Phase-transition temperatures

Oxides such as CaO, MgO, and Y2O2 are added to Zr02 to stabili2e the tetragonal phase at temperatures below the tetragonal to monoclinic phase-transition temperature. Without stabili2et, the phase transition occurs spontaneously at temperatures below 850—1000°C, and no fracture toughness enhancement occurs (25). 

Hydrated bilayers containing one or more lipid components are commonly employed as models for biological membranes. These model systems exhibit a multiplicity of structural phases that are not observed in biological membranes. In the state that is analogous to fluid biological membranes, the liquid crystal or La bilayer phase present above the main bilayer phase transition temperature, Ta, the lipid hydrocarbon chains are conforma-tionally disordered and fluid ( melted ), and the lipids diffuse in the plane of the bilayer. At temperatures well below Ta, hydrated bilayers exist in the gel, or Lp, state in which the mostly all-trans chains are collectively tilted and pack in a regular two-dimensional... 

Of the variety of quantum effects which are present at low temperatures we focus here mainly on delocalization effects due to the position-momentum uncertainty principle. Compared to purely classical systems, the quantum delocalization introduces fluctuations in addition to the thermal fluctuations. This may result in a decrease of phase transition temperatures as compared to a purely classical system under otherwise unchanged conditions. The ground state order may decrease as well. From the experimental point of view it is rather difficult to extract the amount of quantumness of the system. The delocahzation can become so pronounced that certain phases are stable in contrast to the case in classical systems. We analyze these effects in Sec. V, in particular the phase transitions in adsorbed N2, H2 and D2 layers. 

The central quantity is the order parameter as a function of temperature (see Fig. 13). The phase transition temperature Tq of the classical system can be located around 38 K. At high temperatures, the quantum curve of the order parameter merges with the classical curve, whereas it starts to deviate below Tq. Qualitatively, quantum fluctuations lower the ordering and thus the quantum order parameter is always smaller than its classical counterpart. The inclusion of quantum effects results in a nearly 10% lowering of Tq (see Fig. 13). 

Figure 18 Molecular weight dependencies of the phase transition temperature (T,) from orthorhombic to hexagonal phase and the melting temperature Tm) of the hexagonal phase of PE. O = phase transition from orthorhombic to hexagonal phase A A = melting of the hexagonal phase. (From Ref. 131.)...

In a fundamental sense, the miscibility, adhesion, interfacial energies, and morphology developed are all thermodynamically interrelated in a complex way to the interaction forces between the polymers. Miscibility of a polymer blend containing two polymers depends on the mutual solubility of the polymeric components. The blend is termed compatible when the solubility parameter of the two components are close to each other and show a single-phase transition temperature. However, most polymer pairs tend to be immiscible due to differences in their viscoelastic properties, surface-tensions, and intermolecular interactions. According to the terminology, the polymer pairs are incompatible and show separate glass transitions. For many purposes, miscibility in polymer blends is neither required nor de-... 

Thermodynamic, statistical This discipline tries to compute macroscopic properties of materials from more basic structures of matter. These properties are not necessarily static properties as in conventional mechanics. The problems in statistical thermodynamics fall into two categories. First it involves the study of the structure of phenomenological frameworks and the interrelations among observable macroscopic quantities. The secondary category involves the calculations of the actual values of phenomenology parameters such as viscosity or phase transition temperatures from more microscopic parameters. With this technique, understanding general relations requires only a model specified by fairly broad and abstract conditions. Realistically detailed models are not needed to un-... 

The phase-transition temperatures for Pu and Pu02 that were used, are given In Table II. 

The development of monoalkyl phosphate as a low skin irritating anionic surfactant is accented in a review with 30 references on monoalkyl phosphate salts, including surface-active properties, cutaneous effects, and applications to paste and liquid-type skin cleansers, and also phosphorylation reactions from the viewpoint of industrial production [26]. Amine salts of acrylate ester polymers, which are physiologically acceptable and useful as surfactants, are prepared by transesterification of alkyl acrylate polymers with 4-morpholinethanol or the alkanolamines and fatty alcohols or alkoxylated alkylphenols, and neutralizing with carboxylic or phosphoric acid. The polymer salt was used as an emulsifying agent for oils and waxes [70]. Preparation of pharmaceutical liposomes with surfactants derived from phosphoric acid is described in [279]. Lipid bilayer vesicles comprise an anionic or zwitterionic surfactant which when dispersed in H20 at a temperature above the phase transition temperature is in a micellar phase and a second lipid which is a single-chain fatty acid, fatty acid ester, or fatty alcohol which is in an emulsion phase, and cholesterol or a derivative. 

Covalently crosslinked siloxane containing liquid crystalline networks with elastic properties were prepared 349). In all of the networks liquid crystalline phases of the linear precursors were retained. For low degrees of crosslinking the phase transition temperatures remained nearly unchanged, whereas higher degrees of crosslinking reduced the phase transition temperatures. 

The compound in Fig. 3b exhibits two smectic phases (Sm and Sm ) in addition to nematic, whereas the compound in Fig. 3a exhibits only a nematic phase. The substitution of an alkoxy for an alkyl tail is known to shift phase transition temperatures considerably. In the cyano-biphenyls (Fig. 4), substitution of an alkoxy tail raises the melting point from 24 to 48 °C and T from 35 to 68 °C [22]. 

The question arises as to how useful atomistic models may be in predicting the phase behaviour of real liquid crystal molecules. There is some evidence that atomistic models may be quite promising in this respect. For instance, in constant pressure simulations of CCH5 [25, 26] stable nematic and isotropic phases are seen at the right temperatures, even though the simulations of up to 700 ps are too short to observe spontaneous formation of the nematic phase from the isotropic liquid. However, at the present time one must conclude that atomistic models can only be expected to provide qualitative data about individual systems rather than quantitative predictions of phase transition temperatures. Such predictions must await simulations on larger systems, where the system size dependency has been eliminated, and where constant... 

The rapid rise in computer speed over recent years has led to atom-based simulations of liquid crystals becoming an important new area of research. Molecular mechanics and Monte Carlo studies of isolated liquid crystal molecules are now routine. However, care must be taken to model properly the influence of a nematic mean field if information about molecular structure in a mesophase is required. The current state-of-the-art consists of studies of (in the order of) 100 molecules in the bulk, in contact with a surface, or in a bilayer in contact with a solvent. Current simulation times can extend to around 10 ns and are sufficient to observe the growth of mesophases from an isotropic liquid. The results from a number of studies look very promising, and a wealth of structural and dynamic data now exists for bulk phases, monolayers and bilayers. Continued development of force fields for liquid crystals will be particularly important in the next few years, and particular emphasis must be placed on the development of all-atom force fields that are able to reproduce liquid phase densities for small molecules. Without these it will be difficult to obtain accurate phase transition temperatures. It will also be necessary to extend atomistic models to several thousand molecules to remove major system size effects which are present in all current work. This will be greatly facilitated by modern parallel simulation methods that allow molecular dynamics simulations to be carried out in parallel on multi-processor systems [115]. 

As computer power continues to increase over the next few years, there can be real hope that atomistic simulations will have major uses in the prediction of phases, phase transition temperatures, and key material properties such as diffusion coefficients, elastic constants, viscosities and the details of surface adsorption. 

Fr kjaer et al., 1984 Grit et al., 1989). An example of the pH dependency on the hydrolysis rate of liposomes consisting of soybean phosphatidylcholine is presented in Fig. 6. Hydrolysis kinetics changed rather abruptly around the phase transition temperature. 

It had been discovered long ago that the character of conduction in Agl changes drastically at temperatures above 147°C, when (I- and I -Agl change into a-Agl. At the phase transition temperature the conductivity, o, increases discontinuously by almost four orders of magnitude (from 10 to 1 S/cm). At temperatures above 147°C, the activation energy is very low and the conductivity increases little with temperature, in contrast to its behavior at lower temperatures (see Fig. 8.2). 

The phase transition temperatures (lower critical solution temperature, LCST) of the pol5miers were obtained from the change in the transmittance of their aqueous solutions (Figure 1). The aqueous solution of the obtained pol5uner was prepared and its transmittance at 500 nm was monitored with increase in the ambient temperature. Both of poly-NIPA and poly-NEA showed a sudden decrease in the transmittance at 37.5 and 69.2 °C, respectively. The result shown in Figure 1 clearly suggests the thermosensitivity of the pol5mers, and the obtained LCST values are close to those reported for poly-NIPA (34.8 °C) [8] and poly-NEA (72 °C) [9]. 

I2H2O as a function of the reciprocal temperature. The points are data obtained from fits of the Mdssbauer spectra (Fig. 6.6). The broken curve is a fit to the Einstein model for a Raman process. The dotted curve corresponds to a contribution from a direct process due to interactions between the electronic spins and low-energy phonons associated with critical fluctuations near the phase transition temperature. (Reprinted with permission from [32] copyright 1979 by the Institute of Physics)... 

Lee, A. G., Effects of charged drugs on the phase transition temperature of phospholipid bilayers, Biochim. Biophys. Acta 514, 95-104 (1978). 

Every ionic crystal can formally be regarded as a mutually interconnected composite of two distinct structures cationic sublattice and anionic sublattice, which may or may not have identical symmetry. Silver iodide exhibits two structures thermodynamically stable below 146°C sphalerite (below 137°C) and wurtzite (137-146°C), with a plane-centred I- sublattice. This changes into a body-centred one at 146°C, and it persists up to the melting point of Agl (555°C). On the other hand, the Ag+ sub-lattice is much less stable it collapses at the phase transition temperature (146°C) into a highly disordered, liquid-like system, in which the Ag+ ions are easily mobile over all the 42 theoretically available interstitial sites in the I-sub-lattice. This system shows an Ag+ conductivity of 1.31 S/cm at 146°C (the regular wurtzite modification of Agl has an ionic conductivity of about 10-3 S/cm at this temperature). 

The phase-transition temperature, 7 , and the width of transition, A7j/2, were operationally defined based on EPR data, as shown in Figure 10.6a. As a rule, in the presence of polar carotenoids the phase transition broadens and shifts to lower temperatures (Subczynski et al. 1993, Wisniewska et al. 2006). The effects on Tm are the strongest for dipolar carotenoids, significantly weaker for monopolar carotenoids, and negligible for nonpolar carotenoids. The effects decrease with the increase of membrane thickness. Additionally, the difference between dipolar and monopolar carotenoids decreases for thicker membranes (Subczynski and Wisniewska 1998, Wisniewska et al. 2006). These effects for lutein, P-cryptoxanthin, and P-carotene are illustrated in Figure 10.6b... 

Recently, due to increased interest in membrane raft domains, extensive attention has been paid to the cholesterol-dependent liquid-ordered phase in the membrane (Subczynski and Kusumi 2003). The pulse EPR spin-labeling DOT method detected two coexisting phases in the DMPC/cholesterol membranes the liquid-ordered and the liquid-disordered domains above the phase-transition temperature (Subczynski et al. 2007b). However, using the same method for DMPC/lutein (zeaxanthin) membranes, only the liquid-ordered-like phase was detected above the phase-transition temperature (Widomska, Wisniewska, and Subczynski, unpublished data). No significant differences were found in the effects of lutein and zeaxanthin on the lateral organization of lipid bilayer membranes. We can conclude that lutein and zeaxanthin—macular xanthophylls that parallel cholesterol in its function as a regulator of both membrane fluidity and hydrophobicity—cannot parallel the ability of cholesterol to induce liquid-ordered-disordered phase separation. 

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