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BE 534

MACROMOLECULAR SCIENCE
AND ENGINEERING
Lecture-4
November 13, 2017
Lecture Outline
CHARACTERIZATION OF MACROMOLECULES
Mechanical Behavior
Molecular Weight
Mechanical Properties
Material selection: Cost,
availability, material properties
Material properties: Thermal and
chemical resistance, density,
mechanical properties, ease of
processing
Mechanical properties: Tensile Kevlar bullet proof vest
strength, stiffness, impact strength
etc.
Terminology
Load: The force applied to a material
during.
Engineering stress (): The applied load,
or force, divided by the original
(undeformed) cross-sectional area of the
material.

Engineering strain (): The amount that a


material deforms per unit length in a
tensile test.

where l0 is the initial length, l is the


deformed length
Hooks Law
A solid material subjected to a tensile force would
extend in the direction of traction by an amount that
is proportional to the load (force) (Hookes Law).

Hooks Law =Ex


Stress

Strain
pounds per inch square (psi) or
newtons per meter square (N/m2) or
pascal (Pa).
1 psi = 6894.75 N/m2 = 6894.75 Pa

Chapter 7 -
Elastic Constants
By using these definitions of stress and strain, Hookes law can be expressed in
quantitative terms:

Tension or compression ;
=E
tensile modulus or
Youngs modulus

Shear ; =G
shear modulus

Both moduli are inherent properties of the material (free of geometrical


dependence).
Stress-Strain Test (Tensile Test)

SPECIMEN

In tensile test:
Apply tension until material fractures
Maintain constant strain rate,
e.g. 120 mm/min.

MACHINE
Tensile Test
Elasticity
During elastic straining, the atoms are
displaced only slightly by reversible stretching
of the interatomic bonds.

Fracture stress

Brittle Fracture: Microscopic defects, which are present in all real materials, will
eventually begin to grow rapidly under the influence of the applied tensile or shear
stress, and the specimen will fail suddenly by brittle fracture. Until this brittle failure
occurs, the stressstrain diagram does not deviate from a straight line, and the stress
at which failure occurs is called the fracture stress.

Examples of brittle polymers: PMMA (bone cement) and unmodified PVC, epoxy resin, phenol-
formaldehyde resins.
Elastic Deformation
1. Initial 2. Small load 3. Unload

bonds
stretch

return to
initial

F F Linear-
elastic
Non-Linear-
Elastic means reversible. elastic

Plastic Deformation

Once plastic deformation starts, the strains produced are very much greater
than those during elastic deformation; they are no longer proportional to the
stress and they are not recovered when the stress is removed. This
happens because whole arrays of atoms under the influence of an applied
stress are forced to move, irreversibly, to new locations
Large scale displacement of atoms without
complete rupture of the material, i.e., plastic
deformation, is only possible in the presence of
the metallic bond so only metals and alloys
exhibit true plastic deformation.

Plastic deformation is very useful for shaping


metals and alloys and is called ductility or
malleability. The total permanent (i.e., plastic)
strain exhibited up to fracture by a material is a
quantitative measure of its ductility.
Plastic Deformation (Metals)
1. Initial 2. Small load 3. Unload
bonds
stretch planes
& planes still
shear sheared

elastic + plastic plastic

F
F
linear linear
elastic elastic
Plastic means permanent.
plastic
Other properties can be derived from the
tensile stressstrain curve:
The tensile strength or the
ultimate tensile stress (UTS) is the
stress that is calculated from the
maximum load experienced during
the tensile test.

The area under the tensile curve is


proportional to the work required to
deform a specimen until it fails

(A=stress x strain)Work/volume. A is a
measure of toughness and reflects a
materials resistance to crack propagation

Yield strength is a measure of resistance to plastic deformation. It is the value of


stress at the yield point, calculated by plotting young's modulus at a specified
percent of offset (usually offset = 0.2%).
MECHANICAL PROPERTIES
(TERMINOLOGY)

Strong: able to withstand a load without


deformation and fracture; or resistant to
failure, given by the applied stress (or
load per unit area)

Tough: resistant to shock and able to


deform without rupturing. Toughness
measures the energy required to crack
a material; it is important for things
which suffer impact.

Increasing strength usually leads to


decreased toughness
MECHANICAL PROPERTIES
(TERMINOLOGY)
Hard: resistant against indentation and scratching.

Elastic: able to return to its original shape after the load is removed.

Plastic: able to deform permanently without breaking or rupturing.

Brittle: Breaks without deforming.

Ductile: able to stretch, bend, or twist without cracking or breaking. This


property makes it possible for a material to be drawn out into a thin wire.

Malleable: ability to deform by compressive forces without developing defects. A


malleable material is one that can be stamped, hammered, forged, pressed, or
rolled into thin sheets
Stress-Strain Characteristics of Polymers
If we look at the stress-strain
curves of glassy polymers
and semicrystalline
polymers above Tg, they
represent brittle and ductile brittle polymer
behavior respectively.
plastic
Tensile (TS)
On the other hand, or ultimate
elastomers (rubber) are tensile
strength
elastic but non-linear (UTS)
behavior is often observed Yield Amorphous above Tg
stress
up to strains of 500% or elastomer
more. Furthermore, even in
the initial Hookean regions
of the stress-strain behavior
of polymers, anelastic
responses are often typical.
Anelastic materials recover
fully after removal of the
load but if sufficient time is
given but elastic materials
recover instantaneously.
Stiffnes
Semi-crystalline polymers stiffness depends
on whether they have low or high Tg. brittle polymer
Conformational freedom in amorphous
plastic
domains is restricted by crystalline domains.
E strongly depends on the crystallinity
degree.
Amorphous above Tg
Stifness can be explained by the stifness of elastomer
the bonds and more importantly how they
are arranged spatially

Silica amorphous solid.


Diamond-very stiff Arrangement is not
material ordered. It has less
stiffnes
Rubbers are fully amorphous. They have low Tgs at
ordinary temperatures. They respond to a load by
changing their distribution of chain conformations.
The chains become more extended as the material is
stretched before the covalent bonds take the load.
Yielding: Flexible Semi-Crystalline Polymers
Lets start by looking at a simple
polymer, polyethylene. Flexible semi-
crystalline polymers such as this (where
the Tg of the amorphous domains is
below room temperature) usually
display a considerable amount of
yielding or cold-drawing. For small
deformations, Hookean elastic-type
behavior (more or less) is observed, but
beyond what is called the yield point,
irreversible deformation occurs.
At the yield point, a neck forms and
there is an actual decrease in stress
while the sample stretches out
considerably. After deformation has
continued at an almost constant stress
the sample regains some resistance to
strain and ultimately breaks at a higher
load.
Tensile Response: Brittle & Plastic
(MPa) fibrillar
Near Failure structure
x brittle failure
near
onset of
failure
necking plastic failure
x
Initial
unload/reload


aligned, networked
cross- case crystalline
linked regions
case slide
semi-
crystalline amorphous
crystalline
case regions
regions align
elongate
Stress-strain curves adapted from Fig. 15.1, Callister 7e. Inset figures along plastic response curve adapted from
Figs. 15.12 & 15.13, Callister 7e. (Figs. 15.12 & 15.13 are from J.M. Schultz, Polymer Materials Science, Prentice-
Hall, Inc., 1974, pp. 500-501.)
Tensile Response: Elastomer Case
(MPa)
x brittle failure Stress-strain curves
adapted from Fig. 15.1,
Callister 7e. Inset
figures along elastomer
curve (green) adapted
from Fig. 15.15, Callister
plastic failure
x 7e. (Fig. 15.15 is from
Z.D. Jastrzebski, The
Nature and Properties of
x Engineering Materials,
elastomer 3rd ed., John Wiley and
Sons, 1987.)
final: chains
are straight,
still
cross-linked
initial: amorphous chains are Deformation
kinked, cross-linked. is reversible!
Compare to responses of other polymers:
-- brittle response (aligned, crosslinked & networked polymer)
-- plastic response (semi-crystalline polymers)
Viscoelasticity
Some features that are observed in polymeric materials that do
not seem to be noticeable in metals or ceramics
1. Mechanical properties depend on Temperature
2. Mechanical properties depend on Strain Rate
3. Creep (noticed in metals at high temperatures)
4. Stress Relaxation
Viscoelasticity

Spring model of elastic behavior


CREEP (VISCOELASTIC BEHAVIOR)
For polymers, only elastic or only
viscous flow behavior is not valid.

Dash pot and spring model of a


viscoelastic material

Permenant
deformation
Stress Relaxation (VISCOELASTIC BEHAVIOR)
Think of a polymer specimen loaded with a constant strain.

Note that both linear elastic


and viscous fluid behaviors
are present.
Note that there seems to
be some residual stress at
the end, i.e. the material
does not completely
recover. There is both
elasticity and plasticity.
Stress Relaxation: Progressive loss of stress (load) over
time under constant strain (deformation), usually at high
temperatures
Influence of T and Strain Rate on Thermoplastics

Decreasing T...
(MPa)
-- increases E 80 4C Plots for
-- increases TS semicrystalline
-- decreases %EL 60 PMMA (Plexiglas)
20C
Increasing 40 40C
strain rate...
-- same effects 20
as decreasing T. to 1.3
60C
0
Increasing temperature increases
relative space between chains and
0 0.1 0.2 0.3
Adapted from Fig. 7.24, Callister & Rethwisch 3e. (Fig. 7.24 is from T.S.
makes uncoiling easier. Carswell and J.K. Nason, 'Effect of Environmental Conditions on the
Mechanical Properties of Organic Plastics", Symposium on Plastics,
Slowing the strain rate means American Society for Testing and Materials, Philadelphia, PA, 1944.)
there is more time for chain
reconfiguration.
Chapter 7 - 28
Molecular Weight
The fundamental characteristics of
polymer materials, the ultimate source
of their interesting and in some cases.
unique properties (like rubber elasticity),
is their long chain nature. The struggle
to establish the macromolecular concept
(by Hermann Staudinger) was long and
difficult.

The ultimate test of the existence of polymers is, of course, provided by a


measure of their size, but this is by no means an easy task for large molecules.

29
Colligative Properties
Traditional methods for measuring molecular
weight date from the dawn of physical chemistry
in the 19th century. These relied on so called
colligative property measurements such as
boiling point elevation and freezing point
depression. However, even a polymer with a
relatively low molecular weight of 10.000 g/mole
will give very small freezing point depressions or
boiling point elevations, of the order of 0.01 K.
These particular methods are therefore simply
not accurate enough to measure the molecular
weights of very large molecules with any
precision.

30
Molecular Weight Distributions
Remember that a big problem with
describing the molecular weight of
synthetic polymers is that there is always
a distribution of chain lengths (though
certain polymerizations can give very
narrow distributions) and it is necessary
to define an average. Which of the
following definitions describes the weight
average molecular weight?

31
Determination of Molecular Weight
Here is the list of some of the major
methods for measuring the molecular
weight of polymers on the right,
separated into two categories.
Absolute methods give a direct
measure of a particular average, while
relative methods require samples of
known molecular weight to calibrate
the instrument. We will just consider
two methods that are most widely
used: viscosity and size exclusion (SEC)
or gel permeation chromatography
(GPC).

32
Viscosity: A Measurement of
Molecular Weight
In everyday life, it is common to refer to a
viscous fluid as thick, while a low viscosity
fluid is referred to as thin. Viscosity is a
measure of resistance to flow of a fluid. The
study of viscous properties of materials is
called rheology. Since viscosity is related to
friction between the molecules, one would
expect that such frictional forces to increase
with size or molecular weight. Thus, it is
possible to use viscosity measurements to
determine molecular weight of polymers
but with a semi-empirical manner, i.e. using
both theory and experimental observations.

33
Poiseuilles Law
French physicist and physician, Jean PoiseuilIe,
who was interested in the circulation of blood in
the body studied the flow of liquids through
capillaries pipes with a very fine diameter. He
summarized his experimental results in an
equation we call Poiseuilles Law, where the rate
of flow of fluid (volume/sec) is directly
proportional to pressure and inversely
proportional to viscosity. The units of viscosity is
in poise. To be more precise, this is the dynamic
or absolute viscosity. There is also something
called kinematic viscosity, which is the dynamic
viscosity divided by density.

34
Measuring the Viscosity of Polymer
Solutions
So. if we measure the rate of flow of polymer
solution through capillaries, we can get a
measure of their viscosity. Two simple
laboratory viscometers that allow one to do
this are shown on the right. Essentially. they
are used to measure how long it takes the
solution to pass between two marks under
the pressure imposed by gravity on the head
of fluid. What we are actually trying to
measure, however, is the frictional forces
between the polymer and the solvent, not
just the viscosity of the solution as a whole.
We therefore determine the relative
viscosity, rel, the viscosity of the solution
divided by the viscosity of the pure solvent.
35
Relative Viscosity
In order to determine the frictional forces between a
single polymer molecule and the solvent, then we need
to make the measurements in dilute solution, so that
there is no contribution from polymer-polymer
interactions. The relative viscosity is obtained by
rearranging PoiseuilIes equation to express the
viscosity in terms of the rate of flow, realizing that the
pressure, P, maintaining the flow is simply proportional
to the density of the solutions or pure solvent, while
the rate of flow is simply proportional to the time taken
to go between the two marks.
(The subscript 0 refers to the pure solvent.) Since density of the solutions and
solvent is (about) the same (for dilute solutions), the relative viscosity being
equal to the ratio of the time it takes the solution to pass between the marks
relative to the time taken by the pure solvent.

36
Relative Viscosity
If the relative viscosity depends in a
simple way on the frictional forces
between the polymer and solvent, then
one might expect that a plot of rel vs c,
the concentration, would be linear, as
rel, should increase with how much
polymer is present. Its slope, however.
should be proportional to the size of the
polymer molecule, in that you would
expect rel to increase at a faster rate
with concentration for larger molecules.
Al low concentrations, plots of relative
viscosity vs. concentration are indeed
usually linear, but, as might be
expected, show deviations from
linearity at higher concentrations.

37
Intrinsic Viscosity
A power series can be used to fit the
relative viscosity data, which at low
concentrations can be truncated after
a couple of terms:

Both [] and k are constants, the


square brackets around the former
being part of the symbol. [] is called
the intrinsic viscosity and the quantity
that we will relate to the molecular
weight of the polymer.
38
Specific Viscosity

To minimize fitting errors, another viscosity term, specific viscosity,


denoted as sp has been introduced as given above.

39
Huggins Equation
After truncating the power series to neglect
terms in c3 or higher, rearrange the equation
so that the right-hand side is linear in c. The
specific viscosity is then simply rel - 1. The
intrinsic viscosity, [], just the intercept, the
value of sp/c as goes to zero.
Huggins found that the slope of plots of sp/c
versus c is apparently proportional to []2.
Incorporating this assumption results in the
Huggins equation highlighted at the bottom.

40
Inherent Viscosity: Kraemer Equation
Kraemer defined the intrinsic viscosity in
a different way as shown in the box. The
quantity ((ln rel)/c) is called the inherent
viscosity. It can be expressed as a power
law in c in a similar fashion to the
Huggins equation. In addition, ln rel, can
be expanded in powers of sp. Comparing
these equations it can be shown that:
k = k

41
Intrinsic Viscosity

Both the Huggins and Kraemer equations lead to the same extrapolated value
of [] so it has become common practice to use both equations on the same
plot, as shown schematically above. This, combined with the imposition of
the requirement that k = k increases confidence in the extrapolation,
but not all data looks as good as that shown here.

42
Intrinsic Viscosity
In systems with strong intermolecular
interactions, such as solutions of
polymers or polyelectrolytes severe
deviations from linear behavior can be
observed even at low concentrations.
This should reinforce a point that is
general to all extrapolation to zero
concentration methods: the experiments
should be performed at lowest
possible concentrations but this is
where the largest errors in measurement
are bound to occur.

43
Definitions

44
Intrinsic Viscosity and Molecular
Weight
The relationship between the intrinsic viscosity and the molecular weight was
first established empirically from plots of log [] vs log mol wt. which were
found to be linear, meaning that the relationship between the two quantities
has the form:
Mark-Houwink-Sakurada Equation

45
Mark-Houwink-Sakurada Equation
Mark-Houwink-Sakurada equation
is the basis for determining
molecular weight using solution
viscosity measurements. The
method is not absolute but relative
requiring the initial determination
of the intrinsic viscosity of a set of
monodisperse samples of known
molecular weight (determined by
osmotic pressure or light-scattering
measurements).

A plot of log [] vs log mol wt. then allows the determination of the
constants K and a, characteristic of that polymer in that solvent at that
temperature. If the intrinsic viscosity of a sample of unknown molecular
weight is then measured in the same solvent at the same temperature its
molecular weight can be calculated.
46
Viscosity Average Molecular Weight
In viscosity measurements, you are
actually measuring a new average,
called the viscosity average
molecular weight:

This equation can be obtained in a


straight forward manner by
assuming that the specific viscosity
of the (dilute) solution is simply the
sum of the contributions from all
the chains present, and through the
algebra shown on the right.

47
Size Exclusion Chromatography
Chromatography, is a wide range of techniques
that are used to separate the components of a
mixture. The field has its origin in the work of a
botanist, Mikhail Tswett, who (in 1906)
separated plant pigments (chlorophylls) by
pouring a petroleum ether extract of green
leaves over a column of powdered CaCO3 held
in a glass column. The components of the
mixture migrated down at different speeds so
that the column became marked with horizontal
bands of different colors -a chromatogram (from
the Greek colored record). Size exclusion
chromatography was first developed using
cellulose-based materials that act as molecular
sieves and are capable of separating large
molecules such as proteins and synthetic
polymers according to size (1959 by Flodin and
Porath). 48
Definitions
When crosslinked insoluble polymers are used in a column in order
to separate size, these polymers swell in the solvent thus forming a
gel, and the technique was referred to as gel filtration
chromatography (used for separating biological materials in
aqueous media) or gel permeation chromatography (used for
separating synthetic polymers in organic solvents).
However, the polymer gels initially used for separations were soft
and could not stand up to the high pressures that are needed to
reduce long separation times. Many modem instruments therefore
use rigid silica-based materials in the form of porous beads packed
into a column or more often, a set of columns, and the technique is
more correctly referred to as size exclusion chromatography.

49
Size Exclusion Chromatography

The experimental protocol is straightforward. Solvent, or a mixture of solvents


is pumped through the packed columns. There is an injection port at some
point in the solvent stream before it reaches the columns. A polymer solution
is injected at this point. The solution passes through the columns and through
a detector that measures the amount of polymer in the eluent stream (e.g..
something that measures the refractive index of the solution, which varies
systematically with polymer concentration).

50
Size Exclusion Chromatography

Small particles or molecules not only flow around the beads as a solution is
pumped through the columns, but can also diffuse in and out of the pores of
the beads. Their average path length through the column is therefore much
longer than that of a very large molecule that may by completely excluded
from the pores. Molecules that are intermediate in size may diffuse in and out
of large pores, but be excluded from smaller ones. Thus, molecules have
different path lengths through the column according to their size and are
eluted at different times.
51
Size Exclusion Chromatography
Sample chromatogram of a polydisperse
polymer is given here. In SEC, the amount
of polymer eluted from the columns is
plotted against the elution volume (the
amount of liquid that has come through
the column from a given starting time, say,
when the polymer was injected into the
solvent stream). There may be just a small
amount of very high molecular weight
material that comes off first, and small
amounts of low molecular weight material
that comes off last, and in between, a
curve that reflects the molecular weight
distribution of the sample.

52
Calibrating the Columns
SEC or GPC is not an absolute method of
measuring molecular weight. Nevertheless.
there must be a relationship between the
molecular weight (or more accurately size) of
the molecules and the time it takes them to
pass through the column, as measured by the
elution volume. A particular column or columns
must therefore be calibrated by first passing
through monodisperse samples of known
molecular weight. A calibration curve can then
be constructed by plotting the log of the
molecular weight against the elution volume
for these samples. This can then be used to
determine the molecular weight distribution of
an unknown sample.
53
Calibrating the Columns
There is a linear relationship between the
molecular weight and elution volume but only
over a certain range. This is because a
particular set of columns has a restricted
range where selective separation occurs.
Outside this range, at small elution volumes,
total exclusion of molecules larger than a
certain size occurs. In other words, all these
big molecules pass around the beads and are
not separated. Similarly total permeation of
small molecules occurs - molecules less than a certain size elute at the same
volume. The columns that are designed for specific molecular weight ranges
should be used. The size of a given polymer coil in solution varies with the
nature of the polymer and solvent (hence their interactions) and the
temperature. Accordingly, the type of calibration shown above as only good for a
given polymer-solvent system at a specified temperature.

54
Calculating the Molecular Weight
Distribution
SEC data of a typical polydisperse sample
appears as given in this figure. This curve
can be effectively cut into narrow slices
defined by equal increments of elution
volume, V. If these slices are sufficiently
narrow, the polymer eluting in each of
these elements of volume may be
regarded as monodisperse and total area
of curve can be regarded as the sum of
the heights of the individual slices. The
weight fraction of any slice can be given
by:

55
Calculating Averages
The molecular weight of the ith species is
then obtained from the calibration curve at
point Vi, and the molecular weight averages
can be calculated using:

The intrinsic viscosity can be calculated


using:

56
Hydrodynamic Volume

SEC is good for calculating the molecular weight distribution and molecular
weight averages as long as monodisperse or more accurately very narrow
molecular weight standards of the same polymer are available since the size of a
molecule in solution, its hydrodynamic volume, depends upon the nature of the
polymer-solvent pair and the temperature. When we say the nature of the
polymer this also includes chain architecture; a linear polystyrene with the same
number of segments as a star-shaped sample occupies a higher hydrodynamic
volume (more of the segments are bunched together in the middle of the
molecule where the arms of the star meet). If these polymers are in a good
solvent, both may occupy a bigger hydrodynamic volume than a chemically
different linear polymer in the same solvent at the same temperature.

57
Hydrodynamic Volume
In effect, different calibration curves are
necessary for different polymer solvent
pairs or even the same polymer/solvent
pair if the microstructure of the polymer
is different to that of the standards that
are available. Sometimes, molecular
weight averages based upon linear
polystyrene standards are reported. but
this can obviously lead to large errors
making SEC is tedious and limited
method. To overcome these limitations
modification of this method has been
developed.

58
Hydrodynamic Volume
Benoit and coworkers recognized that separations
occur on the basis of hydrodynamic volume rather
than molecular weight and made the connection to
intrinsic viscosity, which also depends upon the size
of a molecule in solution and can be related to the
volume of an equivalent hydrodynamic sphere, Vh.
The intrinsic viscosity of a dilute solution is related
to Vh and the molecular weight by the equation:

where A is the Avogadros number and M is the


molecular weight of the polymer.

59
Universal Calibration Curve
Rearranging this:

Benoit et al. then reasoned that all


polymers regardless of chemical
structure and chain architecture should
lie on the same plot of log ([]M) vs.
elution volume. And most of them do as
shown on the plot on the right which is
called the universal calibration curve. (It
is actually not quite universal as data
from thin like liquid crystalline polymers
that have extended-chain rather than
coil conformations in solution do not all
lie on this curve.)
60
Universal Calibration Curve
First a universal calibration curve is prepared
using for example polystyrene standards. This
is plotted as log J versus elution volume
where for the ith sample:

The intrinsic viscosity of the samples can be


measured or directly calculated if Mark-
Houwink-Sakaruda constants, K, and a, are
known for the same solvent and temperature
of SEC experiments. In SEC we determine Vi
from which we can get Ji using the universal
calibration curve. Finally we get Mi, using the
last equation.

61