BULLETIN VC-453C

(Supersedes VC-453B)
Rheology of
AQUALON

Water-Soluble Polymers in Solution

AQUALON

water-soluble polymers are used to thicken, suspend, stabilize, gel, solidify, or in other
ways modify the flow characteristics of water or other solvents or solutions. For most established uses,
detailed information on these effects is available in other Aqualon bulletins specific to the product and/or
the use.
For newer uses, however, where development and formulation are still in process, a broader under-
standing of the behavior of these polymers in solution is needed. Viscosity, thixotropy, dilatancy, elasticity,
pseudoplasticity, and viscoelastic behavior become important areas for study.
The purpose of this bulletin is to define and characterize these areas and to illustrate their interrelation-
ships, using specific data on selected Aqualon water-soluble polymers. And, since so many of the uses for
these hydrocolloid polymers involve a wide range of shearing conditions in both preparation and applica-
tion, which has a marked rheological effect on behavior, it is important for the user to know how the system
will respond.
Rheology is the science of the deformation and flow of matter when subjected to an applied force. The
magnitude of this applied force may range all the way from the gravitational force on a single, small,
suspended particle to the very high shear rates encountered in high-speed mixing or homogenization.
For water itself, for the common solvents, and for noninteracting liquid systems and solutions where
the dissolved material is low in molecular weight, nonassociating, and with limited solute-solvent inter-
action or solvation, the characterization of flow is simple. Flow is directly proportional to the force applied,
and the system is said to be Newtonian.
More complex solutions, however, tend to respond in a nonlinear manner to applied stress. Here, the
dissolved or solvated molecules are large, the tendency to entangle and/or reassociate is high, and the sol-
vent must exert some solvating force to maintain the polymer in solution. Such solutions are classified as
non-Newtonian. Since solutions of Aqualon water-soluble polymers are of this latter type, with nonlinear
flow response, their rheological characterization has become an important part of Aqualon technology.
Hercules Incorporated
Aqualon Division
Hercules Plaza
1313 North Market Street
Wilmington, DE 19894-0001
(800) 345-0447
www.aqualon.com
Technical Information
The products and related information provided by Hercules are for manufacturing use only. Hercules
makes no express, implied, or other representation, warranty, or guarantee concerning (i) the handling, use,
or application of such products, whether alone, in combination with other products, or otherwise, (ii) the
completeness, definitiveness, or adequacy of such information for users or other purposes, (iii) the quality
of such products, except that such products are of Hercules standard quality. Users are advised to make
their own tests to determine the safety and suitability of each such product or product combination for their
own purposes. Read and understand the Material Safety Data Sheet (MSDS) before using this product.
Hercules does not recommend any use of its products that would violate any patent or other rights.
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CONTENTS
Page
I. BASIC CONCEPTS OF FLOW AND DEFINITION OF TERMS . . . . . . . . . . . . . . . . . . . . . . 3
Newtonian Flow . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
Non-Newtonian Flow . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
II. HOW VISCOSITY IS MEASURED . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Capillary Viscometers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Rotational Viscometers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Falling-Sphere and Bubble Viscometers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Vibrational Viscometers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Miscellaneous . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
III. FLOW CHARACTERISTICS OF AQUALON

WATER-SOLUBLE POLYMER SOLUTIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

IV. THIXOTROPY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
V. ELASTICITY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
Figures
Figure 1. Basic Concepts of Flow . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
Figure 2. Different Ways of Plotting Newtonian Flow . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
Figure 3. Types of Non-Newtonian Flow . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
Figure 4. Viscosity of Several Aqualon

Polymers at Various Concentrations . . . . . . . . . . . . 9

Figure 5. Shear Stress vs. Shear Rate for Aqualon

CMC and Natrosol

HEC . . . . . . . . . . . 10
Figure 6. Effect of Shear on Viscosity of Natrosol Solution . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Figure 7. Aqualon

CMC in Various States of Aggregation . . . . . . . . . . . . . . . . . . . . . . . . . . 11

Figure 8. Effect of Polymer Disaggregation on Viscosity of the System . . . . . . . . . . . . . . . . 12
Figure 9. Effect of Solutes on Viscosity of Aqualon

CMC in Solution . . . . . . . . . . . . . . . . . . 12
Figure 10. Rheograms for Thixotropic Flow . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Figure 11. Effect of High Power Input on Thixotropic Structure . . . . . . . . . . . . . . . . . . . . . . . . 14
Figure 12. Rheograms of a Thixotropic Aqualon

CMC Solution Containing Some

Gel Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
Figure 13. Viscoelastic Flow . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
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BASIC CONCEPTS OF FLOW AND DEFINITION OF TERMS
When a force is applied to a system, the system may respond in a number of ways. One of these
responses is to relieve the strain by flowing, in which case the system is said to be a liquid. The system will
resist this imposed flow to a greater or lesser degree, or it would have no original form at all. Viscosity is
the internal friction of a flowing material and measures the tendency of the liquid to resist the applied
shearing force. Thus, viscosity is a property of all material capable of flowing.
The basic concepts of flow are best understood by reference to Figure 1.
Figure 1
Basic Concepts of Flow
This drawing shows a cross-section normal to two parallel planes (1 and 2) separated by distance (x),
the space in between the planes being filled with liquid. A constant force (F) is applied to the top layer having
area (A), not shown, sufficient to maintain the top layer moving with velocity (Y). The unit force applied is
the shear stress (S) and may be defined as S = F/A, in dynes/cm
2
(dyne is the force necessary to give an
acceleration of 1 cm/sec/sec to 1 g of mass). The liquid between the two planes obviously flows at various
speeds, depending on its distance from plane 2. Thus, the layer next to 2 at point (b) has zero velocity,
while the layer next to 1, at point (a), moves with the velocity of (Y). Intermediate layers move at interme-
diate velocities. The velocity gradient across the liquid is Y/x. This is the response of the system and is
called the shear rate or rate of deformation (D). Thus, Y
D=(sec-
1
).
(1)
x
The ratio of the shear stress (S) to the shear rate (D) is the coefficient of viscosity (). Thus, = S/D,
in poises, where 1 poise = 1 dyne-sec/cm
2
. Thus, the coefficient of viscosity, usually referred to simply as
viscosity, may be regarded as a measure of the force per unit area required to maintain a given rate of flow.
As will be discussed in the next section, shear stress and shear rate are not measured directly, but are
derived from measurable quantities such as seconds of flow or fall, rpm, scale readings, etc.
(1)
This expression is true only for fluid flows with a linear velocity gradient.
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Typical examples of expressed viscosity are:
Matter Viscosity, poises
Air 0.0001
Water 0.01
Oils 1-1,000
Resins 1,000-1,000,000
Newtonian Flow
As pointed out in the introduction, viscous flow can be either one of two types, Newtonian or non-
Newtonian. When Newtonian flow occurs, the coefficient of viscosity (S/D) is constant even though the
shear stress and the shear rate vary. Another way of expressing this is: When the viscosity is measured at
varying shear rates and shear stresses and the results are plotted, the straight line thus formed passes
through the origin. The slope of the line is constant, as shown in Figure 2. Examples of Newtonian liquids
are dilute salt and sugar solutions, glycerin, and light oils.
Figure 2
Different Ways of Plotting Newtonian Flow
Non-Newtonian Flow
In many systems, however, the response to shear stresses is not linear. The viscosity for these systems,
then, is not a constant value. It varies, depending on the shear stress and the rate of application of stress.
This results in non-Newtonian flow; different types are shown in Figure 3, page 5.
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Figure 3
Types of Non-Newtonian Flow
Pseudoplastic (associated with the presence of swollen particles, solvation, and aggregation such as
emulsions and polymer solutions whose long-chain molecules are oriented by the flow).
Dilatant (occurs in suspensions containing large amounts of solids and associated with deflocculation
and close packing of these solids, such as icings).
Plastic (associated with the properties of a system requiring the application of at least a minimum
amount of shear stress before flow begins. Catsup is an example).
As is shown, the viscosity of pseudoplastic materials decreases, and that of dilatant materials increases,
with the rate of shear (D). Consequently, for the viscosity of non-Newtonian systems to be meaningful, the
rate of shear must be specified. The viscosity of pseudoplastic and dilatant materials is generally referred to
as the apparent viscosity (app.). Plastic systems have a yield pointthat is, a certain amount of stress must
be applied to the system before flow occurs.
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II. HOW VISCOSITY IS MEASURED
As has been mentioned, shear stress and shear rate are not measured directly, but are derived from
measurable quantities such as rate of flow, torque, rpm, etc. Numerous instruments exist for making
these measurements.
Capillary Viscometers
In this method a liquid is forced, or allowed to flow, through a fine-bore tube, and the viscosity is deter-
mined from the flow rate, pressure applied (gravitational or otherwise), and tube dimensions. The main
advantages of this type of viscometer are simplicity, ease of operation, wide range, and precision. Examples
are Ubbelohde, Instron, Saybolt, and Zahn viscometers.
Rotational Viscometers
A rotating body experiences a viscous drag, or retarding force, the amount of which varies with the
speed of rotation. In rotational viscometers, the viscosity is determined by measuring the drag on a spindle
rotating in the material. The chief advantages of these instruments
(2)
are:
They are simple to use.
Continuous measurements can be made at a given rate of shear or stress.
The dependency of viscosity on time can be readily determined.
Yield stresses can be determined.
Examples are the Brookfield Synchro-Lectric, Rheometrics, Stormer, MacMichael, Bohlin, Haake, and
Brabender viscometers.
Falling-Sphere and Bubble Viscometers
In these instruments, the time required for a sphere of some sort to pass through a liquid is measured.
The sphere may be a falling ball or a rising bubble. This method is particularly good for low-shear measure-
ments. Examples are the Hoeppler rolling-ball viscometer and the Gardner-Holdt comparative-bubble tubes.
Vibrational Viscometers
In these instruments, the damping of a blade that vibrates at high frequency is measured. They are useful
in measuring low viscosities and changes in rheological properties during processing, as well as determin-
ing viscoelastic properties. The shear rate, however, cannot be readily changed. An example is the Bendix
Ultra-Viscoson.
Miscellaneous
Other such instruments include compression or extension viscometers, penetrometers, and parallel-
plate viscometers.
(2)
Other rotational viscometers include bob-and-cup, cone-and-plate, and parallel plate.
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III. FLOW CHARACTERISTICS OF
AQUALON

WATER-SOLUBLE POLYMER SOLUTIONS

One of the important characteristics of pseudoplastic systems is the variation of viscosity with concen-
tration. Figure 4, page 9, shows the effect of concentration on the viscosities of solutions of a number of
cellulosics measured with a rotational viscometer (Brookfield Synchro-Lectric). The same types of curves
are obtained for all these pseudoplastic materials.
One way of studying the flow behavior is to determine shear stress at various shear rates, as shown in
Figure 5, page 10. Here the shear stress (S) is plotted versus the shear rate (D). If these solutions had been
Newtonian, straight lines would have resulted. However, these solutions deviate from a straight line, the
deviation being greater at high shear stresses and shear rates.
A more useful way of picturing the flow behavior of water-soluble polymers is shown in Figure 6, page 10,
where the apparent viscosity of hydroxyethylcellulose is plotted versus shear rate. Remember that shear
rate is the response to an applied stress. The data are taken from a plot similar to that shown in Figure 5.
Since a Newtonian system would give a straight line of zero slope, it is seen that the low-viscosity material
is less pseudoplastic than the high. This is true of other cellulose derivatives as well. This figure also shows
how the shear rate varies with use. Normally, the viscosity is measured at an intermediate shear-rate range
using, for example, a Brookfield rotational viscometer. However, as seen in Figure 6, the differentiation
obtained by Brookfield measurements may not hold under use conditions. Thus, if high viscosity at high
shear rate is wanted, it might be desirable to use a type of gum designated as low viscosity when measured
in the intermediate shear range.
As discussed earlier, the performance of pseudoplastic solutions is associated with the presence of
swollen particles (gel centers), solvation, and aggregation. Cellulosics in solution may exist in various
states of aggregation, and the possible states are illustrated in Figure 7, page 11.
When Aqualon cellulose gum or, in fact, any solid polymer is added to a liquid and brought to equilib-
rium, the powder may do several things: remain as a suspended powder (Figure 7A), swell to a point where
all the liquid is imbibed into the particles (7D), or dissolve completely into its individual molecules (7F).
The effect on viscosity of these various states is illustrated in Figure 8, page 12. The capacity of the
liquid (which can be a single substance or a mixture) to act as a solvent is one of the important factors in
determining the state of the cellulose gumthat is, its position on this aggregation-disaggregation curve.
Thus, if the cellulose gum neither swells nor dissolves, it is in State I. In State II, we have maximum
swelling or maximum solvent imbibition, and thus maximum viscosity. Here the discrete gel particles
occupy almost the enire volume of the system. In going from State I to State II, some, but not all, of the
internal associations are broken. As we go from State II to State III, more of the internal associations are
broken; the particle becomes less readily deformed and begins to approach molecular dispersion. In State
III, the molecule is completely dispersed. The flow properties of cellulosics will thus vary with their degree
of aggregation. Aggregation, in turn, is affected by the nature and composition of the solvent, the composi-
tion of the polymer, and the shear history of solution (see Section IV, page 13).
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A number of factors enter into the performance of Aqualon

cellulose gum when it is added to a solvent.

The solvent can attach itself to the cellulose gum through hydrogen bonding or through association with
polar or ionic groups of the polymer. The greater the solvation, the greater the tendency of the cellulose
gum to disaggregate. In addition, the solvent may associate the mobile counterions derived from an ionic
cellulose gum, thereby reducing the energy required to separate the counterion from the vicinity of the
polymeric ion and promoting dispersion. The use of poor solvents or the presence of salts maintains these
areas of interpolymer association (the so-called crystalline areas) and inhibits dispersion.
The effects of solutes such as salts or polar nonsolvents on a type of carboxymethylcellulose (CMC)
containing many of these areas is shown in Figure 9, page 12. If the CMC is thoroughly dissolved in water
and then the solute is added, the solute has only a small effect on the viscosity. However, if the solute is dis-
solved before the CMC, the solute inhibits breaking up of the crystalline areas and lower viscosities are
obtained. This effect of solutes is less noted with more uniformly substituted material containing fewer
crystalline areas.
Solution rate and molecular dispersion of cellulosics are enhanced by several factors:
Degree of Substitution (DS): The higher the degree of substitution, the more readily a cellulosic will
dissociate or disaggregate. Thus, CMC of DS 1.2 will disaggregate more completely than CMC of DS 0.4,
since it contains fewer crystalline areas and also a larger number of strongly solvating groups.
Molecular Weight: The lower the molecular weight, the faster the rate of solution.
Uniformity of Substitution: The more uniformly the material is substituted, the fewer will be the
crystalline areas and the more readily it will disaggregate. Solutions of cellulosics that have a high DS and
low molecular weight and that are uniformly substituted are therefore the most nearly Newtonian in their
flow characteristics. The viscosity characteristics of their solutions are less affected by the presence of
other solutes.
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Figure 4
Viscosity of Several Aqualon

Polymers
at Various Concentrations
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Figure 5
Shear Stress vs. Shear Rate for Aqualon

CMC and Natrosol

HEC
Figure 6
Effect of Shear on Viscosity of Natrosol Solution
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Figure 7
Aqualon

CMC in Various States of Aggregation

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Figure 8
Effect of Polymer Disaggregation
on Viscosity of the System
Figure 9
Effect of Solutes on Viscosity of Aqualon

CMC in Solution
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IV. THIXOTROPY
Some fluids exhibit a time-dependent flow pattern.
Fluids that thin under fixed flow conditions are termed
thixotropic. Thixotropy arises when a reversible sol
gel system exists. Some sort of three-dimensional
structure, albeit weak, is necessary. In thixotropic solu-
tions, this internal structure is temporarily broken down
by shaking or stirring, but reforms upon standing.
Typical flow curves for a thixotropic system,
Aqualon

CMC-7H, are shown in Figure 10, at right.

As the shear stress is increased, the shear rate varies in
typical pseudoplastic fashion. However, when the
shear stress is rapidly decreased, the flow curve is less
non-Newtonian in character (10A). The reason is that
originally the CMC was not molecularly dispersed
that is, it contained structure (Figure 11A). As the
shear stress is increased, the aggregates, or structural
units, become dispersedthat is, the gel structure is
broken (Figure 11B). The area of the loop between the
two curves (10A) is a measure of the thixotropic break-
down. Upon standing, structure will re-form with time,
and the viscosity will increase (10B). Depending on
the material, the temperature, and the shear history, the
final viscosity may be the same as, greater than, or less
than the original viscosity. (Figure 10C shows a typical
case.) If the cellulosic polymer has a low DS and is not
uniformly substituted, gels may form. Thixotropic structure
is also enhanced by the presence of multivalent cations.
The presence of gel structure in a solution of CMC
is reflected in the appearance of a spur at the bottom of
the ascending curve, as shown in Figure 12A, page 14,
or in very high viscosity at low shear rate, as shown in
Figure 12B.
Also, shearing stresses below the yieldpoint are
considered to be in the elastic regionbelow the yield
value all deformation is completely recoverable. This
is discussed in Section V, page 15.
Figure 10
Rheograms for Thixotropic Flow
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Figure 11
Effect of High Power Input on Thixotropic Structure
Figure 12
Rheograms of a Thixotropic Aqualon

CMC
Solution Containing Some Gel Structure
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V. ELASTICITY
When some systems (doughs, plasters, cements) are subjected to continued stress, they exhibit (1) a
small, instantaneous, reversible deformation and (2) a slower, reversible deformation exponentially related
to time. These reversible deformations, which can show up as changes in volume or shape, are referred to
as elastic deformations and are always a function of the applied stress. The ratio of stress to strain, in this
area of full recovery to original shape, is called the elastic modulus.
Thus, the properties of many systems are not characterized adequately if only the viscosity is mea-
sured; it is necessary to measure the combined viscoelastic properties. This is particularly true of systems
such as doughs, plaster, putty, and asphalt. In general, measurements of the viscoelastic properties are more
complex than are measurements of the viscosity only.
The behavior of a simple viscoelastic system is shown in Figure 13, page 16. A force is applied to a
system that causes the system to elongate and is maintained from time T
1
to T
2
. If the system were purely
elastic it would stretch immediately, maintain this elongation for time T
1
to T
2
, and at time T
2
would return
to its original length. This behavior is shown in Figure 13A, and by the broken line in Figure 13B.
However, if the system is viscous as well as elastic, response of the system would be gradual, the viscosity
slowing down the elastic response. When the applied force is removed, the system gradually returns to its
original length. This viscoelastic behavior is shown by the solid line in Figure 13B. We can consider the
purely elastic system to perform as a spring that stretches as soon as a force is applied and relaxes as soon
as the force is removed (13C). The performance of the viscoelastic system shown can be considered as a
spring in parallel with a dashpot, the dashpot representing the viscosity and slowing down the elastic
response (13D). The combination of the two effects gives curvature to the response.
In general, it is not necessary to determine the viscoelastic properties of cellulosics in simple solution
to approximate their characteristics. However, in order to determine their effect on complex systems, it is
often necessary to determine the viscoelastic properties of the system in which they are used. Viscoelastic
properties of fluid materials can be measured under oscillatory shear on rotational rheometers such as
Rheometrics RFS or Bohlin VOR.
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Figure 13
Viscoelastic Flow
10-01
Aqualon, 2001.