References: Flow properties of polymer melts – Brydson J.A.

An Introduction to Polymer Rheology and Processing – Nicholas P

Cheremisinoff
Rheology
 The science concerned with the flow and deformation of matter is
known as rheology.
 For making progress in polymer processing techniques, we must study
the flow properties of the polymers.
Benefits of rheological studies:
 It is possible to understand processing faults and defects which are of
rheological origin.
 Hence to make logical suggestions for adjusting the processing
conditions for either minimising or completely removing the fault.
 It is possible to make a more intelligent selection of the best polymer or
polymer compound to use under a given set of circumstances.
 They can lead to qualitative, and to some extent quantitative,
relationships between such factors as output, power consumption,
machine dimensions, material properties and operational variables
such as temperature and pressure.
 They are of some, limited use in providing information on molecular
structure.
Rheological equations of state:
 At times, some polymers appear to behave very much like
“conventional” solids, at other times, like liquids.
 Sometimes, such as when they are rubbery, they have at the same
time the characteristics of both solids and liquids.
 Most polymers have at some time or other the characteristics
both of elastic solids and viscous liquids.
 For such materials we often use the term viscoelastic.
 The studies of dynamic properties and creep behaviour, are
mainly concerned with viscoelastic behaviour.
 When being processed, polymers are basically fluid but may
show elastic overtones, such as die swell in extrusion.
 Such behaviour is being increasingly known as elastic viscous
behaviour.
 There is one common factor between solids, liquids and all these
intermediate materials.
 If we apply a stress or load on any of them they will deform or
strain.
 The deformation may be instantaneous, or it may continue with
time.
 When expressed mathematically, such relationships are known
as rheological equations of state (r.e.s.)
 Let us now consider, the rheological equations of state of some of
the more important classes of rheological materials.
 1) The Ideal (Elastic) solid (Hookean solid):
 The ideal elastic solid obeys Hooke’s law.
 The stress in it is proportional to the strain.
 For tensile strains, we can write
 τT = E ϒT = E ΔL/L
 τT is the imposed tensile stress, ϒT is tensile strain  increase in
length ΔL as compared with the original length L.
 E is the modulus of elasticity.
 A similar relationship holds in shear.

 If a shear force F is applied to the top and bottom surfaces of the

body shown in figure.
 Each of which has an area A, the shear stress is defined as F/A and
represented by τ.
 If the distance between the two surfaces is Lo and the horizontal
displacement of the top surface is ΔL, then
 τ = G(ΔL/Lo) = G ϒs
 G is shear modulus and ϒs is shear strain.
 The behaviour of a Hookean solid is described by figure.

 The stress is applied at time t1, a strain occurs instantaneously

and remains constant until the stress is removed at time t2.
 At this moment the strain also drops to zero.
 In figure (b) the slope being equal to the modulus.
2) The Pascalian Fluid:
 A Pascalian fluid obeys Pascal’s law in that pressure applied to a
fluid at a point is transmitted to all other points of the fluid
without loss.
 Such a state of affairs is not true in any real liquid in a state of
shear (which causes energy dissipation).
 The law will also be valid where the liquid is subject to pressure
but constrained to be at rest.
3) The Ideal Fluid (Newtonian Fluid):
 The stress-deformation behaviour of a Newtonian fluid is best
considered by imagining two parallel plates of very large area (A)
separated a distance “r” by the ideal fluid.
 A shear force F is applied to the top plate; i.e. There is a shear
stress = F/A
 The top plate moves with a uniform velocity u.
 The arrows indicate the velocity of the various layers of fluid
relative to the top and bottom plate velocities.
 Shear stress is directly proportional to shear rate.
 Fluids which obey the following simple relation
𝒖 𝒅𝒖
 𝝉= 𝝁 or 𝝉 = 𝝁 are known as Newtonian fluids.
𝒓 𝒅𝒓
 µ  coefficient of viscosity
 Simple liquids closely approach Newtonian behavior.
 If the distortion in time dt be dL, u = dL/dt
 dL=udt
 If we define the differential strain dγs as dL/r,
𝒅𝒖
 dγs = udt/r = 𝒅𝒕
𝒅𝒓
𝐝𝛄𝐬 𝐝𝐮
 =
𝐝𝐭 𝐝𝐫
 Figure (a) shows the stress-time and strain-time relationship for
an ideal (Newtonian) fluid.
 Application of a fixed stress at t1 causes a deformation which
increases steadily with time until t2 when the stress is released
and the deformation becomes constant.
 Figure (b) shows the shear stress –shear rate relationship for an
ideal (Newtonian) fluid.
 The slope is equal to the coefficient of viscosity.
Units of measurement for shear flow:

cgs SI fps
Shear stress dyn cm-2 Nm-2 lbf ft-2

Shear rate s-1 s-1 s-1

Coeff. of dyn s cm -2 Ns m -2 lbf s ft -2

viscosity (poise)

𝐝𝛄𝐬 𝐝𝐮
=
𝐝𝐭 𝐝𝐫
 These equivalent expressions are known as the shear rate (𝜸)
 τ = µ𝜸
 If we plot stress-time and strain-time curves for a Newtonian
fluid analogous to those for a Hookean solid.
Non-Newtonian Fluids:
 The coefficient of viscosity of Newtonian fluids is constant
irrespective of the shear stresses involved, and is independent of
time, by definition.
 Many real materials, particularly polymer melts and solutions
and suspensions of particles in liquids such as PVC pastes do not
exhibit the simple characteristics of a Newtonian fluid.
 This behavior is known as Non-Newtonian behavior.
 3 broad classes of flow behavior are recognized.
 a) Time- independent fluids: fluids in which the rate of shear at a
given point is some function of shearing stress at the point .
 A Newtonian fluid is , in fact, the simplest example of this class.
 b) Time-dependent Fluids: more complex systems in which shear
stress-shear rate relationships depends on how the fluid has
been sheared and on its previous history.
 c) Elastico viscous fluids: systems which are predominantly
viscous but which exhibit partial elastic recovery after
deformation.
 This class could be considered as a special sub-class of time-
dependent fluids.
 Time-independent fluids:
 Time-independent fluids are defined mathematically by the
equation
 𝜸 = f(τ)
 Or graphically by a curve of shear stress plotted against shear
rate.
 Four basic types are indicated in figure.
 Figure shows the shear stress-shear rate relationships for
Bingham bodies, dilatant fluids and pseudoplastic fluids
compared with a Newtonian material.
 τy is the yield point.
 For the Newtonian fluid,
 𝜸 = τ/µ
 So f (τ) = τ/µ
 Bingham body is an idealized material which is considered to have
an internal structure which collapses above a yield stress τy, above
which the shear rate increases linearly with shear stress.
𝟏
 𝜸= (𝝉 − 𝝉𝒚 ) when τ ≥ τy .
µ
 Yield stress is the minimum stress value that must be exceeded for
deformation to occur.
 A number of suspensions, slurries and pulps approximate in their
behavior to Bingham bodies although the τ-𝜸 relationship above
𝝉𝒚 𝐦𝐚𝐲 𝐛𝐞 non-linear.
Pseudoplastics:
 Shear rate increases at a more than linear rate with increase in shear.
 For pseudoplastic flow curve, there is no constant of proportionality
between shear stress and shear rate.
 Therefore, instead of coefficient of viscosity, which we use with
Newtonian liquids, it is more common to use “ apparent viscosity”,
µa, defined as shear stress/shear rate.
 Such an apparent viscosity decreases with rate of shear for
pseudoplastics, is independent of rate of shear for Newtonian
fluids and increases with rate of shear for dilatant fluids.

 Pseudoplastic behavior can arise in a number of ways.

 Two explanations are commonly given:
 A) Assymmetric molecules or particles are extensively entangled
or randomly oriented at rest.
 Under shear the molecules become oriented and points of
entanglement are reduced.
 The orientation may be opposed by disorienting effects of
Brownian motion.
 At very high shear rates orientation may be complete and in this
range near-Newtonian behavior may be observed.
 B) Highly solvated molecules or particles may be present.
 With increase of shear rate, solvated layers may be sheared away
resulting in decreased interaction of the particles and
consequent reduction in apparent viscosity.
Power law equation:
 The only equation which has found any real use is the power law
equation (also known as the Ostwald-de Waele equation)
 This equation takes the form
 𝛕 = 𝐊(𝛄)𝐧
 K is consistency index and n is flow behavior index
(pseudoplasticity index).
Classification of non-Newtonian behavior through flow curves:
 A plot of τ Vs 𝛄 results in a straight line passing through the
origin and having slope µ.  for Newtonian fluids
 The resultant plot is known as a flow curve.
 Fluid materials that display non-linear behavior through the
origin at a given temperature and pressure are non-Newtonian.
 Non-Newtonian fluids are broadly classified time-independent
fluids, time-dependent fluids and viscoelastic fluids.
 The first category is comprised of fluids for which the shear rate
at any point is solely a function of the instantaneous shear stress.
 In contrast, time-dependent fluids are those for which shear rate
depends on both the magnitude and duration of shear.
 Less common viscoelastic fluids display the behavior of partial
elastic recovery upon the removal of a deforming shear stress.
 A large variety of industrial fluid-like materials may be described
as being pseudoplastic.
 In examining the curve, it is characterized by linearity at very low
and very high shear rates.
 The slope of the linear region of the curve at the high shear rate
range is referred to as the viscosity at infinite shear;
 Whereas the slope in the linear portion near the origin is the
viscosity at zero shear rate.
 A logarithmic plot of 𝛕 Vs 𝛄 is found to be linear over a relatively
wide shear rate range and hence may be described by a power law
expression (known as the Ostwald-de Waele model)
 𝛕 = 𝐊(𝛄)𝐧
 The slope n and intercept K are given the names “ Flow behavior
index” (or pseudoplasticity index) and “consistency index”
respectively.
 The power law exponent ranges from unity to zero with
increasing plasticity (i.e. at n=1, the equation reduces to that of a
Newtonian fluid)
 The value of the consistency index is obtained from the intercept
on the τ axis and hence represents the viscosity at unit shear rate.
 K is very sensitive to temperature, where as n is much less
sensitive.
 In logarithmic form, the equation may be written
 log τ = log K + n log𝛄
 This means that log-log plots of τ verses 𝛄 will yield a straight
line.
 It is found that for polymer melts reasonable straight lines can be
drawn over 1-2 decades of shear rate but over a wider range such
real materials tend to give curves.
 i.e. n tends to decrease with rate of shear.
 log τ-log𝛄 plots for a) a dilatant material obeying the power law
b) a Newtonian material c) a pseudoplastic material obeying the
power law d) a typical polymer melt which is pseudoplastic but
which does not obey the power law.
 The relationship between apparent viscosity η or µa and the
power law constants K and n:
 η = τ/𝛄
 And 𝛕 = 𝐊(𝛄)𝐧 the power law.
 Combining these two equations:
 By analogy to Newton’s law, the apparent viscosity of a power law
fluid is:
 η =𝐊(𝛄)𝐧−𝟏
 Since n<1, the apparent viscosity of a pseudoplastic fluid
decreases with increasing shear rate, and hence these materials
are often referred to as shear thinning.
 It is also possible to relate the apparent viscosity to shear rate and
n ; in terms which do not involve K.
 If η is the apparent viscosity at some shear rate (𝛄) and ηr is the
apparent viscosity at some arbitrary reference shear rate 𝛄r, then
 𝐧−𝟏
𝛈 𝛄
 =
𝛈𝐫 𝛄𝐫
 When 𝛄𝐫 is put equal to 1 s-1 this simplifies to
 η = η1𝛄n-1
 η1 𝐢𝐬 the apparent viscosity at a shear rate of 1 s-1
 The opposite behavior to pseudoplasticity is known as dilatancy.
 Dilatant materials show an increase in the apparent viscosity
with increasing shear rate.
 Dilatancy is often exhibited by highly concentrated suspensions,
particularly PVC pastes.
 The effect appears most common with materials consisting of
irregularly shaped particles which do not pack easily under high
rates of shear.
 It does not seem to have been observed with polymer melts
except under special conditions where crystallisation of the melt
is occurring during flow.
 The power law equation is the most useful empirical equation to
describe dilatancy.
 But in this case the value of n is greater than 1.
Time-dependent fluids:
 There is a number of liquids whose flow properties, such as
apparent viscosity change with the time of shearing.
 In some cases the change is reversible, or at least the viscosity
eventually recovers its initial value after a sufficiently long rest
period after cessation of shear.
 In other cases, such as in the mastication of rubber, irreversible
changes occur because of changes in the molecular structure.
 It is often assumed that polymer melts are time-independent but
the disentanglement of molecules during shear may cause time-
dependent effects.
 Most time-dependent behavior have been concerned with
reversible effects such as thixotropy and rheopexy.
 Thixotropy is that property of a body by virtue of which the
apparent viscosity is temporarily reduced by previous
deformation.
 This means that with thixotropic material the viscosity depends
on the time of stirring as compared with a pseudoplastic material
which depends on the rate of shear.
 A thixotropic material is often also pseudoplastic but the reverse
is not very common.
 The most characteristic feature of thixotropic behavior can be
demonstrated using a rotary viscometer.
 The sample is stirred for a fixed period of time, for example one
minute, at a low shear rate.
 The torque measured is recorded at sometime during this period.
 The speed is then increased stepwise without stopping the
machine and the torque measured at the new shearing rate.
 This is then repeated over several increased stirring rates.
 A curved plot will result.
 Without stopping the viscometer, measurements are then made
at a series of decreasing stirring rates and the torque measured.
 In the time-interval between making the measurements when
increasing speeds and making measurements at decreasing
speeds the viscosity will have dropped.
 The resulting curve will be below the curve made when making
measurements in the sequence of increasing speeds.
 The term “anti-thixotropy” is used when the apparent viscosity is
an increasing function of the duration of flow and when, as with
thixotropy, the body recovers its initial state after a long enough
rest.
 Once again a hysteresis loop is produced in the rotary viscometer
experiment but is in the opposite sense.
 An example of anti-thixotropy is the considerable increase in the
viscosity of a 5 % aqueous polymethacrylic acid solution when
sheared at a shear rate of 10 s-1 for 1 min.
 The word “rheopexy” has also been used to describe an increase
in the viscosity of a body with time (not necessarily under
deformation).
 It should be noted that any thixotropic material increases in
viscosity as the intensity of shear is reduced.
 The term “rheopexy” should be used to refer to an increased rate
of solidification on gentle movement.
Two-parameter models:
 These models contain two adjustable material parameters, which
depend on temperature, concentration (for solutions) and the
filler loading (for filled systems).
 Some of the commonly used models of this type are:
 (i) Ostwald de Waele or power law model, 𝝉 = 𝒌(𝜸)𝒏
 Where k is the consistency index and n is the non- Newtonian or
the flow behavior index (k & n are parameters), 𝝉 is the shear
stress and 𝜸 is the rate of shear.
 For n<1, the fluid is pseudoplastic, n=1, the fluid is Newtonian,
and n>1, the fluid is dilatant.
 The equation when plotted on a double log scale gives a straight
line with a slope of n and an intercept of k.
 The apparent viscosity ηa, can be calculated as
𝝉
 η𝒂 = = 𝒌(𝜸)𝒏−𝟏
𝜸
 This equation shows the viscosity to be function of 𝜸 such that it
will increase with 𝜸 for n>1 and decreases for n<1.
 The equation gives a good data fit for a large number polymer
and rubber melts, polymer solutions, low to moderately filled
rubber in the intermediate range of rate of shear.
 Depending on the material the intermediate range may lie
between 10-1 to 105 s-1.
 In the low and high shear region the power law model deviates
considerably from the experimental data and should not be
extended to these ranges at all.
 To describe the behavior in these zones other equations have
been developed.
(ii) Eyring Prandtl model:
 This model has been derived from the Eyring kinetic theory of
liquids and is applicable only to the pseudoplastic fluids in the
low and intermediate shear region.
 𝟏
 The equation is 𝝉 = 𝑨 sinh−𝟏 [− 𝛄]
𝐁
 Where A and B are two adjustable parameters.
 As 𝜸 → 𝟎, η𝒂 → 𝑨 𝑩 (constant), giving the Newtonian behaviour at
low shear rate.
 This equation is unable to predict the high shear rate behavior.
(iii) Bingham model:
 This model describes the fluids, which show the yield stress and
then flow as Newtonian fluids.
 Such liquids are known as Bingham plastic fluids and follow the
equations.
 𝝉 − 𝝉𝒚 = 𝜷𝜸 for 𝝉 ≥ 𝝉𝒚 ------ (1)
 𝜸 = 𝟎 𝐟𝐨𝐫 𝝉 < 𝝉𝒚 ------- (2)
 𝝉𝒚 is the yield stress and 𝜷 is the consistency index or the
coefficient of rigidity or the coefficient of plastic viscosity.
Three-parameter models:
(i) Viscoplastic fluids model:
 The fluids having both yield stress as well pseudoplasticity are
known as the viscoplastic materials.
 These fluids show the shear thinning flow behavior after the
shear stress exceeds the yield stress value.
 The corresponding equations are:
 𝝉 − 𝝉𝒚 = 𝜷(𝜸)𝒏 for 𝝉 ≥ 𝝉𝒚 ----- (3)
 𝜸 = 𝟎 𝒇𝒐𝒓 𝝉 < 𝝉𝒚 ----- (4)
 Where n is the flow behavior or non-Newtonian index.
(ii) Ellis model:
 This empirical model describes the rheological behavior of a
number of polymer and rubber melts in the low and
intermediate shear region.
 The relationship is of the form
η𝟎 𝜸 𝜸
 𝝉=[ 𝜶−𝟏 ] = [ ] ---- (4)
𝟏+ 𝝉 ∅𝟎 +∅𝟏 𝝉 𝜶−𝟏
𝝉𝟏 𝟐
 The parameters ηo, 𝝉𝟏 𝟐 , α or øo, ø1 and α are inter related and can
be calculated from the experimental data.
 These variables have physical significance, i.e.
 ηo = lim η𝒂 , which, is known as zero shear viscosity
𝝉→𝟎
 𝝉𝟏 𝟐 =𝝉 𝒂𝒕 η=η𝟎 𝟐 ,
 α≈ 𝟏 𝒏,
 ∅𝟎 = 𝟏 η𝟎 = the fluidity of the system at very low shear rate and
𝟏
 ∅𝟏 = [ 𝜶−𝟏 ] ------- (5)
η𝟎 𝝉𝟏 𝟐
 Also if α>1, the fluid is pseudoplastic, if α<1 it is dilatant and if
α=1, then it is Newtonian.
 As τ 0, the model reduces to a Newtonian model with a
constant viscosity of η𝟎.
(iii) Eyring-Powell model:
 This model is a modification of two-parameter Eyring-Prandtl
model to extend its application to the high shear region.
 It is expressed as:
 𝝉 = 𝑨𝜸 + (𝟏 𝑩) sinh−𝟏 [𝜸 𝑪] ----(6)
 Where A, B and C are the material parameter.
 For both lower and upper Newtonian regions this equation
reduces to Newton’s law of viscosity such that
 As 𝜸 → 𝟎, 𝝉 → [𝑨 + 𝟏 𝑩𝑪] 𝜸 and η𝒂 → η𝟎 = [𝑨 + 𝟏 𝑩𝑪], and
 As 𝜸 → ∞, 𝝉 → 𝑨𝜸 and η𝒂 → η∞ = 𝑨
 At the intermediate region the equation gives the shear thinning
behavior.
 This equation cannot be used for the dilatant fluids unlike the
power law model or the Ellis model.
(iv) Carreau model:
 It is a three-parameter model applicable for the low shear and
intermediate region only.
 It does not cover the high shear region.
 The equation is written as
 𝝉 = [𝑨 (𝟏 + 𝑩𝜸)𝑪 ]𝜸 -----(7)
 A, B and C are the three material parameters.
 For a number of polymers this model has been found to give a
better representation of the data as compared to the Ellis model.
 The data for a large number of systems under different
temperatures has been used to compare these models and it has
been found that this model predicts the viscosity within a close
range of experimental data.