PROPERTIES AND CHARACTERIZATION OF INORGANIC POLYMERS

Table of Contents

➢ Introduction………………………………………………………….2
➢ Mechanical properties………..……….……………………………..3
o Elasticity………………………………………………………3
o Viscosity……………………………………………………….5
o Viscoelasticity………………………………………………....6
o Skeletal Flexibility…………………………..…………………7
➢ Characterization Techniques……………………………………….7
o FTIR……………………………………………..…………….8
o Raman spectroscopy……………………………….…………..9
o Fluorescence spectroscopy…………………………………….10
o Uv visible spectrascopy…………………………….…………10
o Nuclear magnetic resonance spectroscopy……………………11
o Electron Spin Resonance……………………………………..12
➢ References…………………………………………………..……...14

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PROPERTIES AND CHARACTERIZATION OF INORGANIC POLYMERS

➢ INTRODUCTION

The word polymer is

combination of two
Greek words, poly and
mers; poly means many
and mers mean parts
(repeating units). Hence,
polymers are
macromolecules (high
molecular weight
compounds) formed by
linking large numbers of
repeating units called
monomers.

In inorganic polymers, the chain (backbone of skeleton) consists of elements other than
carbon. Example: Polythiazyl (Sulphur based inorganic polymer), polyphosphazines,
silicones, chalcogenide glass, etc.

polythiazyl

The use of the term inorganic polymer is not limited to materials with plastic or elastomeric
properties; The inorganic macromolecule concept has a wide application to many materials that
merge studies on plastics, rubbers, glasses and ceramics.

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PROPERTIES AND CHARACTERIZATION OF INORGANIC POLYMERS

➢ MECHANICAL PROPERTIES

Material property is the key term that helps us recognize material characteristics and use them in
the application to get the most out of it with minimal effort. Like the length, width, and height of
an object, a material also has certain properties that distinguish it from others like elasticity,
tensile strength, viscosity, these are termed as mechanical properties.

o DEFINITION

Mechanical properties are physical properties that a material exhibits when a force is applied.
Examples include modulus of elasticity, tensile strength, elongation, hardness, and fatigue
resistance.

➢ MECHANICAL PROPERTIES OF INORGANIC POLYMERS

Some important mechanical properties if inorganic polymers are listed below:

✓ ELASTICITY

If the material deforms under the action of an external force, it tries to regain its original shape
after removing this force. This mechanical property of materials is called elasticity. When the
body fully recovers its shape as before, it is said to be a perfectly elastic body.

Inorganic polymers ranges from having high elasticity to the low. Like polyphosphonitrilic
chlorides exhibit high elasticity and can be stretched many times reversibly on the other hand
chalcogenide glass possess lower softening
point, tensile strength and higher refractive
indices.

During elongation near room temperature a

stress–strain curve obtained for a typical
partially crystalline, uncross-linked polymer
is shown in figure:

Typical non-equilibrium stress–strain curve in

elongation.

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PROPERTIES AND CHARACTERIZATION OF INORGANIC POLYMERS

Data is recorded on an Instron tester and no attempt is made to achieve mechanical equilibrium.
In this experiment, a strip of polymer is mounted between two clamps that move apart at a
constant speed. A typical rate would be 100% per minute, which means that a sample that was
originally one inch long would grow to two centimeters after one minute. The elongation or
relative length of the sample is indicated by the symbol γ and is plotted along the abscissa. Stress
is indicated by the symbol s and is the force per unit undeformed cross-sectional area. The stress
is plotted along the ordinate. The relationship between any stress value and the corresponding
strain value is called the modulus. It is a direct measure of a material's resistance to strain. Only
in the low-strain region of the curve stress and strain are directly proportional to each other.
Therefore, the modulus is only constant in this area.

When the elongation reaches what is known as "stretch elongation", curve becomes very non-
linear. The stress at this point, the "yield point", is high enough to move the crystallites in their
highly viscous environment, to melt them and then recrystallize in new orientations that partially
relieve stress.

Then the curve rises monotonously until it breaks. The stretch at this point is called "maximum
extensibility" and the tension is called "maximum resistance." The area under the curve to the
breaking point corresponds to the integral of fdL and, therefore, it is the work or energy required
for breaking. It is the standard measure of toughness. The larger the area, the stronger the
material will be. Curves for typical polymeric materials are shown:

This is for a soft and weak material, for example, a silicone

rubber. Soft means low value of modulus while weak means
having low ultimate strength.

The next is hard and brittle

like polystyrene. Hard means
having large initial slope and
modulus and brittle have small maximum extensibility. As
these two have small area under curve so are not very tough.

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Then curve of a soft and strong material like natural rubber.

The initial small slope and modulus shows that the material is
soft. However, at higher elongations, crystallization occurs and
this strengthens the elastomer, so its final strength is excellent
and therefore quite strong.

Next is hard and strong, like

Nylons. High initial slope and modulus shows hardness.

Soft and tough refers to thermoplastic

elastomers. The initial modulus is small
yet high extensibility gives large area
under the curve. Due to high toughness lot of energy is required for
rupture.

Some of the polycarbonates are hard

and tough. Large area is due to high values of the ultimate
strength and maximum extensibility.

✓ HOOKEAN ELASTICITY

s/γ = constant = G

This relationship is known as Hookean Elasticity. It is ratio of the stress to strain and when its
constant we say that polymer has Hookean elasticity. This ratio is known as Youngs
Modulus(G).

✓ VISCOSITY

Viscosity of fluid is given by the formula below and is represented by symbol η.

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PROPERTIES AND CHARACTERIZATION OF INORGANIC POLYMERS

s= η d γ / dt = η γ

s = force per unit area required for deformation

γ = rate of flow or shear

If a shearing stress increases rate of deformation γ then the proportionality factor is known as
viscosity η. If it is constant then the flow is said to be Newtonian, if not it is non-Newtonian.
These two sketches show viscous flow where the
reciprocal of the slope viscosity. In figure 1 both slope
and viscosity are constant so the fluid is Newtonian. In the
second, the viscosity is first high with low slope and then
decreases due to increase in stress. For example, “Non-
drip” paints (temporary gel-like structure).

Retarded flow
shown in third figure is extreme case of type 2. The
viscosity is infinite i.e. zero slope until a threshold value
of the stress is reached. After this point the flow can be
either Newtonian or non-Newtonian.

✓ VISCOELASTICITY

It is the combiation of viscous and elastic

characteristics. There are two viscoelastic models one
is Maxwell and other is the Voigt model. Here is
figural representation of two models.

A spring having a modulus G shows the elastic

response. The viscous response is shown by “dashpot.”
A piston is there in a cylinder containing a viscous
fluid of viscosity η. If a downward force on cylinder
increases the flow inside, whereas an upward force

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PROPERTIES AND CHARACTERIZATION OF INORGANIC POLYMERS

causes some of the fluid to flow out. Due to high viscosity the flow is retarded thus models the
retarded movement and flow of polymer chains.

The series combination of spring and dashpot is called the Maxwell model, as is investigated by
Maxwell who was famous for his work on gases and molecular statistics. It is used to check the
viscoelastic behavior of uncross-linked polymers. The spring describes the recoverability of the
chains that are elongated, and the dashpot determines the permanent deformation or creep.

On the other hand parallel arrangement is called the Voigt model. It checks the behavior of a
cross-linked but sluggish polymer like polyacrylates. Both the deformation and the recoverability
are retarded due to parallel movement of both spring and dashpot.

✓ SKELETAL FLEXIBILITY

There is a close connection between the presence of a flexible polymer skeleton and the
flexibility of the bulk material. Usually a glass transition temperature Tg is used to see the
macromolecular flexibility. Below this temperature the backbone bonds have insufficient thermal
energy so less torsional motions and are known as glass polymers.

On increasing temperature above Tg torsional motion occurs so that individual molecules can
twist and yield to stress and strain. In this state the polymer is an elastomer unless the bulk
material is stiffened by microcrystallite formation. Such polymers are believed to have a
backbone that offers more resistance to bond torsion than a polymer with a low Tg.

➢ CHARACTERIZATION TECHNIQUES

The characterization of the polymer is a substantial part of the polymer technology. These
techniques are performed to confirm chemical structures and to evaluate properties for usage and
physical behaviors. There are numerous instruments available for the characterization of
polymers. For the characterization of the chemical structure of polymers, infrared spectroscopy
(IR) , Raman spectroscopy , ultraviolet-Vis (UV-Vis) spectroscopy, nuclear magnetic resonance
(NMR) spectroscopy and electron spin resonance (ESR) are commonly used. X-ray diffraction
(XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) are
commonly used and atomic force microscopy (AFM) are used to study the structure and
morphology of polymers.

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Here are few important techniques:

✓ INFRARED SPECTROSCOPY

Infrared spectroscopy (IR spectroscopy or vibrational spectroscopy) is spectroscopy that deals

with the infrared region of the electromagnetic spectrum, which is light with a longer
wavelength and lower frequency than visible light. Covering series of techniques based
primarily on absorption spectroscopy. As with all spectroscopic techniques, it can be used to
identify and study chemicals. For a given sample (solid, liquid, or gaseous) the infrared
spectroscopy method uses an instrument called an infrared spectrometer (or spectrophotometer)
to generate a infrared spectrum. Infrared spectroscopy is based on the change of the dipole
moment of the polymer molecule. The infrared portion of the electromagnetic spectrum
(generally divided into three regions; the near, middle and far infrared named for their relation to

infrared absorption regions for characteristic bands

the visible spectrum.

Infrared (IR) spectroscopy is used to characterize long-chain polymers because the IR active
groups present along the chain absorb as if each was a localized group in a simple molecule. IR
arises due to the interaction between the frequency of the incident IR radiation and that of a
certain mode of vibration. It is used to determine both the degree of crystallinity and the degree
of chain orientation in a polymer.

✓ EXAMPLE:

FT-IR investigation of silicate polymer is done in this research article. Here FT-IR spectroscopy
allows differentiation of various bonds in a material on a molecular level. In this work, the FT-IR
absorption spectra of the inorganic polymer were compared to known absorption lines in

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literature. The position of the main Si–

O–X stretching band (X = Si, K, or H)
gives an indication of the length and
angle of the bonds in a silicate network.
For amorphous silica, this peak occurs at
approximately 1100 cm-1. A shift of the
Si–O–X stretching band to lower wave
numbers indicates a lengthening of the
Si–O–X bond, a reduction in the bond
angle, and thus a decrease of the
molecular vibrational force constant.
This shift can be attributed to an
increase in the proportion of silicon sites
with non-bonding oxygens (NBO).

The IR bands are identified as follows:

Si– O stretching is located in the range
1000–1200 cm-1 , Si–O bending is
found at 800 cm-1 and between 890 and
975 cm-1 . The band at approximately
1100 cm-1 is assigned to the Si–O
stretching of Q4 units and the band at 1050 cm-1 is assigned to Q3 units with one non-bridging
oxygen (Si–O–NBO) per SiO4 tetrahedron.

(Simonsen, M. E., Sønderby, C., Li, Z., & Søgaard, E. G. (2009). XPS and FT-IR investigation of silicate
polymers. Journal of materials science, 44(8), 2079-2088.)

✓ RAMAN SPECTROSCOPY

Raman spectroscopy is a spectroscopic technique for observing vibrational, rotational, and low-
frequency modes in a system. It is commonly used to obtain a fingerprint that can be used to
identify molecules. Since instruments are relatively expensive, the Raman method is more
difficult to apply to colored materials. In this effect inelastic scattering of light occurs when a

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monochromatic light irradiates on the molecule and analyzes only thick polymer samples.
Raman effect responds to the symmetric vibrational modes.

✓ EXAMPLE

The application of Raman spectroscopy to the study of crystalinity in polymers has been
examined. In this review it has been demonstrated that the technique is used to assign
characteristic modes of vibration to the amorphous and crystalline regions of certain polymers.
Additionally, trans and gauche conformations of polymer chains may be differentiated. Studies
of the following crystalline polymers have been reported in recent literature and are discussed in
this review: polyethylene, polystyrene, poly(ether ether ketone), polyamides, poly(ethylene
terephthalate), elastomers, liquid crys- talline polymers, inorganic polymers and certain polymer
blends.

The thermal transitions of a germanium-based polymer, poly(di-n-hexylgermane) (PDHG), have

been investigated using FT-Raman spectroscopy [28]. A correlation between the band splitting
of the CH 2 bending modes at 1444, 1453 and 1469 cm -1 and the packing of the hexyl side-
chains was observed.

(Stuart, B. H. (1996). Polymer crystallinity studied using Raman spectroscopy. Vibrational

spectroscopy, 10(2), 79-87.)

✓ FLUORESCENCE SPECTROSCOPY
The fluorescence spectroscopy requires a fluorescent probe at lowest concentration. Zammarano
et al. reported the formation of polymer nanocomposites. Yu et al. studied about the synthesis of
the extracellular polymeric substances (EPS), which was extracted from aerobic and anaerobic
sludges in the treatment of wastewater. Sorgjerd et al. studied the synthesis of pre-fibrillar
oligomer aggregates of transthyretin. Yu et al. reported the formation of a continuous layer of
biofilm having a thickness of 20–100 μm.

✓ UV-VISIBLE SPECTROSCOPY
UV-Vis (UV-Vis) spectroscopy is used to qualitatively and quantitatively detect chromophores
in material when matter undergoes n -> p* and p -> p* transitions on exposure to light. Due to its
sensitivity it is particularly useful for identifying impurities in polymers like inhibitors,
antioxidant etc. UV–Vis spectra are most commonly used to detect conjugation.

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✓ EXAMPLE

The results of study indicate that polyacrylamide polymers used for water and wastewater
treatment strongly absorb light in the 191.5–230 nm range, and the peak absorbance was mea-
sured at 191.5 nm for all of the seven polymers tested in this study.

The detection limits in distilled water were different for different polymers. In distilled water
samples, the detection limits were below 0.1 mg / L for all polymers at 191.5 nm. The lowest
detection limit measured was 0.05 mg / L. For raw and clarified water and centrate samples
collected from treatment plants, the detection limits varied between 0.07 and 1.35 mg / L
depending on the poly- mer type and impurities in the sample. The in-line UV–vis
spectrophotometer used in this study provided a powerful tool for accurate and sensitive
measure- ment of polymer concentration.

(Al Momani, F. A., & Örmeci, B. (2014). Measurement of polyacrylamide polymers in water and
wastewater using an in-line UV–vis spectrophotometer. Journal of Environmental Chemical
Engineering, 2(2), 765-772.)

✓ NMR SPECTROSCOPY

NMR is used for the determination of stereochemical structure and conformational preferences.
Another application is the determination of chemical composition and chemical sequence
distributions in copolymers. It is also used in study of relaxation processes and molecular
movements in general, including the determination of transition temperatures from changes in
the widths of the resonance lines. NMR is useful to study polymer stereochemistry and monomer
sequencing. The chemical shifts of 1 H nuclei in various chemical environments have been
determined by measuring the 1 H NMR spectra of a large number of compounds with known,
relatively simple structures. . Bertmer et al. reported the synthesis of biodegradable polymer
networks through UV curing, and characterization was done by solid-state NMR

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✓ EXAMPLE.

Figure 1 depicts the 31P-NMR spectrum of aniline-substituted polyphosphazene having signals

at 2.3 and −15 ppm, which
are attributed to the
phosphorus atoms in
different environments with
aniline and chlorine,
respectively. Zhang and
coworkers have investigated
an important reaction
conditions like temperatures,
time, and concentrations on
poly
(bis(phenoxy)phosphazene)
using various 31P-NMR
spectra to correlate specific
structural defects.

➢ ELECTRON SPIN RESONANCE

Electron spin resonance (ESR) works on the same principle as NMR , except that it uses
microwaves instead of radio wave frequencies and records the spin transitions of unpaired
electrons instead of nuclei. NMR spectra record absorbance directly, but ESR spectrometers
record the first derivative of of the absorbance curve. ESR in polymer chemistry is used
primarily to investigate free radical processes such as polymerization, degradation, and
oxidation. There are two common ways to use free nitroxide radicals:

(i) They can be covalently attached to polymer chains.

(ii) They can be mechanically (diffusion) introduced into a polymeric (or composite)
matrix.

The first is known as spin labelling and the second as the spin probe method.

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➢ EXAMPLE

ESR was performed to study the reaction of F NS2+, N(SC1)Z' AND NS+ with tetrahydrofuran.
Intense spectra were recorded for NS2+.AsF6- and N(SC1),'*ASF6- solutions having g-factors (
= 2.0110 f 0.0001) appropriate to
sulphur-centred free radicals;

NS+.AsF6- in THF gave no signal.

The ESR spectrum from
NS2+.AsF,- and THF consists of a
1:2:3:2:1 quintet arising from two
equivalent nitrogen nuclei. The
spectrum shows high-field
broadening owing to the high
viscosity.

Solutions of N(SC1),+-AsF6- in THF give an

ESR spectrum which is clearly a mixture of
two sulphur-centred free radicals, both
containing two equivalent nitrogen nuclei,
one is radical cation. The spectrum shows
high-field asymmetric line broadening owing
to the high viscosity.

(Fairhurst, S. A., Hulme‐Lowe, A., Johnson, K. M.,

Sutcliffe, L. H., Passmore, J., & Schriver, M. J.
(1985). An ESR study of the polymerization of
tetrahydrofuran with simple inorganic cations containing sulphur and nitrogen. Magnetic resonance in
chemistry, 23(10), 828-831.)

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