LINSEIS Handbook1

LINSEIS
Thermal Analysis
LINSEIS Industrial Application Handbook
Thermal Analysis
DTA x DSC x HDSC x TG x TMA x DIL x
MS/FTIR COUPLING
i
LINSEIS
Thermal Analysis
Table of Contents
Preface 1
Definition of Thermal Analysis 2
Thermal Analysis Categories 3
Differential Thermal Analysis (DTA) 4
Definitions of Differential Thermal Analysis (DTA) 4

Standards 4
Measuring Process 5
Measuring Signal 5
Apparatus 6
Differential Scanning Calorimetry (DSC) 7
Definition of Differential Scanning Calorimetry 7

Standards 7
Measuring Signal 8
Apparatus 8
Definitions of Thermogravimetry (TG) 9
Standards 9
Measuring Signal 9
Apparatus 10
Thermomechanical Analysis (TMA) 11
Definition 11
Standards 11
Thermodilatometry (DIL) 12
Definition 12
Standards 12
Measuring Signal 12
Apparatus 13
Furnaces 13
Measuring System 13
ii
LINSEIS
Thermal Analysis
Applications DTA 14
Barium Carbonate 15
Lanthangallat 16
Simultaneous DTA measurement with the LINSEIS Dilatometer

Rock crystal 17
Applications DSC
Crystallization enthalpy of mercury (Hg) 19

Melting enthalpy of mercury (Hg) 20
Oxidative Induction Time (OIT) of Polyethylene (PE-LD) I 21
Experiments: Oxidative Induction Time (OIT) of Polyethylene (PE-LD) 22
Oxidative Induction Time (OIT) of Polyethylene (PE-LD) II 23
Thermo analytical examination of several samples of sugar 24
Determination of glass point, late crystallization and melting point of PET 25
Applications HDSC
Determination of the phase change of caliumchromat (K2CrO4) 27

Determination of the phase transition temperature of silversulfat (AG2SO4) 28
Determination of the phase change temperature of potassium sulfate (K2SO4) 29
Applications TG
Determination of the quantity of chalk of a PE-foil (PE) 31

Reaction behavior of aluminum powder in nitrogen and argon atmosphere 32
Pyrolysis of Polyethylene (PE) 33
Pyrolysis of Polyethylene PE-LD und PE-HD 34
Applications TG - DTA
Reaction temperature between aluminum and nitrogen 36

Thermal behavior of aluminum hydroxide (dehydration and phase change) 37
Decomposition of calcium oxalate (CaC2O4) under air 38
Decomposition of calcium oxalate (CaC2O4) under argon atmosphere 40
Decomposition of Rubber 41
Dehydration of raw gypsum 42
Burning of loam (clay) 44
Measurement of Kaolin 45
Applications TMA
Glass transition and melting point with a Polyamide sample 47
iii
LINSEIS
Thermal Analysis
Applications DIL
Dilatation of glass ceramics 49

Sintering behavior of aluminum-oxide samples under different sinter programs 50
Thermal expansion (dilatation) of two different glass ceramics 51
Dental Ceramics 52
Quenching of a steel sample 53
Detection of the softening-point 54
Expansion measurement of Cordierite 56
RITA (Rapid Induction Thermal Analysis)

Alpha Beta transition of steel 58
Applications TG FTIR/MS Coupling
FTIR Determination of the decomposition of calcium oxalate 60

CaC2O4 under nitrogen atmosphere
MS Determination of the decomposition of calcium oxalate 62

CaC2O4 under argon atmosphere
References 63
iv
LINSEIS
Thermal Analysis
Introduction
Welcome to Linseis
Linseis International is a manufacturing concern, consisting of key

people in the field of physics, engineering, manufacturing and
marketing.
Our expertise lies in manufacturing a wide range of
Thermal Analysis
o Thermodilatometry (DIL)
o Thermomechanical Analysis (TMA)
o Thermogravimetric Analysis (TGA)
o Differential Thermal Analysis (DTA)
o Simultaneous Thermal Analysis (TG DTA/DSC)
o Evolved Gas Analysis (EGA): Mass Spectrometry
(MS), Fourier Transform Infrared Spectroscopy
(FTIR)
Recording Instruments and
Data Loggers
We achieve our goals by means of an expert team of highly competent

and qualified personal, adding value in the science and medical sector,
the commercial and industrial industry, as well as in Universities.
1
LINSEIS
Thermal Analysis
Definitions of Thermal Analysis
A group of techniques in which a property of the sample is

monitored against time or temperature while the
temperature of the sample, in a specified atmosphere, is
programmed.
The generic term for a group of techniques in which the

temperature of a matter is varied according to a specified
program and the matters properties are measured as a
function of the temperature.
The above are definitions of Thermal Analysis by the International

Confederation for Thermal Analysis and Calorimetry (ICTAC) and the
Japanese Industrial Standards (JIS).
The top definition is from ICTACs For Better Thermal Analysis and
Calorimetry, 3rd Edition, published in 1991.
The lower is the definition for thermal analysis found in JIS K-0129
General Principles of Thermal Analysis.
ICTAC and JIS both define all methods in which a property of the
measurement object (sample) is monitored while the temperature of
the sample is program-controlled as falling in the category of thermal
analysis.
2
LINSEIS
Thermal Analysis
Thermal Analysis Categories
Name Measurement Unit

Object
DTA Differential Thermal Analysis Temperature C V*
Difference
DSC Differential Scanning Thermal Flow W=J/sec
Calorimetry
TG Thermogravimetry Mass mg
TMA Thermomechanical Analysis Length m
DMA Dynamic Mechanical Analysis Elasticity Pa,
dyn/cm2
DIL Thermodilatometry Expansion m
*The electromotive force of the thermocouple is output directly.
There are multiple methods in thermal analysis, and each is defined as

a technique depending on the type of a samples properties that are
detected.
Of these techniques for detecting properties, the six shown above are
commonly used techniques representative of thermal analysis.
The six techniques are:
Differential Thermal Analysis, which detects temperature

(temperature difference), Differential Scanning Calorimetry
which detects enthalpy changes (heat flow difference),
Thermogravimetry which detects Mass (mass change),
Thermomechanical Analysis that detects kinetic properties,
Dynamic Thermomechanical Analysis detecting Elasticity
changes and Thermodilatometry. The name of each technique
is abbreviated as follows: DTA, DSC, TG, TMA, DMA, DIL.
3
LINSEIS
Thermal Analysis
Differential Thermal Analysis (DTA)
The DTA Technique employs a block that can be heated and cooled at
a constant rate. This block contains the substance to be investigated
and an inert reference material. In order to detect reactions in the
substance during heating or cooling, the temperature difference
between the sample and the reference is measured by a
thermocouple.
Definitions of Differential Thermal Analysis (DTA)

A technique in which the difference in temperature between the
sample and a reference material is monitored against time or
temperature while the temperature of the sample, in a specified
atmosphere, is programmed.
A technique in which the temperature of reference material and

a sample is varied according to a specified program and the
temperature difference between reference material and the
sample is measured as a function of the temperature.
The above are definitions of Differential Thermal Analysis (DTA).
The first is the definition from ICTAC publication For Better Thermal
Analysis and Calorimetry and the second is from JIS K-0129 General
Principles of Thermal Analysis.
Standards:
DIN 51007: Differential Thermal Analysis

ASTM E 474: Evaluation of Temperature Scales for Differential
Thermal Analysis
ASTM E 537-86: Assessing the Thermal Stability of Chemicals by
Methods of Differential Thermal Analysis
4
LINSEIS
Thermal Analysis
Measuring Process:
(LINSEIS: DTA - L62D1550)
As stated in the definitions, DTA is a technique that

detects the temperature difference between the
sample and reference material. With this
technique, temperature difference between the
sample and the reference material, which changes
in response to melting or other reaction of sample
to temperature change, is detected.
The measuring head, shown in the picture carries

two crucibles, one for the reference material and
one for the sample substance, each sitting on a
thermocouple. The two thermocouples are wired
such as to measure the temperature difference between the sample
and the reference material. The absolute temperature is measured
with the reference thermocouple.
Measuring Signal:
Temperature dependence
T (T) = TS (T) TR (T)
With:
TS: sample temperature

T R: reference Temperature
T: absolute temperature
Time dependence:
T (t) = TS (t) TR (t)
With:
T = T0 + t
T0: starting temperature
: heating rate
5
LINSEIS
Thermal Analysis
Apparatus:
L62 D 1550 DTA Differential Thermal Analyzer
The Linseis DTA uses a dynamic measuring principle. It can measure

endothermal and exothermal heat flows between the sample and the
reference. These heat flows are result of physical or chemical changes
of the samples. Very often a DTA is used for purity measurements of
mixtures of metals. This is due to the fact that the melting point
changes in dependence to differing amounts of impurities.
Purity measurements
Melting point determination (onset / offset)
Energy content of explosives
Stability of explosives (storage)
Features
Temperature range -150C up to +1600C

Low heat capacity measuring head
Different furnaces available / -150C up to +500C, RT up to
1600C
Vacuum up to 10E-5mbar
Static and dynamic gas atmospheres
MS Windows 32 Bit Software
6
LINSEIS
Thermal Analysis
Differential Scanning Calorimetry (DSC)
JIS Definition
DSC is the generic term for the following two measurement methods.
Power Compensation DSC
A technique in which difference of thermal energy that is applied

to the sample and the reference material per unit of time is
measured as a function of the temperature to equalize their
temperature, while temperature of the sample unit, formed by
the sample and reference material, is varied in a specified
program
Heat Flux DSC
A technique in which the temperature of the sample unit, formed

by a sample and reference material, is varied in a specified
program, and the temperature difference between the sample
and the reference material is measured as a function of
temperature.
The above is Differential Scanning Calorimetry (DSC) as defined by

JIS. JIS defines DSC as a generic term for the two techniques
mentioned above.
While Power Compensation DSC performs heat flow supply with a

microheater as a heat flow feedback technique, Heat Flux DSC
conducts feedback with heat exchange from a heat sink.
As a result, the temperature difference measurement also serves as

heat flow measurement. ICTAC defines DSC as a term that combines
the two above techniques defined by JIS.
Standards:
ASTM E 793-85: Heats of Fusion and Crystallization By Differential

Scanning Calorimetry
ASTM E 794-85: Melting and Crystallization Temperatures by
Thermal Analysis
7
LINSEIS
Thermal Analysis
ASTM E 928-85: Mol Percent Impurity by Differential Scanning
Calorimetry
ASTM E 967-83: Temperature Calibration of Differential Scanning
Calorimeters and Differential Thermal Analyzers
ASTM E 968-83: Heat Flow Calibration of Differential Scanning
Calorimeters
Measuring Signal:
r = dqr/dt = -K(T) TPR(T)
TPR = temperature difference (measuring signal including baseline

correction)
r = heat flux
qr = heat
K = calibration factor (sensitivity)
T = time
T2
K
qr
E 'T
T1
PR (T )dT
Apparatus:
The differential scanning calorimeter L63/45 is a well-proven

DSC system. It is a highly precise instrument and the principle of
operation is based on heat flux between the sample and the
reference. The heat flux is measured while the temperature is
changing.
The Linseis HDSC, L62 H 1550 uses a heat flux measuring

principle. These heat flows are result of physical or chemical
changes of the samples. Only the development of the HDSC
made it possible to make DSC measurements over 700C.
The temperature ranges from 150C up to 1550C.
8
LINSEIS
Thermal Analysis
Definitions of Thermogravimetry (TG)
A technique in which the mass of the sample is monitored

against time or temperature while the temperature of the
sample, in a specified atmosphere, is programmed.
A technique in which the mass of a sample is measured as the

function of the temperature while varying the sample
temperature in a specified program. (JIS definition)
The above are definitions of Thermogravimetry (TG) by ICTAC and JIS.

As defined above, TG is a technique that measures mass change in a
sample, and it is used to detect evaporation, melting, oxidation and
other effects of temperature change that cause mass changes.
Standards:
ASTM E 914-83: Evaluating Temperature Scale for

Thermogravimetry
ASTM E 1131-86: Compositional Thermal Analysis by
Thermogravimetry
DIN 51006: Thermogravimetry
Measuring Signal:
Temperature dependence:
M = m(T) or m = m(T) m0
Time dependence:
M = m(t) or m = m(t) m(t0)
m: sample mass
m0: original sample mass
T: temperature
t: time
t0: start of measurement
9
LINSEIS
Thermal Analysis
Apparatus: (L81 / L81 II / L81-Platinum)
The model L81 Research Balance is a well proven Thermal

Balance, which is built up very robust with large possible sample
sizes of 25 gram / 3 ml sample volume. The L81 balance system
uses a zero deflection / zero balance principle of detection. When
a weight change is detected the balance reacts by attempting to
move the balance arm.
This balance series can be used for many different furnace types
from low temperatures -150C up to +2400C.
Economy Line Thermal Balance L81-II, vertical mode of

operation. Resolution 1 microgram max. sample weight 25 gram
DTA/DSC measurements simultaneously (STA) Temperature
ranges RT up to 1000/1250/1600C vacuum tight 10E-3mbar
(mid range vacuum)
Top Line Thermal Balance L81-Platinum, vertical mode of

operation. Prepared for Autosampler Resolution 1 microgram
max. sample weight 25 gram automatic weight tare temperature
range RT up to 1000/1600C prepared for FTIR and MS-coupling
10
LINSEIS
Thermal Analysis
Thermomechanical Analysis (TMA)
Definitions of
A technique in which a deformation of the sample under non-

oscillating stress is monitored against time or temperature while
the temperature of the sample, in a specified atmosphere, is
programmed. The stress may be compression, tension, flexure
or torsion.
A technique in which a deformation of the sample under

compression, tension, flexure, torsion and other non-oscillating
load is measured as a function of temperature while the
temperature of a sample is varied in a specified program. (JIS)
The above are definition of TMA by ICTAC and JIS.
TMA is a technique in which deformation of a sample under non-

oscillating load (uniform load) is measured against temperature. Types
of load include compression, tension and torsion.
Standards:
ASTM E 831-03: Standard Test Method for Linear Thermal Expansion

of Solid Materials by Thermomechanical Analysis
ASTM E 831-86: "Linear Thermal Expansion of Solid Materials by
Thermomechanical Analysis"
EN 103: "Ceramic Tiles: Determination of Linear Thermal
Expansion"
EN 821: "Advanced Technical Ceramics - Thermo physical
Properties: Part 1 - Determination pf Thermal
Expansion"
DIN 51045: "Determination of Thermal Change in Length of
(Part 1-5) Solid Materials"
DIN 52324: "Glass: Determination of the Mean Coefficient of
Thermal Expansion"
11
LINSEIS
Thermal Analysis
Thermodilatometry (DIL)
Definitions of
A technique in which a dimension of a substance under negligible load

is measured as a function of temperature while the substance is
subjected to a controlled temperature program (ICTA, ASTM E 473
85)
Standards
EN 103: Ceramic Tiles: Determination of Linear Thermal Expansion

EN 821: Advanced Technical Ceramics Thermo physical Properties:
Part 1 Determination of Thermal Expansion
DIN 51045, Parts 1 to 5: Determination of Thermal Change in Length
of Solid Materials
Measuring Signal:
Coefficient of Thermal Expansion
1 wl
D1 T (DIN 1304)
l0 wT p
l0 = Sample length
T0 = Reference temperature
Mean Coefficient of Thermal Expansion
1 l T l T0 1 'l
D 1 T0 ;T
l0 T T0 l0 'T
with
l0 = sample length at room temperature

l(T);l(T0) = sample length at temperatures T, T0
l = Change of sample length between temperaturesT,T0
12
LINSEIS
Thermal Analysis
Apparatus
Model L 76* L 75 Horizontal L 75 Vertical
L76 / 1000 L75HS / 1000 L75VS / 1550

Temperature L76 / 1250 L75HS / 1250 L75VS / 1750
Range L76 / 1550 L75HS / 1550 L75VS / 2000
L75VS / 2300
(Furthermore numerous special customized Dilatometers)
*L76 not vacuum tight / economic version
The basic LINSEIS Dilatometer Unit consists of a frame holding the

expansion sensor; the sample holder and the moving slide for the
furnace. There are many features available to customize the
Dilatometer for specific applications and material characterizations.
Single and Dual Push rod Dilatometers are available. Whereby the later
can perform two absolute or one differential measurement.
Furnaces
The extensive Furnace program encounters a large variety of Units

ranging from 150C up to 2300C.
Temperature range Sample holder Sample TC Type
-150C 400C Quartz 7 mm K
RT 1000C Quartz 7 mm K
RT 1400C Quartz 7 mm K
RT 1550C AL2O3 7 mm S
RT 1750C AL2O3 On request B
RT 2400C Graphite On request C
Measuring Systems
The measuring system of a Dilatometer consists of a sample holder

and a push rod. The push rod is used to transfer the expansion of the
sample material out of the heated zone to the LVDT.
(single push rod sample holder) (dual push rod sample holder)
13
LINSEIS
Thermal Analysis
APPLICATIONS
DTA
14
LINSEIS
Thermal Analysis
Barium Carbonate
Determination of the phase change temperature of Barium Carbonate

(BaCO3)
Test Parameters:
Sample: BaCO3 (barium carbonate)

Quantity of sample: 443 mg und 28 mg
Sample preparation: powder
Material of crucible: Platinum closed
Atmosphere: air
Heat up rate: 20 K/min
Commentary:
The temperature, at which the crystal structure of barium carbonate

changes from a orthorhombic structure to a hexagonal structure can
be determined by means of the DTA method (differential thermal
analysis). You can also see, that when using larger sample quantities,
the DTA signal comes out a lot bigger. However in these cases the
peak maximum is shifted to higher temperatures, whereas the onsets
of the changes are recorded at identical temperatures.
15
LINSEIS
Thermal Analysis
Lanthangallat
Determination of the phase change of Lanthangallat (LaGaO3)
Test Parameters:
Sample: Lanthangallat (LaGaO3)

Quantity of sample: sample 1: 216.0 mg
sample 2: 119.90 mg
Material of crucible: Aluminum, closed
Atmosphere: air
Commentary:
At sample one you can see at 154,2C the endothermal phase change
from an orthorhombic structure to a rhomboethric Perowskitphase.
The doping of the sample with strontium and magnesium (sample 2)
leads already at room temperature to a stabilizing of the cubic high
temperature phase and this is why there is no phase change at
identical measuring conditions.
16
LINSEIS
Thermal Analysis
Simultaneous DTA measurement with the LINSEIS Dilatometer
The dilatometer-evaluation has a pretty new feature: Now the DTA-

signal can be calculated from a standard dilatometer measurement. To
do this, the theoretical temperature is taken as a base line, and the
temperature measured is subtracted. So, endo- and exothermal effects
in the sample will change the shape of the temperature measured, and
the difference to the temperature calculated shows the classic known
DTA-peaks (of course this method is less sensitive than a real DTA, but
in the dilatometer, bigger samples are used anyway). A measurement
of a small piece of rock-crystal (3x4x5mm, app. 450mg) shows the
alpha to beta transition of quartz (crystalline quartz, SiO2, NOT fused
silica, where the crystalline structure has been destroyed by melting).
This transition is endothermic during heating and exothermal during
cooling. The literature-value is 573C, which is almost exactly the
onset-temperature measured (571.7C). To do this, the desired
dilatometer- (*.IPR)-file is loaded, and "Create DTA-file" from
evaluation menu is selected. Now, a DTA- (*.TPR)-file is created, with
the same name like the related *.IPR-file. Then the standard DTA-
evaluation is used for further evaluation (smoothing, peak-evaluation,
etc.).
Sample measurement of rock crystal:
17
LINSEIS
Thermal Analysis
APPLICATIONS
DSC
18
LINSEIS
Thermal Analysis
Determination of the crystallization enthalpy of mercury (Hg)
Test Parameters:
Sample: mercury (Hg)

Quantity of sample: 88.56 mg
Preparation: drops
Material of crucible: aluminum, closed
Atmosphere: air
Cooling rate: 5 K/min
Commentary:
During a linear cooling rate of 5K/min the sample crystallizes at

approx. 38,4C. The released crystallization energy (exothermal) is
approx. 11J/g. The mercury drop needs approx. 2 minutes for the
total crystallization.
19
LINSEIS
Thermal Analysis
Determination of the melting enthalpy of mercury (Hg)
Test Parameters:
Sample: mercury (Hg)

Preparation: drops
Atmosphere: air
Heating rate: 5 K/min
Commentary:
The determination of the melting enthalpy of mercury can be done by

means of DSC. The proceeding starts during a linear heating speed of
5K/min at 38C. The melting enthalpy was determined to 11.2J/g.
20
LINSEIS
Thermal Analysis
Determination of the Oxidative Induction Time (OIT) of

Polyethylene (PE-LD)
Test Parameters:
Sample: polyethylene "low density" (PE-LD)

Preparation: granulate
Material of crucible: aluminum, open
Atmosphere: argon
Commentary:
The sample of polyethylene will be heated under argon with a heating

rate of 10K/min up to 200C. You can see the endothermal melting
procedure at 122C. The holding time at 200C is 75min. Under these
conditions there is no chemical reaction or decomposition recognizable.
This result is the assumption for the following examinations concerning
oxidation of PE-samples.
21
LINSEIS
Thermal Analysis
Experiments for determination of the Oxidative Induction

Time (OIT) of Polyethylene (PE-LD)
Test Parameters:
Sample: Polyethylene "low density" (PE-LD)

Atmosphere: argon/oxygen
Heating rage: 10 K/min
Commentary:
The polyethylene sample will be heated under argon to 200C with a

heating rate of 10K/min. After 3 minutes at the equilibrium the
atmosphere of argon will be changed to oxygen. After 5 additional
minutes the exothermal oxidation of the sample will start.
22
LINSEIS
Thermal Analysis
Determination of the Oxidative Induction Time (OIT) of

Polyethylene (PE-LD)
Test Parameters:
Sample: Polyethylene "low density" (PE-LD)

Quantity of sample: 16 mg
Atmosphere: argon/oxygen
Commentary:
The polyethylene sample will be heated under argon up to 250C by a

heating rate of 10K/min. After 3 minutes in the equilibrium the
atmosphere of argon will be changed to oxygen. After 30 sec. you can
recognize a rapid oxidation of the sample.
23
LINSEIS
Thermal Analysis
Thermo analytical examination of several samples of sugar
Test Parameters:
Sample: glucose fructose saccharose

Quantity of samples: 6,76 mg 8,78 mg 6,46 mg
Preparation: powder
Atmosphere: air
Commentary:
The melting point of every substance can be determined exactly by

means of the Dynamic Differential Calorimetry. Therefore this method
will be used very often for identification of unknown substances or
mixture of substances. Also connections with the same molecular
weight (for example fructose and glucose) can be distinguished by
means of this method.
24
LINSEIS
Thermal Analysis
Determination of glass point, late crystallization and melting

point of PET (Polyethylene-terephthalat)
Test Parameters:
Sample: PET (Polyethylene-terephthalat)

Sample preparation: granulate
Material of crucible: Aluminum, closed
Atmosphere: air
Commentary:
PET (Polyethylene-terephthalat), shows at about 77C a very

significant endothermal glass point, when looking at partial crystalline
thermo plastic materials. The relation between the exothermal cold
crystallization (131C) and the endothermal melting peak is a method
for the degree of crystallization of the material. In the case of PET the
crystalline part is very small, giving the material a very good
transparency. This is why drinking bottles (coca cola) are very often
produced from PET.
25
LINSEIS
Thermal Analysis
APPLICATIONS
HDSC
26
LINSEIS
Thermal Analysis
Determination of the phase change of caliumchromat (K2CrO4)
Test Parameters:
Sample: caliumchromat (K2CrO4)

Preparation: powder
Material of crucible: aluminum oxide
Atmosphere: air
Commentary:
The crystalline structure of K2CrO4 changes from a orthorhombic to a

hexagonal structure at 665C. This endothermal phase change can be
evaluated by means of HDSC, relative to temperature, as well as
relative to the energy, that is needed for the phase change.
27
LINSEIS
Thermal Analysis
Determination of the phase transition temperature of

silversulfat (AG2SO4)
Test Parameters:
sample: silversulfat (AG2SO4)

Crucibles made out of: Al2O3
Atmosphere: air
Commentary:
Silversulfat (AG2SO4) changes its crystalline structure from a

orthorhombic configuration to a hexagonal system at 424C. The
energy that is needed for this crystalline restructuring can be very
good determined by means of the HDSC method (High temperature
Differential Scanning Calorimetry).
28
LINSEIS
Thermal Analysis
Determination of the phase change temperature of potassium

sulfate (K2SO4)
Test Parameters:
Sample: potassium sulfate (K2SO4)

Material of crucible: Aluminum oxide
Atmosphere: air
Commentary:
Potassium sulfate (K2SO4) is changing its crystal structure from a

orthorhombic to a hexagonal system at 582C. The energy that is
needed for this restructuring can be determined with the HDSC
method quantitatively (high temperature differential scanning
calorimetry).
29
LINSEIS
Thermal Analysis
APPLICATIONS
TG
30
LINSEIS
Thermal Analysis
Determination of the quantity of chalk of a PE-foil (PE)
Test Parameters:
Sample: Polyethylene (PE)

Quantity of sample: 39,32 mg
Preparation: foil
Crucibles made out of: aluminum oxide
Atmosphere: nitrogen: 2 l/h
Commentary:
The pyrolisis starts at approx. 400C under conditions almost free of

oxygen. The chalk which is added as fill stuff splits off at a
temperature of approx. 600C. From the lost of weight you can
determine the quantity of chalk. If there was pure chalk taken you can
determine the content of chalk to 55,4%.
31
LINSEIS
Thermal Analysis
Comparison of the reactional behaviour of aluminum powder in

nitrogen and argon atmosphere
Test Parameters:
Sample: Aluminum
Atmosphere: nitrogen/argon: 2 l/h
Commentary:
Aluminum powder does not show any mass change under identical
measuring conditions in argon atmosphere over a temperature ranging
from 25C up to 1400C. However the same measurements under a
nitrogen atmosphere shows a reaction with ALN at about 1000C.
32
LINSEIS
Thermal Analysis
Pyrolysis of polyethylene (PE)
Test Parameters:
Sample: PE (Polyethylene)
Atmosphere: nitrogen 2 l/h
Commentary:
With the thermal decomposition of polyethylene (PE-LD) inert

atmosphere you can show by means of the Thermogravimetric method
that the polymer does not contain any filling material. The weight loss
that can be detected is nearly the complete sample weight.
33
LINSEIS
Thermal Analysis
Pyrolysis of Polyethylene PE-LD und PE-HD
Test Parameters:
Sample: PE-LD and PE-HD (Polyethylene)

Atmosphere: nitrogen (N2), 2 l/h
Commentary:
A comparison between two different polyethylene samples (PE-LD

Low density and PE-HD high density) under identical pyrolysis
conditions shows nearly no difference of its Thermogravimetric
behavior. The thermal decomposition under inert gas in the
temperature range between 400C and 500C is a quantitative one.
34
LINSEIS
Thermal Analysis
APPLICATIONS
TG - DTA
35
LINSEIS
Thermal Analysis
Determination of the reaction temperature between aluminum

and nitrogen
Test Parameters:
Sample: Aluminum
Atmosphere: nitrogen: 2 l/h
Commentary:
By means of the DTA method you can determine the melting point of
aluminum (658C) as well as the reaction temperature of the very
strong exothermal nitride reaction (1100C). You can see a clear
increase of the sample mass with the Thermogravimetric analysis (TG
signal), which can be determined quantitatively. There is a correlation
between the increase of weight and the content of aluminum of the
sample.
36
LINSEIS
Thermal Analysis
Thermal behavior of aluminum hydroxide (dehydration and

phase change)
Test Parameters:
Sample: Al(OH)3 (Aluminum hydroxide)

Material of crucible: aluminum oxide
Atmosphere: air
Commentary:
At about 150C you can see that 1,7% humidity is leaving the sample.
Between 300 and 600C you can watch the endothermal change from
aluminum hydroxide to aluminum oxide (loss of weight: approx. 14%).
Between 1250 and 1350C you can find another phase change, which
is not connected to any Thermogravimetric signal.
37
LINSEIS
Thermal Analysis
Determination of the decomposition of calcium oxalate

(CaC2O4) under air
Test Parameters:
Sample: calcium oxalate (CaC2O4)

Material of crucible: aluminum oxide (Al2O3)
Atmosphere: air
Commentary:
Thermal decomposition in steps of calcium oxalate hydrate

(CaC2O4*H2O) on air
1.) Decomposition of crystal water: Dm = 12,32 %

2.) Decomposition of carbon monoxide: Dm = 19,16 %
3.) Decomposition of carbon dioxide: Dm = 30,12 %
38
LINSEIS
Thermal Analysis
All three decomposition reactions that can be recognized by means of
the thermal balance are endothermal. That means one should expect
with the DTA method endothermal peaks at the corresponding
temperatures. If the reaction is made under air, which means in
atmosphere containing oxygen, you can see a second reaction
(decomposition of CO) and following another strong exothermal
reaction (the oxidation of CO to CO2). The DTA signal of this oxidation
over shadows normally the endothermal decomposition of CO.
If however the thermal decomposition of calcium-oxalate-hydrate

(CAC2O4*H2O) is done under oxygen free conditions the oxidation of
carbon monoxide is suppressed and only endothermal DTA signals can
be watched.
39
LINSEIS
Thermal Analysis
Determination of the decomposition of calcium oxalate CaC2O4

under argon atmosphere
Test Parameters:
Sample: CaC2O4 (Calcium oxalate)

Commentary:
The thermal decomposition of CaC2O4 under argon atmosphere is

different to the same decomposition under air, as under argon there is
no oxygen available to enable the endothermal oxidation (at 500C) of
the free carbon monoxide to carbon dioxide.
This is why there are only endothermal DTA signals that show the
decomposition of water, carbon monoxide and carbon dioxide.
40
LINSEIS
Thermal Analysis
Decomposition of Rubber
Test Parameters:
Sample: Rubber
Quantity of sample: 24.6mg
Sample preparation: Solid piece
Material of crucible: Aluminum
Atmosphere: N2/O2
Heating rate: 30K/min up to 300C, 6min dwell time, N2
30K/min up to 600C, 5min dwell time, N2
30K/min up to 950C, 15min dwell time, O2
Commentary:
In the first step of weight loss, the dehydration of the sample takes
place. The amount of water was 9.27%. In the second reaction step,
the volatile components are released by pyrolysis under N2
atmosphere. The amount of these components is 35.99%. For the
third reaction step, the atmosphere is changed to O2 all organic
components are burned out. The loss in weight is 14.33%. The
remaining rest of 40.41% are inorganic components like ashes, slake
or fillers.
41
LINSEIS
Thermal Analysis
Dehydration of raw gypsum CaSO4 + 2 H2O
Test Parameters:
Sample: CaSO4 + 2 H2O (raw gypsum)

Material of crucible: aluminum
Atmosphere: air
Heating rate: 10K/min
Commentary:
Dehydrate Semi hydrate + Water Anhydrate + Water

CaSO4 +2 H2O =>CaSO4 + H2O + 1 H2O n => CaSO4 + H2O n
1) Raw gypsum is the dehydrate. There are two molecules of water

attached to a single CaSO4 molecule.
2) By heating up to app. 160C the semi hydrate gypsum is built.
This is the stuff usually is used to plaster. 1 molecules of water
are released; so two CaSO4 molecules are sharing a single water
molecule.
42
LINSEIS
Thermal Analysis
3) By heating to higher temperatures (400C) the anhydrate is

built. This is the so-called "dead burned gypsum", also known as
alabaster. In this state no water at all is attached to the CaSO4
molecules.
By means of the molecules-weight of the compounds, the change in

weight can be calculated:
Heating
CaSO4 * 2 H2O ---------------------------> CaSO4 * H2O + 1 H2O
The resulting mass-change can be calculated easily, by means of the

MOL-weights:
1 MOL Ca = 40.080g
1 MOL S = 32.064g
1 MOL O = 15.999g
1 MOL H = 1.008g
1 MOL CaSO4 * 2 H2O = 172.17g

1 MOL CaSO4 * H2O = 145.15g
1 MOL CaSO4 = 136.14g
So, the change from CaSO4 * 2 H2O to CaSO4 * H2O will result in a
15.7% weight loss, and to CaSO4 (anhydrate) to an additional weight
loss of 5.2% (in respect to CaSO4 * 2 H2O)
43
LINSEIS
Thermal Analysis
Burning of loam (clay)
Test Parameters:
Sample: Loam
Sample preparation: Paste
Material of crucible: Aluminum
Atmosphere: Air
Commentary:
From room temperature up to app. 200C the dehydration takes place

(endothermic). Between app. 200C and 450C the organic
compounds are burned out (exothermic). From app. 500C up the
600C the kaolinite (Al2O3 * SiO2 * H2O) is modified to Metakaolin
(Al2O3 * SiO2 + H2O -). At app. 570C the endothermic alpha to beta
transition of the contained SiO2 is visible.
44
LINSEIS
Thermal Analysis
DTA and TG measurement of Kaolin
Test Parameters:
Sample: Kaolin
Atmosphere: air
Commentary:
By means of the DTA method you can determine the dehydration of

water (RT to 100 C), from 450 C to about 700 C you see the
Dehydroxylation of the kaolinite (loss of lattice water, Kaolinite and
Metakaolin). The second peak from 950 C to 1100 C determines the
reaction from Spinel to Mullite. The TG-Signal determine the organic
material burn out from 100 C to about 700 C
45
LINSEIS
Thermal Analysis
APPLICATIONS
TMA
46
LINSEIS
Thermal Analysis
Determination of glass transition and melting point with a
Polyamide sample
Test Parameters:
Sample: Polyamide
Static sample load: 100mN
Dynamic sample load: 250mN
Frequency: 0.05Hz
Commentary:
Measurement of a polyamide sample where the glass transition was

found at 89.1C, the melting point is app. 178C.
47
LINSEIS
Thermal Analysis
APPLICATIONS
DILATOMETRY
48
LINSEIS
Thermal Analysis
Dilatation of glass ceramics
Test Parameters:
Sample: glass ceramics

Sample length: 15.00 mm
Sample preparation: cubic sample preparation
Sample holder: SiO2-glass
Atmosphere: air
Commentary:
The dilatometric method is an excellent method to determine the

thermal expansion (CTE) and the softening point of glass ceramic
materials. Besides the absolute expansion and the expansion
coefficient (alpha tech / alpha phys) you can find also the first
derivative of the absolute expansion in the above figure. Where the
first derivative goes through zero you can determine the max. of the
thermal expansion and thus the softening point of the material were
exact.
49
LINSEIS
Thermal Analysis
Comparison of the sintering behavior of aluminum-oxide
samples, when using different sinter programs
Test Parameters:
Sample: Aluminum-oxide Al2O3

Sample length: sample 1: 12 mm
sample 2: 9 mm
Sample preparation: green body
Atmosphere: air
Heat up rate: sample 1: 10-20-10 K/min
sample 2: 10-20-5 K/min
Dwell time: sample 1: no
sample 2: 15 min
Commentary:
Up to a temperature of 1100C no sintering behavior can be seen at

both samples. With the following slower heat up rate and a dwell time
of 15min at 1600C sample 2 shows a resulting sintering of 17,11%,
reflecting in a density of 3,898g/ccm (the green body has a density of
2,22g/ccm).
50
LINSEIS
Thermal Analysis
Comparison of the thermal expansion (dilatation) of two
different glass ceramics
Test Parameters:
Sample: glass ceramics

Sample length: 15.00 mm
Sample preparation: cubic sample
Sample holder: SiO2-Glas
Atmosphere: air
Commentary:
The dilatometric method is an excellent means to determine the

thermal expansion and the softening point of glass ceramic materials.
When two measurements are being compared on one screen you can
compare not only the expansion behavior, but also, you can
determine, by means of the first derivative where the softening points
are.
51
LINSEIS
Thermal Analysis
Dental Ceramics
Test Parameters:
Sample: Dental Ceramics

Sample length: 23,70 mm
Sample preparation: cubic sample preparation
Sample holder: SiO2-Glas
Atmosphere: air
Commentary:
The embedded dental mass should ideally have a similar coefficient of

thermal expansion as the dental alloy after the burning process.
Referring to the UNI EN ISO Norm the coefficient of thermal expansion
is to be determined and evaluated at a temperature of 500C and
550C.
If the coefficient of thermal expansion for dental mass and the dental
alloy are equivalent, this will guarantee an excellent fit of the artificial
tooth, even whilst strong temperature changes.
At about 250C and 570C the phase transition from low to high
temperature modifications of cristobalite and quartz are shown.
Changes in mixture can influence the technical coefficient of thermal
expansion.
52
LINSEIS
Thermal Analysis
Quenching of a steel sample
Test Parameters:
Sample: Stainless steel

Dimension: 21x3mm
Sample holder: Fused silica
Atmosphere: air
Cooling: Water shower
Commentary:
The sample is heated up to 550C, with a dwell time of one hour. Then
the heating is stopped and the sample is quenched rapidly with a
water shower. The initial cooling rate is app. 30K/s.
So, in app. 100 seconds the sample is cooled down to 100C.
53
LINSEIS
Thermal Analysis
Detection of the softening-point
Test Parameters:
Sample: Al2O3 based ceramic

Length: 23.1mm
Sample holder: Al2O3
Atmosphere: air
Threshold: -10m
Commentary:
For each controller segment, a change in length threshold can be

specified. If this threshold is reached, the actual controller segment is
finished, before the target temperature of the segment is reached. In
the example above, the first segment was a heating segment, up to
1750C, and the threshold was set to 10m. The second segment
was the cooling segment. During heating, the minimum and maximum
readings of the change in length signal are compared to the actual
change in length. If the threshold is negative, and the actual reading
becomes less than maximum threshold, the heating segment is
54
LINSEIS
Thermal Analysis
finished and cooling starts. If the threshold entered is positive, things
work the other way round. Due to this feature, the softening point of a
sample can be determined without controlling the change in length
manually. Its also a powerful tool, to prevent the damage of the
sample holder by melting the sample by accident if it starts shrinking
the heating is stopped.
55
LINSEIS
Thermal Analysis
Expansion measurement of Cordierite
Test Parameters:
Sample: Honeycomb out of cordierite

Sample length: 20.2mm
Reference: Fused silica, NIST SRM 739
Reference length: 20mm
Atmosphere: air
Heating rate: 10K/min up to 810C
Commentary:
Cordierite is the basic ceramic material for automotive catalysts. Its

coated with platinum alloy as active surface. The honeycomb like
ceramic block is mounted in a metal housing. To prevent the ceramic
from breaking or loosening during the change in temperature during
operation, the coefficient of thermal expansion of the ceramics must
be matched by the coefficient of thermal expansion of the housing.
This is done during the production of the honeycombs by arranging the
grains of the polycrystalline ceramics in a certain direction. Since the
thermal expansion of the three axis of the cordierite crystal is
56
LINSEIS
Thermal Analysis
different, the average expansion can be adjusted by this procedure.
So, for process control, the thermal expansion must be measured to
give a feed back to the production of the ceramic. Since the thermal
expansion of cordierite is very small (3.6E-7/K), a dual push rod
dilatometer is to be used.
57
LINSEIS
Thermal Analysis
Alpha o Beta transition of steel
RITA (Rapid Induction Thermal Analysis)
Test Parameters:
Sample: Steel 16MnCr5

Dimension: Tube, 6x1x10mm
Sample holder: Fused silica
Cooling/Inert gas: Argon
Heating/Cooling rate: 50K/s
Commentary:
In the diagram the actual temperature (red trace), the calculated set-
value of the temperature (blue trace), the measured change in length
(green trace) and the heating power applied (purple trace) are
displayed. At T=15s the alpha to beta transition of the steel takes
place. The expansion changes to a temporary shrinkage, additional
power is consumed by the sample for the phase change. Between
T=50...70s the opposite transition occurs. The shrinkage changes to
an expansion and the temperature decreases slower, since the energy
stored is set free.
58
LINSEIS
Thermal Analysis
APPLICATIONS
Coupling MS/FTIR
59
LINSEIS
Thermal Analysis
Application: TG/DTA FTIR-coupling

under nitrogen atmosphere
Test Parameters:
Sample: CaC2O4 + 1 H2O (Calcium oxalate)

60
LINSEIS
Thermal Analysis
Commentary:
The evolved gases from the decomposition of calcium oxalate have

been fed to the FTIR with a heated capillary, made of stainless steel.
In the graphics the absorption for the wave numbers 1000...4000 is
displayed over time. The three groups of peaks relate to the evolved
gases H2O, CO and CO2.
61
LINSEIS
Thermal Analysis
TG/DTA MS-coupling

under argon atmosphere
Test Parameters:
Sample: CaC2O4 + 1 H2O (Calcium oxalate)

Commentary:
The evolved gases from the decomposition of calcium oxalate have

been fed to the mass spec with a heated capillary, made of quartz. In
the graphics, the ion currents for mass numbers 18 (water), 28
(carbon monoxide) and 44 (carbon dioxide) has been imported.
62
LINSEIS
Thermal Analysis
REFERENCES
63
LINSEIS
Thermal Analysis
J.O.Hill (de.):
For better Thermal Analysis,
Edition III; ICTA 1991
W.WM. Wendlandt:
Thermal Methods of Analysis,
John Wiley & Sons, New York, London, Sidney, Toronto, 1974
B. Wunderlich:
Thermal Analysis,
Academic Press Inc., Boston, San Diego, New York, 1990
A. Blazek:
Thermal Analysis,
Van Norstrand, London, 1972
Peter Haines
Principles of Thermal Analysis and Calorimetry
Royal Society of Chemistry; 1st edition (August 1, 2002)
Adrian Bejan
Advanced Engineering Thermodynamics,
Wiley-Interscience; 2nd edition (October 2, 1997)
T. Hatakeyama, Liu Zhenhai

Handbook of Thermal Analysis
John Wiley & Sons (March 5, 1999)
Randall M. German
Sintering Theory and Practice
John Wiley & Sons (January 19, 1996)
by James S. Reed
Principles of Ceramics Processing, 2nd Edition
Wiley-Interscience; 2 edition (January 9, 1995)
64
LINSEIS
Thermal Analysis
P. Barnes, J. Bensted
Structure & Performance of Cements
Spon Press; 2nd edition (January 15, 2002)
R.C. MacKenzle
Differential Thermal Analysis Fundamental
Academic Pr (June 1, 1970)
Werner Smykatz-Kloss
Differential Thermal Analysis: Application and Results in Mineralogy,
(Ecological Studies,)
Springer-Verlag (December, 1974)
M.I. Pope
Pope Differential Thermal Analysis - A Guide to the Technique and Its
Applications,
John Wiley and Sons Ltd (May 6, 1977)
65

LINSEIS Handbook1

Загружено:

Сведения о документе

Оригинальное название

Авторское право

Доступные форматы

Поделиться этим документом

Поделиться или встроить документ

Параметры публикации

Этот документ был вам полезен?

Это неприемлемый материал?

Авторское право:

Доступные форматы

LINSEIS Handbook1

Загружено:

Авторское право:

Доступные форматы

LINSEIS

LINSEIS Industrial Application Handbook

Thermal Analysis Categories 3

Differential Thermal Analysis (DTA) 4

Definitions of Differential Thermal Analysis (DTA) 4

Differential Scanning Calorimetry (DSC) 7

Definition of Differential Scanning Calorimetry 7

Definitions of Thermogravimetry (TG) 9

Thermomechanical Analysis (TMA) 11

Simultaneous DTA measurement with the LINSEIS Dilatometer

Crystallization enthalpy of mercury (Hg) 19

Determination of the phase change of caliumchromat (K2CrO4) 27

Determination of the quantity of chalk of a PE-foil (PE) 31

Reaction temperature between aluminum and nitrogen 36

Glass transition and melting point with a Polyamide sample 47

Dilatation of glass ceramics 49

RITA (Rapid Induction Thermal Analysis)

Applications TG FTIR/MS Coupling

FTIR Determination of the decomposition of calcium oxalate 60

MS Determination of the decomposition of calcium oxalate 62

Linseis International is a manufacturing concern, consisting of key

Our expertise lies in manufacturing a wide range of

We achieve our goals by means of an expert team of highly competent

A group of techniques in which a property of the sample is

The generic term for a group of techniques in which the

The above are definitions of Thermal Analysis by the International

Name Measurement Unit

There are multiple methods in thermal analysis, and each is defined as

Differential Thermal Analysis, which detects temperature

Definitions of Differential Thermal Analysis (DTA)

A technique in which the temperature of reference material and

The above are definitions of Differential Thermal Analysis (DTA).

DIN 51007: Differential Thermal Analysis

As stated in the definitions, DTA is a technique that

The measuring head, shown in the picture carries

T (T) = TS (T) TR (T)

TS: sample temperature

T (t) = TS (t) TR (t)

L62 D 1550 DTA Differential Thermal Analyzer

The Linseis DTA uses a dynamic measuring principle. It can measure

Temperature range -150C up to +1600C

Power Compensation DSC

A technique in which difference of thermal energy that is applied

Heat Flux DSC

A technique in which the temperature of the sample unit, formed

The above is Differential Scanning Calorimetry (DSC) as defined by

While Power Compensation DSC performs heat flow supply with a

As a result, the temperature difference measurement also serves as

ASTM E 793-85: Heats of Fusion and Crystallization By Differential

r = dqr/dt = -K(T) TPR(T)

TPR = temperature difference (measuring signal including baseline

The differential scanning calorimeter L63/45 is a well-proven

The Linseis HDSC, L62 H 1550 uses a heat flux measuring

The temperature ranges from 150C up to 1550C.

A technique in which the mass of the sample is monitored

A technique in which the mass of a sample is measured as the

The above are definitions of Thermogravimetry (TG) by ICTAC and JIS.

ASTM E 914-83: Evaluating Temperature Scale for

M = m(t) or m = m(t) m(t0)

Apparatus: (L81 / L81 II / L81-Platinum)

The model L81 Research Balance is a well proven Thermal

Economy Line Thermal Balance L81-II, vertical mode of

Top Line Thermal Balance L81-Platinum, vertical mode of