Mechanical properties, polyimide films

PES/polyimidc blends are interesting for several reasons. First, little information about these blends is available in the literature although PES has been reported to be miscible with poly(ethylene oxide) [5,6] and with phenoxy resin [7]. Second, PES costs less than polyimide and has somewhat similar mechanical properties. Tliird, films of the blends have indicated that the brittle nature of pure PI is decreased by mixing with PES. Thus PES/PI blends offer a potential improvement over the pure materials. 

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. 

However, fluorocarbon compounds might be of considerable interest for LB-layer fabrication. Their dielectric and mechanical characteristics and thermal and chemical stability are not inferior to those of polyimides, and highly developed synthesis technology makes it possible to create systems with various predictable properties. Such films have been found to demonstrate a high degree of perfection and excellent dielectric characteristics.69,70... 

Metal ion modified polyimide films have been prepared to obtain materials having mechanical, electrical, optical, adhesive, and surface chemical properties different from nonmodified polyimide films. For example, the tensile modulus of metal ion modified polyimide films was increased (both at room temperature and 200 0 whereas elongation was reduced compared with the nonmodif ied polyimide (i). Although certain polyimides are )cnown to be excellent adhesives 2) lap shear strength (between titanium adherends) at elevated temperature (275 0 was increased by incorporation of tris(acetylacetonato)aluminum(III) (2). Highly conductive, reflective polyimide films containing a palladium metal surface were prepared and characterized ( ). The thermal stability of these films was reduced about 200 C, but they were useful as novel metal-filled electrodes ( ). 

There are several difficulties in the application of this technique to the analysis of sodium barrier properties of these polyimide films. First, as we have seen above, large shifts in the surface potential characteristics of MPOS structures can be associated with electronic conduction in the polyimide and charging of the polyimide-oxide interface. These shifts are not readily separable from any that might be caused by the inward drift of sodium ions. Second, the effect of the electronic charging process is to buck out the electric field in the polyimide which is needed to drive the ion drift mechanism. As seen in Figure 6, the electric field is reduced to very small values in a matter of minutes or less, particularly at the higher temperatures where ion drift would normally be measured. 

The last 20 years have seen enormous progress in the development of high-performance fluoropolymers. Fluorine-containing polyimides stand out as one of the few types of materials that simultaneously possess outstanding thermal stability and mechanical properties, low dielectric permittivity, and thin-film processability. This combination of properties makes them ideal for use as high-performance insulators in electronic devices. 

Table 14.4. Mechanical Properties of Perfluorinated (10FEDA/4FMPD), Partially Fluorinated (6FDA/TFDB), and Unfluorinated (PMDA/ODA) Polyimide Films ...

Adhesion of polyimides to inorganic substrates is of great importance to the microelectronics industry [1, 2]. The polyimide films are deposited most often by spin coating the polyamic acid (PAA) usually from a TV-methylpyrrolidone (NMP) solution onto the substrate surface followed by thermal imidization at temperatures up to 400<>C. The most studied polyimide is the pyromellitic dianhydride-oxydianiline (PMDA-ODA), which exhibits excellent mechanical and dielectric properties, but not so good adhesion characteristics. The latter has been generally overcome by application of an adhesion promoter, such as y-aminopropyltriethoxysilane [3-7]. The reactions of APS (coated from water solution) with the silicon dioxide surface as well as with polyamic acid have been well characterized by Linde and Gleason [4] however, we do not have such detailed information available on APS interaction with other ceramic surfaces. 

Earlier investigations on the dynamic mechanical properties of PPMI over a wide range of temperatures indicated the existence of two distinct relaxations at around 250 and 400 K [15,16]. The former relaxation was assigned to adsorbed water molecules in the polyimide chain and the latter was due to local relaxation modes of the backbone. Recently Ahlbom reported the mechanical relaxation of various polymers at low temperatures [17]. In the film sample of PPMI, the small relaxation at 93 K. attributed to the motion of phenyl rings was observed, although the dominant damping peak at 198 K is not yet explained. 

Kapton polyimide has been widely used in the electronic industry because of its low dielectric constant, good mechanical properties and high thermal stability. Many applications require good adhesion between Kapton polyimide film and metal. Various processes to improve adhesion of metal to Kapton polyimide have been reported in the literature. DeAngelo et al., (D describe a process to form metal oxides on the surface of polyimide to improve adhesion. Other efforts to improve adhesion of a metal layer involve roughening of the surface of polyimide substrate by methods such as cathodic sputtering (2), chemical attack (2., 1), and reactive ion etching (1,4). 

When used as an interlevel dielectric, even greater demands are placed on the polyimide. Because integrated circuit processing includes as a final step a metal sinter at 400 C, the interlevel insulator film must withstand such exposures without degradation of electrical, chemical, or mechanical properties. In addition, the deposition, cure, and etch process must provide for reliable interconnection between the metal layers above and beneath the film (the "via contact") [8]. Issues of ion motion, moisture uptake, and electrical conduction both in bulk and at interfaces must also be considered carefully. 

Highly reflective, surface-metallized, flexible polyimide films containing silver are accessible by the incorporation of [Ag(hfac)] into poly(amic acid) solutions followed by thermal curing to 300 "C . The silvered films are thermally stable and maintain mechanical properties similar to those of the parent polyamide. 

The mechanical properties of the polyimide films (the sample size 10-mm length, 10-mm width) were examined at room temperature using a specially made machine with a constant drawing rate of 1 mm min"1. A profile of elongation vs. load for PI(BHDA+BBH) film is shown in Figure 4. The polyimide film possessed a tensile modulus of 2.1 GPa and a tensile strength of 52 MPa, and these values can compete in terms of strength with those of a commercial polycarbonate (PC).[8] The authors believe that this is the first example of a fully alicyclic polyimide for which the mechanical property was evaluated. 

---