Rheology

Learning Objectives:
At the end of 3-hour leacture discussion, the students will be able to: Define rheology. Provide examples of fluid pharmaceutical products exhibiting various rheologic behaviors. Describe the application of of rheology in the the pharmacuetical science. Undertsand anf define the different concepts in rheology. Appreciate the fundamentals of practical determination of rheologic properties using the four types of viscometers.

Content Outline:
Definition

Classification of Rheologic Systems Thixothropy Determination of Rheologic Properties Application o Rheology in Pharmacy

Rheology
rheo to flow logos science Science of describing the flow and deformation of matter under stress.
Viscosity ( ) - the resistance of fluid to flow - the higher the viscosity, the greater the resistance.

Significance
formulation of medicinal and cosmetic creams, pastes and lotion. formulation in emulsion, suspension, suppositories and tablet coatings fluidity of solutions for injection in mixing and flow of materials, their packing into containers, their removal prior to use ( whether by pouring from a bottle, extrusion from a tube or passage through a single syringe needle). affect patient acceptability, physical stability and even biological availability.

Classification of Rheologic Systems

Newtonian System Non-Newtonian System

Newtons Laws
1. Every body continues in its state of rest or uniform motion in a straight line unless it is acted upon by another force. 2. The rate of change of momentum is proportional to the applied force and in the direction of the applied force. 3. For every action there is equal and opporiste reaction.

Newtonian System Newtonians Law of Flow

Newtonian Flow

Definitions
Shear
- the movement of material relative to parallel layer

Shear Stress ( F )
- the force per unit area required to bring about a flow

Shear rate ( G ) - the difference in velocity (dv) between two

planes of liquids separated by distance (dr)

The rate of shear should be directly proportional to the shearing stress.

The unit of viscosity is poise. - 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. Poise = dyne sec / cm2 cgs = g / cm sec

Definitions
Fluidity the reciprocal of viscosity

Definitions
Kinematic Viscosity - the absolute viscosity divided by the density of liquid at a specific temperature

Where p is the density of the liquid The unit is Stoke (s) or centistoke (cs).

Definitions
Relative Viscosity - the relation of the solution viscosity to the viscosity of the solvent standard o.

Examples
1. The viscosity of acetone at 25 C is 0.313 cp, its density at 25 C is 0.788 g/cm3. What
is the kinematic vsicosity at 25 C?

2.

Water is usually used a standard of liquids. Its viscosity at 25 C is 0.89 cp. What is the viscosity of acetone relative to that of water at 25 C ?

Non-Newtonian Systems
Non-Newtonian fluid - one in which the relationship between shear stress and shear rate is not a constant When the shear rate is varied, the shear stress
doesnt very in the same proportion. The viscosity of such fluids will therefore change as the shear rate is varied. Seen in liquid and solid heterogenous dispersions such as colloids, emulsions, liquid suspension and ointments.

Non-Newtonian Systems
Three Classes Plastic Flow Pseudoplastic Flow Dilatant Flow

Plastic Flow
known as Bingham bodies
A Bingham body does not begin to flow until a shearing stress corresonding to the yield value is exceeded. Yield value (f) is an indication of the force that must be applied to a system to convert it to a Newtonian System. - an indication of the force of flocculation - the more flocculated the suspension, the higher will be the yield.

Plastic Flow
At stresses below the yield value, the
substance acts as elastic material. Substances that exhibit a yield value solid Substances that begin to flow at the smallest shearing stress and show no yield liquid Plastic flow is associated with the preparation of flocculation and aggregation of particles in concentrated suspension.

Plastic Flow

Plastic Flow
The slope of the rheogram is termed MOBILITY, analogous to fluidity in Newtonian system and its reciprocal is known as Plastic Viscosity (U).

where f is the yield value

Example
A plastic material was found to have a yield value of 5200 dyne/cm2. At a shearing stress above the yield value, F was found to increase linearly with G. If the rate of shear was 150 sec -1 when F was 8000 dyne/cm2. calculate the plastic viscosity of the sample.

Pseudoplastic Flow
known as shear-thinning the curve begins at the origin, there is no yeild value occurs in dispersion of polymers ( synthetic or natural gum) As the shearing-stress is increased, disarranged molecules orient themselves to thee direction of flow. This orientation reduces internal friction and resistance of the molecules an allows a greater rate of shear at each stress.

Dilatant Flow
known as shear-thickening Certain suspension with a high percentage of dispersed solids exhibit an increase in resistance to flow with increasing rates of shear. System has increase in volume when sheared and hence DILATANT. Type of flow is is the inverse of the the flow properties possessed by the pseudoplastic system. When stress is removed, a dilatant system returs to its original state of fluidity.

Reasons for Dilatency

1. At rest particles are closely packed with minimal inter-particle volume (void), so the amount of vehicle to fill in voids and permits particles to move at low rate of shear. 2. Increase shear stress, the bulk of the system expand (dilate) and the partciles take an open form of packing.

3. The vehicles becomes insufficient to fill the viods between particles. Accordingly, particles are no longer completely wetted (lubricated) by the vehicle.

Reasons for Dilatency

4. Finally, the suspension will set-up as a firm paste. 5. This process is reversible.

Characteristics of Dilatent System

Resting Sheared

-Closed packed particles - Minimum void volume - Relatively low consistency

-Open packed particles - Increased void volume - Insuffiecient vehicle - Relatively high consistency

Significance of Dilatency
Suggests appropriate precautions used during the processing of dilatent materials.

Mixing ( powder + granulating liquid) is usually conducted in high speed mixers, dilatent materials may solidify under these consditions thereby damage the equipments.

Review
1. What is rheology? 2. What are the classifications of rheological systems? Describe each. 3. What are the 3 classes of non-newtonian systems?

Assignment
1. What is thixothropy? 2. What are the apparatus used in the determination of rheologic properties? What are the principles involved in the use of each apparatus? 3. What are the applications of the principles of rheology in pharmacy?

RECAP
1. Rheology 2. Classifications of rheological systems.

3. 3 Classes of non-newtonian systems.

- Psuedoplastic - Plastic

- Dilatant

Thixotropy
The decrease in viscosity as a function of time upon shearing, then recovery of original viscosity as a function of time without shearing.

Thixotropy
The system contain asymetric particles forming a loose network through sample. At rest, this structure impart rigidity to system resembling gel.

As shear is applied, the structure begin to break and the material undergo Gel-to-Sol transformation and exhibit shear thinning. Finally, at rest the structure is restored again Sol-to-Gel.

Thixotropy

Thixotropy
Thixotropic samples

- ketchup, paints, yoghurt, mayonnaise - suspension

- emulsion, lotions, creams and ointments

Measurement of Thixotropy
2 approaches

First To determine structural breakdown with time at constant rate of shear Second To determine the structural breakdown due to increasing shear rate.

Measurement of Thixotropy
2 approaches

First To determine structural breakdown with time at constant rate of shear

Thixotropic coefficient, B
U1 t1 U2 plastic viscosities time, seconds
and t2

Measurement of Thixotropy
2 approaches

Second To determine the structural breakdown due to increasing shear rate.

Thixotropic coefficient, M, dynes sec/ cm2

U1 t1 U2 plastic viscosities time, seconds
and t2

Negative Thixitropy

An increase in viscosity with time

Rheopexy

Solid forms a gel more readily when gently shaken or sheared than allowed to form a gel while the materials is kept.
Rheopectic system gel is the equilibrium form

Antithixotropy sol is the equilibrium form

Determination of Viscosity
Newtonian System - Capillary viscometer

- Falling Sphere viscometer

Newtonian and Non-Newtonian System

- Cup-and-Bob viscometer - Cone-and-Plate viscometer

Capillary Viscometer
also known as ostwald viscometer

determined by measuring the time required for the liquid to pass between two marks as it flows by gravity through a vertical capillary tube
the time of flow of the liquid under test is compared with the time required for a liquid of known viscosity (usually water) to pass between the 2 marks.

Capillary Viscometer

Example
What is the viscosity of acetone at 25 C when the time required for acetone to flow between two marks on the capillay viscometer was 45 sec and for water the time was 100 sec at 25 C. The density of acetone is 0.786 g/cm3 and that of water is 0.997 g/cm3 at 25 C.

Falling - Sphere Viscometer

A glass or steel ball rolls down an almost vertical glass tube containing the test liquid at known temperatue. the rate at which a ball of particular density and diameter falls is an inverse function of the viscosity of the sample.

the time required for the ball to fall between two marks is accurately measured and repeated several times.

Falling - Sphere Viscometer

t the time interval in seconds for the ball to fall between two points Sb Sf - specific gravities of the ball and fluid B constant for a particular ball and is supplied by manufacturer.

Cup-and-Bob Viscometer
a sample is sheared in the space between the outer wall of a bob and the inner wall of a cup to which the bob fits.
popular instrument is the Stormer instrument.

Stormer Instrument
the test system is placed between the cup and the bob and allowed to make reach temperature equilibrium.

a weight is placed in the hanger and the time required for the bob to make 100 revolutions is recorded. the data is converted to revolutions per minute
the weigh is incresed and the whole procedure is repeated.

Stormer Instrument

U plastic viscosity in poises Wf yield value in grams

Stormer Instrument
A driving weight, w, of 450g produced a bob velocity v, of 350 rpm. A series of velocities was obtained using other driving weights. The yield value intercept, Wf , extrapolating the curve to the shearing stress axis where v = o and the value of Wf was found to be 225g. The instrument constant Kv is 52.0 and Kf is 20.0 . What is the plastic viscosity?

Cone Plate Viscometer

Ferranti-Shirley , popular example

the sample is placed at the center of the plate, which is then raised into position under the cone. a variable speed motor drives the cone and the sample is sheared in the narrow gap between the stationary plate and the rotating cone.

Cone Plate Viscometer

the rate of shear in revolutions per minute is increased and decreased by a selector dial and the viscous traction or torque (shearing stress) produced on the cone is read on the indicatpr scale.

Cone Plate Viscometer

Newtonian Liquid
C instrument constant T torque reading v speed of the cone in revolutions per minute

Non-Newtonian ( Plastic flow)

Tf torque at the shearing stress axis Cf instrymental constant

Cone Plate Viscometer

A new ointment base was designed and subjected to rheology analysis at 20C in a cone-plate viscometer with instrument constant, C, 6. 277 cm-3. At a cone velocity of v=125 rpm the torque reading, T, was `287.0 dyne cm. The torque tf, at the shearing stress axis was found to be 63.5 dyne cm. What is the plastic viscosity of the ointment base?

Pharmaceutical Area in which Rheology is Significant

1. Fluids Mixing
Particle-size reduction of disperse system with shear Passage through orifices, including pouring, paackaging on bottles and passage through hypodermic needles. Fluid transfer, including pumping and flow through pipes Physical stability of disperse system

Pharmaceutical Area in which Rheology is Significant

2. Quasisolids Spreading and adherence on the skin
Removal from jars or extrusion from tubes Capacity of solids to mix with miscible liquids Release of the drug from the base

Pharmaceutical Area in which Rheology is Significant

3. Solids
Flow of powders from hoppers and into die cavities in tableting or into capsules during encapsulation packagability of powdered or granular solids

4. Processing
processing capacity of the equipment processing effeciency

Assignment
1. Define the three classes of complexes.
2. What are chelates and their physical properties?

3. What are the uses of chelates?