acs award lecture - princeton university

Colloidal Dispersions:Controlling Interactions

andUnderstanding the Consequences

William B. RusselDepartment of Chemical Engineering

Princeton University

Colloid and Surface Chemistry Award Lecture

in memory ofDudley A. Saville

1933-2006

March 2007

OUTLINE

Reflections on colloid science 1950-2000model particles and experimental toolsforces and phase behaviorrheology and dynamics

Recent interestshard sphere crystals and glassesfilm formation and cracking

model colloids experimental techniques principals

1956 polymer colloids Vanderhoff1968 silica Stöber1970 hydrous metal oxides Matijevic1974 dynamic light scattering Schaefer, Pusey, Pecora

modern rheometers Rheometrics, Inc., Deerelectrophoretic light scattering Ware

1978 surface forces Israelachvili1979 octadecyl silica de Kruif1983 light scattering under shear Ackerson and Clark

quantum dots Brus1986 PMMA/PHSA Ottewill1988 dielectric spectroscopy Saville

rheo-optics Fuller, WagnerSANS under shear de Kruif

1990 TIRM Prieve1991 colloidal probe AFM Ducker

ellipsoidal latices Carruthers, Keller, Ottewill1992 plates and rods Lekkerkerker, Philipse1995 confocal microscopy van Blaaderen, Wiltzius

model colloids principals








model colloids principals







ellipsoidal latices Carruthers, Ottewill, Keller1992 plates, rods Lekkerkerker, Philipse1995 confocal microscopy van Blaaderen, Wiltzius

experimental techniques principals





rheo-optics Fuller, Wagner, de Kruif1990 TIRM Prieve1991 colloidal probe AFM Ducker


Dso

Ds∞

I-Iocosθ

increasingshearrate

experimental techniques principals

1956 polymer colloids Vanderhoff1968 silica Stöber1970 hydrous metal oxides Matijevic1974 dynamic light scattering Schaefer, Berne, Pusey, Pecora







10 µm

forces phase transitions principals

1966 electrostatic Hogg, Healy, Fuerstenau1968 polymeric stabilization Napper1969 colloidal crystals Krieger, Hachisu1970 dispersion Ninham, Parsegian1973 self-consistent field Dolan, Edwards1978 charge regulation Healy, White1979 Brownian/shear-induced flocculation Higashitani, Schowalter1980 scaling de Gennes1981 depletion gas/liquid/solid Sperry, Vincent, Vrij, Gast1983 hydration Pashley, Israelachvili1984 fractal growth Witten, Weitz1985 lattice theory, brushes Scheutjens, Fleer, Tirrell1986 hard sphere crystal Pusey, van Megen

gelation Wiltzius, de Kruif1987 hard sphere glass transition van Megen, Pusey1988 compressed brushes Milner, Witten, Cates1992 two-component depletion Lekkerkerker, Pusey

associative brushes Milner, Witten1994 adhesive sphere gels/spinodal/fluid-solid Russel, Dhont, Zukoski1996 liquid crystal transitions Fraden, Lekkerkerker1997 slow Brownian flocculation Borkevec, Behrens1999 non-ergodic transitions Bergenholtz, Fuchs

forces principals

1966 electrostatic Hogg, Healy, Fuerstenau1968 polymeric stabilization Napper1969 colloidal crystals Krieger, Hachisu1970 dispersion Ninham, Parsegian1973 self-consistent field Dolan, Edwards1978 charge regulation Healy, White1979 rapid Brownian flocculation Higashitani

shear-induced flocculation Zeichner, Schowalter1980 scaling de Gennes1981 depletion gas/liquid/solid Sperry, Vincent, Vrij, Gast1983 hydration Pashley, Israelachvili1984 fractal growth Witten, Weitz1985 lattices & brushes Scheutjens, Fleer, Tirrell, Klein

hard sphere crystal Pusey, van Megengelation Wiltzius, de Kruif

1987 hard sphere glass transition van Megen, Pusey1992 two-component depletion Lekkerkerker, Pusey1994 adhesive sphere gel/spinodal/fluid-solid Russel, Dhont, Zukoski1996 liquid crystal transitions Fraden, Lekkerkerker1997 slow Brownian flocculation Borkevec, Behrens1999 non-ergodic transitions Bergenholtz, Fuchs

forces principals

1966 electrostatic Hogg, Healy, Fuerstenau1968 polymeric stabilization Napper1969 colloidal crystals Krieger, Hachisu1970 dispersion Ninham, Parsegian1973 self-consistent field Dolan, Edwards1978 charge regulation Healy, White1979 Brownian/shear-induced flocculation Higashitani, Schowalter1980 scaling de Gennes, Joanny1981 depletion gas/liquid/solid Sperry, Vincent, Vrij, Gast1983 hydration Pashley, Israelachvili1984 fractal growth Witten, Weitz1985 lattices & brushes Scheutjens, Fleer, Tirrell, Klein1986 hard sphere crystal Pusey, van Megen

gelation Wiltzius, de Kruif1987 hard sphere glass transition van Megen, Pusey1988 compressed brushes Milner, Witten, Cates1992 two-component depletion Lekkerkerker, Pusey

associative brushes Milner, Witten1994 adhesive sphere gel/spinodal/fluid-solid Russel, Dhont, Zukoski1996 liquid crystal transitions Fraden, Lekkerkerker1997 slow Brownian flocculation Borkevec, Behrens1999 non-ergodic transitions Bergenholtz, Fuchs

non-adsorbed polymer

grafted brush

Biggs

phase transitions principals

1966 electrostatic Hogg, Healy, Fuerstenau1968 polymeric stabilization Napper1969 colloidal crystals Krieger, Hachisu1970 dispersion Ninham, Parsegian1973 self-consistent field Dolan, Edwards1978 charge regulation Healy, White1979 rapid Brownian flocculation Higashitani

shear-induced flocculation Zeichner, Schowalter1980 polymer-induced de Gennes1981 depletion gas/liquid/solid Sperry, Vincent, Vrij, Gast1983 hydration Pashley, Israelachvili1984 fractal growth Witten, Weitz1985 lattices & brushes Scheutjens, Fleer, Tirrell, Klein1986 hard sphere crystal Pusey, van Megen

gelation Wiltzius, de Kruif1987 hard sphere glass transition van Megen, Pusey1992 two-component depletion Lekkerkerker, Pusey1994 adhesive sphere gel/spinodal/fluid-solid Russel, Dhont, Zukoski1996 liquid crystal transitions Fraden, Lekkerkerker1997 slow Brownian flocculation Borkevec, Behrens1999 non-ergodic transitions Bergenholtz, Fuchs

ADD SALT REDUCE SOLVENCY


1966 electrostatic Hogg, Healy, Fuerstenau1968 polymeric stabilization Napper1969 colloidal crystals Krieger, Hachisu1970 dispersion Ninham, Parsegian1973 self-consistent field Dolan, Edwards1978 charge regulation Healy, White1980 polymer-induced de Gennes1981 depletion gas/liquid/solid Sperry, Vincent, Vrij, Gast1983 hydration Pashley, Israelachvili1984 fractal growth Witten, Weitz1985 lattice theory Scheutjens, Fleer1986 polymer brushes Tirrell


1987 hard sphere glass transition van Megen, Pusey1992 two-component depletion Lekkerkerker, Pusey1993 adhesive sphere gels Chen, Russel1995 adhesive sphere spinodal Dhont1996 liquid crystal transitions Fraden, Lekkerkerker

fluid-solid adhesive spheres Zukoski1999 non-ergodic transitions Bergenholtz, Fuchs

polymer concentration




1987 hard sphere glass transition van Megen, Pusey1992 two-component Lekkerkerker, Pusey. Poon

depletion1993 adhesive sphere gels Grant, Russel1995 adhesive sphere spinodal/fluid-solid Dhont, Zukoski1996 liquid crystal transitions Fraden, Lekkerkerker1997 slow Brownian flocculation Borkevec, Behrens1999 non-ergodic transitions Bergenholtz, Fuchs

a/rg=12.5 fluid gel crystalgas-liquid liquid gas a/rg=1.75

fluid-crystal

A2-4

a/rg 0.54 0.97 1.52 3.37cpkgM3

gas-liquid gas-solid

2.8 2.5 2.2 1.4

5.0 5.0 5.0 5.0

10.0 10.0 Sperry 1984

Kose & Hachisu 1973

crystal

fluid

a/rg= 3

crystal

Gast, Hall, and Russel 1983

rheology principals

1964 Bingham stress Michaels, Bolger1972 hard spheres Krieger

pair interactions Batchelorshear thickening Hoffman

1974 wave-number dependent diffusion Schaefer, Pusey, Pecora1978 Brownian dynamics Ermak, McCammon

electrophoresis O’Brien, Whitecharged spheres Krieger, Russel, Buscall

1981 dielectric response White1984 associative polymers Rohm & Haas

Stokesian dynamics Bossis, Brady1986 consolidation of gels Buscall, White

dynamic Stern layer Saville, Zukoski1989 electrorheology Zukoski1991 adhesive hard sphere de Kruif

non-ergodic glasses van Megen, Pusey1992 thickening mechanism Brady1993 depletion / fluid Buscall1995 shear thickening Bender, Wagner1997 elasticity of gels Buscall, Russel, Zukoski2000 dynamic heterogeneities Weitz, Kegel,

in glasses van Blaaderen

fluid crystal

ηo

σc

η∞

cp




1987 hard sphere glass transition van Megen, Pusey1992 two-component depletion Lekkerkerker, Pusey1993 adhesive sphere gels Grant, Russel1995 adhesive sphere spinodal/fluid-solid Dhont, Zukoski1996 liquid crystal transitions Fraden, Lekkerkerker1997 slow Brownian flocculation Borkevec, Behrens1999 non-ergodic transitions Bergenholtz, Fuchs

crystal fluid glass

gel

metastable spinodal binodal

A2-4

rheology principals

1964 Bingham stress Michaels, Bolger1972 hard spheres Krieger

pair interactions Batchelorshear thickening Hoffman

1974 wave-number dependent diffusion Schaefer, Pusey, Pecora1978 Brownian dynamics Ermak, McCammon

electrophoresis O’Brien, Whitecharged spheres Krieger, Russel, Buscall

1981 dielectric response White1984 associative polymers Rohm & Haas

Stokesian dynamics Bossis, Brady1986 consolidation of gels Buscall, White

dynamic Stern layer Saville, Zukoski1989 electrorheology Zukoski1991 adhesive sphere fluid de Kruif

non-ergodic glasses van Megen, Pusey1992 thickening mechanism Brady1993 depletion / fluid Buscall1995 shear thickening Bender, Wagner1997 elasticity of gels Buscall, Russel, Zukoski2000 dynamic heterogeneities Weitz, Kegel,

in glasses van Blaaderen

!o

µ= 1+ 2.5" + 5.9" 2 +O " 3( )

!o

µ"( )

!"

µ#( )

a3!

o

kT"( )

total viscosity

hydrodynamic

Brownian

FLUIDS, GLASSES, AND CRYSTALSAdventures encountered while tagging along with Paul Chaikin

Princeton University Jixiang Zhu Martin Rutgers See-Eng Phan Zhengdong ChengNASA Glenn W.V. Meyer R.B. RogersBristol University R.H. OttewillCrews of Space Shuttle Columbia, STS-73, 83

CDOT Is the disorder-order transition affected by (µ−)gravity?

φ = 0.58 0.59 0.63

J. Zhu, et al.,Nature 387

883-885(1997)YES!

• dendritic growth of crystallites• crystallization of glasses

HARD SPHERE GLASS OR METASTABLE FLUID?

0.1

1.0

10.0

100.0

0 1 2 3 4 5 6 7

! /(0.64"! )

#$ %

PMMA/DT25/640nm

PMMA/DT20/640nm

PMMA/D25/640nm

PMMA/D20/640nm

PMMA/MS20/602nm

PMMA/MS20/475nm

SiO2/EGGly20/488nm

Doolittle

Adam-Gibbs

PMMA/PHSA/decalin 475, 602, 640 nmSiO2/ethylene glycol 488 mn

• simulations by Torquato - osmotic pressure diverges as Π~1/(0.64-φ ) no thermodynamic transition

• glasses crystallize in microgravity but not on earth

• measurements of (very) low shear viscosities by Phan and Cheng consistent with exponential divergence at φ = 0.64 a la Adam-Gibbs

non-ergodic transitionmode coupling theory

dynamic light scattering - van Megen, Pusey, Underwoodreal space dynamics via confocal microscopy - Weeks & Weitz, Kegel

dynamic arrestcrystallization or not - Pusey & van Megen, Zhu et al.(very) low shear viscosities - Phan and Chengreal space dynamics via confocal microscopy - Kegel

HARD SPHERE GLASSES

structural arrest crystals ηo <x2(∞)>

no crystals non-ergodic transition

DLS <x2(τ)>

MCT

perhaps…• structural arrest atrandom close packingφ = 0.64

• non-ergodic transitionat φ = 0.56-0.58

non-uniform evaporation

pressure driven flow

compression

tension

Film Formation, Non-Uniformities, and CrackingDriven by Capillary Pressure

early time

transparent film

water flows

stresses

CollaboratorsP.R. Sperry Rohm & HaasA.F. Routh *97 Cambridge Univ.M. Tirumkudulu IIT BombayWeining Man *05

Film Cracking: High Tg Particles 2a=342 nm hdry=79.5 µm 2a=95 nm hdry=101 µm E=2.5 µm/min, RH=66%, T=23.5 oC E=6.7 µm/min, RH=35%, T=24.4 oC

Simple and reproducible, but howto understand the mechanism?

Create uniform and controllablecapillary pressure field by

suppressing evaporation in apressure filtration cell

membranewater out

film porous support

gasTeflon o-rings polycarbonate

chamber

Capillary Pressure Required for Cracking

• energy criterion lower bound

• packing flawsinitiate cracks

• grain boundaries and notches nucleation sites

disordered packings

ordered packings

• pressure at first crack independent of particle radius variables two dimensionless variables ph/γ Gh/(1-v)γ p kg/m-s

one must be function of the other h m • energy criterion γ kg/s

G/(1−ν) kg/m-s

notched O-rings

crystal

!hpcap

crack

"# 2.0

Gh

1!$( )"%

&'(

)*

2 /5

Critical Thickness via Spin Coating

K.B. Singh & M.S. Tirumkudulu (in preparation)

• hypothesis: When capillary pressure exceeds 12.5γ/a withoutcausing cracking, the water front simply recedes into film.

}}Cima, et}al. 1993}

prediction

!pcapmaxh

"= 2.0

Gh

1!#( )"$

%&'

()

2 /5

* hcrit

a= 0.047

Ga

1!#( )"$

%&'

()

2 / 3

With thanks to

Priscilla on our 35th anniversary

my advisers, colleagues,students, and postdocs

the scientists and engineers who comprisethe international and interdisciplinary

colloids community

acs award lecture - princeton university

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