Chemical Education Journal (CEJ), Vol. 14, No. 1/Registration No. 14-5 http://chem.sci.utsunomiya-u.ac.jp/~cej/v14n1/2Dey/tania.

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Chemical Education Journal (CEJ), Vol. 14, Issue 1 /Registration No. 14-5 /Received June 11, 2011.
URL = http://chem.sci.utsunomiya-u.ac.jp/cejrnlE.html

Importance of Viscosity in the Context of Teaching Polymers

Tania Dey1,2

1
Physical Chemistry and Polymer Science Group, Vrije Universiteit Brussel, Pleinlaan 2, 1050
Brussels, Belgium
2
Brain Mass Inc. 76 Prospect Street, New Market, Ontario L3Y 3T2, Canada

E-mail: taniadey hotmail.com

Abstract
Teachers can highlight the application and importance of a particular topic, to make courses more
meaningful. Polymers are a part of our daily life. This article elucidates why students should take interest
in 'polymer viscosity'. Some viscosity based nomenclatures are introduced at the beginning. It is being
shown how some practically important parameters such as molecular weight of polymer, average
end-to-end distance of polymer and degree of branching in polymer can be derived from the intrinsic
viscosity values. Some interesting experiments are suggested at the end, which can nurture curiosity and
critical thinking among students and improve correlation between courses and real world things.

Keywords: polymers; intrinsic viscosity; Flory-Fox theory; end-to-end distance; radius of gyration;
molecular weight; Ubbelohde viscometer; waste plastic bottles; real world application; critical thinking;
comprehension; enthusiasm

Contents
Introduction

Intrinsic viscosity

Classification based on viscosity

Significance of viscosity

Molcular weight of polymer

Average end-to-end distance of polynmer molecule

Degree of branching of the polymer

Measurement of viscosity and proposed experiments

Conclusion

Acknowledgment

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References

Introduction

'Polymer' is included in Physical Chemistry courses in India and Europe, whereas in USA it is considered
as a part of Organic Chemistry. These categorizations are just to simplify and organize courses and as we
all know, when it comes to research, these discipline-based barriers vanish very quickly.

Irrespective of this debate regarding which discipline it should belong, 'polymer' is an integral part of our
daily life, no doubt. Students sometimes fail to see the relevance of chemistry and can not connect their
lessons with real world things. Highlighting the application and importance of a particular topic during
teaching, can make courses more meaningful and invoke enthusiasm.

Intrinsic viscosity
One of the fundamental properties of polymer solution is its 'viscosity'. Intrinsic viscosity, [η], of a
polymer solution is expressed as follows:
[η] = lim [η]red = lim [η]sp / c ······ (1)
aaaaa c→0 aaaaaaaac→0

where reduced viscosity, [η]red, is equal to specific viscosity divided by concentration of polymer solution
and specific viscosity,

[η]sp = [η]rel - 1 ······ (2)

Relative viscosity, [η]rel is again equal to η / η0, where η and η0 are the viscosities of polymer solution
and pure solvent respectively. Apparently the unit of intrinsic viscosity is inverse of concentration unit
e.g. dL/g.

Classification based on viscosity

Viscosity is the measure of resistance of a fluid to flow. Water has a viscosity of 1 cps (centipoise) at
room temperature and is considered as a standard. Newtonian fluids have a viscosity which is dependent
only on temperature, not on shear rate and time e.g. sugar solution. On the other hand, depending on how
viscosity changes with time, the flow behavior of non-Newtonian fluid can be categorized as: (a)
thixotropic (time thinning, i.e. viscosity decreases with time) e.g. yoghurt and (b) rheopetic (time
thickening, i.e. viscosity increases with time) e.g. gypsum paste.

The viscosity of a Non-Newtonian time independent fluid is dependent not only on temperature but also
on shear rate (Figure 1). Depending on how viscosity changes with shear rate, the flow behavior is
classified as:

shear thinning - the viscosity decreases with increased shear rate e.g. paint
shear thickening - the viscosity increases with increased shear rate e.g. wet sand
plastic - exhibits a so-called yield value, i.e. a certain shear stress must be applied before flow
occurs e.g. grease

Sear thinning fluids are also called pseudoplastic and shear thickening fluids are also called dilatant.

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Figure 1 Schematic plot of shear force vs. shear rate for Newtonian and Non-Newtonian fluids.

Significance of viscosity
One can find the above-mentioned terminologies and expressions in any standard textbook of polymer
chemistry. But why should students really want to know about polymer viscosity? Why is it important?
Because it offers a wealth of information about the polymer sample. What are those? Three important
parameters can be derived from intrinsic viscosity data of a polymer solution - (a) molecular weight of
polymer, M (b) average end-to-end distance of polymer molecule, <h2>1/2 and (c) degree of branching of
the polymer, g.

Molecular weight of polymer

Mark-Houwink equation [1] gives a relationship between intrinsic viscosity, [η] and molecular weight, M
of a polymer solution, expressed as:

[η] = KMa ······ (3),

where the constants, a and K, depend on the particular polymer-solvent system. A value of a = 0.5 is
indicative of 'theta solvent'. A value of a = 0.8 is typical for 'good solvents'. For most flexible polymers,
0.5 ≤ a ≤ 0.8. For semi-flexible polymers, a ≥ 0.8. For polymers with an absolute rigid rod, such as
Tobacco Mosaic Virus, a = 2.0.

Averaging of polymer molecular weight is required, as polymer is a mixture of various molecular weights
and molecular sizes. Depending on the experimental techniques used, polymers may have four different
kinds of average molecular weights [1]: (a) weight average molecular weight, Mw (light scattering) (b)
number avergae molecular weight, Mn (colligative properties) (c) Z-average molecular weight, Mz
(centrifugation data) and (d) viscosity average molecular weight, Mv (viscometric behavior) and the
relative order of their values are: Mz > Mw > Mv > Mn (Figure 2). Molecular weights based on viscosity
measurements are less precise, as it depends on the solvent used, but is less expensive and easy to
perform.

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Figure 2 Four average momlecular weights of polymer

Average end-to-end distance of polymer molecule

According to Flory-Fox theory [2], the intrinsic viscosity [η] is given by:

[η] = φ<h2>3/2 / M ······ (4),

where [η] is the intrinsic viscosity of a polymer solution in a given solvent and at a given temperature,
<h2>1/2 is the average end-to-end distance of the polymer molecule in a given solvent and at a given
temperature, M is the molecular weight of the polymer and φ is universal viscosity constant independent
of the polymer-solvent system, the most acceptable value being 2.5x1021 mol-1 for flexible and hetero-
disperse polymers in good solvents. Hence after determining [η] and M experimentally, it is possible to
calculate <h2>1/2. Flory-Fox theory assumes a flexible polymer molecule as a non-draining coil and in an
'ideal' solution it can be approximated to a hydrodynamic sphere.

Degree of branching of the polymer

Consider a polymer chain as an assembly of mass elements (structural units) of mass mi, each located at a
distance ri from the center of mass of the molecule. By definition, the radius of gyration at a particular
configuration is given by:

<RG>2 = <∑ miri>2 / mi.

Mean-square end-to-end distance, <h2>, is a value which is meaningful only for perfectly linear polymers
having two ends. Macromolecules, which do not have a free end (e.g. macrocycles) or have several free
ends (e.g. branched polymers, star polymers etc) can not be described by end-to-end distance. It is more
appropriate to use mean-square radius of gyration, <RG>, as a measure of chain dimension. The inter-
relation is as follows, derivation of which is beyond the scope of this text [3]:

<h2> = 6<RG>2 ······(5),

Hence using equations (4) and (5),

[η] = φ.6 3/2.(<RG>2)3/2 / M = φ'.(<RG>2)3/2 / M,

where φ' = φ.6 3/2, or

<RG>2 = [η] M / φ' ······(6)

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The degree of branching (g) is defined as:

g = <RG>2 (branched) / <RG>2 (linear)······(7)

where the suffixes (branched) and (linear) stands for the branched and linear polymers respectively,
having same molecular weights and same number of repeat units.

Hence for a given polymer having same 'M', one can obtain from equations (6) and (7),

g3/2 = [η] (branched) / [η] (linear).

[η] can be determined experimentally for both branched and linear chain polymers, which in turn will give
'g', provided the polymers have the same molecular weight.

Measurement of viscosity and proposed experiments

Viscometers can be of three types: (a) to measure kinematic viscosity e.g. Ubbelohde viscometer (b) to
measure rotational viscosity e.g. Brookfield viscometer and (c) to measure dynamic viscosity e.g.
controlled stress rheometer from TA Instruments.

Simple experiments can be designed to ignite curiosity, nurture critical thinking and provide hands-on
experience among students. An interesting experiment will be to ask the students to bring different types
of waste plastic bottles (also a good opportunity to introduce different plastic recycling symbols often
used in consumer goods: Figure 3 [4]), ask to measure the corresponding viscosities and hence calculate
the respective molecular weights of the polymers and identify different polymers based on molecular
weight.

Figure 3 Common plastic recycling symbols

Most of the bottles for carbonated drinks, mineral water, edible oil and personal care products are made of
poly(ethylene terephthalate), PET and their intrinsic viscosity values range from 0.7-0.85 dL/g, depending
on the length of the polymer chain (the longer the polymer chains, the more entanglements between the
chains and therefore the higher the viscosity).
Students should prepare sample solutions according to ASTM D4603-03 standard test method [5]. This

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test method is for the determination of inherent viscosity of PET soluble at 0.50% concentration in a
60/40 phenol/1,1,2,2-tetrachloroethane solution by means of a glass capillary Ubbelohde viscometer. A
50/50 by weight mixture of phenol and 1,2-dichlorobenzene will work as well. The polymer is first
weighed and then dissolved in the solvent, as mentioned above. The solution and the viscometer are
placed in a constant temperature water bath, until thermal equilibrium is obtained. Time required for 100
ml of this solution to flow through the capillary viscometer from the upper to the lower graduation mark
(Figure 4) at the fixed temperature, is noted down which is proportional to the viscosity of the sample
solution, η. Students will repeat this experiment for five different concentrations of polymer solution. Also
the flow time for the solvent under the same conditions is noted down, which is proportional to the
viscosity of solvent, η0.

Figure 4 A portion of Ubbelohde viscometer showing the upper and lower graduation marks, 'a' and 'b'
respectively.

Concentration and times are then used to calculate the reduced viscosity of the polymer solution using
equations (1) and (2). A plot of reduced viscosity vs. concentration will produce a straight line and
extrapolating the straight line to zero concentration, the intrinsic viscosity of the polymer solution can be
obtained from the y-intercept (Figure 5). Molecular weight of the polymer will be calculated thereafter
using equation (3).

Figure 5 A plot of reduced viscosity vs. concentration of a polymer solution, y-intercept corresponding to
intrinsic viscosity

Conclusion

In conclusion, this article shows some viscosity-based nomenclatures, how a wealth of information can be
derived from polymer intrinsic viscosity, and proposes some lab experiments to ignite enthusiasm and
better comprehension among students.

Acknowledgment
The author is thankful to her mother, P. Dey, who, having a background in science as well as in education, has been an inspiration
to the author.

References

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1. Leslie Howard Sperling, "Introduction to physical polymer science", 4th ed, John Wiley & Sons
Inc., 2005.
2. James E. Mark, "Physical properties of polymers handbook", American Institute of Physics, Feb
1996.
3. R. H. Boyd and P. J. Phillips, "The Science of Polymer Molecules", Cambridge University Press,
June 1996.
4. http://www.all-recycling.de/recycle-waste/plastic-recycling-symbols.html (retrieved November 7
2011).
5. http://www.astm.org/Standards/D4603.htm (retrieved November 7 2011).

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