Charecterizations of Polymers

Structural Properties:
INFRARED SPECTROSCOPY (IR)

▪ Both qualitative and quantitative analyses could be done

by FT-IR spectroscopy:
❑ Structural analysis (homopolymer, copolymer etc.)
❑ Crystallinity analysis
❑ Analysis of intermolecular interactions such as
❑ H bonds.
❑ Polymer – polymer interactions
❑ Polymer – solvent interactions

▪ Determination of crystallinity by using FT-IR spectroscopy:

The ratio of absorbances of specifically chosen wavelengths gives crystallinity, XC

Ac Ac = Absorbance of the crystalline region

XC = 𝐴𝑎 = Absorbance of the amorphous region
Aa
UV-VISIBLE SPECTROSCOPY (UV-VIS)

▪ UV-vis spectroscopy can be applied to polymers having

functional groups that can absorb electromagnetic
radiation, such as:

▪ C–O
▪ C=O
▪ O–R
▪ NH2
▪ N–C
▪ C=C

▪ UV-vis measurements are maden on the solutions of

polymers in suitable solvents.
NUCLEAR MAGNETIC RESONANCE (NMR)

NMR Spectroscopy
NMR spectroscopy is one of the most powerful and widely used techniques for analyzing the
structure of organic molecules and polymers. It is based on the interaction between atomic
nuclei and radiofrequency energy in a magnetic field, producing detailed structural
information. Compared to IR spectroscopy and Mass Spectrometry, NMR provides much more
comprehensive data about molecular environments and connectivity. In ¹H NMR analysis, the
most important information obtained includes the number of signals, chemical shifts, peak
integration, and spin–spin splitting.

▪ By using NMR analysis, many structural properties of polymers can be revealed:

▪ Chain structure of polymers
▪ New bonding of polymers of copolymers
▪ Decomposition of polymers
▪ MW of polymers (from the peak areas)
▪ Polymerization ratios monomer/polymer ratio)
▪ Ratios of monomers in copolymers
▪ Isomerism
▪ Branched structures
MASS SPECTROSCOPY (MS)

▪ By using Maldi-Tof-MS, molecular weight and chain structure of the

polymers can be analyzed.
Molecular weights of Polymers:

Yildiz Technical University, Metallurgical and Materials Engineering.

Experimental methods for determination of molecular weight:
 • Mn: Brittleness (resin versus
Impact of MW on elastomer), stressstrain properties

Physical Properties
• Mw: Tensile strength, hardness

• Mz: Flex life, stiffness, melt

viscosity

• Mv: Solution viscosity,

extrudablility, molding properties
Density:
• The density of polymers is very low, especially when
compared to metals.
▪ Pure polymer density, 0.83-2.5 g/cm3

▪ Polymeric foams density, 0.01 g/cm3

▪ Filler added polymers, upto 3.5 g/cm3

▪ Pure aluminum density 2.7g/cm3

▪ Pure iron density 7.874 g/cm3

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 Thermal Properties of Polymers:
▪ Thermal behavior of a polymer is directly related to its crystallinity.
▪ Glass transition temperature (Tg) is the temperature that the polymer chains
at amorphous regions start moving due to getting enough thermal energy
to bend and twist.
▪Amorphous polymers show
only Tg, they don’t have Tm.

▪ Semi-crystalline polymers show

both Tg and Tm.

▪ 100% crystalline polymers only

show Tm.

▪ But commercially available

polymers are never 100%
crystalline. So as the percentage
of crystallinity increases, the
thermal behavior of the polymer
looks more like a truly crystalline
polymer.
▪ Tg directly effects the thermal properties and determines the
usage areas of a polymer.
▪ Example: PE (Tg ≈ -100° C)
▪ When an external mechanical force is applied, polymers used
above their Tg distributes the energy in polymer mesh by chain
movements.
▪ These types of polymers can tolerate folding, wrinkling, twisting
etc. since they are used above their Tg in daily usage and do
not deform.
▪ PE is used as shopping bags and it is soft.
▪ Example: PS (Tg ≈ 100° C), PET (Tg ≈ 80° C)
▪ Polymers that are used below their Tg are rigid and easily
brake.
▪ PS is used as yougrt cups and PET is used as water bottles. They
are both hard.
Some properties of polymers affect Tg:

▪ Chain flexibility: The ability of polymer chains to turn around

chemical bonds.
▪ Branching
▪ Crystallinity,
▪ Tacticity,
▪ The preparing conditions of the test sample,
▪ Measurement method,
▪ Rate of heating/cooling
▪ If the sample is fast cooled Tg is low,
▪ If the sample is slowly cooled Tg is high.
▪ – CH2 – CH2 – , –Si – O – Si – , – CH2 – O – CH2 – on polymer backbone provides flexibility.

▪ Benzene [ ] on polymer backbone stiffens the polymer chain.

▪ Examples:
▪ Polyethylene Polyethylene Oxide Polyphenylene Oxide

Tg = -115 °C Tg = -67 °C Tg = 80 °C
▪

▪ Amide , sulfone , carbonile groups stiffen the polymer chains.

▪ As the polarity of side groups increases, Tg increases.

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 Differential Scanning Calorimetry (DSC)

Thermal Propertıes of Polymers 22

Thermogravimetric Analysis (TGA)

Thermal Propertıes of Polymers 23

Isothermal Gravimetric Analysis

TGA curves of expandable PLA microspheres weight loss as a

function of temperature.

Thermal Propertıes of Polymers 24

Mechanical Properties of Polymers:
▪ Mechanical properties are responses of materials to five external
forces;
▪ Tension: Forces applied to two ends of the material, opposite to the surface,
▪ Compression: A force applied towards the surface of the material,
▪ Bending: Forces at an angle to the material,
▪ Torsion: A force that twists the material around its axis
▪ Shear: Opposite forces that are parallel to the surfaces of material.

▪ Different materials respond varyingly to

mechanical forces applied on them. They could;
▪Break,
▪Elongate,
▪Twist,

▪Tear,
▪Fracture,
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Mechanıcal Propertıes of Polymers

▪Decompose. 25
▪ Like other materials, polymers could be subjected
to different forces;
▪ Plastic bags are pulled down (tension),
▪ Plastic flooring is compressed,
▪ Car tires are compressed and bent.

▪ Thus, mechanical properties of polymers provide

information regarding to suitable processing
techniques and application areas. For example;
▪ Polystyrene: not used in areas requiring high toughness,
HIPS
▪ High impact polystyrene (HIPS)/styrene-butadiene rubber Polystyrene

(SBR): are hard and less brittle. foam

▪ Mechanical properties of polymers depend on their;

▪ Chemical and physical structure,
▪ Processing method,
▪ Usage conditions (temperature and pressure),
▪ Usage life.
▪ Loading temperature and duration are significantly effective on mechanical
properties of polymers.
▪ Polymeric materials are subjected to;
▪ Tensile test,
▪ Impact test,
▪ Compression test,
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▪ Hardness test to determine their mechanical properties.
Deformation
▪ Deformation is a term comprises the change in size or shape, yielding and
the behavior in between of an object that is subjected to force.
▪ Solids deform by changing their size or shape,
▪ Liquids deform by flowing.
▪ Reversible deformation: Deformation that is retrieved to return the material
to its original shape once the force is removed.
▪ The mechanical energy is absorbed to increase bond vibrations and change
bond angles,
▪ When the force is removed, the energy is used to return to the initial shape,
▪ Elastic deformation is unique to solids.
▪ Permenant deformation: The deformation that cannot be reversed even if
the force is removed.
▪ Liquids flow under the influence of forces,
▪ Solids elongate, crack, fracture, etc. under forces high enough irreversibly deform
the material.

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Tensile Test of a Thermoplastic Polymer
▪ A: Yield point, maximum
crystallinity, all the chains
are ordered.
▪ D: Breaking point.
▪ Slope: Elastic modulus, as
modulus increase,
hardness increase.

Mechanıcal Propertıes of Polymers 28

Elastic Modulus
▪ Elastic modulus is directly proportional to temperature and ratio of
crystalline areas of the polymer.
▪ Crystalline regions restrict the decline of elastic modulus, so as
crystallinity decrease, the elastic modulus decrease.

Mechanıcal Propertıes of Polymers 29

▪ Hard plastics (e.g. PET, PS) and fibers have high elastic modulus
and low tensile strength, so they show high resistance to
deformation.
▪ Thermosets are hard polymers due to their crosslinks. Their elastic
modulus is 3-10 times higher that of thermoplastics’.
▪ Soft polymers (e.g. PE, PP) have moderate elastic modulus and
tensile strength.
▪ Elastomers have low elastic modulus and break at low loads. But
they show high elongation and have good impact resistance.
They can elongate up to 5-10 times of their initial length without
permanent deformation.
▪ Ethermoplastic > 1000 x Erubber

Mechanıcal Propertıes of Polymers 30

Impact Tests of Polymers
▪ The highest amount of energy which could a
material absorb before breaking or fracture is
equal to the area under its stress-strain curve.

▪ This energy is measured by impact test.

▪ The unit of this energy is J/m3.

Area = Toughness = dF x dL

▪ Hard and brittle polymers have a low impact

resistance and break easily.

▪ Soft and tough polymers have high impact

resistance. So it is appropriate to use them in
areas requiring high toughness like car tires.

Mechanıcal Propertıes of Polymers 31

ENVIRONMENTAL TESTS
▪ Environmental factors on polymers:
▪ Pressure ▪ Ozone
▪ Humidity ▪ Sun light (UV, IR rays…)
▪ Temperature ▪ Wind
▪ Composition of the atmosphere, O2 ▪ Water (rain, snow…)

▪ Due to these effects, materials fade, break, loose their luster or crack.

▪ Goods that are open to atmosphere such as tables, chairs, roofs, building
sidings, paintings, greenhouse covers, traffic lights, car parts like seats,
headlights, bumpers are affected.

▪ These goods are analyzed with aging tests.

▪ Polymers are subjected to heat, light (UV), pressure and moisture to

check durability.

▪ UV does the most significant damage among these factors.

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EFFECT OF LIQUIDS
▪ Polymers are widely used as packages so their
interactions with liquids are important:
▪ Water
▪ Cleaning materials
▪ Chemical materials
▪ Drinks
▪ Paintings
▪ Glue

▪ Polymers can be in an equilibrium with these liquids or

can degrade.

▪ Ex: Polyvinyl alcohol, polyacrylamide, polyacrylic acid

dissolve in water so can not be used in aqueous
media.

33
▪ In general, it is desirable that polymers do not interact with
chemicals at all.
▪ But sometimes when making a composite material, i.e.
reinforcing the polymer with additives like flame retardants or
plasticizers, the interaction of polymer and additive is
desired.
▪ When polymers come into contact with chemicals, the
following reactions may occur:
▪ Oxidation
▪ Chain scission
▪ Branching
▪ Grafting
▪ Cross-linking
▪ Swelling: Polymers can absorb solvents. Water absorption is very common in
environments such as sea and rain where polymer-water interaction is high.
▪ Dissolution: If a polymer dissolves in water, it gets unusable.

▪ PE and PP are water resistant and has no water absorption.

STRUCTURAL ANALYSES APPLIED TO

34
POLYMERS
COMBUSTION OF POLYMERS
When polymeric materials are brought closer to a flame source;
1. Heat up
2. Begins to degrade under the influence of heat, combustible gases are
formed, chains break down into small chains or molecules
3. Flame and ignite

▪ Burning stops when polymers are removed from the flame source.
Polymers are self-extinguishing materials.

▪ Toxic gases released during the burning of polymers are harmful to

human health. Thus, flame retardant additives are added to
everyday polymeric items such as carpets, cloths and seats.

COMBUSTION OF POLYMERS 35
▪ Burning speed of polymers: SBR > LDPE > PP > HDPE

▪ When PP is burning, it releases propane gas which is

more flammable than PP.

▪ When PVC and Teflon are burning, they release

halogen gases like HCl and HF which are heavier than
air. These gases cover the material and remove O2.

▪ Combustion wastes, such as ash, formed during the

burning of thermosets prevent further combustion.

COMBUSTION OF POLYMERS 36
Electrical Properties

Magnetic Properties

Optical Properties

Etc.