Phase gelation

In the case of ionic substances the stabilization of colloidal suspensions in their sol form is based on electrostatic repulsion and the development of electrie double layers. Besides the chemical interaction between the dispersed and continuous phases, gelation can be induced by lowering the temperature of the system and increasing the concentration of the dispersed phase. 

Groenewold J, Kegel WK (2004) Colloidal eluster phases, gelation and nuclear matter. J Phys Condens Matter 16 S4877-S4886... 

Fibers spun by this method may be isotropic or asymmetric, with dense or porous walls, depending on the dope composition. An isotropic porous membrane results from spinning solutions at the point of incipient gelation. The dope mixture comprises a polymer, a solvent, and a nonsolvent, which are spun into an evaporative column. Because of the rapid evaporation of the solvent component, the spinning dope solidifies almost immediately upon emergence from the spinneret in contact with the gas phase. The amount of time between the solution s exit from the spinneret and its entrance into the coagulation bath has been found to be a critical variable. Asymmetric fibers result from an inherently more compatible solvent/nonsolvent composition, ie, a composition containing lower nonsolvent concentrations. The nature of the exterior skin (dense or porous) of the fiber is also controlled by the dope composition. 

Water-soluble polymers (qv) can increase the viscosity of the foam external phase. This improves foam stabihty and reduces mobihty. Gelation of... 

Resoles. Like the novolak processes, a typical resole process consists of reaction, dehydration, and finishing. Phenol and formaldehyde solution are added all at once to the reactor at a molar ratio of formaldehyde to phenol of 1.2—3.0 1. Catalyst is added and the pH is checked and adjusted if necessary. The catalyst concentration can range from 1—5% for NaOH, 3—6% for Ba(OH)2, and 6—12% for hexa. A reaction temperature of 80—95°C is used with vacuum-reflux control. The high concentration of water and lower enthalpy compared to novolaks allows better exotherm control. In the reaction phase, the temperature is held at 80—90°C and vacuum-refluxing lasts from 1—3 h as determined in the development phase. SoHd resins and certain hquid resins are dehydrated as quickly as possible to prevent overreacting or gelation. The end point is found by manual determination of a specific hot-plate gel time, which decreases as the polymerization advances. Automation includes on-line viscosity measurement, gc, and gpc. 

Most ultrafiltration membranes are porous, asymmetric, polymeric stmctures produced by phase inversion, ie, the gelation or precipitation of a species from a soluble phase (see Membrane technology). 

Polyelectrolyte complex membranes are phase-inversion membranes where polymeric anions and cations react during the gelation. The reaction is suppressed before gelation by incorporating low molecular weight electrolytes or counterions in the solvent system. Both neutral and charged membranes are formed in this manner (14,15). These membranes have not been exploited commercially because of then lack of resistance to chemicals. 

To prepare stable emulsions ia this way gelation of the continuous medium is necessary. The appearance of a Hquid emulsion may be retained by choosing a polymer for the continuous phase, giving a thixotropic solution with short breakdown and buildup times. The polymers used for this purpose are natural gums (qv) or synthetic polymers. Clay particles also act as viscosity enhancers. The members of the bentonite family derived from... 

In addition to acting as impact modifiers a number of polymeric additives may be considered as processing aids. These have similar chemical constitutions to the impact modifiers and include ABS, MBS, chlorinated polyethylene, acrylate-methacrylate copolymers and EVA-PVC grafts. Such materials are more compatible with the PVC and are primarily included to ensure more uniform flow and hence improve surface finish. They may also increase gelation rates. In the case of the compatible MBS polymers they have the special function already mentioned of balancing the refractive indices of the continuous and disperse phases of impact-modified compound. 

One prominent example of rods with a soft interaction is Gay-Berne particles. Recently, elastic properties were calculated [89,90]. Using the classical Car-Parrinello scheme, the interactions between charged rods have been considered [91]. Concerning phase transitions, the sohd-fluid equihbria for hard dumbbells that interact additionally with a quadrupolar force was considered [92], as was the nematic-isotropic transition in a fluid of dipolar hard spherocylinders [93]. The influence of an additional attraction on the phase behavior of hard spherocylinders was considered by Bolhuis et al. [94]. The gelation transition typical for clays was found in a system of infinitely thin disks carrying point quadrupoles [95,96]. In confined hquid-crystalline films tilted molecular layers form near each wall [97]. Chakrabarti has found simulation evidence of critical behavior of the isotropic-nematic phase transition in a porous medium [98]. 

In the case of the segmented polymers, the domains that form during phase separation will lead to the rapid buildup of viscosity and gelation, much like a crosslinking urethane, although these polymers are linear. An an-ologous expression for the viscosity rise in these systems is given by [36] ... 

Concentration of TEOS in all these cases has been restricted up to 50 wt% with respect to the mbber. Beyond 50 wt%, all the hybrids show phase separation which may be due to higher amount of water condensate that is continuously generated and acts as nonsolvent for the mbbers. This is easily understood from the visual appearance of the samples phase-separated composites slowly turn opaque in the course of gelation. 

Contrary to the phase separation curve, the sol/gel transition is very sensitive to the temperature more cations are required to get a gel phase when the temperature increases and thus the extension of the gel phase decreases [8]. The sol/gel transition as determined above is well reproducible but overestimates the real amount of cation at the transition. Gelation is a transition from liquid to solid during which the polymeric systems suffers dramatic modifications on their macroscopic viscoelastic behavior. The whole phenomenon can be thus followed by the evolution of the mechanical properties through dynamic experiments. The behaviour of the complex shear modulus G (o)) reflects the distribution of the relaxation time of the growing clusters. At the gel point the broad distribution of... 

The gel/sol transitions cannot be distinguished for pectins extracted by after acid treatment and water-soluble pectins after extrusion. A minimal pectin concentration of 0.2% is required for gelation and no gels can be obtained below a sucrose concentration of 45 %. Commercial pectin (Hercules) with a dm 73 % has a lower phase transition line with a minimal pectin concentration of 0.1 % and sucrose concentration of 40 %. 

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