Philips Research

When a material is heated its structural and chemical composition can

undergo changes such as fusion, melting, crystallization, oxidation,

decomposition, transition, expansion and sintering. Using Thermal

Analysis such changes can be monitored in every atmosphere of interest.

The obtained information is very useful in both quality control and

problem solving.

Materials Analysis

Thermal Analysis (TA)

• quality control

• purity

• phase changes

• thermal behavior
Fig. 1: A detailed view of the microbalance.
Instrumentation
A thermal analysis system contains a graphite
resistor furnace that can heat a sample from
room temperature to 1750°C. The atmos-
phere in the system can be either inert (vacu-
um, nitrogen, helium, argon) to protect the
sample from oxidation or active (air, oxygen,
hydrogen) to react with the sample. To deter-
mine small weight changes of the sample dur-
ing heating a microbalance is used (fig.1) that
has a resolution of 0.03 µg.
Options
Thermal analysis is a general name for a group
of analytical techniques used to monitor the
behavior of a material as a function of tem-
perature (or time at a specific temperature).
Table 1 shows an overview of the different
techniques that will be discussed in this note.
To characterize a variety of samples, different
sample holders are available (fig. 2).
Homemade sample holders are also available
that allow the detailed characterization of thin
layers.
Thermogravimetric Analysis (TGA)
In TGA the exact mass of a sample is
determined while it undergoes a temperature
treatment. It is possible to keep the sample
at a constant temperature or a linear temper-
ature gradient can be applied.
Alternatively, the sample can be heated until a
constant mass is obtained.
Example I: Dehydration and decomposition
of calcium oxalate
Starting materials in production can contain
impurities like an unknown quantity of water.
This water can reduce reactivity or add
unwanted weight to the material – both of
which can cause production problems. To
prevent this from happening a TGA analysis can
help to identify the state of the material.
In this example calcium oxalate is analyzed
using TGA (fig. 3). The first loss of sample
weight is due to the dehydration of water
(12 %).The loss of sample weight is equal to the
quantity of one mole of crystal water.
The second loss of sample weight is due to loss
of CO (19 %) and the third step to loss of CO2
(30 %).When the sample would have been con-
taminated with e.g. barium or strontium
oxalate more peaks would be visible. Absence
of these peaks indicates that the material is a
monohydrate and no other major contamina-
tion is present in this material.

Table 1: Different TA techniques and their Fig. 2: Sample holders as used in TGA (right)
applications. DSC (middle) and for thin films (left).

Technique Abbreviation Property Applications

Thermogravimetric TGA Mass Sample purity

Analysis difference Decomposition
Dehydration
Oxidation

Differential DTA Temperature Phase changes

Thermal Analysis difference Dehydration
Decomposition
Reactions

Differential DSC Energy Heat capacity

Scanning difference Phase changes
Calorimetry Reactions
Calorimetry
 110 1
Ca(COO)2-H2O
100

Weight change (wt.%/min)

DTG 0
Sample weight (wt.%)

90 Ca(COO)2
-1
80
-2
70 CaCO3
-3
60
-4
50
40 CaO -5
TGA
30 -6
0 100 200 300 400 500 600 700 800 900 1000 1100
Sample temperature (°C)

Example II: The combustion rate of carbon
In production processes, gas purity can be
critical.When carbon parts are heated to high
temperatures, the presence of oxygen can
decrease lifetime. With TGA it is possible to
determine what oxygen concentration can be
tolerated without degrading the carbon parts.
To do so, a carbon sample is heated to
1100°C in a few minutes using a nitrogen
atmosphere with different oxygen concentra-
tions (<2, 200, 500 vol.ppm). The weight loss
is monitored during 2 hours at 1100°C. The
combustion rate is calculated by measuring
the loss of weight during a specified time.The
results of the TGA measurements are shown
in figure 4, where the sample mass is plotted
as function of time. The combustion rate is
determined from the slope of the curves. By
plotting the combustion rate of carbon at
1100°C against the oxygen concentration, a
linear relation is observed in this concentra-
tion range. The maximum oxygen concentra-
tion in nitrogen that can be tolerated in a
process can be determined on the basis of
this information.
Fig. 3: Thermogravimetric analysis of calcium It is also possible to couple a gas analyzer to
oxalate, the first derivative signal (DTG) shows the thermal analysis system to identify the
how fast the weight change occurs. emitted vapors, for example to unravel mech-
anisms of transformations. Typical analyzers
Differential Scanning Calorimetry are a mass-spectrometer (MS) or a fourier-
(DSC) transform infrared instrument (FT-IR). Emitted
DSC is used to determine the temperature vapors can also be absorbed in gas-trapping
and enthalpy of a phase transformation. This bottles or organic sampling tubes. In this way
type of information is very useful for quality analyses can be performed off-line.
control as phase transformations are very
sensitive for purity, thermal stability and Example III: Dehydration of copper
compositions of mixtures. DSC uses addition- sulphate pentahydrate
al metal calibration standards which make it Figure 5 shows the results of a TGA-DSC
possible to calculate the energy emitted or measurement of copper sulphate pentahy-
absorbed by a sample (enthalpy). drate. The different dehydration steps that
occur during heating of the material are
difficult to distinguish in the TGA-signal, but
Hyphenated techniques are clearly visible in the DSC-result. The
The above described thermal analysis majority of the water is lost below 150°C,
techniques can be performed stand-alone or but the monohydrate is stable until 244°C.
combined. The most common hyphenated The loss of water from the monohydrate
techniques are TGA-DSC and TGA-DTA. corresponds to a weight loss of 7.0%.
Fig. 4: Carbon oxidation as studied at different
oxygen concentrations.

Differential Thermal Analysis (DTA)

Differential Thermal Analysis is an analytical
method in which the sample and an inert 155.3
reference material are heated concurrently,
155.1
each having its own temperature sensing and
154.9
recording apparatus.The temperature changes combustion rate: 0.13 µg/min
Sample mass (mg)

that occur in the course of heating are 154.7

combustion rate: 4.73 µg/min
plotted.This thermogram provides data on the 154.5
chemical and physical transformations that 153.3
combustion rate: 11.05 µg/min
have occurred, such as melting, sublimation, 154.1
glass transitions, crystal transitions, and 153.9 2 vol.ppm O2
crystallization. 229 vol.ppm O2
153.7
537 vol.ppm O2
153.5
0 1000 2000 3000 4000 5000 6000 7000 8000 9000
Time (sec)
 P h i l i p s R e s e a rc h M a t e r i a l s A n a l y s i s
offers a full range of analytical methods and
expertise to support both research and
105 5 manufacturing, serving customers by taking an
Ca(COO)2-H2O
integral, solution-oriented approach.
DSC
95
0
Sample weight (wt.%)

85 making the invisible visible

Related heat flow (µV)

-5
75 CuSO4-H2O
Fo r m o re i n f o r m a t i o n :
Δm = -7.0% CuSO4 -10
65
Tel./fax: +31 -40-27 43210/43075
TGA
E-mail: materialsanalysis@philips.com
55 -15 http://www.philips.com/materialsanalysis
http://pww.natlab.research.philips.com:25222/
45 -20
0 50 100 150 200 250 300 350 400 450
Te c h n i c a l N o t e 1 8
Sample temperature (°C)
December 2005
Jeroen van den Berg

Fig. 5: The analysis of copper sulphate pentahy-

drate with TGA-DSC.

Example IV: Character ization of epoxy The TGA results are comparable too. For both
resins with TGA-DSC epoxy resins an ash residue of 59 wt.% is
TGA-DSC can also be used to investigate the found. The TGA-DSC results show that rele-
thermal and chemical properties of a material. vant properties of the epoxy resins are the
In this example a customer wanted to replace same and that the process parameters do not
a standard epoxy resin with a new epoxy have to be changed. Fig. 6: Epoxy resin analysis with TGA-DSC.
resin. The most obvious difference between
the old and new epoxy resin is the color, due
to the addition of another pigment. It is
important to know the thermal and chemical
differences between both epoxy resins before 110.00 4
this change is made in the factory. By using 3
the coupled TGA-DSC the thermal effect of 100.00
Sample weight (wt.%)

2
the hardening reaction was determined using
90.00 1
DSC and the ash residue was measured simul-
0
taneously by TGA. 80.00
-1

Heat flow (µV)

The samples are first put in a nitrogen atmos-
phere at 30°C. Then, the temperature is 70.00 -2
TGA Epoxy Black
increased to 300°C and held there for 15 min- TGA Epoxy Orange -3
60.00 DSC Epoxy Black
utes. During this period the atmosphere is -4
DSC Epoxy Orange
changed from nitrogen to air, which allows -5
50.00
combustion of the sample. Subsequently, the 0 100 200 300 400 500 600 700 800 900 1000
temperature is increased to 1000°C.The TGA Sample temperature (°C)
and DSC signals are monitored during the
whole procedure. The results of the TGA and
DSC measurements are shown in figure 6.The
DSC result of the black epoxy is comparable
with that of the orange epoxy resin. An
exothermic reaction is observed at 155°C.
The enthalpy is 17 J/g for both materials.