INTRINSIC RESTRICTIONS UPON RHEOLOGICAL SELECTION RULES FOR BINARY COMPOSITES WITH LINEAR VISCOELASTIC COMPONENTS

H. Paven
Chemical Research Institute, CP 87, OfP 12, Bucharest-78123, ROMANIA

ABSTRACT By using the technique of differential rheological operators, and taking into account, in a Takayanagi-Kawai manner, the effect of the morphological features of the real composite, the corresponding composite rheological operators are obtained starting from those of components and interphase, in the realm of linear viscoelastic behaviour. Given the peculiarities of the "simple" and "double" interphase layers, respectively, the distinct contributions are considered, and the rheological consequences are pointed out. Furthermore, the analysis reveals the existence of well defined morpho-rheological selection rules, controlled by the intrinsic restrictions due to interphase, the allowed rheological state of the composite being provided in terms of those of rheological states of components and interphase . KEYWORDS: BINARY COMPOSITE SYSTEMS, RHEOLOGICAL EFFECTS, MIXING RULES, LINEAR VISCOELASTICITY, SELECTION RULES, INTRINSIC RESTRICTIONS INTRODUCTION Obtaining improved mixing rules expressing in a more realistic manner the rheological properties of solid composites in terms of those of components ones, corresponding volume fractions, morphology and interphase, represents a major challenge of materials science [1, 3, 6]. Moreover, in the case of the solid composites with linear viscoelastic components, besides the well known problems appearing in the framework of elastic behaviour, further difficulties are encountered [2, 5, 7, 8, 10, 13-19]. Furthermore, by now is of outmost importance to be aware of the fact that for composite systems with linear viscoelastic components there is a relevant counterpart to the traditional mixing rules approach. RHEOLOGICAL EQUATIONS In the case of the a/b binary composite with linear viscoelastic components, where the rheological properties are expressed by using the well known P, Q differential operators, the component rheological operators Pa, Qa and Pb, Qb respectively, will be involved [2, 4, 9, 11, 12]. Taking into account the two "basic" morpho-rheological couplings, one obtain the corresponding rheological operators [24, 28] P[V]=PaPb, Q[V]=vaPbQa+vbPaQb (1) in the case of Voigt, -like coupling, while for the Reuss, -like coupling, results [24, 28] P[R]=vaPaQb+vbPbQa, Q[R]=QaQb (2)

where the amount of components is given by the corresponding volume fractions - va and vb. On the other hand, in the case of the Takayanagi-Kawai model coupling [20, 21], by taking into account the contribution of the matrix as well as of the matrix- anddispersed- phase, the corresponding rheological operators are [24, 29] P[TK]=C[TK]Pa2Qb+D[TK]PaPbQa, (3) Q[TK]=A[TK]PbQa2+B[TK]PaQaQb where A, B, Cand D depend on the volume fraction of the dispersed component as well as on the model parameter. It is interesting to point out that as a direct outcome of the form of rheological operators of the considered model composites, the mixing rules for different rheological parameters of composite are provided in terms of those of components. Moreover , the corresponding mixing rules for moduli are thus obtained in a straightforward manner without the manipulation of the linear elasticityviscoelasticity principle of correspondence. Henceforth, there are well defined "allowed" composite rheological states which result as a consequence of the morphorheological couplings of rheological states of components (ma|na) and (mb|nb). In fact, in this manner, the existence of some " rheological selection rules" is evidenced. In the case of the basic Voigt[V], -like direct coupling, result the selection rules [30, 34] m[V]=ma+mb, n[V]=max.(ma+nb, mb+na) (4) while for the basic Reuss[R], -like direct coupling, one obtain [30, 35] m[R]=max.(ma+nb, mb+na), n[R]=na+nb (5) On the other hand, in the case of the Takayanagi-Kawai coupling the selection rules are [31] m[TK]=max.(2ma+nb, ma+mb+na), n[TK]=max.(mb+2na, ma+na+nb) (6) In the case of other well established models, e.g. Nielsen [22], and the composite averages models [23], the corresponding selection rules can also be obtained [25, 26, 32, 33]. Aiming at establishing better relationships between the properties of the a/b binary composite, on the hand, and those of components (Pa, Qa and Pb, Qb , respectively) and interphase (Pi, Qi - for "simple"(i), and Pi, Qi and Pj, Qj for "double" layer), on the other hand, the overall composite morpho-rheological coupling is considered as the resultant of definite contributions. Thus, for the case of "simple" i-layer interphase, taking into account the effects of {1} - matrix(a), {2} - matrix(a) and interphase(i), as well as of {3} - matrix(a), interphase(i) and disperse phase(b), the composite rheological operators are given as follows P[aib]=P1P2P3, Q[aib]=U1P2P3Q1++U2P1P3 Q2 +U3P1P2Q3 (7) where P1, P2 and P3, are expressed in terms of the P, Q rheological operators of components and interphase, and some conventional volume fractions V1, V2 and V3, while

Q1, O2,and Q3 are given solely as functions of Q operators, and U1, U2 and U3 represent volume "weights" of the characteristic block contributions. The net result follows in the form P[aib]=A1Pa3QbQi2+A2Pa2PbQaQi2+ +A3Pa2PiQaQbQi+A4PaPbPiQa2Qi+ (8. 1) +A5PaPi2Qa2Qb and Q[aib]=B1Pa2QaQbQi2+B2PaPbQa2Qi2+ +B3PaPiQa2QbQi+B4PbPiQa3Qi+ (8. 2) +B5Pi2Qa3Qb On the other hand, in the case of the "double"(ij)-layer interphase, taking into account the effect of {1} - matrix(a), {2} - matrix(a) and interphase(j), {3} - matrix(a), interphase layer(j) and interphase layer(i), as well as of {4} - matrix(a), interphase layer(j), interphase layer(i) and disperse phase(b), the resulting composite rheological operators are expressed as P[aijb]=P1P2P3P4, Q[aijb]=U1P2P3P4 Q1+U2P1P3P4 Q2+ +U3P1P2P4Q3+U4 P1P2P3Q4 (9) where P1,..., P4 are given in terms of P, Q rheological operators of components and interphase layers, and different V1,...,V4 conventional volume fractions, while Q operators are expressed as functions of only component Q operators, and U1,...,U4 stand for the "weights" of different characteristic contributions. Accordingly, P[aijb]=A1Pa4QbQi2Qj3+A2Pa3PbQaQi2Qj3+ +A3Pa3PiQaQbQiQj3+A4Pa3PjQaQbQi2Qj2+ +A5Pa2PbPiQa2QiQj3+A6Pa2PbPjQa2Qi2Qj2+ +A7Pa2Pi2Qa2QbQj3+A8Pa2Pj2Qa2QbQi2Qj+ +A9Pa2PiPjQa2QbQiQj2+A10PaPbPj2Qa3Qi2Qj+ +A11PaPbPiPjQa3QiQj2+A12PaPj3Qa3QbQi2+ +A13PaPiPj2Qa3QbQiQj+A14PaPi2PjQa3QbQj2 (10. 1) and Q[aijb]=B1Pa3QaQbQi2Qj3++B2Pa2PbQa2Qi2Qj3+ +B3Pa2PiQa2QbQiQj3+B4Pa2PjQa2QbQi2Qj2+ +B5PaPbPiQa3QiQj3+B6PaPbPjQa3Qi2Qj2+ +B7PaPi2Qa3QbQj3+B8PaPj2Qa3QbQi2Qj+ +B9PaPiPjQa3QbQiQj2+B10PbPj2Qa4Qi2Qj+ +B11PbPiPjQa4QiQj2+B12PiPj2Qa4QbQiQj+ +B13Pi2PjQa4QbQj2+B14Pj3Qa4QbQi2 (10. 2) INTRINSIC SELECTION RULES Better understanding of the potential behaviour of real composites can be achieved by pointing out the morphorheological selection rules , by which the allowed rheological state of the composite, (m[aib]|n[aib]) - in the case of the i-layer, and (m[aijb]|n[aijb]) - in the case of ijlayer, is expressed in terms of those of components - and interphase . Consequently, the intrinsic restrictions are evidenced for the case of "simple" interphase layer by the selection rules m[aib]=max.( 3 ma+nb+2 ni, 2 ma+mb+na+2 ni, 2 ma+mi+na+nb+ni, ma+mb+mi+2 na+ni, ma+2 mi+2 na+nb ), n[aib]=max.( 2 ma+na+nb+2 ni, ma+mb+2 na+2ni, ma+mi+ 2 na+nb+ni, mb+mi+3 na+ni, 2 mi+3 na+nb) (11) while in the case of "double" interphase layer the selection rules are m[aijb]=max.(4ma+nb+2ni+3nj, 3 ma+mb+na+2 ni+3 nj, 3 ma+mi+na+nb+ni+3 nj,

3 ma+mj+na+nb+2 ni+2 nj, 2 ma+mb+mi+2 na+ni+3 nj, 2 ma+mb+ mj+2 na+2 ni+nj, 2 ma+2 mi+2 na+nb+3 nj, 2 ma+2 mj+2 na+ nb+2 ni+ nj, 2 ma+mi+mj+2 na+nb+ni+2 nj, ma+mb+2 mj+3 na+2 ni+nj, ma+mb+mi+mj+3na+ni+2nj, ma+3 mj+3 na+nb+2 ni, ma+ mi+2 mj+3 na+nb+ni+nj, ma+2 mi+mj+3 na+nb+2 nj) n[aijb]=max.(3ma+na+nb+2ni+3nj, 2 ma+mb+2na+2 ni+3 nj, 2 ma+mi+2na+nb+ ni+3 nj, 2 ma+mj+2 na+nb+2 ni+2 nj, ma+mb+mi+3 na+ni+3 nj, ma+mb+mj+3 na+2ni+2 nj, ma+2mi+3na+nb+3nj, , ma+2mj+3na+nb+2 ni+ nj, ma+mi+mj+3na+nb+ni+2 nj, mb+2mj+4 na+2 ni+nj, mb+mi+mj+4 na+ ni+2 nj, mi+2 mj+4 na+nb+ni+ nj, 2 mi+mj+4 na+nb+2 nj, 3 mj+4 na+nb+2 ni ) CONCLUSION

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The non-coventional approach of rheological operators in the framework of linear viscoelastic behaviour shifts the attention on the mixing rules for rheological parameters and the potential quantitative and qualitative rheological effects rather than on the traditional modulus/compliance/ pattern, and enable us to point out some "critical" aspects concerning the potential rheological behaviour of real composites. REFERENCES 1. L. H. Van Vlack, "Elements of Materials Science", Addison-Wesley, Reading, (1970), pp. 375-395. 2. R. D. Bland, "The Theory of Linear Viscoelasticity", Academic Press,Oxford, (1960), pp. 21-45. 3. J. A. Manson, and L. H. Sperling, "Polymer Blends and Composites" , Hayden, New York, (1976), pp. 271457. 4. W. Flugge, "Viscoelasticity'", Springer, Berlin, (1976), pp. 4-33. 5. C. B. Bucknall, "Toughened Plastics", Appl. Sci. Publ., London, (1977), pp. 108-135. 6. R. M. Christensen, "Mechanics of Composite Materials'", Wiley, New York,(1979), pp. 37-146. 7. A. A. Berlin , S. A Volfson ., N.S. Enikolopian, S.S.Negmatov , "Principles of Polymer Composites", Springer, Berlin,(1986), pp.37-80 8. P. S. Theocaris, "The Mesophase Concept in Composites", Springer, Berlin ,(1988 ), pp. 9-109 9. N. W. Tschoegl, "The Phenomenological Theory of Linear Viscoelastic Behaviour" , Springer, Berlin, (1989), pp. 35-156. 10. L. E. Nielsen, and R.F. Landel ,"Mechanical Properties of Polymers and Composites", Marcel Dekker, New York, (1994), pp. 377-447. 11. Ch. L. Rohn, "Analytical Polymer Rheology", Hanser, Munich, (1995), pp. 189-218.

12. P. J.Carreau, D. C. R. De Kee, and R. P. Chhabra, "Rheology of Polymer Systems", Hanser, Munich, (1997), pp. 162-193. 13. R. S. Lakes , 'Viscoelastic Solids", CRC Press Boca Raton, (1998), Univ. of Wisconsin, 20 Dec. 1999, <http://silver.neep.wisc.edu/~lakes/ VEbook.html>. 14. R. A. Schapery, in "Mechanics of Composite Materials", (Ed. G. P. Sendeckyj), Academic Press, New York, (1974), pp. 85-168. 15. H. H. Kausch , Angew. Makromol. Chem . (1977) 60/61 139-155. 16. Yu. S. Lipatov, Adv. Polym .Sci . (1977) 22 1-59. 17. M. Shen , and H. Kawai , AIChE J (1978) 24 1-20. 18. B. J. Schmitt, Angew. Chem. (1979) 31 286-309. 19. R. A. Dickie, in "Polymer Blends", Vol. 1, (Eds. D. R.Paul, and S. Newman ) Academic Press, London, (1980), pp.353-391. 20. M. Takayanagi, H. Harima, and Y. Iwata, Mem. Fac. Eng. Kyushu Univ. (1963) 23 1-13. 21. K. Fujino, Y. Ogawa , and H. Kawai , J. Appl . Polym. Sci. (1964) 8 2147-2161. 22. S. Popovics, Am . Ceram .Soc. Bull. (1969) 48 10601064. 23. L. E. Nielsen , J. Appl. Polym. Sci . (1977) 21 15791584. 24. H. Paven, and V. Dobrescu, Polymer Bulletin (1980) 2, 727-730. 25. H. Paven, and S. Popovics , Rev .Chim. (1992) 43 716722. 26. H. Paven, and V. P. Mihu, Rev. Chim. .(1993) 44 10461053. 27. H. Paven , and V. Dobrescu , Intern .Chem. Eng (1994) 34 114-126. 28. H. Paven, and V. Dobrescu , Intern. Chem. Eng. (1994) 34 127-134. 29. H. Paven, and V. Dobrescu , Intern. Chem. Eng. (1994) 34 135-142. 30. H. Paven, Rev .Chim. (1996) 47 636-641. 31. H. Paven, Rev. Chim. (1996) 47 922-927. 32. H. Paven, Rev. Chim. (1997) 48 111-115. 33. H. Paven, Rev. Chim. (1997) 48 773-779. 34. H. Paven, Rev. Chim. (1998) 49 610-615. 35. H. Paven, Rev. Chim. (1998) 49 878-883.