Rubber adhesion

Synthetic resins are extensively used, e.g., in surface finishes, in the fabrication and repair of boat and motor vehicle bodies, in the manufacture of laminated boards, for electrical components, in pattern making and in paints and varnishes. Non-rubber adhesives made from fish glues and from cotton derivatives (e.g. cellulose acetate) tend not to be sensitizing but, depending upon composition and the manner of use, many other types may pose significant dermatitic and fume hazards. 

Raphael, E. and de Gennes, P.G., Rubber-rubber adhesion with connector molecules. J. Phys. Chem., 96, 4002-4007 (1992). 

Wi is the weight fraction of the elastomer, W2 the tackifier, W3 a further compatible additive, such as an oil, and so forth, for the remaining components in the formulated PSA. Application of the Fox equation to the poly (/-butylstyrene) tackified natural rubber adhesive (cited above) gives a value of —11°C, in good agreement with the interpolated value of — 13°C. 

Thermoplastic block copolymers were used for pressure-sensitive and hot-melt rubber adhesives as from the middle sixties. These adhesives found application in packaging, disposable diapers, labels and tapes, among other industrial markets. The formulation of these adhesives generally includes an elastomer (generally containing styrene endblocks and either isoprene, butadiene or ethylene-butylene midblocks) and a tackifier (mainly a rosin derivative or hydrocarbon resin). 

One of the most common rubber adhesives are the contact adhesives. These adhesives are bonded by a diffusion process in which the adhesive is applied to both surfaces to be joined. To achieve optimum diffusion of polymer chains, two requirements are necessary (1) a high wettability of the adhesive by the smooth or rough substrate surfaces (2) adequate viscosity (in general rheological properties) of the adhesive to penetrate into the voids and roughness of the substrate surfaces. Both requirements can be easily achieved in liquid adhesives. Once the adhesive solution is applied on the surface of the substrate, spontaneous or forced evaporation of the solvent or water must be produced to obtain a dry adhesive film. In most cases, the dry-contact adhesive film contains residual solvent (about 5-10 wt%), which usually acts as a plasticizer. The time necessary... 

The dry adhesive films on the two substrates to be joined must be placed in contact to develop adequate autoadhesion, i.e. diffusion of polymer rubber chains must be achieved across the interface between the two films to produce intimate adhesion at molecular level. The application of pressure and/or temperature for a given time allows the desired level of intimate contact (coalescence) between the two adhesive film surfaces. Obviously, the rheological and mechanical properties of the rubber adhesives will determine the degree of intimacy at the interface. These properties can be optimized by selecting the adequate rubber grade, the nature and amount of tackifier and the amount of filler, among other factors. 

The diffusion process in natural and polychloroprene rubber adhesives can be explained by Campion s approach [1] which considers the concept of molecular free volume. This free volume is mainly affected by the solvent mixture of the adhesive (which will determine the degree of uncoiling of rubber chains) and by the ingredients in the formulation (mainly the amount and type of tackifier). 

Natural rubber adhesives were traditionally used as contact adhesives. However, synthetic polymers are more generally used today. Polychloroprene adhesives are the most common contact adhesives based on synthetic rubber, although recently some have been displaced by polyurethane and acrylic polymers [2]. 

In recent years, the use of solvent-borne adhesives has been seriously restricted. Solvents are, in general, volatile, flammable and toxic. Further, solvent may react with other airborne contaminants contributing to smog formation and workplace exposure. These arguments have limited the use of solvent-bome adhesives by different national and European regulations. Although solvent recovery systems and afterburners can be effectively attached to ventilation equipment, many factories are switching to the use of water-borne rubber adhesives, hot melts or 100% solids reactive systems, often at the expense of product performance or labour efficiency. 

Because most latices have low viscosities by compounding, most of the waterborne rubber adhesives are sprayable. Thickeners such as fumed silicas can be added to increase viscosity and thixotropy. This means that even at relatively large viscosities (over 10 Pas) many water-based rubber adhesives can be sprayed. Dip and curtain applications require viscosities between 0.05 and 0.3 Pas, whereas brush application works with viscosities between 1 and 50 Pa s. 

Typieal composition of a solvent-borne rubber adhesive Elastomer 100 phr... 

Typical composition of a water-borne rubber adhesive Latex polymer 100 phr... 

Typical formulation of a pressure-sensitive rubber adhesive... 

Typical formulation of hot-melt rubber adhesive Thermoplastic elastomer 100 phr... 

Natural rubber can be obtained from the sap of a number of plants and trees, the most common source is the Hevea brasiliensis tree. Although natural rubber was known in Central and South America before the arrival of Christopher Columbus in 1492, the first use as an adhesive was established in a patent dated in 1891. As rubber became an important part of the industrial revolution, the rubber adhesives market grew in importance. To comply with the increasing demand on natural rubber materials, plantations of Hevea brasiliensis trees were established in southeast Asia in the early 20th Century, mainly to supply the demand from the automobile industry. 

Butyl phenolic resin is a typical tackifier for solvent-borne polychloroprene adhesives. For these adhesives, rosin esters and coumarone-indene resins can also be used. For nitrile rubber adhesives, hydrogenated rosins and coumarone-indene resins can be used. For particular applications of both polychloroprene and nitrile rubber adhesives, chlorinated rubber can be added. Styrene-butadiene rubber adhesives use rosins, coumarone-indene, pinene-based resins and other aromatic resins. 

Rubber-grade resins are mostly in the softening point range 70-100°C R B. A deviation of 5-10°C in softening point may cause problems. The softening point of a resin affects the properties of adhesives. Hence, for pressure-sensitive rubber adhesives the decrease in the softening point of the resin produces a more tacky adhesive with less cohesive strength. 

Plasticizers can be classified according to their chemical nature. The most important classes of plasticizers used in rubber adhesives are phthalates, polymeric plasticizers, and esters. The group phthalate plasticizers constitutes the biggest and most widely used plasticizers. The linear alkyl phthalates impart improved low-temperature performance and have reduced volatility. Most of the polymeric plasticizers are saturated polyesters obtained by reaction of a diol with a dicarboxylic acid. The most common diols are propanediol, 1,3- and 1,4-butanediol, and 1,6-hexanediol. Adipic, phthalic and sebacic acids are common carboxylic acids used in the manufacture of polymeric plasticizers. Some poly-hydroxybutyrates are used in rubber adhesive formulations. Both the molecular weight and the chemical nature determine the performance of the polymeric plasticizers. Increasing the molecular weight reduces the volatility of the plasticizer but reduces the plasticizing efficiency and low-temperature properties. Typical esters used as plasticizers are n-butyl acetate and cellulose acetobutyrate. 

To reduce cost. Clay and talc are the most common fillers in rubber adhesives. 

Aromatic amines are the most effective primary antioxidants (Fig. 34) but they are discolouring and can only be used where the darker colours are acceptable (for instance in rubber adhesive formulations containing carbon blacks as fillers). The... 

Another method for slowing oxidation of rubber adhesives is to add a compound which destroys the hydroperoxides formed in step 3, before they can decompose into radicals and start the degradation of new polymer chains. These materials are called hydroperoxide decomposers, preventive antioxidants or secondary antioxidants. Phosphites (phosphite esters, organophosphite chelators, dibasic lead phosphite) and sulphides (i.e. thiopropionate esters, metal dithiolates) are typical secondary antioxidants. Phosphite esters decompose hydroperoxides to yield phosphates and alcohols. Sulphur compounds, however, decompose hydroperoxides catalytically. 

Antioxidant activity is not a linear function of concentration. As the antioxidant level increases, less and less improvement in oxidative stability is noted. Therefore, only enough antioxidant should be added to rubber adhesives, typically 1 to 2 phr. 

Nitrile rubber adhesives. The main application corresponds to laminating adhesives. PVC, polyvinyl acetate and other polymeric films can be laminated to several metals, including aluminium and brass, by using NBR adhesives. NBR adhesives can also be used to join medium-to-high polarity rubbers to polyamide substrates. The adhesive properties of NBR rubbers can be further improved by chemical modification using polyisocyanate or by grafting with methyl methacrylate. 

This chapter reviews the main aspects of rubber base adhesives. A detailed description of the main ingredients of rubber base adhesive has been given because most of the previous contributions in this area did not consider this important aspect. On the other hand, update of the literature in water-base rubber adhesives has been done. 

Information provided by Mr. Juan Jose Hemandez-Gonzalez from Adhesivos Heman (Leon, Mexico) on water-borne polychloroprene adhesives is greatly acknowledged. The financial support for research in rubber adhesives from the Spanish Research Agency (MCYT) and the University of Alicante is greatly appreciated. Finally, my deep recognition and acknowledgement to my wife and children for the time I took from them to write this chapter. 

Silicones. Silicones are useful where high temperature resistance or compatibility with silicone components such as molded seals are needed. Silicone firewall insulation materials and silicone gaskets and seals are bonded with silicone rubber adhesives. 

Some items, such as electrolytic capacitors and two-part adhesives, may deteriorate when dormant. Others, such as rubber, adhesive tape, and chemicals, deteriorate with the passage of time regardless of use. These are often referred to as Shelf Life Items or Limited Life Items . Dormant electronic assemblies can deteriorate in storage and provision should be made to retest equipment periodically or prior to release if in storage for more than one year. 

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