DSC, phase transitions

Nakazawa et al. (1984) argued that when starch-water mixtures (30-50% starch) are held at a certain temperature (55-80 °C), for a certain period (0-45 h), and depending on the time-temperature combination, starch granules increase their amorphous portion and decrease their crystalline portion. These amorphous and crystalline phases melted sequentially during DSC phase transition experiments. Their experiments... 

Thermogravimetry (TG - loss of sample mass over a range of 30-550 C) and DSC (phase transition curves recorded over a range of 30-250 C) were used to... 

Differential scanning calorimetry (DSC), DMA and TG were used by Tabaddor and co-workersl l to investigate the cure kinetics and the development of mechanical properties of a commercial thermoplastic/ thermoset adhesive, which is part of a reinforced tape system for industrial applications. From the results, the authors concluded that thermal studies indicate that the adhesive was composed of a thermoplastic elastomeric copolymer of acrylonitrile and butadiene phase and a phenolic thermosetting resin phase. From the DSC phase transition studies, they were able to determine the composition of the blend. The kinetics of conversion of the thermosetting can be monitored by TG. Dynamic mechanical analysis measurements and time-temperature superposition can be utilized to... 

This method is used to locate phase transitions via measurements of the endothennic enthalpy of phase transition. Details of the teclmique are provided elsewhere [25, 58]. Typically, the enthalpy change associated with transitions between liquid crystal phases or from a liquid crystal phase to the isotropic phase is much smaller than the melting enthalpy. Nevertheless, it is possible to locate such transitions with a commercial DSC, since typical enthalpies are... 

Fig. 30. DSC traces showing the phase transition of the model membrane in its monomeric and polymeric form. Note the difference in the enthalpies of the transition monomer AH = 56 J/g, polymer AH = 26 J/g...

Fig. 2. DSC-trace of cyclododecane showing the melting transition at 333.4 K and an additional phase transition at 184.4 K. The sensitivity for the upper curve and the baseline reference was increased ten times. Heating rate 2.5 K/min. (Ref.7))...

Fig. 4. DSC-trace of octamethyltetra-siloxane showing the melting transition at 298 K and a solid state phase transition at 262 K. Heating rate lOK/ min. (Ref. 10))...

The DSC spectra confirm that the fluid phase of the polymerized vesicles remains and the phase transitions are retained with the introduction of the spacer group. As can been seen in Figure 8 of the DSC spectrum of the monomeric lipid, there is a peak around 28°C which corresponds to the phase transition of monomeric lipid. As the result of the presence of the spacer group, a similar phase transition can also be observed clearly in the spectrum of the polymerized lipid as shown in Figure 9, but the transition temperature is increased to 36°C by the presence of the polymer chains. 

Figure 9 Differential scanning calorimetric (DSC) curve showing the phase transitions observed on heating the amorphous form (glass) of polyethylene terephthalate. (Reproduced with permission from Ref. 38.)...

First-order phase transitions can be detected by various thermoanalytical techniques, such as DSC, thermogravimetric analysis (TGA), and thermomechanical analysis (TMA) [31]. Phase transitions leading to visual changes can be detected by optical methods such as microscopy [3], Solid-solid transitions involving a change in the crystal structure can be detected by X-ray diffraction [32] or infrared spectroscopy [33], A combination of these techniques is usually employed to study the phase transitions in organic solids such as drugs. 

Phase transitions, whether first-order or second-order, are potent sources of instability of solid drugs and can usually be detected and studied by thermal methods of analysis (e.g., DSC, TGA, TMA, ODSC, DMA, DEA). In crystalline solids, typical first-order transitions are polymorphic or desolvation transitions. In amorphous solids, second-order transitions, such as glass transitions, are common. 

Unfortunately, data on the temperature-dependent solution behaviour of these fractions are not available to date, although it will be of considerable interest to compare, e.g., HS-DSC and NMR results for the bound and unbound fractions of poly(NiPAAm-co-NVIAz) over the temperature range characteristic of the conformational and phase transitions of NiPAAm homopolymers and copolymers. 

Another technique that has been employed for studying certain types of changes in solids is infrared spectroscopy, in which the sample is contained in a cell that can be heated. By monitoring the infrared spectrum at several temperatures, it is possible to follow changes in bonding modes as the sample is heated. This technique is useful for observing phase transitions and isomerizations. When used in combination, techniques such as TGA, DSC, and variable-temperature spectroscopy make it possible to learn a great deal about dynamic processes in solids. 

Differential scanning calorimetry (DSC) compares the two different heat flows one to or from the sample to be studied, the other to or from a substance with no phase transitions in the range to be measured e. g. glassmaking sand. Figure 1.45 is the scheme of a DSC system Fig. 1.46 is a commercial apparatus for DSC measurements. 

The phase transition from amorphous to crystalline can sometimes be promoted by thermal treatment (annealing) [ 1.45]. In a laboratory scale, this can be done relatively simple. In a production scale the process must be proven as reproducible and reliable by a validation process, which is time consuming. It is therefore recommended, that a search for CPAs and process conditions, which would lead to crystallization be carried out, using methods such as DTA, DSC, ER and DRS (see Section 1.1.5) also see Yarwood [1.46. If this is not successful, time and temperature for TT should be chosen in such away, that the tolerances for time and temperature are not to narrow, e. g. -24.0 °C 0.5 °C and 18 min 1 min are difficult to operate, while -30 °C 1.5 °C and 40 min 2 min might be easier to control. 

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