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. regulation to limit their use. BUT •VOCs are health hazard. binder. Evaporation thickness Drying Particle deformation coalescence pigment binder (polymer particles) cracking Latex: Water-borne dispersion . additives •Traditional paints contained volatile organic compounds •VOCs soften particles during deformation. solvents.

(φ≥φrcp) 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 F F F = kx “linear” ! ! F ! ~ G# 2 2 "R “non-linear” ! Network of springs ! G: particle modulus ε : 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 : Young’s modulus of substrate latex dispersion mirror α substrate .

1 0.5 0.(a) (b) (c) (d) 0.5 0.1 0.9 1 ˆ t * t E /(h o (1 + )o )) .1 0.2 0.2 ' 0.6 0.6 Non-film forming dispersion (c) (e) Critical Cracking Stress (d) 0.3 0.8 0.4 (b) # ! Ro $ % & 2" (0.4 0.3 (a) (e) (f) (f) 0 0 -0.7 0.

E surface menisci ! ~ "h 2 3 •Critical Stress for cracking. " c ~ G (# h ) 1 3 ! Elastic energy = Surface energy ! . ! E elastic ~ h 2"# (~stress x strain x vol) •Increase in Surface energy.Critical Stress for Cracking •Stress-Strain relation " ~ G# 2 ! h !o (Stress=modulus x strain2) ! substrate •Recovered Elastic energy.

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. 2005) .Critical stress vs. film thickness 1 # ! c .i Ro $ % & ' 2" ( 0. Langmuir.

2Ro=250 nm.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. 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. Phys Rev Lett. 31 GPa Alumina: 230-489 nm. 1.64 % % ( 10 4 3 # GM !rcp Ro 1 $2 2" # 2" & % & & ( ' Pmax Ro ) ) 3 $2 10 5 10 6 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" . 2007) .6 GPa Zirconia: 200 nm. (m2) Gives a guideline for formulation of paints & coatings (Singh & Tirumkudulu.41 ( GM!rcpR3/2")1/2 Identical particles 10 max h . 0. 156 GPa Polystyrene: 300 nm. (m) -4 10-5 Acrylic: 82-353 nm. 1.0 GPa Silica: 22.8 GPa S-B: 250 nm. 81 GPa max h /R 102 10-6 101 10 3 hmax = 0. 330 nm.

E-04 1.E-04 2W = 3.Multiple Cracks 1.E-03 2W (m) Acrylic.E-05 1. 82nm (IITB) 1.4076 h 1.E-06 1.E-06 1. 13nm (Shorlin) PMMA.E-03 1.E-02 Styrene-Butadiene. 95nm (MT&WBR) 1. 250nm (IITB) Acrylic. 133nm (IITB) 1.E-01 Crack spacing vs Thickness Alumina.E-02 Thickness: h (m) .E-05 1.

b) . Langmuir 2009(a.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.

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

India AkzoNobel. UK .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.

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