Fusion Crystallization

Another concern with freeze-drying LEH is the instability of liposome structure upon lyophilization. Vesicle formation occurs in the presence of bulk water and when water is removed, loss of structural integrity is inevitable. Fusion, crystal formation, and phase transition are observed, resulting... 

Vemeuil (flame fusion) Crystal growth from the melt mby, sapphires, and stars spinel rutile strontium titanate... 

The latent heat of fusion (crystallization) or the enthalpy difference... 

Table 17.1 Temperatures and Enthalpies of Fusion/Crystallization of PE Phase of MIX, COP, COP 120, and Their Fractions .

The degree of crystallinity can be determined by number of techniques. These techniques involve the measurement of density, volume in dilatometer, ratio of the intensity of absorption bands corresponding to crystalline and amorphous fractions in infrared (IR) spectroscopy, heat of fusion/ crystallization in differential scanning calorimetry (DSC), and area under the diffraction peaks in wide-angle x-ray diffraction (WAXD). The response parameters used to monitor the process of crystallization in these techniques are different and require the data on the properties of the 100% crystalline polymer. These methods are useful for quantitative evaluation of the degree of crystallinity. 

Education of crystal growth engineers will help in establishing this optimum technology and will reduce the multiyear training required to become a flame-fusion crystal grower. 

Fig. 13. B-Co-Fe. Melting point and heat of fusion/crystallization of Fegs-xCOxBiv alloy...

The properties of the solids most commonly encountered are tabulated. An important problem arises for petroleum fractions because data for the freezing point and enthalpy of fusion are very scarce. The MEK (methyl ethyl ketone) process utilizes the solvent s property that increases the partial fugacity of the paraffins in the liquid phase and thus favors their crystallization. The calculations for crystallization are sensitive and it is usually necessary to revert to experimental measurement. 

Sulphur. THE LASSAIGNE SODIUM TEST. The sodium fusion will have converted any sulphur present in the original compounds to sodium sulphide. Dissolve a few crystals of sodium nitroprusside, Na8[Fe(CN)5NO],zH20, in water, and add the solution to the third portion of the filtrate obtained from the sodium fusion. A brilliant purple coloration (resembling permanganate) indicates sulphur the coloration slowly fades on standing. Note, (i) Sodium nitroprusside is unstable in aqueous solution and therefore the solution should be freshly prepared on each occasion, (ii) This is a very delicate test for sulphides, and it is essential therefore that all apparatus, particularly test-tubes, should be quite clean. 

Nitrogen. Pour 2-3 ml. of the filtered fusion solution into a test-tube containing 0 -1-0-2 g. of powdered ferrous sulphate crystals. Heat... 

The normal boiling point of 2-methylthiazole is 17 0= 128.488 0.005°C. The purity of various thiazoles was determined cryometrically by Handley et al. (292), who measured the precise melting point of thiazole and its monomethyl derivatives. Meyer et al. (293, 294) extended this study and, from the experimental diagrams of crystallization (temperature/degree of crystallization), obtained the true temperatures of crystallization and molar enthalpies of fusion of ideally pure thiazoles (Table 1-43). 

We begin our application of thermodynamics to polymer phase transitions by considering the fusion (subscript f) process crystal -> liquid. 

Figure 4.3b is a schematic representation of the behavior of S and V in the vicinity of T . Although both the crystal and liquid phases have the same value of G at T , this is not the case for S and V (or for the enthalpy H). Since these latter variables can be written as first derivatives of G and show discontinuities at the transition point, the fusion process is called a first-order transition. Vaporization and other familiar phase transitions are also first-order transitions. The behavior of V at Tg in Fig. 4.1 shows that the glass transition is not a first-order transition. One of the objectives of this chapter is to gain a better understanding of what else it might be. We shall return to this in Sec. 4.8. 

As the bulkiness of the substituents increases, the chains are prevented from coming into intimate contact in the crystal. The intermolecular forces which hold these crystals together are all London forces, and these become weaker as the crystals loosen up owing to substituent bulkiness. Accordingly, the value for the heat of fusion decreases moving down Table 4.2. 

This relationship is sketched in Fig. 4.7a, which emphasizes that P, must vary linearly with 6 and that P, ° must be available, at least by extrapolation. The heat of fusion is an example of a property of the crystalline phase that can be used this way. It could be difficult to show that the value of AH is constant per unit mass at all percentages of crystallinity and to obtain a value for AHj° for a crystal free from defects. Therefore, while conceptually simple, the actual utilization of Eq. (4.37) in precise work may not be easy. 

The crystallization of poly(ethylene terephthalate) at different temperatures after prior fusion at 294 C has been observed to follow the Avrami equation with the following parameters applying at the indicated temperatures ... 

Several recent patents describe improvements in the basic belt process. In one case a higher soHds polymerization is achieved by cooling the starting monomer until some monomer crystallizes and then introducing the resulting monomer slurry onto the belt as above. The latent heat of fusion of the monomer crystals absorbs some of the heat of polymerization, which otherwise limits the soHds content of the polymerization (87). In another patent a concave belt is described which becomes flat near the end. This change leads to improved release of polymer (88). 

Barium fluoride [7782-32-8] Bap2, is a white crystal or powder. Under the microscope crystals may be clear and colorless. Reported melting points vary from 1290 (1) to 1355°C (2), including values of 1301 (3) and 1353°C (4). Differences may result from impurities, reaction with containers, or inaccurate temperature measurements. The heat of fusion is 28 kj/mol (6.8 kcal/mol) (5), the boiling point 2260°C (6), and the density 4.9 g/cm. The solubiUty in water is about 1.6 g/L at 25°C and 5.6 g/100 g (7) in anhydrous hydrogen fluoride. Several preparations for barium fluoride have been reported (8—10). 

The crystallized iodine is decanted and transferred into a fusion kettie. The melted product is contacted with strong sulfuric acid to remove organic impurities and humidity. Finally the iodine is flaked or prilled and packed. 

Lead borate moaohydrate [14720-53-7] (lead metaborate), Pb(B02)2 H20, mol wt 310.82, d = 5.6g/cm (anhydrous) is a white crystalline powder. The metaborate loses water of crystallization at 160°C and melts at 500°C. It is iasoluble ia water and alkaHes, but readily soluble ia nitric and hot acetic acid. Lead metaborate may be produced by a fusion of boric acid with lead carbonate or litharge. It also may be formed as a precipitate when a concentrated solution of lead nitrate is mixed with an excess of borax. The oxides of lead and boron are miscible and form clear lead-borate glasses in the range of 21 to 73 mol % PbO. 

Naphthalenol. 2-Naphthol or p-naphthol or 2-hydroxynaphthalene/7i3 -/5 -i7 melts at 122°C and boils at 295°C, and forms colorless crystals of characteristic, phenoHc odor which darken on exposure to air or light. 2-Naphthol [135-19-3] is manufactured by fusion of sodium 2-naphthalenesulfonate with sodium hydroxide at ca 325°C, acidification of the drowned fusion mass which is quenched ia water, isolation and water-washing of the 2-naphthalenol, and vacuum distillation and flaking of the product. A continuous process of this type has been patented (69). The high sulfate content ia the primary effluent from 2-naphthol production is greatiy reduced ia modem production plants by the recovery of sodium sulfate. 

Naphthalenediol. This diol is prepared by the alkah fusion of 2-hydroxynaphthalene-6-sulfonic acid (Schaffer acid) at 290—295°C. Schaffer acid is usually produced by sulfonation of 2-naphthol with the addition of sodium sulfate at 85—105°C. This acid is also used as a coupling component in the production of a2o dyes such as Acid Black 26. 2,6-Naphthalenediol is used as a component in the manufacture of aromatic polyesters which, as is also tme of the corresponding amides, display Hquid crystal characteristics (52). 

The potassium salts are the most soluble and other salts usually are precipitated by addition of the appropriate metal chloride to a solution of the corresponding potassium salt. The metaniobates, MNbO, and orthoniobates, MNbO, generally are prepared by fusion of the anhydrous mixed oxides. The metaniobates crystallize with the perovskite stmeture and are ferroelectric (131) (see Ferroelectrics). The orthoniobates are narrow band-gap semiconductors (qv) (132). 

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