Silicones/Silicone adhesives

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. 

The surface of the substrate, the silicone/substrate interface, and the bulk properties of silicones all play significant and influential roles that affect practical adhesion and performance of the silicone. The design of silicone adhesives, sealants, coatings, encapsulants or any products where adhesion property is needed requires the development chemist to have a thorough understanding of both silicone chemistry and adhesion phenomena. 

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.

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

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. 

Pure PDMS networks are mechanically weak and do not satisfy the adhesive and cohesive requirements needed for most applications in which the silicone adhesive joint is subjected to various stresses. For crosslinked silicones to become high performing adhesives, they need to be strengthened. 

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. 

An unprimed silicone adhesive implies that it is free of any adhesion promoter and that the substrate does not need to be activated or primed i.e. adhesion relies mainly on chemical and/or mechanical mechanisms. The chemical adhesion... 

Fillers can also be used to promote or enhance the thermal stability of the silicone adhesive. Normal silicone systems can withstand exposure to temperatures of 200 C for long hours without degradation. However, in some applications the silicone must withstand exposure to temperatures of 280 C. This can be achieved by adding thermal stabilizers to the adhesive formulations. These are mainly composed of metal oxides such as iron oxide and cerium oxide, copper organic complexes, or carbon black. The mechanisms by which the thermal stabilization occurs are discussed in terms of radical chemistry. 

In silicone adhesives used to bond structural glazing assemblies, the silicone network is made of very long PDMS chains and is filled with silica that improves the elastomeric properties of the adhesive. The strength of such an adhesive is strongly enhanced through various mechanisms of energy absorption. 

The theories proposed for the mechanisms of adhesion have been reviewed in detail elsewhere [44,45,55-58]. However, for the purpose of this chapter, we are presenting them in the context of silicone adhesion. The various theories underlying each mechanism will be briefly outlined and qualitatively illustrated with specific examples. 

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. 

The adhesion promotion of an organic matrix to an inorganic substrate using a silane has been studied to model the structure of the created interphase [64-66]. The polymer/silane interphase is influenced by the solubility parameter of both the silane coupling agent and the polymer. More interdiffusion occurs when the solubility parameters of the polymer and the silane closely match together. It is believed that this model can be applied to silicone adhesive/solid substrate system. 

Although the primary function of sealants is to seal, adhesion promoters are often added, which allows them to adhere to the adjoining base materials. It is therefore sometimes difficult to distinguish between an adhesive and a sealant. For example, structural silicone adhesives are used in the building construction industry owing to their sealing, adhesive, elastomeric properties, and their resistance to harsh environmental conditions [67,70,77]. 

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... 

We have attempted to relate the basics of silicone chemistry to applications where adhesion is an important property. These applications cover a vast industrial arena that does not make a review of this sort easy. Instead, we focused on the fundamental aspects of silicone physics and chemistry and related them to adhesion and adherence properties. We have attempted to use a logical structure to help the reader understand silicone adhesion. Adhesion and cohesion have been considered as they both determine the ultimate performance of an adhesive joint. 

The design of a silicone adhesive naturally considers both the creation of adhesive and cohesive strengths to provide the performance needed. 

Wake, W.C., Silicone adhesives, sealants and coupling agents. Crit. Rep. Appl. Chem., 16, 89-111 (1987). 

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. 

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