Basic Lab

Differential Thermal
Test-No.: M110
Analysis (DTA)

Aim : Determination of thermal dehydration of crystal water with thermal analysis, as an

example Gypsum CaSO4.2H2O.

Table of Contents

1 Introduction

2 Basics
2.1 Thermodynamic Background
2.2 Differential Thermal Analysis
2.2.1 Influence of the Furnace Atmosphere
2.2.2 Influence of the Heating Rate
2.2.3 Influence of the Reference Substances

3 Technical Importance / Practical Use

4 Experimental Steps
4.1 Equipment
4.2 Procedures
4.2.1 Starting the Control Unit
4.2.2 Temperature Program
4.2.3 Measurements
4.2.4 Reference Measurement
4.2.5 Measuring the Sample Material

5 Analysis

6 Questions

7 Bibliography

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1 Introduction
In most cases heating a system (element, compound, mixture) causes physical and chemical
changes. Possible transformations are summarized in the following table:

Table 1: Thermal transfomations

Physical changes Examples Chemical changes Examples

change in -, -, -Fe chemisorption H2 on Pt
modification
melting ice water desolvation (e.g. CuSO4.5H2O
dehydration) Na2CO3.10H2O
evaporation water, ethanol decomposition NaHCO3 Na2CO3
sublimation Ammoniumchlorid oxidation Cu + O2 CuO
absorption gas in water solid state reaction PZT Pb(Zr, Ti)O3
desorption gas in oxides reactions with the gas NiJ + H2 Ni + 2 HJ
phase
crystallisation NaCl from solution

Knowledge of these properties and the changes are important for scientific and practical
interest, especially for material preparation, determination of phase diagrams and phase
stability.

2 Basics
2.1 Thermodynamic Background
Measuring methods, which measure physical or chemical properties of a substance, a mixture
of substances and/or reaction mixtures as a function of temperature are defined as Thermal
Analysis (DIN 51005, ICTA-International Conferation for Thermal Analysis).

In a DTA-experiment (Differential Thermal Analysis) the temperature difference between the

sample under investigation and an inert reference material is measured as a function of
temperature. Both samples are treated with the same temperature program and the same
heating and cooling rates.

During heating a sample of the mass m, the sample receives energy. In consequence the state
of the sample might change. Either a phase transition occurs or the internal energy changes.
Without phase transition, the received heat quantity, q, is proportional to the increase of the
temperature, T,
q = mCT (1)
with C = specific heat capacity. The heat capacity is depending on the conditions, the system
is treated: If the heat transfer is measured at constant volume, the heat capacity is defined as
CV. If the heat capacity is measured at constant pressure, the heat capacity is defined as Cp. In
the case of constant pressure the volume changes. Therefore CP and CV are different:

V P
Cp CV T (2)
T P T V

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 M110: Differential Thermal Analysis (DTA)

An important state variable, the enthalpy H, can be defined as

H = U + pV (3)

with U = internal energy, p = pressure and V = volume. At constant pressure (dp = 0) the
increase of H is equal to the received heat (besides the change in volume):

dH = (dq)P (4)
H
CP . (5)
T P

the change of the enthalpy while heating the system from T1 to T2 is then:

T
H T12 CP dT, (6)

where Cp is a function of temperature, too.

The transformation of a substance from one modification to another causes a change of the
enthalpy HU. If a substance is permanently heated, the temperature increases untill the
transfomation temperature TU is reached. Additional heat is used as latent heat for the
transformation. Hence the increase of the temperature is reduced during transformation.
During the transformation process the temperature is constant. After the transformation, the
temperature increases regularly again:
T T
H T U C P dT H U T 2 CP dT (7)
1 U

Upon cooling the same transition heat is released. The temperature is decreasing before and
after the transition point, while constant during the transition. Thermograms can be calculated
from the cooling curves of melts from different concentrations of the system under
investigation.

Figure 1 shows the temperature differences of a iron sample and a platinum sample as
function of time while cooling in the same furnance. At a temperature of 906 C the iron
cooling slows down, because here the -form (fcc) transforms into the -form (bcc). There is
jumpwise increment in the temperature difference between iron and platinum. The second
noticeable phenomenon at 768 C is the ferromagnetic transition in -iron (paramagnetic to
ferromagnetic). The crystallographic order of the atoms (bcc) doesnt change during this
transition. This transition temperature is called Curie-temperature. At this transition point the
3d-electron spins turn parallel and energy is released. The type of phase transition at the curie
point can be investigated with DTA measurements.

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M110: Differential Thermal Analysis (DTA)

Fig. 1: Time-dependent cooling-curve of iron

Figure 2 shows a schemetic curve for the specific heat for - and -iron (TCF: ferromagnetic
Curie-temperature, TCAF: antiferromagnetic Curie-temperature). The strong increase of the
specific heat before and the following abrupt decrease at the curie point cause a similar trend
in the DTA curve (Fig. 3, curve 3). In the cooling curve the same effect occurs, but with
opposite sign.

Fig. 2: specific heat CV per mol for - and -iron

Fig. 3: DTA-curve (3): heating, (4): cooling of a ferromagnetic substance

Transitions of this kind are called transitions of higher order. In contrst to transitions of first
order no latent heat is consumed or released. The changes in heat capacity CP, heat
conductivity and thermal expansion of the substance are discontinuous. Glas transitions of
amorphous substances are phase transitions of higher order, too. Phase transitions of first
order are for example melting, boiling and most of the modification changes.

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 M110: Differential Thermal Analysis (DTA)

Phase transition :

With G=H-TS results:

G G
S, V (8)
T P P T
The chemical potentials and for the phases and can be calculated as follows:

Vm 0, (9)
P T P T P T
H m

S m 0. (10)
T P T P T P T T

If the first derivative of the chemical potentials changes jumpwise (discontinous) at the
transition point, it is a transition first order. If the first derivative of the chemical potentials
changes continous and the second derivative changes jumpwise, it is a transition second order.
Figure 4 shows the changes of the thermodynamic quantities at the phase transitions.

Fig. 4(a): Changes of the thermodynamic quantities for a first order transition

Fig. 4(b): Changes of the thermodynamic quantities for a second order transition

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M110: Differential Thermal Analysis (DTA)

2.2 Differential Thermal Analysis

Figure 5 shows a schematic setup of the DTA. The substance under investigaton and an inert
reference are heated under the same conditions simultaneously in a furnance. The increase of
the temperature in the furnance should be linear. Both, sample and reference are connected to
thermocouples. These thermocouples are connected together. The differences of the voltages,
which are correlated to the differences of the temperatures, are measured. As shown in Fig. 6,
the control unit shows no thermovoltage as long as there is no heat consumed or released,
because there is the same temperature Ts = Ti in the sample and in the inert reference and
hence T = 0. If there is an endothermic reaction in the sample, the sample temperature
increases slower as the reference temperature (Ts1 < Ti1) and the gauge shows a thermovoltage
according to a temperature difference T1 = Ts1 - Ti1, which is negative. If there is an
exothemic reaction in the sample, the sample temperature increases faster as the reference
temperature (Ts2 > Ti2) and the gauge shows a thermovoltage according to a temperature
difference T2 = Ts2 -Ti2, which is positive. The DTA curve can be determined by
substraction of the curve Ts and Ti (Fig. 6b).

Fig. 5: Scheme for the DTA: 1 furnance, 2 sample substance, 3 inert reference, 4 control unit
for heating, 5 temperaturdifference gauge, 6 temperature gauge

Fig. 6: DTA curves: a) Ts: temperature-time-curve of the sample, Ti: temperature-time-curve

of the reference, b) temperature difference-time-curve
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 M110: Differential Thermal Analysis (DTA)

In the following chapters some of the factors which may influence the results of the DTA
experiments will be explained.

2.2.1 Influence of the Furnace Atmosphere

The equilibrium temperature of reversible transitions is dependent on the pressure in the
furnance resp. of the partial pressures of the components. A pressure change results mainly in
a temperature shift of the peak.

Secondly the gases of the furnance atmosphere may react with the substance or with volatile
products during decomposition of the sample. With change of the composition of the furnance
atmosphere some characteristic peaks may disappear or extra peaks may appear.

The mechanisms of many chemical reactions are influenced by the atmosphere in particular
by the gas pressure.

Figure 7 shows DTA-curves of gypsum in streaming nitrogen-steam-atmosphere with

different steam partial pressures. The dehydration reaction occurs in two steps:

CaSO4.2H2O CaSO4.0.5H2O + 1.5 H2O (11)

CaSO4.0.5H2O CaSO4 + 0.5 H2O (12)

Fig. 7: DTA curve of gypsum with different steam partial pressures

With increasing steam partial pressure the second step of the dehydration reaction moves to
higher temperatures. With higher steam partial pressure the DTA effects are more pronounced
and the peaks are narrower.

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M110: Differential Thermal Analysis (DTA)

The steam formed by the decomposition reaction diffuses slower into the furnace atmosphere
than new steam is produced. Above the sample surface the partial pressure of steam increases.
Consequently the equilibrium temperature of the dehydration process increases. The DTA
peak is broadened. The local steam pressure can only increase up to the total pressure in the
furnace. The lower the given initial steam pressure is, the more the local steam pressure may
increase. Due to sluggish diffusion there are locally different partial pressures of the gaseous
decomposition product.

2.2.2 Influence of the Heating Rate

As the substance turnover per time unit increases with faster temperature rise, with increasing
heating rate the peaks are growing. The temperature difference T is approximately
proportional to the substance turnover (Fig. 8).

In addition, the DTA peaks as a function of temperature T are broadened, because the
temperature gradient in the sample increases with higher heating rate. As a function of time t
the peaks seem to be smaller (Fig. 9). With faster temperature rise the turnover needs less
time, but the temperature difference T is increasing. Therefore the area Tdt is constant.

Fig. 8: Influence of increasing temperature rate as a function T=f(T).

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 M110: Differential Thermal Analysis (DTA)

Fig. 9: Influence of increasing temperature rise as a function T=f(t). The vertically marks
show the same sample temperatures.

With higher heating rate the DTA-peaks of chemical reactions move to higher temperatures.
In addition, there may be local changes in the furnance atmosphere and on the sample surface
as a result of the temperature dependence of the reaction rate. The higher the heating rate, the
less gas diffuses out of the sample environement during the decomposition process.
Consequently, the partial pressure is locally higher and the decomposition temperature
increases.

The broadening and the different shifting of the DTA effects at high heating rate may result in
overlapping of normal successively effects. For higher resolution of the DTA curves, the peak
temperatures are near the thermodynamic equilibrium temperatures, thus, the heating rate
should be as low as possible. It is useful to notice that the peaks become flater.

2.2.3 Influence of the Reference Substances

A reference substance for DTA measurements has to fullfill the following conditions:
1. no transitions in the measured temperature range
2. similar heat conductivity and heat capacity as the measured substance

If reference material is mixed into the sample to achieve similar heat conductivity and heat
capacity of the sample and the reference chamber, the constitutents (sample and a reference
material) should not react with each other.

It is generally impossible, to fulfill both conditions 1 and 2 simultaneouly, because during the
transition heat capacity and heat conductivity are changing in the sample substance. Therefore
often a reference is chosen which remains as the product after heating the sample, e.g. caoline
for clay minerals.

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M110: Differential Thermal Analysis (DTA)

For measuring small samples no inert substance is used. The reference temperature is
measured with empty sample holder.

These are only a few parameters which influence the DTA results. Nevertheless comparing
diagrams of different DTA-apparatuses is difficult. There are standards for the experiments,
but these standards are often different from the best actual conditions. So it is useful to note
the experiment conditions.

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 M110: Differential Thermal Analysis (DTA)

3 Technical Importance / Practical Use

The differential thermal analysis shows at which temperatures a substance reacts and if the
heat change is positive or negative. Nevertheless it is impossible to determine with DTA
measurements of which kind a detected reaction is. DTA is a dynamical method, equilibrium
conditions can not be established. With DTA determined reaction or equilibrium temperatures
are dependent on the measurement conditions. So they may differ from the equilibrium
temperatures. It is important to use other measuring methods. Very useful is information of
the same sample at the same conditions as in the DTA measurements. For this reason there are
combined devices which can registrate simultaneously the following additional parameters:
weight change
rate of weight change
evolving gases

However, differential thermal analysis is used for explaining many questions in physics and
chemistry. Examples are homogenous and heterogenous chemical reactions in liquid and solid
phases, determination of phase transitions, thermal decomposition, calorimetric and kinetic
data. Differential thermal analysis is a quick method which does not require complicated
instruments. With modern DTAs the measurements can be automatized so that the analysis is
not very time-consuming.
During heating and cooling of one-component systems only simple phase transitions occur. In
multicomponent systems there are additional phenomena such as formation and
decomposition of mixtures, formation of compounds etc.. By measuring these transitions as
function of composition with DTA it is possible to determine the corresponding phase
diagrams.
Figure 10 shows DTA curves of some mixtures in the Na2SO4-NaCl-system. Temperature,
form and height of these thermal effects depend in a characteristic manner on the composition
of the mixture. If a melt has the eutectic composition, the DTA curve looks like a curve of a
pure phase. To determine liqudus temperatures cooling curves should be used, whereas for
solidus temperatures the heating curves are more useful.
For determination of complex phase diagrams, a great number of DTA-curves at different
compositions have to be measured. For explanation of the thermal effects further methods
such as X-ray diffraction or microscopy are needed.

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M110: Differential Thermal Analysis (DTA)

Fig. 10: Phase diagram and DTA-curves of the Na2SO4-NaCl-system

The differential thermal analysis can be used for determination of caloric data. The holding
time in temperature-time-curves is often used as a semiquantitative evaluation for the
transition heat. This time is equal to the time from the beginning of the thermal effect to the
time of the peak maximum. During the phase transition the temperature is constant for this
time. The peak area is a useful value for the determination of heat capacities. In a DTA-
diagram the heat of reaction H is proportional to the area between baseline and the DTA-
curve (Fig. 11), H=KF. The factor K is dependent on the apparatus, the chosen sensitivity
and the temperature and has to be determined by calibration measurements. Another direct
quantitative method for the determination of the amount of heat conversion, respectively, the
enthalpy change is DSC (differential scanning calorimetry). In the DSC a sample and a
reference are heated. The difference in heating energy between the sample and the reference
during a phase transition is measured.

Fig. 11: DTA diagram, schematic.

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 M110: Differential Thermal Analysis (DTA)

Another important application for differential thermal analysis is the characterization of

ceramic materials. The starting materials for fine ceramics can be very different in their
mineral composition. Sometime they contain large amount of impurities. This results in
different product qualities. Pure caolin segregates water at 500 C. At 987 C a solid state
reaction occurs, Al-Si-spinell phase and amorphous SiO2 are formed from metacaolin. On the
other hand caolin contaminated with Illite shows three endotherm dehydration peaks in the
thermal analysis, at 67 C, 268 C and 499 C.

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M110: Differential Thermal Analysis (DTA)

4 Experimental Steps
4.1 Equipment
For this experiment the DTA typ 701 from Bhr Thermoanalyse GmbH is used.
First read the instruction!

Befor beginning the measurements the cooling circuit has to be switched on. After the
measurements it has to be switched off.

4.2 Procedures

4.2.1 Starting the Control Unit

After switching on the control unit there is the main menu (Hauptmen) for DIL 801 on the
monitor. With finishing the dilatometer program the main menu for DTA 701 is opened.

4.2.2 Temperature Program

In the main menu for DTA 701 the menu Programm erzeugen (generate program) has to be
chosen. If there is no useful program for the measument the temperature program has to be
written. The temperature program includes the following parameters: temperature
(Temperatur), heating rate (Heizrate), segment time (Segmentzeit) [hh:mm:ss] and values
(Werte) [%]. For holding the temperature the heating rate is 0, for cooling the values are
negative. For entering the segment the Enter-key has to be pressed. Then the temperature
program is saved. There are two temperature programs needed:

Program 1:
1) Segment 1: 250 C; 20 K/min; 12 min; 40 %
2) Segment 2: 250 C; 0 K/min; 10 min; 10 %
3) Segment 3: 20 C; -20 12 min; 40 %
K/min;
4) Segment 4: 20 C; 0 K/min; 10 min; 10 %

Program 2:
1) Segment 1: 250 C; 5 K/min; 46 min; 40 %
2) Segment 2: 250 C; 0 K/min; 10 min; 10 %
3) Segment 3: 20 C; -5 K/min; 46 min; 40 %
4) Segment 4: 20 C; 0 K/min; 10 min; 10 %

4.2.3 Measurements
Open the menu messen (measuring). Fill in the following data: temperature program
(Temperaturprogramm), lab name (Versuchsname), sample material (Probenmaterial), sample
weight (Probengewicht), reference material (Referenzmaterial), reference weight
(Referenzgewicht), date (Datum), atmosphere (Atmosphre), crucible material
(Tiegelmaterial). By pressing the icon Ofen ffnen (opening furnance) the furnance will be
unlocked and can be opened within 10 seconds. The furnance cant be opened when the
temperature is higher than 200 C. The measuring cell should be open as short as possible to
avoid pollution and damage.

4.2.4 Reference Measurement

For the reference measurement two empty aluminiumoxid crucibles are used. Thus sample
and reference material are equal. The temperature program is startet by pressing the icon

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 M110: Differential Thermal Analysis (DTA)

Messung starten. This reference measurement has to be stored when it is finished. For both
temperature programs reference measurements are needed.

4.2.5 Measuring the Sample Material

Gypsum CaSO4.2H2O is used as sample material. Gypsum is an important construction
material. It is used in the cement industry, in the building industry and in the medicine. Due to
the low dehydration temperatures gypsum is suitable for DTA measurements.

The aluminiumoxid crucible has to be filled half of its heigth and to be weighted. The
measurements are done with above described programs in air. For each measurement new
samples are used. After the measurement is done, the samples are weighted again for
controlling the weight reduction.

The crucible has to be put on the left sample plate, the reference on the right. It is important to
avoid material (sample) particles on the outside of the crucible, otherwise the crucible may
stick on the plate. To avoid contamination of the crucible it has to be handled with tweezers.

5 Analysis
For analysing the experiments the reference measurements are used for correction. The
DTA curves of the sample material have to be substracted from the reference curves. These
calculations have to be done direct on the computer with the DTA-software.
The dehydration temperatures have to be determinated.
Discuss the influence of the different temperature curves.
Answer the following questions

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M110: Differential Thermal Analysis (DTA)

6 Questions
1. Descripe the correlation between uptaking and release of heat and the corresponding
changes of the thermodynamic state of the sample.
2. Descripe the different types of phase transitions.
3. Descripe the principle of the differential thermal analysis.
4. Which test conditions can influence the results of the DTA? How are the results dependent
on parameters like heat conductivity, temperature conductivity, density and geometry of
the samples, sample weight, geometry of the thermocouples and latent heat of the
reactions?

7 Bibliography
1. P.W. Atkins
Physical Chemistry
VCH Verlagsgesellschaft mbH, Weinheim 1987, 1988, 1990, ...

2. E. Post, S. Winkler
TA for ceramic materials
Netsch Industrial Applications Volume 6/93

3. R.F. Speyer
Thermal analysis of materials
Marcel Dekker, Inc., New York, 1994

4. T. Hatakeyama, Zhenhai Liu

Handbook of thermal analysis
Wiley, Chichester, 1998

5. D. Schultze
Differentialthermoanalyse
Verlag Chemie GmbH Weinheim/Bergstr., 1972

6. W. Schatt
Einfhrung in die Werkstoffwissenschaft
Deutscher Verlag fr Grundstoffindustrie, Leipzig 1972

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