HAAKE CaBER 1

Jint Nijman
Thermo Electron, Karlsruhe, Germany

Contents
Introduction - Why an extensional rheometer? Basics of extensional rheometry
- Types of extensional flow - Rheological quantities - Shear and extensional flow curves

Experimental techniques
- for melts - for fluids

The HAAKE CaBER 1

- how it works - the instrument

Theory Applications
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Why an extensional rheometer ?

Extensional flows occur in many industrial processes and applications and influence these processes often to a great extent. As a consequence the knowledge of extensional properties is important. Extensional properties can not be measured with rotational rheometers. In industry and research the interest in extensional rheometry is growing. A commercial available extensional rheometer for fluids did not exist until now.
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The CaBER 1
The only commercially available extensional rheometer for fluids !!

CaBER closed

CaBER half opened

CaBER fully opened

Designed and built by : Developed by :

vx
X

Basics of extensional rheometry

A short introduction

Kinematics
Most flows are complex. The goal of rheometry is to decompose flow into primary elements Uniaxial Extensional Flow
Simplest extensional deformation Streamlines converge Velocity profile in direction of the flow
y

vx
X

Steady Simple Shear Flow

Streamlines are parallel Velocity profile perpendicular to the direction of the flow
y

vx

A Complex Flow
Flow (extrusion) of a polymer solution or melt through a die.

Die entrance
(Illustration: Pahl, Gleile, Laun) (images Tretheway (2001)

Shear flow plus extensional flow. The extension rate is highest in the center of the flow

Die channel
Shear flow Partial relaxation of extensional deformation

Die exit
Unrelaxed extensional deformations result in die swell.

Extensional flow

Motion of a droplet in shear flow

Deformation of a droplet in the entrance region (arrow) is dominated by extensional flow

Extensional Flow
Shear flow
Property : Slimy

Extensional flow
Property : Sticky

strain

= x/ h

Hencky strain stress viscosity

= ln( L /L0 ) = 22 11 e = ( 22 11 ) / &

shear stress 21 viscosity = 21 / &

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Types of extensional deformation

1

11 = 0

The main extensional deformation is e0 = e11 The secondary extensional deformation is smaller by a factor m
2

22 = m 0
3

In the case of incompressible media the sum of all the extensional deformation rates is zero That defines the third extensional deformation
Top view side view

33 = (1 + m) 0

Uniaxial

m = -1/2
Before after extension

Biaxial

m=1

Planar

m= 0

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Types of extensional deformation

Uniaxial
fiber spinning

Biaxial
Film blowing thermoforming

Planar
Calendering Compression molding Squeeze flow
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Extensional flow rheological quantities

(Hencky) strain
natural logarithm of the relative extension

= ln(

L ) L0

Shear flow

(Hencky) strain-rate
change of strain per unit of time

&=

1 dL [1/s] L dt
Fn A
&

& = V / h

Tensile stress
Force per surface area

=
e =

[Pa] [Pa.s] L0

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Extensional viscosity
Quotient of tensile stress and strain-rate

Trouton-Ratio
Quotient of elongational and shear viscosity.
Tr = e = 3 Newtonian

FN L
Uniaxial extension of a cylinder

FN

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Extensional flow

Typical flow curves

Extensional viscosity
Extensional flow curves of various kinds of liquids

log Viscosity E [Pas]

. . log Deformation rate [s -1]

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(Illustration: Crspulo Gallegos)

Strain hardening and Shear thinning

Extensional flow curves of polymer melt

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Extensional viscosity
Extensional flow curve of solution of polybutadiene in decaline showing three different regions

log Viscosity E [Pa.s]

Extensional thickening region

Extensional thinning region

Coil stretch region

. log Deformation rate /s -1

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(Illustration: Crspulo Gallegos)

(Illustration: Pahl, Gleile, Laun)

Shear and extensional viscosity

Shear thinning of a dilute fibre solution . . in extensional and shear deformation. Trouton ratio = 3 for or 0

log Viscosity or E [Pas]

Extension Trouton ratio

Shear

. . log Deformation rate or [s -1]

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Fz (t)

R(z,t)

Extensional flow

Experimental techniques

(Illustration: Crspulo Gallegos)

Experimental techniques for melts

pulley encoder Motor control and Transducer readout motor wire

Cogswell / Mnstedt
Uniaxial flow Isothermal homogenous extension Controlled stress or controlled strain Sample in or on oil bath
(Illustration: Pahl, Gleile, Laun) (Illustration: Pahl, Gleile, Laun)

Insulated chamber

Moving grip sample Heated oil in transducer

Meiner

(Rheometrics/TA)

Uniaxial or biaxial flow Rotary clamps hold sample Force measurement Sample floating on oil bath

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Experimental techniques for melts

Extensional die (Thermo Electron )
isothermal conditions . Flow rate is applied, pressure drop is measured suited for online measurement

Rheotens

(Gtffert)

Extruded melt is extended using two rolls Flow rate is applied, force is measured Difficult to achieve isothermal conditions

Strain rate is not spatially constant

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Experimental techniques for fluids

Siphon flow
Fluid is sucked upwards into nozzle Extensional deformation rate is calculated from flow rate Tensile stress is calculated from force acting on nozzle.

Triple jet flow

Extended fluid jet Centre jet is pulled by two side jets Extensional deformation is measured from images Tensile stress is calculated from force acting on centre nozzle.

Tractor jet

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Experimental techniques for fluids

Entrance flow
L

Extensional deformation rate is calculated from flow rate Tensile stress is calculated from pressure drop

2R

pressure
pc

+ Stationary flow + Relatively easy to handle

- inhomogeneous flow-field - Big sample volume

p laminar

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(Illustration: Pahl, Gleile, Laun)

Experimental techniques for fluids

Opposed jet Dehnrheometer (u.a. Rheometics RFX)
Vacuum

Two opposed jets of fluid create an extensional flow at the position where they hit + Stationary flow - inhomogeneous flow-field - Big sample volume - Difficult to handle

Force measurement
Q & = A d

Sample fluid

E =
& =

Fd Q
Q A d

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Experimental techniques for fluids

Problems with techniques for extensional flow of fluids They are difficult to handle The measured forces are very small Inertia forces and shear forces at boundaries need to be taken into account. The flow is not uniform

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Extensional Rheometry
Available techniques for measuring the extensional viscosity:
106
Meissner Apparatus
Melt s

105 104 103

Zero-Shear Rate Viscosity [Pa.s] 102

Cap illary Brea kup Rhe 101 ome ters 0 10 -1 10 Dilu 10-2 te S
oluti ons

Filament Stretching Rheometers Ideal Elastic Liquids (Boger fluids) Concentrated Solutions Adhesives Suspensions Physical gels & colloidal systems Paints, Foodstuffs, Dyes...

Opposed Jet Devices Contraction Flows Apparent Extensional Viscosity Indexers

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HAAKE CaBER 1

The Capillary Break-up E xtensional R heometer

The CaBER 1
The only commercially available extensional rheometer for fluids !!

CaBER closed

CaBER half opened

CaBER fully opened

Designed and built by : Developed by :

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CaBER: How it Works

CaBER means :
Phase I :
The fluid is exposed to a rapid extensional step strain by moving the upper plate upwards, thereby forming a fluid filament.

Capillary Breakup Extensional Rheometer

Phase II :
The filament evolution is controlled by the balance of surface tension and viscous/elastic forces. Surface tension is trying to "pinch off" the filament and the extensional rheological properties of the fluid are trying to prevent that. that.

A small quantity of a sample is placed between two parallel circular plates.

D0 A laser micrometer measures the midpoint diameter of the gradually thinning fluid filament, after the upper plate has reached its final position. The duration of a measurement varies between ca. 100 ms and 100 s. This time is solely influenced by the sample properties.

[Click [Click to to continue] continue]

Sample volume < 0.2 ml Plate diameter = 6 mm Initial gap = 3 mm

[Click image to repeat animation]

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CaBER: How it Works in Short Words

What we do

What we measure

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CaBER: how it works

Examples of two different CaBER measurements

[Click image to repeat animation]

[Click image to repeat animation]

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Movies: Dr. A Tripathi

Different Flow Behaviour

Newtonian Oil

500 ppm Polymer Solution

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CaBER: how it works

Data conversion

Laser micrometer

Measurement D= D(t )

Apparent viscosity

Sample

Apparent extensional viscosity

Result :

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CaBER 1: Diameter vs Time

diameter / mm
0

10

Gravity Surface tension

Filament life time

10

-1

dR

final Height: 11 mm gap: 3 mm striketime: 20 ms

Extensional rate = dR/dt

dt

Amount of extension

10

-2

0.0

0.1

0.2

0.3 time / s

0.4

0.5

0.6

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CaBER 1, a CS or a CR rheometer ?
Not a controlled-rate instrument The extensional rate changes as a function of time Not a controlled-stress instrument The capillary pressure (tensile stress) changes as a function of time Extensional viscosity

& (t ) =

dRmid (t) Rmid (t ) dt

E (t )
E (t ) =

Rmid (t )

E & (t ) dRmid ( t) dt

... but close to technical processes like jet break-up, atomization and spraying, misting, coating flow ... and easy-to-use !

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CaBER 1: how it works

Main components
Linear motor

Laser micrometer

Micrometer screw

Plates

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CaBER 1: how it works

Temperature control
Connected with linear motor

Temperature controlled block Upper plate Lower plate

Connection to circulator Connected with micrometer screw Inert gas connection

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CaBER 1: specifications

Hencky strain :

up to 0 = 10 (i.e. R0/R = 148) 0.01 < < 300 s-1 10-5 < < 10 s-1 10 - 106 mPas 4 < Dplate < 8 mm, standard = 6 mm 0 80 C 30,000 Hz 40 x 34 x 60 cm

Strain rate range Imposed strain rate : Strain rate in sample : Shear viscosity range : Plate diameter : Temperature range : Data acquisition rate : Dimensions :

. .

Laser micrometer resolution : 10 m

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HAAKE CaBER 1

Application Examples

Application areas
Application fields : Industry; product development, quality control Research; extensional rheology Applications : Adhesives / coatings
- measurement of tackiness - misting, stringiness in roll coating - influence of solvent loss or gain

Industrial resins
- relaxation time spectrum - spinnability - constitutive modelling

Food products
- strand formation / stringiness - time to breakup - relaxation of dough

Consumer goods
- filling of bottles - time to breakup - processability

Personal care products

- Filling of shampoo

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Example: Filling of containers (shampoo)

Filling properties of shampoos 1,2 good 3,4,5 bad

Nozzle Fluid filament

No correlation with shear viscosity

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Example: Filling of containers (shampoo)

Short break-up time is the wanted behaviour

good

bad

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Example: Filling of containers (shampoo)

Short break-up times correlate with lower extensional viscosities

bad good

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Example: Printing or Coating

Coating material

Coating roll

The printing speed is often limited by the formation of small droplets, the so called misting.

The release of the ink follows an elongational pattern.

Material to which coating is applied

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Example: Offset Printing

Offset inks, which performed good could not be differentiated by rotation or oscillation measurements from samples showing misting during the printing process. Rotation Oscillation

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Example: Offset Printing

The break-up times showed a significant difference. Shorter times lead to less misting.

less misting

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Example: Offset Printing

Also the extensional viscosities of the two inks were significantly different with the better ink having the lower ext. viscosity.

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Example: Paper coating colors

Samples that behave (very) similar in shear flow, clearly differentiate in extensional flow
/ Pas
100 Com 90350
100

app. extensional viscosity / Pa s

10

2 3 5 6

10

2 3 5 6

1
RVM conc. Cylinders T = 23 C

0.1 0.01

0.1

1
-1 / s

10

100

1000

0.01

0.1

1
Data: N. Willenbacher, BASF

Hencky strain / -

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Example: Wall paint (1)

Spattering of wall paint (during application with a roller) Sample B (good) > Sample A (better) > Standard

Correlation with filament lifetime shorter lifetime = less spattering

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Example: Wall paint (2)

Spattering of wall paint (during application with a roller) Sample B (good) > Sample A (better) > Standard

Correlation with extensional viscosity lower ?E = less spattering

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Example: Cardboard glue

Corrugated cardboard manufacturing Glue is applied with a roll

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Concentrated polymer solution consisting of a copolymer mixed with a resin (tackifier) and a plasticizer Widely used in industry
Packaging, release coatings, labels, pharmaceutical applications

Processing Instabilities: Roll Coating

Flow becomes spatially or temporally inhomogeneous Fibrillation, ribbing, stringiness Name Rating Solvent C7 C7 C7 C6/C7 C6 C7 C6

Seven PSA samples

Rated according to ease of processability (strand formation)

A1 A2 A3 A4 A5 A6 A7

OK Good Good OK Bad Good Bad

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Good Processability
Fluid A2

Bad Processability
Fluid A5
Strand formation
52 6mm

(Tripathi, Whittingstall, and McKinley (2000) Rheol. Acta, 39, 321-337.)

Example: Pressure Sensitive Adhesives

(Tripathi, Whittingstall, and McKinley (2000) Rheol. Acta, 39, 321-337.)

Example: Pressure Sensitive Adhesives (PSA)

 Measure D mid (t) for all seven adhesive formulations Shorter break-up time correlates with better performance

Increasing Ad

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Example: Polymer/Clay Nanocomposites

Use of a small wt.% of nanosized clay filler particles to enhance the material properties of engineering plastics (Giannelis et al., Adv. Polym. Sci . 1999)
Enhanced flame-retardance, heat distortion, gas impermeability, wettability... Little or no degradation in modulus or impact resistance, enhanc ed toughness...
(Hojun Lee (2003) unpublished)

but In steady shear flow: Strong yield stress observed for 3 wt.%

MMT
10
4

[Pa.s]

10

10 % 6% 3% 1% 0%

10

10

10

yx [Pa]

10

10

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(Tripathi, Whittingstall, and McKinley (2000) Rheol. Acta, 39, 321-337.)

Example: Pressure Sensitive Adhesives

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Example: Polymer/clay nano-composites

Below certain wt% value: nano clay particles reduce chain extensibility Above certain wt% value: paste-like response
(Hojun Lee (2003) unpublished)

High extensional viscosity for small strains Little extensibility or cohesive strength: Failure of material at small strains

1000
8 Extensional Viscosity [Pa*s] 6 4

2 0% 3% 10% Fit 0% Fit 3% Fit 10% 2 4 6 Strain 8

0 % Nano clay

10 wt% Nano clay

100
8 6 4

3 wt% Nano clay

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Example: Enhanced Oil Recovery

Use of aqueous polymer solution for enhanced oil recovery. Flow through porous media with changing pore sizes
Porous stone or sand particles

Pore with large diameter

Pore with small diameter

Extended polymer Relaxed polymer

Injection Well
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Production Well

Example: Enhanced Oil Recovery

5000 ppm Polymer in Saltwater (Polymer 1 and 2)

Shape indicates extended coils

Difference in break-up time

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Example: Enhanced Oil Recovery

5000 ppm Polymer in Saltwater (Polymer 1 and 2)

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Example: Enhanced Oil Recovery

5000 ppm Polymer in Saltwater (Polymer 1 and 2)

Increasing Viscosity

Steady Drop in Viscosity

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Example: Enhanced Oil Recovery

5000 ppm Polymer in Saltwater (Polymer A)

20 C

Shape Indicates Flexible Coil

80 C

shorter brake-up time i.e. longer relaxation time

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Example: Enhanced Oil Recovery

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Example: Enhanced Oil Recovery

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Application range of the CaBER 1

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Thank You for Your Attention

any questions?

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