20084 bpri presentation bart rimez

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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




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

http://www.benelux-scientific.com/





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



















http://www.netzsch-thermal-analysis.com/





Estimated Distribution of ThermoanalyticalMethods in Polymer Analysis

esa mplesamplecarr iergasoutletee

DSC

60%

DMA/TMA

20%

TG

20%



































Estimated Distribution of ThermoanalyticalMethods in Elastomer and Rubber Analysis


DSC

10%

DMA

20%

TG

70%



































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






























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®
































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 ®



























Outline







Summary






























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

Unknown NR/SBR Rubber MixtureDetermination of the Plasticizer Content


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


















































Using Peak Separation software (PKS) in nitrogen atmosphere:A plasticizer content calculated to 11.8 %


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















































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



Mass loss / % DTG % / min

Temperature / °C

Plasticizermass loss: - 13.10 %

NRmass loss: - 36.97 %

SBRmass loss: - 10.33 %


Atmosphere: VACUUM

3. Vacuum Method (approx. 0.1 mbar)















































Peak Separation software + vacuum provides a content of 14.9 %Client gave afterwards exact composition: 15 weight %


dMass / dt / (% / min)

Plasticizer

NR

SBR

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


Atmosphere: VACUUM

Temperature / °C

4. Peak Separation (PKS) on the Vacuum Measurement Result















































Outline







Summary






























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)






























































Outline







Summary






























Coupling of TG 209 F1 Iris ASC withFTIR Tensor 27 and QMS 403 C Aëolos



































Coupling of TG to an FTIR Tensor –cooperation with Bruker Optics


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

















































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
























































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



































































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







































































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













Library Spectrum for

Styrene Butadiene Rubber (SBR)

Rolf Schönherr, “TG-FTIR Atlas Elastomere” , Verlag W.K. Schönherr, D-Burgdorf, 1996.

Decomposition of SBR












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








































































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

























































Outline






• C-DTA ® - primary heat information

Summary































Outline



• Vacuum – separation additives and polymers• Switching gases – triggered degradation


• C-DTA ® - primary heat information

Summary






























Calculative Differential Temperature Analysis – c-DTA ®

principle

Sample thermocouple

Oven thermocouple












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










































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


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





















































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, …



























Selected Customers from the Automotive andRubber Field





20084 bpri presentation bart rimez

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