SISOM 2009 and Session of the Commission of Acoustics, Bucharest 28-29 May

THERMORHEODYNAMICAL CHARACTERIZATION OF STANDARD LINEAR VISCOELASTIC SOLID MODEL IN STRAIN-CONTROLLED CONDITIONS. I. DIRECT PRIMARY QUANTITIES

Horia PAVEN*, Sandor POPOVICS**

*

National Institute of Research and Development for Chemistry and Petrochemistry - ICECHIM, Bucharest, ROMANIA, e-mail: htopaven@netscape.net ** Drexel University, Philadelphia, 19104-PA, USA

By using an extended model of standard linear viscoelastic solid, the isothermal and isochronal circumstances are taken into account in case of direct primary rheodynamic quantities including the storage and the loss modulus in strain- controlled conditions. Correspondingly, the monotonic variation of the storage modulus as well as the peak-like one of the loss modulus are approached from the standpoint of maximum and inflection criteria, respectively, the meaning of - and T-characteristic equations being pointed out. Keywords: thermorheodynamical standard linear viscoelastic model, circumstances, strain-controlled conditions, direct primary quantities. isothermal/isochronal

1. INTRODUCTION Extensive theoretical and experimental work has gone into approaching rheological properties of emergent materials [1] - [6]. Accordingly, the present work is highly motivated by the essential need to point out the intrinsic peculiarities of frequency, , and temperature, T, dependences of direct primary dynamic viscoelastic quantities in strain-controlled conditions, including the storage modulus, M ( , T ) , and the loss modulus, M ( , T ) , in the realm of the model of standard linear viscoelastic solid.The general form of the ~ dynamic rheological equation in case of a sinusoidal strain-controlled excitation, , and resulting sinusoidal ~ stress, , of same frequency but shifted in time, is expressed as [7] ~ ~ (1 + i ) = ( M l + i M h ) (0.1)

where M l , M h represent the low- and high-frequency limit of storage modulus, respectively, the
Arrhenius-like relaxation time being given as

(T ) = exp(T / T )

(0.2)

() , and T stands for a virtual activation temperature defined as the A / R ratio, ( A is the
-Arrhenius activation energy, and R = 8,314 J / mol * K stands for the universal gas constant). Typical definitions of extremum(maximum)- and inflection-conditions in case of isothermal cirumstances, i. e., the frequency dependence at given temperature - ( ;T ) , and of isochronal one, i. e., the temperature dependence at given frequency - (T ; ) , are used to generate the - and T-characteristic equations wich provide the values of corresponding independent variables. 2. METHOD AND RESULTS Storage moduls. Taking into account the basic definitions (0.1), (0.2), the general expression of the storage modulus is

Horia PAVEN, Sandor POPOVICS

154
2T T

given as

M ( , T ) =

M l + M h 2 e
2

1 + 2 e
2

2T T

(1.0)

Frequency dependence in isothermal circumstances - ( ; T ) . If there is a maximum of the storage modulus, M ( ;T ) , at the frequency m{M ( ;T )} , this is the solution of the first -characteristic equation, i. e., where

m{M ( ;T )} = sol[ D M (; T ) = 0]
D M ( ;T ) M (; T )

(1.1.1) (1.1.2)

is the corresponding first order -derivative, if a (+,-) sequence of corresponding signs exists. The resulting first -characteristic equation is i. e., without a m{M ( ;T )} > 0 solution.

=0

(1.1.3)

On the other hand, if there is an inflection of M ( ;T ) at the frequency i{M ( ;T )} , it is given as the positive solution of the second -characteristic equation, i. e.,

i{M ( ;T )} = sol[ D ( 2 ) M (;T ) = 0]

where

(1.1.4)

D M (; T )
( 2)

2 M ( ;T ) 2

(1.1.5)

is the corresponding second order -derivative, if there is a (+,-) signs sequence of the second derivative. The resulting second -characteristic equation is

1 3 2 e
2

2T T

=0
T

(1.1.6)

with a i{M ( ;T )} > 0 solution

i{M ( ;T )} = ( 3 / 3) /( e T )
the signs criterium being fulfilled. Temperature dependence in isochronal circumstances - (T ; ) .

(1.1.7)

By definition, the maximum of the storage modulus, M (T ; ) , at a temperature Tm{M (T ; )} , represents the positive solution of the first T-characteristic equation, i. e., where

Tm{M (T ; )} = sol[ DT M (T ; ) = 0] DT M (T ; ) M (T ; ) T

(1.2.1) (1.2.2)

depicts the corresponding first order T-derivative, if a (+,-) signs sequence of this derivative exists.

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Thermorheodynamical characterization of standard linear viscoelastic solid model. I. direct primary quantities

The resulting first T-characteristic equation is

eT = 0
without a positive solution Tm{M (T ; )} .

(1.2.3)

On the other part, the inflection of M (T ; ) at the temperature Ti{M (T ; )} is the positive solution of the second T-characteristic equation, i. e.,

Ti{M (T ; )} = sol[ DT M (T ; ) = 0]
( 2)

(1.2.4)

where

DT

( 2)

M (T ; )

2 M (T ; ) T 2
2T

(1.2.5)

is the second order T-derivative, if there is a signs inversion of this derivative. The resulting second T-characteristic equation is

(T + T ) (T T ) 2 e T = 0
2

(1.2.6)

with a presumed positive solution, if the above quoted condition for derivative exists. Loss modulus. In virtue of the basic definitions (0.1), (0.2), the loss modulus is given as

M ( , T ) =

( M h M l) 0e T 1 + 0 e
2 2 2T T

(2.0)

Frequency dependence in isothermal circumstances - ( ; T ) . As is well established, if there is a maximum of the loss modulus, M ( ; T ) , at the frequency

m{M ( ;T )} , it is obtained as the positive solution of the first -characteristic equation, i. e., m{M ( ;T )} = sol[ D M ( ;T ) = 0]
where

(2.1.1) (2.1.2)

D M ( ;T )

M ( ; T )

represents the first order -derivative, if a (+,-) sequence of derivative signs is present. The resulting first -characteristic equation is
2T T

1 2 e
2

=0
T T

(2.1.3)

with a - positive solution

m{M ( ;T )} = 1 /( e )
obeying to the above quoted signs criterium. Further, in case of existence of a M ( ; T ) inflection at a frequency i{M ( ;T )} , the second -characteristic equation has a positive solution, i. e.,

(2.1.3a)

i{M ( ;T )} = sol[ D ( 2) M ( ;T ) = 0]

(2.1.4)

Horia PAVEN, Sandor POPOVICS

156

where

D M (; T )
( 2)

2 M ( ;T ) 2
2T T

(2.1.5)

express the corresponding second order T-derivative, if there is a typical (-,+) sequence of derivative signs. The resulting second -characteristic equation

3 + e
2 2

=0
T

(2.1.6)

admits the positive solution

i{M ( ;T )} = 3 /( e T )
and satisfies the referred to signs sequence condition. Temperature dependence in isochronal circumstances - (T ; )

(2.1.6a)

If a maximum of the loss modulus, M (T ; ), exists at temperature Tm{M (T ; )} , it results to be the positive solution of the first T-characteristic equation, i. e., where

Tm{M (T ; )} = sol[ DT M (T ; ) = 0] M (T ; ) T

(2.2.1)

DT M (T ; )

(2.2.2)

is the first order T-derivative, if there is a (+,-) signs sequence of this derivative. The resulting first T-characteristic equation is
2T T

1 + 2 e
2

=0

(2.2.3) (2.2.3a)

with the positive solution

T m{M (T ; )}=
supposed to fulfill the derivative signs restriction.

T ln[1 /( )]

Moreover, if there is an inflection of M (T ; ) at temperature Ti{M (T ; )} , this corresponds to the positive solution of the second T-charcteristic equation, i. e.,

Ti{M (T ; )} = sol[ DT M (T ; ) = 0]
( 2)

(2.2.4)

where

DT M (T ; )
( 2)

2 M (; T ; ) T 2

(2.2.5)

is the second order T-derivative, if there is a derivative signs inversion. The resulting second T-characteristic equation is
2T T 4T T

(T + 2T ) 6 T e
2 2

+ (T 2T ) e
4 4

=0

(2.2.6)

with expected positive solutions Ti{M (T ; )} , if the corresponding signs inversion of the second order T-derivative is fulfilled.

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Thermorheodynamical characterization of standard linear viscoelastic solid model. I. direct primary quantities

3. CONCLUSIONS The use of the proposed frequency and temperature coupled model of standard linear viscoelastic behaviour point out in a meaningful manner intrinsic features revealed by the direct primary rheodynamic quantites given in an explicit form, as frequency and temperature effects: - in case of frequency dependence, in isothermal circumstances, the storage modulus shows a monotonic increase with frequency, as well as an inflection, whereas the loss modulus presents a peak-like trend, including a maximum and then, at higher frequencies, an inflection, in the sequence i{M ( ;T )} < m{M ( ;T )} < i{M ( ;T )} ; - in case of temperature dependence, in isochronal circumstances, experimental data for the storage modulus reflects a decrease, and an increase with the frequency, as well as the existence of an inflection-like effect, while the loss modulus presents both maximum peak- and inflection trends, resulting on the basis of analytical solutions of T- characteristic equations.

REFERENCES
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