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POLYMER PROPERTIES AND

CHARACTERISATION

PRESENTED BY
ARCHANA S NAIR
MPHARM PART I
PHARMACEUTICS
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CONTENTS
• Introduction
• Properties
• Molecular weight determination
• Vibrational spectroscopy
• Nuclear magnetic resonance spectroscopy
• Microscopy
• Thermal analysis
• X-ray diffraction methods
• Mechanical and rheological analyses
• Conclusion
• References
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INTRODUCTION
• “Polymer” means “many parts.”
• Use of polymer in drug delivery is guided by various properties like;

 molecular properties

 bulk properties

• Polymer characterization is the process of determining the size,

structure and physical properties (such as thermal and mechanical
properties) of polymeric materials.
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CRYSTALLINE AND AMORPHOUS

POLYMERS
• If the structure is linear, polymer chains can pack together in
regular arrays.

• For e.g.; polypropylene chains

• With increased temperature, the crystal cells (crystallites) start to

melt and the whole polymer mass suddenly melts at a certain
temperature.

• Amorphous structure is formed due to either rapid cooling of a

polymer melt in which crystallization is prevented.
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CRYSTALLINE AND AMORPHOUS

POLYMERS
• Crystalline
▫ Ordered

• Amorphous
▫ Random

• Semi-crystalline
▫ Consists of both
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CRYSTALLINE AND AMORPHOUS

POLYMERS
• Polymer strength and stiffness increases with crystallinity.
• With increase in crystallinity, the optical properties of a polymer are
changed.
• Crystallinity increases the barrier properties of a polymer
packaging.
• Crystallinity topology and isomerism, molecular weight,
intermolecular forces, rate of cooling etc.
• Anisotropy.
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THERMAL TRANSITIONS
• Volume of a polymer can change with temperature as first or second
order transition.
• Tm – first order thermal transition.
• Tg – second order thermal transition.
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GLASS TRANSITION TEMPERATURE

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GLASS TRANSITION TEMPERATURE

• Rigid glass state – soft rubber state.

• 100◦C to above 300◦C.
• Important in solid dosage form.
• Tg of a polymer depend on many factors,
 length of polymer chain, side chain group.
 polymer chain flexibility.
 polymer chain branching, polymer chain cross linking.
 processing rate, plasticizers.
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GLASS TRANSITION TEMPERATURE

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GLASS TRANSITION Vs MELTING

Glass Transition Melting

 Property of the amorphous region  Property of the crystalline region

 Below Tg: Disordered amorphous  Below Tm: Ordered crystalline

solid with immobile molecules solid

 Above Tg: Disordered amorphous  Above Tm: Disordered melt

solid in which portions of
 A first-order transition
molecules can wiggle around

 A second order transition

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Techniques of Tg measurement

Differential scanning calorimetry

Refractive index
Dynamic mechanical measurements
Specific heat measurements
Thermo mechanical analysis
Thermal expansion measurement
Micro-heat-transfer measurement
Isothermal compressibility
Heat capacity
Elastic modulus or hardness
Broad-line NMR
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IMPROVED PROCESSING AND HANDLING

QUALITIES – SPRAY DRYING
• Non-sticky and sticky products.
• Sticky products - difficult to spray dry.
• Remain as syrup or stick on the dryer wall, or form unwanted
agglomerates in the dryer chamber and conveying system .
• Mainly due to the low glass transition temperature (Tg) of the low
molecular weight sugars present in such products, essentially
sucrose, glucose, and fructose.
• For bulky side groups-T g is higher
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GLASS TRANSITION IN SPRAY DRYING

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IMPROVED DISSOLUTION AND BIOAVAILABILITY

• Indomethacin & nifedipine are poorly water soluble drugs exhibiting
dissolution rate limited oral bioavailability.
• Both are prepared as glass solutions.
• Glass solutions showed increased drug dissolution rate than
crystalline forms of drugs.
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VISCOELASTIC PROPERTIES
• Neither a pure elastic nor a pure fluid material.
• Have ability to store energy and to dissipate it.
• Viscoelastic materials
• Eg: PVC
• Creep test , polymer is first loaded with a certain weight and its
deformation is then monitored over the time.
• Stress relaxation test, polymer is first deformed to a certain extent,
and then its stress relaxation is monitored with the time.
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CREEP TEST
• Using a tensile specimen to which a constant stress is applied, often by the
simple method of suspending weights from it.

• Surrounding the specimen is a thermostatically controlled furnace, the

temperature being controlled by a thermocouple attached to the gauge
length of the specimen.

• The extension of the specimen is measured by very sensitive extensometer,

results of the test are then plotted on a graph
of strain versus time to give a curve .
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STRESS RELAXATION TEST

• Determine a sample's creep properties when subjected to a prolonged
tensile or compressive load at a constant temperature. The rate of
deformation of a sample to stress at a constant temperature is known as the
creep rate. It is the slope created by the creep vs. time.
• If creep recovery is measured, the test will determine the stress-relaxation -
the rate of decrease in deformation that takes place when the load is
removed.
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MECHANICAL PROPERTIES
• Polymers resist differently when they are stressed.

• Can resist against stretching, compression, bending, sudden stress,

and dynamic loading.

• With increasing molecular weight , polymers display superior

properties under an applied stress.

• Flexible polymer can perform better under stretching whereas a

rigid polymer is better under compression.
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MECHANICAL PROPERTIES
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MOLECULAR WEIGHT
• Average molecular weight-Fundamental characteristic of a polymer
sample.
• Controls the function of biomedical polymers.
• Pure sample contain molecules differing only in degree of
polymerization.
• Molecular weight may be
a) Number averaged molecular weight
b) Weight averaged molecular weight
c) Viscosity averaged molecular weight
d) z-averaged molecular weight
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MOLECULAR WEIGHT

d) Viscosity average molecular weight

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NUMBER AVERAGE MOLECULAR WEIGHT

• The number average molecular weight(Mn) is the statistical average
molecular weight of all the polymer chains in the sample.

• Mn can be predicted by polymerization mechanisms.

• Measured by methods that determine the number of molecules in a

sample of a given weight; for example, colligative methods such as
end-group assay.
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WEIGHT AVERAGE MOLECULAR WEIGHT

• Molecular weight of a chain in determining contributions to the
molecular weight average.

• The more massive the chain, the more the chain contributes to Mw.

• Mw is determined by methods that are sensitive to the molecular

size rather than just their number, such as light scattering
techniques.
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VISCOSITY AVERAGE MOLECULAR

WEIGHT
• The molecular weight of the polymer is measured by using
viscometer and the molecular weight obtained by this technique is
called viscosity average molecular weight.

• From the Mark-Houwink equation the relationship among the

molecular weight and viscosity are given below
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Z- AVERAGED MOLECULAR WEIGHT

• Mz is especially sensitive to the presence of high molecular weight chains.

• Mz may be determined directly by sedimentation

equilibrium(ultracentrifugation) & light scattering.
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TECHNIQUES TO DETERMINE MOLECULAR

WEIGHT
Methods Measured M.Weight Upper Limit
Parameter Measured (g per mole)

Membrane Osmotic pressure of Mn 5x10⁴

osmometry polymer solvent

Light scattering Intensity of light Mw, Mz 1x10⁸

(LS) scattered by dilute
polymer solutions

Elution volume of the Mn , Mw 1 x 108

Gel permeation polymer
chromatography solution through a
(GPC) GPC column
packed with porous
microparticles
Flow time of polymer Mv 1 x 108
Viscometry solution
through a capillary
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MOLECULAR WEIGHT
• The molecular weight of polymers can be determined by a number
of physical and chemical methods
• Light scattering
• Gel permeation chromatography (GPC)
• Viscometry
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LIGHT SCATTERING
 Rayleigh scattering.

 Additional scattering shows presence of solute molecules, this may

be a function of the concentration, as well as their size and shape.

 By measuring differences in intensity of scattered light, averaged

size of polymer solutes and their molecular weights can be
determined.
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LIGHT SCATTERING
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GEL PERMEATION CHROMATOGRAPHY

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VISCOMETRY
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VISCOMETRY
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VIBRATIONAL SPECTROSCOPY —
INFRARED AND RAMAN SPECTROSCOPY
• At low temperatures, a molecule will exist in its ground vibrational
state and will be excited to a higher vibrational state if radiant
energy is absorbed.
• ∆E is related to the frequency of radiation (µ) absorbed, and the
relationship is given by,
∆E = hµ
• The spectral transitions are detected by scanning through the entire
IR frequency.
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VIBRATIONAL SPECTROSCOPY —
INFRARED AND RAMAN SPECTROSCOPY
• The energies of molecular vibrations of interest for analytical work
mostly correspond to wavelengths in the range 2.5 to 25 µm.

• Results in identification of the functional groups and the modes of

their attachment to the polymer backbone.

• Characterize the polymer’s molecular and material structure.

• Eg: Determination of level of amine groups in chitosan.

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VIBRATIONAL SPECTROSCOPY —
INFRARED AND RAMAN SPECTROSCOPY
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RAMAN SPECTROSCOPY
• Detects the inelastic scattering of photons by molecules.
• Provide a fingerprint by which molecules can be identified.
• Used to observe vibrational, rotational, and other low-frequency
modes in a system.
• The laser light interacts with molecular vibrations, photons or other
excitations in the system, resulting in the energy of the laser
photons being shifted up or down.
• The shift in energy gives information about the vibrational modes in
the system.
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RAMAN SPECTROSCOPY
• Stokes shift.
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RAMAN SPECTROSCOPY
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NUCLEAR MAGNETIC RESONANCE

SPECTROSCOPY
• Microstructure and chain configuration of polymers, both in
solution and in the solid state.
• Identification of certain atoms or groups in a polymer molecule as
well as their positions relative to each other can be obtained by one-,
two- and three-dimensional NMR spectra .
• When a strong external magnetic field is applied to material
containing nuclei possessing property of spin, behave like bar
magnets -orientate themselves in two energy states, a low-energy
state & a high-energy state.
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NUCLEAR MAGNETIC RESONANCE

SPECTROSCOPY
• The transition of a nucleus from one energy state to another occurs
if a discrete amount of energy is absorbed from an electromagnetic
radiation.
E = hV = 2µH0

• If the resonance frequency for all nuclei of the same type in a

molecule were identical, only one line or peak would be observed.
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NUCLEAR MAGNETIC RESONANCE

SPECTROSCOPY
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MICROSCOPY
• Characterization of polymer material ultrastructure.
• Used to examine the detailed shape, size and distribution of
polymeric micro and nanoparticles, and their interactions with
biological environments.
• These include traditional optical microscopy, scanning electron
microscopy (SEM), transmission electron microscopy (TEM) and
scanning probe microscopy (SPM).
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OPTICAL MICROSCOPY
• Microstructural information with a resolution on the order of 1 µm.
• Imaging is carried out using both reflected and transmitted light.
• If the absorption coefficient varies regionally within a sample, when
a beam of light travels through such a sample, contrasting regions of
intensity will be obtained in the final image.
• For a specimen that can be prepared as a thin film, by
casting on the microscope slide, examination using
transmitted light is most useful
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OPTICAL MICROSCOPY
• Two common are polarized-light microscopy and phase-contrast
microscopy.
• Former exploits the ability of crystalline materials to rotate the plane of
polarized light.
• Structure of polymer liquid crystals may also be studied using polarizing
microscopy.
• Reflected-light microscopy - topographical features of solid polymer
materials.
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SCANNING ELECTRON MICROSCOPY

• SEM is very valuable electron microscopy technique with a
resolution of about 5 nm.

• A fine beam of electrons is scanned across the surface of an opaque

specimen, and an appropriate detector collects the electrons emitted
from each point.

• An image having a great depth of field and a remarkable three-

dimensional appearance is built up line by line.
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SCANNING ELECTRON MICROSCOPY

• To produce stable images, the specimen is usually coated with a
conducting film prior to examination.

• The typical film thickness is about 20 nm.

• Coating materials can give a high secondary electron yield and thus
increase image contrast.
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TRANSMISSION ELECTRON MICROSCOPY

• Involves transmitting a beam of electrons instead of light through a
sample in a high-vacuum environment.
• Images and associated contrasts arise from regional differences in
electron densities.
• Resolution of about 1 to 100 nm.
• Specimen needs to be very thin in order to transmit electron beams
through the sample.
• Specimens are placed on copper grids or carbon-coated copper grids
and viewed through the holes in the grid.
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TRANSMISSION ELECTRON MICROSCOPY

• Replication, heavy-metal staining, are widely used to increase image
contrast.

• Rapidly adjusted to provide electron diffraction pattern from a

selected area, facilitating the investigation of crystal structure and
orientation and particular morphological features to be identified.
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TRANSMISSION ELECTRON MICROSCOPY

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TRANSMISSION ELECTRON MICROSCOPY

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SCANNING PROBE MICROSCOPY

• When a probe tip is brought very close to a surface, the physical
phenomenon, may be exploited to produce a three-dimensional
topographical image of the surface.
• The resolution is at the nanometre level.
• The most popular scanning probe microscopy (SPM) techniques include
 scanning tunnelling microscopy (STM)
 atomic force microscopy (AFM).
• AFM operates by measuring attractive or repulsive forces between a tip
and the sample surface, and can image samples both in air and in
liquids.
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SCANNING TUNNELLING MICROSCOPY

• Imaging surfaces at the atomic level.
• STM is based on the concept of quantum tunnelling.
• A conducting tip is brought very near to a metallic semi conducting
surface, a bias between two can allow electrons to tunnel through
vacuum between them.
• Variations in the tunnelling current as the probe passes over the
surface are translated in to an image.
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SCANNING TUNNELLING MICROSCOPY

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ATOMIC FORCE MICROSCOPY

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THERMAL ANALYSIS
• Structure dependent physical properties of the polymer are
measured as a function of temperature or time, while a polymer is
subjected to a controlled temperature program.
• The most common techniques are
 Differential scanning calorimetry (DSC),
 Thermal gravimetry (TG),
 Dynamic mechanical analysis (DMA).

• Used to identify and characterize both polymers and drug-loaded

polymeric delivery systems.
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DIFFERENTIAL SCANNING CALORIMETRY

• Whenever a polymer undergoes a phase transition, temperature
tends to remain constant while energy is taken into the system.
• Differences between the energy acquired or released as a function of
temperature or time while subject to a controlled temperature rise.
• Useful for recording thermal transitions such as the glass transition
temperature Tg, melt temperature Tm, and degradation or
decomposition temperature TD.
• Used to characterize the liquid crystal state of organization and
other forms of self-assembly.
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THERMAL GRAVIMETRY
 Used to measure the change in weight of a polymer sample while it
is heated, using a sensitive balance.
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DYNAMIC MECHANICAL ANALYSIS

• Properties of a polymer are studied as it goes through a time-dependent
mechanical change.
• Analytical technique is able to give important information on polymer
relaxation processes and phase morphologies.
• Useful method for identifying segmental and side-chain motion within a
chain and can also be used to study copolymers and polymer blends.
• It is most useful for studying the
viscoelastic behaviour of polymers.
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X-RAY DIFFRACTION METHODS

• Useful method for investigating arrangements of atoms or molecules
within a material.
• If there is an orderly arrangement of substructures within a material
with repeat distances of a similar magnitude to the wavelength of light
used (0.05–0.25 nm), interference patterns are produced.
• Such patterns provide information on the geometry of polymer
structures.
• Two methods used are
• Wide-angle x-ray scattering (WAXS)
• Small-angle x-ray scattering (SAXS).
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WAXS
 Distance from sample to the detector is shorter and diffraction
maxima at larger angles are observed.
 Degree of crystallinity of polymer samples.
 Sample is scanned in a wide-angle X-ray goniometer, and the
scattering intensity is plotted as a function of 2θ angle.
 Crystalline solid consists of regularly spaced atoms (electrons) that
can be described by imaginary planes.
 Distance between these planes is called the d-spacing.
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SAXS
• Value of angles used is from 1o to 5o.
• Useful in detecting large periodicities from 5 to 70 nm in a structure
such as lamellae or distribution of particles or voids in materials.
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MECHANICAL AND RHEOLOGICAL

ANALYSES
• It is a reflection of the polymers molecular properties.
• Carried out in order to establish if the polymer is fit for the purpose.
• Tensile properties of solid polymers can be characterized by their
deformation behaviour.
• Rubbery polymers - lower modulus or stiffness.
• Glass and semi crystalline polymers - higher moduli and lower

extensibility.
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MECHANICAL AND RHEOLOGICAL

ANALYSES
 Used to obtain information related to the flow behaviour of polymer melts and
polymer solutions.

 Capillary and rotational rheometers.

 Polymer fluids are non-Newtonian in behaviour, mostly being shear- thinning or

pseudoplastic.

 Viscoelasticity is a unique property of certain polymers, which display both

viscous- and elastic-type behaviour at ordinary temperatures and loading rates.
 Useful way of assessing hydrogels
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CONCLUSION
• Polymer materials have been used for the administration of
pharmaceuticals & play an important role in fabrication of various
controlled release and drug targeting systems.
• The use of a polymer for drug delivery is controlled by its molecular
properties.
• Considering the polymer’s functional properties, it is important that
adequate polymer characterization is available.
• Many methods available for the characterization of polymers.
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REFERENCES
• Alfred martin. Physical pharmacy; (4): 556-92
• Alan.R.Katritzky, Sulev Sild. Quantitative structure – property
relationship correlation of glass transition temperature of high
molecular weight polymers: Journal of Chemical Information and
Modeling;Feb 1998(2):300-304
• P. Debye. Molecular weight determination by light scattering.The
Journal of Physical Chemistry;Jan 1947,51(1):18-32
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REFERENCES
• A.W Craig, D.A Henderson. A viscometer for dilute polymer
solutions. Journal of polymer science; Jan 1956,Vol 10:124-32

• Heinz.W.Siesler. Vibrational spectroscopy of polymers.

International Journal for Polymer Analysis and Characterization;
Nov 2011,8(16)

• Swee Chye Yeo, A. Eisenberg. Advancement in Modern polymer

Technology Journal of Applied Polymer Science; April 1977,21(4):
875-898
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