Temperature DSC and

We thank A. E. Novembre and D. A. Mixon for help with GPC data, R. G. Tarascon for initial etching studies, S. A. Heffner for assistance in obtaining low temperature DSC and S. Nakahara for transmission electron microscopy. 

Traditionally, simple combinations of linear heating or cooling rates and isothermal segments have been employed. Modern methods, however, frequently impose cyclic temperature programs coupled with Fourier analyses to achieve particular advantages and added information. These approaches are referred to as modulated techniques, and temperature is the most commonly modulated parameter. Note that in DMA, stress or strain is the modulated parameter and that in DEA, the electric field is modulated, but in modulated temperature DSC and modulated temperature TMA, it is the temperature that is modulated. 

Many publications present research that has been done on biodiesel from production to properties, such as oxidative stability, cold flow properties, and thermal decomposition, etc. [2, 11, 32, 39, 46]. Differential Scanning Calorimetry (DSC), Modulated Temperature-DSC and Pressure-DSC are among the techniques used to characterize biodiesel. Some of these techniques will be discussed in the following chapter. 

Thermal analysis iavolves techniques ia which a physical property of a material is measured agaiast temperature at the same time the material is exposed to a coatroUed temperature program. A wide range of thermal analysis techniques have been developed siace the commercial development of automated thermal equipment as Hsted ia Table 1. Of these the best known and most often used for polymers are thermogravimetry (tg), differential thermal analysis (dta), differential scanning calorimetry (dsc), and dynamic mechanical analysis (dma). 

Mixing Cell Calorimetry (MCC) The MCC provides information regarding the instantaneous temperature rise resulting from the mixing of two compounds. Together, DSC and MCC provide a reliable overview of the thermal events that may occur in the process. 

Differential scanning calorimetry (DSC) is fast, sensitive, simple, and only needs a small amount of a sample, therefore it is widely used to analyze the system. For example, a polyester-based TPU, 892024TPU, made in our lab, was blended with a commercial PVC resin in different ratios. The glass transition temperature (Tg) values of these systems were determined by DSC and the results are shown in Table 1. 

DSC helps in determining the glass-transition temperature, vulcanization, and oxidative stability. TG mainly is applied for the quantitative determination of major components of a polymer sample. TMA or DLTMA (dynamic load thermomechanical analysis) measures the elastic properties viz. modulus. 

The techniques referred to above (Sects. 1—3) may be operated for a sample heated in a constant temperature environment or under conditions of programmed temperature change. Very similar equipment can often be used differences normally reside in the temperature control of the reactant cell. Non-isothermal measurements of mass loss are termed thermogravimetry (TG), absorption or evolution of heat is differential scanning calorimetry (DSC), and measurement of the temperature difference between the sample and an inert reference substance is termed differential thermal analysis (DTA). These techniques can be used singly [33,76,174] or in combination and may include provision for EGA. Applications of non-isothermal measurements have ranged from the rapid qualitative estimation of reaction temperature to the quantitative determination of kinetic parameters [175—177]. The evaluation of kinetic parameters from non-isothermal data is dealt with in detail in Chap. 3.6. 

Characterization439 Inherent viscosity before and after solid-sate polymerization is 0.46 and 3.20 dL/g, respectively (0.5 g/dL in pentafluorophenol at 25°C). DSC Tg = 135°C, Tm = 317°C. A copolyester of similar composition440 exhibited a liquid crystalline behavior with crystal-nematic and nematic-isotropic transition temperatures at 307 and 410°C, respectively (measured by DSC and hot-stage polarizing microscopy). The high-resolution solid-state 13C NMR study of a copolyester with a composition corresponding to z2/zi = 1-35 has been reported.441... 

Thermoanalytical techniques such as differential scanning calorimetry (DSC) and thermogravi-metric analysis (TGA) have also been widely used to study rubber oxidation [24—27]. The oxidative stability of mbbers and the effectiveness of various antioxidants can be evaluated with DSC based on the heat change (oxidation exotherm) during oxidation, the activation energy of oxidation, the isothermal induction time, the onset temperamre of oxidation, and the oxidation peak temperature. 

The thermal properties of tyrosine-derived poly(iminocarbonates) were also investigated. Based on analysis by DSC and thermogravi-metric analysis, all poly(iminocarbonates) decompose between 140 and 220 C. The thermal decomposition is due to the inherent instability of the iminocarbonate bond above 150°C and is not related to the presence of tyrosine derivatives in the polymer backbone. The molecular structure of the monomer has no significant influence on the degradation temperature as indicated by the fact that poly(BPA.-iminocarbonate) also decomposed at about 170 C, while the structurally analogous poly(BPA-carbonate) is thermally stable up to 350 C. 

Fig. 18.1 Melting temperature (squares) and temperature of crystallization (triangles) for CZX-1 as a function of the DSC cooling rate. A plateau in the crystallization temperature is observed for cooling rates below l°/min resulting in a no-crystallization region of about 15°.

The worst hazard scenarios (excessive temperature and pressure rise accompanied by emission of toxic substances) must be worked out based upon calorimetric measurements (e.g. means to reduce hazards by using the inherent safety concept or Differential Scanning Calorimetry, DSC) and protection measures must be considered. If handling hazardous materials is considered too risky, procedures for generation of the hazardous reactants in situ in the reactor might be developed. Micro-reactor technology could also be an option. Completeness of the data on flammability, explosivity, (auto)ignition, static electricity, safe levels of exposure, environmental protection, transportation, etc. must be checked. Incompatibility of materials to be treated in a plant must be determined. 

Degradation products of LDPE/(BHT, Chimassorb 944) after long-term exposure to compost, water and air (chemical hydrolysis at pH 5 and pH 7) at room temperature were examined by GC-MS [277] the structural changes in the LDPE film were monitored by DSC and SEC. Among the 79 low-MW degradation products identified by GC-MS the main components were... 

Thermal Properties. The glass transition temperature (Tg) and the decomposition temperature (Td) were measured with a DuPont 910 Differential Scanning Calorimeter (DSC) calibrated with indium. The standard heating rate for all polymers was 10 °C/min. Thermogravimetric analysis (TGA) was performed on a DuPont 951 Thermogravimetric Analyzer at a heating rate of 20 °C/min. 

There is a potentially dangerous reaction of carbon tetrachloride with dimethylformamide in presence of iron. The same occurs with 1,2,3,4,5,6-hexachlorocyclohexane, but not with dichloromethane or 1,2-dichloroethane under the same conditions [1], A quantitative study of the reaction by DSC and ARC techniques shows that in a 1 1 wt. mixture with carbon tetrachloride in absence of iron, an exothermic reaction sets in below 100°C. Under adiabatic conditions, the heat release (207.6 J/g) would take a runaway reaction to over 240°C. In presence of 3% of iron powder, the same mixture shows 2 exotherms, one at 56°C (108 J/g) and the second at 94°C (275 J/g), a final adiabatic temperature exceeding 285°C being possible [2], Dimethylacetamide behaves similarly but more so. 

Delays in working up the crude product caused violent explosions during attempted vacuum distillation. An alternative method of crystallisation is described [1]. There is a very high rate of pressure increase in exothermic decomposition [2], Energy of decomposition (in range 180-420°C) measured as 2.19 kJ/g by DSC, and Taj,24 was determined as 147°C by adiabatic Dewar tests, with an apparent energy of activation of 168 kJ/mol [3], The initial decomposition temperature by ARC was 166°C. 

The explosive decomposition of the solid has been studied in detail [6], The effect of moisture upon ignitibility and explosive behaviour under confinement was studied. A moisture content of 3% allowed slow burning only, and at 5% ignition did not occur [7], Thermal instability was studied using a pressure vessel test, ignition delay time, TGA and DSC, and decomposition products were identified [8], The presence of acyl chlorides renders dibenzoyl peroxide impact-sensitive [9], There is a further report of a violent explosion during purification of the peroxide by Soxhlet extraction with hot chloroform [10], Residual traces of the peroxide in a polythene feed pipe exploded when it was cut with a handsaw [11]. The heat of decomposition has been determined as 1.39 kJ/g. The recently calculated value of 69° C for critical ignition temperature coincides with that previously recorded. 

---