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Prepared By:
Mr. Rohit Kamboj
Assistant Professor
2
 Introduction
 Definition
 Importance
 Newton'slaws
 Types offlow
Contents
INTRODUCTION
3
 Rheo – to flow
 logos – science
 Rheology is the study of the flow and deformation of matter under stress.
 Rheology is the science/physics that concerns with the flow of liquids and the
deformation of solids.
 Study of flow properties of liquids is important for pharmacist working in the
manufacture of several dosage forms, viz., simple liquids, gels, ointments, creams,
and pastes.
 These systems change their flow behavior when exposed to different stress
conditions.
IMPORTANCE & FUNDAMENTALS
 Manufacturing of dosage forms: Materials undergo
process such as mixing, flowing through pipes, filling
into the containers etc. Flow related changes influence the
selection of mixing equipment.
 Handling of drugs for administration: The syringibility
of the medicines, the pouring of the liquids from
containers, extrusion of ointment from tubes, all depend
on the changes in flow behavior of dosage forms.
5
TYPES OF FLOW
1. Newtonian Flow
2. Non-Newtonian Flow
5
NEWTONIAN FLOW:
6
 A Newtonian fluid is a fluid whose stress versus rate of shear curve is linear
and passes through the origin. The constant of proportionality is known as the
viscosity.
 Examples= Water, chloroform, Castor oil, ethyl Alcohol etc.
 According to NEWTONS LAW higher the
viscosity of a liquid, the greater is the force
per unit area (shearing stress F) required to
produce a certain rate of shear( G).
• rate of shear α shearing stress
Shear stress, F= F’/ A
Rate of shear, G=dv/dr
F= η G
Where
η = viscosity
Unit of viscosity is Poise or
dyne.sec/cm2.
NON NEWTONIAN FLOW
7
• A non newtonian flow is defined as one for which the relation
between F and G is not linear.
• In other words when the shear rate is varied, the shear stress is not
varied in the same proportion.
• It can be seen in liquids and in solid heterogeneous dispersions
such as emulsions, suspensions, colloids and ointments.
NON NEWTONIAN SYSTEMS
8
Three classes:
 PLASTIC FLOW
 PSEUDOPLASTIC FLOW
 DILATENT FLOW
PLASTIC FLOW:
9
origin, the substance behaves• In which curve does not pass through the
Initially Elastic body and it fails to flow when less amount of stress is applied.
• As increase the stress, leads to non-linear increase in shear rate but after that
curve is linear.
• The linear portion extrapolated intersects the x-axis at the point called as
yield value
So, plastic flow shows Newtonian flow above the yield value.
•The curve represents plastic flow, such materials are called as Bingham
bodies.
10
shearing stress is corresponding to•Bingham bodies does not flow until the
yield Value exceeded.
•So, yield value is important property of certain
dispersions.
•The reciprocal of mobility is Plastic viscosity
EXAMPLES: ZnO in mineral oil, certain pastes , paints and ointments.
Shearing
stress, F
Rate of shear,
G
Yield
value
Plastic flow explained by flocculated particles in
concentrated suspensions, ointments, pastes and gels.
11
Flocculated
Particles
Individual
particles
Yield value
Increase
stress
Flow
PSEUDO PLASTIC FLOW
12
Many P’ceutical products liquid dispersion of natural and synthetic
gums shows pseudoplastic flow.
eg. 1. Tragacanth in water
2. Sod. Alginate in water
3. Methyl cellulose in water
4. Sodium CMC in water
• With increase in the shearing stress the disarranged molecules
orient themselves in the direction of flow, thus reducing friction
and allows a greater rate of shear at each shearing stress.
• Some of the solvent associated will be released resulting in
decreased viscosity.
• This type of flow behavior is also called as shear thinning
system.
13
Graph for pseudo plastic flow is like this
14
 In which curve is passing from origin (Zero shear stress), so no
yield value is Obtained.
 As shear stress increases, shear rate increases but
not linear.
Rate of shear,
G
Shearing stress, F
Stress
Polymer long chain
with water molecules
 In storage condition, arrange randomly in dispersion.
15
 Pseudo plastic flow can be explained by Long chain
molecules of polymer.
Polymer & water molecules
align on direction of force
Water
DILATANT FLOW
16
 Certain suspensions with high % of dispersed solids shows an
increase in resistance to flow with increasing rates of shear, such
system increase in volume when sheared, such system called as
dilatant flow.
 Also, called as “ Shear thickening system” i.e. when stress is
removed, dilatant system return to its original position
Graph for dilatant flow is like this
17
 In which curve is passing from origin (Zero shear stress), so no yield
value is Obtained.
 Non-linear increase in rate of shear.
 Increase resistance to flow on increase rate of shear
Shearing stress, F
Rate of shear, G
 In which, particles are closely packed with less voids spaces,
also amount of vehicle is sufficient to fill the void volume.
At rest close packed Less
void volume Sufficient
vehicle Low consistency
Open packed High void
volume Insufficient
vehicle High consistency
This leads particles to move relative to one another at low rate of shear.
Increase rate of
shear
18
THIXOTROPHY (GEL-SOL-GEL)
19
It is defined as, isothermal and comparatively slow recovery on standing of
material of a consistency lost through shearing.
It is shear thinning system, when agitated and kept aside it is expected to
return its original state of fluidity, but takes longer time to recover
compared to the time taken for agitation.
Thixotropic behavior can be shown by plastic and pseudo plastic system.
THIXOTROPHY
INTERACTIONS)
20
Multi point contacts
(High consistency
or high viscosity)
Contacts break down
(low consistency
or low viscosity)
At rest
(On storage)
Gel state
On shear
(equilibrium) Sol state
Particle contacts form
due to brownian
motion
Set aside
(removal of
stress)
Rapid process
slow process
CONCEPT (PARTICLE – PARTICL
(GEL – SOL – GELTRANSFORMATION)
Gel State
The Rheogram of thixotropic
material depends on:
21
 Rate at which shear increased or decreased.
 Length of time during which sample is subjected to any one rate of
shear.
The thixotrophy phenomena can be
observed by constructing
consistency curves.
 From the graph up curve ab is
obtained, up to maximum point b.
If the rate of shear is reduced,
then down curve bc is obtained.
 In Non-Newtonian system, the
down curve is displaced to left of
the up curve.
In this graph, the material has low
consistency at any rate of shear on
down curve compared to that
shown on up curve.
Shear stress, F
Rateofshear,G
a
b
c
Plastic
system
Pseudo plastic
system
22
Kinematic Viscosity
It is Defined as viscosity divided by the density of the
liquid.
K.V= η/ρ
η= Viscosity
ρ= Density
Unit of Kinematic viscosity is stokes (s)
MEASUREMENT OF
VISCOSITY
24
DETERMINATION OF RHEOLOGIC
(FLOW) PROPERTIES
Selection of viscometer
Multi point
Cup and bob
Cone and plate
Single point viscometer
viscometer
Ostwald viscometer
viscometer
Falling sphere viscometer
viscometer
Principle
Stress α rate of shear
Equipment works at
Single rate of shear
Principle
Viscosity det. at several
rates of shear to get
consistency curves
Application
Newtonian flow
Application
Newtonian flow
non -Newtonian flow 41
SINGLE POINT VISCOMETERS
26
Ostwald viscometer (Capillary)
The Ostwald viscometer is used to
determine the viscosity of Newtonian
fluid.
The viscosity of Newtonian fluid is
determined by measuring time required
for the fluid to pass between two marks.
Principle: When a liquid flows by gravity, the time required for
the liquid to pass between two marks ( A & B) through the
vertical capillary tube. the time of flow of the liquid under test
is compared with time required for a liquid of known viscosity
(Water).
Therefore, the viscosity of unknown liquid
(η1) can be determined by using following
equation:
27
Where,
ρ1 = density of unknown liquid
ρ2 = density of known liquid
t1 = time of flow for unknown liquid
t2 = time of flow for known liquid
η2 = viscosity of known liquid
28
FALLING SPHERE VISCOMETERS
29
It is called as Hoeppler falling sphere viscometers.
Principle: A glass or ball rolls down in vertical glass tube
containing the test liquid at a known constant temperature. The rate at
falls is aninversewhich the ball of particular density and diameter
function of viscosity of sample.
Construction:
Glass tube position vertically.
Constant temperature jacket
with Water circulation around
glass tube
Working: A glass or steel ball is dropped into the liquid & allowed to reach
equilibrium with temprature of outer jacket. The tube with jacket is then
inverted so that, ball at top of the inner glass tube. the time taken by the ball
to fall between two marks is measured, repeated process for several times to
get concurrent results. For better results select ball which takes NLT 30 sec.
to fall between two marks.
Where,
t = time in sec.for ball to fall between two marks
Sb & Sf = Specific gravities of ball and fluid under
examination.
B = Constant for particular ball.
η = t ( Sb – Sf ) B
30
MULTI POINT VISCOMETERS
(ROTATIONAL)
31
Cup and Bob
Various instruments are available, differ mainly whether
torque results from rotation of cup or bob.
 Couette type viscometers: Cup is rotated, the viscous drag on the bob
due to sample causes to turn. The torque is proportional to viscosity of
sample.
Ex. McMichael viscometer
 Searle type viscometers: Bob is rotated, the torque resulting from the
viscous drag of the system under examination is measured by spring or
sensor in the drive to the bob.
Ex. Stormer viscometer
Working: The test sample is place in space between cup and bob & allow
to reach temperature equilibrium. A weight is place in hanger and record
the time to make 100 rotations by bob, convert this data to rpm. This
value represents the shear rate, same procedure repeated by increasing
weight.
32
So then plotted the rheogram rpm Vs weights the rpm values
converted to actual rate of shear and weight converted into units of
shear stress, dy/cm2 by using appropriate constants.
33
Mathematical treatment:
For, rotational viscometers, the relationship can be expressed as,
η = Kv w/v
where
v, rpm generated by weight w, in gm
Kv is obtained by analyzing material of known viscosity in poise.
Cone and plate viscometer
(Rotational viscometer)
 Principle: The sample is placed on at
the center of the plate, which is raised
into the position under the cone.
 The cone is driven by variable speed
 motor and sample is sheared in the narrow
 gap between stationary plate and rotating cone.
 Rate of shear in rpm is increased & decrease by
selector dial and viscous traction or torque (shearing
stress) produced on the cone. 34
Viscosity for Newtonian system can be estimated
by,
35
Where,
C = Instrument constant,
T = Torque reading & V = Speed of the cone (rpm)
Plastic viscosity determined by,
Yield value (f) = Cf × Tf
Tf = Torque at shearing stress axis (extrapolate from linear
portion of curve). Cf = Instrumentconstant
η = C T/V eq.1
U = Cf T – Tf / v eq.2
PHARMACEUTICAL APPLICATIONS
36
1. The viscosity of creams and lotions may affect the rate of absorption of the
products by the skin.
2. A greater release of active ingredients is generally possible from the softer,
less viscous bases.
3. The viscosity of semi-solid products may affect absorption of these topical
products due to the effect of viscosity on the rate of diffusion of the active
ingredients.
4. The rate of absorption of an ordinary suspension differs from thixotropic
suspension.
5. Thixotropy is useful in the formulation of pharmaceutical suspensions and
emulsions. They must be poured easily from containers (low viscosity)
37
21-Feb-16
38

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Rheology

  • 1. Prepared By: Mr. Rohit Kamboj Assistant Professor
  • 2. 2  Introduction  Definition  Importance  Newton'slaws  Types offlow Contents
  • 3. INTRODUCTION 3  Rheo – to flow  logos – science  Rheology is the study of the flow and deformation of matter under stress.  Rheology is the science/physics that concerns with the flow of liquids and the deformation of solids.  Study of flow properties of liquids is important for pharmacist working in the manufacture of several dosage forms, viz., simple liquids, gels, ointments, creams, and pastes.  These systems change their flow behavior when exposed to different stress conditions.
  • 4. IMPORTANCE & FUNDAMENTALS  Manufacturing of dosage forms: Materials undergo process such as mixing, flowing through pipes, filling into the containers etc. Flow related changes influence the selection of mixing equipment.  Handling of drugs for administration: The syringibility of the medicines, the pouring of the liquids from containers, extrusion of ointment from tubes, all depend on the changes in flow behavior of dosage forms. 5
  • 5. TYPES OF FLOW 1. Newtonian Flow 2. Non-Newtonian Flow 5
  • 6. NEWTONIAN FLOW: 6  A Newtonian fluid is a fluid whose stress versus rate of shear curve is linear and passes through the origin. The constant of proportionality is known as the viscosity.  Examples= Water, chloroform, Castor oil, ethyl Alcohol etc.  According to NEWTONS LAW higher the viscosity of a liquid, the greater is the force per unit area (shearing stress F) required to produce a certain rate of shear( G). • rate of shear α shearing stress Shear stress, F= F’/ A Rate of shear, G=dv/dr F= η G Where η = viscosity Unit of viscosity is Poise or dyne.sec/cm2.
  • 7. NON NEWTONIAN FLOW 7 • A non newtonian flow is defined as one for which the relation between F and G is not linear. • In other words when the shear rate is varied, the shear stress is not varied in the same proportion. • It can be seen in liquids and in solid heterogeneous dispersions such as emulsions, suspensions, colloids and ointments.
  • 8. NON NEWTONIAN SYSTEMS 8 Three classes:  PLASTIC FLOW  PSEUDOPLASTIC FLOW  DILATENT FLOW
  • 9. PLASTIC FLOW: 9 origin, the substance behaves• In which curve does not pass through the Initially Elastic body and it fails to flow when less amount of stress is applied. • As increase the stress, leads to non-linear increase in shear rate but after that curve is linear. • The linear portion extrapolated intersects the x-axis at the point called as yield value So, plastic flow shows Newtonian flow above the yield value.
  • 10. •The curve represents plastic flow, such materials are called as Bingham bodies. 10 shearing stress is corresponding to•Bingham bodies does not flow until the yield Value exceeded. •So, yield value is important property of certain dispersions. •The reciprocal of mobility is Plastic viscosity EXAMPLES: ZnO in mineral oil, certain pastes , paints and ointments. Shearing stress, F Rate of shear, G Yield value
  • 11. Plastic flow explained by flocculated particles in concentrated suspensions, ointments, pastes and gels. 11 Flocculated Particles Individual particles Yield value Increase stress Flow
  • 12. PSEUDO PLASTIC FLOW 12 Many P’ceutical products liquid dispersion of natural and synthetic gums shows pseudoplastic flow. eg. 1. Tragacanth in water 2. Sod. Alginate in water 3. Methyl cellulose in water 4. Sodium CMC in water
  • 13. • With increase in the shearing stress the disarranged molecules orient themselves in the direction of flow, thus reducing friction and allows a greater rate of shear at each shearing stress. • Some of the solvent associated will be released resulting in decreased viscosity. • This type of flow behavior is also called as shear thinning system. 13
  • 14. Graph for pseudo plastic flow is like this 14  In which curve is passing from origin (Zero shear stress), so no yield value is Obtained.  As shear stress increases, shear rate increases but not linear. Rate of shear, G Shearing stress, F
  • 15. Stress Polymer long chain with water molecules  In storage condition, arrange randomly in dispersion. 15  Pseudo plastic flow can be explained by Long chain molecules of polymer. Polymer & water molecules align on direction of force Water
  • 16. DILATANT FLOW 16  Certain suspensions with high % of dispersed solids shows an increase in resistance to flow with increasing rates of shear, such system increase in volume when sheared, such system called as dilatant flow.  Also, called as “ Shear thickening system” i.e. when stress is removed, dilatant system return to its original position
  • 17. Graph for dilatant flow is like this 17  In which curve is passing from origin (Zero shear stress), so no yield value is Obtained.  Non-linear increase in rate of shear.  Increase resistance to flow on increase rate of shear Shearing stress, F Rate of shear, G
  • 18.  In which, particles are closely packed with less voids spaces, also amount of vehicle is sufficient to fill the void volume. At rest close packed Less void volume Sufficient vehicle Low consistency Open packed High void volume Insufficient vehicle High consistency This leads particles to move relative to one another at low rate of shear. Increase rate of shear 18
  • 19. THIXOTROPHY (GEL-SOL-GEL) 19 It is defined as, isothermal and comparatively slow recovery on standing of material of a consistency lost through shearing. It is shear thinning system, when agitated and kept aside it is expected to return its original state of fluidity, but takes longer time to recover compared to the time taken for agitation. Thixotropic behavior can be shown by plastic and pseudo plastic system.
  • 20. THIXOTROPHY INTERACTIONS) 20 Multi point contacts (High consistency or high viscosity) Contacts break down (low consistency or low viscosity) At rest (On storage) Gel state On shear (equilibrium) Sol state Particle contacts form due to brownian motion Set aside (removal of stress) Rapid process slow process CONCEPT (PARTICLE – PARTICL (GEL – SOL – GELTRANSFORMATION) Gel State
  • 21. The Rheogram of thixotropic material depends on: 21  Rate at which shear increased or decreased.  Length of time during which sample is subjected to any one rate of shear.
  • 22. The thixotrophy phenomena can be observed by constructing consistency curves.  From the graph up curve ab is obtained, up to maximum point b. If the rate of shear is reduced, then down curve bc is obtained.  In Non-Newtonian system, the down curve is displaced to left of the up curve. In this graph, the material has low consistency at any rate of shear on down curve compared to that shown on up curve. Shear stress, F Rateofshear,G a b c Plastic system Pseudo plastic system 22
  • 23. Kinematic Viscosity It is Defined as viscosity divided by the density of the liquid. K.V= η/ρ η= Viscosity ρ= Density Unit of Kinematic viscosity is stokes (s)
  • 25. DETERMINATION OF RHEOLOGIC (FLOW) PROPERTIES Selection of viscometer Multi point Cup and bob Cone and plate Single point viscometer viscometer Ostwald viscometer viscometer Falling sphere viscometer viscometer Principle Stress α rate of shear Equipment works at Single rate of shear Principle Viscosity det. at several rates of shear to get consistency curves Application Newtonian flow Application Newtonian flow non -Newtonian flow 41
  • 26. SINGLE POINT VISCOMETERS 26 Ostwald viscometer (Capillary) The Ostwald viscometer is used to determine the viscosity of Newtonian fluid. The viscosity of Newtonian fluid is determined by measuring time required for the fluid to pass between two marks.
  • 27. Principle: When a liquid flows by gravity, the time required for the liquid to pass between two marks ( A & B) through the vertical capillary tube. the time of flow of the liquid under test is compared with time required for a liquid of known viscosity (Water). Therefore, the viscosity of unknown liquid (η1) can be determined by using following equation: 27
  • 28. Where, ρ1 = density of unknown liquid ρ2 = density of known liquid t1 = time of flow for unknown liquid t2 = time of flow for known liquid η2 = viscosity of known liquid 28
  • 29. FALLING SPHERE VISCOMETERS 29 It is called as Hoeppler falling sphere viscometers. Principle: A glass or ball rolls down in vertical glass tube containing the test liquid at a known constant temperature. The rate at falls is aninversewhich the ball of particular density and diameter function of viscosity of sample. Construction: Glass tube position vertically. Constant temperature jacket with Water circulation around glass tube
  • 30. Working: A glass or steel ball is dropped into the liquid & allowed to reach equilibrium with temprature of outer jacket. The tube with jacket is then inverted so that, ball at top of the inner glass tube. the time taken by the ball to fall between two marks is measured, repeated process for several times to get concurrent results. For better results select ball which takes NLT 30 sec. to fall between two marks. Where, t = time in sec.for ball to fall between two marks Sb & Sf = Specific gravities of ball and fluid under examination. B = Constant for particular ball. η = t ( Sb – Sf ) B 30
  • 31. MULTI POINT VISCOMETERS (ROTATIONAL) 31 Cup and Bob Various instruments are available, differ mainly whether torque results from rotation of cup or bob.  Couette type viscometers: Cup is rotated, the viscous drag on the bob due to sample causes to turn. The torque is proportional to viscosity of sample. Ex. McMichael viscometer
  • 32.  Searle type viscometers: Bob is rotated, the torque resulting from the viscous drag of the system under examination is measured by spring or sensor in the drive to the bob. Ex. Stormer viscometer Working: The test sample is place in space between cup and bob & allow to reach temperature equilibrium. A weight is place in hanger and record the time to make 100 rotations by bob, convert this data to rpm. This value represents the shear rate, same procedure repeated by increasing weight. 32
  • 33. So then plotted the rheogram rpm Vs weights the rpm values converted to actual rate of shear and weight converted into units of shear stress, dy/cm2 by using appropriate constants. 33 Mathematical treatment: For, rotational viscometers, the relationship can be expressed as, η = Kv w/v where v, rpm generated by weight w, in gm Kv is obtained by analyzing material of known viscosity in poise.
  • 34. Cone and plate viscometer (Rotational viscometer)  Principle: The sample is placed on at the center of the plate, which is raised into the position under the cone.  The cone is driven by variable speed  motor and sample is sheared in the narrow  gap between stationary plate and rotating cone.  Rate of shear in rpm is increased & decrease by selector dial and viscous traction or torque (shearing stress) produced on the cone. 34
  • 35. Viscosity for Newtonian system can be estimated by, 35 Where, C = Instrument constant, T = Torque reading & V = Speed of the cone (rpm) Plastic viscosity determined by, Yield value (f) = Cf × Tf Tf = Torque at shearing stress axis (extrapolate from linear portion of curve). Cf = Instrumentconstant η = C T/V eq.1 U = Cf T – Tf / v eq.2
  • 36. PHARMACEUTICAL APPLICATIONS 36 1. The viscosity of creams and lotions may affect the rate of absorption of the products by the skin. 2. A greater release of active ingredients is generally possible from the softer, less viscous bases. 3. The viscosity of semi-solid products may affect absorption of these topical products due to the effect of viscosity on the rate of diffusion of the active ingredients. 4. The rate of absorption of an ordinary suspension differs from thixotropic suspension. 5. Thixotropy is useful in the formulation of pharmaceutical suspensions and emulsions. They must be poured easily from containers (low viscosity)
  • 37. 37