Enthalpy measurement, scanning

A) Ambient (25 deg C) temperature preparation for O.lh followed by programmed heat-up to 180 deg C. This schedule results in complete cure (i.e., no reaction enthalpy can be measured in a subsequent scan). The enthalpy measured during the heat-up is AH(k). Since we assume that cure is negligible during the O.lh after mixing, AH(k) corresponds to the maximum reaction enthalpy for each composition. Tg is measured during a second heat-up. 

Enthalpy Measurements. A Perkin Elmer Differential Scanning Calorimeter Model DSC 1-B was used throughout. The instrument measures the heat flow rate (cal/s) by maintaining the sample and the reference isothermal to each other while they are heated or cooled with a linear known temperature rate (Scan speed, °C/min). (19)... 

The differential scanning calorimetry (Figure 15.3) is a thermoanalytical assay in which the difference in the amount of heat required to increase the temperature of a sample is measured as a function of temperature (temperature increases linearly as a function of time). In cereals, DSC analysis of starch-rich and starch-water slurries have been used to determine quantitatively starch gelatinization as an enthalpy (-AHg) of gelatinization (Table 15.3). Enthalpy measurements also can be used to measure the return to crystallinity in aged starch gels. The endotherm excursions... 

Cure kinetics of thermosets are usually deterrnined by dsc (63,64). However, for phenohc resins, the information is limited to the early stages of the cure because of the volatiles associated with the process. For pressurized dsc ceUs, the upper limit on temperature is ca 170°C. Differential scanning calorimetry is also used to measure the kinetics and reaction enthalpies of hquid resins in coatings, adhesives, laminations, and foam. Software packages that interpret dsc scans in terms of the cure kinetics are supphed by instmment manufacturers. 

Although there are other ways, one of the most convenient and rapid ways to measure AH is by differential scanning calorimetry. When the temperature is reached at which a phase transition occurs, heat is absorbed, so more heat must flow to the sample in order to keep the temperature equal to that of the reference. This produces a peak in the endothermic direction. If the transition is readily reversible, cooling the sample will result in heat being liberated as the sample is transformed into the original phase, and a peak in the exothermic direction will be observed. The area of the peak is proportional to the enthalpy change for transformation of the sample into the new phase. Before the sample is completely transformed into the new phase, the fraction transformed at a specific temperature can be determined by comparing the partial peak area up to that temperature to the total area. That fraction, a, determined as a function of temperature can be used as the variable for kinetic analysis of the transformation. 

Isoperibolic instruments have been developed to estimate enthalpies of reaction and to obtain kinetic data for decomposition by using an isothermal, scanning, or quasi-adiabatic mode with compensation for thermal inertia of the sample vessel. The principles of these measuring techniques are discussed in other sections. 

Apart from the qualitative observations made previously about suitable solvents for study, the subject of solvates has two important bearings on the topics of thermochemistry which form the main body of this review. The first is that measured solubilities relate to the appropriate hydrate in equilibrium with the saturated solution, rather than to the anhydrous halide. Obviously, therefore, any estimate of enthalpy of solution from temperature dependence of solubility will refer to the appropriate solvate. The second area of relevance is to halide-solvent bonding strengths. These may be gauged to some extent from differential thermal analysis (DTA), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC) solvates of "aprotic solvents such as pyridine, tetrahydrofuran, and acetonitrile will give clearer pictures here than solvates of "protic solvents such as water or alcohols. 

Experimental Methods Measurements of specific heat and enthalpies of transition are now usually carried out on quite small samples in a Differential scanning calorimeter (DSC). DSC is applied to two different moles of analysis, of these the one is more closely related to traditional calorimetry and is described here. In DSC an average-temperature circuit measures and controls the temperature of sample and reference holders to conform to a Organisation and Qualities... 

Differential scanning calorimetry has been used88 to measure the enthalpy change, AH0 for the exothermic decarbonylation reaction... 

The enthalpies of phase transition, such as fusion (Aa,s/f), vaporization (AvapH), sublimation (Asut,//), and solution (As n//), are usually regarded as thermophysical properties, because they referto processes where no intramolecular bonds are cleaved or formed. As such, a detailed discussion of the experimental methods (or the estimation procedures) to determine them is outside the scope of the present book. Nevertheless, some of the techniques addressed in part II can be used for that purpose. For instance, differential scanning calorimetry is often applied to measure A us// and, less frequently, AmpH and AsubH. Many of the reported Asu, // data have been determined with Calvet microcalorimeters (see chapter 9) and from vapor pressure against temperature data obtained with Knudsen cells [35-38]. Reaction-solution calorimetry is the main source of AsinH values. All these auxiliary values are very important because they are frequently required to calculate gas-phase reaction enthalpies and to derive information on the strengths of chemical bonds (see chapter 5)—one of the main goals of molecular energetics. It is thus appropriate to make a brief review of the subject in this introduction. 

Differential scanning calorimetry (DSC) was designed to obtain the enthalpy or the internal energy of those processes and also to measure temperature-dependent properties of substances, such as the heat capacity. This is done by monitoring the change of the difference between the heat flow rate or power to a sample (S) and to a reference material (R), A

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A sample of the polymer to be studied and an inert reference material are heated and cooled in an inert environment (nitrogen) according to a defined schedule of temperatures (scanning or isothermal). The heat-flow measurements allow the determination of the temperature profile of the polymer, including melting, crystallization and glass transition temperatures, heat (enthalpy) of fusion and crystallization. DSC can also evaluate thermal stability, heat capacity, specific heat, crosslinking and reaction kinetics. 

Differential Scanning Calorimetry (DSC) This is by far the widest utilized technique to obtain the degree and reaction rate of cure as well as the specific heat of thermosetting resins. It is based on the measurement of the differential voltage (converted into heat flow) necessary to obtain the thermal equilibrium between a sample (resin) and an inert reference, both placed into a calorimeter [143,144], As a result, a thermogram, as shown in Figure 2.7, is obtained [145]. In this curve, the area under the whole curve represents the total heat of reaction, AHR, and the shadowed area represents the enthalpy at a specific time. From Equations 2.5 and 2.6, the degree and rate of cure can be calculated. The DSC can operate under isothermal or non-isothermal conditions [146]. In the former mode, two different methods can be used [1] ... 

Method 2 A sample is cured for various times until no additional curing can be detected. The samples are then scanned (heating rate ranging from 2 to 20°C/min) in order to measure the residual enthalpy, AHres. The degree of cure is calculated directly by Equation 2.25,... 

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