SISOM 2007 and Homagial Session of the Commission of Acoustics, Bucharest 29-31 May

MULTIFUNCTIONALITY SELECTION CRITERIA IN THE DYNAMIC

THERMORHEOLOGICAL CHARACTERIZATION OF SOLID-LIKE POLYMER
MATERIALS. I. PMMA IN TENSILE CONDTIONS

Horia PAVEN*, Mariana CRISTEA**, Bogdan C. SIMIONESCU**

*ICECHIM - National Research and Development Institute of Research for Chemistry and Petrochemistry, Bucharest;
email: htopaven@netscape.net
**Petru Poni - Institute of Macromolecular Chemistry, Iassy.

The expose is a tentative towards a meaningful comprehensive evaluation of the potential

multifunctionality from the view point of thermorheological behaviour by means of dynamic
mechanical analysis. Experimental data obtained for PMMA in tensile conditions using a stress controlled system working at constant heating rate and multiple oscillation frequencies mode,
including the storage and loss moduli as well as the loss factor, are further processed in order to
complete the self contained set of characteristic dual modulus/compliance quantities both in
temperature and frequency descriptions.
Key words: multifunctionality,thermorheology, dynamic behaviour, PMMA..

1. INTRODUCTION
Realistic identification of the secure range of functionality variables in case of polymer materials needs
both the improvement of phenomenological approaches as well as the use of advanced experimental
equipment, the requirement being of outmost relevance rather when new generation hybrid systems are in
view [1], [2].
The rheological behaviour of many materials, especially of polymer-like ones, shows a high sensivity
from the standpoint of temperature, time, frequency, pressure, etc., the separate and cumulate effects
requiring the possibility to ensure a programmable control of variables, e.g., dynamic strain-(or stress-)
controlled excitation conditions at constant rate heating and different frequencies, or a frequency scaning and
different temperatures [3]-[9].
Accordingly, the full set of rheodynamic quantities, including for strain()-controlled conditions, the
primary quantities - the storage, M ( ) , loss, M ( ) , and absolute modulus, | M * ( ) | , as well as the

( ) , loss, J M ( ) , and
corresponding loss factor, M ( ) , - and the secondary ones - the storage, J M
absolute compliance, | J ( ) | , as well as the corresponding loss factor, J M ( ) , and in case of stress()*

controlled state, the primary quantities - the storage, J ( ) , loss, J ( ) , and absolute compliance,

| J * ( ) | , as well as the corresponding loss factor, J ( ) , - and the secondary ones - the storage, M J ( ) ,
loss, M J ( ) , and absolute compliance, | M J ( ) | , as well as the corresponding loss factor, J M ( ) , are
*

to be taken into account.

2. RESULTS AND DISCUSSION
Dynamic mechanical thermal analysis was conducted on Perkin Elmer Diamond DMA with the tensile
mode of deformation. The controlled temperature was from 15 to 190C with a constant heating ramp of

65

Multifunctionality selection criteria in the dynamic thermorheological characterization of solid-like polymer materials

2C/min. The active dimensions of a standard PMMA sample were 20.00 x 8.03 x 0.23 mm. The working
frequencies were 0.5; 1.0; 2.0;5.0; 10.0 Hz.
It is noteworthy to point out that while many available DMA instruments operate in a slow isothermal
step mode when performing frequency multiplexing experiments, with a lot of difficulties from the
standpoint of data collection, in case of employed system, owing to real-time FT technology and Synthetic
Oscillation (SO) mode, a complex sine stress which contains five simultaneous frequencies is applied to the
sample. Then, the resulting complex strain and stress sine waves are deconvoluted, and operated to compute
the different quantitative dynamic viscoelastic quantities [4]-[7], the shortcoming of only one discrete
frequency sequentially applied at a time in traditional systems being overcomed in case of SO mode option
when the sample is subjected to all five frequencies simultaneously.
The storage quantities (e.g., M ( , T ) and J ( , T ) ) are directly and inversely proportional,
respectively, to the recoverable component of energy of strain- and stress-controlled processes, respectively,
while the loss quantities (e.g., M ( , T ) and J ( , T ) ) relates to the corresponding dissipation
components. Furthermore, the absolute quantities (e.g., | M * ( , T ) | and | J * ( , T ) | )) l are measures of
overall dynamic rigidity

and compliance, respectively, whereas the

M ( , T ) = tan M ( , T )

M ( , T ) = tan M ( , T ) giving the loss factor in both considered cases appear to be rather an index of
viscoelasticity issued as a direct consequence of the lag between the dynamic stress and strain.
The dependence of the full set of rheodynamic quantities vs. temperature at different frequencies
(Figure 1), is presented on the basis of primary data - the storage and loss modulus as well as the
corresponding loss factor. The essential trends show, at given frequency, D , a monoton decrease with the
rise of temperature in case of

M (D , T ) and | M * ( D , T ) | , and a similar monoton, but increase, for

J (D , T ) and | J * ( D , T ) | . Furthermore, at given frequencies, distinct peaks corresponding to well defined

dynamic relaxation/relaxation or mixed processes, are observed in the increasing sequence - M ( D , T ) ,
M (D , T ) , J (D , T ) . Moreover, as result of the increase of control frequency, higher values in the former
case or shifts of the peaks towards higher temperatures in the later one, are observed.
In virtue of these results, a lot of functionality criteria may be defined in terms of differences and ratios
of characteristic temperatures (Table 1), as well by using the dynamic Arrhenius-like apparent activation
energies for typical rheodynamic relaxation/retardation or mixed processes (Figure 2).
Conversely, the dependence of the complete set of rheodynamic quantities vs. frequency at different
temperatures (Fig. 3), reveals distinctive trends, too. Thus, temperature-controlled effects, indicate, at given
temperature, TD , in case of M ( , TD ) and | M * ( , TD ) | nonlinear rise with increase of frequency, the
positions of TD -curves being in an ascending order, whereas a similar monoton, but decreasing with rise of
frequency, for J ( , TD ) and | J * ( , TD ) | , are present. Moreover, in case of available frequency range,

different loss rheodynamic quantities point out dissimilar tendencies - for E ( , TD ) , T TE , an increase,
and, for T TE , an inversion of relative positions of frequency controlled curves ; for tan D , T Ttan D ,
approximately constant values, and, for T Ttan D , decrease, with higher values; for J , T TJ , an
approximately constant value, and, for T TJ , a decrease, with higher values.

Horia PAVEN, Mariana CRISTEA, Bogdan C. SIMIONESCU

a.1-E1(T)

66

a.2-E1(T)

4.50E+09

1.00E+10

4.00E+09
3.50E+09

1.00E+09

f=0.5Hz

2.50E+09

f=1.0Hz
f=2.0Hz

2.00E+09

f=5.0Hz

E1[Pa]

E1[Pa]

3.00E+09
f=0.5Hz
f=1.0Hz

1.00E+08

f=2.0Hz
f=5.0Hz

f=10.0Hz

f=10.0Hz

1.50E+09
1.00E+07

1.00E+09
5.01E+08
1.00E+06

1.00E+06

0.00E+0 2.00E+0 4.00E+0 6.00E+0 8.00E+0 1.00E+0 1.20E+0 1.40E+0 1.60E+0 1.80E+0 2.00E+0
0
1
1
1
1
2
2
2
2
2
2

0.00E+0 2.00E+0 4.00E+0 6.00E+0 8.00E+0 1.00E+0 1.20E+0 1.40E+0 1.60E+0 1.80E+0 2.00E+0
0
1
1
1
1
2
2
2
2
2
2

T[C]

]T[C

b.1-E2(T)

b.2-E2(T)

3.50E+08

1.00E+09

3.00E+08

1.00E+08

2.00E+08

f=0.5Hz
f=1.0Hz
f=2.0Hz

1.50E+08

f=5.0Hz

E2[Pa]

E2[Pa]

2.50E+08

f=0.5Hz
f=1.0Hz

1.00E+07

f=2.0Hz
f=5.0Hz

f=10.0Hz

f=10.0Hz

1.00E+08

1.00E+06
5.00E+07

1.00E+05

0.00E+00
0.00E+0 2.00E+0 4.00E+0 6.00E+0 8.00E+0 1.00E+0 1.20E+0 1.40E+0 1.60E+0 1.80E+0 2.00E+0
0
1
1
1
1
2
2
2
2
2
2
T[C]

0.00E+0 2.00E+0 4.00E+0 6.00E+0 8.00E+0 1.00E+0 1.20E+0 1.40E+0 1.60E+0 1.80E+0 2.00E+0
0
1
1
1
1
2
2
2
2
2
2
]T[C

c.1-|E*|(T)

c.2-|E*|(T)

4.50E+09

1.00E+10

4.00E+09

1.00E+09
1.00E+08

3.50E+09

1.00E+07

3.00E+09

1.00E+06

f=1.0Hz
f=2.0Hz
f=5.0Hz

2.00E+09

|E*|[Pa]

|E*|[Pa]

f=0.5Hz
2.50E+09

f=0.5Hz
f=1.0Hz

1.00E+05

f=2.0Hz
f=5.0Hz

1.00E+04

f=10.0Hz
1.50E+09

f=10.0Hz

1.00E+03

1.00E+09

1.00E+02

5.00E+08

1.00E+01

0.00E+00

1.00E+00

0.00E+0 2.00E+0 4.00E+0 6.00E+0 8.00E+0 1.00E+0 1.20E+0 1.40E+0 1.60E+0 1.80E+0 2.00E+0
0
1
1
1
1
2
2
2
2
2
2

0.00E+0 2.00E+0 4.00E+0 6.00E+0 8.00E+0 1.00E+0 1.20E+0 1.40E+0 1.60E+0 1.80E+0 2.00E+0
0
1
1
1
1
2
2
2
2
2
2

T[C]

T[C]

d.2-tanDELTA(T)

d.1-tanDELTA(T)
1.00E+01

2.00E+00
1.80E+00
1.60E+00
1.40E+00
f=0.5Hz
f=1.0Hz
1.00E+00

f=2.0Hz
f=5.0Hz

8.00E-01

f=10.0Hz

tanDELTA

tanDELTA

1.00E+00
1.20E+00

6.00E-01

0.00E+0 2.00E+0 4.00E+0 6.00E+0 8.00E+0 1.00E+0 1.20E+0 1.40E+0 1.60E+0 1.80E+0 2.00E+0
0
1
1
1
1
2
2
2
2
2
2

f=0.5Hz
f=1.0Hz
f=2.0Hz
f=5.0Hz
f=10.0Hz

1.00E-01

4.00E-01
2.00E-01
0.00E+00
0.00E+0 2.00E+0 4.00E+0 6.00E+0 8.00E+0 1.00E+0 1.20E+0 1.40E+0 1.60E+0 1.80E+0 2.00E+0
0
1
1
1
1
2
2
2
2
2
2

1.00E-02
]T[C

T[C]

e.2-J1(T)

e.1-J1(T)
1.00E-06

6.00E-07

0.00E+0 2.00E+0 4.00E+0 6.00E+0 8.00E+0 1.00E+0 1.20E+0 1.40E+0 1.60E+0 1.80E+0 2.00E+0
0
1
1
1
1
2
2
2
2
2
2
5.00E-07

1.00E-07

f=0.5Hz
f=1.0Hz

3.00E-07

f=2.0Hz
f=5.0Hz
f=10.0Hz

J1 [1/ P a ]

J1[1/P a]

4.00E-07

f=0.5Hz
f=1.0Hz
f=2.0Hz
f=5.0Hz
f=10.0

1.00E-08

2.00E-07

1.00E-09

1.00E-07

0.00E+00
0.00E+0 2.00E+0 4.00E+0 6.00E+0 8.00E+0 1.00E+0 1.20E+0 1.40E+0 1.60E+0 1.80E+0 2.00E+0
0
1
1
1
1
2
2
2
2
2
2

1.00E-10

]T[C

T[C]

f.2-J2(T)

f.1-J2(T)
1.00E+00

1.60E-07

0.00E+0 2.00E+0 4.00E+0 6.00E+0 8.00E+0 1.00E+0 1.20E+0 1.40E+0 1.60E+0 1.80E+0 2.00E+0
1
1
1
1
2
2
2
2
2
2
1.00E-01 0

1.40E-07

1.00E-02
1.20E-07

1.00E-03
1.00E-04

f=0.5Hz
f=1.0Hz

8.00E-08

f=2.0Hz
f=5.0Hz
f=10.0Hz

6.00E-08

J2[1/Pa]

J2[1/Pa]

1.00E-07

f=0.5Hz
1.00E-05

f=1.0Hz
f=2.0Hz

1.00E-06

f=5.0Hz
f=10.0Hz

1.00E-07
4.00E-08

1.00E-08

2.00E-08

1.00E-09
1.00E-10

0.00E+00
0.00E+0 2.00E+0 4.00E+0 6.00E+0 8.00E+0 1.00E+0 1.20E+0 1.40E+0 1.60E+0 1.80E+0 2.00E+0
0
1
1
1
1
2
2
2
2
2
2

1.00E-11
]T[C

T[C]

g.1-|J*|(T)

g.2-|J*|(T)

6.00E-07

1.00E+00
0.00E+0 2.00E+0 4.00E+0 6.00E+0 8.00E+0 1.00E+0 1.20E+0 1.40E+0 1.60E+0 1.80E+0 2.00E+0
0
1
1
1
1
2
2
2
2
2
2

1.00E-01

5.00E-07
1.00E-02
1.00E-03

f=0.5Hz
f=1.0Hz

3.00E-07

f=2.0Hz
f=5.0Hz
f=10.0Hz

2.00E-07

|J*|[1/Pa]

]J*|[1/Pa|

4.00E-07

1.00E-04

f=0.5Hz
f=1.0Hz

1.00E-05

f=2.0Hz
f=5.0Hz
f=10.0Hz

1.00E-06
1.00E-07

1.00E-07
1.00E-08
1.00E-09

0.00E+00
0.00E+0 2.00E+0 4.00E+0 6.00E+0 8.00E+0 1.00E+0 1.20E+0 1.40E+0 1.60E+0 1.80E+0 2.00E+0
0
1
1
1
1
2
2
2
2
2
2
]T[C

1.00E-10
T[C]

Figure 1. Rheodynamic quantities vs. temperature at different frequencies.

Multifunctionality selection criteria in the dynamic thermorheological characterization of solid-like polymer materials

67

Table 1. Maxima of rheodynamic quantities, corresponding temperatures, ratios and differences.

f

E2m

TE2m

[Hz]

[MPa]

[K]

0.5

220.19
217.74
219.8
221.1
222.9

392.24
392.56
392.96
394.16
394.67

2
5
10

1.747
1.701
1.685
1.65
1.631

TtanDm

J2m

TJ2m

[K]

[1/MPa]

[K]

404.51
406.69
408.72
412.33
415.64

0.139
0.14
0.14
0.139
0.14

421.17
423.64
429.02
435.4
438.23

TtanDm
TJ2m
TtanDm
TJ2m
/
/
TE2m TtanDm TE2m TtanDm
[K]
[K]
1.0313
1.036
1.0401
1.0461
1.0531

1.0412
1.0417
1.0497
1.056
1.0543

12.27
14.13
15.76
18.17
20.97

f(1/T)
3

2.5

2
y = -174375x + 444.13
r2 = 0.9677
1.5
LN{f[Hz]}

tanDm

E2
tanD
J2
Linear (E2)
Linear (tanD)
Linear (J2)

y = -45333x + 111.48
r2 = 0.9923
1
y = -30698x + 72.256
r2 = 0.9835
0.5

0
2.25E-03

2.30E-03

2.35E-03

2.40E-03

2.45E-03

2.50E-03

2.55E-03

-0.5

-1
1/T[K]

Figure 2. Dynamic Arrhenius plots.

Table 2. E2, tanD and J2 Arrhenius - like apparent activation

energies

Frequency
ratio
f1/f05
f2/f1
f5/f2
f10/f5
f10/f1
Aver. val.

Activation energy [kJ/mole]

E2
tanD
J2
2772.958
2222.439
983.2930
1757.810
1405.670
1455

434.882
471.877
355.637
298.38
361.562
374

416.287
194.682
223.043
388.543
243.595
258

2.60E-03

16.66
16.95
20.3
23.07
22.59

Horia PAVEN, Mariana CRISTEA, Bogdan C. SIMIONESCU

a.1- E1(f)

68

a.2- E1(f)

4.50E+03

1.00E+04

4.00E+03

3.50E+03
1.00E+03

2.50E+03

T=25C
T=50C
T=75C

2.00E+03

T=100C
T=125C

E1[MPa]

E1[MPa]

3.00E+03
T=25C
T=50C
T=75C
T=100C

1.00E+02

T=125C

1.50E+03
1.00E+01

1.00E+03

5.00E+02

0.00E+00
0.00E+00

2.00E+00

4.00E+00

6.00E+00

8.00E+00

1.00E+01

1.20E+01

1.00E+00
1.00E+00

1.00E-01

f[Hz]

f[Hz]

b.1- E2(f)

b.2- E2(f)

3.50E+02

1.00E+01

1.00E+03

3.00E+02

2.50E+02

1.50E+02

T=25C
T=50C
T=75C
T=100C

E2[MPa]

E2[MPa]

1.00E+02
T=25C
T=50C
T=75C
T=100C

2.00E+02

T=125C

T=125C
1.00E+01

1.00E+02

5.00E+01

0.00E+00
0.00E+00

2.00E+00

4.00E+00

6.00E+00

8.00E+00

1.00E+01

1.20E+01

1.00E+00
1.00E+00

1.00E-01

f[Hz]

1.00E+01

f[Hz]

c.1- |E*|(f)

c.2- |E*|(f)

4.50E+03

1.00E+04

4.00E+03

3.50E+03
1.00E+03

T=25C
T=50C
T=75C
T=100C
T=125C

2.50E+03

2.00E+03

|E*|[MPa]

|E*|[MPa]

3.00E+03
T=25C
T=50C
T=75C
T=100C
T=125C

1.00E+02

1.50E+03
1.00E+01

1.00E+03

5.00E+02

0.00E+00
0.00E+00

2.00E+00

4.00E+00

6.00E+00

8.00E+00

1.00E+01

1.20E+01

1.00E+00
1.00E+00

1.00E-01

f[Hz]

d.2- tanDELTA(f)

1.20E+00

1.20E+00

1.00E+00

1.00E+00

8.00E-01
T=25C
T=50C
T=75C
T=100C
T=125C

6.00E-01

tanDELTA

tanDELTA

8.00E-01

T=25C
T=50C
T=75C

6.00E-01

T=100C
T=125C

4.00E-01

4.00E-01

2.00E-01

0.00E+00
0.00E+00

1.00E+01

f[Hz]

d.1- tanDELTA(f)

2.00E-01

2.00E+00

4.00E+00

6.00E+00

8.00E+00

1.00E+01

1.20E+01

0.00E+00
1.00E+00

1.00E-01

f[Hz]

1.00E+01

f[Hz]

e.1- J1(f)

e.2- J1(f)
1.00E+00
0.00E+00

5.00E-03

2.00E+00

4.00E+00

6.00E+00

8.00E+00

1.00E+01

1.20E+01

4.50E-03
4.00E-03
1.00E-01

J1[1/MPa]

3.00E-03
2.50E-03

T=25C
T=50C
T=75C

2.00E-03

T=100C
T=125C

J1[1/MPa]

3.50E-03

T=25C
T=50C
T=75C
T=100C
T=125C

1.00E-02

1.50E-03
1.00E-03

1.00E-03
5.00E-04
0.00E+00
0.00E+00

2.00E+00

4.00E+00

6.00E+00

8.00E+00

1.00E+01

1.20E+01

1.00E-04

f[Hz]

f[Hz]

f.2- J2(f)

f.1- J2(f)
6.00E-03
1.00E-01

1.00E+00
1.00E+00

1.00E+01

5.00E-03
1.00E-01

T=25C
T=50C
T=75C

3.00E-03

T=100C
T=125C

1.00E-02

T=25C
T=50C
T=75C
T=100C
T=125C

J2[1/MPa]

J2[1/MPa]

4.00E-03

1.00E-03
2.00E-03

1.00E-03

0.00E+00
0.00E+00

1.00E-04

2.00E+00

4.00E+00

6.00E+00

8.00E+00

1.00E+01

1.20E+01

1.00E-05

f[Hz]

f[Hz]

g.2- |J*|(f)

g.1- |J*|(f)
8.00E-03
1.00E-01

1.00E+00
1.00E+00

1.00E+01

7.00E-03

6.00E-03

1.00E-01

T=25C
T=50C
T=75C

4.00E-03

T=100C
T=125C

|J*|[1/MPa]

|J*|[1/MPa]

5.00E-03

1.00E-02

3.00E-03

T=25C
T=50C
T=75C
T=100C
T=125C

2.00E-03
1.00E-03
1.00E-03

0.00E+00
0.00E+00

2.00E+00

4.00E+00

6.00E+00
f[Hz]

8.00E+00

1.00E+01

1.20E+01

1.00E-04
f[Hz]

Figure 3. Rheodynamic quantities vs. frequency at different temperatures.

69

Multifunctionality selection criteria in the dynamic thermorheological characterization of solid-like polymer materials

At the end, further criteria of evaluating intrinsic multifunctionality from the view point of potential
of polymeric material within the realm of linear viscoelastic behaviour may be considered both the frequency
and/or temperature Cole-Cole patterns of rheodynamic quantities (Figure 5).
E2(E1)

tanDELTA(E1)

3.50E+08

2.00E+00
1.80E+00

3.00E+08
1.60E+00
1.40E+00

f=0.5Hz

2.00E+08

f=1.0Hz
f=2.0Hz
f=5.0Hz

1.50E+08

tanDELTA

E2[Pa]

2.50E+08

f=10.0Hz

1.20E+00

f=0.5Hz
f=1.0Hz

1.00E+00

f=2.0Hz
f=5.0Hz

8.00E-01

f=10.0Hz

6.00E-01
1.00E+08
4.00E-01
5.00E+07

2.00E-01
0.00E+00

0.00E+00
0.00E+00 5.00E+08 1.00E+09 1.50E+09 2.00E+09 2.50E+09 3.00E+09 3.50E+09 4.00E+09 4.50E+09

0.00E+0 5.00E+0 1.00E+0 1.50E+0 2.00E+0 2.50E+0 3.00E+0 3.50E+0 4.00E+0 4.50E+0 5.00E+0
0
7
8
8
8
8
8
8
8
8
8

]E1 [Pa

]E1[Pa

J2(J1)

tanDELTA(J1)
2.00E+00

1.60E-07

1.80E+00

1.40E-07

1.60E+00
1.20E-07
1.40E+00

f=0.5Hz
f=1.0Hz

8.00E-08

f=2.0Hz
f=5.0Hz
f=10.0Hz

6.00E-08

1.20E+00
tanDELTA

J2[1/Pa]

1.00E-07

f=0.5Hz
f=1.0Hz

1.00E+00

f=2.0Hz
f=5.0Hz
f=10.0

8.00E-01
6.00E-01

4.00E-08
4.00E-01
2.00E-08

2.00E-01
0.00E+00

0.00E+00
0.00E+00

1.00E-07

2.00E-07

3.00E-07

4.00E-07

5.00E-07

6.00E-07

0.00E+00

1.00E-07

2.00E-07

3.00E-07

4.00E-07

5.00E-07

6.00E-07

]E1[Pa

J1[1/Pa]

Figure 5. Temperature Cole - Cole patterns.

4. CONCLUSIONS
The versatility of the used DMA system enables a comprehensive characterization of viscoelastic
behaviour versus temperature and frequency, respectively, for complete sets of modulus- and compliancelike quantities substantiated as proper indicators of rheodynamic multifunctionality.
The considered storage and especially rheodynamic loss quantities represent key measures of dynamic
relaxation/retardation and mixed processes, accounting for the outstanding potential of polymeric materials
generated at different levels of structural architecture.
REFERENCES
1. MEZGER ,T. G., The Rheology Handbook, Vincentz Network, Hannover, 2006.
2. SPERLING, L. H., Introduction to Polymer Science, Wiley, 2006.
3. PAVEN, H., Private communication, ICM-PP, Iassy, 1 March 2007.
4. MENARD, K., Dynamic Mechanical Analysis, CRC Press, Boca Raton, 1999.
5. MENARD, K., Basic DMA: Part 1-How DMA works, Perkin Elmer, AN 90, 2002.
6. MENARD, K., Basic DMA: Part 2- Thermoplastic Transitions and Properties, Perkin Elmer, AN 91, 2002.
7. MENARD, K., Basic DMA: Part 3- Frequency effects in Materials, Perkin Elmer, AN 92, 2002.