Measuring thermal transition

Figure 5.4 A differential scanning calorimeter for measuring thermal transitions in dilute solution...

The recent technique of micro-thermal analysis ()U-TA), which now has a variety of measurement modes, is included here because usually two or more measurements are made simultaneously. Micro-TA combines the imaging capabilities of atomic force microscopy (AFM) with a form of localised thermal analysis, and is able to measure thermal transitions on an area of a few microns. A good introduction to the whole family of these methods is available on the internet, from which application studies can... 

Various characterization methods both in vitro and in vivo can provide information to understand, predict, and improve the performance of drug delivery systems. Selection of methods depends on the material properties and their applications. Viscoelastic properties can be measured using both DMA and oscillatory shear rheometry. DSC is a most useful method of measuring thermal transitions. Various microscopic methods are available to obtain the microstrac-ture and shape of the materials. Amorphous and crystaUine materials have different packing patterns of molecules, and these properties can be determined from XRD or density measurements. Surface properties such as surface elemental composition and material porosity can be obtained from various spectroscopic methods as well as from BET measurements. The biocompatibility of the material can be determined from both in vitro and in vivo assays. In vitro dissolution testing can be utilized to correlate with the in vivo performance of polymeric drug delivery systems. All these characterization methods can provide valuable information... 

Thermal analyzer (TMA). Measures the variation in the length of a sample as temperature is increased. It is good for comparing this property with a sample of another compoimd. TMA also measures thermal transition points by predicting the point and rate at which a compound will melt as well as determining the temperature at which blistering will occur if a molded part has not been properly postbaked. 

The Rheometric Scientific RDA II dynamic analy2er is designed for characteri2ation of polymer melts and soHds in the form of rectangular bars. It makes computer-controUed measurements of dynamic shear viscosity, elastic modulus, loss modulus, tan 5, and linear thermal expansion coefficient over a temperature range of ambient to 600°C (—150°C optional) at frequencies 10 -500 rad/s. It is particularly useful for the characteri2ation of materials that experience considerable changes in properties because of thermal transitions or chemical reactions. 

The heat flow into (endothermic) or out (exothermic) of a sample as a function of temperature and time is measured using the technique of DSC. In particular, it is used to study and determine the temperature of thermal transitions. For polymers, these include Tg, the glass transition temperature, Tc, the (exothermic) temperature of crystallisation for polymers that can crystallise, and Tm, the (endothermic) melting temperature. A DSC measurement requires only a small amount of sample 2-20 mg of a film, powder, fibre or liquid samples can be analysed in a DSC pan. 

Temperature(s). See also Blackbody temperature sensor Cure temperature Curie temperature Eutectic temperature Fictive temperature Furnace temperature Glass- transition temperatures Heat entries Heating Hot entries Refrigeration Target temperature emperature measurement Thermal entries Thermo-entries Transition temperatures in analysis of water, 26 35 biofiltration system, 10 76 in biological wastewater treatment,... 

Experimental Methods In Differential thermal analysis (DTA) the sample and an inert reference substance, undergoing no thermal transition in the temperature range under study are heated at the same rate. The temperature difference between sample and reference is measured and plotted as a function of sample temperature. The temperature difference is finite only when heat is being evolved or absorbed because of exothermic or endothermic activity in the sample, or when the heat capacity of the sample changes abruptly. As the temperature difference is directly proportional to the heat capacity so the curves are similar to specific heat curves, but are inverted because, by convention, heat evolution is registered as an upward peak and heat absorption as a downward peak. 

Yu, L. and Christie, G. (2001). Measurement of starch thermal transitions using differential scanning calorimetry. Carbohydr. Polym. 46, 179-184. 

NMR evidence 115 demonstrated that a designed 20-residue peptide (betanova) adopts a three-stranded (3-sheet in water CD was also measured but the spectrum was not shown. The CD at 217 nm is negative and was used to monitor the thermal unfolding of the peptide. CD and fluorescence indicate a cooperative thermal transition. These CD and fluorescence data can be interpreted as evidence for a two-state cooperative thermal transition. However, a... 

Kadomtseva et al. (2000) measured thermal expansion and longitudinal and transverse magnetostriction in pulsed magnetic fields up to 25 T in Lai - Sr MnOj single crystals (x = 0.1,0.125 and 0.15). The results were ascribed to a suppression of the O phase and field-induced transitions to a new orbital-ordered ferromagnetic state. 

With heating from 5 to 45°C, thermal changes in conformation in the major /3-casein are observed by spectral methods (Garnier 1966). From measurements of the optical density at 286 nm and of the specific optical rotation at 436 nm, a rapidly reversible endothermic transition (AH 30 kcal/mole) with a half-transition temperature of 23-24°C is observed. The optical rotatory dispersion data suggest a decrease in the poly-L-proline II structure (12 to 5%) and a slight increase in a-helix (11 to 16%) with increasing temperature. This transition probably occurs prior to association, since it is rapid, and the carboxyacyl derivative of the monomer, which does not polymerize with increasing temperature, also demonstrates the optical rotatory disperson thermal transition. 

A recent study has employed the new technique of quasi-elastic light scattering for estimation of diffusion constants (257). The result for the native enzyme at 24° is in close agreement with the data given in the tabulation. The value of D as a function of temperature was measured through the thermal transition. The method was also used to follow the kinetics of the urea-induced transition. 

In an analogous manner to DMA, dielectric thermal analysis (DETA) represents a technique to apply an alternating electric field across the tested sample, which contributes to a polarization of the material with consequent current flow. DETA enables measurement of dielectric properties, which can further be related to material properties and thermal transitions as described below. 

Miyashita et al. carried out miscibility characterization of CA blends with poly(N-vinyl pyrrolidone) (PVP), poly(vinyl acetate) (PVAc), and poly(N-vinyl pyrrolidone-co-vinyl acetate) random copolymers [P(VP-co-VAc)s] [ 104]. On the basis of thermal transition data obtained by differential scanning calorimetry (DSC), a miscibility map (Fig. 8) was completed as a function of the degree of substitution (DS) of CA and the VP fraction in P(VP-co-VAc). Figure 9 compares results of the DSC measurements between two blending pairs of CA/P(VP-co-VAc) corresponding to the polymer combinations marked as A and B in Fig. 8. In the data (Fig. 9b) for the blends of CA (DS = 2.95) with P( VP-co-VAc) of VP = 51 mol %, we can readily see a sign of poor miscibility, as is evidenced from the lack of an appreciable shift in the... 

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