UNIT IV

THERMAL ANALYSIS OF POLYMERS

4.1. Differential Scanning Calorimeter (DSC) & Differential Thermal
Analyser (DTA)]
Introduction
Whenever a material undergoes a change in physical state, such as melting
(Or) Transition from one crystalline form another (or) whenever it reacts chemically, heat
is either absorbed (or) liberated.
DSC/DTA reflect change in energy of the system under investigation. Changes
maybe physical (or) chemical.
DTA (Differential Thermal Analysis)
DTA measure the difference in temp between the sample and reference materials
is measured as function of temperature.
It involves in observing the heat absorbed (or) emitted by chemical reaction by
measuring temp difference between that system and reference material.
The temp difference (T1- T2) is continuously recorded as function of either temp
of sample (Ts) (or) reference temp (Tr) or furnace (T)
Differential thermo gram shows peaks. Those appearing above zero are for
exothermic changes like oxidation, adsorption.
While appearing below zero are for endothermic change like fusion,
vapourisation, sublimation, absorption and desorption.
Crystalline transformation and chemical reaction may either exothermic or
endothermic. .
Apparatus

The sample is placed in one chamber and reference material such as Al 2O3 is
placed in other chamber.

The sample and reference materials heated by same heating element.

Thermocouples inserted in the center of material and measure the difference in

temperature between sample and reference.

The difference in temp is recorded on y-axis and furnace temp is recorded on xaxis.

DTA used in temp range from -1900 to 16000C.

Fig 4.1 Differential thermal analysis

DSC (Differential scanning Calorimetry)
When a thermal transition occur in the sample (or) reference material ,thermal
energy is added to either the sample (or) reference material in order to maintain both
sample and reference at same temp.
DSC measure heat required to maintain the same temperature in the sample versus
an reference materials in furnace. Enthalpy changes due to changes of sample are
determined.
A number of important physical changes in a polymer may be measured by DSC.
These includes Tg the crystallization temp (Tc), the melting temp (Tm) and degradation
(or) decomposition temp (Td)
Apparatus

DSC cell uses disk as primary means of transferring heat to sample and reference
position.

In DSC and DTA, sample and reference material are placed on cup (or) pan, made
up of Aluminum.

The sample and reference are placed in separate pans and heated by separate
heater.

Thermocouple indicate temp difference, Heat is added to cooler.

Sample size varies from 0.1 to 100mg.

It has max accuracy in temp 1700 to 7500C.

It involves heating the sample and reference substance by continuously increasing

Temp.

Heat is added to sample (or) reference so as to maintain the both sample and
reference at same temp.

The Added heat to sample (or) reference compensate for heat lost (or) gained
respectively as a consequence of endothermic (or) exothermic reaction occuring
in sample.

Heat energy supplied to sample (or) reference is continuously recorded as a

function of temp.

Usually heat supplied to sample is positive sign and supplied to reference is

negative sign.

Area under DSC peak [max (or) min] related to enthalpy change occurring.

Fig 4.2 Differential scanning calorimeter

Applications of DSC & DTA

1. The peak area of DSC thermogram given by

A = Km H
K is independent of temp at which reaction occur in DSC.

DSC finds wide spread use in calculating enthalpy of transition such as enthalpy
of melting, enthalpy of crystallization, Enthalpy of fusion etc, for polymeric
materials.

DSC curve also provide simple and accurate way of determining melting, Boiling
and decomposition points of organic compounds.

2. DTA provides information about

(i) Phase transformation (ii) structure inversion (iii) dehydration (iv) decomposition (or)
dissociation (v) oxidation (or) reduction. Fusion, adsorption, degradation,
The area (T Time) enclosed under DTA peak is given by,
T2

m. H

Peak area = Tdt =

T1

= km H
g. k

Where,
m= mass of sample
H= enthalpy of reaction
T= Differential Temp
dt = differential operation.
g = geometrical Factor
k = Thermal conductivity
H = + reaction is endothermic
- reaction is exothermic.
3. Phase transitions

One application of DTA is generation of phase diagram are study phase

transitions.

DTA Thermo gram for pure sulphur.

Fig 4.3 DTA curve for sulphur

Peaks at 1130C, 1240C, 1790C and 4460C corresponds respectively to the solid phase
change from Rhombic to monoclinic form, melting point of sulphur,a transition
among three forms of sulphur and boiling point of sulphur.
4. Melting and boiling points of Organic Compounds:
DTA provide accurate way of determining the melting and boiling points organic
compounds.
DTA Benzoic acid at atmosphere is given by

Fig 4.4 DTA for benzoic acid

The first peak corresponds to the melting point. While second peak corresponds to the
boiling point.
5. Characterisation of Polymer
DTA has been widely used to study and characterization of polymers.
It shows various Types of transitions that may be encountered during heating of
polymer.

Fig 4 .5: Characterization of polymer during heating

6. Polymer Mixture
DTA can be used for qualitative analysis of polymer mixture.
Each peak gives characteristic melting point of one of the polymers.

Fig 4.6: Melting point of mixture of polymer

7. Decomposition of calcium oxalate

Differential Thermogram of calcium oxalate monohydrate [CaC2O4] in flowing air

obtained by increasing Temp.

It contains two minima [Endothermic] ie) decomposition Reaction.

One maxima [indicates exothermic] ie) oxidation reaction.

The single maxima indicates the oxidation of CaC2O4 to CaCO3 and CO2 is
exothermic.

Fig 4.7 Decomposition of calcium oxalate

DTA and DSC provides informations about following

(1) Phase transformations (2) Structure inversion (3) dehydration (4) Decomposition (5)
Oxidation or reduction (6) formation of crystalline lattice structure (7) multiple transition
in crystalline structure.
S.no
1

2
3
4
5

DTA
The temperature of the sample is
compared with that of a reference
materials as both are heated at a
same heater
Measure
the
difference
in
temperature between sample and
reference
DTA provide plots (Tf-Ts) Vs
temperature of the furnace(T0)

DSC
The temperature of the sample is
compared with that of a reference
materials as both are heated at a separate
heater
Heat energy is supplied to sample or
reference materials, so as to keep both as
same temperature
DSC output plots heat energy supplied to
the sample (or reference) Vs identical
temperature of two.
It provides calorimetric accuracy in It provides calorimetric accuracy in the
the temperature range of -190 to temperature range of -170 to 750
1600
No secondary power source is Secondary heat source is required to
required
maintain the sample and reference
material as same temperature.

4.2. Thermogravimetric Analysis (TGA)

Principle:
Thermo gravimetric analyzer is a technique in which change in the weight of
substance is measured as function of time and temp.
The change in sample weight is recorded.
TGA curve may be either
o the weight loss of sample
o in differential form
TGA has

two

primary

application

includes

quantitative

identification

compositional analysis.
It involves in recording continuously, the mass of the sample as its
temperature is increased linearly from ambient to as high 1,2000C.
The change is mass of a sample, on heating, may occur due to the
following physical and chemical changes:
(i) Vaporization of moisture/volatile components present in free state in the substance.

(ii) Dehydration of the substance, due to partial or complete loss of water crystallization
(iii) Decomposition of the substance with the evolution of a gas or vapour.
(iv) Dissociation of the substance to form volatile products.
(v) Combination with the environment gases to form new products.
(vi) Oxidation of the substance by environment oxygen or other gases component
present in the environment.
(vii) Reduction of the substance with simultaneous evolution of a gaseous product, etc.
Instrumentation:
The basic instrumental requirement for thermogravimetry is a precision balance
with a furnace programmed for a linear rise of temperature with time.
Fig. 1 is a block diagram showing the main components of thermobalance.
The major components of a thermobalance are the balance and furnace assembly.
Samples are placed in a shallow platinum crucible (sample container) that is connected to
an automatic recording microbalance.
The most usual type of balance system employed in thermogravimetry is the null
point balance. In the null-point system, when there is a change in weight, the balance
beam will deviate its usual position.
A sensor detects this deviation and initiates a force that will restore the balance to
the null position. This restoring force is proportional to the change in weight.
The sample container is placed in a quartz and Pyrex glass housing located within
the furnace. A thermocouple, located immediately below the sample container, is used to
monitor the furnace temperature. The resulting signal is connected directly to the x-axis
of the recorder.

Fig 4.8 TGA APPARATUS

A modern thermobalance is fully computer-controlled, allowing a wide variety of

heating, cooling and iso-thermal modes. A new computer controlled enables the user to
change sample atmosphere conditions automatically. Another important feature is that the
cooling time between experiments is a matter of a few minutes in going form 1,000 c to
ambient temperature.
Characteristics of good thermobalance design
(a) The thermobalance should be capable of continuously registering the weight change
of the sample studied as a function of temperature or time.
(b) The furnace should reach the maximum desired temperature (with some modern
thermobalances, a temperature range of -150 to 2400 C can be obtained).
(c) The rate of heating is linear and reproducible.
(d) The sample holder should be in the hot zone of the furnace and this zone should be of
uniform temperature
(e) The temperature of the sample must be measured as accurately as possible.
(f) Use balance sensitivity suitable for studying small sample weight.
Applications:
(i) In qualitative Analysis:
A TGA curve indicates the horizontal portions (which represents no
weight change and slinting downwards curves (which represent weight loss, due to
dehydration/rupture/formation of volatile products)
The thermogram for decomposition of pure calcium oxalate
(CaC2O4.H2O) obtained by increasing the temperature at a rate of 50C/min. It is
thermally stable up to 1000C and water is evolved slightly above 100 0C. At about
2260C, a break is obtained in the downward curve at the stoichiometry corresponding
to anhydrous salt (CaC2O4). The horizontal portion between 226 346 0C indicates
that anhydrous salt is thermally stable in this range. At slightly above 346 0C it again
starts losing CO is yield CaCO3. This process is complete at about 4200C. Beyond
4200C, CaCO3 is stale up to about 6600C. Beyond 6600C, there is evolution of CO2 to

give CaO. At 8400C, this decomposition is complete. At 8400C and above, the
horizontal portion represents the stable CaO.

Fig 4.9 Thermogram of pure calcium oxalate (CaC2O4.H2O)

Quantitative analysis
The Graph given below explains the application of TGA to the analysis
of a mixture of Ca2+, Sr2+ and Ba2+ions. These are first precipitated as monohydrated
oxalates (MC2O4. H2O) and then subjected to heating at a rate of 50C/min.
The mass loss between 320 0C and 4000C corresponds to the combined
loss of water by three anhydrous salts forming MC2O4.
Mass between 580 0C and 6200C corresponds to the combined mass of
the three carbonates (MCO3)
The mass loss in the next two steps represents loss of CO 2 by CaCO3 (to
form CaO) and SrCO3 (to form SrO) respectively
From this data, we can easily calculate the mass of the each element
present in the sample.

Fig 4.10 Thermogram of CaC2O4.H2O, SrC2O4 H2O

Study of polymers
The most important application of TGA is found in the study of polymers.
TGA thermogram provides valuable information about their decomposition
mechanism. However each kind of polymer follow the particular characteristic
pattern and hence TGA thermogram can be used for identification purposes.

Fig 4.11 Thermogram of Study of polymers

Fillers
Thermal expansion can be seen in the determination of mineral filler in PP.
Sample is heated in air atm to decompose completely the poly propylene and the
remainder, is mineral filler.
Amount of volatiles, polymer, and filter is obtained by analysis of weight loss
curve.

 The small weight loss (35%) occurring over the temperature range of 7500 - 8000C
Polymer carbon black fillers:
Heating the rubber sample an inert atmosphere of nitrogen from room
temperature at 9500C and then quickly changing atm to air.
The heating causes carbon black to undergo combustion to produce the loss of
weight.

Complex mixtures
Polyhydrazoid-poly (1, 3, 4 oxadiaxole)

Thermogravimeter study of polyhydrazide poly (1,3,4 oxadiazole) derived from

1,3 phenylene hydrazide.

One hydrazide shows weight loss upto 1000C due to the loss of absorbed H2O.

The second weight loss step starting at temperature of 2750 involves thermal
cyclodegradation of polyhydrazide to poly (1,3,4 oxidiazole)

Final step is attributed to decomposition of poly (1,3,4 oxidiazole).

Polymer blends
A polymer blend usually give a thermogram consist of two separate weight
loss region corresponding to the components.
A mixture of polychlorotrifluoro ethylene and poly tetra fluoroethylene
showed resolved steps corresponding to decomposition of individual polymers.

CoPolymer and Polymer Blends

The TG curves of homopolymer of styrene and methyl styrene, the random
copolymer and block copolymer are presented below.

The random copolymer undergoes a smooth weight loss and curve lies between
two homopolymer.

But the block copolymer shown as individual initial weight loss and curve lies
between two homopolymer

General thermal stability:

From detail TG data some of the following correlations have been obtain.
a) Isotactic polypropylene oxide is more stable than atactic polypropylene oxide.
c) The rate of depolymerisation of highly syndiotactio poly x-methyl styrene substantially
slower than that of atactic polymer.
d) Fully aromatic polyamides the order stability was found to be.
Para Para >Para meta > meta meta > Ortho Ortho

Factors affect TGA Results:

Deviation caused by instrumental factors include furnace, a size and shape
of furnace and sample holder material and resistance to corrosive attack. Sample
characteristic, particle size, packing density, amount of sample thermal conductivity of
sample, heat capacity.

4.3. Thermal Mechanical Analyzer

It measure physical expansion (or) contraction of a material (or) change in its
modulus (or) its viscosity as function of temp.
It measures the penetration, expansion, contraction and extension of sample as
function of temp.
Construction
TMA Analyzer has following Parts
(i) Transducer
(ii) LVDT
(iii) Furnace
(iv) Quartz Tube.
Transducer:
A device that converts one form of energy into another.
Primary Transducer:
It is a device that converts changes in the Physico-chemical properties of a
material into a displacement.
Secondary Transducer:
In this device, the mechanical displacement is used to move the core of LVDT. Hence
a electrical signal is produced.
Linear Variable Differential Transformer (LVDT)
It consists of a primary winding P 1 and two secondary windings S1 and S2 wound on a
cylindrical former. The secondary Windings have equal number of turns and are
identically placed on either side of the primary windings. The primary winding is
connected to an alternating current source. A movable soft iron core is placed inside
the former.

The probe is made from quartz, because it has a low thermal expansion
coefficient.
The sample holder is also made from quartz.
The probe is loaded with finite weight.
Principle
Any movement of the sample is translated into movement of transformer core and
result in output that is proportional to displacement of the probe.

Fig 4.12. Thermal Mechanical Analyser

Operation:

The probe is connected mechanically to the core of LVDT.

The core is coupled to sample by means of quartz probe. Which contain a

thermocouple for measuring the sample temp.

The sample is placed in the furnace surrounded by heat sink and coolant.

The another end of LVDT attach to float suspension and weight tray.

Any movement of the sample is translated into movement of transformer core and
result in output that is proportional to displacement of the probe.
Penetration and Expansion
The probe is placed onto the sample and it is surrounded by furnace.
The expansion with respect to temperature is observed under no load condition.
The TMA probe is slightly pushed up by the expansion of the polymer solid.
Expansion of sample is directly calculated by using LVDT.
As the melting point is reached, the lightly loaded probe penetrates the sample.
In penetration a weight tray attached to upper end of probe allow a
predetermined force applied to sample to study variation under load.
Probe with small tip diameter and loaded weight tray are used.
When the sensitive detection of softenng temp, HDT and Tg are of interest.
Tg value can be read directly from plot where expansion coefficient undergoes a
sudden changes.

Extension

For measurement of sample extension, the sample stage and probe are replaced by
a sample holder system containing stationary and moveable hooks constructed of fused
silica. This permit extension measurement on films and fibers.
Uses
Determination of Tg
Determination of coefficient of expansion
VST and HDT correlate
4.4. Gas Chromatography
Introduction:
Gas chromatography is a technique for the separation of thermally stable and
volatile organic and inorganic compounds.
Gas chromatography is a technique by which a mixture is separated into its
constituents by a moving gas phase passing over a stationary adsorbent. The stationary
phase maybe either liquid (or) solid. In this chromatography if adsorption process is
taking place, the technique is known as gas solid chromatography [GSC], while it is
called gas-liquid chromatography [GLC], when partition process is taking place.
Principle

In GSC the column is packed with active solid stationary phase and components
of mixture are distributed between the gas phase and active solid phase. Due to
difference in adsorption behavior of components of mixture, the separation is
achieved.

In GLC the column is packed with porous solid, which is coated with a thin layer
of a non volatile liquid. Separation takes place due to difference in partitioning of
sample between the mobile gas phase and thin layer of liquid coated on inert
support.

Instrumentation
A gas chromatography consists following
(i) A supply of carrier gas [He, Ar or N 2) from a high pressure cylinder having a pressure
regulator and flow meters.
(ii) Sample injection system.

(iii) Packing materials in packed column

(a) In GSC activated carbon, silica gel and alumina
(b) In GLV porous materials like glass beads, ground fire bricks, finely divided
celite or polymers like tenax GC, poropak, chromosorb etc. In GLC the column
containing porous materials is filled with non volatile liquid such as silicone oil,
polyethylene glycol, grease etc.
(iv) The detector is situated at the exit of the separation column which sense and
measures the separate amount of the separated component present in the carrier gas
leaving the column. Commonly used detectors are thermal conductivity detector,
Wheatstone bridge circuit, and flame ionization detector.

Fig 4.13 Gas chromatograph

Procedure
Sample mixture is introduced quickly into moving carrier gas [such as N 2, He, H2,
Ar]
The mixture is then swept along through the thermostated GLC (or) GSC column.
During the passage of mixture through column, the components of the mixture
distribute themselves between two phases.
Some components are absorbed (or) adsorbed by stationary phase better than
others and hence they are retained for longer time in column.

 Each component of the mixture is carried along the column at different rate and
finally emerge from the column at different time.
In other words, the time for passage through column is characteristic for each
component.
As component leaves the column, it is detected by instrumental means.
A strip chart recorder, attach to detector show a peak for each component which is
separated.
The size of peak indicates the amount of particular component in the mixture and
its location on the chart indicates its nature.
The apparatus employed is called gas chromatograph and series peak obtain
called chromatogram.
Merits:
(i) It aims at producing only one peak per component, maximum height per peak,
minimum peak width and max retention time.
(ii) A very small amount of sample is sufficient for analysis, since the sensitivity of this
method is high.
(iii) It given good precision and accuracy.
(iv)

It provides quick and easy way of determining the different components in a

mixture, together with presence of impurities in substance (or) in the identification of

compound hence it is more suitable for routine analysis.
Demerits
(i) Suitable only for compound having sufficient volatility and thermal stability.
(ii) The separation of number of components of similar type, but widely varying
volatility, a difficulty arise, if the experiment carried out constant temp.
Application
1. It is used in the gasoline plants
2. Refinery gases
2. Synthetic rubber and plastic intermediate
3. It is used in medical field for the alcohol content in human blood can be calculated
4. Complex separation is done by this method.
5. The multicomponent analysis can be carried out in a relatively short time.

Fig 4.14: A gas chromatogram of a mixture containing six components

4.5 Mass spectroscopy

Mass spectroscopy is a technique that allows us to measure the molecular
weight of a compound.
In addition we obtain structural information about unknown by measuring the
masses of fragments produced when high energy molecules fly apart.

Fig 4.15: Mass spectrometer

Principle
(i) A small amount of sample is introduced into mass spectrometer and bombarded
with stream of high energy electrons.
(ii) The energy of the beam of electrons is usually to 70 eV [electron volts] (or)
1600 kcal /mole.
(iii) When a high energy electron strikes an organic molecule it disloges one of
the electrons of the molecule, producing a positively changed ion called molecular
ion.
eM
Molecule

M+ + eMolecular ion.

(iv) In addition to causing ionization, electron bombardment transfer such

large amount of energy to sample molecule that molecular ions fragment; they
literally fly apart into numerous smaller pieces some of which retain a positive
charge, and some of which are neutral.
(v) The fragments then pass through a strong magnetic field, where they
are deflected according to their mass to charge ratio (m /e).Neutral fragments are
not deflected by the magnetic field and are lost on the walls of the instrument.
(vi) Positive charged fragments however are sorted by the spectrometer
onto the detector, which records them as peaks as proper ratio. Since the number of
charge, e, is usually 1, the peaks represents the masses of the ions.
(vii) The mass spectrum of a compound is usually presented as a bar graph
with m/e values on the x axis, and intensity on the y axis. The highest peak is called
base peak and is arbitrarily assigned an intensity of 100%.
Mass spectrum of Methane
The mass spectrum of methane is quite simple. Few fragmentations are possible.
The base peak has m/e =16, which correspond to unfragmented methane, molecular
ion [m+]. The mass spectrum also shows ion at m/e=15, and 14. Corresponding to
cleavage of molecular ion into CH3*, CH2 * fragments.

[CH3] + + H.*
H
-eCH4

m/e=15

..
H: C: H
..

H
m/e=16

[CH2] ++ 2H.
m/e=14

Fig 4.16: The mass spectrum of methane

Mass spectrum of Propane
For larger molecules, the fragmentation pattern is usually complex and molecular ion is
often not the highest peak. For mass spectrum of propane has a molecular ion [m/e=44]
only about 30% as high as the base peak at m/e=29. Therefore propane has a base peak at
m/e =29
CH3CH2+ (m/e =29)
CH3CH2CH3
(m/e=44)
.CH3 (Neutral)

Fig 4.17: Mass spectrum of Propane

Mass spectra of 2,2 dimethylpropane
The most information that can be obtained by studying the mass spectrum of a
compound is molecular weight. Certain compound, 2.2, dimethyl propane fragments so
readily that no molecular ion is observed.

Fig 4.18. Mass spectra of 2,2 dimethylpropane

Mass spectrum of Hexane

Let as consider the mass spectrum of hexane .It shows molecular ion m/e
=86 and substantial fragment ion at m/e =71, 57, 43 and 29.

Fig. 4.19 Mass spectra of 2,2 dimethylpropane

Fig. 4.20 Fragmentation of hexane

Determination of molecular structure
The mass spectrum of an measurement of unknown molecular weight. For
example, if the mass spectrum of unknown compound shows a molecular ion at m/e
=110.The molecular formula is likely to be C8H4, C7H10O, C6H6O2, C6H10N2.

Fragmentation patterns
Fragmentation pattern allows us to derive the structural information about the
sample. Fragmentation occurs when high energy cation radical files apart by spontaneous
cleavage of a chemical bond.
One of the two fragments retains the positive charge and other fragment is a
neutral free radical.
For example propane tends to fragment in such a way that the positive charge
remains with ethyl group rather than with methyl .Therefore propane has a base peak at
m/e =29 and barely detectable peak m/e =15.
CH3CH2+ (m/e =29)
CH3CH2CH3
(m/e=44)
.CH3

4.6. X-ray Diffraction:

The X ray diffraction method is a powerful tool to investigate orderly
arrangement of atom or molecules through the interaction of electromagnetic radiation to
give interference effects with structure comparable size to the wave length of the
radiation.
X-ray diffraction is used to the polymer material is amorphous or crystalline one
is determined by this method.
Principle:
The X-ray source is passed into the sample, the screen shows the broad fringes is
called amorphous polymer, screen shows the well-defined fringes ie, finger prints is
called crystalline region.
Apparatus:
1. X-ray source
2. collimeter
3. Screen

4. Polymer sample
Procedure:
X ray are usually produced by bombaring a metal target (usually tungsten,
molybdenum, vanadium) with a beam of high voltage electrons.
The monochromatic light falls on the grating, the light waves emerging from the
grating interface with one another, to either amplify or elimate the light in a particular
direction and finally give alternately dark and bright bands on the screen.

Fig. 4.21 X ray diffraction

Fig. 4.22 X ray diffraction patterns (a) crystalline (b) amorphous

When X rays focused on a polymer sample, two types of scattering occur. If a
sample is crystalline, the X ray are scattered coherently (No change in wavelength
between the incident light and scattered rays). Coherent scattering is determined by wide
angle X ray diffraction (WAXS).

If the sample is amorphous, the X ray are scattered coherently (Change in

wavelength between the incident light and scattered rays). InCoherent scattering is
determined by small angle X ray diffraction (SAXS).
The amorphous polymer shows very broad and diffuse X ray diffraction patterns.
For crystalline polymer shows sharp and well diffused patterns.
Types of X ray Diffraction
1. Small angle X ray diffraction
2. Wide angle X ray diffraction
Wide angle X ray diffraction
Wide angle X ray scattering refers to studies of scattering at relatively large angle.
According to Braggs law d = n / 2 sin : if the increases, the distance between plane
(d) decreases. This yields distance smaller than 1 nm.
WAXS used for investigation of small scale structure ( < 10 A) such as crystal
unit cell structure ,cell identification and the measurement of cell dimension ,lamella
thickness.
WAXS is used for the determination of fractional cryatallinity or degree of
crystallinity .A typical WAXS diffraction pattern of a semicrystalline polymer consists of
sharp bragg reflection due to crystalline regions and diffused scattering pattern indicating
the amorphous region.
Few wide angle instruments are shown below

Small Angle X ray Scattering

SAXS is concered with scattering phenomenon occurring at small angle (0.022 to
2.2). The distance between planes d, is 10-1000 times greater than that of waxs.
(According to Braggs law if is small, the distance between scattered planes d, is very
large. Therefore SAXS is used to study large scale morphological features. (10 -104 A)
The need to measure the scattered beam intensity at very small angles require
collimators of sharply focusing the incident beam and more specialized detectors than
required for WAXS. There are several collimation methods are used.
1. Pinhole Collimation
2. Slit collimation
SAXS is used for assessment of supermolecular structure in both semi crystalline
and crystalline polymers. SAXS is used for determining size of the spherulites.