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=
+
(R
2
= 0.9992) (1)
0.53
2.66 = (R
2
= 0.9648) (2)
As shown in Fig. 2, when the temperature grew
from 30 C to 75 C, the VES acid fluid changes from
a non Newtonian power law fluid to a linear Newto-
nian fluid [9]. At the temperature of 75 C, the rela-
tionship of shear stress and shear rate has changed to a
straight line and can be described by k = (k: a
constant) as its constitutive equation.
As to the relation between viscosity and shear
rate, the results show that the viscosity of the VES
acid system is inversely proportional to shear rate at
temperature of 30 C as shown in Fig. 3, which is just
the characteristics of viscosity-shear rate relation of
non Newtonian power law fluid.
The results show that the shear stress at a high
temperature of 75 C is in direct proportion to shear
rate when the shear rate is in a range of acidification
(between about 20 s
1
to 200 s
1
), and the viscosity is
almost a constant value with the changing of the shear
rate. It means that at higher temperatures (60 C or
75 C) the VES acid system fluid is almost a kind of
linear Newtonian fluid.
3.2 Storage modulus and loss modulus at differ-
ent pH
Storage modulus G and loss modulus G can be
used to indicate the viscoelasticity performance of a
VES acid system [10]. For pure viscous fluids, storage
modulus G equals to zero, while for pure elastomers
loss modulus G is zero. CSL2-500 rheometer was
used to determine their value during the reaction
process between the VES acid and carbonate forma-
tion (with the changing of pH of the system at differ-
ent reaction stages). When the pH of the acid system
increases from about 0 to 4.44, the storage modulus G
changes from 20 Pa to 80 Pa, indicating an obvious
increase in viscosity of the acid system. The loss
modulus G is a small value at a low pH, showing that
the VES acid system has a low viscosity. When pH
grows to 0.01 or more, the G increases obviously
with VES gel formation at this moment as shown
in Fig. 4.
Figure 2 Variation of measured shearing stress with
shearing rate at different temperatures
temperature/C: + 30; 45; 60; 75
Figure 3 Variation of measured viscosity with shearing
rate at different temperatures
temperature/C: + 30; 45; 60; 75
Chin. J. Chem. Eng., Vol. 18, No. 3, June 2010 513
Figure 4 Variations of measured storage modulus G and
loss modulus G with oscillation frequence at different pH
G at pH= 4.44; G at pH= 0.01; G at pH= 0.05;
G at pH= 4.44; G at pH= 0.01; G at pH= 0.05
The ratio of G and G, tg, shows the viscidity
and elasticity of the VES acid system at the same time.
A small value of tg of the VES acid system indicates
a better elastic performance related to viscosity. Fig. 5
shows that tg decreases with the growing of the pH
of the VES acid system at the same oscillation fre-
quence. Therefore, the increase of the pH can result in
the enhancement in the elasticity of the VES acid sys-
tem related to viscosity since the VES gel has been
formed at this stage.
Figure 5 Variations of measured tg with pH
pH: 0.50; 0.01; 4.44
3.3 G and G with different percent of VES in
the acid system
VES results in the high viscoelasticity of the acid
system, therefore, the content of VES in the acid sys-
tem has an obvious effect on the viscosity and the
elasticity of the acid system. Figs. 6 to 8 show the dif-
ferent storage modulus G, loss modulus G, and com-
plex modulus G* with the changes of the VES content
in the acid system. Fig. 6 shows that at a fixed oscilla-
tion frequence, when the VES content changes from
3% to 6%, the storage modulus G increases obviously,
which means the augmentation of the elasticity of the
acid system. It is the same for the loss modulus G
and complex modulus G*, indicating that both the
viscosity and elasticity of the acid system increase
with increasing amount of the VES in the acid system.
Moreover, Fig. 8 shows that when the content of VES
increased from 5% to 6% in the acid system, the com-
plex modulus G* has just a limited increase. Consid-
ering the amplification of the viscoelasticity because
of the addition of VES and the cost of the VES acid,
5% of the VES content in the acid is suitable in the
practice usage.
3.4 The influence of the temperature to the vis-
coelasticity of the VES acid
The storage modulus G and loss modulus G
Figure 6 Variations of measured storage modulus G with
different VES contents
3%VES; 4%VES; 5%VES; + 6%VES
Figure 7 Variations of measured loss modulus G with
different VES contents
3%VES; 4%VES; 5%VES; + 6%VES
Figure 8 Variations of measured complex modulus G*
with different VES contents
3%VES; 4%VES; 5%VES; + 6%VES
Chin. J. Chem. Eng., Vol. 18, No. 3, June 2010 514
were tested at 20 C, 40 C, 60 C and 80 C, then the
ratio of G and G, tg, was calculated. A small tg of
the VES acid system indicates that it has better elastic
performance related to viscosity, and inversely a better
viscosity than elasticity. The relation of tg and tem-
perature is shown in Fig. 9. When the temperature
changed from 20 C to 80 C, tg increased at first,
then decreased to a value even lower than that at the
low temperature. The change of the tg value shows
that the elasticity of the acid system decreases at first,
then increases to a higher level than the value at the
beginning after the temperature grow to about 45 C.
In other words, the viscosity increases at first, then
decreases, which means that the changing trend of tg
is consistent with the relation between viscosity and
temperature.
Figure 9 Variations of measured tg with temperature
tg; fitting line
4 CONCLUSIONS
In this paper, the main parameters of viscoelas-
ticity performance of a new VES acid system were
investigated by the method of Small Amplitude Oscil-
lation dynamic examination. The constitutive equation
for the VES acid system has been elicited out from the
tests. The VES acid fluid is a non Newtonian power
law fluid at low temperature and it changes to a linear
Newtonian fluid at high temperature. The storage
modulus G, loss modulus G etc. have been measured
and the results show that the VES acid system has
viscosity and elasticity simultaneously. The viscoelas-
ticity of the VES acid was increased with an addition
of the VES. The viscosity increases at first and then
decreases with increasing temperature, while the elas-
ticity of the acid system is just the opposite.
NOMENCLATURE
G storage modulus
G loss modulus
G* complex modulus
tg ratio of G and G
shear stress, Pa
shear rate, s
1
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