RHEOLOGICAL EQUATIONS AND SELECTION RULES FOR LINEAR VISCOELASTIC COMPOSITE SYSTEMS H.

Paven Chemical Research Institute, CP 87, OfP 12, Bucharest-78123, ROMANIA Real composite materials are multi-component and multi-phase systems displaying well defined complex sets of different properties owing to the peculiarities of their structure at different levels, (1-3). The case of composites containing at least one polymer component represents a major challenge from the standpoint of identifying the form of mixing rules, as well as concerning the potential quantitative and qualitative rheological effects. Accordingly, the principal task of this contribution is to reveal the manner in which the consequences of the simplest morphological models can be pointed out by using the view of "morpho-rheological interactions", meant as natural coupling of rheological states of components, in order to identify the allowed rheological state of composite if those of components are given. The use of differential operators technique for the phenomenological description of rheological behaviour of composite systems with linear viscoelastic components provides an unified way to describe both the solid/solid and liquid/liquid circumstances, well known from the traditional approach (4, 8). As a matter of fact, for the sake of simplicity only the condition of simple shear is considered, with the mention that, in the case of a solid component, the shear stress and the shear strain are the natural rheological variables, while in the instance of the liquid one, the shear stress and the shear strain rate are the proper rheological variables appearing in the rheological equations. In the case of the a/b binary composite system, the Pa, Qa and Pb, Qb rheological operators of components are involved, the rheological state of composite resulting in different forms controlled by composite morphology. The basic, direct morpho-rheological couplings - [] and [] - are characterised by the rheological operators, (5, 9), P[]=PaPb, Q[]=vaPbQa+vbPaQb [1. 1] and P[]=vaPaQb+vbPbQa, Q[]=QaQb [2. 1] respectively . On the other hand, in the case of the Takayanagi-Kawai model coupling the rheological operators are, (5, 10), P[TK]=C[TK]Pa2Qb+D[TK]PaPbQa, Q[TK]=A[TK]PbQa2+B[TK]PaQaQb, where A[TK1]=1-1, B[TK1]=1, C[TK1]=1-1+vb, D[TK1]=1-vb in the case of a "sigma"-like coupling, whereas for a "pi"-like coupling one obtain A[TK2]=2-vb, B[TK2]=1+vb-2, D[TK2]=2, C[TK2]=1-2 the two model systems being equivalent if 1=1+vb-2. For the Nielsen[N] model coupling, result the rheological operators, (7, 13), P[N]=D[N]Pa2PbQb+E[N]PaPb2Qa, where Q[N]=A[N]Pb2Qa2+B[N]Pa2Qb2+C[N]PaPbQaQb, A[N]=va"vb', B[N]=va'vb", C[N]=va'vb"+va"vb'+va'+vb', D[N]=vb', E[N]=va' In the case of the composite averages model, (6, 14), for the [A] coupling, the rheological operators are P[A]=vaPa2PbQb+vbPaPb2Qa, Q[A]=Avavb(Pa2Qb2+Pb2Qa2)+(1-2Avavb)PaPbQaQb while in the case of the [H] coupling the rheological operators are given as P[H]=Hvavb(Pa2Qb2+Pb2Qa2)+(1-2Hvavb)PaPbQaQb, [5. 1] [4. 1] [3. 1]

Q[H]=vaPaQaQb2+vbPbQa2Qb

[6. 1]

The form of composite rheological operators enable us to obtain the rheological operators of model composite in terms of the rheological parameters of components. Moreover, taking into account the order (ma|na) and (mb|nb) of rheological states of components, respectively , the order of the allowed rheological state of the composite is given by well defined selection rules. In the case of the basic [] direct coupling, the corresponding selection rules are, (11, 15), m[]=ma+mb, n[]=max.(ma+nb, mb+na) while for the basic [] direct coupling, results, (11, 16), m[]=max.(ma+nb, mb+na), n[]=na+nb [2. 2] [1. 2]

On the other hand, in the case of Takayanagi-Kawai coupling, the selection rules are, (12), m[TK]=max.(2ma+nb, ma+mb+na), n[TK]=max.(mb+2na, ma+na+nb) while for the Nielsen[N] model coupling one obtain, (13), m[N]=max.(2ma+mb+nb, ma+2mb+na), n[N]=max.(2ma+2nb, 2mb+2na, ma+mb+na+nb) [4. 2] [3. 2]

In the case of the composite averages model, the resulting selection rules are given as, (14), m[A]=max.(2ma+mb+nb, ma+2mb+na), n[A]=max.(2ma+2nb, 2mb+2na, ma+mb+na+nb) for the [A] -like coupling, whereas for the [H]-like one the mixing rules are m[H]=max.(2ma+2nb, 2mb+2na, ma+mb+na+nb), n[H]=max.(ma+na+2nb, mb+2na+nb) [6. 2] [5. 2]

To summarize, the non-conventional phenomenological method of differential rheological operators allows us to point out the existence of potential quantitative or qualitative rheological effects in the case of different model composites with linear viscoelastic components, (17, 18). Moreover, the relationships providing the rheological operators of composite versus those of components supply the mixing rules for rheological parameters of composite as function of those of components Henceforth, it is noteworthy to mention the full compatibility of this approach with the traditional ones, where rather the moduli or viscosities are used in connection with the so-called principle of correspondence elasticity-viscoelasticity. It is believed this "counterpart-approach" is suitable for further improvements, by taking into account not only pure mechanical, but also physical and/or chemical effects, and even if apparently the attention was focussed on the circumstances which are substantially important for polymeric systems, it is expected the results would be of interest for different composites in the framework of linear viscoelastic behaviour of components. References 1). Vinogradov G. V., Malkin A. Ya., Polymer Rheology, Mir, Moscow, 1979;2). Vostroknutov E. G., Vinogradov G. V., Rheological Foundations of Elastomer Processing, Khimiya , Moscow, 1988; 3). Nielsen L. E., Polymer Rheology, Marcel Dekker, New York, 1977 ; 4). Tschoegl N. W., The Phenomenological Theory of Linear Viscoelastic Behaviour, Springer, Berlin, 1989; 5). Paven H., Dobrescu V., Polymer Bulletin, 2, 727 (1980); 6). Paven H., Popovics S., Rev. Chim., 43, 716 (1992); 7). Paven H., Mihu V. P., Rev. Chim., 44, 1046 (1993); 8). Paven H., Dobrescu V., Intern. Chem. Eng., 34 114 (1994); 9). Paven H., Dobrescu V., Intern. Chem. Eng., 34, 127 (1994); 10). Paven H., Dobrescu V., Intern. Chem. Eng., 34, 135 (1994); 11).Paven H., Rev. Chim., 47, 636 (1996); 12). Paven H., Rev. Chim., 47, 922 (1996) ; 13). Paven H., Rev. Chim., 48, 111 (1997); 14). Paven H., Rev. Chim., 48, 773 (1997); 15). Paven H., Rev. Chim., 49, 610 (1998); 16). Paven H., Rev. Chim., 49, 878 (1998); 17). Paven H., Popovics S., Proc. Ann. Symp. Inst. Solid Mech. Romanian Acad., Bucharest, 173 (1999); 18). Paven H., Popovics S., Proc. Ann. Symp. Inst Solid Mech. Romanian Acad.,Bucharest, 185 (1999).