Micro- and nanoscale modifications for polymer …2010/10/11 · 3-D resist preform Therm....
Transcript of Micro- and nanoscale modifications for polymer …2010/10/11 · 3-D resist preform Therm....
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Micro- and nanoscale modificationsfor polymer functionalization
Prof. Dr. Per Magnus Kristiansen
Prof. Dr. P.M. Kristiansen Micronarc Industrial Forum - 10.11.2010 2
Outline
• Introduction– INKA ; from polymer nanotechnology to functionalization
• Physical surface modification – micro/nanostructuring– Towards industrially feasible micro/nanostructured polymer surfaces
• Chemical functionalization - patterned surface grafting– selective tuning of surface chemistry
• Bulk modification of polymers – morphology control– From traditional fillers to nanoscaled or supramolecular additives
• Summary
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Who is INKA?Das Institut ist eine gemeinsame Einrichtung der Fachhochschule
Nordwestschweiz und des Paul Scherrer Instituts
Inst. f. Kunststoff-technik der HTNW
Labor für Mikro- undNanotechnologie LMN
Ressourcen INKA:Prof. Dr. Ing. Jens Gobrecht, LeiterProf. C. Dransfeld, Stv. FHProf. Dr. M. KristiansenDr. H. Schift, Leiter INKA-PSI4 Assistenten @ FH2 Wissensch. + 1 Techniker @ PSI1 Ing. + 3 Doktoranden @PSITechniker-pools IKT und LMN
Zugriff auf: Kunststofflabors im IKT,im KATZ, auf Reinraumlabors undGrossanlagen im PSI
IKT
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IKTInstitut fürKunststofftechnik
INKAInstitut fürnanotechnischeKunststoffanwendungen
INKA-PSI
LMN - Labor für Mikro- und Nanotechnologie
Vorteile für INKA• Zugriff auf volle Infrastruktur des PSI und der HT (inkl. KATZ)• Zugriff auf knowhow auf beiden Seiten• „Pooling“ der Personalressourcen INKA/IKT und INKA/LMN
IKT & INKA
Differenzen• Unterschiedliche Prioritäten betr. Output• Unterschiedliche Kulturen• Priorisierung der Forschung
Röntgen-optik
Nano-Magnetics etc.
Technologie-entwicklung
Die volle Durchlässigkeit der Grenzen zur HTNW und zum PSI macht INKA einzigartig!
I N K A
10 km
INKA – a „joint venture“ between FHNW & PSI
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Scientific and technological vision
year
0.1 nm
0.1 µm
0.1 mm
1960 1980 2000 2020 2040
Nano
Micro
Macro
Dim
ensi
ons
Future: Bridging the gap between nano‐ and macroscale, and building with nanoobjects by design
Cellbiology
Molecularbiology Molecular
design
Electricalengineering
Electronics
Nano-devices
Micro-electronics
Top-
dow
nPolymer
Chemistry SupramolecularChemistry
ComplexChemistry
Bot
tom
-up
Self-assembly
Nanotechnology
Mesotechnology
Courtesy of H.-W. Schmidt, Uni Bayreuth
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PS, ABS, SAN PE, PP, PVC
PMMA
PPE mod.
PAPBTPOMPMPPUR
PC
PBIPITPIPAI
PES, PPSUPEI, PSUPC‐HT
PEKPEEKLCP, PPSPTFE, PFAETFE, PCTFEPVDF
High performancepolymers
Engineeringplastics
Commodityplastics
amorphous semi-crystalline
< 1%
< 15%
> 85%
PET
The world of plastics
Major challenge in polymer science, with respect to novel functional and even multifunctional materials, is the understanding and control of hierarchical functional polymer structures created by (macro)molecular self-assembly.
Advanced functional polymers
Courtesy of H.-W. Schmidt, Uni Bayreuth
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Polymer functionalization – modifications on the micro- & nanoscale
Surface modification Bulk modification
Processing
topographic chemical
Self‐assembly
ordered disordered
morphology
particlesphasesorientation
„buckling“
fillers
fibers
Injection & other molding, extrusion (e.g. films), spinning, etc.
grafting
coating
Hot embossing
additives
compoundingblending
compounding
After‐treatment: metallization, CVD/PVD, particle or biochemical modification
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Contents
Physical surface modification – micro/nanostructuring
Chemical functionalization ‐ patterned surface grafting
Bulk modification – morphology control
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Tooling problem: Machining technologies with resolution < 1 mm
milli micro nano
10-3 10-6 10-9
Tech
nol o
gies
for
patte
rnde
finiti
o nTy
pica
lob
ject
s
mechanicalmachining
optical lithography
beam lithography
SPM lithpography
R e p l i c a t i o nm
Auflösung
LIGA gears chip Quantum devices moleculeswatch parts
light e- beam
Self-organisation
Tech
nolo
gica
lGap
erosionlaser ablation
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Nanopatterning Production and Applications based on NanoimprintingLithographyThe project targets scalablenanomanufacturing processes forarbitrary 3-dimensional surfaces
Industrial Demonstrators–Planar Diffractive Optical Element
(PDOE)–Emissive Head-Up Display (eHUD)–Light Directional Elements (LDIR)
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Silicon mold masters made by lithographic processes
Advantage: extremely precise, tolerances << 1 µm (microelectronic process), very hard material, i.e. low wear; durable mold inserts nickel copies
Disadvantage: very brittle (breakage risk), only planar geometries, direct moldingfrom silicon requires glueing or clamping (both not ideal but sufficient forprototyping)
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Towards super-small structural features
exposure station at SLS-XIL beamline
• X-ray interference lithography–Resolution ~10nm
• e-beam lithography–Resolution ~20nm
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Hot embossing Technology
Tight process control:
Temperature and T-profiles, Vacuum, clamping force, speed of closing/ emolding
Both sides of tool adjustable withina few micrometers laterally
Optional possibilities
• device for measuring demolding forces
• UV-assisted nanoimprint lithography
Jenoptik Hex03
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Replication of Micro- and Nanostructures by Injection Molding
• Interest from vastly different industries– Optics, Security, Decoration– Life science, Bioanalytics
• Entire value chain in-house– Lithography (e-beam, XIL), etch processes– Tool design: construction, CAD, FEM– Laser machining at IPPE
• Present research focus– Optimisation of super-fine structure replication– Variotherm-concepts ; 2-side structured molding– Alternative mold insert materials– Hierarchical structures (nano+micro)– Microfluidics and human liquid handling
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INKA Reference Activities (1)
period 200 nm
AFM calibration chips madeof plasticsPSI – FHNW – Nanosurf AG
Replication of sub-micronstructures by inj. moldingKATZ – FHNW – PSI – Bayer AG
CD-injection molding ofnanostructuresPSI – FHNW – KATZ –AWM Moldtech AG – Netstal AG
Main focus:Master creation (Si, Ni, ..), Replication processes,Tooling developmentPolymer processing
One-way cuvette, nanostructured on inside improvesde-wettingproperties forautomatizedbioanalytics
World record in controlled replicationof nanostructureswith injectionmolding17 nm channels in COC
Microcantilevers withd=20µm for Bionalyticts.top: Laserstructured mold
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Application example: Dewetting surfaces for bioanalytics
Problem: structuring of non-planar surfacessolution 1 (Microstructures): Laser Micromachiningsolution 2 (sub-micron structures): Photolithography Nickel foil
Injection molded part (PP)
Kooperationspartner: Roche Diagnostics AG und 3D AG
liquid 1 liquid 2
planar surface 66° 70°
100 nm lines 120° 134°
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Injection molded micro-cantilevers
Nominal cantilever dimensions:Width: 100µmLength: 500µmThickness: currently 30µm
Target 10µm
PVDF COC
Laser-machined mold insert
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15min / 110 °C
15min / 115 °C 15min / 120 °C
no reflow !resist pattern / molecular weights
Thermal post-processing of 3-D resist patternPMMA resist layer (500 nm high) after development
Reference: A. Schleunitz and H. Schift, J. Micromech. Microeng. 20 (2010) 095002.
slope inclination~ 11 °
reflow
AFM analysis
2 umselective melting !
not exposed during EBL
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Variation of slope inclination by no. of steps
angle ~ 12.5° angle ~ 17.5°
5-level pattern 4-level PMMA pattern
3-D
resi
st p
refo
rmTh
erm
. pos
t-pro
cess
ing
PMMA resist layer (1050 nm high) after development and thermal treatment
transforming multi-level structures to continuous slopes
Reference: A. Schleunitz and H. Schift, submitted to Microelectronic Engineering (2011).
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2 um
3-D grating pattern transferred into silicon
25.7° 27.7°
PMMA resist after reflow and corresponding silicon pattern after dry-etching
silicon
cross section 26.6° -
pattern transfer by dry-etching
PMMA pattern on silicon 3-D silicon structures
2 um
Reference: A. Schleunitz and H. Schift, Proceedings of the 9th International Conference on Nanoimprint and Nanoprint Technology (NNT 2010), Oresund & Copenhagen, October 13-15, 2010.
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Reflow of polymer microstructures
substratewithout surfactant coating
(hydrophilic)
substratewith surfactant coating
(hydrophobic)
17 µm
24h
2h
11 µm
2h
6.7 µm
2.8 µm
24h
2.8 µm
6.7 µm
3 µm
3.5 µm
Ridge-type PMMA preforms after annealing at 160 °C for various times
Courtesy of A. Schleunitz, H. Schift, INKA-PSI
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nucleation point120 nm
100 nm
polymer lines with nodes
hydrophobic surface
regularly ordered nanospheres
silicon stamp AFM measurement
x 2 um / divz 500 nm / div
controlling dewetting effect !
Modified silicon stamp for controlled coagulationExpended lines width (node) provoke nucleation points during reflow (16h @ 160 °C)
Courtesy of A. Schleunitz, H. Schift, INKA-PSI
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Contents
Physical surface modification – micro/nanostructuring
Chemical functionalization ‐ patterned surface grafting
Bulk modification – morphology control
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Grafting of polymer brushes on polymers
Exposure to particlesor photons e.g. EUV
degassing
heating
Pattern of radicals, stabilised as hydroperoxides
Immersion intomonomer solutione.g. acrylic acid
Polymer film (e.g. ETFE)
Pattern of polymer brushes
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XIL: EUV interferencelithography
Beamlines at the Swiss Light Source
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area of high radical density
area of high radical density
direct beam
direct beam
Creation of radicals using EUV interference lithography
membrane mask
beam stop ETFE film
periodic patternof radicals
1st order diffracted beams
incoming beam(synchrotron light)
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ETFE irradiated at the XIL-Beamline(92eV Photons) grafted with 5 % acrylic acid
Non-contact AFM images → topography
Surface microstructures: EUV exposure through TEM grids
Courtesy of C. Padeste, INKA-PSI
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Examples of grafted brush structures
4 interfering beams, 283 nm period dot structure
Nanostructuring: Poly-GMA grafted onto ETFE after EUV interference exposure
106º
91º
10º
Adaptation of surface propertieslarge area, un-structured brush
ETFE substrate:low surface energy
GMA-brush
Sulfonated brush
Ar-plasma exposure, grafting with GMA
NaHSO3Grafted 2µm period structure after binding of fluorescent labelled streptavidin
Bio-functional Brush
Courtesy of S. Neuhaus & C. Padeste, INKA-PSI
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Contents
Physical surface modification – micro/nanostructuring
Chemical functionalization ‐ patterned surface grafting
Bulk modification – morphology control
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Highly oriented polymers for structural applications
• special processing technologies–Solvent-borne processing
yields super-strong fibers
• Further processing of said fibers–Keep orientation !– Introduce as layers in CF-composites
• Mechanical properties–Outstanding tensile properties–Interesting damping characteristics
Ref: J. Lefèvre, Ultra-high performance polymer foils, Diss ETH Nr. 17603 (2008)
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Polymeric foams – main interest: structural foams
• Batch foaming as R&D tool– Saturation at high pressures– Separate foaming
• Morphology & Properties– Control cell density, size & form– Improved mechanics of cell walls through
nanoscale reinforcement & nucleation
• Modification of melt strength as key– Additives, Nanoparticles, fibrillar fillers– MW build-up, Polymer blends– Rheotens characterization
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Functionalization of polymers by nanofillers or specialty additives
• Processing of nanocomposites–Ultrasonic, Dispenser, ball mill,
extruders, kneaders–Safety aspects important!
• Characterization–Dispersion quality / QC methods
Effects:–Antimicrobial, functional– Improvements in mechanical,
(di)electric & thermal properties–Modified melt properties–Enabler for certain technologies
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Antimicrobial Polymer Composites using HeiQ Additives
H2OBacteriaFiber or plastic
Fiber or plastic article
Silver additive H2O
AgAg+
H2OBacteriaFiber or plastic
Fiber or plastic article
Silver additive H2O
AgAg+
H2OBacteriaFiber or plastic
Fiber or plastic article
Silver additive H2O
AgAg+
Mechanism of functionalisation and of Ag+ release
HeiQ
INKA
HLS-FHNW EMPA
Plastics Textiles
Antimicrobial nanopowders
Masterbatch
Plastic test plates
Anti-microbial testing
Antimicrobial nanopowders
Surface-functionalized nanopowders
Ion release quantification
Fiber & textile test plates
CTI Project structure
Effect of Nano-Silber-Composites on growthof Escheria coli bacteria after 24 h
Partner:HeiQ Materials AGBad Zurzach
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“Plastics without additives are not viable. Additives are essential to make plastic processable and assure the end-use properties.” (*)
ExamplesAntioxidantsLight-stabilizers Acid scavengersLubricantsProcessing aidsAntistatic additivesAntimicrobialsColorantsOptical brighteners Fillers and ReinforcementsFlame retardantsSmoke suppressantsNucleating agentsClarifying agents
* Plastics Additives Handbook, Hanser (2001)
World of plastic additives
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central core with 1,3,5‐substitutionsymmetry and planarity
moieties forming hydrogen bondsone dimensional crystal growth self assembly
peripheral apolar substituentsmanipulation of crystallographic order dissolution in polymer melt
H.‐W. Schmidt et al., Europ. Pat. Appl. EP 0940 431 A1 (1998): nucleators for crystallizable thermoplastic polymersH.‐W. Schmidt et al., US Pat. Appl. 60/251,396 (1999): polypropylene resin composition
Concept – molecular structure of 1,3,5-Trisamide derivatives
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Dissolved additive in polymer melt Primary aggregation
Nucleation of polymer Supramolecular nanoobjects
10 ‐ 20nm
1 ‐ 2nm
Cooling
self assembly under cooling
Ø 0.02 ‐ 2µm
Cooling
heating
Supramolecular additives - concept
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Courtesy of H.-W. Schmidt, Uni Bayreuth
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High‐efficiency, next generation clarifier for polypropylene
Ciba® IRGACLEAR® XT 386
introduced to market 27.09.2006
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Trisamide additive - platform
70nm
α‐Nucleation and clarification of i‐PP
1 µm1 cm
β‐Nucleationof i‐PP
1 µm
NH
RO N
H R
O
NH
OR
Modification ofPP and PE waxes
PP electrets
Processing aidsfor LLDPE
Nucleation of PBT and PVDF
Nanofilters
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Summary
• A large toolbox of modifications is available for polymer functionalization–Let‘s try to make use of it to enable novel solutions for specific needs
• Increasing importance of joining forces between academia and industry–Pioneering approaches for innovative companies
• Applications are there, but yet much more to come–The potential is huge but only fractions are used today
• Functional polymer systems will continue to grow–Joined forces between physics, chemistry, biology & polymer science
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Acknowledgements
Physical surface modification – micro/nanostructuringArne Schleunitz, Christian Spreu, Helmut Schift, PrabithaUrwyler (PSI), Christian Rytka, Mirco Altana, Armin Stumpp, Beat Lüscher (FHNW)
Chemical functionalization – patterned surface graftingSonja Neuhaus, Celestino Padeste
Bulk modification – morphology controlMirco Altana, Giovanni Conigliaro (FHNW), Murray Height (HeiQ), Hans‐Werner Schmidt (Uni Bayreuth), Paul Smith (ETH), Daniel Müller (BASF)
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Point of contact – Polymer Technology
Institut für nanotechnische Kunststoffanwendungen (INKA)Institute of Polymer Nanotechnology
Prof. Dr. Per Magnus Kristiansen
Klosterzelgstrasse 25210 WindischT +41 56 462 45 41M +41 76 432 01 28F +41 56 462 45 [email protected]/technik/inka