Revista de Chimie, 2005: 56(2), 173-176.

BASIC PHENOMENOLOGICAL MODELLING OF RHEOLOGICAL BEHAVIOUR OF TERNARY PHASE IN PHASE POLYMER COMPOSITE SYSTEMS. II. UNIFORM STRESS APPROACH Horia PAVEN, Chemical Research Institute-ICECHIM, Bucuresti, Splaiul Independentei, nr. 202 (htopaven@netscape.net)

Aiming at to reveal the intrinsic peculiarities of phenomenological principles of modelling ternary phase in phase composite systems with linear viscoelastic polymeric components, the second basic case of uniform stress approximation is considered. In the proposed approach the rheological behaviour laws-selection rules-mixing rules hierarchical path is followed, the Reuss-like morpho-rheological interactions underlying the form of the dependence of composite rheological variables on those of component ones. The resulting selection rules and the corresponding quantitative and qualitative effects, as well as the primary mixing rules for rheological parameters, are pointed out and illustrated for distinct cases of mono- and bi-relaxant (retardant) rheological behaviour cases. Keywords: Rheological phenomenology, linear viscoelastic behaviour, ternary phase in phase composite systems, polymer components, uniform stress modelling.

Extensive industrial demands on new materials such as high polymers and polymeric based composite systems are to be emphasized, with particular attention to sensitive questions about the modelling, numerical analysis and characterization of the effective response of materials /1-7/. Given the intricate spectrum of morpho-rheological interactions in polymeric composite systems, i.e., the morphologically controlled dependence of composite rheological variables on those of components, the natural need to model and analyze the intrinsic manner in which the mixing rules for the rheological quantities in the framework of linear viscoelastic behaviour is becoming growing imperative from both academic and engineering technics standpoint /8-10/.

Accordingly, in addition to the earlier presented case of Voigt-like, uniform deformation approach, that of Reuss-like, uniform stress one, is considered /11/.

Basic [3R] inter-relationships Let a / b / c the ternary phase in phase composite system with a, b and c linear viscoelastic components in the {a}, {b} and {c} rheological states, respectively, given by the corresponding rheological equations Pa a = Qa a Pb b = Qb b Pc c = Qc c where the component rheological operators are defined as (2.1) (2.2) (2.3)

Pa = p0,a + p1,a D + p 2,a D 2 + ... + p ma ,a D ma Qa = q0,a + q1,a D + q 2,a D 2 + ... + q na ,a D na Pb = p0,b + p1,b D + p 2,b D 2 + ... + p mb ,b D mb Qb = q0,b + q1,b D + q 2,b D 2 + ... + q nb ,b D nb Pc = p0,c + p1,c D + p 2,c D 2 + ... + p mc ,c D mc Qc = q0,c + q1,c D + q 2,c D 2 + ... + q nc ,c D nc

(2.1.1) (2.1.2)

(2.2.1) (2.2.2)

(2.3.1) (2.3.2)

and a , a ; b , b ; c , c represent the component natural rheological variables - the stress and strain, respectively, and Dk = dk/dtk is the k-th order time derivative. In the case of Reuss-like, uniform stress, composite model, the [3R] basic morphorheological interaction, i.e., the [3R] morphologically controlled interaction of component rheological states, can be given symbolically in the form
3R {a} + {b} + {c} [] {a / b / c}[3R] 3R (ma, na) + (mb, nb) + (mc, nc) [] (m[3R], n[3R])

(2.4.1.1) (2.4.1.2)

As a direct consequence of the relationships between the composite and component characteristic rheological variables

[3R ] = a = b = c

(2.4.2.1) (2.4.2.2)

[ 3 R ] = v a a + vb b + v c c

where [ 3 R ] , [ 3 R ] are the [3R] model composite rheological variables, and v a , vb , vc depict the component volume fractions, (v a + vb + vc = 1) , the corresponding [3R] rheological equation, which express the [3R] model composite behaviour law, is
P[ 3 R ] = Q[ 3 R ]

(2.5)

the composite rheological operators being given in terms of those of components as

P[ 3 R ] = v a Pa Qb Qc + vb Pb Qa Qc + v c Pc Qa Qb Q[ 3 R ] = Qa Qb Qc

(2.6.1) (2.6.2)

Accordingly, the [3R] selection rules are given in the form

m[ 3 R ] = Ord.{Q[3R]} = max ( ma + nb + nc ,

mb + n a + nc , mc + n a + n b ) n[ 3 R ] = Ord.{P[3R]} = n a + nb + nc and the morpho-rheological interaction parameters are presented in table 2.1

(2.7.1) (2.7.2)

------------------------------------------------------------------------Table 2.1 [3V] morpho-rheological interaction parameters --------------------------------------------------------------------------

Furthermore, the corresponding [3R] specific mixing rules for the viscoelastic moduli are, in the case of complex moduli,
* * 1 / M [*3 R ] = va / M a + vb / M b + vc / M c*

(2.8)

whereas for storage- and loss- modulus yield

* * M [3 R ] = {v a M a / M a + vb M b / M b + v c M c / M c* } / X 2

(2.8.1.1) (2.8.1.2)

* * M [ R ] = {v a M a / M a + vb M b / M b + v c M c / M c* } / X 2 3

and
* * X = {v a [ M a / M a + vb M b / M b + vc M c / M c* ]2 + * * + [v a M a / M a + vb M b / M b + vc M c / M c* ] 2 }1 / 2 2 2 2 2 2 2

(2.8.2)

[3R] morpho-rheological effects

Aiming at to illustrate the different quantitative and qualitative forms of [3R] morphorheological effects, one consider for components three simple rheological models, e.g., - Hooke model: {1}: (m = 0, n = 0), P{1} = p 0,r , Q{1} = q 0, r ; r = 1, 2, 3; - Kelvin-Voigt model: {2}: (m = 0, n = 1), P{2} = p 0,r , Q{2} = q 0, r + q1,r D ; r = 1, 2, 3; - Poynting-Thomson-Zener model: {3}: (m = 1, n = 1), P{3} = p 0, r + p1,r D , Q{3} = q 0,r + q1,r D ; r = 1, 2, 3; the results being presented in table 2.2. --------------------------------------------------------------Table 2.2 [3V] morpho-rheological effects --------------------------------------------------------------

It is useful to point out that given the typical symmetrical form of composite rheological operators from the standpoint of component permutation, a well defined invariance property arise. Moreover, significant consequences are observed from the point of view of morpho-rheological effects, as follows. Firstly, it appears that there are well defined cases in which the composites have the same rheological state, i.e., they are of the same rheological potential:

- {1} rheological state, for the {1}/{1}/{1} composite; - {2} forbidden rheological state ; - {3}rheological state, for {1}/{1}/{2}, {1}/{1}/{3} , {1}/{2}/{1}, {1}/{3}/{1}, {2}/{1}/{1} and {3}/{1}/{1} composite; - {4} forbidden rheological state; - {5}, for {1}/{2}/{2}, {1}/{2}/{3}, {1}/{3}/{2},{1}/{3}/{3}, {2}/{1}/{2}, {2}/{1}/{3}, {2}/{2}/{1}, {2}/{3}/{1}, {3}/{1}/{2}, {3}/{1}/{3}, {3}/{2}/{1} and {3}/{3}/{1} composite; - {6}, for {2}/{2}/{2}; - {7} rheological state, for {2}/{2}/{3}, {2}/{3}/{2}, {2}/{3}/{3}, {3}/{2}/{2}, {3}/{2}/{3}, {3}/{3}/{2} and {3}/{3}/{3} composite systems. Secondly, it is possible that the rheological order of the composite rheological equation to be equal to that of the highest component one, typical quantitative morpho-rheological effects resulting as follows: - {1} rheological state, for {1}/{1}/{1}; - {3}, for {1}/{1}/{3}, {1}/{3}/{1} and {3}/{1}/{1}model composites. Finally, well defined qualitative morpho-rheological effects arise, when the rheological order of composite is higher than those of all components: - {3} rheological state, for {1}/{1}/{2}, {1}/{2}/{1} and {2}/{1}/{1}; - {5}, for {1}/{2}/{2}, {1}/{2}/{3}, {1}/{3}/{2}, {1}/{3}/{3}, {2}/{1}/{2}, {2}/{1}/{3}, {2}/{2}/{1}, {2}/{3}/{1}, {3}/{1}/{2}, {3}/{1}/{3}, {3}/{2}/{1} and {3}/{3}/{1}composite systems; - {6}, for {2}/{2}/{2}; - {7} rheological state, for {2}/{2}/{3}; {2}/{3}/{2}, {2}/{3}/{3}, {3}/{2}/{2}, {3}/{2}/{3}, {3}/{3}/{2} and {3}/{3}/{3} composites.

[3R] primary mixing rules

Aiming at to exemplify the way in which the composite rheological parameters are obtained, as a direct consequence of behaviour law, in terms of the component rheological parameters and composition, two specific situations are taken into account for the components: - the (1, 1) - rheological model, i.e. the mono-relaxant (retardant) , and

- the (2, 2) - rheological model of bi-relaxant (retardant) behaviour.

In the first case, of (1, 1) components, the corresponding rheological operators are
Pa = p 0,a + p1,a D , Pb = p 0,b + p1,b D , Pc = p 0,c + p1,c D , Qa = q 0,a + q1,a D Qb = q 0,b + q1,b D Qc = q 0,c + q1,c D

(2.9.1) (2.9.2) (2.9.3)

and the composite rheological operators are given by

P[3 R ] = p0 + p1 D + p 2 D 2 + p3 D 3 Q[3 R ] = q0 + q1 D + q 2 D 2 + q3 D 3
where the resulting rheological parameters are
p 0 p 0,[ 3 R ] = v a p 0,a q 0,b q 0,c + vb p 0,b q 0, a q 0,c + v c p 0,c q 0,a q 0,b

(2.10.1) (2.10.2)

(2.10.1.1)

p1 p1,[ 3 R ] = v a [ p 0 , a ( q 0 ,b q1,c + q 0 ,c q1,b ) + p1, a q 0 ,b q 0 ,c ] + + v b [ p 0 ,b ( q 0 , a q1,c + q 0 ,c q1, a ) + p1,b q 0 , a q 0 ,c ] + + v c [ p 0 ,c ( q 0 , a q1,b + q 0 ,b q1, a ) + p1,c q 0 , a q 0 ,b ]
p2 p2,[3R ] = va [ p0,a q1,b q1,c + p1,a (q0,b q1,c + q0,c q1,b )] + + vb [ p0,b q1,a q1,c + p1,b (q0,a q1,c + q0,c q1,a )] + + vc [ p0,c q1,a q1,b + p1,c (q0,a q1,b + q0,b q1,a )] p 3 p 3 ,[ 3 R ] = v a p 1, a q 1,b q 1, c + v b p 1,b q 1, a q 1, c + v c p 1, c q 1, a q 1,b

(2.10.1.2)

(2.10.1.3)

(2.10.1.4)

and
q 0 q 0,[ 3 R ] = q 0,a q 0,b q 0,c q1 q1,[3 R ] = q 0,a (q 0,b q1,c + q 0,c q1,b ) + q 0,b q 0,c q1,a q 2 q 2,[ 3 R ] = q 0, a q1,b q1,c + ( q 0,b q1,c + q 0,c q1,b ) q1, a q 3 q 3,[ 3 R ] = q1,a q1,b q1,c

(2.10.2.1) (2.10.2.2) (2.10.2.3) (2.10.2.4)

In the second case, of (2, 2) components, the rheological operators are defined as

Pa = p0,a + p1,a D + p 2,a D 2 , Pb = p0,b + p1,b D + p 2,b D 2 , Pc = p0,c + p1,c D + p 2,c D 2 ,

Qa = q0,a + q1,a D + q 2,a D 2 Qb = q0,b + q1,b D + q 2,b D 2 Qc = q0,c + q1,c D + q 2,c D 2

(2.11.1) (2.11.2) (2.11.3)

the resulting composite rheological operators are

P[3 R ] = p0 + p1 D + p 2 D 2 + p3 D 3 + p 4 D 2 + p5 D 5 + p6 D 6 Q[3 R ] = q0 + q1 D + q 2 D 2 + q3 D 3 + q 4 D 2 + q5 D 5 + q6 D 6
where
p 0 p 0,[3 R ] = v a p 0,a q 0,b q 0,c + vb p 0,b q 0,a q 0,c + v c p 0,c q 0,a q 0,b

(2.12.1) (2.12.2)

(2.12.1.1)

p1 p1,[ 3 R ] = v a [ p 0,a (q 0,b q1,c + q 0,c q1,b ) + p1,a q0,b q 0,c ] + + vb [ p 0,b (q 0,a q1,c + q0,c q1,a ) + p1,b q 0,a q 0,c ] + + vc [ p o ,c (q 0,a q1,b + q 0,b q1,a ) + p1,c q 0,a q 0,b ]
p 2 p 2,[ 3 R ] = v a [ p 0, a (q0,b q 2,c + q1,b q 1,c + q 0,c q 2,b ) + + p1,a (q 0,b q1,c + q 0,c q1,b ) + p 2,a q 0,b q 0,c ] + + vb [ p 0,b (q 0,a q 2,c + q1,a q1,c + q 0,c q 2,a ) + + p1,b (q 0,a q1,c + q 0,c q1,a ) + p 2,b q 0,a q 0,c ] + + vc [ p 0,c (q 0,a q 2,b + q1,a q1,b + q 0,b q 2,a ) + + p1,c (q0,a q1,b + q 0,b q1,a ) + p 2,c q 0,a q 0,b ]
p3 p3.[3 R ] =v a [ p 0,a (q1,b q 2,c + q 2,b q1,c ) + + p1,a (q 0,b q 2,c + q1,b q1,c + q 0,c q 2,b ) + + p 2,a (q 0,b q1,c + q 0,c q1,b )] + + vb [ p 0,b (q1,a q 2,c + q 2,a q1,c ) + + p1,b (q0,a q 2,c + q1,a q1,c + q0,c q 2,a ) + + p 2,b (q 0,a q1,c + q 0,c q1,a )] + + vc [ p0,c (q1,a q 2,b + q 2,a q1,b ) + + p1,c (q 0,a q 2,b + q1,a q1,b + q 0,b q 2,a ) + + p 2,c (q 0,a q1,b + q 0,b q1,a )] (2.12.1.4)

(2.12.1.2)

(2.12.1.3)

p 4 p 4,[3 R ] = v a [ p 0,a q 2,b q 2,c + p1,a (q1,b q 2,c + q 2,b q1,c ) + + p 2,a (q 0,b q 2,c + q1,b q1,c + q 0,c q 2,b )] + + vb [ p 0,b q 2,a q 2,c + p1,b (q1,a q 2,c + q 2,a q1,c ) + + p 2,b (q0,a q 2,c + q1,a q1,c + q 0,c q 2,a )] + + vc [ p 0,c q 2,a q 2,b + p1,c (q1,a q 2,b + q1,b q 2,a ) + + p 2,c (q0,a q 2,b + q1,a q1,b + q0,b q 2,a )] p 5 p5,[3 R ] = v a [ p1,a q 2,b q 2,c + p 2,a (q1,b q 2,c + q1,c q 2,b )] + + vb [ p1,b q 2,a q 2,c + p 2,b (q1,a q 2,c + q1,c q 2,a )] + + v c [ p1,c q 2,a q 2,b + p 2,c (q1,a q 2,b + q1,b q 2,a )]
p 6 p 6,[3 R ] = v a p 2, a q 2,b q 2,c + vb p 2,b q 2,a q 2,c + v c p 2,c q 2,a q 2,b

(2.12.1.5)

(2.12.1.6)

(2.12.1.7)

and
q 0 q 0,[ 3 R ] = q 0,a q 0,b q 0,c q1 q1,[3 R ] = q 0,a q 0,b q1,c + ( q 0,a q1,b + q 0,b q1,a ) q 0,c

(2.12.2.1) (2.12.2.2) (2.12.2.3)

q 2 q 2,[3 R ] = q 0,a q 0,b q 2,c + (q 0,a q1,b + q 0,b q1,a )q1,c + + (q0,a q 2,b + q1,a q1,b + q 0,b q 2,a )q 0,c
q3 q3,[ 3 R ] = (q 0,a q1,b + q 0,b q1,a )q 2,c + + (q 0,a q 2,b + q1,a q1,b + q 0,b q 2,a )q1,c + + (q1,a q 2,b + q1,b q 2,a )q 0,c

(2.12.2.4)

q 4 q 4,[3 R ] = (q0,a q 2,b + q1,a q1,b + q 0,b q 2,a )q 2,c + + (q1,a q 2,b + q1,b q 2,a )q1,c + q 2,a q 2,b q 0,c
q 5 q 5,[ 3 R ] = ( q1,a q 2,b + q1,b q 2, a ) q 2,c + q1,c q 2, a q 2,b q 6 q 6,[ 3 R ] = q 2,a q 2,b q 2,c

(2.12.2.5)

(2.12.2.6) (2.12.2.7)

are the composite rheological parameters in terms of component ones. It is useful to draw attention on the fact that, as a consequence of inner logic of [3R] morpho-rheological interactions, the dependences of the composite rheological operators versus those of components point out, in the case of composite Q operators, relationships including only similar operators of components, whereas the composite P operators are expressed as a mixed

dependence of both P and Q operators of components. Naturally, as can be seen, the rules are similar for the rheological parameters.

Conclusions

The uniform stress approach for ternary phase in phase composie systems with linear viscoelastic components including polymeric materials, accomplished within the realm of of rheological behaviour laws - selection rules - mixing rules hierarchical procedure, affords relevant facts on the evaluation of rheological response. In the case of Reuss-like morpho-rheological interactions, the expressions providing the composite rheological operators, appearing in the behaviour laws, versus those of components can be derived in a meaningful way. The selection rules and the mixing rules resulting as direct consequences are pointed out and illustrated for components defined by well defined established rheological models, in the case of mono- and bi-relaxan (retardant) rheological states. The comparison of effects arising in Voigt - uniform deformation, and Reuss - uniform stress approach, respectively, shows significant dissimilarities outcoming in virtue of intrinsic features of morpho-rheological interactions.

References

1. JONES, R. M., Mechanics of Composite Materials, Wiley, New York, 1975. 2. CRIVELLI-VISCONTI, I., Materiali Compositi. Tecnologie et Progettazione, Tamburini, Milano, 1975. 3. COOPER, S. L., ESTES, G. M., (eds.), Multiphase Polymers, Am. Chem. Soc., Washington, 1979. 4. TSAI, S. W., HAHN, H. T., Introduction to Composite Materials, Technomic, Westport, 1980. 5. BERTHELOT, J. -M., Composite Materials. Mechanical Behavior and Structure Analysis, Springer, New York, 1999. 6. NAKATANI, A. I., HJELM, R. P., GERSPACHER, M., KRISHNAMOORTI, R., Filled and Nanocomposite Polymer Materials, Mater. Res. Soc., Boston, 2001. 7. SCHAPERY, R. A., J. Compos. Mater., 1, 1967, p. 228. 8. CHRISTENSEN, R. M., J. Mech., Phys. Solids, 38, nr. 3, 1990, p. 379. 9. BRINSON, L. C., KNAUSS, W. G., J. Mech. Phys. Solids, 39, nr. 7, 1991, p. 859. 10. HASHIN, Z. V., J. Mech. Phys. Solids, 40, nr. 4, 1992, p. 767. 11. PAVEN, H., Rev. Chim., 55, nr.6, 2004, p. 444.

Table 2.1 [3 R] morpho-rheological interaction parameters

[3 R]

ma 1 0 0 0

na 0 1 1 1

mb 0 1 0 0

nb 1 0 1 1

mc 0 0 1 0

nc 1 1 0 1

m1 m2 m3 n1

Table 2.2 [3R] morpho-rheological interactions

Crt. No.

a/b/c Composite m a

Components b n 0 0 0 0 0 0 0 0 0 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 m 0 0 0 0 0 0 1 1 1 0 0 0 0 0 0 1 1 1 0 0 0 0 0 0 1 1 1 n 0 0 0 1 1 1 1 1 1 0 0 0 1 1 1 1 1 1 0 0 0 1 1 1 1 1 1 m 0 0 1 0 0 1 0 0 1 0 0 1 0 0 1 0 0 1 0 0 1 0 0 1 0 0 1 c n 0 1 1 0 1 1 0 1 1 0 1 1 0 1 1 0 1 1 0 1 1 0 1 1 0 1 1 m1 0 1 1 1 2 2 1 2 2 0 1 1 1 2 2 1 2 2 1 2 2 2 3 3 2 3 3 m2 0 1 1 0 1 1 1 2 2 1 2 2 1 2 2 2 3 3 1 2 2 1 2 2 2 3 3 m3 0 0 1 1 1 2 1 1 2 1 1 2 2 2 3 2 2 3 1 1 2 2 2 3 2 2 3 n1 0 1 1 1 2 2 1 2 2 1 2 2 2 3 3 2 3 3 1 2 2 2 3 3 2 3 3 [3 R] m 0 1 1 1 2 2 1 2 2 1 2 2 2 2 3 2 3 3 1 2 2 2 3 3 2 3 3 n 0 1 1 1 2 2 1 2 2 1 2 2 2 3 3 2 3 3 1 2 2 2 3 3 2 3 3

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27

{1} / {1} / {1} {1} / {1} / {2} {1} / {1} / {3} {1} / {2} / {1} {1} / {2} / {2} {1} / {2} / {3} {1} / {3} / {1} {1} / {3} / {2} {1} / {3} / {3} {2} / {1} / {1} {2} / {1} / {2} {2} / {1} / {3} {2} / {2} / {1} {2} / {2} / {2} {2} / {2} / {3} {2} / {3} / {1} {2} / {3} / {2} {2} / {3} / {3} {3} / {1} / {1} {3} / {1} / {2} {3} / {1} / {3} {3} / {2} / {1} {3} / {2} / {2} {3} / {2} / {3} {3} / {3} / {1} {3} / {3} / {2} {3} / {3} / {3}

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 1 1 1 1 1 1 1 1

Table 2.3 [3V] and [3R] morho-rheological effects Crt. No. Components a 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 {1} {1} {1} {1} {1} {1} {1} {1} {1} {2} {2} {2} {2} {2} {2} {2} {2} {2} {3} {3} {3} {3} {3} {3} {3} {3} {3} b {1} {1} {1} {2} {2} {2} {3} {3} {3} {1} {1} {1} {2} {2} {2} {3} {3} {3} {1} {1} {1} {2} {2} {2} {3} {3} {3} c {1} {2} {3} {1} {2} {3} {1} {2} {3} {1} {2} {3} {1} {2} {3} {1} {2} {3} {1} {2} {3} {1} {2} {3} {1} {2} {3} a/b/c Composite [3 V] {1} {2} {3} {2} {2} {4} {3} {4} {5} {2} {2} {4} {2} {2} {4} {4} {4} {6} {3} {4} {5} {4} {4} {6} {5} {6} {7} [3 R] {1} {3} {3} {3} {4} {5} {3} {5} {5} {2} {4} {4} {4} {4} {6} {4} {6} {6} {3} {5} {5} {5} {6} {7} {5} {7} {7}