Polymorphous melting

A white to creamy-white crystalline powder. M.p. 124° to 130° a polymorph melting at 119° to 123° may also occur. 

The samples cooled at l°C/min and 5°C/min (Figure 7a) both have minor inflections in the curve at this same temperature (17.5°C), but they also have a major peak endotherm at around 15°C. This may correspond to an a-polymorphic melt. It is thus suggested that cooling at l°C/min results in a mixmre of a and p polymorphs, and cooling at 5°C/min results predominantly in the a polymorph. These predictions correspond to the findings of previous studies on AMF employing similar crystallization conditions using DSC and powder X-ray diffraction (34). 

These authors observed that binaphthyl crystallize in two polymorphs. The one is stable at lower temperature, is centrosymmetric and is not optically active. This polymorph melts at 145 °C. The second polymorph is stable at higher temperature but is metastable at room temperature. It is optically active and melts at 158 °C. Wilson and Pincock show that as one cycles in temperature between room temperature and 150 °C a sample which is initially the optically inactive low temperature polymoiph transforms to an optically active solid. After three or four cycles one achieves the maximum optical resolution which corresponds to 56% ee. The crux of the Wilson and Pincock experiment is that at 150 °C, the reaction physically resembles a solid state reaction in which the low temperature form is melting in the near presence of high temperature polymorph crystals. These chiral crystals are therefore nucleating sites for further chiral crystal growth. As at room temperature binaphthyl retains its chirality, the resultant samples can then be dissolved with retention of stereochemistry. 

Temperature where nematic droplets appear due to cyclotrimerization reaction on POM when heating at 10°C/min. Polymorphic melting point behavior due to mixture of isomers. 

Polymorph Melting pointfC Transition pointfC Habit... 

The density of the a-polymorph is 1.98 g cm amorphous PVDF has a density of 1.68 g cm . Thus, commercial samples with a density of 1.75-1.78 g cm have 45% crystaUinity. The a-polymorph melts at 170 °C however, the processed polymer, because of its polymorphism, displays no sharp melting point but melts between 150 and 190 °C. The thermal decomposition becomes significant at T > 300°C. Pyrolysis of PVDF yields hydrogen fluoride, the monomer C2H2F2 and C4F3H3 [12]. Up to 600 °C, pyrolysis also yields polyaromatic structures by cyclization of polyenic intermediates formed through HF ehmination [16]. This is a particular advantage over PTFE, which is less likely to yield carbonaceous products. Thus in obscurant applications, PVDF is preferred over PTFE as a fluorine source (see Chapter 11). 

It is a white, deliquescent solid, very powdery, which exhibits polymorphism on heating, several different crystalline forms appear over definite ranges of temperature -ultimately, the P4O10 unit in the crystal disappears and a polymerised glass is obtained, which melts to a clear liquid. 

Unlike other synthetic polymers, PVDF has a wealth of polymorphs at least four chain conformations are known and a fifth has been suggested (119). The four known distinct forms or phases are alpha (II), beta (I), gamma (III), and delta (IV). The most common a-phase is the trans-gauche (tgtg ) chain conformation placing hydrogen and fluorine atoms alternately on each side of the chain (120,121). It forms during polymerization and crystallizes from the melt at all temperatures (122,123). The other forms have also been well characterized (124—128). The density of the a polymorph crystals is 1.92 g/cm and that of the P polymorph crystals 1.97 g/cm (129) the density of amorphous PVDF is 1.68 g/cm (130). 

Polymorphism. Many crystalline polyolefins, particularly polymers of a-olefins with linear alkyl groups, can exist in several polymorphic modifications. The type of polymorph depends on crystallisa tion conditions. Isotactic PB can exist in five crystal forms form I (twinned hexagonal), form II (tetragonal), form III (orthorhombic), form P (untwinned hexagonal), and form IP (37—39). The crystal stmctures and thermal parameters of the first three forms are given in Table 3. Form II is formed when a PB resin crystallises from the melt. Over time, it is spontaneously transformed into the thermodynamically stable form I at room temperature, the transition takes about one week to complete. Forms P, IP, and III of PB are rare they can be formed when the polymer crystallises from solution at low temperature or under pressure (38). Syndiotactic PB exists in two crystalline forms, I and II (35). Form I comes into shape during crystallisation from the melt (very slow process) and form II is produced by stretching form-1 crystalline specimens (35). 

Crystalline Silica. Sihca exists in a variety of polymorphic crystalline forms (23,41—43), in amorphous modifications, and as a Hquid. The Hterature on crystalline modifications is to some degree controversial. According to the conventional view of the polymorphism of siHca, there are three main forms at atmospheric pressure quart2, stable below about 870°C tridymite, stable from about 870—1470°C and cristobaHte, stable from about 1470°C to the melting point at about 1723°C. In all of these forms, the stmctures are based on SiO tetrahedra linked in such a way that every oxygen atom is shared between two siHcon atoms. The stmctures, however, are quite different in detail. In addition, there are other forms of siHca that are not stable at atmospheric pressure, including that of stishovite, in which the coordination number of siHcon is six rather than four. 

Anatase and mtile are produced commercially, whereas brookite has been produced by heating amorphous titanium dioxide, which is prepared from an alkyl titanate or sodium titanate [12034-34-3] with sodium or potassium hydroxide in. an autoclave at 200—600°C for several days. Only mtile has been synthesized from melts in the form of large single crystals. More recentiy (57), a new polymorph of titanium dioxide, Ti02(B), has been demonstrated, which is formed by hydrolysis of K Ti O to form 20, followed by subsequent calcination/dehydration at 500°C. The relatively open stmcture... 

Riboflavin forms fine yellow to orange-yeUow needles with a bitter taste from 2 N acetic acid, alcohol, water, or pyridine. It melts with decomposition at 278—279°C (darkens at ca 240°C). The solubihty of riboflavin in water is 10—13 mg/100 mL at 25—27.5°C, and in absolute ethanol 4.5 mg/100 mL at 27.5°C it is slightly soluble in amyl alcohol, cyclohexanol, benzyl alcohol, amyl acetate, and phenol, but insoluble in ether, chloroform, acetone, and benzene. It is very soluble in dilute alkah, but these solutions are unstable. Various polymorphic crystalline forms of riboflavin exhibit variations in physical properties. In aqueous nicotinamide solution at pH 5, solubihty increases from 0.1 to 2.5% as the nicotinamide concentration increases from 5 to 50% (9). 

Bismuth Trioxide. Bismuth(Ill) oxide [1304-76-3] has a compHcated polymorphism. At times some of the reported phases deviate from Bi202 by baying too Htfle or too much oxygen at least in one instance, because of the ready contamination of Bi202 melts with siHcon, the reported phase... 

Alkenoic acids also have polymorphic crystalline forms. For example, both oleic and elaidic acids are dimorphic with melting points of 13.6 and 16.3°C for oleic, and 43.7 and 44.8°C for elaidic acid (14). 

For (Z)-cinnamic acid [102-94-3], three distinct polymorphic forms have been characteri2ed. The most stable form, referred to as aHocinnamic acid, has a melting point of 68°C, and the two metastable forms, isocinnamic acids, have melting points of 58°C and 42°C, respectively. (E)-Cinnamic acid can be converted to the (Z)-isomer photochemicaHy through kradiation of a solution with ultraviolet light. 

Attachment of a hot or cold stage to the ordinary microscope stage allows the specimen to be observed while the temperature is changed slowly, rapidly, or held constant somewhere other than ambient. This technique is used to determine melting and freezing points, but is especially useful for the study of polymorphs, the determination of eutectics, and the preparation of phase diagrams. 

Of course, freezing of a liquid - or its inverse - are themselves phase transformations, but the scientific study of freezing and melting was not developed until well into the 20th century (Section 9.1.1). Polymorphism also links with metastability thus aragonite, one polymorphic form of calcium carbonate, is under most circumstances metastable to the more familiar form, calcite. 

The mixture of diastereomers has been separated into its two principal components by Izatt, Haymore, Bradshaw and Christensen who had previously identified the two principal diastereomers as the cis-syn-cis and cis-anti-cis isomers. Their previous separation technique involved a protracted chromatography on alumina but the new method relied upon the difference in water solubility between the lead perchlorate and hydroniur perchlorate complexes. The lead perchlorate complex is essentially insoluble in aqueous solution and precipitates from it. Using this method, one may obtain 39% of the high-melting polymorph (mp 83—84°) and 44% of the low-melting compound (mp 62—63°). Note that the former also exists in a second crystalline form, mp 69—70°. 

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