Lower critical solution temperature thermodynamics

It is widely known that poly(N-isopropylacrylamide), poly(IPAAm), in water has a lower critical solution temperature (LCST) at 32 °C. LCST was originally observed in PEG solutions a long time ago. Rowlinson et al. [40] (1957) explained the lower consolute temperature for PEG in water in terms of negative entropies. The first paper on the LCST of poly(IPAAm) at about 31 °C was presented by Heskins and Guillet in 1968 [41]. They reported that aqueous solution of poly(IPAAm) showed phase separation above this temperature, and ascribed it primarily to an entropy effect on the basis of thermodynamical considerations. 

The volume change in these gels is not due to ionic effects, but rather to a thermodynamic phenomenon a lower critical solution temperature (LCST). The uncrosslinked polymer which makes up the gel is completely miscible with water below the LCST above the LCST, water-rich and polymer-rich phases are formed. Similarly, the gel swells to the limit of its crosslinks below the LCST, and collapses above the LCST to form a dense polymer-rich phase. Hence, the kinetics of swelling and collapse are determined mostly by the rate of water diffusion in the gel, but also by the heat transfer rate to the gel. 

Phase dissolution in polymer blends. The reverse process of phase separation is phase dissolution. Without loss of general validity, one may assume again that blends display LCST behavior. The primary objective is to study the kinetics of isothermal phase dissolution of phase-separated structures after a rapid temperature-jump from the two-phase region into the one-phase region below the lower critical solution temperature. Hence, phase-separated structures are dissolved by a continuous descent of the thermodynamic driving force responsible for the phase separation. The theory of phase separation may also be used to discuss the dynamics of phase dissolution. However, unlike the case of phase separation, the linearized theory now describes the late stage of phase dissolution where concentration gradients are sufficiently small. In the context of the Cahn theory, it follows for the decay rate R(q) of Eq. (29) [74]... 

Miscible blends of poly(vinyl methyl ether) and polystyrene exhibit phase separation at temperatures above 100 C as a result of a lower critical solution temperature and have a well defined phase diagram ( ). This system has become a model blend for studying thermodynamics of mixing, and phase separation kinetics and resultant morphologies obtained by nucleation and growth and spinodal decomposition mechanisms. As a result of its accessible lower critical solution temperature, the PVME/PS system was selected to examine the effects of phase separation and morphology on the damping behavior of the blends and IPNs. 

There is, however, a mass transfer problem of demixing at lower temperatures caused by high viscosities. Concentrated polymer solutions tend to take hours to form two distinct liquid phases. A solution to this problem is the use of the lower critical solution temperature. Because of their thermodynamic nature, all polymer-solvent mixtures tend to form two liquid phases ( LL ) with low viscosities, at higher temperatures (LCST) as depicted in Figure 3. 

The most basic question when considering a polymer blend concerns the thermodynamic miscibility. Many polymer pairs are now known to be miscible or partially miscible, and many have become commercially Important. Considerable attention has been focussed on the origins of miscibility and binary polymer/polymer phase diagrams. In the latter case, it has usually been observed that high molar mass polymer pairs showing partial miscibility usually exhibit phase diagrams with lower critical solution temperatures (LCST). 

Polymer blends typically show a decrease in miscibility with increasing temperature. [27] McMaster has used a modified Flory equation of state thermodynamic model to show that the existence of a lower critical solution temperature (LCST) is caused mainly by differences in the pure component thermal expansion coefficients. 

It is now established both theoretically and experimentally that many thermodynamic variables assume a simple power-law behaviour at or near critical points in both pure and mixed fluids. The actual functional dependence of one variable on another can be characterized by the so-called critical indices a, 5, etc. The critical index j8, for example, defines both the shape of the gas-liquid coexistence curve for a pure fluid and the liquid-liquid coexistence curve of a binary mixture in the vicinity of either an upper or a lower critical solution temperature. The correspondence between critical phenomena in one-, two-,... 

Sophiea et al. published the first classical composition-temperature phase diagram, working with the semi-IPN Mct-polyurethane-jMtcr-poly(vinyl chloride) (Sophiea et al. 1994). They found a lower critical solution temperature, LCST S 120 °C below this temperature the system was one phased and above two phased. Such behavior is now known to be characteristic of most polymer blends (see Chap. 2, Thermodynamics of Polymer Blends ). 

Cite the following fact to illustrate the difficulties in the phase analysis of polymer systems. For the poly(vinyl alcohol)- -water system, some researchers propose a state diagram of amorphous phase separation with an upper critical solution temperature, others — ainor]>hons separation with a lower critical solution temperature about 100 C there are some who think that there is no region of amorphous separation below 150 -instead, they observe liquid-crystal phase separation. Such are the discrepancies on the basic question of thermodynamics ... 

Phase equilibria are strongly affected by temperature raising the temperature of a solution may increase the miscibility of the two components or, less frequently, may result in a decrease of their miscibility. In the first case, as depicted in the phase diagram in Figure 18, the two components are totally miscible above a point known as the upper critical solution temperature (UCST). At any temperature below the UCST, compositions lying outside the curve constitute homogeneous phases, while compositions inside the curve are thermodynamically unstable and will phase-separate. When the miscibility of a polymer in a solvent decreases as the temperature increases, the mixture possesses a lower critical solution temperature (LCST Fig. 18). For temperatures below this point, the two components are totally miscible. 

The thermodynamic properties of concentrated polymer solutions were studied by Floryi and independently by Huggins. The Flory-Huggins theory of polymer solutions still forms the basis for much discussion of these solutions in industry and even in academic research. Understanding this model is important for making coimections to much of the literature. Flory also substantially improved this model to include compressible fluids. The Flory-OrwoU theory of polymer solutions is still transparent and easily applicable, predicting both upper and lower critical solution temperatures. More-empirically adequate theories of concentrated solutions do not lend themselves to simple lecture presentation and often require detailed computer calculations to obtain any results. Concentrated solutions also introduce the phenomenon of viscoelasticity. An extensive treatment of the full distribution of relaxation times necessary to imderstand the dynamic properties of polymers in concentrated solution is presented. 

Miscibility in polymer blends has been studied by both theoreticians and experimentalists. The number of polymer blend systems that have been found to be thermodynamically miscible has increased in the past 20 years. Systems have also been found to exhibit the upper or lower critical solution temperatures. So complete miscibility is found only in limited temperature and composition ranges. A large number of polymer pairs form two-phase blends. This is consistent with the small entropy of mixing that can be expected of high polymers. These blends are characterized by opacity, distinct glass transition temperatures, and deteriorated mechanical properties. Some two-phase blends have been made into composites with improved mechanical properties. Often, incompatibility is the general rule, and miscibility or even partial miscibility is the exception. 

This is a simple model and cannot account for all the issues of mixture thermodynamics. Interaction parameters deduced from various phase behavior information are often believed to include other effects than purely enthalpic ones. This way, the LCST (lower critical solution temperature) behavior observed in polymer blends can be explained and accounted for quantitatively. These theories refine the binary interaction parameter by removing extraneous effects. EOS effects do not favor phase... 

When polymers undergo phase separation in thin films, the kinetic and thermodynamic effects are expected to be pronounced. The phase separation process can be controlled to effect desired morphologies. Under suitable conditions a film deposition process can lead to pattern replication. Demixing of polymer blends can lead to structure formation. The phase separation process can be characterized by the binodal and spinodal curves. UCST is the upper critical solution temperature, which is the temperature above which the blend constituents are completely miscible in each other in all proportions. LUST behavior is not found as often in systems other than among polymers. LUST is the lower critical solution temperature. This is the... 

The importance of water soluble polymers such as the polyacrylamides is well established but only now are fundamental data on these systems beginning to accumulate. The unperturbed dimensions of these polymers tend to depend on the lateral substituent, and specific interactions are thought to produce large chain expansions with a corresponding low chain flexibility. In some cases the specific interactions can lead to a system exhibiting a pseudo-lower critical-solution temperature. The characteristic parameter C for polyacrylamide in water has also been reassessed in the belirf that the published value is too high. The excluded volume parameter and unperturbed dimensions have also been measured for poly ( -1,1-dimethyl-3-oxobutylacrylamide) in MEK. Many of the papers mentioned in Table 1 contain additional data on the sedimentation behaviour and thermodynamic parameters. 

Krammer Hans Werner, Inoue Takashi, and Ougizawa Toshiaki. Upper and lower critical solution temperature behavior in polymer blends and its thermodynamic interpretation. Polymer. 30 no. 5 (1989) 888-892. 

Madbouly Wolf, 2002, Equilibrium phase behavior of polyethylene oxide and of its mixtures with tetrahydronaphthalene or/and p ly (ethylene oxide-block-dimethylsiloxane), /, Chem. Phys., Vol. 117, No. 15, PP. 7357-7363 Maderek et al. 1983, High-temperature demixing of poly(decyl methacrylate) solutions in isooctane and its pressure-dependence, Makromol. Chem., Vol. 184, No. 6, PP. 1303-1309 Lower critical solution temperatures of poly(decyl methacrylate) in hydrocarbons, Eur. Polym.., Vol. 19, No. 10, PP. 963-965 Patterson Robard, 1978, Thermodynamics of polymer compatibility. Macromolecules, Vol. 11, No. 4, 690-695... 

Stimuli responsiveness includes conformational and thermodynamic phase transitions (e.g., lower critical solution temperature [LCST]), aggregation, abihty to encapsulate and release other agents (e.g., drugs), abihty to interact with surfactants, other polymers, etc. StimuU producing these responses include tanperature, light, pH, ionic strength, specific small molecules, surfactants, solvent type and mixtures, etc [104-109]. 

Chand, A. McQuillan, A. R. Fenby, D. V. Thermodynamic study of systems with lower critical solution temperatures H20 + (C2H5)3N, D20 + (C2H5)3N Fluid Phase Equilib. 1979, 2, 263-274... 

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