A history of adhesive bonding from ancient times to today

by

Robert Adams [1] and Paul Fay [2]

[1] Solid Mechanics Group Department of Engineering Science Parks Road Oxford OX1 3PJ UK [2] Dunton Technical Centre Ford Motor Company Basildon, Essex SS15 6EE UK

Abstract
Adhesives have been in use for thousands of years. Today, most cars, buses, aircraft and trains use structral or semi-structural adhesives and to be without their use in the home and general day-to-day life is unthinkable. The future will be dependent on adhesives in various forms, particularly as we make efficient structures and components by joining dissimilar materials. In this paper, we present an historical perspective of the development and application of adhesives, beaking it down into three basic parts, Ancient Times, the Middle Ages, and the 20th Century.

Introduction
Adhesives are substances that stick to the surface of most materials and can be made to harden so as to form a technologically useful means of transferring load from one component to another. Probably the first awareness of adhesives was more of a nuisance than anything else. Resin deposits on trees would have provided an obvious early encounter, while pulling limpet shells from rocks would have provided a challenge when scavenging for food. It was only a matter of time before man used his natural inventiveness to turn the problem to his advantage. Although adhesives have been in use for thousands of years, there is, of course, no definite date we can establish as the beginning, and archaeologists are regularly making new discoveries of the use of adhesives. Tools and weapons for hunting and fighting were the main needs of early man. Later, adhesives were used for decorative purposes in jewellery and veneers, for furniture, and for construction. The objective of this paper is to study the development of adhesives and their application to the benefit of mankind over the millennia.

Ancient times As far as we can tell, the history of manufactured adhesives appears to have started long before the existence of modern humans. Neanderthal tools dating from at least 80,000 years ago were found in Koenigsaue in the Harz Mountains in Germany in 1963. Residues of an adhesive substance were detected on them which later analysis has shown was derived from processed birch pitch (Koller et al, 2001). Similarly, tools dating from around 40,000 BC found at Umm el Tiel in Syria used bitumen, which had been subjected to extreme temperature, as a hafting material joining the tools to their handles (Boda et al, 1996). The production of such materials would have required careful processing at exactly the right temperatures, possibly in the absence of oxygen, and clearly demonstrates the technical abilities of the Neanderthals to manufacture usable and useful adhesives. While painting is hardly the application of structural adhesives, cave painting required that the painters knew how to get their pigments to stick to rock surfaces. This implies some knowledge of what works as it is unlikely that the evidence we have today, which has lasted for tens of thousands of years, was either the first example or simply luck. The oldest known cave paintings are about 30,000 years old and some are to be found in Bhimbhetka in Madhyah Pradesh. The oldest discovery of the use of adhesives by modern humans to date was made in the Nahal Hemar Cave to the northwest of Mount Sedom in Israel. When this cave was excavated in 1983, many of the artefacts unearthed were found to carry residues of a collagen based material believed to be derived from animal skins. This adhesive has been carbon dated to over 8,000 years ago (Bar-Yosef and Schick, 1989). Studies of burial sites dating from before 4000 BC revealed vessels made from broken pottery which had been repaired with sticky resins from tree. Statues found in Babylonian temples from around the same time have also been discovered, with ivory eyeballs glued into their sockets with a tar like glue which was still holding after 6000 years (Stumbo,1965). In 1991, the frozen mummy of a man, Otzi, from the Late Neolithic period (c 3300 BC) was discovered in a Tyrolean glacier. A number of weapons were found, consisting of flint arrowheads and a copper hatchet, bonded to wooden shafts with an adhesive like material (Spindler, 1995). Detailed analytical techniques have identified it as a pitch prepared by pyrolysis of bark from birch trees [similar to that used by the Neanderthals]. By the time of the early Egyptians, adhesives from a wide range of different sources appear to have been in regular use. Lucas [1927] lists the principal adhesives employed, or possibly employed in Ancient Egypt (in alphabetical order) as: albumin, beeswax, clay, glue, gum, gypsum, natron, resin, salt, solder and starch. Clear evidence of the use of glue by the Egyptians can be found in a wall carving from around 2000 BC, found in the Tomb of Rekhmara (Bogue, 1922). It shows the gluing of a thin veneer of wood to a thicker plank. The glue pot, being heated over a fire, the application of the glue with a brush and the use of weights to hold the veneer in place as the glue set can be clearly seen. The Egyptians used adhesives for a wide range of different applications. These included: fastening wood together; inlaying and veneering of wood; preparation of plaster and similar materials; as a binder in paints and pigments; fastening gold leaf to plaster and sealing and repairing alabaster jars. One interesting

application of animal glue was a prosthetic toe produced sometime before 600 BC found on a mummy in Thebes. It was manufactured from cartonnage (linen impregnated with animal glue), which gave it a smooth, tan-coloured coating similar to modern day prostheses. Another application of adhesives was in the Egyptian compound bow [similar to that used by the Tartars] which used horn, wood, and sinews to produce a short and powerful bow for hunting and fighting, often from chariots. Around the same time (c530 BC), in what is probably the earliest allusion to structural bonding of metal, Theodurus of Samos is credited with developing a new technique described as "gluing metal to metal (Feldhaus, 1931). In Babylon, there is ample evidence of the use of bitumen in construction. A roadway was constructed using bitumen, sand, and stones which still exists, and the buildings used baked mud bricks with bitumen strengthened with vegetation instead of cement. Lucretius, writing in around 50 BC, considered the affinity existing between different materials and stated that, Wood is joined together with bulls glue, so that the grain of boards often gapes open with a crack before the joints of the bulls glue loosen their hold. Pliny the Elder described various adhesive materials which came from trees. Examples include different varieties of "mastich", gum from the Egyptian thorn, and the resin of the pitch pine, used for coating wine casks. Pliny was obviously also familiar with animal glue. He claimed that, "The finest glue is made from the ears and genitals of bulls" but also identified glue being made from "any old skins and even from shoes". There can be no doubt that adhesives [and sealants] were widely used in the ancient world, and various sources were exploited including animals, plants, and naturally occurring bitumen.

The Middle Ages

Very few written records exist regarding the use of adhesives in the period immediately following the decline of Greece and Rome and it is likely that, like so many other technologies, they fell out of common use for several hundred years. Stumbo [1965], for example, reports that the study of furniture made between the fall of the Roman Empire and the sixteenth century shows that the art of gluing fell into disuse. This appears to be not strictly true and, to trace the continuing use of adhesives, it is necessary to delve into the world of the medieval artists. A huge body of finished works and associated texts demonstrate that the use of adhesives featured heavily in art, particularly religious art, during this period. One of the most interesting written records describing the use of adhesives is De Diversis Artibus by Theophilus, written around 1140. This work deals with the techniques required by clerics for decorating churches, making religious vessels, illuminating manuscripts and so on (de Camp, 1977). These included the manufacture and use of adhesives made from animal hides and horn, fish bladders and casein. Towards the end of the medieval period, Cennini produced his comprehensive "Libro dell'arte" in 1437, now regarded as the best source on the methods of late medieval artists. Cennini provides recipes for paper glues (made from flour), cements for mending stones, dishes and glass, fish glue, goat glue and glue made from cheese (Thompson 1933). The use of adhesives by the medieval artists has been analysed and

documented by a number of modern authors, most notably Laurie and Thompson (1956). Both confirm the widespread and successful use of glue in medieval art. Thompson, in particular states that: "Among the many troubles which beset medieval paintings in our time, one of the rarest is for the glued joints of the wood to separate; and the strength is largely due to the use of the strange, homely adhesive".

A general renaissance in the use of adhesive bonding began around this time and is clearly demonstrated by the changing construction methods used for furniture. The use of adhesives for inlaying work re-started in the 16th century and veneering in the 17th (Stumbo, 1965). But it was not until the 18th century that adhesives had an impact on the production and design of furniture and by the 19th century furniture makers were starting to rely solely on the strength of the glue bonds to ensure joint security [Tout, 2000]. During the early days in the history of adhesives, materials were produced on a very small scale, possibly in the kitchens of the individual users. However, by around 1700, the production of adhesives started to undergo transformation into a major industry. Bogue [1922] suggested that the earliest record of the practical manufacture of glue dates from Holland in around 1690. Shortly afterwards, the industry was introduced to England and established as one of her permanent industries around 1700. The first mention of glue in patent literature comes from a British patent for a kind of glue called fish glue in 1754 (British Patent, 1754). Over the next hundred years, this was followed by other patents pertaining to preparation of various types of animal glues. Most of the glue produced at this time was of animal or vegetable origin, mainly for bonding wood or paper products, and the manufacturing methods established by these early glue factories remained largely unchanged for over a hundred years. But things were beginning to improve. By 1917, it was reported, in an annual report on the progress of applied chemistry, that some of the larger glue works were employing competent chemists (Wood, 1917).The introduction of scientific discipline had a number of effects. Firstly, a great deal of the available knowledge of glue manufacture, testing and use was written down and published, often for the first time. Secondly, the importance of quality control was accepted and many controls on raw materials and manufacturing processes were implemented. Finally, comprehensive testing of the adhesive products became standard practice. The 19th Century close with glue production on an industrial scale and the beginning of quality control.

Modern times
Until the 1920s, most, if not all of the adhesives used for structural applications were of still of natural origin. Judge [1921] lists the adhesives available at this time for aircraft and automobile manufacture as:

1) 2) 3) 4) 5) 6) 7) 8) 9)

Animal glues (hide, bone or hoof); Fish glue Liquid glues (animal glues in liquid, ready to use state) Marine glue (made from indiarubber, naphtha and shellac) Casein glues Waterproof glues (modified ordinary glue) Vegetable glues Flexible glue (modified animal glue) and Albumen glues.

Although enormous efforts had been made in the manufacture of animal glue in the period up to 1925, much bigger developments were taking place which were to have the most significant effect on the history of adhesives in thousands of years the development of synthetic polymers. The first man-made polymer did not appear until the introduction of celluloid by Alexander Parkes in 1862. Phenol-formaldehydes are generally regarded as the first true, fully synthetic polymers. They were discovered several times before the significance of the discovery was fully appreciated and the time was appropriate for their further development and exploitation. The first record of the successful interaction of phenol and formaldehyde to produce resins was made by Baeyer in 1872. This was followed by similar experiments by a number of other chemists, before Leo Baekeland produced a synthetic resin with marketable possibilities in 1907, sold under the trade name Bakelite. The first suggestion that phenol-formaldehyde resins could be used as adhesives appears to have been made by Baekeland around 1912. By 1918, trials of a thin sheet of paper impregnated with phenolic resin for use in the manufacture of plywood were underway although it was not until around 1930 that such products were commercial available. The high cost of the material limited its early use to highly demanding applications for waterproof plywood such as aircraft and boat building. In later years, phenolic adhesives were developed in different forms (such as water emulsions and dry powders) which gave them more universal appeal. The phenol-formaldehydes were the first in a long series of synthetic polymers used as adhesives. The major landmark introductions were summarised by Hartshorn [1986] as shown in Table 1. Urea-formaldehyde resins followed quickly after the phenol-formaldehydes. The earliest materials were produced by Hans John in 1918, who suggested their use as adhesives. The development of these resins into industrial products was continued by many others, most notably by Frits Pollak throughout the 1920s and 30s [Morrell, 1943]. A modern review of the development of bonded aircraft structures reports that urea-formaldehyde adhesives were being used in aircraft construction from around 1937 [Bishopp, 1997]. Other important developments around this time were the developments of polyvinyl acetate, polyvinyl chloride and acrylic adhesives. Vinyl acetate and vinyl chloride monomers were first synthesised in 1912 and polymerised soon after. Polyvinyl acetate was unusual among the early plastics because it physical properties made it unsuitable for use in shaped articles and its use was primarily in adhesives, paints and surface coatings.

Approximate date of commercial availability 1910 1930 1940 1950 1960 1970

Adhesive Phenol-formaldehyde Urea-formaldehyde Nitrile-phenolic, vinyl-phenolic, acrylic, polyurethane Epoxies, cyanoacrylates, anaerobics Polyimide, polybenzimidazole, polyquinoxaline Second-generation acrylic

Table 1: Historical Development of Structural Adhesives (Hartshorn 1986)

Acrylates were first prepared in around 1873 and polmerised around seven years later . Acrylic polymers later formed the basis for a complex family of adhesives including cyanocrylates, anaerobics, u.v. hardening adhesives and two-part toughened acrylic adhesives. The development of acrylic adhesives has been described in Hartshorn [1986]. Polyurethane polymers were developed by Otto Bayer in Germany in around 1937. His patented isocyanate polyaddition process led to a versatile range of new materials which found applications in coatings; paint; foams; elastomers, mouldings and many other forms. Their potential as adhesives was discovered in 1940 and, since then, a wide range of applications for polyurethane adhesives have emerged including bonding of glass, composites, rubber, wood and leather. Probably the single most important landmark in the history of structural adhesives is the emergence of epoxy (or epoxoid) resins in the late 1930s. The first synthesised resins were produced by Pierre Castan in Switzerland in 1936, whilst resins using epichlorhydrin and bispenol A were first produced by Greenlee in the United States in 1939. A review of these developments (and the earlier work on which they were built) is provided by Lee and Neville [1982]. Castan was, at the time of his discovery, working for a dental products manufacturer who made attempts to market his products as casting resins for dental use. These attempts were unsuccessful and the patents were licensed to CIBA A G of Basle. CIBA continued development of the materials and, at the Swiss Industries Fair in 1946, launched an epoxy resin adhesive and four electrical casting resins the start of commercial exploitation of epoxy technology [Potter, 1976]. Epoxy adhesives gained rapid success in aerospace, automotive, construction, electronic and woodworking applications, largely because of their ease of use, versatility and mechanical properties. Typically, they possessed high shear strengths but relatively low toughness and peel strength. Attempts were therefore made to improve these properties. Various different approaches were tried, using additives and developing epoxy hybrids (such as polyamide fortified epoxies) but the most important breakthrough came in the early 1970s with the introduction of butadiene based rubber modifiers from Goodrich. These transformed the

performance of both epoxy and acrylic adhesives, adding peel, impact and fatigue resistance without compromising the existing performance characteristics. There are now many adhesives which are found in every household. These range from self adhesive cellophane tape to the cyanoacrylate polymer used in Superglue and include adhesives for mending shoes and furniture together with various rapid or slow curing 2-part epoxy adhesives for stronger and more durable bonds. This would be an appropriate point at which to end an historical review of adhesives the major technological developments which form the basis of today's structural adhesives have been introduced and the structural adhesives industry can be considered mature and sophisticated. Alongside the developments in the synthetic polymers, there have also been parallel developments in the analytical tools, surface analysis methods, stress analysis, fracture mechanics and inspection techniques necessary to exploit their potential. A number of key industries dependent on adhesive technology for their success - most notably the aerospace, automotive and electronics industries have emerged and developed alongside these other developments. Future automotive needs will be based on lightweight vehicles based on multimaterial construction. As an example, there is a European project called Litebus [http://www.litebus.com]for building a lightweight intercity coach based on composites and sandwich construction in which adhesives are extensively used for joining the various prefabricated parts.

Conclusions
We can see how man has used his ingenuity over the centuries to produce strong and durable adhesives. Until the 20th Century, all adhesives were based on animal and plant products, together with naturally occurring bitumen. The developments of modern chemistry have seen an enormous increase in the use of a wide range of adhesives from aerospace tp simple household products.

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