41

Technology of Cyanoacrylate Adhesives for Industrial Assembly

William G. Repensek
National Starch and Chemical Company, Oak Creek, Wisconsin, U.S.A.

I. INTRODUCTION Adhesives have been used since ancient times, but only since the advent of synthetic polymers (plastics) has their use become of major importance because manufacturers can now synthesize polymers and compound adhesive formulations to t the requirements of the application. In other words, adhesives can be engineered for improved characteristics such as speed of cure, heat resistance, and impact resistance. Cyanoacrylates are just such an adhesive. Cyanoacrylate adhesives can be dened as single-component chemically active liquids that react very rapidly with moisture or other weakly alkaline materials to form clear, hard solids. Their important characteristics are: 1. 2. 3. 4. 5. Very fast curing Applied as liquids Cured by a chemical reaction Activated by alkaline materials Form hard plastic materials after curing.

II.

CHEMISTRY OF THE SYSTEM

The term cyanoacrylate comes from the chemical structure of these materials. Figure 1 depicts the general formula for cyanoacrylates. As the gure shows, cyanoacrylate adhesives are made up of carbon, hydrogen, oxygen, and nitrogen. The way these atoms are

Figure 1 General formula for cyanoacrylate adhesives.

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arranged in the molecule is important because the arrangement or conguration of the atoms aects the chemical properties of the molecule. The CN group is called a nitrile or cyano group. In addition to giving these adhesives part of their name, the cyano group is highly polar and gives the molecule some of its strong adhesive character. The remainder of the molecule, the acrylate portion, is also polar and further enhances its adhesive character. The letter R is used in organic chemistry to represent a part of a molecule that diers within a family of compounds. In the cyanoacrylate family, the R group is the alcohol that forms the ester with the acylic acid portion of the molecule. The type of alcohol used gives the cyanoacrylate adhesive its name. Thus methyl cyanoacrylate is the ester formed between methyl alcohol and cyanoacrylic acid. Figure 2 shows the conguration of some of the commercially available cyanoacrylate adhesives. All of the molecules shown in Fig. 2 are thin, watery liquids at room temperature. In this low-viscosity state, these molecules are capable of owing freely onto the surface of the parts to be bonded. However, such thin liquids would have little or no ability to bridge the gap between the mated parts. The carbon-to-carbon double bond shown in Fig. 2 to be common to all cyanoacrylates is capable of reacting such that adjacent molecules are linked together to form a large chain. The chains become so large that the adhesive changes from a liquid to a hard, tough solid. The chemical reaction involved, called polymerization, is depicted in Fig. 3. The initiator that drives the polymerization or curing reaction of cyanoacrylate adhesives can be any of the chemicals that generate free radicals. Electromagnetic

Figure 2 Conguration of common cyanoacrylate adhesives.

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Figure 3 Polymerization of cyanoacrylate adhesives.

radiation in the form of heat or ultraviolet light can also trigger the reaction, but usually only enough to cause problems with product shelf life. The more likely route for cyanoacrylate polymerization is by an ionic initiation. Any molecule more alkaline than water can initiate the curing reaction. This type of polymerization is characteristically much faster than a free-radical type and is the reason that cyanoacrylates cure so rapidly. It is this cure speed more than any other property that makes these adhesives so popular on the production line. Many adhesives are stronger or more durable than cyanoacrylates, but none can cure as quickly and to such a wide variety of substrates as the cyanoacrylates. Although it is not essential to understand the chemistry of cyanoacrylate polymerization to be able to use these adhesives, knowing that a chemical reaction is taking place helps the user to understand how application conditions aect their performance. Consider the fact that the common polymers, such as polyethylene, polystyrene, and poly(vinyl chloride) (PVC), are made in sophisticated reactors. Parameters such as temperature, monomer concentration, and amount of activator are carefully controlled. With cyanoacrylate adhesives, the reactor used to convert the liquid monomer to the hard solid is the space between the parts being bonded. When conditions vary in this space, the performance of the adhesive will vary. Such parameters as temperature, humidity, space between the parts, and the type of surface being bonded can vary considerably in a given application. Figure 2 shows a number of dierent types of cyanoacrylic esters. There are subtle dierences between them that can be utilized in specic applications. Methyl cyanoacrylate is a more polar compound than any of the others. This gives the cured adhesive a higher cohesive, or internal, strength. As a result, it has a higher shear strength which can be utilized on metal parts and other parts that are rigid enough themselves to benet from the strength of this hard, brittle polymer. Ethyl cyanoacrylate is a little less polar than methyl cyanoacrylate, and has the ability to wet plastic surfaces more readily, and is a better solvent for plastics. With this added ability to make intimate contact with the surface, the bonds on plastic are stronger with ethyl cyanoacrylate than with the methyl ester. This dierence in performance gives rise to the adage that methyl is for metal and ethyl is for everything else. Sometimes this dierence can be utilized in reverse to good advantage to avoid stress cracking on such sensitive plastics as polycarbonate and polyacrylate. Also shown in Fig. 2 is an allyl cyanoacrylate. This molecule contains a second double bond that can be made to react after the initial polymer chain is formed. This secondary bonding can occur between adjacent polymer chains, causing cross-linking of the chains. Such cross-linked polymer chains are more heat resistant than is the uncrosslinked polymer. The data presented in Table 1 compare the heat resistance of allyl cyanoacrylate and methyl cyanoacrylate determined by heating a steel lap shear specimen for 1 week
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Table 1 High-Temperature Resistance of Allyl Cyanoacrylate Shear strengtha Temperature ( C) 25 100 120 150 250 Allyl 3000 3900 900 1500 1700 Methyl 3600 250 0 0 0

a Steel/steel per ASTM D1002. Aged 1 week at temperature indicated, cooled and measured at 25 C.

at various temperatures. At room temperature the two types are essentially equal in strength. The slightly higher strength of the methyl cyanoacrylate caused by its higher polarity can be seen clearly in the higher value obtained in the test cured and aged at room temperature. The eect of exposure to 100 C shows up in the loss of strength for the uncrosslinked methyl cyanoacrylate and a higher strength for the allyl cyanoacrylate because of the extra strength contributed by the reaction of the double bond in the allyl cyanoacrylate. After exposure to 120 C, all the strength of the straight-polymer-chain methyl cyanoacrylate is lost. The strength of the cross-linkable allyl cyanoacrylate is also reduced, suggesting the loss of the contribution to its strength by intermolecular association. Only the contribution from the allyl group survives. Higher temperature causes the allyl double bonds to react faster. As a result, more cross-linking can take place and more of the strength is retained. Resistance to temperature above 120 C is possible provided that the parts are clamped during the curing process. Because of the extensive cross-linking, the resultant polymer is very brittle and it is recommended only for metal and other rigid, higher-temperature-resistant substrates. The fourth type of cyanoacrylates presented in Fig. 2 are the alkoxyalkyl esters. Methoxyethyl cyanoacrylate and methoxyisopropyl cyanoacrylate esters have all the desirable properties of the methyl, ethyl, and allyl cyanoacrylates, with the added advantage of low vapor pressure. As a result, these monomers have little or no odor, which makes them popular for use in environments where ventilation is a problem. The low vapor pressure also reduces the fogging of adjacent parts so often seen with regular cyanoacrylates on damp days, a problem discussed in more detail below. In addition to the benets of low odor and reduced fogging, these adhesives form stronger bonds to low-energy substrates such as EPDM rubber, natural rubber, and other dicult-to-bond plastics. This property seems to be a function of the solvent action of the uncured adhesive, so care must be taken to avoid stress cracking when the adhesive is used on sensitive substrates such as polycarbonates and polyacrylates. While the alkoxy cyanoacrylates cure by the same mechanism as regular cyanoacrylates, the cure speed is a bit slower and the overall strength is about 20% lower than that of ethyl cyanoacrylates. The strength is well in excess of the strength of more plastic substrates, however; the 20% reduction in strength is not signicant.
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Figure 4 Hot strength of allyl cyanoacrylate, 100 cP Brookeld, bond cured at room temperature for 24 h, heated for 2 h at temperature and tested hot.

Table 2 Temperature Performance of Allyl Cyanoacrylates Lap shear strength (psi) (steel) Room temperature 100 C (212 F) 250 C (480 F) 3112 3353 1493

III.

HOT STRENGTH

In general, standard industrial cyanoacrylates do not operate eectively above 180 F (see Fig. 4). However, the new allyl types of cyanoacrylates can operate as high as 480 F before the bond loses sucient strength to be operationally eective (see Table 2). Allyl cyanoacrylates for metal-bonding applications have proven eective in wave solder and under-hood (automotive) applications. In Fig. 4, bonded assemblies are cured at room temperature for 24 h. The assemblies are heated for 2 h and tested hot.

IV. SPEED OF CURE A typical cure curve for 100-cP methyl cyanoacrylate is shown in Fig. 5. The speed of cure is inuenced by the thickness of the bond, the activity of the surface, and the designed speed of the adhesive. 1. Versatile. There are few materials to which cyanoacrylate will not bond/adhere, even dissimilar materials (polyethylene, polypropylene, and Teon are some materials that require pretreatment). One-component without solvent, therefore easily dispensed. Economical. A small drop goes a long way. It is important to apply the least amount for maximum strength (see Table 3).

2. 3.

The following equivalents are for application of the adhesive to actual parts. 1 lb 30,000 bonds 1 in. square and 1 mil thick 1 oz 1,875 bonds 1 in. square and 1 mil thick 2 g 132 bonds 1 in. square and 1 mil thick
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Figure 5 Typical cure curve for 100- cP methyl cyanoacrylate.

Table 3 Approximate Conversion Chart for Estimating Usea 1 drop = 0.006 g 2 drops = 0.012 g 5 drops = 0.030 g 10 drops = 0.060 g 50 drops = 0.300 g (1 3 g) 167 drops = 1.00 g 330 drops = 2.00 g 4,666 drops = 1 oz 75,500 drops = 1 lb
a

Based on the assumption that 1 drop = 0.006 g.

Figure 6 Gap-lling capability of cyanoacrylate.

Cyanoacrylate adhesives have limited gap-lling capability (see Fig. 6). Lowviscosity grades can ll gaps to approximately 2 mils, medium viscosity up to 10 mils, and high viscosity up to 15 to 20 mils. However, note that the speed of cure will be slower and the ultimate strength lower as the gap increases. For example, when the gap is 15 mils it requires 1 h for sucient handling strength, but with a gap of 1 mil it takes only 10 s. Cure speed can be increased by the use of a chemical accelerator. Moisture and water resistance is limited. Resistance against water, although poor when two rigid parts are bonded, is markedly improved when at least one of the two parts is exible.
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Table 4 Typical Fixture Time with Activatora Gap (in.) 0.000 0.005
a

With activator 1s 50 s

Without activator 10 s 600 s

Steel/steel, 25 C, ethyl cyanoacrylate.

V. ACTIVATORS Since bases are catalysts for the curing reaction and acids are stabilizers for the cyanoacrylates, the pH value of the surface will control the cure speed. Surfaces that tend to be acidic will cure slowly compared to a neutral surface, which in turn will cure more slowly than an alkaline surface. In most applications the objective is to speed the cure; therefore, all the commercially available activators are weak bases dissolved in a volatile carrier. Applying an activator to a surface places a layer of the weak base in position to initiate the cure. Since they are stronger bases than moisture, they are able to neutralize the stabilizer systems in the adhesive more eectively, and thus they can tolerate larger gaps than would be possible with moisture alone. In general, the xturing time is 10 times faster with activator than without it. Even with activator, the eect of the gap is clear (see Table 4). Another advantage of the activator is the ability to cure a lm or drop of the adhesive on a surface. The activator can be applied either to the surface being coated or to the top surface of the adhesive. The adhesive cures to a clear, hard, dry plastic that can be used to locate parts in position or to form a protective coating. Because the curing reaction is ionic, it is not sensitive to oxygen as are free-radical reactions, and it will cure through to the surface without the tackiness associated with free-radical curing systems.

VI. IMPROVED COMMERCIAL CYANOACRYLATE COMPOUNDS A. New Flexible Cyanoacrylates

New cyanoacrylate compounds exhibit good adhesion to various plastics and elastomeric surfaces, such as Mylar, copper foil, and vinyl lms. These products show better impact resistance and good exibility compared to standard cyanoacrylates, good resistance to cracking under exing or bending, and a longer open time than that of standard products. B. New Cure-Through-Gap Cyanoacrylates

Through changes in the manufacturing process, cyanoacrylates can now be highly puried. This added purication step has led to the development of a group of materials that can cure through a gap without the typical reduction in shear strength and overall performance. More traditional formulations show a dramatic reduction in shear strength as the gap increases (see Fig. 6). Table 5 shows cure through a gap and the corresponding shear strength for these new, highly puried cyanoacrylates.
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Table 5 Time (h) 2 24 72

Percent Cure Through 0.008-in. Gap Gap-lling cyanoacrylate 25 100 100 Regular cyanoacrylate 13 40 100

Table 6 Set Time Across a 0.004-in. Gap Time (s) Product viscosity (cP) 100 500 1500 8000
a

Surface-insensitive cyanoacrylate 68 712 812 812

Ethyl cyanoacrylate 55 >60 >60 n.a.a

Not applicable.

C. New Ultrafast-Cure Surface-Insensitive Cyanoacrylates The new range of surface-insensitive cyanoacrylates provides ultrafast cures independent of gap. In addition, these cyanoacrylates will rapidly bond acidic and low-energy surfaces. The fast cure also minimizes the occurrence of frosting and fogging. Table 6 shows a comparison of these new surface-insensitive materials compared to a standard ethylgrade cyanoacrylate. These products are also suited to bonding various wood substrates and porous surfaces without the use of activators. D. New Low-Odor Cyanoacrylates Owing to unique manufacturing processes and chemical reformulations, cyanoacrylates can now be completely odor free. These products, which have almost no detectable odor, improve worker comfort and acceptance. Also, there is no unsightly fogging (chlorosis) of expensive parts adjacent to the bond line as can be seen with other types of cyanoacrylate adhesives on hot, humid days. This improves production rates of acceptable parts.

VII. A.

SIGNIFICANT CYANOACRYLATE CHARACTERISTICS Polypropylene and Polyethylene Bonding

Polyolen bonding has been advanced using cyanoacrylates through the use of surface primers. These primers promote adhesion to untreated polyethylene (PE), polypropylene (PP), and EPDM rubber. Table 7 shows comparison bonds using standard industrialgrade cyanoacrylates.
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Table 7 Comparison Bonds Using Standard Industrial-Grade Cyanoacrylates PE/PE Lap shear (psi) After 15 min, room temperature After 24 h, room temperature Primed 90 108 Unprimed 50 50 Primed 185 200 PP/PP Unprimed 52 52

Figure 7 Durability of cyanoacrylate adhesives. Asterisk denotes substrate failure.

B.

Medical-Grade Materials

When fully cured, cyanoacrylates will meet class VI standards for plastics, the highest class of safety and biocompatibility as dened by the United States Pharmacopoeia (USP). C. Thermal Conductivity Cyanoacrylates are essentially thermally nonconductive materials. The value for a typical methyl-grade cyanoacrylate is 2.1 (Btu-in.)/(hr-ft2- F). D. Durability Assemblies joined with cyanoacrylate adhesives exhibit good long-term durability, particularly when the materials are somewhat exible, such as rubbers and most plastics (see Fig. 7). Bonded lap shear specimens have been aged outdoors for 7 years with good retention of strength (see Table 8). When impact resistance and/or strength is required, it can be improved dramatically by the rubber sandwich technique. In this case, a rubber sheet bonded between the rigid plastic or metal substrates will absorb all peel and impact forces. It is also useful in absorbing stresses when thermal expansion and contraction occur.

VIII.

CHLOROSIS

There are times when various environmental factors can aect bonding results. One such phenomenon is chlorosis, in which white particles appear on the bonded parts. Chlorosis
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Table 8 Strength Retention of Cyanoacrylate Bonds After Outdoor Weathering Percentage strength retention when stored at 73 F and 50% relative humidity for (yr): Material bonded Neoprene to neoprene Neoprene to acrylic Butyl rubber to aluminum Polystyrene to polystyrene Rigid PVC to rigid PVC
a

1 100 93 65a

1.5

2 80 87

5 93

7 60

92a 80a 93a

55a 83 100a
a

55a

Substrate failure.

may occur with the use of cyanoacrylate, depending on the bonding method, bonding conditions, atmospheric inuences, and other factors. The usual reaction received from users when chlorosis does occur is concern over the possible eect on the strength of the bond and the unsightly external appearance. The phenomenon of chlorosis is nothing more than an adhesion of particles to the surface of the part and has no eect on the quality of the bond. Chlorosis develops when a portion of liquid evaporates in the air without being solidied (polymerized). It becomes a powdery resin through a polymerization reaction with moisture in the air. The powdered resin falls back to the surface of the bonded parts. Chlorosis can develop under the following conditions: 1. 2. 3. Excessive amounts of adhesive. Bonding under conditions of high room moisture content (relative humidity), as may be the case during a rainy period. Subjecting the bonded portion to airtight or almost airtight conditions immediately after bonding.

Chlorosis can be avoided by taking the following actions: 1. 2. Avoid the use of adhesive in excessive amounts. Perform the bonding operation under appropriate moisture conditions (avoid excessive accumulation of water on the material surface); 50% relative humidity is ideal. a. Allow several minutes after removal of grease from the object being bonded. b. Thoroughly dry the object to be bonded before actual bonding. c. Wear polyethylene gloves during the bonding operation. Attempt as much as possible to scatter vaporizing monomer. a. Avoid subjecting bonded material to airtight or nearly airtight conditions immediately after the bonding operation. b. Ventilate the bonded object immediately after the bonding operation by use of an electric hot-air blower or other appropriate means. c. Perform the bonding operation under conditions of free air circulation. Promote the polymerization reaction (resinication). a. Assure appropriate heat conditions for the bonded object [up to about 158 F (70 C)]. b. Blow heated air over the bonded area immediately after the bonding operation.

3.

4.

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5.

Form a protective shield on the surface where chlorosis is likely to develop by applying oil to the area surrounding the material surface immediately before or after the bonding operation.

Chlorosis can be eliminated by the following: 1. 2. Wipe the particles carefully with a dry cloth. Wipe o the particles with solvent.

The particles can readily be wiped o by the use of a cloth containing a solvent such as dimethylformamide, nitromethane, acetone, or chlorinated or uorinated solvents. In this case, however, if the bonded object is plastic, caution must be exercised because plastics can be aected adversely by solvents. Poor bonding arises from problems associated with the adhesive itself: for example, its decreased adhesive power. The simplest method of checking on the spot for any decrease in adhesive power is to test with Bakelite samples. If the adhesive is found to have decreased adhesive power, it has probably been stored improperly. Material kept in the work environment up to 6 months will not suer deterioration. For periods over 6 months, storage in 40 F or below can triple the useful shelf life.

IX.

SUMMARY

Cyanoacrylates have shown themselves well in permanent outdoor assemblies as well as in temporary manufacturing aids. They are safe, convenient materials to incorporate in plant operations. New developments in technology have improved moisture resistance, setting times, gap lling, clarity, high-temperature resistance, and exibility, and most recently, cyanoacrylates have become less surface sensitive. As always, thorough testing of a specic application should precede specication. New research has led to improved commercially available models that are nding use in applications previously thought unsuitable for cyanoacrylates. Where appropriate, cyanoacrylates can increase productivity dramatically and reduce fundamental costs, to produce high-integrity parts for aircraft, industrial, agricultural equipment, electronic, automotive, and maintenance applications.

BIBLIOGRAPHY
Bittence, J. C., Machine Des. (June 1976). Cagle, C. V., Adhesives Bonding, McGraw-Hill, New York, 1968. Chastain, C. E., Appliance Eng. 8(4) (1974). Coover, H. W. Jr., Adhesive Mater. (1958). Graham, J. A., Machine Des. (1976). Helmstetter, G., Fundamentals of Cyanoacrylate Adhesives, unpublished manuscript, Permabond International, 1988. Lees, W. A., Adhesives in Engineering Design, Pitman, London, 1984. Pagel, W. A. and McKown, A. G., Industrial Adhesives for Metal and Plastic Symposium, Madison, Wis., Feb. 1966. Peace, R., Adhesives Age 22(9) (1979). Petrie, E., Assembly Eng. (June 1976).
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Repensek, W.G., Technology and Use of Cyanoacrylate Adhesives in Industrial Assembly Applications, American Fabricating Institute of Technology, Chicago, Sept. 1983. Repensek, W. G., Technolog Advances in Cyanoacrylate Adhesives for Industrial Applications, Society of Manufacturing Engineers, Dearborn, Mich., Nov. 1990. Schneberger, G. L., Adhesives Age (Jan. 1980). Weyher, D. F. Ch., Adhesives in Modern Manufacturing, Society of Manufacturing Engineers, Dearborn, Mich., 1970.

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