Handbook of
`A dh esive Tech n o logy
`Second Edition, Revised and Expanded
`
`edited by
`A. Pizzi
`Universite' de Nancy I
`Epinal, France
`K. L. Mittal
`Hopewell Junction, New York, U.S.A.
`
`M A R C E L
`
`D E K K E R
`
`
`
`MARCEL DEKKER, INC.
`
`NEW YORK BASEL
`
`Copyright © 2003 by Taylor & Francis Group, LLC
`
`EX. 1027
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`Although great care has been taken to provide accurate and current information, neither the
`author(s) nor the publisher, nor anyone else associated with this publication, shall be liable for
`any loss, damage, or liability directly or indirectly caused or alleged to be caused by this book.
`The material contained herein is not intended to provide specific advice or recommendations for any
`specific situation.
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`Trademark notice: Product or corporate names may be trademarks or registered trademarks and are
`used only for identification and explanation without intent to infringe.
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`Library of Congress Cataloging-in-Publication Data
`A catalog record for this book is available from the Library of Congress.
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`ISBN: 0-8247-0986-1
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`This book is printed on acid-free paper.
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`PRINTED IN THE UNITED STATES OF AMERICA
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`Copyright © 2003 by Taylor & Francis Group, LLC
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`Preface to the Second Edition
`
`What can one say about the second edition of any book, especially one like this
`compendium that contains 50% more material and pages than the rather popular first
`edition, is heavily revised, expanded, and modernized, and contains 10 new chapters?
`As editors we can simply say we are elated. This is all true, of course, but it sounds so dull!
`Some readers (particularly younger ones) may expect some profound truth in a preface,
`a noteworthy dedication, or even an unusual phrase to remember such as the one that
`graced the preface of another book (Advanced Wood Adhesives Technology, Marcel
`Dekker, Inc., 1994). So here it is: On my (AP) first day as a university professor (at the
`University of the Witwatersrand in Johannesburg), I was profoundly impressed by
`the motto printed on the paper bookmark that was given to me by the administration
`clerk, ‘‘Wherever a site of higher learning stands, there stands a light in the darkness of
`human folly.’’ The university meant this to signify how good they were (and they were
`good, too). It goes much deeper than this, however. A site of learning does not need to be a
`university, or an industrial/research laboratory, but it can be more broadly defined as any
`source of learning, even, for instance, a book in such an arcane, specialized, but always
`fascinating, field as adhesives. It is for this reason that this volume has been revised and
`expanded, to function as a site of learning and a springboard for budding adhesive
`technologists. It is dedicated to next generations in the hope that they may build, and build
`rapidly, on the cumulative wisdom of many specialists distilled in this handbook.
`This book, containing bountiful information, should serve for veterans as a commen-
`tary on the current state of knowledge regarding adhesives, and as a Baedeker for those
`who wish to make their maiden voyage into the wonderful and technologically important
`area of adhesives. In essence it should be valued by and of use to everyone interested,
`centrally or peripherally, in adhesives and should appeal to polymer chemists, surface
`chemists, adhesionists, and engineers, as well as users of adhesives.
`We now have the pleasant task of thanking all those who helped in many and varied
`ways to bring this project to fruition. First, we are profoundly thankful to all the authors
`of the first edition for consenting to again be part of this much enlarged effort. Many
`contributors devoted time and effort to update their chapters. As any handbook can
`benefit from an injection of new blood, so our particular thanks must go to the contri-
`butors of new chapters. Our appreciation is extended to the staff of Marcel Dekker, Inc.
`for giving this book its form. In closing, we can happily say that it has been great fun
`working with all involved in this project.
`
`A. Pizzi
`K. L. Mittal
`
`Copyright © 2003 by Taylor & Francis Group, LLC
`
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`Preface to the First Edition
`
`Bonding different materials together by means of an adhesive may appear to most people
`as a mundane occurrence. In reality a great deal of technology backs the apparently simple
`action of bonding. Thus, a complex and advanced technology, or series of technologies,
`has arisen to deal with adhesives and their applications in many fields. The diversity of
`substrates and the continuous introduction of new processes and materials has ensured
`that the field of adhesives technology is one of the more swiftly expanding manufacturing
`endeavors. Some excellent handbooks on adhesives already exist although there are very
`few indeed. However, the expansion and diversity of this field has by necessity limited the
`number of technologies and relevant aspects described in such volumes. This volume is no
`exception to such a trend.
`The editors and authors do not pretend that overlaps with other similar works do not
`exist since basic background is often necessary to understand more advanced concepts.
`This volume however covers some aspects of technology that are not described in other
`volumes of this type. It also often looks at already reported technologies from a very
`different angle. It is hoped that such a volume will help to fill some of the technological
`gaps between the existing literature and industrial reality.
`The volume is divided into four main sections, the first being an introductory overview.
`The remaining three sections are concerned with (1) fundamental aspects, (2) adhesive
`classes, and (3) some fields in which application of adhesives is very extensive. All the
`contributors are known specialists in their fields who practice their specialties on a daily
`basis. Their chapters are the results of considerable knowledge and experience in their
`particular niches.
`It is a pleasant duty for the editors and authors, on completing a volume of this nature,
`to acknowledge the help willingly given by friends, colleagues, their companies, and their
`institutions. Without their help and encouragement most of the chapters presented would
`not have seen the light of day. Last, but definitely not least, our thanks go to Marcel
`Dekker, Inc. and its staff for originating this book, for their help and encouragement, and
`for prompting us to finish it.
`
`A. Pizzi
`K. L. Mittal
`
`Copyright © 2003 by Taylor & Francis Group, LLC
`
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`Contents
`
`PrefacetotheSecondEdition
`PrefacetotheFirstEdition
`Contributors
`
`Part 1: Review Topics
`1.HistoricalDevelopmentofAdhesivesandAdhesiveBonding
`Fred A. Keimel
`2.InformationResources
`William F. Harrington
`
`7.
`
`Part 2: Fundamental Aspects
`3.TheoriesandMechanismsofAdhesion
`J. Schultz and M. Nardin
`4.TheMechanicalTheoryofAdhesion
`D. E. Packham
`5.Acid–BaseInteractions:RelevancetoAdhesionandAdhesiveBonding
`Mohamed M. Chehimi, Ammar Azioune, and Eva Cabet-Deliry
`6.InteractionsofPolymersinSolutionwithSurfaces
`Jean-Franc¸ ois Joanny
`Tailoring Adhesion of Adhesive Formulations by
`MolecularMechanics/Dynamics
`A. Pizzi
`8.PrinciplesofPolymerNetworkingandGelTheoryinThermosetting
`Adhesive Formulations
`A. Pizzi
`9.ApplicationofPlasmaTechnologyforImprovedAdhesionofMaterials
`Om S. Kolluri
`10.SilaneandOtherAdhesionPromotersinAdhesiveTechnology
`Peter Walker
`11.TestingofAdhesives
`K. L. DeVries and P. R. Borgmeier
`12.ThePhysicalTestingofPressure-SensitiveAdhesiveSystems
`John Johnston
`13.DurabilityofAdhesiveJoints
`Guy D. Davis
`14.AnalysisofAdhesives
`David N.-S. Hon
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`15.FractureofAdhesive-BondedWoodJoints
`Bryan H. River
`16.FractureMechanicsMethodsforInterfaceBondEvaluationsof
`Fiber-ReinforcedPlastic/WoodHybridComposites
`Julio F. Davalos and Pizhong Qiao
`17.SpectroscopicTechniquesinAdhesiveBonding
`W. J. van Ooij
`18.UltravioletStabilizationofAdhesives
`Douglas Horsey
`19.ThermalStabilizationofAdhesives
`Neal J. Earhart, Ambu Patel, and Gerrit Knobloch
`
`Part 3: Adhesive Classes
`20.ProteinAdhesivesforWood
`Alan L. Lambuth
`21.AnimalGluesandAdhesives
`Charles L. Pearson
`22.CarbohydratePolymersasAdhesives
`Melissa G. D. Baumann and Anthony H. Conner
`23.NaturalRubber-BasedAdhesives
`Sadhan K. De
`24.ElastomericAdhesives
`William F. Harrington
`25.PolysulfideSealantsandAdhesives
`Naim Akmal and A. M. Usmani
`26.PhenolicResinAdhesives
`A. Pizzi
`27.NaturalPhenolicAdhesivesI:Tannin
`A. Pizzi
`28.NaturalPhenolicAdhesivesII:Lignin
`A. Pizzi
`29.ResorcinolAdhesives
`A. Pizzi
`30.Furan-BasedAdhesives
`Mohamed Naceur Belgacem and Alessandro Gandini
`31.Urea–FormaldehydeAdhesives
`A. Pizzi
`32.Melamine–FormaldehydeAdhesives
`A. Pizzi
`33.IsocyanateWoodBinders
`Charles E. Frazier
`34.PolyurethaneAdhesives
`Dennis G. Lay and Paul Cranley
`35.PolyvinylandEthylene–VinylAcetates
`Ken Geddes
`36.UnsaturatedPolyesterAdhesives
`A. Pizzi
`37.Hot-MeltAdhesives
`A. Pizzi
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`38.ReactiveAcrylicAdhesives
`Dennis J. Damico
`39.AnaerobicAdhesives
`Richard D. Rich
`40.AerobicAcrylics:IncreasingQualityandProductivitywith
`CustomizationandAdhesive/ProcessIntegration
`Andrew G. Bachmann
`41.TechnologyofCyanoacrylateAdhesivesforIndustrialAssembly
`William G. Repensek
`42.SiliconeAdhesivesandSealants
`Loren D. Lower and Jerome M. Klosowski
`43.EpoxyResinAdhesives
`T. M. Goulding
`44.Pressure-SensitiveAdhesives
`T. M. Goulding
`45.ElectricallyConductiveAdhesives
`Alan M. Lyons and D. W. Dahringer
`
`4: Application of Adhesives
`Part
`46.AdhesivesintheElectronicsIndustry
`Monika Bauer and Ju¨rgen Schneider
`47.AdhesivesintheWoodIndustry
`Manfred Dunky
`48.BioadhesivesinDrugDelivery
`Brian K. Irons and Joseph R. Robinson
`49.BondingMaterialsandTechniquesinDentistry
`Eberhard W. Neuse and Eliakim Mizrahi
`50.AdhesivesintheAutomotiveIndustry
`Eckhard H. Cordes
`
`Copyright © 2003 by Taylor & Francis Group, LLC
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`Contributors
`
`Naim Akmal* University of Cincinnati, Cincinnati, Ohio, U.S.A.
`Interfaces, Traitement, Organisation et Dynamique des Syste`mes
`Ammar Azioune
`(ITODYS), Universite´ Paris 7–Denis Diderot, Paris, France
`Andrew G. Bachmann Dymax Corporation, Torrington, Connecticut, U.S.A.
`Monika Bauer Fraunhofer Institute of Applied Materials Research, Teltow, Germany
`Melissa G. D. Baumann Forest Products Laboratory, USDA–Forest Service, Madison,
`Wisconsin, U.S.A.
`Mohamed Naceur Belgacem Ecole Franc¸ aise de Papeterie et des Industries Graphiques
`(INPG), St. Martin d’He`res, France
`P. R. Borgmeier University of Utah, Salt Lake City, Utah, U.S.A.
`Eva Cabet-Deliry Laboratoire d’Electrochimie Mole´culaire, Universite´ Paris 7–Denis
`Diderot, Paris, France
`Interfaces, Traitement, Organisation et Dynamique des Syste`mes
`Mohamed M. Chehimi
`(ITODYS), Universite´ Paris 7–Denis Diderot, Paris, France
`Anthony H. Conner Forest Products Laboratory, USDA–Forest Service, Madison,
`Wisconsin, U.S.A.
`Eckhard H. Cordes Mercedes-Benz AG, Bremen, Germany
`Paul Cranley The Dow Chemical Company, Freeport, Texas, U.S.A.
`D. W. Dahringer AT&T Bell Laboratories, Murray Hill, New Jersey, U.S.A.
`Dennis J. Damico Lord Corporation, Erie, Pennsylvania, U.S.A.
`Julio F. Davalos West Virginia University, Morgantown, West Virginia, U.S.A.
`Guy D. Davis DACCO SCI, Inc., Columbia, Maryland, U.S.A.
`Indian Institute of Technology, Kharagpur, India
`Sadhan K. De
`K. L. DeVries University of Utah, Salt Lake City, Utah, U.S.A.
`Manfred Dunky Dynea Austria GmbH, Krems, Austria
`Neal J. Earhart CIBA-GEIGY Corporation, Ardsley, New York, U.S.A.
`Charles E. Frazier Virginia Polytechnic Institute and State University, Blacksburg,
`Virginia, U.S.A.
`Alessandro Gandini Ecole Franc¸ aise de Papeterie et des Industries Graphiques (INPG),
`St. Martin d’He`res, France
`Ken Geddes Crown Berger Limited, Darwen, Lancashire, England
`T. M. Goulding Consultant, Johannesburg, South Africa
`
`*Current affiliation: Teledyne Analytical Instruments, City of Industry, California, U.S.A
`
`Copyright © 2003 by Taylor & Francis Group, LLC
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`William F. Harrington Adhesive Information Services, Mishawaka,
`Indiana, U.S.A.
`David N.-S. Hon Clemson University, Clemson, South Carolina, U.S.A.
`Douglas Horsey CIBA-GEIGY Corporation, Ardsley, New York, U.S.A.
`Brian K. Irons* Columbia Research Laboratories, Madison, Wisconsin, U.S.A.
`Institut Charles Sadron, Strasbourg, France
`Jean-Franc¸ ois Joanny
`John Johnston Consultant, Charlotte, North Carolina, U.S.A.
`Fred A. Keimel Adhesives and Sealants Consultants, Berkeley Heights, New Jersey, U.S.A.
`Jerome M. Klosowski Dow Corning Corporation, Midland, Michigan, U.S.A.
`Gerrit Knobloch CIBA-GEIGY Corporation, Basel, Switzerland
`Om S. Kolluri HIMONT Plasma Science, Foster City, California, U.S.A.
`y
`Boise Cascade Corporation, Boise, Idaho, U.S.A.
`Alan L. Lambuth
`Dennis G. Lay The Dow Chemical Company, Freeport, Texas, U.S.A.
`Loren D. Lower Dow Corning Corporation, Midland, Michigan, U.S.A.
`Alan M. Lyons AT&T Bell Laboratories, Murray Hill, New Jersey, U.S.A.
`Eliakim Mizrahi University of the Witwatersrand, Johannesburg, South Africa
`M. Nardin Centre de Recherches sur la Physico-Chimie des Surfaces Solides, CNRS,
`Mulhouse, France
`Eberhard W. Neuse University of the Witwatersrand, Johannesburg, South Africa
`D. E. Packham Center for Materials Research, University of Bath, Bath, England
`Ambu Patel CIBA-GEIGY Corporation, Ardsley, New York, U.S.A.
`Charles L. Pearson Swift Adhesives Division, Reichhold Chemicals, Inc., Downers Grove,
`Illinois, U.S.A.
`A. Pizzi Ecole Nationale Supe´rieure des Technologies et Industries du Bois, Universite´ de
`Nancy I, Epinal, France
`Pizhong Qiao The University of Akron, Akron, Ohio, U.S.A.
`William G. Repensek National Starch and Chemical Company, Oak Creek, Wisconsin,
`U.S.A.
`Richard D. Rich Loctite Corporation, Rocky Hill, Connecticut, U.S.A.
`Bryan H. River Forest Products Laboratory, USDA–Forest Service, Madison, Wisconsin,
`U.S.A.
`Joseph R. Robinson University of Wisconsin, Madison, Wisconsin, U.S.A.
`Ju¨ rgen Schneider Fraunhofer Institute of Applied Materials Research, Teltow, Germany
`J. Schultz Centre de Recherches sur la Physico-Chimie des Surfaces Solides, CNRS,
`Mulhouse, France
`A. M. Usmani Firestone, Carmel, Indiana, U.S.A.
`W. J. van Ooij University of Cincinnati, Cincinnati, Ohio, U.S.A.
`Peter Walker Atomic Weapons Establishment Plc, Aldermaston, Berkshire, England
`
`*Current affiliation: University of Wisconsin, Madison, Wisconsin, U.S.A.
`y
`Deceased.
`
`Copyright © 2003 by Taylor & Francis Group, LLC
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`1H
`
`istorical Development of Adhesives and
`Adhesive Bonding
`
`Fred A. Keimel
`Adhesives and Sealants Consultants, Berkeley Heights, New Jersey, U.S.A.
`
`I.
`
`INTRODUCTION
`
`The history of adhesives and sealants is closely related to the history of humankind. Some
`of what are thought of as relatively ‘‘new’’ uses of adhesives have their origins in ancient
`times, and although most of these materials have been subject to vast changes, others have
`been changed very little over time. As new materials are developed, a review of the history
`of uses can lead one to see where they might be applied to improve old applications, and
`sometimes to satisfy requirements of entirely new applications.
`
`II. EARLY HISTORY OF ADHESIVES AND SEALANTS
`
`‘‘Insects, fish and birds know the art of producing mucous body fluids suitable for gluing.
`The load-carrying capacity of the hardened glue, as exemplified by egg-fastening and
`nest-building, is comparable to that of modern structural adhesives’’ [1, p. 1]. As human-
`kind evolved, inquisitive persons observed and thought about insect and bird building
`and repair of nests with mud and clay. They encountered spider webs and naturally
`occurring ‘‘sticky’’ plant and asphaltic materials that entrapped insects, birds, and
`small mammals.
`Unlike species that use an inherited instinct to perform a single task, human beings
`adopted the techniques of many species. They observed the natural phenomenon of sticky
`substances, then gathered and used these materials in locations away from their origins,
`exemplified today by the recently discovered Stone Age natives of South America’s
`Amazon region and those in the interior of Borneo and New Guinea.
`As rains fell, and then drying set in, many sticky materials regained their sticky
`properties, and some of the leaves used by ancient peoples to wipe sticky residues
`from their hands retained small quantities of water. Observing this, the first crude
`waterproof containers were manufactured using what we now call pressure-sensitive
`adhesives.
`Our early ancestors used mud, clay, snow, and other natural materials to
`keep vermin, wind, and inclement weather out of their dens, warrens, caves, and other
`
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`habitations. Today we use materials called sealants to perform similar functions in the
`construction and maintenance of modern buildings.
`Straw and other vegetable material found its way into the muds and clays and
`reinforced them, forming the first crude composites. These materials later developed into
`bricks, which were in turn joined with the same or other materials used as mortars.
`As human beings developed tools and weapons, sharp stones had to be fastened to
`handles to make axes and spears. Some of these were bound with vines, fibers, pieces of
`animal skin, or tendons or other body parts, and some had natural self-adhering proper-
`ties to supplement the use of knots. To enhance the joining process, observing users soon
`smeared on sticky materials found locally.
`When some natural materials fell on rocks heated by the sun, they softened and
`became sticky, and later hardened in the cool of the night. Observers made use of these
`natural phase-change materials as they chanced upon them. When lightning started fires,
`some materials melted and then cooled in interesting shapes. Observers, using the fires to
`harden their sharpened stick weapons, put out the fires by rubbing their sticks on the
`ground, and some contacted and melted resins, which when cooled, again hardened. Thus
`was born the technology we now call hot-melt adhesives.
`Some of the other materials used by early human beings as adhesives are now called
`beeswax, rosin, rubber, shellac, sulfur, tar, and vegetable gums. Later, as people developed
`bows and arrows, it was found that feathers fastened to an arrow shaft helped to stabilize
`the arrow’s flight. The same sticky or heat-softened materials soon supplemented the use
`of natural fibers to attach the feathers.
`If Noah really did build an ark, the seams had to be sealed to keep out the water.
`And early human beings must have floated their possessions across bodies of water in bark
`or leaf containers with the seams sealed with sticky, waterproof materials.
`Prehistoric peoples made pottery, and contrary to the Bible admonition in Jeremiah
`19:11, ‘‘as one breaks a potter’s vessel, so that it can never be mended,’’ they often used
`rosin to reassemble broken vessels to retain food buried with the dead, as we know from
`remnants found in archaeological digs.
`Bituminous cements were used to fasten ivory eyeballs in statues in 6000-year-old
`Babylonian temples, and combinations of egg whites and lime were used by the
`Goths 2000 years ago to fasten Roman coins to wood, bonds that remain intact
`today [2, p. ix]. ‘‘Bitumen was supposedly the mortar for the Tower of Babel; beeswax
`and pine tar were used in caulking Roman vessels that dominated the Mediterranean
`Sea’’ [3, p. 62]. ‘‘Plant gums and mucilage have been known and in use since very early
`times, reference being made to them in the Bible; they seem to have been of commer-
`cial value for several thousand years, especially in India, Asia, Africa, Australia, and
`China’’ [4, p. vii].
`In historic times the Egyptians used crude animal and casein glues to laminate
`wood for bows and furniture, including wood veneers, many of which have endured to
`modern times in that dry climate. To make these products it is likely that they were
`familiar with the production of bonded abrasives in the form of sand bonded to
`papyrus or cloth with animal glue. They developed starch pastes for use in bonding
`papyrus to textiles and to bond leather, and a plaster of calcined gypsum identical to
`today’s plaster of Paris. Later the Greeks used slaked lime as a mortar, and both the
`Greeks and Romans mixed the lime with volcanic ash and sand to create a material
`still known as pozzolanic cement. This was used in the construction of the Roman
`Pantheon and Colosseum. Thus was born the rude beginnings of the art and science
`we now call adhesive bonding technology.
`
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`III. MODERN ADHESIVES AND SEALANTS
`
`From the earliest days, the materials that we later called cements, glues, gums, mucilage,
`mortars, resins, pastes, and finally, adhesives and sealants, were used interchangeably.
`Only in modern times have we attempted to differentiate between adhesives and sealants.
`For the most part it has been a vain attempt, as many so-called adhesives also serve as
`sealants, and all sealants have adhesive properties. Some polyurethane and silicone sea-
`lants have strength properties similar to those of structural adhesives. Only seals, which
`have no adhesive properties (gaskets, O-rings, stuffing boxes, etc.), have been excluded
`from the technical definitions, but even here, seals and sealants are often combined in the
`literature and in use, as they often perform in similar applications. Mixtures of glycerin
`and litharge, alone and with additives, were used for many years [5, p. 358] as both an
`adhesive and a sealant, and are still used in the repair and restoration of older aquariums.
`In his book The Technology of Adhesives [6], John Delmonte tells us that the first
`commercial glue plant was founded in Holland in 1690, that casein glues appear to have
`been manufactured in Germany and Switzerland in the early nineteenth century, and that
`the first U.S. patent (number 183,024) on a casein glue was issued in 1876. He mentions
`that starch adhesives were used on postage stamps when they were first issued in 1840, and
`that the first U.S. patent (number 61,991) on a dextrin adhesive was issued in 1867.
`Before the advent of synthetic resin adhesives, semisynthetic cellulosic materials were
`developed, but when they were first dissolved in solvents and used as an adhesive is not
`clear from the literature. ‘‘Historically, the first thermoplastic synthetic adhesive (only
`partly synthetic) was the cellulose ester cellulose nitrate, often called nitrocellulose, and
`it is still one of the most important. Later, other esters such as the acetate were developed,
`as well as certain mixed esters’’ [1, p. 295].
`Inorganic sodium silicate adhesives had minor commercial use in 1867, but it was not
`until 1900 that their use as a glue became of commercial importance as a replacement for
`starch in the production of corrugated and solid fiber paperboard [5, p. 279]. Very fine
`silicate frit mixed with phosphoric acid was used as a dental cement [5, p. 376] before
`the twentieth century. Magnesium chloride inorganic cements were used at least as
`far back as 1876 in hospital kitchen floors, as they provide resistance to greases and oils
`[5, pp. 355–356].
`There is little agreement in the literature about the dates when various adhesives and
`sealants were first developed or used in a specific application. This is due to simultaneous
`developments in many parts of the world and the fact that references in the literature are
`almost exclusively from the more developed countries. Table 1 show Delmonte’s [6, p. 4]
`viewpoint on the times of adhesive developments, up to the year of publication of his
`work. In the accompanying text he notes that ‘‘The developments are tabulated according
`to their first public disclosure, whether by patent or citation in technical literature.’’
`Some experts trace the roots of the first modern adhesives technology to 1839, when
`Charles Goodyear discovered that a mixture of rubber and sulfur changed from a plastic
`to an elastic state when heated. In 1843 this process was termed vulcanization by Thomas
`Hancock, who is believed to have used his hard rubber (Ebonite) for bonding to metals,
`possibly discovering its effectiveness when trying to remove the mixture from metal con-
`tainers used in its preparation. As it also bonded to natural rubber during vulcanization, it
`was used for many years as the only practical means of joining metal to rubber—but it had
`serious limitations as a thermoplastic [7, pp. 1–3].
`The rubber cement used in early rubber-to-metal bonding was a simple dispersion of
`rubber sheeting in benzene and later toluene or other solvent. It was brushed on the metal
`
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`Table 1 Chronological Developments of Adhesives in the United States
`
`Year
`
`1814
`1872
`1874
`1875
`1909
`1912
`1915
`1917
`1920–1930
`1927
`1928
`1928–1930
`1930
`1930–1935
`
`1935
`1939
`1940
`1941
`
`1942
`1943
`1944
`1945
`
`Source: Ref. 6.
`
`Material
`
`Glue from animal bones (patent)
`Domestic manufacture of fish glues (isinglass)
`First U.S. fish glue patent
`Laminating of thin wood veneers attains commercial importance
`Vegetable adhesives from cassava flour (F. G. Perkins)
`Phenolic resin to plywood (Baekeland-Thurlow)
`Blood albumin in adhesives for wood (Haskelite Co.)
`Casein glues for aircraft construction
`Developments in cellulose ester adhesives and alkyd resin adhesives
`Cyclized rubber in adhesives (Fischer-Goodrich Co.)
`Chloroprene adhesives (McDonald–B. B. Chemical Co.)
`Soybean adhesives (I. F. Laucks Co.)
`Urea–formaldehyde resin adhesives
`Specialty pressure-sensitive tapes: rubber base (Drew–Minnesota
`Mining & Mfg. Co.)
`Phenolic resin adhesive films (Resinous Products & Chemical Co.)
`Poly(vinyl acetate) adhesives (Carbide & Carbon Chemicals Co.)
`Chlorinated rubber adhesives
`Melamine–formaldehyde resin adhesives (American Cyanamid Corp.)
`and Redux by de Bruyne (Aero Research Ltd).
`Cycleweld metal adhesives (Saunders-Chrysler Co.)
`Resorcinol–formaldehyde adhesives (Penn. Coal Products Co.)
`Metal-bond adhesives (Havens, Consolidated Vultee-Aircraft Corp.)
`Furane resin adhesives (Delmonte, Plastics Inst.) and Pliobond
`(Goodyear Tire and Rubber Co.)
`
`and dried prior to contact with the bulk rubber to be bonded to the metal by vulcanization
`in a heated press. In 1862, Charles Sanderson, in a British patent (number 3288), specified
`that metal be brass plated by electrodeposition to obtain a strong bond to rubber [7, p. 3].
`In 1911 the process was used in the production of rubber rolls, but was not used as a
`general commercial process until the 1920–1930 period.
`Efforts to bond rubber to metal without the use of metal plating led to what is
`believed to be the first research efforts in surface preparation prior to adhesive bonding.
`Strong and durable bonds of rubber to metal were necessary for rubber shock mounts for
`automobiles in the late 1920s, but they were limited to proprietary formulations used on
`specific metals. In 1927 solvent-based thermoplastic rubber cements for metal-to-rubber
`bonding were prepared from rubber ‘‘cyclized’’ by treatment with sulfuric or other strong
`acids. With these rubber cements strong bonds could be made to either vulcanized or
`unvulcanized rubber.
`Thermosetting solvent-based rubber cements for rubber-to-metal bonding, based on
`halogenated rubber compounds, first became available between World Wars I and II, but
`like much of the rubber-to-metal bonding technology, most of the work was proprietary
`and only glimpses of the technology involved can be found in the patent literature. The
`first use of natural rubber-based ‘‘tacky’’ adhesives on a backing is credited to Henry Day,
`who was issued a U.S. patent (number 3,965) in 1845. James Corbin of Minnesota Mining
`and Manufacturing Co. (now 3M Company), in a 1952 paper, ‘‘Practical Applications of
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`Copyright © 2003 by Taylor & Francis Group, LLC
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`EX. 1027
`APPLE INC. / Page 13 of 999
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`Pressure-Sensitive Adhesives’’ [8, p. 139], states that 1925 is generally considered to be the
`birth date of the pressure-sensitive tape industry. He mentions that prior to the time, both
`cloth-backed surgical tapes and cloth-backed friction tape for use by electricians were in
`limited use. Both were apparently tried as masking tapes for the new two-toned automo-
`biles, but failed to resist paint penetration and to strip clean. A crepe-paper backing,
`impregnated with animal glue and glycerin and coated with a pressure-sensitive adhesive
`(PSA), was developed in 1925.
`Synthetic rubber, a dimethylbutadiene, was developed as a substitute for natural
`rubber in Germany during World War I and saw limited use as an adhesive. In the
`early 1930s, neoprene rubber (then called Duprene) became available to adhesive manu-
`facturers in the United States, and shortly thereafter in Great Britain. Today, neoprene
`rubber adhesives are available as both thermoplastic and cross-linking systems in both
`solvent and emulsion formulations. Neoprene rubber is the major base resin for contact
`adhesives. A limited amount of neoprene rubber is also used in sealants.
`It was not until the commercialization of synthetic plastics resins in the 1930s that an
`almost unlimited variety of base materials became available for compounding into adhe-
`sives and sealants. Most of the thermoplastic resins were soluble in organic solvents
`and were used as solvent adhesives for molded plastic articles of the same base composi-
`tion and sometimes for other materials. Poly(vinyl chloride) (PVC), a thermoplastic devel-
`oped in 1927, is used today in solvent formulations to bond PVC articles such as coated
`fabrics, films, foams, and pipe. In the early 1930s, phenolics came into importance as
`adhesive resins. Before that time they were used as coating varnishes [9, p. 239]. ‘‘About
`1931 development of the use of a new phenolic resin for plywoods and veneers began’’
`[9, p. 239].
`Poly(vinyl acetate) was used as a solvent-based adhesive in the 1930s, and later as a
`hot melt, but was not of commercial importance until its introduction in the 1940s, as an
`emulsion adhesive used mainly to bond paper and wood. Today, in emulsion form as a
`white glue,
`it
`is the most widely used thermoplastic adhesive worldwide. Vinyl
`acetate–ethylene (VAE) emulsion adhesives, with over 55% vinyl acetate content, were
`developed in the early 1950s but did not become of commercial importance in the United
`States until the mid-1960s.
`Acrylic adhesives first appeared about 1937; ‘‘the acrylic resins may be considered as
`belonging to the vinyl family’’ [1, p. 305]. Today, acrylic adhesives appear in many forms:
`as both pressure-sensitive and non-pressure sensitive formulations in organic solvent and
`emulsion forms; as monomer and polymer cements; as anaerobics; as cyanoacrylates; as
`so-called reactive or ‘‘honeymoon’’ two-part systems; and as radiation curing formula-
`tions. ‘‘Commercial production of acrylic polymers began in the late 1920s, but it was
`not until 1958 that the first acrylic sealant was developed’’ [10, p. 226]. ‘‘The solvent-
`based acrylic sealants were first introduced to the construction industry in about 1960’’
`[11, p. 121].
`Urea–formaldehyde adhesives were patented in 1920 but were first commercialized
`around 1937. During World War II, starch was modified with urea resins to make both
`waterproof adhesives and impregnants for paper, which led in the 1940s to phenolic-
`impregnated paper for the first du