10/12/2019 Viscosity of Polymer Solutions

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POLYMER PHYSICS VISCOSITY OF POLYMER SOLUTIONS SUMMARY

RELATED TOPICS: PART I: INTRINSIC VISCOSITY OF DILUTE SOLUTIONS INTRINSIC VISCOS

Reptation and Tube Model is a measure for the int

High molecular weight polymers greatly increase the viscosity of liquids in which
in polymer solutions at
Viscosity Average Molecular they are dissolved. The increase in viscosity is caused by strong internal friction
Weight zero polymer concentra
between the randomly coiled and swollen macromolecules and the surrounding
this quantity describes
solvent molecules. How much a polymer increases the viscosity of a solvent will
Viscosity of Polymer Melts completely separated p
depend on both the nature of the polymer and solvent.
chains on the solution v
Melt Flow Index
Three important quantities frequently encountered in the field of polymer solution
rheology are the relative viscosity, the specific and reduced specific viscosity. These
quantities are defined as follows: MARK-HOUWINK R
B A C K TO INDE X
The viscosity of very di
ηrel = η / ηS
solutions can be descr

ηsp = (η - ηS) / ηS = ηrel - 1 simple power law, know

LINKS: Mark-Houwink relation

ηred = ηsp / c = (ηrel - 1) / c

P O LY ME R V I S C O SI T Y
where η is the viscosity of the solution, ηS that of the solvent and c is the polymer The Mark-Houwink par
concentration, usually expressed in grams per 100 cm³ or in grams per cm³. Another be determined from a d
important quantity in very dilute solutions at vanishing shear rate is the intrinsic logaritmic plot of intrins
RHEOMETER
viscosity (also called limiting viscosity number) which is defined as versus molecular weigh
SUPPLIERS
yields straight lines.
TA Instruments
Brookfield

[η] describes the increase in viscosity of individual polymer chains. Assuming the GEL PERMEATION
CHROMATOGRAPH
polymers are spherical impenetrable particles, the increase in viscosity can be
MARK-HOUWINK
CONSTANTS calculated with Einstein's viscosity relationship: is frequently used to m
molecular weight distrib
TA B L E η = ηS (1 + 5/2 φp)
polymer sample. The re
time of a polymer in a G
or
is directly proportional
ηsp = 5/2 φp = 2.5 Np vh / V = 2.5 NA c vh / M Thus a GPC seperates
polymers by their hydro
where Np / V is the number of particles per unit volume, vh the hydrodynamic volume volume.
of a polymer particle and M its molecular weight. The hydrodynamic volume of a
particle can be rewritten as follows
A GPC chromatogram
vh / M = 4/3 · π · (Rh2 / M)3/2 M1/2
molecular weight distrib
polymer sample becau
Then the specific viscosity of a very dilute solution reads

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10/12/2019 Viscosity of Polymer Solutions

[η] = (10 π / 3) NA (Rh,02 / M)3/2 M1/2 hydrodynamic volume

particle is directly relate
This and similar expressions for other particle geometries can be found in many text molecular weight.
books.1 In the case of dissolved, soft polymer particles, Einsteins relation has to be
modifed. It has been shown that the equation is still applicable to dissolved polymers
if the hard sphere radius is replaced by the hydrodynamic radius of the polymer coil.
Then the equation can be rewritten in the form

[η] = k NA (⟨Rh,02⟩ / M)3/2 M1/2αh3 = Φ (⟨Rh,02⟩ / M)3/2 M1/2αh3

where αh = Rh / Rh,0 is the expansion of a polymer coil in a good solvent over that of

one in θ-solvent and Rh,0 is the radius of an unperturbed polymer. The equation is

known as the Flory-Fox equation.9 Under θ-conditions it simplifies to

[η]θ = Φθ ⟨Rh,02⟩3/2 / M

The constant Φθ has a value of about 4.2·1024 for rigid spherical particles if [η] is

expressed as a function of the radius of gyration.1,7 If the intrinsic viscosity is

measured in both a very dilute θ-solvent and in a "good" solvent, the expansion can

be directly estimated:5

αh3 = [η] / [η]θ

The values of αh typically vary between unity for a θ-solvent to about three for very

good solvents increasing with molecular weight.

Both 〈Rh,02〉 and αh can be expressed as a function of molecular weight M:

〈Rh,02⟩1/2 = C1 (M / M0)1/2; 〈Rh2⟩1/2 = C1 (M / M0)ν

αh = (vh / vh,0)1/3 = C2 (M / M0)(ν - 1/2)

where C1 and C2 are constants, M0 is the molar mass of a monomer and ν is a

scaling exponent. The value of ν depends on the solvent-polymer system and its
temperature. For example, under θ-conditions the scaling exponent has the value ν
= 1/2 and in a good solvent ν = 3/5. With these expressions, the equation for the
intrinsic viscosity can be written in the form

[η] = K M(3ν - 1) = K Ma

K = const M0-3ν

This equation is known as the Mark-Howink or Mark-Howink-Staudinger equation2-4,

where K has the dimensions cm³/g x (g/mol)a. Mark-Houwink parameters have been

tabulated for a large number of polymer-solvent systems in standard references.6

These parameters are usually determined from a double logaritmic plot of intrinsic
viscosity versus molecular weight:

ln [η] = ln K + a ln M

INTRINSIC VISCOSITY VERSUS MOLECULAR WEIGHT

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10/12/2019 Viscosity of Polymer Solutions

Example:

0.1 g of atactic polystyrene of unknown molecular weight is dissolved in 100 ml

benzene. The Mark-Houwink parameters of this system are a = 0.73 and K = 11.5

10-3. To estimate the molecular weight, the viscosity of both the solvent and the
solution have to be measured. A measurement with an Ubbelohde capillary
viscometer yields following results:

Pure benzene: 100 sec.

Polystyrene solution: 160 sec.

The viscosity is given by

ηrel = η / ηS = 160 / 100 = 1.6

ηsp = ηrel - 1 = 0.6

ηred = ηsp / c = 0.6 / 0.001 g/ml = 600 ml/g

Assuming the concentration is sufficiently close to zero so that [η] ≈ 6.0 102 ml/g, the
molecular weight can be estimated with the the Mark-Houwink relation:

[η] = K Ma

600 = 11.5 10-3 M0.73 ⇒ M = 2.9 106 g/mol

References

1. M.D. Lechner, K. Gehrke and E.H. Nordmeier, Makromolekulare Chemie, Birkhaeuser, Basel
1993
2. H. Mark, in R. Saenger, Der feste Koerper, Hirzel, Leipzig, 1938
3. R. Houwink , J. Prakt. Chem., Vol. 157, Issue 1-3, p. 15 (1940)
4. H. Staudinger, Die Hochmolekulare Organischen Verbindungen, Julius Springer, Berlin 1932
5. H.K. Mahabadi, and A. Rudin, Poly. J., Vol. 11, No.2, pp 123-131 (1979)
6. J. Brandup, E.H. Immergut, and E.A. Grulke, Polymer Handbook, 4th ed., Wiley, New York 1999

7. The ratio Rh / Rg is typically in the range 0.65 - 0.75.8

8. L.J. Fetters, J.S. Lindner, and J.W. Mays, J. Phys. Chem. Ref. Data, Vol. 23, No. 4 (1994)
9. T.G. Fox, P.J. Flory, J. Am. Chem. Soc., 73, 1904-1908 (1951)

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