Polymers and its characterization

POLYMERS AND ITS
Presented by-
Siddharth Raju Adsul
M.Pharm Sem-I
PRN:57400144B
Guided by-
Prof. Satish Polshettiwar
MAEER’S,
MAHARASHTRA INSTITUTE OF
PHARMACY
PUNE - 411038
2016-2017

CONTENT
• INTRODUCTION
• CLASSIFICATION OF POLYMERS
• CHARACTERIZATIONTECHNIQUES OF POLYMERS
• CASE STUDY
• REFERENCES
5/9/2017 2CHARACTERIZATION OF POLYMERS-by Siddharth.R.Adsul

INTRODUCTION
• Polymers are derived from Greek words, POLY- many & mers- parts of units of high
molecular mass, each molecule of which consists of a very large no of single structural units
joined together in a regular manner.
• In other words, Polymers are giant molecules of high molecular weight called
macromolecules, which are build up by linking together of a large no of small molecules,
called Monomers.
• Monomers:- The small molecule or repeating units or the building block in the structure of
polymer is called monomer.
• The reaction by which the monomers combine to form polymer is known as
Polymerization.
• Polymerization is a chemical reaction in which 2 or more substances combine together with
or without evolution of anything like water, heat or any other solvents to form a molecule
of High molecular weight.
• The product is called Polymer and the starting material is called as monomer.
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CHARACTERIZATION OF POLYMERS-by Siddharth.R.Adsul

Examples of Polymerisation reaction:-
The transformation of ethene to polythene and interaction of hexamethylene diamine and
adipic acid leading to the formation of Nylon 6, 6 are examples of two different types of
polymerisation reactions.
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Degree of Polymerisation (DP) :- Number of monomers or repeating unit (n) in the polymer
chain is called DP.
DP is used to calculate the average molecular weight of Polymer.
Average molecular weight of Polymers= DP *Weight of repeating units
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Classification of Polymers
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8. Based on interaction with water:-
a) Non – biodegradable Hydrophobic Polymers :
These are inert compounds and are eliminated intact from the site of
application.
e.g. polyethylene – vinyl acetate, polyvinyl chloride.
b) Hydrogels :
They swell but do not dissolve when brought in contact with water.
e.g. polyvinyl pyrrolidone
c) Soluble Polymers :
These are moderate mol. wt uncross-linked polymers that dissolve in water.
e.g. HPMC, PEG
d) Biodegradable Polymers :
These slowly disappear from the site of administration in response to a
chemical reaction such as hydrolysis.
e.g. Polyacrylic acid. Polyglycolic acid.

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9. Based on Bio- stability:-
a. Bio-degradable polymers- The polymers which gets decomposed under aerobic or
anerobic conditions, as a result of the action of micro-organisms/ enzymes.
Eg:- Nylon-2, Nylon-6
b. Non-biodegradable polymers- The polymers which contains long chain of carbon and
Hydrogen atoms. The interatomic bonding of these molecules is adamant, which makes it
tough for microbes to break the bonds and digest them.
Eg:- polyethylene,Teflone.

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List of characterization techniques of polymers:-
• X-ray diffraction
• Infrared spectroscopy
• Thermal analysis
• Surface tension/ contact angle surface tension(Surface energy)
• X-ray photoelectron spectroscopy, XPS
• Scanning force microscopy SFM
• Ellipsometry ELLI
• Infrared attenuated total reflection ATR-FTIR
• X-ray reflectometry, Grazing incidence x-ray small angle scattering GISAXS
• Scanning electron microscopy
• Focused ion beam FIB
• Electrokinetic measurements/ Zeta potential
• Inverse Gas chromatography IGC
• Mechanical properties

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1.Tensile strength
 It is used to determine elastic modulus, ultimate stress, and
ultimate strain.
Apparatus- It is a dog bone shaped. Sample is placed in the grips
of movable & stationary fixtures in a screw driven device. Which
pulls the sample until it breaks and measures applied loadVs
elongation of the sample.
Elongation is typically measured by the extensometer in volts and
must be converted to millimeters.
Tensile strength testing is a destructive characterization
technique.

2.X-ray Diffraction
1.It is used to determine the atomic arrangements( i.e. crystal structure) of the material.
2. X-rays (wavelength ≈ 1Å) diffract through a thin polymer sample with long-range order in
the arrangement of atoms.
3.The diffracted x-rays yield an interference pattern on a screen or photographic film.
4. Deconvoluting the interference pattern yields spacing between atoms.
(Deconvolution almost always requires sophisticated numerical analysis.)
5. A sample without long-range order (crystallinity) will not show an interference pattern.
6. X-rays diffract poorly off hydrogen; thus, x-ray crystallography does not yield information
about the placement of hydrogens (placement must be inferred.
7. Resolution is > 0.1 Å.

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Identification of semicrystalline polymers and recognition of crystalline phases
(polymorphism) of polymers.
Fig-A series of wide-angle X-ray
diffraction photographs from crystals
located along the vertical line within
a spherulite of poly(hydroxyl butarate)
shown in the left inset.The enlarged
diffractograms are from three areas
separated by 60micron meter as shown
In the optical micrograph (courtesy
of C. Riekel, ESRF).

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3.Infrared spectroscopy
The chemical composition & the bonding arrangements of constituents in a homopolymer,
copolymer, polymer composite & polymeric materials in general can be obtained using IR
spectroscopy.
The IR spectroscopy permits the determination of components or groups of atoms that
absorb in the infrared at specific frequencies permitting identification of the molecular
structure.
These techniques are not limited to chemical analysis. In addition the tacticity, crystallinity &
molecular strain can also be measured.

4.Ubbelohde & Cannon-FenskeViscometer:-
It is used to determine the viscosity of a liquid polymer.
It is a relative method and requires calibration with samples of polymer of known molecular
weight.
Principle of viscometry is based on Poiseuille's law.
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5.Differential Scanning Colorimetry:-
It is used to-
• Identifying unknown polymer.
• Monitoring effects of aging.
• Determining phase seperation( polymer blend, copolymer)
• Estimating % crystallinity
• Measuring Heat capacity
• DeterminingThermal stability(oxidation induction time)
• Determining effects of additives(blends, fillers, plasticizers)
• Comparing quality(failure analysis, new material evaluation)
• Determining best processing temperatures(cure, injection molding, extrusion, heat
welding)
• Heat of Fusion
• Glass transition temperature
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Principle used in DSC-
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Differential scanning calorimetry or DSC is a thermo-analytical technique in which the
difference in the amount of heat required to increase the temperature of a sample and
reference is measured as a function of temperature. Both the sample and reference are
maintained at nearly the same temperature throughout the experiment.
The sample and a reference substance, which does not undergo a thermal transition in the
temperature range of interest, are placed in 2 small metal containers and heated by
individual electric heaters.
The temperature of both samples, are
monitored by thermocouples, is then
gradually raised in such a manner that the
temperature of sample and reference
remain the same.
In this way, transition temperatures can
be very accurately measured by monitoring
the electric current going to the heaters.
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6.Atomic force microscopy(AFM):-
The Atomic force microscopy or AFM provides
information on structure through nanoscale
imaging of topography which is usually acquired
in tapping mode.
The information obtained fromAFM includes
morphology, dispersion, domain size,
internal structure.
Fig-Schematic describing the
operation of atomic force microscope5/9/2017
25CHARACTERIZATION OF POLYMERS-by Siddharth.R.Adsul

7.X-ray Photoelectron spectroscopy:-
It is also known as Electron spectroscopy for chemical analysis(ESCA)
Advantages-
• Surface sensitivity ( 1-10nm sampling depth)
• Elemental and chemical state identification.
• Quantitative without the use of standards.
• Ability to examine highly insulating samples.
uses soft X-rays to detach electrons from surfaces
Binding Energy of Electron = hν - Emitted electron
energy
valence electrons⇒ chemical information
core electron⇒ localized elemental analysis
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8.Time of flight-Secondary ion mass spectrometry(TOF-SIMS):-
The main attributes are-
• Surface sensitivity(<0.5nm sampling depth)
• Elemental and molecular identification
• Ability to chemically map elements/ molecules on a surface with <1 micrometer image
resolution.
• Ability to examine highly insulating samples.
Principle-
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9.Nuclear Magnetic Resonance(NMR):-
It is used for-
 Identifications of the polymers/functional groups
 Monitor progress of polymerization process
 Composition
 Chain molecular structure:type of copolymer
 Tacticity
 End groups
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CASE STUDY-1
CONDUCTIVITY AND DSC STUDIES OF POLY(ETHYLENE GLYCOL) AND ITS
SALT COMPLEXES
Reference- Indian journal of Engineering and Material sciences
Vol-7, October-December 2000, p.p. 456-458
Objective-To determine conductivity and melting range of poly(ethylene glycol) and its
salt complexes.
Methods- Electrical conductivity is obtained by the standard DC conductivity technique by
measuring resistance with the help of Keithley solid state electrometer(model 610)
&
Melting point of PEG is carried out by DSC in temperature range of 303-343k usingT.A.
instrument, model- DSC 2010.
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Results-The doping of PEG with KCL and KBR increases the conductivity about 2.5 times for
KCL and 6.25 times for KBR & doping with KI reduces the conductivity to about 0.05 times
its pure component value.
&
Analysis of DSC results confirm that the reaction is endothermic & its melting peak shifts
towards the higher value for different salt complexes as compared to PEG.
Conclusion-The tempearture response of conductivity may be employed to study the effect
of doping on PEG, thereby giving the information on the ionic transport of salt complexes in
general and on the structure of these complexes in particular.
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CASE STUDY-2
Structural Analysis of Ciprofloxacin-Carbopol Polymeric Composites by X-Ray Diffraction
and FourierTransform Infra-Red Spectroscopy.
Reference-Tropical Journal of Pharmaceutical Research June 2011; 10 (3): 273-280
Objective-To evaluate physicochemical changes in ciprofloxacin following incorporation in
Carbopol polymeric composites.
Methods-The ciprofloxacin and Carbopol were mixed in water in a drug:polymer ratio of 1:5
(w/w) and homogenized to produce uniform composites. X-ray powder diffraction analysis
of the pure ciprofloxacin and the Carbopol polymeric composites of the drug were obtained
using a powder diffractometer. Spectra for the materials were also generated by Fourier
transform infrared (FTIR) spectroscope interfaced with an infrared (IR) microscope operated
in reflectance mode.
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Results-Based on the Hanawalt system, three prominent x-ray diffractogram (XRD) peaks
of the pure ciprofloxacin and the drug in the polymeric composites exhibited d-spacing at
similar 2θ values, but the relative intensity of these peaks was higher in the polymeric
composites. FTIR analysis indicates that there were intermolecular hydrogen bonding and
esterification between the drug and polymer in the polymeric composites.
Conclusion-The changes that occurred in ciprofloxacin indicate increase in stability,
decrease in solubility and delayed release of the drug from polymeric composites which
could facilitate the formulation of a sustained release form of the drug.
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BIBLIOGRAPHY:-
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• Sergei N Magonov & Darrell H Reneker, Characterization of polymer surfaces with
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