Solvent film casting

To achieve good compatibility with functionalized acrylic and epoxy resins a bis cyclic urea with n=3> and R=-(CH2)7-(see Scheme I) was synthesized. Acrylic- and epoxypolymer solutions were prepared using 15% by weight of the bis cyclic urea (based on the dry polymer) and methyl ethyl ketone as solvent. Films cast from these solutions on steel sheets were clear, and had a thickness of 0.4 mil. 

Solution processes are used mainly for coating, film casting and fibre spinning, i.e. in processes where the distance the solvent has to diffuse out of the solution once coated, cast or spun is short. Regulation of this diffusion process is important if products of even quality are to be obtained. 

As an indication of the changes in deformation modes that can be produced in ionomers by increase of ion content, consider poly(styrene-co-sodium methacrylate). In ionomers of low ion content, the only observed deformation mode in strained thin films cast from tetra hydrofuran (THF), a nonpolar solvent, is localized crazing. But for ion contents near to or above the critical value of about 6 mol%, both crazing and shear deformation bands have been observed. This is demonstrated in the transmission electron microscope (TEM) scan of Fig. 3 for an ionomer of 8.2 mol% ion content. Somewhat similar deformation patterns have also been observed in a Na-SPS ionomer having an ion content of 7.5 mol%. Clearly, in both of these ionomers, the presence of a... 

Thermal treatment and the nature of the casting solvent can also affect the deformation modes achieved in strained films of ionomers. For example, in films cast from polar dimethylformamide (DMF), the solvent interacts with ion-rich clusters and essentially destroys them, as is evident form absence of a second, higher temperature loss peak in such samples. As a result, even in a cast DMF sample of Na-SPS ionomer of high ion content (8.5 mol%), the only deformation mode observed in tensile straining is crazing. However, when these films are given an additional heat treatment (41 h at 210°C), shear... 

In order to examine the effect of solvents, films of a solvent-free epoxypolyamine were cast, mounted in cells and their resistances measured in dilute and concentrated potassium chloride solution . All the films had / properties with resistances in the range 10 -I0 flcm. ... 

Tetrahydrofuran has been reported to exhibit an absorption maximum at 280 nm (52,56), but several workers have shown that this band is not produced by the purified solvent (30,41,57). Oxidation products from THF have been invoked in order to account for the appearance of the 280-nm band in PVC films that are solvent-cast from THF in air (57. 581. However, in some reported cases (56,59), this band was undoubtedly produced, at least in part, by a phenolic antioxidant (2.6-di-tert-butyl-p-cresol)(59) in the solvent. Since certain -alkylphenols have now been shown to be powerful photosensitizers for the dehydrochlorination of PVC (60), it is clear that antioxidant photosensitization might well have been responsible for some of the effects attributed previously (56) to THF alone. On the other hand, enhanced rates of photodegradation under air have also been observed for PVC films cast from purified THF (57), a result which has been ascribed to radical formation during the photooxidation of residual solvent (57,61). Rabek et al. (61) have shown that this photooxidation produces a-HOO-THF, a-HO-THF, and y-butyro-lactone, and they have found that the hydroperoxide product is an effective sensitizer for the photodehydrochlorination of PVC at X = 254 nm (61). 

Even at their best, the models are able to predict only macroscopic properties of the films, yielding no information on microscopic parameters that may affect resist performance. It is highly probable that spin casting induces some structure or preferential chain orientation into the films, or causes secondary effects such as the aggregation observed by Law. These effects are barely addressed in the currently available literature. However, some earlier works (3.17-191 on solvent (static) cast films have investigated the molecular orientation of polymer chains as well as chain relaxation due to thermal annealing. 

The film casting solution is usually a mixture of the polymer (e.g., cellulose acetate), a solvent (e.g., acetone), and an essentially nonsolvent swelling agent (e.g., aqueous solution of magnesium perchlorate, or formamide). The film making... 

The important conclusion drawn from the above studies on PS(OH)/PMMA in solution and bulk is that complexes formed in dilute solutions can be preserved during the process of film casting. In particular, when we use an inert solvent whose Ejp is close to zero, the critical hydroxyl contents in proton-donating polymers for complexation estimated by viscosity or LLS are comparable to that for the miscibility-to-complex transition in bulk, which can be easily detected by DSC or TEM. Therefore, by combining the results from both solution and bulk, it should be possible to construct a map for a given blend system visualizing how the immiscibihty, miscibihty and complexation of the blend depend on the content of interacting sites. 

The diffusion and the permeability are inversely related to the density, degree of crystallinity, orientation, filler concentration, and crosslink density of a polymeric film. As a general rule, the presence of plasticisers or residual solvents increases the rate of diffusion in polymers. Films cast from poor solvents have high permeability. The rate of diffusion or permeability is independent of the molecular weight of the polymer, providing the polymer has a moderately high molecular weight. 

Materials and Methods. The isomeric compositions of the four polybutadienes used are listed in Table I. Samples were prepared for infrared measurement from solutions of the polymer without further purification. Most films were cast from carbon disulfide solutions on mercury or on glass plates, but a few films were cast from hexane solutions to determine whether or not the solvent affected the radiation-induced behavior. No difference was observed for films cast from the different solvents. The films were cured by exposure to x-rays in vacuum. (Doses were below the level producing detectable radiation effects.) They were then mounted on aluminum frames for infrared measurements. The thicknesses of the films were controlled for desirable absorbance ranges and varied from 0.61 X 10 s to 2 X 10 3 cm. After measuring the infrared spectrum with a Perkin-Elmer 221 infrared spectrophotometer, the mounted films were evacuated to 3 microns and sealed in glass or quartz tubes (quartz tubes only were used for reactor irradiations). 

Measurement of Practical Photosensitivity. The photosensitivity of the polymer was measured by a gray-scale method (15) as follows. The polymer solution (10%) in cyclohexanone was cast on a copper plate by using a rotary applicator and dried. The Kodak step tablet No. 2 (Eastman Kodak Co.) was placed upon the polymer film cast on the plate, exposed on a chemical lamp (15w x 7) from 3 cm for 1 min., and then the exposed film was developed by the solvent for 2 min. 

Films of the polyisoimides were cast from DMAC at 55 °C under reduced pressure (0.1 mm). A study of the isomerization reaction was conducted by FTIR and showed that the isomerization began at approximately 100 °C and was complete after 3 h at 250 °C. In all cases the thermally treated films were insoluble in all solvents tested. Composite films were produced with XVII and three commercial matrix systems a polyarylsulfone (Radel), a polysulfone (Udel), and an acetylene terminated isoimide thermosetting resin (IP-600). Films of the matrix and XVII were cast from DMAC. Slightly cloudy films, indicating some phase separation, resulted with both the Radel and Udel systems. Composite films cast with IP-600, however, were completely clear and showed no signs of phase separation. The structural similarity of the IP-600 resin and XVII may account for the greater homogeneity of the system. Property assessment of these films before and after thermal treatment is currently underway. 

Solution blends of 20-25% by weight were formed in DM Ac, with conventional dry spinning and film casting techniques used to produce blend fiber and film, respectively. Blend powders were prepared by precipitating the dope with a non-solvent (water). All materials were extensively washed in methanol or water to reduce residual solvent to less than 1 wt %. Neat resin tensile bars and plaques were compression molded from both powder and fiber. 

Two methods, annealing and film-casting by slow solvent evaporation, have been used effectively to develop maximum crystallinity in PVDF blends. The... 

The crystallization tendency of polycarbonate is enhanced by the action of solvents. For example, crystallization may be accomplished by slow evaporation of solvent from cast film (14, 17) or by treatment with swelling agents such as ethyl acetate or acetone. 

Incorporating small amounts of plasticizer during the manufacture of solvent-cast polycarbonate films results in films with a higher modulus of elasticity, a higher stiffness, and higher heat distortion temperatures than films cast from unplasticized polymer. 

Films containing the various additives were obtained by casting from methylene chloride by conventional techniques. The films, from 1 to 3 mils in thickness, were dried at room temperature for 24 hours. Those with glass transition temperatures above 100°C. were then heated in an oven at 100° to 110°C. for 2 hours to ensure the removal of all solvent. Films with lower transition temperatures were heated under reduced pressure in an oven for 24 hours at temperatures ranging from 40° to 65°C., depending on the transition temperatures. 

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