OUR LADY OF FATIMA UNIVERSITY

Antipolo City Camp

Rheology
 Learning Objective
At the end of this unit, the students are expected
to:
• Define rheology and viscosity
• Determine the different types offlow
• Determine the different apparatus used tomeasure
viscosity and their principles.
• Determine the pharmaceutical applicationof
rheology
 Unit Outline
•Rheology
•Types of Flow
•Thixotrophy
•Rheopexy
•Determination of RheologicProperties
 Rheology
• Greek word – rheo “flow” logos “science”
• Heraclitus (actually coming from the writings of Simplicius),
panta rei, "everything flows.“
• Suggested by Bingham and Crawford
• Rheology is a science or physics that deals with the flow of liquids
and also the deformation of a solids

• Viscosity – resistance to flow

• Viscosity is the expression of resistance of a fluid to flow.
• ↑ the viscosity the greater the resistance
• An understanding on the viscosity of a liquid, solutions, and
dilute system has both practical and theoretical value
• Use: study of paints, inks, doughs, road builidng materials,
cosmetics, dairy products and other materials.
 Rheology in pharmacy
- Scott blair introduced the important of
application of rheology to pharmacy
• Application in the formulation
• Analysis of pharmaceuticapplicational product:
✓ Emulsion
✓ Pastes
✓ Suppositories
✓ Tablet coating
✓ Medicinal and cosmetic creams
✓ Lotion

- The manufacturers of medicinal paste, creams, and lotions must be capable of

producing product with acceptable consistency and smoothness and they have
to produce these qualities each time a new batch is prepared and manufactured
 Types of flow
- fluids can be classified according
to their types of flow such as:
1. Newtonian flow/system
2. Non Newtonian flow/system
 Types of flow
- fluids can be classified according to their types of
flow
• Newtonian system
• Poise - unit of viscosity
- viscosity decreases when there is increasing temperature.
•Cgs unit = for poise is dyne sec/cm² or gcm-1sec-1 or g/cmsec
• Centipoise (cp) plural (cps) 1 cp = 0.01 poise
• Fluidity - ᶲ - reciprocal to viscosity
- Fluidity increases as the temperature increases

- Centipoise is the most convenient unit for most work.

 Kinematic viscosity
• The USP kinematic viscosity – absolute viscosity
• Can be obtained by dividing the dynamic viscosity
by the viscosity at specific temperature
• Kinematic viscosity = ᶯ/ᵖ

• Unit:
• Stoke (s)
• Centistoke (cs)
• Measure : arbitrary scale, Saybolt, Redwood,
Engler
 Viscosity enhancing agent
• Acacia • Povidone
• Agar • Pectin
• Bentonite • Colloidal silicon dioxide
• Carbomer • Starch
• SCMC and CCMC • Tragacanth
• Carrageenan • Xanthan gum
• Dextrin
• Gelatin
 Temperature and viscosity
• Gas = ↑viscosity ↑ temperature
- Increased viscosity = increased temperature

• Liquid = inversely proportional

• ↑Viscosity ↓ temperature
• The increased the viscosity, will give decreased in
temperature
• Activation energy – energy required to initiate flow
between molecules
• The dependence on viscosity of liquid on
temperature is expressed approximately for
many substances by an equation analogous to
Arrhenius equation of chemical kinematics

• It can be seen on that equation that there is an

energy required to initiate flow between
molecules , we call that energy required as
Activation Energy
 Non newtonian system
- also called Non Newtonian fluids
• Non Newtonian behavior is generally exhibited by

✓ Liquid and solid heterogeneous dispersions such as colloidal solution

✓ Emulsions
✓ Liquid suspension
✓ Oitment
✓ And other products

• ANALYZED: Analyzed in a rotational viscometer

• Majority of the fluid in pharmaceutical product are not simple liquids, meaning they do
not follow newtons law
• If the liquids do not follow newtons law, these liquids are referred to as Non Newtonian
fluids
 Three classes of flow
• Plastic flow
• Pseudoplastic
• Dilatant
RHEOGRAM
- Plot of shear rate as a function of shear stress

Newtonian flow: linear curve

Newtonian fluid – defined as one way constant viscosity
- The shear rate is directly proportional to the shear stress causing a
line and passes the point of origin

Non Newtonian flow

Includes:
1. Plastic flow
2. Pseudoplastic flow
3. Dilatant flow
 Plastic flow
The curve represents a body that exhibits the plastic flow, the materials that
exhibit plastic flow are called as Bingham bodies – modern rheology and the first
investigator to study the plastic substances in a systematic manner

Bingham bodies – was named after the one who pioneered plastic substances in a
systematic manner, BINGHAM

Plastic flow curve do not pass the origin but rather intersect the shearing stress
axis in a particular point referred to as Yield Value

• Those substances that exhibit a yield value is defines as solids -> the
substances that begins to flow at the smallest shearing stress and show no
yield value are defined as liquids
Mobility – slope of rheogram –> same to fluidity of Newtonian system and is
reciprocal is called plastic viscosity (U)
 Plastic flow
• presence of flocculated particles
in concentrated suspensions.
• Yield value indicate the force of
flocculation
• The more flocculated = the ↑ yield value
 Pseudoplastic flow
• Also known as Shear thinning system
• Apparent viscosity decreases with increased stress
• Examples: Paper pulp in water, latex paint, ice,
blood, syrup, molasses

• Typically, it is exhibited by the polymers in solution

• The consistency curved for pseudoplastic materials
begins at the point of origin. Therefore, there is no
yield value.
 Dilatant flow
• Also known as: Shear thickening system
• Suspension with high percentage of dispersed solid exhibit an
↑ in resistance to flow with ↑ rate of shear
• Dilatant – system that ↑ in volume when sheared
• Apparent viscosity increases with increased stress
• Suspensions of corn starch or sand in water
• Inverse with pseudoplastic system
• Shear thickening system – when stress is removed, a
dilatant system return to its original state of fluidity
• Invariably suspension containing ↑ concentration (about
50% or↑) of small defloculated particles
 Dilatant
• Shear stress ↑ the bulk of system expands or
dilates → dilatant
• Dispersion → Solid particles → highspeed mixers,
blenders or mils
• Advantageous compare to plasticand
pseudoplastic
• May solidify under these condition ofhigh shear
→ overloading and damaging the processing
equipment
Thixotrophy
 thixotrophy
• Apparent viscosity decreases with duration of stress[
• Some Clays, Some Drilling Mud, many paints, synovial fluid,
Honey under certain conditions
• An isothermal and comparatively slow recovery, on
standing of material, of consistency lost thru shearing
• Shear thinning system
• Gel to sol transformation and exhibit shear thinning ->
remove of stress -> reform to gel
• Note: not instantaneous; it is progressive restoration of
consistency
 thixotrophy
• Negative thixotrophy or antithixotrophy
• Magnesia magma alternately increase and
decrease rate of shear -> magma thickens
• Not same with dilantancy or rheopexy
• Dilatant system – are deffloculated and ordinarily
contain greater than 50% by vol of solid dispersed
phase
• Antithixotrophic system – low solid content 1-10%
and are flocculated
 Rheopexy
• Phenomenon in which a solid forms a gel more
readily when gently shaken or otherwise sheared
that when allowed to form the gel while material is
kept at rest

• Rheopectic - Apparent viscosity increases with

duration of stress (lubricant and whipped cream)
• Note: rheopectic system: gel – equilibrium state
• Antithixotropy: solution – equilibrium state
 Thixotrophy in formulation
• Is a desirable property in liquid pharmaceutical
system -> high consistency in the container ->
pour and spread easily
• Well formulated thixotrophic susp will not settle out
readily in container -> fluid on shaking -> will remain
long enough for a dose to be dispensed -> regain
consistency rapidly enough (maintain particles in
suspended state)
• Emulsion, lotions, creams and ointnment and
parenteral suspensions (IM)
 Suspension stability

• There is a relationship between Degree of thixotrophy and rate of

sedimenatation
• Greater thixotrophy, lower the rate of settling
• Concentrated parenteral suspension containing 40-70% w/v of procaine pen
G -> high inherent thixotrophy and shear thinning -> caused to pass thru
hypodermic needle
• Formation of depot of drug at the site of injection in the muscle from which
drug was slowly removed and made available to the body
• Thixotrophy – pen – specific surface

• Those are the properties where a thixotropic, rheopectic and other slope
property have a significant effect for the stability of a product, and it also
affect the biological availably and also the effects on patient acceptability.
Determination of rheologic
properties

- successful determination of rheologic properties

depends in large part in choosing the correct
instrumental method

- the choice of viscometer place an important part in

successful determination and evaluation of rheologic
properties
 Choice viscometer
• Newtonian system – shearing stress -> single rate of shear called as
“one point” instrument
- Shear rate is directly proportional to shear stress
- SINGLE POINT INSTRUMENT: provides a single point on the rheogram

• Non Newtononian system – variety of rates of shear called as

“multipoint” instrument

• Note : all viscometer – Newtonian

• Only those with variable shear stress control can be used for Non
Newtonian
 Choice of viscometer
• Tackiness, stickiness, “body”, “slip” and
spreadability → difficult to measure using
conventional apparatus → no precisemeaning

• Individual factors such as the viscosity, yield, thixotropy

and other properties can contribute to total consistency
of Non Newtonian system

• Pseudoplastic materials – instrument caplable of a

wide range shearingrates
 Capillary viscometer
• Aka: Ostwald viscometer
• Ubbelohde viscosimeters
• Used in measuring the: Newtonian liquid – measuring
time required for a liquid to pass between two marks as
flows by gravity thru a vertical tube
• USP suggest capillary apparatus for determining the
viscosity of high viscosity types of methyl cellulose
solution
 Falling sphereviscometer
• A glass or steel ball rolls down an almost
vertical glass tube containing the test liquid at
a known constant temp.
• Example: Hoeppler viscometer

• Variety of glass and steel ball of

different diameter – can be used over
range 0.5 to 200,000 poise
• Best result ball used NLT 30 sec
 Cup and bob viscometer
• This is under the multipoint instrument
• The sampled is sheared in the space between the outer wall of a bob and the inner wall
of a cup into which the bob fits

• 2 types of cup and bob viscometer:

1. Couette – cup is rotated
2. Searle – stationary cup and rotating bob

• 20-50 ml sample
• Disadvantage: variable shear stress across the sample between the bob and
the cup
• Brookfield viscometer is a rotational viscometer of a Searle type – QC
– Newtonian and Non- Newtonian liquid and empirical viscosity
measurement on paste and other semisolid materials
 Plug Flow
• To determine the Gap between the cup and the bob
• Use the Largest bob with a cup of a definite
circumference so to reduce the gap and minimize
the chance of plug flow
• Important in paste and concentrated suspension
thru an orifices
• Extrusion of toothpaste in tube
 Cone and plate viscometer
• The sample is placed at the center of the plate which is then
raised into position under the cone
• The cone angle generally ranges from 0.3⁰ to 4⁰ smaller
angle is being preferred.
• Advantage :
– time save in cleaning and filling
– Temperature stabilization of the sample during a run
(constant temperature)
– 0.1 to 0.2 ml sample (small sample is needed)
– Semisolids (also applicable)
 Viscoelasticity
• Kelvin material -"Parallel" linear combination
of elastic and viscouseffects
• Anelastic - Material returns toa well-defined
"rest shape”
 Viscoelasticity
• Based on the mechanical properties of materials that
exhibit both viscous properties of liquid and elastic
properties of solid

- PROPERTIES:
• Creams
• Lotion
• Ointments
• Suppositories
• Suspension
• Colloidal dispersing
• Emulsifying and suspending agent
• Biologic material: blood, sputum and cervical fluid
 Psychorheology
• Organoleptc evaluation
• Feel, spreadability, color, odor and other
psychologic and sensory characteristics

• Dermatologist three classes:

• Class I – soft and are for ophthalmic use
• Class II – commonly medicated ointment of
intermediate consistency
• Class III – involved stiff protective products use for moist
ulcerative condition
 psychorheology
• Example: USP bacitracin ointment decreased
when temperature was raised from 20⁰ to 35⁰C

• Three attributes:
• Smoothness – coefficient of friction
• Thinness – Non Newtonian
• Warmth (required further studies)
Applications to pharmacy
 Pharmaceutical areas in which
rheology is significant
• Fluids
– Mixing
– Particle size reduction or disperse
system with shear
– Passage thru orifices, including pouring,
packaging in bottles and passage thru
hypodermic needle
– Fluid transfer, including pumping and
flow thru pipes
– Physical stability of disperse system
 Pharmaceutical areas in which
rheology is significant
• Quasisolids
– Spreading and adherence on the skin
– Removal from jars or extrusion from
tubes
– Capacity of solids to mix with miscible
liquids
– Release of drug from the base
 Pharmaceutical areas in which
rheology is significant
• Solids
– Flow of powders from hoppers and into die cavities
in tabletting or into capsules during encapsulation
– Packagability of powdered or granular solids
• Processing
– Production capacity of the equipment
– Processing efficiency
• Poloxamers (Pluronics) – dermatologic bases or
topical ophthalmic preparation because of its low
toxicity and ability to form clear water based gel
• Polymer solution – ophthalmic preparation as
wetting solution for contact lensand as tear
replacement solution “dry eye syndrome”
• dextran (natural) and polyvinyl alcohol
(synthetic) + preservatives
• High MW preparation of Sodium (Na) hyaluronate at
0.1 to 0.2% - dry eye syndrome
• In the study of rheologic properties, microcrystalline cellulose is an
ingredient incorporated into wet powder masses to facilitated
manufacture in the tablets and granules
• There are authors that designs a mixer torque hydrometer to
measure the torque changes as water was added to the mixture
• Torque – is the force acting to produce rotation of a body.
MEASUREMENT: 1Nm= 1 joule

• Pendular state – early addition of liquid

- lenses of liquid at contact point of the particles
• Funicular state – mixture of air and liquid between
particles
• Capillary state – pores filled with liquid
• Liquid droplet state – envelop particles
• The approximate viscosity in centistokes
at room temperature of:
• ether is 0.2;
• of water,1;
• of kerosene, 2.5;
• of mineral oil, 20 to 70;
• and of honey, 10,000.
 References
• Sinko, P.J., Martin’s Physical Pharmacy and
PharmaceuticalSciences. Philadelphia, PA : Wolters
Kluwer. 2017
Smith, B. Remington Education: PhysicalPharmacy.
London :Pharmaceutical Press.2016
• Kumar, D. S. ) Applied thermodynamics. S. K. Kataria&
Sons. 2017
• Helmer, Erica Drug design and medicinal chemistry
Callisto Reference.2015
• Atkins Elements of Physical Chemistry. 2017
 Video Links
• Rheology Introduction =
https://www.youtube.com/watch?v=_RSNSGkSqSw
• What is Rheology? =
https://www.youtube.com/watch?v=eSHH_ssMkSo
Thank you