39

Anaerobic Adhesives
Richard D. Rich
Loctite Corporation, Rocky Hill, Connecticut, U.S.A.

I. INTRODUCTION Anaerobic adhesives are mixtures of acrylic esters that remain liquid when exposed to air but harden when conned between metal surfaces. These mixtures can be used for a large number of industrial purposes, such as locking threaded fasteners, sealing threaded pipe connections, retaining cylindrical machine components, sealing ange joints, bonding structural components, sealing porous metal castings, welds and powdered metal parts, and many other applications that are still being found more than 50 years after the initial invention [1]. Several reviews have been published that describe anaerobic adhesives and their applications [26]. The rst anaerobic adhesives were made at the General Electric Company by aeration of a polyethylene glycol dimethacrylate. This Anaerobic Permal required continuous aeration to prevent hardening [7]. Although a number of internal applications had been identied, the problems associated with shipping and storage made the product so impractical that the company decided to discontinue its manufacture. Vernon Krieble, chairman of the Chemistry Department at Trinity College in Hartford, Connecticut, learned about the product through his son, Robert Krieble, who was employed at General Electric. Vernon Krieble found a chemical solution to the problem by using cumene hydroperoxide (I) (see Section XII for all structures) as the initiator and packaging in half-lled oxygen-permeable polyethylene bottles [8]. He licensed the GE patent and in 1954 founded the American Sealants Corporation, which later became Loctite Corporation [9]. At the present time anaerobic adhesives and sealants are manufactured or sold on every continent by more than a dozen companies. Applications in virtually every industry, and technological innovation, as measured by patent activity, continue unabated. II. FORMULATION

A large number of variations are possible for anaerobic curing products, but all will consist of the following components: 1. Monomer. Methacrylate esters are used in almost all anaerobic products. Acrylates, acrylic and methacrylic acids, and few other vinyl polymerizable monomers may be used for special purposes.
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2. Initiator. A hydroperoxide (typically, cumene hydroperoxide) is almost always used as an initiator, although there are some variations and it is also possible to take advantage of small amounts of native hydroperoxide present in the methacrylate monomers. 3. Accelerator. A large number of chemical accelerators have been developed which can catalyze the anaerobic cure and reduce the large dierences in cure speed on dierent surfaces. The most commonly used accelerators are saccharin [benzoic sulmide (II)] and aromatic amines such as N,N-dimethyl-p-toluidine (III) and 1,2,3,4-tetrahydroquinoline (IV). 4. Stabilizers. All methacrylate monomers must contain some free-radical inhibitor if they are to be shipped and stored safely. Hydroquinone and p-methoxyphenol are most commonly used for this purpose. Most formulations will also contain benzoquinone, naphthoquinone, and similar stabilizers. Since the anaerobic compositions are strongly catalyzed by traces of metals, many formulators have found it advantageous to add chelators such as tetrasodium ethylenediaminetetraacetic acid (EDTA) (V). 5. Modiers. A very large number of modications in the cured and uncured properties of anaerobic formulations can be brought about by the addition of components that have little or no eect on the fundamental anaerobic cure chemistry. These modiers can increase the viscosity, control thixotropy, add color or uorescence, increase sealing eectiveness, reduce strength, increase toughness, increase heat resistance, provide lubrication, and reduce settling of llers. 6. Surface activators. In some applications anaerobic sealants will cure more rapidly if the surface is treated with a solution containing a metal salt or other chemical that will catalyze the polymerization. These substances will often be components that could not be added to the sealant without causing premature gellation. III. REACTION MECHANISM

Anaerobic adhesives and sealants have been developed primarily in industrial laboratories, and most of the published literature are patents. A number of papers have been published within the last two decades which discuss the reaction mechanisms of anaerobic adhesive cure [1020]. A. Oxygen Inhibition

The polymerization mechanism of anaerobic adhesives is similar to that of other freeradical initiation systems except for the special ways in which the inhibiting eect of oxygen is used to delay the polymerization, and in the chemical activation that occurs at the metal surface. Initiation: Inhibition: Propagation: Termination: I ! I I M ! M M O2 ! MOO M M ! M M M ! M2 M I ! MI

Weak free radical Free radical lost Free radical lost

The reaction rate of oxygen with free radicals is very high and the peroxy radical formed is a relatively poor initiator. When the supply of oxygen is used up within a thin
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bond line, the propagation step can provide rapid development of adhesive strength. Although there is little disagreement about the importance of oxygen in the propagation step, the greatest interest and study has been directed to the initiation step in the process described above. The role of the bonding surfaces and the eect of dierent types of accelerators account for most of the literature on the cure mechanism of anaerobic adhesives. B. Transition Metals

An important factor in the initiation of anaerobic adhesive cure is the redox reaction between a hydroperoxide and transition metals with adjacent oxidation states [10]. Fe2 ROOH ! Fe3 RO OH Fe3 ROOH ! Fe2 ROO H In the reactions above, other transition metals will react similarly, and copper is particularly active. Where cumene hydroperoxide (CHP) is used, R C6H5C(CH3)2. C. Accelerators The use of saccharin and N,N-dimethyl-p-toluidine (DMPT) results in a substantial acceleration of the initiating reaction. Although each of these components itself is an accelerator, their combination has a strong synergistic eect. It has been suggested that a charge-transfer complex is formed by these materials [11]. It is not clear whether this complex is itself an initiator or whether it acts on other components to generate initiating species.

This same study indicated that the rate of anaerobic polymerization was nearly independent of the concentration of CHP and proceeded at a signicant but slower rate with no hydroperoxide. This does not indicate that the hydroperoxide is not essential to the anaerobic cure but that it does not participate in the rate-determining step. The use of 1-acetyl-2-phenylhydrazine [APH (VI)] and saccharin resulted in a somewhat slower reaction rate than with DMPT unless a catalytic amount of copper was added. In this study the concentration of CHP was found to be very important where the molar ratio of CHP/APH was less than 1. Where the ratio was greater than 1, the rate was independent of CHP [12]. These papers [11,12] have been reviewed [13]. The accelerating eect of the salts of saccharin and 6-methyl-1,2,3,4-tetrahydroquinoline (VII), 1,2,3,4-tetrahydroquinoline (IV), or 1,2,3,4-tetrahydroquinaldine (VIII) on the anaerobic polymerization of methyl methacrylate were studied. No organic peroxides were required for these polymerizations [14].
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The eect on initiation reactions of charge-transfer complexes of o-benzosulfanilide (IX) and tertiary aromatic amines with various substituents was studied. The rates increased with increasing electron donor and decreasing acceptor properties of the substituents on the amine [15]. Aromatic tertiary amines mixed with benzosulmides formed charge-transfer complexes whose decay products were eective catalysts for polymerization of polyethylene glycol dimethacrylate. The most eective catalyst system was DMPT with dibenzenesulfonamide (X). The eectiveness of the system was increased by the addition of CHP [16]. A study using a model reaction system consisting of cumene hydroperoxide (CHP), N,N-dimethyl-p-toluidine (DMPT), and o-benzoic sulmide (saccharin) in toluene (without reactive acrylic monomer) showed conclusively that the DMPT was depleted signicantly during the initiation step of an anaerobic reaction. The saccharin concentration was unchanged during this process. The initiating species may be radical anions derived from DMPT rather than reactive free radicals derived from the CHP [17]. A dilatometric study was carried out on the polymerization of an anaerobic system containing diethylene glycol dimethacrylate, DMPT, CHP, saccharin, and iron lings. DMPT was more eective than N,N-dimethylaniline (XI), triethylamine, or tributylamine. Saccharin was more eective than benzoyl cyanamide (XII), phthalimide (XIII), or succinimide (XIV) [18]. D. Role of Saccharin It has been suggested that one of the functions of the saccharin in anaerobic cure is to dissolve metal ions from the surfaces in order to catalyze the decomposition of CHP. X-ray photoelectron spectroscopy of a model anaerobic adhesive cured in contact with a metal surface indicates that trace amounts of metal or metal ions are found at the interface [19]. E. Oxygen Absorption

Studies of the oxygen absorption of triethylene glycol dimethacrylate indicate that the reaction is catalyzed by DMPT and by DMPT with saccharin. This oxygen absorption appears to be continuous, although the active oxygen content of the system appears to level o due to decomposition of the peroxide formed. Oxalic acid substantially inhibits the absorption of oxygen [20].

IV.

MONOMERS

The rst anaerobic patents mentioned only the polyglycol dimethacrylates with tetraethylene glycol dimethacrylate (XV) as the dominant example [7,8]. Neopentylglycol dimethacrylate (XVI) was rst mentioned in a patent assigned to Borden [21]. The use of acrylic or methacrylic acids to improve adhesion to smooth surfaces was mentioned in a patent assigned to Loctite [22]. The use of diallylphthalate (XVII) and diallylphthalate prepolymer as comonomers with tetraethylene glycol dimethacrylate was claimed in a patent led by Kalinowski [23]. A series of polyurethane polyacrylates were prepared by reaction of toluene diisocyanate (XVIII), other isocyanates, and isocyanate-terminated oligomers with hydroxyalkyl methacrylates [24]. These monomers could be tailored to provide the
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strength and toughness required for some structural adhesive applications. The incorporation of hard and soft segments into the polyurethane backbones provided signicant improvements in toughness, cure-through-gap, and cryogenic strength properties [25]. The use of monomethacrylates in anaerobic formulations was disclosed in a patent assigned to Loctite. Specically mentioned were hydroxyethyl (XIX), hydroxypropyl (XX), cyclohexyl (XXI), tetrahydrofurfuryl (XXII), dimethylaminoethyl (XXIII), and glycidyl methacrylates (XXIV), and cyanoethyl acrylate [26]. Methacrylate esters containing residual carboxylic acid groups were prepared by the reaction of hydroxyethyl methacrylate with phthalic anhydride (XXV), pyromellitic dianhydride (XXVI), and benzophenonetetracarboxylic acid dianhydride (XXVII). The residual acid provided improved adhesion [27,28]. The reaction product of hydroxyalkylmethacrylates with maleic anhydride (XXVIII) also produced monomers with residual acid as well as additional curable unsaturation [29]. The dimethacrylates of the bisglycol esters of dicarboxylic acids were used to formulate anaerobic adhesives. Among the dicarboxylic acids mentioned were phthalic (XXIX), maleic (XXX), fumaric (XXXI), and malonic (XXXII) [30]. Three Bond Company used trimethylolpropane trimethacrylate (XXXIII) [31] and ethoxylated bisphenol A dimethacrylate (XXXIV) [32] in anaerobic formulations. These monomers have some advantages in providing improved heat resistance. At Henkel & Cie. dicyclopentadienyl methacrylate (XXXV) was used in anaerobic formulations with high strength [33]. Rohm and Haas has disclosed the use of dicyclopentenyloxyethyl acrylate (XXXVI) and methacrylate in anaerobic formulations [34]. These monomers provide good cure strength on metal parts that have not been degreased and also have lower odor and volatility than do the corresponding dicyclopentadienyl esters. Silicone methacrylates have been formulated by Dow Corning [35] and Toshiba Silicones [36]. Methacrylate esters have been prepared by the reaction of methacrylic acid with epoxies such as the diglycidyl ethers of bisphenol A (XXXVII) [37]. Methacrylate esters suitable for anaerobic adhesives have also been prepared by the reaction of glycidyl methacrylate (XXXVIII) with a hydroxyl-terminated polyester [38]. The reaction of isocyanatoethyl methacrylate (XXXIX) with polyols resulted in monomers that could be formulated into anaerobic adhesives and sealants [39].

V. INITIATORS The most commonly used initiator for anaerobic adhesives is cumene hydroperoxide. Many other hydroperoxides have been disclosed, such as t-butylhydroperoxide (XL), p-menthane hydroperoxide (XLI), diisopropylbenzene hydroperoxide (XLII), pinene hydroperoxide (XLIII), and methyl ethyl ketone hydroperoxide (XLIV) [40]. Some diperoxides, such as di-t-butylperoxide (XLV) and dicumylperoxide (XLVI), have been claimed, but these may function only because of hydroperoxide contamination [41]. Storage-stable anaerobic formulations can be prepared with no hydroperoxide if the methacrylate resin is aerated in the presence of an amide and a tertiary amine [42]. Anaerobic adhesives have been formulated with alkyl hydroxyethyl peroxides such as t-butyl-2-hydroxyethyl peroxide (XLVII) [43]. An adhesive formulated with t-butylperoxymaleic acid has improved surface adhesion (XLVIII) [44].
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VI.

ACCELERATORS

The rst accelerator used in an anaerobic adhesive was tributylamine [45]. Saccharin was also found to be an eective accelerator [46] and the combination of saccharin and N,N-dimethyl-p-toluidine was particularly eective if properly stabilized [47]. A large number of patents have been issued on various accelerators and combinations thereof. N-Aminorhodanine (XLIX) [48], 1-acetyl-2-phenylhydrazine (VI) [49,50], benzenesulfonylhydrazide (L) [51], dibenzenesulfonamide (X) [52], and similar compounds have been disclosed. The use of saccharin has been of particular interest and a number of compounds have been prepared that have a similar chemical structure and reactivity. The reaction of sulfuryldiisocyanate (LI) with acetic acid gives a disulfonamide that is an eective accelerator [53]. Similar reactions of p-toluenesulfonyl isocyanate (LII) and chlorosulfonyl isocyanate (LIII) can be used to prepare many dierent compounds which are active accelerators [54,55]. These methods allow the preparation of accelerators with improved solubility.

VII.

STABILIZERS

The monomers used in anaerobic adhesives and sealants generally contain at least one free-radical stabilizer, such as hydroquinone or p-methoxyphenol. It was found that benzoquinone, naphthoquinone, and similar compounds provided improved shelf stability without retarding the anaerobic cure [56]. It was also found that anaerobic formulations could be stabilized with a stable nitroxide free radical such as di-t-butyl nitroxide (LIV) [57]. The use of a soluble metal chelating agent such as tetrasodium EDTA (V) was found to be an eective method of stabilizing an anaerobic formulation against small amounts of metal contamination [58].

VIII. MODIFIERS The wide variety of applications of anaerobic adhesives and sealants is made possible by the modications that make the viscosity appropriate to the application. An application that requires penetration into close-tting parts should have very low viscosity, while a product used with large, loose-tting parts should have a high viscosity. A styrene acrylate copolymer could be used to increase the viscosity [59]. Polymethacrylates, cellulose esters, butadienestyrene copolymers, acrylonitrilebutadienestyrene copolymers, poly(vinyl chloride), copolymers of vinyl chloride and vinyl acetate, poly(vinyl acetate), cellulose ethers, polyesters, polyurethanes, and other thermoplastic resins have also been used to control the ow characteristics of anaerobic sealants [60]. The ow characteristics of anaerobic formulations can also be controlled by the addition of fumed silica and other solid additives which can impart thixotropic properties [61]. Many anaerobic adhesives and sealants may require a relatively low strength so that the components can be disassembled for repair or replacement. Many liquid plasticizers have been used for this purpose [62], but the use of a low-molecular-weight polyester has been found to be advantageous [63]. The toughness properties of anaerobic adhesives can be enhanced by the addition of a reactive elastomer [64]. The heat resistance of anaerobic adhesives and sealants can be enhanced by the addition of a bismaleimide
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(LV) [65]. These maleimide additives appear to be relatively unreactive during the initial anaerobic cure. As the adhesive is exposed to high temperatures the methacrylate backbone degrades and the methacrylates can then copolymerize with the maleimides, forming a more heat-resistant matrix [66]. The addition of dyes to anaerobic adhesives and sealants assists in identication and inspection of the products. Automated inspection procedures are made possible with dyes that uoresce under ultraviolet light. Titanium dioxide pigments can make the sealants more visible. Solid llers are added to some anaerobic adhesives and sealants for various purposes. Mica, talc, and other mineral llers can help to provide an instant seal capability to anaerobic pipe sealants. The sensitivity of the anaerobic cure system to metal contamination requires that these llers be chosen very carefully. Powdered graphite, polytetrauoroethylene, and polyethylene can function as lubricants in pipe sealants and thread-locking compounds. This lubrication can prevent galling in close-tting pipe threads [67]. Lubricating additives in thread-locking sealants can provide control of the clamping force exerted by a fastener at a given tightening torque [68].

IX.

PRIMER/ACTIVATORS

The cure speed and adhesion of an anaerobic sealant can be increased by treatment of the surface with a solution containing activating chemicals. Early anaerobic thread lockers were strongly aected by part cleanliness, and degreasing the parts with a chlorinated solvent improved performance dramatically. The condensation product of an aldehyde and a primary or secondary amine, a sulfur-containing free-radical accelerator (LVI), or a compound of an oxidizable transition metal were some of the materials that could be added to activate the anaerobic cure [6971]. Ferrocene (LVII), a derivative containing the ferrocene moiety, or a polymer incorporating ferrocene was an eective activator for anaerobic adhesives [72]. The copper, cobalt, manganese, or chromium salts of an acid phosphate acrylic monomer (LVIII) were found to be eective activators as well as adhesion promoters [73].

X. APPLICATIONS 1. Thread locking. The rst applications for anaerobic adhesives were for locking threaded fasteners. Filling the inner space between a nut and bolt with a hard, dense material prevents self-loosening. 2. Thread sealing. The eect of lling the space between threaded parts or the space between inner and outer pipe threads provides a seal that can prevent the leakage of oil and other uids in machinery as well as prevent corrosion of the threaded parts. 3. Retaining. Cylindrical press-ts and bearing assemblies can be retained with anaerobic adhesives, allowing accurate alignment and relaxed tolerances. Retaining and sealing of cup plugs and oil seals in castings is a major application. 4. Impregnation. Powdered metal parts, porous castings, and welds can be sealed against leakage of liquids or gases. This impregnation can also allow such parts to be plated and improves their machinability.
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5. Preapplied. Thread lockers and sealants are made that can be coated on threaded parts in the form of a dry-to-the-touch lm. These preapplied materials remain inert until assembly releases a quick-curing resin. 6. Gasketing. Anaerobic ange sealants can be applied manually or by automated methods such as tracing, stenciling, and screen printing. These products can eliminate a variety of preformed, precut gaskets and can also be used as a gasket dressing. 7. Structural bonding. Tough structural bonds can be achieved with some anaerobic adhesives for bonding components such as ferrite magnets, honing stones, identication tags, and decorative inserts. Other applications include the fabrication of foundry molds [74,75] and the surface mounting of electronic components [76].

XI.

STANDARDS AND SPECIFICATIONS

Testing standards and performance specications for anaerobic adhesives and sealants have been established by government agencies and industrial organizations in several countries. In the United States there are military specications for thread lockers, sealants, and retaining compounds. Mil-S-22473E, 12 April 1983, Sealing, Locking and Retaining Compounds: (Single Component) covers 15 of the earliest letter grade products. Specications are set for color, viscosity, locking torque on 3 8-24 steel nuts and bolts, and uid tightness. The eects of immersion in a number of uids, heat aging at 149 C, and hot strength at 149 C (or 93 C for some grades) are also measured. This specication calls for measurement of an average locking torque after 90, 180, 270, and 360 degrees of turn. Mil-S-46163A, 12 July 1983, Sealing, Lubricating and Wicking Compounds: Thread-Locking, Anaerobic, Single-Component covers nine grades of product for sealing (type I), lubricating (type II), and wicking (type III). Specications are set for color, viscosity, locking torque (break and prevailing torque) on 3 8-16 steel, zinc- and cadmium-plated nuts and bolts, uid tightness, lubricity, and wicking into preassembled fasteners. The immersion, heat aging, and hot strength tests are similar to those done in Mil-S-22473E. Mil-R-46082B, 10 June 1983, Retaining Compounds Single Component, Anaerobic (Amendment 6, 9 January 1990) covers three types of retaining compounds, which are tested with a pin-and-collar compressive shear specimen. The three types vary primarily in viscosity, although there are also dierences in heat resistance and strength. These products are subjected to immersion, heat aging, and hot strength tests similar to those described above. In the United Kingdom the Ministry of Defence (MOD) has issued specications DTD 56285633, which cover test procedures and performance requirements for a range of products. Five strength bands and four viscosities, from penetrating to thixotropic, are dened. The torque strengths are tested on M8 nuts and bolts and the shear strength in 12-mm pins and collars. The development of these specications and the test procedures have been described by C. L. Brett at the MOD. The breakloose torque on nuts and bolts requires particular attention to a transient measurement where the rst torsional motion is detected. Other products show somewhat dierent behavior, with no distinct breakloose, and the torque at which the sealant begins to yield is not easily detected [77]. British Standard BS 5292 relates to the use of anaerobic sealants on gas appliances.
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In Germany, standards have been published describing the Compression Shear Test (DIN 54452), Dynamic Viscosity Determination of Anaerobic Adhesives by Rotational Viscometer (DIN 54453), Initial Breakaway Test at Bonded Threads (DIN 54454), and Torsion Shear Test (DIN 54455). DIN 54455 is particularly interesting since it is one of a very few tests in which a nut and bolt (M10) are seated to a measured torque before the anaerobic sealant is allowed to cure. In the United States the Industrial Fastener Institute has published standards entitled Test Procedure for Locking Ability Performance of Non-metallic Locking Element Type Prevailing Torque Lock Screws and Test Procedure for the Locking Ability Performance of Chemical Coated Lock Screws. The American Society for Testing and Materials (ASTM) has published a Standard Test Method for Shear Strength of Adhesives Using Pin-and-Collar Specimen (ASTM D4562-90, October 1990). A subcommittee of ASTM Committee D-14 on Adhesives has studied torque strength tests and performance standards for anaerobic adhesives. The International Organization for Standardization (ISO) has nalized an International Standard (ISO/DIS 10964: 1993) AdhesivesAnaerobic Adhesives Determination of Torque Strength of Anaerobic Adhesives on Threaded Fasteners. This standard describes testing procedures for liquid and preapplied sealants using manual and graphical procedures.

XII.

LIST OF STRUCTURES

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