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2 Dynamic Methods
Measurements at Elevated Temperatures
Different possible routes:
3 Dynamic Methods
DTA - Differential Thermal Analysis
Historically developed from the DTA: Difference Measurement
simple evaluation of cooling
curves:
Sample Reference
T
Massive Samples
Furnace (TF)
Slow experiment
Tm No control of TS TR
parameters (free
cooling) Temperature program for furnace
Measurement of T = TR-TS
Small samples
Exothermic effect Fast experiment
(e.g. crystallization) Controlled temperature program
t
4 Dynamic Methods
Thermal Reactions
All thermal reactions are connected with the exchange of heat
5 Dynamic Methods
Thermal Reactions Multi Component Systems
Gibbs Phase Rule:
P+F=C+2
Pnumber of phases, Fdegrees of freedom, C number of components
P+F=C+1
Types of reactions:
Invariant reactions: F = 0; T is fixed to a certain value during the reaction
Other reactions: F > 0; the reaction occurs within a temperature interval
6 Dynamic Methods
The DTA Signal
TR
T
TF T
TS
linear
Reaction onset
Temperature
exponential
relaxation
baseline
t t, Ts
Idealized Curves of T(t) and T(t)
for the determination of an invariant reaction
the simplest case
7 Dynamic Methods
Factors Influencing the Shape of the DTA Signal
DTA /(uV/mg)
0
heating
1009.2 C
930.0 C
-0.050
-0.100
1000.1 C
905.5 C 953.6 C [1.4]
-0.150
-0.200
cooling
-0.250
-0.300
-0.350
8 Dynamic Methods
Heat Flow in the Instrument
DTA is a dynamic method. Heat is transferred between furnace, crucible,
sample (reference) and thermocouple during the whole experiment.
Furnace T
ideal
Sample
Crucible
real
Thermocouple
TS
Sample Reference
10 Dynamic Methods
Influence of Heating Rate
Calculated temperature distribution for
spherical sample at different heating rates
Radial heat transfer from the
surface to the core of the sample:
Inhomogeneous temperature
distribution within the sample!
11 Dynamic Methods
Factors Influencing the Base Line
Reference Material:
Should show no thermal reactions and thermal behavior similar
to the sample.
different heat capacity base line drift
Sample Mass:
Usually between 0.5 and 1000 mg.
resolution sensitivity
12 Dynamic Methods
Example Sample Shape & Base Line
First heating
Second heating
Melting
13 Dynamic Methods
Evaluation of DTA Curves: Characteristic Points
Heating Curve
1
2 3 4 5
14 Dynamic Methods
DTA-Curves: Phase Diagram Ag-Sn
Characterization:
The composition of samples and the crystal structure have to be
investigated separately before and after the measurement.
Combination:
DTA experiments tell us that something is happening at a specific
temperature. They usually do not tell us, whats happening. Combination
with other methods like X-ray diffraction, spectroscopy, microscopic
investigation and composition analysis (e.g. Electron probe
microanalysis) are required to interpret the results
16 Dynamic Methods
DTA: Experimental Setup
17 Dynamic Methods
From DTA to DSC
Heat flow Differential Scanning Calorimetry (DSC) = Quantitative DTA
heat flow
Rthermal resistance
Ofurnace DTA: DSC:
Psample separated crucibles defined heat flow
high sensitivity high reproducibility
Rreference
qualitative quantitative
18 Dynamic Methods
From DTA to DSC
Linear heating rate Stationary heat flow (OP, OR)
A thermal reaction causes a deviation from stationary conditions
dqr
r = = k (T ) TRP (T )
dt
t2
heat flow qr = k (T ) TRP (T )dt
Rthermal resistance t1
Ofurnace
Psample qrheat of reaction
Rreference k(T)calibration constant
19 Dynamic Methods
DSC-Measurement Modes
Tm
Cp(T)
Hm
q r = k (T ) TRP (T )dt
t1
T2
k (T )
qr = TRP (T )dT
T1
qrheat of reaction
k(T)calibration constant Peak area
evaluated
21 Dynamic Methods
Baseline Correction
[W. Hemminger 1989] Baseline shift connected with thermal
effect correction necessary
etc (iteration)
22 Dynamic Methods
DSC Calibration
qR (or HR) is proportional to the integrated peak area.
The respective constant k(T) has to be determined by calibration!
k(T)
Sn
Pb
In Sensitivity Curve of the Instrument
Zn
measurement of Hm of standards
measurement of cp of standards
electrical calibration
T
23 Dynamic Methods
Evaluation of cP
The heat capacity cP of a sample can be evaluated from the baseline.
24 Dynamic Methods
Kinetics: Basics
Heterogeneous Reaction Need:
Base line correction
: reaction extent; = /max Calibration of Sensitivity
Deconvolution correction for the
d time constant of the instrumental
= k (T ) f ( ) setup
dt
Determination of using
Using DSC we determine a square test signal:
U
dH Signal
( )
d
= dt Response
dt H R t
25 Dynamic Methods
DSC - Instrumental Setup
26 Dynamic Methods
Example DTA Pure Compounds
NH4NO3, 10Kmin-1 KNO3, 5Kmin-1
1 2 3 4
1: ortho II ortho I
Heating curve:
2: ortho I tetragonal
polymorphic transformation & melting
3: tetragonal cubic
Cooling curve:
4: cubic liquid
supercooling & metastable
5: decomposition
transformation
27 Dynamic Methods
Phase Diagrams by DTA (1)
1500
Al50Ni20Si30 1400
Al-Ni-Si
1300 Vertical section at 20 at% Ni
1200
1100
Al50Ni20Si30
T / C
1000
900
28 Dynamic Methods
Phase Diagrams by DTA (2)
1500
1400
Series of measurements: Al-Ni-Si
Within a section, but with different 1300 Vertical section at 20 at% Ni
compositions
identification of thermal arrests at 1200
T / C
1000
900
Invariant 800
Non-Invariant
700
Liquidus
Liquidus 600
500
0 10 20 30 40 50 60 70 80
at% Si
29 Dynamic Methods
Phase Diagrams by DTA (3)
1500
Combination with other Methods:
1400
Identification of the phase composition
of the samples by various isothermal 1300
methods: L
1200
L+(Si)
X-ray powder diffraction (XRD) 1100
Optical microscopy (metallography)
T / C
L+NiSi2-xAlx
Electron probe microanalysis (EPMA) 1000
L+(Al3Ni2) L+(Si)+NiSi2-xAlx
900
Combination with information on L+(Al3Ni)+(Al3Ni2)
L+(Al3Ni2)+(Si)
limiting systems 800
(Al3Ni2)+(Si)+NiSi2-xAlx
(Si)+NiSi2-xAlx
(Al3Ni)+L
L+3+(Si)
700 L+3+(Al3Ni) 3+(Si)+
Evaluation according to Phase (Al3Ni2)
L+(Si)+
diagram rules 600 (Al3Ni)
(Al3Ni)+3+(Si)
(Al3Ni)+(Al)+(Si)
500
Additional Sections at other 0 10 20 30 40 50 60 70 80
compositions at% Si
30 Dynamic Methods
Phase Diagrams by DTA (4)
1500
1500
1400
1400 Al-Ni-Si
1300
Al-Ni-Si
Vertical section at 20 at% Ni
1300 Vertical section at 20 at% Ni
1200
1200
1100
1100
T / C
1000
T / C
1000
900
900
800
800
700
700
600
600
Limiting Binary Al-Ni 500
0
500 10 20 30 40 50 60 70 80
0 10 20 30 40 50 60 70 80
at% Si
at% Si
31 Dynamic Methods
Phase Diagrams by DTA (5)
1500
1400
Al-Ni-Si
1300 Vertical section at 20 at% Ni
1200
1100
T / C
1000
900
800
700
600
32 Dynamic Methods
Phase Diagrams by DTA (6)
1500
1400
Al-Ni-Si
1300 Vertical section at 20 at% Ni
T = 550C
1200
40
(Al3Ni2)
NiSi2-xAlx
3 30
1100
(Al3Ni) at% Ni
T / C
20 1000
10
900
0
Al 0 10 20 30 40 50 60 70 80 90 100
Si 800
at% Si
700
Isothermal section at 550
600
Independent experimental
determination necessary! 500
0 10 20 30 40 50 60 70 80
at% Si
33 Dynamic Methods
Phase Diagrams by DTA (7)
1500
1400 Al-Ni-Si
Vertical section at 20 at% Ni
Rule of Landau and Palatnik:
1300
L
r1 = r d- - d+ 0 1200
L+(Si)
1100
r: dimension of phase diagram
T / C
L+NiSi2-xAlx
r1: dimension of the boundary 1000
of neighboring phase fields L+(Al3Ni2) L+(Si)+NiSi2-xAlx
900
d-: number of phases that L+(Al3Ni)+(Al3Ni2)
(Al3Ni2)+(Si)+NiSi2-xAlx
(Si)+NiSi2-xAlx
d+: number of phases that (Al3Ni)+L
L+3+(Si)
700 L+3+(Al3Ni)
appear 3+(Si)+
(Al3Ni2)
L+(Si)+
600 (Al3Ni)
(Al3Ni)+3+(Si)
(Al3Ni)+(Al)+(Si)
500
0 10 20 30 40 50 60 70 80
at% Si
34 Dynamic Methods
Phase Diagrams by DTA (8)
1500
Reaction Scheme / Scheil Diagram:
1400 Al-Ni-Si
Vertical section at 20 at% Ni
1300
L
1200
L+(Si)
1100
T / C
L+NiSi2-xAlx
1000
L+(Al3Ni2) L+(Si)+NiSi2-xAlx
900
L+(Al3Ni)+(Al3Ni2)
L+(Al3Ni2)+(Si)
800
(Al3Ni2)+(Si)+NiSi2-xAlx
(Si)+NiSi2-xAlx
(Al3Ni)+L
L+3+(Si)
700 L+3+(Al3Ni) 3+(Si)+
(Al3Ni2)
L+(Si)+
600 (Al3Ni)
(Al3Ni)+3+(Si)
(Al3Ni)+(Al)+(Si)
500
0 10 20 30 40 50 60 70 80
at% Si
35 Dynamic Methods
DTA: Variation of Experimental Parameters
Citric acid / Citric acid monohydrate
Conflicting information on melting point
10 Kmin-1
1: Dried sample
2: Open crucible
3: Cover with hole
4: Closed crucible
36 Dynamic Methods
DSC: Evaporation of Water
2.18 mg Water, 10 Kmin-1
Heat of evaporation by simple DSC experiment
Boiling point
determination
not possible with
this experiment!
37 Dynamic Methods
DSC: Glass Transition an Crystallization (1)
PETP sample, measurement on
heating
Endo
Recrystallization
Melting
Glass transition
38 Dynamic Methods
DSC: Glass Transition an Crystallization (2)
Series of samples with different
thermal history
crystalline amorphous
Endo
39 Dynamic Methods
DSC: Polymerization Reaction
Sample TEDMA Polymerization by different methods
1: Thermal Polymerization
2: Peroxo Initiator
(25 mmol/l DBPO)
3: Peroxo Initiator
(50 mmol/l DBPO)
40 Dynamic Methods
DSC: Polymer Mixtures (1)
Melting Behavior:
LDPE: 1 Step, ~105C
LDPE LLDPE LLDPE: 2 Steps, ~120C
Concentration
determination by area
integration
41 Dynamic Methods
DSC: Polymer Mixtures (2)
Different Mixtures
Integration of peak
areas yields linear
dependence
42 Dynamic Methods
DSC: Purity of Pharmaceuticals (1)
RT 02
T0 Tm = xB
H f ,A
1
xB = x B*
F
Fmolten part of
T0 the sample
(lever rule!)
Tm
RT 02 1 T
T0 TF = x B*
H f ,A F F xB* xB
43 Dynamic Methods
DSC: Purity of Pharmaceuticals (2)
The molten part, F, is determined by DSC:
2
RT 1
T0 TF = xB
*
0
Part of the peak area at TF using the onset
H f ,A F angle for extrapolation plus the
respective part of the relaxation curve.
45 Dynamic Methods
TGA: Balance systems
The balance is the most critical part of the instrument
Sample masses: mg g
Sensitivity: g to sub - g range
Constant position required (thermal expansion!)
Effective separation of furnace chamber and balance unit
Balance
Balance
Balance
46 Dynamic Methods
The TGA Curve (1)
A constant heating rate is usually applied. The change of mass is
recorded as a function of temperature.
- H2O m:
Ideally significant steps. Loss (or
- CO
gain) of weight according to the
stoichiometry of the reaction.
eg.:
- CO2 Ca(COO)2H2O Ca(COO)2 + H2O(g)
Ca(COO)2 CaCO3 + CO(g)
CaCO3 CaO + CO2(g)
47 Dynamic Methods
The TGA Curve (2)
The temperature range belonging to each step strongly depends
on experimental parameters
Temperature:
Evaluation of inflection point
(steepest part of the m/T curve)
48 Dynamic Methods
The Influence of the Gas Phase
Composition of the gas phase and reaction temperature
(equilibrium) are fundamentally linked:
Equilibrium constant Kp
[P.Haines, 1995]
50 Dynamic Methods
Quasi-Isothermal DTA
In case of DTA, separation of effects is often a difficult problem.
Systematic errors occur for non-invariant effects
T sample
T sample
time time
e.g.: liquidus in the vicinity
of a eutectic point
51 Dynamic Methods
TGA Instrumental Setup
Autostep mode:
Conventional TG 1.5%/min.: on
20 Kmin-1 0.25%/min: off
53 Dynamic Methods
Example: Quality Characterization of Coal
Characteristic steps:
H2O
Volatiles
Carbon
Ash
[P.Haines, 1995]
54 Dynamic Methods
TGA - Combinations
DTA, DSC and TGA are standard methods for the characterization of the
thermal behavior of materials. Many commercial Instruments are
available.
56 Dynamic Methods
Dilatometry
Measurement of the thermal expansion of solid samples.
Thermal expansion coefficient
1 dl
=
l 0 dT p
Investigation of:
Thermal Expansion of Polycrystalline and single crystalline material
Phase transitions
Change of microstructure
Recrystallization
Thermal treatment of lattice distortions and stress
Manufacturing processes (sintering etc.)
58 Dynamic Methods
Example: Sintering Barium Zirconate
Heating: 10 Kmin-1, 1Kmin-1, isothermal 1590 C
Atmosphere: air
Pressed powder
pellet with binder
(green body)
binder burning
shrinkage due to
sintering process
start of grain
growth
Optimum density at
3.5 hours
59 Dynamic Methods
Determination of expansion coefficient
Accurate thermal
expansion studies are
challenging due to
sample material
porosity
anisotropic behavior
microstructure
dependent
60 Dynamic Methods
Thermomechanical Analysis TMA
61 Dynamic Methods
Thermomechanical Analysis TMA
Standardized testing
procedures for the industry.
62 Dynamic Methods