You are now at www.wernerblank.com HOME NEWS PUBLICATIONS LECTURES PATENTS DOWNLOADS Polymer Fundamentals for Coatings Werner J. Blank King Industries Inc Science Road Norwalk, CT 06852 wblank@kingindustries.com werner@wernerblank.com
7000 RESIN CONSUMPTION 1985-1997 6000 5000 4.6 % SPECIAL MM lbs 4000 3000 2000 3.5 % ARCHIT OEM 1000 0 1985 1997 Year SL2375
COATING FORMULATIONS POWDER SYSTEM UV CURE WATERBORNE HIGH SOLIDS LOW SOLIDS WATER SOLVENT PIGMENT RESIN 0 20 40 60 80 100 WEIGHT, % SL2376
700 SOLVENT CONSUMPTION ACTUAL & PREDICTED GALLON MM 600 500 400 300 200 100 THINNERS WATER BASED SOLV BASED 0 85 act 90 pred. 97 act 02 pred YEAR SL2374
OEM RESINS LBS. 2002 APPLICATION Automotive Machinery Paper Can Furniture Wood Plastic Coil Electric Appliance Marine Transportation Miscellaneous 0 100 200 300 400 RESIN, MM. lb. SL2367
RESINS OEM 2002 MM. LB POLYESTER RESIN TYPE ACRYLIC EPOXY ASPHALT PVC ALKYDS POLYURETHANE 0 200 400 RESIN, MM. lb. SL2370
RESINS OEM 2002 MM. LB RESIN TYPE OTHER PVACET PVDC SILICONE CELLULOSICS POLYIMIDE ELASTOMER 0 20 40 60 RESIN, MM. lb. SL2371
Specialty Coatings 2002 RESINS MM. LB APPLICATION Military Camouflage Aerosol Fire Retardant Traffic Paint Automotive Refinishing Industrial Maintenance 0 100 200 300 RESIN, MM. lb. SL2369
RESINS SPECIALTY 2002 MM. LB RESIN TYPE ACRYLIC EPOXY ALKYDS POLYURETHANE OTHERS ISOCYANATE POLYESTER SILICONE PVACET NITROCELLULOSE PVC 0 50 100 150 200 RESIN, MM. lb. SL2373
ARCHITECTURAL 2002 RESINS MM. LB APPLICATION Other Exterior SB Exterior WB Interior SB Interior WB 0 200 400 600 RESIN, MM. lb. SL2368
RESINS ARCHITECTURAL 2002 MM. LB RESIN TYPE ASPHALT PV ACETATE ACRYLIC ALKYDS URETHANES OLEORESINS EPOXY NITROCELLULOSE SHELLAC SBR PVDC 0 200 400 600 RESIN, MM. lb. SL2372
Architecture Linear
Branched
Highly branched
Dendrimer
Random Copolymer Flexible
Block Rigid - flexible
Homo polymer Rigid
Alternating
Flexible
Structure Glass Transition Temperature Mobility of polymer chains Free volume Molecular weight Functional groups Crosslinking Tg Viscosity Physical properties Chemical properties
Tg of copolymer 1 Tg = W 1 + Tg 1 Tg 2 + Tgn W n = weight fraction
WLF Equation log η T = 13-17.44(T-Tg) 51.6+(T-Tg) η = Poise T, Tg = K or C L.E.Nielsen, Polymer Rheology, Marcel Dekker, 1977, pp33,74,133
VISCOSITY, POISE 1E6 1E5 1E4 1E3 1E2 1E1 1E0 VISCOSITY as a FUNCTION OF Tg WILLIAMS,LANDEL,FERRY EQUATION Tg of polymer 17 7-13 -33-53 -73 1E-1 0 20 40 60 80 100 TEMPERATURE C SL1513bw
300 250 k=25000 Tg vs MOLECULAR WEIGHT OF OLIGOMERS 200 Tg in K 150 100 50 k=50000 0-50 k=100000 Tgo = Tg- K Mn -100 0 500 1000 1500 2000 2500 MOLECULAR WEIGHT SL1504
VISCOSITY vs. HYDROXYL CONTENT NPG/TMP/DIBASIC ACID VISCOSITY (POISE) 400 300 200 100 220 210 200 190 Tg 0 0 1 2 3 4 5 HYDROXYL mol/1000 180 Visc. Tg
WLF Equation log η T = 13-17.44(T-Tg) 51.6+(T-Tg) Tg s =C o -C 1 xw s
VISCOSITY OF K-FLEX UD-320-100 VISCOSITY, LOG POISE, 25 C 5 3 1 Tgs = C 0 -C 1 xws C 0 = 243.9 C 1 = 365 Methanol C 1 = 339 Water C 1 = 320 Acetone C 1 =239 Bu-acetate -1 0 0.1 0.2 0.3 0.4 WEIGHT FRACTION OF SOLVENT SL1507 METHANOL WATER ACETONE BU ACETATE
Polyurethane polyol 100 1E1 1E2 1E3 1E4 MOLECULAR WEIGHT 90 80 70 60 50 40 30 20 10 0
Viscosity and MW log η = Α + C x Mw 1/2 Number average chain length P.J.Flory J.Am.Chem..Soc., 62, 1057 (1940)
4 VISCOSITY OF POLYESTER BLEND AT 109 C VISCOSITY (log POISE) 3 2 1 0 50 100 150 200 TIME IN MINUTES at 109 C MEASURED DATA POINT SL2307
Solubility Parameter Interaction parameter Cohesive energy Hildebrand, Prausnitz Hansen parameter δ 2 = δ d 2 + δ p 2 + δ h 2
Interaction parameter Weak Poly.-Sol. Strong Poly.-Sol.
Solubility Parameter Solvent WATER METHANOL 2-METHOXYPROPYLENE GLYCOL N-BUTANOL 2-BUTOXYETHANOL ACETONE BUTYL ACETATE 2-METHOXYPROPYLACETATE METHYLISOBUTYLKETONE TRICHLOROETHYLENE m-xylene OCTANE 0 20 40 cal 1/2 cm -3/2 Dispersion Polar Hydrogen SL2386
Solubility Parameter Resin EPOXY MW 1000 CELLULOSE ACETATE HMMM PV ACETATE NITROCELLULOSE PMMA ALKYD SHORT POLYISOBUTYLENE ALKYD LONG POLYSTYRENE 0 5 10 15 cal 1/2 cm -3/2 Dispersion Polar Hydrogen SL2387
Waterborne Coatings Soluble Dispersion
Waterborne coatings Acid number Appearance Soluble 50-200 Clear Colloid 20-50 Turbid Dispersion 0-20 White
VISCOSITY OF DISPERSION 1E3 VISCOSITY 1E2 1E1 1E0 1E-1 Continous phase 0 0.1 0.2 0.3 0.4 0.5 VOLUME FRACTION SPHERE SPH SW SPH FLOC SL2094
Mooney Equation k e V i log η =log η e 2.303 (1- Vi/θ) η e = viscosity of medium k e = shape constant (2.5) θ = packing factor Vi = volume fraction
Coalescence
Crosslinking Creation of networks + solvent resistance hardness chemical resistance durability flexibility Tg - elongation flexibility
NETWORK FORMATION A4 + B2 DEGREE OF POLYMERIZATION 10 8 6 4 2 0 Ws Mw Mn P(X4) P(X3) 2 1.8 1.6 1.4 1.2 1 0.8 0.6 0.4 0.2 0 FRACTION 0 0.2 0.4 0.6 0.8 1 CONVERSION
8000 STRESS-STRAIN FRONT FACTOR = 1 STRESS, PSI 6000 4000 2000 0 1 1.1 1.2 1.3 1.4 EXTENSION RATIO \ HILTON93\ NETWO RK3\ EXTENSION 500 1000 1500 2000 SL1707
SWELL RATIO
SWELL RATIO AND MWxl MW between X-LINKS 3000 2500 2000 1500 1000 500 0 1 1.1 1.2 1.3 1.4 1.5 LINEAR SWELL RATIO HILTON\ SWELCOM1 SL1757
POLYMERS CHAIN GROWTH FREE RADICALS ACRYLIC, VINYL STEP GROWTH CONDENSATION POLYESTER, ALKYD EPOXY MELAMINE
CHAIN GROWTH FREE RADICALS ACRYLIC, VINYL R O O R' n R= -H, -CH 2 CH 2 OH, C 1 -C 8
STEP GROWTH CONDENSATION Polyester R-OH + R COOH R-OCOR +H 2 O Epoxy O O O OH O O O
Acknowledgment King Industries Inc. wblank@kingindustries.com werner@wernerblank.com