Polyimides, properties

Bending beam theory calculation of elastic modulus, 361-362 calculation of glass temperature, 362 calculation of thermal expansion coefficient, 362 layer stress determination, 361 Benzophenone-3,3, 4,4 -tetracarboxydi-anhydride-oxydianiline-m-phenylenediamine (BTDA-ODA-MPDA) polyimide, properties, 115-116 Bilayer beam analysis schematic representation of apparatus, 346,348/ thermal stress, 346 Binary mixtures of polyamic acids curing, 116-124 exchange reactions, 115 Bis(benzocyclobutenes) heat evolved during polymerization vs. 

The preparation of composites prepared by high temperature decomposition reactions have mainly concentrated on polyimides and reactive inorganic additives (e.g., simple salts and complexes). In many cases polymer-metal composites have been unintentionally produced by workers whose primary goal was the modification of polyimide properties by incorporation of metal ions. For example, approximately 30 years ago Angelo briefly reported in a patent the addition of metal ions to several types of polyimides for the purpose of forming particle-containing transparent polyimide shaped structures. Ten years... 

The synthesis of polymers from a mixture of several diamines and dianhydrides, and especially the synthesis of block copolyimides, represents wide opportunities of directed regulation of polyimides properties, including giving them solubility. One of the methods of the block copolymers synthesis is getting them on the basis of presynthesized oligomers with determination molecular weight and with different functional groups. 

Guided by the criteria for proper materials selection discussed above, consider a zeolite 4A-PI membrane while recalling the intrinsic polyimide properties provide... 

Polyimide films are used in a variety of interconnect and packaging applications including passivation layers and stress buffers on integrated circuits and interlayer dielectrics in high density thin film interconnects on multi-chip modules and in flexible printed circuit boards. Performance differences between poly-imides are often discussed solely in terms of differences in chemistry, wiAout reference to the anisotropic nature of these films. Many of the polyimide properties important to the microelectronics industry are influenced not only by the polymer chemistry but also by the orientation and structure. Properties such as the linear coefficient of thermal expansion (CTE), dielectric constant, modulus, strength, elongation, stress and thermal conductivity are affected by molecular orientation. To a lesser extent, these properties as well as properties such as density and volumetric CTE are also influenced by crystdlinity (molecular ordering). 

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... 

BiaxiaHy oriented films have excellent tensile strength properties and good tear and impact properties. They are especially well regarded for their brilliance and clarity. Essentially all poly(ethylene terephthalate) film is biaxiaHy oriented, and more than 80% of polypropylene film is biaxiaHy oriented. Polystyrene film is oriented, and a lesser amount of polyethylene, polyamide, poly(vinyl chloride), and other polymers are so processed. Some of the specialty films, like polyimides (qv), are also oriented. 

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. 

Synthesis and Properties. Several methods have been suggested to synthesize polyimides. The predominant one involves a two-step condensation reaction between aromatic diamines and aromatic dianhydrides in polar aprotic solvents (2,3). In the first step, a soluble, linear poly(amic acid) results, which in the second step undergoes cyclodehydration, leading to an insoluble and infusible PL Overall yields are generally only 70—80%. 

Synthesis and Properties. In 1972, Du Pont marketed a series of linear aromatic polyimides called NR-150 (105) based on... 

Property ASTM method Polyisocyanurate XEPS EPs Polyimide Polyethylene PhenoHc... 

Possible tape materials include polyimide, polyester, polyethersulfone (PES), and polyparabanic acid (PPA) (18). Of these, polyimide is the most widely used material because its high melting point allows it to survive at temperatures up to 365°C. Although polyester is much cheaper than other materials, its use is limited to temperatures less than 160°C. PES and PPA, on the other hand, are half as cosdy as polyimide, and can survive maximum short-term temperatures of 220 and 275°C, respectively. PES has better dimensional stabiUty than polyimide, absorbs less moisture, and does not tear as easily however, it is inflammable and can be attacked by certain common solvents. Table 7 Hsts various plastic tapes and their properties. Common bump materials are gold, copper, and 95% Pb/5% Sn solder (see Tables 6 and 8 for properties see also References 2 and 21). 

Du Pont produces this polymer under the trade names of Kapton, Pyrafin, Vespel, and Pyre-ML. The trade names refer to polyimides used for film, semiconductor coatings, mol ding applications, and wire enamel, respectively. They have exceUent thermal, electrical, and physical properties. 

Since successful commercialization of Kapton by Du Pont Company in the 1960s (10), numerous compositions of polyimide and various new methods of syntheses have been described in the Hterature (1—5). A successful result for each method depends on the nature of the chemical components involved in the system, including monomers, intermediates, solvents, and the polyimide products, as well as on physical conditions during the synthesis. Properties such as monomer reactivity and solubiHty, and the glass-transition temperature,T, crystallinity, T, and melt viscosity of the polyimide products ultimately determine the effectiveness of each process. Accordingly, proper selection of synthetic method is often critical for preparation of polyimides of a given chemical composition. 

Because a wide range of properties are realized with various compositions, polyimides are used in diverse areas of appHcation. 

Table 2. Properties of High Temperature Polyimide Films...

Relatively few processible polyimides, particularly at a reasonable cost and iu rehable supply, are available commercially. Users of polyimides may have to produce iutractable polyimides by themselves in situ according to methods discussed earlier, or synthesize polyimides of unique compositions iu order to meet property requirements such as thermal and thermoxidative stabilities, mechanical and electrical properties, physical properties such as glass-transition temperature, crystalline melting temperature, density, solubility, optical properties, etc. It is, therefore, essential to thoroughly understand the stmcture—property relationships of polyimide systems, and excellent review articles are available (1—5,92). 

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). 

Cycloahphatic diamines react with dicarboxyUc acids or their chlorides, dianhydrides, diisocyanates and di- (or poly-)epoxides as comonomers to form high molecular weight polyamides, polyimides, polyureas, and epoxies. Polymer property dependence on diamine stmcture is greater in the linear amorphous thermoplastic polyamides and elastomeric polyureas than in the highly crosslinked thermo set epoxies (2—4). 

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