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Techniques for the Characterization of Fluoroelastomers

Technical Report · January 2009

DOI: 10.13140/2.1.1534.0329

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 Copy No. _____
Defence Research and Recherche et développement
Development Canada pour la défense Canada

&
DEFENCE DÉFENSE

Techniques for the Characterization of

Fluoroelastomers

John A. Hiltz
Sophia Smith

Defence R&D Canada – Atlantic

Technical Memorandum
DRDC Atlantic TM 2009-246
December 2009
This page intentionally left blank.
Techniques for the Characterization of
Fluoroelastomers

John A. Hiltz
Sophia Smith

Defence R&D Canada – Atlantic

Technical Memorandum
DRDC Atlantic TM 2009-246
December 2009
 Principal Author

Original signed by John A. Hiltz

John A. Hiltz

Approved by

Original signed by Leon Cheng

Leon Cheng
Head Dockyard Laboratory Atlantic

Approved for release by

Original signed by Ron Kuwahara for

Calvin V. Hyatt
Chair Document Review Panel DRDC Atlantic

© Her Majesty the Queen in Right of Canada, as represented by the Minister of National Defence, 2009
© Sa Majesté la Reine (en droit du Canada), telle que représentée par le ministre de la Défense nationale,
2009
Abstract ……..

Fluoroelastomers are synthetic elastomers containing fluorine. They have excellent chemical and
heat resistance and are specified for many applications where chemical and heat resistance is
required. They are among the best materials for use in the marine, automotive, aerospace, oil, and
chemical industries where they are used as seals, O-rings, gaskets, and fuel hoses. In this
memorandum four fluoroelastomers, A Type, B Type, GFLT Type and GLT Type, were
characterized using Fourier transform infrared (IR) spectroscopy, differential scanning
calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), and
pyrolysis gas chromatography/mass spectrometry/mass spectrometry (Py-GC/MS/MS). The
objective of this characterization was two-fold; firstly to amass physical and chemical
information on the elastomers and secondly to determine which technique or combination of
techniques could be used to positively identify the four fluoroelastomers.

IR spectroscopy indicated that there are peaks that could be used to differentiate between the four
types of fluoroelastomers. TGA weight loss versus temperature and temperature of maximum
rate of weight loss data was different for the four fluoroelastomers studied and in conjunction
with other experimental data could be used to identify the four elastomers. The glass transition
temperatures (Tg) of the four elastomers measured, using both DSC and DMA, were different.
For new unadulterated elastomer samples, the Tg could be used in conjunction with IR data to
differentiate between the four fluoroelastomers studied in this work. Py-GC/MS/MS could be
used to differentiate between the four fluoroelastomers. Each of the elastomers produced a
distinctive chromatogram (pyrogram). The mass spectra of the compounds giving rise to the
peaks in the pyrograms contained ions that could only be produced by elastomers containing, for
instance, perfluoro(methylvinylether) and therefore have the best potential to positively identify a
fluoroelastomer.

Résumé ….....

Les élastomères fluorés (ou fluoroélastomères) sont des élastomères synthétiques qui contiennent
du fluor. Ils possèdent une excellente résistance à la chaleur et aux produits chimiques et, par
conséquent, leur utilisation est recommandée lorsque ces propriétés sont requises. Ils font partie
des meilleurs matériaux ayant des applications dans les industries navale, automobile,
aérospatiale et pétrolière, ainsi que dans celle des produits chimiques, où ils servent à fabriquer
des joints d’étanchéité, des joints toriques, des joints statiques et des tuyaux de combustible.
Dans le cadre des travaux faisant l’objet du présent document, on a caractérisé quatre
fluoroélastomères, soit ceux des types A, B, GFLT et GLT, par spectroscopie infrarouge à
transformée de Fourier (IRTF), par analyse calorimétrique différentielle (ACD), par analyse
thermogravimétrique (ATG), par analyse mécanique dynamique (AMD) et par pyrolyse
et chromatographie en phase gazeuse/spectrométrie de masse/spectrométrie de
masse (Py-CG/SM/SM). L’objectif des travaux de caractérisation était bipartite, soit une première
étape visant à recueillir des renseignements sur les propriétés physiques et chimiques des
élastomères et une seconde ayant pour but de déterminer quelle technique, ou quelle combinaison
de techniques, permettrait d’identifier avec certitude les quatre fluoroélastomères.

DRDC Atlantic TM 2009-246 i

Les résultats des analyses par IRTF indiquent que certains pics pourraient servir à différencier les
quatre types de fluoroélastomères. En ce qui a trait aux résultats obtenus par ATG, les
diagrammes de la perte de masse en fonction de la température et les valeurs de la température à
laquelle la vitesse de perte de poids est maximale sont différents pour les quatre
fluoroélastomères étudiés et ces données pourraient être utilisées, de concert avec d’autres
données expérimentales, pour les identifier. Les valeurs de la température de transition
vitreuse (Tg) des quatre élastomères, mesurées par ACD et AMD, sont différentes. Dans le cas
d’éprouvettes d’élastomère non traité, la valeur de Tg pourrait être utilisée, de concert avec les
données des analyses par IRTF, pour différencier les quatre fluoroélastomères étudiés dans le
cadre de ces travaux. Les analyses par Py-CG/SM/SM pourraient aussi servir à les différentier,
car chaque élastomère est caractérisé par un chromatogramme (pyrogramme) qui lui est propre.
Les spectres de masse des composés qui produisent les pics des pyrogrammes indiquent la
présence d’ions qui ne peuvent être produits que par des élastomères comportant, par exemple,
une fonction méthylvinyléther perfluorée, et ils constitueraient donc le meilleur moyen pour
identifier avec certitude un fluoroélastomère donné.

ii DRDC Atlantic TM 2009-246

Executive summary

Techniques for the Characterization of Fluoroelastomers

John A. Hiltz, Sophia J. Smith; DRDC Atlantic TM 2009-246; Defence R&D Canada
– Atlantic; December 2009.

Introduction: Fluoroelastomers are synthetic elastomers containing fluorine. They have excellent
chemical and heat resistance and are specified for many applications where chemical and heat
resistance is required. They are among the best materials for use as seals, O-rings, gaskets, and
fuel hoses in the marine, automotive, aerospace, oil, and chemical industries. Because of the
superior sealing capabilities and heat and chemical resistance of fluoroelastomers, their use in
these industries also helps address environmental concerns arising from chemical leaks and spills
related to elastomer failure.

Fluoroelastomers are differentiated based on the weight percent of fluorine in their make-up and
the method used to cure them (bisphenol or peroxide cure). The performance of a fluoroelastomer
is directly related to its chemical make-up and cure. The higher the fluorine content, the better the
fluid resistance. Peroxide cured fluoroelastomers have superior water and acid resistance
compared to bisphenol cured fluoroelastomers. To ensure that the fluoroelastomer with the
required properties for a particular application is used, techniques to positively identify the
elastomer are required. Several analytical techniques for the identification of fluoroelastomers
are investigated and discussed in this report.

Results: Infrared (IR) spectroscopy indicated that there were peaks that could be used to
differentiate between the four types of fluoroelastomers. Thermogravimetric (TGA) weight loss
versus temperature and temperature of maximum rate of weight loss data was different for the
four fluoroelastomers studied and in conjunction with other experimental data could be used to
identify the four elastomers. The glass transition temperatures (Tg) of the four elastomers
measured, using both differential scanning calorimetry (DSC) and dynamic mechanical analysis
(DMA), were different. For new, unadulterated elastomer samples, the Tg could be used in
conjunction with IR data to differentiate between the four fluoroelastomers studied in this work.
Pyrolysis gas chromatography/mass spectrometry/mass spectrometry (Py-GC/MS/MS) could be
used to differentiate between the four fluoroelastomers. Each of the elastomers produced a
distinctive chromatogram (pyrogram). The mass spectra of the compounds giving rise to the
peaks in the pyrograms contained ions that could only be produced by elastomers containing, for
instance, perfluoro(methylvinylether) and therefore have the best potential to positively identify a
fluoroelastomer.

Significance: Techniques that allow the characterization and positive identification of

fluoroelastomers have been identified. These will ensure that the correct fluoroelastomer is used
for an application and reduce or eliminate failures arising from use of an elastomer with less than
optimum properties for a particular application. This will reduce equipment downtime and
maintenance costs and increase operational readiness of systems and components in which these
elastomers are used.

DRDC Atlantic TM 2009-246 iii

Future plans: The use of pyrolysis-gas chromatography/ mass spectrometry/ mass spectrometry
to identify fluoroelastomer formulations will be further developed.

iv DRDC Atlantic TM 2009-246

Sommaire .....

Techniques de caractérisation de fluoroélastomères

John A. Hiltz, Sophia J. Smith; RDDC Atlantique TM 2009-246; R & D pour la
défense Canada – Atlantique; décembre 2009.
Introduction : Les élastomères fluorés (ou fluoroélastomères) sont des élastomères synthétiques
qui contiennent du fluor. Ils possèdent une excellente résistance à la chaleur et aux produits
chimiques et, par conséquent, leur utilisation est recommandée lorsque ces propriétés sont
requises. Ils font partie des meilleurs matériaux pouvant être utilisés comme joints d’étanchéité,
joints toriques, joints statiques et tuyaux de combustible dans les industries navale, automobile,
aérospatiale et pétrolière, ainsi que dans celle des produits chimiques. La capacité d’étanchéité
supérieure et l’excellente résistance à la chaleur et aux produits chimiques des fluoroélastomères
utilisés dans l’industrie permettent aussi de résoudre des problèmes de nature environnementale
comme les fuites et les déversements de produits chimiques causés par la défaillance de
composants à base d’élastomères.

La différenciation des fluoroélastomères est basée sur leur teneur en fluor, exprimée en
pourcentage massique, et la méthode employée pour les durcir (durcissement au moyen de
bisphénol ou de peroxyde). L’efficacité d’un fluoroélastomère est directement liée à sa
composition chimique et à la méthode de durcissement employée. Plus sa teneur en fluor est
élevée, plus sa résistance aux fluides est bonne. Les fluoroélastomères durcis au moyen de
peroxyde présentent une meilleure résistance à l’eau et aux acides, par rapport à ceux durcis au
moyen de bisphénol. Afin de garantir qu’un fluoroélastomère choisi pour une application
particulière possède les propriétés requises, il faut utiliser des techniques permettant de
l’identifier avec certitude. Le présent rapport contient des détails sur l’étude de plusieurs
techniques d’analyse pouvant servir à identifier des fluoroélastomères, ainsi qu’une discussion
connexe.

Résultats: Les résultats des analyses par spectroscopie infrarouge à transformée de

Fourier (IRTF) indiquent que certains pics pourraient servir à différencier les quatre types de
fluoroélastomères. En ce qui a trait aux résultats obtenus par analyse thermogravimétrique
(ATG), les diagrammes de la perte de masse en fonction de la température et les valeurs de la
température à laquelle la vitesse de perte de poids est maximale sont différents pour les quatre
fluoroélastomères étudiés et ces données pourraient être utilisées, de concert avec d’autres
données expérimentales, pour les identifier. Les valeurs de la température de transition
vitreuse (Tg) des quatre élastomères, mesurées par analyse calorimétrique différentielle (ACD) et
par analyse mécanique dynamique (AMD), sont différentes. Dans le cas d’éprouvettes
d’élastomère non traité, la valeur de Tg pourrait être utilisée, de concert avec les données des
analyses par IRTF, pour différencier les quatre fluoroélastomères étudiés dans le cadre de ces
travaux. Les analyses par pyrolyse et chromatographie en phase gazeuse/spectrométrie de
masse/spectrométrie de masse (Py-CG/SM/SM) pourraient aussi servir à les différentier, car
chaque élastomère est caractérisé par un chromatogramme (pyrogramme) qui lui est propre. Les
spectres de masse des composés qui produisent les pics des pyrogrammes indiquent la présence
d’ions qui ne peuvent être produits que par des élastomères comportant, par exemple, une

DRDC Atlantic TM 2009-246 v

fonction méthylvinyléther perfluorée, et ils constitueraient donc le meilleur moyen pour identifier
avec certitude un fluoroélastomère donné.

Portée : On a déterminé quelles sont les techniques qui permettent de caractériser et d’identifier
avec certitude des fluoroélastomères. Leur utilisation assurera que le fluoroélastomère adéquat est
utilisé pour une application donnée et permettra de réduire, voire d’éliminer, les risques de
défaillance que présente l’utilisation d’un élastomère n’offrant pas des propriétés optimales à ces
fins. Ceci entraînera une réduction des temps d’arrêt causés par les pannes d’instruments et des
coûts d’entretien, ainsi qu’un accroissement de l’état de préparation opérationnelle des dispositifs
et des composants dans lesquels ces élastomères sont utilisés.

Recherches futures : L’utilisation de la technique d’analyse par pyrolyse et chromatographie en

phase gazeuse/spectrométrie de masse/spectrométrie de masse fera l’objet d’études plus poussées
et de travaux de mise au point additionnels.

vi DRDC Atlantic TM 2009-246

Table of contents

Abstract …….. ................................................................................................................................ i

Résumé …..... .................................................................................................................................. i
Executive summary ..................................................................................................................... iii
Sommaire ..... ................................................................................................................................. v
Table of contents .........................................................................................................................vii
List of figures ............................................................................................................................... ix
List of tables ................................................................................................................................. xi
1 Introduction ............................................................................................................................. 1
2 Experimental ............................................................................................................................ 2
2.1 Materials ....................................................................................................................... 2
2.2 Infrared spectroscopy.................................................................................................... 3
2.3 Thermogravimetric analysis ......................................................................................... 3
2.4 Pyrolysis gas chromatography/ mass spectroscopy/ mass spectroscopy ....................... 3
2.5 Differential Scanning Calorimetry ................................................................................ 4
2.6 Dynamic Mechanical Analysis ..................................................................................... 4
2.7 Scanning Electron Microscopy and Electron Dispersive X-ray Spectroscopy .............. 4
3 Results and Discussion ............................................................................................................ 5
3.1 Fourier Transform Infrared Spectroscopy ..................................................................... 5
3.2 Thermogravimetric Analysis ...................................................................................... 10
3.3 Differential Scanning Calorimetry .............................................................................. 13
3.4 Dynamic Mechanical Analysis ................................................................................... 15
3.5 Pyrolysis-Gas Chromatography/ Mass Spectrometry/ Mass Spectrometry ................. 19
3.6 Scanning Electron Microscopy and Energy Dispersive X-ray Spectroscopy .............. 28
4 Conclusions ........................................................................................................................... 29
References ..... .............................................................................................................................. 30
Distribution list ............................................................................................................................ 31

DRDC Atlantic TM 2009-246 vii

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viii DRDC Atlantic TM 2009-246

List of figures

Figure 1: Chemical structures of vinylidene fluoride (VF2), tetrafluoroethylene (TFE),

hexafluoropropylene (HFP), and perfluoro(methyl vinyl ether) (PMVE). .................... 2
Figure 2: FT-IR spectrum of Type A fluoroelastomer. ................................................................... 5
Figure 3: FT-IR spectrum of Type B fluoroelastomer. ................................................................... 6
Figure 4: FT-IR spectrum of Type GFLT fluoroelastomer. ............................................................ 6
Figure 5: FT-IR spectrum of Type GLT fluoroelastomer. .............................................................. 7
Figure 6: Overlay of the FT-IR spectra of Type A (blue), Type B (red), Type GFLT (green),
and Type GLT (black) fluoroelastomers....................................................................... 7
Figure 7: Overlay of FT-IR spectra of Type A (blue), Type B (red), Type GFLT (green), and
Type GLT (black) fluoroelastomers betweem 2900 cm-1 and 2800 cm-1. ..................... 8
Figure 8: Overlay of FT-IR spectra of Type A (blue), Type B (red), Type GFLT (green), and
Type GLT (black) fluoroelastomers between 1500 cm-1 and 1300 cm-1. ...................... 9
Figure 9: Overlay of FT-IR spectra of Type A (blue), Type B (red), Type GFLT (green), and
Type GLT (black) fluoroelastomers between 950 cm-1 and 700 cm-1. .......................... 9
Figure 10: Plots of % weight loss vs. temperature and the derivative of % weight change vs.
temperature for Type A fluoroelastomer. ................................................................... 11
Figure 11: Plots of % weight loss vs. temperature and the derivative of % weight change vs.
temperature of Type B fluoroelastomer. ..................................................................... 11
Figure 12: Plost of % weight loss vs. temperature and the derivative of % weight change vs.
temperature of Type GFLT fluoroelastomer. .............................................................. 12
Figure 13: Plots of % weight loss vs. temperature and the derivative of % weight change vs.
temperature of Type GFLT flurorelastomer. .............................................................. 12
Figure 14: Thermogram of Type A fluoroelastomer. .................................................................... 14
Figure 15: Thermogram of Type B fluoroelastomer. .................................................................... 14
Figure 16: Thermogram of Type GFLT fluoroelastomer. ............................................................. 15
Figure 17: Thermogram of Type GLT fluoroelastomer. ............................................................... 15
Figure 18: Plot of storage modulus and loss modulus vs. temperature for A Type
fluoroelastomer at 1 Hz. ............................................................................................. 17
Figure 19: Plot of storage modulus and loss modulus vs. temperature for B Type
fluoroelastomer at 1 Hz. ............................................................................................. 17
Figure 20: Plot of storage modulus and loss modulus vs. temperature for GFLT Type
fluoroelastomer at 1 Hz. ............................................................................................. 18
Figure 21: Plot of storage modulus and loss modulus vs. temperature for GLT Type
fluoroelastomer at 1 Hz. ............................................................................................. 18

DRDC Atlantic TM 2009-246 ix

Figure 22: Pyrograms of A Type fluoroelastomer pyrolyzed at 900oC (top), 800oC (middle),
and 700oC (bottom). ................................................................................................... 19
Figure 23: Pyrograms of A Type fluoroelastomer from 3.5-15 minutes pyrolyzed at 900oC
(top), 800oC, and 700oC (bottom). .............................................................................. 20
Figure 24: Pyrograms of B Type fluoroelastomer from 0-40 minutes pyrolyzed at 900oC
(top), 800oC, and 700oC (bottom). .............................................................................. 20
Figure 25: Pyrograms of B Type fluoroelastomer between 3.5 and 15 minutes pyrolyzed at
900oC (top), 800oC, and 700oC (bottom). ................................................................... 21
Figure 26: Pyrograms of GFLT Type fluoroelastomer from 0-40 minutes pyrolyzed at 900oC
(top), 800oC, and 700oC (bottom). .............................................................................. 21
Figure 27: Pyrograms of GFLT Type fluoroelastomer from 3.5-15 minutes pyrolyzed at
900oC (top), 800oC, and 700oC (bottom). ................................................................... 22
Figure 28: Pyrograms of GLT Type fluoroelastomer from 0-40 minutes pyrolyzed at 900oC
(top), 800oC, and 700oC (bottom). .............................................................................. 22
Figure 29: Pyrograms of GLT Type fluoroelastomer from 3.5-15 minutes pyrolyzed at 900oC
(top), 800oC, and 700oC (bottom). .............................................................................. 23
Figure 30: Pyrograms of A Type (blue), B Type (red), GFLT Type (green), and GLT Type
(black) fluoroelastomers between 3.5 and 15 min. All samples were pyrolyzed at
700oC. ......................................................................................................................... 23
Figure 31: Mass spectra of peaks (from top to bottom) at 8.73 min, 10.97 min, 11.66 min and
14.11 min in the pyrogram of A Type fluoroelastomer. ............................................. 24
Figure 32: Mass spectra of peaks (from top to bottom) at 6.76 min, 6.90 min, and 8.73 min in
the pyrogram of B Type fluoroelastomer. ................................................................... 25
Figure 33: Mass spectra of peaks (from top to bottom) at 6.91 min, 7.35 min, 7.96 min and
8.73 min in the pyrogram of GFLT Type fluoroelastomer. ........................................ 26
Figure 34: Mass spectra of peaks (from top to bottom) at 8.73 min, 9.09 min, 11.02 min and
14.27 min in the pyrogram of GLT Type fluoroelastomer. ......................................... 27

x DRDC Atlantic TM 2009-246

List of tables

Table 1: First weight loss, second weight loss, and temperatures of maximum rate of first and
second weight losses of the four fluoroelastomers...................................................... 10
Table 2: Average glass transition temperatures (Tg) from DSC data with standard deviation...... 13
Table 3: The glass transition temperatures of the four fluoroelastomers measured using DSC
and DMA.................................................................................................................... 16
Table 4: The elemental composition of the inorganic residues from the four fluoroelastomers
following heating in air to 800oC. They were determined by SEM-EDX. ................. 28

DRDC Atlantic TM 2009-246 xi

 This page intentionally left blank.

xii DRDC Atlantic TM 2009-246

1 Introduction

Fluoroelastomers are synthetic elastomers containing fluorine. They have excellent chemical and
heat resistance and are specified for many applications where chemical and heat resistance is
required. They are among the best materials for use in the marine, automotive, aerospace, oil, and
chemical industries where they are used as seals, O-rings, gaskets, and fuel hoses [1]. Because of
the superior sealing capabilities and heat and chemical resistance of fluoroelastomers, their use in
these industries also helps address environmental concerns arising from chemical leaks and spills
related to elastomer failure [2].

Fluoroelastomers are differentiated based on the weight percent of fluorine in their make-up and
the method used to cure them (bisphenol or peroxide cure). The performance of a fluoroelastomer
is directly related to its chemical make-up and cure. The higher the fluorine content the better the
fluid resistance2. Peroxide cured fluoroelastomers have superior water and acid resistance
compared to bisphenol cured fluoroelastomers [2].

There are several monomers used to prepare fluoroelastomers: vinylidene fluoride (VF2),
tetrafluoroethylene (TFE), hexafluoropropylene (HFP), and perfluoromethylvinylether (PMVE).
Because of the relationship between the structure and performance of these elastomers, it is
important to ensure that a fluoroelastomer with the required properties is used in a particular
application. Therefore analytical techniques that can positively identify the various
fluoroelastomer types are very important.

The objective of this work is to assess the ability of analytical techniques to distinguish between
different types of fluoroelastomers, specifically FR10/80 A TYPE, FR17/75 B TYPE, FR25/80
GLT TYPE, and LR6316/75 GFLT TYPE. Several techniques were investigated to determine
their usefulness in the characterization and identification of fluoroelastomers. These techniques
were Fourier transform infrared (FT-IR) spectroscopy, thermogravimetric analysis (TGA),
differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), pyrolysis-gas
chromatography/ mass spectrometry/ mass spectrometry (Py-GC/MS/MS) and scanning electron
microscopy coupled with energy dispersive x-ray analysis (SEM-EDX). In this Technical
Memorandum, the results of the study are reported and the applicability of the analytical
techniques to the positive identification of the four types of fluoroelastomers is discussed.

DRDC Atlantic TM 2009-246 1

2 Experimental

2.1 Materials
The four fluoroelastomers, FR10/80 A TYPE, FR17/75 B TYPE, FR25/80 GLT TYPE, and
LR6316/75 GFLT TYPE, used in this study were purchased from James Walker MFG. Co.

The A Type fluoroelastomer was a copolymer of hexafluoropropylene (HFP) and vinylidene

fluoride (VF2). It is a general purpose fluoroelastomer with a low compression set and can be
used in a temperature range between −18°C and 200°C [1].

The B Type fluoroelastomer was a terpolymer of HFP, VF2, and tetrafluoroethylene (TFE). It is a
general purpose fluoroelastomer with improved fuel resistance compared to A Type
fluoroelastomers and can be used in a temperature range between −12°C and 210°C [1].

The GLT Type fluoroelastomer was a tetrapolymer composed of HFP, VF2, TFE, and
perfluoromethylvinylether (PMVE). It is a low temperature (LT) grade fluoroelastomer with
superior rapid gas decompression properties. It can be used in a temperature range between
−41°C and 200°C [1].

The GFLT Type fluoroelastomer was a tetrapolymer composed of HFP, VF2, TFE, and PMVE
and was formulated to have improved low temperature properties compared to A Type and B
Type fluoroelastomers and superior chemical resistance compared to GLT. It is a low temperature
(LT) grade fluoroelastomer with high fluorine content and can be used in a temperature range
between −29°C and 205°C [1].

H F F F

C C C C

H F F F

(VF2) (TFE)

F
F F

F F O C F
C C
F C C C F
F
F F F

(HFP) (PMVE)

Figure 1: Chemical structures of vinylidene fluoride (VF2), tetrafluoroethylene (TFE),

hexafluoropropylene (HFP), and perfluoro(methyl vinyl ether) (PMVE).

2 DRDC Atlantic TM 2009-246

The low temperature capabilities of GFLT and GLT Type fluoroelastomers are due to the
presence of VF2 and PMVE. These lower the glass transition temperature of the elastomer and
promote low temperature flexibility [2]. The chemical structures of the monomers are shown in
Figure 1.

2.2 Infrared spectroscopy

All infrared spectra were acquired on a Vertex 70 Fourier Transform infrared spectrometer
(Bruker) using a single bounce attenuated total reflectance (ATR) accessory (Spectra-Tech
Thunderdome, Thermo Scientific). The ATR was fitted with a germanium crystal. A background
was obtained prior to acquiring the spectra of each fluoroelastomer. The spectra, acquired
between 4000 cm-1 to 600 cm-1, were the average of 100 scans at a resolution of 4 cm-1. All
spectra were baseline corrected and normalized.

2.3 Thermogravimetric analysis

Thermogravimetric analysis was carried out on a Q500 thermogravimetric analyser (TA
Instruments, New Castle, Delaware). All analyses were carried out in aluminum pans. Nitrogen
was used as the balance and sample gas at flow rates of 40.0 mL/min and 60 mL/min
respectively. The sample sizes ranged from ~5 mg to ~40 mg.

All analyses were carried out in the high resolution mode. The temperature was equilibrated at
35°C, and then ramped at 50°C/min until the rate of weight loss exceeded an operator selected
rate. The temperature of the sample was then kept isothermal until the rate of weight dropped
below an operator selected rate. The temperature ramp of 50°C/min was then resumed until the
temperature reached 650°C. At 650 °C, the gas was changed from N2 to air and the temperature
ramp of 50°C/min resumed until the rate of weight loss exceeded the operator determined rate.
The temperature of the sample was then kept isothermal until the rate of weight dropped below an
operator selected rate. The temperature ramp was then resumed. The experiment was terminated
at 800 °C. Three samples of each elastomer were analyzed. The reported percentage weight
losses and temperatures of maximum rate of weight loss were the average values of three
analyses.

2.4 Pyrolysis gas chromatography/ mass spectroscopy/ mass

spectroscopy
All pyrolysis were carried out in a platinum coil pyroprobe (Pyroprobe 2000, Chemical Data
Systems, Oxford, PA). Approximately 0.1 mg of the sample was centered in a 25 mm quartz tube
and heated to a final temperature of 900°C, 800°C, or 700°C using a heating ramp of 20°C/ms.
The hold time at the final temperature was 20 seconds. The pyrolysis products were separated on
a 30 m long X 0.25 mm inside diameter 5% phenyl polydimethylsiloxane capillary column. The
inlet was set to a split flow of 50 mL/min., with a split ratio of 50:1. The flow rate of the carrier
gas (He) was 1 mL/min at constant flow. The heating program used for the gas chromatograph
(Trace GC Ultra, Thermo Scientific) consisted of holding the oven temperature at 40°C for 4
minutes, then ramping the temperature to 300°C at a rate of 10°C/min, and finally holding the
temperature at 300°C for 10 minutes. Each GC run took 40 minutes to complete.

DRDC Atlantic TM 2009-246 3

A Triple Stage Quadrupole (TSQ) (Thermo Scientific) MS/MS was used to detect the ions of the
pyrolysis products. The MS/MS was used in the full scan mode, scanning from 50 atomic mass
units (amu) to 500 amu using a scan time of 0.5 seconds.

2.5 Differential Scanning Calorimetry

Differential scanning calorimetry (DSC) was carried out on a Q1000 differential scanning
calorimeter (TA Instruments, New Castle, Delaware). The apparatus was calibrated using an
Indium standard. The samples were equilibrated at -60°C and then the temperature was ramped at
a rate of 10°C/min to 60°C. The difference in heat flow (W/g) into the sample and the reference
pans were recorded as a function of temperature. Three samples of each elastomer were analysed.
The Tg was calculated from the tangents to the heat flow versus temperature curve before the
transition, after the transition and at the point in the transition with the maximum slope. The
reported glass transition temperature (Tg) was the average value of the Tg for the three analyses.

2.6 Dynamic Mechanical Analysis

Dynamic mechanical analysis was carried out on a Q800 dynamic mechanical analyzer (TA
Instruments, New Castle, Delaware) with a dual cantilever clamp. The samples were equilibrated
at -60°C and the complex modulus was measured over a range of frequencies from 0.1 Hz to 100
Hz. The temperature was increased 5°C, equilibrated and the complex modulus was measured
over a range of frequencies from 0.1 Hz to 100 Hz again. The heating, equilibration and
measurement of the complex modulus steps were repeated until the final temperature of 25°C was
reached. The samples were ~35 mm in length, ~12 – 13 mm in width, and ~1-2 mm in thickness.
Three samples of each elastomer were analysed. The reported glass transition temperature (Tg)
was the average value of the Tg for the three analyses.

2.7 Scanning Electron Microscopy and Electron Dispersive X-

ray Spectroscopy
A scanning electron microscope (SEM) (Leo 1455VP) was used to analyze the fluoroelastomer
residues obtained from the thermogravimetric analysis. The residues were affixed to an aluminum
stub and were examined uncoated. The SEM was operated using an accelerating voltage of 20kV,
a working distance of 15 mm, and a take-off angle of 29 degrees. Energy dispersive x-ray (EDX)
analysis spectroscopy was performed using a Princeton Gamma Tech IMIX system with the
ZAF program and a live time of 100 seconds.

4 DRDC Atlantic TM 2009-246

3 Results and Discussion

Four fluoroelastomers were analysed, A Type, B Type, GFLT Type, and GLT Type. The results
of FT-IR, TGA, DSC, DMA, and Py-GC/MS/MS analysis of the fluoroelastomers and energy
dispersive x-ray (EDX) analysis of the ash following TGA analysis are presented and discussed.

3.1 Fourier Transform Infrared Spectroscopy

The infrared spectra of A Type, B Type, GFLT Type, and GLT Type fluoroelastomers are shown
in Figure 2 through Figure 5. An overlay of these four spectra is shown in Figure 6. In general
the IR spectra of the four fluoroelastomers are quite similar. However, there are differences in
several regions of the IR spectra. Three areas will be discussed, from 2900 cm-1 to 2800 cm-1,
from 1500 cm-1 to 1300 cm-1, and from 1000 cm-1 to 700 cm-1.
100
80
Transmittance [%]
40 20 60

3500 3000 2500 2000 1500 1000

Wavenumber cm-1

Figure 2: FT-IR spectrum of Type A fluoroelastomer.

An expanded view of the IR spectra between 2900 cm-1 and 2800 cm-1 is shown in Figure 7. IR
absorbance peaks between 2950 cm-1 and 2800 cm-1 are characteristic of symmetric and
asymmetric C-H stretching. As vinylidene fluoride is the only monomer used in these
fluoroelastomers containing C-H bonds, the strength of the absorbance for a particular
fluoroelastomer should correlate with the vinylidene fluoride content of that elastomer. Typical
values [2] for the percentage of vinylidene fluoride in the four types of elastomers are 60%
vinylidene fluoride for A Type fluoroelastomer, 54% vinylidene fluoride for the GLT Type
fluoroelastomer, 45% vinylidene fluoride for the B Type fluoroelastomer, and 36% vinylidene
fluoride GFLT Type fluoroelastomer. Referring to Figure 7, the A Type fluoroelastomer has the
most intense absorbance and GFLT Type has the least intense absorbance. This corresponds well
with the percentage of vinylidene fluoride in the elastomers.

DRDC Atlantic TM 2009-246 5

 100
80
Transmittance [%]
40 20 60

3500 3000 2500 2000 1500 1000

Wavenumber cm-1

Figure 3: FT-IR spectrum of Type B fluoroelastomer.

100
80
Transmittance [%]
40 20 60

3500 3000 2500 2000 1500 1000

Wavenumber cm-1

Figure 4: FT-IR spectrum of Type GFLT fluoroelastomer.

6 DRDC Atlantic TM 2009-246

 100
80
Transmittance [%]
40 20 60

3500 3000 2500 2000 1500 1000

Wavenumber cm-1

Figure 5: FT-IR spectrum of Type GLT fluoroelastomer.

100
80
Transmittance [%]
40 20 60

3500 3000 2500 2000 1500 1000

Wavenumber cm-1

Figure 6: Overlay of the FT-IR spectra of Type A (blue), Type B (red), Type GFLT (green), and
Type GLT (black) fluoroelastomers.

DRDC Atlantic TM 2009-246 7

 95
Transmittance [%]
90
85
80

2900 2880 2860 2840 2820 2800

Wavenumber cm-1

Figure 7: Overlay of FT-IR spectra of Type A (blue), Type B (red), Type GFLT (green), and Type
GLT (black) fluoroelastomers betweem 2900 cm-1 and 2800 cm-1.

An expanded view of the IR spectra between 1500 cm-1 and 1300 cm-1 is shown in Figure 8.
There is a shoulder on the absorbance peak at 1350 cm-1 in the spectra of the A Type and B Type
fluoroelastomers that is not present in the spectra of the GFLT Type and GLT Type
fluoroelastomers. An expanded view of the spectra between 950 cm-1 and 700 cm-1 is shown in
Figure 9. Comparison of the spectra of the A Type and B Type fluoroelastomers indicates that
the B Type fluoroelastomer has a weak absorbance peak at ~930 cm-1 that is not present in the A
Type fluoroelastomer. In addition, the position of the absorbance peak between 850 cm-1 and 800
cm-1 is different for the A Type and B Type fluoroelastomers. The absorbance peak for the A
Type fluoroelastomer is at ~830 cm-1 and the B Type fluoroelastomer is at ~820 cm-1. The
presence of a shoulder on the absorbance peak at 1350 cm-1 peak and absorbance peaks at ~930
cm-1 and 820 cm-1 are characteristic of a B Type fluoroelastomer, whereas a peak at ~1350 cm-1,
no peak at ~930 cm-1 and an absorbance peak at ~830 cm-1 are characteristic of an A Type
fluoroelastomer.

Although the GFLT Type and GLT Type fluoroelastomers have no absorbance peak at ~ 1350
cm-1, there are subtle differences in their IR spectra between 950 cm-1 and 700 cm-1. For instance,
the GLT fluoroelastomer has a weak absorbance peak at ~830 cm-1 that is not present in the
spectrum of the GFLT Type fluoroelastomer whereas the GFLT Type fluoroelastomer has
absorbance peaks at ~820 cm-1 and ~ 790 cm-1 that are not present in the GLT Type
fluoroelastomer spectrum.

There is some variation in the position of the major absorption peak (between 950 cm-1 and 700
cm-1) in the IR spectra of the four fluoroelastomers. The major peak is at ~888 cm-1 for the B

8 DRDC Atlantic TM 2009-246

Type and GFLT Type fluoroelastomers and at ~880 cm-1 for the A Type and GLT Type
fluoroelastomers.

100
90
80
Transmittance [%]
60 50
40
30 70

1500 1450 1400 1350 1300

Wavenumber cm-1

Figure 8: Overlay of FT-IR spectra of Type A (blue), Type B (red), Type GFLT (green), and Type
GLT (black) fluoroelastomers between 1500 cm-1 and 1300 cm-1.
100
80
Transmittance [%]
40 20
0 60

950 900 850 800 750 700

Wavenumber cm-1

Figure 9: Overlay of FT-IR spectra of Type A (blue), Type B (red), Type GFLT (green), and Type
GLT (black) fluoroelastomers between 950 cm-1 and 700 cm-1.

DRDC Atlantic TM 2009-246 9

3.2 Thermogravimetric Analysis
The TGA plots of percent weight loss versus temperature and the derivative of percent weight
loss versus temperature for the four fluoroelastomers are shown in Figure 10 to Figure 13. For
each of the elastomers the weight loss takes place in two steps. The first is at ~500 oC and the
second is at ~670 °C. The percent weight loss and the temperatures of the maximum rate of
weight loss for the four fluoroelastomers and the weight of residue are listed in Table 1.
Table 1: First weight loss, second weight loss, and temperatures of maximum rate of first and
second weight losses of the four fluoroelastomers.

Tmax1 (oC) of Second Tmax2 (oC) of

Sample First weight
first weight weight loss second weight Residue (%)
Name loss (%)
loss (%) losss

A Type
61.52 ± 0.40 487.91 ± 3.01 29.79 ± 0.49 661.75 ± 4.54 8.32 ± 0.17

B Type
70.02 ± 0.68 501.06 ± 0.99 18.85 ± 0.57 661.43 ± 4.45 10.48 ± 0.12

GFLT
62.09 ± 0.18 504.67 ± 0.57 36.77 ± 0.57 672.94 ± 5.78 0.81 ± 0.23
Type
GLT
59.97 ± 0.08 497.11 ± 0.01 39.39 ± 0.10 677.53 ± 3.42 0.38 ± 0.15
Type

The percent weight loss in the first step was similar for A Type (61.52 ± 0.40%), GFLT Type
(62.09 ± 0.18%), and GLT Type (59.97 ± 0.08%) fluoroelastomers. However, the B Type
fluoroelastomer lost ~70% (70.02 ± 0.68) of its weight in the first step. The temperature of
maximum rate of weight loss, Tmax1, for the first weight loss step was similar for the B Type
(501.06 ± 0.99°C), GFLT Type (504.67 ± 0.57°C), and GLT Type (497.11 ± 0.01°C)
fluoroelastomers while the A Type fluoroelastomer had a Tmax1 (487.91 ± 3.01oC) that was
approximately 10°C lower than the others.

The percent weight loss for the second weight loss step was different for each of the
fluoroelastomers. The A Type fluoroelastomer lost ~30% (29.79 ± 0.49%), the B Type
fluoroelastomer lost ~19% (18.85 ± 0.57%), the GFLT Type fluoroelastomer lost ~ 37% (36.77 ±
0.57%), and the GLT Type fluoroelastomer lost ~40% (39.39 ± 0.10). The temperature of
maximum rate of weight loss for the second weight loss step, Tmax2, was similar for the A Type
(661.75 ± 4.54°C) and B Type (661.43 ± 4.45°C) fluoroelastomers. The Tmax2 for the GFLT Type
(672.94 ± 5.78°C) and GLT Type (677.53 ± 3.42°C) fluoroelastomers were higher than the Tmax2
for the A Type and B Type fluoroelastomers.

10 DRDC Atlantic TM 2009-246

 120 8
487.25°C

100
6

Deriv. Weight Change (%/°C)

80
61.36%
(7.327mg) 4
Weight (%)

60

665.71°C
2

40

30.16%
0
20 (3.601mg)
Residue:
8.117%
(0.9693mg)

0 -2
0 200 400 600 800
Temperature (°C) Universal V4.5A TA Instruments

Figure 10: Plots of % weight loss vs. temperature and the derivative of % weight change vs.
temperature for Type A fluoroelastomer.

120 10
502.04°C

100 8

Deriv. Weight Change (%/°C)

80 6

70.70%
Weight (%)

(6.443mg)
60 4

40 656.83°C 2

18.29%
20 (1.667mg) 0
Residue:
10.34%
(0.9422mg)
0 -2
0 200 400 600 800
Temperature (°C) Universal V4.5A TA Instruments

Figure 11: Plots of % weight loss vs. temperature and the derivative of % weight change vs.
temperature of Type B fluoroelastomer.

DRDC Atlantic TM 2009-246 11

 120 10
505.00°C

100 8

Deriv. Weight Change (%/°C)

80 6
61.93%
(8.667mg)
Weight (%)

60 4

679.51°C

40 2

37.03%
20 (5.182mg)0

Residue:
0.8557%
(0.1197mg)
0 -2
0 200 400 600 800
Temperature (°C) Universal V4.5A TA Instruments

Figure 12: Plost of % weight loss vs. temperature and the derivative of % weight change vs.
temperature of Type GFLT fluoroelastomer.

The A Type fluoroelastomer (8.32 ± 0.17 %) and the B Type fluoroelastomer (10.48 ± 0.12 %)
had significantly larger amounts of residue compared to the GFLT Type (0.81 ± 0.23 %) and the
GLT Type (0.38 ± 0.15 %) fluoroelastomers. The larger percentage residue in the A Type and B
Type fluoroelastomers are most likely due to the presence of additives, such as fillers, in these
elastomers.
p Q
120 8
496.87°C

100
6

Deriv. Weight Change (%/°C)

80
59.98%
(9.794mg) 4
Weight (%)

60

2
681.66°C
40

39.44%
(6.439mg)
0
20

Residue:
0.3076%
(0.05023mg)
0 -2
0 200 400 600 800
Temperature (°C) Universal V4.3A TA Instruments

Figure 13: Plots of % weight loss vs. temperature and the derivative of % weight change vs.
temperature of Type GFLT flurorelastomer.

12 DRDC Atlantic TM 2009-246

The temperature at which a polymer degrades is directly related to its composition, that is, the
monomeric material or materials used to synthesize it, and its resulting structure. Therefore
polymers with different compositions and structures will degrade at different temperatures. In
general, TGA results provide good supporting information for the identification of polymeric
materials. However, the technique by itself cannot be used to positively identify a polymeric
material.

3.3 Differential Scanning Calorimetry

The DSC thermograms of the A Type, B Type, GFLT Type, and GLT Type fluoroelastomers are
shown in Figures 14 to 17. The thermograms are plots of heat flow versus temperature. At the
glass transition temperature (Tg), the heat capacity of a material changes rapidly causing a change
in the heat flow into the sample and therefore the slope of the heat flow versus temperature plot
also changes. The Tg is calculated from the tangents to the heat flow versus temperature curve
before the transition, after the transition and at the point in the transition with the maximum slope.

The Tg values for the four fluoroelastomers are listed in Table 2. The B Type fluoroelastomer has
the highest Tg (−12.74 ± 0.23°C), followed by A Type (−16.79 ± 0.91°C), GFLT Type (−25.03 ±
0.17°C), and GLT Type (−31.29 ± 0.70°C). The Tg correspond well with published values for
these four types of fluoroelastomers [2].
Table 2: Average glass transition temperatures (Tg) from DSC data with standard deviation.

Sample Name Average Tg (oC)

A Type -16.79 ± 0.91
B Type -12.74 ± 0.23
GFLT Type -25.03 ± 0.17
GLT Type -31.29 ± 0.70

The results of DSC analysis, like those from TGA, provide good supporting evidence for the
identification of polymeric materials. However, the Tg of a polymer is related to its structure and
the presence of additives, and these can be affected by a number of factors while in service.
These factors include the absorption of fluids and aging (thermal, oxidative, and ultra violet
degradation). The absorption of fluids by the polymer most often leads to a reduction in the Tg of
the sample. This is referred to as plasticization. If a material has been in service and in contact
with a fluid or fluids that act to plasticize the sample the measured Tg will be lower than a sample
of the same material that has not been exposed to the fluid. Thermal, oxidative or ultraviolet
degradation can lead to a number of changes in the structure of a polymer. In some polymers
degradation leads to an increase in cross linking in the polymer while it others in make result in a
decrease in cross linking. Additives, such as plasticizers, can also be lost from a polymer over
time. These changes will result in changes to the Tg of the material.

DRDC Atlantic TM 2009-246 13

 -0.10

-0.12

Heat Flow (W/g)

-0.14
-21.21°C

-17.81°C(I)
-0.16

-15.07°C

-0.18

-0.20
-60 -40 -20 0 20 40 60
Exo Up Temperature (°C) Universal V4.5A TA Instruments

Figure 14: Thermogram of Type A fluoroelastomer.

-0.10

-0.12

-0.14
-15.94°C
Heat Flow (W/g)

-0.16 -13.00°C(I)

-9.69°C

-0.18

-0.20

-0.22
-60 -40 -20 0 20 40 60
Exo Up Temperature (°C) Universal V4.5A TA Instruments

Figure 15: Thermogram of Type B fluoroelastomer.

14 DRDC Atlantic TM 2009-246

 -0.06

-0.08

-0.10
-27.94°C
Heat Flow (W/g)

-25.02°C(I)
-0.12

-22.17°C

-0.14

-0.16

-0.18
-60 -40 -20 0 20 40 60
Exo Up Temperature (°C) Universal V4.5A TA Instruments

Figure 16: Thermogram of Type GFLT fluoroelastomer.

Comment: Tg / Melt analysis Instrument: DSC Q1000 V9.9 Build 303
-0.10

-0.12

-0.14

-33.98°C
Heat Flow (W/g)

-0.16 -31.47°C(I)

-28.86°C
-0.18

-0.20

-0.22

-0.24
-60 -40 -20 0 20 40 60
Exo Up Temperature (°C) Universal V4.3A TA Instruments

Figure 17: Thermogram of Type GLT fluoroelastomer.

3.4 Dynamic Mechanical Analysis

DMA plots of the storage and loss modulus versus temperature (at 1 Hz) for the four
fluoroelastomers are shown in Figures 18 to 21. The storage modulus is the measure of
recoverable strain of a deformed material and the loss modulus is the measure of energy lost as

DRDC Atlantic TM 2009-246 15

heat due to the deformation of the material [4]. The storage modulus of a polymeric material
changes by orders of magnitude at the glass transition while the loss modulus increases to a
maximum value at the glass transition temperature. Tan delta, the ratio of the loss modulus to the
storage modulus, also increases to a peak value in the vicinity of the glass transition temperature.
The peak of the loss modulus versus temperature plot and the peak of tan delta versus temperature
plot have been used to determine the glass transition temperature. In this report, the peak in the
loss modulus was used.

The B Type fluoroelastomer had the highest Tg (−10°C) followed by A Type (−15°C), GFLT
Type (−25°C), and GLT Type (−30°C) fluoroelastomers. The glass transition temperature of the
elastomers measured using DSC and DMA are shown in Table 3. Comparison indicates that the
measured values of the Tg for a particular elastomer are not the same using DSC and DMA.
However, the order of the Tg, from highest to lowest, is the same.
Table 3: The glass transition temperatures of the four fluoroelastomers measured using DSC and
DMA.

Sample Name DSC Tg (oC) DMA Tg (oC)

A Type -17 -15
B Type -13 -10
GFLT Type -25 -25
GLT Type -31 -30

The results of DMA, like those from TGA and DSC analysis, provide good supporting evidence
for the identification of polymeric materials. However, as was noted for DSC, the Tg of a
polymeric is related to its structure and is affected by a number of factors. These factors will
affect the measured Tg.

16 DRDC Atlantic TM 2009-246

 8000 1000
-15.00°C

800
6000

[ – – – – ] Loss Modulus (MPa)

Storage Modulus (MPa)

600

4000

400

2000
200

0 0
-60 -40 -20 0 20
Temperature (°C) Universal V4.3A TA Instruments

Figure 18: Plot of storage modulus and loss modulus vs. temperature for A Type fluoroelastomer
at 1 Hz.
10000 1000
-9.99°C

8000 800

[ – – – – ] Loss Modulus (MPa)

Storage Modulus (MPa)

6000 600

4000 400

2000 200

0 0
-60 -40 -20 0 20
Temperature (°C) Universal V4.3A TA Instruments

Figure 19: Plot of storage modulus and loss modulus vs. temperature for B Type fluoroelastomer
at 1 Hz.

DRDC Atlantic TM 2009-246 17

 8000 1200
-24.97°C

1000

6000

[ – – – – ] Loss Modulus (MPa)

800
Storage Modulus (MPa)

4000 600

400

2000

200

0 0
-60 -40 -20 0 20
Temperature (°C) Universal V4.3A TA Instruments

Figure 20: Plot of storage modulus and loss modulus vs. temperature for GFLT Type
fluoroelastomer at 1 Hz.

8000 1400

-29.97°C

1200

6000
1000

[ – – – – ] Loss Modulus (MPa)

Storage Modulus (MPa)

800

4000

600

400
2000

200

0 0
-60 -40 -20 0 20
Temperature (°C) Universal V4.3A TA Instruments

Figure 21: Plot of storage modulus and loss modulus vs. temperature for GLT Type
fluoroelastomer at 1 Hz.

18 DRDC Atlantic TM 2009-246

3.5 Pyrolysis-Gas Chromatography/ Mass Spectrometry/ Mass
Spectrometry
In a Py-GC/MS/MS experiment, a polymeric material is thermally degraded in the pyroprobe, the
resulting thermal degradation products are separated on a chromatographic column, and the
degradation products are detected and identified using mass spectrometry. The thermal
degradation products of a material are dependent on the composition and structure of that
material. If two materials have different compositions their degradation products will reflect that
difference.

The pyrograms of A Type fluoroelastomer following pyrolysis at 900°C, 800°C, and 700°C are
shown in Figures 22 and 23. Figure 22 shows the chromatograms from 0.0 to 40.0 min while
Figure 23 shows the chromatograms between 3 and 15 min. The pyrograms for the B Type,
GFLT Type, and GLT Type fluoroelastomers following pyrolysis at 900°C, 800°C, and 700°C
are shown in Figures 24 and 25, Figures 26 and 27 and Figures 28 and 29 respectively. Pyrolysis
was carried out at three temperatures to determine if a change in the pyrolysis temperature would
affect either the number or intensity of the degradation products. Comparison of the pyrograms
for a particular elastomer indicated that the thermal degradation products were little affected by
the pyrolysis temperature. On the basis of this, it was decided to use a pyrolysis temperature of
700°C.

Figure 22: Pyrograms of A Type fluoroelastomer pyrolyzed at 900oC (top), 800oC (middle), and
700oC (bottom).

DRDC Atlantic TM 2009-246 19

Figure 23: Pyrograms of A Type fluoroelastomer from 3.5-15 minutes pyrolyzed at 900oC (top),
800oC, and 700oC (bottom).

Figure 24: Pyrograms of B Type fluoroelastomer from 0-40 minutes pyrolyzed at 900oC (top),
800oC, and 700oC (bottom).

20 DRDC Atlantic TM 2009-246

Figure 25: Pyrograms of B Type fluoroelastomer between 3.5 and 15 minutes pyrolyzed at 900oC
(top), 800oC, and 700oC (bottom).

Figure 26: Pyrograms of GFLT Type fluoroelastomer from 0-40 minutes pyrolyzed at 900oC
(top), 800oC, and 700oC (bottom).

DRDC Atlantic TM 2009-246 21

 Figure 27: Pyrograms of GFLT Type fluoroelastomer from 3.5-15 minutes pyrolyzed at 900oC
(top), 800oC, and 700oC (bottom).

Figure 28: Pyrograms of GLT Type fluoroelastomer from 0-40 minutes pyrolyzed at 900oC (top),
800oC, and 700oC (bottom).

22 DRDC Atlantic TM 2009-246

 Figure 29: Pyrograms of GLT Type fluoroelastomer from 3.5-15 minutes pyrolyzed at 900oC
(top), 800oC, and 700oC (bottom).
RT: 3.50 - 15.00
8.72 NL:
100 4.00E8
TIC MS
14.10 viton_a_pyro7
00-run5
50
10.97 11.66
3.53 4.74 7.79 9.30 9.98
3.68 6.11 6.64 13.04 13.53
0
6.76 8.73
NL:
Relative Abundance

100 5.51E7
TIC MS
6.90 viton_b_pyro7
00-run8
50
3.53 3.98 5.73 7.39 7.95 9.53
10.38 11.61 12.78 14.10

0
6.92 7.36 NL:
100 3.23E6
TIC MS
viton_gflt_pyr
4.03 7.97 8.74
5.49 o700-run10
50
5.42 6.02 9.10 9.60 12.00
10.44 13.04 14.66

0
9.09 NL:
100 3.75E7
8.73
14.27 TIC MS
11.02
vtion_GLT_py
12.21 13.66 ro700_run5
50
9.68 9.99
3.98 4.63 7.36 7.69
6.43
0
4 6 8 10 12 14
Time (min)

Figure 30: Pyrograms of A Type (blue), B Type (red), GFLT Type (green), and GLT Type (black)
fluoroelastomers between 3.5 and 15 min. All samples were pyrolyzed at 700oC.

DRDC Atlantic TM 2009-246 23

The pyrograms of the four fluoroelastomers (700°C) are shown in Figure 30. Each of the
fluoroelastomers yields degradation products and degradation product intensities that are different
from the other three elastomers. This is referred to as a fingerprint. Some of the peaks, and
therefore the compounds that give rise to them, are found in more than one elastomer. The A
Type fluoroelastomer has major peaks at 8.72, 10.97, 11.66, and 14.10 min with the peak at 8.72
min being the most intense. The B Type fluoroelastomer has peaks at 6.76, 6.90, and 8.73 min.
The peaks at 6.76 and 8.73 minutes are the most intense. The GFLT Type fluoroelastomer has
peaks at 6.93, 7.36, 7.97, and 8.74 min. The peaks at 6.93 and 7.36 min are the most intense.
The GLT Type fluoroelastomer has peaks at 8.73, 9.09, 11.02, and 14.27 min. The peak at 9.09
min is the most intense.

The mass spectra of the compounds giving rise to the most intense peaks in the pyrograms of A
Type, B Type, GFLT Type and GLT Type fluoroelastomers are shown in Figures 31 through
Figure 34 respectively.

163 NL: 1.70E8

100
viton_a_pyro700_run6
#1009 RT: 8.73 AV: 1
T: + c EI Q1MS
50 [50.000-500.000]
113
133 165
77 224 259
273 337 367 433 471 497
0
163 NL: 3.05E7
Relative Abundance

100
viton_a_pyro700_run6
#1267 RT: 10.97 AV:
1 T: + c EI Q1MS
50 [50.000-500.000]
113
109 207 227 271
335 361 381 431 476
0
163 NL: 2.15E7
100
viton_a_pyro700_run6
#1346 RT: 11.66 AV:
1 T: + c EI Q1MS
50 [50.000-500.000]
113 133 165
77 207 229 288
335 379 399 431 451
0
163 NL: 4.70E7
viton_a_pyro700_run6
40000000
#1628 RT: 14.11 AV:
30000000 1 T: + c EI Q1MS
[50.000-500.000]
20000000
113 133 165
10000000 77 197 229
293 337 352 399 443 475
0
100 200 300 400 500
m/z

Figure 31: Mass spectra of peaks (from top to bottom) at 8.73 min, 10.97 min, 11.66 min and
14.11 min in the pyrogram of A Type fluoroelastomer.

24 DRDC Atlantic TM 2009-246

The major ions in the mass spectra of the four degradation products of the A Type
fluoroelastomer (Figure 31) are similar. The ion with m/z 163 is the most intense in all four mass
spectra. This corresponds to an ion with a molecular formula (C4F6H)·+. The ions with m/z 133
and m/z 113 correspond to ions with molecular formulas (C3F5H2)·+and (C3F4H)·+ respectively.
However, there are other ions in each of the four spectra that are unique to the various
compounds.

163 NL: 2.10E7

100
viton_b_pyro700-
run9#782 RT:
80
6.76 AV: 1 T: + c
EI Q1MS
60
[50.000-500.000]
40 113

20 165
77 197 229 263
327 371 391 459 485
0
113 NL: 1.54E7
100
viton_b_pyro700-
Relative Abundance

run9#798 RT:
80
6.90 AV: 1 T: + c
EI Q1MS
60
[50.000-500.000]
40
133
20 69 77 165 213 257 277 321
353 392 419 482
0
163 NL: 1.70E7
viton_b_pyro700-
15000000 run9#1009 RT:
113
8.73 AV: 1 T: + c
EI Q1MS
10000000 [50.000-500.000]

5000000 133
77 165 224
209 259 317 337 387 407 471 497
0
100 200 300 400 500
m/z

Figure 32: Mass spectra of peaks (from top to bottom) at 6.76 min, 6.90 min, and 8.73 min in the
pyrogram of B Type fluoroelastomer.

The major ions in the mass spectra of the three degradation products of the B Type
fluoroelastomer (Figure 32) vary. Ions at m/z 163, 113, and 133 are prominent for the
degradation products at 6.76 min and 8,43 min. However, the mass spectrum of the degradation
product at 6.90 min has no ion at m/z 163 but has an ion ion at m/z 165. Differences in the
structure and intensity of the degradations products produced by the B Type fluoroelastomer
compared to the A Type fluoroelastomer result from the difference in composition of the two
elastomers. The A Type fluoroelastomer is a copolymer of VF2 and HFP while the B Type
fluoroelastomer is a terpolymer of VF2, HFP and TFE. As was observed for the mass spectra of
the degradation products of the A Type fluoroelastomer, the mass spectra of the B Type

DRDC Atlantic TM 2009-246 25

fluoroelastomer degradation products shown have ions that are unique to them. Comparison of
the mass spectra of the degradation products at 8.43 min for the A Type and B Type
fluoroelastomers indicates that they are similar and result from the same compound. This
compound would arise from the thermal degradation of a portion of the elastomers containing
VF2 and HFP.

113 NL: 1.00E7

100
viton_GFLT_pyro700-
run8#798 RT: 6.91
AV: 1 T: + c EI Q1MS
50 [50.000-500.000]
133
69 77 165 213 257 277 321 353 393 464 485
0
179 NL: 4.10E6
Relative Abundance

100
viton_GFLT_pyro700-
91 run8#849 RT: 7.35
AV: 1 T: + c EI Q1MS
50 113 [50.000-500.000]

133 255 311 319

207
407 439 496
0
113 NL: 4.69E6
100
viton_GFLT_pyro700-
run8#919 RT: 7.96
AV: 1 T: + c EI Q1MS
50 [50.000-500.000]
133
69
85 145 195 213 257
321 383 403 461 482
0
113 NL: 4.49E6
4000000 viton_GFLT_pyro700-
run8#1008 RT: 8.73
3000000 AV: 1 T: + c EI Q1MS
[50.000-500.000]
2000000
1000000 69 77 133 165
224 285 317 363 415 484
0
100 200 300 400 500
m/z

Figure 33: Mass spectra of peaks (from top to bottom) at 6.91 min, 7.35 min, 7.96 min and 8.73
min in the pyrogram of GFLT Type fluoroelastomer.

The mass spectra (and most intense ions) of the major degradation products of the GFLT Type
fluoroelastomer (Figure 33) indicate that some of degradation products of this elastomer are the
same as found for the A Type and B Type fluoroelastomers. For instance, the mass spectrum of
the compound giving rise to the peak at 6.91 min is the same as that for the compound giving rise
to the peak at 6.90 min in the B Type fluoroelastomer pyrogram. The mass spectrum he
compound giving rise to the peak at 8.73 min is the same as that for the compound giving rise to
the peak 8.73 min in the A Type and B Type fluoroelastomer pyrograms.

The mass spectra of three of the four degradation products of GLT Type fluoroelastomer (shown
in Figure 33) also have an ion at m/z 85. The GFLT Type fluoroelastomer is made using PMVE

26 DRDC Atlantic TM 2009-246

(perfluoromethylvinylether). Cleavage of the bond between the polymer chain and the methyl
vinyl ether oxygen produces an ion (OCF3) with an m/z of 85. The mass spectrum of the
degradation product at 7.35 min has ions at m/z 179 (C4F6OH·+) and m/z 91 (C3F2O·+) that can
be attributed to the portion of the elastomer containing PMVE.

113 NL: 1.05E7

100
vtion_GLT_pyro700_ru
n5#1010 RT: 8.73 AV:
1 T: + c EI Q1MS
50 [50.000-500.000]

69 133 165 224

285 317 366 402 467 495
0
179 NL: 5.36E6
Relative Abundance

100
vtion_GLT_pyro700_ru
n5#1051 RT: 9.09 AV:
69 91 1 T: + c EI Q1MS
50 [50.000-500.000]
113 133
212 307
276
336 371 403 422 466
0
113 NL: 6.71E6
100
vtion_GLT_pyro700_ru
n5#1274 RT: 11.02
AV: 1 T: + c EI Q1MS
50 [50.000-500.000]

133
69 85 179 223 285 311 350 387 432 449 498
0
113 NL: 5.29E6
vtion_GLT_pyro700_ru
4000000 n5#1648 RT: 14.27
AV: 1 T: + c EI Q1MS
[50.000-500.000]
2000000 133
165
77 197 229 285 337 357 434 464 491
0
100 200 300 400 500
m/z

Figure 34: Mass spectra of peaks (from top to bottom) at 8.73 min, 9.09 min, 11.02 min and
14.27 min in the pyrogram of GLT Type fluoroelastomer.

The mass spectra of the four major degradation products of the GLT Type fluoroelastomer are
shown in Figure 34. Ions at m/z 85, m/z 91 and m/z 179 are present in the mass spectra and can
be attributed to degradation products from the portion of this elastomer containing PVME.
Although there are some similarities in the ions found in the mass spectra of the major
degradation products of the GFLT Type and GLT Type fluoroelastomers, there are a number of
differences that result from the difference in the composition of the two elastomers. These are
sufficient to differentiate the two elastomers.

DRDC Atlantic TM 2009-246 27

3.6 Scanning Electron Microscopy and Energy Dispersive X-
ray Spectroscopy
The elemental compositions of the residues of the A Type, B Type, GFLT Type, and GLT Type
fluoroelastomers following heating in air to 800oC are shown in Table 4. The constituents of the
residues of the A Type and B Type fluoroelastomers were calcium (Ca), barium (Ba), magnesium
(Mg), sulphur (S), aluminum (Al), and silicon (Si). Ca was the most abundant element in the
residue followed by Ba and Mg. There were trace amounts of the other elements relative to Ca.

Table 4: The elemental composition of the inorganic residues from the four fluoroelastomers
following heating in air to 800oC. They were determined by SEM-EDX.

Fluoroelastomer Residue Elemental

Composition

A Type Ca, Ba, Mg, S, Al, Si

B Type Ca, Ba, Mg, S, Al, Si

GFLT Type Ba, Ca, Al, Zn, Fe, S,

Mg

GLT Type Al, Zn, Ca, Fe, Cu,

Mg, Si, Cr, K, Ti, Ni,
Cl, S

The residue of the GFLT Type fluoroelastomer contained Ba, Ca, Al, zinc (Zn), iron (Fe), S, and
Mg. Ba was the major constituent and there were trace amounts of the other elements present
relative to Ba. The residue of the GLT Type fluoroelastomer had a slightly different composition
than that of the GFLT Type fluoroelastomer. Al was the major constituent with smaller amounts
of Zn, Ca, Fe, copper (Cu), Mg, Si, chromium (Cr), potassium (K), titanium (Ti), nickel (Ni),
chlorine (Cl), and S present.

Residue elemental analysis data is of little use in the identification of a particular type of
fluoroelastomer. However, if one wishes to confirm that a fluoroelastomer is the same as another
and a sample of the other is available, elemental residue analysis data is very useful. The nature
inorganic residue can provide information on additives, such as fillers, curing agents, uv
stabilizers and antioxidants, used in the preparation of the elastomer. If the constituents of the
inorganic residue are the same and their relative concentrations are similar then the two
elastomers are most likely the same.

28 DRDC Atlantic TM 2009-246

4 Conclusions

Four fluoroelastomers have been characterized using FT-IR, TGA, DSC, DMA and Py-
GC/MS/MS. FT-IR provided information that could be used to differentiate the four
fluoroelastomers. Absorbance due to symmetric and asymmetric C-H bonding (2800cm-1 - 2950
cm-1) in the fluoroelastomers is indicative of the VF2 in the elastomer formulation and the strength
of the absorbance was found to correlate with the published percentages of VF2 in each of the
elastomers. Absorbance peaks at ~1350 cm-1, ~930 cm-1, and ~825 cm-1 can also be used to
differentiate between the elastomers.

Weight loss versus temperature plots and temperatures of maximum rate of weight loss,
determined using TGA, were different for the four fluoroelastomers. This information, in
conjunction with FT-IR or py-GC/MS/MS data, and a Tg from DSC or dynamic mechanical
analysis, would allow positive identification of the fluoroelastomers. The Tg of the four
fluoroelastomers, determined using either DSC or DMA, were different. As was stated for the
TGA results, this information in conjunction with FT-IR or Py-GC/MS/MS data would allow
positive identification of these fluoroelastomers.

Each of the fluoroelastomers had a unique pyrogram. This indicates that Py-GC/MS/MS can be
used to identify the fluoroelastomers studied in this report. The gas chromatographic separation
of pyrolytic degradation products and subsequent identification of the degradation products using
mass spectrometry are advantages of this technique compared to the others investigated in this
report. Although FT-IR can be used to identify the fluoroelastomer studied in this Technical
Memorandum, these fluoroelastomers had not been in service and therefore were not adulterated.
The presence of a fluid in a sample could mask some of the IR peaks used to identify an
elastomer. Adulteration could also affect the Tg of a sample. Although the presence of a
contaminant, such as oil, would affect the pyrogram of a sample, the pyrolytic degradation
products of the contaminant would be separated from the degradation products of an elastomer
prior to mass spectral detection. In addition, the mass spectra of the individual components
would enable identification of products arising from the elastomer or the adulterant.

DRDC Atlantic TM 2009-246 29

References .....

[1] “James Walker: Sealing Products & Materials for the Oil & Gas Industry”. Retrieved May14
2009 from:
http://www.jameswalker.biz/docs/jwco/Oil_and_gas_guide.pdf

[2] Albert L. Moore, Fluoroelastomers Handbook: The definitive user’s guide and databook,
William Andrew Inc., New York (2006).

[3] CWC- “Fillers for rubber compounds”. Retrieved July 31 2009 from:
http://www.p2pays.org/ref/13/12534.pdf

[4] R. M. Paroli, and J. Penn, “Measuring the Glass Transition Temperature of EPDM
Roofing Materials: Comparison of DMA, TMA, and DSC Techniques”, Assignment of
the Glass Transition, ASTM STP 1249, R. J. Seyler, Ed., American Society for Testing and
Materials, Philadelphia, 1994, pp. 269-276.

30 DRDC Atlantic TM 2009-246

Distribution list

Document No.: DRDC Atlantic TM 2009-246

LIST PART 1: Internal Distribution by Centre

2 Dr. John A, Hiltz, 1CD, 1 hardcopy

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3 DRDC Atlantic Library, 1 hardcopy and 2 CDs

11 TOTAL LIST PART 1

LIST PART 2: External Distribution by DRDKIM

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DRDC Atlantic TM 2009-246 31

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32 DRDC Atlantic TM 2009-246

 DOCUMENT CONTROL DATA
(Security classification of title, body of abstract and indexing annotation must be entered when the overall document is classified)
1. ORIGINATOR (The name and address of the organization preparing the document. 2. SECURITY CLASSIFICATION
Organizations for whom the document was prepared, e.g. Centre sponsoring a (Overall security classification of the document
contractor's report, or tasking agency, are entered in section 8.) including special warning terms if applicable.)

Defence R&D Canada – Atlantic UNCLASSIFIED

9 Grove Street
P.O. Box 1012
Dartmouth, Nova Scotia B2Y 3Z7
3. TITLE (The complete document title as indicated on the title page. Its classification should be indicated by the appropriate abbreviation (S, C or U)
in parentheses after the title.)

Techniques for the Characterization of Fluoroelastomers

4. AUTHORS (last name, followed by initials – ranks, titles, etc. not to be used)

Hiltz, J. A., Smith, S. J

5. DATE OF PUBLICATION 6a. NO. OF PAGES 6b. NO. OF REFS
(Month and year of publication of document.) (Total containing information, (Total cited in document.)
including Annexes, Appendices,
etc.)
December 2009 48 4
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e.g. interim, progress, summary, annual or final. Give the inclusive dates when a specific reporting period is covered.)

Technical Memorandum
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Defence R&D Canada – Atlantic

9 Grove Street
P.O. Box 1012
Dartmouth, Nova Scotia B2Y 3Z7
9a. PROJECT OR GRANT NO. (If appropriate, the applicable research 9b. CONTRACT NO. (If appropriate, the applicable number under
and development project or grant number under which the document which the document was written.)
was written. Please specify whether project or grant.)
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10a. ORIGINATOR'S DOCUMENT NUMBER (The official document 10b. OTHER DOCUMENT NO(s). (Any other numbers which may be
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activity. This number must be unique to this document.)

DRDC Atlantic TM 2009-246

11. DOCUMENT AVAILABILITY (Any limitations on further dissemination of the document, other than those imposed by security classification.)
Unlimited

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Document Availability (11). However, where further distribution (beyond the audience specified in (11) is possible, a wider announcement
audience may be selected.))

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 13. ABSTRACT (A brief and factual summary of the document. It may also appear elsewhere in the body of the document itself. It is highly desirable
that the abstract of classified documents be unclassified. Each paragraph of the abstract shall begin with an indication of the security classification of the
information in the paragraph (unless the document itself is unclassified) represented as (S), (C), (R), or (U). It is not necessary to include here abstracts in
both official languages unless the text is bilingual.)

Fluoroelastomers are synthetic elastomers containing fluorine. They have excellent chemical and
heat resistance and are specified for many applications where chemical and heat resistance is
required. They are among the best materials for use in the marine, automotive, aerospace, oil and
chemical industries where they are used as seals, O-rings, gaskets, and fuel hoses. In this
memorandum four fluoroelastomers, A Type, B Type, GFLT Type and GLT Type, were
characterized using Fourier transform infrared (IR) spectroscopy, differential scanning
calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA),
and pyrolysis gas chromatography/mass spectrometry/mass spectrometry (Py-GC/MS/MS). The
objective of this characterization was two-fold; firstly to amass physical and chemical
information on the elastomers and secondly to determine which technique or combination of
techniques could be used to positively identify the four fluoroelastomers.

IR spectroscopy indicated that there are peaks that could be used to differentiate between the four
types of fluoroelastomers. TGA weight loss versus temperature and temperature of maximum
rate of weight loss data was different for the four fluoroelastomers studied and in conjunction
with other experimental data could be used to identify the four elastomers. The glass transition
temperatures (Tg) of the four elastomers measured, using both DSC and DMA, were different.
For new unadulterated elastomer samples, the Tg could be used in conjunction with IR data to
differentiate between the four fluoroelastomers studied in this work. Py-GC/MS/MS could be
used to differentiate between the four fluoroelastomers. Each of the elastomers produced a
distinctive chromatogram (pyrogram). The mass spectra of the compounds giving rise to the
peaks in the pyrograms contained ions that could only be produced by elastomers containing, for
instance, perfluoro(methylvinylether) and therefore have the best potential to positively identify a
fluoroelastomer.

14. KEYWORDS, DESCRIPTORS or IDENTIFIERS (Technically meaningful terms or short phrases that characterize a document and could be
helpful in cataloguing the document. They should be selected so that no security classification is required. Identifiers, such as equipment model
designation, trade name, military project code name, geographic location may also be included. If possible keywords should be selected from a
published thesaurus, e.g. Thesaurus of Engineering and Scientific Terms (TEST) and that thesaurus identified. If it is not possible to select
indexing terms which are Unclassified, the classification of each should be indicated as with the title.)

Fluoroelastomers, Characterization, Identification, Fourier transform infrared (FT-IR), Differential

scanning calorimetry (DSC), Thermogravimetric analysis (TGA), Dynamic mechanical analysis
(DMA), pyrolysis Gas chromatography/Mass spectrometry/Mass spectrometry (py-GC/MS/MS)
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