Professional Documents
Culture Documents
By:
AMK
CONTENTS
Definition & basic concepts
Newtonian systems
Non-Newtonian systems
Thixotropy/ Anti-thixotropy/Rheopexy
Rheology of emulsions & suspensions
Determination of rheological properties- Viscometers
Application of rheology
INTRODUCTION
It is derived from Greek word rheo means to flow and logos means science as
suggested by BINGHAM.
Scientifically, it is defined as:
the study of flow of fluids under applied stress (deformation forces)
Oil and water flow in familiar, normal ways, whereas honey, mayonnaise,
peanut butter flow in complex and unusual ways. In rheology, we study the
flows of unusual or interesting materials.
The two-plates model mathematically describes this definition.
All materials range on an imaginary scale from solid to liquid. In
scientific terms, solid materials are specified as elastic, while liquids
are viscous. However, most materials are not purely elastic, nor
entirely viscous, but viscoelastic. Depending on their properties,
substances can be classified as viscoelastic solids (like e.g. gels) or
viscoelastic liquids (like e.g. hair shampoo).
Viscometry deals with ideally viscous
fluids, and - with certain limitations - also
with viscoelastic liquids, i.e. viscous
substances with an elastic portion.
If a fluid flows easily, its resistance to
deformation is low. It is a low-viscosity
fluid. Fluids with greater resistance to
deformation do not flow easily. They are
highly viscous. At the same temperature high-viscosity fluids
flow more slowly than low-viscosity fluids
But how the flow of liquids is affected by stress or
deformation forces?????
Or G = dv/dr
When we talk about liquid flow, concept of
viscosity comes in our mind..
VISCOSITY ()
The term 'viscosity' simply means fluid's thickness.
A measure of fluids resistance to flow by an applied stress or deformation force.
It describes the internal friction of moving liquids and therefore its thickness.
Fluids with high viscosity resist motion because its structure and morphology results in lot of
internal friction between neighboring molecules that are moving with different velocities. E.g
Honey
In case of less viscous liquids, there is very little internal friction (between layers) when the
liquid is in motion. E.g. Water
Relationship between shear stress (F) is shear rate (G) is the basis of viscosity .i.e.
= F/G
where is the coefficient of viscosity, usually referred to simply as viscosity.
Fluidity, , a term sometimes used, is defined as the reciprocal of
viscosity:
= 1/
Where:
f = yield value, or intercept, on the shear stress
axis
(dynes/cm2), and
F = Shear stress
G = Shear rate
At stresses below the yield value, the substance
acts as an elastic material.
Those substances that exhibit a yield value
(Bingham bodies) Solids,
Substances that begin to flow at the smallest
shearing stress and show no yield value Liquids.
--------(1)
Where;
F = Shear stress
G = Shear rate
= viscosity coefficient
N = exponent
N rises as flow becomes increasingly non-Newtonian.
When N = 1, the above equation reduces to equation (
) and flow is Newtonian.
Following rearrangement, we can write the previous equation in the
logarithmic form:
--------(1)
In this case,
N is always less than 1 and decreases as degree of dilatancy increases.
As N approaches 1, the system becomes increasingly Newtonian in behavior.
In short, the value of n or N indicates the type of flow:
N = 1 (Newtonian flow)
N > 1 (Pseudoplastic flow)
N < 1 (Dilatant flow)
Dilatant behavior can be explained as follows:
At rest; particles are closely packed with minimal
interparticle volume (voids). The amount of vehicle in
the suspension is sufficient, however, to fill voids and
permits particles to move relative to one another at low
rates of shear. Thus, a dilatant suspension can be poured
from a bottle because under these conditions it is
reasonably fluid.
At increased shear stress; As shear stress is increased,
the bulk of the system expands or dilates; hence the
term dilatant. The particles, in an attempt to move
quickly past each other, take on an open form of
packing, as depicted in Figure 193.
Such an arrangement leads to a significant increase in interparticle void
volume. The amount of vehicle remains constant and, at some point,
becomes insufficient to fill the increased voids between particles.
Accordingly, resistance to flow (viscosity) increases because particles are no
longer completely wetted, or lubricated, by the vehicle. Eventually, the
suspension will set up as a firm paste.
Behavior of this type suggests that appropriate precaution be used during
processing of dilatant materials.
IMPORTANT PRECAUTION Processing of dispersions containing solid particles
is facilitated by the use of high-speed mixers, blenders, or mills.
Although this is advantageous with all other rheologic systems, dilatant materials
may solidify under these conditions of high shear, thereby overloading and
damaging processing equipment.
Example:
Substances possessing dilatant flow properties
are suspensions containing a high concentration
(about 50% or greater) of small, deflocculated
particles.
This can readily be seen with a mixture
Oobleck.????
Corn starch and water (oobleck)
Cornstarch is a common thickening agent used in cooking. It is also a
very good example of a shear thickening system. When a force is
applied to a 1:1.25 mixture of water and cornstarch, the cornstarch
acts as a solid and resists the force.
Quicksand
Quicksand is a natural case of a shear thinning, non-Newtonian fluid.
This is the opposite of a dilatant. As its strain rate increases, its
resistance to shear will decrease causing the system to act more like a
liquid than a solid. Hence, as one thrashes about in quicksand one
sinks faster as the mixture's resistance decreases.
THIXOTROPY
Viscosity of a system not only depends on shear rate but is also time
dependent.
It may have been assumed that if the rate of shear were reduced
once the desired maximum had been reached, the down curve
would be identical with, and superimposable on, the up curve.
Although this is true for Newtonian systems, the down curve for
non-Newtonian systems can be displaced relative to the up curve.
Typical rheograms for plastic and
pseudoplastic systems exhibiting this
behavior are shown in Figure.
With shear-thinning systems (i.e.,
pseudoplastic), the down curve is
frequently displaced to the left of the
up curve (as in figure)
This indicates a breakdown of
structure (and hence shear thinning)
that does not reform immediately
when stress is removed or reduced.
The discussed phenomenon is known as thixotropy or shear duration
thinning, and can be defined as:
Where,
B = Thixotropic coefficient (which indicates the rate
of break down with time at constant shear rate)
U1, U2 = Plastic viscosities
t1, t2 = time duration
ii) The second approach is to determine the structural breakdown
due to increasing shear rate
Where,
M = Thixotropic coefficient
U1, U2 = Plastic viscosities
V1, V2 = shear rates
Bulges & Spurs
Dispersions employed in pharmacy may yield complex
hysteresis loops when sheared in a viscometer. Two such
complex structures Includes:
Bulges
A concentrated aqueous bentonite gel (10% to 15% by
weight), produces a hysteresis loop with a characteristic
bulge in the up-curve.
It is presumed that the crystalline plates of bentonite form
a house-of-cards structure that causes the swelling of
bentonite magmas.
This three-dimensional structure results in a bulged
hysteresis loop as observed in Figure.
Bulges & Spurs
Spur
In still more highly structured systems, such as a procaine
penicillin gel, the bulged curve may actually develop into a
spur-like protrusion.
The structure demonstrates a high yield or spur value, ,
that traces out a bowed up-curve when the three
dimensional structure breaks in the viscometer, as observed
in Figure.
The spur value represents a sharp point of structural
breakdown at low shear rate.
It is difficult to produce the spur, and it may not be
observed unless a sample of the gel is allowed to age
undisturbed in the cup-and-bob assembly for some time
before the rheologic run is made.
Negative thixotropy or Antithixotropy
Generally, thixotropic systems are shear thinning i.e.
with a decrease in consistency in the down curve.
But some materials like magnesia magma (1-10%)
shows deviation from suggested behavior.
The down curve falls to the right of up-curve and it
continuously thickened and finally reached
equilibrium at which the up and down curves overlap
each other.
After reaching equilibrium, the system was found
to have gel-like property and showing greater
suspendability.
When allowed to stand, however, the material
returned to its sol-like properties.
It is believed that antithixotropy results from an increased
collision frequency of dispersed particles or polymer molecules
in suspension, resulting in increased interparticle bonding with
time.
This changes an original state consisting of a large number of
individual particles and small floccules to an eventual
equilibrium state consisting of a small number of relatively
large floccules.
At rest, the large floccules break up and gradually return to the
original state of small floccules and individual particles.
Rheopexy
Rheopexy is:
a phenomenon in which a sol forms a gel more readily when gently shaken or
sheared.
Example:
Gel preparation stored in a tube; gel from the tube does not start
flowing on opening the cap or inverting the tube. It only flows with
application of pressure. The reason behind is nothing but
thixotropy (i.e. shear thinning)
Same principle also apply for suspensions.
At rest high viscosity, with well suspended particles.
Upon shaking viscosity gets reduced which supports easy pouring from
the container.
Where,
r = radius of the inside of the capillary (cm)
t = time of flow,
P = pressure head (dyne/cm2)
l = length of the capillary
V = volume of liquid flowing
The absolute viscosity of unknown liquid is obtained by using following
equation:
Where,
1 = viscosity of the unknown liquid
2 = viscosity of standard liquid
1 and 2 = respective densities of the liquids
t1 and t2 = respective flow times (sec)
Example:
Hoeppler viscometer
Principle:
It consists of glass tube, which is positioned vertically.
The glass tube is filled with test sample.
A ball (steel or glass) is dropped in the tube as soon as temperature equilibrium
is achieved (between inner tube and outer jacket).
The tube and jacket assembly is then inverted, which places the ball at the top
of inner tube.
The time for the ball to fall between 2 marks is accurately measured.
The viscosity is then calculated as:
Where,
t = time interval taken by ball to fall between the two points (sec)
Sb and Sf = specific gravities of the ball and fluid, respectively.
B = constant for a particular ball
Where,
Kv is a constant for the instrument
W = weight placed on hanger (g)
V = rpm or shear rate
U = plastic viscosity (poise)
Wf = yield value intercept (g)
Example:
FerrantiShirley viscometer,
Brookfield viscometer
Principle:
the sample is sheared in the narrow gap between
the stationary plate and the rotating cone.
The speed of cone can be varied using variable -
speed motor.
The rate of shear in rpm is increased and decreased
by a selector dial and the viscous traction or torque
(shearing stress) produced on the cone is read on
the indicator scale.
A plot of rpm (rate of shear) versus scale reading
(shearing stress) can thus be constructed.
For Newtonian liquids:
Where,
C = instrumental constant,
T = torque reading,
v = speed of the cone in rpm
Where,
Tf = torque at the shearing stress axis (extrapolated from the linear portion of the curve)
Cf = instrumental constant.
f = Yield value =
Types of Viscosity
Absolute Viscosity (Shear/ Dynamic Viscosity)
= F/G
Where,
A = constant depending on the molecular weight and molar
volume of the liquid
Ev = activation energy required to initiate flow between
molecules.
R = Gas constant
T = Temperature (K)
RHEOLOGY OF SUSPENSIONS