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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)

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Outline

Introduction11

44

22









33


Colloids and DNA

Silica in Tires







| 7

Introduction: Phase Diagram of Colloids

| 8

Outline

Introduction11

44

22









33


Colloids and DNA

Silica in Tires







| 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

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Outline

Introduction11

44

22









33


Colloids and DNA

Silica in Tires







| 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

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Outline

Introduction11

44

22









33


Colloids and DNA

Silica in Tires







| 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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