Adhesion promoters silicone adhesives

Silicone Heat-Cured Rubber. Sihcone elastomers are made by vulcanising high molecular weight (>5 x 10 mol wt) linear polydimethylsiloxane polymer, often called gum. Fillers are used in these formulations to increase strength through reinforcement. Extending fillers and various additives, eg, antioxidants, adhesion promoters, and pigments, can be used to obtain certain properties (59,357,364). 

Hirayaina et al. [22] have shown that polyhydrogenmethylsiloxane can bind to aluminum, copper and steel surfaces via activation with a suitable platinum complex. The attached polymer promotes the adhesion of silicone materials whose cure involves SiH/SiVinyl hydrosilylation. Presumably, it would also be effective with other unsaturated organic polymer phases. 

This chapter first reviews the general structures and properties of silicone polymers. It goes on to describe the crosslinking chemistry and the properties of the crosslinked networks. The promotion of both adhesive and cohesive strength is then discussed. The build up of adhesion and the loss of adhesive strength are explained in the light of the fundamental theories of adhesion. The final section of the chapter illustrates the use of silicones in various adhesion applications and leads to the design of specific adhesive and sealant products. 

The performance of a product where adhesion plays a role is determined both by its adhesive and cohesive properties. In the case of silicones, the promotion of adhesion and cohesion follows different mechanisms [37]. In this context, adhesion promotion deals with the bonding of a silicone phase to the substrate and reinforcement of the interphase region formed at the silicone-substrate interphase. The thickness and clear definition of this interphase is not well known, and in fact depends on many parameters including the surface physico-chemistry of... 

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. 

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]. 

Control of fiber friction is essential to the processing of fibers, and it is sometimes desirable to modify fiber surfaces for particular end-uses. Most fiber friction modifications are accomplished by coating the fibers with lubricants or finishes. In most cases, these are temporary treatments that are removed in final processing steps before sale of the finished good. In some cases, a more permanent treatment is desired, and chemical reactions are performed to attach different species to the fiber surface, e.g. siliconized slick finishes or rubber adhesion promoters. Polyester s lack of chemical bonding sites can be modified by surface treatments that generate free radicals, such as with corrosive chemicals (e.g. acrylic acid) or by ionic bombardment with plasma treatments. The broken molecular bonds produce more polar sites, thus providing increased surface wettability and reactivity. 

Most commercially available silicone elastomers, and especially those which polymerize by addition-cure, do not, or weakly, adhere to most surfaces. Adhesion promoters known as surface primers are available and are often used to adhere the silicone to the protected... 

Baseline Process. DuPont PI2545, PI2555 and Hitachi PIQ as received from the manufacturer, were spun in a class 100 clean room environment at appropriate spin speeds to achieve 0.5 - 6 y film thickness. The silicon wafer substrates were pre-spun (5K rpm, 30") with 0.05% DuPont VM651 (y-amino propyltriethoxy silane) adhesion promoter in 95/5 (v/v) methanol/HzO. The polyimide film cast on the silane-coated silicon wafer was pre-baked... 

Conditions have been defined for applying polyimide coatings onto the silicon wafer as passivation and/or dielectric. Processing variables studied included the critical areas of adhesion, cure cycle and thermostability. Aminosilane was shown to be effective adhesion promoter. The rate of imidization was followed by F.T.I.R. employing time lapse technique. 

Experiments like those described above have been performed to evaluate sodium ion barrier properties of Hitachi PIQ and DuPont PI 2540 polyimide films. Also included in the comparison were silicon nitride coatings plasma deposited in both tensile and compressive stress modes. The structure of the samples is illustrated in Figure 9. N-type, (111) oriented silicon substrates were cleaned and oxidized in dry oxygen ambient at 1100°C to form a 1060 A Si02 film. Wafers intended for polyimide characterization were coated with an organic silane film (gamma glycidal amino propyl trimethoxysilane) to promote adhesion of the polyimide to the oxide surface. The polyimide resins were spun onto the wafers at speeds to produce final... 

On the other hand, the alkoxide system presented several problems in formulation. The system first chosen as a model consisted of a trimethoxymethyl silane crosslinker, 8000 centistoke HEB siloxane, and a catalyst. A number of catalysts were used and each exhibited different cure rates and electrical properties. DuPont tetraalkoxytitante-Tyzor appears to he one of the better catalysts used in this type of curing system. Fillers are usually incorporated into the silicone formulation to improve mechanical properties, promote adhesion, and to serve as light screening and pigment agents. Cab-o-sil, a form of fumed silica, carbon-black, titanium dioxide and calcium carbonate are then used as RTV fillers. 

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). 

Acrylics. There are two principal classes of acrylic sealants latex acrylics and solvent-release actylics. High molecular weight latex acrylic polymers are prepared by emulsion polymerization of alkyl esters of acrylic acid, The emulsion polymers are compounded inlo sealants by adding fillers, plasticizers, freeze-thaw stabilizers, thickeners, and adhesion promoters. As is true of the silicone lalex sealants, die acrylic latex sealants are easy to apply and clean with water. 

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