Critical solution temperature, interfacial

In these examples, as one would expect, the interfacial tensions are small and diminish as the critical solution temperature is approached. The differences between the surface tensions of the two phases are generally too small to decide whether the interfacial tension approaches zero asymptotically in all cases although such appears to be the case in the phenol water system we notice however that the temperature coefficient is very small indeed, as is the case for surface tensions of liquids near their critical point, but to a still greater degree. 

In a blend of immiscible homopolymers, macrophase separation is favoured on decreasing the temperature in a blend with an upper critical solution temperature (UCST) or on increasing the temperature in a blend with a lower critical solution temperature (LCST). Addition of a block copolymer leads to competition between this macrophase separation and microphase separation of the copolymer. From a practical viewpoint, addition of a block copolymer can be used to suppress phase separation or to compatibilize the homopolymers. Indeed, this is one of the main applications of block copolymers. The compatibilization results from the reduction of interfacial tension that accompanies the segregation of block copolymers to the interface. From a more fundamental viewpoint, the competing effects of macrophase and microphase separation lead to a rich critical phenomenology. In addition to the ordinary critical points of macrophase separation, tricritical points exist where critical lines for the ternary system meet. A Lifshitz point is defined along the line of critical transitions, at the crossover between regimes of macrophase separation and microphase separation. This critical behaviour is discussed in more depth in Chapter 6. 

As binary PPE/SAN blends form the reference systems and the starting point for the foaming analysis, their miscibility will be considered first. As demonstrated in the literature [41, 42], both miscibility and phase adhesion of PPE/SAN blends are critically dependent on the composition of SAN, more precisely on the ratio between styrene and acrylonitrile (AN). Miscibility at all temperatures occurs up to 9.8 wt% of AN in SAN, whereas higher contents above 12.4 wt% lead to phase separation, independent of the temperature. Intermediate compositions exhibit a lower critical solution temperature behavior (LCST). Taking into account the technically relevant AN content SAN copolymers between 19 and 35 wt%, blends of SAN and PPE are not miscible. As the AN content of the SAN copolymer, selected in this work, is 19 wt%, the observed PPE/SAN blends show a distinct two-phase structure and an interfacial width of only 5 nm [42],... 

The interfacial tension between water and mercury is 426-427 dynes/cm. in absence of oxygen, but if measured in presence of air it varies between 375 and 427. The effect of pressure on interfacial tension varies with the pressure and may be positive (increasing a) or negative withp in lb./in.2 the values of (100/or)(do /d ) at about 5000 atm. are Hg/H2O+0 74, Hg/ether+1-23, water/ether—20-73, chloroform/water—0-73, carbon disulphide/water+2 37. The interfacial tension between two liquids vanishes at the critical solution temperature.4... 

The separate phases will be rich in one component but may have the other present as a minor component. In order to control compatibility the elastomer may have reactive end groups to enhance interfacial adhesion. A common example in epoxy-resin technology is the carboxy-terminated butadiene-acrylonitrile copolymer (CTBN). The structure is shown in Scheme 1.47. In this resin the solubility in the epoxy resin is conferred by the acrylonitrile group, and an increase in the fraction present decreases the upper critical solution temperature, with 26% acrylonitrile conferring total miscibility of CTBN with a DGEBA-based epoxy resin (Pascault et al, 2002). 

INTERFACIAL TENSION OF DEMIXED POLYMER SOLUTIONS NEAR CRITICAL SOLUTION TEMPERATURE... 

A particular polymer blend was found to have negative values for - dyJdT) for its interfacial tension. Does this blend exhibit an upper or lower critical solution temperature What is your reasoning ... 

SI-IMP has been used for synthesis of different types of stimuli-responsive polymer brushes that are responsive to several external stimuli, such as pFI, temperature, and ionic strength [28,58-65]. Because materials interact with their surroundings via their interfaces, the ability to fashion soft interfacial layers and tune the range, extent, and type of physicochemical interactions across interfaces is central to a variety of applications. Rahane et al. carried out sequential SI-IMP of two monomers to create bilevel poly(methacrylic acid)-Woc/c-poly(N-isopropylacrylamide) (PMAA-b-PNIPAM) block copolymer brushes that can respond to multiple stimuli [28]. They observed that each strata in the bilevel PMAA-b-PNIPAM brush retained its customary responsive characteristics PMAA being a "weak" polyelectrolyte swells as pH is increased and the thermoresponsive PNIPAM block collapses as temperature is raised through the volume phase transition temperature due to its lower critical solution temperature (LCST) behavior. As a result of ions added to make buffer solutions of various pH and because of the effect of surface confinement, the swollen-collapse transition of the PNIPAM layer occurs at a... 

In general, and for polymers that exhibit a miscibility gap at lower temperatures (blends that show upper critical solution temperature, UCST, behavior), interfacial tension is found to decrease linearly with increasing temperature, with temperature coefficients of the order of 10 dyn/(cm C) [10]. This is about one half of the values observed for the temperature coefficients of polymer surface tension [10,120,176]. 

For polymer blends exhibiting lower critical solution temperature (LCST) behavior, e.g., the system polystyrene/poly(vinyl methyl ether), one may anticipate the opposite behavior for purely phenomenological reasons. Interfacial tension should increase with increasing temperature in the two-phase region since the tie lines become longer with increasing temperature in that case... 

Because of thermodynamic criteria, the majority of existing homopolymers form immiscible mixtures constituted of two or more phases. Some couples form complex mixtures exhibiting partial and conditional miscibility. They display lower critical solution temperature (LCST) or upper critical solution temperature (UCST). Indeed, depending on temperature and composition (i.e., position in the phase diagram), the blend can be miscible or immiscible. In monophase blends, the final macroscopic properties are most often intermediate between those of the corresponding parent homopolymers. In contrast, additive properties of immiscible blends can only be obtained if a good level of interfacial adhesion, and appropriate particle size, shape, and distribution of the dispersed phase are reached via adequate compatibilization routes. 

For polymer pairs that have an upper eonsolute curve and an UCST (upper eritieal solution temperature), the interfaeial tension decreases with inereasing temperature and vanishes at the upper eonsolute temperature. This is the case for most pairs of immiscible polymers. On the other hand, for polymers that have a lower eonsolute curve and an LCST (lower critical solution temperature), the interfacial tension vanishes at the lower eonsolute point and increases with increasing temperature in the immiscible region. A few polymer pairs appear to behave this way (24). 

FORMATION. Aqueous solutions of highly surface-active substances spontaneously tend to reduce interfacial energy of solute-solvent interactions by forming micelles. The critical micelle concentration (or, c.m.c.) is the threshold surfactant concentration, above which micelle formation (also known as micellization) is highly favorable. For sodium dodecyl sulfate, the c.m.c. is 5.6 mM at 0.01 M NaCl or about 3.1 mM at 0.03 M NaCl. The lower c.m.c. observed at higher salt concentration results from a reduction in repulsive forces among the ionic head groups on the surface of micelles made up of ionic surfactants. As would be expected for any entropy-driven process, micelle formation is less favorable as the temperature is lowered. 

The temperature (or salinity) at which optimal temperature (or optimal salinity), because at that temperature (or salinity) the oil—water interfacial tension is a minimum, which is optimum for oil recovery. For historical reasons, the optimal temperature is also known as the HLB (hydrophilic—lipophilic balance) temperature (42,43) or phase inversion temperature (PIT) (44). For most systems, all three tensions are very low for Tlc < T < Tuc, and the tensions of the middle-phase microemulsion with the other two phases can be in the range 10 5—10 7 N/m. These values are about three orders of magnitude smaller than the interfacial tensions produced by nonmicroemulsion surfactant solutions near the critical micelle concentration. Indeed, it is this huge reduction of interfacial tension which makes micellar-polymer EOR and its SEAR counterpart physically possible. 

With adiabatic combustion, departure from a complete control of m by the gas-phase reaction can occur only if the derivation of equation (5-75) becomes invalid. There are two ways in which this can happen essentially, the value of m calculated on the basis of gas-phase control may become either too low or too high to be consistent with all aspects of the problem. If the gas-phase reaction is the only rate process—for example, if the condensed phase is inert and maintains interfacial equilibrium—then m may become arbitrarily small without encountering an inconsistency. However, if a finite-rate process occurs at the interface or in the condensed phase, then a difficulty arises if the value of m calculated with gas-phase control is decreased below a critical value. To see this, consider equation (6) or equation (29). As the value of m obtained from the gas-phase analysis decreases (for example, as a consequence of a decreased reaction rate in the gas), the interface temperature 7], calculated from equation (6) or equation (29), also decreases. According to equation (37), this decreases t. Eventually, at a sufficiently low value of m, the calculated value of T- corresponds to Tj- = 0, As this condition is approached, the gas-phase solution approaches one in which dT/dx = 0 at x = 0, and the reaction zone moves to an infinite distance from the interface. The interface thus becomes adiabatic, and the gas-phase processes are separated from the interface and condensed-phase processes. 

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