Download - MCF Korea-2012
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“Inventing Plastic Microcapillary Films”
BY
MALCOLM MACKLEY.With Acknowledgement to;
Dr Bart HallmarkDr Christian Hornung
Dora MedinaSina Bonyadi and Hui Cheah
Nuno ReisFrederik Scheiff, David Agar and Matthais Mendorf
DEPARTMENT OF CHEMICAL ENGINEERING AND BIOTECHNOLOGY.
UNIVERSITY OF CAMBRIDGE.
LG. Korea 2012
2
Plastic Fantastic
Sub millimetre Process Engineering
3
Plastication of polymer
Band heaters
hopper
high pressure gas
metering device
static mixer nucleationPolymer
Polymer/gas solution formation
Nucleation and Cell growth
plasticating screw
Conventional Foaming Processing
4
Background. Plastic Micro Capillary Films
(MCFs)
Bart Hallmark and Malcolm Mackley 2005
5
6
Haul off
Hollow extrudate
Heatedbarrel
Gear pumpT1 T2 T3 T4
T5 T6Motor
Hopper
Screw
Flange with filter
P2
Nitrogen supply
Gas flow control
Primary pressureregulator
Secondary pressureregulator
F
Rotameter
Die
T7
P1
Gas injector
Convergent die
Edge of quartz window
Early experiments 2002
PE
7
Heatedbarrel
Gear pumpT1 T2 T3 T4
T5 T6Motor
Hopper
Screw
Flange with filter
P2
Die
T7
P1
Haul off
Hollow extrudate
Gas entrainment
Convergent die
Edge of quartz window
MCF Process Development
Hallmark et al. J. Non-Newtonian Fluid. Mech (2005)
8
Quench bath
Melt drawing length, L
Extrudate to haul off
Polymer flow
Die land
MCF extrudate
Brass ‘roller’
Gas entrainment – die and injector design
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Low voidage MCF
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Die design
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T1 T2 T3 T4
T5 T6P2
Single screw extruder
MCF extrusion
die
Chilled rollers
Spooling
Guide rollers
Gear pump
MCF
PLAN VIEW
MCF
Chill rollers
Direction of flow
Array of 19 entrainment nozzles
Entrainment body
Air inlet
Polymer melt
Die exit
Quenching length, L
The MCF process
Hallmark et al Adv. Eng. Mat., (2005).
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A1
A2 A3
1
322 A
AA
31
21 AA
A
= 9.6 %
= 10.3%
Initial die voidage
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Low Voidage MCF
Standard MCF
0
50
100
150
200
250
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19
Capillary number
Hyd
rau
lic d
iam
eter
(μ
m)
340 μm
MCF voidage ≈ 9-11 %
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Drawing Low Voidage MCF
D. I. Medina B. Hallmark T. D. Lord M. R. Mackley The development of voidage and capillary size within extruded plastic films. J Mat Sci, in press
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MCF
Fixedlowerclamp
Upper Clamp
Mechanical Drawing of MCFs (using stable Microsystems texture analyser)
MCF
Upper Clamp
Fixedlowerclamp
RoomTemperature
Mechanical drawing process - Increases orientation but limits drawability
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Diameters after Mechanical Drawing of MCFs
0102030405060708090
100110120130140150160170180190200210
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Capillary number
Hyd
rau
lic d
iam
eter
(μ
m)
Standard MCF
Diameters after Mechanical Drawing
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COLD DRAWN
0
20
40
60
80
100
120
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19
Capillary number
Hyd
rau
lic d
iam
eter
(μ
m)
MCF voidage ≈ 8.5 %
Necking
Post-neckmaterial
Material in neck
Undrawn material
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0
5
10
15
20
25
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19
Capillary number
Hyd
rau
lic
dia
met
er (
μm
)
HOT DRAWN
MCF voidage ≈ 9-11 %
Optic micrograph of top view MCFs
Drawing direction
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V2
Extrusion die
Chilled rolls 9 °C
Hot roll T = 60-120°C
MCF
Quenching
Extruder
Hot drawing - Second stage Hot draw-
Molecular orientation
Melt T=170 °C
little
orie
nta
tion
Hig
h o
rien
tatio
n
V1
Draw ratio λ = V1/V2
Solid
Thermal camera image
X-Ray diffraction
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MCF Product from continuous drawing
Optic micrograph of top view MCFs
100 μm
Drawing direction
0
20
40
60
80
100
120
140
160
180
200
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Capillary number
Hyd
rau
lic
dia
met
er (
μm
)
21
High Voidage MCF
D Medina J Mat Sci 2008
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T1 T2 T3 T4
T5 T6P2
Compressed air
Isolationvalve
Conventional extrusion line MCF extrusion die
Chilled rollers
High-speed air quench
Needlevalve
Mass flow control valve
Spooling
Guide rollers
TP P
P Pressure sensor
T Temperature sensor
Manual valve
Control valve
High Voidage MCFsBy rapid cooling and or injecting air under pressure into capillaries during melt processing it is possible to produce “High voidage MCFs”
Develop orientation
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High voidage MCFs
100 μm
MCF-MCF hv2- big voidage
0
50
100
150
200
250
300
350
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19
Capillary number
Hyd
rau
lic
dia
met
er (
μm
)
200 m
Hydraulic diameter varies from 150 μm to 417 μm
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(110)
(200)
Orientation present
X-Ray
Extrusion direction
Solid MCF
Air entrainmentneedle
SolidificationInterface zone
Die exit
Air quench jet
Air quench jet
MoltenMCF Chill rollers
Extrusion direction
Solid MCF
Air entrainmentneedle
SolidificationInterface zone
Die exit
Air quench jetAir quench jet
Air quench jetAir quench jet
MoltenMCF Chill rollersChill rollers
Melt residence time << 1 sMelt relaxation time < 1 s
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Extrusion direction
Solid MCF
Air entrainmentneedle
Solidificationinterface
Die exit
Air quench jet
Air quench jet
MoltenMCF
Chill rollers
To << Ti
ηo
ηi
To
Ti
u1A1, u2A2,
ηo >> ηi
High-voidage MCF
Asymmetry in temperature profile Asymmetry in viscosity profile Asymmetry in the velocity profile
Symmetry planeInjector needle
2D schematic
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Ultra High Voidage MCF
D. I. Medina B. Hallmark T. D. Lord M. R. Mackley The development of voidage and capillary size within extruded plastic films. J Mat Sci, in press
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MCF
Fixedlowerclamp
Upper Clamp
Mechanical drawing of High Voidage MCFs
Capillary direction
MCF
Upper Clamp
Fixedlowerclamp
RoomTemperature
It breaks
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Upper Clamp
MCF
Fixedlowerclamp
MCF
Fixedlowerclamp
Upper Clamp
Mechanical drawing of MCFs Transverse direction
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HV-MCF is unfolded to form
the UHV-MCF
Dora Medina
Go to MCF UHV movie
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ULTRA HIGH VOIDAGE MCFs
1000 μm
1000 μm
1000 μm
SEM UHV-MCF
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High Voidage die
Bart Hallmark 2008
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A1
A2 A3
1
322 A
AA
31
21 AA
A
= 30%
= 60%
Initial die voidage
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High Voidage Die – some interesting results
Melt draw, chill rollers, haul off
Die quench, haul off
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Microcapillary Monoliths
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An addition to the MCF family – Microcapillary Monoliths (MCMs)
500μm
200μm
7mm
Christian Hornung
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Plastic Fantastic
MCF applications
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MCF Development; Pressure Drop
Christian Hornung
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MCF Development RTD
0
5
10
15
20
25
30
35
40
45
50
0 5 10 15 20 25 30t [min]
c [m
g/l]
inletoutlet
length = 20 mflow rate = 0.5 ml/min
PE, EVOH and FEP
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MCF Commercialisation
2 flat silicon heaters (200 W each) PID control - Temperature monitoring at top and bottom heater
plates
Tmax = 150 °C developed by
Lamina Dielectrics Ltd.& Cambridge University
Teflon coatedhot plates
Temperature control
Reactor disk tray
Patrick Hestor Lamina Ltd
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MCF Development; Microflow
Organic.Kerosene, 1.8 mPasOil, 27 mPasVegetable oil. 50 mPas
Water, 1 mPas, glycerol 10-50 mPas or methanol
Video,Methanol into Veg oil
Nuno Reis
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MCF Development; Slug separation
Scheiff et al. Lab on a Chip. 2011
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Multi channel flow
Nuno Reis
Go to MCF multi channel flow
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MicrocapillaryFlow disc
Vegetable oil
Glycerol
Biodiesel
Methonal pluscatalyst
Input Output
MCF Development; Biodiesel Microreactor
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MCF Microreactor; BiodieselMethanol
Veg oil
Methanol pluscatalyst
Glycerol
Glycerol
Biodiesel
45A Edwards et al Lab on a Chip 2011
MCF Protein Assay Nuno Reis and Al Edwards
FEP/EVOH
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Bore fluid
NitrogenGas
Cylinder
Polymer Solution
Die
External Coagulant
Haul-off
Single Capillary,MCF membranes
Air-gap
Glass Water Bath
MCF Development. Microporous MCF membranes
Sina Bonyadi
PVDF/NMP (18/82 wt%)
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Water coagulation
bath
Bore Fluid
Polymer Solution
Air-gap
MCF Membrane Fabrication Concept
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Microporous MCFs
2 µm
100 µm
2 µm
1 µm
Bonyadi et al. Journal of Membrane Sci 2012
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Plastic Fantastic
Microcapillary Films (MCFs)
•Polymer processing lessons learnt.
•A new material form looking for the right application.