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An equation of state for non-Newtonian fluids

This article has been downloaded from IOPscience. Please scroll down to see the full text article. 1966 Br. J. Appl. Phys. 17 803 (http://iopscience.iop.org/0508-3443/17/6/315) View the table of contents for this issue, or go to the journal homepage for more

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BRIT. J. APPL. PWYS.,

1966, VOL. 17

ation of state for non-Newtonian

A. KAYE Department of Mathematics, Manchester College of Science and Technology
MS. received 3vd February 1966
Abstract, An equation of state for non-Newtonian fluids is suggested which should apply to polymer solutions and melts. It assumes that the polymer molecules form temporary crosslinks in solution and that the lifetimes of these crosslinks are stressdependent. Irrespective of the form of the stress-dependence it is shown that a consequence of the equation of state is that
PU2 X P I I
-P22

where p u ( i , j = 1,2, 3) are the components of the stress tensor in simple shear flow referred to the usual axes. l.:Introduction Lodge (1956, 1964) has suggested the following equation of state for an incompressible material

where pij are the rectangular Cartesian coordinates of the stress tensor, p is the magnitude of the isotropic stress, xi and x i are the rectangular Cartesian coordinates of a typical particle at times t and t respectively, Tis the absolute temperature and k is Boltzmanms constant. S is a numerical constant approximately equal to 2, and N ( t - t, T ) is a function of t - t and T which depends on the material in question. This equation of state was derived from that of a material which obeys the kinetic theory of rubber elasticity (Treloar 1958) by assuming, inter alia, that the cross links of that theory are time-dependent in the sense that they break and reform but the total number remains constant-thus the equation of state should describe a material which contains long molecular chains with temporary crosslinks. A comparison with the rheory of rcibber elasticity enables a physical interpretation of S and N ( t - t, T ) to be given: N ( t - t, T ) dt is the nnmber of crosslinks and SN(t - t, T ) dt the number of chain segments per unit volume which are formed or join the network at the time t in an interval of time dt and still remain joined to the network at time t. This equation of state gives a good qualitative description of the properties of polymer solutions and melts but does not give a quantitative description; for example, it predicts a stress-independent viscosity. One assumption made in Lodges theory is that the rate of breakage of crosslinks does not depend on the stress. Not only is this physically unlikely but leads directly to a viscosity independent of shear rate. It is the purpose of this paper to devise an equation of state, similar to that of Lodge, in which the rate of breakage of crosslinks is stress-dependent.
2. The equation of state

We consider a special form of Lodges equation of state. Consider a number of crosslinks A,dt which are formed at time t in an interval of time dt. At time t let the number of these crosslinks which remain unbroken be Adt. The rate of breakage of these cross803

804

A . Kaye

links, (dA/dt) dt, will in Lodges theory be a function of t - t and A ; we only consider a special case in which the rate of breakage is proportional to Adt, that is

This is, of course, the physically reasonable assumption that the rate of breakage is proportional to the number left. Noting that when t = t, A = A,, we find
A ( t ) = Aoe-t@-t) (3) where A ( t ) dt is the number of crosslinks still unbroken at time t of the group A,dt which were formed in the interval of time dt at time t. That is, we may take
A ( t ) = N ( t - t, T ) (4) if A refers to unit volume. Now, if the total number of crosslinks in the network at time t is No,this will be given by

No=
f=

N ( t - t, T ) dt =
03

A,,-k(t-t)

A dt = 0 k

(5)

tf=-03

Hence
N(t
-

t, T ) = kNoe-k(t-t)

(6)

where of course k and N o may be functions of T. Let us now assume that the rate of breakage depends not only on A but also on the stress. Since the rate of breakage is a scalar we must take dA/dt as a function of the invariants of the stress. Moreover, since the material we are considering may be assumed to be incompressible these invariants should be independent of the magnitude of the isotropic stress. It is shown in the Appendix that the two such invariants are Q 1 = PI2- 3Pz Q2 = 2?,S - 9?l?2 f 273, where
(7)

P I =a = lPaa

(9)

P, = det pap.
Hence we may take

where g is some function of Q1 and Q z which specifies how the rate of breakage of crosslinks depends on stress and g*(t) is that function oft which is equal to g ( Ql, 0,) when the stress invariants are evaluated at time I. Integrating we find
t = t

A ( t ) = A. exp (f

j g*(t) dt).
t

At time t the rate of breakage of crosslinks per unit volume is g*(t)No since by hypothesis the rate of breakage is independent of the time of formation and is proportional to the number of crosslinks. Since we also assume that the rate of breakage is equal to the rate of formation, the number formed at time t in an interval dt, A&, is given by g*(t)N,dt. Hence
t

~ ( tt,, T ) = g * ( ( t ) ~exp , (I

g*(t> d i t ) .

(14)

An equation of state for non-Newtonian fluids

805

N ( t , t', T ) dt' is the number of crosslinks which were formed in time dt' at time t' and are still unbroken at time t. N ( t , t', T ) is now not necessarily a function of t - t'. By an argument similar to that of Lodge we now arrive at an equation of state for a materia1 with stress-dependent crosslinks
t
t

The consequences of this equation in steady shear flow are now examined.

3. Steady shear flaw Choosing the xl axis parallel to the streamlines and the x2 axis normal to the shearing planes, the state of flow in steady shear flow may be defined by the equations
XI

= XI'

+ G(t - t') xZ'

xz = Xg' x3 = x ;

where G is the shear rate. NOW,since the flow is steady, the components of the stress pij will be constant and hence g will be independent of time. Thus, inserting equations (16) (17) and (18) into (15) we find that
PI1 - P22
= (SkT2No/g2)G2

(19)

Pnn - P33 = 0
= (SkT Nolg)
Y13

=P 2 8 = 0

where g is a function of the invariants of pij. The invariants of pij, Q1and Q 2 ,are given in the present case by

where g = g ( Q i , (22). If g were known as a function of Qland Q 2 then these equations would enable g to be found as a function of G, and hence the variation of p l l - p z 2 and plz with G could be found. Now it is physically reasonable that the rate of breakage of crosslinks should increase with stress. Hence the form of g ( Q 1 , Q,) should be such that g does not fall with Q, and Q2whatever values the pij take. Ql is easily proved to be a non-negative function of the stress components ; hence g=g+PQi where a and /3 are positive constants, certainly meets this requirement and gives a viscosity (7 = p12/G)which falls with increasing shear rate. Again, from equations (19)-(22)) we see at once that S~kTNOCpl, - Pzz) = P l 2 and hence, irrespective of the form of the stress-dependence of the crosslink lifetime for a given material, p I z 2should be proportional to p l , - p n 2 .

806

A . Kaye

This conjecture has been discussed in the literature from a different point of view. The quantity s where
S=
PI1

-P22
P12

has been called the 'recoverable shear' and the variation of s with p12 has been considered. Various workers have reported a linear relation between s and p12 and hence pI1 - p z z proportional to pl:. Philippoff, Brodnyan and Gaskins (1957) have found such a relation for low concentrations of polyisobutylene in dekalin, and Kotaka, Kurata and Tamura (1959, 1462) for polystyrene in toluene and dekalin. Yamomoto (1958) has considered the dependence of crosslink lifetimes on chain length and number of chain segments and has also, by a semi-quantitative argument, arrived at the conclusion that pll - p 2 ?should be proportional to p l r 2 for Gaussian chains.
Acknowledgments The author wishes to thank Dr. A. B. Tayler for many useful discussions. Part of this work was carried out at the College of Aeronautics, Cranfield. Appendix Let

pij' = p6ij f ~ i j (All and let Plr:P2', P3' be the invariants of pij', defined in a manner similar to the definitions given in equations (9), (10) and (11). Consider the second-order invariant

and hence, if then

3a' f p' = 0
Q1 = (P: - 3P2) is independent of p .

Similarly by considering the third-order invariant

- 2 -0 a ' P1'3 - prPz'Pl' f YIP,'

we find that

Q2 = 2P13 - gPLP2t 27P3

and is also independent of p .
References KOTAKA, T., KURATA, M., and TAMURA, M., 1959, J. Appl. Phys., 30, 1705-12.

-1962, Rheol. Acta., 2, 179-86.

LODGE, A. S . , 1956, Trans. Faraday, Soc., 52, 120-30. - 1964, Elastic Liquids (London : Academic Press). ~ I P P O F F w., , BRODhrYAN, J. G., and GASKINS, F. H., 1957, Trans. Soc. Rheol., 1, 109-18. TRELOAR, L. R. G., 1958, The Physics of Rubber Elasticity, 2nd edn (Oxford: Clarendon Press). YAMOMOTO, M., 1958, J.Phys. Soc. Japan, 13, 1200-11.