Solutions of polymers

When spraying solutions of polymers, the spraying process is usually limited to viscosities less than 0.5 Pa s under spraying conditions. Higher viscosities give rise to the formation of fiber-particle mixtures and deformed spheres. Finally, at p. 10 Pa s only fibers are formed (Lohner et al., 2005 Eggers and Villermaux, 2008). The same behavior can be observed when highly viscous melts are sprayed, see for example, Walz and Mayer (1966). 

Some general mles about polymer solubility are  

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Evaluate ASj for ideal solutions and for athermal solutions of polymers having n values of 50, 100, and 500 by solving Eqs. (8.28) and (8.38) at regular intervals of mole fraction. Compare these calculated quantities by preparing a suitable plot of the results. 

Extrusion Processes. Polymer solutions are converted into fibers by extmsion. The dry-extmsion process, also called dry spinning, is primarily used for acetate and triacetate. In this operation, a solution of polymer in a volatile solvent is forced through a number of parallel orifices (spinneret) into a cabinet of warm air the fibers are formed by evaporation of the solvent. In wet extmsion, a polymer solution is forced through a spinneret into a Hquid that coagulates the filaments and removes the solvent. In melt extmsion, molten polymer is forced through a multihole die (pack) into air, which cools the strands into filaments. 

Phosgene addition is continued until all the phenoHc groups are converted to carbonate functionahties. Some hydrolysis of phosgene to sodium carbonate occurs incidentally. When the reaction is complete, the methylene chloride solution of polymer is washed first with acid to remove residual base and amine, then with water. To complete the process, the aqueous sodium chloride stream can be reclaimed in a chlor-alkah plant, ultimately regenerating phosgene. Many variations of this polycarbonate process have been patented, including use of many different types of catalysts, continuous or semicontinuous processes, methods which rely on formation of bischloroformate oligomers followed by polycondensation, etc. 

Experimental values of X have been tabulated for a number of polymer-solvent systems (4,12). Unfortunately, they often turn out to be concentration and molecular weight dependent, reducing their practical utility. The Flory-Huggins theory quahtatively predicts several phenomena observed in solutions of polymers, including molecular weight effects, but it rarely provides a good quantitative fit of data. Considerable work has been done subsequentiy to modify and improve the theory (15,16). 

Polymeric Calcium Phosphate Cements. Aqueous solutions of polymers such as poly(acryHc acid), poly(vinyl alcohol), gelatin, etc, and/or autopolymerizable monomer systems, eg, 2-hydroxyethyl methacrylate, glycerol dimethacrylate, calcium dimethacrylate, etc, have been used as Hquid vehicles (41,42,76) for the self-setting calcium phosphate cement derived from tetracalcium phosphate and dicalcium phosphate [7757-93-9J. 

Membrane eleetrodes with obtained PVP-dye adduets in polymerie matrixes are developed to measure free eoneentrations of polymer in solution. Membrane film eleetrodes ar e prepar ed using polyvinyl ehloride as a matrix. We investigated properties of eleetrodes eontaining triphenylmethane - PVP and azodye - PVP adduets in water solution of polymer in presenee of different eleetrolytes. 

The last quantity that we discuss is the mean repulsive force / exerted on the wall. For a single chain this is defined taking the derivative of the logarithm of the chain partition function with respect to the position of the wall (in the —z direction). In the case of a semi-infinite system exposed to a dilute solution of polymer chains at polymer density one can equate the pressure on the wall to the pressure in the bulk which is simply given by the ideal gas law The conclusion then is that [74]... 

Again, the OLMC bead-spring model (Sec. IIB 2) is used, with a host matrix of an equilibrated dense solution of polymer chains quenched at different concentrations Cots. Eq. (7) for the probability IF of a random monomer displacement in direction Ax, Ay, Az is given by... 

In HOPC, a concentrated solution of polymer is injected. The concentration needs to be sufficiently higher than the overlap concentration c at which congestion of polymer chains occurs. The c is approximately equal to the reciprocal of the intrinsic viscosity of the polymer. In terms of mass concentration, c is quite low. For monodisperse polystyrene, c is given as (4)... 

Other reasons for a wide propagation of polymerization in water include (1) reduction of energy consumed to separate the initial monomer in crystal form (acrylamide is produced and used in the aqueous solution form), which, in addition, is associated with the probability of its spontaneous polymerization, and (2) recovery of the organic solvents, which results in less environmental pollution and the elimination of the stage of solution of polymer reagents used, as a rule, in the form of the aqueous solutions. 

Proton nuclear magnetic resonance spectra of 15-20% solutions of polymers in CC14 were obtained with Varian T-60 or HR-300 spectrometers. Chemical shifts are reported... 

In order to form a solution of polymer in solvent, F must be greater than or equal to the forces F and F. If either F or F is greater than F the molecules with the biggest intermolecular attraction will cohere and fail to mix with the dissimilar molecules. Under such circumstances the system will remain two-phased. 

Other uses of thickening agents include pharmaceutical preparations, paper production, and oil well drilling fluids. This latter use is necessary because oil is obtained from rock that is porous. In order to remove the oil without altering the mechanical properties of the porous rock, viscous liquids ( drilling fluids ) are pumped into the rock to replace the oil. Among the substances that can be used for this purpose are thickened aqueous solutions of polymers such as poly(acrylic acid) or poly(acrylonitrile). 

Unlike the case with dilute solutions of polymer, the variation of the melt viscosity and molar mass is far from completely understood. However, the melt viscosity, has been found to vary uniformly with number of carbon atoms in the chain above about 300-500, according to the equation ... 

Table 6.2 Colligative properties of a solution of polymer of molar mass 20 000 at a concentration o/O.Ol g (from F. W. Billmeyer, Textbook of Polymer Science , John Wiley Sons, New York, 1962)...

The extremely low rates of solution of polymers and the high viscosities of their solutions present serious problems in the application of the delicate calorimetric methods required to measure the small heats of mixing or dilution. This method has been applied successfully only to polymers of lower molecular weight where the rate of solution is rapid and the viscosity of the concentrated solution not intolerably great.22 The second method requires very high precision in the measurement of the activity in order that the usually small temperature coefficient can be determined with sufficient accuracy. 

Thermal Phase Inversion Thermal phase inversion is a technique which may be used to produce large quantities of MF membrane economically. A solution of polymer in poor solvent is prepared at an elevated temperature. After being formed into its final shape, a sudden drop in solution temperature causes the polymer to precipitate. The solvent is then washed out. Membranes may be spun at high rates using this technique. 

Cazes, J. and Fallick, G., Application of liquid chromatography to the solution of polymer problems, Polym. News, 3, 295, 1977. 

When a thin liquid film with a thickness of approximately 2 pm prepared by spin coating of a 15% benzene solution of polymer 1 was irradiated with a 500-W Xe-Hg lamp for 300 s in air, a transparent solid film was obtained. The UV spectrum of this solid film shows that an absorption at 235 nm due to phenyldisilanyl units vanishes after UV-irradiation (Figure 1). This clearly indicates that photolytic cleavage of silicon-silicon bonds leading to the cross-linking occurred. Similar photolysis of the thin liquid films under a nitrogen atmosphere again afforded transparent solid films whose UV spectra show no absorption at 235 nm due to phenyldisilanyl units. 

The viscosity of a dilute solution of polymer depends on the molecular weight of the polymer. This gives us a simple method for measuring molecular weight based on viscosity, which is readily measured. 

To perform this analysis, we first prepare a dilute solution of polymer with an accurately known concentration. We then inject an aliquot of this solution into a viscometer that is maintained at a precisely controlled temperature, typically well above room temperature. We calculate the solution s viscosity from the time that it takes a given volume of the solution to flow through a capillary. Replicate measurements are made for several different concentrations, from which the viscosity at infinite dilution is obtained by extrapolation. We calculate the viscosity average molecular weight from the Mark-Houwink-Sakurada equation (Eq. 5.5). 

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