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授課教師: Professor 吳逸謨 教授

Do not use outside class.

Principles of Instrumental
Analysis
Section Six
Miscellaneous Methods p. 893
Chapter 31
Thermal Methods
Contents: TGA, DTA, DSC
Time: 3 hrs (1 week) 1
 Miscellaneous Methods
Chap. 31 Thermal Methods DSC, DTA, TGA

The following Chapters are not covered:

• Chap. 32 Radiochemical
• Chap. 33 Automated analyses
• Chap. 34 Particles size determination

Laboratory items – 下學期實驗課

DSC – Differential scanning calorimeter

[Note: DTA is similar to DSC. DTA is less often used now.]

TGA (2008購) – Thermogravimetric analyzer

2
 Chapter 31 Thermal Analysis p.894

Thermal Analysis – Definition

Techniques in which a physical (thermal) property of a
substance is measured as a function of temperature while
the substance is subjected to a controlled temperature
variation.

More than a dozen of such thermal techniques are used.

But only three techniques are covered in this chapter:
1. Thermogravimetry analysis (TGA)
2. Differential thermal analysis (DTA)
3. Differential scanning calorimetry (DSC)
3
TGA p. 894
The mass of a sample in a controlled atmosphere is recorded
continuously as a function of temperature (or time) as the temperature
of the sample is increased.

TGA thermogram:
- A plot of mass percent as a function of time or temperature.
[TGA measures the change in weight of a sample as it is heated, cooled or
held at constant (isothermal) temperature.]
Instrumentation of TGA includes the following:
(1) A sensitive analytical balance
Range : up to 100 mg.
Sample holder is in furnace. However, the rest of the balance must be thermally
isolated from the furnace.
(2) furnace
Temperature range: up to 1500oC.
(3) purge gas system
For prevention of oxidation: N2, Ar, He, etc.
For oxidation: O2 or air.
(4) Temperature control and a computer for data acquisition /display.
4
FIGURE 31-1. Thermobalance components. The balance beam is shown as
A. The sample cup and holder are B; C is a counterweight. D is a lamp and
photodiodes, E is a magnetic coil, and F is a permanent magnet. The
computer data-acquisition, data-processing, and control systems are
components G, H, and I. Component J is the printer and display unit.
5

Ch31 Thermal Methods P.895

儀分實驗儀器 (2008/11)
[Perkin-Elmer TGA-6]
上承載式 (Top-loading)
Cross section: Oven/heater for heating,
ceramic rod/pan, and balance.

6
 Different type of TGA:
TA Q500 TGA
懸吊式

The TGA instrument continuously weighs a sample as it is

heated to temperatures of up to 2000 °C for coupling with FTIR
and Mass spectrometry gas analysis.

7
TGA can provide information about physical phenomena, such as second-
order phase transitions, including vaporization, sublimation, absorption,
adsorption, and desorption.

Likewise, TGA can provide information about chemical phenomena including

chemisorptions, desolvation (especially dehydration), decomposition, and
solid-gas reactions (e.g., oxidation or reduction).[1]

TGA is commonly used to determine selected characteristics of materials that

exhibit either mass loss or gain due to decomposition, oxidation, or loss of
volatiles (such as moisture).

Common applications of TGA are:

(1) materials characterization through analysis of characteristic decomposition
patterns,
(2) studies of degradation mechanisms and reaction kinetics,
(3) determination of organic content in a sample, and
(4) determination of inorganic (e.g. ash) content in a sample, which may be
useful for corroborating predicted material structures or simply used as a
chemical analysis. 8
PHB90-scPLA 新購儀分實驗儀器 (2008/11) – TGA thermograms

PHepT

9
FIGURE 31-2 Controlled atmospheric thermogram for a bituminous coal
sample (containing various hydrocarbons - bitumen).
A nitrogen atmosphere was used for about 18 min followed by an oxygen
atmosphere for 4 to 5 min. The experiment was then completed in nitrogen.
10

Ch31 Thermal Methods P.895

31A-2 Applications of TGA:
Decomposition /oxidation reactions in materials.
Physical processes: vaporization, sublimation, desorption, etc., in
materials.
Decomposition mechanisms/physical processes in polymers.
Typical applications for TGA include:
• Solvent
• Moisture
• Polymer/resin
• Filler
• Ash
• Glass
• Carbon black
• Evaluation of stabilizers
• Loss on drying
• Proximate analysis
• Lubricating oil analysis
• Oxidation studies
 All above materials upon heating will involve mass changes, which can be
recorded as TGA thermograms for analysis. 11
 Thermal stability
TGA can be used to evaluate the thermal stability of a material. In a
desired temperature range, if a species is thermally stable, there will be no
observed mass change.
Negligible mass loss corresponds to little or no slope in the TGA trace.
TGA also gives the upper use temperature of a material. Beyond this
temperature the material will begin to degrade.

High performance fibers can be compared using TGA as an evaluation of

thermal stability.

From the TGA, polyoxazole (PBO) has the highest thermal stability of the four
fibers as it is stable up to ca. 500 °C.

Ultra-high-molecular-weight polyethylene (UHMW-PE) has the lowest thermal

stability, as it begins to degrade around 200 °C.

12
FIGURE 31-3 TGA Thermograms for some common polymeric materials.

PVC = polyvinyl chloride; PMMA = polymethyl-methacrylate; LDPE

= low-density polyethylene; PFE = polytetrafluoroethylene; Pl = aromatic
polypyromelitimide.
13

Ch31 Thermal Methods P.896

FIGURE 31-4 Thermogravimetric determination of carbon black
in polyethylene. 14

Ch31 Thermal Methods P.897

FIGURE 31-5. Thermogram for decomposition of
CaC2O4‧H2O in an inert atmosphere.
15

Ch31 Thermal Methods P.897

FIGURE 31-6 Decomposition of CaC2O4‧H2O, SrC2O4‧H2O,
and BaC2O4‧H2O.
(b) Derivative curve shows the rate of mass changes. 16

Ch31 Thermal Methods P.898

31B. Differential Thermal Analysis (DTA) p.897

31B-1 Instrumentation
31B-2 General principles
31B-3 Applications
DTA
- A technique in which the difference in
temperatures between a substance and a reference
material is measured as a function of temperature
while the substance and reference material are
subjected to a controlled temperature program.

17
In today’s market most manufactures no longer make a true DTA but rather
have incorporated this technology into a Thermogravimetric analysis (TGA),
which provides both mass loss and thermal information. TGA-DTA
With today’s advancements in software, even these instruments are being
replaced by true TGA-DSC instruments that can provide the temperature and
heat flow of the sample, simultaneously with mass loss.

TGA-DTA

18
 31B-3 Applications – DTA p. 899

As suggested in Figure 31-7, DTA peaks result

from both physical changes and chemical reactions
induced by temperature changes in the sample.
Physical processes that are endothermic include
fusion, vaporization, sublimation, absorption, and
desorption. Adsorption and crystallization are
generally exothermic.
Chemical reactions may also be exothermic or
endothermic.
Endothermic reactions include dehydration,
reduction in a gaseous atmosphere, and
decomposition.
Exothermic reactions include oxidation in air or
oxygen, polymerization, and catalytic reactions.
19
DTA thermogram –
showing Tg, Tc, Tm,
oxidation, decomposition,
etc.

Peak areas:
A = -k G mΔH
= -k’ mΔH

where
k: thermal conductivity
G: calibration const.
m: mass of reference

FIGURE 31-7 Differential thermogram (DTA) showing types of

changes encountered with polymeric materials.

20

Ch31 Thermal Methods P.898

 31B-3 Applications - DTA

• In general, DTA is considered a qualitative technique.

 Although able to measure the temperatures at which various
changes occur, DTA is unable to measure the energy
associated with each event.
• DTA is a widely used tool for studying and characterizing
polymers (or metals and ceramic materials, etc).
• Figure 31-7 illustrates the types of physical and chemical
changes in polymeric materials that can be studied by
differential thermal methods.
• Note that thermal transitions for a polymer often take place
over an extended temperature range because even a pure
polymer is a mixture of homologs (similar structures) and not a
single chemical species.
21
Instrumentation of DTA P.

-Furnace (to 1500oC)

-Thermocouples
-Purge gas system
FIGURE 31-8
Schematic diagram of
a typical instrument for
DTA. TC = thermocouple.

Sample size: 1~20 mg

Reference: inert materials
(e.g., Al2O3 , SiC, glass, etc.)

Schematic diagram for DTA instrument

– see figure inset 22
 Applications – cont’d
• DTA is also widely used in the ceramics and
metals industry.
• The technique is capable of studying high
temperature processes (up to 2400oC for some
units) and relatively large sample sizes
(hundreds of milligrams).
• For such materials, DTA is used to study
decomposition temperatures, phase
transitions, melting, and crystallization
points, and thermal stability.
23
 Phase diagrams using DTA
• Phase diagrams – Sulfur (next page) An important use of
DTA is for the generation of phase diagrams and the study of
phase transitions.
• An example is shown in Figure 31-9, which is a differential
thermogram of sulfur, in which the peak at 113oC corresponds
to the solid-phase change from the rhombic to the monoclinic
form.
• The peak at 124oC corresponds to the melting point of the
element.
• Liquid sulfur is known to exist in at least three forms, and the
peak at 179oC apparently involves these transitions,
whereas the peak at 446oC corresponds to the boiling point of
sulfur.
24
 • Phase transitions in sulfur: p. 899
• 113oC: rhombic  monoclinic crystal form (Tcc).
• 124oC melting of monoclinic crystal form (Tm)
• 179oC: liquid liquid transform (Tll)
• 446oC: liquid vapor (vaporization temp.)

FIGURE 31-9 Differential thermograms (DTA) for sulfur. 25

Ch31 Thermal Methods P.900

 Applications – cont’d
• The DTA method also provides a simple and accurate
way of determining the melting, boiling, and
decomposition points of organic compounds.
• Generally, the data appear to be more consistent and
reproducible than those obtained with a hot stage or a
capillary tube.

• Figure 31-10 shows thermograms for benzoic acid at

atmospheric pressure (A) and at 13.79 bar (B). The
first peak corresponds to the melting point and the
second to the boiling point of the acid.

26
FIGURE 31-10 Differential thermogram (DTA) for benzoic acid.
Curve-A taken at atmospheric pressure. Curve-B taken at a pressure
of 13.79 bar (200 lbs/in.2). 27

Ch31 Thermal Methods P.900

DTA thermograms for glass samples
Lithium triborate glass (LBO) in the system (1-x)|3B2O3.Li2O| (x)Nb2O5 yPr3+
zYb3+ wNd3+ with 0 £ x £ 20 mol% (y, z and w in mol%).

Pr3+-doped LBO and Pr3+/Yb3+-doped LBO samples show an increase of the glass
transition and crystallization temperatures and a decrease of the fusion temperature
associated with the increase of the praseodymium (Pr3+) concentration in the 28
LBO matrix.
Post-note on DTA:
Applications
A DTA curve can be used only as a finger print for identification purposes but usually the
applications of this method are the determination of phase diagrams, heat change
measurements and decomposition in various atmospheres.

-DTA is widely used in the pharmaceutical and food industries

-DTA may be used in cement chemistry, mineralogical research and in

environmental studies.

-DTA curves may also be used to date bone remains or to study archaeological
materials.

In today’s market most manufactures no longer make a DTA but rather have
incorporated this technology into a Thermogravimetric analysis (TGA), which
provides both mass loss and thermal information. [as commented before]

With today’s advancements in software, even these instruments are being replaced
by true TGA-DSC instruments that can provide the temperature and heat flow of the
sample, simultaneously with mass loss.
29
31-C Differential Scanning Calorimetry (DSC) P. 900

DSC - A thermal technique in which the differences in heat

(energy or power) flow into a substance (sample) and a
reference (blank pan) are measured as a function of
temperature while the two are subjected to a controlled
temperature program (heating, cooling, etc.)
As discussed earlier, by comparison:
DTA (Differential Thermal Analysis) - A thermal technique
in which the difference in temperature between a substance
(sample) and a reference material (inert such as Al2O3
powder) is measured as a function of temperature while the
substance and reference material are subjected to a
controlled temperature program (heating, or cooling at
various different rates)
30
Summary: Differences between DTA and DSC: P.900

DTA and DSC are used in slightly different applications.

Of these two, DSC is more widely used.
DTA: differences between temperatures are recorded.
DSC: differences in energy (heat) are measured.
DTA: for qualitative thermal analysis.
DSC: for qualitative & quantitative thermal analysis.
(e.g., measurement of heat of transition, kinetic analysis, etc.)
DTA: designed for temperature range up to 1500oC. (for metals and
inorganic materials).
DSC: limited to temperature range up to 750oC (max). (for organics,
polymers, and low-melting metals)

31
 31C-1 Instrumentation – DSC P.900

• There are three different types of DSC

instruments:
• power-compensated DSC,
• heat-flux DSC, and
• modulated DSC (new but less used).
• Each produces a plot of power (heat flow)
versus temperature, called a DSC
thermogram.

32
31C-1 Instrumentation of DSC P.900

Type 1: Power-Compensated DSC Instruments

• In power-compensated DSC, the temperatures of the sample
and reference are kept equal to each other while both
temperatures are increased or decreased linearly.
• The power needed to maintain the sample temperature equal
to the reference temperature is measured.
-The sample and reference material are heated by separate heaters in
such way that their temperatures are kept equal while these
temperatures are decreased (or decreased) linearly.
-The power supplied to sample (or reference) in order to maintain the
same temperature is recorded.

33
Characteristics of power-compensated type DSC: p.900

a. Use of Pt resistance thermometer (not thermocouple).

-More precise, and better linearity in wide temp. range.
b. Separate furnaces (cells) for sample and reference:
- Two small furnaces (about 1 g each). One is for heating the
sample, while the other for heating the reference.
Demonstration – DSC Pt-furnace cell.
c. Capable of rapid cooling, heating, and equilibration of temperature
due to the design of small size of the furnaces.
- Platinum resistance thermometers, in contact with the
sample and reference holders, sense any difference between
the programmed temperature and the temperatures of the
sample and reference.
The error signal is used to adjust the power applied to the sample and the
power applied to the reference platinum resistance heaters.
- The DSC output signal is the difference in the power required
between the sample and the reference so that both equal the
programmed temperature. 34
FIGURE 31-11 Power-compensated DSC sample and reference holders
and heaters. A temperature program is generated by the computer system.
Platinum resistance thermometers, in contact with the sample and reference
holders, sense any difference between the programmed temperature and
the temperatures of the sample and reference. The error signal is used to
adjust the power applied to the sample and the power applied to the
reference platinum resistance heaters.

The DSC output signal is the difference in the power required between
the sample and the reference so that both equal the programmed 35
temperature. Ch31 Thermal Methods P.901
 Demonstration
- Pt furnace and sample holder in DSC
• Power-compensated DSC has lower
sensitivity than heat-flux DSC, but its
response time is more rapid.
• This makes power-compensated DSC well
suited for kinetics studies in which fast
equilibrations to new temperature settings are
needed.
• Power-compensated DSC is also capable of
higher resolution than heat-flux DSC.
36
 Type-2: Heat-Flux DSC Instruments p.901

• In heat-flux DSC, the difference in heat flow into the sample

and reference is measured while the sample temperature is
changed at a constant rate. Both sample and reference are
heated by a single heating unit.

• Heat flows into both the sample and reference material via an
electrically heated constantan thermoelectric disk, as shown
in Figure 31-12.

• Small aluminum sample and reference pans sit on raised

platforms on the constantan disk. Heat is transferred through
the disks and up into the material via the two pans.

• The differential heat flow to the sample and reference is

monitored by Chromel-constantan thermocouples formed by
the junction between the constantan platform and Chromel
disks attached to the underside of the platforms.
37
 Heat-flux DSC： p.901

- The sample and reference material are heated by the same heater in
such way that the difference in heat flow into the sample and
reference is measured as the sample temperature is increased (or
decreased) linearly.
- Use of Chromel*/Constantan* disk thermocouples (TC) to measure
the temperature difference between sample and reference.
- Heat flux is then calculated from the temp. difference by an equation:
ΔH = kΔT
where k = calibration const.
----------------------------------------------------------------------------------
*Note:
Constantan: alloy with 60 % copper and 40 % nickel.
Chromel: a series of alloys containing (chromium + nickel + iron).
----------------------------------------------------------------------------------

Note: Sometimes, “alumel” is used instead of “constantan”.

- Alumel is an alloy consisting of approximately 95% nickel, 2% manganese, 2%
aluminium and 1% silicon 38
 儀分實驗儀器 DSC [Perkin-Elmer DSC-6, Heat-flux type]

FIGURE 31-12 Heat-flux DSC.

39
A typical DSC curve is shown in Fig. 31-13.
There is an exothermic event at approximately 90℃ and
an endothermic event at 160℃. A glass transition (Tg)
is also evident in both cases, but no oxidation peak is found in the DSC curve
because the experiment was carried out in an atmosphere of nitrogen.

FIGURE 31-13 Typical DSC scan for a polymeric material. Note the step
transition at about 63℃ (Tg). 40

Ch31 Thermal Methods P.902

 Modulated DSC (MDSC) Instruments
• Modulated DSC (MDSC) uses the same heating and cell arrangement as
the heat-flux DSC method.
• In MDSC, a sinusoidal function is superimposed on the overall
temperature program to produce a micro heating and cooling cycle as
the overall temperature is steadily increased or decreased.
• Using Fourier transform methods, the overall signal is mathematically
de-convoluted into two parts, a reversing heat flow signal and a
nonreversing heat flow signal.
• The reversing heat flow signal is associated with the heat capacity
component of the thermogram, and the nonreversing heat flow is related
to kinetic processes.
• Usually, step transitions, such as the glass transition, appear only in the
reversing heat flow signal and exothermic or endothermic events may
appear in either or in both signals.
• [Note: MDSC became very popular about 10~15 years ago. But
popularity died down about 10 years ago. Gradually, it was less
used. Nowaday, it is almost no longer mentioned or used in the
literature.]
41
 Cont’d - Modulated DSC
• A plot showing the decomposition of the total heat flow
signal into reversing and nonreversing components is
shown in Figure 31-14.
• Note that the transition near 60oC appears in the reversing
heat flow component associated with the heat capacity part
of the total heat flow. The endothermic process near 250oC
also appears in the reversing component, and the
exothermic event near 150oC appears in the nonreversing
component.

FIGURE 31-14
Deconvoluted
thermogram
from an MDSC
apparatus

42
DSC experiment, DSC calibration, DSC analysis p. 903
Experiment
• Sample pan – aluminum, gold, glass, carbon, etc.
• Aluminum pan is most often used (up to 600oC) [Al
melts at ~650oC].
• Sample is weighed and sealed with a cover.
• Purge gases – nitrogen or helium.
Calibration:
• Baseline calibration and subtraction
• Heat flow calibration: Indium
• Heat capacity calibration: sapphire
43
DSC data analysis: Figure 31-15 shows: A glass transition (Tg).
Onset temperature of an endothermic event. Note how thermal transition
temperatures are read from a DSC thermogram.

FIGURE 31-15 Determination of onset temperatures for a

transition and an exothermic event (crystallization). 44

Ch31 Thermal Methods P.903

31C-2. Applications of DSC p. 904

-Determination of transition temperatures (Tg, Tm, Tc, etc.),

and the energies involved in the transitions.
Heat of fusion, extents of crystallization, etc.
Glass transition and melting temperatures.

-Kinetics studies (isothermal experiments）

Crystallinity and crystallization rates
Reaction kinetics

-Determination of purity in compounds – by measuring Tm

45
Applications of thermal methods
Reference books for thermal analysis techniques:
- There are many other applications to materials of
thermal analysis based on DSC (or DTA).
A good reference book:
“Thermal Characterization of Polymeric Materials”,
Ed. E.A. Turi, 1981, Academic Press.

46
 31-D. Microthermal analysis p.904

• Microthermal analysis combines thermal analysis with

atomic-force microscopy (AFM - a new technique).
• It is actually a family of scanning thermal microscopy
techniques in which thermal properties of a surface are
measured as a function of temperature and used to produce a
thermal image.
• In microthermal analysis, the tip of an atomic-force microscope
(AFM) is replaced by a thermally sensitive probe such as
thermister or a thermocouple.
• The surface temperature can be changed externally or by the
probes acting both as a heater and as a temperature-
measuring device.
• Figure 31-16 (next) shows a microthermal analysis probe.
47
Microthermal analysis = (DSC+ Microscopy Probe)

Microthermal analysis is a materials characterization technique which combines

the thermal analysis principles of differential scanning calorimetry (DSC) with high
spatial resolution of scanning probe microscopy.

FIGURE 31-16 A microthermal analysis probe. 48

Ch31 Thermal Methods P.905

Micro-thermal analysis was launched
commercially in March 1998.

Microthermal analysis has been

extended to higher spatial resolution
to nanothermal analysis which
uses microfabricated self-heating
silicon cantilevers to probe
thermomechanical properties of
materials with sub-100 nm spatial
resolution.

FIGUER 31-17 Microthermal analysis apparatus.

The first examples of applications have been to polymers but case studies
have indicated that micro-thermal analysis will have many uses in studies of
metals, ceramics, electronic components, foods and catalysts. 49

Ch31 Thermal Methods P.905

FIGURE 31-18 Comparison of conventional atomic force
microscopy topographic image (a), with thermal image (b)
of a paracetamol pharmaceutical tablet.
50

Ch31 Thermal Methods P.906

 Difference in Thermal Stability:
New and Used Oil – appendix for TGA
TG /% DTG /(%/min)

100 307 .4 °C 312 .0 °C

Used One
0

80

Oil Samples -5

60

-10

40 Sample mass: ~7 mg
Crucible: Alumina -15
Atmosphere: Air, 20 ml/min New Sample
20 Heating rate: 10 K/min
-20
332.0 °C
337 .4 °C
0
50 100 150 200 250 300 350 400 450
Temperature /°C
Example of TGA application on silicon wafer:
Organic Contaminations on Si Wafers
[Left: TGA wt%, Right: DTGA (%/min)]

Sample: Si Wafer
Sample mass: 1606 mg
Crucible: Pt+lid
Heating rate: 10 K/min
Atmosphere: Air/50 ml/min
Sensor: TG type S
The STA 449 C Jupiter® -
TGA-DSC-Cp on Glass:
DSC applicaions in isothermal crystallization analysis

54
  液晶(liquid crystals) – DSC is commonly used for
investigating their phase transitions, or for proving
existence of such properties. LC by definition, is a phase at
liquid state, possessing anisotropic behavior. Materials with
such a phase are called “liquid crystals”。
Liquid crystals are applied in photoelectronic products. In
structural polymers, liquid crystalline properties are used for
improving processability.
In biochemistry, many bio-reactions are related to liquid
crystalline properties.
Next page PPT shows DSC analysis on an extracted product from fats,
固醇酯 (cholestery esters), which shows liquid crystalline properties.
There are three phase transitions related to liquid crystals:
1. From solid →smectic，(liq. Crystal with 2 orders)
2. From smectic→cholesteric (one order), then
3. From cholesteric→liquid (isotropic - no order). 55
56
End of Chapter 31
Thermal methods: TGA, DTA, DSC (three types of DSC),
- theories, instrumentation, and applications.
This semester 儀分/化分: Analytical Chemistry (qualification+ quantification]
• Atomic (AA, AF, AE ) spectroscopy [two chapters], X-ray Spectroscopy;
• Luminescence; UV-Vis spectroscopy [two chapters]; FT-IR spectroscopy [two
chapters]
• GC–separation [two chapters]; LC – HPLC separation, GPC.
• Thermal methods (DSC, DTA, TGA)

Laboratory class (儀分-實驗課) next semester: [8 instrument methods]

• AA (atomic absorption) -Quantitative analysis - spectroscopy
• UV-Vis absorption (one) -Quantitative analysis – spectroscopy
• Fluorescence spectroscopy
• FT-IR (one) -Qualitative analysis - spectroscopy
• GC+LC (two) -separations
• GPC (one) -Separation, MW determinations (for polymers)
• DSC+TGA (two) -Misc./thermal analysis methods

儀分 期末考 – To be announced. UV-Vis (Chaps. 13,14), Luminescence

(Chap. 15); FT-IR (Chap.16), GC (Chaps. 26-27), thermal analysis (Chap. 57
31).