Composite matrix resins, adhesives

Adhesive bonding is an integral part of virtually all composite structure. Early composite matrix resins could in some cases act as an adhesive, such as with self-filleting systems used for honeycomb sandwich fabrication. As composite systems became more optimized for minimum resin content and limited flow, supplementary adhesives became more common. Modern-day composite structure relies on adhesives almost as much as bonded metallic structure. 

Following this initial period of polyimide development, interest reached a steady-state and remained there until the late 1970s. During this time a major impetus to the polyimide area was provided by the aerospace industry. The need for composite matrix resins as well as structural adhesives with excellent oxidative and thermal stability appeared to be at least partially met by polyimide type resins. Ultimately, requirements of high flow and low void content in relatively thick parts directed these efforts into different directions. Another upswing occurred in the early 1980s with the potential application of... 

Parker et al. (30) reported the synthesis of phosphorous containing bismaleimides and demonstrated their outstanding non-flammability characteristics. Graphite fabric composites prepared from such P-containing BMI as a matrix resin show a LOI of 100 and an anaerobic char yield of 88% at 700 °C. Other P-containing BMI have recently been synthesized (31) for example, bis(3-maleimidophenoxy-4-phenyl)phenyl phosphine oxide (Figure 8) has been tested as a composite matrix resin with the aim of improving the fibre/resin interfacial adhesion. 

A family of acetylene-terminated phenyl quinoxalines have been synthesized by the Polymer Branch of the Materials Laboratory. ( 1) These phenyl quinoxalines are remarkable for their thermooxidative stability and resistance to moisture. These materials have potential for structural applications as adhesives or composite matrix resins.(2) The feature of moisture resistance makes the materials especially attractive for bonding aluminum. However, problems arise from the fact that aircraft aluminum alloys (and their surface oxiges) are altered by exposures to temperatures above 177 C (350 F) and this is much lower than the polymerization temperatures of the acetylene-terminated oligomers. 

Polyester resins (alkyds) were commercialized for coatings use in 1926, and unsaturated polyesters were used as thermoset fiberglass composite matrix resins in the 1940s, but the early resins made poor adhesives. When flexibilized resins appeared in the 1950s, they were used as adhesives. Today, unsaturated polyesters are widely used as adhesives for thermoset plastics bonding, and even for metal bonding in most countries, but are seldom used as adhesives in the United States, where the more expensive epoxy adhesives are used in similar applications. The saturated polyesters, used as thermoplastic hot-melt adhesives, seem to have appeared in the literature first in the 1954—1957 period. 

Polyimides (PI) were among the eadiest candidates in the field of thermally stable polymers. In addition to high temperature property retention, these materials also exhibit chemical resistance and relative ease of synthesis and use. This has led to numerous innovations in the chemistry of synthesis and cure mechanisms, stmcture variations, and ultimately products and appHcations. Polyimides (qv) are available as films, fibers, enamels or varnishes, adhesives, matrix resins for composites, and mol ding powders. They are used in numerous commercial and military aircraft as stmctural composites, eg, over a ton of polyimide film is presently used on the NASA shuttle orbiter. Work continues on these materials, including the more recent electronic apphcations. 

S.2.2.2. Composite adherends. Composite adherends are bonded in both the cured and uncured states. Wherever possible the adhesive and all adherends are cured simultaneously to avoid the added cost of additional autoclave cure cycles. In many cases this is not practical due to part size and complexity. Cured parts can be bonded to uncured parts, which is known as cobonding, and fully cured parts can be bonded together, which is known as secondary bonding. Adhesives for composites are formulated to be compatible with matrix resins in either cured or uncured states. 

The single filament pull out test, sometimes called the microdebond test, has received attention for some years as a way to assess the adhesion between fibers and matrices in fiber composite [90,91]. It provides a direct measure of interfacial adhesion and can be used with both brittle and ductile matrix resins. 

FE data have been collected from the fracture of a wide variety of single and multi-component solids, ranging from single crystals of molecular solids to fiber-reinforced composites, and also from the peeling of adhesives 0-16 ). In this paper, we will restrict our attention to FE arising from the failure of polymer composites (fibrous and particulate), and the individual components thereof (fibers and matrix resins). 

Addition poly(imide) oligomers are used as matrix resins for high performance composites based on glass-, carbon- and aramide fibers. The world wide market for advanced composites and adhesives was about 70 million in 1990. This amounted to approximately 30-40 million in resin sales. Currently, epoxy resins constitute over 90% of the matrix resin materials in advanced composites. The remaining 10% are unsaturated polyester and vinylester for the low temperature applications and cyanate esters and addition poly(imides) for high temperatures. More recently thermoplastics have become important and materials such as polyimides and poly(arylene ether) are becoming more competitive with addition polyimides. 

Adhesion promoters were first used to treat glass fibers and other fdlers before they are incorporated into liquid resin to make composite materials. In the fiber industry, adhesion promoters are also known as finishes. Certain finishes have been specially developed to match a fiber with a resin matrix. Without adhesion promoters, the interfacial resin-glass fiber adhesion is weak, and water can diffuse along the interface with catastrophic results on the end properties of the composite. 

Adhesives that give satisfactory results on the resin matrix alone may also be used to bond composites. The three adhesives most often used to bond composites are epoxies, acrylics, and urethanes. 

Polyimides for microelectronics use are of two basic types. The most commonly used commercial materials (for example, from Dupont and Hitachi) are condensation polyimides, formed from imidization of a spin-cast film of soluble polyamic acid precursor to create an intractable solid film. Fully imidized thermoplastic polyimides are also available for use as adhesives (for example, the LARC-TPI material), and when thermally or photo-crosslink able, also as passivants and interlevel insulators, and as matrix resins for fiber-reinforced-composites, such as in circuit boards. Flexible circuits are made from Kapton polyimide film laminated with copper. The diversity of materials is very large readers seeking additional information are referred to the cited review articles [1-3,6] and to the proceedings of the two International Conferences on Polyimides [4,5]. 

Highly cross-linked epoxy resins combine high strength stiffness thermal, chemical, and environmental stability adhesion low weight processability excellent creep resistance and favorable economics. These resins are widely applied as coatings, casting resins, structural adhesives, and matrix resins of advanced composite materials. The broad spectrum of applications ranges from the automotive and aerospace industries to corrosion protection and microelectronics. 

In the aerospace industry, resinous polymers encompass a wide variety of hardware applications for aircraft, missiles, and space structures. In aircraft, resins are used as a matrix material for primary (flight-dependent) and secondary fiber-reinforced composite (FRC) structures, adhesives for the bonding of metal and composite hardware components, electronic circuit board materials, sealants, and radomes. Missile applications include equipment sections, motor cases, nose cones, cartjon-carbon composites for engine nozzles, adhesive bonding, and electronics. As the exploration of outer space intensifies, applications will become even more exotic. FRC will be used to construct telescopes, antennas, satellites, and eventually housing and other platform structures where special properties such as weight, stiffness, and dimensional stability are important. 

Epon HPT . [Shell] Epoxy matrix resin used for advanced composites with glass, carbon, aramid or b n fibers, high-performance structural laminates and adhesives, preptegs. 

Epoxy resins are among the most important of the high performance thermosetting polymers and have been widely used as structural adhesives and matrix for fiber composites. Epoxy resins are characterized by the presence of epoxide groups before cure, and they may also contain aliphatic, aromatic, or heterocyclic structures in the backbone. The epoxy group can react with amines, phenols, mercaptans. 

Although they are not elastomers, other phosphazenes also offer potential In areas requiring heat and fire resistance. Mixed fluoroalkoxy - aryloxy substituted cyclic phosphazenes are currently attracting Interest for fire resistant fluid applications (46). In other studies, cyclophosphazene matrix resins have been prepared which have potential for high temperature adhesive applications (47) and as composite matrix materials (48). These studies serve to further demonstrate the enhanced thermal stability and fire resistance which can be achieved with these phosphorus - nitrogen systems. 

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