SynopsisCalculations have been carried out, based on Flory-Huggins solution theory, to analyze the behavior of the ternary nonsolvent-solvent-polymer phase diagram for typical membraneforming systems. Consideration is given to the behavior of the spinodal as well as binodal curves, tie-line slopes, and critical points as a function of various parameters, most especially those related to the concentration dependency of the interaction parameters. Implications regarding membrane structure formation are discussed, and the suitability of different functional forms for the interaction parameter concentration dependence is also analyzed.The net result of these calculations is to demonstrate the importance of the various parameters in controlling the phasediagram behavior and particularly to show the critical role of the concentration dependence of the solvent-polymer interaction parameter in affecting the nature of the miscibility gap.
Composite film production based on cotton stalk xylan was studied, and the mechanical and physical properties of the films formed were investigated. Xylan and lignin were separated from cellulose by alkali extraction and, then, lignin was removed using ethanol washing. Self-supporting continuous films could not be produced using pure cotton stalk xylan. However, film formation was achieved using 8-14% (w/w) xylan without complete removal of lignin during xylan isolation. Keeping about 1% lignin in xylan (w/w) was determined to be sufficient for film formation. Films were produced by casting the film-forming solutions, followed by solvent evaporation in a temperature (20 degrees C) and relative humidity (40%) controlled environment. The elastic modulus and hypothetical coating strength of the films obtained by using 8% xylan were significantly different from the ones containing 10-14% xylan. The water vapor transfer rates (WVTR) decreased with increasing xylan concentration, which made the films thicker. The glycerol addition as an additional plasticizer resulting in more stretchable films having higher WVTR and lower water solubility values. As a result, film production was successfully achieved from xylan, which was extracted from an agricultural waste (cotton stalk), and the film-forming effect of lignin on pure xylan has been demonstrated.
Xylooligosaccharide (XO) production was performed from xylan, which was obtained by alkali extraction from cotton stalk, a major agricultural waste in Turkey. Enzymatic hydrolysis was selected to prevent byproduct formation such as xylose and furfural. Xylan was hydrolyzed using a commercial xylanase preparation, and the effects of pH, temperature, hydrolysis period, and substrate and enzyme concentrations on the XO yield and degree of polymerization (DP) were investigated. Cotton stalk contains about 21% xylan, the composition of which was determined as 84% xylose, 7% glucose, and 9% uronic acid after complete acid hydrolysis. XOs in the DP range of 2-7 (X6 approximately X5>X2>X3) were obtained with minor quantities of xylose in all of the hydrolysis conditions used. Although after 24 h of hydrolysis at 40 degrees C, the yield was about 53%, the XO production rate leveled off after 8-24 h of hydrolysis. XO yield was affected by all of the parameters investigated; however, none of them affected the DP of the end product significantly, except the hydrolysis period. Enzyme hydrolysis was maintained by the addition of fresh substrate after 72 h of hydrolysis, indicating the persistence of enzyme activity. The optimal hydrolysis conditions were determined as 40 degrees C, pH 5.4, and 2% xylan. The obtained product was fractionated via ultrafiltration by using 10, 3, and 1 kDa membranes. Complete removal of xylanase and unhydrolyzed xylan was achieved without losing any oligosaccharides having DP 5 or smaller by 10 kDa membrane. After a two-step membrane processing, a permeate containing mostly oligosaccharides was obtained.
Differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA) were used to investigate the thermal behavior of glycidyl azide polymer (GAP) and GAP-based binders, which are of potential interest for the development of highperformance energetic propellants. The glass transition temperature (T g ) and decomposition temperature (T d ) of pure GAP were found to be Ϫ45 and 242°C, respectively. The energy released during decomposition (⌬H d ) was measured as 485 cal/g. The effect of the heating rate on these properties was also investigated. Then, to decrease its T g , GAP was mixed with the plasticizers dioctiladipate (DOA) and bis-2,2-dinitropropyl acetal formal (BDNPA/F). The thermal characterization results showed that BDNPA/F is a suitable plasticiser for GAP-based propellants. Later, GAP was crosslinked by using the curing agent triisocyanate N-100 and a curing catalyst dibuthyltin dilaurate (DBTDL). The thermal characterization showed that crosslinking increases the T g and decreases the T d of GAP. The T g of cured GAP was decreased to sufficiently low temperatures (Ϫ45°C) by using BDNPA/F. The decomposition reaction-rate constants were calculated. It can be concluded that the binder developed by using GAP/N-100/ BDNPA/F/DBTDL may meet the requirements of the properties that makes it useful for future propellant formulations.
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