Cloud point, phase separation

Based upon the use of nonionic surfactant systems and their cloud point phase separation behavior, several simple, practical, and efficient extraction methods have been proposed for the separation, concentration, and/or purification of a variety of substances including metal ions, proteins, and organic substances (429-441. 443.444). The use of nonionic micelles in this regard was first described and pioneered by Watanabe and co-workers who applied the approach to the separation and enrichment of metal ions (as metal chelates) (429-435). That is, metal ions in solution were converted to sparingly water soluble metal chelates which were then solubilized by addition of nonionic surfactant micelles subsequent to separation by the cloud point technique. Table XVII summarizes data available in the literature demonstrating the potential of the method for the separation of metal ions. As can be seen, factors of up to forty have been reported for the concentration effect of the separated metals. 

Preparation of Two-Phase Epoxy Thermosets. Two-phase epoxy thermosets were prepared from homogeneous stoichiometric mixtures of DGEBA and diamine (DDM or DDS), which contained varying amounts of liquid rubber (ESR or VR). The rubber was dissolved first in DGEBA at 70 °C. Then the diamine (DDM or DDS) was added and the mixture was stirred at 70 °C until the diamine dissolved (about 15 min). The homogeneous (one-phase) transparent mixture was then degassed before it reached its cloud point (phase separation). The formulations cross-linked with DDS were cured at 150 °C for 2 h, whereas the formulations cross-linked with DDM were cured first at 75 °C for 4 h and then at 150 °C for 2 h. 

When the temperature of an aqueous solution of a polymer is raised above a certain critical temperatnre (which is often referred to as the transition tem-peratnre, lower critical solntion temperatnre (LOST), or cloud point ), phase separation takes place. An aqneous phase that contains practically no polymer and a polymer-enriched phase are formed. Both phases can be easily separated by decanting, centrifugation, or filtration. The temperature of the phase transitions depends on the polymer concentration and molecnlar weight (Fig. 3) (13,14). The phase separation is completely reversible, and the polymer dissolves in water when the temperature is reduced below the transition temperatnre. 

Non-ionic surfactants do not exhibit Krafft points. Rather the solubility of nonionic surfactants decreases with increasing temperature and the surfactants begin to lose their surface active properties above a transition temperature referred to as the cloud point. This occurs because above the cloud point a separate surfactant-rich phase of swollen micelles separates the transition is visible as a marked increase in dispersion turbidity. As a result, the foaming ability of, for example, polyoxyethyle-nated non-ionics, decreases sharply above their cloud points. The addition of electro-... 

Many solutions of common nonionic surfactants and water separate into two phases when heated above a certain temperature (the cloud point), and some investigators call the phase of greater surfactant concentration, a microemulsion. Thus, there is not even universal agreement that a microemulsion must contain oil. 

Miscible blends of high molecular weight polymers often exhibit LOST behavior (3) blends that are miscible only because of relatively low molecular weights may show UCST behavior (11). The cloud-point temperatures associated with Hquid—Hquid phase separation can often be adequately determined by simple visual observations (39) nevertheless, instmmented light transmission or scattering measurements frequendy are used (49). The cloud point observed maybe a sensitive function of the rate of temperature change used, owing to the kinetics of the phase-separation process (39). 

Recent publications indicate the cloud-point extraction by phases of nonionic surfactant as an effective procedure for preconcentrating and separation of metal ions, organic pollutants and biologically active compounds. The effectiveness of the cloud-point extraction is due to its high selectivity and the possibility to obtain high coefficients of absolute preconcentrating while analyzing small volumes of the sample. Besides, the cloud-point extraction with non-ionic surfactants insures the low-cost, simple and accurate analytic procedures. 

For fluorescence PAH determination in tap water acid-induced cloud point extraction was used. This kind of extraction based on the phase separation into two isotropic liquid phases a concentrated phase containing most of the surfactant (surfactant-rich phase), where the solubilised solutes are exttacted, and an aqueous phase containing a surfactant concenttation closes to the critical micellar concentration. 

Aniline and mixed aniline point (DIN 51 775 modified). It is similar to the cloud point test except that the solvent is aniline, a very polar liquid. The aniline point is defined as the temperature at which a mixture of equal parts of aniline and the resin show the beginning of phase separation (i.e. the onset of clouding). Phase separation for aromatic resins occurs between I5°C and below zero for resins with intermediate aromaticity, it lies between 30 and 50°C and for non-aromatic resins, it is 50 to 100°C. Sometimes the mixed aniline point is used. It is similar to the aniline point except that the solvent is a mixture of one part of aniline and one part of w-heptane. The problem of both procedures is that precipitation of resins can be produced before the cloud is generated. 

The critical point (Ij of the two-phase region encountered at reduced temperatures is called an upper critical solution temperature (UCST), and that of the two-phase region found at elevated temperatures is called, perversely, a lower critical solution temperature (LCST). Figure 2 is drawn assuming that the polymer in solution is monodisperse. However, if the polymer in solution is polydisperse, generally similar, but more vaguely defined, regions of phase separation occur. These are known as "cloud-point" curves. The term "cloud point" results from the visual observation of phase separation - a cloudiness in the mixture. 

The measurements were carried out while increasing the temperature in 0.5 °C increments at intervals of 30 min., using an aqueous solution of the polymers in Pyrex tubes(5 ml volume). Each tube contained a short glass rod which was used to stir the solution after being filled with the polymer solution of 0.05 -2.5 wt %, each tube was evacuated and sealed. The warm up to 70 °C was carried out in a water bath. The cloud point was taken as the temperature at which phase separation was first noted it was compared with the temperature at which the solution first became clear again while cooling. 

The adsorption of block and random copolymers of styrene and methyl methacrylate on to silica from their solutions in carbon tetrachloride/n-heptane, and the resulting dispersion stability, has been investigated. Theta-conditions for the homopolymers and analogous critical non-solvent volume fractions for random copolymers were determined by cloud-point titration. The adsorption of block copolymers varied steadily with the non-solvent content, whilst that of the random copolymers became progressively more dependent on solvent quality only as theta-conditions and phase separation were approached. 

Cloud-point measurements were also made with the block polymers even though the theta concept has little meaning in this case. With the block copolymers the cloud-point is less easily seen as the change is to a low turbidity only. Unlike the random copolymers and the homopolymers, where gross phase separation... 

This phenomenon can be exploited for separation and concentration of solutes. If one solute has certain affinity for the micellar entity in solution then, by altering the conditions of the solution to ensure separation of the micellar solution into two phases, it is possible to separate and concentrate the solute in the surfactant-rich phase. This technique is known as cloud point extraction (CPE) or micelle-mediated extraction (ME). The ratio of the concentrations of the solute in the surfactant-rich phase to that in the dilute phase can exceed 500 with phase volume ratios exceeding 20, which indicates the high efficiency of this technique. Moreover, the surfactant-rich phase is compatible with the micellar and aqueous-organic mobile phases in liquid chromatography and thus facilitates the determination of chemical species by different analytical methods [104]. 

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