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# Thermal Analysis

SSK 4242

Thermogravimetry (TG)

1. Isothermal Thermogravimetry
2. Quasi-isothermal Thermogravimetry
3. Thermogravimetry dynamic

T3 > T2 > T1

Isothermal Thermogravimetry
The sample is heated at a T3

constant temperature, and the Mass change
T2
mass change is monitored
T1

Time

Lecture 3 4-Nov-04 1

Thermal Analysis SSK 4242 Quasi-isothermal Thermogravimetry f g The temperature is programmed as Mass Mass follows: i) raised to a level (a – b) h i ii) maintained at a constant temperature (b – c) c d iii) raised again to a final value (c – d) a b Temperature Time Thermogravimetry Dynamic Mass The temperature is raised continuously at a constant rate and the mass change is monitored continuously Temperature Lecture 3 4-Nov-04 2 .

and it is more convenient to use the Derivative Thermogravimetry (DTG) method. Thermal Analysis SSK 4242 Characteristics of a Thermogravimetry (TG) A(s) B(s) + C(g) A(solid) Ti = initial temperature (or Tf procedural decomposition Ti temperature) Mass Tf = final temperature ( mass change is maximum/ B(solid) the reaction is completed Tf . Lecture 3 4-Nov-04 3 .Ti = reaction temperature range Temperature The Use of a TG Thermogram:  To determine the stages of decomposition.  To determine the temperature range and the fraction of mass loss if each reaction can sufficiently be separated. Determination of the resolution of two closely consecutive reaction on a TGA curve is difficult.

Derivative Thermogravimetry (DTG) is a plot of the rate of mass change per unit time (dm/dt) versus temperature or time. TG curve DTG curve Lecture 3 4-Nov-04 4 . Thermal Analysis SSK 4242 Definition of Thermogravimetric Analysis Thermogravimetric Analysis (TGA) is a technique where the mass change of a sample is monitored versus time or temperature while the sample temperature is programmed under certain atmosphere.

This method is with the atmosphere during the useful in the study of thermal heating process. Thermal Analysis SSK 4242 Thermogravimetric Process When a sample is heated. it will undergo some changes:  It may decompose and liberates gas. Lecture 3 4-Nov-04 5 .  The decomposition reaction takes place parallel to the temperature rise The TGA Curve … is a graphical representation of the thermo reaction where the slope represents mass loss and returns to horizontal line when the mass is back to constant. an increase in The isothermal measurement gives mass may be observed if the relationship between the mass sample reacts and combines change and time. In some cases. or other volatile compounds and the mass is reduced. Mass loss takes place within a temperature range. decomposition reaction kinetics.

i. the material is not stable towards heat. and then reduces to show that during the heat treatment. vi) Continuously increasing mass of the sample to show that the sample reacts with the atmosphere while undergoing heat treatment vii) The mass of the sample increases. Lecture 3 4-Nov-04 6 .e. Thermal Analysis SSK 4242 Various Thermogravimetric Curves (i) Horizontal line indicates that the sample is inert and stable towards heat treatment ii) The curve begins with a decrease in temperature to indicate loss of water molecules (drying) iii) Two horizontal lines to show that the sample losses mass in a small range of temperature and then become stable iv) The curve has several horizontal lines to show several reactions have taken place v) The curve slopes continuously to show that the sample losses mass continuously. the sample reacts with the atmosphere but the product is not stable towards heat.

The TGA instruments should consist of the following components:  Thermo-balance and its control system  Furnace and the temperature sensor  Temperature programmer and computer  Recorder. 1600 or 2400 oC.01 %. TGA instruments have a large operational temperature range of -20 oC to 1000. •Measurement of temperature: 1 % or better Lecture 3 4-Nov-04 7 . Thermal Analysis SSK 4242 Thermogravimetric Instrumentation Combination of a thermo-balance or an electronic microbalance and the temperature programmer. or data collection device • Sensitivity of a thermo-balance is around 1 µg • Maximum load of the thermo-balance is around 1 g. Measurements precision: •Measurement of mass loss: 0.

(a) and (c) Hanging (b) Top loading (d) Horizontal The magnet position for the purpose of Curie point determination is shown in (c) Lecture 3 4-Nov-04 8 . Thermal Analysis SSK 4242 The choice of positioning the sample holder in a thermal analytical balance.

Lecture 3 4-Nov-04 9 . Avoid using corrosive gasses. Such an effect is also called “buoyancy effect”. As an example. When the min free movement is comparable to the instrumental dimensions. • Thermomolecular Flow Thermomolecular flow takes place when the thermo-balance is used at a very low pressure and there is a temperature gradient around the sample or the support system. Normally an inert gas such as N2 or Ar is used. the molecular flow of the atmospheric gas will cause an “apparent mass change”. Thermal Analysis SSK 4242 • Physical effects due to usage of the thermo-balance:  radiation  convection current  magnetic effect due to the heating of the furnace • To avoid/minimise such effects:  Separate/protect the balance from the physical effects  Place the measuring device in a different atmosphere • Interpretation of data from the analyte samples may be assisted by the understanding of the effects of various atmosphere used on the thermal events. with a temperature difference of 100 K and pressure of 10-1 torr. the thermomolecular flow effect may cause an increase to 100 g of apparent mass change.

314 J/(K mol). it will experience upward force that is equivalent to the weight of the displaced liquid of the same volume of the immersed part of the body. measured mass.8 mg when the by the sample and the temperature changed from 300 K to sample seemed to have an 1000 K.8 mg.028 kg). Thermal Analysis SSK 4242 Buoyancy Effect • Buoyancy effect becomes apparent when the sample size is very large. Lecture 3 4-Nov-04 10 . the buoyancy will upward force experienced change abour 0. the mass (m) of ideal gas with molar mass M that is displaced at temperature T is: m = MpV/RT • When a sample is heated. Mass of the sample will be apparent increase in the apparently increased by 0. If the molar gas constant R reduction in the Archimedes is 8. If the sample volume and the sample holder is V m3 and the pressure p Pa. Example: the atmospheric gas density The volume of a sample and crucible is reduces at a greater extent 1 cm3 or 10-6 m3 at an atmospheric than that of the solid pressure of about 105 Pa gas N2 ( M = sample. • This phenomena may be explained by the Archimedes principle which states that when a body is immersed in a liquid. This leads to 0.

8 x 10-3 cm3 that is equivalent to 10 mg MgO. Lecture 3 4-Nov-04 11 .  If the twin furnace (Figure on Twin Furnace) is used where the volumes of the sample and the crucible on bothsides of the balance are the same. the buoyancy effect will cancelled each other. Thermal Analysis SSK 4242 Ways To Overcome The Buoyancy Effect  Run the experiment on the “blank” buoyancy by using an inert sample with the same volume as the real sample  The use of very small sample and crucible will reduce the effect of buoyancy  If the volume is reduced to 2. the sample mass appeared to increase as much as 2.2 mg.

particularly when involves samples with low heat conductivity such as polymer or inorganic glass Lecture 3 4-Nov-04 12 . Thermal Analysis SSK 4242 Furnace System a) Heating with Electrical Resistance • Can be located inside or outside of the furnace cage • Fulfill the following requirements  Non-inductive heating coil  Can raise the temperature between 100 – 200 oC higher than the desired working temperature  It has a relatively long uniformly hot zone  Rapidly reach the desired initial temperature (low heat capacity)  Does not give any effect on the balance mechanism either through heat radiation or convection. The transfer of heat into the balance should be avoided by placing a shield or an heat insulator  Heating the sample by conduction of heat through the solid or gas  Large heat gradient is unavoidable.

for example under a low pressure (< 10-4 Pa) to a high pressure (> 3000 kPa). by using infra-red or microwave. Lecture 3 4-Nov-04 13 .  Thermal balance is normally placed in a metal or glass cage to enable operation in various conditions. Thermal Analysis SSK 4242 Furnace System (Cont’d) b) Heating by using radiation  Heating may also be done by using radiation. the micro- balance frequently has buoyancy effect due to lack of symmetry in the weighing system. especially at higher temperature. Besides. oxidising or corrosive gas. correction is needed. in an inert.

the atmosphere used may be static or dynamic Dynamic atmosphere has several advantages:  Reduce condensation of reaction products on any cooler parts of the thermo balance  Remove any corrosive products  Reduce the possibility of secondary reactions  Acts as coolant for the thermal system Lecture 3 4-Nov-04 14 . Thermal Analysis SSK 4242 Atmosphere Under atmospheric pressure.

but causes a shift of the zero setting  Noise is also increased when the cross section of the hanging tube becomes bigger  The problems of noise may be reduced by introducing baffles into the balance tube. See Figures 10 & 11 Lecture 3 4-Nov-04 15 . Thermal Analysis SSK 4242 Noise  Noise is a problem in trace TGA under pressure > 20 kPa  Noise increases when temperature is increased due to thermal convection  Noise is more dominant when higher density carrier gas is used under high pressure in the region of high temperature gradient  Change in the rate of gas flow does not significantly change the effect of noise.

Ts. and Ts cannot easily be measure without disturbing the weighing process.  Measurement of the temperature is usually carried out by using a thermocouple. TF. is normally lagged behind (due to thermal lag) compared to the temperature of the furnace.  Calibration of the temperature is done by using the Curie Point of several metal standards (Curie Point: Figure 3_12 & 13). Thermal Analysis SSK 4242 Measurement and Temperature Calibration  The sample temperature.Ts may reach 30 oC depends on the operational conditions. The difference of TF . Lecture 3 4-Nov-04 16 . A separate thermocouple should be used to measure the sample temperature and the temperature of the furnace. respectively.

Lecture 3 4-Nov-04 17 . the magnetic pulling force diminishes and the sample appears to be loosing weight.13). at temperatures below the Curie Point.  At the Curie point.  By using ferromagnetic materials. Thermal Analysis SSK 4242 Curie Point  Curie Point is a temperature where a ferromagnetic material losses its magnetism while undergoing heat treatment.  If a magnet is placed under the ferromagnetic material. the total force that pulls down the sample is a combination of weight of the sample and the magnetic pulling force. various temperature calibration can be made because Curie Point is a characteristic of each metal or steel standard (Figure 3.

An example of thermogravimetric analysis parameters that are commonly used are as follows: Sample : Calcium oxalate monohidrate Crucible : Platinum disc Heating rate : 10 K/min Atmosphere : Nitrogen. homogeneous  It is better to use small sample size since large sample may have differences among various areas of the same sample. 20 cm3/min Mass : 10. Lecture 3 4-Nov-04 18 .  Small sample size (homogeneous.5 g. powder) and placed evenly in the crucible. Thermal Analysis SSK 4242 Sample and the Sample Holder  Solid materials  Sample selection  Pure materials.

Thermal Analysis SSK 4242 Examples of TGA Crucibles/Sample holders Example of a TGA system (Figure 3_14&15) Lecture 3 4-Nov-04 19 .