Curing silicone adhesives

Scheme 9. Crosslinking reaction of a two-part moisture cure silicone adhesive system.

The electrical properties, especially for the high-purity semiconductor-grade silicones, are excellent even at temperature extremes of —80 °C and 200 °C and in high humidity. Silicone adhesives are available as electrically conductive and as electrically insulative types. Typical electrical properties for moisture- and heat-cured silicone adhesives are given in Table 3.12. 

Information on particular types of adhesive may be found in articles cited above and in the following entries Hot melt adhesives. Selection of adhesives. Silicone adhesives addition cure. Silicone adhesives condensation cure. Toughened adhesives. 

Lin SB. Addition-cured silicone adhesive technology vinyl silicone crosslinker. J Appl Polym Sci. 2003 54(13) 2135-2145. 

Newer silicone adhesives having solids levels up to 97% are also commercially available [109]. Instead of using silanol condensation reactions, they rely on addition chemistry between vinyl functional silicone oligomers and silicon hydride terminated silicones. This addition reaction is typically facilitated with platinum derived catalysts. This hydrosilation process can be run at reduced oven temperatures, but the finished products typically do not yield the same balance of properties as seen for condensation cure materials. 

Silicone release coatings are the workhorses of the easy release industry because the very nature of the molecule fulfills most requirements for low adhesion. When well cured, silicone networks are fairly inert and present a very low sur-... 

A chemical property of silicones is the possibility of building reactivity on the polymer [1,32,33]. This allows the building of cured silicone networks of controlled molecular architectures with specific adhesion properties while maintaining the inherent physical properties of the PDMS chains. The combination of the unique bulk characteristics of the silicone networks, the surface properties of the PDMS segments, and the specificity and controllability of the reactive groups, produces unique materials useful as adhesives, protective encapsulants, coatings and sealants. 

Silicone adhesives are generally applied in a liquid and uncured state. It is therefore the physical and chemical properties of the polymers, or more precisely of the polymer formulation, that guide the various processes leading to the formation of the cured silicone network. The choice of the cure system can be guided by a variety of parameters that includes cure time and temperature, rheological properties in relation with the application process, substrates, the environment the adhesive joints will be subjected to and its subsequent durability, and of course, cost. 

Scheme 5. Common moisture RTV condensation cure systems for silicone adhesives and sealants. R is typically methyl (CH3-) or ethyl (CH3CH2-) group.

Like the 1-RTV systems, the two-part room temperature vulcanization systems (2-RTV) cure to produce flexible elastomers that resist humidity and other harsh environments. Interestingly, they display primerless adhesion property to many substrates, and are used in silicone adhesives, sealants, seals, and gaskets, to name a few. 

There are many applications for silicone adhesives, sealants, or coatings where the condensation curing systems are not suitable. This is because they are relatively slow to cure, they require moisture to cure that can itself be in some cases uncontrollable, and they evolve by-products that cause shrinkage. Adhesives needed in automotive, electronics, microelectronics, micro electromechanical systems, avionic, and other hi-tech applications are usually confined to vei7 small volumes, which can make access to moisture difficult. Also, their proximity to very sensitive mechanical or electronic components requires a system that does not evolve reactive chemicals. 

PDMS based siloxane polymers wet and spread easily on most surfaces as their surface tensions are less than the critical surface tensions of most substrates. This thermodynamically driven property ensures that surface irregularities and pores are filled with adhesive, giving an interfacial phase that is continuous and without voids. The gas permeability of the silicone will allow any gases trapped at the interface to be displaced. Thus, maximum van der Waals and London dispersion intermolecular interactions are obtained at the silicone-substrate interface. It must be noted that suitable liquids reaching the adhesive-substrate interface would immediately interfere with these intermolecular interactions and displace the adhesive from the surface. For example, a study that involved curing a one-part alkoxy terminated silicone adhesive against a wafer of alumina, has shown that water will theoretically displace the cured silicone from the surface of the wafer if physisorption was the sole interaction between the surfaces [38]. Moreover, all these low energy bonds would be thermally sensitive and reversible. 

The chemical bonding theory of adhesion applied to silicones involves the formation of covalent bonds across an interface. This mechanism strongly depends on both the reactivity of the selected silicone cure system and the presence of reactive groups on the surface of the substrate. Some of the reactive groups that can be present in a silicone system have been discussed in Section 3.1. The silicone adhesive can be formulated so that there is an excess of these reactive groups, which can react with the substrate to form covalent bonds. It is also possible to enhance chemical bonding through the use of adhesion promoters or chemical modification of the substrate surface. 

Typical components of a silicone adhesive based on hydrosilylation addition cure system... 

When formulating a silicone adhesive, sealant, or coating, based on hydrosilylation addition cure, one must consider the following properties of the uncured product pot life, dispensing technique, rheology, extrusion rate, cure performance. These characteristics directly affect the processing properties of the polymer base or crosslinker parts. The degree of cure conversion at the temperature of interest is determined by properties such as tack free time, cure profile and cure time. Once... 

Cold cure silicone rubbers and available as pastes. These pastes are mixed with an organometallic catalyst and silicate and cured at room temperature. These are used as adhesives, and as encapsulating materials for electronic components. They are also used for textile coating and in moulds. 

Most moisture-curing silicones have good general adhesion to a variety of substrates. However, adhesion can be markedly improved with different combinations of silanes. The more common silane adhesion promoters are categorized as amine functional, eg, 3-aminopropyltrimethoxysilane [13822-56-5]y 3-aminopropyltriethoxysilane [919-30-2] y or IV-(2-aminoethyl)-3-aminopropyltrimethoxysilane [1760-24-3] as epoxy functional, eg, 3-glycidoxypropyltrimethoxysilane [2530-83-8] (2) and 2-3(3,4-epoxycyclohexyl)ethyltrimethoxysilane [3388-04-3] (3) as mercapto functional, eg, 3-mercaptopropyltrimethoxysilane [4420-74-0] or as methacrylate functional, eg, 3-methacryloxypropyltrimethoxysilane [2530-85-0] (4). 

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