近代分析实验原理：第十四课-热分析.pptVIP

Gas flow, however, generates concerns about possible thermal shielding and/or buoyancy effects. Thermal shielding can be understood from Figure 10.22. Gas flow downward to the sample holder will make the holder shield the thermocouple junction from convective heat transfer through the flowing gas. Consequently, the thermocouple junction temperature will not be the same as for a sample with flowing gas. The buoyancy （浮力） effect is illustrated in Figure 10.24. Gas flow upward will generate a lifting force on the sample holder. This effect is similar to weight loss of a sample body in liquid. Such gas flow effects are difficult to eliminate. Careful calibration and good instrument design reduce such problems to a minimum. * When the Curie point of a ferromagnetic sample is reached, the magnetic downward force disappears and weight loss will be recorded in the TA curve The fusible line method can also be used as a calibration temperature. A fusible wire with known melting temperature connects the microbalance suspension wire and inert mass pieces. The fusible wire should locate the position of sample in the furnace. Melting of the wire at its melting temperature causes mass loss, which is recorded in the TG curve. * The heating rate affects TG curves considerably, similar to DTA and DSC. For example, with endothermic decomposition, a high heating rate will increase the starting and finishing temperatures of decomposition. Also, the temperature range from start to finish will be wider at a higher heating rate than a lower heating rate. Figure 10.26 shows an example of the effect of heating rate on the TG curve of polyvinyl chloride (PVC). There are two reasons for heating rate effects. First, high heating rate is more likely to generate a temperature difference between the sample and thermocouple junction. The real sample temperature may lag behind that of the thermocouple. Second, in decomposition with volatile products, it takes time for those products to diffuse out o