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. I. THE STORAGE 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 case of the ternary phase-in-phase in phase composite systems with linear viscoelastic components is considered from the standpoint of mixing rules for the storage modulus. Taking into account the four well defined basic morpho-rheological interactions corresponding to VV, VR, RV and RR morphological architectures, the composite storage modulus is obtained in terms of component rheodynamic quantities and of two independent volume fractions. Further, in order to illustrate the intrinsic effects due to different morpho-rheological interactions, the mono-relaxant (retardant) rheological model is used to describe the component behaviour, the frequency-controlled 3D effects being pointed out.

1. INTRODUCTION In order to ensure a realistic analysis of the dependence of rheological properties of different composite systems in terms of component properties, composition, morphological architecture and different physicalchemical interactions, the phenomenological approach in the framework of linear viscoelastic behaviour is to be considered /1/. The physical and chemical interactions present in actual composite materials suggest the high application potential of phase-in-phase in phase composite systems, the identification of essential peculiarities of processing-structure-properties relationships implying both the compatibilization of earlier approaches and of emerging ones, based on multi-level approaches /2-4/. 2. PHASE-IN-PHASE IN PHASE MORPHO-RHEOLOGICAL INTERRELATIONSHIPS The case of phase in phase composite systems, when the discrete phase is embedded in a continuous matrix phase, is well known in practice, the control of the corresponding properties depending on the level of increase of the number of dispersed components. However, there is a more promising solution, that of phasein-phase in phase composite systems, when the discrete phase itself is a composite one, the so-called VV, VR, RV and RR basic morphologies arising in a natural manner. In the case of a//b/c phase-in-phase in phase composite system with linear viscoelastic components, if the basic [VV] morpho-rheological coupling of a and b/c nominal components is present, the resulting rheological behaviour laws is (I.1.1) P[VV ] = Q[VV ] i.e., explicitly

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

(I.1.2)

163 Basic mixing rules and rheodynamic effects in ternary

where

phase-in-phase in phase composite systems. I. the storage modulus

Pa , Qa ; Pb , Qb ; Pc , Qc are the rheological operators of intrinsic components, while Va , Vbc and

vb , vc are the appropriate volume fractions of nominal matrix and composite dispersed phase, respectively, and of corresponding intra-components ( Va + Vbc = vb + v c = 1 ).
Accordingly, from the standpoint of mixing rules, one obtains for the composite complex modulus * * * (I.1.3) M [* ] = Va M a + Vbc vb M b + Vbc vc M c VV

and for the primary rheodynamic quantity - the storage modulus, M [VV ] , the specific mixing rule M [VV ] = Re{M [*VV ] } = Va M a + Vbc v b M b + Vbc vc M c
(I.1.4) On the other hand, if the basic [VR] morpho-rheological coupling of a and b/c nominal components is considered, the corresponding rheological behaviour laws is (I.2.1) P[VR ] = Q[VR ] i.e., in an explicit form

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

(I.2.2) (I.2.3)

From the standpoint of mixing rules, one obtains for the composite complex modulus

and the specific mixing rule for the primary rheodynamic quantity - the storage modulus, M [VR ] , is
* M [VR ] = Re{M [*VR ] } = Va M a + Vbc (vb M b / M b + vc M c / M c* ) / xbc ,[ R ] 2 2 2

(I.2.4) (I.2.5)

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

If the basic [RV] morpho-rheological coupling of a and b/c nominal components is present, the corresponding rheological behaviour laws is (I.3.1) P[ RV ] = Q[ RV ] i.e., explicitly (I.3.2) Consequently, from the standpoint of mixing rules, one obtains for the composite complex modulus * * * * * (I.3.3) 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 for the the storage modulus, M [RV ] , results the specific mixing rule
* M [RV ] = Re{M *[ RV ] } = [Va M a / M a + Vbc (vb M b + vc M c ) xbc ,[V ] ] / X [ RV ] 2 2 2

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

(I.3.4)

where
* * 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 (I.3.5) 2 2 2 2

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

(I.3.6)

Furthermore, if the basic [RR] morpho-rheological coupling of a and b/c nominal components is present, the corresponding rheological behaviour laws is (I.4.1) P[ RR ] = Q[ RR ] i.e., in an explicit form

(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 )

(I.4.2) (I.4.3)

From the viewpoint of mixing rules, one obtains for the composite complex modulus

and the specific mixing rulefor the storage modulus, M [VR ] , results

Horia PAVEN, Sandor POPOVICS

* * * M [RR ] = Re{M [*RR ] } = [Va M a / M a + Vbc (vb M b / M b + vc M c / M c )] / X [ RR ] 2 2 2

164
2

(I.4.4) (I.4.5) (I.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 In order to illustrate the consequences of different rheodynamic effects, the case of (1, 1)- rheological model is considered, and for the characteristic rheological parameters the following realistic values are taken into account for the rheological parameters, e.g.

storage modulus, is the relaxation time, and indicates the characteristic frequency of the -relaxation process). The results are summarized in Fig. I.x.1 to I.x.5, for the storage modulus at given frequencies. As result of the intrinsic frequency dependence of component storage modulus and the considered values of natural frequencies (a<b<c) there is a well defined order of component moduli (M1a>M1b>M1c). Moreover, at low frequencies (=0.1 and 1 rad/s) the composite storage modulus corresponding to VV basic morphology shows a linear dependence on v and V, the characteristic volume fractions; the M1VR presents a M1(v) -, and M1RV a M1(V) - maximum effect, whereas M1RR presents both M1(v) and M1(V) -maximum effects, respectively. At intermediate frequencies (=10 and 100 rad/s) the non-linear composition dependence effects are present in different patterns in the case of M1VV and M1VR , as well as M1RV and M1RR morphologies. At high frequency (=1000 rad/s) the features of composition effects are somewhat similar to those occuring in the intermediate frequency range. 4. CONCLUSIONS The storage modulus of phase-in-phase in phase composite systems with linear viscoelastic components depends only in the case of VV morphology on similar quantities of components. As a matter of fact, for other basic morphological architectures, including VR, RV and RR cases, there is a cumulate contribution of both primary components of complex modulus - the storage as well as the loss modulus - the degree of complexity being significantly increased. Accordingly the control of synthesis and processing, which are responsible for component properties and composite morphology , is to be considered with greatest care to guarantee the reproducibility of composite properties within reasonable limits. Henceforth, the trend of volume fractions dependence of the composite storage modulus at different frequencies inside and outside the range of component characteristic frequencies indicates well defined dissimilarities, suggesting the need for further examination of other 3D dependences as well as the set up of an appropriate minning search of relevant 2D representations.

A0 a (= M 0 a ) = 1 MPa, B1a (= 1 / a ) = 1 s / rad , A1a (= M a / a ) = 1000 MPa * s / rad A0b (= M 0b ) = 1 MPa, B1b (= 1 / b ) = 0.1 s / rad , A1b (= M b / b ) = 100 MPa * s / rad A0 c (= M 0c ) = 1 MPa, B1c (= 1 / c ) = 0.01 s / rad , A1c (= M c / c ) = 10 MPa * s / rad where M0 denotes the zero frequency storage modulus, whereas M stands for the infinite frequency

165 Basic mixing rules and rheodynamic effects in ternary

phase-in-phase in phase composite systems. I. the storage modulus

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

Horia PAVEN, Sandor POPOVICS

166

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

167 Basic mixing rules and rheodynamic effects in ternary

phase-in-phase in phase composite systems. I. the storage modulus

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

Horia PAVEN, Sandor POPOVICS

168

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

169 Basic mixing rules and rheodynamic effects in ternary

phase-in-phase in phase composite systems. I. the storage modulus

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