Rebecca L DeRosa

Inamori School of Engineering

Alfred University
© 2008

Intrinsic Viscosity Characterization of PS and PMMA

Laboratory Preparation
In order to adequately prepare for this laboratory exercise you should:
• Review lab procedures and safety information
Note: Samples for this experiment must be dissolved at least 24 hours before the start
of lab.

Objectives
After in-class presentation, completion of hands-on laboratory experiment and review of
the information provided, you should be able to:
• Identify several laboratory methods for molecular weight analysis of polymers.
• Confidently discuss the differences between the methods of analysis for polymer
molecular weight.
• Discuss how polymer solution behavior affects molecular weight measurements.

Introduction to Polymer Viscosity

Not until the early 1900’s were scientists able to determine the molecular weight
of large, polymeric molecules. Since then, several techniques have been developed to
measure the molecular weight of a polymer. The techniques are separated into two
categories, absolute and relative. Absolute methods, which include osmometry and light
scattering, depend on theoretical observations for molecular weight calculations.
Relative methods, such as intrinsic viscosity and size exclusion chromatography rely on
calibration standards based on absolute methods. Most often, relative methods are
used due to ease of use and inexpensive cost of operation.
Viscosity measurements are used to determine the molecular weight of a
polymer by correlating the polymer size with the viscosity. A pure solvent under laminar
flow experiences a shear rate gradient due to frictional forces at the walls of the
capillary. As a polymer particle in solution flows through the capillary it experiences
different shear rates depending on its size. The result is in an increase in drag and
therefore an increase in the viscosity of the solution. The viscosity is therefore related to
the size. The relative viscosity, ηrel, of the polymer solution is given by the ratio of the
solution viscosity, η, to the solvent viscosity, ηo.
η
Equation 1 η rel =
ηo

The specific viscosity , ηsp, is the relative viscosity minus one.

Equation 2 η sp = η rel − 1
Finally, the intrinsic viscosity, [η], is the zero concentration limit of the specific viscosity
divided by the concentration.

Page 1 of 4
Rebecca L DeRosa
Inamori School of Engineering
Alfred University
© 2008

⎡η sp ⎤
Equation 3 ⎢ ⎥ = [η ]
⎣ c ⎦ c =1
Intrinsic viscosities are calculated experimentally by using the Huggins and
Kraemer relationships.
η sp
= [η ] + k ' [η ] c
2
Equation 4 (Huggins)
c
(ln η rel )
= [η ] − k "[η ] c
2
Equation 5 (Kraemer)
c
When using an Ubbelhode capillary viscometer, the viscosity is measured by the
time it takes for the solution to pass through the viscometer. The specific viscosity using
this relation is giving in Equation 6.

t
Equation 6 η sp = −1
to
Once [η] is calculated, the Mark-Houwink relationship given in Equation 7, is used to
determine the viscosity average molecular weight, Mv. K and a are constants specific to
the polymer and solvent pair that is used. The value of a typically varies from 0.5 to 0.8.
Equation 7 [η ] = KM va
In this experiment, you will use intrinsic viscosity measurements to determine the
molecular weight of polystyrene, PS, or poly(methyl methacrylate), PMMA.

Page 2 of 4
Rebecca L DeRosa
Inamori School of Engineering
Alfred University
© 2008

Materials
Item
Polystyrene or Poly(methyl methacrylate)
Ubbelhode viscometer 1 (1C & OC)
100 ml Erlhemeyer
Chloroform (good solvent for PMMA)
Methanol/toluene (9/5 v/v) (theta solvent
for PMMA)
THF ( poor solvent for PMMA)
Water bath 25° C
45 μm nylon filter
15ml syringe

Procedure
Caution: Your Ubbelhode must be clean in order to obtain accurate results.

1. (TA responsibility before lab) Prepare a water bath at 25°C.

2. (TA responsibility before lab) Filter 70 ml of selected solvent and place it in the
Ubbelhode viscometer.
3. Check that the solvent in the viscometer has reached an equilibrium temperature
with the water bath.
4. Measure the viscosity of the solvent by timing the flow of the liquid through the
capillary. Follow the instructions that came with your specific viscometer.
a. Repeat the measurements four (4) times if using viscometer size1 (i.e.
THF)
b. Repeat the measurements five (5) times if using viscometer size 1C ( i.e.
chloroform)
c. Repeat the measurement three (3) times if using viscometer size OC (i.e.
methanol/toluene).
5. Next, prepare a 30 ml solution of 0.75 wt. % polymer in your selected solvent. To
save time you may use the already filtered solvent from before.
6. Filter the solution using the 45 μm nylon filters to remove any contaminants.
7. Put the solution in the Ubbelhode viscometer and check that the temperature has
reached equilibrium with the water bath.
8. After the solution temperature is constant, measure the time it takes for the
solution to pass through the bulb on the viscometer.
a. Repeat the measurement: four (4) times using viscometer size 1 (repeat
five (5) times if using 1C, and three (3) times if using OC).

Page 3 of 4
Rebecca L DeRosa
Inamori School of Engineering
Alfred University
© 2008

b. Carry out the same instructions for solutions diluted to 0.5 wt/v%, 0.25
wt/v%, and 0.1 w/v wt%. (Caution: Make sure your math is correct for
each dilution).

Reporting
You will be required to submit a report based on your work and calculations. The
report should include the abstract, introduction and background information, necessary
references, an experimental section and a written results section. The results section
should have graphics correctly placed in the document. The following are a set of
guidelines for the intrinsic viscosity report:

1. Write a concise abstract, introduction, thorough experimental and detailed results

section for your report. Include your data tables and Huggins and Kraemer plots.
2. Report the type and size of viscometer used.
3. Calculate the specific, relative and intrinsic viscosities of the polymer.
(ln η rel ) η sp
4. Provide a data table showing c, t0, ts, ηr, ηsp, , and .
c c
5. Plot your data using the Huggins and Kraemer equations and calculate [η], k’ and
k” from your plot. (if the lines do not match up at the intercept, report a separate
[η] for each line.
6. Finally, calculate the viscosity average molecular weight of the polymer using the
Mark-Houwink relationship and K & a values found in the literature (make sure to
reference the K & a vaules). If you are reporting two [η] values, then report the
molecular weight as a range between the two.

This work is licensed under the Creative Commons Attribution-Noncommercial-Share

Alike 3.0 Unported License. To view a copy of this license, visit
http://creativecommons.org/licenses/by-nc-sa/3.0/ or send a letter to Creative Commons,
171 Second Street, Suite 300, San Francisco, California, 94105, USA.

Page 4 of 4