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problem solving.
Materials Analysis
• quality control
• purity
• phase changes
• thermal behavior
Fig. 1: A detailed view of the microbalance. Example I: Dehydration and decomposition
of calcium oxalate
Instrumentation To characterize a variety of samples, different Starting materials in production can contain
A thermal analysis system contains a graphite sample holders are available (fig. 2). impurities like an unknown quantity of water.
resistor furnace that can heat a sample from Homemade sample holders are also available This water can reduce reactivity or add
room temperature to 1750°C. The atmos- that allow the detailed characterization of thin unwanted weight to the material – both of
phere in the system can be either inert (vacu- layers. which can cause production problems. To
um, nitrogen, helium, argon) to protect the prevent this from happening a TGA analysis can
sample from oxidation or active (air, oxygen, help to identify the state of the material.
hydrogen) to react with the sample. To deter- Thermogravimetric Analysis (TGA) In this example calcium oxalate is analyzed
mine small weight changes of the sample dur- In TGA the exact mass of a sample is using TGA (fig. 3). The first loss of sample
ing heating a microbalance is used (fig.1) that determined while it undergoes a temperature weight is due to the dehydration of water
has a resolution of 0.03 µg. treatment. It is possible to keep the sample (12 %).The loss of sample weight is equal to the
at a constant temperature or a linear temper- quantity of one mole of crystal water.
Options ature gradient can be applied. The second loss of sample weight is due to loss
Thermal analysis is a general name for a group Alternatively, the sample can be heated until a of CO (19 %) and the third step to loss of CO2
of analytical techniques used to monitor the constant mass is obtained. (30 %).When the sample would have been con-
behavior of a material as a function of tem- taminated with e.g. barium or strontium
perature (or time at a specific temperature). oxalate more peaks would be visible. Absence
Table 1 shows an overview of the different of these peaks indicates that the material is a
techniques that will be discussed in this note. 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).
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 Fig. 3: Thermogravimetric analysis of calcium It is also possible to couple a gas analyzer to
In production processes, gas purity can be oxalate, the first derivative signal (DTG) shows the thermal analysis system to identify the
critical.When carbon parts are heated to high how fast the weight change occurs. emitted vapors, for example to unravel mech-
temperatures, the presence of oxygen can anisms of transformations. Typical analyzers
decrease lifetime. With TGA it is possible to Differential Scanning Calorimetry are a mass-spectrometer (MS) or a fourier-
determine what oxygen concentration can be (DSC) transform infrared instrument (FT-IR). Emitted
tolerated without degrading the carbon parts. DSC is used to determine the temperature vapors can also be absorbed in gas-trapping
To do so, a carbon sample is heated to and enthalpy of a phase transformation. This bottles or organic sampling tubes. In this way
1100°C in a few minutes using a nitrogen type of information is very useful for quality analyses can be performed off-line.
atmosphere with different oxygen concentra- control as phase transformations are very
tions (<2, 200, 500 vol.ppm). The weight loss sensitive for purity, thermal stability and Example III: Dehydration of copper
is monitored during 2 hours at 1100°C. The compositions of mixtures. DSC uses addition- sulphate pentahydrate
combustion rate is calculated by measuring al metal calibration standards which make it Figure 5 shows the results of a TGA-DSC
the loss of weight during a specified time.The possible to calculate the energy emitted or measurement of copper sulphate pentahy-
results of the TGA measurements are shown absorbed by a sample (enthalpy). drate. The different dehydration steps that
in figure 4, where the sample mass is plotted occur during heating of the material are
as function of time. The combustion rate is difficult to distinguish in the TGA-signal, but
determined from the slope of the curves. By Hyphenated techniques are clearly visible in the DSC-result. The
plotting the combustion rate of carbon at The above described thermal analysis majority of the water is lost below 150°C,
1100°C against the oxygen concentration, a techniques can be performed stand-alone or but the monohydrate is stable until 244°C.
linear relation is observed in this concentra- combined. The most common hyphenated The loss of water from the monohydrate
tion range. The maximum oxygen concentra- techniques are TGA-DSC and TGA-DTA. corresponds to a weight loss of 7.0%.
tion in nitrogen that can be tolerated in a
process can be determined on the basis of
this information. Fig. 4: Carbon oxidation as studied at different
oxygen concentrations.
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