Principles of TG, DSC, STA and EGA

Ekkehard Post NETZSCH Gerätebau GmbH Wittelsbacherstrasse 42 D-95100 Selb, Germany
Belgium February 2009 1 E. Post/NETZSCH

Thermal Analysis

Definition (ICTAC): Thermal analysis (TA) is a group of techniques in which changes of physical or chemical properties of the sample are monitored against time or temperature, while the temperature of the sample is programmed. The temperature program may involve heating or cooling at a fixed rate, holding the temperature constant (isothermal), or any sequence of these.

Belgium February 2009 2 E. Post/NETZSCH

Methods of Thermal Analysis (TA)

Differential Scanning Calorimetry
(DSC, DTA)

Thermogravimetry
(TG)

Thermomechanical Analysis
(TMA) Dilatometry (DIL) Dynamic-Mechanical Analysis (DMA)

Physical and chemical processes related to thermal effects can be characterized

Mass changes due to evaporation, decomposition and interaction with the atmosphere

Dimensional changes, deformations, viscoelastic properties, transitions, density

Evolved Gas Analysis (EGA)
Belgium February 2009 3 E. Post/NETZSCH

∆L Crystallization ∆H ∆L Softening ∆L Decomposition ∆m ∆H ∆L Glass-ceramics. ∆Cp ∆L Decomposition ∆m ∆H ∆L Belgium February 2009 4 E. polymers Liquid Crystal .Thermal analysis for the characterization of solids Solids Crystalline Polymorphism ∆H ∆L Phase transition ∆H. Post/NETZSCH Amorphous Glass transition ∆Cp.

Post/NETZSCH .Principle of thermogravimetry (TG) Belgium February 2009 5 E.

Post/NETZSCH Hang down .Thermogravimetry Mass change versus temperature and/or time Thermobalance types horizontal Top loading Belgium February 2009 6 E.

Post/NETZSCH .TG Curve .Principle Belgium February 2009 7 E.

Principle Belgium February 2009 8 E. Post/NETZSCH .DTG Curve .

Post/NETZSCH .Belgium February 2009 9 E.

2. and 11. Belgium February 2009 10 E. swim). 17 and 103 g respectively. Post/NETZSCH . 27. If the volume of each is 10 cubic cm then their masses are 2.Thermogravimetry: Buoyancy effect Equal Volumes Feel Equal Buoyant Forces Suppose you had equal sized balls of cork. yielding apparent masses of -8 (the cork would accelerate upward. aluminum and lead.3. Each would displace 10 grams of water. with respective specific gravities of 0.2.7. and 113 g.

Post/NETZSCH .Thermogravimetry: Buoyancy effect Buoyant Force Buoyant force is also present in gases. but much smaller compared to liquids (density difference) Belgium February 2009 11 E.

The buoyancy force (Archimedes‘ principle) is reduced with increasing temperature. This depends also on density of the gas. the balance shows an apparent weight increase. Belgium February 2009 12 E. Post/NETZSCH .STA 409PC Luxx The sample holder „swims“ in the atmosphere.

3 0.STA 449 F1: Buouancy Reproducibility TG /mg 0.2 0.4 Two Baselines 0.1 100 200 300 400 500 Temperatur /°C 600 700 800 900 Belgium February 2009 13 E.000 mg -0. Post/NETZSCH .1 -> microgram accuracy! Difference of the two baselines 0.5 0.0 0.

Post/NETZSCH .TG of Calcium Oxalate Monohydrate Belgium February 2009 14 E.

ρ2) Belgium February 2009 15 E.Bouyancy and Convection Dependent on Atmosphere Type of sample carrier Heating rate Crucible size Fa = g • ρ • VK ∆Fa = g • VK • (ρ1. Post/NETZSCH .

Bouyancy and Convection Dependent on Atmosphere Type of sample carrier Heating rate Crucible size Belgium February 2009 16 E. Post/NETZSCH .

20 20 K/min 0.5 K/min -0.10 -0.30 0.Bouyancy and Convection TG /mg 0.0 10 K/min 2.10 -0.30 100 200 300 400 500 600 Temperature /° C 700 800 900 Belgium February 2009 17 E. Post/NETZSCH .20 -0.40 Dependent on Atmosphere Type of sample carrier Heating rate Crucible size 0.

0(K/min)/990 900 950 dolomit-heizraten.7 ° C 100 K/min 80 75 70 65 60 55 550 Main 2008-09-03 10:21 User: Ekkehard.Post Dolomite in nitrogen 2 K/min 20 K/min 600 Date 2008-08-30 2008-08-30 2008-08-30 650 Identity xxx-3-08-06 xxx-0-08-4 xxx-3-08-5 700 Sample dolomit dolomit 2 K dolomit 750 Temperature /° C Mass/mg 41.dt6 xxx-3-08-5. 420 420 420 Belgium February 2009 18 E.0ml/min / N2. 20. 20.0ml/min / N2.9 °C 95 90 85 701.129 37. 20. 20.0ml/min / N2.Heating Rate – Atmosphere generated TG /% 100 861.0ml/min N2. 20.dt6 Segment 1/1 1/1 1/1 Atmosphere N2.0(K/min)/990 20/2.092 39.0ml/min N2.8 °C 783.dt6 xxx-0-08-4. 20.ngb [#] Instrument [1] TG 209 F3 [2] TG 209 F3 [3] TG 209 F3 File xxx-3-08-06. Post/NETZSCH .0(K/min)/990 20/20.0ml/min Corr.307 800 850 Range 20/100.

Application – Ferromagnetic Metals Measurements in a Static Magnetic Field Belgium February 2009 19 E. Post/NETZSCH .

: Ar flow rate: 70 -2 ml/min heating rate: 20 K/min -3 200 400 600 Temperature /°C 800 1000 1200 Belgium February 2009 20 E.0 ° C 741.6 ° C STA 449 Jupiter Sample: Ironboride -1 mass: 17.000 % C 2 1 97 Curie-transition 1051.2 ° C 3 99 melting Sample: Ironboride 98 Measurement in magnetic field gradient! 421.0 ° 100.0 ° C 4 100 magnetic reentrance due to crystallization! 1153.6 J/g 95 crystallization 94 554.285 % C 1188.Amorphous Metal: Ironboride (II) TG /% DSC /(mW/mg) ↓ exo 5 550.9 ° C 280 J/g! 1066. atm.5 ° 3.4 ° C 101 421.2 ° C 660.74 mg crucible: Pt+Al2O3 lin. Post/NETZSCH .1 ° C -151 J/g 0 96 1.

Post/NETZSCH .Differential Thermal Analysis (DTA) Differential Scanning Calorimetry (DSC) Belgium February 2009 21 E.

thermocouple voltage). t1 – temperature at the soldering joint. Thermocouples for measuring temperature differences according to the Seebeck effect: Metal A soldering joint Metal B EMF If an electric conductor is exposed to a temperature gradient.Temperature Measurement Temperature is one of the most frequently measured quantities. EMF = resulting voltage.. t2 – reference temperature Belgium February 2009 22 E. Post/NETZSCH . which causes an electromagnetic force (EMF. Measurement with thermocouples or resistance thermometers. S – Seebeck Coefficient. an electron flow is generated inside the conductor.

1600° Thermocouple type E usually used for low temperature DSC instruments Belgium February 2009 23 E... Post/NETZSCH . working temperature range Notes N NiCrSi (Nicrosil) NiSi 30 38 39 0 … 1100°C E R NiCr CuNi 68 8 81 11 13 -200 … 800°C 0 … 1600°C Pt13Rh Platinum Platin13%Rhodium Pt10Rh Platinum Platin10%Rhodium Pt30Rh Pt6Rh PlatinPlatinum30%Rhodium 6%Rhodium S 8 9 11 0 … 1550°C B 1 5 9 0 .Thermocouples according to ITS 90 and IEC 584-1 Thermocouple type (+) Leg (-) Leg Generated emf change in µV/°C (reference junction at 0°C) at 100°C K T J Ni-Cr (Chromel) Cu Fe Ni-Al (Alumel) CuNi (Constantan) CuNi 42 46 54 at 500° C 43 56 at 1000°C 39 59 0 …1100°C -185 … 300°C 20 … 700°C most suited for oxidising atmospheres excellent for low temperatures used in reducing atmospheres as an unprotected thermocouple very stable output signal at high temperatures highest thermal emf per °C high resistance to oxidation and corrosion similar characteristics to type R similar characteristics to type R and S approx.

DTA and DSC Principle Furnace Sample Refer. Q PR ∆T . Belgium February 2009 24 E. Difference of heat flow rate between sample and reference During a phase transition a temperature difference (heat flux difference) between the sample and reference can be measured by means of a thermocouple. Post/NETZSCH .

Generation of the DSC Signal Melting of a metal Belgium February 2009 25 E. Post/NETZSCH .

Glass transitions. crystallization and melting effects can easily be studied. Post/NETZSCH .Transformation Energetics of a Slag The DSC 404 C Pegasus® allows examination of nearly all transformation energetics over a wide temperature range. Belgium February 2009 26 E.

75 K/min. Post/NETZSCH .Dehydration of Al(OH)3.4 mg. helium static Belgium February 2009 27 E. Crystallization of Al2O3 and Melting DSC /(uV/mg) 6 ↓ exo 348 °C Al(OH)3 5 4 3 2 1 0 -1 500 1000 dehydration 2057 °C α γ 1136 °C Al(OH)3 Al2O3 gamma Al2O3 1259 °C crystallization 1378 °C alpha Al2O3 melting 1500 Temperature /° C 2000 Al(OH)3 42. tungsten crucible.

Phase diagrams Crystallization temperatures Degree of crystallinity Glass transition temperatures Decomposition effects Reaction kinetics Purity determinations SPECIFIC HEAT Belgium February 2009 28 E.Application of DSC Melting temperatures Transition enthalpies Phase transformations. Post/NETZSCH .

The sensitivity is determined from the sapphire measurement sensitivit y = signal difference ( sapphire − baseline ) mass ( sapphire ) • heating rate • theoret . sapphire and sample).Calculation of Specific Heat Cp = signal difference ( sample − baseline ) sample mass • heating rate • sensitivit y The specific heat of a material can be calculated from 3 measurements (baseline. Cp ( sapphire ) Belgium February 2009 29 E. Post/NETZSCH .

to obtain stable start conditions. Belgium February 2009 30 E. Post/NETZSCH .Calculation of the specific heat (Ratio Method) Isothermal segment of about 5-10 min.

• • • • Belgium February 2009 31 E. reference crucible stays empty The crucibles should have during the 3 measurements the same positions (for example mark with the tweezers).Calculation of specific heat • All 3 measurements have to be performed with the same crucibles and the same conditions Only sample crucible will be filled. Cp values are only valid when no weight loss occurs. Post/NETZSCH . Switch off the STC.

Calculation of specific heat sample sapphire Specific heat Belgium February 2009 32 E. Post/NETZSCH .

Post/NETZSCH . /° C 150 dynamic 100 isothermal 10 20 30 Time /min 40 isothermal 50 0 ASTM E 1269 : Test method for determining specific heat capacity by differential scanning calorimetry Belgium February 2009 33 E.10 0.20 0.Specific Heat Capacity of Sapphire DSC /(mW/mg) ↓ exo 0.05 0.00 -0.05 -0.15 0.10 50 Temp.

12 0.06 0.Specific Heat Capacity of Sapphire DSC /(mW/mg) ↓ exo 0.10 0.00 0 20 40 60 80 100 120 Temperature /° C 140 160 0.5 DSC signal sapphire 1 DSC signal sapphire 2 literature values of the temperature dependent change of the specific heat capacity of sapphire 1. Post/NETZSCH .04 0.08 0.16 0.0 Belgium February 2009 34 E.0 1.0 measured values of the temperature dependent change of the specific heat capacity of sapphire 0.02 0.5 Cp /(J/(g*K)) 2.14 0.

Specific Heat of stab.9000 0. The specific heat measured with the DSC is close (less than 3% ) to the literature values for such materials.0 600.6000 0. Zirconia Sample weight: 127.0 1200.0 1400.0 Stab.4000 0.3000 200.0 Temperature /° C 1000. Post/NETZSCH .0 800.8000 Sample: Stab. zirconia is a ceramic material often used for industrial applications such as thermal barrier coating or electrolyte material.07 mg Crucibles Pt + lids Heating rate: 20 K/min Atmosphere: Argon Sensor: DSC-cp type S 0.5000 0.0 400. Belgium February 2009 35 E.0000 0. Zirconia Cp /(J/(g*K)) 1.7000 0.

Q PR ∆T . DSC applied simultaneously to the same sample.Simultaneous Thermal Analysis (STA) Furnace Sample Refer. TG Thermogravimetry + DSC Differential Scanning Calorimetry = STA TG. Belgium February 2009 36 E. Post/NETZSCH .

Direct comparison of TG and DSC possible (same measurement conditions on exactly the same sample) Exact determination of enthalpy changes (sample mass continuously monitored) Belgium February 2009 37 E. Post/NETZSCH .Advantages of STA TG and DSC are applied simultaneously to the same sample! Time effective! Also (expensive) sample material can be saved.

Exchangable Furnaces Automatic Sample Changer (ASC) Double furnace hoist Exchangable Sample Carriers (TG. Post/NETZSCH . ...) Various Crucibles and Accessories Flexible Temperature Program (-150.2000° C) Different Gas Atmospheres Coupling with MS and/or FTIR Belgium February 2009 38 E. TG-DSC...

Ni.4 ml Materials: Al2O3. Pt/Rh. TG-DTA.Various Crucibles (I) Various Crucibles for TG. Pt/Ir. Post/NETZSCH . TG-DSC (STA) (also TG-plate. ZrO2. steel Belgium February 2009 39 E. Cu. graphite. TG-basket) Volumes: 40µl … 3. Ag. Al Au.

Post/NETZSCH .STA Interchangeable Sensors Belgium February 2009 40 E.

Post/NETZSCH . robust) Chimney effect! (sensor contamination avoided. less purge gas required which is good for EGA) Vacuum tight for defined atmospheres! Belgium February 2009 41 E.Schematics (A) Toploading design! (easy handling.

23 % MnO2 -> Mn2O3 619.14 mg crucible: Pt atm.: Synth.2 ° C 1200.1 J/g 92 179. air flow rate: 70 ml/min heating rate: 20 K/min DSC /(mW/mg) ↓ exo 6 4 Solid state phase transition 96 Sample: MnO2 -9.83 J/g 1147.7 ° C 2 94 71.Inorganic Application: MnO2 TG /% 102 evaporation of humidity 100 -0.8 ° C -3.20 % 958.45 J/g 432.7 J/g Mn2O3 -> Mn3O4 0 -71. Post/NETZSCH .1 ° C 98 STA 449 Jupiter Sample: MnO2 mass: 32.07 % -2 90 88 cooling -4 86 200 400 600 800 Temperatur /°C 1000 1200 1400 Belgium February 2009 42 E.

STA measurement of Fe2O3 3Fe2O3 2Fe3O4+1/2O2 Belgium February 2009 43 E. Post/NETZSCH .

Post/NETZSCH .A very short excourse about the influence of measurement parameters Belgium February 2009 44 E.

Hexatriacontane Belgium February 2009 45 E. Post/NETZSCH .

12 mg Cruciblel: Al2O3 Atmosphere: syn.20 1.0 Belgium February 2009 46 E.0 1. Post/NETZSCH .81 % 70 60 -29. 30 ml/min Heating rate: 10 K/min -12.0 0.Calciumoxalat Monohydrate Instrument: TG 209 Iris Sample mass: 10.0 -2.0 2.0 50 40 30 100 200 300 400 500 600 700 Temperature /°C 800 900 0.48 % -1.0 0.0 -5.0 0 0 0.0 -3.15 -1.0 -3.0 -2.05 % TG /% 100 90 80 DTG /(%/min) c-DTA /K Gram Schmidt ↓ exo 3.05 0 -6. air.Gas atmosphere .0 -4.10 -18.

47 % 200 300 400 500 600 Temperature /° C 700 800 900 Belgium February 2009 47 E.96 % -18.Gas atmosphere .32 % -12.01 % 80 synthetische Luft 70 60 50 40 30 100 Synthetic air Nitrogen -18. Post/NETZSCH .78 % -30.06 % -29.Calciumoxalat Monohydrate TG /% 100 90 Stickstoff -12.

0 -30.0 0 -4.0 0. Post/NETZSCH .10 3.Calciumoxalat Monohydrate Instrument: TG 209 Iris Sample mass: 9.02 % -1.02 % -2.0 0.06 1.0 0.84 mg Crucible: Al2O3 Atmosphere: N2.Gas atmosphere . 30 ml/min Heating rate: 10 K/min TG /% DTG /(%/min) c-DTA /K Gram Schmidt ↓ exo 1.0 -19.02 50 40 100 200 300 400 500 600 700 Temperature /°C 800 900 -1.0 0 Belgium February 2009 48 E.0 0 100 90 80 70 60 -12.04 -3.32 % 0.0 0.08 2.

Gas atmosphere - Calciumoxalat Monohydrate

CaC 2 O 4 ∗ H 2 O ≈ 150°C → CaC 2 O 4 + H 2 O 

CaC 2 O 4 ≈ 500° C → CaCO 3 + CO 
CO +
1 ≈ 500° C O 2  → CO 2 2

CaCO 3 ≈ 750° C → CaO + CO 2 

Belgium February 2009 49 E. Post/NETZSCH

Gypsum (CaSO4 - Dihydrate) - Pt-Crucibles

Sample: CaSO104 Sample mass: 38.68 mg Crucibles: Pt+lids Heating rate: 20 K/min Atmosphere: Air Sensor: TG/DSC type S

Belgium February 2009 50 E. Post/NETZSCH

Gypsum (CaSO4 - Mixture) - Al-Crucibles (with 50 micron hole)

Sample: Sample mass: Crucibles: Heating rate: Atmosphere: Sensor:

CaSO4 ≈ 12 mg Closed Al 30 K/min Air TG/DSC type S

Self-generated water vapor
Belgium February 2009 51 E. Post/NETZSCH

Post/NETZSCH .Coupling with MS and/or FTIR STA-MS-FTIR STA-FTIR STA-MS Belgium February 2009 52 E.

9 ° C 3.58 mg crucible: Pt atm.7 ° C -2 0. 1.Fe(OH)SO4 TG /% 100 DSC /(mW/mg) Ion Current *10-9 /A ↓ exo -2.00 0 1.50 4 Probe: Fe(OH)SO4 562.46 % 4.50 30 100 200 300 400 500 600 Temperature /°C 700 800 900 0 1000 -4 Belgium February 2009 53 E. Post/NETZSCH .48 % 70 Ferrofluid 2 2.50 60 246 J/g 1170 J/g 2.31 % 90 80 STA 449 Jupiter Sample: Fe(OH)SO4 mass: 30.: N2 flow rate: 70 ml/min heating rate: 20 K/min 6 750.00 -45.9 ° C amu 18 H2O amu 32 O2 amu 64 SO2 40 This material is a possible precursor for the production of iron oxide particles.50 -4.00 759.00 3.3 ° C 4.50 50 567.

EGA methods combined with TGA MS FTIR GC-MS GC-FTIR Mass Spectrometry Fourier Transform Infrared Spectroscopy Gas Chromatography with MS GC with FTIR Belgium February 2009 54 E. Post/NETZSCH .

Mass Spectrometer Couplings Most common mass spectrometer types which are used for TGA coupling are Quadrupol Mass Spectrometer Belgium February 2009 55 E. Post/NETZSCH .

Post/NETZSCH .Quadrupol Mass Spectrometer (QMS) + - electrons cathode evolved gas inlet ion source detector Principle of Function Belgium February 2009 56 E.

Post/NETZSCH .Ionization (II) Molecule fragments ABC + eABC+ + 2eAB+C+ + 2eAB+ + C + 2eA + BC+ + 2eA+ + BC + 2eAC+ + B + 2eAC + B+ + 2ered = ionized blue = neutral Belgium February 2009 57 E.

2% = 1. Post/NETZSCH .Ionization (III) CO2 spectra of the 11 most intense fragments Natural Abundancies 18O = 0.1% 13C Belgium February 2009 58 E.

Post/NETZSCH .Gas flow in the STA furnace Belgium February 2009 59 E.

.98 mg temp.. 960°C HR 10 K/min Air. 80 ml/min Belgium February 2009 60 E. Post/NETZSCH . 25 .Hydromagnesite (STA-MS Capillary) mass 25.

.STA 409 C/5 Skimmer Belgium February 2009 RT.. Post/NETZSCH ..2000° C (1550° C) 61 E.

Skimmer Pressure Reduction Steps divergent nozzle Sample chamber molecule cloud Belgium February 2009 62 E. Post/NETZSCH .

Skimmer Coupling 10 mbar -5 Q uadrupol analyzer Ion s ource 10-1 mbar S kimmer O rifice S ample 1013 mbar H eater S ample carrier Belgium February 2009 63 G overflow as E. Post/NETZSCH .

08 mg temp. Post/NETZSCH .. 75 ml/min I2 Belgium February 2009 Impurities: Selenium excess..STA-MS Skimmer: CuGaSe2 mass 333. 1170°C HR 10 K/min He. Iodine 64 E. 10 .

Post/NETZSCH .STA – FTIR Coupling BRUKER TensorTM 27 STA 449 C Jupiter® Belgium February 2009 65 E.

5 to approx.TG-FTIR Coupling IR spectra Wave lengths 2. 15 micron Wave numbers 4000 to 600 cm-1 Change in Dipolmoment Nonsymmetrical Molecules Bending Change of Bonding Length Belgium February 2009 66 Streching Change of Bonding Angle E. Post/NETZSCH .

FTIR Principle Fixed Mirror Michelson Interferometer Principle Globar Sample Detector Beamsplitter Movable Mirror Interferogram Spectra Belgium February 2009 67 E. Post/NETZSCH .

Post/NETZSCH .FTIR Coupling System Thermocouple Adapter Thermocouple Transferline (230°C) Thermocouple Microfurnace Sample Sample carrier Outlet FTIR gas cell (230°C) TG Belgium February 2009 68 E.

Pyrolysis of PVC Belgium February 2009 69 E. Post/NETZSCH .

060 | NETZSCH TG 209 F1 | Z:\Commissions\823-xxx-06\006-3-06-TG209F1-FTIR-MS\006-3-06-12_PVC\006-3- Belgium February 2009 70 E.3 0.1 Absorbance Units 0.HCl emission during PVC pyrolysis 0.0 4000 0.2 0.0 10. Post/NETZSCH .5 3500 3000 2500 2000 Wavenumber cm-1 PVC 1500 1000 Y:\Commissions\823-xxx-06\006-3-06-TG209F1-FTIR-MS\006-3-06-12_PVC\006-3-06-12_PVC_308.0 P:\measurement\0_libspectra\HCl.4 0.

Post/NETZSCH .Thank you for your attention Belgium February 2009 71 E.

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