Thermogravimetry

 TG: measuring mass change of a sample with temperature.

 A sample to be measured is placed in a furnace and its mass change is monitored by a

thermobalance.

 The main application: to analyze material decomposition and thermal stability through
mass change as a function of temperature in scanning mode or as a function of time in the
isothermal mode.

 TG curves are plotted as mass change expressed in percent versus temperature or time.

Figure 10.19 Thermogravimetric curves that exhibit decomposition

starting temperature Ti and finish temperature Tf.
Instrumentation

The TG includes a microbalance, furnace, temperature programmer, and computer.

The key component is the microbalance, which measures the mass change. A typical
microbalance is able to measure mass change of ±1 g with maximum mass of 100 mg.

A commonly used microbalance is the null-point type. The null-point microbalance

can maintain the sample in a vertical position when its mass changes.

Figure 10.21 Structure of a Cahn microbalance with

capability to measure the mass loss of a sample without the
sample moving downward.
Experimental Aspects

Samples

 Sample mass, volume, and form are important for recording accurate and reproducible TG
curves. Reliable TG curves rely on minimization of deviation between sample temperature
and programmed temperature.
 Small sample mass is better than large mass for minimizing temperature deviation. TG
sample mass is usually about several milligrams.

 Samples can be in block, flake, fiber, or powder form. Sample form is the second most
important parameter affecting TG curves.

Figure 10.23 Effects of sample form on TG curve of a polymethyl

methacrylate (PMMA) sample. Experimental conditions: 5 mg PMMA
and a heating rate of 5 K min−1.
Atmosphere

 TA can be run in either a reactive or nonreactive atmosphere.

 Reactive atmospheres include corrosive, oxidizing, and reducing gases.

 Nonreactive atmospheres should be an inert gas with little water vapor. Dry Ar and N 2 are
commonly used for nonreactive atmospheres.

 Gas flows through the furnace tube around the sample and carries volatile products out. A
flow rate of 15–25 ml min-1 is recommended for a sample mass of about 2–10 mg.

Temperature Calibration

 Temperature calibration is more complicated in TG instruments than in other

types of TA instruments because the thermocouple junction cannot touch either
the sample or sample holder. Good TA results can only be ensured with careful
temperature calibration.

 A Curie point method has been used to calibrate the temperature of TG instruments.
Figure 10.25 (a–c) The Curie point method for temperature
calibration.
Heating Rate

 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.

 The temperature range from start to finish will be wider at a higher heating rate than
a lower heating rate.

 There are two reasons for heating-rate effects. First, a high heating rate is more likely to
generate a temperature difference between the sample and thermocouple junction. Secondly,
in decomposition with volatile products, it takes time for those products to diffuse out of the
sample and to be carried away by flowing gas.

 A low heating rate is more likely to generate thermal equilibrium and give a reproducible
result for the analysis. A heating rate of about 5–100 C min-1 is recommended for TG
examination.
Interpretation of Thermogravimetric Curves

Types of Curves
TG curves can be classified into seven types:

(i) no decomposition with mass loss of volatile products

over the temperature range.
(ii) rapid mass loss at the initial stage of a TA curve. (the
sample has gone through drying or desorption)
(iii) one-stage decomposition curve (the stability limit of a
sample)
(iv) curve of multistage decomposition with stable
intermediates.
(v) curve of multistage decomposition, but there is no
stable intermediate.
(vi) indicates that a chemical reaction with mass gain
has occurred in the sample (typical example is
oxidation of metal samples).
(vii) indicates a mass-gain reaction occurs and then a
mass-loss reaction occurs at a higher temperature in
the sample, which is rarely seen.
A slope change of a TG curve is the main feature used to analyze a sample.
Sometimes, the slope change is uncertain; in this case, a derivative thermogravimetry
(DTG) curve can be used.

Figure 10.28 Schematic comparison of (a) TG curves and (b)

corresponding DTG curve
Temperature Determination

The determination of characteristic temperatures in TG curves is similar to that in DTA and

DSC curves. As illustrated in Figure 10.29, the temperature at which decomposition starts is
defined as the intersection of initial line tangent and
tangent of line portion when the slope changed. The finishing temperature of
decomposition is defined in a similar manner, as shown in Figure 10.29. A
midpoint temperature between the starting and finishing temperature can be
defined as TB.

Figure 10.29 Temperature determination from a single-stage

TG curve
Applications

The TG technique is simple but effective for assessing thermal stability and chemical
reactions by monitoring mass change in materials.

Figure: TG curves of CuSO4·5H2O in a range of ambient

temperature to 5000C.
TG curves do not always show obvious decomposition temperatures

It is often desirable to plot DTG curves with TG curves to reveal the decomposition
temperatures of polymers.

Figure 10.31 TG and DTG curves of a natural

rubber–butadiene rubber blend.

TG curves can also be used for quantifying

compositions of composites containing thermally Figure 10.32 TG curves of hydroxyapatite (HA)–ultrahigh
molecular weight polyethylene (UHMWPE) composites with
decomposable components. different content HA particles.
 ST
Time 5 min

1. Why small mass of sample for TG analysis is

preferred ? (3)

2. Name a method to be applied for the calibration of a

TG instrument. (2)

3. What are the effects of heating rate on TG curve? (3)

4. How you will identify the temperature if slop change

in a TG curve is uncertain ? (2)