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. II. DERIVATE 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 use of the frequency and temperature extended model of linear viscoelastic behaviour to describe both the frequency dependence in isothermal circumstance as well as the temperature dependence in isochronal one, is proposed for derivate primary rheodynamic quantities represented by the absolute modulus and the loss factor for strain-controlled conditions. Accordingly, the monotonic trends of the absolute modulus as well as of the typical loss factor peak are evaluated by using the resulting - and T-caracteristic equations. Keywords: thermorheodynamical standard linear viscoelastic model, circumstances, strain-controlled conditions, derivate primary quantities. isothermal/isochronal

1. INTRODUCTION The large range of variation of end-use conditions of viscoelastic-like model materials needs deeper know-why understanding of control mechanisms providing meaningful scientific and practical-technical data [1]-[11]. Correspondingly, to complete the spectrum of intrinsic peculiarities of frequency, , or temperature, T, dependence of primary dynamic viscoelastic quantities in straincontrolled conditions, the derivates ones, including the absolute modulus, | M * ( ; T ) | , and the loss factor,

M (; T ) , in the coupled frequency and temperature realm of standard linear viscoelastic solid, are
considered [12]. Basic definitions of extremum(maximum)- and inflection-conditions in 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 providing the values of corresponding independent , T variables. ~ ~ In the situation of a sinusoidal strain-controlled condition, , and resulting sinusoidal stress, , of same frequency, but shifted in time, the typical rheological equation ~ ~ (1 + i ) = ( M l + i M h ) (0.1) is coupled with the Arrhenius definition of relaxation time = exp(T / T ) (0.2)

where M l , M h represent the low- and high-frequency limit of storage modulus, respectively, ()
and T stands for a virtual activation temperature defined as the A / R ratio, ( A is the Arrhenius activation energy, while R = 8,314 J / mol * K express the universal gas constant).

159

Thermorheodynamical characterization of standard linear viscoelastic solid model. II. derivate primary quantities

2. METHOD AND RESULTS Absolute modulus. As a consequence of basic relations (0.1), (0.2), the general expression of the absolute modulus is
2T T

| M * ( , T ) |= (

2 2 2 M l + M h 2 e

1 + 2 e
Frequency dependence in isothermal circumstances - ( ; T ) .

2T 2 T

)1 / 2
(3.0)

If the absolute modulus, | M * ( ; T ) | , shows a maximum at the frequency m{| M *( ;T )|} , this frequency is the solution of the first -characteristic equation, i. e., where

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

D | M * ( ;T ) | | M * ( ;T ) |

(3.1.1) (3.1.2)

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

which means it is without a positive solution m{| M *( ;T )|} .

=0

(3.1.3)

In case of 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

(3.1.4)

( 2)

| M * ( ;T ) |

2 | M * ( ;T ) | 2

(3.1.5)

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

+ M l 2 2 M l e
2 2 2

2T T

3 4 M h e
4 2 2

4T T

=0
2 T T

(3.1.6)

with a positive solution

i{| M *(T ; )|} = ( 3 / 3)( M l / M h )

satisfying the above quoted signs sequence criterium.

1 + 3M h / M l 1 /( e )

(3.1.6a)

Temperature dependence in isochronal circumstances - (T ; ) . The maximum of the absolute modulus, | M * (T ; ) | , at the temperature Tm{| M *(T ; )|} means this is the solution of the first T-characteristic equation, i. e.,

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

(3.2.1)

Horia PAVEN, Sandor POPOVICS

160

where

DT | M * (T ; ) |

| M * (T ; ) | T

(3.2.2)

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

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

(3.2.3)

The existence of an inflection of | M * (T ; ) | at the temperature Ti{| M *(T ; )|} , indicates this is given as the positive solution of the second T-characteristic equation, i. e.,

Ti{| M *(T ; )|} = sol[ DT

where

( 2)

| M * (T ; ) |= 0]

(3.2.4)

DT

( 2)

2 | M * (T ; ) | | M * (T ; ) | T 2
2T T 4T T

(3.2.5)

is the corresponding second order T-derivative, if the signs inversion is present. The resulting second T-characteristic equation is

2(T + T ) M l + [(T + 2T ) M h (T 2T ) M l ] 2 e
2 2 2 2 4

(3.2.6)

2(T T ) 4 M h e
2

=0

with presumed Ti{| M *(T ; )|} > 0 solution, obeying to the signs inversion criterium. Loss factor In virtue of the basic definitions (0.1), (0.2), the general expression of the loss factor is defined as

M ( , T ) =

( M h M l) e M l + M h 2 e
2

T T

2T T

(4.0)

Frequency dependence in isothermal circumstances - ( ; T ) . If the loss factor, M ( ; T ) , is characterized by the presence of a maximum at the frequency
M

m{
i. e.,

( ;T )} ,

the value of this frequency is given as the positive solution of the first -characteristic equation,

m{
where

( ;T )}

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

(4.1.1) (4.1.2)

D M ( ;T )

is the first order -derivative, if a (+,-) sequence of derivative signs is existent. The first -characteristic equation is
2 + M l 2 M h e

=0

(4.1.3)

providing a positive solution

161

Thermorheodynamical characterization of standard linear viscoelastic solid model. II. derivate primary quantities
M l /( e T ) Mh

m{

( ;T )}

(4.1.3a)

satisfying the (+,-) sequence of signs restriction. Further, if an inflexion of M ( ; T ) exists at the frequency i{ M ( ;T )} , it represents the positive solution of the second -characteristic equation, i. e.,

i{
where
( 2)

( ;T )}

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

(4.1.4)

D M ( ;T )

2 M ( ;T ) 2
2T T

(4.1.5)

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

3M l + M h e
2 2

=0
T

(4.1.6)

with the positive solution

i{
satisfying the (-,+) signs sequence.

= 3 M ( ;T )}

M l /( e T ) Mh

(4.1.6a)

Temperature dependence in isochronal circumstances - (T ; ) . The arise of a peak-value of the loss modulus, M (T ; ) , at the temperature Tm{ M (T ; )} indicates the existence of a 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

(4.2.1) (4.2.2)

is the first order T-derivative, if the (+,-) signs sequence of corresponding derivative is present. The resulting first T-characteristic equation is
2 M l 2 M hT e 2T T

=0

(4.2.3)

with the positive solution

Tm{ M (T ; )} =
satisfying the signs sequence requirement.

T ln[ M l / M h /( )]

(4.2.3a)

At the end, the presence of a inflection of M (T ; ) at the temperature Ti{ M (T ; )} , needs the existence of a positive solution

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

(4.2.4) where

DT M (T ; )
( 2)

2 M (T ; ) T 2

(4.2.5)

is the corresponding second order T-derivative, if there is an signs inversion of the corresponding derivative .

Horia PAVEN, Sandor POPOVICS

162
4T

The resulting second T-characteristic equations is

(T + 2T ) M l 6 2 M lM hT e
2 2

2T T

+ (T 2T ) 4 M h e T = 0
4 2

(4.2.6)

with a presumed positive solution satisfying the above quoted criterium of derivative signs sequence. 3. CONCLUSIONS The standard linear viscoelastic solid model provides in a well perceptive way typical peculiarities of derivate primary rheodynamic quantities expressed in terms of both frequency and temperature influences: - in case of frequency dependence, in isothermal circumstances, the absolute modulus represents a well definite cumulate contribution of a monotonic increase of the storage modulus with frequency, and that of a peak-like one of the loss modulus, the overall result for the absolute modulus being, on the hand, higher values, and on the other hand, monotonic variation, such that for the corresponding characteristic frequencies

i{| M *( ;T )|} < i{M ( ;T )}

while, for the loss factor, reflecting rather an viscoelasticity index than exclusively a measure of a dissipative mechanism, a new peak-like effect identified by the ensuing frequencies

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

occurs; - in case of temperature dependence, in isochronal circumstances, the absolute modulus evidences the net result of the contribution of peak-like form of loss modulus and that of the monotonic decrease with temperature of the storage modulus, the effect is given by the characteristic temperatures Tm{M (T ; )} < Tm{ M (T ; )} , whereas, for the loss factor, the temperature dependence of loss modulus to storage modulus results in a new peak-like effect defined by the solutions of a T-characteristic equation. Furthermore, basic recommendations of realistic confidence criteria for the isothermal frequency dependence as well as for isochronal temperature one are the natural development step of forthcoming approaches. REFERENCES
1. MENCZEL, J. D., PRIME, R. B. (Eds.), Thermal Analysis of Polymers. Fundamentals and Applications, Hoboken, Wiley, pp. 387-595, 2009. 2. KIM, Y. R., Modeling of Asphalt Concrete, McGraw Hill, New York, pp. 89-137, 2009. 3. GABBOTT, P. (Ed.), Principles and Applications of Thermal Analysis, Oxford, Blackwell, pp. 119-163, 2008. 4. CHENG, S. Z. D., Phase Transitions in Polymers. The Role of Metastable Phases, New York, Elsevier, pp. 18-59, 2008. 5. STROBL, G., The Physics of Polymers, Berlin, Springer, pp. 223-286, 2007. 6. MARK, J. E. (Ed.), Properties of Polymers Handbook, New York, Springer, pp. 455-478, 2007. 7. WARD, I. M., SWEENEY J., The Mechanical Properties of Solid Polymers, Chichester Wiley, pp. 53-120, 2004. 8. PHAN-THIEN N., Understanding Viscoelasticity, Berlin, Springer, pp. 59-99, 2002. 9. PUSKAR, A., Internal Friction of Materials, Cambridge, Cambridge International Science Publs., pp. 5-180, 2001. 10. BARNES, H. A., HUTTON, J. F., WALTERS K., Introduction to Rheology, Amsterdam, Elsevier, pp. 37-54, 1989. 11. TSCHOEGL, N. W., Phenomenological Theory of Linear Viscoelastic Behavior, New York, Springer, pp. 69-243, 1989. 12. PAVEN, H., Relatii exacte in analiza fenomenologica a proceselor de relaxare/retardare in vascoelasticitatea liniara a sistemelor polimerice. I.1 Marimi caracteristice primare in cazul proceselor reodinamice de deformare controlata, Materiale Plastice 40, 4, pp. 171-176, 2003.