Capillary Rheometry: Application

to the Extrusion Process and

Equipment Design

Olivier Catherine
Technical Director - Cloeren Incorporated
Orange, Texas
SPE Webinar April 27, 2021
Introduction
Cloeren Incorporated designs and manufactures Flat Film Extrusion Dies and Feedblocks

Example of Cloeren Reflex™ Die for Cast Stretch film

application – Running at K2019.
Why Is Viscosity Important for Extrusion?

Simplified Flow analysis (Newtonian):

Manifold channel ⇒ Pipe flow:
8𝜼𝜼𝑄𝑄𝑄𝑄
∆𝑃𝑃 =
𝜋𝜋𝜋𝜋 4
Preland ⇒ Parallel plate flow:
12𝜼𝜼𝑄𝑄𝐿𝐿
∆𝑃𝑃 = 3
ℎ 𝑊𝑊

Die Design Goals:

• Uniform flow distribution
• Pressure drop adapted to
process
• Residence time distribution
adapted to the polymer
Shear Viscosity is a critical
parameter for flow equations,
which are at the basis of die
design
Shear Rheology

Newtonian Transition Shear thinning Newtonian

Plateau Power Law Plateau
Region
Shear Viscosity η (Pa.s)

MWD

Shear Rate 𝛾𝛾̇ (1/s)

Too slow Competition between Disentanglement rate Fully disentangled
deformation to de-entanglement and > recoiling rate
disentangle polymer recoiling
melts
Measurement Techniques for Polymer Melts
Melt Flow Index

MELT FLOW INDEX (MFI) is defined by the weight

of material (in grams) collected for a time frame
(e.g. 10 min) for a given plunger weight (2.16 kg)
and temperature (190 °C)

The test gives no information about temperature

or shear rate dependency, which is critical for
extrusion
Melt Flow Index
Polymers with same MFI could have a different shear flow
behavior
Shear rate at which the
MFI measurement is
Viscosity η (Pa.s)

performed

Shear Rate 𝛾𝛾̇ (1/s)

Rotational Rheometry / Dynamic Measurements
Rotational Rheometry / Dynamic Measurements
Small Amplitude Oscillatory Shear Dynamic strain is imposed:
(SAOS) Measurements 𝛾𝛾 ∗ = 𝛾𝛾0 exp 𝑖𝑖𝑖𝑖𝑖𝑖

Delayed Shear stress response :

𝜏𝜏 ∗ = 𝜏𝜏0 exp 𝑖𝑖 (𝜔𝜔𝜔𝜔 + 𝛿𝛿)

𝛾𝛾 ∗
𝛾𝛾0 𝜏𝜏 ∗
𝜏𝜏0
t
 Rotational Rheometry / Dynamic Measurements
Imaginary = Viscous

Complex modulus
G*
G”

δ
Real = elastic
G’

Polymer
melts

Ideally viscous Ideally elastic

Viscoelastic Behavior of Extrusion Coating Resins
1.E+06 LDPE1– 7MI .917 1.E+06 LDPE2– 7MI .917

1.E+05 1.E+05

1.E+04 1.E+04

G’ or G” [Pa]
G' or G” [Pa]

Viscous

Viscous
Elastic

Elastic
1.E+03 1.E+03

G” G”
1.E+02 1.E+02

G’
1.E+01 G’ 1.E+01

T = 280°C T = 280°C
1.E+00 1.E+00
1.E-01 1.E+01 1.E+03 1.E+05 1.E-01 1.E+01 1.E+03 1.E+05
aTxω [rad/s] aTxω [rad/s]
Viscoelastic Behavior of Extrusion Coating Resins
1.E+06 LDPE1– 7MI .917 1.E+06 mPE – 19MI .918

1.E+05 1.E+05

1.E+04 1.E+04
G' or G” [Pa]

G’ or G" [Pa]

Viscous

Elastic
Viscous
Elastic
1.E+03 1.E+03

G”
1.E+02 1.E+02
G”

1.E+01 G’ 1.E+01

T = 280°C G’ T = 280°C
1.E+00 1.E+00
1.E-01 1.E+01 1.E+03 1.E+05 1.E-01 1.E+01 1.E+03 1.E+05

aTxω [rad/s] aTxω [rad/s]

Viscoelastic Behavior of Extrusion Coating Resins
1.E+06 LDPE1– 7MI .917 LDPE 1.E+06 LDPE3– 16 MI .917

1.E+05 1.E+05

1.E+04 1.E+04
G' or G” [Pa]

G’ or G” [Pa]

Viscous

Elastic
Viscous
Elastic
1.E+03 1.E+03

G” G”
1.E+02 1.E+02

G’ G’
1.E+01 1.E+01

T = 280°C T = 280°C
1.E+00 1.E+00
1.E-01 1.E+01 1.E+03 1.E+05 1.E-01 1.E+01 1.E+03 1.E+05
aTxω [rad/s] aTxω [rad/s]
Viscoelastic Behavior of Extrusion Coating Resins
1.E+03
LDPE2
LDPE1
Reduced complex viscosity |η*|/aT [Pa.s]

LDPE3
mPE
1.E+02

1.E+01

T = 280°C
1.E+00
1.E-02 1.E-01 1.E+00 1.E+01 1.E+02 1.E+03 1.E+04 1.E+05

Reduced angular frequency ω×aT [Rad.s-1]

 Transient Extensional Rheometry

Extensional
Rheometer
Fixture

Strain Rate 1.0 1/s

Thermocouple (actual speed)
Convection oven
 LDPE1– 7MI .917
1.E+05
mPE – 19MI .918 m-PE
1.E+06
0.3 s-1

Transient Elongational viscosity ηE+ [Pa.s]

1 s-1 0.1 s-1
3 s-1
Transient Elongational viscosity ηE+ [Pa.s]

10 s-1
1.E+05 25 s-1
LVE 1.E+04
3 s-1 LVE

0.1 s-1
1.E+04
10 s-1 1 s-1

1.E+03

1.E+03

1.E+02
T = 140°C T = 120°C
1.E+02
1.E-03 1.E-02 1.E-01 1.E+00 1.E+01 1.E+02 1.E+03 1.E-03 1.E-02 1.E-01 1.E+00 1.E+01 1.E+02 1.E+03
Time [s] Time [s]
Capillary Rheometry

Rosand RH2000
Principle

Driven Plunger
(PC controlled
velocity)

Heated Barrel

Polymer melt
• Shear Rate calculated from Die Diameter, Plunger
diameter and velocity
Pressure • Shear Stress calculated from Pressure measurement,
Transducer Die Length, Die Diameter
• Viscosity = Shear Stress / Shear Rate
• Corrections
Capillary Die
 Rabinowitsch Correction
Velocity profiles as a function
of the pseudoplastic index
2.5
𝑄𝑄 “Apparent” shear rate calculation
𝛾𝛾̇ = 4 3
𝜋𝜋𝑅𝑅𝐶𝐶 assumes a Newtonian velocity profile
2

Velocity / Average velocity

1.5

3𝑛𝑛 + 1 𝑄𝑄 Rabinowitsch corrected shear rate calculation

𝛾𝛾𝑐𝑐̇ = 4
4𝑛𝑛 𝜋𝜋𝑅𝑅𝐶𝐶 3 uses the “local” pseudoplastic index n 1

0.5

𝑑𝑑 𝑙𝑙𝑙𝑙𝑙𝑙 𝜏𝜏𝑤𝑤 Practically, 𝑛𝑛 is determined by plotting 𝑙𝑙𝑙𝑙𝑙𝑙 𝜏𝜏𝑤𝑤 0

𝑛𝑛 = =f(𝑙𝑙𝑙𝑙𝑙𝑙𝛾𝛾)
̇ and fitting the plot with a polynomial
𝑑𝑑 𝑙𝑙𝑙𝑙𝑙𝑙̇ 𝛾𝛾
-1 -0.5 0 0.5 1
r/R
function 0 0.1 0.2 0.3 0.4 0.5

0.6 0.7 0.8 0.9 1

Rabinowitsch Correction
PVB SAMPLE 3 - RABINOWITSCH CORRECTIONS
1.E+04

The Rabinowitsch correction will

NO RABINOWITSCH result in higher shear rates, especially
CORRECTION -
1.E+03 T=180°C in the area of higher shear-thinning.
LINEAR n -
Shear viscosity (Pa.s)

T=180°C

QUADRATIC n - Practically, the quadratic fit (2nd order

T=180°C
polynomial function) and the cubic fit
1.E+02
CUBIC n - T=180°C
(3rd-order) are most accurate.

1.E+01
1.E+00 1.E+01 1.E+02 1.E+03 1.E+04
Corrected shear rate (/s)
 Bagley Correction
Pressure

ΔPE

PMEASURED
ΔPC

ΔPEXIT

Entrance

LC LM
Capillary Die:
RC
PExit

The pressure measurement is a combination

of the entrance effect, the shear and
elongational flows in the capillary, and the exit
effect.
Historical Bagley
Extrapolating the pressure back to a zero length die should give a zero pressure
drop.

𝛥𝛥𝑃𝑃𝑐𝑐
𝛼𝛼𝑛𝑛 𝜏𝜏𝑤𝑤 = 𝑅𝑅𝑐𝑐
2𝐿𝐿𝑐𝑐
𝛼𝛼1
𝛥𝛥𝑃𝑃𝑐𝑐,𝑖𝑖
𝛼𝛼𝑖𝑖 = 2𝑅𝑅𝑐𝑐
Measure the pressure drop 𝐿𝐿𝑐𝑐
on a series of dies of
decreasing length
Bagley Corrected 𝛼𝛼𝑖𝑖
Linear extrapolation to a Length: 𝜏𝜏𝑤𝑤,𝑖𝑖 =
Die (L/D) ratio of 0 Shear Stress 4
But, there is and entrance effect
Twin-Bore Rheometer
• With a long capillary and “orifice die” (L/D≈0) on a twin-bore instrument it is possible
to get direct measure of entrance pressure drop.
• No extrapolation is needed and the Bagley correction allows for accurate shear stress
calculations
Example of Corrected vs. Uncorrected Data
PVB SAMPLES - BAGLEY CORRECTION COMPARISON
1.E+04

1.E+03 Bagley Correction results in

lower viscosity compared to
Shear viscosity (Pa.s)

SAMPLE 3 BAGLEY
CORRECTON - uncorrected data.
T=180°C
Depending on how elastic the
1.E+02 SAMPLE 3 NO
CORRECTON -
melt is, the difference can be
T=180°C significant.

1.E+01
1.E+00 1.E+01 1.E+02 1.E+03 1.E+04
Corrected shear rate (/s)
 Melt Fracture / Flow instability
FEP

Some fluoropolymers have a very distinct

flow behavior with a very sharp transition
PFA
from stable to unstable flow

Unstable flow is seen as melt fracture and

Example Melt Fracture in unstable
is undesirable in extrusion flow region observed in capillary
rheometry.
Understanding rheology can help design
equipment to avoid unstable flow
Melt Fracture / Flow instability
18 1200
Unstable flow Stable flow
16
1000 1.0E+04
14 stable unstable
12 800

Shear rate (1/s)

Pressure (MPa)

Shear Rate

10 1.0E+03
Critical

600

Viscosity (Pa.s)
8

6 400
1.0E+02 350 °C (Input)
4 370 °C (Input)
200 390 °C (Input)
350 °C (Carreau-WLF)
2
370 °C (Carreau-WLF)
390 °C (Carreau-WLF)
0 0
1 10 100 1000 10000
1.0E+01
Time (s)
1.0E+00 1.0E+01 1.0E+02 1.0E+03 1.0E+04 1.0E+05

Flow Curves from capillary rheometer Shear Rate (1/s)

Imposed Shear Rate
Measured Pressure Determination of “critical shear rate / shear stress”
 Melt Fracture / Flow instability - Application

Critical Shear Rate / Shear Stress is

• A customer is experiencing determined by capillary rheometry
unstable flow at the edges of a PFA
sheet. Temperature Apparent Shear Corrected Shear Stress
[⁰C] rate [s-1] Shear rate [s-1] [kPa]
• The die was manufactured by a 370 3.4 3.7 53.9
competitor.
385 10.2 12.7 126.4
• Customer states that the lip gap is 400 20.3 25.1 163.7
large and should not result in high
shear stress.
Melt Fracture / Flow instability - Application

Flow simulation of the extrusion process reveals a high

velocity at the edges, especially in the preland region
Melt Fracture / Flow instability - Application
Shear Stress > 90 kPa
Critical Shear Stress = 54 kPa

Flow model show shear rates,

shear stress above the critical
shear rate values in the preland.

Flow is unstable at the edges!

 Thermal Stability
Example of Time Sweep with Capillary
for ECTFE
4 Polymer w/ additive at 290 ⁰C

3.5
Measured Melt Pressure (MPa)

2.5

1.5
Polymer w/ additive at 270 ⁰C
1
Neat Polymer at 270 ⁰C
0.5
Neat Polymer at 290 ⁰C
0
0 1000 2000 3000 4000
Time (s)
Thermal Stability vs. Residence Time
60

50

Residence time (s)

40

30

20

10

0
0 200 400 600 800 1000 1200
Transverse Direction – Distance from
CenterLine (mm)

• Residence time is not a simple number

• It is important to consider the whole process (extruder, melt pipes, screen changers etc.)
• A direct comparison between degradation time and residence time is not always
straightforward
PVB Film Extrusion Troubleshooting Example
Background

A real example of PVB film extrusion:

• A film die was designed specifically for the process
• Die was installed in Asia on existing extrusion line
• Initial flow distribution was not matching theoretical expectations
• After manual and automatic lip adjustments, flow distribution and
film thickness became acceptable – however, the process did not
behave as expected.
PVB Rheology PVB Sample supplied by processor
Data: capillary rheometer, Bagley (twin-
10000
bore), and Rabinowitsch corrections.
180°C
200°C Model: Cross (shear rate dependent) and
Corrected Shear Viscosity [Pa.s]

220°C WLF (temperature dependent) model

1000 η 0 × aT
η (γ, T ) = 1− m
η × a 
1 +  0 T γ 
 τ* 

 C1 (T − Tref ) 
100 aT = exp − 
 C + (T − T ) 
 2 ref 

Parameter Value
η0 (Pa.s) 6.67 ×103
10 τ∗ (Pa) 2.14.104
m 0.38335
1 10 100 1000 10000
Tref (K) 473.15 (200°C)
Corrected shear rate [1/s] C1 104.26
C2 (K) 2591.3
Flow Simulation Conditions
Process Value
parameter
Die wall 210°C
temperature
Initial melt 210°C
temperature
Extrusion output 800 kg/h

• Die designed by Cloeren Incorporated.

• Constant cross-section manifold
channel
• Optimization of non-linear preland
dimensions for uniform flow
distribution
• Targeted pressure drop ≈10 MPa
3D Flow Simulation Results
Total Pressure drop = 12.5 MPa
Uniform development of isobars

Uniform velocity at die exit

Linear decrease of flow rate in manifold channel
Flow Distribution Prediction
300

250
Velocity (mm/s)

200

150

100

50

0
0 200 400 600 800 1000 1200 1400 1600
Distance from centerline (mm)

Exit Velocity profile predicted by 3D Flow Analysis:

A 2σ variation to the average of 1.3%
 Start-up Thickness Profiles
Profile measured online in
uniform lip gap
Start-up with

stable extrusion condition

without any lip adjustment:
Average thickness = 780
μm
2σ = 16.8%
Heavy end flow

Profile measured online

After Automatic
lip adjustment

in stable extrusion
condition after lip
adjustment:
Average thickness = 780 μm
2σ <2%
Automatic Lip Adjustment

Thermal translator
(with heater)

Push Rod
Die lips
 Troubleshooting Methodology
The initial online gauge measurement is not acceptable and far from design
predictions – that is not usual.
Investigations online and offline to determine the origin of this discrepancy:
1) Melt temperature measurement
2) Confirmation with IR thermal imaging of melt curtain in air gap
3) Rheology assessment of actual material extruded at start-up
4) Possible CFD analysis if enough difference with design parameters is observed
Melt Temperature Measurement
Elbow
T P3 Existing melt temperature TC P2 P1
vacuum

Static mixer (6x), oil

temp control

TSE, 11 barrel sections

adapter 2
Filter 2

Gear Pump

Filter 1
adapter 1
Barrel flange
Die

T Existing melt temperature TC

Variable-Depth T/C
240

Measured melt temperature (°C)

230

220

210

200

190

180

170

160
0 0.2 0.4 0.6 0.8 1
Implementation of a Variable Thermocouple Dimensionless Position (x/R)
Depth thermocouple to evaluate
Near the centerline of the flow channel, melt
temperature gradients in melt
temperature is ≈ 227°C for a 210°C target
flow channel at the elbow
adapter, just upstream from the Near the wall, measurements indicate 180°C
die due to the low temperature set point
Thermal Imaging

LHSLD: average = 211.3°C LHSLD: average = 217.9°C LHSLD: average = 212.1°C

220
temperature near center

218
216 • IR camera emissivity set at ε =0.95
Average curtain

214
• No calibration –measurements are “relative”, not absolute.
212
• Curtain melt temperature is higher than the melt
(°C)

210
208 temperature target (210°C) or die temperature (200°C) on
206 average.
204
202
• Strong influence of extrusion output indicate excessive
0 200 400 600 800 1000 shear heating in the extrusion system
Extrusion output (kg.h-1)
Shear Rheology A PVB sample was taken during start-up and test
was performed with same capillary rheometer as
10000
for the original sample
180°C Bagley and Rabinowitsch corrections are applied
Cross and WLF model was fit to the data
200°C
220°C
η 0 × aT
1000 η (γ, T ) =
Shear viscosity (Pa.s)

1− m
240°C η × a 
1 +  0 T γ 
 τ* 

 C1 (T − Tref ) 
aT = exp − 
 C + (T − T ) 
100
 2 ref 

Parameter Value
η0 (Pa.s) 2.25 ×103
τ∗ (Pa) 9.303.104
m 0.17687
Tref (K) 473.15 (200°C)
C1 3218.7
10 C2 (K) 89559
1 10 100 1000 10000
Corrected shear rate (/s)
Comparison - Shear Flow Viscosity models at reference
temperature
10000

Original
Parameter Value
𝜼𝜼𝟎𝟎 (Pa.s) 6.67 ×103
𝝉𝝉∗ (Pa) 2.14.104
m 0.38335

Shear Viscosity [Pa.s]

1000
Tref (K) 473.15 (200°C)
C1 104.26
C2 (K) 2591.3

100
Start-up material Original
Parameter Value
𝜼𝜼𝟎𝟎 (Pa.s) 2.25 ×103 Start-up
𝝉𝝉∗ (Pa) 9.303.104
m 0.17687 material
Tref (K) 473.15 (200°C)
10
C1 3218.7
1 10 100 1000 10000
C2 (K) 89559
Corrected Shear rate [1/s]
New Flow Simulations
3D flow simulation considering the parameters observed during the start-up:
• Melt temperature of 225°C (higher than originally specified)
• New Rheological behavior (lower zero-shear viscosity, more shear-thinning at
high shear rate)

Total pressure drop through the die decreased to 10.4 MPa

(compared to 12.5 MPa) due to overall lower melt viscosity.
New Flow Simulations - Velocity

Velocity contour plot shows non-uniformity at die lips

New Flow Simulations – Exit Velocity Profile
250

200
Velocity (mm/s)
150

100

50

0
0 200 400 600 800 1000 1200 1400 1600
Distance from centerline (mm)

Exit velocity profile shows heavy end flow.

2𝜎𝜎
Standard deviation to average : = 14.8%
𝑎𝑎𝑎𝑎𝑎𝑎
Agreement with observed extrusion process and online gauge
measurement during start-up (16.8%)
• Study shows excellent correlation between 3D CFD
analysis and observations during extrusion trial

• When designing an extrusion die, the exact

knowledge of the “melt quality”, i.e. temperature
gradient in the melt stream and rheology, is critical to
achieve the highest flow channel performance

• With slightly inaccurate “melt quality” parameters, the

die still delivers good flow distribution but relies
excessively on lip adjustment to achieve this result
Conclusions
• Rheology and flow characterization of polymer melts is the foundation of extrusion
equipment design.
• While capillary and rotational / oscillatory rheometers have both their own
advantages, capillary rheometry can provide a wealth of relevant information.
• Extrusion dies are custom-designed: there is no generic design. The best flow
performance can only be achieved with careful characterization of the flow
behaviors.
• A combination of rheology and flow simulation is a powerful tool for design and
process troubleshooting.
• Interpretation of data is as important as data accuracy.
• Understanding phenomena that can affect the viscosity data is critical:
• Flow instability
• Non-classic flow behaviors (rubbers, highly loaded materials)
• Thermal degradation
 Thank You!

Olivier Catherine
Technical Director - Cloeren Incorporated
www.cloeren.com
ocatherine@cloeren.com
+1 409-951-7632