42

Silicone Adhesives and Sealants

Loren D. Lower and Jerome M. Klosowski
Dow Corning Corporation, Midland, Michigan, U.S.A.

I. INTRODUCTION Silicone adhesives and sealants were introduced approximately 40 years ago and many of the silicones used in the early days are still performing. Products are available in a variety of forms, from pastelike materials to owable adhesives. Both single- and multicomponent versions are available, with several dierent cure chemistries. Most of the silicones of commerce are based on polydimethylsiloxane (PDMS) polymers. Other siloxane polymers may be used when resistance to ultrahigh temperature, ultralow temperature, or solvents is required. Applications are extremely broad. A partial list includes construction, highway, automotive, appliance assembly, original-equipment manufacture, maintenance, electronics, aerospace, and consumer uses. In some cases, silicones compete with other materials, such as polyurethanes, polysuldes, and acrylics, whereas in applications requiring longterm durability, silicones alone are specied. Silicones are often chosen for their excellent resistance to weathering and temperature extremes, their adhesion, and their ability to accommodate substrate movement. When silicone sealants and adhesives are mentioned, the thought of excellent durability comes to most readers minds. Silicones [named for the similarity of the (CH3)2SiO polymer repeat unit to the analogous organic ketones, R2C O] occupy a unique position between inorganic and organic materials. The saturated inorganic Si O Si polymer backbone provides exibility and stability to sunlight, while the methyl groups ensure low intermolecular forces. Some of the key attributes of silicones, which are responsible for their unique properties and durability are [1]: Low surface tension High water repellence Partially ionic backbone Large free volume Low apparent energy of activation for viscous ow Low glass transition temperature Freedom of rotation around bonds Small temperature variations of physical constants High gas permeability High thermal and oxidative resistance Low reactivity
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Insolubility in water High siliconoxygen bond energy Selected properties of PDMS are as follows: Critical surface tension of wetting Water contact angle Glass transition temperature Energy of rotation Activation energy for viscous ow SiO bond energy Percent polar contribution 24 mN/m 110 150 K 0 kJ/mol 14.7 kJ/mol 445 kJ/mol 41%

The saturated backbone and high Si O bond energy result in products that perform very well in applications involving exposure to sunlight. Since the silicone polymer does not absorb energy in the ultraviolet (UV) region of the light spectrum, one must be cautious with the use of clear silicones. The silicones need no UV absorbers to be stable (and contain none); thus the UV light from the sun can pass through clear silicones to the surface below the sealant. If the surface is sensitive to UV light, deterioration of the substrate may occur. Except for light-protected areas and unsensitive substrates (such as glass), the most judicious choice is a pigmented silicone. The pigment acts as a UV blocker and protects the substrate beneath the silicone. Because of the unparalleled stability to UV radiation, silicones are the sealants of choice for wet glazing techniques and the only generic class of sealants allowed for structural glazing (the adhering of glass and other building materials to structures with no attachment other than the silicone). Structural glazing is used in all-glass buildings and skyscrapers. Other types of sealants often contain large amounts of ller and UV stabilizers to aord some degree of longevity in sunlight. This makes the nonsilicones satisfactory for some applications, but not in applications in which the sun shines directly on the bond line. This application is reserved for silicones. A specialty application for silicones, which further illustrates their UV-light durability, is in the sealing of accelerated UV-weathering test machines. The excellent stability to UV light is true only for pure silicones and is not true of siliconized organics or modied silicones. These contain very little silicone and thus have durability characteristics determined primarily by their base polymer systems. Silicones have low intermolecular forces that result in relatively at physical property response with temperature change. An example of this at response is shown in Fig. 1, in which the viscosity of silicone polymers and a hydrocarbon oil are plotted as a function of temperature [2,3]. The relatively low response of silicone properties to temperature is important during sealant application (e.g., no heating needed in cold weather and no ow in hot weather). Even more important, however, is the fact that the performance of the cured sealant or adhesive will be less temperature dependent than will most organicbased products. This has practical implications: in building joints, for example. In cold weather, the building components shrink, and joint sealants must maintain elasticity to accommodate this movement. This is also fundamental to their use as a structural glazing sealant/adhesive. The sides of all-glass buildings can get very warm in the summer sun, and the silicone must not lose strength at these temperatures. While this rather constant performance is critical in some construction applications, it is also important in many industrial and appliance applications, such as steam irons, where the sealant simultaneously prevents water leakage and acts as an assembly adhesive.
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Figure 1

Viscosity versus temperature.

Silicone sealants are rated for their movement capability, with classes at 12.5%, 25%, 50%, and even higher joint movement capability. This too is quite unique, since high-movement nonsilicone sealants rarely perform for long periods of time above 25% joint movement.

II.

CURE CHEMISTRY

Silicones are available in one- and multicomponent forms. The one-component types are commercially the most important and will be the focus of most of this discussion. These products, which generally cure by reaction with atmospheric moisture, are called RTV (room-temperature vulcanizing) sealants or adhesives. The surface cure rate of these products is a function of the cure system, but the rate of cure in depth depends on the ability to transmit water vapor through the mass of sealant. Silicones are highly permeable to moisture vapor, and generally the one-component types cure at a rate of about 0.3 cm/day. Due to this high vapor permeability, the one-component silicones typically cure faster than do their nonsilicone counterparts. The multicomponent products generally do not rely on moisture penetration for cure. Their chief attribute is fast cure in very deep sections. Thus many industrial production lines that demand fast cure use a two-component sealant (including the use of silicone encapsulants for electrical components). Cure of these two-part systems can be accelerated further by additional catalyst or exposure to elevated temperatures.
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One of the more common two-part cure chemistries is based on the addition reaction of Si H cross-links with vinyl functional polymers using platinum catalysts. This chemistry is shown below. One advantage of this addition chemistry is that it produces no cure by-products. Another common two-part chemistry involves condensation cure with alkoxysilane cross-linkers using Sn(IV) catalysts. SiMe2 OSiMe2 CH CH2 HSi ! SiMe2 OSiMe2 CH2 CH2 Si A simplied cure mechanism for the one-component silicone RTV sealants or adhesives is shown below. Reaction of cross-linker with polymer ends: 2RSiX3 HOSiMe2 OMe2 SiOn SiMe2 OH ! X2 RSiOMe2 SiOn SiRX2 2HX Reaction of cross-linker with polymer ends: X2 RSiOMe2 SiOn SiRX2 H2 O ! OHXRSiOMe2 SiOn SiRX2 HX A Reaction of resultant polymer end with another polymer: A B ! X2 RSiOMe2 SiOn SiRX O SiXROMe2 SiOn SiRX2 HX As indicated, the X groups above are hydrolyzable. Repeated hydrolysis and reaction of resultant polymer end groups leads to full cure, with elimination of HX as the leaving group. Examples of leaving groups, cross-linkers, and the common cure system names are given in Table 1. Numerous other cross-linkers may be used. For the trifunctional cross-linkers, the R group may be methyl, ethyl, vinyl, and several other groups, with methyl the most common. In some cases tetrafunctional and higher-functionality cross-linkers or polymeric cross-linkers may also be employed. The acetic acid cure system should be avoided where substrates are subject to acid corrosion. Two other classes of silicones deserve mention. These are the water-based silicones that are used in sealant and coating applications and the silicone pressuresensitive adhesives. Water-based silicones can be prepared by anionic polymerization of siloxanes in water using a surface-active catalyst such as dodecylbenzenesulfonic acid [4]. The resulting emulsion can then be cross-linked in several ways, including the use of alkoxysilane copolymerization or tin catalysts in conjunction with colloidal silica. The result is essentially an emulsion of cured PDMS in water. Various llers and other components are added, resulting in a sealant composition. Upon evaporation of water, B

Table 1

Examples of Leaving Groups, Cross-Linkers, and Cure Systems Cross-linker CH3Si[OC(O)CH3]3 CH3Si(OCH3)3 CH3Si[ONC(CH3)C2H5]3 CH3Si[OC(CH2)CH3]3 CH3Si[N(CH3)C(O)C6H5]3 Cure system Acetic acid Alcohol Oxime Acetone Benzamide

Leaving group (HX) HOC(O)CH3 HOCH3 HONC(CH3)(C2H5) CH3C(O)CH3 HN(CH3)C(O)C6H5

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a silicone elastomer results. These sealants have the advantages of low odor, ease of installation, and easy cleanup. Their properties are rather close to those of their conventional silicone counterparts. The components of the silicone pressure-sensitive adhesives (PSAs) are analogous to their organic counterparts [5]. Generally, a silicate resin and a silicone polymer or gum are dissolved in solvent. Both the resin and the polymer typically contain silanol (Si OH) groups that are reacted during processing of the PSA, leading to a cross-linked network. Additional reactions can be accomplished through the use of free-radical catalysts. The extent to which these cross-linking reactions occur, the resin/polymer ratio, as well as the respective molecular weights of these components, are important in setting the properties of the PSA. Silicone PSA products are used in a number of medical and industrial applications, ranging from a variety of PSA tapes and transfer lms to automotive bonding. Advantages for the silicone PSA products include resistance to temperature extremes, chemical resistance, conformity to irregular surfaces, and electrical properties. They are also unique to most PSAs in their ability to adhere to dicult low-energy substrates, such as polytetrauoroethylene and other silicones.

III.

PROCESSING CONSIDERATIONS

Silicone adhesives and sealants typically contain polymer, llers, cross-linker, catalyst, and other additives. The most common llers are the reinforcing fumed silicas or the less reinforcing grades of calcium carbonate. Other llers and pigments, such as carbon black and titanium dioxide, are also used. Silicones are typically made in high shear, vertical change can mixers, but continuous processing equipment may also be employed. Processing details are generally held proprietary, but some general guidelines are in order. Since most silicones cure through reaction with water, it is important that the moisture content of llers and other additives be controlled. The moisture content of fumed silica, for example, can vary from 0.2 to over 2%, depending on the humidity conditions during storage. It is also critical that introduction of moist air be kept to a minimum during mixing. Air incorporated during processing must generally be removed to reduce the tendency toward cured gels and related appearance problems in the nal product. The dispersion of the ller particles is also important to nal sealant appearance. With increasing costs of llers, it is also important to optimize dispersion to maximize the rheological and reinforcement benets provided by the llers. Manufacturers must balance the mixing time and energy required for complete dispersion with resultant product appearance and physical properties.

IV. PROPERTY DETERMINATIONS Since most silicone adhesives and sealants are elastomeric in nature, their physical property testing often parallels classical rubber testing approaches. Common tests include durometer, tensile strength, elongation, and modulus. Several methods are available for the measurement of rubber properties, but the most commonly used are the American Society for Testing and Materials (ASTM) D-412, Test Method for Rubber Properties in Tension, and the ASTM C-661, Standard Test for Indentation Hardness of ElastomericType Sealants by Means of a Durometer. These properties vary widely with the product
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and its intended application. Durometer measurements can range from Shore A less than 20 to over 50. Tensile strength ranges from less than 0.2 to greater than 5 MPa, and elongation varies from about 100 to 2000%. Cure time testing tends to be somewhat subjective, but again there are methods available, such as ASTM C-679, Tack-Free Time of Elastomeric Sealants. Tack-free time is the curing time required for the product to develop a skin that is not damaged when subjected to application and removal of a plastic lm. It is important in all cases to determine the cure characteristics of the product in actual working conditions. Since most silicones cure by reaction with moisture in the air, the sensitivity of cure time to humidity should be determined. Surface cure rates can usually be tailored to meet application requirements. The rheological properties of adhesives and sealants are important in many applications. When these products must be pumped or applied through automated equipment, the ow characteristics at pertinent shear rates are critical. Sophisticated rheological measurements can be performed to predict performance. The rheology of silicone adhesives and sealants can be tailored through adjustment of polymer viscosity, ller loading, and incorporation of various additives. Often, only the extrusion rates of adhesives and sealants are measured, which is accomplished by subjecting the product to a given pressure and measuring its ow rate through a nozzle of known diameter (see ASTM C-1183, Extrusion Rate of Elastomeric Sealants). For many sealant applications, the sealant must not ow under its own weight in conditions of low shear rate. In this case, some measurement of slump is generally made. Several methods are available for measuring slump [see ASTM D-2202, Standard Test for Slump of Sealants, and ASTM C-639, Standard Test for Rheological (Flow) Properties of Elastomeric Sealants]. Again, it is important to determine the rheological performance of the product in the actual application. Adhesion testing is a matter of some controversy. There is, however, a growing trend among manufacturers, speciers, and standards organizations to move toward tests that better predict performance in application. The 180 peel adhesion test is often used as an internal quality control tool by manufacturers. This test allows for measurement of lot-tolot consistency of products. The methodology for this test can be found in ASTM C-794, Test Method for Adhesion In-Peel of Elastomeric Joint Sealants. In its typical form this test involves placing a bead of the product onto the substrate, with a exible member embedded in the product. The product is allowed to cure, and the member is then pulled away from the substrate. The force required for peel is noted, along with the mode of failure. The advantages of this test are that it is fast and lends itself well to subjecting the adhesive bond to environmental stresses such as hot-water exposure. A series of tests that are better predictors of performance of sealants involves the preparation of tensile-adhesion joints or H pieces. In this case, the sealant bead is placed between blocks of the two substrates of interest and allowed to cure. This joint can then be pulled to destruction, with measurement of strength and failure mode. In addition, various environmental stresses may be applied, such as UV light exposure (weatherometry), water exposure, and cyclic movement. Testing in this way allows for improved prediction of movement capability and long-term performance. The methodology involved in this testing is included in the following methods: ASTM C-1135, Determining Tensile Adhesion Properties of Structural Sealants, and ASTM C-719, Test for Adhesion and Cohesion of Elastomeric Joint Sealants Under Cyclic Movement. Any sealant or adhesive that is expected to perform in outdoor applications should be tested after exposure to light, heat, and water. For most forms of weatherometry, 500 to
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1000 h is considered approximately the equivalent of 1 year outside in most climates (United States). If a minimum of 5 years of service is expected from the sealant, no less than 2500 h, and probably 5000 h in a UV uorescent accelerated weathering machine should be used (as the conditioning cycle for rubber property testing). This is true for silicones and all other sealants that are expected to perform in such applications. This is a startling contrast to the 250 to 500 h used in most present standards (see Refs. 6 and 7).

V. BASIC FORMULATIONS As mentioned in the processing section, silicone sealants and adhesives generally contain polydimethylsiloxane (PDMS) polymer, cross-linkers, llers, catalysts, and other additives. These additives may be pigments, plasticizers (often unreactive PDMS polymers), and adhesion additives (such as silane coupling agents). Given below are simple formulations and properties (Table 2) for oxime-cured silicone sealants [8]. In these examples, the use of a nonreactive silicone plasticizer and a nonreinforcing carbonate ller results in substantial modulus reduction. This approach can also be used to modify the physical properties of silicones based on other cure chemistries. Low-modulus sealants are often used in sealant applications requiring high movement capability. High-modulus sealants are used more in structural and adhesive applications. A. High-Modulus Oxime Sealant
Percent by weight Hydroxyl-ended PDMS polymer Fumed silica Oxime cross-linker Sn(IV) catalyst 8085 510 57 0.050.10

B.

Medium-Modulus Oxime Sealant

Percent by weight

Hydroxyl-ended PDMS polymer Silicone plasticizer Fumed silica Calcium carbonate Oxime cross-linker Sn(IV) catalyst

6080 520 26 2030 57 0.050.10

Table 2

Properties of Oxime-Cured Silicone Sealants Sealant

Property Tack-free time (min) Durometer (Shore A) Tensile strength (MPa) Elongation (%) 100% Modulus (MPa)

High modulus 2030 2535 1.22.1 200400 0.50.9

Medium Modulus 3060 2030 0.91.4 400700 0.350.5

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VI.

SUBSTRATE BONDING

Applications for silicones in bonding are numerous. Generally, one sealant will not bond to all substrates and it is common practice to develop new formulations to meet the everincreasing list of requirements. In some instances primers are used for certain substrates, but silicones are usually self-priming. This self-priming feature is important from the standpoints of reducing installation costs and in reducing dependency on high-solvent primers, which are sometimes subject to environmental regulations. The surface characteristics for a given type of substrate can vary considerably between substrate manufacturers. For this reason it is always advisable to check adhesion before specifying a particular sealant. In addition, the importance of proper substrate cleaning and preparation should not be overlooked. Most adhesive and sealant producers will recommend the proper procedures for surface preparation. Some of the more common substrates and related applications for silicones are given in Table 3.
Table 3 Substrate Masonry Applications of Substrates Examples Concrete Mortar Brick Marble Granite Sandstone Unpainted Painted Typical applications Construction Highway Consumer Construction

Natural stone

Wood

Glass

Float Reective

Metals

Aluminum Steel Copper Stainless steel Galvanized steel Paints Fluorocarbon Polyester PVC PMMA Polyester Engineering plastics

Coated metals

Plastics

Construction Glazing Consumer Maintenance Construction Glazing Maintenance Original-equipment Consumer Construction Glazing Electronics Maintenance Original-equipment Consumer Construction Glazing Maintenance Original-equipment Construction Glazing Maintenance Automotive Sanitary Original-equipment Consumer

manufacturing

manufacturing

manufacturing

manufacturing

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REFERENCES
1. M. J. Owen and J. M. Klosowski, in Adhesives, Sealants and Coatings for Space and Harsh Environments (L. H. Lee, ed.), Plenum Press, New York, 1988, p. 283. 2. E. G. Rochow and H. G. LeClair, J. Inorg. Nucl. Chem. 1: 92 (1955). 3. J. M. Klosowski and G. A. L. Gant, Plastic Mortars, Sealants, and Caulking Compounds, ACS Series 113 (R. B. Seymour, ed.), American Chemical Society, Washington, D.C., 1979, p. 117. 4. D. T. Liles and N. E. Shephard, in Science and Technology of Building Seals, Sealants, Glazing and Waterproong, Vol. 2, ASTM STP 1142 (J. M. Klosowski, ed.), American Society for Testing and Materials, Philadelphia, 1992. 5. L. A. Sobieski and T. J. Tangney, in Handbook of Pressure Sensitive Adhesive Technology (D. Satas, ed.), Van Nostrand Reinhold, New York, 1989, pp. 508517. 6. L. B. Sandberg, J. Mater. Civil Eng. 3(4): 278291 (1991). 7. G. R. Fedor, 2nd Symposium on Science and Technology of Building Seals, Sealants, Glazing and Waterproong, Ft. Lauderdale, Fla., ASTM C-24 FT., American Society for Testing and Materials, Philadelphia, 1992. 8. J. M. Klosowski, Sealants in Construction, Marcel Dekker, New York, 1989, pp. 269270.

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