Curing acrylic adhesives

Acrylic adhesives cure by a free radical chain growth mechanism. In contrast, epoxy and urethane adhesives cure by a step growth mechanism. This has a major impact on the cure kinetics, as well as the composition of the adhesive during cure ([9], pp. 6-9). Cyanoacrylate adhesives (such as Super Glue ) also cure by chain growth, but the mechanism is ionic with initiation by surface moisture. 

Fig. 32.5 shows a thin-layer rigid adhesive bond, made with an acrylic adhesive cured under UV light The expansion and deflection of the bonded substrates causes stress peaks at the ends of the overlaps, which is why the adhesive layer is beginning to break down at this point The central part of the bond face, on the other hand, contributes very little to the load-bearing capacity of the joint. 

Acrylic adhesives cure by addition polymerization reactions. These chain reactions are initiated by the formation of free radicals that result in the adhesive curing by way of a very rapid polymer chain growth. This cure chemistry is significantly more rapid than a typical cure curve (i.e., condensation type) found in epoxy and urethane adhesives. A comparison of the cure profile of condensation (epoxy and urethane) versus addition... 

Because many acrylic adhesives cure very rapidly with a significant exotherm, manufacturers generally recommend that quantities greater than a pint (ca. 0.47 L) should not be mixed at one time. As a consequence of the rapid exothermic cure of many acrylic adhesives, the use of dual component cartridges is often ideal. Most products can be purchased in ready-to-use cartridges. For large continuous operations, various automated types of meter-mix-and-dispense equipment are marketed by a number of engineering companies. 

Some adhesives will bond cured elastomers. Typically, a thin layer (0.0025 mm thickness) of the activator is applied to one of the adherends and a layer of the adhesive (0.026-0.26 mm) is placed on the other adher-end. The two substrates are then pressed together and secured until adequate handling strength develops. Most acrylic adhesives cure to this point in 2-20 minutes, but some cure in as little as 10 seconds. In all cases, cure is completed within 24 hours. These adhesives provide excellent shear, peel, and impact strengths at temperatures ranging from -107°C to -i-121 °C. These adhesives can withstand short exposures up to 177°C. ... 

Acrylic adhesives cure by addition polymerisation reactions, which provide a rapid setting of the adhesive once the cure has initiated. 

Fig. 14 shows a thin and a thick-layer rigid adhesive bond made with an acrylic adhesive cured under UV light. The expansion and deflection of the... 

The reluctance of acrylic monomers to polymerise in the presence of air has been made a virtue with the anaerobic acrylic adhesives. These are usually dimethacrylates such as tetramethylene glycol dimethacrylate. The monomers are supplied with a curing system comprising a peroxide and an amine as part of a one-part pack. When the adhesive is placed between mild steel surfaces air is excluded, which prevents air inhibition, and the iron present acts as a polymerisation promoter. The effectiveness as a promoter varies from one metal to another and it may be necessary to use a primer such as cobalt naphthenate. The anaerobic adhesives have been widely used for sealing nuts and bolts and for a variety of engineering purposes. Small tube containers are also available for domestic use. 

Advantages are similar to the epoxy system, in that these can be solventless and do not require thermal energy. Disadvantages unique to this system, however, include the need to inert the cure chamber to avoid air-inhibition of cure as well as some release instability with acrylate adhesives [72]. 

These results demonstrate some interesting chemical principles of the use of acrylic adhesives. They stick to a broad range of substrates, with some notable exceptions. One of these is galvanized steel, a chemically active substrate which can interact with the adhesive and inhibit cure. Another is Noryl , a blend of polystyrene and polyphenylene oxide. It contains phenol groups that are known polymerization inhibitors. Highly non-polar substrates such as polyolefins and silicones are difficult to bond with any technology, but as we shall see, the initiator can play a big role in acrylic adhesion to polyolefins. 

Acrylic polymers are also important in the preparation of other classes of adhesives, especially pressure sensitive adhesives. This discussion will be limited to adhesives that cure by the reaction of unsaturated acrylic functional groups. These adhesives are also sometimes termed Methacrylate , Methacrylic or Structural Acrylic adhesives. This is consistent with the long-standing habit of organic chemists to assign multiple names to the same substance. 

The cure reaction of structural acrylic adhesives can be started by any of a great number of redox reactions. One commonly used redox couple is the reaction of benzoyl peroxide (BPO) with tertiary aromatic amines. Pure BPO is hazardous when dry [39]. It is susceptible to explosion from shock, friction or heat, and has an autoignition temperature of 79°C. Water is a very effective stabilizer for BPO, and so the initiator is often available as a paste or a moist solid [40], The... 

There are other initiator systems of lesser commercial importance. Cumene hydroperoxide is reported to cure acrylic adhesives in the presence of alkyl or pyridyl thioureas [105]. These initiators have been combined with a phosphated acrylate to promote adhesion to metal [106]. Thiourea-based initiators can be applied as a one-part on galvanized metal, where the metal surface provides the second part of the redox initiator [107]. 

The ability to tailor acrylic adhesives to fast cure times allows their use on fast, highly mechanized production lines such as those for audio speakers [150]. 

In other studies [115], the bond strengths of joints made from steel substrates coated with a variety of oils and waxes ( 6 mg/cm ) and Joined with acrylic adhesive were investigated. Lap-shear strengths up to 15 MPa were obtained with room temperature curing. Very little degradation was seen after 1000 h of... 

Table 3 lists the selected properties [16] that we have measured for several commercially available acrylate resins manufactured by the Sartomer Company and the Rohm and Haas Company. The resins were cured in an AECL Gammacell Model 240. The temperature rise was measured for an 8-g sample using Acsion s (formerly AECL Radiation Applications Branch) Gamma Calorimetry method [17]. All of this information is being used to evaluate the applicability of EB-cured acrylate adhesives for repairing composite structures. Combinations of these adhesives can be used to create electron-curable adhesives suitable for composite repair. 

Loctite has developed several acrylate adhesives that can be used as EB-curable adhesives [12]. Some of the resins were cured and tested for EB curing properties... 

Lap shear strengths for EB-cured acrylic adhesives on graphite composites... 

EB curing and shrinkage properties for selected EB-cured acrylic adhesives... 

Cyanoacrylates and Light-Curing Acrylic Adhesives - These types of adhesives have achieved widespread acceptance in high-speed manufacturing because they cure rapidly, offer high bond strength to many substrates and are easy to dispense 9. (See Reference 189 for the structure of these chemicals.)... 

Generally, acrylic adhesives are cured with a two-part redox system—one part of which (the initiator ) is in the base component, and the second (the curative ) in the accelerator. Most often the former is a hydroperoxide, while the curative is a reaction product of aniline and n-butyraldehyde. 

Paste adhesives are supplied as either one- or two-component adhesive systems. They can be used in applications where pressure cannot be applied. Some two-part pastes cure at room temperature after the appropriate proportions are mixed. Epoxy, urethane, and acrylic adhesives are all available as paste adhesives. 

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