Thermal Analysis
A class of techniques to measure chemical or physical
properties of a substance as function of temperature or time
C-3110 [6110]; Fall 2011
Technique Output
TGA Mass change vs. T
DTA T (Sample Ref) vs. T
DSC Power vs.T
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1. ThermoGravimetric Analysis TGA
I.Process: weight changes of a specimen as a function of temperature
II.General instrumentation
III.Output: plot of mass versus temperature
Principles of Insturmental Analysis 6th ed., Skoog, Holler and Crouch 3
TGA
Thermocouple
Gas out
Temperature Programmer
Furnace
S
Amplifier and data
collection
Display-Recorder
computer
Gas in Sensor
assembly
4
TGA instrumentation:
Sample holder (metallic/ceramic pans)
Microbalance
Programmable heater (furnace)
Gas flow control
Temperature control (thermostat)
Temperature sensor (thermocouple)
Read-out
Calibration:
Temperature calibration: use of a reference with a known Curie point
Mass calibration: use of a reference with exact known mass
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How a typical microbalance works?
-A balance beam which is connected to the sample cup and a magnetic coil through
its two extremes Principles of Insturmental Analysis 6th ed.,
Skoog, Holler and Crouch
-There is a lamp and two photodiodes
-A permanent magnet surrounding the coil
After a mass change in sample,
Step 1. balance beam is deflected
Step 2. Disturbance of the balance beam will change the shutter position to
develop a current in photodiode as a result of the upcoming light from the lamp
Step 3. So, the imbalance induces a current in the magnetic foil
Step 4. The current in the magnetic foil generates a magnetic field that forces the
balance beam to its original position
Step 5. Photodiode current is amplified
Step 6. The amplified current is translated to mass-loss information
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Thermocouple: Thomas Seebeck
Any conductor subjected to a thermal gradient will develop a voltage
(thermoelectric or Seebeck effect)
V
T1 T1<T2 T2
MetalA
Types:
e
K: chromel-alumel
E: chromel-Constantan
HEAT V
J: iron-constantan
N: nicrosil-nisil MetalB
e
Pt types
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Applications of thermogravimetry
i.Analysis of mixtures
Each part of a mixture behaves differently with temperature change
ii.Oxidation studies
Study of the oxidation of metals at a constant temperature
iii.Reduction studies
Study of the reduction of a solution/suspension of metal(s)
iv.Exact chemical identification
Different TGA behaviours of identical samples with different history
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Undergraduate Instrumental Analysis 6th Ed.,
Robinson, Frame and Frame
CaC2O4.H2O CaC2O4 + H2O T ~ 100 C
CaC2O4 CaCO3 + CO T ~ 500 C
CaCO3 CaO + CO2 T ~ 800 C 9
Analysis of mixtures
Undergraduate Instrumental Analysis 6th Ed.,
Robinson, Frame and Frame
10
Polymer Degradation and Stability
91 (2006) 3312
11
Principles of Insturmental Analysis 6th ed., Skoog, Holler and Crouch 12
N2
O2
Journal of Analytical and Applied Pyrolysis 92 (2011) 407.
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Errors in TGA
Drift effect or buoyancy effect (weight gain with temperature)
External vibrations
External heat
Thermocouple (position and decomposition)
Heat of reaction
Thermal conductivity
Mass and packing of sample
Slow recorder/readout equipment
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2. Differential Scanning Calorimetry DSC
Difference in heat flow to a sample and to a reference is monitored
against time/temperature:
1.Power-compensated DSC
1. Separate heating of sample and reference
2. Identical temperature difference
3. Measurement of electrical power
2.Heat flux DSC
1. In-concert heating of sample and reference
2. Measurement of temperature change
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DSC (Power Compensated )
Principles of Insturmental Analysis 6th ed., Skoog, Holler and Crouch
Gas DTA or DSC (Heat flux)
out
Furnace
S R
Display-Recorder
computer
Sensor
Gas assembly
in
Amplifier and data
collection
Programmer
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DSC (and DTA) instrumentation:
Sensors plus amplifier
Cu for low temperature
Pt-Rh for high temperature
Furnace and temperature controller
Ceramic
Ag (high thermal conductivity)
Atmosphere control
Reference material (Al2O3 or SiC)
Recorder and read-out
Fast-response data acquisition
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Theory of DSC
Heat
Energy transfer between two bodies due to thermal communication
Calorimetry
Measuring the heat of physical/chemical interactions
Heat capacity
The amount of heat needed to increase temperature of a substance
Enthalpy (Joule) H = mCp. T
Cp = H/mT
First derivative over time Cp = 1/m [(H/t)/(T/t)]
Where T/t = (scan rate: K/min)
Then, specific heat capacity Cp (J/K.Kg)= Heat flow/m
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Calibration:
1.Baseline: correction for the baseline slope of a blank run (no pan)
2.Heat flux and temperature: melting a reference (Indium) of known heat flux
3.Heat capacity: use of a reference of known heat capacity (i.e. sapphire)
Principles of Insturmental Analysis 6th ed., Skoog, Holler and Crouch 20
Principles of Insturmental Analysis 6th ed., Skoog, Holler and Crouch 21
Differential thermal analysis:
recording any temperature difference between sample and reference being
subjected to identical thermal cycles
finger print for identification
Undergraduate Instrumental Analysis 6th Ed., Robinson, Frame and Frame 22
Applications
DSC DTA
1. Glass transition 1. Heat of reaction
temperature 2. Corrosion
2. Crystallinity and 3. Identification of polymers
crystallization rate 4. Ceramic and metals
3. Reaction kinetics industry
4. Heat of reactions 5. Structural studies:
5. Corrosion decomposition
temperature
phase transitions
melting-boiling
crystallization point
thermal stability
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Hyphenated techniques
Where a second technique provides additional useful information
I. TGA-DSC
II. TGA-DTA
III. TGA (or DTA, DSC)-MS
IV. TGA (or DTA, DSC)-GC
V. TGA (or DTA, DSC)-GCMS
Evolved gas analysis
Undergraduate Instrumental Analysis 6th Ed., Robinson, Frame and Frame 24
Undergraduate Instrumental Analysis 6th Ed., Robinson, Frame and Frame 25
Undergraduate Instrumental Analysis 6th Ed., Robinson, Frame and Frame
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Thermal analysis
Advantages
Accurate
Low detection limit (up to 10-7 g)
Reliable data
Easy to use
Rather cheap
Minimal sample preparation
Disadvantages
Destructive
Limited range of samples
Time consuming
Usually not qualitative
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TO-KNOW LIST
9 TGA and DSC (DTA) definitions and theories
9 Operation
9 Simplistic schemes for TGA and DSC instruments
9 Role of each part in TGA and DSC instruments
9 General interpretation of TGA and DSC (and DTA) plots
9 Selected applications + examples
9 Advantages and disadvantages
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