Graduate School of Education, Hiroshima University 1
1. 2. TG, TG-DTA 3. 4. TG 5. TG-DTA 6. TG 7. TG 8. TG 9. TG-DTA-EGA 2
3
(Thermogravimetry) TG (Derivative TG) DTG (Evolved Gas Detection) EGD (Evolved Gas Analysis) (Emanation Thermal Analysis) EGA ETA (Differential Thermal Analysis) DTA H (Differential Scanning Calorimetry) DSC (Thermodilatometry) (Thermomechanical Analysis) TMA (Dynamic Thermomechanometry) DMA (Thermosonimetry) (Thermoacoustimetry) (Thermoelectrometry) (Thermomagnetmetry) 4
1. TG 1.1 TG 5
1.2 (1) TG N S 6
1.2 (2) (a) Suspending (b) Top-loading (c) Horizontal 7
1.2 (3) 8
1.2 (4) R S C A A C T T 9
1.3 (1) TG N S 1
2. 2.1 (1) (2) CaC 2 O 4 H 2 O (1) CaC 2 O 4 H 2 O CaC 2 O 4 +H 2 O (2) CaC 2 O 4 CaCO 3 +CO 2 (3) CaCO 3 CaO+CO 2 Mass change / mg -1-2 -3-4 -5 -H 2 O (-12.3%) -CO (-19.2%) -CO 2 (-3.1%) 2 4 6 8 Temperature / C 11
2.2 (1) (1) N S (a) Experimental arrangement Apparent mass A: Permanorm B: Ni C: Mumetal D: Permanorm 5 E: Trafoperm 2 4 6 8 T / C (b) TG curve for GM761 12
2.2 (2) (2) Zn 418.6 ( ) In 156.4 Sn 231.9 Pb 327.4 Zn 419.5 Al 66.4 13
2.2 (3).4.5-1 m / mg.3.2.1. DTA TG 327.5 358.3 419.5 DTG.4.3.2.1. (d m/dt) / mg min -1-2 -3-4 DTA / µv -.1 3 325 35 375 4 425 45 T / C -5 Pb(1.29mg), Zn(6.63mg), Ni(54.99mg) 14
3. TG 3.1 (1) (2) (3) (4) (6) (5) 15
3.1 Isothermal Measurement T / K 6 55 5 45 4 35 (1) Isothermal W (d W/dt) T -1-2 -3 W / mg.3.2.1. -.1 -.2 (d W/dt) / mg min -1 3-4 5 1 15 2 25 3 -.3 t / min CuCO 3 Cu(OH) 2 2CuO + CO 2 + H 2 O 16
3.1 17
3.1 Nonisothermal Measurement T / K 65 6 55 5 45 (2) Nonisothermal W T (d W/dt) -1-2 -3 W / mg.2. -.2 -.4 -.6 (d W/dt) / mg min -1 4-4 4 8 12 16 2 24 -.8 t / min CuCO 3 Cu(OH) 2 2CuO + CO 2 + H 2 O 18
3.1 (1) CuSO 4 5H 2 O CuSO 4 3H 2 O + 2H 2 O (2) CuSO 4 3H 2 O CuSO 4 H 2 O + 2H 2 O (3) CuSO 4 H 2 O CuSO 4 + H 2 O 19
3.1 (Self-cooling Effect) (1) CaC 2 O 4 H 2 O CaC 2 O 4 +H 2 O (2) CaC 2 O 4 CaCO 3 +CO 2 (3) CaCO 3 CaO+CO 2 DTA 2
3.1 Li 2 SO 4 H 2 O Li 2 SO 4 + H 2 O 21
3.1 Controlled Rate Measurement T / K 8 7 6 5 4 3 (3) Constant Rate W T (d W/dt) -1-4 1 2 3-2 -3 W / mg.4.2. -.2 -.4 (d W/dt) / mg min -1 t / min CuCO 3 Cu(OH) 2 2CuO + CO 2 + H 2 O 22
3.2 (1) 23
3.2 (2) TG-DTA 24
3.2 (3) 1. Fractional reaction α.8.6.4.2. 1 2 3 Time / min 4 2.5 mg 5. mg 1. mg 2. mg Li 2 SO 4 H 2 O Li 2 SO 4 + H 2 O 5 6 25
3.3 (1) (2) B A D (3) C 26
3.3 27
4 TG-DTA TG DTA TG DTA 28
4 TG-DTA TG-DTA 12 1 T / K 1 8 6 4 5 1 15 DTA TG 2 25-1 -2-3 -4-5 3 Weight change W / mg 5-5 -1-15 -2 δ T / µv Time / min 29
5. TG 5.1 Mass change / x1-3 mg 8 4-4 (a) (b) -1-2 -3-4 -5 Mass change / mg 2 4 6 8 Temperature / C TG 3
5.2 (mg) (%) 1 (mg) Mass change / mg -1-2 -3-4 -5 -H 2 O (-12.3%) -CO (-19.2%) -CO 2 (-3.1%) 2 4 6 8 Temperature / C 31
5.3 TG (dm/dt) (dm/dt) (DTG) vs. T.5. T e.o dm/dt / mg min -1 -.5 -.1 -.15 -.2 -.25 T o T o : T e.o. : -.3 8 1 12 14 16 T p Temperature / C 18 2 22 T p : 32
5.4 α = m m m m f m : m f : m: Fractional reaction α 1..8.6.4.2. 1 12 14 16 Temperature / C 18 2 4 3 2 1 (dα/dt) / x1-3 s -1 33
6. TG 6.1 (CRTA) (a) (b) CRTA Chronometer Programmer Chronometer Programmer X-meter Thermometer X-meter Thermometer Recorder Controller Recorder Controller 34
6.1 CRTG B A TG circuit DTG circuit CRTA Prog. Temp. Prog. Recorder Chronometer C Regulator Thermometer CRTA Controller 35
6.2 CRTG T / K 8 7 6 5 4 3 (3) Constant Rate W T (d W/dt) -.4-4 1 2 3 t / min -1-2 -3 W / mg CuCO 3 Cu(OH) 2 2CuO + CO 2 + H 2 O.4.2. -.2 (d W/dt) / mg min -1 36
6.3 CRTG 11.6 T / K 1 W -4 9 T 8-8 7 6-12 5-16 4 (d W/dt) 3-2 2 4 6 8 Time / min Mass change W / mg.4.2. -.2 -.4 -.6 (d W/dt) / mg min -1 CaCO3 CaO + CO 2 37
6.4 CRTG 38
7. TG 39
7.1 TG(/DTA)-FTIR 4
7.2 TG(/DTA)-MS 41
7.3 TG(/DTA)-GC-MS 42
7.4 TG-FTIR TG-MS TG-FTIR TG-MS He, Air, N 2 43
7.5 TG-MS (a) m / mg (b) I / x1-9 A (c) I / x1-9 A -1-2 -3-4 12 1 8 6 4 2 8 6 4 2 DTA TG 2 4 6 8 TIC m/z=18 m/z=28 m/z=44 1 2 3 4 51 2 3 4 51 2 3 4 5 T / C m/z 5-5 -1-15 -2-25 -3-35 DTA / µv (1) CaC 2 O 4 H 2 O CaC 2 O 4 +H 2 O (2) CaC 2 O 4 CaCO 3 +CO 2 (3) CaCO 3 CaO+CO 2 44
7.6 CREGA-TG 45
7.7 CREGA-TG 5 5.2 m / mg -2-4 -6 (a) TG H 2 O CO 2 DTA 4 3 2 1 2-2 -4 / g m -3 DTA / µv T / K 45 4 35 (b) T CO 2 TG.15.1.5. -2-4 -6 / g m -3 m / mg -6 3 35 4 45 5 55 T / K 3 3 6 9 12 15 18 time / min CuCO 3 Cu(OH) 2 2CuO + CO 2 + H 2 O 46