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BPRI Conference 22nd of October 2008 1
Rubber AnalysisRubber Analysis byby
AdvancedAdvanced ThermogravimetryThermogravimetry (TG):(TG):Vacuum Vacuum ,, evolved evolved gas gas analysis analysis ,, c c - - DTADTA® ®
dr Bart Rimez, dr Stephan Knappe, Danny Pattyn, Jan De Munck
Sales & ApplicationsBenelux-Scientific – Netzsch-Gerätebau GmbH
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BPRI Conference 22nd of October 2008 2
Distributor of scientific equipment:• Thermal testing
Netzsch, Hot disk, Rubotherm
• Mechanical analysisNetzsch, Tinius Olsen, Bose
• Surface characterizationAltimet, FEI
• Sample preparationRayRan, Fritsch
Office: Begoniastraat 17, Eke, Belgium
Contact: +32 (0)9 252 54 00Site w w w . b e n e l u x - s ci e n t i f i c . co m
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BPRI Conference 22nd of October 2008 3
Producer of thermal analysisinstruments, 2nd globally• Thermal transitions
DSC, TGA, STA,…
• Mechanical analysisDMA, TMA, Dilatometry
• Thermal conductivityLaser flash, guarded hot plate, heatflow meter
• Refractory testing
Rupture under load (RUL)
Loacted in Selb, Bavaria, GermanySite: w w w .n e t z s ch - t h e r m a l - a n a l y s i s. c om
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BPRI Conference 22nd of October 2008 4
Estimated Distribution of ThermoanalyticalMethods in Polymer Analysis
esa mplesamplecarr iergasoutletee
DSC
60%
DMA/TMA
20%
TG
20%
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BPRI Conference 22nd of October 2008 5
Estimated Distribution of ThermoanalyticalMethods in Elastomer and Rubber Analysis
esa mplesamplecarr iergasoutletee
DSC
10%
DMA
20%
TG
70%
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BPRI Conference 22nd of October 2008 6
Outline
Introduction to TG 209 F1 iris ® - measuring principle
Use of hyphenated techniquesMore information during one single experiment
• Vacuum – separation additives and polymers
• Switching gases – triggered degradation
• Evolved gas analysis – degradation identification
• C-DTA ® - Heat information
Summary
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BPRI Conference 22nd of October 2008 7
TG 209 F1 Iris ®
High resolution 0.1 µg
Wide measuring range 2 g
ASC (automatic sample changer) for
up to 64 different crucibles
Electronic gas flow control (MFC) for
precise gas flows (3x)
Vacuum-tight thermo-microbalancefrom 10 to 1000°C
Integrated AutoVac for automatic
evacuation and re-fill
Simultaneous coupling to MS and
FTIR, also when using the ASC
c-DTA®
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BPRI Conference 22nd of October 2008 8
Design of the TG 209 F1 Iris ®
gas outlet
sample
cooling
cooling
hoistsample carrier
balancegas inletprotective
gas inletpurge
relief valve
pressure sensor
cover support
sample carrier
vacuum
with Sample Thermocouple of Platinel ®
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BPRI Conference 22nd of October 2008 9
Outline
Introduction to TG 209 F1 iris ® - measuring principle
Use of hyphenated techniquesMore information during one single experiment
• Vacuum – separation additives and polymers
• Switching gases – triggered degradation
• Evolved gas analysis – degradation identification
• C-DTA ® - Heat information
Summary
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BPRI Conference 22nd of October 2008 10
Outline
Introduction to TG 209 F1 iris ® - measuring principle
Use of hyphenated techniquesMore information during one single experiment
• Vacuum – separation additives and polymers
• Switching gases – triggered degradation
• Evolved gas analysis – degradation identification
• C-DTA ® - Heat information
Summary
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BPRI Conference 22nd of October 2008 11
Normal pyrolysis in nitrogen atmosphere:A calculated plasticizer content of 9.9 %
Unknown NR/SBR Rubber MixtureDetermination of the Plasticizer Content
esa mplesamplecarr iergasoutletee
Mass loss / %
Plasticizermass loss: -9.87 %
NR
mass loss: -38.81 %
SBRmass loss: -14.79 %
Temperature / °C
DTG % / min
Sample: NR/SBR
Sample mass: 20.64 mgCrucible: Pt open
Heating rate: 20 K/min
Atmosphere: N2
1. Standard TGA Measurement
P l as t i c i z er i s s h o u l d e r o f
b i g d e g r a d a t i o n p e a k
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BPRI Conference 22nd of October 2008 12
Using Peak Separation software (PKS) in nitrogen atmosphere:A plasticizer content calculated to 11.8 %
esa mplesamplecarr iergasoutletee
dMass / dt / (%/min)
Plasticizer
NR
SBR
DTG-curve calculated: solid lineDTG-curve measured: dotted
Sample: NR/SBRSample mass: 20.64 mgCrucible: Pt openHeating rate: 20 K/min
Atmosphere: N2
Temperature / °C
2. Peak Separation (PKS) of the Standard TGA Measurement
Unknown NR/SBR Rubber MixtureDetermination of the Plasticizer Content
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BPRI Conference 22nd of October 2008 13
Boiling point depression in vacuum provides a plasticizer content of 13.1 %
Unknown NR/SBR Rubber MixtureDetermination of the Plasticizer Content
esa mplesamplecarr iergasoutletee
Mass loss / % DTG % / min
Temperature / °C
Plasticizermass loss: - 13.10 %
NRmass loss: - 36.97 %
SBRmass loss: - 10.33 %
Sample: NR/SBRSample mass: 20.64 mgCrucible: Pt openHeating rate: 20 K/min
Atmosphere: VACUUM
3. Vacuum Method (approx. 0.1 mbar)
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BPRI Conference 22nd of October 2008 14
Peak Separation software + vacuum provides a content of 14.9 %Client gave afterwards exact composition: 15 weight %
esa mplesamplecarr iergasoutletee
dMass / dt / (% / min)
Plasticizer
NR
SBR
DTG-curve calculated: solid lineDTG-curve measured: dotted
Sample: NR/SBRSample mass: 20.64 mgCrucible: Pt openHeating rate: 20 K/min
Atmosphere: VACUUM
Temperature / °C
4. Peak Separation (PKS) on the Vacuum Measurement Result
Unknown NR/SBR Rubber MixtureDetermination of the Plasticizer Content
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BPRI Conference 22nd of October 2008 15
Outline
Introduction to TG 209 F1 iris ® - measuring principle
Use of hyphenated techniquesMore information during one single experiment
• Vacuum – separation additives and polymers
• Switching gases – triggered degradation
• Evolved gas analysis – degradation identification
• C-DTA ® - Heat information
Summary
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BPRI Conference 22nd of October 2008 16
Outline
Introduction to TG 209 F1 iris ® - measuring principle
Use of hyphenated techniquesMore information during one single experiment
• Vacuum – separation additives and polymers
• Switching gases – triggered degradation
• Evolved gas analysis – degradation identification
• C-DTA ® - Heat information
Summary
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BPRI Conference 22nd of October 2008 17
0 20 40 60 80 100Time /min
20
40
60
80
100
TG /%
100
200
300
400
500
600
700
800
900
Temp. /°C
-6
-5
-4
-3
-2
-1
0
1
2
DTG /(%/min)
152.1°C 342.0°C
429.0°C
647.7°C
vacuum refill withnitrogen
oxygen
volatilesrubbercompound 1
rubber compound 2
combustion ofcarbon black
ash content
-20.04 %
-42.86 %
-9.08 %
Residual Mass: 28.03 % (102.5 min)
TG 209 F1 I ris
sample mass: 10.05 mgcrucible: Al2O3heat ing rates: 10 K/ minvacuum !
Autovac® : creating vacuum, refilling with autosamplingexample: tyre mixture filled with carbon black (unknown weight)
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BPRI Conference 22nd of October 2008 18
Outline
Introduction to TG 209 F1 iris ® - measuring principle
Use of hyphenated techniquesMore information during one single experiment
• Vacuum – separation additives and polymers
• Switching gases – triggered degradation
• Evolved gas analysis – degradation identification
• C-DTA ® - Heat information
Summary
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BPRI Conference 22nd of October 2008 19
Outline
Introduction to TG 209 F1 iris ® - measuring principle
Use of hyphenated techniquesMore information during one single experiment
• Vacuum – separation additives and polymers
• Switching gases – triggered degradation
• Evolved gas analysis – degradation identification
• C-DTA ® - Heat information
Summary
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BPRI Conference 22nd of October 2008 20
Coupling of TG 209 F1 Iris ASC withFTIR Tensor 27 and QMS 403 C Aëolos
esa mplesamplecarr iergasoutletee
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BPRI Conference 22nd of October 2008 21
Coupling of TG to an FTIR Tensor –cooperation with Bruker Optics
esa mplesamplecarr iergasoutletee
FTIR gas cell(230°C)
transfer line(230°C)
controlthermocouple
adaptor head(250 °C)
controlthermocouple
micro furnace
sample
sample carrier
controlthermocouple
IR detector
TG cell
gas outlet
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BPRI Conference 22nd of October 2008 22
NR/SBR Tyre Mixture with Gas Flow Monitoring
TG with DTG Signal
100 200 300 400 500 600 700 800 900Temperature /°C
-20
0
20
40
60
80
100
TG /%
0
50
100
150
200
250
Flow /(ml/min)
-8
-6
-4
-2
0
DTG /(%/min)
purge gas 1: nitrogen 20 ml/min
purge gas 2: air 30 ml/minprotective: nitrogen 10 ml/min
plasticizer
NR
SBR
carbonblack
ashcontent
Elastomer
-6.98 %
-38.37 %
-30.35 %
-20.03 %
4.28 % (799.0 °C)383.0 °C
448.0 °C
549.0 °C
TG 209 F1 I r is
sample mass: 14.85 mgcrucible: Al2O3heat ing rate: 10 K/ min
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BPRI Conference 22nd of October 2008 24
NR/SBR Tyre Mixture –TG-FTIR with extracted IR Spectra
8 9 1 . 4
0
1000150020002500300035004000
Wavenumber cm-1
0 . 0
0
0 . 0
2
0 . 0
4
0 . 0
6
0 . 0
8
0 . 1
0
0 . 1
2
A b s o r b a n c e
U n i t s
Extracted single spectrum at 390°C
Extracted single spectrum at 450°C
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BPRI Conference 22nd of October 2008 25
NR/SBR Tyre Mixture (Zoom)TG-FTIR with Extracted IR Spectra
8 9 1 . 9
3
80010001200140016001800
Wavenumber cm-1
0 . 0
0 0
0 . 0
0 5
0 . 0
1 0
0 . 0
1 5
0
. 0 2 0
0 . 0
2 5
A b s o r b a n c e
U n i t s 891.4 cm-1
Zoom
450°C
390°C
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BPRI Conference 22nd of October 2008 26
Library Spectrum for Natural Rubber (NR)with Wave Number Peak at 892 cm-1
Rolf Schönherr, “TG-FTIR Atlas Elastomere” , Verlag W.K. Schönherr, D-Burgdorf, 1996.
Decomposition of NR
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BPRI Conference 22nd of October 2008 27
Library Spectrum for
Styrene Butadiene Rubber (SBR)
Rolf Schönherr, “TG-FTIR Atlas Elastomere” , Verlag W.K. Schönherr, D-Burgdorf, 1996.
Decomposition of SBR
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BPRI Conference 22nd of October 2008 28
8 9 1 . 9
3
80010001200140016001800
Wavenumber cm-1
0 . 0
0 0
0 . 0
0 5
0 . 0
1 0
0 . 0
1 5
0
. 0 2 0
0 . 0
2 5
A b s o r b a n c e
U n i t s 891.4 cm-1
Zoom450°C:
SBR
NR/SBR Tyre Mixture - identification peaks
390 °C:Natural rubber
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BPRI Conference 22nd of October 2008 29
100 200 300 400 500 600 700Temperature /°C
20
30
40
50
60
70
80
90
100
TG /%
-0.02
0
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0.16
Gram Schmidt /Import
-8
-7
-6
-5
-4
-3
-2
-1
0
1
DTG /(%/min)
rubber mixture
TG
DTG
total IR chromatogram
450.2 °C
390.2 °C
382.5 °C
447.1 °C
Residual Mass: 23.66 % (699.6 °C)
TG 209 I r i s sample mass: 10.81 mgcrucible: Al2O3heat ing rate: 10 K/ min
NR/SBR Tyre Mixture - identification peaks
NR SBR
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BPRI Conference 22nd of October 2008 30
Outline
Introduction to TG 209 F1 iris ® - measuring principle
Use of hyphenated techniquesMore information during one single experiment
• Vacuum – separation additives and polymers
• Switching gases – triggered degradation
• Evolved gas analysis – degradation identification
• C-DTA ® - primary heat information
Summary
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BPRI Conference 22nd of October 2008 31
Outline
Introduction to TG 209 F1 iris ® - measuring principle
Use of hyphenated techniquesMore information during one single experiment
• Vacuum – separation additives and polymers• Switching gases – triggered degradation
• Evolved gas analysis – degradation identification
• C-DTA ® - primary heat information
Summary
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BPRI Conference 22nd of October 2008 32
Calculative Differential Temperature Analysis – c-DTA ®
principle
Sample thermocouple
Oven thermocouple
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BPRI Conference 22nd of October 2008 33
esa mplesamplecarr iergasoutletee
c-DTA® = T = T (Furnace - dotted) – T (Sample - full)
Mass loss / %
Time / min
c-DTA / K Temperature / °C
Calculative Differential Temperature Analysis – c-DTA ®
principle
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BPRI Conference 22nd of October 2008 34
c-DTA ® Curve of a Filled Thermoplastic Elastomer (TPO)
esa mplesamplecarr iergasoutletee
Additional information by c-DTA ® :Melting of the hard segments at 127°C (PE) and 161°C (PP)
TG / %
TG
DTG
exoc-DTA / K DTG / % / min
c-DTA
Temperatur / °C
Probe: TPE
Einwaage: 8,25 mg
Tiegel: Al
Heizrate: 10 K/minAtmosphäre: N2
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BPRI Conference 22nd of October 2008 35
Summary
• Thermogravimetry (TG):
Decomposition behavior => Thermal stability
• Vacuum method for quantitative determination oflow volatiles (plasticizer)
• AutoVac ® for on-line evacuating and refilling of the
TG with nitrogen, even with ASC
• TG-FTIR Coupling:
Identification of the platicizer and elastomericcomponents
C-DTA ® - calculated differential temperature analysis
determination reactions, melting of materials, post-crosslinking, post-vulcanisation, …
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BPRI Conference 22nd of October 2008 36
Selected Customers from the Automotive andRubber Field