ThermalAnalysis:methods,principles,applica5on

AndreyTarasov
LectureonThermalanalysis
26.16.2012
Andrey Tarasov, Thermal analysis, Lecture series heterogeneous catalysis, FHI MPG, 26.10.12
 Main definitions

Heat

Heat Capacity

C=Q/T, [J/mol/K]

Thermal conductivity
=aCp =[J/s/m/K]=[W/m/K]
a thermal diffusivity, m2/s

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 Deni5onofTA
Groupofphysicalchemicalmethodswhichdealwithstudyingmaterials
and processes under condi5ons of programmed changing's of the
surroundingtemperature.

Differential Heat equation

r, - polar coordinates
z - applicate
Main Thermo-physical properties of materials
Thermal conductivity , J/(cm*s*K)
Mathema5cal Cp Thermal capacity, J/(g*K)
Property/Characteris5c Unit Method
expression
density, g/(cm3)
Thermalconduc5vity (T)=aCp(T)(T) W/(m*K) LFA Q heat of the process (reaction)
degree of conversion
Thermallinear
=1/r*(dr/dT) %/K DIL
expansion a thermal diffusivity, cm2/s
Enthalpy dQ/dt=mCp(dT/dt) J/g DSC
Weight/Composi5on/
=(mo-mi)/mo % TG
Conversion

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 Thermal conductivity, thermal diffusivity

Andrey Tarasov, Thermal analysis, Lecture series heterogeneous catalysis, FHI MPG, 26.10.12 4
 Laser Flash Method (LFA)

(T)=aCp(T)(T)

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 Dilatometry (DIL)

=1/r*(dr/dT)

thermal expansion coefficient

r sample length

DIL Measurement Information

Linear thermal expansion

Determination of coefficient of thermal expansion
Sintering temperatures
Softening points
Phase transitions

SiN thermal shrinkage

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 Basic Principles and Terminology

Principleofcombinedthermocouple
Registra5onthetemperatureoftheobjectandtemperaturedierence
betweensampleandreference

Consequence
Dependingontheengineeringdesign,measuringcellconstruc5onandtheway
ofdatarepresenta5on,varietyofmethodshasbeenarisen:DTG,DTA,DSC,STA
etc.

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 Basic Principles and Terminology
DSC-TG

DSC(Dieren5alScanningCalorimetry):
VoltagetokeepT=TSTR=0vs.T
RDTA(ReverseDieren5alThermalAnalysis) TG
dt/dTvs.T

InAC TA(Thermalanalysis)
ThermoLab
TSvs.t DTA-TG
TG(Thermogravimetricanalysis)
mvs.T
DTA(Dieren5alThermalAnalysis)
T=TSTRvs.T Calvet-DSC
Calvet TA
DDTA(Deriva5veDTA)
dT/dtvs.T

STASimultaneousThermalAnalysis:TGDSC;EVAEvolvedgasanalysis:MS,FTIR,GC
Hyphenated techniques
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 Basic Principles and Terminology
Thermocouples
Type Composi+on Temperaturerange,K Outputvoltage
Tmin Tmax (0C),mV
T Cu/constantan 3 670 20
J Fe/constantan 70 870 34
E chromel/constantan 970 45
K chromel/alumel 220 1270 41
S Pt/PtRh(10) 270 1570 13
R Pt/PtRh(13) 220 1570 12
C W/WRe(26) 2670 39
N Nicrosil/Nisil 1200 39
Constantan - 58% Cu, 42% Ni Alumel 94% Ni, 2% Al, 1,5% Si, 2,5 % Mn

Chromel 89% Ni, 10% Cr, 1%Fe Nicrosil/Nisil Ni, Cr, Silicon/Ni, Silicon

Cu/Constantan Pt-PtRh(10)
CuNi disk sensor
disk sensor on diskshaped
on Ag plate.
Si(X) waffer. thermocouple
sensor sensor
Andrey Tarasov, Thermal analysis, Lecture series heterogeneous catalysis, FHI MPG, 26.10.12 8
 Basic Principles and Terminology
TG DSC (Heat flux)

SMP g = ((mSC + mS + mA) - (VSC + VS + VA) gas) g

FB

SMP - Measurement signal

FB - Buoyancy force , f(T) STA
mA - Mass of adsorbed gas, f(T)
mSC - Mass of sample container
mS - Mass of sample , f(T)
VA - Volume of adsorbed gas , f(T)
VSC - Volume of sample container
VS - Volume of sample, f(T)
gas - Density of gas, f(T)

Andrey Tarasov, Thermal analysis, Lecture series heterogeneous catalysis, FHI MPG, 26.10.12 9
 Basic Principles and Terminology

sensor sensor

reference sample

Andrey Tarasov, Thermal analysis, Lecture series heterogeneous catalysis, FHI MPG, 26.10.12 10
 General Theory (Heat equation for inert material)

Temperature lag

r, - polar coordinates
b heating rate, K/min
a -Temperature conductivity coefficient, cm2/s
Thermal conductivity , J/(cm*s*K)
Cp Thermal capacity, J/(g*K)
density, g/(cm3)

Andrey Tarasov, Thermal analysis, Lecture series heterogeneous catalysis, FHI MPG, 26.10.12 11
 General Theory (Temperature field in active sample)

Exothermic
Q>0, H<0

Temperatureandreac5onextenteldforexothermicprocesses

Endothermic
Q<0, H>0

Temperatureandreac5onextenteldforendothermicprocess
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 General Theory

DSC TG
Pb(S) Pb(L), H298= 5 kJ/mol CuO(S)+H2(g) CuO(s)+H2O(g) , H298= -86 kJ/mol

Setup baseline (zero line) Blank measurement (zero line)

Baseline interpolated

Endothermic peak

Shift of the baseline could appear due to Measurements may have a significant
change in thermal resistance of the setup. change in weight due to changes in gas
Position is depending on measuring-history. density and viscosity.

Andrey Tarasov, Thermal analysis, Lecture series heterogeneous catalysis, FHI MPG, 26.10.12 13
 General Theory

Heat balance (T) heattransfercoecient

c measuringcellheatcapacity
Mmassofthemeasuringcell
Tgeneratedtemperaturedierence
normalizedconversion
Heat of the process is determined as follows:

S availablesurfaceforheatexchange
msamplemass
Tgeneratedtemperaturedierence

K(T) instrumentconstant
radradia5onenergybetweenovenandsample
s samplethermalconduc5vity

A DSCpeakarea

Andrey Tarasov, Thermal analysis, Lecture series heterogeneous catalysis, FHI MPG, 26.10.12 14
 General Theory

Calibration Standards

Standard Mel+ngPoint,C HeatofFusion,J/g

In 156,6 28,6
Sn 231,9 60,1
Bi 271,4 53,1
Pb 327,5 23,0
Zn 419,5 107,5
Al 660,0 397,0
AlSi 577880
Ag 961,8 104,6
Au 1064,2
Unalloeydsteels 11471536
Ni 1455,0 290,4
Pd 1554,8 157,3
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 General Theory (DTA equation)

hea/ngrate,K/min

1. ExperimentalDTAcurve
2. DTAcurvecorrectedtoheattransfercondi5ons
3. TruebaselineofDTAcurve
4. Interpolatedbaseline;
5. Experimentalbaseline;
6. Experimentalbaselinealerprocess,shiledbecauseof
thermalcapacitychanges.

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 General Theory

DSC Artifacts

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 General Theory

3 major aspects of correct DSC measurement:

Baseline

Gradient T Calibration, KDTA,

Andrey Tarasov, Thermal analysis, Lecture series heterogeneous catalysis, FHI MPG, 26.10.12 18
 General Theory

Baseline definition.
1 Linear Baseline
It should be used for measurements in which no significant Cp
changes are observed during melting. The linear baseline is
generally used.

2 Sigmoidal Baseline
This baseline is used when the melting process is
accompanied by a notable Cp change.

3 Tangential Area-Proportional Baseline

This baseline is used when the melting process is
accompanied by a notable Cp change and a sloping
baseline exists.

Andrey Tarasov, Thermal analysis, Lecture series heterogeneous catalysis, FHI MPG, 26.10.12 19
 General Theory
Au(S) Au(L), H298= 12,6 kJ/mol In(S) In(L), H298= 3.3 kJ/mol

sigmoidal linear

CuO/ZnAl2O4+H2 Cu/ZnAl2O4+H2O

tangential
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 General Theory

DSC peak Correction

In(S) In(L), H298= 3.3 kJ/mol

Issues by uncorrected data

1. Temperature on the peak point does not

correspond to the melting temperature (but from
physical point of view the sample temperature
should be equal to melting point)
2. After peak maximum the signal diminishes slowly.
(Although it is known that the sample is completely
molten)

Andrey Tarasov, Thermal analysis, Lecture series heterogeneous catalysis, FHI MPG, 26.10.12 21
 General Theory

Bad thermal contact Good Thermal contact

Long melting time Short melting time
Broad, low peak Sharp peak

The slope of the peak left side is depended on thermal resistance

Peak area is the same and equals melting enthalpy.
Andrey Tarasov, Thermal analysis, Lecture series heterogeneous catalysis, FHI MPG, 26.10.12 22
 General Theory

f(t) evolved heat

F(t) measured signal g(t)=exp(-t/)
g(t) response function

small

big

The peak right side is depended on instrument

time constant.

1 < 2
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 General Theory

DSC peak Correction

Original signal
Time constant correction
Full correction

Andrey Tarasov, Thermal analysis, Lecture series heterogeneous catalysis, FHI MPG, 26.10.12 24
 General Theory

Theproper5esofthesystemsamplesensorstronglyinuencetheexperimentalTAcurves

FeaturesofTASetup Characteris5csofthesample

a)Reac5onAtmosphere a) Par5clesize
b)Sizeandshapeoftheoven b) Thermalconduc5vity
c)Sampleholdermaterial c) Thermalcapacity
d)Sampleholdergeometry d) Packingdensityofpar5cles(powder,pill,tablet)
e)Hea5ngrate e) Sampleexpansionandshrinking
f)Thermocouple(wirediameter) f) Samplemass
g)Thermocoupleloca5on g) Inertller
h)Response5me h) Degreeofcrystallinity

Informa5onobtaineddependsonprocedure
Notfundamentalproperty
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 Influence of external gas flow
Setup:NetzschSTAJupiter

24n224+n23+1/22+2
1stage 2stage 3stage

Dehydration of CaC2O4nH2O in an open crucible in a dry air

flow (red curve) and in a static atmosphere (green curve).

Andrey Tarasov, Thermal analysis, Lecture series heterogeneous catalysis, FHI MPG, 26.10.12 26
 Influence of external atmosphere
Setup:NetzschSTAJupiter

TG

Dr. Andrey Tarasov, Thermal analysis, Lecture series heterogeneous catalysis, FHI MPG, 26.10.12 27
 Influence of external atmosphere

k1

M=CuxZn1-x
DSCTGsampleholder,
Sampleweight:10mg

Vacuum 10-4 bar

Ar, 100ml/min

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 Influence of sample mass

k1

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 Influence of heating rate
Independent processes

Ea1<Ea2

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 Influence of heating rate
Subsequent processes

La(OH)3LaOOH+H2O
LaOOHLa2O3+H2O

Andrey Tarasov, Thermal analysis, Lecture series heterogeneous catalysis, FHI MPG, 26.10.12 31
 Influence of heating rate
Competitive process processes

Ea1<Ea2

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 Influence of the pan material
Setup:NetzschSTAJupiter

Al Pt Al2O3 Ni Cu Quartz

PyrolisisofFluoropolymer:TFEVDF,{C2F4}n{C2H2F2}m,F42inAlanAupans

in Al

in Au

10Kpm,Ar,100ml/min
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 Strong exothermic reactions
Setup:NetzschSTAJupiter

Interac5onofTaandNbwithFluoropolymer:TFEVDF,{C2F4}n{C2H2F2}m,F42
with A. Alikhanjan, and I. Arkhangelsky (2009)

Ta-F42

-strong heat evolution, narrow T

-2 stages by interaction
-sharp weight loss due to reaction between
two solid interfaces.

Mass loss: reflects the available metal

surface which is in contact with polymer.

Andrey Tarasov, Thermal analysis, Lecture series heterogeneous catalysis, FHI MPG, 26.10.12 34
 Strong exothermic reactions
Setup:NetzschSTAJupiter

Exothermic
Endothermic (due to water traces)

Two effects coinsides resulting in endothermic effect.

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 Measurementininert.Isthesystemoxygenfree?
Setup:NetzschSTAJupiter

CuC2O40.5H2OCu+2CO2

Cu+1/2O2CuO

O2tracesof0.25ppm

DSCTGsampleholder,
Al2O3pan,Ar100ml/min
Sample:CuC2O40.5H2O
Weight:9.1mg

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 Measurementininert.Isthesystemoxygenfree?
Setup:NetzschSTAJupiter

DSCTGsampleholder,
Al2O3pan,Ar100ml/min
Sample:Ni/MgAl2O4
Weight:14.1mg

Ni+1/2O2NiO

@RTO2tracesof1.7ppm

Andrey Tarasov, Thermal analysis, Lecture series heterogeneous catalysis, FHI MPG, 26.10.12 37
 Measurementininert.Isthesystemoxygenfree?
Setup:RubothermMSB
CuC2O40.5H2OCu+2CO2 TGsampleholder,
Al2O3pan,Ar250ml/min
Cu+1/2O2CuO Sample:CuC2O40.5H2O
Weight:301.8mg

O2tracesof7ppm

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 Determina5onofcrystallinitydegree

TFEVDF,{C2F4}n{C2H2F2}m,F42

=f/Hfo

X-degree of crystallinity

Hfo enthalpy of polymer with 100% degree of crystallinity

Hfo = 99.3J/g

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 TA-MS Coupling systems

Skimmer coupling system

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 TA-MS Coupling systems

Capillary coupling system

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 Main Problems of TA-MS coupling system

Pressure reduction
103mbar 10-5mbar

Condensation and secondary reactions

Unfalsified gas transfer
Different viscosity Demixing

Attribution of a fragment to a chemical process

Pyrolysis or evaporation
MS fragmentation or sample behavior

Overlapping of thermal processes

hydrolysis and oxidation due to rest water and
oxygen background in the feed.

Disadvantages: shock sensitive, no direct MS inlet.

Kaiserberger (1999)
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 (PulseTA) Adsorption of Methanol on -AlF3
M. Feist et. al. 2010
Sample:AlF3
Sampleweight:43.81mg
m=0.15mg, Determining Lewis acidity
N270ml/min

TA-MS curves for a PulseTA experiment on pretreated (2 h, 250 C; vacuum)

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 (PulseTA) Titration of Ni surface with O2
Sample:Ni/MgAl2O4
** Assuming O/Ni=2, dNi=9nm in agreement with TEM Sampleweight:30.8mg
m=1.14mg,
Ar100ml/min

O(chemisorbed)/Ni(reduced)=0.22

PTA curves of NiO/MgAl2O4 after reduction, isothermal at 45C with O2 injections,

Interupted by a H2 pulse
Andrey Tarasov, Thermal analysis, Lecture series heterogeneous catalysis, FHI MPG, 26.10.12 44
 Resources

J. Sestak, Thermophysical properties of solids (Academia, Prague, 1984)

G. Hhne, W. Hemminger, H.-J.Flammersheim, Differential Scanning Calorimetry

(Springer, Berlin, 1996)

E. Moukhina, J. Therm Anal. Calorim. (2012) 109: 1203-1214

http://www.netzsch.com

Andrey Tarasov, Thermal analysis, Lecture series heterogeneous catalysis, FHI MPG, 26.10.12 45
 Acknowledgments

Dr. Elena Moukhina, Netzsch Gertebau GmbH, Selb

Dr. Jan Hanss, Netzsch Gertebau GmbH, Selb

Dr. Michael Feist, HU Berlin

Prof. Igor Arkhangelsky, MSU Moscow

Dr. Alexander Dunaev, MSU Moscow

analysis
thermal

Andrey Tarasov, Thermal analysis, Lecture series heterogeneous catalysis, FHI MPG, 26.10.12 46
Thank you!

47