Polyimides resists

Certain polyimides resist high-energy radiation well. For example, the properties of certain grades are still suitable after exposure to 10 and 10 Mrad. 

The effective bulk polyimide resistivity can be extracted from comparison of the measured curves in Figure 6 with this model, and values at 100°C and 158°C are shown in Figure 7, which is a reproduction of the Arrhenius plots of Figure 4. It is seen that both the values of the resistivity and the temperature dependence are in good agreement with those obtained from the dc conduction measurements. In addition, the saturated value of the measured threshold instability is well predicted by the model. 

Curing of epoxy resins can be initiated photochemically by release of imidazole from photolabile protected derivatives, such as AT-(2-nitrobenzyloxycarbonyl)imi-dazole. Positive working polyimide resists derived from 2-nitro-p-xylyleneoxy-amine have been synthesized and studied and 2-nitrobenzyloxy derivatives are included in a formulation for submicron imaging. ... 

Positive polyimide resists have also been developed. One example starts from a solnble polymer [60] with a formulation analogons to a novolac positive resist o-naphthoquinone diazide was used as a photoreactant linked to the polymer (Figure 6.25). 

For the fabrication of M/NEMS and chemical sensors, often thicker layers of resist are needed to buUd up channels or to define fluid reservoirs. In these cases SU-8 [15] or polyimide resist layers can be used [1]. Thicker layers are frequently used for molding or for microfluidic devices [16] for stereolithography [11], the desired pattern is defined in resin by scanning a laser through a thin layer of the material in a sequential fashion. 

Figure 5.126 summarizes the relative radiation resistance of plastics. At higher doses, all plastics are increasingly damaged, whereby the most resistant plastics (epoxy resins, polystyrene, polyimide) resist doses as high as 10 MGy. Excessive crosslinking and degradation result in embrittlement. 

Polyimide. Polyimide is a biaxiaHy oriented high performance film that is tough, flexible, and temperature- and combustion-resistant. Its room temperature properties compare to poly(ethylene terephthalate), but it retains these good characteristics at temperatures above 400°C. Its electrical resistance is good and it is dimensionally stable. The principal detriment is fairly high moisture absorbance. The main uses are for electrical insulation, particularly where high temperatures are prevalent or ionizing radiation is a problem. The films may be coated to reduce water absorption and enhance... 

Moleculady mixed composites of montmorillonite clay and polyimide which have a higher resistance to gas permeation and a lower coefficient of thermal expansion than ordinary polyimides have been produced (60). These polyimide hybrids were synthesized using montmorillonite intercalated with the ammonium salt of dodecylamine. When polymerized in the presence of dimethyl acetamide and polyamic acid, the resulting dispersion was cast onto glass plates and cured. The cured films were as transparent as polyimide. 

A number of thermally stable polymers have been synthesized, but in general the types of stmctures that impart thermal resistance also result in poor processing characteristics. Attempts to overcome this problem have largely been concentrated on the incorporation of flexible groups into the backbone or the attachment of stable pendent groups. Among the class of polymers claimed to be thermally stable only a few have achieved technological importance, some of which are polyamides, polyimides, polyquin oxalines, polyquinolines, and polybenzimidazoles. Of these, polyimides have been the most widely explored. 

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. 

Polyimides of 6FDA and aUphatic diamines with good low temperature processkig and low moisture swelling are known to be useful as hot-melt adhesives (109). Aluminum strips bonded by this polymer (177°C/172 kPa (25 psi) for 15 min) exhibited a lap-shear strength of 53 MPa (7690 psi) at room temperature and 35 MPa (5090 psi) at 100°C. The heat- and moisture-resistant 6F-containing Pis useful ki electronic devices are prepared from... 

In addition to carbon and glass fibers ia composites, aramid and polyimide fibers are also used ia conjunction with epoxy resias. Safety requirements by the U.S. Federal Aeronautics Administration (FAA) have led to the development of flame- and heat-resistant seals and stmctural components ia civiUan aircraft cabias. Wool blend fabrics containing aramids, poly(phenylene sulfide), EDF, and other inherently flame-resistant fibers and fabrics containing only these highly heat- and flame-resistant fibers are the types most frequently used ia these appHcations. 

Other Polymers. Besides polycarbonates, poly(methyl methacrylate)s, cycfic polyolefins, and uv-curable cross-linked polymers, a host of other polymers have been examined for their suitabiUty as substrate materials for optical data storage, preferably compact disks, in the last years. These polymers have not gained commercial importance polystyrene (PS), poly(vinyl chloride) (PVC), cellulose acetobutyrate (CAB), bis(diallylpolycarbonate) (BDPC), poly(ethylene terephthalate) (PET), styrene—acrylonitrile copolymers (SAN), poly(vinyl acetate) (PVAC), and for substrates with high resistance to heat softening, polysulfones (PSU) and polyimides (PI). 

The newer open-ceU foams, based on polyimides (qv), polyben2imida2oles, polypyrones, polyureas, polyphenylquinoxalines, and phenoHc resins (qv), produce less smoke, are more fire resistant and can be used at higher temperatures. These materials are more expensive and used only for special appHcations including aircraft and marine vessels. Rigid poly(vinyl chloride) (PVC) foams are available in small quantities mainly for use in composite panels and piping appHcations (see Elame retardants Heat-RESISTANTPOLYA rs). 

Carboxyhc acids react with aryl isocyanates, at elevated temperatures to yield anhydrides. The anhydrides subsequently evolve carbon dioxide to yield amines at elevated temperatures (70—72). The aromatic amines are further converted into amides by reaction with excess anhydride. Ortho diacids, such as phthahc acid [88-99-3J, react with aryl isocyanates to yield the corresponding A/-aryl phthalimides (73). Reactions with carboxyhc acids are irreversible and commercially used to prepare polyamides and polyimides, two classes of high performance polymers for high temperature appHcations where chemical resistance is important. Base catalysis is recommended to reduce the formation of substituted urea by-products (74). 

For reasons that are not fiiUy understood, PPSF exhibits generally improved compatibiUty characteristics over either PSF or PES in a number of systems. An example of this is blends of PPSF with polyaryletherketones (39,40). These blends form extremely finely dispersed systems with synergistic strength, impact, and environmental stress cracking resistance properties. Blends of PPSF with either PSF or PES are synergistic in the sense that they exhibit the super-toughness characteristic of PPSF at PSF or PES contents of up to 35 wt % (33,34). The miscibility of PPSF with a special class of polyimides has been discovered and documented (41). The miscibility profile of PPSF with high temperature (T > 230° C) polysulfones has been reported (42). 

Diels-AIder Copolymers. The Diels-Alder reaction can also be employed to obtain thermosetting polyimides. If bismaleimide (the bisdienophile) and the bisdiene react nonstoichiometricaHy, with bismaleimide in excess, a prepolymer carrying maleimide terminations is formed as an intermediate, which can then be cross-linked to yield a temperature-resistant network. 

Polyamide or polyimide polymers are resistant to aliphatic, aromatic, and chlorinated or fluorinated hydrocarbons as well as to many acidic and basic systems but are degraded by high-temperature caustic exposures. 

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