High-temperature resins properties

Dynamic mechanical analysis provides a useful technique to study the cure kinetics and high temperature mechanical properties of phenoHc resins. The volatile components of the resin do not affect the scan or limit the temperature range of the experiment. However, uncured samples must be... 

Sulfur cross-links have limited stability at elevated temperatures and can rearrange to form new cross-links. These results in poor permanent set and creep for vulcanizates when exposed for long periods of time at high temperatures. Resin cure systems provide C-C cross-links and heat stability. Alkyl phenol-formaldehyde derivatives are usually employed for tire bladder application. Typical vulcanization system is shown in Table 14.24. The properties are summarized in Tables 14.25 and 14.26. 

The thermal polymerization of reactive polyimide oligomers is a critical part of a number of currently important polymers. Both the system in which we are interested, PMR-15, and others like it (LARC-13, HR-600), are useful high temperature resins. They also share the feature that, while the basic structure and chemistry of their imide portions is well defined, the mode of reaction and ultimately the structures that result from their thermally activated end-groups is not clear. Since an understanding of this thermal cure would be an important step towards the improvement of both the cure process and the properties of such systems, we have approached our study of PMR-15 with a focus only on this higher temperature thermal curing process. To this end, we have used small molecule model compounds with pre-formed imide moieties and have concentrated on the chemistry of the norbornenyl end-cap (1). 

The high-temperature resins described above provide the main elements in the adhesive formulator s recipe. However, there are also additives, fillers, etc., that can further enhance the thermal properties of more conventional epoxy adhesives. These additional components improve thermal resistance by providing oxidation resistance, toughening, and control of bond line stress. 

The only high-temperature resin family that retains a moderate amount of flexibility is the polysiloxanes. A significant amount of research has been devoted to trying to marry the properties of siloxanes with epoxy resins to obtain less brittle, high-temperature adhesives. However, these efforts have yet to result in commercial adhesives systems. 

Small nitrile-rubber inclusions in epoxy resin electrical en-capsulants have been examined in both amine (29-31) and acid (32) epoxy cures, in filled and unfilled systems. The value of rubber inclusion in a boron trlfluorlde/amine complex epoxy cure has also been demonstrated (33), where elevated-temperature, high-humldlty testing showed electrical properties retention to be better than a comparable system cured with dodecenylsucclnic anhydride. Rubber benefits low-temperature properties specifically and thermocycling in general. It affects high temperature insulation properties negatively therefore, the amount of rubber incorporated must be judiciously chosen. 

General Description DuPont Selar PA is an amorphous nylon (polyamide [PA]) resin that exhibits superior transparency good barrier properties to gases, water, solvents, and essential oils and high-temperature structural properties.P ]... 

Bismaleimides (BMI). The hismaleimide resins have found their niche in the high-temperature aircraft design applications where temperature requirements are in the 177°C (350°F) range. BMI is the primary product and is based upon the reaction product from methylene dianiline (MDA) and maleic anhydride bis (4 maleimidophynyl) methane (MDA BMI). Variations of this polymer with compounded additives to improve impregnation are now on the market and can be used to impregnate suitable reinforcements to result in high-temperature mechanical properties (Table 2.33). 

Dynamic mechanical analysis provides a useful technique to study the cure kinetics and high temperature mechanical properties of phenolic resins. The volatile components of the resin do not affect the scan or limit the temperature range of the experiment. However, uncured samples must be supported by a braid, a scrim, or paper. This does not influence the kinetic results and can be corrected in the calculations of dynamic mechanical properties (qv). Recent DMA work on phenolic resins has been used to optimize the performance of structural adhesives for engineered wood products and determine the effect of moisture in wood product on cure behavior and bond strength (75-77). 

In the sheeting market, the low density polyethylenes are less important than the high density resins. The high density resins have excellent chemical resistance, stress-crack resistance, durabiUty, and low temperature properties which make them ideal for pond liners, waste treatment faciUties, and landfills. In thicker section, HMW-HDPE sheet makes good containers, trays, tmck-bed liners, disposable items, and concrete molds. The good durabiUty, abrasion resistance, and light weight are critical elements for its selection. 

Mechanical properties are retained up to 200°C, even in continuous service, which is better than with most plastics. At high temperatures, these copolymers react with duorine, duorinating agents, and molten alkaU metals. They are commercially available under the Du Pont trademark Tedon FEP duorocarbon resin. A similar product is manufactured by Daikin Kogyo of Japan and sold under the trademark Neodon. The People s RepubHc of China also manufactures some FEP products. 

Mech nic lProperties. Extensive Hsts of the physical properties of FEP copolymers are given in References 58—63. Mechanical properties are shown in Table 3. Most of the important properties of FEP are similar to those of PTFE the main difference is the lower continuous service temperature of 204°C of FEP compared to that of 260°C of PTFE. The flexibiUty at low temperatures and the low coefficients of friction and stabiUty at high temperatures are relatively independent of fabrication conditions. Unlike PTFE, FEP resins do not exhibit a marked change in volume at room temperature, because they do not have a first-order transition at 19°C. They ate usehil above —267°C and are highly flexible above —79°C (64). 

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. 

In addition to the semicrystalline nylons, which comprise the vast majority of commercial resins, nylon is also available in an amorphous form that gives rise to transparency and improved toughness at the expense of high temperature properties and chemical stress crack resistance. Table 2 shows the properties of some different polyamide types. 

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