SISOM 2004, BUCHAREST, 20-21 May

BASIC MIXING RULES AND RHEODYNAMIC EFFECTS IN TERNARY PHASE-IN-PHASE IN PHASE COMPOSITE SYSTEMS WITH LINEAR VISCOELASTIC COMPONENTS. II. THE LOSS MODULUS

Horia PAVEN*, Sandor POPOVICS** * Research-Development National Institute for Chemistry and Petrochemistry-ICECHIM, Spl. Independentei, 202, Bucharest-060021, ROMANIA, htopaven@netscape.net ** Drexel University, Philadelphia, PA-19401, USA

Abstract: The peculiarities of frequency-controlled mixing rules for the primary rheodynamic quantity represented by the loss modulus are established in the case of ternary phase-in-phase in phase composite systems with linear viscoelastic components on the basis of corresponding composite behaviour laws. Aiming at to identify relevant features of different VV, VR, RV and RR morpho-rheological interactions, the mono-relaxant (retardant)-like rheological model is considered for components. The basic rheodynamic effects are evidenced in the realm of 3D representation. 1. INTRODUCTION In the case of viscoelastic behaviour the loss modulus is a natural measure of the vibration damping availability, and if the composite systems are considered, it is reasonable to suppose that the composite properties express the individual and cumulate, direct and cross-over contribution of components, the composite structural peculiarities at different levels, the amount of componens as well as the intrinsic interface physical-chemical interactions /1/. Consequently, in order to complete the phenomenological analysis of rheodynamic data for phase-inphase in phase composite systems with linear viscoelastic components, the loss modulus of ternary systems is also of significant interest /2-4/ 2. PHASE-IN-PHASE IN PHASE MORPHO-RHEOLOGICAL INTERRELATIONSHIPS Taking into account that for the a//b/c ternary phase-in-phase in phase composite system with linear viscoelastic components, in the case of the basic [VV] morpho-rheological coupling, the corresponding rheological behaviour law stands (II.1.1) P[VV ] = Q[VV ] or,

( Pa Pb Pc ) = (Va Pb Pc Qa + Vbc vb Pa Pc Qb + Vbc vc Pa Pb Qc )

* * M [* ] = Va M a + Vbc vb M b + Vbc vc M c* VV

(II.1.2) (II.1.3) (II.1.4)

from the mixing rule for the complex modulus

the specific mixing rule for the primary rheodynamic quantity - the loss modulus, M [VV ] , is obtained as M [VV ] = Im{M [* ] } = Va M a + Vbc vb M b + Vbc v c M c VV
If the basic [VR] morpho-rheological coupling operates, the corresponding rheological equation which express the rheological behaviour law is:

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Basic mixing rules and rheodynamic effects in ternary phase-in-phase in phase composite systems. II. The loss modulus

P[VR ] = Q[VR ]
i.e., in an explicit form,

(II.2.1)

(vb Pa Pb Qc + vc Pa Pc Qb ) = (Va vb Pb Qa Qc + Va vc Pc Qa Qb + Vbc Pa Qb Qc )

* * * * * M [* ] = (Va vb M a M c* + Va v c M a M b + Vbc M b M c* ) /(vb M c* + vc M b ) VR

(II.2.2) (II.2.3)

Then the mixing rule for the complex modulus is

and for the primary rheodynamic quantity, the loss modulus, M [VR ] , results the specific mixing rule
* M [VR ] = Im{M [*VR ] } = Va M a + Vbc (vb M b / M b + v c M c / M c* ) / xbc ,[ R ] 2 2 2

(II.2.4) (II.2.5) (II.3.1) (II.3.2) (II.3.3)

2

where
* * xbc ,[ R ] = [(vb M b / M b + vc M c / M c* ) 2 + (vb M b / M b + vc M c / M c* ) 2 ]1 / 2 2 2 2 2

If the basic [RV] morpho-rheological coupling works, the resulting behaviour law is

P[ RV ] = Q[ RV ]

and the explicit expression of behaviour law takes the form the resulting mixing rule for the complex modulus being

(Va vb Pa Pc Qb + Va vc Pa Pb Qc + Vbc Pb Pc Qa ) = (vb Pc Qa Qb + v c Pb Qa Qc )

* * * * * M [*RV ] = (vb M a M b + v c M a M c* ) /(Va vb M b + Va v c M c* + Vbc M a )

and the specific mixing rule for the loss modulus one obtains
* M [RV ] = Im{M [*RV ] } = [Va M a / M a + Vbc (vb M b + vc M c) xbc ,[V ] ] / X [ RV ] 2 2 2 2 2 2

(II.3.4) (II.3.5) (II.3.6) (II.4.1) (II.4.2) (II.4.3)

* * X [ RV ] = {[Va M a / M a + Vbc M bc xbc ,[V ] ] 2 + [Va M a / M a + Vbc M bc xbc ,[V ] ] 2 }1 / 2

xbc ,[V ] = 1 /[(vb M b + vc M c ) 2 + (vb M b + vc M c) 2 ]1 / 2

Finally, the [RR] morpho-rheological coupling is defined by the behaviour law

P[ RR ] = Q[ RR ]

i.e.,

(Va Pa Qb Qc + Vbc vb Pb Qa Qc + Vbc vc Pc Qa Qb ) = (Qa Qb Qc )

* * * * * * M [*RR ] = M a M b M c* /(Va M b M c* + Vbc vb M a M c* + Vbc vc M a M b )

and for the complex modulus the corresponding mixing rule is the specific mixing rule for the loss modulus, M [ ] , resulting as RR
* * M [RR ] = Im{M [*RR ] } = [Va M a / M a + Vbc (vb M b / M b + vc M c / M c* )] / X [ RR ] 2 2 2 2

(II.4.4) (II.4.5) (II.4.6)

where
* * X [ RR ] = {[Va M a / M a + Vbc M bc ,[ R ] xbc ,[ R ] ] 2 + [Va M a / M a + Vbc M bc ,[ R ] xbc ,[ R ] ] 2 }1 / 2 2 2 * * xbc ,[ R ] = {[vb M b / M b + v c M c / M c* ] 2 } + [vb M b / M b + vc M c / M c* ] 2 }1 / 2 2 2 2 2 2 2

3. 3D-REPRESENTATION OF MIXING RULES Aiming at to point out the consequences of different rheodynamic effects from the standpoint of specific mixing rules for the loss modulus, the case of (1, 1)- rheological model described by the rheological behaviour law,

p0 + p1 Dt = q0 + q1 Dt

(II.5)

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is considered, where p 0 , p1 ; q 0 , q1 are the nominal rheological parameters, and the corresponding characteristic rheological parameters are

A0 a = 1 MPa, B1a = 1 s / rad , A1a = 1000 MPa * s / rad A0b = 1 MPa, B1b = 0.1 s / rad , A1b = 100 MPa * s / rad A0 c = 1 MPa, B1c = 0.01 s / rad , A1c = 10 MPa * s / rad
The results are summarized in Fig. II.x.1 to II.x.5, for the loss modulus at given frequencies. The frequency dependence of (1, 1)loss modulus reveals the existence of the characteristic loss peak corresponding to the value of component characteristic frequency of dynamic relaxation. In principle, in the case of the considered composite system, as result of intrinsic morpho-rheological interactions, the component contribution is controlled by v and V volume fractions, and as result of cumulation of loss and storage moduli, it is rather difficult to establish analytical meaningful criteria of evaluation and comparison. However, some qualitative guidance accounts can be evidenced from the viewpoint of frequency control of specific mixing rules. At low frequencies (=0.1 and 1 rad/s), the v and V dependences are linear for M2VV, and nonlinear for M2VR, M2RV and M2RR. At intermediate values (=10 and 100 rad/s), there is an increase of non-linear trend of mixing rules for M2VV and M2VR, while for M2Rv and M2RR, M2(V)-maximum effects occur. At high frequencies (=1000 rad/s), the v and/or V composition effects are increasingly non-linear for morphologies from VV to RR. 4. CONCLUSIONS The loss modulus of phase-in-phase in phase composite systems with components showing linear viscoelastic behaviour results solely in terms of similar quantities of components in case of VV morphology. The morpho-rheological interactions corresponding to VR, RV and RR basic models lead to relatively complicated expressions for the composite loss modulus, when there is a well defined contribution of different terms including both the loss- and storage-modulus. It is useful, both from scientific and application end use of approach, to continue the development of the interactive knowledge data base for rational underlying of 2D-3D representation of rheodynamic morpho-rheological interrelationships. ACKNOWLEDGEMENT The research was supported in part by the Grant no.6158/2000-2002 from ANSTI/MEC and by Contract CERES no. 144/2001-2004 from MEC, respectively. REFERENCES
1. Paven H., Dobrescu V., Model Reological Equations of State in the Linear Viscoelasticity of Polymeric Composites, Polymer Bulletin (Berlin), 1980, 2, 727-730. 2. Paven H., Dobrescu V., Viscoelastic Models in the Rheology of Hybrid Polymeric Composites of Phase-in-Phase in Phase Type, in Rheology - Applications, vol. III, Astarita G., Marrucci G., Nicolais L. (eds.), Plenum Press, New York, 1980, 229-233. 3. Paven H., Basic Interactions in Phenomenological Rheology of Ternary Hybrid Composites with Linear Viscoelastic Solid Components, Proc. Ann. Symp, Inst Solid Mech., Romanian Academy, 1992, 77-82. 4. Paven H., Dobrescu V., Rheology of Polymer Composites. VI. Linear Viscoelasticity of Hybrid Composites of Phase-in-Phase in Phase Type, Intern. Chem. Eng., 1994, 34, 143-155.

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Basic mixing rules and rheodynamic effects in ternary phase-in-phase in phase composite systems. II. The loss modulus

Fig. II.x.1. Phase-in-phase in phase rheodynamic mixing rules for the loss modulus for different morphological architectures - VV, VR, RV, RR - and at = 0.1 rad/s.

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Fig. II.x.2. Phase-in-phase in phase rheodynamic mixing rules for the loss modulus for different morphological architectures - VV, VR, RV, RR - and at = 1 rad/s.

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Basic mixing rules and rheodynamic effects in ternary phase-in-phase in phase composite systems. II. The loss modulus

Fig. II.x.3. Phase-in-phase in phase rheodynamic mixing rules for the loss modulus for different morphological architectures - VV, VR, RV, RR - and at = 10 rad/s.

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Fig. II.x.4. Phase-in-phase in phase rheodynamic mixing rules for the loss modulus for different morphological architectures - VV, VR, RV, RR - and at = 100 rad/s.

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Basic mixing rules and rheodynamic effects in ternary phase-in-phase in phase composite systems. II. The loss modulus

Fig. II.x.5. Phase-in-phase in phase rheodynamic mixing rules for the loss modulus for different morphological architectures - VV, VR, RV, RR - and at = 1000 rad/s.