

Crystal Directions
Directions in the form of [uvw]: find the projections along the three axes in fractions of the unit
distances on each axis & reduce them to smallest integers

Crystal Planes
Planes in the form of (hkl): find the intercepts on the three axes in fractions of the unit distances
on each axis, take the reciprocals and reduce them to smallest integers. For planes parallel to
one of the axes, one of the intercepts can be infinity, giving the number zero with its reciprocal.

Single vs Polycrystals
Sİngle Crystals: Properties vary with direction (anisotropic), for example in BCC iron the
elastic modulus varies with crystal direction (crystal direction dependent).
Polycrystals: Properties may or may not vary with direction. If grains are randomly oriented,
properties are isotropic (since all grains are randomly oriented, the overall effect we observe
is a kind of average over all possible orientations) but if they are textured they are anisotropic
(since textured structure is more ordered and thus more similar to single crystal structure).

Using x-rays to confirm crystal structure


We can use x-rays to confirm crystal structure of matter since atoms scatter electromagnetic
rays. This diffraction occurs only at certain angles; these critical angles (theta) provide us

with information about atomic spacing (d) where . In order for diffraction
to occur, the x-rays must exhibit the in-phase property - the x-ray which is travelling longer must
have this difference in travelling a multiple of the wavelength .
Go over this in the book for more examples - ideal place to ask questions from!

Chapter 4: Imperfections in Solids

What types of defects arise in solids? Can the number and type of defects be varied and
controlled? How do these defects affect material properties? Are they always undesirable?

Point Defects: vacancy atoms (“gaps”), interstatial atoms (“extras”), substitutional atoms
Line Defects: dislocations
Area Defects: grain boundaries

To create vacancies we need to give energy to the system since the overall energy of a system
with vacancy will increase.

Equilibrium concentration of point defects can be calculated with thermodynamical statistical


formulas:

where k is the Boltzmann constant

Atoms that vacate their position form “islands” on the surface.

- insert missing lecture notes from 25.10.2010 here -

Bond Breaking and Remaking

The energy provided to the structure causes the bonds to stretch, break etc. and when it
exceeds a certain threshold, dislocation occurs. The difference in energy per atom in a perfect
and non-perfect lattice would be this threshold.

Dislocations and Crystal Structure

Dislocation motion requires the successive bumping of a half plane of atoms. Bonds across the
slipping planes are broken and remade in succession. Since heat increases atomic vibrations
uniformly, such dislocations cannot be created by the means of providing heat to the system,
but requires the application of force instead. This dislocations slides or glides along the row of
atoms. Movement along close-packed directions and planes are preferred. In the process of
extrusion, for example, billions and billions of dislocations occur.

FCC: many close-packed planes and directions, dislocations occur easily


HCP: only one plane, 3 directions
BCC: none

The ionic nature of ceramic materials requires a very high dislocation energy, but when such
high energy is given to the ceramic we break the bonds completely instead, resulting not in
shape change but two “broken” pieces - this is what makes the material brittle.

Area defects: Grain Boundaries


Due to the broken bonds along the boundary atoms between grains, the atoms are in a higher
energy state, which gives rise to surface energy. The higher the angle of misalignment, the
more broken bonds we have along that boundary, and thus a higher energy boundary. If we
increase temperature of the system we can make the big grains bigger and small grains smaller

Optical Microscopy
Useful up to 2000x magnification. Polishing removes surface features such as scratches.
Etching changes reflectance, depending on crystal orientation. Grain boundaries are
imperfections and are more susceptible to etching, revealed as dark lines since light is reflected
away from the edges of the groove.

Chapter 5: Diffusion in Solids

How does diffusion occur? Why is it an important part of processing? How can its rate be
predicted, how does it depend on structure and temperature?

At all finite temperatures diffusion occurs in materials, since all atoms have a certain energy
and some will have enough energy to overcome the activation energy barrier. This is required
because as the atom moves through the structure it will cause distrubances around and thus
increase the energy of the system.

Interdiffusion: Blocks of 100% Cu and Ni side by side, over time atoms tend to migrate from
regions of large concentration, forming a gradient in the concentration profile.

Self-diffusion: In an elemental solid, atoms also migrate, invidivual atoms change places.

Mechanisms of Diffusion

Substitutional Diffusion: applies to substitutional impurities, atoms exchanging places with


vacancies. Rate depends on number of vacancies and activation energy to exchange. Always
occurs, even at room temperature, rate increases with temperature.

Interstitial Simulation: applies to interstitial impurities, more rapid than vacancy diffusion, for
example a smaller atom jumping from one interstatial site to another in BCC structure

In certain (very rare) cases, atoms may be able to diffuse on the 2D surface without any
activation energy required.

Processing Using Diffusion

Case Hardening: diffuse carbon atoms into the host iron atoms at the surface of, say, a gear.
example of interstitial diffusion is a case hardened gear. As a result, C atoms “lock” planes
from shearing and thus make it hard to deform, and due to the compression of the surface it
becomes hard to deform. By diffusing the carbon just at the surface and not throughout all the
material, we have the advantage of a hard surface and soft insides, thus gaining resistance
to wear on the surface but not becoming brittle. Easier to perform than other coating methods
since the material essentially “coats itself”.

Silicon Doping: deposit P-rich layers on the surface and heat it to obtain doped semiconductor
regions.

Modeling Diffusion: Flux

A directional quantity describing the movement of particles in a direction through a unit area A.

Fick’s First Law:

relating the concentration gradient to flux in a given direction - the steeper


the concentration profile, the greater the flux!

Steady State Diffusion


the concentration profile doesn’t change with time, , so the slope
must be constant with respect to position.

Non Steady State Diffusion

Use conservation of matter (the derivative of the difference between left and right flux with
repect to position should be equal to ) and the derivative of Fick’s first law wrt x to obtain:

For a semi-infinite metal bar with a pre-existing concentration and given surface

concentration of diffusing atoms, we can obtain the general solution

where erf is the error function (intermediate values can be linearly interpolated). See relevant
slides for graph. In this manner we can calculate the necessary parameters to obtain a desired
hardness using a given treatment.

Copper diffuses into a bar of aluminum. 10 hours at 600 degrees C gives desired C(x). How
many hours would it take to get the same C(x) if we processed at 500 degrees?

key point 1:

key point 2: both cases have the same and


result: Dt should be held constant

Diffusion and Temperature

diffusivity

T=1.98 if activation energy is given in terms of ??


T=8.31 if activation energy is given in terms of ??
Interstitial diffusivity (e.g C in Fe variants) >> Substitutional diffusivity (e.g Fe in Fe variants,
Al in Al, Cu in Cu, Zn in Cu..) since substitutional diffusion is mostly due to vacancies - the
activation energy in this kind of diffusion is dependent on not only structure distortion but also
vacancy formation and is thus higher.

Diffusion is faster for open crystal structures, lower melting T materials, materials with
secondary bonding, smaller diffusing atoms, lower density materials
Diffusion is slower for close-packed structures, higher melting T materials, materials with
covalent bonding, larger diffusing atoms, higher density materials

Chapter 6: Mechanical Properties

Stress and strain. Elastic and plastic behavior. Toughness and ductility.

Elastic Deformation

Reversible. When a small load is applied the bonds stretch, and when the load is removed we
return to the initial condition. Materials can be linear or non-linear elastic in terms of the amount
of deformation/elongation with respect to the applied force.

Actually, for rubbers and elastomeric polymeric materials we don’t really have elastic
deformation but the “chains” that make up the polymer straightening, and bond stretching to a
much lesser degree.

Plastic Deformation

Permanent. Unlike elastic deformation, when the applied force is released we don’t recover the
initial state but still have some elongation, the planes become sheared beyond a critical amount
of force. Can be observed together with elastic deformation, when the force is removed the
elastic elongation will be removed but the plastic one will not.

Engineering Stress

Tensile Stress: force applied along the axis of the material,

Shear Stress: force applied is parallel to the plane of area,

where the area is the original area (ie before the force was applied and any stretching etc
occured).
Other states of stress also exist: simple compression, bi-axial tension, hydrostatic compression

Engineering Strain

Always dimensionless - tensile, lateral and shear strain. See slides for definitions.

Linear Elastic Properties

modulus of elasticity, E:

Hooke’s Law (only applicable in the elastic part! not in the plastic part):

Poisson’s ratio , ~0.33 for metals, ~0.25 for ceramics, ~ 0.40 for polymers
Eceramics > Emetals >> Epolymers

The critical stress where noticeable (when ) plastic deformation starts occuring
is named as yield stress. Ceramics >> metals >> polymers. For ceramics it’s hard to measure
since in tension, fracture occurs before yield.

Tensile strength: maximum possible engineering stress in tension. signified by: metals-
>noticeable necking, ceramics->crack propagation, polymers->polymer backbone aligning.
Beyond this point, the material will certainly fracture.

fracture (under static load) - fatigue (under dynamic load) - creep (under static load in elevated
temperature)

Ductility, plastic tensile strain at failure:

material is brittle if %EL < 5%, ductile if %EL>5%. Another measure:

These two are often comparable since crystal slip does not usually change material volume.
Amount of plastic deformation is much greater in ductile materials.

Toughness: energy to break a unit volume of material, approximated by the area under the
stress-strain curve (stress * strain). metals >> unreinforced polymers > ceramics
Impact tests are used to measure this (swing a weight from the pendulum, release it on the
material, measure difference in height to measure loss in potential energy=absorbed energy)

Hardness: resistance to permanently indenting the surface, apply force and measure the indent
- insert missing lecture notes from 09.11.2010 here -