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PHN TCH POLYME
(POLYMER ANALYSIS)
TS. on Th! Thu Loan

Is a branch of polymer science dealing with analysis and characterisation of

polymers.
The complication of macromolecular chains, the dispersion in molecular
weight, tacticity, crystallinity, orientation, composition of polymers etc. and
complex morphological systems
analysis of polymer the small organic materials
Focus on viscoelastic properties, dynamic mechanical testing.
Polymer analysis
Instron mechanical tester
Vicker hardness tester
DMA
Melt flow indexer
Torsions Rheometer

-AFM, SEM
-FT-IR
-Pull-out test
Instruments
FT-IR
IR-microscope
GPC ( size exclusion chromatography
SEC)
-Viscosimetry
-X-ray (WAXS and SAXS)
-EM, SEM, TEM, AFM
-Dynamic and static methods for contact
angle measurements.
-Tensile, flexural, impact,
compression, hardness tests,
-Rheological and viscoelastic
properties, stiffness and
modulus, surface tension,
permeation and diffusion in
polymers, adhesion tests,
density
-Surface roughness,
-Chemical
composition,
-Interface
characetrisation
-Molecular weight determination,
-Microstructural characterisation and
compositional analysis,
-Crystallinity,
-Investigation of polymer morphology,
particle size,
-Contact angle and wettability
measurements
Mechanical and Physical
Properties
Surface
Characterisation
Chemical, Molecular and Structural
Characterisation
Methods of polymer analysis
GC
pH meter
HPLC
Karl-Fischer titration
Thermogravimetric analyser (TGA)
TGA-FTIR coupled technique
Differential scanning calorimetry (DSC)
Modulated differential scanning
calorimetry (ADSC)
Dynamic thermomechanical analyser
(DMTA)
Dielectric relaxation
Instruments
Inolab conductivity
meter

Purity and molecular

weight of small
molecules, water content
in organic solvents,
surface tension
measurement, pH
-Melting point, glass transition
temperature, free rotation temperature,
-Degradation and stability behaviour of
polymers
Conductivity, electric
current in solution,
light emitting and
electromagnetic
properties
Miscellaneous (hon tap) Thermal Behaviour
Electrical and Optical
Properties
Methods of polymer analysis
-For quality control
-For predicting service performance
-To generate design data
-To investigate failures
Purpose of polymer analysis
Essential to identify the purpose of testing, because the requirements for each
of the purposes are different.
-Precision
-Reproducibility
-Rapidity
Balance of these attributes,
according to the purpose of
the test
-Complexity
-Automated test
-Nondestructive test
-Cost
Nondestructive methods are advantageous and indeed essential when
100% of the output is being tested.
The tests should be simple and inexpensive, and automation will
probably aid the rapidity of testing.
Tests related to product performance are preferred.
Quality Control Tests
The most important factor is that the tests relate to service conditions
and to aspects of product performance.
should not be too complex, although rapidity and cheapness are less
important than was the case with quality control.
Nondestructive tests are not always appropriate when predicting product
performance, as it may be necessary to establish the point at which failure
occurs.
Tests Predicting Product Performance
Usually test pieces are of a simple shape and a specified size, whereas
the product may be of a different geometry and size
Data must be presented in a form that enables the designer to allow for
changes in geometry, time scale, etc.. which implies detailed and
comprehensive understanding of material behavior
It follows that data of this type are expensive to produce and that results
are unlikely to be obtained with great rapidity.
However, automation may be advantageous, particularly in the case of
tests running for a long time (creep tests)
Tests for Producing Design Data
Some understanding of the various mechanisms of failure is necessary before
suitable tests can be chosen.
Tests need not be complex but must be relevant
Ex: a simple measurement of product thickness may establish that there has
been a departure from the specified design thickness.
The absolute accuracy of the test may not be important, but it is essential that
it be capable of discriminating between the good and the bad product.
Tests for Investigating Failures
What are our expectations of polymer materials?
Excellent Characteristics:
Mechanical and Physical Properties
Thermal Behaviour
Surface and interface Characteristics
Electrical and Optical Properties
Safe to use
Light weight
Reliable, durable
Low cost
Less adverse environmental impact
Good resistance to environmental attacks
Mechanical Testing
of Polymers
Types of Mechnical Tests
Tensile test (a)
Flexural test (d) (e) (f)
Compression test (b) Shear (g)
(h)
(i)
Impact test (h) (i)
Scope:
Measure the force required to break a specimen and the extent to which the
specimen stretches or elongates to that breaking point.
Produce a stress-strain diagram, which is used to determine tensile modulus.
The data is often used to specify a material, to design parts to withstand
application force and as a quality control check of materials.
Since the physical properties of many materials (especially thermoplastics) can
vary depending on ambient temperature test materials at temperatures that
simulate the intended end use environment.
Tensile test
Specimen Size:
The most common specimen for ISO 527 is the ISO 3167 Type 1A
multipurpose specimen.
ASTM D882 uses strips cut from thin sheet or film.
*The multipurpose test specimen:
+150 mm long,
+The center section: 10 mm wide *4 mm thick *80 mm long.
Tensile test
A tensile dog bone specimen
b
W
l

For the composite samples
Longitudinal test
Transverse test
Test Procedure:
Specimens are placed in the
grips and pulled until failure.
For ASTM D638, the test
speed is determined by the
material specification.
For ISO 527 the test speed
is typically 5 or 50mm/min for
measuring strength and
elongation
+and 1mm/min for measuring
modulus.
An extensometer is used to
determine elongation and
tensile modulus.
Tensile test
Tensile2.wmv
Characteristics of stress-strain behavior:
Modulus of elasticity (stiffness, elastic
modulus, Youngs modulus) is the slope of
the stress-strain curve in the elastic region
Yield strength (
y
) is the stress applied to a
material that just causes permanent
deformation
Tensile strength (TS) is defined at the
fracture point and can be lower than the
yield strength
Ultimate tensile strength is the stress that
corresponds to the maximum load
Elongation at break (%) the increase in
length of a specimen under tension before
it breaks (Strain).
Stress Strain Behavior
P= Applied load
A = Original cross-sectional area
Strain,
S
t
r
e
s
s
,

y

F

F
2% 0

E
= /l
Stress-train behavior of polymers
Stress Strain Behavior
Moduli of elasticity for polymers are ~ 10MPa-4GPa (compare to metals ~ 50 -
400 GPa)
Tensile strengths are ~ 10 -100MPa (compare to metals, hundreds of MPa to
several GPa)
Elongation can be up to 1000 % in some cases (< 100% for metals)
Polymers are also very sensitive to the rate of deformation (strain rate).
Decreasing rate of deformation has the same effect as increasing T.
Stress Strain Behavior
TENSILE RESPONSE: ELASTOMER CASE
Deformation of Amorphous Polymers
Stress-strain curves
Deformation of Semicrystalline and crosslinked Polymers
Flexural test
Scope:
Measures the force required to bend a
beam under 3 point loading conditions.
The data is often used to select materials
for parts that will support loads without
flexing.
Flexural modulus is used as an indication
of a materials stiffness when flexed.
can test materials at temperatures that
simulate the intended end use environment.
Most commonly the specimen lies on a span and the load is
applied to the center by the loading nose producing three point
bending at a specified rate.
The parameters for this test are :
+The support span;
+The speed of the loading
+The maximum deflection for the test.
These parameters are based on the test specimen
thickness, and are defined differently by ASTM and ISO.
Specimen Size:
A variety of specimen shapes can be used
The most commonly used specimen size:
+ 3.2mm x 12.7mm x 125mm for ASTM D790
+10mm x 4mm x 80mm for ISO 178
Test Procedure:
Flexural test
Flexural strength
Flexural modulus
Flexural test
b
b
L
F

3
3
4 h b
L m
E
b
=
2
2
3
h b
L F
b
=
m : initial slope of the load vs. deflection curve
For relatively thin samples two point loading
For thick samples 4 point loading
Flexural test
Izod Impact Testing
(Notched Izod)
Notched Izod Impact is a single point test that measures
a materials resistance to impact from a swinging
pendulum.
Izod impact is defined as the kinetic energy needed to
initiate fracture and continue the fracture until the
specimen is broken.
Izod specimens are notched to prevent deformation of
the specimen upon impact.
This test can be used as a quick and easy quality control
check to determine if a material meets specific impact
properties or to compare materials for general toughness.
Scope:
64 x 12.7 x 3.2 mm for ASTM D256
The preferred thickness is 6.4 mm because it is not as likely to bend or crush
The depth under the notch of the specimen is 10.2 mm
80 x 10 x 4 mm for ISO 180
The depth under the notch of the specimen is 8mm
Specimen Size:
Izod Impact Testing
(Notched Izod)
The specimen is clamped into the pendulum impact test
fixture with the notched side facing the striking edge of the
pendulum.
The pendulum is released and allowed to strike through
the specimen.
If breakage does not occur, a heavier hammer is used
until failure occurs.
Since many materials (especially thermoplastics) exhibit
lower impact strength at reduced temperatures to test
materials at temperatures that simulate the intended end
use environment
izodimpact.wmv
Izod Impact Testing
(Notched Izod)
Test Procedure:
The specimens are conditioned at the specified temperature in a freezer
until they reach equilibrium.
The specimens are quickly removed, one at a time, from the freezer and
impacted.
Neither ASTM nor ISO specify a conditioning time or elapsed time from
freezer to impact - typical values from other specifications are 6 hours of
conditioning and 5 seconds from freezer to impact.
Reduced Temperature Test procedure:
ASTM
Impact energy is expressed in J/m or ft-lb/in.
Impact strength is calculated by dividing impact energy in J (or ft-lb) by the
thickness of the specimen.
The test result is typically the average of 5 specimens.
ISO
Impact strength is expressed in kJ/m
2
Impact strength (a
cU
) is calculated by dividing impact energy in J by the
area under the notch.
Data
3
cU
10 a =
b h
W
W: energy
b = width of the sample
h = thickness of the sample
The test result is typically the average of 10 specimens.
The higher the resulting number, the tougher the material.
Impact Testing
Compressive properties describe the behavior of a
material when it is subjected to a compressive load.
Loading is at a relatively low and uniform rate.
Compressive strength and modulus are the two most
common values produced.
Compression test
Blocks or cylinders
For ASTM D695:
+The typical blocks: 12.7 x 12.7 x 25.4mm
+The cylinders:12.7mm diameter and 25.4mm long
For ISO 604: the preferred specimens:
+50 x 10 x 4mm for modulus
+10 x 10 x 4mm for strength
Specimen size:
Scope:
The specimen is placed between compressive plates
parallel to the surface.
The specimen is then compressed at a uniform rate.
The maximum load is recorded along with stress-strain
data.
An extensometer attached to the front of the fixture is
used to determine modulus.
Compression test
Compressive strength
maximum compressive load
minimum cross-sectional area
=
Compressive modulus
change in stress
change in strain
=
Test Procedure:
Rockwell Hardness tester
Standard specimen of 6.4mm thickness
is molded or cut from a sheet.
Specimen size:
A hardness measurement based on the net increase in
depth of impression as a load is applied.
Hardness numbers have no units and are commonly
given in the R, L, M, E and K scales.
The higher the number in each of the scales, the harder
the material
The harder the material better resistance to plastic
deformation or cracking in compression, better wear
properties
Scope:
Durometer Hardness - Shore Hardness
Determine the relative hardness of soft materials,
usually plastic or rubber.
The test measures the penetration of a specified
indentor into the material under specified conditions of
force and time.
The hardness value is often used to identify or
specify a particular hardness of elastomers or as a
quality control measure on lots of material.
Scope:
Generally 6.4mm ( in) thick for ASTM D 2240.
Specimen size:
Durometer Hardness - Shore Hardness
The specimen is first placed on a hard flat surface.
The indentor for the instrument is then pressed into the specimen making sure
that it is parallel to the surface.
The hardness is read within one second (or as specified by the customer) of firm
contact with the specimen.
Test Procedure:
The hardness numbers are derived from a scale.
Shore A and Shore D hardness scales are common, with the A scale being used
for softer and the D scale being used for harder materials.
Data:
Density is the mass per unit volume of a material.
Specific gravity is a measure of the ratio of mass of a given volume of
material at 23C to the same volume of deionized water.
Specific gravity and density are especially relevant because plastic is
sold on a cost per pound basis and a lower density or specific gravity
means more material per pound or varied part weight.
Density and Specific Gravity
ASTM D792, ISO 1183
Scope:
For sheet, rod, tube and molded articles.
The specimen is weighed in air then weighed when immersed in distilled water at
23C using a sinker and wire to hold the specimen completely submerged as
required. Density and Specific Gravity are calculated.
Any convenient size
+Specific gravity = a/[(a + w)-b]
a = mass of specimen in air.
b = mass of specimen and sinker (if used) in water.
W = mass of totally immersed sinker if used and partially immersed wire.
+Density, kg/m3 = (specific gravity) x (997.6)
Test procedures:
Bulk density is defined as the weight per unit volume of material.
Bulk density is primarily used for powders or pellets.
The test can provide a gross measure of particle size and dispersion which can affect
material flow consistency and reflect packaging quantity.
A funnel is suspended above a measuring cylinder.
The funnel is filled with the sample and allowed to freely flow into the measuring
cylinder.
The excess material on top of the measuring cylinder is scraped off with a straight
edge.
The sample and the cylinder is then weighed and the weight / volume (Bulk Density) is
determined.
Apparent density value is recorded as g/cm
3
Bulk Density
ASTM D1895B
Thermal Analysis
Thermal analysis (TA) is frequently used to describe analytical experimental
techniques which investigate the behaviour of a sample as a function of temperature.
TA refers to conventional TA techniques such as:
+Differential thermal analysis (DTA)
+Differential scanning calorimetry (DSC)
+Dynamic mechanical analysis (DMA)
+Thermogravimetry (TG/TGA)
Representative TA curves
The advantages of TA over other analytical methods can be summarized as follows:
(i) the sample can be studied over a wide temperature range using various temperature
programmes
(ii) almost any physical form of sample (solid, liquid or gel) can be accommodated using
a variety of sample vessels or attachments
(iii) a small amount of sample (0.1 g-10 mg) is required
(iv) the atmosphere in the vicinity of the sample can be standardized
(v) the time required to complete an experiment ranges from several minutes to several
hours
(vi) TA instruments are reasonably priced
Thermal Analysis
Scope:
As the sample goes through the programmed temperature change, there is no
temperature difference until the sample undergoes an exothermic or endothermic
chemical reaction or change of physical state.
The thermal event (a temperature difference between the sample and the
reference (T)) will be recordedT versus time or temperature plot
Measure the differential temperature between a sample and a reference pan
to determine the temperature of the transitions
Test procedures:
Differential thermal analysis (DTA)
Schematic of a DTA apparatus
Differential thermal analysis (DTA)
A DTA curve
The subscripts represent: s-sample, r-reference, i-initial,f-final.
T
r
Tg = Glass Transition Temperature = The temperature (C) at which an amorphous
polymer or an amorphous part of a crystalline polymer goes from a hard, brittle state to
a soft, rubbery state.
Tm = melting point = The temperature (C) at which a crystalline polymer melts.
Hm = the amount of energy in (joules/gram) a sample absorbs while melting.
Tc = crystallization point = is the temperature at which a polymer crystallizes upon
heating.
Hc = the amount of energy (joules/gram) a sample releases while crystallizing.
The data can be used to identify materials, differentiate homopolymers from
copolymers or to characterize materials for their thermal performance.
Differential Scanning Calorimeter(DSC)
Scope: DSC measures:
A sample of 10 to 20 mg in an aluminum
sample pan is placed into the differential
scanning calorimeter.
The sample is heated at a controlled
rate (usually 10/min)
a plot of heat flow versus temperature
is produced.
The resulting thermogram is then
analyzed.
Test Procedure:
Dsc3.wmv
DSC
1. Does the sample contain volatile components?
2 to 3% water/solvent can lower the glass transition temperature (T
g
) by up to
100
o
C
Evaporation creates endothermic peaks in standard (non-hermetic) DSC pans and
can be suppressed with use of hermetic DSC pans.
2. At what temperature does the sample decompose?
Set the upper limit of the DSC experiment based on decomposition temperature
(TGA). No meaningful DSC data can be obtained once decomposition results in a
5% weight loss
Decomposition affect: the quality of the baseline due to both endothermic and
exothermic heat flow, the quality of the baseline for future experiments and can affect
the useful lifetime of the DSC cell due to corrosion.
Some factors influence on DSC resultsc
3. How does thermal history (temperature and time) affect DSC results on the sample?
4. Identical materials can look totally different based on:
- Storage temperature and time.
- Cooling rate from a temperature above Tg or above the melting point.
- Heating rate.
- Different kinds of experiments may need to be performed in order to measure the
current structure vs. comparing samples to see if the materials are the same.
Some factors influence on DSC results
5. How is the Influence of the atmosphere (air or inert gases (N
2
, argon,..))
Use >10
o
C/min heating rates
Tg sensitivity
Thermogravimetry (TG)
To characterize the decomposition and the thermal stability of materials.
To provide an indication of the composition of the sample, including volatiles and
inert filler
The change of mass as function of temperature (scanning mode) or time
(isothermal mode)
To get information about the following processes:
v Decomposition
v Desorption
v Absorption
v Vaporization
v Oxidation
v Reduction
Block diagramof a thermobalance
Tma.wmv
Set the inert (usually N2) and oxidative (air, O2) gas flow rates to provide the
appropriate environments for the test.
Place the test material in the specimen holder and raise the furnace.
Set the initial weight reading to 100%, then initiate the heating program.
The gas environment is preselected for :
v either a thermal decomposition (inert - nitrogen gas), an oxidative decomposition
(air or oxygen)
v or a thermal-oxidative combination.
Test procedure:
v Sample amount: 10 to 15 milligrams
TG curve
The three steps in Figure are:
(1)The loss of H
2
O to form anhydrous oxalate
(2)The loss of CO to form the carbonate ,and (3)The loss of CO to form CaO
TG and DTG curves for the thermal decomposition of calcium
oxalate (CaC
2
O
4.
H
2
O in argon at 20
o
C/min(3).
100 200 300 400 500 600
-20
0
20
40
60
80
100
120
0
5
10
15
20
25
D
e
v
i
a
t
i
o
n
W
e
i
g
h
t

(
%
)


As received_J3
NaOH_J3
NaOH/(APS+XB)_J3
NaOH/Y9669_J3

Temperature(C)
TG and DTG curves of jute fibre with different treatments
Dynamic Mechanical Analysis (DMA)
Determines elastic modulus (or storage modulus, G'),
viscous modulus (or loss modulus, G'') and damping
coefficient (Tan D) as a function of temperature, frequency
or time.
Results are typically provided as a graphical plot of G',
G'', and Tan D versus temperature.
Identifies transition regions in plastics, such as the glass
transition, and may be used for quality control or product
development.
Can recognize small transition regions that are beyond
the resolution of DSC (Differential Scanning Calorimetry).
Scope:
-Typically 56 x 13 x 3 mm, cut from the center section of an ASTM Type I tensile bar,
or an ISO multipurpose test specimen.
Specimen size:
Dynamic Mechanical Analysis (DMA)
The test specimen is clamped between the movable and stationary fixtures, and
then enclosed in the thermal chamber.
Frequency, amplitude, and a temperature range appropriate for the material being
tested are input.
The Analyzer applies torsional oscillation to the test sample while slowly moving
through the specified temperature range.
Test Procedure:
Is DMA Thermal Analysis or Rheology
Definitions
Thermal Analysis is the measurement of some characteristic of a
substance as a function of temperature or time.
Rheology is the science of flow and deformation of matter.
DMA is the general name given to an instrument that mechanically deforms
a sample and measures the sample response. The deformation can be
applied sinusoidally, in a constant (or step) fashion, or under a fixed rate.
The response to the deformation can be monitored as a function of
temperature or time.
Deformation
Response
Phase angle
l An oscillatory (sinusoidal)
deformation (stress or strain)
is applied to a sample.
l The material response
(strain or stress) is measured.
l The phase angle , or phase
shift, between the deformation
and response is measured.
Dynamic Mechanical Testing
Stress
Strain
= 0
= 90
Purely Elastic Response
(Hookean Solid)
Purely Viscous
Response
(Newtonian Liquid)
Stress
Strain
Dynamic Mechanical Testing
Phase angle 0 < < 90
Strain
Stress
Dynamic Mechanical Testing:
Viscoelastic Material Response
DMA Viscoelastic Parameters
The Elastic (Storage) Modulus:
Measure of elasticity of material. The
ability of the material to store energy.
G' = (stress/strain)cos
G" = (stress/strain)sin
The Viscous (loss) Modulus:
The ability of the material to dissipate
energy. Energy lost as heat.
The Modulus: Measure of materials
overall resistance to deformation.
G = Stress/Strain
Tan = G"/G'
Tan Delta:
Measure of material damping - such
as vibration or sound damping.
Storage and Loss of a Viscoelastic Material
SUPER BALL
TENNIS
BALL
X
STORAGE
LOSS
DMA Viscoelastic Parameters: Damping, tan
Phase angle
G*
G'
G"
Dynamic measurement
represented as a vector
l The tangent of the phase angle is the ratio of the
loss modulus to the storage modulus.
tan = G"/G'
l "TAN DELTA" (tan ) is a measure of the
damping ability of the material.
DMA 2980 : Schematic
UNIQUE PATENT-PENDING DESIGN
SAMPLE
BIFILAR-WOUND FURNACE
CLAMPS
AIR BEARING
SLIDE
AIR
BEARING
OPTICAL
ENCODER
DRIVE MOTOR
LOW MASS, HIGH STIFFNESS
CLAMPING FIXTURES
DMA : Dual Cantilever Mode
Sample
Stationary
Clamp
Movable
clamp
DMA : Single Cantilever Mode
Sample
Stationary
Clamp
Movable
clamp
DMA : 3-Point Bend Mode
Moveable
Clamp
Force
Sample
Stationary Fulcrum
DMA : Tension Mode
Movable clamp
Sample
(film, fiber,or thin sheet)
Stationary
Clamp
DMA : Shear Sandwich Mode
Movable
Clamp
Stationary
Clamp
Sample
DMA : Compression Mode
Stationary clamp
Sample
Movable Clamp
PSA: Glass Transition Measurement
INTERFACES IN COMPOSITES
Questions that need to be answered:
Are interfacial properties important at all?
What is the role/effect of interfaces with respect to overall
mechanical properties of composites?
How can we measure interfacial adhesion in composites?
Can we develop analytical models that are useful for design
purposes?
Is it possible to tailor interfacial adhesion?
EXAMPLES OF PRACTICAL RELEVANCE
(VARIOUS FIELDS)
Thin coatings on critical surfaces (reflective coatings on optical
components, plating for corrosion protection, magnetic films for
data storage)
Interfaces in composites (carbon-epoxy, glass-PP, SiC-SiC, PE-
PE)
Interaction of biological systems or media with engineering
materials (tissue bonding of prostheses, dental implants,
artificial hips, cell adhesion [cells remain alive only if they
adhere to a substrate])
Wetting and adhesive strength
Adequate wetting is a necessary (but not sufficient!) condition for
good adhesion between a liquid and a solid surface.
The contact angle between a liquid droplet and a surface is an
indication of compatibility between these.
If q < 90, the liquid wets the solid surface.
If q = 0, the liquid spreads on the surface (complete wetting).
If q = 180, the liquid does not wet the surface
In terms of surface energies:

Surface energies ()

solid
vapor
liquid

SV

LV

SL
(S = Solid, V = Vapor, L = Liquid)
The equilibrium wetting or contact angle q is dictated by the
Young equation, obtained by a balance of horizontal forces:

SV
=
LV
cos +
SL
Thus, good wetting ( = 0 or small) arises when the surface energy
of the solid is equal to or greater than the sum of the liquid
surface energy and the solid-liquid interface surface energy.

SV
*
LV
+
SL
[Interface surface energies are difficult to measure (and may be
influenced by chemical reactions) but are often smaller than the values
for the phases in air]
The lower the contact angle, the greater the wettability:
Liquid is attracted to
itself, not to solid
Liquid is attracted to
solid, less to itself
Indirect measurement can be made by immersing the fiber into the liquid
of interest and measuring the force of immersion or emersion (= Wilhelmy
microbalance technique). A force balance permits the calculation of the
contact angle if the fiber perimeter and surface energy of the liquid are
known (see Bascom).
Sessile drop method
Capillary-rise method
Wilhelmy method

L i q u id
G l a ss co n t a i n e r
Fi b r e
M i c r o b a l a n c e
Kr s s
t e n s i o m e t e r
Co m p u t e r
D r i v e
s y s t e m
Fiber-matrix interfacial adhesion
Two general methodologies:
Indirect (or macromechanical) testing - focuses on the collective
behavior of fibers in a polymer matrix [interfacial strength is
interpreted via simplistic approximations; fast but questionable
data collection]
Direct (or micromechanical) testing probes interfacial behavior
of individual fibers interacting with a polymer matrix [more
fundamental information; variability within and between
techniques; issue of relevance to real-life composites (scaling-
up)]
Indirect (or macromechanical) testing
1. The transverse tensile test
2. The short-beam shear (or interlaminar shear
strength -ILSS) test
3. Asymetrical 4-point (Iosipescu) bend test
(And other macroscopic tests )
CONCLUSION They are simple to perform, but yield
ambiguous, inaccurate data.
Direct (or micromechanical) testing
a) b)
Fibre
Matrix
Indentor
Microscope
Objective
Composite
F
Fibre
Matrix
Sustrate
l
e
c)
Knife edge
F
l
e
d)
Micromichanical tests : (a)fragmentation, (b) microindentation, (c) pull-out
and (d) microbond test
Load cell
Mesurement
object
Single fiber pull-out test
Greszczuks model for pull-out
A small single fiber is embedded in a resin and the debonding load for the
pull-out of the fiber from the resin is measured and calculated for the
interfacial shear strength (IFSS, t) using the following equation:
where F is the debonding load, r
f
the fiber radius, and $ the embedded length.
This technique has been successfully studied in carbon and boron fibers in
an epoxy resin.
l
f
i
r
F

2
=
2. The single-fiber microcompression (or MIT) test
Tricky test, difficult to perform, fiber-matrix interfacial fracture is often
only partial due to slight off-axis moments, loading must be exactly
parallel to the fiber axis.
3. The single-fiber fragmentation test
Single fiber
embedded in matrix
Fragmented fiber
Pre-conditions for successful test: (a) failure strain of the fiber is much
smaller than that of matrix; (b) Interfacial bonding must be fair to good.
Glass fibre
D C B A
Interphase Epoxy
0
Penetration depth (nm)
I
n
d
e
n
t
a
t
i
o
n
f
o
r
c
e

(

N
)
23
2.6
A B C
D
dF
dh
Fmax
hmax hc
Loading
Unloading
Mapping Nanomechanical Properties by AFM
Nanoindentation
Stiffness
contrast
Cyclic Loading - AFM-Topography at Failure
APS
Pulloutaps.000 Pulloutaps.001
Virgin fiber After cyclic loading
R
a
= 3.5 nm, R
max
= 151 nm R
a
= 4.2 nm, R
max
= 48 nm
Examine surface irregularities or fracture areas in a part for plastics applications.
Measure the thickness (in cross section) of thin coatings.
Study surface topography and failure analysis
Test specimens are sputter coated with gold, then placed in a vacuum chamber for
viewing on the computer monitor at up to 10,000x magnification.
Polaroid photos are taken for a permanent record. Approximately 0.25" x 0.25"
Polaroid photos can be scanned into electronic documents.
Scanning Electron Microscopy (SEM)
Untreated jute
NaOH-treated jute
NaOH/PAPS-jute
PP/jute composite without treatment
PP/jute composite with treatment
Fourier Transform Infrared Spectrometry (FTIR)
-ASTM E1252
-Identify of polymer
-Detect organic layers or fiberglass
-Detect surface coatings
-Also examine contaminants and some fillers within the polymers
-A small amount (few grams) of sample is needed.
-Three basic spectrometer components:
+Radiation source
+Interferometer (giao thoa k),
+and detector
Simplified optical layout of a typical FTIR spectrometer
Fourier Transform Infrared Spectrometry (FTIR)
-The sample is inserted into a detector
and the amount of Infrared Light absorbed
at each frequency is determined.
The most commonly used interferometer is a Michelson interferometer.
Consists of 3 active components: a moving mirror, a fixed mirror, and a beamsplitter
The two mirrors are perpendicular to each other.
The beamsplitter is often made by depositing a thin film of germanium onto a flat KBr
substrate
Radiation from the broadband IR source impinges on the beamsplitter
At the beamsplitter, half the IR beam is transmitted to the fixed mirror and the
remaining half is reflected to the moving mirror
After the divided beams are reflected from the two mirrors, they are recombined at the
beamsplitter. Due to changes in the relative position of the moving mirror to the fixed
mirror, an interference pattern is generated.
The resulting beam then passes through the sample and is eventually focused on the
detector.
Fourier Transform Infrared Spectrometry (FTIR)
Wavenumber ( ):
=1 /
['gm%]
['reidiou]
ultraviolet
Infrared Region(IR)
electromagnetic spectrum

c h
h! E

= =
The energy of the wave (E):
: frequency
:wavelength
The infrared region (14,000 cm
-1
to 10 cm
-1
): near, mid and far-infrared region
Mid-infrared region (4,000 cm-1 to 400 cm-1):
the most interest region
corresponds to changes in vibrational energies within molecules
The far infrared region (400 cm
-1
to 10 cm
-1
):
useful for molecules containing heavy atoms such as inorganic compounds
requires rather specialised experimental techniques.
FTIR
Symmetrical
stretching
Asymmetrical
stretching
In-plane bending
Out- of -plane
bend
Molecular Vibrations
Major vibrational modes for a nonlinear group, CH
2
Stretching vibration
Bending vibration
Out-of-plane bending
(When a compound absorbs the energy of Infrared radiation)
FTIR
Single Bonds to Hydrogen
FTIR
Double Bonds
FTIR
Bending Vibrations
Single Bonds (not to Hydrogen)
Triple Bonds
['naitrail]
FTIR
-The aromatic ring, (C6H5):
+ the group of bands (C-H) above 3010
+a distinctive C=C stretch at about 1600cm-1
-The saturated main chain CH groups: the bands below 3010
C C
H
H H
n
T
r
a
n
s
m
i
s
s
i
o
n
FTIR of polystyrene
I
s
, I
R
: intensities in the sample and reference beams
-Sample preparation dependent on the physical form of the sample to be analysed.
1. Solids
-Nujol mull
-Potassium bromide disks
-Preparing a solution in a suitable solvent
*Nujol Mull
-The sample is ground to give a very fine powder
-A small amount is then mixed with nujol a paste
-Several drops of this paste are then applied between two sodium chloride plates
-The plates are then placed in the instrument sample holder ready for scanning.
Sample Preparation
FTIR
*Potassium Bromide disk
-A very small amount of the solid (approximately 1-2 mg) is added to pure
potassium bromide powder (KBr, 200 mg) and ground up as fine as possible.
-This is then placed in a small die and put under pressure mechanically (several
minutes)
-Removing the die and the KBr disk formed. The disk is then placed in a sample
holder ready for scanning.
Sample Preparation
FTIR
2. Liquids
-The simplest and most common method of sample preparation.
-A drop of the sample is placed between two potassium bromide or sodium chloride
circular plates to produce a thin film.
-The plates are then placed in a holder ready for analysis.
3. Thin Films
-Placing a sample in a suitable holder, such as a card with a slot cut for the
sample window.
Sample Preparation
FTIR