Chartwell International, Inc. “Adhesion Promotion for Waterborne and Solventborne I nks, Coatings, Adhesives & Powder Coatings” Presented by: Adrian Thomas Chemicalia Pty Ltd
Adhesion Definition: W a = F ∆ x The energy or work required when an external stress is applied to two, separate joined materials. 2
The Importance of Adhesion W c1 : cohesive strength of adherend (substrate) 1 W c2 : cohesive strength of adherend (substrate) 2 W a1 : adhesive strength (energy required to separate the adhesive from adherend (substrate) 1) W a2 : adhesive strength (energy required to separate the adhesive from adherend (substrate) 2) W a1 > W c1 and W a2 > W c2 3
Adhesive and Cohesive Failure 4
Theories of Adhesion Physical Adsorption Theory Chemical Bonding Theory Diffusion Theory Electrostatic Theory Mechanical Interlocking Theory Weak Boundary Layer Theory 5
Chemical Bonding Theory E + - = z 1 z 2 e 2 4 πε 0 ε r r where: E + - = Potential Energy of two ions of charge z 1 e and z 2 e separated by distance r ε r = Relative Permittivity (Dielectric Constant) of the medium ε r air = 1.00054 ε r water = 80.1 at 20°C 6
WJ Funke (Stuttgart University) Studied the specific phenomena of corrosion on coated metals. Concluded that wet adhesion is the most important factor for corrosion protection of metal surfaces. Although the coating film serves as a barrier, retarding access of water and oxygen to the metal surface, all films have capillaries and pores through which water, oxygen, and salts will pass, driven by a concentration gradient. 7
Flexural Strength (Mpa) Retention with Selected Silane Coupling Agents (Adhesion Promoters) on Glass Fibre Reinforced Polyester Treatment Dry Wet % Retention None 386 240 62.2 Ethyltrichlorosilane 238 179 75.2 Allyltriethoxysilane 399 402 100.7 Methyacryalto chrome 502 427 85.1 8
Effect of Silane Coupling Agents (Adhesion Promoters) on the Adhesion of Glass Fibres to an Epoxide Resin Silane Change (% ) in interfacial shear strength Silane 1% 5% solution solution N-(2-Aminoethyl)- 62 -14 aminopropyltrimethoxysilane (AAMS) 3-Aminopropyltrimethoxysilane (APMS) 17 -20 9
Use of Coupling Agents or Adhesion Promoters 1. Primer 2. Incorporated into binding polymer 10
Reaction of APMS with the Surface of Glass 1. Hydrolysis of –Si(OCH 3 ) 3 (Trimethoxy) to –Si(OH) 3 (Trisilanol) – fast. 2. Condensation polymerization of Trisilanol and surface –OH groups to produce polysiloxane network covalently bonded to surface - slow. 11
Aqueous Stability of Chartwell B-515.4W v. Dow Corning Z-6020 Upper right: Fresh 2% aqueous Upper left: Fresh 2% aqueous solution of DC Z-6020 solution of B-515.4W Lower left: 2% aqueous solution Lower right: 2% aqueous solution of B-515.4W aged 8 months of DC Z-6020 aged 8 months CONCLUSION: Chartwell B-515.4W is indefinitely stable. Silane monomer has polymerized, resulting in opacity of the water solution. Performance depends on concentration of silane monomer. 12
Chartwell Adhesion Promoters: An Overview Chemical Description Unique compositions based upon proprietary organofunctional metal organics supplied as solutions in water, ethylene glycol, propylene glycol, or dipropylene glycol. Compatible and stable in water-borne and solvent-borne systems. Applications COATINGS � Commercially used in all industrial solvent-borne, water-borne and powder coatings � Improves wet adhesion to metals, concrete, plastics, wood, etc. � Use on metals increases corrosion resistance and salt fog resistance; generally by two fold � Reduces creep at the scribe � Easy post add to water-borne coatings Competition: Silanes (and other adhesion promoters) INKS � Commercially used to markedly improve adhesion of WB inks (acrylic & PUD) to plastic films Competition: Silanes ADHESIVES � Commercially used in all water-borne and 2K epoxy or 2K urethane adhesives � Substantial increase in adhesion to metals, plastics and elastomers Major competition: OSi A-1100, Dow Corning Z-6020, Z-6040 13
Chartwell Adhesion Promoters: An Overview RUBBER � Excellent adhesion of formed rubber articles to metal, rubber and synthetics, i.e. PVC, etc. � Improved abrasion resistance � Improved tensile and tear strengths � Commercially used in SBR, EPDM, nitrile rubbers Major competition: Degussa Si-69*, A-189 OTHER � Metal Pretreats: Treating metals with dilute aqueous solutions provide marked increase in adhesion of varied coatings � Abrasives: Improves wear resistance and durability � Plastics: Improved physical strength properties of both thermosets and thermoplastics Competition: Silanes, chromates (metal pretreats) Chartwell Advantages: � Cost is less than 50% of a competitive silane and is used as a 1:1 replacement � Products are hydrolytically stable. Improvements in adhesion measured at time of coating, ink or adhesive preparation DO NOT decrease after 60 days or more of aging � Customer-oriented and dedicated supplier. All sample requests and orders shipped promptly. 14
Chartwell Adhesion Promoters Recommended for Improved Adhesion to: � CRS, Galvanized Steel, Phosphated Steel, Aluminum, Copper, Brass � SBR, Nitrile, Natural Rubbers � ABS, PVC, Polyester Film � Concrete, wood, ceramics � Treated PP, PE (>35 dynes/ cm) Not Recommended for Adhesion to: � Untreated PP/ PE � Fiberglass (or glass substrates) Recommended for Improved Dispersion of: � Carbon black, phthalo blue/ green � Magnetic ferrites � Zinc anti-corrosive pigments � All mineral fillers (including calcium carbonate) � Alumina and other abrasives 15
Silanes in Water (i) (RO) 3 SiR’X + 3H 2 0 (HO) 3 SiR’X + 3 ROH OR OR (ii) (H0) 3 SiR’X XR’ Si -O-Si R’X + H 2 0 OR OR X= amine, epoxy, mercapto, methacryloxy, etc. (i) Rapid hydrolysis of silane in the presence of any moisture to form silanol with release of alcohol (ii) Condensation of silanol groups to siloxane linkages Performance α [silane monomer] 16
Product Definition {HO} - [M] - (CH 2 ) n - {X}* {substrate reactive} Organoreactive group [M] = proprietary metal(s); simplified representation All products are defined by three variables: 1. Single metal type or combination of two different metals [M] 2. Organofunctional group {X} 3. Solvent carrier (see below) Ethylene Glycol Products (B-) B-505.1, B-505.6, B-515.1, B-515.1/ 2H, B-515.4, B-515.4HR, B-515.71 (HR, 1.5H), B-516.5, B-517.4, B-525.1, B-545.1 Dipropylene Glycol Products (D-) Propylene Glycol Products (C-) C-505.1/ 2H, C-515.71HR, C-515.71/ 1.5H, D-525.3, D-531.1, D-535.1 C-523.2, C-523.2H, C-531.1 Ethylene Glycol/ Butyl Ether Water Products (B-XXX.W) of Ethylene Glycol (B-) B-515.1W, B-515.4W, B-515.5W, B- 515.71W, B-516.5W, B-535.1, B-600 B-523.2W, B-523.6W, B-523.6WH 17
Organoreactive Groups -(CH 2 ) X SH, x < 6 B-505.1, B-505.6, C-505.2, E-505.2 -CH(NH 2 ) – (CH 2 ) x SH, x= 1-2 B-511.1 B-515.1, B-515.4, B-515.4W, B-515.5W, -(CH 2 ) X NH 2 , x < 4 E-515.2, B-515.71, B-515.71W -CH(NH 2 ) – (CH 2 ) x – NH 2 , x-4-6 B-516.5, B-516.5W -(CH 2 ) X B-517.4, B-517.4W -CH(OH) – CH(OH) – COOH N C-523.2, B-523.2W, B-523.6W H -(CH 2 ) X COOH, x = 4-6 B-525.1, B-525.3, D-525.3 -(CH 2 ) X COOH, x >10 B-531.1, C-531.1, D-531.1 -(CH 2 ) X , x > 13 B-535.1, C-535.1, D-535.1 -C(CH 3 ) – CH 2 B-545.1 -(CH 2 ) X – S – S – (CH 2 ) Y COOH B-600 18
Understanding Chartwell Adhesion Promoter Choices 1. “W” Products Supplied as water solutions – ZERO VOC 2. Solvent Carriers (B, C, D Types) All non-water Chartwell products are supplied as adhesion promoter solutions in: B = Ethylene Glycol D = Dipropylene Glycol C = Propylene Glycol 3. “H”, “1.5H”, and “2H” Products Higher active matter versions of the non- “H” analogs; more cost effective. H = 1.38x non-H solids 1.5H = 1.5x non-H solids 2H = 2x non-H solids 4. HR Products Products in which the organoreactive portion of the molecule has been increased 2x (higher reactivity at the polymer reactive end) 5. Chartsil Solid Adhesion Promoters For use in powder coating and rubber only 19
Chartwell B-515.71 Family of Aminofunctional Products Variables: B = Ethylene Glycol 1. Solvent Carrier C = Propylene Glycol W = Water 2. Active Matter content non-H: Standard solids 1.5H: Has 1.5x solids of non-H. Use level is 0.7x non-H use level 3. Organofunctionality content non-HR: Equivalent weight of 1500 based upon amine content HR: 2x amine. Equivalent weight of 750 4. Heat Activated Amine “M” 5. Product options: • B-515.71 Ethylene Glycol, standard solids, standard amine • B-515.71/ 1.5H Ethylene Glycol, 1.5x solids, standard amine • C-515.71/ 1.5H Propylene Glycol, 1.5x solids, standard amine • B-515.71W Water, conventional solids • B-515.71HR Ethylene Glycol, standard solids, 2x amine • C-515.71HR Propylene Glycol, standard solids, 2x amine • B-515.71M Amine weakly complexed with Zinc (for 1K epoxy) 20
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