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1. Introduction
Thermal Analysis is the term applied to a group of
methods and techniques in which chemical or
physical properties of a substance, a mixture of
substances or a reaction mixture are measured as
function of temperature or time, while the substances
are subjected to a controlled temperature programme.
References:
* Introdcution to Thermal Analysis, M.E. Brown -- Chapman
and Hall
* Thermal Analysis - Techniques and Applications, ed. E.L.
Charsley and S.B. Warrington -- Royal Society of Chemistry
* Thermal Analysis of Materials, Robert F. Speyer –Marcel
Dekker, Inc.
The following table is a list of the main thermal
analysis methods:
While carrying out these measurements, the
furnace atmosphere can either be static air or a
continuous flow of gas (purging). Examples are
inert conditions (nitrogen) to inhibit oxidation, or
reducing condition (e.g. purging hydrogen), etc.
General thermodynamic relationships
Thermal analyses are usually run under conditions of constant pressure, the
underlying thermodynamic equation is the Gibbs-Helmholtz expression:
G0=H0-TS0
where G=free energy of the system, H=enthalpy of the system, S=entropy
of the system, T=temperature in kelvins
d (G )
S
dT
LINSEIS L81
Thermogravimetric instrumentation should include several basic
components to provide the flexibility necessary for the
production of useful analytical data:
a) A balance,
b) A heating device,
c) A unit for temperature measurement and control,
d) A means for automatically recording the mass and
temperature changes,
e) A system to control the atmosphere around the sample.
2.1.1 The Thermobalance
Two typical designs of the thermobalance are shown in the following:
Balances must remain precise and accurate continuously
under extreme temperature and atmosphere conditions, and
should deliver a signal suitable for continuous recording.
Sort, pressure and flow rate of the gas in the sample chamber
influence the following parameters:
•Sample reaction
Sample reactions with the gas (oxidation in the presence of oxygen).
•Heat transitions
Different heat conductivity of the gases used in an experiment.
ATTN:
Three factors should be noted when you get a TG curve:
1. General shape,
2. The particular temperatures at which changes in mass occur
(severely affected by many experimental conditions),
3. The magnitudes of the mass changes (much more use directly
related to the specific stoichiometries of the reactions,
independent of the many factors that affect the shape of the
curves. Can be used for precise quantitative analysis).
Analytical calculations
Under controlled and reproducible conditions, quantitative data
can be extracted from the relevant TG curves. Most commonly,
the mass change is related to sample purity or composition.
Example: A pure compound may be either MgO, MgCO3, or MgC2O4. A
thermogram of the substance shows a loss of 91.0 mg from a total of 175.0 mg
used for analysis. What is the formula of the compound? The relevant possible
reactions are
MgO No reaction
MgCO3 MgO+CO2
MgC2O4 MgO+CO2+CO
Solution: % Mass loss Sample=(91.0/175.0)(100%)=52.0
% Mass loss if MgCO3=(44/84.3)(100%)=52.2
% Mass loss if MgC2O4=((44+28)/112.3)(100%)=64.1
If the preparation was pure, the compound present is MgCO3.
3. Dynamic Mechanical Analysis
E cL4 vr2 / d 2
Damping: log10(A1/A2)=log10(A2/A3)
For elastic materials, the modulus E is simply the constant
ratio between the stress and the resulting strain, but for
viscoelastic materials, the modulus is a complex quantity:
E* = E' + iE"
where E' is the storage modulus or in-phase component
and E" is the loss modulus or out-of-phase component. The
ratio E" / E' is the tangent of the phase angle, .
* For this forced-vibration situation, complex variables (i.e. ) is used for
analysis The modulus can also be written as G* = G + iG where G is
called the storage modulus and G is called the loss modulus.
* The outputs of the test are usually temperature variation plots of either tan
, G and/or G or some other combinations of these parameters.
* The sample is set in cyclic tensile load, a linear variable differential transformer
(LVDT) is used to monitor the frequency and the amplitude of vibration.
* The preset oscillation amplitude is maintained by a feedback control loop and the
driving force required to do so is a measure of the energy dissipation of the sample
3.4 Applications
DSC cell
* T<500°C : usually contained in aluminium sample pans
which can be sealed either by crimping or by cold-welding for
holding volatile samples
* T>500°C : use quartz, alumina (Al2O3), gold or graphite
pans
* the reference material in most DSC applications is simply an
empty sample pan
* purging of gas into the DSC sample holder is possible, e.g.
N2, O2, etc.
* the mass of (sample+pan+lid) should be recorded before and
after a run so that further information about the processes can
be deduced
The reference sample
For all difference methods (DTA, DSC) reference samples like Al2O3 are
needed to ensure that the heat flow from the furnace to the sample and from
the furnace to the reference sample is identical!
For small weights of the sample and when no precise measurements are
required an experiment without a reference sample is possible.
In such case an empty crucible can be used as reference.
4.3 Interpretation of DSC curves
Cp
H C p dT S
T2 T2
dT
T1 T1 T
G = H - TS
4.4.2 Measurement of thermal conductivity
hs Rs ls d c2 Tc
s c
hc Rclc d s Ts
2
Corresponding
TG curve
* Detection of solid-solid phase transition and the measurement
of H for these transitions