Andrey Tarasov Thermal Analysis 121026

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
Deni5onofTA
Groupofphysicalchemicalmethodswhichdealwithstudyingmaterials
and processes under condi5ons of programmed changing's of the
surroundingtemperature.
Differential Heat equation
Main Thermo-physical properties of materials

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

Basic Principles and Terminology

Principleofcombinedthermocouple
Registra5onthetemperatureoftheobjectandtemperaturedierence
betweensampleandreference
Consequence
Dependingontheengineeringdesign,measuringcellconstruc5onandtheway
ofdatarepresenta5on,varietyofmethodshasbeenarisen:DTG,DTA,DSC,STA
etc.

DSC-TG
DSC(Dieren5alScanningCalorimetry):
VoltagetokeepT=TSTR=0vs.T
RDTA(ReverseDieren5alThermalAnalysis) TG
dt/dTvs.T
InAC
ThermoLab
TA(Thermalanalysis)
TSvs.t
TG(Thermogravimetricanalysis)
mvs.T
DTA(Dieren5alThermalAnalysis)
T=TSTRvs.T
DTA-TG
Calvet-DSC
Calvet TA
DDTA(Deriva5veDTA)
dT/dtvs.T
STASimultaneousThermalAnalysis:TGDSC;EVAEvolvedgasanalysis:MS,FTIR,GC
Hyphenated techniques

Thermocouples
Temperaturerange,K Outputvoltage
(0C),mV
Tmin
Tmax
Type
Composi+on
Cu/constantan
670
20
Fe/constantan
70
870
34
chromel/constantan
970
45
chromel/alumel
220
1270
41
Pt/PtRh(10)
270
1570
13
Pt/PtRh(13)
220
1570
12
W/WRe(26)
2670
39
Nicrosil/Nisil
1200
39
Constantan - 58% Cu, 42% Ni

Chromel 89% Ni, 10% Cr, 1%Fe
Cu/Constantan
disk sensor on
Si(X) waffer.
sensor
Alumel 94% Ni, 2% Al, 1,5% Si, 2,5 % Mn

Nicrosil/Nisil Ni, Cr, Silicon/Ni, Silicon
CuNi disk sensor
on Ag plate.
Pt-PtRh(10)
diskshaped
thermocouple
sensor

TG
DSC (Heat flux)
SMP g = ((mSC + mS + mA) - (VSC + VS + VA) gas) g
FB
SMP - Measurement signal
FB - Buoyancy force , f(T)
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)
STA
gas - Density of gas, f(T)

sensor
reference
sensor
sample
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)
11
General Theory (Temperature field in active sample)
Exothermic
Q>0, H<0
Temperatureandreac5onextenteldforexothermicprocesses
Endothermic
Q<0, H>0
Temperatureandreac5onextenteldforendothermicprocess
12
General Theory
DSC
TG
Pb(S) Pb(L), H298= 5 kJ/mol

Setup baseline (zero line)
CuO(S)+H2(g) CuO(s)+H2O(g) , H298= -86 kJ/mol

Blank measurement (zero line)
Baseline interpolated
Endothermic peak
Shift of the baseline could appear due to

change in thermal resistance of the setup.
Position is depending on measuring-history.
Measurements may have a significant

change in weight due to changes in gas
density and viscosity.
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
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
15
General Theory (DTA equation)
hea/ngrate,K/min
1.
2.
3.
4.
5.
6.
ExperimentalDTAcurve
DTAcurvecorrectedtoheattransfercondi5ons
TruebaselineofDTAcurve
Interpolatedbaseline;
Experimentalbaseline;
Experimentalbaselinealerprocess,shiledbecauseof
thermalcapacitychanges.
16
General Theory
DSC Artifacts
17
General Theory
3 major aspects of correct DSC measurement:
Baseline
Gradient T
Calibration, KDTA,
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.
Sigmoidal Baseline
This baseline is used when the melting process is
accompanied by a notable Cp change.
Tangential Area-Proportional Baseline

This baseline is used when the melting process is
accompanied by a notable Cp change and a sloping
baseline exists.
19
General Theory
Au(S) Au(L), H298= 12,6 kJ/mol
sigmoidal
In(S) In(L), H298= 3.3 kJ/mol
linear
CuO/ZnAl2O4+H2 Cu/ZnAl2O4+H2O
tangential
20
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)
21
General Theory
Bad thermal contact

Long melting time
Broad, low peak
Good Thermal contact

Short melting time
Sharp peak
The slope of the peak left side is depended on thermal resistance

Peak area is the same and equals melting enthalpy.
22
General Theory
f(t) evolved heat

F(t) measured signal
g(t) response function
g(t)=exp(-t/)
small
big
The peak right side is depended on instrument

time constant.
< 2
23
General Theory
DSC peak Correction
Original signal
Time constant correction
Full correction
24
General Theory
Theproper5esofthesystemsamplesensorstronglyinuencetheexperimentalTAcurves
FeaturesofTASetup
a)Reac5onAtmosphere
b)Sizeandshapeoftheoven
c)Sampleholdermaterial
d)Sampleholdergeometry
e)Hea5ngrate
f)Thermocouple(wirediameter)
g)Thermocoupleloca5on
h)Response5me
Characteris5csofthesample
a)
b)
c)
d)
e)
f)
g)
h)
Par5clesize
Thermalconduc5vity
Thermalcapacity
Packingdensityofpar5cles(powder,pill,tablet)
Sampleexpansionandshrinking
Samplemass
Inertller
Degreeofcrystallinity
Informa5onobtaineddependsonprocedure
Notfundamentalproperty
25
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).
26
Influence of external atmosphere

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
28
Influence of sample mass

k1
29
Influence of heating rate

Independent processes
Ea1<Ea2
30

Subsequent processes
La(OH)3LaOOH+H2O
LaOOHLa2O3+H2O
31

Competitive process processes
Ea1<Ea2
32
Influence of the pan material

Al
Pt
Al2O3
Ni
Cu
Quartz
PyrolisisofFluoropolymer:TFEVDF,{C2F4}n{C2H2F2}m,F42inAlanAupans
in Al
in Au
10Kpm,Ar,100ml/min
33
Strong exothermic reactions

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.
34
Strong exothermic reactions

Exothermic
Endothermic (due to water traces)
Two effects coinsides resulting in endothermic effect.
35
Measurementininert.Isthesystemoxygenfree?
CuC2O40.5H2OCu+2CO2
Cu+1/2O2CuO
O2tracesof0.25ppm
DSCTGsampleholder,
Al2O3pan,Ar100ml/min
Sample:CuC2O40.5H2O
Weight:9.1mg
36
DSCTGsampleholder,
Sample:Ni/MgAl2O4
Weight:14.1mg
Ni+1/2O2NiO
@RTO2tracesof1.7ppm
37
Setup:RubothermMSB
CuC2O40.5H2OCu+2CO2
Cu+1/2O2CuO
TGsampleholder,
Sample:CuC2O40.5H2O
Weight:301.8mg
O2tracesof7ppm
38
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
39
TA-MS Coupling systems

Skimmer coupling system
40
TA-MS Coupling systems

Capillary coupling system
41
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)
42
(PulseTA) Adsorption of Methanol on -AlF3

Sample:AlF3
Sampleweight:43.81mg
m=0.15mg,
N270ml/min
M. Feist et. al. 2010
Determining Lewis acidity
TA-MS curves for a PulseTA experiment on pretreated (2 h, 250 C; vacuum)

43
(PulseTA) Titration of Ni surface with O2

** Assuming O/Ni=2, dNi=9nm in agreement with TEM
Sample:Ni/MgAl2O4
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
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
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
thermal
analysis
46
Thank you!
47

Andrey Tarasov Thermal Analysis 121026

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ThermalAnalysis:methods,principles,applica5on

Main Thermo-physical properties of materials

a thermal diffusivity, cm2/s

Thermal conductivity, thermal diffusivity

Laser Flash Method (LFA)

DIL Measurement Information

SiN thermal shrinkage

Basic Principles and Terminology

Basic Principles and Terminology

Basic Principles and Terminology

Constantan - 58% Cu, 42% Ni

Alumel 94% Ni, 2% Al, 1,5% Si, 2,5 % Mn

Basic Principles and Terminology

DSC (Heat flux)

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

gas - Density of gas, f(T)

Basic Principles and Terminology

General Theory (Heat equation for inert material)

General Theory (Temperature field in active sample)

Pb(S) Pb(L), H298= 5 kJ/mol

CuO(S)+H2(g) CuO(s)+H2O(g) , H298= -86 kJ/mol

Shift of the baseline could appear due to

Measurements may have a significant

Heat of the process is determined as follows:

General Theory (DTA equation)

Tangential Area-Proportional Baseline

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

Issues by uncorrected data

Bad thermal contact

Good Thermal contact

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

f(t) evolved heat

The peak right side is depended on instrument

Influence of external gas flow

Dehydration of CaC2O4nH2O in an open crucible in a dry air

Influence of external atmosphere

Influence of external atmosphere

Vacuum 10-4 bar

Influence of sample mass

Influence of heating rate

Influence of heating rate

Influence of heating rate

Influence of the pan material

Strong exothermic reactions

-strong heat evolution, narrow T

Strong exothermic reactions

TA-MS Coupling systems

TA-MS Coupling systems

Main Problems of TA-MS coupling system

Disadvantages: shock sensitive, no direct MS inlet.

(PulseTA) Adsorption of Methanol on -AlF3

M. Feist et. al. 2010

Determining Lewis acidity

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

(PulseTA) Titration of Ni surface with O2

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

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

Dr. Elena Moukhina, Netzsch Gertebau GmbH, Selb

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