BPRI Presentation Bart Rimez

Rubber Analysis by Advanced Thermogravimetry (TG):
Vacuum, evolved gas analysis, c-DTA
dr Bart Rimez, dr Stephan Knappe, Danny Pattyn, Jan De Munck Sales & Applications Benelux-Scientific Netzsch-Gertebau GmbH
BPRI Conference 22nd of October 2008
Distributor of scientific equipment: Thermal testing

Netzsch, Hot disk, Rubotherm
Mechanical analysis
Netzsch, Tinius Olsen, Bose
Surface characterization
Altimet, FEI
Sample preparation
RayRan, Fritsch
Office: Begoniastraat 17, Eke, Belgium Contact: +32 (0)9 252 54 00 Site www.benelux-scientific.com
Producer of thermal analysis instruments, 2nd globally Thermal transitions Mechanical analysis
DSC, TGA, STA, DMA, TMA, Dilatometry Laser flash, guarded hot plate, heat flow meter Rupture under load (RUL)
Thermal conductivity Refractory testing
Loacted in Selb, Bavaria, Germany Site: www.netzsch-thermal-analysis.com

Estimated Distribution of Thermoanalytical Methods in Polymer Analysis
DMA/TMA 20%
e l p u o f c r m t n h i e c a n r r t a e l c p u m o s g r e i l p m
DSC 60%
TG 20%
Estimated Distribution of Thermoanalytical Methods in Elastomer and Rubber Analysis
DSC 10%
DMA 20%
TG 70%
Outline
Introduction to TG 209 F1 iris - measuring principle Use of hyphenated techniques

More information during one single experiment Vacuum separation additives and polymers Switching gases triggered degradation Evolved gas analysis degradation identification C-DTA - Heat information
Summary
TG 209 F1 Iris
High resolution 0.1 g 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-microbalance from 10 to 1000C Integrated AutoVac for automatic evacuation and re-fill Simultaneous coupling to MS and FTIR, also when using the ASC c-DTA
Design of the TG 209 F1 Iris

gas outlet cover support
with Sample Thermocouple of Platinel

sample
sample carrier vacuum
cooling gas inlet purge cooling
pressure sensor relief valve gas inlet protective
hoist sample carrier balance
Outline Introduction to TG 209 F1 iris - measuring principle Use of hyphenated techniques

Summary

Summary
10
Unknown NR/SBR Rubber Mixture Determination of the Plasticizer Content

1. Standard TGA Measurement
Mass loss / % Plasticizer mass loss: -9.87 % NR mass loss: -38.81 % DTG % / min
Plasticizer is shoulder of big degradation peak

Sample: Sample mass: Crucible: Heating rate:
NR/SBR 20.64 mg Pt open 20 K/min
SBR mass loss: -14.79 %
Atmosphere: N2
Temperature / C
Normal pyrolysis in nitrogen atmosphere: A calculated plasticizer content of 9.9 %

11

2. Peak Separation (PKS) of the Standard TGA Measurement
dMass / dt / (%/min)
Plasticizer
e l p u o f c r m t n h i
e c a n r
r t a e l c p u m o s g
r e i l p m
SBR
DTG-curve calculated: solid line DTG-curve measured: dotted
NR
Sample: Sample mass: Crucible: Heating rate:
NR/SBR 20.64 mg Pt open 20 K/min
Atmosphere: N2
Temperature / C
Using Peak Separation software (PKS) in nitrogen atmosphere: A plasticizer content calculated to 11.8 %
12

3. Vacuum Method (approx. 0.1 mbar)
Mass loss / % Plasticizer mass loss: - 13.10 % DTG % / min
e c a n r
r e i l p m
NR mass loss: - 36.97 % Sample: Sample mass: Crucible: Heating rate: NR/SBR 20.64 mg Pt open 20 K/min
Atmosphere: VACUUM
SBR mass loss: - 10.33 %
Temperature / C
Boiling point depression in vacuum provides a plasticizer content of 13.1 %

13

4. Peak Separation (PKS) on the Vacuum Measurement Result
dMass / dt / (% / min)
Plasticizer
SBR
NR Sample: Sample mass: Crucible: Heating rate: NR/SBR 20.64 mg Pt open 20 K/min
DTG-curve calculated: solid line DTG-curve measured: dotted
Atmosphere: VACUUM
Temperature / C
Peak Separation software + vacuum provides a content of 14.9 % Client gave afterwards exact composition: 15 weight %
14

Summary
15

Summary
16
Autovac : creating vacuum, refilling with autosampling example: tyre mixture filled with carbon black (unknown weight)
TG /%
TG 209 F1 Iris sample mass: 10.05 mg crucible: Al2O3 heating rates: 10 K/min vacuum !
vacuum -20.04 % refill with nitrogen oxygen
Temp. /C DTG /(%/min) 2 1 0 900 800 700 600 500 400 300 200 100
100
80
-1 -2
60
152.1C
volatiles
342.0C
rubber compound 1
-42.86 % 647.7C
combustion of carbon black
-3 -4
-9.08 %
40
429.0C
-5 20 0 20
rubber compound 2 ash content
-6
Residual Mass: 28.03 % (102.5 min)
40
60 Time /min
80
100
17

Summary
18

Summary
19
Coupling of TG 209 F1 Iris ASC with FTIR Tensor 27 and QMS 403 C Aolos
e c a n r
r e i l p m
20
Coupling of TG to an FTIR Tensor cooperation with Bruker Optics

FTIR gas cell (230C) control thermocouple adaptor head (250 C) control thermocouple
transfer line (230C)

control thermocouple
micro furnace sample
gas outlet
sample carrier TG cell
IR detector
21
NR/SBR Tyre Mixture with Gas Flow Monitoring TG with DTG Signal
TG /% DTG /(%/min) Flow /(ml/min)
Elastomer
100 80 60 40 20
purge gas 1: nitrogen 20 ml/min 448.0 C protective: nitrogen 10 ml/min 0 purge gas 2: air 30 ml/min 383.0 C -6.98 % plasticizer 549.0 C
250
-38.37 % NR
200 -2 150
-30.35 % SBR -20.03 % carbon black 4.28 % (799.0 C) ash content
TG 209 F1 Iris sample mass: 14.85 mg crucible: Al2O3 heating rate: 10 K/min
-4 100 -6 50 -8
-20 100 200 300 400 500 600 Temperature /C 700 800 900
22
NR/SBR Tyre Mixture TG-FTIR with Gram Schmidt Plot

TG /% DTG /(%/min) Gram Schmidt /Import
rubber mixture
TG
0.16 1
450.2 C
100 90 80 70 60 50 40
DTG 390.2 C
0.14 0.12 0.10 0.08 0.06 0.04
0 -1 -2 -3 -4 -5 -6 -7 -8
TG 209 Iris sample mass: 10.81 mg crucible: Al2O3 heating rate: 10 K/min
447.1 C
0.02 0
30 20
total IR chromatogram 382.5 C Residual Mass: 23.66 % (699.6 C)
-0.02
100
200
300
400 500 Temperature /C
600
700
23
NR/SBR Tyre Mixture TG-FTIR with extracted IR Spectra

Extracted single spectrum at 390C Extracted single spectrum at 450C
0.10 0.12
891.40
0.00
0.02
Absorbance Units 0.04 0.06 0.08
4000
3500
3000 2500 Wavenumber cm-1
2000
1500
1000
24
NR/SBR Tyre Mixture (Zoom) TG-FTIR with Extracted IR Spectra Zoom

0.025
891.93
450C 390C
Absorbance Units 0.010 0.015 0.020
891.4 cm-1
0.000
0.005
1800
1600
1400 Wavenumber cm-1
1200
1000
800
25
Library Spectrum for Natural Rubber (NR) with Wave Number Peak at 892 cm-1 Decomposition of NR
Rolf Schnherr, TG-FTIR Atlas Elastomere, Verlag W.K. Schnherr, D-Burgdorf, 1996.
26
Library Spectrum for Styrene Butadiene Rubber (SBR) Decomposition of SBR
Rolf Schnherr, TG-FTIR Atlas Elastomere, Verlag W.K. Schnherr, D-Burgdorf, 1996.
27
NR/SBR Tyre Mixture - identification peaks

891.93
Zoom
450C: SBR
0.025 Absorbance Units 0.010 0.015 0.020
891.4 cm-1
390 C: Natural rubber
0.000
0.005
1800
1600
1400 Wavenumber cm-1
1200
1000
800
28
NR/SBR Tyre Mixture - identification peaks

DTG /(%/min) Gram Schmidt /Import
TG /%
rubber mixture
TG
NR SBR
450.2 C 390.2 C
0.16 1 0.14 0.12 0.10 0.08 0.06 0.04 0 -1 -2 -3 -4 -5 -6 -7 -8
100 90 80 70 60 50 40
DTG
TG 209 Iris sample mass: 10.81 mg crucible: Al2O3 heating rate: 10 K/min
447.1 C
0.02 0
30 20
total IR chromatogram 382.5 C Residual Mass: 23.66 % (699.6 C)
-0.02
100
200
300
400 500 Temperature /C
600
700
29

More 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
30

More 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
31
Calculative Differential Temperature Analysis c-DTA principle
Oven thermocouple Sample thermocouple
32
Calculative Differential Temperature Analysis c-DTA principle

Mass loss / % c-DTA / K Temperature / C
e c a n r
r e i l p m
Time / min
c-DTA = T = T (Furnace - dotted) T (Sample - full)

33
c-DTA Curve of a Filled Thermoplastic Elastomer (TPO)

TG / % TG DTG Probe: Einwaage: Tiegel: Heizrate: Atmosphre: c-DTA TPE 8,25 mg Al 10 K/min N2
c-DTA / K DTG / % / min exo
Temperatur / C
Additional information by c-DTA: Melting of the hard segments at 127C (PE) and 161C (PP)
34
Summary Thermogravimetry (TG):

Decomposition behavior => Thermal stability Vacuum method for quantitative determination of low 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 elastomeric components C-DTA - calculated differential temperature analysis determination reactions, melting of materials, postcrosslinking, post-vulcanisation,
35
Selected Customers from the Automotive and Rubber Field
36

BPRI Presentation Bart Rimez

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Rubber Analysis by Advanced Thermogravimetry (TG):

Vacuum, evolved gas analysis, c-DTA

Distributor of scientific equipment: Thermal testing

Thermal conductivity Refractory testing

Loacted in Selb, Bavaria, Germany Site: www.netzsch-thermal-analysis.com

Estimated Distribution of Thermoanalytical Methods in Polymer Analysis

BPRI Conference 22nd of October 2008

Estimated Distribution of Thermoanalytical Methods in Elastomer and Rubber Analysis

BPRI Conference 22nd of October 2008

Introduction to TG 209 F1 iris - measuring principle Use of hyphenated techniques

BPRI Conference 22nd of October 2008

BPRI Conference 22nd of October 2008

Design of the TG 209 F1 Iris

with Sample Thermocouple of Platinel

sample carrier vacuum

cooling gas inlet purge cooling

pressure sensor relief valve gas inlet protective

hoist sample carrier balance

BPRI Conference 22nd of October 2008

Outline Introduction to TG 209 F1 iris - measuring principle Use of hyphenated techniques

BPRI Conference 22nd of October 2008

Outline Introduction to TG 209 F1 iris - measuring principle Use of hyphenated techniques

BPRI Conference 22nd of October 2008

Unknown NR/SBR Rubber Mixture Determination of the Plasticizer Content

Plasticizer is shoulder of big degradation peak

Sample: Sample mass: Crucible: Heating rate:

NR/SBR 20.64 mg Pt open 20 K/min

SBR mass loss: -14.79 %

Normal pyrolysis in nitrogen atmosphere: A calculated plasticizer content of 9.9 %

Unknown NR/SBR Rubber Mixture Determination of the Plasticizer Content

DTG-curve calculated: solid line DTG-curve measured: dotted

Sample: Sample mass: Crucible: Heating rate:

NR/SBR 20.64 mg Pt open 20 K/min

Unknown NR/SBR Rubber Mixture Determination of the Plasticizer Content

SBR mass loss: - 10.33 %

Boiling point depression in vacuum provides a plasticizer content of 13.1 %

Unknown NR/SBR Rubber Mixture Determination of the Plasticizer Content

DTG-curve calculated: solid line DTG-curve measured: dotted

Outline Introduction to TG 209 F1 iris - measuring principle Use of hyphenated techniques

BPRI Conference 22nd of October 2008

Outline Introduction to TG 209 F1 iris - measuring principle Use of hyphenated techniques

BPRI Conference 22nd of October 2008

Residual Mass: 28.03 % (102.5 min)

BPRI Conference 22nd of October 2008

Outline Introduction to TG 209 F1 iris - measuring principle Use of hyphenated techniques

BPRI Conference 22nd of October 2008

Outline Introduction to TG 209 F1 iris - measuring principle Use of hyphenated techniques

BPRI Conference 22nd of October 2008

BPRI Conference 22nd of October 2008

Coupling of TG to an FTIR Tensor cooperation with Bruker Optics

transfer line (230C)

micro furnace sample

sample carrier TG cell

BPRI Conference 22nd of October 2008

NR/SBR Tyre Mixture TG-FTIR with Gram Schmidt Plot

0.14 0.12 0.10 0.08 0.06 0.04

400 500 Temperature /C

BPRI Conference 22nd of October 2008

NR/SBR Tyre Mixture TG-FTIR with extracted IR Spectra

Absorbance Units 0.04 0.06 0.08

3000 2500 Wavenumber cm-1

BPRI Conference 22nd of October 2008