The excitement of watching paints dry

Mahesh S Tirumkudulu
Department of Chemical Engineering

Coating Flows
Cracking in Geological Systems

FLUID MECHANICS COLLOIDS & INTERFACES SOLID MECHANICS

Atomization

Film Formation and Cracking in Films

Craquelure

Film Formation & Cracking

Paints contain pigments, binder, solvents, additives Traditional paints contained volatile organic compounds VOCs soften particles during deformation, BUT VOCs are health hazard, regulation to limit their use.
Evaporation thickness Drying Particle deformation

coalescence

pigment

binder (polymer particles)

cracking

Latex: Water-borne dispersion

(rcp)
2! wa rc

Drying
uniform evaporation
P="

transverse flow

transverse flow

Capillary rise
P =0

P="
P = 0!

2# wa R

!
! 2R

Coffee ring problem

Particle Deformation
Liquid menisci

F
spring Equivalent ! model film

F = kx
linear

F ! ~ G# 2 2 "R
non-linear

!
Network of springs

G: particle modulus : strain

Particle pairs replaced by non-linear springs

Drying and Cracking

Polymer particles (350 nm) in water

microscope

~500 microns

Why do drying films crack ?

"1 "2
Drying film Bimetallic strip ! ! !

Low pressure

("1 > " 2 )

If the metal films are separate when cooled :

For the bimetallic strip :

Tensile Compressive

Measurement of Transverse Stress

laser

" xx

3 hs G! = 6 L f H (H + hs )

position detector

hs : substrate thickness H : film thickness Lf : length of film G : Youngs modulus of substrate

latex dispersion

mirror

substrate

(a)

(b)

(c)

(d)

0.6

Non-lm forming dispersion

(c)

(e)

Critical Cracking Stress

(d)

0.5

0.4

(b)

# ! Ro $ % & 2" (0.2 '

0.1

0.3

(a) (e) (f)

(f)

0 0 -0.1 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

t * t E /(h o (1 + )o ))

Critical Stress for Cracking

Stress-Strain relation

" ~ G# 2

!
h
!o

(Stress=modulus x strain2)

!
substrate

Recovered Elastic energy, !

E elastic ~ h 2"#

(~stress x strain x vol) Increase in Surface energy, E

surface

menisci

~ "h
2 3

Critical Stress for cracking,

" c ~ G (# h )

1 3

!
Elastic energy = Surface energy
!

Critical stress vs. film thickness

1

# ! c ,i Ro $ % & ' 2" (

0.1

Identical particles
PPG342: Experiment PPG342: Short time limit PPG342: Long time limit GMA610: Experiment GMA610: Short time limit GMA610: Long time limit
1 3 2 3

" c ~ G (# h )

!
100 1000

0.01 10

# h ) $ N *% o o & ' 2 Ro )c (

(Tirumkudulu & Russel, Langmuir, 2005)

Critical Cracking Thickness

Maximum Crack Free thickness
P =0

P="
Height (Angstroms)

2# wa R

P = 0!

Maximum Crack Free Thickness

A B

menisci
Scan Length (mm)

(Styrene Butadiene particles, 2Ro=250 nm, Tg=65 oC)

" ~ G (# h ) ~ $Pmax % h ~

1 3

2 3

#G

1 2 3 2

($Pmax )

10

-3

Stress-Limited Regime
acrylic styrene-butadiene silica alumina polystyrene zirconia hmax = 0.41 ( GM!rcpR3/2")1/2

Identical particles

10
max h , (m)

-4

10-5

Acrylic: 82-353 nm; 0.8 GPa S-B: 250 nm; 1.0 GPa Silica: 22, 330 nm; 31 GPa Alumina: 230-489 nm; 156 GPa Polystyrene: 300 nm; 1.6 GPa Zirconia: 200 nm; 81 GPa

max h /R

102

10-6

101 10
3

hmax = 0.64 % % (
10
4

3 # GM !rcp Ro

1 $2

2"

# 2" & % & & ( ' Pmax Ro ) )

3 $2

10

10

10-7 10-13 10-12 10-11 10-10

GM!rcp R / 2 "

10-9

10-8

10-7

10-6

GM!rcpR3/2" , (m2)

Gives a guideline for formulation of paints & coatings

(Singh & Tirumkudulu, Phys Rev Lett, 2007)

Multiple Cracks
1.E-01

Crack spacing vs Thickness

Alumina, 13nm (Shorlin) PMMA, 95nm (MT&WBR)

1.E-02 Styrene-Butadiene, 250nm (IITB) Acrylic, 82nm (IITB) 1.E-03

2W (m)

Acrylic, 133nm (IITB)

1.E-04

2W = 3.4076 h

1.E-05

1.E-06 1.E-06

1.E-05

1.E-04

1.E-03

1.E-02

Thickness:

h (m)

Latex Blends
Closer to real paints and coatings Mixture of hard and soft particles: pigments and binder How to predict the mechanical properties of such a film ? What is the effective modulus ? Will the same theoretical framework apply to blends ?

Singh et al, Langmuir 2009(a,b)

Conclusions
Capillary pressure is responsible for cracking. Scaling for the critical stress for an isolated crack agrees well with experiment for stable dispersion. Critical cracking thickness, measurements agree with predictions Blends-mixed results, more theoretical work required

Acknowledgement
Students
Karnail Singh (PhD) Laxman Bhosale (MTech) Girish Deoghare(DD) V Ranganath (MTech) Arijit Sarkar (PhD student) T Venugopal (MTech student)

Collaborators
Martin Murray (AkzoNobel)

Funding
DST, India AkzoNobel, UK