Viscous

Models for Liquids:

Temperature Dependence
Brian G. Higgins
Department of Chemical Engineering and
Materials Science
University of California, Davis

(DraF, 2014)

Temperature Dependence of Viscosity:

For historical perspec.ve of how the empirical viscosity
formula developed to account for the eect of
temperature, can be gleaned from the monograph
A. E. Dunstan and F. B. Thole, The viscosity of Liquids,
Longmans, Green and Co, New York, 1914

In this book the reader can get a perspec.ve of how the

empirical viscosity formula developed to account for the
eect of temperature.

The notable researchers at the .me were Poiseuille,

SloNe, Graetz

Temperature Dependence of Viscosity:

Early Models

Poiseuille (1840):

He proposed a formula for the varia.on in viscosity as a func.on of

temperature similar to that of density

0
=
1 + T + T 2

= constant coefficients

T = temperature in degrees Celsius

0 = absolute viscosity at 0

SloNe (1881,1892):
He proposed a formula with three constants:

c
=
(a + T )n

Graetz (1888):
He proposed the formula

A( T )
(T T1 )

in which is the cri.cal temperature, T 1 a temperature (in C)

below the mel.ng point where the viscosity is innite

Arrhenius Dependence: The Early Scouts

E. C. Andrade
In 1889 Arrhenius expressed an equa.on for temperature
dependent chemical reac.on rates.

k = k0 exp[ E/RT ]

Since then, many temperature dependent chemical and physical

processes have been found to behave in accordance with
Arrhenius-like equa.ons.
Arrhenius dependence for viscosity is aNributed to de Guzman in
1913, but popularized by Andrade in 1930, some 20 years later

= 0 exp[B/T ]

J. de Guzman, Anales de la Sociedad Espanola de Fisica y Quimica, 1913,11,353.
Andrade, Enda C. "Viscosity of liquids." Nature 125.3148 (1930): 309-310
Andrade, E. D. C. (1934). LVIII. A theory of the viscosity of liquids-Part II. The
London, Edinburgh, and Dublin Philosophical Magazine and Journal of Science,
17(113), 698-732.

Arrhenius Dependence: The Early Scouts:

C. V. Raman
(C. V. Raman, "A theory of the viscosity of liquids", Nature (London) 111 532-533 (1923))

Before Andrades work, the Nobel Prize Physicist Raman proposes an

Arrhenius law for viscosity.
He starts by consider only binary encounters between molecules, and
then applies the Boltzmann's distribu.on law to dierent aggregates of
molecules.
He also draws on the work of Sutherland and Chapman (of Chapman-
Enskog fame).
He takes benzene viscosity data (from Thorpe and Rodgers) as an example
and applies his formula

= A exp(B/T )

Raman notes that the constants A and B cannot be directly related to the
parameters in the Boltzmann distribu.on, but are sugges.ve of the
exponen.al form.

Arrhenius Dependence: The early Scouts:

A. G. Ward
(A. G. Ward, "The viscosity of Pure Liquids",
Transac.ons of the Faraday Society,1937, 33, pp. 88-97 )

The American scien.st A. G. Ward independently derived

Arrhenius law for viscosity, and was about to publish his
ndings when he heard of the work of Andrade.
His formula for viscosity was

= A exp(B/R T )
Ward also suggests that the constants A and B can
depend on temperature
In his paper he gives a list of references that explore the
Arrhenius behavior, including work by Raman 1923;
Frenkel 1926; Andrade 1930,1931,1934; Sheppard 1930;
Eyring 1936;

Viscosity Dependence on
Temperature: Data
The next couple of slides show some data on
the viscosity dependence on temperature for
small molecules

Viscosity of Small Molecules

(Davies & Matheson, Trans.Faraday Soc., 1967)

CH2 I2
CHCl3

poise

D2 O

HF

H2 O

CH3 Cl

TiBr4
MelTng point

Br2

NH3

HCN
K

Arrhenius Viscosity:

log = A + E/R T

T increasing

Viscosity of Large Molecules

(Davies & Matheson, Trans.Faraday Soc., 1967)

cyclohexane

cyclopentane
C(NO2 )4
(CH3 )3 Cl

C 2 H6
C(CH3 )4

C 2 H4
CH3 CCl3

T increasing

Arrhenius Viscosity:

log = A + E/R T

Viscosity of Polymers: Overview

(Abstracted from : Polymer and Composite Rheology, R.K. Gupta, 1977)

A polymer, whether amorphous or crystalline, is a hard briNle, glassy solid at low

temperature.
At suciently high temperature, an un-cross-linked polymer turns into a viscous
liquid.
The transi.on between these two states is not sharp; there is an intermediate
rubbery stage in which the material behaves like an elastomer, or as an elas.c
solid.
The temperature at which a hard glassy polymer becomes rubbery material is
called the glass transi.on temperature, Tg.
The rubbery region extends over a signicant temperature range because ow is
hampered by the presence of polymer chain entanglements that act like
temporary crosslinks.
The glass transi.on temperature is interpreted as the temperature below which
only the vibra.onal mo.on of atoms, or short coopera.ve mo.on of a small
collec.on of atoms, can take place.
Above Tg the magnitude of the shear viscosity is dependent on the availability of
free volume, which on a microscopic level is that part of the sample volume not
actually preoccupied by polymer molecules.

Viscosity Models for Polymer Melts

Williams, Landel & Ferris Model (WLF):

The WLF equa.on is found to be applicable to all polymers in a temperature range

Tg < T < Tg + 100K

For temperatures far above the glass transi.on temperature or mel.ng point for
crystalline polymers, there is ample free volume available, and the temperature
dependence of the zero shear viscosity is determined by energy barriers to mo.on.

Arrhenius or Andrade Model:

Vogel-Tamann-Fulcher Model:

= 0 exp

B
T

T0

Andrade or Arrhenius EquaTon for Polymers

AcTvaTon Energy

Gas Constant

Temperature (K)

Thus a rise in temperature for polypropylene from 300K to 310K, result

in a decrease is viscosity by

(300)/(310) = 1.67
Data from: Gupta, Polymer Composite Rheology, 1977

Tg- scaled Arrhenius Plot

(Liu, He, Keunings & Bailly, Macromolecules, 39, 8867 2006)

Tg

Temperature increasing

Viscosity of Polystyrene Melts

(Eect of molecular weight)
(from StraNon, JCIS, 1966)

Polymer melts are oFen shear thinning!

Carreau Model

= 0 [1 + ( )2 ](n

1)/2