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The Relationship between Steady Shear Viscosity and

Complex Viscosity
a a a
Shu‐Ping Li , Ge Zhao & Hong‐Yuan Chen
a
Laboratory of Life Analytical Chemistry, Department of Chemistry, Nanjing University,
Nanjing, China
Published online: 21 Aug 2006.

To cite this article: Shu‐Ping Li , Ge Zhao & Hong‐Yuan Chen (2005) The Relationship between Steady Shear Viscosity and
Complex Viscosity, Journal of Dispersion Science and Technology, 26:4, 415-419, DOI: 10.1081/DIS-200054555

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 Journal of Dispersion Science and Technology, 26:415–419, 2005
Copyright # Taylor & Francis, Inc.
ISSN: 0193-2691 print/1532-2351 online
DOI: 10.1081/DIS-200054555

The Relationship between Steady Shear Viscosity

and Complex Viscosity
Shu-Ping Li, Ge Zhao, and Hong-Yuan Chen
Laboratory of Life Analytical Chemistry, Department of Chemistry, Nanjing University, Nanjing, China

Theoretical analysis on the relationship of complex viscosity (h
) and steady shear viscosity (h)
indicates that viscous viscosity (h0 ) measured under linear viscoelastic region equates with
steady shear viscosity at low shear rates, and the Cox-Merz Rule applies only to the suspension
whose viscous viscosity of the system dominates the whole response. From theoretical analysis,
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complex fluids with network structure such as hydrotalcite-like compounds (HTlc)/montmor-

illonite (MT) suspensions are not suitable to the Cox-Merz Rule, and departure from the rule
has been found in all the HTlc/MT suspensions examined. The theoretical deduction and
experimental results from HTlc/MT suspensions show that thixotropic types can be deter-
mined by the change of h0 in the linear viscoelastic region after the system has been pre-
sheared; the increase of h0 with time means positive thixotropy while the decrease of h0 with
time means negative thixotropy. First increase and then decrease of h0 with increasing of
time or vice versa means complex thixotropy. A very useful method to examine the thixotropic
types in the undisturbed states has been found for the first time.

Keywords Viscosity, thixotropy, complex fluids

INTRODUCTION frequency is identical to the functional dependence of the

Dispersions are widely used in various fields, such as paints, steady shear viscosity expressed as a function of shear rate
adhesives, and paper coating and drilling fluids, but the suspen- (Cox and Merz 1958; Doraiswamy et al. 1991). That is
sions are always applied under nonlinear shear conditions, jh
ðvÞj ¼ hðgÞjg ¼ v
which means the colloidal systems do not show a linear or 00

Newtonian shear response. Hence, non-Newton viscosity where h
(v) ¼ h0 (v) 2 ih (v) is the complex viscosity at fre-
p 0 00

plays an important role in the actual process. Unfortunately,
it is very difficult to measure the viscosity of the system for
some dispersions such as coater, it is less difficult to measure
the linear viscoelastic behavior of the suspension at high fre-
quencies. From the point of view of deformation, measure-
ments of linear viscoelastic properties probe a much different
response of the material than steady shear properties. But
from the point of view of deformation rates, the two types of
experiments may probe similar behavior (Chae et al. 2001).
This is the thinking behind our theoretical deduction, in
which we want to find out the relationship between steady
shear viscosity and dynamic viscosity.
One relevant theory is the Cox-Merz Rule, which is really a
hypothesis stating that the functional dependence of the
complex viscosity’s magnitude expressed as a function of
Received 1 November, 2004; Accepted 13 November, 2004.
Address correspondence to Hong-Yuan Chen, Laboratory of Life
Analytical Chemistry, Department of Chemistry, Nanjing University,
Nanjing 210093, China. E-mail: hychen@nju.edu.cn
415
quency v, jh
(v)j ¼ h 2 þ h 2 indicates the magnitude of
complex quantity, and h(ġ) is the steady shear viscosity at
the shear rate ġ.
But this hypothesis has many restrictions, and there are
many reports about departure from the Cox-Merz Rule. (Lee
and David 2002) think the Cox-Merz Rule applies only to
fluids without a “structure” that can be disrupted by large
strain. (Miyoshi and Nishinari 1999) consider if the mechanical
spectra for solutions show a weak-gel behavior, jh
(v)j is sig-
nificantly larger than h(ġ), indicating that the weak-gel struc-
ture can survive small oscillatory deformation but may be
ruptured by large deformation. Therefore, these solutions
tend to depart from the Cox-Merz Rule.
What is the real relationship between h
and h(ġ) and why
can the departure from the Cox-Merz Rule usually be found
in complex fluids? In this article, we will answer these ques-
tions from the theoretical deduction and apply the deductive
results to hydrotalcite-like compounds (HTlc)/sodium mon-
tmorillonite (MT) suspensions.
Hydrotalcite-like compounds (HTlc) are special kinds of
compounds that bear positive charges (Constantino et al.
 416 S.-P. LI, G. ZHAO, AND H.-Y. CHEN
1997), and sodium montmorillonite (MT) is a kind of clay
mineral commonly used in agriculture, cosmetics, adhesives,
and so on. MT bears negative charges because of isomorphous
substitution (Li et al. 2003a), and the HTlc compounds bear
positive charges. The suspension of HTlc/Na-montmorillonite
shows many novel properties, which have been extensively
covered in our previous studies (Li et al. 2001, 2003a, b).
We found that the suspension of HTlc/MT easily forms
three-dimensional gel-like structures and that HTlc/MT sus-
pension is a kind of complex fluid that shows thixotropy, vis-
coelasticity, yield stress, shear-thinning, or shear-thickening
(Li et al. 2001, 2003a, b). So we can conclude that the Cox-
Merz Rule does not apply to the HTlc/MT suspension
because of the formation of the network structure.
The thixotropic properties of HTlc/MT suspensions have
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been extensively studied in our previous articles (Li et al.
2001, 2003a, b). The classical definition of thixotropy is a
kind of suspension behavior where time-dependent, reversible
breakdown of the particulate network structure occurs under
shear, followed by structural reformation on resting
(Mujumdar et al. 2002). In our studies, thixotropy is usually
studied by monitoring the recovery process under the low
shear rates as a function of time after intensive shearing,
which is called the “shearing-rest” method. The increase of
h(ġ) with time means positive thixotropy, while the decrease
of h(ġ) with time means negative thixotropy. First increase
and then decrease of h(ġ) with increasing of time or vice
versa means complex thixotropy. It seems more reasonable
that thixotropy should be determined in the linear-viscoelastic
region or in the undisturbed state, than in the linear region; no
irreversible changes of the structure in the suspension take
place, then thixotropy determined in linear viscoelasticity can
represent inherent properties of the system, and relevant
reports in the literature have not been found.
EXPERIMENTS SECTION
Materials
The preparation and analysis of HTlc: HTlc was synthesized
by the co-precipitation method. The pre-designed metal
chloride was dissolved into the deionized water, then the
solution of NH3 . H2O was slowly pumped into the mixed
solution of metal chloride, with the amount of NH3 . H2O
TABLE 1
Chemical composition and chemical formula of the examined HTlc samples
Sample Raw material
number Sample molar ratio
1 Mg/Al/Fe 2:1:0.1
2 Mg/Al/Fe 2:1:0.6
3 Mg/Al/Fe 2:1:1
4 Mg/Al/Fe 4.5:1:1
controlled to adjust the pH to about 9.5. The product was
delicate flocs suspended in the aqueous solution of
NH3 . H2O. Then the product was filtered and washed in the
filter with deionized water to remove the excess NH3 . H2O;
finally, the filter cake was peptized at about 808C in an oven
for about 24 hours to convert it into HTlc sol.
The chemical composition was found with a 3080E2 type
automatic X-ray fluorescent spectrometer (made in Japan); a
JEM-100cx II model transmission electron microscope (made
in Japan) was used to examine particle morphology. The
lattice parameters of HTlc were obtained from X-ray powder
diffraction analysis (XRD) on a D/max-g A model diffract-
ometer using Cu Ka radiation (40 kV and 80 mA). All the
chemical compositions are listed in Table 1.
Preparation of MT clay (Mujumdar et al. 2002) was carried
out by clay the first being suspended in distilled water by
stirring and then decanted, leaving a residue of coarse particles.
Thirty milliliters of 100 vol H2O2 were added to 4.5 liters of
10% clay to oxidize any organic matter. The dispersion was
then heated to 708C to remove excess H2O2. It was then cen-
trifuged and the supernatant (containing the electrolyte)
replaced several times with double-distilled water until its con-
ductivity was relatively low (4  1025 V21 cm21), indicat-
ing that most of the electrolytes had been removed. The final
concentration of the clay can be determined by evaporation.
A weight amount of the sodium montmorillonite was mixed
with distilled water (double-distilled water in a glass apparatus)
using a high-speed mixer (Model GJ-1, Jiangyin Second Elec-
trical Machinery Plant) for 20 min; this procedure ensured suf-
ficient dispersion of the powder in water. Then, after aging in a
sealed container for 24 hours, the sodium montmorillonite can
be used in the experiments.
Measurements
Rheological measurements were made with a Haake RS 75
Rheometer at a constant temperature of 25 + 0.28C. A cone-
plate sensor was used, with a diameter of 20 mm and a cone
angle of 0.5. The sample thickness in the middle of the
sensor was 0.03 mm. The apparent viscosity h(ġ) was
obtained with the steady-shear experiments. The oscillatory
experiments were also carried out using the controlled stress
Haake RS 75 Rheometer, and the computer connected to it
recorded all measured data.
Chemical composition
[Fe0.034Mg0.65Al0.32(OH)2]Cl0.14(OH)0.22
[Fe0.21Mg0.46Al0.33(OH)2]Cl0.11(OH)0.41
[Fe0.29Mg0.42Al0.29(OH)2]Cl0.10(OH)0.48
[Fe0.16Mg0.68Al0.16(OH)2]Cl0.18(OH)0.14
 RELATIONSHIP BETWEEN STEADY SHEAR AND COMPLEX VISCOSITY 417

All the samples examined were kept at rest for 20 min The ratio of the stress to the strain is the complex modulus
before the measurements started in order to reduce the influ- G
(v); the following expression can then be obtained:
ence of the mechanical treatment associated with the s
G
G0 þ iG00 G00 G0
deposition of the sample into the rheometer. h
¼ ¼ ¼ ¼  i ð7Þ
g_
iv iv v v
The mixture of MT and HTlc was stirred by the high-speed
mixer (Model GJ-1, Jiangyin Second Electrical Machinery The complex viscosity also can be divided into the real and
Plant) for 20 min, then aged for about 24 hours before the imaginary part, then
experiments. The mass ratio of HTlc to MT was designated h
¼ h0  ih00
as R, e.g., R ¼ WHTlc/WMT. The montmorillonite contents in
the HTlc/MT suspension studied were 3% by weight, and Hence,
the pH values of the suspensions were adjusted to 9.60 + 0.2. G00 00 G0
h0 ¼ ;h ¼ ð8Þ
v v
RESULTS AND DISCUSSION Usually, h0 is called viscous viscosity, which represents the
fluid properties of the system:
Theory
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First, we will deduce the relationship between h
and h G00 G tm

h0 ¼ ¼ ð9Þ
from the Maxwell system. v 1 þ ðvtm Þ2
For a simple Maxwell model, there exists:
The characteristic decay time is given by the ratio of the vis-
s_ s cosity to the shear modulus:
g_ ¼ þ ð1Þ
G h h
tm ¼ ð10Þ
G
where G is the shear modulus h is the viscosity of the New-
tonian fluids, and s is the stress due to the applied strain g. Then, viscous viscosity changes to
In order to describe the material properties as a function of h
h0 ¼ ð11Þ
frequency for a body that behaves as a Maxwell model, we 1 þ ðvtm Þ2
need to express the applied sinusoidal wave in the exponential
form of complex number notation: Then
h0 ðv ! 0Þ ¼ h ð12Þ
g
¼ g0 expðivtÞ; g_
¼ ivg0 expðivtÞ ¼ ivg
ð2Þ
For Newtonian fluids, h ¼ h (ġ), but for Non-Newtonian
The term v is the radial frequency, which is equal to 2pf fluids, only under low shear rates does the relationship h  h
where f is the applied frequency measured at Herz. (ġ) stand up.
Then the stress response is shifted through a phase angle d, Then in the linear viscoelastic limit for a liquid, dynamic
which is the phase difference in radians between the peak value viscosity equates with low shear rate viscosity:
of the stress and peak value of the strain:
h0 ðv ! 0Þ  hðg_ Þjg_ ! 0 ð13Þ


s ¼ s0 exp½iðvt þ dÞ; 0
When the viscous viscosity h dominates the material
s_
¼ ivs0 exp½iðvt þ dÞ ¼ ivs
ð3Þ response, and the viscosity contribution from the “elastic-
00
plastic” region h can be neglected, the magnitude of h
(v) and
According to the theory of linear viscoelasticity, the the value of h0 are almost equal. At this condition, Equation (13)
complex modulus can be represented by changes to
G
ðvÞ ¼ G0 ðvÞ þ iG00 ðvÞ h
ðv ! 0Þ  hðg_ Þjg_ ! 0 ð14Þ
Equation (14) is valid in the linear viscoelastic region, but
ðvtm Þ2 vtm
¼G 2
þ iG ð4Þ for some materials this rule can be extended into nonlinear
1 þ ðvtm Þ 1 þ ðvtm Þ2 response regime, the steady shear viscosity as a function of
shear rates equating the dynamic viscosity as a function of fre-
Then:
quencies (Goodwin and Hughes 2000). This is the expression
ðvtm Þ2 of the Cox-Merz rule:
G0 ðvÞ ¼ G ð5Þ
1 þ ðvtm Þ2 jh
ðvÞj ¼ hðg_ Þjg_ ¼ v ð15Þ
vtm Then we can conclude from the theory part that:
G00 ðvÞ ¼ G ð6Þ
1 þ ðvtm Þ2
1. According to jh0 (v ! 0)j  h(g)jg ! 0, the viscous vis-






The complex viscosity is h ¼ s /ġ ¼ s /i v g cosity measured in the linear viscoelastic region under
 418 S.-P. LI, G. ZHAO, AND H.-Y. CHEN

low frequencies equates with steady shear viscosity at low

shear rates. Usually, we determine the thixotropic proper-
ties according to the recovery viscosity measured under
low steady shear (Li et al. 2001), and we also can judge
the thixotropy by means of the viscous viscosity in the
linear viscoelastic region; the thixotropic types determined
by the two different methods should be identical.
2. Only when the viscous viscosity h0 of the system dominates
the material response and the contribution from “elastic-
plastic” region can be neglected may the Cox-Merz Rule
be applied. Lots of complex fluids show high elasticity,
and the contribution of the elasticity results in jh
j . h(ġ),
which leads to departure from the Cox-Merz Rule.
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Experimental Results FIG. 2. Evolution of viscosity of Fe-Al-Mg-HTIc/MT (sample 4) suspen-

First, we applied the Cox-Merz Rule to different HTlc/MT
suspensions, with the R values of the systems examined all
designed as 0.17. Figure 1 shows the steady shear viscosity
and complex viscosity as a function of shear rate or frequency
for four systems. In the dynamic measurements, the exper-
iments were all carried out in the linear-viscoelastic region.
From Figure 1, the values of h
(v) and h decrease monoto-
nically with the increase of frequency or shear rate, and h
(v)
is larger than h. Clearly, and as expected, the rule does not
apply for any of the HTlc/MT suspensions because of the for-
mation of the network structure. Closer examination of
Figure 1 indicates that the slopes of the viscosity and
complex viscosity data for different HTlc samples are nearly
identical; similar reports have been found for the magnetic
ink dispersions (Doraiswamy et al. 1991).
Figure 2 shows the recovery process of HTlc/MT suspen-
sions under the low shear rate (3 s21) after being pre-sheared
at 1000 s21 for 20 s. Three different thixotropic systems have
been selected; the HTlc sample is fixed as sample 4, and the
sions with various R values. R(w/w): A ¼ 0.013, B ¼ 0.051, C ¼ 0.091.
R values are respectively 0.013, 0.051, and 0.091. From
Figure 2, the apparent viscosity recovers in different ways;
according to the definition of thixotropy, they belong to
positive, complex, and negative thixotropy, respectively.
Figure 3 shows the recovery process of the three systems
under the linear viscoelastic region after being pre-sheared at
1000 s21 for 20 s. It must be emphasized that the experiments
were carried out under low frequencies (0.1 Hz). From
Figure 3, h
always increases with time, indicating the for-
mation of network structure (Li et al. 2003b), but the change
of h0 with time is almost the same as the change of h with
time under low steady shear. On the basis of theoretical
analysis, the thixotropy can be judged from the change of h0
in the linear region. For the system with R ¼ 0.013, h0
increases with time, showing positive thixotropy; for the
system with R ¼ 0.051, h0 first increases then decreases with
time, showing complex thixotropy; for the system with
R ¼ 0.091, h0 decreases with time, showing negative

FIG. 1. Dynamic and steady shear viscosities h
(v) and h, as a function of FIG. 3. Recovery of h
and h0 after cessation of steady shear for the
frequency and shear rate for HTIc/MT suspensions with different HTIc HTIc/MT suspension with different R values: 1, R ¼ 0.013, 2, R ¼ 0.051, 3,
samples, 1–4. R ¼ 0.091.
 RELATIONSHIP BETWEEN STEADY SHEAR AND COMPLEX VISCOSITY
thixotropy. The thixotropic results obtained from two different
methods are the same, which proves the coherence of the two
methods. But from Figures 2 and 3, for the same suspension,
the value of viscosity is lower than the viscous viscosity;
probably the shear rates destroy the structure to some degree,
which then leads to the lower viscosity (Li et al. 2003c).
It is more suitable to judge thixotropy in the linear visco-
elastic region; in this region no irreversible changes of the
structure for the suspension take place, but in the steady
shear experiments, the microstructure in the system will be dis-
turbed during the measurements (Li et al. 2003a).
This article has described a new and most useful way to
determine the thixotropic properties for fluids, especially
complex fluids.
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ACKNOWLEDGMENT
This work was supported by Jiangsu Planned Projects for
Postdoctoral Research and Chinese Postdoctoral Science
Foundation.
419
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