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RHEOLOGY

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O
B 1.) Define and discuss the concept of
J rheology and its importance.
E 2.) Explain the measurement use to
C describe reheology.
3.) Discuss the types of flow.
T 4.) Explain the types of viscometer used
I for determiantion of rheologic
V properties.

E
S
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A RHEOLOGICAL PARADOX

Sometimes it does ____ Sometimes it doesn’t ____

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RHEOLOGY
• a study of how a material deforms
during and after a force is applied.
• defined as the study of flow of liquids
and deformation of solids.
• Rheos – means to flow
• Suggested by Bingham and Crawford

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RHEOLOGY
The deformation of any pharmaceutical
system can be arbitrarily divided into
two types:
1) Spontaneous reversible deformation,
called elasticity.
2) Irreversible deformation, called flow.

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RHEOLOGY

Why is rheology important?


a.) Mixing
Rheology affects ease of mixing
b.) Dispensing whether by hand or with a static mix
tube.
c.) Settling
d.) Flow Control Rheology dictates how a material is
applied whether by spatula, spray,
Rheology affects the way a pump, syringe, tube, or pouring.
material flows. High flow allows easy
entry into intricate spaces versus a low
flow which prevents flow into critical Rheology affects the degree and
areas. rate at which substances settle.
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RHEOLOGY
- Can affect patient acceptability, physical
stability, and even biologic availability.

- Rheologic properties of pharmaceutical system


can influence the choice of processing
equipment to be used in its manufacture.

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RHEOLOGY
Shear - the duration and amount of any force
applied to the material.

Shear stress - refers to a stress state that will cause


shearing.

Shear rate – change of deformation per unit time.

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Shear stress

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Shear Rate

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VISCOSITY
The measurement use to describe rheology is
VISCOSITY.
- is an expression of the resistance of a fluid to
flow.
- the higher the viscosity, the greater the
resistance.
- is the proportionality constant between the
shear rate (D) and shear stress (S).
η = S/D
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VISCOSITY

VISCOSITY
- CGS System: dynes-sec/cm 2
g/cm-sec
poise
- SI unit: N-sec/m2 1 N-sec/m2 = 10 poise

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TYPES OF FLOW

a.) Newtonian Systems


- are “ideal liquids”, which means as the shear rate
changes the viscosity remains constant (water, oils,
solvents).

b.) Non-newtonian Systems


- These fluids are affected by shear and are divided into:
* Power Law Fluids (Plastic, Pseudoplastic or Dilatant)
* Time Dependent Fluids (Rheopectic or Thixotropic).

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Newtonian Systems

Newton was the first scientist to observe the flow


properties of liquids in quantitative terms.
Liquids that obey Newton’s law of flow are called
Newtonian liquids, E.g. simple liquids.
Newton’s equation for the flow of a liquid is
η = S/D
The shear stress and shear rate are directly
proportional, and the proportionality constant is the
Co-efficient of viscosity (η).
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Newtonian Systems

η η

Newtonian Flow
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Non-Newtonian Systems

Heterogeneous dispersions such as colloidal solutions,


emulsions, liquid suspensions and ointments have
complex rheological behavior and thus do not obey
Newton’s law of flow and thus they are called Non-
Newtonian liquids.

Power Law Fluids Time-Dependent Fluids

A) Plastic flow A.) Thixotropic


B) Pseudo-plastic flow B.) Rheopectic
C) Dilatant flow
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Non-Newtonian Systems

Plastic Flow
- are called Bingham bodies.
- The substance initially behaves like an elastic body and
fails to flow when less amount of stress is applied.
Further increase in the stress leads to a nonlinear increase
in the shear rate which then turns to linearity.

Yield Value

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Non-Newtonian Systems

Apparent Yield Stress

A certain shear stress has to be applied in order to let the sample


flow

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Non-Newtonian Systems

Examples of Substances that exhibit Plastic Flow:

A.) Pastes ( tomato paste, chili paste, tooth pastes)


B.) Concentrated dispersions (ketchups, mayonnaises, chocolate melts,
butter, margarine, gels, filled polymers, sealants, fillers, dispersion
paints)
C.) Offset printing inks
D.) Ceramic Suspensions
E.) Lip sticks
F.) Ointments
G.) Creams
H.) Cataplasms
I.) Cerate
J.) Dough
K.) Putties and modeling clay 19
Non-Newtonian Systems

Plastic Flow

Mechanism of Plastic Flow

Yield value represents the stress required to break the inter-


particular contacts so that particles behave individually. 20
Non-Newtonian Systems

Pseudo-plastic Flow
(Shear-Thinning System)
The relationship between shear stress and the shear rate is
not linear and the curve starts from origin. Thus the viscosity
of these liquids cannot be expressed by a single value.

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Non-Newtonian Systems

Pseudo-plastic Flow
(Shear-Thinning System)
Normally, pseudo plastic flow is exhibited by polymer
dispersions like:

a.) Tragacanth water


b.) Sodium alginate in water
c.) Methyl cellulose in water
d.) Sodium carboxy methyl cellulose in water

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Non-Newtonian Systems

Dilatant Flow
(Shear-Thickening System)
In this type of liquids resistance to flow (viscosity) increases
with increase in shear rate. When shear stress is applied their
volume increases and hence they are called Dilatant. This
property is also known as shear thickening.

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Non-Newtonian Systems

Dilatant Flow
(Shear-Thickening System)
Dilatant flow is observed in suspensions containing more than
50% v/v of solids.

Example: Suspension of starch in water


Aqueous glycerin and methylene blue

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Non-Newtonian Systems

Pseudoplastic (Shear-Thinning)
Dilatant (Shear-Thickening )

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Non-Newtonian Systems

Thixotropic
Viscosity decreases over time when using a
constant shear rate.

As shear rate decreases the material will


gradually recover the original internal structure
before shear, this can take seconds or days to
fully recover.

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Non-Newtonian Systems

Rheopectic (Negative Thixotropy)

Viscosity increases as a function of time.

Examples would be a mixed epoxy increasing in


viscosity as curing takes place.

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Determination of Rheologic Properties

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Determination of Rheologic Properties

A.) Finger

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Determination of Rheologic Properties

B.) Ford Cup

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Determination of Rheologic Properties

B.) Ford Cup


Method: Measurement of the time that a defined sample
volume needs to flow through a nozzle.

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Determination of Rheologic Properties

C.) Falling Ball


Method: Measurement of the time that the ball needs to
fall through a distance of 100 mm in a tube of 10O inclination.

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Determination of Rheologic Properties

C.) Falling Ball

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Determination of Rheologic Properties

D.) Capillary Viscometer


- measures the viscosity of a newtonian liquid by
measuring the time required for the liquid to pass between
two marks as it flows by gravity through a vertical capillary
tube known as an Ostwald viscometer.

η1 = ρ1t1
η2 ρ 2 t2

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Determination of Rheologic Properties

d.) Capillary Viscometer


η1 = ρ1t1
η2 ρ 2 t2

Ex. Assume that the time required for acetone to flow


between the two marks on the capillary viscometer was 45
seconds, and for water the time was 100 seconds at 25OC.
The density of acetone is 0.786 g/cm3 and that of water is
0.997 g/cm3 at 25OC. The viscosity of water is 0.8904
centipoise at this temperature. What will be the viscosity of
acetone at 25OC?

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Determination of Rheologic Properties

E.) Rotational Viscometer

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Determination of Rheologic Properties

E.) Rotational Viscometer

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