Film Formation from Latexes
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1 Film Formation from Latexes CHEM 550, Spring 2006 San Luis Obispo polymerscoatings.calpoly.edu Latex film formation Water Evaporation (Depends on Humidity) Particle Deformation Driven by capillary forces as final water evaporates Polymer Diffusion Rarely Fully Achieved Note: Particle deformation and polymer diffusion usually require coalescing solvents to achieve hard films with good mechanical properties. Too high humidity can result in too much coalescent evaporation before the water evaporates. California Polytechnic State University 1
2 Minimum Film Formation Temperature (MFFT, MFT) Important Factors Controlling MFFT Tg Plasticizer (Coalescent) Water Plasticization Particle size Particle size distribution Surface Tension Interfacial Tension Capillary forces Double layer California Polytechnic State University 2
3 Visschers, et al., JCT (2001) Film Formation Analytical Tools MFFT BAR SAN SAX AFM Fluorescence California Polytechnic State University 3
4 Coalescents Hoy (JPT, 1973) Solvent Tg effect Fox equation to determine Tg of swollen polymer Sovent Partitioning between water and latex polymer Taylor and Klots (PCI, 2002) Tg of a large number of solvents Relative evaporation rates California Polytechnic State University 4
5 Interfacial Material Volume Particle Diameter (nm) Interfacial Volume Fraction Dispersed particle volume fraction is 0.3 in all cases Latex Film Formation Mechanism Dillon, Matheson, and Bradford (JCS, 1951) Coalescence results from polymer interfacial tension sufficient to overcome the viscous force Excess Pressure from Young Laplace eqn. Brown (JPS,1956) Interfacial tension forces are secondary Dillon et al. polymer-water interfacial tensions (25-30 dyne/cm too high) Capillary forces are more in the range Introduced maximum modulus for film formation California Polytechnic State University 5
6 Latex Film Formation Mechanism Voyutskil (JPS,1958) Added importance of autohesion (mutual interdiffusion of free polymer ends across particleparticle surface) Vanderfoff (BPJ,1970) surface tension & capillary are complimentary Other more important radii of curvature must be taken into account Evidence for autohesion and fate of emulsifier Film Formation Theory Visschers, Laven, and van der Linde (JCT, 2001) Easy route vs hard route Kan (1999) Role of particle size on latex deformation Tg versus MFFT Address conflicting results on particle size dependence of film formation Water plasticization California Polytechnic State University 6
7 What happens to additives? Moving drying front can concentrate surfactants, etc. at last point to dry Surfactants migrate to film-air or filmsubstrate interface El-Aasser et al. (JCT, 2001) Reactive surfactant sodium dodecyl allyl sulfosuccinate Urban (POC, 2000) ATR studies on waterborne urethanes Kan, JCT (1999) California Polytechnic State University 7
8 Cross-Linking & Film Formation Epoxy-amine Isocyanate-polyol Acetoacetate-amine Other California Polytechnic State University 8
9 Cross-Linking & Film Formation Competition between cross-linking and film formation Pot life versus cure time 1K systems Film Formation Vs Cross-Linking (JCT, 1998) California Polytechnic State University 9
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