43

Epoxy Resin Adhesives

T. M. Goulding
Consultant, Johannesburg, South Africa

I. INTRODUCTION Epoxy or epoxide resins are a group of reactive compounds that are characterized by the presence of the oxirane group

They are capable of reacting with suitable hardeners to form cross-linked matrices of great strength and with excellent adhesion to a wide range of substrates. This makes them ideally suited to adhesive applications in which high strength under adverse conditions is a prerequisite. Their unique characteristics include negligible shrinkage during cure, an open time equal to the usable life, excellent chemical resistance, ability to bond nonporous substrates, and great versatility. Although they were hailed as wonder products when rst introduced, it has now been accepted that they will not do everything. They have, however, clearly established niches, especially in high-technology applications, and have shown steady growth, generally ahead of the industry average. Sales of epoxy resins in Europe, for example, totaled 101,000 metric tons in 1980, 150,000 metric tons in 1985, and 205,000 metric tons in 1990. Although work on epoxy resins started in the mid-1920s, the rst commercially useful epoxy resins appeared during World War II. These were based on the diglycidyl ether of bisphenol A (usually referred to as DGEBA resins), and today these resins, in a range of molecular weights, constitute the majority of all epoxy resins used. By contrast, however, hardeners come in a variety of shapes and sizes, including amines and amides, mercaptans, anhydrides, and Lewis acids and bases. Choice of hardener depends on the application requirements, and the wide range of hardeners available increases the versatility of adhesives based on epoxy resins.
Copyright 2003 by Taylor & Francis Group, LLC

II.

CHEMISTRY OF EPOXY RESINS

Epichlorhydrin is capable of reacting with hydroxyl groups, with the elimination of hydrochloric acid. The most widely used epoxy resins are the family of products produced by the reaction between epichlorhydrin and bisphenol A.

This reacts with additional epichlorhydrin to produce a molecule of general structure

Commercially useful grades are relatively low-molecular-weight products in which n ranges from 0 to about 4. When n is between 0 and 1, the product is a liquid, and this is the most useful product for adhesive applications. As n increases, the product moves toward a brittle solid. Solid grades nd application principally in paints. Regardless of molecular weight, the resulting resin has two epoxy groups per molecule. Resins of greater functionality can be produced from polyols having more than two hydroxyl groups per molecule. Thus phenol novolac resins, having the general structure can be reacted with epichlorhydrin to produce epoxy novolac resins.

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These products may have much greater functionality, although stearic considerations limit the useful size of the molecule. Because of their higher functionality, epoxy novolacs have greater cross-link density, generally yielding better temperature resistance at the expense of increased brittleness. They are thus seldom used on their own, but make useful modiers of the properties of DGEBA resins. Other products that may be epoxidized in this way include dihydric and trihydric phenols, aliphatic polyols such as glycerol, and simple alcohols such as butanol or allyl alcohol. These products, especially the monofunctional glycidyl ethers, are used at relatively low percentages to modify properties of DGEBA resins, particularly to achieve lower viscosities. Epoxy groups may also be produced by oxidation of olenic unsaturation within animal and vegetable oils. The resulting products have too low a functionality for use as resins in their own right, but are added to DGEBA resins to introduce a measure of exibility. Major manufacturers of epoxy resins include Shell, Dow and CIBA-GEIGY. The resulting epoxy resin is capable of reacting with various products, or itself, to form a solid, infusible product of considerable strength. The fact that these reactions generally occur without the production of low-molecular-weight by-products means that shrinkage during cure is negligible. This reduces stresses in the cured structure, contributing to the strength of the cross-linked matrix and eliminating the need for sophisticated clamping techniques. The two cross-linking reactions are external, by reaction of the oxirane group with active hydrogen, and internal, by homopolymerization through the oxirane oxygen. The former is typical of cross-linking by hardeners and the latter of catalyzed cross-linking. Both hardeners and catalysts are referred to as curing agents. The classic epoxy curing mechanism is illustrated by the reaction between a primary amine and an epoxy group:

This product can react with an additional epoxy group to continue the cross-linking process.

This reaction is characteristic of hardeners having active hydrogens available, including amines, amides, and mercaptans. The reaction is catalyzed by hydroxyl groups, especially phenolic hydroxyls and tertiary amines. Because of the bulk of the substituent groups involved, steric factors have a major inuence on the reaction rate. Thus low-molecularweight hardeners tend to react more vigorously and produce more cross-linked structures, while hardeners of high molecular weight tend to react more sluggishly. Hardeners may
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thus be selected to produce highly exothermic reactions or reactions that take place only under the inuence of external heat. Similarly, DGEBA resins having both epoxy groups at the ends of the molecule will react more readily with hardeners than will epoxy novolacs or other types of epoxies in which one or more of the functional groups may be hindered by the rest of the molecule. Homopolymerization occurs readily in the presence of catalysts, especially at elevated temperatures.

Again this reaction is accelerated by hydroxyl groups or tertiary amines. This is also the predominant reaction with anhydrides. In fact, reactions with resin and hardener or catalyst are very much more complex than these idealized reactions, and both reactions as well as a number of side reactions probably occur to varying extents in any cross-linking mechanism. Major suppliers of curing agents include Anchor Chemicals, Dow, Shell, and Cray Valley Products.

III. A.

PROPERTIES OF EPOXIES Resins

Epoxy resins react with hardeners in stoichiometric quantities. Thus a knowledge of the number of reactive sites is needed in order to calculate correct ratios. For the resin this is given by the epoxide equivalent weight (EEW), which is the quantity of resin required to yield one epoxy group. For a DGEBA type in which n 0, the molecular weight is 340. Since there are two epoxy groups per molecule, the EEW is thus 170. Typically, the pure liquid DGEBA resins commercially available for adhesive applications have EEW in the range 180 to 310, usually 190 to 210, while for paints or special applications, EEW may reach 2000 or more. The epoxy novolacs usually have EEW in the range 150 to 250, usually around 180. The viscosity of a DGEBA resin is dependent primarily on molecular weight. Even at low molecular weight, viscosity is typically in excess of 6,000 cP, while at EEW 190 viscosity is usually around 12,000 cP. For applications requiring low viscosity it is thus necessary to include other types of epoxy resin or to use reactive or nonreactive diluents to achieve the desired viscosity.

B.

Hardeners

Stoichiometric ratios can be calculated similarly for hardeners. In principle, each active hydrogen will react with one epoxy group. Thus a low-molecular-weight aliphatic polyamine such as diethylene triamine (DETA) has a molecular weight of 103 and ve active hydrogens. The hydrogen equivalent is thus 20.6. The stoichiometrically correct ratio with an epoxy resin of EEW 200 would thus be 100 parts resin to 10.3 parts of DETA. In practice there is always a percentage of homopolymerization, especially at the temperature
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of reaction, and smaller amounts of DETA will still cause a complete cure, at the expense of increasing brittleness. In general, suppliers of proprietary hardeners do not furnish detailed chemical descriptions. Instead, they supply data on recommended mix ratios, and from this the formulator can calculate the correct quantities. With catalysts, stoichiometry is not critical, in theory. In practice, however, the quantity used will aect both the rate of cure and the cured properties. Thus with catalysts, in practice, the mix ratio is sometimes more critical than is the case with hardeners.

C. Mixed Product During cure of epoxies, especially systems with a short pot life or large mixes, considerable heat is evolved. This accelerates the cure, leading to even greater heat evolution. Mixes larger than 5 kg can reach excessive temperatures even with systems that have relatively long pot lives in quantities of 100 g. In addition to shortening the pot life dramatically, exothermic reactions can push the peak temperature to the point where thermal degradation occurs, or at least to a level that creates excessive stresses in the curing matrix, causing it to crack on cooling. Except in certain circumstances, peak exotherm temperature should be limited by formulation to 150 C or preferably less in the mix quantities used. Cured epoxy resins may be formulated to be extremely hard, with Shore D hardeners of 80 or more, or soft, exible products that barely produce a reading on the Shore A scale. When cured at approximately stoichiometric ratios and unmodied with diluents or plasticizers, however, they are generally hard and tough to brittle, especially DGEBA and epoxy novolac types. Heat distortion temperature (HDT) or deection temperature (DT) is a measure of the tendency of cured product to soften when heated. It is a feature of the inherent thermoplasticity in cured epoxy compounds as a result of the relatively low cross-linking density, and may be any value from below 50 C to about 250 C, depending on formulation and cure cycle. Resins and hardeners of high functionality tend to have higher HDT. Postcuring at elevated temperature can increase HDT signicantly.

IV. FORMULATING EPOXY ADHESIVES Epoxy resins oer a unique combination of properties for adhesive applications. These include the ability to formulate liquid systems without solvents or carriers, the ability to convert these systems to cured products without the production of low-molecular-weight by-products, the ability to bond dissimilar or nonporous surfaces, and the ability to produce thick sections without subsequent stress cracking due to shrinkage. Although epoxy resin and hardener may be used in unmodied form in adhesive systems, most systems will consist of components that have been modied by incorporation of various additives to achieve specic eects. Formulators will add catalysts or blend hardeners to obtain a specic usable life of the mix and to control the curing temperature. Reactive diluents may be added to modify viscosity or exibility. Fillers impart improved compression strength and reduce shrinkage and cost. Solvents may be used to reduce viscosity or improve adhesion. Various additives may be added, usually at a low percentage, to reduce aeration, improve adhesion to dicult surfaces, or minimize settlement of llers. Depending on the application, particular properties such as ame retardency,
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electrical insulation or conductivity, or chemical resistance may be improved by formulating. A. Resins

Although DGEBA resins provide the backbone of most epoxy formulations, they may be blended with other types to achieve modications. Epoxy novolacs, having higher functionality, increase the cross-linking density, which improves heat resistance but decreases impact resistance. Incorporation of epoxidized oils increases exibility at the expense of heat and chemical resistance. Low-viscosity polyfunctional epoxies based on polyols or polyhydric phenols reduce viscosity and can increase functionality without impairing cured properties. Monofunctional reactive diluents will also decrease viscosity and form part of the polymer backbone, to impart a measure of exibility without the possibility of migration. Properties of commercially available epoxy resins and diluents from various suppliers are listed in Table 1.

B.

Curing Agents

Use of mixed hardener systems is common. Hardeners may be blended to achieve properties intermediate to the individual components, to reduce exotherm or accelerate cure, to modify the cured properties, or simply to arrive at a more convenient mix ratio. Several classes of curing agents each having distinctive characteristics may be used. 1. Aliphatic primary amines. Common examples are diethylene triamine (DETA), tetraethylene pentamine (TEPA), n-aminoethyl piperazine, and isophorone diamine. They give good room-temperature cure at stoichiometric ratios, but have poor HDT, inconvenient mix ratios, high peak exotherm, and are strongly irritant. Isophorone diamine produces very light colored mixes with good color stability. 2. Aromatic primary amines. These oer improved heat and chemical resistance and longer pot life with reduced exotherm, but poor color stability and sluggish cure. They are generally solids and require some formulating to produce easily handleable products. Reactions proceed best at elevated temperatures, where their irritancy can be a problem. For room-temperature cures they should be used with catalysts, of which phenols, BF3 complexes, and anhydrides are the best. m-Phenylene diamine (MPDA) and methylene dianiline (MDA) are the best examples. 3. Amine adducts. Both aliphatic and aromatic amines can be adducted with small amounts of mono- or diglycidyl epoxies to produce amine adducts of medium to high viscosity that have decreased volatility and irritancy, more convenient mix ratios, and often, better reactivity. 4. Tertiary amines. Although their primary use is as catalysts with other hardeners, tris(dimethylaminomethyl) phenol (DMP 30) is an eective curing agent on its own, at both room and elevated temperatures. 5. Amides. Although amides on their own are too unreactive, reaction products of polyamines with fatty acids to produce amidopolyamines provide the largest group of commercial hardeners for adhesive applications. Reduced volatility and irritancy and a convenient mix ratio oer the compounder ease of handling. The mix ratio is relatively noncritical; increasing hardener levels yield increased exibility and adhesion but reduced HDT and chemical resistance. Initially, amidoamines have poor compatibility and an induction period is necessary to allow the reaction to start. Pot lives are relatively long
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Table 1 Resina

Epoxy Resins Chemical type 1:4 Butanediol diglycidyl ether Propylene glycol diglycidyl ether Propylene glycol diglycidyl ether Glycerol triglycidyl ether Linoleic acid diglycidyl ether DGEBA DGEBA DGEBA DGEBA DGEBA DGEBA DGEBA Epoxy novolac Epoxy novolac Epoxy novolac Allyl glycidyl ether Butyl glycidyl ether Versatic acid glycidyl ether 2-Ethylhexyl glycidyl ether EEW 110115 305335 175205 140160 390470 185196 182192 185192 180192 230280 230250 400500 170180 176181 176181 114 143 240250 190205 Viscosity (cP at 25 C) 10 55100 3060 100170 400900 12,00016,000 11,00014,000 10,00016,000 9,00012,000 (Softens at 3540 C) Not given 20,00030,000 50,000 3,5007,000 at 52 C 20,00050,000 at 52 C 1 3 78 23 Supplier CIBA GEIGY Dow Dow Shell Shell CIBA GEIGY Dow Shell Hoechst Shell Dow Hoechst CIBA GEIGY Shell Dow Shell Dow Shell Hoechst

Low viscosity Araldite DY026 DER 732 DER 736 Epikote 812 Epikote 871 Medium viscosity Araldite GY260 DER 331 Epikote 880 Beckopox EP 140 High viscosity Epikote 834 DER 337 Beckopox EP 151 Araldite EPN 1139 Epikote 154 DEN 438 Monofunctional Allyl Glycidyl Ether Dow BGE Cardura E Beckopox EP 080
a

Note that trade names and grade designations may vary from country to country.

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and exotherms low, but low-temperature cure is poor. Small quantities of imadazoline improve adhesion to metal. Dicyandiamide is a special example of an amide that can be used on its own. Its low reactivity yields a usable life in excess of 6 months, but at elevated temperatures it reacts quickly. 6. Mercaptans. Most mercaptans on their own are unreactive, but with catalysts produce exible cures. Certain mercaptans in conjunction with DMP 30 provide extremely rapid cure, with low exotherm, making them ideally suited to retail applications. 7. Acids and anhydrides. This group of curing agents provides the best hightemperature performance. Boron triuoride monoethylamine, oxalic acid, and maleic and phthalic anhydride are used for electrical or high-temperature applications, often with catalysts such as benzyldimethyl amine (BDMA) or DMP 30. Table 2 lists properties and characteristics of various curing agents. C. Reactive Diluents In addition to the monofunctional epoxies described under resins, products with active hydrogens, such as furfuryl alcohol, coal tars, or phenols, will react with the epoxy resins
Table 2 Epoxy Curing Agents Usage (phr)a 1012 1315 58 2225 1215 Uncatalyzed cure ( C) Ambient Ambient 4080 Ambient 60100 150180 Longer-pot-life general-purpose expoxies HDT ( C) 80100 Applications Short pot life Ambient curing systems

Curing agent Aliphatic primary amines Diethylene triamine Tetraethylene pentamine Diethylamine propylamine n-Aminoethyl piperazine Aromatic primary amines m-Phenylene diamine

Methylene dianiline Tertiary amines Benzyl dimethylamine Tris (dimethylaminomethyl) phenol Amides Dicyandiamide Acids Boron triuoride monoethylamine Oxalic acid Anhydrides Phthalic anhydride Maleic anhydride
a

2528 610 36

60100 60100 2060 80100 Catalysts, especially with polysulde

35

120160

120

Latent catalysts for one-pack epoxies Heat-resistant epoxies Catalyst for anhydrides Encapsulation

24 510

120150 120160

175 60120

6080 5080

120140 80120

120150

DGEBA epoxy of EEW 200.

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to form part of the cured structure. Triphenyl phosphite both reacts and accelerates. Lactams also react with the hardeners. Since all these products tend to degrade the performance of the cured product, it is preferable to use difunctional low-viscosity epoxies to reduce viscosity. Where applicable, functionality of reactive diluents must be allowed for when calculating ratios. D. Plasticizers Conventional plasticizers may be used in formulated products. Phthlate esters are the preferred plasticizers. They exhibit little tendency to migrate and have good compatibility with both resins and hardeners. Addition rates are typically 5 to 20%. Chlorinated plasticizers may be used to reduce ammability, especially in conjunction with antimony trioxide. The eect of plasticizer additions is generally to degrade most physical properties, although at low additions the eect is usually small. The eect of plasticizer additions on various important properties is as follows: Pot life: lengthened Impact resistance: increased Peak exotherm, tensile strength, chemical resistance, HDT: decreased It should be noted that plasticizers do not introduce marked exibility into epoxy resin systems. Nor is this generally a desirable attribute in adhesive applications, where epoxies are usually selected because of their great strength. E. Fillers

Two types of llers may be incorporated into formulated epoxy systems. Powder llers are added to increase viscosity, improve abrasion resistance and gap-lling properties, impart specic electrical or mechanical properties, or reduce cost and shrinkage. Addition levels may be 50 to 300 parts by weight of resin (phr). Although most llers will increase the density of the cured product, certain lightweight llers will decrease density. Viscosity increases depend on surface area, oil absorption, and ller type. Chemical resistance may be improved or made worse, depending on llers selected. Highly alkali llers should be avoided, especially with acid-cured systems, as they may retard setting. Fibrous llers may be added to impart specic rheological properties or to reinforce the system. They will usually improve both tensile strength and impact resistance. Addition levels are much lower at 10 to 50 phr, as they usually cause much more rapid thickening. Table 3 lists common llers. Settlement of llers during storage depends primarily on the particle size of the ller and its density, and the viscosity of the formulated product. Settlement can be reduced or eliminated by proper formulation. Fine particle llers with relatively low specic gravity in high-viscosity products will settle much less, especially if the product is at all thixotropic. Where coarse llers must be used, an approach toward a fully lled voidless system where the volume of liquid is such as just to ll the voids will solve the problem. Incorporation of ne llers, use of a pigment-dispersing aid, and where application permits, use of a thixotroping agent will help to reduce or eliminate settlement. Depending on addition levels, llers will generally increase the usable life and extend the cure time of the mix. Tensile and compressive strength usually increase maximally then decrease on further additions. Most llers have relatively little eect on HDT. Chemical resistance will vary from ller to ller. Shrinkage is usually reduced.
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Table 3 Filler

Fillers and Extenders Specic gravity 2.52.7 2.52.7 2.62.8 2.32.6 2.02.2 2.52.7 8.89.0 3.2 2.42.6 Oil absorption (%) 2030 1530 1525 3060 Relative cost Low Low Low Low Medium High High Medium High Low Medium Usage level 50500 50300 50300 20100 550 20100 20100 50200 1050 520 1050 Purpose Bulk, price reduction, stability, and reduced exotherm Thermal and electrical conductivity Abrasion resistance Low-density Reinforcement Reinforcement

Silica Quartz Calcium carbonate China clay Carbon Aluminum powder Copper powder Silica carbide Microballoons Asbestos Glass ber

F.

Solvents

Although a major advantage of epoxy adhesives is their ability to be formulated without solvents, under certain circumstances solvents may be included. On porous substrates solvents may be added to reduce viscosity and assist penetration. On certain nonporous substrates, particularly some plastics, addition of a small percentage (1 to 3%) of a suitable solvent will improve adhesion. Common solvents are low-boiling aromatic solvents, ketones, or esters. G. Additives

Additives are typically products added at levels of 0.1 to 0.5% to modify specic properties. Most commonly used additives are defoamers, antisettling or wetting agents, thixotropes, and adhesion promoters. Use of antioxidants or preservatives is rare. Because of their minimal shrinkage, compressive strength of cured epoxies is very high. Since aeration will reduce this substantially, use of defoamers, especially in heavily lled systems, is quite common. Many defoamers are suitable, but silicone-based defoamers should be avoided on surfaces where adhesion in critical. Addition levels of 0.05 to 0.2% usually suce. Antisettling agents, pigment dispersers, or wetting agents may be included in lled formulations. Depending on the formula, particularly the selection of llers, such products may reduce or eliminate settlement. Usuage will generally be at a level of 0.1 to 0.3% of formulation. These agents are best added prior to incorporation of the llers. Various thixotropes are used in epoxy formulations to reduce or eliminate ow in products designed for use on vertical surfaces, to improve gap-lling properties, or to reduce settlement of llers. Fumed silica is widely used at levels of 0.1 to 3%. At low levels, the eect on viscosity is small except in high-viscosity systems, but settlement will be reduced. At higher addition levels, even low-viscosity products can be converted to rm pastes. To improve the eciency of fumed silica, especially in the resin component, small quantities of polar liquids may be added. Other thixotroping agents include Bentones and Tixogels, of which a number of grades are available, and China clay or kaolin, usually added as a ller, but which imparts thixotropy to the formulated product. Organofunctional silanes are extremely eective
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adhesion promoters. Added at levels of 0.05 to 0.2%, they can improve adhesion to certain nonporous substrates, such as glass, metals, and certain plastics. Formulators can select from a number of dierent functional groups, but generally epoxy functional types will be used in the resin component and amine functional grades in the hardener. H. Elastomers Occasionally, elastomers may be included in solvent-based formulations. Poly(vinyl butyral) improves adhesion to metal, as does nitrile rubber, while natural and synthetic rubbers may be incorporated to improve exibility.

V. APPLICATIONS Epoxy resin adhesives are used mainly in niche applications rather than as general-purpose adhesives. Due to the high strengths that can be achieved and the relatively high costs, they are generally used in structural applications in both concrete and metal bonding. Their good electrical properties allied to low shrinkage and good durability suit them for potting and encapsulating. Low shrinkage and good gap lling make epoxies ideal for applications where clamping is dicult, while the fact that both components are generally liquid up to the moment of cure means that they can be used where applications constraints require long open or assembly times. Conversely, systems with very short cure times are perfect for consumer applications. Good adhesion to nonporous surfaces allows them to be used in demanding situations. They nd major outlets in the construction, automotive, and electronics industries.

A.

Building and Construction

Water-based epoxy primers are ideal for damp porous substrates, as such primers will penetrate to an adequate depth to ensure good adhesion and produce a sound surface for bonding. Emulsiable resins and hardeners are available, and the better systems deactivate the emulsier system during cure to ensure that the cured system is not unduly water sensitive (Section VI.A). Solventless epoxy primers are used for bonding new concrete to existing concrete. Polyamide hardeners are preferred because of their ability to cure satisfactorily in the presence of water. Accelerators and diluents may be added, but llers are generally omitted. The primer is applied to the existing concrete, and the fresh concrete cast before the resin has set (Section VI.B). Epoxy adhesives are suitable for tiling, both for oor tiles in applications requiring acid or chemical resistance and in high-hygiene areas and also for tiling on vertical surfaces, where it is essential that tiles should not delaminate. Epoxy tiling systems are suitable for glazed tiles, clay and ceramic tiles, and decorative marble or granite tiles, where priming is recommended. Adhesives will usually be lled and thixotropic, especially for vertical tiling. Epoxies are also used for decorative paving in commercial and residential properties. Flooring made of small pebbles of dierent colors and textures bonded with relatively small proportions of epoxy are attractive and provide good drainage of water in areas such as swimming pool surrounds. Light-colored systems with good ultraviolet (UV) resistance are required. Hardeners should be based on isophorone diamine because of its good color stability, and UV stabilizers may be included.
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Self-leveling oors are produced from low-viscosity epoxy systems. Low-exotherm, unlled systems are preferred. The entire oor should be cast in one operation, and thickness should preferably be at least 5 mm over the entire area. Because of their excellent chemical resistance to a wide range of chemicals, epoxies are often selected for ooring in chemical plants. Systems vary from trowelable to pourable or brushable and are usually lled. Choice of hardener and ller will depend on the specic chemicals encountered. Although tables of chemical resistance from suppliers will aid in selection of a suitable system, this system should always be tested using the chemicals that the oor is expected to withstand. B. Metal Bonding

While construction applications usually require reactive hardener systems to give good room-temperature cure, many metal bonding applications require strength at elevated temperatures. Usually, however, they also permit heat curing and postcuring. Surface preparation is crucial to achieving high bond strength and will always involve at least degreasing and abrading. Because of the high strength of the substrates, joint design is also very important and should always aim to provide the largest practicable bonded areas. Since high-strength epoxies are generally hard, joint design should aim to produce bonds that are in tension or compression rather than shear or peel. Solvent-free systems may include adhesion promoters such as silicones, exibilizers such as liquid polysulde rubbers, and reinforcing llers, either brous or micronized. Room-temperature to mildly elevated-temperature systems will be cured with amidopolyamine hardeners, often at ratios considerably in excess of stoichiometric requirements. This increase in hardener quantity improves exibility and adhesion at the expense of tensile strength and heat distortion temperature. For applications at higher temperatures, use is made of more reactive polyamine hardeners, often with metal powder as ller. These will have postcuring cycles of several hours at temperatures that are increased in steps up to 150 to 180 C. Alternatively, solvent-based hybrid systems can be formulated, incorporating phenolic resins, nitrile rubbers, and poly(vinyl acetals). These solvent-based systems are typically single-component, applied to both mating surfaces. After the solvent has ashed o, the assembly is clamped and cured at elevated temperature. This type of system is particularly suited to applications such as bonding of brake linings to their backing pads (Section VI.C). C. Road Making Epoxy adhesives nd applications in various aspects of road making. Two major areas are bullnosing and xing of reective road studs. Bullnosing requires a system with good impact and compressive strengths and a pot-life time of 1 to 4 h. Cast masses are on the order of 5 to 25 kg, so low-exotherm systems should be used. Fillers and exibilizers may be included. Fixing of road studs is often performed on roads that are in use, so cure time should be as short as is practicable. Again, good impact and compressive strengths are required. D. Wood Bonding Although PVA adhesives for nonstructural applications and formaldehyde-based resins for structural applications have price advantages over epoxies and oer excellent
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performance, epoxies have advantages in certain applications. First, the open time may be as long as required. Second, with suitable primers they give more reliable bonds on dicult species, such as very dense or oily timbers. Third, they may be used to bond wood to other surfaces, such as metal or concrete, although in this case the formulator will concentrate more on the other substrate, as wood is not a dicult surface for epoxy adhesives. Primers may be emulsions in water or, particularly on oily surfaces, a conventional epoxy reduced to low viscosity with suitable solvents. The adhesive may also contain solvents to reduce viscosity and allow high ller loadings.

E.

Engineering Applications

Epoxies nd many applications in industry, especially on the engineering side. Grouting of bolts into concrete or rock surfaces, either to strengthen a rock face or for xing of heavy machinery, is a common application. Such adhesives are usually lled systems, often using reactive hardeners to achieve rapid setting. Epoxy systems for horizontal grouting will usually be thixotropic to prevent the adhesive from slumping or owing out (Section VI.D). Crusher backing epoxies are used to ll the gap between the replaceable liners and the outer housing in industrial crushers. These products have conicting requirements: fast setting but with low exotherm even in large volumes, low viscosity for easy pouring but with minimal settlement of llers. In addition, they must have good impact resistance, negligible shrinkage, and be easy to remove when the liners are replaced. F. Electrical Applications

Excellent electrical insulation makes epoxy systems suitable for potting and encapsulation of electrical and electronic components. Here use is made of one-pack epoxies employing latent curing agents such as dicyandiamide. At the curing temperature the system will have very low initial viscosity, ensuring good wetting and bubble release. The low residual stresses protect components from mechanical damage. Fillers or pigments may be added to render the cured article opaque. The low shrinkage and good durability of epoxies also ts them for capable jointing compounds. Here a measure of exibility is desirable. The cured article may need to be worked on from time to time, so systems that can be cut or peeled o may be required. Usable lives of 15 min to 1 h are the norm. Components should be selected for good water resistance (Section VI.E).

G.

Film Adhesives

Latent catalysts used in conjunction with either liquid or solid resins are cast in thin lms on plastic or release paper for unsupported lms or onto absorbent papers or cloths for supported lms and then cured to B stage. These lms can subsequently be cut to shape and placed between mating surfaces for subsequent heat curing (Section VI.F). H. Miscellaneous Applications Epoxy adhesives are popular for retail or consumer applications. They may be supplied as liquids, pastes, putties, or as one-pack systems in stick form. Considerable ingenuity has
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been employed in the packaging to ensure that stoichiometric ratios are roughly correct. They are usually available as 5 min systems using mercaptan accelerators or standard setting systems where amidopolyamine hardeners are preferred because their mix ratios are relatively noncritical, and they lend themselves to formulating 1:1 mix ratios (Section VI.G). Mercaptan accelerators are also used for systems with very short pot life, in automatic dispensing machines which meter the components, mix, and dispense in seconds. Systems with pot lives of 40 s can be handled in automated production lines. Epoxy resins are employed in a number of other niche applications, including adhesives to control static buildup in computer installations, carveable epoxies for pattern making and tooling, and acid-resistant adhesives for fastening tops to automotive batteries and for laminating and repair of glass-reinforced plastics. A selection of guide formulations for various applications follows.

VI.

GUIDE FORMULATIONS

Parenthetical numbers that follow the components listed in the formulations below correspond to these suppliers: 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. Hoechst AG Cray Valley Products Dow Chemicals Anchor Chemicals Degussa Thiokol Corp. Shell Chemicals Union Carbide Sud Chemie AG CIBA GEIGY SKW Trostberg Diamond Henkel

A.

Water-Based Epoxy Primer

20.0 20.0 5.010.0 55.050.0

Beckopox EP 140 (1) Versaduct 429 (2) n-Butanol Water

B.

Epoxy Adhesive for Bonding New Concrete to Old

DER 331 (3) Epodil L (3) Aerosil 200 (5) Water 80.0 15.0 4.5 0.5 100.0 Hardener: Ancamine MCA (4) Ancamide 500 (4) Anchor K54 (4) Thiokol LP 3 (6) 30.0 24.0 6.0 40.0 100.0

Base:

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C. Metal-to-Metal Adhesives 1. Ambient Cure

Base: Epikote 880 (7) Epikote 834 (7) Silane A 187 (8) 80.0 19.8 0.2 100.0 Beckopox EP 151 (1) Beckopox EP 140 (1) Quartz powder Beckopox EH 610 (1) Beckopoz EH 652 (1) 16.0 16.0 50.4 7.2 10.4 100.0

Hardener:

Versamid 125 (2)

100.0

2. Elevated Cure
Base: Hardener: Beckopox EP 140 (1) Amicure CG 1200 (4) Ancamine 2014 AS (4) Amicure UR (4) 100.0 7.0 2.0 3.0 12.0 DER 331 (3) DEN 438 (3) Phenodur PR 263 (1) Mowital B30H (1) Nitrile rubber Methyl ethyl ketone Toluene Cure schedule: 15 min/180 C 5.0 20.0 25.0 5.0 5.0 10.0 30.0 100.0

Cure schedule: 60 min/130 C

D. Grouting Adhesive
Base: DER 331 (3) DER 732 (3) Silica 150 mesh Tixogel VZ (9) 45.0 5.0 46.0 4.0 100.0 Hardener: MDA Thiokol LP 3 (6) m-Cresol Silica 150 mesh Tixogel VZ (9) 15.0 15.0 15.0 50.0 5.0 100.0

E.

Cable Jointing Epoxy

Araldite GY 260 (10) Epodil L (4) Quartz our 100.0 20.0 15.0 135.0 Hardener: Ancamine LV (4) Quartz our Magnesium silicate 60.0 72.0 3.0 135.0

Base:

F.

Film Adhesives for Preimpregnation

100.0 86.0 3.0 189.0 Solvent type DER 652 (3) Dyhard 100 S (11) Dimethyl formamide Dowanol PM (3) BDMA 133.0 4.0 15.0 15.0 0.3 167.3

Hot-melt type Epikote 880 (7) Epiclon B570 (4) Amicure DB/U (4)

Copyright 2003 by Taylor & Francis Group, LLC

G.
Base:

Fast-Setting Retail Epoxy Liquid

DER 331 (3) 100.0 Hardener: Capcure 3-800 (12) Capcure EH-30 (12) 90.0 10.0 100.0

VII.

SUMMARY

Advantages of epoxy resin adhesives may be summerized as follows: 1. 2. 3. 4. 5. 6. 7. 8. Ability to bind a wide range of substrates. Negligible shrinkage during cure, which minimizes stresses. Elimination of galvanic corrosion when bonding dissimilar metals. Solvent-free liquids with open times similar to pot life. Minimal clamping requirements. High strength, good durability, and resistance to a wide range of environments. Flexible formulating, permitting a wide range of pot lives, application conditions, and cured properties. Stoichiometrically cured epoxies generally inert and physiologically harmless.

Disadvantages are: 1. 2. 3. 4. 5. 6. 7. 8. Two-component systems require mixing in correct ratios, with attendant pot-life problems. Many components toxic or irritants. Relatively poor heat resistance of many cured systems. Inherent brittleness, requiring careful joint design. Poor cure at low temperatures. Careful surface preparation required. Need for skilled applicators. High cost.

ACKNOWLEDGMENTS My thanks to Hoechst AG, Dow Chemicals, and Anchor Chemical Division of Air Products for the information and assistance provided.

BIBLIOGRAPHY
Dow Epoxy Resins in Adhesives, Dow Chemical Company, technical bulletin. Formulating with Dow Epoxy Resins, Dow Chemical Company, technical bulletin. Lee H. and Neville, K., Handbook of Epoxy Resins, McGraw-Hill, New York, 1967. Reader, C. J. and Hunt, N. T., Adhesives, Tooling, Electronic Insulation and Laminating, Anchor Chemicals, Division of Air Products, technical bulletin.

Copyright 2003 by Taylor & Francis Group, LLC