Pavan Muttil, Ph.D.

PHRM 701
Pharmaceutics I
Fall 2014

From rheo(toflow)andlogos(science)
Studyofdeformationandflowpropertiesofmatter

Canbeappliedtoallformsofmatter
Primarilyfocusedonliquidsandsemisolidsinpharmaceutical
sciences

Usedtodescribetheconsistencyofdifferentproducts
Viscosity measureofresistancetofloworthickness
Elasticity stickinessorstructure

Newtonian
Rheologyof
semisolids

Non
Newtonian
Thixotropy

Plastic
Pseudoplastic
Dilitant

ShearStress
Velocity(v)ofamaterialspread
overasmalldistance(x)thatit
travels(rateofshear)is
proportionaltosheerstress
applicationofhorizontalforce
(F)overaunitarea(A)

Coefficientofviscosity()
Parameterthatdefinesthe
resistancetoflow

Shearstress
Unitsofforce/unitarea=dynes/cm2

Rateofshear
Unitsofvelocity/unitsofdistance=(cm/s)/cmor1/secorsec1

Viscosity()
(dynes/cm2)s
dynes=g(cm/s2)
[g(cm/s2)]s/cm2 =g/cms
poise
cps(usedforlowviscosityliquids)1cps=(1/100)poise

Reciprocalofviscosity
=1/
Rheogram

units for fluidity- cm s/g (reciprocal of poise)

Rate of Shear (s-1)

Graphicrepresentationofrateofshear
versussheerstress
Slope = fluidity

Shear Stress (dynes/cm2)

Thefollowingdatashowtherateofshearasafunction
ofshearstressforaNewtonianfluidat25C.
Determinethefluidityandviscosityofthefluid.
Rate of Shear (s-1)

200

400

600

800

1000

Shear Stress
(dynes/cm2)

50

100

150

200

250

Rate of Shear (s-1)

200

400

600

800

1000

Shear Stress
(dynes/cm2)

50

100

150

200

250

Viscosity= 50/200 = 0.25

Fluidity = 1/0.25 = 4

Viscosityisindependentofshearstress
AlsoknowasAbsoluteViscosity
Slopeisconstant

Commonlyhavelowmolecularweightsand
molecularhomogeneity
Acetone,water,ethanol,oliveoil,glycerin

Viscositydecreasessharplywithincreasing
temperature

Viscositydecreasessharplywithincreasingtemperature

Y= b + mx
Ev = Activation energy (cal/mol or kcal/mol)
R = Universal Gas Constant (1.987 cal/mol K)

Slope = Ev/R
ln

A = Constant (same units as viscosity)

Y-int = ln A

T = Absolute temperature (C + 273)

1/T (K-1)

Theviscosityofhumanplasmaat37Cis1.2
cps.Assumingtheplasmabehaveslikea
Newtonianfluid,determinetheviscosityof
plasmarequiredforaninfusionthatiskeptat
roomtemperature(25C).
Theactivationenergyofplasmais4.25x103 cal/mole

Observedincomplexheterogeneoussystems
(Relationshipbetweenshearstressandrateofshearis
nonlinear)

3types

Plasticrheology

Pseudoplastic
rheology

Dilatant rheology

Describesasituationinwhichnoflowoccursin
responsetoshearstressuntilatransitionpoint
isreached
Yieldvalue()
Minimumshearstressrequiredbythesystem
beforeitdeformsandbeginstoflow
Onceyieldvalueisreached,therelationship
betweenshearstressandrateofshear
becomeslinear

Rate of Shear (s-1)

Slope = fluidity

= yield value

Shear Stress (dynes/cm2)

Binghambodies
Seeningels,ointments,andcreams
Importanttodetermine offinalproduct
Magnitudeofstressiscriticalforpatientuseofproduct
Measurementofforcerequiredtospreadtheproductonthe
skin
Toohighavaluewillnotalloweasyrubbing
Toolowavaluewillresultinaproductthatruns

The following data show the rate of shear as a

function of shear stress for a topical formulation that
exhibits plastic rheology. Determine the yield value
and viscosity of the fluid.
Rate of Shear (s-1)

250

500

Shear Stress
(dynes/cm2)

162.5 275

750

1000

387.5 500

1500
725

Observedinsystemsthatdeformandflow
instantaneouslywithappliedstress
Relationshipisnotlinear

Shearthinningsystem

Rate of Shear (s-1)

viscosityatpointAishigherthanat
pointB

Tears
A

Ketchup

Shear Stress (dynes/cm2)

10

Increase shear stress

Decrease shear stress

(higher viscosity)

Uncoiled Form

Rate of Shear
(s-1)

Globular Form

(lower viscosity)
B

A
Shear Stress
(dynes/cm2)

Observedinsystemsthatdeformandflow
instantaneouslywithappliedstress
Relationshipisnotlinear
Rate of Shear (s-1)

Shearthickeningsystem
viscosityatpointAislower
thanatpointB

Whippingcream
Shear Stress (dynes/cm2)

11

Thecomparativelyslowrecoveryofthematerial
structureonstandingthatwaslostbyshear
thinning
Timerequiredfortherecoveryofpolymerconfigurationoncestress
hasbeenREMOVED
Rate of Shear (s-1)

DegreeofHysteresis
C
B

maytakeashorterorlongertimeto
reacquirestructureandbecomeviscous
uponstanding

Suspensionandemulsions

D
A
Shear Stress (dynes/cm2)

SpreadingandAdherencetotheSkin
Removalfromjarsorextrusionfromtubes
Capacityofsolidstomixwithmiscibleliquids
Releaseofdrug frombase

12