Zwick testXpo 2018

Capillary Rheometry – A Method to Predict Flow

Properties under Processing Conditions

Torsten Remmler, Malvern Panalytical GmbH

© 2018 Malvern Panalytical

 Overview

• Range of Applications for Capillary Rheometry

• Introduction into capillary rheometry: Principle of Operation and

theoretical background

• Test results on LDPE: Complete Capillary Characterisation

• Advanced Test Types: Relaxation, Thermal Degradation etc.

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Capillary Rheometry: Main Applications

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 Typical Shear Rates

Levelling, Sagging
Sedimentation Extrusion, Pumping

Dipping, Brushing, Mixing Roller Coating, Spraying

10-3 10-1 100 101 102 103 104 106 s-1

Rotational-Rheometer
Sample: Water up to solids
Results: Shear-Viscosity, Yield Stesses, Visco-Elasticity, Relaxation...
High Pressure Capillary-Rheometer
Sample: Water up to high viscous
Results: Shear-Viscosity, Elongational-Viscosity, Wall Slip...

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 Principle of Operation
Given quantity: piston speed  wall shear rate
Measured quantity: pressure drop  wall shear stress

Bore v
Full pressure drop

=
L P
Entrance pressure drop

P1 Fully developed flow region +

2R
Pw
Shear pressure drop

entry

0
0 L
Z

 small ram extruder

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 Laminar Pipe Flow
Isothermal, stationary Flow of an incompressible fluid
Newtonian
Newtonian

. 4  Q
  3 Non-
app  R -R 0 R
Newtonian

  R  P
app
2  L
-R 0 R

Q=Volume Flux, R= Die Radius

L=Die Length, P=Pressure Drop

0 
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What are we doing to get flow curves?

measurement : Ramp in steps

v p

t t

. 4  Q
  
3 true
app  R corrections
  .

true

  R  P
app
2  L
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 Correction:
Entrance zone of a capillary die

Convergent
Pressure Flow
transducer Capillary die

Aim of the test: to separate entrance pressure and shear

pressure drop!
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 Rosand Twin Bore Principle

v v

Pfull
pentrance pentrance

L 2R pshear

Pfull= Pshear + Pentrance left: capillary right: orifice

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 How do we get
the Extensional Viscosity?
Cogswell`s Convergent Flow Model  Extensional Viscosity

9 (n+1)2 (Pe)2
Pfull= Pshear + Pentrance
= .
32   2
• Special Orifice Die according
to Uni Zlin Model enables characterisation
of very small extensional rates too.

.
  10-1 - 103 s-1
d (log )
n= Non-Newtonian Index (Ostwald-de Waele)
d (log )

F. Cogswell, “Polymer Melt Rheology”, Woodhead Publishing Limited (1981)

Zatloukal, Vlcek, Tzoganakis, Saha J. Non-Newtonian Fluid Mech. 107 (2002) 13–37
© 2018 Malvern Panalytical
 Example LDPE

LDPE at 190°C
1,0E+05
Low Shear Test Zero Shear
Shear Viscosity / Extensional Viscosity (Pas)

Viscosity
Low Shear 2.0mm

1,0E+04 Standard Shear 1mm

Standard Shear Melt Fracture

High Shear 0.5mm

1,0E+03

Low Extension 2.0mm

Standard Extension 1mm

1,0E+02
Standard Extension Melt
Rupture
High Extension 0.5mm

1,0E+01
1,0E-04 1,0E-02 1,0E+00 1,0E+02 1,0E+04 1,0E+06

Shear Rate / Extensional Rate (1/s)

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Extensional Rheology of LDPE
Blow Moulding

 Blow Moulding is mainly influenced by Extension!

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 Surface Instabilities LDPE

Surface shape

Cooling air

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How can the process be improved?

Dehnviskosität - Vergleichskurven zwischen Homopolymer PE und Polymerblend PE-PP

1,0E+05

Sample 2
Extensional Viscosity (Pas)

1,0E+04 Sample 2

Sample 2

Sample 2

1,0E+03
Sample 1

1,0E+02
1,0E-04 1,0E-02 1,0E+00 1,0E+02 1,0E+04 1,0E+06

Extensional Rate (1/s)

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 Another Example: Co-Extrusion

Similar instabilites

High
acceleration

Low
acceleration

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 LDPE in Co-Extrusion Die

Instabilities caused by Extensional Flow Behaviour of LDPE

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Zatloukal et. al. Journal of Applied Polymer Science, 98 (2005) 153
 Further Applications: Wall Slip
• Wall Slip Velocity of chromium catalyzed HDPE at 190°C

No wall slip Wall slip

Vmax Vmax

Vw = 0 Vw = 0

Wandgleitgeschwindigkeit bei 190°C

0,9

0,8

0,7

0,6

Wall Slip Velocity (m/s)

0,5
Wall Slip according to Mooney
0,4 Model
Wall slip velocity increases 0,3
Critical Stress

dramatically at just above 0,2

0,1
critical stress 120 kPa

0.1 MPa. 0

-0,1
0 50 100 150 200 250 300 350 400
Shear Stress (kPa)
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 Equilibrium Pressure: Homogeneity

Pressure drop is important

homogeneous inhomogeneous

 For polymer blens, filled polymers, suspensions, emulsions, composites etc.

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 Thermal degradation / Curing

Thermischer Abbau at 260°C

6 70

Shear Rate (/s) / Extruded Volume (cm 3)

Prinzip: 5
60

50

v Pressure (MPa)
4

40 Pressure Drop
3 Shear Rate
30
Extruded Volume
2
20

t 1
10

0 0
0 1000 2000 3000 4000 5000 6000
real time (sec)

 Gives maximum process times under high temperatures

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 Stick-Slip
Flow Instabilities

Linear Ramp

Melt fracture

 What is the max processing pressure / Shear Rate?

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 Melt Fracture

Unstable flow, poor product

quality.
1000000

?
Shear Stress (Pa)

100000 100

10

Pressure (Mpa)
10000
1 10 100

Shear Rate (1/s)

PO PC

0.1
1,000s-1 0 50 100 150
Time
200 250 300
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 Relaxation LDPE
What happens after processing

Relaxation 190°C LDPE

25 12000

10000
20

Prinzip:
Pressure Drop (MPa)
8000

15

v Relaxation Time
6000
Online Pressure Drop
10  = 26.75 sec Shear Rate
( Mono-exp. Decay) 4000

5
2000
Thermal Equilibrium Time

0 0

t 0 50 100 150 200 250

Real Time (sec)
300 350 400

 inner stresses can lead to surface crack (automotive industry)

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 Rheometer Types
Benchtop RH2000 and Floor Standing RH7/10

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 Summary

• Capillary Rheometry gives correlation with processing flow properties

• Calculation of extensional viscosity according Cogswell method

• Flow curves up to very high shear end extensional rates

• Prediction of flow instabilities

• Correlation with structural changes during processing

Thank you for your attention.

Email: torsten.remmler@malvernpanalytical.com

© 2018 Malvern Panalytical