Viscosity and Polymer Melt Flow: Rheology-Processing / Chapter 2 1

Viscosity
and
Polymer Melt Flow
Rheology-Processing / Chapter 2 1
Viscosity: a fluid property → resistance to flow
(a more technical definition resistance to shearing)
Remember that:
du
τμ
dy
shear stress F/A shear rate: ≈ U/H
viscosity
POLYMER MELTS
THE VISCOSITY DECREASES AS THE

SHEAR RATE (du/dy) INCREASES
(due to molecular alignments and disentanglements)
A characteristic value is the limiting viscosity for zero shear rate

(frequently referred to as zero shear viscosity) usually denoted with
ηo .
ZERO SHEAR VISCOSITY is a function of
POLYMER MOLECULAR WEIGHT
Critical molecular weight Mc ....... for

entanglements to become effective.
Mc critical molecular weight for entanglements.

Mc ≈ 4,000 for PE, Mc ≈ 36,000 for PS
Most (NOT all) commercial polymers have Mw=50,000 to 500,000
In characterization of polymers, the solution viscosity is often used.
For a polymer dissolved in a solvent:

viscosity ↑ as concentration ↑
(solution viscosity definitions in pages 2.4 and 2.5)
ηsolution  ηsolvent
For instance, the specific viscosity: ηsp  ηsolvent
 ηsp 
or the intrinsic viscosity: [ η]   
 C  C 0
The intrinsic viscosity is found by plotting ηsp/C against C and
extrapolating to zero concentration
The so called viscosity average molecular weight, introduced in chapter
1, can be found from the Mark-Houwink equation:
[η]  ΚΜ α
[η]: intrinsic viscosity

M: (viscosity) average molecular weight
K, a: experimentally determined
constants (depend on polymer solvent
system)
SHEAR-THINNING BEHAVIOR OF POLYMERS
τ shear stress Pa 
From Newton’s law of viscosity μ  Pa  s
du shear rate1 s 
dy
Viscosity is constant for Newtonian fluids
BUT
it DECREASES as SHEAR RATE INCREASES for polymer solutions and melts
(non-Newtonian fluids)
This behavior is called: SHEAR-THINNING

(due to molecular alignments and disentanglements )
We cannot talk about a constant viscosity μ in polymers, but rather about
shear stress Pa 
vis cos ity 
shear rate1 s 
We usually
symbolize it
with the
Greek letter
η
Most popular model to express the shear-thinning behavior: POWER-LAW
τ  mγ n
(shear stress) = m (shear stress)n

n 1
or τ  ηγ or η  mγ viscosity is a
function
of shear rate
• m is called consistency index (the larger the m the more

viscous the melt)
• n indicates the degree of Non-Newtonian behavior
n=1 means Newtonian
n<1 for SHEAR THINNING POLYMERS
The power-law relation gives
log η  log m  n  1 log γ
Note that consistency index m is equal to viscosity η at γ  1s 1
On a log-log paper η vs γ is a straight line and the slope is equal to n-1
• The power-law fit is OK for high shear rates, but

for low shear rates polymers exhibit a
Newtonian plateau (e.g. at values say γ  3s 1 )
• The power-law model is good for most polymer
processing operations because the shear rate is
between 100 s-1 and 5000 s-1
WHAT ABOUT FITTING THE WHOLE VISCOSITY CURVE?
THE MOST POPULAR MODELS:
Carreau–Yasuda:    1    
n 1
a a
where ηo is the viscosity at zero shear and λ, α and n are

fitted parameters

Cross model:  
1   
1 n
 UNFORTUNATELY NO ANALYTICAL SOLUTIONS ARE POSSIBLE

WITH THESE VISCOSITY MODELS
 USED IN COMPUTER SIMULATIONS FOR DETAILED LOCAL
FLOW ANALYSIS
The consistency index m is sensitive to temperature. A common
representation is:
 b T To 
m  mo e
where mo the consistency index at a reference temperature To
Typical values:
For polymer melts at usual processing conditions m=1000 – 100000 Pa·sn
n=0.2 – 0.8
b=0.01 – 0.1 oC-1
For example, for a commercially available polystyrene (PS) the following
parameters were obtained by curve fitting of viscosity data
mo=10800 Pa·sn, n=0.36, To=200oC, b=0.022 oC-1
The above value b corresponds to a viscosity reduction ~20% for 10oC
temperature rise. For isothermal flows we can use the power-law viscosity
model to solve problems of practical importance using analytical methods
of solution.
To solve general flow problems we must set a momentum balance. It turns
out that the momentum balance can be written verbally
• Polymers are characterized by extremely high viscosities (about a
million times more viscous than water) in molten state.
Therefore:
0  p   τ
• Pressure p is a scalar
• Velocity is vector V i.e. Vx, Vy, Vz having components in the
x, y and z directions
• Stress is defined as the ratio Force/Area and can be normal or
tangential
• Stress is a tensor having nine components:
(τxx, τyy, τzz) → normal stresses
The rest components → shear stresses
For planar unidirectional flows the equation 0  p   τ
is simplified to
A good way to remember it, is symbolically:

p τ yx
0  p  ( shear stress )
x y 0
 
 
 direction of flow  normal to flow 
PRESSURE DRIVEN FLOW OF A POWER-LAW FLUID
BETWEEN TWO FLAT PLATES (book page 2.15)
The absolute value || is needed because sometimes Vx y is negative and n-1<0 for polymers.
←boundary condition
Delicate point: the right-hand side is negative and thus

Vx y must be negative.
Apply NO-SLIP boundary condition: Vx=0 at y=b
This is the
velocity profile!
The maximum velocity Vmax is at y=0
The average velocity Vavg is calculated by
The volume flow rate per unit width W (plate width) is given by
The pressure drop may then be easily calculated
From a previous relation we saw that
which means that the stress varies linearly in the gap.
The maximum value is at the wall (i.e. at y=b)
the w subscript refers to…. “wall”
The negative sign simply indicates that when this quantity is multiplied by the
area, it gives a force (i.e. Fw=τw·A) that is exerted by the plate on the fluid which is,
of course, in the negative x direction. The force exerted by the fluid on the wetted
plate should therefore be positive.
Another important quantity that we need to calculate is the shear rate
We may then calculate the shear rate at the wall (absolute value)
The maximum shear stress at the wall can also be expressed as
PRESSURE DRIVEN FLOW OF A POWER-LAW FLUID
IN A TUBE (book page 2.19)
governing equation
Boundary conditions
The solution gives the following
velocity profile
maximum velocity
average velocity
volume flow rate
pressure drop
• In the previous equations if we set n=1 we end up with the well-known Hagen-
Poiseuille formula for Newtonian fluids.
• Pressure driven flows are also referred to as Poiseuille flows.
For SHEAR-THINNING fluids, the velocity profiles are more flat than
the parabolic profiles of Newtonian fluids.
From the previous equations it is easy to see that the stress varies linearly
and the maximum value is at the wall (i.e. at r=R)
The linearity of the stress is often expressed as

τw is taken as positive
The shear rate is:
And the shear rate at the wall:
The maximum shear stress at the wall can be then calculated from
CAPILLARY VISCOMETER ANALYSIS (book page 2.23)
For Newtonian fluids, the Hagen-Poiseuille formula
can be used for direct determination of viscosity μ, from the measurement of pressure
drop ΔP at flow rate Q, through a tube of length L and radius R.
For non-Newtonian fluids, the viscosity η is a function of the shear rate γ (i.e. ηγ  )
and special treatment is necessary. We will determine the viscosity from its basic
definition τ
ηγ  
γ
The wall shear stress can be calculated from
The shear rate requires special manipulations. Again for Newtonian fluids (n=1) the
shear rate can be obtained by differentiating the velocity profile
and using the Hagen-Poiseuille formula we get
For non-Newtonian fluids we will develop a general expression for the shear rate at the
wall by starting from the definition of the volume rate of flow through a tube
(see subsequent steps followed in pages 2.24 and 2.25. Next slide goes directly to the result)
This equation is usually referred to as the Rabinowitsch equation. It gives the shear
rate in terms of Q, R and τw. The term in the parentheses may be considered as a
“correction” to the Newtonian expression which is simply 4Q/πR3. To obtain γw we
must plot Q versus τw on logarithmic coordinates to evaluate the derivative dlnQ/dlnτw
for each point of the curve.
The previous method can be simplified if POWER-LAW fluid is assumed
τ  mγ n
We may then write an empirical expression
n
 4Q 
τ  m΄  3 
 πR 
in which n is the slope of the logτw versus log(4Q/πR3) plot, that is
d log τ w
n
 4Q 
d log 3 
 πR 
It turns out that for the derivative dlnQ/dlnτw we have dlnQ/dlnτw=1/n, therefore
4Q  3 1  4Q 3n  1
γw  3 
  3
πR  4 4n  πR 4n
This means that the relation between the apparent m΄ and the true m is
n
 4n 
m  m΄  
 3n  1 
STEPS FOR DETERMINATION OF m and n
1. Determine τw from pressure drop Δp data

4Q
2. Determine γapp 
πR 3
3. Plot logτw versus log(4Q/πR3) to get n (slope)

and m΄ (intercept at γapp  1s ) 1
n
 4n 
4. Correct m΄ using m  m΄  
 3n  1 

Viscosity and Polymer Melt Flow: Rheology-Processing / Chapter 2 1

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Viscosity and Polymer Melt Flow: Rheology-Processing / Chapter 2 1

Uploaded by

Copyright:

Available Formats

Viscosity

THE VISCOSITY DECREASES AS THE

A characteristic value is the limiting viscosity for zero shear rate

Critical molecular weight Mc ....... for

Mc critical molecular weight for entanglements.

For a polymer dissolved in a solvent:

[η]: intrinsic viscosity

This behavior is called: SHEAR-THINNING

(shear stress) = m (shear stress)n

• m is called consistency index (the larger the m the more

• The power-law fit is OK for high shear rates, but

THE MOST POPULAR MODELS:

where ηo is the viscosity at zero shear and λ, α and n are

 UNFORTUNATELY NO ANALYTICAL SOLUTIONS ARE POSSIBLE

where mo the consistency index at a reference temperature To

A good way to remember it, is symbolically:

Delicate point: the right-hand side is negative and thus

The average velocity Vavg is calculated by

The pressure drop may then be easily calculated

which means that the stress varies linearly in the gap.

The maximum value is at the wall (i.e. at y=b)

the w subscript refers to…. “wall”

The maximum shear stress at the wall can also be expressed as

The solution gives the following

volume flow rate

and the maximum value is at the wall (i.e. at r=R)

The linearity of the stress is often expressed as

And the shear rate at the wall:

and using the Hagen-Poiseuille formula we get

1. Determine τw from pressure drop Δp data

3. Plot logτw versus log(4Q/πR3) to get n (slope)

You might also like