MT3054 - Characterization of Materials
Thermal Analysis: TG/DTA/DSC
Prof. Galhenage A. Sewvandi
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Outline
• Introduction to Thermal Analysis
• Thermogravimetry (TG/TGA)
• Differential thermal analysis (DTA)
• Differential Scanning Calorimetry (DSC)
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Introduction to Thermal Analysis
• Thermal analysis (TA) is a group of analytical techniques that
measure properties or property changes of materials as a
function of temperature.
• TA relies on material reactions to thermal energy flow in or out
of solids. Such reactions are referred to as thermal events.
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Thermal Events
Thermal events during heating of a solid in an inert atmosphere.
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Thermal methods
Technique Measured Property Uses
Thermogravimetry (TG/TGA) Mass change Decompositions
Dehydrations
Oxidation
Differential thermal analysis Temperature Phase changes
(DTA) difference Reactions
Differential scanning Heat flow Heat capacity
Calorimetry (DSC) Phase changes
Reactions
Calorimetry
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Thermogravimetry (TG/TGA)
• TG is a technique for measuring mass change of a sample with
temperature.
• The main application of TG is to;
- Analyze material decomposition and thermal stability through
mass change as a function of temperature in scanning mode or
as a function of time in the isothermal mode.
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Mechanisms of Weight Change in TGA
• Weight Loss:
–Decomposition: The breaking apart of chemical bonds.
–Evaporation: The loss of volatiles with elevated
temperature.
–Reduction: Interaction of sample to a reducing atmosphere
(hydrogen, ammonia, etc).
–Desorption.
•Weight Gain:
–Oxidation: Interaction of the sample with an
oxidizing atmosphere.
–Absorption or Adsorption.
All of these are kinetic processes (i.e. there is a rate
at which they occur).
DOI: 10.1016/j.jallcom.2015.01.010
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Factors Eeffect on a TG curve
• The sample-form
• Heating Rate
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Interpretation of Thermogravimetric Curves
• Type (i) - nearly horizontal line that indicates there is no decomposition
with mass loss of volatile products over the temperature range.
• Type (ii) - rapid mass loss at the initial stage of a TA curve. It is likely that
the sample has gone through drying or desorption.
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• Type (iii) - one-stage decomposition curve that is typical in
TG curves. It can define the stability limit of a sample.
• Type (iv) - multistage decomposition with stable
intermediates.
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Analysis of TGA data
Draw tangents of the
curve to find the onset
(the temperature where
the curve deviates from
the interpolated sample
baseline) and the offset
points
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Plot DTG curves with TG curves
When the slope change is uncertain; a derivative
thermogravimetry (DTG) curve can be used.
The DTG curve is a plot of dm/dT versus
temperature.
-A peak in a DTG curve represents a maximum of
mass change rate.
-DTG does not contain any new information other
than the original TG curve.
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To enhance the steps in the TG curve, the
derivative thermogravimetric (DTG) trace
is frequently drawn. DTG is the plot of the
rate of mass change with time, dm/dt.
Typical TG (solid) and DTG (dashed) curves 13
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• TG curves can also be used for quantifying compositions of composites
containing thermally decomposable components.
TG curves of hydroxyapatite (HA)–ultrahigh molecular weight
polyethylene(UHMWPE) composites with different content HA particles
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Activity 01
Decomposition of Magnesium Hydroxide (Mg(OH)2)
• The chemical equation for the reaction is:
Mg(OH)2(s) = MgO(s) + H2O(g)
Calculate the weight loss% due to H2O evaporation. (molecular weight:
H=1, O=16, Mg=24)
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• The chemical equation for the reaction is:
• Mg(OH)2(s) = MgO(s) + H2O(g)
The calculated loss;
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TG and DTG curves for magnesium hydroxide, 7.04 mg, heated in a Pt crucible at 10
K/min, nitrogen.
Water
loss = 27%
Adsorbed or
Trapped Water
OR carbonate impurity
total mass loss of 30.9%
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TG and DTG curves for calcium oxalate monohydrate, 12.85 mg,
Pt crucible, 20 K/min, nitrogen.
loss = 12%
loss = 19%
loss = 30%
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A set of reactions to explain the losses
Since the first loss-starts around 100 C, we might consider loss of
water vapour.
A very good agreement between theory and experiment
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• Despite the excellent agreement of the calculated and experimental values,
it is most unwise to deduce reaction schemes from this evidence alone!
• The products, both gaseous and solid, should be characterized by other
analytical methods, such as X-ray diffraction for solids and chemical tests
for gases.
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Differential Thermal Analysis (DTA)
• DTA is a technique measuring the difference in temperature between a
sample and a reference (a thermally inert material) as a function of the time
or the temperature.
• ‘‘Differential’’ emphasizes that analysis is based on differences between
sample material and a reference material in which the examined thermal
events do not occur.
• The thermal events examined by DTA; solid-phase transformation, glass
transition, crystallization, and melting.
• The DTA method enables any transformation to be detected for all the
categories of materials.
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DTA
• When sample experience energy change associated with
physical/chemical phenomena, the difference in the temperature
profiles S and R identifies the transition.
• Eg: if sample melts, its temperature lag behind TR as it absorb heat
energy for melting.
• ΔT against time or temperature curve shows endothermic peak
due to heat absorption.
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DTA curve
• The DTA curve is a plot of ∆T versus reference temperature or heating time
when heating rate is constant.
DTA curve for a
polymer sample
under a constant
heating rate
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Activity -02
Explain the reason for appearance of the second peak in DTA but no
any indications in the TG.
TG- only measure changes caused by mas loss
DTA- can record thermal events without mass changes ( crystal
structure changes, melting , glass transition)
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Differential Scanning Calorimetry (DSC)
• DSC is a technique determining the variation in the
heat flow given out or taken in by a sample when it
undergoes temperature scanning in a controlled
atmosphere.
• With heating or cooling any transformation taking
place in a material is accompanied by a exchange of
heat.
• DSC enables the temperature of this transformation
to be determined and the heat from it to be
quantified.
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Differential Scanning Calorimetry (DSC)
• There are two widely used DSC systems to measure the heat-
flow difference between sample and reference.
1. The heat flux DSC; measures the temperature difference.
2. The power-compensated DSC; measures the enthalpy change
of a sample during a thermal event.
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A, furnace
B. Heaters
Heat flux DSC-measures the Power compensation DSC-directly
temperature difference directly measures the enthalpy change of a sample
and then converts it to a heat-flow during a thermal event. Compensate heat
difference heat release or gain during thermal event28
DSC Curve
• A DSC curve is a plot of heat flow versus temperature
Schematic DSC curves for a polymeric sample
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Experimental Aspects DTA or DSC
Samples: in the form of dense powders or small disks.
•Low-mass samples are also preferred
•The lower limit of sample size relates to the nature of the sample
materials.
-for composites and polymer blends, large sample size of about 10mg
•The scanning rate of DTA and DSC instruments commonly varies from 0.1
to 40 ◦Cmin−1.
•Scanning-rate effects are difficult to eliminate, particularly for polymeric
samples.
•The scanning rate should be reported with the DTA and DSC results.
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Determination of the temperatures of thermal events from a
DTA or a DSC curves
Crystallization
Glass
Transition Temperatures transition
-Measuring transition temperatures
is the primary task of DTA and DSC.
-The common transitions are
melting, crystallization, and glass
transition
Melting
The DTA curve of a glass–ceramic sample 31
The glass-transition temperature (Tg)
The glass-transition temperature (Tg) can be determined at the point
where the curve deviates from the linearity of the sample baseline.
When the point of the curve
deviating from the sample
baseline is not certain- the
intersection between two
tangents to the sample
baselines before and after
slope change.
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Crystallization temperature (Tc) and melting temperature (Tm) should be
defined at the intersection of the tangent to the maximum rising slope of
the peak and the extrapolated sample baseline.
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Measurement of Enthalpy Change
• The enthalpy change of phase transformation can be directly measured from
the corresponding peak area of a DSC curve.
DSC curve of octadecane 34
Determination of Specific Heat Capacity
• ASTM E 1269;Standard Test Method for Determining Specific
Heat Capacity by DSC
• Applicable to thermally stable solids and liquids.
• The normal operating range of the test is from − 100 to 600°C (The temperature
range can be extended, depending upon the instrumentation and specimen holders
used.)
• Summary of Test Method
This test method consists of heating the test material at a controlled rate in a
controlled atmosphere through the region of interest. The difference in heat flow
into the test material and a reference material or blank due to energy changes in
the material is continually monitored and recorded.
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• Significance and Use
• Differential scanning calorimetric measurements provide a rapid, simple method for
determining specific heat capacities of materials.
• Specific heat capacities are important for reactor and cooling system design
purposes, quality control, and research and development.
• Interferences
• Since milligram quantities of specimen are used, it is essential that specimens are
homogeneous and representative.
• The occurrence of chemical changes or mass loss on heating during the
measurement may invalidate the test. Therefore, the temperature range and
specimen holders should be chosen so as to avoid these processes.
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• Sampling
• Powdered or granular specimens should be mixed prior to sampling and should be
sampled by removing portions from various parts of the container. These portions, in turn,
should be combined and mixed to ensure a representative specimen for the
determinations.
• Liquid specimens may be sampled directly after stirring.
• Solid specimens may be sampled by cutting or slicing with a clean knife or razor blade.
Sample uniformity should be ascertained, since segregation within the solid is possible.
• Solid specimens should be so sampled as to maximize contact with the surface of the
specimen holder.
• Samples are usually analyzed as received. If some heat or mechanical treatment is applied
to the specimen prior to analysis, this treatment should be noted in the report.
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empty specimen holder • The thermal curve of the weighted empty specimen holder
plus lid and a reference specimen holder plus lid .
The thermal curve of standard sample plus lid and a
sapphire standard reference specimen holder plus lid
test specimen
The thermal curve of test sample plus lid and a reference
specimen holder plus lid
Reference Material—Synthetic sapphire
Specific Heat Capacity Thermal Curves of Standard Sapphire, and Unknown Specimens 38
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Instrumentation
Common features in all TA techniques
1.A furnace- a sample is heated (or cooled) with
a controllable environment
2.A transducer- the property changes in
materials are monitored
3.Thermobalance
4.Temperature Programing
5.Data acquisition system
General instrumentation for thermal analysis
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Experimental Parameters
For reliable TA data;
•Sample dimension and mass should be small-prefer less than 10mg
•The heating rate- a slow heating rate is often favorable in order to approach
thermal equilibrium. A fast heating rate will generate a thermal lag between
the heating source and sample.
•The atmosphere surrounding the sample serves to transfer heat and supply
or remove gaseous reactants or products. Thus, its chemical nature and flow
affect the TA data. In most TA methods, we need an inert atmosphere to
prevent the sample from oxidation reactions.
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DT-Q600 Simultaneous TGA / DSC
The Q600 provides
simultaneous
measurement of weight
change (TGA) and true
differential heat flow
(DSC) on the same sample
from ambient to 1,500 ˚C.
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Platinum pans and ceramic cups.
The platinum cups are recommended for operation to 1000
˚C, and for their general inertness and ease of cleaning. The
ceramic cups are advised for operation to 1,500˚C, and for
samples that react with platinum.
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Comparison of TG-DSC for
variety of
physicochemical
processes
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References
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