The use of analytical centrifugation in the characterization

The Use of Analytical Centrifugation in the Characterization
of Correlation between Dispersibility and Functional
Performances of Polymeric Nanosolutions
Prof. Dr. Hsien-Tang Chiu
Department of Materials Science and Engineering
National Taiwan University of Science and Technology
Taipei Taiwan
Jent Polymer Lab / NTUST

Outline
1. Introduction:
Polymer Nanosolutions, Applications, S.T.E.P Technology
2. Experimental:
A. Evaluation of optimum formula in monophase oil-based polymeric nanosolution.
B. Evaluation of optimum processing in fabrication functional coatings.
C. Evaluation of foam structure/functional performance correlation in water-based
polymeric foam coating.
D. Evaluation of the correlation between dispersiblity and electrical conductivity of
triphase polymeric nanosolution in in-situ polymerization system.
3. Conclusions

Location

4
Polymeric Nanosolutions
Aerospace
Automotive
Anti-UV Coating
IR Cut-Off Coating
Protective Coating
Construction
EMI-Shielding Coating
Heat Resistant Coating
Wear-Resistant Coating
Industrial
Anti-Static Coating
Protective Coating
Medical
Biocompatible Coating
Anti-Microbial Coating
Marine
Anti-Corrosion Coating
Sports & Leisure
Waterproof Coating
Applications
Raymond HF. Nanocomposite and Nanostrucutred coatings:recent
advancements Nanotechnology applications in coatings,2009.pp.2-21

Functional Performance
Dispersibility
Stable Unstable
Well-Dispersed Worst-Dispersed
Good Performance Bad Performance
Polymeric nanosolution
Material Parameter Process Parameter
Polymeric Dispersant Content
Samples After One Day
Sediment
Dispersibility
Megual O et al. Colloids and surfaces A,1999;152(2):111-123 5

CoalescenceAggregation
Flotation
Sedimentation
homogeneous
Nanosolution
Particle Migration Problem
Stability-instability
6Lerche D et al. Power technology, 2007;174(1):46-49

3 Indirect Analytical Methods to Predict migration
A Density
B Particle Size Distribution
D Zetapotential
C Viscosity Behaviour
2 Direct Analytical Methods to Detect migration
A Microscopy
B Conductivity Measurements
Subjective Observation by Naked Eyes1
Inaccuracy, but not Objective
Accurate, but not Time Dependence
Quick, but not too Reliable
Dispersability measurements
7Lerche D et al. Power technology, 2007;174(1):46-49

STEPTM
– Technology
Space and Time resolved Extinction Profiles
STEP-Technology
8
LUMiSizer
http://www.lum-gmbh.com/

9
Experimental
Nano-solutions
LUMiSizer
STEPTM
- Technology
Particle Size
Distribution
Particle Migration Shelf life Prediction
Stability
Measurement
DLS SEM
Homogenizer
High Shear Mixer
TMPEOTA Resin
Binder
Dispersant
PEGMEA
Functional
Nanoparticle
Zeta Potential
30 min
5000 rpm, 1 hr
25 ℃，3500 rpm，Δt=10s
Different Binder/Dispersant ratios
ITO/Al2O3
Formula Particles Foams In-situ Polymerization

10
Materials
TMPEOTA: Trimethylolpropane ethoxylated (6) triacrylate (Miwon Commercial)
Binder: acrylic copolymer type oligomer diluted with diethylene glycol monoethylether
(Chemtech-37W-PC-2, Chembridge International)
Dispersant: (solsperse39000, Lubrizol
PGMEA: propylene glycol monomethyl ether acetate, Lubrizol)
ITO/Al2O3 : indium tin oxide/alumina particle (Titan Kogyo)
SEM images of raw ITO/Al2O3 powder

11
Dispersing Method
High Shear Mixer
Homogenizer
 dispersing dispersion
 Break up the agglomerate
 homogenization
High Viscosity
Temperature too high
Not optimum dispersion
Notice of dispersion
Particles Re-agglomerate
Velamakanni BV et al. Powder technology,1993;75(1):11-19

12
Stabilization with Binder
0-0 1-0
5-0 10-0
without Dispersant
1 wt% Binder

13
Stabilization with Dispersant
0-0 0-1
0-5 0-10

14
Dispersibility
Dispersibility: 0-10 > 0-5> 0-1 > 0-0 > 1-0 > 5-0 > 10-0
Binder
Dispersant
Nanoparticle

15
Shelf Life
*Zeta potentials (greater than 25 or less than –25)
can prevent agglomeration,CeramInt 2000, 26, 93.
RCF(gravity) ＝ ω2 × r ÷ 9.81
＝rpm2 × r (m) ÷ (29.9093)2
V(μm/s) ＝ V’’ (mm/hr) ÷ RCF(g)
Shelf life (mm/day)：
V(μm/s) × 0.001 × 3600 × 24 ＝ V(μm/s) × 86.4
Shelf life (mm/week)：
V(μm/s) × 86.4 × 7
(RCF = centrifugal acceleration/earth gravity)

16
Particle Size Distribution
10-0 0-0
0-10
~500 nm
~300 nm
~200 nm
The particle size distribution of coating sample 0-10 in contrast with LUMiSizer and DLS

25 ℃，3500 rpm，Δt=10s
Polymer Nanosolution Coating
STEPTM
- Technology
Particle Size
Distribution
Roll to Roll Coat
Stability
Measurement
Ball Milling
Homogenizer
Polymer MatrixFunctional Fillers
UV-cured
Functional Coat
SEM TEM Characterization
UV curing
500mW/cm2 for 5 min
Thickness:10 μm
Milling:3.5 hrs
homogenizer:15 min
Experimental
A.Blue Pigment Powder (Heliogen® Blue L 6700, BASF)
B.NIR Cut-off Powder (CIR-1081,JapanCarlit Co.,Ltd)
Fixed Binder/Dispersant ratios

sedimentsediment
sediment
The Zirconia beads with diameter of 300 μm
95 wt% in Composition Ratio
1 hr 2.5 hrs
3.5 hrs
3000 rpm
25 ℃
11.7 mm
9.5 mm
10.3 mm
Sample:
Pigments content 40 wt%
Milling Time

◆3.5 hrs ◆2.5 hrs ◆1 hr
Dispersibility

Particle Size
TEM Image
1 hr 2.5 hrs 3.5 hrs

Blue Color Filter
UV-VIS Spectrum
Coated PC Film

Dispersiblity
NIR Cut-Off Fillers 10 wt%

Dispersiblity
a. 5 min
b. 10 min
c. 15 min

Dispersiblity

25
Experimental
Nanofoam solutionsLUMiSizer
Waterborne
Polyurethane
AutoFoam®
Heat Seal
Medical Pouch
Crosslinker
Blowing agent
Stabilizer
Thickener
Performance
Evaluations
Foam Stability
Foam Structure
EtO sterilization
Morphology , Flexibility , Tack Property , Durability
Adhesion, Peel Strength, Scratch Resistance , Air Permeability
STEPTM
- Technology Coated 10, 30, 50, and 100 µm on Tyvek® medical paper
(ASTM D823),Oven dry time: 10 min
Foaming
Heat sealed with Tyvek® /LLDPE film
• Temperature: 130 °C
• Dwell time: 0.7 s
• Platen pressure: 0.5 MPa
25 ℃，2000 rpm，Δt=10s

26
Materials
Impranil® DLU: PU dispersion
Vibond® FIL: Crosslinkers
Vicarlan® BA: Blowing agent
Vicarlan® BR: Foam stabilizer
Vicarlan® TC-42: Thickener
Sherman M. Medical device packaging handbook,1998
• Spun-boned
• Non-woven
• Random fibrous
Polyethylene film
Foaming with different stirring speed:
1:1000 rpm ; 2:2000 rpm; 3:3000 rpm etc.

27
Foam Stability
Most stable
A is a constant related to the temperature and physical properties of PU
B is related to the deformation mechanics of cellular materials
Centrifugal Force
Compressive Strength
PUF coating-5 with greatest compressibility&stability
Foams deformed but did not burst or coalesce
log (compressive strength ) = log A + B log (foam density)Power Law:
Frisch KC. Journal of macromolecular science part A-chemistry,1981;15(6):1089-1112

28
Morphology
cell density(cells/cm3)
PUF coat-1 2.1×106
PUF coat-2 3.3×107
PUF coat-3 2.7×108
PUF coat-4 8.0×108
PUF coat-5 6.3×109
PUF coat-1 PUF coat-2
PUF coat-3 PUF coat-4
PUF coat-5
2/32







A
nM
N f
Average cell density
A : area of the micrograph
M: magnification factor
Zeng C et al. polymer,2010;51(3):655-664
Foam density
Cell density

29
Tack Property
Probe Material Analyzer : ASTM D2979
Pressure :100 g/cm2
Probe movement rate: 1 cm/s
Dwell time: 1 s

30
Adhesion
Zehntner Cross-cut tester: ASTM D3359

31
Scratch Resistance
Pencil Hardness Tester: ASTM D3363
45°
7.5 ± 0.1 N

32
Flexibility
Cylindrical Mandrel Bending Tester : ASTM D522
conical mandrel 1/8th inch

33
Durability
UV Condensation Weathering Device UV2000 (ATLAS) For 336 h
ASTM G154
Hunterlab Colorflex spectrophotometer
ASTM E313
Y
ZX
YI
)06.1-28.1(100

CIE XYZ

34
Peel Strength
ASTM F88
A constant rate : 30.48 cm/min
PUF coat-3
PUF coat-1
PUF coat-4
PUF coat-2
PUF coat-5
PUF coat-1
PUF coat-5
Sherman M. Medical device packaging handbook,1998
Suitable peel strength:454-1360 g/in

35
Air Permeability
Gurley air permeabilimeter
ISO 5636-5
Morris BA. Journal of plastic film and sheeting,2002;18(3):157-167

36
Experimental
Homogenizer
In-Situ Polymerization
UV Curing TMPEOTA Resin
Isopropyl Alcohol(IPA)
Photoinitiator
Electrical Conducting
formula
UV-Curable
Nanocomposite Coatings
UV-Cured
Nanocomposite Coats
Conductivity
Measurement
Morphology
Observation
Thermal Stability
Durability
Investigation
LUMiSizer
STEPTM
- Technology
25 ℃，1000 rpm，Δt=10s
PSD Dispersibility
Ultrasonication
30 min
Coated 10 μm on PET film
UV irradiation for 5 min
PPy
PPy/CB
PPy/CNT
PPy/CB/CNT
Py PPy
200 W, 20 KHz
30 min
FeCl3/Py molar ratio = 2.4

Materials/samples PPy PPy/CB PPy/CNT PPy/CB/CNT
TMPEOTA(g)
Pyrrole(g)
Carbon Black(g)
Carbon nanotube(g)
FeCl3(g)
IPA(g)
Photoinitiator(g)
100
15
─
─
8
50
10
100
15
10
─
8
50
10
100
15
─
10
8
50
10
100
15
5
5
8
50
10
37
Materials
•Trimethylolpropane ethoxylated (6) triacrylate (TMPEOTA), Miwon Commercial Co, Ltd.
•Pyrrole monomer, Acros Oragnics
•carbon black (VULCAN XC72), CABOT Co., Ltd.
•Multiwall carbon nantotube (VGCF-X), SHOWA DENKO.
•Iron(Ⅲ) Chloride,FeCl3, SHOWA chemicals.
•Photoinitiator (Chemcure-709), Chembridge International Co. Ltd.
TMPEOTA VULCAN XC72
PSD:~40 nm
VGCF-X
PSD:~100 nm

38
Dispersibility
PPy
PPy
CB
PPy
CNT
PPy
CNT
CB
Most stable
Dispersibility: PPy > PPy/CB> PPy/CNT > PPy/CB/CNT

39
Surface Morphology
PPy PPy/CB
PPy/CNT PPy/CB/CNT
PPy
PPy
CB
CNT
PPy
PPy
CNT
CB

40
~80 nm ~150 nm
~250 nm ~457 nm
Well-dispersed Slightly aggregated
aggregated Strongly aggregated
*CB: ~40 nm *CNT: ~100nm

41
Thermal Stability
TGA-Q500, TA Instruments
Heating rate of 10 ℃/min
Test temp. : 50~800℃
Decomposition temperature (℃)
@UV-Cured Resin
PPy 320℃&410℃
PPy/CB 350℃&450℃
PPy/CNT 400℃&465℃
PPy/CB/CNT 440℃&490℃
PPy
225 ℃
UV-Cured Resin
320℃ & 410℃
CB
535 ℃
CNT
680 ℃
Carrasco PM et al. Synthetic metals,2006;156(5):420-425

42
Durability
Scratch resistance: ASTM D3363
Adhesion resistance: ASTM D3359

43
Electrical Conductivity
2
3
0
32
36
)(
K
Lqf




Polypyrrole Conductivity
)(f )(f
L  FeCl3/Py molar ratio = 2.4
Broken L
Shorter L
increase
decrease
4.3×10-6 S/cm
8.3×10-5S/cm
3×10-4 S/cm
1×10-3 S/cm










CNTPPyCBPPy
CNTPPyCBPPy
series
//
//
2



PPy/CB/CNT Hybrid System
cal exp
1×10-3 S/cm 1.3×10-4 S/cm
Synergistic Effect
Cassignol C. Polymer,1999;40(5):1139-1151, Balta Calleja FJ.Journal of materials science,1988;23(4):1141-1415

44
Ultrasonication Effects
Stability measurement
More stable
~310 nm
Slightly aggregated
Conductivity: 0.45 S/cm
CNT
PPy
CB
Martin CA. Composites science and technology,2004;64(15):2309-2316

Conclusion
Established a complete dispersibility evaluation method and system for polymer-
based solution to characterize the relationship between dispersibility and performance
in polymeric nanosolutions.
1. Determination of optimum binder/dispersant ratios in monophase oil-based
polymeric nanosolution.
2. Determination of optimum processing in fabrication functional coatings based
on polymeric nanosolution.
3. Determination of foam structure/functional performance in water-based
polymeric nanofoam solution.
4. Established the correlation between dispersiblity and electrical conductivity of
triphase polymeric nanosolution in in-situ polymerization system.

The End
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The use of analytical centrifugation in the characterization

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