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Rheology: rheo (to flow) and logos (science)

Described the flow of liquids and the defor-
mation of solids.
Viscosity :
Expression of the resistance of a liquids to flow;
the higher the viscosity, the greater the resistace.
Pharmacy:
Application in formulation and and analysis of
pharmaceutical product .
e.g. emulsions, pastes, suppositories, and tablet
coatings.
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Rheology:
Involved in:
The mixing and flows of materials,
Packaging into containers, and their removal
prior to use.
Affects its patient acceptability,
Physical stability
Biological availability.
Influence the selection of processing equip-
ment used in its manufacture
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NEWTONIAN
SYSTEMS

'
dr
dv
A
F
q =
dv/dr: rate of shear = G
F/A : shearing stress = F
q = poise =dyne s/cm
2
= g/cm s.
Fluidity :

1
= |
Kinematic Viscosity = q/ stoke
1 centipoise (cP) = 1 millipascal second (mPa s)
1 poise (P) = 0.1 pascal second (Pa s)
G
F
= q
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Calculate the rate of shear (dv/dr) applied by a
patient in rubbing a 200 m thick film of ointment
on the skin surface at a rate of 10 cm/s.
1 -
2
s 500
10 2
10
=

=

dr
dv
S=G : rate of shear:
Slop = fluidity = 1/q
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The following data show the rate of shear as function of shear
stress for a Newtonian fluid at 25
o
. Plot the data and determine
the fluidity and viscosity of the fluid.
(rate of shear, s
-1
) 200 400 600 800 1000
(shear stress,dynes/cm
2
) 50 100 150 200 250
1 2
1 2
x x
y y

= |
cp 25 poise 25 . 0
4
1

1
= = = =
|
q
s dyne / cm 4
50 250
200 1000
2
=

=
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Absolute Viscosity Of Some Newtonian Liquids At 20
o
C
liquid viscosity (cp)
Castor Oil)
Chloroform
Ethyl alcohol
Glycerin, 93%
Olive Oil
Water
1000
0,563
1,19
400
100
1,0019
Temperature
Dependance
RT E
v
Ae
/
= q
T R
E
A
v
1
ln ln + = q
A = constant
E
v
= Activation energy
R = Gas constant
T = Absolut temperature
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The viscosity of human plasma at 37
0
C is 1.2 cp. Assuming
that plasma behave as a Newtonian fluid, determine the
viscosity of plasma required for infusion that is kept at
room temerature (25
0
C). The activation energy of plasma
is 4.25 X 10
3
cal/mole. R = 1.987 kal.
0
K
-1
mol
-1

cp 10 21 , 1 718 , 6 ln
310
1
987 , 1
10 25 , 4
ln (1,2) ln
K) 310 (T 37 At
3
3
0

= =

+ =
=
A A
A
C
( )
cp 58 , 1 460 , 0 ln
298
1
987 , 1
10 25 , 4
10 21 , 1 ln ln
25 25
3
3
25
= =

+ =

q q
q
First determine the A value, using the
equation
T R
E
A
v
1
ln ln + = q
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NONNEWTONIAN SYSTEM
S=G: rate of shear:
Plastic
Flow
Plastic
viscosity, U:
( )
G
f F
U

=
f : yield value
UG=F-f
F=UG+f
F
G
Yield value: the minimum shear stress required
by the system before it deforms and begin to
flow
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Extrapolating the straight line to the x axis, the yield value,
f, will be approximately 50 dynes/cm
2

plastic viscosity U= 1/slop or (x
2
-x
1
)/(y
2
-y
1
)
U =(725-162.5)/(1500-250) = 0.45 p = 45 cps
The following data show the rate of shear as function of shear
stress for topical formulation that exhibts plastic rheologic
profile. Plot the data and determine the yield value and plastic
viscosity of the formulation.
Rate of shear (s
-1
) 250 500 750 1000 1500
Shear stress (dyne/cm
2
) 162.5 275 387.5 500 725
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S=G: rate of shear:
Pseudoplastic Flow
G F
N
' =
Log G= N log F log q
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Pseudoplastic system reffered as shear-thinning
system because at increasing shear stress, the
viscosity decreases..
Clasical example is ketchup (tomato sauce). To
get ketchup out of the bottle, one must shake
the bottle several times. Shaking the bottle is
incresing shear stress.
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S=G: rate of shear:
Dilatan Flow
shear-
thickening
system
Suspensions containing high concentration (>40-50%) of
small, deflocculated particles.
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THIXOTROPY
An isothermal and comparatively slow recovery of the
material on standing that was lost by shear thinning.
Shear thinning is a desirable property of pharmaceutical
suspensions and emulsions that should have high
viscosity upon standing to prevent settling and aggre-
gation but should pour easily from the container once it
is shaken.
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Tixotropy Measurement
1
2
2 1
ln
t
t
U U
B

=
1
2
2 1
ln
v
v
U U
M

=
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Structure of hysteresis loop
bulge spur
Bentonit gel, 10-
15% by weight
Procaine penicillin
gel for i.m. injection
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Negative Thixotropy (Antithixotropy)
Represents an increase rather than decrease in consistency
on the down curve.
The difference between dilatancy and rheopexy.
Dilatant systems are deflocculated and ordinarily contain
greater than 50% by volume of solid dispersed phase,
whereas antithixotropic systems have low solids content
(1% 10%) and are focculated.
Rheopexy is a phenomenon in which a solid forms a gel
more readily when gently shaken or otherwise sheared than
when allowed to form the gel while the material is kept at
rest. In a rheopectic system, the gel is the equilibrium form,
whereas in antithixotropy, the equilibrium state is the sol.
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DE T E RMI NAT I ON OF V I S COS I T Y
Capilary Viscometer
(a)Ostwald viscometer , (b) Ubbelohde,
(c) Ostwald-Cannon-Fenske
2 2
1 1
2
1
t
t

q
q
=
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Hoeppler Falling Ball Viscometer
( )B S S t
f b
= q
t is the time interval in
seconds for the ball to fall
between two points, S
b
and
S
f
are specific gravities of
the ball and fluid. B is
constant for particular ball
and is supplied by the
manufacture.
Falling Ball
Viscometer
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Cup And Bob Viscometer
(Rotational Viscometer):
Viscometer Stormer
v
w
K
v
= q
where K
v
is a
constant for the
instrument. V, the
rpm generated by
the weight, w, in
grams,
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Ferranti-Shirley
Cone-and-Plate Viscometer
v
T
C = q
where C is an instrumental constant, T is
the torque reading, and v is the speed of
the cone in revolutions per minute.
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Rotational Viscometer :
Viscometer Brookfield
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VISCOEI.ASTICITY
Oscillatory and creep measurements are also of considerable
importance for investigating the properties of semisolid drug
products, foods, and cosmetics that are classified as viscoelastic
materials.
Viscoelastic measurements are based on the mechanical
properties of materials that exhibit both viscous properties of
liquids and elastic properties of solids.
Many of the systems studied in pharmacy belong to this class,
examples being creams, lotions, ointments, suppositories,
suspensions, and the colloidal dispersing, emulsifying, and
suspending agents. Biologic materials such as blood, sputum,
and cervical fluid also show viscoelastic properties
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Semi solid: Liquid

Solid
G
F
= q
Hookes Law
Newton Law

F
E =
a) Liquid b) Solid c) Viscoelastic
Parallel combination,
Voight or Kelvin
element
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( )
t /
1
t
e J J =

The strain applied to the mechanical model is expressed as a
deformation or compliance, J, of the test material, in which J is
strain per unit stress. The compliance of a viscoelastic material
following the Voigt model is given as a function of time, t, by the
expression:
where J

: is the compliance or strain per unit stress at infinite

time and t is viscosity per unit modulus, q/E (dyne sec
cm2/dyne cm2), which is called retardation time and has the
unit of seconds.
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A-B : elastic movement
B-C : viscoelastic region
C-D : viscous flow
DE equivalent AB
EF equivalent BC
The compliance
equation
corresponding to
the observed
behavior of wool fat
as simulated by
theMaxwellVoigt
model :
( ) ( )
F
e J e J
F
J
n m
t
n
t
m

1 1

/ /
0
+ + + =

0
: instantaneous strain, F : constant applied shear stress; J
m
and J
n
:
mean compliance of bond in the material; t
m
and t
n
mean retardation
time for the two Voight units..
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PSIKORHEOLOGY
Topical preparations must meet criteria of: feel,
spreadability, color, odor, and other psychologic and
sensory characteristics.
Sensations in the mouth, between the fingers, and on the
skin are important considerations for manufacturers of
foods, cosmetics, and dennatologic products.
Boylan showed that the thixotropy, consistency, and yield
value of bacitracin ointment, USP, decreased markedly as
the temperature was raised from 20C to 35C.
The consistency of a material could be accurately as-
sessed by a panel of untrained subjects by the use of only
three attributes: smoothness, thinness, and warmth.
Smooth-ness was related to a coefficient of friction and
thinness to non-Newtonian viscous parameters that could
be measured with appropriate instruments. The
characteristic of warmth was found to be sufficiently
complex to require further study..
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APLICATION OF RHEOLOGY IN PHARMACY
Polymer solutions :in ophthalmic preparations, as wetting
solutions for contact lenses, and as tear replacement
solutions for the condition known as dry eye syndrome.
Both natural (e.g., dextran) and synthetic (e.g., polyvinyl
alcohol) polymers are used with the addition of various
preservatives.
The rheologic properties of suppositories at rectal temper-
atures can influence the release and bioabsorption of drugs
from suppositories, particularly those having a fatty base.
The cosmetic sticks contained propylene glycol,
polyethylene glycol 400, and polyethylene glycol 600 as
humectants and the topically active drugs panthenol,
chiorphenesin, and lignocaine. Thixotropic breakdown was
much lower in these medicated sticks than in comparable
bases.
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