Thermal Analysis

Terry A. Ring
Chemical Engineering
University of Utah

11 Sept 07 1
Different Techniques
 Thermometric Titration (TT)
 Heat of mixing
 Thermal Mechanical Analysis (TMA)
 Thermal Expansion Coefficient
 Dynamic Mechanical Analysis (DMA)
 Viscoelastic Properties
 Differential Scanning Calorimetric (DSC)
 Heat flow during Transitions
 Thermal Gravimetric Analysis (TGA)
 Weight Loss due to decomposition
 Derivative Thermogravimetric Analysis (DTG)
 Differential Thermal Analysis (DTA)
 Heat of Transitions
 Temperature Programmed Desorption (TPD)
 Temperature at which gas is desorbed from (catalyst) surface
 Emission gas Thermoanalysis (EGT)

11 Sept 07 2
Basic Principle
 Sample is heated at a constant heating
rate
 Sample’s Property Measured
 Wt TGA
 Size TMA
 Heat Flow DSC
 Temp DTA
 Gas evolved TPD
11 Sept 07 3
TGA
 Constant Heating
Rate
 Initial Temp
 Final Temp
 Heating Rate
(°C/min)
 Data
 Weight vs Time
 Weight vs Temp.
 Differential This
Data (DTG)
11 Sept 07 4
DSC

11 Sept 07 5
DSC
 Constant Heating Rate
 Initial Temp
 Final Temp
 Heating Rate (°C/min)
 Data
 Heat flow to sample
minus Heat flow to
reference vs Time
(Temp.)
 Measures heat of
crystallization
Polymer without weight change in this temperature range
11 Sept 07 6
DTA
 Sample and Reference Placed in Heater
 Constant Heating Rate
 Initial Temp
 Final Temp
 Heating Rate (°C/min)
 Data
 Temp of Sample vs Time (or Temp)
 Temp of Reference vs Time (or Temp)
 Reference should be inert, e.g. nothing but latent heat
 Measures
 Heat of crystallization
 Glass Transition Temperature
11 Sept 07 7
DTA + DTG

11 Sept 07 8
TMA
 Constant Heating Rate
 Initial Temp
 Final Temp
 Heating Rate (°C/min)
 Data
 Size of Sample vs Time (or Temp.)
 Measures
 Thermal Expansion Coefficient
 Volume change on crystalization or crystal
transformations
 Sintering
 Glass Transitions in Polymers
11 Sept 07 9
TMA

Polymer with glass transition

11 Sept 07 10
DMA
 Constant Heating Rate
 Initial Temp
 Final Temp
 Heating Rate (°C/min)
 Data
 Force vs Time (or Temp.)
 Force delay vs Time (or
Temp.)
 Viscoelastic Properties
 Storage and Loss
Modulus
 Measures Polymer with Glass Transition
 Glass Transition
 Viscoelastic Properties
11 Sept 07 11
We have TGA - only
 Heating a sample of Calcium oxalate

 Ca(C204)*xH2O  Ca(C204) *H2O + x-1 H2O

 Ca(C204)*H2O Ca(C204) + H2O
 Ca(C204)  CaCO3 + CO
 CaCO3  CaO + CO2

11 Sept 07 12
TGA
 Constant Heating
Rate
 Initial Temp
 Final Temp
 Heating Rate
(°C/min)
 Data
 Weight vs Time
 Weight vs Temp.
 Differential This
Data (DTG)
11 Sept 07 13
TGA – Ca(C204)*xH2O

11 Sept 07 14
Different Heating Rates

11 Sept 07 15
Heating Rate
 Heating Too Fast
 Overlaps Transitions
 Interpretation Problems
 Kinetics of Decomposition
 Sample Size
 Mass Transfer
 Convective Mass Transfer
 Pore Diffusion
 Heat Transfer
 Convective Heat Transfer
 Thermal Conductivity
 Porous solid
11 Sept 07 16
Precipitated Zr5O8(SO4)2*15 H2O

This sample was dried fro 48 hrs at 110C before TGA analysis.
11 Sept 07 17
What is going on?
 Analysis of Filtrate from
Precipitation
 Precipitation
 5ZrOCl2 + 2H2SO4 + xH2O  15 H2O Water Loss Wt. Loss % loss
1 18.0152 1.721573
Zr5O8(SO4)2*15 H2O (s) + 10 HCl 2 36.0304 3.443146
3 54.0456 5.164719
4 72.0608 6.886292
 Decomposition 5 90.076 8.607865
6 108.0912 10.32944
 Zr5O8(SO4)2*15 H2O (s)  7 126.1064 12.05101
Zr5O8(SO4)2*14 H2O (s) + H2O (v) 8 144.1216 13.77258
9 162.1368 15.49416
10 180.152 17.21573
11 198.1672 18.9373
 Zr5O8(SO4)2  5
12 216.1824 20.65887
ZrO2 (s) +2 SO2 (v) 13 234.1976 22.38045
14 252.2128 24.10202
15 270.228 25.82359
SO2 1 64.0588 31.9452
2 128.1176 38.0668

11 Sept 07 18
Differentail Thermal Analysis
on soils

Name : Uğur Demirel

ID:1384791

11 Sept 07 19
Outline
 1-)Introduction
 2-)Advantages and Disadvantages
 3-)Clasifications of Soils
 4-)Conclusion

11 Sept 07 20
Information

Differential thermal analysis (DTA)

began soon after the development
of the thermocouple.

11 Sept 07 21
It has progressed through the systematic
development of better equipment and the
cataloguing of typical DTA curves for a
variety of materials until good technique
now requires control of the composition
and pressure of the furnace atmosphere
as well as consideration of the
thermodynamics and kinetics of the
reactions involved.

11 Sept 07 22
 Although differential thermal analyses
have been made for many materials, the
major applications have been concerned
with clay and carbonate minerals.

11 Sept 07 23
 Apparatus

11 Sept 07 24
The key features of a differential
thermal analysis kit are as follows

 1. Sample holder comprising

thermocouples, sample containers and
a ceramic or metallic block.
 2. Furnace.
 3. Temperature programmer.
 4. Recording system.

11 Sept 07 25
Working Principle
 Dta involves a heating a test
sample and a inert material
under identical conditions

 Recording any temperature

difference between the sample
and reference.(ΔT=T1-T2)
11 Sept 07 26
 This differential temperature is then
plotted against time, or against
temperature

 Changes in the sample which lead to

the absorption or evolution of heat
can be detected relative to the inert
reference.
11 Sept 07 27
 If Δt >0, Exothermic reaction

 If Δt <0, Endothermic reaction

 Reference Material (Inert

Material)
 Mostly alumina is used as an inert material
 As temprature rises heat of alumina is also
rises with the same rate, as temprature
drops heat of alumina is also drops with
the same
11 Sept 07 rate 28
In DTA curves for clay minerals the low-
temperature endothermic loop associated
with the loss of water
The hightemperature exothermic loop

accompanying the formation of new

compounds, are changed in shape,
temperature, and intensity by the kind of
exchange cations.

11 Sept 07 29
  Thermal curve for kandites
(10°C/min)
11 Sept 07 30
 Low endothermic peak A:
Removal of adsorbed water

 The main endothermic peak

B:
Removal of combined water

 The first exothermic peak D:

Formation of new minerals

11 Sept 07 31
Advantages of Dta on soils
 Cheapness of apparatus

 Simplicity

 Rapidity (100 minutes for 1

investigation)
11 Sept 07 32
 Gives information not readily obtainable by
any other method
Ex: illite giving a peak at 700 °C must be
quite different from one giving a peak at
550 °C , although their x-ray patterns can
show little difference for identical and
chemical data
 Unlike x-ray techniques, dta is applicable

not only to crystaline but also amorphous

minerals.

11 Sept 07 33
Limitations of DTA
 Apparatus problems:
Aging
Heating Rate

 Different Techniques

 Content (Minerals and organic matter)

11 Sept 07 34
Classification of soils
 Classifications are made acording
to peaks
 Two main peaks
A-) Endothermic peak
B-) Exothermic peak
 These peaks divided into other peaks

like low endothermic peak and main

endothermic
11 Sept 07
peak 35
Endothermic peaks
1-)Low temprature
endothermic peak
 Important feature for halloysite and
allophane
 Removal of constitutional water

 Interlayer water

 Water associated with amorphous silica

 Water sorbed on surface of fine

particles
11 Sept 07 36
The main endothermic peak

 Associated with the expulsion of water

from minarel lattice and is important for
all members of groups

11 Sept 07 37
 Exothermic peaks

 Formation of new crsytals

 After heating minreals to 900 °C there are

some products called fire products

11 Sept 07 38
11 Sept 07 39
 Endothermic and exothermic
peaks of some soil types
Exothermic
Soil type Endothermic (°C ) (°C )

Chlroite 600-650 840-900

Clay mica 550-600 around 900

Kaolonite around 650 950-980

Montmollonite 150-200
11 Sept 07 40
11 Sept 07 41
Conclusion
 Dta is not a very accurate system
 It is rapidity, cheapness and simplicity
makes it a proper test for a classification
of soils.
 We can clasify soils according to their
endothermic and exothermic peaks
 After heating minreals to 900 °C there
are some products called fire products
11 Sept 07 42
References
 The differential thermal investigation of
clays (Mackenzie, R. C.)

 Differential thermal analysis

(Mackenzie)

 Differential thermal analysis of clays

and carbonates (Richards A. Rowland)
11 Sept 07 43
Differential Scanning
Calorimetry (DSC)

Bioanalytical Chemistry
Spring 2004

11 Sept 07 44
Thermal Analysis
 Differential Scanning  Thermal Gravimetric
Calorimetry (DSC) Analysis (TGA)
 Measure heat  Measure change in
absorbed or liberated weight during
during heating or heating or cooling
cooling  Thermomechanical
Analysis (TMA)
 Measure change in
dimensions during
heating or cooling
11 Sept 07 45
What Can You Measure with
DSC?
 Qualitative analysis
 Fingerprinting of minerals, clays, polymers
 Sample purity
 Melting points
 Heat capacity, cp
 Glass transition temperature, Tg
 Crystallization temperature, Tc
 Phase diagrams
11 Sept 07 46
Where Used?
 Pharmaceutical industry
 Purity
 Food industry
 Characterization of fats and oils
 Polymer industry
 Synthetic blends

11 Sept 07 47
 Schematic of DSC Instrument
Sample Reference

T1 T2

Pt thermopile Pt thermopile
Low mass
1 gram heater heater

N2 flow

W

11 Sept 07 48
Variants of DSC
 Heat flux
 1955 Boersma
 1 large (30 – 100 g) furnace
 Power compensated
 Separate small (1 g) microheaters for sample and
reference
 Hyper DSC
 Very fast scan rates 500°C/min
 Mimic processing conditions
 StepScan DSC
 Short dynamic and isothermal scan steps
 Separate reversible and irreversible effects
11 Sept 07 49
 Output
Thermogram
of DSC

exo
dH/dt, mJ/s

Glass transition

melting
crystallization

endo

Temperature, K
11 Sept 07 50
Heat Capacity
 dqp/dt = heat flow
 dT/dt = heating rate
 (dqp/dt) / (dT/dt) = dqp/dT = cp

11 Sept 07 51
Temperature Program
 T(t) = T0 + a * t
where T is temperature, a is a constant
and t is time

 A * t - Dynamic segment
 dT/dt

 T0 - Isothermal segment
 Constant temperature
11 Sept 07 52
Glass Transition Thermogram

 Step in thermogram
 Transition from
disordered solid to

dH/dt, mJ/s
Glass transition
liquid
 Observed in glassy Tg
solids, e.g.,
polymers
 Tg, glass transition
temperature Temperature, K
11 Sept 07 53
Crystallization Thermogram

 Sharp positive peak

 Disordered to
Crystallization
ordered transition

dH/dt, mJ/s
 Material can

crystallize!
Tc
 Observed in glassy

solids, e.g.,
polymers
 T , crystallization Temperature, K
c
temperature
11 Sept 07 54
Melting Thermogram

 Negative peak on
thermogram
Melting
 Ordered to

dH/dt, mJ/s
disordered transition
 Tm, melting
temperature Tm

 NB: melting
happens to Temperature, K
crystalline
11 Sept 07 polymers; 55
Analysis Crystallization

 Sharp positive peak

 Disordered to
ordered transition

dH/dt, mJ/s
 Observed in glassy
solids, e.g.,
polymers Tc

 Tc, crystallization
temperature
Temperature, K
11 Sept 07 56
Instrumental Performance
 Blank test
 No sample, no reference
 Baseline provides info on
 Sample contamination
 Pt thermopile
 4,4’-azoxyanisole – standard
 Netherlands Society for Thermal Analysis (TAWN)
 2 endothermic transitions
 117°C
 134°C
 Resolution
 Return to baseline
 R = 100 * (1 – ((dq/dt)min / (dq/dt)134C))
 Sensitivity
11 Sept 07 57
 Resolution
Thermogram

exo
dH/dt, mJ/s

endo

Temperature, K
11 Sept 07 58
Instrumental Specifications
 Temperature range -170 to 730°C
 Accuracy/precision 0.1°C/0.01°C
 Scan rates 0.01 to 500°C/min
 1 g indium (10°C/min, N2 purge)
 Peak height 7.44 mW  0.15 mW
 FWHM 0.42  0.10°C
 H/W ratio 17.6 mW/°C  1 mW/°C
 Isothermal drift (10 min)
 -150°C < 15 µW
 07
11 Sept 100°C <10 µW 59
Sampling
 Pan
 Al
 Au
 Glass capillary tubes
 Maximize contact between sample and
pan
 Thin films
 Fine granules of uniform size

11 Sept 07 Grind! 60
Calibration
 Calibrants  Accurately known enthalpies
 EX: indium (5 – 10 mg)
 High purity  H(fusion) = 6.80 cal/g, mp
 Metals 156.4°C
 In 156.4°C  K * (Area/mass) =
 Sn 231.9°C H(fusion) = 6.80 cal/g
 Pb 327.4°C  Not hygroscopic
 Zn 419.5°C  Not light sensitive
 Al 660.4°C  High thermal stability
 Inorganics  Relatively unreactive

KNO3 128.7°C  Pan
 KClO4 299.4°C  Atmosphere
 Organics
 Triphenylmethane
 Polystyrene 105°C
 Higher thermal conductivity
than metals

11 Sept 07 61
Calibration
 1 point
 2 point
 Is wide temperature range being used?

11 Sept 07 62
References
 Mendham, J.; Denney, R.C.; Barnes, J.D.;
Thomas, M.J.K. Vogel’s Textbook of
Quantitative Chemical Analysis 6th edition
Prentice Hall: Edinburgh, 2000.
 McNaughton, J.L.; Mortimer, C.T. In IRS;
Physical Chemistry Series 2, 1975, 10, 1-44.
“Differential Scanning Calorimetry.”
 “Differential Scanning Calorimetry.” Avail. At
URL:www.psrc.usm.edu/macrog/dsc.htm
11 Sept 07 63