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    Cox Merz

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    The Cox-Merz rule is an empirical relationship that was observed to occur for many polymeric systems, where the steady state shear viscosity plotted against shear rate corresponds to the magnitude of the complex viscosity plotted against angular frequency. The rule states that for polymeric systems, oscillatory measurements can be used to predict steady state viscosity at high shear rates that are difficult to achieve. While there is no complete theoretical basis, some justifications have been proposed. The rule generally holds for polymer melts and concentrated/semi-dilute solutions but not for all systems like dilute solutions or gels. A similar relationship was proposed by Al-Hadithi, Barnes and Walters for predicting normal stress differences from oscillatory data.

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    Cox Merz

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    John
    485 views4 pages
    The Cox-Merz rule is an empirical relationship that was observed to occur for many polymeric systems, where the steady state shear viscosity plotted against shear rate corresponds to the magnitude of the complex viscosity plotted against angular frequency. The rule states that for polymeric systems, oscillatory measurements can be used to predict steady state viscosity at high shear rates that are difficult to achieve. While there is no complete theoretical basis, some justifications have been proposed. The rule generally holds for polymer melts and concentrated/semi-dilute solutions but not for all systems like dilute solutions or gels. A similar relationship was proposed by Al-Hadithi, Barnes and Walters for predicting normal stress differences from oscillatory data.

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    Rheology

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    Cox-Merz

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    The Cox-Merz rule is an empirical relationship that was observed to occur for many polymeric systems, where the steady state shear viscosity plotted against shear rate corresponds to the magnitude of the complex viscosity plotted against angular frequency. The rule states that for polymeric systems, oscillatory measurements can be used to predict steady state viscosity at high shear rates that are difficult to achieve. While there is no complete theoretical basis, some justifications have been proposed. The rule generally holds for polymer melts and concentrated/semi-dilute solutions but not for all systems like dilute solutions or gels. A similar relationship was proposed by Al-Hadithi, Barnes and Walters for predicting normal stress differences from oscillatory data.

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    © All Rights Reserved
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    485 views4 pages

    Cox Merz

    Uploaded by

    John
    The Cox-Merz rule is an empirical relationship that was observed to occur for many polymeric systems, where the steady state shear viscosity plotted against shear rate corresponds to the magnitude of the complex viscosity plotted against angular frequency. The rule states that for polymeric systems, oscillatory measurements can be used to predict steady state viscosity at high shear rates that are difficult to achieve. While there is no complete theoretical basis, some justifications have been proposed. The rule generally holds for polymer melts and concentrated/semi-dilute solutions but not for all systems like dilute solutions or gels. A similar relationship was proposed by Al-Hadithi, Barnes and Walters for predicting normal stress differences from oscillatory data.

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    of 4

    Thermal Analysis & Rheology

    RHEOLOGY APPLICATIONS NOTE

    THE PRINCIPLES AND APPLICATIONS OF THE COX-MERZ RULE


    Principle of the Cox-Merz rule
    The so-called Cox-Merz "rule" is empirical relationship which has been found to be of great use in rheology. It was
    observed by Cox and Merz [1] that for many polymeric systems correspondence occurred between the steady state shear
    viscosity, , plotted against shear rate, & , and the magnitude of the complex viscosity, |*|, plotted against angular
    frequency, . The complex viscosity is defined by:
    * = G* / i

    (1)

    where G* is the complex modulus. So |*| = |G*| /


    Figure 1 shows the procedure for a poly (vinyl alcohol) solution

    Figure 1

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    )UHTXHQF\
    6ZHHS

    

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    VKHDUUDWHVXQDWWDLQDEOHLQIORZ
    
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    RN-14

    Use of the rule


    It is important in the application of the rule to ensure that the appropriate values for ( & ) and |*()| are used. For
    example, in both cases it is the steady state values which are required, i.e. any transient effects due to flow or oscillation
    start-up, inertia, or thixotropy must have fully decayed. Also important is that geometries are used for which the viscosity
    calculation is exact. This normally means cone and plate.
    If applied correctly, the Cox-Merz rule can be of great value in polymer rheology, and there are several circumstances in
    which it might be used.
    (I)

    The principle use is probably to predict ( &) from oscillatory measurements. For many polymeric systems the
    steady state viscosity is difficult to measure at high shear rates, because of sample fracture, secondary flows and
    so forth. Data obtained from oscillatory experiments are usually more reliable.

    (ii)

    The rule can also be used to predict |*()| from steady state viscosity data, for example in circumstances in
    which the oscillatory operating mode is not available.

    (iii)

    The rule can also be used in an analytical sense. A good deal can be learned about the microstructure of
    materials from the degree to which they adhere to the rule.

    Applicability of the rule


    The applicability of the Cox-Merz rule has recently been reviewed in detail [2]. It has been found to hold for almost all
    polymer melts, and concentrated and semi-dilute solutions. Deviations from the rule occur at high frequencies, and the
    oscillatory data can either over- or under estimate the steady state data. Instances of polymeric systems for which it has
    been found not to apply are Boger fluids and certain other dilute solutions, and cross-linked or gelled systems. The rule
    also fails for most particulate dispersions.

    Theoretical basis
    Until very recently it could confidently be stated that no sound theoretical basis for the Cox-Merz rule had yet been
    provided, and indeed some workers felt that the correspondence was merely fortuitous. Recently, however, several,
    admittedly partial, justifications have been offered [3,4].
    A starting point is a requirement of continuum mechanics that the dynamic viscosity and the steady state viscosity are
    related in the low frequency and shear rate limits, i.e.:

    _ 

    & _ 

    (2)

    where () = G()/. In the limit the two experimental modes are effectively identical. This equality can be used as a
    check on the reliability of oscillatory and steady state data.
    The elastic contribution to () disappears in the low frequency limit, and Equation 2 can be rewritten as:

    _ _ 

    & _ 

    (3)

    This sets a limiting condition for the rule. Milner [3] has used the Doi-Edwards reptation model to provide a theoretical
    basis for the rule, but his analysis is partly heuristic, and applies only to polymers with a broad distribution of molecular
    weights.

    The rule of Al-Hadithi, Barnes and Walters


    The usefulness of the Cox-Merz rule has led other authors to seek similar correspondences between other rheological
    functions [2,5]. These include the relationship proposed by Al-Hadithi, Barnes and Walters, who were concerned with the
    prediction of the first normal stress difference, N1, from oscillatory data. A second requirement of continuum mechanics is
    given by Equation 4:

    1  ( & )

    *

    

    (4)

     & 

    & 

    Taking this and Equation 2 as starting points, and after what they described as much trial and error, the authors arrived at
    the expression:
     
     
    *

    * F *

    
    (5)
    
    

    where 0 is the low shear rate limiting viscosity. It is proposed that a plot of Gc. against will coincide with that of N1/2
    against & when plotted on the same axes. Equally Gc against 2 should coincide with N1/2 & 2 plotted against &. Figure 2
    shows the procedure for the poly (dimethyl siloxane) solution.

    Figure 2
    

    

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    The authors suggest that their expression should be applicable to at least those systems for which the Cox-Merz rule
    holds, and provide example of polymeric systems for which this is the case. It is an acknowledged weakness that a value
    for 0 has to be inserted, or at least determined parametrically. In the case above this was arrived at by fitting a Williamson
    model, = 0 / [1 + (K & )m], to the oscillatory data in Figure 1.

    References
    1.

    W.P. Cox and E.H. Merz, Journal of Polymer Science, 28, 619 (1958).

    2.

    T.S.R Al-Hadithi, H.A. Barnes and K.Walters, Colloid and Polymer Science, 270, 40 (1992).

    3.

    S. Milner, Journal of Rheology, 40, 303 (1996).

    4.

    G. Marrucci and G. Ianniruberto, Proceedings of the Royal Society - Unilever - Indo/UK Forum on the Dynamics
    of Complex Fluids, Cambridge, UK, June 1996.

    5.

    H.M. Laun, Journal of Rheology, 30, 459 (1986).

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    TA Instruments Japan K.K.


    Tokyo, Japan
    Telephone: 813-3450-0981
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    Internet: http://www.tainst.com
    RN-14

    Thermal Analysis & Rheology


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