Contents
•Introduction
•Newtonian and non-Newtonian systems
•Thixotropy
•Determination of viscosity
•Factors affecting rheological properties
•Pharmaceutical applications of rheology
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Objectives
At the end of this lesson you will be able to:
Definerheology
DifferentiateNewtonianandnon-newtoniansystems
Determinethixotropy
Differentiatefactorsaffectingrheology
Determineviscosity
Applyrheologyinpharmaceuticalarena
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The deformation is recoverableif
the material returns to its initial
shape when the stress is removed.
Deformation is permanentif
the material remains deformed
when the stress is removed.
Whileelasticdeformationisrecoverable,plasticdeformationsarenot.
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Recoverable vs permanent deformations
Types of materials based on flow
8
Materialsareclassifiedintotwogeneraltypesdepending
upontheirflowproperties:
Newtonian
Non-Newtonian
Theflowofliquidsorsemisolidsisdescribedbyviscosity.
Measure of the resistance of
liquid to deformationunder
shear stress.
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Afluid’sinternalresistancetoflow
andmaybethoughtofasa
measureoffluidfriction.
The resistance offered when one
part of the liquid flows past
another.
Viscosity
Newtonian fluids: Viscosity
Newtonian fluids: Viscosity…
Theforceperunitarea(F/A)neededtobringaboutthis
flowisknownastheshearingstress,S.
Shear stress (S) = F/ A
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Newtonian fluids: Viscosity…
•Newtonrecognizedthat:thehighertheviscosityofaliquid,the
greatertheforceperunitarearequiredtoproduceacertainrate
ofshear.
•Thus, the rate of shear is to the shearing stress
Newtonian law
17dr
dv
A
F
' dr
dv
A
F
' ShearofRate
StressShearing
G
S
dr
dv
A
F
'
Where(eta)isaconstantknownascoefficientofviscosity,
usuallyreferredtosimplyasviscosityorabsoluteviscosity.
Absolute viscosity
Newtonian fluids: Viscosity…
•Where,
•Sis the shearing stress (dyne.cm
−2
)
•G is the rate of shear (sec
−1
)
•Units: dynes-sec/cm
2
or poise
•SI unit: N-sec/m
2
•1 N-sec/m
2
= 10 poise
18
•1poiseisdefinedastheFrequiredtoproduceavelocity
differenceof1cm/secbetweentwoparallellayersofliquidsof
1cm
2
areaeachandseparatedby1cmdistance.
•LiquidsthatobeyNewton’slawofflow:Newtonianliquids
•Newton’sequationfortheflowofaliquidis:
•PlotofshearstressVsshearrate:theslopegivestheviscosity.
•Thecurvealwayspassesthroughtheorigin
•Thereciprocalofviscosityiscalledfluidity:
1/η=Slope
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S = η * G
Newtonian fluids
•Thepassagethroughtheoriginindicatesthatevenamild
forcecaninduceflowinthesesystems.
•Thelinearnatureofthecurveshowsthattheviscosity(η)
ofaNewtonianliquidisaconstantunaffectedbythevalue
oftherateofshear.
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Characteristics of Newtonian flow
Plastic flow…
•Extrapolationsofthelinearplotgives‘x’intersect:yield
value
•Thiscurvedoesnotpassthroughtheorigin
•Intersectstheshearstressaxisataparticularpoint,yield
value
•Asthecurveaboveyieldvaluetendstobestraight,the
plasticflowissimilartotheNewtonianflowaboveyield
value
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Shear
Flocculatedparticlesinaconcentratedsuspensionsusually
showplasticflow.
Flocculated Suspension: Mechanism of Plastic Flow
Plastic flow…
•Theyieldvaluerepresentsthestressrequiredtobreaktheinter-
particularcontactssothatparticlesbehaveindividually.
•Thusitisindicativeoftheforcesofflocculation
increasedbytheincreasedconcentrationofthe
dispersedphase.
•The more flocculated the suspension the higher will be the yield value.
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Thixotropy…
•Thixotropic systems are usually composed of asymmetric
particles or macromolecules which are capable of interacting
by numerous secondary bonds to produce a loose three-
dimensional structure, so that the material is gel-like when
unsheared.
•The energy imparted during shearing disrupts these bonds, so
that the flowing elements become aligned and the viscosity
falls, as a gel-sol transformation has occurred.
45
Thixotropy…
•When the shear stress is eventually removed the structure will
tend to reform, although the process is not immediate and will
increase with time as the molecules return to the original state
under the influence of Brownian motion.
•Furthermore, the time taken for recovery, which can vary from
minutes to days depending upon the system, will be directly
related to the length of time the material was subjected to the
shear stress, as this will affect the degree of breakdown.
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•Thixotropicsystemscontainasymmetricparticleswhichset
upaloosethreedimensionalstructurewhichisrigidand
resemblesagelwhichisbrokendownonapplyingshear:
Solution
•Onremovingtheappliedstress,thematerialreformits
originalstructureofstate:Gel
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Gel
Solution
Reason for thixotropic property
Thixotropy…
•With shear thinning system the down ward curve is frequently
displaced to the left of the up curve, showing that the material
has a lower consistency at any one rate of shear on the down
curve than it had on the up curve.
•This indicates the break down of structure that does not reform
immediately when the stress is removed.
•The presence of the hysteresis loop indicates that a breakdown in
structure has occurred, and the area within the loop may be used
as an index of the degree of breakdown
50
Thixotropy…
•The area of the hysteresis loop tells us that the time taken by the
material to regain its initial position.
•Large area taking more time to come into its initial position.
•It stands to reason that, the larger the enclosed area, more severe
is the time-dependent behavior of the material under discussion.
•Evidently, the enclosed area would be zero for a purely viscous fluid,
i.e., no hysteresis effect is expected for time-independent fluids.
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Rheopexy…
•The process of reformation of the gel structure after it has been deformed
can be accelerated by applying gentle and regular movement (rolling and
rocking motion).
•The equilibrium stateis gel.Just as the opposite behaviourof becoming
thinner with time is thixotropism(time dependent pseudoplastic
behaviour), rheopectic behaviourmay be described as time-dependent
dilatant behaviour.
•In a rheopectic system , the gel is the equilibrium form, whereas in
antithixothropy, the equilibrium state is solution
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•It is a type of capillary viscometer
•This is ‘U’ shape tube with two bulbs and two marks
61
Ostwald Viscometer
Ostwald Viscometer…
•It is used to determine the viscosity of Newtonian liquids
Principle:
•Whenaliquidflowsbygravity,thetimerequiredfortheliquid
topassbetweentwomarks,uppermarkandlowermark,
throughaverticalcapillarytubeisdetermined.
•Thetimeofflowoftheliquidundertestiscomparedwiththe
timerequiredforaliquidofknownviscosity(usuallywater).
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Ostwald Viscometer…
63
The viscosity of unknown liquid η
1 can be determined using the
equation
ρ
1= Density of unknown liquid
ρ
2= Density of known liquid
t
1= Time of the unknown liquid
t
2= Time of the known liquid
η
2= Viscosity of known liquid 2
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11
1
t
t
Ordinary suspension of
pencillinG
Thixotropysuspension of
pencillinG
I.M injection
Forms no depot, fast dispersion
&
absorption so maintain therapeutic
Level for short time
Forms spherical deposits at site of
injection which resists disintegration
by tissue fluids& Small surface area
( absorption) so maintain
Therapeutic Level for longer time
The formation of depot depends on:
a-high yield value
b-fast thixotropicrecovery after injection.
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(2 )Effect on Drug Absorption:
•Theviscosityofcreamsandlotionsmayaffecttherateof
absorptionoftheproductsbytheskin.
•Agreaterreleaseofactiveingredientsisgenerallypossiblefrom
thesofter,lessviscousbases.
•Theviscosityofsemi-solidproductsmayaffectabsorptionofthese
topicalproductsduetotheeffectofviscosityontherateof
diffusionoftheactiveingredients.
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