Report No. 83 ADHESIVES. February A private report by the PROCESS ECONOMICS PROGRAM PARK, CALIFORNIA STANFORD RESEARCH INSTITUTE I

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1 Report No. 83 ADHESIVES by WING SIEN FONG February 1973 A private report by the PROCESS ECONOMICS PROGRAM STANFORD RESEARCH INSTITUTE I MENLO PARK, CALIFORNIA

2 CONTENTS 1 INTRODUCTION SUMMARY... General Aspects... Technical Aspects... 3 INDUSTRYSTATUS... Classification of Adhesives... Advantages and Disadvantages of Adhesive Bonding... Adhesives Market in the United States by End Use... Adhesives Market in the United States by Base Material... Structure of the Adhesives Industry in the United States.. Adhesives Market in Japan... Adhesives Market in Western Europe ADHESION FUNDAMENTALS Mechanical Theory Chemical (Chemisorption; Molecular Interaction) Theory.. 34 Electrostatic (Electrical; Electronic) Theory Adsorption Theory Diffusion Theory Weak-Boundary-Layer Theory and Adhesive Failures Water Effect Stresses Types of Forces Wetting and Spreading Work of Adhesion and Work of Cohesion Surface Topography Wetting Rate '33 5 FORMULATION MATERIALS AND PHYSICAL FORMS OF ADHESIVES... Base Materials (Binders)... Acrylics... Acrylic Acid Diesters... Acrylonitrile-Butadiene (Nitrile Rubber)... Coumarone-Indene Resins... Cyanoacrylates... Epoxies... Ethylene-Vinyl Acetate Copolymers... Furanes V

3 CONTENTS 5 (continued) Ionomers Isocyanates Melamine Formaldehydes... : 1 : : : : : : 70 Phenol-Formaldehydes Phenoxies 72 Polyamides... 1 : 73 Polyamide-Imides Polybenzimidazoles (PBI) Polycarbonates Polychloroprenes (Neoprenes) Polyesters, Saturated Polyesters, Unsaturated Polyimides (PI) Polyisobutylene, Polybutenes, and Butyl Rubber Polypropylene, Amorphous... '82 Polystyrenes Polysulfides... a4 Epoxy-Polysulfides... a5 Polysulfones Polyurethanes... :.. 87 Polyvinyl Acetals Polyvinyl Acetates Polyvinyl Alcohols Polyvinyl Chlorides... : 91 Polyvinyl Alkyl Ethers Resorcinol Formaldehydes Rubber, Natural Rubber, Reclaimed Silicones Styrene-Butadiene (SBR) Urea-Formaldehydes Additives Antioxidants Defoamers Diluents Extenders... i.. 1 : : 1 : Fillers Plasticizers Preservatives vi 0

4 CONTENTS 5 (continued) Solvents... Tackifiers... Thickeners... Physical Forms of Adhesives... Solutions (Lacquers)... Emulsions and Latexes (Aqueous Dispersions)... Solids... Films (and Tapes)... Pastes... Encapsulated Adhesives... Hot Melt Adhesives INDUSTRIAL ADHESIVES Abrasives Adhesives Anaerobic Adhesives Aerospace and Aircraft Adhesives Automotive Adhesives Construction Adhesives Dental Adhesives Electrical and Electronic Adhesives Glass (Optical) Adhesives High Temperature Adhesives Hot Melt Adhesives Low Temperature Adhesives Metal Adhesives Paper and Related Products Adhesives Photographic Film Adhesives Plastics Adhesives Pressure Sensitive Tapes Rubber Products (Tires) Adhesives Shoe Adhesives Structural Adhesives Surgical Adhesives Textile Adhesives Wood Adhesives Vii

5 CONTENTS 7 BONDINGTECHNIQUES... Joint Design for Structural Parts... Surface Preparation Methods... Quality of Water Used in Surface Preparation... Primers for Protecting Prepared Surfaces... Cleanliness Test for Prepared Surfaces... Preparation of Metals... Preparation of Plastics (Including Reinforced Plastics). Preparation of Elastomers... Preparation of Glass, Ceramics, and Other Inorganic Materials... Preparation of Fibrous Products... Preparation of Wood and Related Products... Application of Adhesives in General... Air-Knife Coating... Brush Coating... Calender Coating... Cast Coating... Curtain Coating... Dip Coating... Dust Coating... Extrusion Coating... Knife (or Blade) Coating... Rod Coating... Roll Coating Screen Coating...: Spray Coating... Methods of Applying Pressure... Methods of Heating... Application of Hot Melt Adhesives... Production of Plywoods and Composition Boards... Adhesive Lamination of Fabrics... Preparation of Adhesive Coated Cords for Tire Manufacturing... 8 EVALUATIONS OF REPRESENTATIVE PROCESSES... Production of Phenol- and Urea-Formaldehyde Resins for Adhesives... Review of Processes... Process Description... Process Discussion... i... Cost Estimates... viii

6 CONTENTS 8 (continued) Manufacture of Continuous, Pressure Sensitive Adhesive Products... Review of Processes... Process Description... Process Discussion... Cost Estimates... APPENDIX DESIGN AND COST BASIS CITED REFERENCES PATENT REFERENCES ix

7 ILLUSTRATIONS. 7.1 Bonding Processes Types of Joints Surface Treatments for Aluminum and Alloys Surface Treatments for Copper and Alloys Surface Treatments for Magnesium and Alloys Surface Treatments for Stainless Steels Surface Treatments for Steel and Ferrous Alloys (Excluding Stainless Steels) Surface Treatments for Titanium and Alloys Surface Treatments for Elastomers Brush and Calender Coatings Typical Roll Arrangements in Roll Coating Screen Coatings Application Methods for Hot Melt Adhesives Typical Production Schemes for Plywoods Typical Production Schemes for Hardboards and Insulation Boards Typical Production Scheme for Particle Boards Typical Adhesive Lamination of Fabrics Preparation of Adhesive Coated Cords for Tire Manufacture Production of Resinous Base Materials for Wood Adhesives Production of Resinous Base Materials for Wood Adhesives Effect of Plant Capacity and Stream Factor on Production Cost Manufacture of Continuous, Flexible, Pressure Sensitive Adhesive Products in Rolls Manufacture of Continuous, Flexible, Pressure Sensitive Adhesive Products in Rolls Effect of Plant Capacity and Stream Factor ' on Production Cost Xi

8 TABLES 2.1 Areas of Application for Various Adhesives Summary of Projected Growth and Recent Consumption Data for Some Major Adhesives and Applications in United States Cost Estimates for the Production of Resinous Base Materials for Wood Adhesives and the Manufacture of Continuous, Flexible, Pressure Sensitive Adhesive Products in Rolls Adhesives Production and End-Use Pattern in Japan, Uses of Some Major Types of Adhesives in Japan Types of Attractive Forces Relative Electronegativity and Dipole Moment for Some Elements and Polar Groups, Some Hydrogen Bond Donors and Acceptors, and Some Easily Polarized Groups Critical Surface Tensions Factors for Formulating or Selecting Adhesives Anaerobic Adhesives Summary of Some Recent Composition-of-Matter Patents Adhesives for the Automotive Industry Adhesives for the Construction Industry Summary of Some Recent Composition-of-Matter Patents Dental Adhesives Summary of Some Recent Composition-of-Matter Patents Adhesives for the Electrical and Electronics Industry Summary of Some Recent Composition-of-Matter Patents Adhesives for Glass and Related Products Summary of Some Recent Composition-of-Matter Patents High Temperature Adhesives Summary of Some Recent Composition-of-Matter Patents Hot Melt Adhesives Typical Ingredients.., Hot Melt Adhesives Summary of Some Recent Composition-of-Matter Patents Xiii

9 TABLES 6.10 Adhesives for Bonding Metal to Metal Summary of Some Recent Composition-of-Matter Patents Adhesives for Bonding Metal to Plastic or Other Nonmetal Summary of Some Recent Composition-of-Matter Patents Adhesives for Paper and Related Products Summary of Some Recent Composition-of-Matter Patents Adhesives for Photographic Film Summary of Some Recent Composition-of-Matter Patents Adhesives for Plastics Summary of Some Recent Composition-of-Matter Patents, Adhesives for Pressure Sensitive Tapes and Related Products Summary of Some Recent Composition-of-Matter Patents Resorcinol-Based Adhesives for Bonding Rubber to Cords (for Tires) Summary of Some Recent Composition-of-Matter Patents Adhesives, Other than Resorcinol-Based, for Bonding Rubber to Cords (for Tires) Summary of Some Recent Composition-of-Matter Patents Adhesives for Shoes Summary of Some Recent Composition-of-Matter Patents., Adhesives for Honeycomb Structures Mechanical Properties Requirements Common Structural Adhesives Typical Properties Structural Adhesives Summary of Some Recent Composition-of-Matter Patents Surgical Adhesives Summary of Some Recent Composition-of-Matter Patents Adhesives for Medical Tapes and Related Products Summary of Some Recent Composition-of-Matter Patents Adhesives for Fabrics in General Summary of Some Recent Composition-of-Matter Patents Adhesives for the Manufacture of Nonwoven, Flocked, and Related Fabric Products Summary of Some Recent Composition-of-Matter Patents xiv

10 TABLES Adhesives for Bonding Wood to Wood or Polymeric Materials Summary of Some Recent Composition-of-Matter Patents.. Adhesives Based on Phenolic Resins Examples of Formulations for Use in Plywood Production of Resinous Base Materials for Wood Adhesives Major Process Equipment and Utilities Summary Production of Resinous Base Materials for Wood Adhesives Total Capital Investment Production of Resinous (Phenolic) Base Materials for Wood Adhesives Production Costs Production of Resinous (Urea) Base Materials for Wood Adhesives Production Costs Manufacture of Continuous, Flexible, Pressure Sensitive Products in Rolls Major Process Equipment and Utilities Summary Manufacture of Continuous, Flexible, Pressure Sensitive Products in Rolls Total Capital Investment Manufacture of Continuous, Flexible, Pressure Sensitive Products in Rolls Production Costs..., ,., xv

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