RHEOLOGY

Rheology
• Rheology is the study of the flow of materials

• Viscosity is the resistance of a fluid to flow; the higher

the viscosity, the greater is the resistance.
Importance
• Formulation of medicinal and cosmetic creams, pastes
lotions, emulsions, suspensions, suppositories, and tablet
coating and fluidity of solutions for injection.
• In mixing of materials and their packaging into the
containers, their removal prior to use, as:
• The pouring from the bottle ,
• Extrusion of a paste from a tube .
• Passage of the liquid to a syringe needle.
• Influence the choice of processing equipments used in
manufacture of pharmaceutical system.
 Inappropriate equipment may result in an undesirable
product, in terms of its flow characteristics.
• The rheology of a particular product, which can range in
consistency from fluid to semisolid to solid, can affect its
patient acceptability, physical stability, and even
biologic availability.

• For example, viscosity has been shown to affect absorption

rates of drugs from the gastrointestinal tract.
SYSTEMS
• When classifying materials according to types of flow and
deformation:

1. Newtonian (Newtonian systems shows constant viscosity

regardless of shear rates applied at a given temperature, exhibit
true or absolute viscosity). Obeys newtons law e.g. water, dilute
suspensions, true solutions)

2. Non-Newtonian systems (Non newtonian systems shows

different viscosity values at different shearing rates at a given
temperature, exhibit apperant viscosity. Does not obey Newtons
law. E.g. colloidal systems).

• The choice depends on whether or not their flow properties are in

accord with Newton’s law of flow.
Newton’s Law of Flow
 Shear – as a stress which is applied parallel to a
face of a material, as opposed to a normal stress
which is applied perpendicularly.

 Shear stress = F / A

 The higher the viscosity of a liquid, the greater is the

force per unit area (shearing stress) required to
produce a certain rate of shear”

 Shear stress
 Measured in (SI unit): pascal
• If the bottom layer is fixed in place and the top plane of liquid is
moved at a constant velocity, each lower layer will move with a
velocity directly proportional to its distance from the stationary
bottom layer.
• The difference of velocity, dv, between two planes of liquid
separated by distance, dr, is the velocity gradient or rate of shear,
dv/dr.
• The force per unit area, F/A, required to bring about flow
is called the shearing stress and is given the symbol F.

• Shear rate is given the symbol G. Hence, G should be

directly proportional to shearing stress, or
shearing stress

• where η is the viscosity.

Shear rate
• Newton's Law states that shear stress is shear
rate times viscosity.

• A representative flow curve, or rheogram, obtained by

plotting F(shear stress) versus G (shear rate).

• A Newtonian fluid is a fluid whose flow curve is linear

and passes through the origin. The constant of roportionality
is known as the viscosity.
• The unit of viscosity is the poise, defined as the shearing force
required to produce a velocity of 1 cm/sec between two parallel
planes of liquid each 1 cm2 in area and separated by a distance of 1
cm.

• The cgs units for poise are dyne sec cm−2 (i.e., dyne sec/cm2) or g
cm−1 sec−1 (i.e., g/cm sec).

• The Centimetre Gram Second System of

units (abbreviated CGS or cgs)
 In common terms, this means the fluid continues to flow,
regardless of the forces acting on it.

 For example, water is Newtonian, because it continues to

exemplify fluid properties no matter how fast it is stirred
or mixed.

 The viscosity of Newtonian fluid, depends only on

temperature and pressure (and also the chemical composition
of the fluid if the fluid is not a pure substance), not on the
forces acting upon it.

 The viscosity of Newtonian fluid increase with increase in

pressure due to decrease spaces between molecules and
increase resistance to flow
Temperature Dependence
• The dependence of the viscosity of a liquid on
temperature is expressed by an equation analogous to
the Arrhenius equation of chemical kinetics:

• where A is a constant depending on the molecular

weight and molar volume of the liquid and
• Ev is an “activation energy” required to initiate flow
between molecules.
Non-Newtonian Fluids
 A non-Newtonian SYSTEMS
 is a fluid whose flow properties are not described by
constant value of viscosity.

 Many polymer solutions and molten polymers are non-

Newtonian fluids, such as starch solution, paint, blood and
shampoo.

 Non-Newtonian behavior is generally exhibited by liquid

and solid heterogeneous dispersions such as colloidal
solutions, emulsions, liquid suspensions, and ointments

 In a non-Newtonian fluid, the relation between the shear

stress and the shear rate is nonlinear, and can be time-
dependent.
 η - Apparent Viscosity
η that analyzed in viscometer categorizes non-Newtonian
fluids into three classes:
 Pseudoplastic flow (shear rate thinning) – η (viscosity)
decreases as shear rate increases

 Dilatant flow (shear rate thickening) – η (viscosity)

increases as shear rate increases

 Plastic flow: η depends on a critical shear stress (t0)

Plastic Flow or Bingham
• Liquid behaves like solid under static conditions with
constant viscosity.

• A certain amount of force must be applied to the fluid before

any flow is induced. This force is called yield value.

• Plastic flow curves straight line do not pass through the origin
but rather intersect the shearing stress axis (or will if the
straight part of the curve is extrapolated to the axis) at a
particular point referred to as the yield value.

• Plastic system resembles a Newtonian system at shear

stresses above the yield value.
• Concentrated flocculated Suspension , ointment, past ,
gels are examples of such fluid. Once the yield value is exceeded
the flow begins.

• Rheology of concentrated flocculated suspensions

exhibit plastic flow system resists flow until a yield value
of stress is reached below this value substance is a solid
where diluted deflocculated suspensions exhibit
Newtonian behavior
 21

floccules
cake
 Pseudo-plastic Flow
• Pseudo-plastic fluids display a decreasing viscosity with
an increasing shear rate,

• This type of behavior is called shear-thinning

• some examples include paints , emulsions and polymers in

solution as liquid dispersions of tragacanth, sodium alginate,
methylcellulose, sodium carboxymethylcellulose.

• Curve for a pseudo-plastic material non linear relation

begins at the origin (or at least approaches it at low rates of
shear). Therefore, there is no yield value as there is in
a plastic system.
Furthermore, because no part of the curve is linear,
the viscosity of a pseudo-plastic material cannot be
expressed by any single value.
Dilatant Flow
• Dilatant is characterized by an increasing viscosity
with an increase in shear rate,

• Dilatancy is also referred to as shear-thickening liquids

• some examples include clay slurries, candy compounds,

corn starch in water, and sand/water mixtures.

• Certain deflocculated suspensions with a high percentage

of dispersed solids exhibit an increase in resistance to
flow with increasing rates of shear.

• Such systems actually increase in volume when

sheared and are hence termed dilatant.
• This type of flow is the inverse of that possessed by
pseudo-plastic systems.

• Whereas pseudo-plastic materials are frequently referred

to as “shear thinning systems,” dilatant materials are
often termed “shear thickening systems.”
• When stress is removed, a dilatant system returns to its original state
of fluidity.
Diagram summary of non-Newtonian fluids:
Non-Newtonian fluids – time
dependent
 THIXOTROPY
• is the property of only non-Newtonian pseudo-plastic fluids
that show a time-dependent change in viscosity; the longer the
fluid undergoes shear stress, the lower its viscosity.

• Thixotropic fluid viscosity decreases over time at a

constant shear rate

• Thixotropy slow recovery of viscosity lost through

shearing applies only to shear thinning materials
gel-sol-gel transformation

• Many gels and colloids are thixotropic materials, exhibiting a

stable gel form at rest but becoming fluid when agitated.
• differences between a thixotropic & a shear thinning fluid:

 A thixotropic fluid displays a decrease in viscosity over time

at a constant shear rate.

 Shear thinning fluid displays decreasing viscosity with

increasing shear rate.

 Some fluids are anti-thixotropic or negative thixotropy :

constant shear stress for a time causes an increase in
viscosity or even solidification.
Thixotropy in Formulation
• Thixotropy is a desirable property in liquid pharmaceutical
systems that ideally should have a high consistency in the
container, yet pour or spread easily.

• For example, a well formulated thixotropic suspension will

not settle out readily in the container, will become fluid on
shaking, and will remain long enough for a dose to be
dispensed.

• Finally, it will regain consistency rapidly enough so as to

maintain the particles in a suspended state.

• A similar pattern of behavior is desirable with emulsions,

lotions, creams, ointments, and parenteral
suspensions to be used for intramuscular depot therapy.
 TYPES of Viscometer Capillary Viscometer

Cup-and-Bob Viscometer

Cone-and-Plate Viscometer
Falling sphere
viscometer
Polymers
• Polymers are long-chain, high–molecular-weight
compounds containing active groups spaced along
their length. A polymer is a large molecule made up of
many small repeating units.

• An oligomer contains 30 - 100 monomeric units.

• Products containing more than 200 monomers are

simply called a polymer

• If one type of monomer is involved, it is called

homopolymer
• Copolymer refers to a polymer in which more than one
type of monomer is involved

Linear Polymer

Stretch

The chains can be stretched, which causes

them to flow past each other. When released,
the polymer will not return to its original form.
Cross-Linked Polymer

Stretch

Relax
The cross-links hold the chains together.
When released, the polymer will return to it's
original form.
• Polymers display different thermal, physical, and
mechanical properties depending on their
structure, molecular weight, linearity, intra- and
intermolecular interactions.

• Biodegradable polymers are classified as natural-

based and synthetic.

• Polysaccharides and protein-based polymers are

obtained from the natural sources.
Pharmaceutical polymers
• In general, the desirable polymer properties in
pharmaceutical applications are

 film forming (coating),

 thickening (rheology modifier),
 gelling (controlled release),
 adhesion (binding) to bind the excipients of the tablet,
 pH dependent solubility (controlled release),
 taste masking, and
 barrier properties (protection and packaging).
• Pharmaceutical polymers can be classified as
1. water-soluble

2. water-insoluble (oil soluble or organic soluble).

• The cellulose ethers with methyl and

hydroxypropyl substitutions are water-soluble,

• whereas ethyl cellulose and a group of cellulose

esters such as cellulose acetate butyrate or
phthalate are organic soluble
HYDROGEL
• Materials, when placed in excess water, are able to swell
rapidly and retain large volumes of water in their
structures. Such aqueous gel networks are called
hydrogels.

• These are usually made of a hydrophilic polymer

that is cross-linked either by chemical bonds or by
other cohesion forces such as ionic interaction, hydrogen
bonding, or hydrophobic interactions.