Pamantasan ng Lungsod ng Maynila

College of Engineering and Technology

Department of Chemical Engineering

STRENGTHENING
MECHANISMS

Submitted by:
BSChE 3
Santos, Amabelle C.
Sison, Bren A.
Torres, Clark Ivan V.
Valdez, Loisroi R.

Submitted to:
Prof. Malenab

October 2016

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 Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

Table of Contents
What is Strengthening? ............................................................................... 3

Mechanical Properties of Materials .............................................................. 5

Strengthening Mechanisms of Metals ........................................................ 11

Strain Hardening ............................................................................. 11

Solid-Solution Strengthening and Alloying ....................................... 13

Precipitation Hardening ................................................................... 16

Grain Boundary Strengthening ........................................................ 17

Transformation Hardening ...................................................................

Strengthening Mechanisms in Amorphous Materials ................................. 18

Polymers.......................................................................................... 18

Glass ...................................................................................................

Applications ..................................................................................................

References ....................................................................................................

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 Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

WHAT IS STRENGTHENING?
Strengthening is the ability of a metal to deform
plastically depends on the ability of dislocations to
move. Hardness and strength are related to easily a
metal plastically deforms, so, by reducing dislocation
movement, the mechanical strength can be improved
but, to the contrary, if dislocation movement is easy
(unhindered), the metal will be soft, easy to deform.

The primary species responsible for work hardening are dislocations.

Dislocations interact with each other by generating stress fields in the
material. The interaction between the stress fields of dislocations can impede
dislocation motion by repulsive or attractive interactions. Additionally, if two
dislocations cross, dislocation line entanglement occurs, causing the
formation of a jog which opposes dislocation motion. These entanglements
and jogs act as pinning points, which oppose dislocation motion. As both of
these processes are more likely to occur when more dislocations are present,
there is a correlation between dislocation density and yield strength.

Plastic deformation occurs when large numbers of dislocations move

and multiply so as to result in macroscopic deformation. In other words, it is
the movement of dislocations in
the material which allows for
deformation. If we want to enhance
a material's mechanical properties
(i.e. increase the yield and tensile
strength), we simply need to
introduce a mechanism which
prohibits the mobility of these
dislocations. Whatever the mechanism may be, (work hardening, grain size
reduction, etc) they all hinder dislocation motion and render the material
stronger than previously. The stress required to cause dislocation motion is
orders of magnitude lower than the theoretical stress required shifting an

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 Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

entire plane of atoms, so this mode of stress relief is energetically favorable.

Hence, the hardness and strength (both yield and tensile) critically depend on
the ease with which dislocations move. Pinning points, or locations in the
crystal that oppose the motion of dislocations, can be introduced into the
lattice to reduce dislocation mobility, thereby increasing mechanical strength.

Dislocations may be pinned due to stress field interactions with other

dislocations and solute particles, or physical barriers from grain boundaries
and second phase precipitates. There are four main strengthening
mechanisms for metals, however the key concept to remember about
strengthening of metallic materials is that it is all about preventing dislocation
motion and propagation; you are making it energetically unfavorable for the
dislocation to move or propagate. For a material that has been strengthened,
by some processing method, the amount of force required to start irreversible
(plastic) deformation is greater than it was for the original material.

In amorphous materials such as polymers,

amorphous ceramics (glass), and
amorphous metals, the lack of long range
order leads to yielding via mechanisms
such as brittle fracture, crazing, and shear
band formation. In these systems,
strengthening mechanisms do not involve
dislocations, but rather consist of modifications to the chemical structure and
processing of the constituent material.

Unfortunately, strength of materials cannot infinitely increase. Each of

the mechanisms elaborated below involves some trade off by which other
material properties are compromised in the process of strengthening.

Methods have been devised to modify the yield strength, ductility, and
toughness of both crystalline and amorphous materials. These strengthening
mechanisms give engineers the ability to tailor the mechanical properties of
materials to suit a variety of different applications. For example, the favorable

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 Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

properties of steel result from interstitial incorporation of carbon into the iron
lattice. Brass, a binary alloy of copper and zinc, has superior mechanical
properties compared to its constituent metals due to solution strengthening.
Work hardening (such as beating a red-hot piece of metal on anvil) has also
been used for centuries by blacksmiths to introduce dislocations into
materials, increasing their yield strengths. (Mittal, 2009)

MECHANICAL PROPERTIES OF MATERIALS

 Concepts of Stress and Strain

To compare specimens of different sizes, the load is calculated per unit area,
also called normalization to the area. Force divided by area is called stress. In
tension and compression tests, the relevant area is that perpendicular to the
force. In shear or torsion tests, the area is perpendicular to the axis of
rotation.

s = F/A0 tensile or compressive stress

t = F/A0 shear stress

The unit is the Megapascal = 106 Newtons/m2.

There is a change in dimensions, or deformation elongation, DL as a result of

a tensile or compressive stress. To enable comparison with specimens of
different length, the elongation is also normalized, this time to the length L.
This is called strain, e.

e = DL/L

The change in dimensions is the reason we use A0 to indicate the initial area
since it changes during deformation. One could divide force by the actual
area, this is called true stress (see Sec. 6.7).

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 Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

For torsional or shear stresses, the deformation is the angle of twist, q and
the shear strain is given by:

g = tg q

Stress—Strain Behavior

 Elastic deformation

When the stress is removed, the material returns to the dimension it had
before the load was applied. Valid for small strains (except the case of
rubbers). Deformation is reversible, non permanent

 Plastic deformation

When the stress is removed, the material does not return to its previous
dimension but there is a permanent, irreversible deformation.

In tensile tests, if the deformation is elastic, the stress-strain relationship is

called Hooke's law:

s=Ee

That is, E is the slope of the stress-strain curve. E is Young's

modulus or modulus of elasticity. In some cases, the relationship is not linear
so that E can be defined alternatively as the local slope:

E = ds/de

Shear stresses produce strains according to:

t=Gg

where G is the shear modulus.

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 Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

Elastic moduli measure the stiffness of the material. They are related to
the second derivative of the interatomic potential, or the first derivative of the
force vs. internuclear distance (Fig. 6.6). By examining these curves, we can
tell which material has a higher modulus. Due to thermal vibrations the
elastic modulus decreases with temperature. E is large for ceramics (stronger
ionic bond) and small for polymers (weak covalent bond). Since the
interatomic distances depend on direction in the crystal, E depends on
direction (i.e., it is anisotropic) for single crystals. For randomly oriented
policrystals, E is isotropic.

 Anelasticity

Here the behavior is elastic but not the stress-strain curve is not immediately
reversible. It takes a while for the strain to return to zero. The effect is
normally small for metals but can be significant for polymers.

 Elastic Properties of Materials

Materials subject to tension shrink laterally. Those subject to compression,

bulge. The ratio of lateral and axial strains is called the Poisson's ratio n.

n = elateral/eaxial

The elastic modulus, shear modulus and Poisson's ratio are related by E =
2G(1+n)

Tensile Properties

 Yield point

If the stress is too large, the strain deviates from being proportional to the
stress. The point at which this happens is the yield point because there the
material yields, deforming permanently (plastically).

 Yield stress

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 Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

Hooke's law is not valid beyond the yield point. The stress at the yield point
is called yield stress, and is an important measure of the mechanical
properties of materials. In practice, the yield stress is chosen as that causing
a permanent strain of 0.002.

The yield stress measures the resistance to plastic deformation.

The reason for plastic deformation, in normal materials, is not that the atomic
bond is stretched beyond repair, but the motion of dislocations, which
involves breaking and reforming bonds. Plastic deformation is caused by the
motion of dislocations.

 Tensile strength

When stress continues in the plastic regime, the stress-strain passes through
a maximum, called the tensile strength (sTS) , and then falls as the material
starts to develop a neckand it finally breaks at the fracture point. Note that it
is called strength, not stress, but the units are the same, MPa. For structural
applications, the yield stress is usually a more important property than the
tensile strength, since once the it is passed, the structure has deformed beyond
acceptable limits.

 Ductility

The ability to deform before braking. It is the opposite of brittleness. Ductility

can be given either as percent maximum elongation emax or maximum area
reduction.

%EL = emax x 100 %

%AR = (A0 - Af)/A0

These are measured after fracture (repositioning the two pieces back
together).

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 Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

 Resilience

Capacity to absorb energy elastically. The energy per unit volume is the area
under the strain-stress curve in the elastic region.

 Toughness

Ability to absorb energy up to fracture. The energy per unit volume is

the total area under the strain-stress curve. It is measured by an impact test.

 True Stress and Strain

When one applies a constant tensile force the material will break after
reaching the tensile strength. The material starts necking (the transverse area
decreases) but the stress cannot increase beyond sTS. The ratio of the force to
the initial area, what we normally do, is called the engineering stress. If the
ratio is to the actual area (that changes with stress) one obtains the true
stress.

 Elastic Recovery During Plastic Deformation

If a material is taken beyond the yield point (it is deformed plastically) and the
stress is then released, the material ends up with a permanent strain. If the
stress is reapplied, the material again responds elastically at the beginning
up to a new yield point that is higher than the original yield point. The amount
of elastic strain that it will take before reaching the yield point is called elastic
strain recovery.

 Compressive, Shear, and Torsional Deformation

Compressive and shear stresses give similar behavior to tensile stresses, but
in the case of compressive stresses there is no maximum in the s-e curve,
since no necking occurs.

 Hardness

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 Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

Hardness is the resistance to plastic deformation (e.g., a local dent or

scratch). Thus, it is a measure of plastic deformation, as is the tensile
strength, so they are well correlated. Historically, it was measured on an
empirically scale, determined by the ability of a material to scratch another,
diamond being the hardest and talc the softer. Now we use standard tests,
where a ball, or point is pressed into a material and the size of the dent is
measured. There are a few different hardness tests: Rockwell, Brinell, Vickers,
etc. They are popular because they are easy and non-destructive (except for
the small dent).

 Variability of Material Properties

Tests do not produce exactly the same result because of variations in the test
equipment, procedures, operator bias, specimen fabrication, etc. But, even if
all those parameters are controlled within strict limits, a variation remains in
the materials, due to uncontrolled variations during fabrication, non-
homogenous composition and structure, etc. The measured mechanical
properties will show scatter, which is often distributed in a Gaussian curve
(bell-shaped), that is characterized by the mean value and the standard
deviation (width).

 Design/Safety Factors

To take into account variability of properties, designers use, instead of an

average value of, say, the tensile strength, the probability that the yield
strength is above the minimum value tolerable. This leads to the use of
a safety factor N > 1 (typ. 1.2 - 4). Thus, a working value for the tensile
strength would be

sW = sTS / N.

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 Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

STRENGTHENING MECHANISMS OF METALS

Strain Hardening

Strain hardening is the phenomenon whereby a ductile metal becomes harder

and stronger as it is plastically deformed. Sometimes it is also called work
hardening, or, because the temperature at which deformation takes place is
“cold” relative to the absolute melting temperature of the metal, cold working.
Most metals strain harden at room temperature.

It is sometimes convenient to express the degree of plastic deformation as

percent cold work rather than as strain. Percent cold work (%CW) is defined
as:

where 𝐴0 is the original area of the cross section that experiences

deformation, and 𝐴𝑑 is the area after deformation

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 Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

Figures a and b demonstrate how steel, brass, and copper increase in yield
and tensile strength with increasing cold work. The price for this
enhancement of hardness and strength is in the ductility of the metal. This is
shown in Figure c, in which the ductility, in percent elongation, experiences
a reduction with increasing percent cold work for the same three alloys. The
influence of cold work on the stress–strain behavior of a low-carbon steel is
shown in figure.

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 Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

The strain-hardening phenomenon is explained on the basis of dislocation–

dislocation strain field interactions. The dislocation density in a metal
increases with deformation or cold work, due to dislocation multiplication or
the formation of new dislocations. Consequently, the average distance of
separation between dislocations decreases—the dislocations are positioned
closer together. On the average, dislocation–dislocation strain interactions are
repulsive. The net result is that the motion of a dislocation is hindered by the
presence of other dislocations. As the dislocation density increases, this
resistance to dislocation motion by other dislocations becomes more
pronounced. Thus, the imposed stress necessary to deform a metal increases
with increasing cold work. Strain hardening is often utilized commercially to
enhance the mechanical properties of metals during fabrication procedures.
The effects of strain hardening may be removed by an annealing heat
treatment.

Solid Solution Strengthening/Alloying

For this strengthening mechanism, solute atoms of one element are added to
another, resulting in either substitutional or interstitial point defects in the
crystal. The solute atoms cause lattice distortions that impede dislocation
motion, increasing the yield stress of the material. Solute atoms have stress

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 Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

fields around them which can interact with those of dislocations. The
presence of solute atoms imparts compressive or tensile stresses to the lattice,
depending on solute size, which interfere with nearby dislocations, causing
the solute atoms to act as potential barriers to dislocation propagation and/or
multiplication.

The shear stress required to move dislocations in a material is:

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∆𝑇 = 𝐺𝑏√𝑐 ∈2

where c is the solute concentration and ε is the strain on the material caused
by the solute. Increasing the concentration of the solute atoms will increase
the yield strength of a material; however, there is a limit to the amount of
solute that can be added, and one should look at the phase diagram for the
material and the alloy to make sure that a second phase is not created. In
general, the solid solution strengthening depends on the concentration of the
solute atoms, shear modulus of the solute atoms, size of solute atoms, valency
of solute atoms (for ionic materials), and the symmetry of the solute stress
field. Note that the magnitude of strengthening is higher for nonsymmetric
stress fields because these solutes can interact with both edge and screw
dislocations whereas symmetric stress fields, which cause only volume
change and not shape change, can only interact with edge dislocations.

High-purity metals are almost always softer and weaker than alloys composed
of the same base metal. Increasing the concentration of the impurity results
in an attendant increase in tensile and yield strengths, as indicated in Figures
a and b for nickel in copper; the dependence of ductility on nickel
concentration is presented in Figure c.

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 Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

Alloys are stronger than pure metals because impurity atoms that go into
solid solution ordinarily impose lattice strains on the surrounding host atoms.
Lattice strain field interactions between dislocations and these impurity
atoms result, and, consequently, dislocation movement is restricted. For
example, an impurity atom that is smaller than a host atom for which it
substitutes exerts tensile strains on the surrounding crystal lattice.
Conversely, a larger substitutional atom imposes compressive strains in its
vicinity. These solute atoms tend to diffuse to and segregate around
dislocations in a way so as to reduce the overall strain energy—that is, to
cancel some of the strain in the lattice surrounding a dislocation. To
accomplish this, a smaller impurity atom is located where its tensile strain
will partially nullify some of the dislocation’s compressive strain. For the edge
dislocation in this would be adjacent to the dislocation line and above the slip
plane.

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 Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

The resistance to slip is greater when impurity atoms are present because the
overall lattice strain must increase if a dislocation is torn away from them.
Furthermore, the same lattice strain interactions will exist between impurity
atoms and dislocations that are in motion during plastic deformation. Thus,
a greater applied stress is necessary to first initiate and then continue plastic
deformation for solid-solution alloys, as opposed to pure metals; this is
evidenced by the enhancement of strength and hardness.

Precipitation Hardening

In most binary systems, alloying above a concentration given by the phase

diagram will cause the formation of a second phase. A second phase can also
be created by mechanical or thermal treatments. The particles that compose
the second phase precipitates act as pinning points in a similar manner to
solutes, though the particles are not necessarily single atoms.

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 Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

The dislocations in a material can interact with the precipitate atoms in one
of two ways (see Figure 2). If the precipitate atoms are small, the dislocations
would cut through them. As a result, new surfaces (b in Figure 2) of the
particle would get exposed to the matrix and the particle/matrix interfacial
energy would increase. For larger precipitate particles, looping or bowing of
the dislocations would occur which results in dislocations getting longer.
Hence, at a critical radius of about 5nm, dislocations will preferably cut across
the obstacle while for a radius of 30nm, the dislocations will readily bow or
loop to overcome the obstacle. The mathematical descriptions are as follows:

𝐺𝑏
For particle blowing: ∆𝜏 = 𝐿−2𝑟

𝛾𝜋
For particle cutting: ∆𝜏 = 𝑏𝐿

Grain Boundary Strengthening

In a polycrystalline metal, grain size has a

tremendous influence on the mechanical
properties. Because grains usually have varying
crystallographic orientations, grain boundaries
arise. While an undergoing deformation, slip
motion will take place. Grain boundaries act as an
impediment to dislocation motion for the following
two reasons:

1. Dislocation must change its direction of motion due to the differing

orientation of grains.

2. Discontinuity of slip planes from grain 1 to grain 2.

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 Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

STRENGTHENING MECHANISMS IN AMORPHOUS MATERIALS

Polymer

Polymers fracture via breaking of inter- and intra-molecular bonds;

(A fracture is the separation of an object or material into two or more pieces
under the action of stress) hence, the chemical structure of these materials
plays a huge role in increasing strength. For polymers consisting of chains
which easily slide past each other, chemical and physical cross linking can be
used to increase rigidity and yield strength. In thermoset polymers
(thermosetting plastic), disulfide bridges and other covalent cross links give
rise to a hard structure which can withstand very high temperatures. These
cross-links are particularly helpful in improving tensile strength of materials
which contain lots of free volume prone to crazing, typically glassy brittle
polymers. In thermoplastic elastomer, phase separation of
dissimilar monomer components leads to association of hard domains within
a sea of soft phase, yielding a physical structure with increased strength and
rigidity. If yielding occurs by chains sliding past each other (shear bands), the
strength can also be increased by introducing kinks into the polymer chains
via unsaturated carbon-carbon bonds.
Increasing the bulkiness of the monomer unit via incorporation of aryl rings
is another strengthening mechanism. The anisotropy of the molecular
structure means that these mechanisms are heavily dependent on the
direction of applied stress. While aryl rings drastically increase rigidity along
the direction of the chain, these materials may still be brittle in perpendicular
directions. Macroscopic structure can be adjusted to compensate for
this anisotropy. For example, the high strength of Kevlar arises from a
stacked multilayer macrostructure where aromatic polymer layers are rotated
with respect to their neighbors. When loaded oblique to the chain direction,
ductile polymers with flexible linkages, such as oriented polyethylene, are
highly prone to shear band formation, so macroscopic structures which place
the load parallel to the draw direction would increase strength.
Mixing polymers is another method of increasing strength, particularly with
materials that show crazing preceding brittle fracture such as
atactic polystyrene (APS). For example, by forming a 50/50 mixture of APS
with polyphenylene oxide (PPO), this embrittling tendency can be almost
completely suppressed, substantially increasing the fracture strength.

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 Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

Glass
Many silicate glasses are strong in compression but weak in tension. By
introducing compression stress into the structure, the tensile strength of the
material can be increased. This is typically done via two mechanisms: thermal
treatment (tempering) or chemical bath (via ion exchange).
In tempered glasses, air jets are used to rapidly cool the top and bottom
surfaces of a softened (hot) slab of glass. Since the surface cools quicker, there
is more free volume at the surface than in the bulk melt. The core of the slab
then pulls the surface inward, resulting in an internal compressive stress at
the surface. This substantially increases the tensile strength of the material
as tensile stresses exterted on the glass must now resolve the compressive
stresses before yielding.
Alternately, in chemical treatment, a glass slab treated containing network
formers and modifiers is submerged into a molten salt bath containing ions
larger than those present in the modifier. Due to a concentration gradient of
the ions, mass transport must take place. As the larger cation diffuses from
the molten salt into the surface, it replaces the smaller ion from the modifier.
The larger ion squeezing into surface introduces compressive stress in the
glass's surface. A common example is treatment of sodium oxide modified
silicate glass in molten potassium chloride.

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 Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

Applications and current research

Strengthening of materials is useful in many applications. A primary
application of strengthened materials is for construction. In order to have
stronger buildings and bridges, one must have a strong frame that can
support high tensile or compressive load and resist plastic deformation. The
steel frame used to make the building should be as strong as possible so that
it does not bend under the entire weight of the building. Polymeric roofing
materials would also need to be strong so that the roof does not cave in when
there is build-up of snow on the rooftop.
Research is also currently being done to increase the strength of metallic
materials through the addition of polymer materials such as bonded carbon
fiber reinforced polymer to (CFRP).

Molecular dynamics simulations

The use of computation simulations to model work hardening in materials
allows for the direct observation of critical elements that rule the process of
strengthening materials. The basic reasoning derives from the fact that, when
examining plasticity and the movement of dislocations in materials, a focus
on the atomistic level is many times not accounted for and the focus rests on
the contiuum description of materials. Since the practice of tracking these
atomistic effects in experiments and theorizing about them in textbooks
cannot provide a full understanding of these interactions, many turn to
molecular dynamics simulations to develop this understanding.
The simulations work by utilizing the known atomic interactions between any
two atoms and the relationship F = ma, so that the dislocations moving
through the material are ruled by simple mechanical actions and reactions of
the atoms. The interatomic potential usually utilized to estimate these
interactions is the Lennard – Jones 12:6 potential. Lennard – Jones is widely
accepted because its experimental shortcomings are well-known. These
interactions are simply scaled up to millions or billions of atoms in some cases
to simulate materials more accurately.
Molecular dynamic simulations display the interactions based upon the
governing equations provided above for the strengthening mechanisms. They
provide an effective way to see these mechanisms in action outside the
painstaking realm of direct observation during experiments.

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 Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

References

Askeland, D. R., & Wright, W. J. (2014). Materials Science and Engineering.

Stamford, USA: Cengage Learning.
Callister, Jr., W. D. (2007). Materials Science and Engineering. USA: John
WIley & Sons, Inc.
Chung, Y.-W. (2007). Materials Science and Engineering. Parkway, New York:
CRC Press.
Hosford, W. F. (2008). Materials for Engineers. New York: Cambridge
University Press.
Rohde/Swearengen. (1982). Mechanical Testing for Deformation Model
Development. Baltimore, Md: American Society for Testing and
Materials.
Smith, W. F. (1990). Principles of Materials Science and Engineering. United
States of America: McGraw-Hill, Inc.

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