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« Applications of Colloids In Industry »
L. Hough, A. Alsayed ,C. Badre, R. Dreyfus,–Complex Assemblies of Soft MatterCOMPASS: UMI 3254
| 2
Outline
Introduction Introduction
11
44
22
Applications of “Soft” Colloids
Conductive Nanogels for Transparent Electrodes
Temperature Sensitive Microgels
Structured Surfactant Liquids for Cleansing
33
Applications of Attractive Colloids
Colloids and DNA
Silica in Tires
Asphaltenes in Crude Oil
HASE Polymers for Rheology Modification
Applications of Anistropic Colloids
Ellipsoidal Colloids for Inks and Paints
Carbon Nanotubes for New Materials
Silver Nanowires for Transparent Electrodes.
| 3
Introduction: Types of Colloidal Systems
Traditional Applications
Paints
Inks
Agriculture Formulations
Foods
| 4
Introduction: Two Modern Applications of Colloids: E-Paper
| 5
Introduction: Two Modern Applications of Colloids: Body Armor (Magnetorheological fluids)
| 6
Outline
Introduction11
44
22
Applications of “Soft” Colloids
Conductive Nanogels for Transparent Electrodes
Temperature Sensitive Microgels
Structured Surfactant Liquids for Cleansing
Applications of “Soft” Colloids
Conductive Nanogels for Transparent Electrodes
Temperature Sensitive Microgels
Structured Surfactant Liquids for Cleansing
33
Applications of Attractive Colloids
Colloids and DNA
Silica in Tires
Asphaltenes in Crude Oil
HASE Polymers for Rheology Modification
Applications of Anistropic Colloids
Ellipsoidal Colloids for Inks and Paints
Carbon Nanotubes for New Materials
Silver Nanowires for Transparent Electrodes.
| 7
Introduction: Phase Diagram of Colloids
| 8
Outline
Introduction11
44
22
Applications of “Soft” Colloids
Conductive Nanogels for Transparent Electrodes
Temperature Sensitive Microgels
Structured Surfactant Liquids for Cleansing
Applications of “Soft” Colloids
Conductive Nanogels for Transparent Electrodes
Temperature Sensitive Microgels
Structured Surfactant Liquids for Cleansing
33
Applications of Attractive Colloids
Colloids and DNA
Silica in Tires
Asphaltenes in Crude Oil
HASE Polymers for Rheology Modification
Applications of Anistropic Colloids
Ellipsoidal Colloids for Inks and Paints
Carbon Nanotubes for New Materials
Silver Nanowires for Transparent Electrodes.
| 9
Replacement of Indium Tin Oxide
Transparent electrodes = critical components of optoelectronic devices such as displays and solar cells
Indium Tin Oxide (ITO) = most used transparent conductive oxide Expensive Limited resources (indium) Not flexible required property for touch
screen and flexible displays [2]
Transparent conductive electrode
PEDOT:PSS High conductive polymer but not enough
Solution: Incorporate new additives in PEDOT:PSS
9 Q. Benito, July 21th 2011
W. Gaynor, G. F. Burkhard , M. D. McGehee , P.
Peumans , Adv. Mater. 2011, XX, 1–6
| 10
N+
N
CH3
CH3
[B(CN)4]-
Ionic LiquidEMIM TCB
PEDOT PSS / EMIM TCB system
additivescoating
Synthesis
Formulation
ILs & PEDOT:PSS are mixed
Easily processable dispersion
Conductive films prepared by spin coating
IL remains in the film after drying
LUBIANEZ, Organic Photovoltaics Conference: Heraeus Precious Metals Conductive Polymers Division, (2011)
| 11
PEDOT:PSS/IL vs PEDOT:PSS/DMSO
55 Ω/
168 Ω/
0.01
0.1
1
10
100
1000
0% 2% 4% 6% 8% 10%
wt% of additive
Res
ista
nce
(kΩ
/)
PEDOT:PSS/IL
PEDOT:PSS/DMSO
4 coating : R reaches 16Ω/€/€/€/€
1.5%DMSO 10 %
• PEDOT:PSS are more compact & connect together when IL are added
• SEM show that IL infiltrates between the particles and remain in the film
T >>>> 97%
ILs is the best additive providing:
the best resistance
an excellent transparency
the best mechanical properties
the best resistance to UV
a good resistance to environmental media
a good stability over time under N2
| 12
Formulation & Films
C. Badre et al. 2012 -
Advanced Functional Materials
96%
PEDOT:PSS + 1.5 wt% EMIM TCB
(single layer) on glass
RMS: 1.52 nm
ITO on glass
RMS: 3.27 nm
| 13
20)
21( −+=
dc
op
sR
ZT
σ
σ
• Z0 = 377 Impedance of free space
• σop & σdc optical and dc conductivities
• Our data σdc/σop = 185.2 ( T = 97% & R = 50 ΩΩΩΩ/square )
Alternative materials for ITO replacementrequirement : T > 90% Rs < 100 Ω/square Minimum industry standard σdc/σop > 35
185.2 is the highest value ever reported in the literature :
Typical values from literature:
σdc/σop ~ 13 for CNTs APL, 2010, 97, 023114
σdc/σop ~ 15 for composite CNTs films APL, 2010, 97, 023114
σdc/σop = 36.3 Adv. Funct. Mater. 2011, 21, 1076
97%
PEDOT:PSS/EMIM TCB composite films
Source: Advanced Functional Materials, C. Badre et al., March 2012
80
85
90
95
100
0
500
1000
1500
2000
2500
0 10 20 30 40 50 600
20
40
60
80
100
Co
nd
uct
ivit
y / S
cm
-1
EMIM TCB / wt%
Th
ickn
ess
/ nm
Tra
nsm
itta
nce
/ %
| 14
Organic Photovoltaic Devices
0 1 2 30
50
100
150
Sh
eet
res
ista
nce
(ΩΩ ΩΩ
/sq
ua
re)
wt % EMIM TCB in solution
0
2
4
RM
S R
ou
gh
nes
s (n
m)
ITO/PEDOT:PSS
4083
PEDOT:PSS
PH 1000
PEDOT:PSS +
5 wt% DMSO
PEDOT:PSS +
1.5 w% EMIM
TCB
Voc (V) 0.60 0.59 0.45 0.58
Jsc (mA/cm2) 8.29 0.0130 2.03 5.21
FF (%) 45.8 25.6 26.7 32.2
ECE (%) 2.4 0.003 0.24 1.02
-0.2 0.0 0.2 0.4 0.6 0.8-10
-5
0
5 ITO/PEDOT:PSS 4083 PH 1000 with additive B(1.5 wt%) PH 1000 with DMSO (5 wt%) PH 1000
Cu
rren
t D
ensi
ty(m
A/c
m2 )
Voltage (V)
ITO/PEDOT:PSS 4083PH 1000 + EMIM TCB (1.5 wt%)PH 1000 + DMSO (5 wt%)PH 1000
| 15
Increasing the conductivity of PEDOT:PSS Rhodia Formulation
Rhodia formulation >>>> 5000 S/cm
| 16
Polymeric Batteries
| 17
PEDOT:PSS with ionic liquid gels and foams
Possible ApplicationsPossible Applications Gels
Electro rheological Fluids
Foams
Electrodes for Batteries
Pressure Sensitive Switches
Biomedical devices and assays
Water Treatment
Scaffolding for Inorganic Catalysis
| 18
Summary
Technical positioningTechnical positioning
Source: NanoMarkets, Transparent conductor markets 2010, ITO & the alternatives, June 2010
2,4
17,1
-86%
By taking into account both material price and
cost of the process, transparent organics
solutions are expected to be fare less
expensive than ITO.
Further calculations to be done for each
COMPASS formulations
2010 material prices $/m²
ITO Transparent organics
Economical positioningEconomical positioning
+
COMPASS formulations Ionic Liquid
ITO
A transparent and conductive material
is efficient when combining high
transparency with low sheet resistance
COMPASS formulations & ITO are
competing in the same range
Total cost
(material & process)
TransparencyConductivity(2)
Flexibility
COMPASS formulations Silver Nanowires
150
50
Transparency %
Sheet
resis
tance Ω
/
100
93 98
| 19
Outline
Introduction11
44
22
Applications of “Soft” Colloids
Conductive Nanogels for Transparent Electrodes
Temperature Sensitive Microgels
Structured Surfactant Liquids for Cleansing
Applications of “Soft” Colloids
Conductive Nanogels for Transparent Electrodes
Temperature Sensitive Microgels
Structured Surfactant Liquids for Cleansing
33
Applications of Attractive Colloids
Colloids and DNA
Silica in Tires
Asphaltenes in Crude Oil
HASE Polymers for Rheology Modification
Applications of Anistropic Colloids
Ellipsoidal Colloids for Inks and Paints
Carbon Nanotubes for New Materials
Silver Nanowires for Transparent Electrodes.
| 20
Propyl group (hydrophobic)
acrylamidegroup (hydrophilic)
N-isopropyl Acrylamide Polymer
Increase
Temperature
~ 4% polymer ,
~96% water
Water flows out
NIPAM Microgel Particles
• Space filling
•Same performance with less material
Objective :Microgel particles that can give specific rheological performance in formulation at low
polymer levels
NIPAM Microgels: A Model System.
| 21
Melting 2 dimensional frustration
NIPAM Microgels: A Model System.
Alsayed, A.M., Islam, M.F., Zhang, J., Collings, P.J., Yodh, A.G., Premelting at defects within bulk colloidal crystals. Science 309,
1207-1210, (2005)
Han, Y., Shokef, Y., Alsayed, A.M., Yunker, P., Lubensky, T.C., and Yodh, A.G., Geometric frustration in buckled colloidal monolayers. Nature 456, 898-903 (2008).
| 22
Jamming Transitions and Aging in a colloidal glass
B. Abou (Laboratoire Matiere et Systemes Complexes, UMR 7057)
A. Al-Sayed
A. Yodh,
Z. Zheng
Zhang, Z., Xu, N., Chen, D.T.N., Yunker, P., Alsayed, A., Aptowicz, K.B., Habdas, P., Liu, A.J., Nagel, S., and Yodh, A.G., Thermal vestige of the zero-temperature jamming transition. Nature 459, 230-233 (2009)
COLIN R., ALSAYED A.M., CASTAING J-C., GOYAL R., HOUGH L.A., and
ABOU B., Soft Matter, 7 (2011) 4504
| 23
Outline
Introduction11
44
22
Applications of “Soft” Colloids
Conductive Nanogels for Transparent Electrodes
Temperature Sensitive Microgels
Structured Surfactant Liquids for Cleansing
Applications of “Soft” Colloids
Conductive Nanogels for Transparent Electrodes
Temperature Sensitive Microgels
Structured Surfactant Liquids for Cleansing
33
Applications of Attractive Colloids
Colloids and DNA
Silica in Tires
Asphaltenes in Crude Oil
HASE Polymers for Rheology Modification
Applications of Anistropic Colloids
Ellipsoidal Colloids for Inks and Paints
Carbon Nanotubes for New Materials
Silver Nanowires for Transparent Electrodes.
| 24
UseBase Formulations for-Body Wash-Hand Soap-Facial Wash-Shampoo
Performance:- stabilizes high amounts of actives like oil/fragrance- rich and creamy foam in presence of oil- creamy and lotion-like texture- easy to formulate
| 25
Lamellar phase in high active blend
pH, Salt
(Shear)
Spherulites (SSL)
Rhodia’s Miracare SLB products are novel surfactant blends
D. Roux
Dilute
(water)
Micellar Phase
- NOT in thermodynamic equilibrium- Spherulitic structure stable over a long time - Rheology behavior : shear thinning with yield stress
SSL PROPERTIES
| 26
Relaxation
Long Time, High
Temperature
Lamellar
Structured Structured
Agitation
Formation of Spherulites
Cross polarizers
| 27
Analogy to Emulsions
F
Increase of the volume fraction
Compression with a force F
Strain ~ (Φ-ΦC)
Increase of the volume fraction
| 28
Rheology of Emulsions
Volume fraction Φ dependence on the static shear modulus G G ~ Φ2(Φ-Φc)σ/R, Φc where droplets first deformed random close packing
- Φ<Φc: undeformed droplets- Φ>Φc: deformed droplets
Laplace pressure = (2σ/R) Control of the deformation Essential role of the interfacial energy
Low frequencies G”(ω) peak = crossover from solid-like to liquid-like
structural relaxationSlip regions: disorder of the droplets packing
PRL Mason, September 1995
PRE Mason, September 1997
PRL Mason, April 1996
))(1( 2/1 γηγτσσ &&∞++= y
| 29shear rate (1/s)
10-2 10-1 100 101 102 103 104
visc
osi
ty (
Pa
s)
0.01
0.1
1
10
10025% SLB 365 increasing rate25% SLB 365 decreasing rate
1
2 3a
3b
shear rate (1/s)
10-2 10-1 100 101 102 103 104
visc
osi
ty (
Pa
s)
0.01
0.1
1
10
10025% SLB 365 increasing rate25% SLB 365 decreasing rate
1
2 3a
3b
Very strong hysteresis must be due to spherulites formationsWe recover nearly the same behavior as before heating
Rheology of the Formation of Spherulites
| 30
Why do Spherulites form?
1) lamellar phase + shear ⇒⇒⇒⇒ spherulites
γγγγ.
3
2+3
φφφφmembran
21polycristalline
(non aligned) lamellar phase
aligned smecticphase
Spheruliticor onionphase
Orientation Diagram ofLamellar Phase under Shear
(D.ROUX et al.)
shear
several surfactant systems known (e.g.):- AOT (+salt/cosurfactants)- cocodiethanolamide- SDS/alcohol/alkane
2) elasticity of bilayer important
vesicularphase
sponge
κκκκ< 0< 0< 0< 0 > 0> 0> 0> 0Micellarphaseκκκκ
φφφφmembrane
polycristallinesmectic phase
((((Roux & Candau 1994)
Phase diagram (at rest) as a functionof bilayer Gaussian moduli
κ : saddle-splay motionκ : amplitude of motion (high κκκκ ⇒⇒⇒⇒ stiff)
κκκκ
elastic stiff elastic
κκκκ
κκκκ
packing parameter P defines curvature
P=1 favors lamellar, P=<1 favors vesicles
| 31
SAXS (small angle X-ray scattering)
|q| = 4π/l*sin(q/2)
X-ray beam
l = 1.54 A
q
Scattering Vector:
sample detector
Information about Phase Structure:Lamellar
Hexagonal
q
⇒⇒⇒⇒ Scattering Intensity: I = S(q)⋅⋅⋅⋅P(q)
Information about Building Blocks:Bilayer
Cylinder
Nanostructure of Spherulites: X-ray Scattering
| 32
Nanostructure of Spherulites: X-ray Scattering
dB
Tkq B
/8
2*
κκκκππππηηηη ====
These data allow us to extract the rigidity product (κκκκB) and the lamellar spacing (d).
| 33
c (wt%)
5 10 15 20 25 30 35
sqrt
(KB
bar
) (P
a m
)
0
20x10-6
40x10-6
60x10-6
80x10-6
100x10-6
120x10-6
140x10-6
c (wt%)
5 10 15 20 25 30 35
d (
m)
02x10-9
4x10-9
6x10-9
8x10-9
10x10-9
12x10-9
14x10-9
16x10-9
Elasticity increases with the concentration
Lamellar spacing decreases with the concentration
X-Ray Scattering
Effective surface tension ~ BK
| 34
Size by Microscopy
FFT mode
280
300
320
340
360
380
400
420
440
0.00E+00 2.00E-02 4.00E-02 6.00E-02 8.00E-02 1.00E-01
Q (Å-1)
I
Obtain Qpeakvalues ~ Radius
| 35
Conductivity – Volume Fraction of Spherulites
Relation between the volume fraction and the conductivity:
concentration (wt%)
0 5 10 15 20 25 30 35
volu
me
frac
tio
n (
φφ φφ)
0.0
0.2
0.4
0.6
0.8
1.0RCP 0.64
0
0
21
1
χ
χ
χ
χ
+
−
=Φ
•10-12% SLB365: undeformed
droplets
•15-30% SLB365: deformeddroplets
| 36
Two Kinds of Rheological Measurements
Viscosity G’, G”
Steady shear rate
sample
Oscillations withincreasing amplitude orfrequency
Steady rate sweep test Dynamic sweep test
• Steady rate sweep test:
• non-linear
• shear rate amplitude
• Dynamic sweep test:
• linear
• angular frequency amplitude atconstant strain / strain amplitude at constant angular frequency
• Different instruments:
• cone: same shear profile
• rough plates: avoid slip
| 37
Rheology of Spherulites
ωωωω (rad/s)
10-3 10-2 10-1 100 101 102 103
G' a
nd
G''
(Pa)
1
10
100G' 15%
G'' 15%
shear rate (1/s)
10-3 10-2 10-1 100 101 102 103
stre
ss (
Pa)
1
10
10015%
15%SLB365-3%NaCl
No phase separation
))(1( 2/1 γηγτσσ &&∞++= y
ωηπ
ω
πω
∞+=
=
xGG
xGG
x
x
2cos"
2sin'
Higher yield stress
| 38
ωωωω (rad/s)
10-4 10-3 10-2 10-1 100 101 102
G' a
nd
G''
(Pa)
0.01
0.1
1
10
100
15% G' 15% G'' yield strain
Strain amplitude
15wt% of Miracare SLB365
• low frequencies, G'>G": solid-like
•G" reaches a peak before decreasing
•cross-over between the two moduli: yield strain
•after this limit G">G':
liquid-like
Rheology of Spherulites
| 39
Spherulite – Emulsion Analogy
φφφφ2222 (φ−φ (φ−φ (φ−φ (φ−φc) ) ) )
0.01 0.10 1.00
G*R
/sq
rt(K
Bb
ar)
0.1
1.0
10.0
Effective surface tension ~ BK
)(~'2
CR
BKG Φ−ΦΦ
dK
κ=
elasticity
lamellar spacing
φ−φφ−φφ−φφ−φc
10-1 100 101
yiel
d s
trai
n
0.01
0.10
1.00
Cy Φ−Φ~γBehavior of an emulsion
Structural disorder and metastability
| 40
strain/φφφφ-φφφφc
10-3 10-2 10-1 100 101 102stre
ss(R
/sq
rt(K
Bb
ar))
φφ φφ2 *(
φφ φφ- φφ φφ
c)2
0.01
0.1
1
10
10022%
25%
30%
20%
Master Curve for the flow behavior of Spherulites
22 )(~ CyR
BKΦ−ΦΦσ
γσ G=
Cy Φ−Φ~γ
Rheology: elasticity, radius and volume fraction
)(~' 2
CR
BKG Φ−ΦΦ
| 41
))(1( 7.0τγσσ &+= y
Flow Behavior of Spherulites
Spherulitic systems have a well defined yield stress, allowing for suspension of additives and a lotion-like texture.
γτγτγτγτ
10-510-410-310-210-1 100 101 102 103 104
σ/σ
σ/σ
σ/σ
σ/σ
00 00
10-1
100
101
102
103
10 wt%15 wt%20 wt%25 wt%35 wt%
1+(γτγτγτγτ)0.7
Master Curve
| 42
Summary
e
δ,δ,δ,δ,ττττe
δ,δ,δ,δ,ττττ d
Macroscopic Microscopic Nanoscopic
•We have found well defined relationships between the microscopic dynamics of spherulites and the bulk relaxation processes.
•We have found well define relationships between bulk rheologyand nanoscopic properties, such as the elasticity of the bilayer.
•Knowledge of the fundamental mechanisms governing the formation of spherulites allow us to design more robust surfactant blends to meet the growing needs of the consumer.
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