Laboratory-Mixers & Extruders

for

Nanocomposite Application
Dr.Ing. A. Frendel / Dipl.Ing. M.Jhrling

Content

Nanocomposites
Instruments (PI)
Mixer
Twin Screw Extruder
MiniLab and MiniJet
References

Source: German Wikipedia, original upload 29. Dez 2004 by APPER

Comparison of Dimensions

Finger nail: If Nano Clay platelets

would be this size, conventional
fillers compare to:
18 beach ball:
Talc / Lime stone particle

1,5m diameter,
1km long tube:
Glass Fiber

Nanotechnology
There is plenty of room at
the bottom (Feynmann, 1959)
Nanotechnology [greek. , dwarf] is structuring or production of materials in
dimensions less than 100 nm. In this scale surface effects play a predominant
role. More molecules are on the surface than inside the particles.
Nanocomposites are matrix materials such as rubber, engineering plastics or
polyolefines with a small content of nanoscale materials. Usually less than 5% of
nanomaterials are used to improve thermal or mechanical properties
Typical ways to produce Nanocomposites are In-Situ-Polymerization and melt
blending / compounding
Three types of nano material are commonly melt blended with plastics: Nano clay,
nano tubes and nano scale particles (SiO2, ZrO2, Ag)

Nanotechnology
Typical nano fillers:
Nano scale particles, like SiO2 , TiO2, Al2O3, ZrO2, Ag, nano diamonds
Carbon nano fibers, carbon nano tubes
Nano clays
Typical applications:
Improving mechanical properties
Increasing the electrical conductivity
Increasing thermal conductivity
Biocide / antibacterial
UV-absorption

Nanoclay
Nanoclay (Silicate platelets, 1nm thick and
70 to 150 nm across) is most commonly
used, and commercially available as
masterbatch or surface modified powder
Nanoclay improves barrier properties
of film against gas and liquids
Task for the compounding is to
achieve good distribution of the clay sheets
(exfoliation)

Helsinki University of Technology, Department of the Chemical Technology

Schematic illustration and terminology of nano

composites formed with organo clays

Melt Compounding

Tactoid

Intercalated

Intercalated,
disordererd

Exfoliated,
delaminated

Material Characterization, Processing Instruments:

Our selection for melt blending of nano composites

PolyLab OS

Twinscrew
Compounder

Moduar Torque Rheometer

with measuring mixers and
measuring extruders for
development of new
compounds

Twinscrew Compounder
for developement and
Pilotplant
(100 g to 200 kg/h)

Mini-Compounder

Mini-Compounder and
Mini-Injection Moulding
for smallest amounts of
material, app. 5 g

PolyLab OS

Laboratory Mixers
Single screw Extruder
Twin screw Extruder

RheoDrive + Mixer/Extruder Sensor

= PolyLab OS
additional
analyzing
sensors

Mixer sensors
RheoDrive

Single screw
extruder sensors

Twin screw
extruder sensor

Rotors

10

Feeding
systems

Screws

Dies

Postex

PolyLab OS Flexible Design

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PolyLab OS Flexible Design

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Laboratory Mixers - measuring principle

Shearing of a test sample

in a heated mixing chamber
with counter rotating rotors

Test results:

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Torque

Melt temperature

Mixer - Rheogram

Temperature

Torque

Energy

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PolySoft evaluation Curve Type 1

Example 1: used to determine exfoliation of monmorillonite
Torque [Nm]

5% organoclay[1]
L
0

M
1

10

Materials:
Polyolefins: PE, PP
Engineering / high performance Plastics:
(PS, PA, PC, PEEK, LCP )
Compounds of a.m. polymers with
organo clays, nano tubes
Point detection:
L = Loading point
M = Minimum point (steady state
torque)
Observe the melting behaviour
and flowability of a compound

Runtime t [min]

We have noted that a simple indicator of the extent of

clay exfoliation within polyethylene is the steady-state
torque recorded during melt compounding1.
[1]Ref.: Influence of clay exfoliation on the physical properties of montmorillonite/polyethylene composites
T.G. Gopakumar, J.A. Lee, M. Kontopoulou*, J.S. Parent
Polymer 43 (2002) 54835491

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PolyLab OS PolySoft Mixer

PolySoft Mixer SW:

- Job stream structure
analog Haake RheoWin
- The user is guided
through the measurement
- Project handling:
several tests can be
saved in a project

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PIM: Critical (powder) loading of feedstock

The erratic reading in the steps for

increased powder load show the
limiting powder [%] in the mixture.
Add powder

Ref. LR45-e, Joseph A. Krudys,

ThermoHaake 2002

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Contact free and fast, high resolution

torque sensors have a big advantage
over old style dynamometer where
the reaction of a heavy motor is
measured, the erratic reading, here
key feature is damped or smoothed

Nanoscale Ceramic Al3O2 Powders for PIM

(Mixer Example 2)
Juliane Kraus (Ref.) describes in detail how to optimize a binder system in a Torque Rheometer
system (R600, roller rotors).

Type modifier (better: lower torque with stearic acid amide)

Minimum content of this modifier (Torque depends only on [%]powder)

batches in a larger scale are produced for the complete PIM process.

8 % stearic ac. amide

9% stearic ac. amide

Torque

stearic ac.

10% stearic ac. amide

24 [%]

27 [%]

[%] powder
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Ref. (in german): Juliane Kraus

Spritzgieen nanoskaliger keramischer Pulver
am Beispiel des Degussa Aluminiumoxid C
Hochschulschrift: Saarbrcken, Univ., Diss., 1999

Nanoclay with Elastomers

Mixer Example 3
Various Composites of organo clays and Elastomers are investigeated by F.
Schn, Univ Freiburg, the mixing was done in the HAAKE Rubber mixer 610.
The organo clay composites are compared to standard silica composites
Parameters: CR and SBR composites mixing for 10 min set Temperature 80
variable speed to stay below 90. At 7 min start of crosslinking started by adding
of vulcanization chemicals.
EPDM Composites were mixed at 130C and grafted EP-g-MAA Composites
at 100C
Practical example: Identical organoclays but from different suppliers were
compounded. For same reinforcement (tensile stress) 2,3% (supplier A) and
6,2% (supplier B) organoclay were needed.
Ref.: (dt.) Elastomer / Schichtsilikat Komposite:
Einfluss der Fllstoffstruktur auf mechanische,
dynamische und Gasbarriere-Eigenschaften, Frank Schn
Dissertation, Universitt Freiburg (2004)

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Electrical Conductivity Measurement

A new approach by combining traditional methods with new
technologies

2
3

4
20

Ram

Control Thermocouple

Rotors

Conductivity Sensor

Rheomex Extruder Application

Extruders are generally used to:

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transport material
plasticize
compress
homogenize
compound
vent
chemical reaction
building up pressure
Measure viscosity

Principle of Twin-screw extruders

Co--rotating
Co

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Counter--rotating
Counter

Twin Screw Extruder: Co- or Counter rotating?

Counter-rotating Rheomex Twinscrew Extruders:
Counter- Defined residence time (good for i.e. rigid PVC)
- High shearing (good for dispersion of Nano fillers)
- Self cleaning
- No controlled feeding needed
- High pressure build up
Co
Co--rotating Rheomex Twinscrew Extruders
Extruders::
- Mixing of shear sensitive material (i.e. Polyolefins
Binder)
- Compounding and Venting
- Controlled shearing
- most flexible (screw design, barrel ports and length)
- Controlled feeding necessary
- Wear resistance as option

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Rheomex CTW100

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Screws for Rheomex PTW OS

Segmented, with slip-on

elements, allowing
variable configuration
Screw diameter: 16 /24 mm
Co rotating, intermeshing,
self cleaning screws
High volume design
Screw shafts:
Design: hexagonal
Material: Heat treated,
wear reduced

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Parallel twin-screw extruder - Screw Elements:

Conveying elements:
elements:
Profiles with open chambers are used:
- in the feeding sections
- for melt exchange
(longitudinal mixing)
- for degassing (venting)
Profiles with closed chambers are used:
- for high pressure built up
- in front of kneading elements

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Parallel twin-screw extruder - Screw Elements:

Mixing Elements :
Mixing Elements are used to introduce
shear energy to the extruded materials.
The disks are arranged in different offset
angles used for:

- plasticizing
- shearing
- mixing
- dispersing

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Mixing elements

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Parallel twin-screw extruder - Screw Elements:

Distributive Flow Elements :

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Distributive Flow Elements are

special mixing elements, used for
the distribution of small quantities
of additives and shear sensitive
materials.

The shearing energy introduced to

the polymer is significantly lower
than that of the kneading elements.

Screw elements: Rheomex PTW16

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Rheomex PTW16
flexible screw configuration

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Screw configuration (Standard Layout 75%)

Feed Screw

Conveying sample
only partly filled
low shear

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Mixing Element

Melting & mixing

completely filled
high shear

Dispersive and Distributive mixing

For nearly all mixing
applications a well dispersed
and well distributed mixture
is required.
Distributive mixing can be
achieved by splitting and
reorienting the flow
repeatedly
Dispersive mixing can be
achieved by passing the
mixture through small
regions of intense
deformation.

Mixing and composites, M. Kontopoulous Chee 18.2. p. 390presentation Queens University

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Maximum flexibility
... Feed ports...
... Length ...

... Screw design ...

... Split Barrel
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PTW16 OS - Maximum flexibility

... Split Barrel

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PTW16 OS - Maximum flexibility

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New PTW16 XL for PolyLab OS

Horizontal split, with a lift-off top to

be opened for ease of cleaning,
simple removal of the screws and
visualisation of the melting process.
The segmented top barrel part is built
with 4D modules to be easily
reconfigured by the user.
Barrel segments are available for
cooling, feeding solids, liquids and
for venting.
Optional extension unit 15D (easy to
bolt on by the user!) to run a 40D
extruder e.g. for reactive extrusion.

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Example Nano Ceramics for PIM (1)

Also for ceramic materials nano materials are of
interest. Smallest parts produced by micro
injection moulding require fine particles to fill the
cavities.
The feedstock production is described in detail
in the lab report LR56e and the relevant PIM
presentation.
For the HAAKE PolyLab OS a RD16, a
PTW16/25 XL parallel twin screw extruder and
two HAAKE metering feeder (binder, ceramic
powder) was used to homogenize the raw
materials (85/15 % wt/wt).The product was
cooled on the conveyor belt, easily cut to pellets
and manually fed to the MiniJet for specimen
production.

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This is material
production for Micro PIM
parts (right)
Ref.: Picture: ARC Seibersdorf research
center Micro PIM part

Example Nano Ceramics for PIM (2)

Instrument setup, RD16, PTW16/25,

split feed with two metering feeders,
die plate and conveyor belt.

A polyethylene wax based binder was

blended with Zirconium oxide.
Separate Feed of wax and powder. Can
reduce wear for production
Output 6 kg/hr

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Use of EVA as compatibilizer in

LDPE/organoclay composites 1
Two kinds of polymer/montmorillonite (MMT)
intercalated nanocomposites were prepared by melt
intercalation under a twin screw extruder (PRISM
TES 16 TC, UK). Low density polyethylene [...] can
intercalate into the layers spaces of org-MMT (a kind
of montmorillonite which was organically modified by
cetyltrimethylammonium bromide through ion
exchange reaction), especially when adding a kind
of compatiblizer, i.e. ethylene vinyl acetate
copolymer (EVA[...]). It is well accepted that LDPE is
a non-polar polymer and can not intercalate into
MMT layers easily because of the poor compatibility
between them. [...]
Incorporation of EVA, a polar polymer, into these
system will acts as a compatibilizer and will improve
the interaction between polymer and modifiers. As a
result the polymers intercalate into MMT layers more
easily.
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[1] The Dynamic Viscoelasticity of

Polyethylene Based Montmorillonite
Intercalated nanocomposites
Hong Mei YANG, Qiang ZHENG*
Department of Polymer Science and
Engineering, Zhejiang University Hangzhou
Chinese Chemical Letters Vol. 15, No. 1, pp 74
76 , 2004

Compounding easy data view (Example 3)

High speed compounding, Output up to 30kg/hr

Optimizing torque and temperature
Heat cool view gives an easy overview

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Compounding MMT/ABS with PTW24 and R600OS

the results are good because an intra
space gallery of 3 nanometres is an
evidence that good intercalation has
been achieved; prior to compounding
the space was 2 nanometres. And
also there are some areas where it is
possible to see that exfoliation has
happened.
This results was achieved with a
commercial MMT, functionalised for
PA, not for ABS (producers are now
less available to optimise their
products for little amounts). So this
is another evidence, in my opinion
the compounding is good because
we reached the best result possible
with the materials available in the
market.

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~30

ABS/5 w/oMMT I.30P

PTW16-40 OS optimizing melt temperature

PP, PP-g-MSA, nano clay

Tm = 208,1

Tm = 206,1
Tm = 202,4

Tm = 201,0

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LR-61 nanocomposites - example on compounding of naoclay

in twinscrew extruders, D. Hauch A. Wunsch A. Frendel, Thermo
Scientific, Karlsruhe 2007

Tm = 199,8

PA and Nanoclay with PTW24-40 OS

LR-61 Nanocomposites - example on compounding of nanoclay

in twin screw extruders, D. Hauch A. Wunsch A. Frendel, Thermo
Scientific, Karlsruhe 2007
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MiniLab
Micro Rheology Compounder

Right from the introduction of the

MiniLab our customers in the
nano material research
recognized this small extruder as
ideal instrument for their material
development.
More than 10 sets in the North
American market are used for
research on Nanocomposites.
Eastman Kodak published
patents on modified clear
Polymers.

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MiniLab

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Micro Rheology Compounder

MiniLab
Micro Rheology Compounder (principle sketch)

Saving your Material: The HAAKE MiniLab combines Batch

Mixer, Extruder and Rheometer
Backflow channel with
rheological slit capillary die

p2
p1

Bypass valve

Output channel

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New barrel design

The new MiniLab improves the handling and accessibility for

cleaning, a slit die is built in. Optional sensor ports available!
Horizontal Split
barrel, fast analysis of
material
Easy cleaning of the
outlet channel
Build in slit die
Improved hardness,
no TiN coating
necessary
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MiniLab (Example 1): Counter Rotating Screws

Intermeshing counter rotating screws are most effective to improve results

melt extrusion of multi wall carbon nanotube composites. Due to higher shear
agglomerates are well distributed. Degradation of Stabilized PMMA and
MWNT was not observed (1).
(1)

R.E. Gorga, R.E. Cohan, (MIT), Toughness enhancements in PMMA by MWNT, Journal of Polymer
Sci. 42 2690-2702 (2004)

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MiniLab (Example 1): Counter Rotating Screws

SEM images of the surface of the axial

cross section for 3 wt % SWNT in
PMMA using (a) DACA co-rotating,
(b) Haake co-rotating, and (c) Haake
counter-rotating screw configurations.
(d) A schematic of the cleaved section
and the imaging surface
Toughness Enhancements in Poly(methyl methacrylate) by Addition of Oriented Multiwall Carbon Nanotubes,
Journal of Polymer Sci. 42 2690-2702 (2004)
RUSSELL E. GORGA, ROBERT E. COHEN
Department of Chemical Engineering, Massachusetts Institute of Technology, 77 Massachusetts Avenue,
Cambridge, Massachusetts 02139

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MiniLab (Example 2)
combining results Meltflow MT + MiniLab (nano tubes)
Jody Ericsson found a linear
correlation of % of nano tubes
with the decreasing MI value of
Polypropylene blend.
The viscosity was measured in
the MiniLab

Ref.: INCORPORATING CARBON

NANOTUBES INTO
POLYPROPYLENE FIBERS, JODY
ERICKSON
Master Thesis 2003, North Carolina State
University

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557-2188

Nano Compounder MiniLab II

Nano Compounder MiniLab II

with counter-rotating screws and manual feeder
MiniLab Nano Compounding bundle (557-2188) consists of:
MiniLab with co-rotating screws
Set of counter-rotating screws with adjustment tool and gears (557-2266)
Manual feeding device for HAAKE MiniLab (557-2256)
Features:
- MiniLab with hardened barrel (58 HRC) and hardened screws (50 HRC) to reduce
wear and contamination with highly abrasive Nano tubes
- Both screw options (co- and counter rotating screws) to enhance flexibility
- Counter rotating screws for best dispersive mixing of Nano tubes
- Counter rotating screws for stable volume feeding the re-circulating channel
to allow Rheometry in the slit die
- Co-rotating screws to compound thoroughly even shear sensitive materials

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Features MiniLab II - Summary:

Stable horizontal design:
Easy cleaning, easy handling

Backflow channel with slit capillary:

Absolute shear stress measurement
Rheological characterization of the sample during mixing process

Pneumatic feeding device:

Controlled, reproducible feeding procedure

Additional measuring ports possible:

Option for additional sensors like UV, NIR,

Option for counter-rotation screws:

for high shear and rheology application

N2-purge for feeder and extruder:

To avoid thermo-oxidative degradation of the sample

Pneumatic ByPass Valve

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HAAKE MiniJet
Numerical controlled

2 Temperatures controlled

Pressure controlled (0.1 bar)

Procedure controlled
1. Injection pressure & duration,
2. Post pressure & duration

All parameter can be stored

Language: English, German

Units: bar, psi - C, F, K

Improved handling

No pressing lever necessary

Easy filling of pellet samples

Increased performance

Same injection pressure form 40% less

feeding pressure

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HAAKE MiniJet vertical alignment

Specifications:

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Melt temperature

400 C

Mould temperature

250 C

Injection pressure

1200 bar

Electrical power

230V / 110V

Max air pressure

10 bar

Dimensions

300x460x710
60 kg

HAAKE MiniJet Micro Injection Moulding

The reservoir can

be connected with
the Minilab to fill in
the melt

Or direct fill in
of pellets into
the reservoir
chamber

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HAAKE MiniJet Micro Injection Moulding

Specific mould design depending on your
task for instance
Tensile testing specimen
Customized moulds e.g. for tablets for
bioavailability studies

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HAAKE MiniJet Moulds

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References
C.R.P. Dr. Laura Martinelli
Use PolyLab with Mixer and PTW24
www.crpo.it
University of Kentucky Dr. Rodney Andrews & Dr. Eric Grulke
Use PolyLab with Mixer and CTW100 Conical Twin
http://www.caer.uky.edu/carbon/home.shtml &
http://www.mrsec.uky.edu/
MIT Dr. Robert Cohen nanotechnology for soldiers
MiniLab
http://web.mit.edu/cohengroup/index.html
National Research Council of Canada
2 MiniLabs for nano research
http://www.imi.nrc-nrc.gc.ca/
McGill Univ Dr. Milan Maric
http://www.mcgill.ca/chemeng/department/academic/maric/

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North Carolina State Univ Dr. Russell Gorga

uses MiniLab
http://www.tx.ncsu.edu/faculty_center/directory/detail.cfm?id=360
Clemson University Dr. Stephen Foulger & Dr. Amod Ogale
uses MiniLab & RheoMix mixers & Haake Rheometers
http://virtual.clemson.edu/groups/caeff/facilit/index.htm
http://mse.clemson.edu/htm/faculty/Foulger.htm
http://www.ces.clemson.edu/chemeng/facultypages/ogale/cv.html