Solution-casting

Perhaps the most common method for preparing polymer-nanotube composites has been to mix the nanotubes and polymer in a suitable solvent before evaporating the solvent to form a composite film. One of the benefits of the solution casting method is that agitation of the nanotube powder in a solvent facilitates nanotube de-aggregation and dispersion. Almost all solution processing methods are variations on a general theme which can be summarized in three major steps  

In general, de-aggregation and dispersion of carbon nanotubes are provided by magnetic stirring, shear mixing, reflux, or, most commonly, ultrasonication. Sonication can be provided in 

It should be pointed out that this method relies on the efficient dispersion of nanotubes in the relevant solvent. The choice of solvent is generally made based on the solubility of the polymer. However, pristine nanotubes usually cannot be well dispersed in most solvents. To get around this problem, Xia et al. (17) compared the dispersion of MWNT-graft-PU, MWNT-OH and raw MWNTs in 0.2% aqueous solution of sodium lauryl sulfate. The results showed that MWNT-graft-PU has a better dispersion stability compared to MWNTs and MWNT-OH. The incorporation of polyurethane-grafted carbon nanotubes had a better reinforcing effect compared to the raw carbon nanotubes. This should be attributed to the improved interfacial interaction between polyurethane matrix and carbon nanotubes. 

Some polymers, like polydiacetylenes with a general formula 

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The basic methods for forming film or sheeting materials may be classified as follows melt extmsion, calendering, solution casting, and chemical regeneration. Of special note is the use of biaxial orientation as part of the critical manufacturing steps for many film and sheet products. 

Solution Casting. The production of unsupported film and sheet by solution casting has generally passed from favor and is used only for special polymers not amenable to melt processes. The use of solvents was generally very hazardous because of their flammabiUty or toxic nature. The cost of recovery and disposal of solvents became prohibitive for many lower price film appHcations. The nature of the drying operations leads to problems with solvent migration and retention that are not problems with melt-processed polymers. 

Dense Symmetrical Membranes. These membranes are used on a large scale ia packagiag appHcations (see Eilms and sheeting Packaging materials). They are also used widely ia the laboratory to characterize membrane separation properties. However, it is difficult to make mechanically strong and defect-free symmetrical membranes thinner than 20 p.m, so the flux is low, and these membranes are rarely used in separation processes. Eor laboratory work, the membranes are prepared by solution casting or by melt pressing. 

Most solution-cast composite membranes are prepared by a technique pioneered at UOP (35). In this technique, a polymer solution is cast directly onto the microporous support film. The support film must be clean, defect-free, and very finely microporous, to prevent penetration of the coating solution into the pores. If these conditions are met, the support can be coated with a Hquid layer 50—100 p.m thick, which after evaporation leaves a thin permselective film, 0.5—2 pm thick. This technique was used to form the Monsanto Prism gas separation membranes (6) and at Membrane Technology and Research to form pervaporation and organic vapor—air separation membranes (36,37) (Fig. 16). 

The first five of these techniques involve deformation and this has to be followed by some setting operation which stabilises the new shape. In the case of polymer melt deformation this can be affected by cooling of thermoplastics and cross-linking of thermosetting plastics and similtir comments can apply to deformation in the rubbery state. Solution-cast film and fibre requires solvent evaporation (with also perhaps some chemical coagulation process). Latex suspensions can simply be dried as with emulsion paints or subjected to some... 

Limited solubility in selected perfluorinated solvents (unique amongst commercial fluoropolymers), enabling solution-cast ultra-thin coatings in the submicrometre thickness range. 

Park et al. [20] reported on the synthesis of poly-(chloroprene-co-isobutyl methacrylate) and its compati-bilizing effect in immiscible polychloroprene-poly(iso-butyl methacrylate) blends. A copolymer of chloroprene rubber (CR) and isobutyl methacrylate (iBMA) poly[CP-Co-(BMA)] and a graft copolymer of iBMA and poly-chloroprene [poly(CR-g-iBMA)] were prepared for comparison. Blends of CR and PiBMA are prepared by the solution casting technique using THF as the solvent. The morphology and glass-transition temperature behavior indicated that the blend is an immiscible one. It was found that both the copolymers can improve the miscibility, but the efficiency is higher in poly(CR-Co-iBMA) than in poly(CR-g-iBMA),... 

Wang and Chen [41] studied the compatibility problems of incompatible NBR-PVC blends. Poly(vinyl-idene chloride-covinyl chloride) is reported to act as an efficient interfacial agent. Blends of PVC, NBR, and the copolymer were prepared by the solution casting technique using THE as a solvent. Improvement in mechanical properties can be achieved in NBR-PVC blend by the addition of different types of rubbers [42]. Different rubbers include NR, styrene butadiene (SBR) and butadiene (BR). Replacement of a few percent of NBR by other rubbers will improve the mechanical properties and at the same time reduce the cost of the blend. 

This survey has demonstrated that the field of conjugated arylene vinylcne pol mere has matured considerably over the past thierty years. Several synthe approaches to poly(arylene vinylenejs have been developed, and many routes ni allow solution casting of polymeric materials, thereby facilitating incorporation... 

Hedrick et al. reported imide aryl ether ketone segmented block copolymers.228 The block copolymers were prepared via a two-step process. Both a bisphenol-A-based amorphous block and a semicrystalline block were prepared from a soluble and amorphous ketimine precursor. The blocks of poly(arylene ether ether ketone) oligomers with Mn range of 6000-12,000 g/mol were coreacted with 4,4,-oxydianiline (ODA) and pyromellitic dianhydride (PMDA) diethyl ester diacyl chloride in NMP in the presence of A - me thy 1 morphi 1 i nc. Clear films with high moduli by solution casting and followed by curing were obtained. Multiphase morphologies were observed in both cases. 

Chitin films can be manufactured from DMAc solutions or by other approaches, for example, blend films of beta-chitin (derived from squid pens) and poly(vinyl alcohol) (PVA) were prepared by a solution casting technique from corresponding solutions of beta-chitin and PVA in concentrated formic acid. Upon evaporation of the solvent, the film having 50/50 composition was found to be cloudy [224]. 

Epoxidized oils were also used to modify PLA Ali et ah (2009) reported that its use as a plasticizer to improve flexibility. Thermal and scanning electron microscope analysis revealed that epoxidized soybean oil is partially miscible with PLA. Rheological and mechanical properties of PLA/epoxidized soybean oil blends were studied by Xu and Qu (2009) Epoxidized soybean oil exhibited a positive effect on both the elongation at break and melt rheology. Al-Mulla et al. (2010b) also reported that plasticization of PLA (epoxidized palm oil) was carried out via solution casting process using chloroform as a solvent. The results indicated that improved flexibility could be achieved by incorporation of epoxidized palm oil. 

The release of steroids such as progesterone from films of PCL and its copolymers with lactic acid has been shown to be rapid (Fig. 10) and to exhibit the expected (time)l/2 kinetics when corrected for the contribution of an aqueous boundary layer (68). The kinetics were consistent with phase separation of the steroid in the polymer and a Fickian diffusion process. The release rates, reflecting the permeability coefficient, depended on the method of film preparation and were greater with compression molded films than solution cast films. In vivo release rates from films implanted in rabbits was very rapid, being essentially identical to the rate of excretion of a bolus injection of progesterone, i. e., the rate of excretion rather than the rate of release from the polymer was rate determining. 

Gong, Y., Huang, H., Hu, Z., Chen, Y, Chen, D Wang, Z. and He, X. (2006) Inverted to normal phase transition in solution-cast polystyrene-poly(methyl methacrylate) block copolymer thin films. Macromolecules, 39, 3369-3376. 

Pervaporation Membranes Pervaporation has a long history, and many materials have found use in pervaporation experiments. Cellulosic-based materials have given way to polyvinyl alcohol and blends of polyvinyl alcohol and acrylics in commercial water-removing membranes. These membranes are typically solution cast (from... 

Spectra of solution cast films of the hydrogenated NBR were recorded on a Nicolet 520 FT-IR spectrophotometer. The final degree of olefin conversion was confirmed by infrared analysis.9... 

Sample Preparation. Samples for mechanical studies were made by compression molding the polymers at 150°C between Teflon sheets for 15 minutes followed by rapid quenching to room temperature in air. These will be referred to as PQ (press-quenched or simply quenched) samples. The thickness of the PQ samples was around 10 mils (0.25 mm). The thermal history of all of the PQ samples (HBIB, HIBI, and LDPE) were essentially the same. They were used within one week after they were pressed. Samples for morphology, SALS and SEM studies were prepared from toluene solutions. These films were cast on a Teflon sheet at 80 C from a 1% (by weight) solution in toluene. These films were about 5 mils in thickness. When the polymer films had solidified (after 5 hrs), they were stored in a vacuum oven at 80°C for two days to remove residual solvent. These samples will be designated by TOL (solution cast from toluene). 

SEM micrographs of two members of these polymers (HB and HBIB-50) are shown in Figure 7 to provide further evidence for superstructure on the micron level within the solution cast films. One can directly observe the surface of the spherulitic structure of the HB homopolymer as well as in that of the copolymer HBIB-50. Clearly, the level of structure (-5 pm) is well above that of the individual domains of either HB or HI and reflects the possible primary nucleation and subsequent growth behavior common to spherulitic semicrystalline polymers. The Hv patterns shown in... 

A comparison of the dynamic mechanical properties of our HB at 35 Hz has been made to that of LDPE in Figures 14 A and B. The thermal and sample preparative history affects the mechanical properties of HB films to such an extent that in order to make a meaningful comparison one has to describe the exact history of the samples. Such a thermal history dependence has been examined for LDPE(54,57) and recently for HB.(12) Shown in Figures A and B are the mechanical spectra for HB-PQ, HB-Tol, and LDPE-PQ films. The compression molded films were prepared 1 to 2 days prior to the test. The solution cast film (from toluene), HB-Tol, was annealed at 80°C for 2-3 days and stored at room temperature for 1 week... 

Figure 14A. Temperature dependence of E at 35 Hz. Data for press-quenched and solution cast HB films.

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