SISOM 2010 and Session of the Commission of Acoustics, Bucharest 27-28 May

THERMORHEODYNAMICAL CHARACTERIZATION OF STANDARD LINEAR VISCOELASTIC SOLID MODEL IN STRESS-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

The extended model of the standard linear viscoelastic solid is considered in case of stress-controlled conditions, the direct primary rheodynamic quantities, including the storage and loss compliances, being taken into account. Accordingly, the trends of these thermodynamic quantities are evidenced from the standpoint of maximum or/and inflection criteria for the frequency dependence in isothermal circumstances, as well as in the case of temperature dependence, if the isochronal circumstances are in view. Keywords: thermorheodynamical standard linear viscoelastic model, isothermal/ isochronal circumstances, stress-controlled conditions, direct primary quantities.

1. INTRODUCTION The present work is motivated by the need to point out the intrinsic peculiarities of frequency, , and temperature, T, dependences of direct primary dynamic viscoelastic quantities in stress-controlled conditions, including the storage compliance, J ( , T ) , and the loss compliance, J ( , T ) , in the realm of the standard linear viscoelastic solid model [1] -[5]. Accordingly, the general form of the dynamic rheological equation in case of a sinusoidal ~ ~ stress-controlled excitation, , and a resulting sinusoidal strain, , of same angular frequency, but shifted in time, is expressed as [6] ~ ~ (1 + i ) = ( J l + i J h ) (0.1)

where J l , J h are the low- and high-frequency limit of storage compliances, respectively, the Arrhenius-like
retardation time being given as [7]

(T ) = exp(T / T )

(0.2)

while () , and T stands for a somewhat virtual activation temperature defined as the A / R ratio, ( A represents the well known -Arrhenius activation energy, and R = 8.314 J / mol * K is the universal gas constant). In order to carry out a self-contained extended approach, typical definitions of extremum (maximum)and inflection-conditions in the case of isothermal cirumstances, i. e., the frequency dependence at given temperature - ( ;T ) , and of isochronal ones, i. e., the temperature dependence at given frequency - (T ; ) , are used to generate the - and T-characteristic equations which provide in a natural way the values of corresponding independent variables.

Horia PAVEN, Sandor POPOVICS

118

2. METHOD AND RESULTS 2. 1 Storage moduls By using the basic definitions (0.1), (0.2), the general expression of the storage compliance results as
2T T

J ( , T ) =

J l + J h e
2 2

1 + e
2 2

2T T

(1.0)

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

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

(1.1.1) (1.1.2)

indicates the corresponding first order -derivative, if there is a well defined (+,-) sequence of the signs of corresponding derivative. The resulting first -characteristic equation is =0 (1.1.3) i. e., without a m{ J ( ;T )} > 0 solution. On the other part, if there is an inflection of the storage compliance, J ( ;T ) , at the frequency

i{ J ( ;T )} , it is in fact the positive solution of the second -characteristic equation, i. e., i{ J ( ;T )} = sol[ D ( 2) J ( ; T ) = 0]
where (1.1.4)

D J (; T )
( 2)

2 J ( ;T ) 2

(1.1.5)

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

1 + 3 e
2 2

2T T

=0
T T

(1.1.6)

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

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

(1.1.7)

By definition, if there is a maximum of the storage compliance, J (T ; ) , at a temperature Tm{ J (T ; )} , it represents the positive solution of the first T-characteristic equation, i. e., where

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

(1.2.1)

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

DT J (T ; )

J (T ; ) T

(1.2.2)

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

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

(1.2.3)

On the other hand, the inflection(s) of the storage compliance, J (T ; ) , at the temperature Ti{ J (T ; )} , is(are) the positive solution(s) of the second T-characteristic equation, i.e.,

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

(1.2.4)

where

DT J (T ; )
( 2)

2 J (T ; ) T 2

(1.2.5)

is the second order T-derivative, if there is(are) (+,-) inversions of derivative signs. The resulting second T-characteristic equation is
2T T

(T + T ) + (T T ) 2 e
2

=0

(1.2.6)

with positive solutions, if the above quoted condition for the second derivative exists. 2. 2 Loss compliance Given the basic relationships (0.1), (0.2), the loss compliance is expressed as

J ( , T ) =

( J l J h ) e T 1 + 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 compliance, J ( ; T ) , at the frequency

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

(2.1.1)

D J ( ;T )

J ( ;T )

(2.1.2)

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

1 2 e
2

=0

(2.1.3)

with a positive solution

Horia PAVEN, Sandor POPOVICS

T

120
(2.1.3a)

m{ J ( ;T )} = 1 /( e T )
which obeys to the above quoted (+, -) order of signs criterium.

In the case of the existence of an inflection of the loss compliance, J ( ; T ) , at a defined frequency,

i{J ( ;T )} , the second -characteristic equation has a positive solution, i. e., i{ J ( ;T )} = sol[ D ( 2) J ( ;T ) = 0]
where (2.1.4)

D
signs.

( 2)

2 J ( ;T ) J ( ;T ) 2

(2.1.5)

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

3 + 2 e
2

2T T

=0
T T

(2.1.6)

has a positive solution

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

(2.1.6a)

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

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

(2.2.1) (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 + e
2 2

=0

(2.2.3) (2.2.3a)

with the positive solution

T m{ J (T ; )}=

T ln[1 /( )]

supposed to fulfill a frequency restriction, too. Moreover, if there is(are) inflection(s) of storage compliance, J (T ; ) , at temperature Ti{ J (T ; )} , it(they) corresponds to the positive solution of the second T-charcteristic equation, i. e.,

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

(2.2.4)

where

DT J (T ; )
( 2)

2 J ( ;T ; ) T 2

(2.2.5)

is the second order T-derivative, if there is(are) inversion(s) of derivative signs.

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

The second T-characteristic equation, with expected positive solution Ti{ J (T ; )} , is

(T + 2T ) 6 T e
2 2

2T T

+ (T 2T ) e
4 4

4T T

=0

(2.2.6)

if appropriate signs inversions take place. 3. CONCLUSIONS The use of the proposed frequency and temperature coupled model of standard linear viscoelastic behaviour points 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 the case of frequency dependence, in isothermal circumstances, the storage compliance shows a monotonic decrease with frequency, with a typical inflection, while the loss compliance presents a peak-like form, with a maximum at intermediate frequencies and then, at higher values, a clear inflection arise, the quoted frequencies being in the sequence

i{ J ( ;T )} < m{ J ( ;T )} < i{ J ( ;T )}

- in the case of temperature dependence, in isochronal circumstances, the resulting experimental data for the storage compliance reflects an increase, as well as the existence of a typical inflection-like effect, while the loss compliance shows both a maximum peak and two inflections, which can be obtained on the basis of analytical solutions of T- characteristic equations. Furthermore, it is essential to mention that while the modulus-based properties points out on the peculiarities of stiffness capacity, the compliance-like ones reveals the distinctiveness of deformational capacity of materials, essential features being involved in dissimilar ways taking into account the loading conditions and the appropriate circumstances. REFERENCES
1. LAKES, R. S., Viscoelstic Materials, Cambridge, Cambridge Univ. Press, pp. 55-89, 207-270, 2009. 2. BRINSON, H. F., BRINSON, L. C., Polymer Engineering Science and Viscoelasticity, New Yok, Springer, pp. 221-364, 2008. 3. MARK, J. E. (Ed.), Properties of Polymers Handbook, New York, Springer, pp. 455-478, 2007. 4. PHAN-THIEN N., Understanding Viscoelasticity, Berlin, Springer, pp. 59-99, 2002. 5. TSCHOEGL, N. W., Phenomenological Theory of Linear Viscoelastic Behavior, New York, Springer, pp. 69-243, 1989. 6. PAVEN, H., Relatii exacte in analiza fenomenologica a proceselor reodinamice de relaxare/retardare in vascoelasticitatea liniara a sistemelor polimerice. II.1 Marimi caracteristice primare in cazul proceselor reodinamice de tensionare controlata, Materiale Plastice, 41(2); 57-61, 2004. 7. KRAUSZ, A. S., EYRING, H., Deformation Kinetics, New York, Wiley-Interscience, pp. 6-28, 107-142, 1975.