Research Report 320: Elastomers For Fluid Containment in Offshore Oil and Gas Production: Guidelines and Review

HSE
Health & Safety

Executive
Elastomers for fluid containment in offshore oil

and gas production: Guidelines and review
Prepared by MERL Ltd for the

Health and Safety Executive 2005
RESEARCH REPORT 320
HSE
Health & Safety
Executive
Elastomers for fluid containment in offshore oil

and gas production: Guidelines and review
Dr R P Campion, Dr B Thomson and Dr J A Harris

MERL Ltd
Tamworth Road
Hertford
SG13 7DG
A set of guidelines has been generated and an associated detailed review developed to cover technical
aspects associated with the use of elastomers for fluid containment in offshore Oil & Gas production.
Information is provided for management systems associated with selecting appropriate material-types
and designs and of acceptable operating strategies to reduce risks. The opportunity is also given to
learn more about background features of elastomers and their behaviour when exposed to fluids.
Elastomeric components (seals, hoses and many others) are employed extensively for such fluid
containment, often in critical locations. Many applications are long-established, with elastomeric
components able to function for many years in fluid containment, e.g. up to 20 years or more. However,
some deterioration is always taking place. The ever-present point of issue is whether deterioration will
lead to failure before the design life is achieved.
In some cases, deterioration can follow predictable routes e.g. with chemical ageing, timedependent
properties such as creep or stress relaxation, or fluid-related kinetic factors such as permeation or
diffusion. Hence, estimations can be made as to whether or not an elastomeric component so-exposed
can function to completion of design life. Other forms of deterioration sometimes seen at high service
pressures, such as “explosive” (rapid gas) decompression or seal-housing extrusion damage, are less
predictable; here, prior testing of materials under realistic laboratory simulations of operating conditions
is necessary to demonstrate the material’s resistance to such failure-modes.
This report and the work it describes were funded by the Health and Safety Executive (HSE). Its
contents, including any opinions and/or conclusions expressed, are those of the authors alone and do
not necessarily reflect HSE policy.
HSE BOOKS
© Crown copyright 2005
First published 2005
ISBN 0 7176 2969 4
All rights reserved. No part of this publication may be
reproduced, stored in a retrieval system, or transmitted in
any form or by any means (electronic, mechanical,
photocopying, recording or otherwise) without the prior
written permission of the copyright owner.
Applications for reproduction should be made in writing to:
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St Clements House, 2-16 Colegate, Norwich NR3 1BQ
or by e-mail to hmsolicensing@cabinet-office.x.gsi.gov.uk
ii
ACKNOWLEDGEMENTS
The HSE and the MERL authors wish to thank those listed below and their employers
for invaluable comments which have helped focus this document on its objectives for
the upstream O & G industry.
Stephen Groves
BP
David Orr
Baker Oil Tools
Steven Paterson, Frans Janssen
Shell
John Boran, Alan Gibson
Nexen Petroleum UK Ltd
Dave Shaw
CB&I/John Brown
Phil Embury
James Walker
Tom Farley
Parker Seal
Bob Jeavons
Gulf Coast Seals
Chris Stowell
Trelleborg
John Davis
Dunlop Oil & Marine
iii
FOREWORD
The HSE require offshore Oil & Gas engineering areas to be managed safely. As part of this,
their objectives for this document are:
(i) Generation of a set of guidelines for the use of elastomers in fluid containment offshore.
These should provide information for management systems associated with the
selection of appropriate designs and acceptable operating strategies.
(ii) Development of a review document relating to the use of elastomers on offshore

installations, to be in sufficient detail to lead to the generation of the guidelines, and to
act as technical background where required when implementing the guidelines.
This document therefore consists of two parts: Part 1 covering the guidelines and Part 2 the
review. The work focuses on elastomer-based components in general upstream oil and gas
(O & G) production usage for the UK continental shelf, with limited comments only being made
on some other components used here and elsewhere. The components assessed are assumed to
contain fluid being transported, either for drilling, completion, production, treatment, control or
safety reasons. Other usage of elastomers offshore are not considered herein, such as elastomer-
based components (e.g. flexelements) whose sole function is to be part of the supporting
structure for all or part of an oilrig etc, or elastomer coating systems, or steel-lined hoses
possessing external elastomeric layers.
iv
EXECUTIVE SUMMARY
To ensure the safe use of elastomeric materials offshore, their behavioural characteristics and an
awareness of how and where risks might be associated with their usage should be well
understood. It should then be possible to identify where suitable risk control measures should
be applied for elastomeric components.
Elastomers constitute the most flexible, deformable and elastic of the three classes of the non
metallic materials “polymers”. As such, elastomers are employed extensively throughout the
industry for fluid containment in offshore oil & gas production, often in critical locations.
Important applications use elastomeric components as seals (including packers, plugs, repair
clamps), hoses/bonded flexible pipes, flexible joints, valve sleeves, pulsation damper bladders
and bellows. Many of these applications are long-established; correctly-specified elastomers
can function for many years in fluid containment, e.g. up to 20 years or more.
Despite this, the nature of elastomers is such that, when used in contact with fluids and/or
subjected to applied forces, significant deterioration may occur. However, modes of
deterioration can follow predictable routes such that an elastomeric component so-exposed can
continue to function, often to completion of design life. In other instances, change-out might be
necessary before design life is complete; prior knowledge of mechanisms involved and
procedures to adopt as a consequence is recommended for all such cases.
To develop such knowledge, functional properties, deterioration modes, and factors affecting
function performance should be considered. These inform on the sequence of key stages of
specification, operation and monitoring. A system audit provides control of all these
procedures. Finally, in the event of failure, suitable analysis should be conducted to ascertain
causes and provide a basis for any redesign.
This document provides information for safe use of elastomers in fluid containment applications
offshore. It is in two parts:
1) As a set of guidelines for management systems associated with the selection of
appropriate materials, designs and acceptable operating strategies to reduce risks. Part 1
seeks to guide both on technical matters and on the management of risk during all stages
from specification to operation.
2) As a review, to provide further detailed information, sufficient to act as technical
background where required when implementing the guidelines – it is a detailed
reference.
The two parts are linked by extensive use of footnoted references to assist the reader to obtain
extra detail in specific areas.
v
vi
ELASTOMERS FOR FLUID CONTAINMENT IN OFFSHORE OIL &
GAS PRODUCTION
Part 1 - GUIDELINES
CONTENTS
1 INTRODUCTION .................................................................................................1
1.1 STRUCTURE OF GUIDELINES ................................................................................2
2 FUNCTIONAL PROPERTIES AND DETERIORATION MODES OF
ELASTOMERS ....................................................................................................5
2.1 FUNCTIONAL PROPERTIES ....................................................................................5
2.2 FUNCTIONAL PERFORMANCE FACTORS .................................................................5
2.3 MODES OF DETERIORATION..................................................................................7
3 DESIGN ASPECTS ...........................................................................................11
3.1 MATERIAL SELECTION ........................................................................................11
3.2 SEAL DESIGN ....................................................................................................11
3.3 DESIGN ASPECTS FOR OTHER COMPONENTS .......................................................12
4 SPECIFICATION ...............................................................................................13
5 QUALIFICATION...............................................................................................17
6 QUALITY CONTROL/QUALITY ASSURANCE DURING MANUFACTURE......19
7 INSTALLATION.................................................................................................21
8 OPERATION AND MONITORING/INSPECTION ..............................................23
9 FAILURE ANALYSIS ........................................................................................25
9.1 ROOT CAUSE ANALYSIS......................................................................................26
10 AUDIT................................................................................................................29
10.1 MANAGERIAL.....................................................................................................29
10.2 TECHNICAL .......................................................................................................29
11 BIBLIOGRAPHY FOR GUIDELINES ................................................................33
vii
viii
GAS PRODUCTION
Part 1 – GUIDELINES
Objective: To provide information for the use of elastomers in fluid containment
offshore for management systems associated with the selection of appropriate designs
and acceptable operating strategies.
1 INTRODUCTION
These guidelines aim to ensure the safe use of elastomeric materials offshore by outlining their
behavioural characteristics and indicating where risks might be associated with their usage. It
should then be possible to identify where suitable risk control measures should be applied for
their components. Relevant technical factors are considered in detail in the review in Part 2,
which provides technical background for reference purposes where required. The main focus of
Part 1 is on matters affecting the selection of appropriate designs/materials and the management
of risk during all stages from specification to operation.
Figure 1 Schematic of an O-ring seal in operation, with some possible deterioration

modes indicated
Elastomeric components that are covered by this document have the prime function of
containing oilfield fluids, both production and operational. Relevant component types include:
• Seals - basic (e.g. Figure 1), packers, plugs, repair clamps
• Hoses/bonded flexible pipes (i.e. “subsea high pressure hoses”, Figure 2)
• Flexible joints
• Valve sleeves
• Rubber bellows
Components such as steel-lined hoses possessing external elastomeric layers (duplex hoses) are
not considered here, as the steel performs the containment function. Other non-containment
usage of elastomers offshore is also excluded, such as elastomer-based components (e.g.
flexelements) whose sole function is to be part of the supporting structure for all or part of an
oilrig etc. Similarly, this document does not consider use of protective coatings (e.g.
polychloroprenes) against the action of fluids. Those interested in this area could access the
DnV Recommended Practice document RP-F1061.
(1) carcass; not fluid-containing. Has other duties.*

(2) internal pressure sheath (liner, to contain fluid)
(3) pressure armour
(4) back-up pressure armour*
(5) inner tensile armour*
(6) outer tensile armour*
(7) outer sheath (cover) For more details, see the indicated sections in
Part 2 (Review):
* optional
Other polymer layers (e.g. anti-slip) may also lie between these
Figure 2 Layers across a bonded elastomeric flexible pipe; with hoses at lower
pressure service, some layers shown are not essential
Comments are focused on elastomeric seals since these are used in a wide variety of fluid
containment applications offshore. Material behaviour when in contact with a fluid is usually
similar whatever component-form it is in, but the different geometries might affect the
associated kinetics of this behaviour. Where appropriate, extra specific comments on other
components are made. These guidelines should apply both to subsea systems - where
completion, production and treatment fluids give rise to the main compatibility issues - and
topsides, where control fluids must also be considered.
Elastomers are one of three nonmetallic material classes that constitute “polymers”; the other
two classes2 are thermoplastics (“plastics”) and thermosets. These other classes are only
considered herein for situations where they support the function of an elastomer (e.g. seal back
up rings). Within the elastomer class, there are many types arising from different base rubbery
polymers3. There are also many elastomer variants for each elastomer-type based on
compounding recipes4 unique to suppliers. With such a variety of elastomeric materials it is
important to have a thorough understanding of the relationship between material composition,
associated properties and their magnitudes, and component performance.
1.1 STRUCTURE OF GUIDELINES
The structure of these guidelines is illustrated in Figure 3. For convenience, numbering used
generally follows the associated section numbers. Key requirements for each section are given
as bullet points at its beginning. In summary, functional properties, deterioration modes and
factors affecting function performance are first discussed. These inform on the following
sections that plot the sequence of key stages from specification to operation and monitoring. To
cover all eventualities, failure analysis is then examined. Finally, system audit is considered.
1
Recommended Practice RP-F106: “Factory Applied External Pipeline Coatings for Corrosion Control” : see
Bibliography
For more details, see the indicated sections in Part 2 (Review):
2
Section 3
3
Sections 3.4 and 3.4.3
4
Section 3.4 and Appendix 1
2
2. Functional properties
- deterioration modes
- functional performance
factors
Key stages
3. Design
- material selection
- component design
4. Specification
10. Audit
5. Qualification
6. Manufacturing QA/QC
7. Installation
8. Operation &
monitoring/inspection
Component
failure
9. Failure analysis
- component failure
- root cause analysis
Figure 3 Structure of guidelines – key stages
2 FUNCTIONAL PROPERTIES AND DETERIORATION MODES

OF ELASTOMERS
This section discusses properties that need to be considered during all stages of the application
of an elastomer, which includes:
• Functional properties
• Functional performance factors
- viscoelastic (frequency or time-dependent) effects, temperature, fluid absorption
• Modes of deterioration
2.1 FUNCTIONAL PROPERTIES
Elastomers (also termed rubbers) are:

• soft
• elastic (nearly)
• incompressible (nearly).
They are therefore used in components that are required to be deformable and flexible. Their
elastic nature leads to their usage in primary seals where sealing stress develops from a
mechanically-applied compression and/or energisation arising from the hydrostatic pressure of
the fluid being sealed5. With hoses, the compliant nature of the whole structure is important,
but this is possible because this ability exists for the basic elastomer6. Incompressibility means
that high stresses can be resisted when elastomers are highly constrained thus seals can
accommodate high pressures and the bonded layers of flexible joints can carry high
compression loads7.
The behaviour of an elastomer can be characterised by property magnitudes. Mechanical

properties commonly employed include modulus (often measured in tensile mode), hardness,
tear strength, and compression set8. The stress/strain plots accompanying the measurement of
modulus indicate how elastic and deformable an elastomer is. Such property measurements are
often used for QA/QC purposes while other properties must often be considered for quantifying
functional performance.
2.2 FUNCTIONAL PERFORMANCE FACTORS
2.2.1 Viscoelastic effects
Although elastomers are largely elastic, they also possess some viscous characteristics which
are associated with frequency or time-dependent changes. This manifests itself in the following
behaviours:
• stress relaxation i.e. loss of force over time under constant deformation
• creep i.e. increasing deformation with time under constant load
• damping i.e. energy dissipation on loading and unloading
• increasing stiffness with rate or frequency of loading

5
Section 2.1
6
Section 2.2
7
Section 2.3
8
Section 3.4.1
5
Thus static seal performance depends on stress relaxation and creep (extrusion through the
extrusion gap) – which affects sealing stress retention or long-term seal integrity9. Damping
and increasing stiffness with frequency are important for dynamic applications: flexible hoses,
flexible joints and pulsation bladders.
2.2.2 Temperature
Property magnitudes depend on temperature; elastomers expand on heating, accompanied by a

loss in strength and related properties. In the extremes:
• when heated to (very) high temperatures, chemical degradation might occur, to weaken the
elastomer even further10
• when cooled to low temperatures, elastomers will become stiff and brittle on approaching
or going below the glass transition temperature Tg11
2.2.3 Fluid absorption
Any contacting fluids (consisting of small molecules) will be absorbed into elastomers; in time,
the elastomer can swell. The presence of absorbed fluid in sufficient quantities, with associated
swelling, can weaken the polymer, the fluid molecules pushing the polymer molecules apart
(plasticization). The contacting fluid might also leach out soluble constituents of the
elastomer’s recipe, to reduce component dimensions. In addition, the fluid might be chemically
aggressive - attacking the elastomer surface initially, and continuing inside its bulk after
absorption - to cause further deterioration in properties and performance of the component12.
Whether an elastomer has a strong tendency to absorb a liquid depends on the closeness of their
respective “solubility parameters13”, this proximity might be additionally affected by other
factors14. The rate of absorption can be determined from the laws of diffusion characterised by
the diffusion and solubility coefficients, D and s. Diffusion rates quicken as temperature
increases - see later15.
Similarly, gases can dissolve into the surface of an elastomer (adsorption) and then diffuse into
its interior. If geometrical and/or surrounding considerations allow, gases will pass right
through the elastomer by dissolving, diffusing, and evaporating, the combination of these
processes being “permeation”16 characterised for a material by the permeation coefficient (Q) a
product of D and s. The diffusion rates of gases are approximately 1-2 orders of magnitude
faster than those for liquid diffusion.
When operating at high pressures (to simulate upstream O & G production service conditions),
gases can compact elastomers up to 15% or so for hydrostatic reasons; in addition, gases
possess a solubility parameter at high pressure (HP), so that - following initial compaction –
swelling can then occur with some gas/elastomer combinations. Test methods using simply-
shaped specimens are well-established for measuring the three coefficients described above at

9
Section 3.4.2 and Appendix 2
10
Sections 4.2 and 4.3
11
Section 3.3
12
Section 4 for fluid effects
13
Section 4.2.1
14
Section 4.2.2
15
Section 4.3.2 and Appendix 4
16
Section 4.3
6
high pressures, e.g. 1,000 bar. The coefficients can then be used for other component
geometries in predicting fluid permeation rates, break-through times or absorbed concentrations.
Regarding long term performance, rates of fluid-induced deterioration of elastomers, whether

occurring by physical or chemical means, can be quantified by assessing performance at or near
to service conditions, by following changes in property magnitudes. In the case of explosive
decompression, assessment is made by inspecting the elastomers after appropriate exposures of
component or sample. Standards exist which recommend procedures here; more details on
some of these are given in the Review17, including overview comments on the NORSOK
M-710 rev. 2 Standard which covers these areas in some detail18. Figure 4 shows an
arrangement for NORSOK ED (or RGD, rapid gas decompression) testing.
Figure 4 Schematic of a spigot/sleeve fixture used to house O-rings for realistic ED

testing (left), with photograph of a mounted O-ring pair before final assembly (right).
2.3 MODES OF DETERIORATION
See also Guidelines section 9
Although an infinitestimal amount of deterioration can be taking place in an elastomer as soon

as it commences its service function, with a material correctly selected to withstand properly-
specified conditions, this usually has no real effect for many years, whatever the mode of
deterioration. During this time, the elastomer will continue to perform as it should; only after
considerable periods of duty, or if exposed unexpectedly to very hostile conditions would the
rate of deterioration be likely to increase to the point where failure might occur. Hence
knowledge of appropriate deterioration mechanisms, especially leading to predictions of
remaining life are important.
After a long period of such deterioration, failure occurs when a component ceases to fulfil its
functional requirement of the transport and containment of fluids, so that failure may result in
leakage. For flexible joints there is an additional requirement to maintain flexibility so that
fatigue issues do not become excessive; elastomer recipes can be optimised to produce good
fatigue resistance whilst retaining the required level of fluid resistance.
Failure is generally associated with either physical or chemical changes or possibly both.
Various modes of eventual failure are considered in generic terms and described in Table 1. A
summary of which components these modes of failure can apply to is given in Table 2. More
details on mechanisms, modes and factors are provided in the review19.

17
Section 8
18
Section 8.1
19
Section 9
7
Table 1 Description of various modes of deterioration
Failure mode Description

Fracture/rapid tearing The ultimate strength properties of the elastomer are exceeded. Should be
considered for extremes of operational requirement (pressure, elevated
temperature, load etc), remembering that the strength properties magnitudes
may reduce with time due to thermal ageing and fluid absorption.
Rapid gas Gas dissolved in the elastomer under high pressure conditions comes out of
decompression or solution and forms bubbles in the material when the external pressure is lost.
explosive The bubbles may grow sufficiently to cause fracture of the material (e.g. seals)
decompression (ED) or of an interface (e.g. between the liner and adjacent layer in a hose).20
Stress relaxation Reduction of force over time under constant deformation conditions resulting
in loss of ability to seal for unenergised seals. Contributions from both
physical effects and chemical ageing effects. It is usually the latter that govern
long-term performance. For seals, the effects are countered by swelling due to
thermal expansion and absorption of fluids.21
Creep Increase in deformation with time under constant force/pressure conditions.
Contributions from both physical effects and chemical ageing effects. It is
usually the later that governs long-term performance. Associated with
extrusion failures in seals.
Swelling Absorption of fluids over time resulting in excessive stress if constrained (e.g.
seal) or excessive deformation and weakening of the elastomer if
unconstrained. Enhanced by thermal expansion effects. Governed by the
compatibility of the fluid with the material.22 A small amount can be
beneficial, e.g. in low pressure gas line seals, abandonment permanent plugs.
Thermal contraction Caused by reductions in temperature which may also result in hardening and
increased stress relaxation; the combined effect may result in loss of sealing
force in seals at low temperatures. Associated with the Tg of the elastomer.23
Chemical degradation Chemical changes due to attack either by a constituent of the contacting fluid,
(ageing) including environmental oxygen (aerobic ageing) or ongoing vulcanisation
(anaerobic ageing)24. Resultant changes in mechanical properties might
include stiffness changes that may affect functional performance, e.g. an
increase in stiffness resulting from ageing may result in excessive fatigue
forces being generated in flexible joints.
UV and ozone cracking Component surfaces exposed to UV and ozone prior to installation or during
service must be sufficiently resistant, e.g. hose covers.
Fatigue crack growth Crack growth under repeated strain cycling in dynamically loaded components
(flexible joints, hoses). Fatigue resistance may be reduced by elevated
temperatures, ageing and swelling by fluids.
Abrasion/erosion Loss of material over time by rubbing against another surface or fluid flow
with and abrasive medium.
Bond failure Hose end fittings and the metal plates in flexible joints are bonded to elastomer
layers. Appropriate bonding agents for the type of elastomer and metal should
be used. The bond is formed during the curing (vulcanization) process.
Inadequate bond strength may be a result of inadequate manufacturing
conditions or degradation caused by fluid ingress and corrosion.

20
Section 4.4
21
Sections 3.2.3, 4.2.3 and Appendix 2
22
Section 4.2 and Appendix 2
23
Appendix 2
24
Sections 4.2, 4.3 and Appendix 4
8
Table 2 Deterioration possibilities for various elastomeric components
Failure mode Static Packers& Repair Dynamic Hoses Flexible Valve Pulsation
seal plugs clamps seal joints sleeves bladder &
bellows
Fracture/rapid x (x)25 (x)25 x x x x x
tearing
Explosive x (x)26 x x
decompression
(ED)
Stress x (x)25 x x
relaxation
Creep/ x (x) 25 (x) 25
extrusion
Swelling x x x x x
25, 27
Thermal x (x)
contraction
Chemical x x x x x x x x
degradation
(ageing)
UV and ozone x x
cracking
Fatigue crack x x x x x
growth
Abrasion/ x x
erosion
Bond failure x x
In general terms, deterioration could arise from:

• incorrect materials selection
• inadequate design
• inadequate specification
• incorrect installation
• operation outside design limits
• careless handling
High temperature (HT) will soften elastomers, increase the rate of diffusion of liquids and gases
and accelerate any chemical degradation. These can occur irrespective of the service pressures
involved. High pressures (HP) will increase the possibility of any physically-based
deterioration processes such as extrusion and ED (when gases are involved).
Chemical reactions can sometimes soften elastomers, causing degradation (e.g. water effects on
some elastomers), but in other cases causing surface embrittlement, with cracking and general
hardening.
When both temperatures and pressures are high, it is possible that the high pressure will worsen
the effects of the temperature-induced deterioration – for instance, a seal material softened by
raising the temperature will be more likely to extrude at high pressures than at low, and if
25
Only with poor design
26
Only if repairing gas/multiphase stream pipeline
27
For some plugs
chemical reactions have caused further softening, the extent of extrusion will be even greater at
high pressures.
Failures with hoses can again be induced by ED if this phenomenon causes liner deterioration so
that the fluid being transported can reach the outer hose layers. These possess less oil-
resistance, being designed for other requirements (e.g. the cover material might need to resist
sea water, and withstand impacts); hence hose failure is likely to occur relatively soon after
liner failure. If it is suspected that such a failure process is under way in production lines
subsea, heat seeking devices (where appropriate, carried by underwater divers) should be used
for confirmation, seeking hot spots on the outer surface of the cover brought about by the
proximity of escaping oil.
Another feature which would allow failure of hoses would be if the end-fittings – chemically
bonded to the hose structure during manufacture – should become detached, that is, the curable-
adhesive bonding layer should fail. Manufacturers go to extensive lengths in trying to ensure
the integrity of these bonded regions during manufacture, with material choice, adhesive choice
and quality, and design (the use of tightly-wrapped thick steel wires as reinforcement). In the
unlikely event that hose leakage will be suspected during service, this would be a region of the
hose requiring inspection. Fatigue aspects might also arise during hose service – it is likely that
manufacturers include fatigue qualification tests when making their choice of elastomers prior
to manufacture.
10
3 DESIGN ASPECTS
This section considers aspects of design in terms of:
• General comments on the factors that should be considered
• Responsibilities and procedures for material selection
• Considerations for seal design
• Design aspects for other elastomeric components
Clearly, each oilfield operation requires its own design criteria. This document does not seek to
provide guidance on procedures for designing components. This is seen as the responsibility of
manufacturers or suppliers, as initially contracted. However, some factors which might be
considered are given in the Review (Part 2)28. All factors (e.g. functional mode of component,
environments, planning for contingencies, etc ) should be allowed for. Good experience gained
with previous successful designs for equivalent ongoing O & G operations should be
incorporated where possible, especially at high pressure/high temperature conditions where
there may be a paucity of data regarding material selection, etc. However, previous experiences
should not be transferred en bloc unless there is high confidence that all operating factors are
identical for previous and new operation. For example, a change in constitution of a gas
mixture for a HP operation where all other factors are the same could bring about hitherto un-
noted swelling of an elastomer seal (dependent on material type) – see comments in section 2.1
and Review29).
Appropriate design codes, guidelines and/or Standards should be used; some of these are
included in the Bibliography list which follows section 8.
3.1 MATERIAL SELECTION
Material selection to meet all specifications may either be the responsibility of the supplier and
be based on the specified operating conditions and design life, or be prescribed by the operator
based on previous operating experience at these or similar conditions. Selection should be made
for specific applications, operating conditions and fluid compatibility; procedure, qualification,
etc. The more critical the service, the more rigorous the material selection and qualification
process should be. In the Review, section 3.4 covers elastomers as a class, with some sub
sections covering how various elastomer types will be selected30, with associated comments31.
If the suppliers make the selection of elastomer types for a specific function, they will do so for
a particular operation based on specifications provided, making their choice against their
knowledge of the selected elastomer’s ability to withstand the conditions. If, instead, the end-
user specifies the elastomer type that the supplier shall provide, the end-user is applying his own
knowledge in this area; implicitly, in this case, the supplier’s responsibility is reduced to that
involving QA/QC so that good quality seals are provided.
3.2 SEAL DESIGN
The design should respond to operational function26, fluid types and conditions; possibilities
include HPHT, dynamic, 20 year design life, costs, etc. Usage includes within stators, pumps,

28
Section 2
29
Section 4.3.2
30
Sections 3.4.3 and 3.4.4
31
Section 3.4.5
11
actuators, plugs, FPSO turrets, packers, well-abandonment packing seals, and as swivels,
dynamic seals and gaskets.
3.3 DESIGN ASPECTS FOR OTHER COMPONENTS
Hoses: a specific point is that the inner lining elastomer (the “liner”) and the outer cover
material are exposed to two very different environments – production fluid and sea water
respectively. Material selection must reflect this26,32, especially regarding fluid compatibility,
but also involving material strength and crack-resistance for the cover, which might be subject
to impacts during service.
For deluge sleeve valve diaphragms, fatigue considerations must be included.33

32
Sections 3.4.3, 3.4.4, 3.4.5, and 4
33
Section 7.3
12
4 SPECIFICATION
This sections considers the factors that specification needs to address in order to meet the
functional life and design life requirements, so includes the following:
• Operating factors that should be considered
• Requirements for the specification of materials
• The use of application specific data sheets
• Storage requirements of elastomeric components
Clearly these relate to the operating conditions, and so this section also includes consideration
of the following:
• Composition of fluids
• Temperatures and pressures
• Short-term fluctuations outside the above temperature and pressure conditions
• Static and dynamic loads
• Regularity of shut downs/decompression cycles
• Temperature changes during shut-down
Supplier descriptions may be generic, notated (a) by the rubber-type or (b) by the type that is
present in greatest amount. Due to (b), it may therefore be necessary to specify or require a
more detailed composition description, particularly for critical applications and/or when no
qualification is to be carried out.
To ensure that all relevant information is included, an application data sheet can be used such as
the example given in Table 3 for elastomeric seals.
In certain cases, specifications might be applied to an assembled component containing

elastomeric units, e.g. a valve containing seals within it. Here, it is also advisable for the
component supplier to inform the end-user fully on the location of such seals etc, and if
requested provide evidence that these elastomers individually meet the specifications.
An important element of the specification process addresses the question of the time of storage
(shelf life) and any associated conditions met by the manufactured elastomeric component
before use. Once conditions and shelf life are established, and appropriate components have
been purchased and stored for use within a prescribed period, traceability then needs to be
addressed as a priority; the similar physical appearance of different types of cured elastomer
possessing quite different behavioural characteristics when exposed to fluids makes absolute
identification to be of prime importance.
Regarding storage, the supplier should specify

(i) limits for temperature (upper and lower), and for humidity for wet climates
(ii) the extent of cleanliness required
(iii) that sunlight, ozone exposure (e.g. arcing from electric motors) & uv light should be
avoided
(iv) that no undue weights or other extraneous forces should be applied to the stored
elastomer, thus causing unwanted “set” or other deformation
Where possible, conditions (ii) and (iii) will be helped by storing inside sealed black polythene
bags.
13
It is usual for the supplier to set the conditions for the end-user’s storage and shelf life
procedures regarding the elastomeric component provided. It is strongly advisable that the end-
user applies procedures which adhere to the supplier’s recommendations, and employs a
realistic process of traceability for the components during procurement and storage.
Table 3 Typical application data sheet for seals
ELASTOMERIC SEAL APPLICATION DATA SHEET

Equipment
Type _____________________
Model _____________________
Service Static Reciprocating Oscillating Other _____________________
Usage Continuous Intermittent Other _____________________
Speed/frequency _____________________
Installation details
Groove length _____________________ depth _____________________
in piston in bore
Shaft/piston OD _____________________ Material _____________________

Coating _____________________ Hardness _____________________
Surface finish _____________________
Bore/housing ID _____________________ Material _____________________

Coating _____________________ Hardness _____________________
Surface finish _____________________
Operating conditions
Temperature
Design Maximum ____________ Minimum ____________
Normal operational Maximum ____________ Minimum ____________
Fluctuating Temperature/Duration ____________ Temperature/Duration ____________
Shut down Maximum ____________ Minimum ____________
Pressure
Design Maximum ____________ Minimum ____________
Normal operational Maximum ____________ Minimum ____________
Fluctuating Pressure/Duration ____________ Pressure/Duration ____________
Shut down Regularity ____________
Fluids
Production liquids Hydrocarbons
Aromatics
Water
Production gases CO2 ____________ H2S ____________ Other ____________

Injection fluids Inhibitors _____________________
Completion fluids _____________________
Acids _____________________
Alcohols _____________________
Duration
Storage time _____________________
Installation time _____________________
Operational life _____________________
14
Many organisations have established their own written procedures covering storage/shelf life
aspects. More formally, Standards exist34 which should be included when developing specific
procedures.
For elastomeric component suppliers, more stringent storage/shelf life procedures apply for their
uncured rubber compounds prior to moulding and curing into components.
Subsequent feedback from the end-user to the supplier on the efficiency of their component’s
performance during service can help the specification of future operations where conditions are
similar, and can reassure the supplier on the quality of his material selection procedures.
For hoses, Standard API 14K covers the parameters against which data should be exchanged
when purchasing bonded flexible hose. This document contains a cross-check for the query
sheets that the end-users might use.
34
BS 3574 (now also numbered BSISO 2230) “Storage conditions and shelf life of vulcanised rubber products”. BS
3F68 “Controlled storage of vulcanised rubbers for use in aerospace applications”; conditions apply generally for
elastomers.
15
16
5 QUALIFICATION
This section considers qualification of materials and/or components in terms of:
• When qualification is required
• How qualification may be carried out and what standards are applicable
• Application of existing knowledge and experience
• Use of modelling and simulation
Qualification is required when:

• Compatibility of fluids is unknown
• Operating conditions are more severe than previous operational experience
• New materials are being introduced
• Always for critical situations e.g.
- when intervention is difficult e.g. downhole,
- under severe conditions e.g. HPHT, H2S
This can be conducted by physical testing, mechanical testing and service-specific exposure or
fatigue testing, supported sometimes by simulation using numerical methods such as finite
element analysis (FEA). A review and definition stage is required for any new field or
operation, particularly if conditions exceed current experience: for example, higher
temperatures, pressures, H2S levels. It is important to understand underlying principles behind
operations, designs, and assess them in terms of conditions expected.
To make some prediction of long term performance, mechanical, chemical and fracture aspects
should be assessed beforehand with accelerated testing. Standards apply in some cases
(NORSOK M-710, API 17K, NACE)35: these are discussed in section 8.1 of the Review.
NORSOK M-710 is relevant in qualifying sealing materials for chemical ageing and explosive
decompression resistance. API 17K is concerned with bonded hose. Various NACE standards
apply for the characterisation of elastomer ageing and explosive decompression resistance.
Although general principles of accelerated ageing should be applied wherever possible, specific
knowledge should be employed if appropriate. Examples are:
• Previous history from a similar well
• Behaviour of particular elastomers36 in specific fluids
- FKM in methanol, giving physical weakening; some (not all37) swell excessively
thus. However, most applications use methanol/water mixtures for treatments - not
100% methanol - with significantly reduced associated swelling2
- FKM in amine or amide-based corrosion inhibitors31 in either aqueous or
hydrocarbon solutions. FKMs again vary greatly in their resistance to highly alkaline
(high pH, high amine no.) solutions. Must check with supplier if unsure.
- HNBRs and NBRs in amine or amide-based corrosion inhibitors31 in aqueous
solutions; absorption/deterioration increase as above.
Material modelling and simulation of seals and other components is possible by FEA for well-
understood situations, e.g. fluid permeation, providing reliable input data are available for the
actual gases/material/conditions involved.

35
Section 8
36
See section 3.4.3 for details of the acronyms for these elastomers
37
Section 4.2.4
17
18
6 QUALITY CONTROL/QUALITY ASSURANCE DURING

MANUFACTURE
This section considers quality control and quality assurance during manufacture including:
• Procedures and data for mixing and moulding
• Appropriate physical testing for materials bonds
• Factory acceptance of the finished component
Compound mixing and moulding QC are nowadays assisted by high technology displays in the
factory which tell operatives when to perform the various stages of mixing. Hence procedures
should be in place, and suitably recorded, which minimise batch-to-batch variability for a
specific recipe. With any manufacturing process, identification of individual parts is essential;
for rubber compounds, as they are invariably black, whatever the base rubber type and recipe
details, accurate labelling, etc of batches and products becomes even more essential.
In seeking methods of detecting flaws in the finished products prior to shipping and service,
non-destructive (NDE) techniques are not well developed for elastomers, due to their inherent
nature. Therefore, for quality assurance it is necessary to rely on visual inspection and
appropriate mechanical test data obtained by component testing of a selection of the final
product. For the particular case of adhesion-bonded interfaces - e.g. rubber-rubber bonds and
rubber-metal bonds in, for instance, the end-fittings of a hose – these cannot be seen after
manufacture to be inspected; the reliability of the bonding system is part of the overall
assessment when the hose as a whole is pressure tested. But experience has led to procedures of
good-quality surface preparation, adhesive application and assembly techniques that are
invariably successful. The essential point is that these procedures are followed; therefore, a
high quality ongoing QC procedure is very important.
Factory acceptance tests must be agreed and established. Where appropriate, some high
pressure fluid testing should be applied if considered necessary through lack of other data.
19
20
7 INSTALLATION
This section considers the important aspects of installation to be considered for:

• Seals in terms of surface finish, lubrication, identification and sensitivity to subsequent
operations
• Hoses and larger items in terms of handling and positioning
Correct installation is particularly important for seals. Problems to be avoided include:

• The compliance of seals generally allows them to conform to undulations in the housing
surfaces. However, scratches, caused by grit or sharp objects, will provide a potential
leakage path, as the seal material may not be able to conform to a sharp-sided “trench”. It is
vital therefore that housing surfaces should be protected from such damage, and inspected
accordingly before seal fitment. Conditions during fitment must preclude the ingress of grit.
• The high friction between an elastomer and a polished metal surface can lead to twisting of
a seal during installation, especially over any rim or the like. This is generally avoided by
use of a lubricant. The lubricant must be chosen to be compatible with the seal material,
and to avoid contamination. Soapy water is frequently adequate.
• As seal composition, and even exact size, are not evident from visual inspection, it is
essential that all seals be clearly marked and/or packaged so that the correct seal for an
operation is installed in the housing.
• No high temperature assembly operations, e.g. welding, should take place in the vicinity of
the seals before or after installation.
Analogous comments apply to the installation of other components. For large items such as
hoses, mechanical means will be used to handle the weights involved. The equipment involved
will be powerful; attention is required to avoid using this power to force the component into
place without having ensured the correct alignment of component and docking location. For
hoses, comments in UKOOA document should be heeded.38
38
UKOOA Flexible Hose Management Guidelines document, issued by the UK Offshore Operators Association, No. 1
January 2003 (co-sponsored by the Institute of Petroleum, and the Health and Safety Executive).
21
22
8 OPERATION AND MONITORING/INSPECTION

This section considers operation and monitoring /inspection in terms of
• Limited accessibility of components and techniques that can be used for
monitoring/inspection
• Maintaining records of operational conditions for comparison with design specifications
There is a general difficulty of inspecting components in oilfield operations. Seals are usually
inaccessible for inspection, so that the monitoring of pressure behaviour in various regions of
the system is necessary to check that these components are functioning properly. For hoses
above sea level, external inspection can be possible, to check the relatively-unlikely occurrence
of whether bulges or cracks have formed (the use of CCTV could be helpful here); for subsea
oil-production line situations (with flexible pipes), on occasions divers with heat seeking
devices are used, or remote control systems. These infra-red (IR) detectors can assess if hot oil,
etc, has penetrated the hose wall construction to approach the outer cover
If the oil-flow is filtered, it can sometimes lead to the detection of a problem at an early stage, as
shown in the case study herewith.
Case study
During a hose operation, a piece of elastomer was filtered out, and identified by a
laboratory as being part of a hose liner. The cost of sending divers down to
inspect with IR detectors was thus justified; on doing this, failure was detected for
the 16th and last hose in the string. On subsequently removing this for fracture
analysis, the laboratory discovered complete breakdown throughout the hose liner
- a major leak in the short term would have been highly likely.
For seals, leakage itself is usually the next sign sign of failure following indications in pressure
recordings; a possible means to avoid this is to employ planned changeout and inspection
procedures, replacing any questionable seals with new ones.
A full record should be kept of operating conditions – e.g. do they vary from original design
specifications etc? – and, if appropriate, these should be compared with any failures. As an
example, more decompression cycles than specified might have occurred, or the contacting
fluids were to be different from those expected. Prior to failure, an educated comparison of any
such changes in conditions from those specified should be made to see if a changeout should be
carried out.
Once again, for hoses, comments in UKOOA document should be heeded.39
39
23
24
9 FAILURE ANALYSIS
This section considers:
• The main deterioration mechanisms that may lead to failure in seals
• Specific aspects of elastomers that should be considered in a root cause analysis
The main deterioration mechanisms that may lead to failure are:

• Seal extrusion
• Explosive decompression
• Chemical ageing
Seals are widely used offshore. They do not often fail. However, if they do so, the
consequences can be significant. In such a case, to help prevent further occurrences of the same
type of failure, if the seal is subsequently retrievable, with experience it is usually possible to
identify the cause. The obvious must always be considered first; (i) appearance – what can be
learned? (ii) if a seal has ruptured under HP service conditions, but there is no gas present, the
reason cannot be explosive (rapid gas) decompression (ED) - as already seen, the mechanism
for this failure type involves the earlier absorption of gas. Extrusion damage would be
suspected for this situation – does the seal now possess a lip, perhaps of a “chewed” appearance,
to support this view? Figure 5 (left) shows an oilfield service example of this, which
culminated in a rupture at the corner between housing groove and extrusion gap.
Figure 5 Left: severely extrusion-damaged O-ring. Right: section of seal showing

permanent set, severe fracturing due to explosive decompression, and material loss
due to extrusion and tear
When ED does occur, it can show up in different ways, involving blisters or splits. Blisters can
be more evident - see example in the Review part40 - but splits (single or multiple) are also
common – see Figure 5 (right). Clearly the single long split there will allow leakage.
It should be stressed that, with correct design of material, seal and housing, ED damage and
other forms of damage can be resisted for many oilfield conditions to a high degree. Minor ED
damage might not lead to leakage - Standards such as Norsok M-710 seek to guide on this.
Papers exist giving information and guidance on seal failures and their avoidance41.

40
Section 4.4
41
see Bibliography – two Guideline papers, one by an end-user, the other by a supplier.
25
The chemical ageing of oilfield sealing elastomers42 is not always obvious. Many materials
stiffen by forming additional crosslinks: this is undesirable for seals and can result in a high
level of set – the new chemical crosslinks make permanent the deformed shape of the elastomer
(Figure 6, which also shows examples of other forms of chemical deterioration, produced after
severe ageing conditions).
Example of specific failure with some FKM elastomers

It has been found that including one particular filler-powder type in an FKM seal
material recipe has led to excessive swelling in sea or completion water; it is the powder
that swells. The result was a break-up of the material, apparent on the seal surface as an
erosion product. Changing the filler type resolved the problem.
Clockwise from top right: HNBR O-ring with high level of permanent
set after high temperature ageing in hydrogen sulphide; cracks in FKM
O-ring after exposure at elevated temperature to formate brine;
fluoroelastomer surface after extended contact with an aggressive
oilfield biocide formulation; surface fracturing of HNBR due to
embrittlement in contact with a treatment chemical.
Figure 6 Examples of chemically aged elastomers

.
For hoses, increased stiffening could affect bending characteristics to render them out of
specification. However, it is more likely that the hose stiffness is dominated by the reinforcing
wires; hence, in the event of a failure, ageing has perhaps causing the liner to deteriorate and
split, or the rubber-to-metal adhesion at the end-fitting interface to deteriorate. It could then be
possible to perform testing on the liner material to assess whether the extent of ageing received
is generally as would be expected from the design life at the specified service conditions.
9.1 ROOT CAUSE ANALYSIS
If a failure incident occurs, root cause analysis (RCA) can be used to identify the most basic
cause. If this cause is within management control, then steps can be taken to control it. If the
cause is design, then a re-design may be the only option. RCA will involve a sequence of
42
Sections 4.2, 4.3 and Appendix 4
26
collecting data, charting events and causal factors, identifying the critical or direct causes, and
the root causes. Barriers to avoid unwanted outcomes may also need to be reviewed. A variety
of techniques is available for RCA, detailed description of which is beyond the scope of this
document. A discussion of the specific aspects that may need to be considered as part of an
RCA of an incident involving elastomeric materials and components used offshore is provided
in Part 243.
For more details, see the indicated section in Part 2 (Review):

43
Section 7.4
27
28
10 AUDIT
This section proves some questions specific to elastomeric components which can be asked as
part of internal auditing procedures and covers
• Management systems
• Technical aspects
10.1 MANAGERIAL
10.1.1 Policy and strategy
What specific policies and strategic objectives are in place for elastomeric components?
Organisations should have in place policies and strategies that deal with the risks associated
with safety, health and environmental concerns – this may be general, but elastomeric
components will be included.
10.1.2 Organisation
10.1.2.1 General
What specialist knowledge and expertise is maintained within the organisation?
What specific skills and competencies are held within the organisation?
Are roles and responsibilities defined?
How is communication with all relevant parties ensured?
How is the integrity management system organised to address elastomer integrity issues?
10.1.2.2 Planning and implementation
Within a project, how are multiple suppliers managed?
What information is used as the basis for specifying elastomeric components?
What inspection and monitoring is carried out and which data are recorded?
How are these data reviewed and what actions may result?
What steps are taken to account for changes in operation conditions that fall outside
specification?
10.2 TECHNICAL
10.2.1 Factors
10.2.1.1 Design and selection
What basis for design or design codes are used?
What procedures are used to select an elastomer solution? (i.e. other solutions considered)?
How do the operating conditions influence design/selection procedures or how are operating
conditions taken into account?
Under what circumstances is development work carried out and why?
What factors of safety are included?
If high pressure gas, what steps are taken to avoid ED failure?
What considerations are given to the compatibility of the elastomer with fluids in contact?
29
What field experience with similar components can be used to guide design and selection?
10.2.1.2 Seals
If high pressure fluids, what consideration is given to avoidance of extrusion damage?
10.2.1.3 Specification
What precautions are taken to ensure the correct elastomer has been specified ?
What information is given to suppliers?
What is done to ensure that the specifications will meet operational requirements?
How is operational information determined for the specification?
For low temperature service, what is done to ensure that the glass transition temperature of the
elastomer is always below service temperature?
For low temperature service, what is done to ensure that the glass transition temperature of the
elastomer is always below shut-down temperatures?
For low temperature service, what is done to ensure that either the glass transition temperature
of the elastomer is always below blow-down temperatures, or that allowance is made for the
temporary stiffening of the elastomer during these operations?
For high temperature service, what temperature was specified as the service continuous upper
temperature?
10.2.1.4 Qualification
What test methods are considered relevant to the application?

What Standards are used?
10.2.1.5 Quality assurance
What quality assurance arrangements are in place?
Do they include auditing of supplier’s QA system and monitoring of quality control
system/supply product quality.
10.2.1.6 Installation
What precautions are taken to ensure the correct rubber has been supplied and installed?
What procedures are in place to ensure correct installation (position, material, personnel-
competency)?
What precautions are taken to ensure that correct seals are installed – i.e. is there a record of the
seal reference used?
Was the correct hose installed – was it compatible with the specifications?
Was the system installed by competent staff to an approved procedure?
10.2.1.7 Operation and monitoring
How do you account for pressure/temperature losses during operation e.g. on shut-down?
What actions are taken if operating conditions are different from the original specification?
What inspection regime is in place?
What are your conditions for component removal and replacement?
What actions are taken in the event of elastomeric component failure?
- Does this include identification of direct and underlying causes?

- How are lessons learnt from incidents fed back to prevent recurrence and facilitate
continuous improvement?
30
10.2.1.8 Review of system
What arrangements are in place to review the elastomer integrity assurance activities in order to
identify weaknesses and areas that need to be improved?
- How are improvements implemented?
31
32
11 BIBLIOGRAPHY FOR GUIDELINES
Design
“Seals and Sealing Handbook”, publ. DuPont de Nemours International S.A., Switzerland
(1985).
UKOOA Flexible Hose Management Guidelines document, issued by the UK Offshore
Operators Association, No. 1 January 2003 (co-sponsored by the Institute of Petroleum, and the
Health and Safety Executive).
“Recommended Practice RP-F106: Factory Applied External Pipeline Coatings for Corrosion
Control” - see:
<http://exchange.dnv.com/BxWmWeb/TaskManager.asp?WCI=MenuArea&WCE=PMA_6_81
2!816!818&uid=ID20041021710580657197>
Guideline papers
S Groves, “Project Guidelines for Selecting Seals for High Pressure Gas Duty and other Oilfield
Service”, Proceedings “17th International Conference on Fluid Sealing”, York, UK, publ. BHR
Group, Cranfield, Beds, UK, (8 – 10 April 2003).
N Page and P Embury, “Elastomeric Seal Failure Analysis and Diagnosis”, Energy Rubber
33
34
GAS PRODUCTION
Part 2 - REVIEW
1 INTRODUCTION .................................................................................................1
2 DESIGN CONSIDERATIONS ..............................................................................3
2.1 SEALS ................................................................................................................3
2.2 HOSES ...............................................................................................................4
2.3 OTHERS..............................................................................................................4
3 POLYMERIC MATERIALS ..................................................................................5
3.1 THE GENERAL PLACE OF ELASTOMERS (RUBBERS) WITHIN THE POLYMER CLASS ......5
3.2 POLYMER BASICS ................................................................................................5
3.3 POLYMER THERMAL TRANSITIONS - TG AND TM .......................................................6
3.4 ELASTOMERS ......................................................................................................7
3.5 THERMOPLASTICS .............................................................................................14
3.6 THERMOSETS ....................................................................................................15
4 ELASTOMER TYPES TO RESIST FLUID EFFECTS........................................17
4.1 INTRODUCTION TO FLUID COMPATIBILITY .............................................................17
4.2 LIQUID INTERACTIONS WITH ELASTOMERS ...........................................................18
4.3 GAS INTERACTIONS WITH ELASTOMERS ...............................................................26
4.4 EXPLOSIVE DECOMPRESSION .............................................................................30
4.5 LIFE PREDICTION TECHNIQUE .............................................................................32
5 QA/QC ...............................................................................................................35
6 SEAL FAILURE.................................................................................................37
6.1 SEAL LEAKAGE MODES.......................................................................................37
6.2 DESIGN, MANUFACTURING AND OPERATIONAL FACTORS IN LEAKAGE ....................37
7 FAILURES FOR OTHER COMPONENTS .........................................................41
7.1 HOSE FAILURE AND LEAKAGE .............................................................................41
7.2 FLEXIBLE JOINTS...............................................................................................42
7.3 DELUGE SLEEVE VALVE DIAPHRAGMS .................................................................42
7.4 ROOT CAUSE ANALYSIS FOR COMPONENT- FAILURE GENERALLY ...........................43
8 INDUSTRY STANDARDS .................................................................................47
8.1 NORSOK M-710 REV 2 ....................................................................................47
8.2 API 17K ...........................................................................................................50
8.3 NACE ..............................................................................................................51
8.4 CORPORATE .....................................................................................................51
9 BIBLIOGRAPHY FOR REVIEW ........................................................................53
i
ii
GAS PRODUCTION
Part 2 - REVIEW
Objective: To provide information relating to the use of elastomers on offshore
installations in some detail, sufficient to lead to the generation of the guidelines and to
act as technical background where required when implementing the guidelines.
1 INTRODUCTION
The foregoing guidelines arise from conclusions made during the review stage of this work,
which is now described. The review is made by applying appropriate scientific principles to all
factors identified as relevant to the functioning of elastomer (rubber) components employed in
offshore oil & gas production. This review was based on existing public domain data and
MERL data, knowledge and experience, and includes some assessment of relevant national and
international Standards. Greater detail is given in this part of the overall work, which can be
consulted if the guideline is considered insufficiently informative for a particular item. For
some aspects, even greater detail is provided in four appendices.
Factors assessed
Factors assessed at various locations throughout the review include:

• Functional mechanisms of elastomeric components in offshore O & G applications.
• Material selection for specific applications, operating conditions and fluid compatibility.
• Seal applications and design (could include usage in stators, pumps, actuators, plugs, FPSO
turrets and swivels, dynamic seals and gaskets).
• Design aspects for other components.
• Quality control during manufacture.
• Qualification testing for life assurance.
• Material time-dependent properties (stress relaxation, fluid diffusion and permeation),
fatigue where applicable, and material modelling and simulation of seals and another
component.
• Seal and hose failure analysis including identification of direct and underlying causes (e.g.,
chemical ageing, explosive decompression, extrusion, end-fitting disbondment).
2 DESIGN CONSIDERATIONS
2.1 SEALS
In (a), the seal operates by expanding in the direction perpendicular to the applied pressure. In
(b), sealing is achieved by energisation causing outward flexure resulting from the applied
pressure.
Figure 1 Sealing mechanisms for two seal geometries
Solid seals are usually circular in cross section (O-rings), but may be of any other regular
sectional shape. The principal mode of operation of solid seals is “tight-gap-filling”, where the
stress in the seal due to its initial compression during assembly provides the main force to
oppose leakage. The pressure of the fluid to be sealed may then further assist sealing leading to
an increased compression of the seal (see Figure 1(a)).
“Profiled seals”, such as lip seals, are relatively loose-fitting in the sealing gap. They usually
require some initial interference so that they start to seal immediately fluid is introduced, but
then the main sealing action is provided automatically by the pressure of the total fluid being
sealed (Figure 1(b)). Usually the seal is designed so that the pressure in the fluid opens the seal
out – forcing it to be a tight fit against the two surfaces to be sealed – a process often known as
energisation.
Standard O-ring housing geometries and dimensions are provided in BS 1806 and equivalent
Standards. Tolerances are important to ensure sufficient initial interference to establish sealing,
and surface finishes which do not compromise sealing. However, at high pressures, these may
need some adjustment, for instance, to help resist damage due to “explosive decompression”
(see section 4.4).
As pressures increase, stiffer materials may need to be incorporated in order to prevent the
relatively soft elastomeric seal from deforming into the gap between the two surfaces to be
sealed – known as the extrusion gap. One solution is to incorporate a fabric reinforcement
bonded to the elastomer as backing; installation may be a problem in this case, as stretching the
material to pass over the housing groove rim will be difficult – the housing may need to have no
outer rim (high pressure side), or a removable rim here. Another common procedure is to use a
stiff thermoplastic as a back-up anti-extrusion ring, or one thermoplastic as a secondary ring
with a very stiff thermoplastic or thermoset as the (third) back-up ring. This procedure can
apply for many geometries; O-rings can operate against a plane-faced back-up ring, whilst
chevron seals or lip seals may require the secondary and/or back-up rings to be profiled
accordingly.
Normal packers – the seals forming the foundation of wells - are a simple form of seal, where an
elastomeric or other flexible material is ‘packed’ into a cavity. The energisation is provided
mechanically by compressing the seal. In many cases the energisation can be ‘topped-up’ to
prevent leakage after periods of use. Alternatively in PBR systems (polished bore receptacles),
which have replaced packers in some of the deepest (HP) wells, seal stacks are used instead of
packers. In these, the sequence - primary seal, secondary seal and back-up seal - is repeated
several times. This approach is based on the concept that, if the first set of seals fails, the
following sets in the sequence will continue the overall sealing (but see later comment under
Design etc factors in leakage44 ).
2.2 HOSES
End fitting Hose
Centre line
Figure 2 Half axial-section of short length of hose at join with end-fitting (courtesy
Dunlop Oil & Marine)
See UKOOA document45. A hose comprises elastomeric cylindrical layers assembled

concentrically successively outside each other, with ever-increasing diameters (schematically
shown in Guidelines Figure 2). The rubbers/elastomers are of types such that their oil resistance
decreases from liner (i.e. inner lining) out to cover; the reason for this is that, as a result, impact
resistance and toughness increase in this outward direction. (Actual material types are discussed
later.) At intervals, layers of helically-spiralled reinforcing wires, cables, fabrics are inserted, to
give the hose strength. Bonded-on steel end-fittings (nipples) – see Figure 2 on previous page
allow hoses to be joined axially; the quality of end-fitting attachment is a major issue.
Deterioration modes are discussed later46.
2.3 OTHERS
Other components employed in upstream offshore duties include flexible joints and deluge
sleeve valve diaphragms. The former type combines the load carrying characteristics of bonded
laminated structures of repeated elastomer-layer/steel-layer combinations – with those of short
hoses; hydrocarbon contacts the inner elastomer layer surface and sea water the outer one.
Deluge sleeves are exposed to sea water only, and probably will never be used for the fire
fighting role they are designed for; however, during development, in their original form they
have been known initially to exhibit an unusual failure – see section 7.3.
44
Review, section 6.2.
45
46
Review, section 7.1.
4
3 POLYMERIC MATERIALS
3.1 THE GENERAL PLACE OF ELASTOMERS (RUBBERS) WITHIN THE

POLYMER CLASS
Other than natural rubber (NR), its trans isomers (gutta percha and balata) and a few other
materials, all polymers are synthetic and are usually derived from oil-cracking products. As NR
is oil-swellable, its only usage in oilfield service is for large structural support systems such as
flexelements in tension leg platforms, or in outer hose covers, where the only exposures are to
sea water or air, and the excellent mechanical, abrasion-resistant and/or fatigue properties of NR
can be utilised.
Polymers can be divided into three broad categories: thermoplastics, elastomers (rubbers) and
thermosets. In general terms, thermosets resist deformation whereas elastomers elongate readily
under a small applied stress; thermoplastics exhibit intermediate stress-strain characteristics.
Thermoplastics can be further subdivided into amorphous and semi-crystalline types (see
below). The vast majority of thermoplastics will soften when heated and can thus be heat-
processed into complex shapes. Fully-formed elastomers and thermosets on the other hand are
characterised by the presence of permanent crosslinks within the polymer matrix; these tie
individual “molecular chains” (see below) into a three-dimensional network which will not
soften when heated (thermosets), or is capable of tolerating large reversible extensions
(elastomers)2. However, both can be moulded using elevated temperature and pressure before
the crosslinks have been formed.
A discussion in some detail of basic polymer properties follows. Although comment is focused
on properties/characteristics of elastomers, some comment will be made at intervals on the other
two polymer classes. These can be used in special cases in areas where elastomers might
dominate, e.g. thermoplastic PTFE is used for sealing where chemical resistance at high
temperatures is paramount, or in areas where their high stiffness means that they can be used in
conjunction with an elastomeric component in its function, e.g. as back-up rings supporting
elastomeric seals.
3.2 P
OLYMER BASICS
Polymers consist of long “chain-like” molecules (macromolecules), formed by the

polymerization of a chemical monomer, which are moving continually under the influence of
kinetic energy with various modes of motion. During synthesis, each chain is built up by the
sequential addition of monomer molecules – each becoming a “repeat unit” – it’s the chain’s
molecular mass (more commonly molecular weight, MW) being the summation of that for each
repeat unit; the polymer MW is then an average of all the individual chain values. If two or
more chemicals are present as alternative monomers, these can react together (copolymerize)
during polymerization to form “copolymers”, “terpolymers”, “tetrapolymers” etc. The
properties of a polymer depend very much on the composition, structure and interactions of its
repeat units and, to a lesser extent, on the average length of the chains comprising the sample.
For instance, very low MW (i.e. short chain) polymers are often viscous liquids but all high
MW materials are essentially solids – albeit deformable ones. Both the thermal behaviour and
mechanical properties of a polymer are strongly influenced by the disposition of chains within
the sample. If the macromolecules are randomly oriented and entangled, then the material is
termed “amorphous” (e.g., elastomers at room temperature or above; polymer melts). In
contrast, some polymer types are capable of closely-packed self-organization to acquire
crystalline domains with three-dimensional order; these polymers (e.g., polyethylene) are
referred to as “semi-crystalline”, regardless of the actual crystalline content. The remaining

non-crystalline regions are amorphous. The whole internal structural arrangement of the
polymer is termed its “morphology”.
Internal “free volume” exists within amorphous regions giving rise to chain flexibility, if not
restricted by neighbouring crystalline regions. Paradoxically, however, the very root of the
flexible nature of polymers, particularly elastomers, reflecting the existence of the free volume
through which macromolecules can move when stressed, also provides the “Achilles heel” for
attack by external fluid species contacting a polymer (see section 4). If available free volume
were not there, the fluid could not enter the polymer matrix, but the polymer would be rigid - as
essentially applying to many thermosets. After fluid has entered, the free volume is reduced but
not eliminated; subsequently, kinetic movements of chain segments then allow some re
generation of free space (often eventually causing the polymer to swell). Certain polymers are
more suitable than others in resisting specific fluids. For situations requiring chemical
resistance but little flexibility (e.g., for back-up rings), the presence of crystallinity is highly
desirable. In terms of sealing, with flexibility and elasticity required, crystallinity should be
avoided where possible: instead, stable crosslinks tying different molecules together lead to the
desired properties. Hence, elastomers are used. However, semi-crystalline thermoplastics are
sometimes used for seals in cases where their ability to resist chemical attack is the over-riding
factor.
3.3 POLYMER THERMAL TRANSITIONS - TG AND TM
Crystalline
log Modulus (Pa)
Tm
Cross-linked
Tg Amorphous
Temperature °K
Figure 3 Structure/property variation in modulus versus temperature plots for 3

polystyrenes
As depicted in Figure 3, in an amorphous polymer at sufficiently low temperature, all large-

scale chain movement47 is “frozen” and no long range order exists; the polymer is in a glassy
state. With heating (putting energy into the system), a temperature is reached at which
segmental chain motion becomes possible, and the polymer stands on the threshold of a rubbery
47
Vibration about mean positions still occurs.
6
condition. This temperature varies with polymer type and is known as the glass transition
temperature (Tg); the vast majority of polymers possess a Tg. In general, the more flexible a
polymer chain (a function of its chemical structure), the lower its Tg. A polymeric glass is
stiffer by several orders of magnitude than the same material above this transition. During
dynamic motions, there is a high energy absorption range in the vicinity of the Tg (envisaged as
the “internal friction” between local small domains of glassy and rubbery regions). For sealing,
the Tg should normally be well below the operational temperature range, as otherwise the loss of
elasticity associated with the high energy absorption near Tg leads to loss of sealing stresses
the seal will take on a permanent set. (If thermoplastics are used as seals, geometrical and/or
mechanical methods of combating set are employed.)
Turning to another major morphological factor, the ability of a polymer to crystallize is heavily
influenced by the structural symmetry and linearity of its chains - linear symmetric
macromolecules can close-pack to form an ordered lattice - and is enhanced in many instances
by intermolecular forces (e.g., hydrogen bonds, polar and ionic interactions48), or by external
orientation during processing (e.g., extrusion, drawing). Crystallization contributes to material
stiffness, but to a lesser extent than does cooling the polymer to a glass through the Tg. A semi
crystalline polymer displays a Tg when its amorphous region become glassy, and overall
stiffness increases further. It also possesses a melting point (Tm), associated with crystallite
fusion. Tm is critical to mechanical performance because the crystallites are the strength-giving
elements of thermoplastics, literally holding the material together, above Tg and furnishing the
polymer with reasonable mechanical strength between these thermal transitions. In this range,
the interdistribution details of crystalline and amorphous regions lead to the degree of toughness
(crack growth resistance) attained. Above the melting point, all thermoplastics exist in a
disordered (amorphous) state and many can flow easily and are thus melt-processable, as
crystals reform after subsequent cooling. Hence the Tm of a semi-crystalline thermoplastic
governs the limiting temperature for its use as back-up rings, for example.
Figure 3 illustrates typical inter-related modulus effects arising from these transitions, in the
case shown for a non-oilfield polymer. Other polymers will have the same overall shapes but
shifted (perhaps widely) along one or both axes.
3.4 ELASTOMERS
Elastomers (rubbers) are an amorphous class of polymer, characterised by their ability to display
large extensions, which are reversible. These polymers are above their Tg at ambient
temperature but to be useful it is necessary to crosslink them, to prevent flow. This requires
heat, and is performed in conjunction with the moulding process. The introduction of a
relatively few crosslinks49 in effect irreversibly anchors the chains in a three-dimensional
network. As a result, permanent chain slippage is largely prevented during elongation and
essentially all chains return to their original location upon release of the strain, that is, the
materials exhibit elastic behaviour. This elastic nature associated with high deformation renders
them useful for many sealing duties.
In summary, at normal working temperatures and pressures, elastomers are:

• deformable;
• largely resilient and reversibly elastic;
48
Hydrogen bond strengths lie in the 1-10 kcal/mol range while the strength of ionic interactions usually exceeds 10
kcal/mol; contrast this with covalent bonds which have strengths of approximately 50 kcal/mol.
49
By a process known as “vulcanization”.
7
• soft, that is, Young's modulus is low for a solid material, and is a function of strain; the
value lies in the range 1-100 MPa with most practical primary sealing materials having
moduli nearer the bottom of this range;
• able to maintain constant volume on deformation; with a very high bulk modulus, similar
to that of water - they are considered virtually incompressible in the dry state, although
some compaction can be noted at high pressures reached in upstream gaseous applications –
see section 4.3.2. Furthermore, because of the high ratio of bulk modulus to shear modulus,
there is almost no volume change on deformation; the fact that rubber deforms at constant
volume, even for high strain deformations, is often wrongly associated with the fact that
Poisson's ratio for rubber is very nearly 0.5. Strictly, Poisson's ratio should only be defined
at infinitesimal or “classical” strains, and under these conditions the value for rubber is
indeed 0.5; if, however, the usual definition of Poisson's ratio (the ratio of lateral
contraction to longitudinal extension) is applied at finite strains in rubber, then very much
smaller values will result, for instance, “Poisson's ratio” will have a value of about 0.3 at
100% extension;
• able to transmit pressure in a similar way to a fluid, i.e. not only in the direction applied - a
very useful feature in many elastomeric seal designs.
For all rubbers, even within one elastomer type, final properties will depend on the recipe
(formulation) developed to provide the cured rubber with the correct property mix. The major
constituents affecting the performance of a seal elastomer compound, and which can be
controlled at the compounding stage of processing, are:
• Base rubbery polymer
• Cure chemicals
• Fillers
• Antidegradants
• Softeners
Details of elastomer compounding aspects are given in Appendix 1.
3.4.1 Elastomer properties
Table 1 indicates the properties (mechanical and otherwise) commonly quantified and used for
design, QA, specification and QC purposes. The Standard numbers for procedures set by a
number of Standards organisations for conducting testing for these properties are also included.
Table 1 Approximately equivalent Standard test methods

Property ISO ASTM BSI DIN
Nomenclature 1629 D1418
Hardness (Durometer) 48 D1415 903/A26 53505
Hardness (2) D224050
Tensile Properties 37 D412 903/A2 53519
Compression Set 815 D395 903/A6 53517
Stress Relaxation 3384 D1390 903/A42
Low Temp Flexibility
Gehman 1432 D1053 903/A13 53545
TR10 Test 2921 D1329
Brittleness point D2137
Heat Ageing 188 D573 903/A19
Volume Change/Fluids 1817 D471 903/A16 53521
Density 2781 D297 903/A1 53479
Tear Resistance 34 D624 903/A3 53507
3.4.2 Stress relaxation
If an elastomer is held at constant deformation at constant temperature, the stress required to do

this reduces with time: this phenomenon is stress relaxation which can be expressed simply as
loss in stress divided by initial stress (often expressed as a percentage of the initial stress). The
rate of stress relaxation will be the above quantity divided by time, or some function of time.
Physical stress relaxation proportionates to log time. Any chemical changes to the elastomer
(e.g. oxidation-induced) can also change relaxation rate, but now proportional to linear time.
Taking seal service as an example of the importance of this property, if the sealing stress relaxes
to zero, then its ability to seal may have finished (although in static systems any adhesion
between seal and metal housing induced earlier whilst stressed can allow sealing to continue
even then). Stress relaxation is closely related to creep - that is the increase in deformation
which occurs when a material is held at constant stress. Another somewhat similar term,
“extrusion”, is also used in oilfield sealing, pipeline, and other circles – here not as a
manufacturing term, but applying when high pressure fluid forces elastomer into gaps between
adjacent rigid surfaces.
The reversal of stress relaxation due to liquid swelling – a feature probably desirable if in a
small degree but unwanted if to a large extent - is discussed in outline in section 4.2.3 and
Appendix 2, which also outlines the major effects temperature changes can have on stress
relaxation.
3.4.3 Elastomer types
Coding of Elastomeric Materials

Nomenclature for elastomers (rubbers) in the rubber industry generally follows Standards
ASTM D1418 and ISO 1629. The last letter denotes the chemical composition of the polymer
chain as follows:-
M - Rubbers having a saturated chain of the polymethylene type
O - Rubbers having oxygen in the polymer chain
50
Includes Shore A ratings, accepted in ASTM D1415 as being equivalent to the International Rubber Hardness
Degrees (IRHD) system used therein.
R - Rubbers having an unsaturated carbon chain, for example, natural rubber and
synthetic rubbers derived at least partly from diolefins
Q - Rubbers having silicon and oxygen in the polymer chain
T - Rubbers having a sulphur in the polymer chain
U - Rubbers having carbon, oxygen and nitrogen in the polymer chain
Z - Rubbers having phosphorus and nitrogen in the polymer chain
This nomenclature is adequate for general purpose rubbers but insufficiently descriptive for
certain fluoropolymers etc. Hence the intent herein is to use the ASTM D1418 approach as a
basis, but provide more details for some rubbers. Use of brackets after the nomenclature can
enable extra detail to be given. A full listing of the nomenclature for different elastomer types is
given in Table 2; some elastomers are homopolymers, some copolymers, and others ter- or
tetrapolymers. In a blend (a well-dispersed mixture of two or more rubbers previously
separately polymerised), the major component polymer should appear first followed by a dash
(-) and the minor component, or, for 50/50 blends, the polymers listed alphabetically and
separated by a stroke (/), as illustrated in Table 2.
10
Table 2 Coding of elastomeric materials

Designation Elastomer type
ACM Acrylic, polyacrylic, ethylene acrylic
AU Poly(ester)urethane
BR(cis,med,trans, 1,2) Polybutadiene (high cis, medium cis, high trans, high vinyl content)
CO Epichlorohydrin homopolymer
CM Chlorinated polyethylene
CR Polychloroprene
CSM Chlorosulphonated polyethylene
ECO Epichlorohydrin copolymer and ethylene oxide homopolymer
EPDM Ethylene-propylene-diene terpolymer
EPM Ethylene-propylene-copolymer
EU Poly(ether)urethane
FCM Fluoro-methyl
FCM (TFEP) Tetrafluoroethylene-propylene copolymer
FFKM Perfluoroelastomer
FKM-2 Fluorocarbon copolymer
FKM-3 Fluorocarbon terpolymer
FKM-4 Fluorocarbon tetrapolymer (cure-site tetramonomer)
FMQ Fluorosilicone (trifluoropropylmethly)
FPM Fluorinated plastic-like polymers
FPM (ETFE) Ethylene-tetrafluoroethylene copolymer
FPM (FEP) Fluorinated ethylene-propylene copolymer
FPM (PFA) Perfluoro-alkoxy
FMP (PTFE) Polytetrafluoroethylene
FZ Phosphonitrilic (fluorinated)
GPO Polypropylene oxide
HNBR Hydrogenated nitrile
IIR Isobutylene-isoprene (“Butyl”)
IR (cis, trans or 1,2) Polyisoprene (synthetic-high cis, high trans or high vinyl)
NBR (H) Butadiene-acrylonitrile (“Nitrile”) (>36%ACN)
NBR (M) Butadiene-acrylonitrile (25-36%ACN)
NBR (L) Butadiene-acrylonitrile (<25%ACN)
XNBR Carboxylated nitrile
NBR-CR Nitrile-polychloroprene blend (nitrile the major component)
NBR/PVC Nitrile-polyvinylchloride blend (50/50)
NR Natural rubber (a cispolyisoprene)
PN Polynorbornene
OT, EOT Polysulphide copolymers
SBR Styrene-butadiene
MQ Silicone (dimethyl)
PMQ Silicone (methylphenyl)
PVMQ Silicone (methylphenylvinyl)
VMQ Silicone (methylvinyl)
YBPO Polyether-polyester thermoplastic rubber
XXX Unspecified polymer
A selection of elastomer types used in offshore sealing applications is provided in Table 3. All
except EPDM are classed as oil-resistant, in practice to varying degrees. The wide range of
elastomers has arisen because different materials display different degrees of chemical and
thermal resistance. For example, EPDM is used for sealing water-based liquids when there is
no chance of oil contact. Other common names of elastomers used offshore (including some
trade names) include NBR (nitrile), HNBR (hydrogenated nitrile), FKM (Viton, Fluorel,
Tecnoflon), FEPM (Aflas, Fluoraz) and FFKM (Kalrez, Chemraz).
11
Table 3 Selected elastomers used in sealing applications
Elastomer Type, comments
EPDM ethylene-propylene-diene monomer, low viscosity, 50-53% ethylene

LOW51 NBR nitrile, 22% acrylonitrile content, cold polymerised
HIGH51 NBR nitrile, 38% acrylonitrile content, cold polymerised
HNBR hydrogenated nitrile, 38% acrylonitrile content, cold polymerised, essentially fully saturated
ECO copolymer of epichlorhydrin and ethylene oxide
FKM I52 copolymer of hexafluoropropylene and vinylidene fluoride; ca 66% fluorine content
FKM II52 tetrapolymer of vinylidene fluoride, tetrafluoroethylene, perfluoromethylvinylether
and a cure site monomer; ca 67% fluorine53 content
FKM III52 speciality fluoroelastomer, high fluorine content
FFKM terpolymer of tetrafluoroethylene, perfluoromethylvinylether and a cure site monomer; fully
fluorinated elastomer
FEPM54 copolymer of tetrafluoroethylene and propylene - sometimes coded TFE/P
It is worth emphasising here that, for particular FKMs, the trademark “Viton” does not refer
to a single elastomer - there are many grades of Viton commercially available, each with
different property levels, and each aimed at different applications. If unspecified, it is likely that
the copolymer (FKM I, the least expensive) elastomer of this group will be used. However,
FKM I (say, Viton A) is deficient in certain properties (e.g., methanol resistance) which is not
the case with some other Viton grades, for example GF (which is an FKM III). The table below
emphases this point, and indicates the wide variation of glass transition temperature (which
influences low temperature performance) associated with the different FKMs from the one
supplier. An analogous argument also applies to the products of other polymer manufacturers
(Tecnoflons from Solvay Solexis, for example), but the above is probably the major example.
Table 4 Examples of the many “Vitons” that exist and some considerably different
characteristics
Viton type Weight % fluorine Tg (°C) Methanol swell (%)
A 66 -17 75 – 105
B 68 -14 35 – 45
F 70 -8 5 – 10
High performance
GLT 64 -30 75 – 105
GBL -15 65
GF 70 -8 5 – 10
GFLT 66.5 -24 5 – 10
ETP 67 -11 low
51
LOW and HIGH refer to acrylonitrile (ACN) content
52
I, II and III are MERL, not Standard, designations; these elastomers are more commonly known by extensions of
their trade names Viton, Fluorel, Tecnoflon or Dai-El – e.g. Viton A is an FKM I
53
This elastomer has the fluid resistance of a 69% fluorine polymer (supplier comment)
54
Tradename Aflas
12
3.4.4 Selection criteria
For satisfactory service an elastomeric seal material must have, and retain for its service life:
• Mechanical property levels appropriate to service pressure, temperature and seal design;
important properties include
Young's modulus
Elongation/strain at break
Tear strength
Compression set
Stress relaxation rate.
• Resistance to swelling/shrinking in fluids which contact the seal during service; swelling
will affect all other physical and mechanical properties (usually reducing property levels).
• Resistance to chemical attack by any of the fluids which contact the seal during service; a
seal is often exposed to two different media; one is often air.
• Stability at the extremes of the service temperature range; temperature effects interact with
all of the above factors.
Since the thrust of this document concerns compatibility issues, it is worth repeating that
elastomers typically possess within themselves more free volume than semi-crystalline
thermoplastics. As a consequence, elastomers are more permeable to liquids and gases than
plastics, and can be susceptible to rupture if, when saturated with high pressure gas, rapid
depressurization occurs. Polymers which fail in this way can be so fractured and distorted that
the phenomenon is often termed “explosive decompression” (see section 4.4.4). The blistering
and/or tearing which results can lead to catastrophic seal and hose lining failures. Explosive
decompression fracturing is a major obstacle to be overcome in certain conditions with
elastomer seals, but significant success has been achieved in resisting it in some cases.
As with the fully fluorinated thermoplastics, the perfluoroelastomers55 possess the ultimate
combination of chemical and thermal stability, although their resistance to tearing is notably
lower than other elastomer types (e.g., HNBR). There is great scope at the compounding stage56
to tailor elastomer properties to the application with the result that a huge number of compound
grades are commercially available.
3.4.5 Information provided by seals’ suppliers
Information provided by seals’ suppliers which is backed by data including results from testing
with standard fluids should be correct and reliable for the test conditions cited within reasonable
experimental error. However, care should be taken for seal service at severe conditions (e.g.
high temperatures and/or pressures, where hostile chemicals are present, etc) that the supplier’s
claims do indeed apply under actual service conditions. If any doubt exists, verification
laboratory testing using service-realistic fluids and conditions should be performed by the
supplier or an independent laboratory; if appropriate, acceptable life prediction techniques
should be applied.
55
Perfluoroelastomer (FFKM) tradenames include Kalrez (DuPont) and Chemraz (Greene Tweed).
56
By adjusting filler level and type, crosslinking system, cure conditions etc. (see Appendix 1).
13
3.4.6 Analysis/Identification
Laboratory techniques for analysing elastomers for suitability, type, ingredients, etc, are:
(i) Simple
(a) Liquid absorption
Absorption of standard hydrocarbon liquids
Toluene absorption
Absorption of Heptane/cyclohexane/toluene selected mixtures
Methanol absorption
(b) Thermal
Tg measurements (via DSC or DMTA)
(c) Mechanical
(E.g. hardness; tensile, tear strength). Before installation, to check against
elastomer specification.
Comments
To give a quick identification or comment on suitability. Tests in group (a) can give indicative
information on resistance to swelling of an elastomer against actual production liquids.
Standard liquids from (a), e.g. ASTM fluids #1, #2 or #3, Jet Fuel A, can give useful indications
if previous calibration of their behaviour against a benchmark elastomer compared with the
crude oil in question is known. Toluene exposures gives a quick assessment of resistance to
aromatics. A more convenient approach for hydrocarbon liquids in general is to use
heptane/cyclohexane/toluene selected mixtures which can be tailored two match a crude oil of
interest on two counts – (i) solubility parameters (see section 4.2.1), and (ii) the proportion of
paraffinic to naphthenic to aromatic hydrocarbon present. (This approach57 has been used as the
basis for liquids used in the NORSOK Standards – see section 8.1.)
Tests with methanol are for a special case of liquid exposure, to ensure, when employing
fluoroelastomers, that correct grades are used; see Table 4 for the considerable differences
possible. The thermal test (b) can indicate whether the correct elastomer for a low temperature
service has been obtained, and the mechanical test (c) is self-evident.
(ii) Sophisticated
Chemical analytical tests – FTIR (plus variations), pyrolysis, EDAX (X-ray
microanalysis), NMR, TGA, GC-MS etc
Comment
#ASTM Standard D297 contains detailed information on procedures for analysing elastomer
compounds for ingredient content, and for base-rubber types for most non-fluorinated
elastomers.
3.5 THERMOPLASTICS
Thermoplastics can be fashioned into complex shapes under the influence of heat and pressure,
usually by extrusion or injection moulding, with cooling preserving the molten profile as a
solid. The process is reversible - subsequent melting of a typical thermoplastic allows the
polymer to be recycled. The limit to which a thermoplastic may be heated and still retain viable
property levels depends on the nature of its repeat unit, the smallest structural portion of the
chain, usually chemically very similar to the monomer. The composition of this unit, and the
57
See “Model test ‘oils’ based on solubility parameters for artificial ageing of polymers”, Proc. Conf. Polymer testing
’96, Rapra, Shawbury, Shrewsbury, UK (1996), author R P Campion.
14
extent to which it interacts with neighbouring units on the same chain and the units on
surrounding chains, largely determines the inherent thermal and mechanical properties of the
polymer. For engineering thermoplastics, these materials are sufficiently rigid to allow back-up
rings (e.g., PEEK) or even high temperature seals (e.g., PTFE) to be machined out of moulded
units.
High performance thermoplastic development and the resulting polymer types are discussed in
Appendix 3.
3.6 THERMOSETS
The formation of a thermosetting polymer involves a two stage process. In the first, a low MW
prepolymer, which is soluble and fusible, is synthesized. The subsequent conversion of the
prepolymer is typically carried out in a heated mould, during which time extensive crosslinking
occurs to yield an intractable product58. The resulting material, although hard and sometimes
brittle, has excellent dimensional and thermal stability, and creep resistance. Thus typical
thermosetting polymers are infusible with generally good chemical resistance and low
equilibrium water absorption. The extent of crosslinking determines mechanical properties, and
a typical thermoset can be viewed (simplistically) as an extremely rigid elastomer. Chemical
bond rotation accompanying extension changes, the general mechanism by which impact energy
is dissipated in deformable polymeric materials, cannot occur in these polymers having a rigid
three-dimensional molecular architecture; the result is that excess absorbed energy is directed
towards the breaking of bonds. Hence thermosets, unlike elastomers of relatively high crosslink
density, are prone to brittle fracture. Thermosets contain filler to improve mechanical
properties, and the filler type has an influence on chemical resistance. Examples of
thermosetting polymers include phenol-formaldehyde, urea-formaldehyde, melamine-
formaldehyde, vinyl ester and epoxy resins.
Thermosets are used in advanced composite structures, being combined with glass or carbon
fibres in these; oilfield-related pipe duties are now in place. Glass reinforced epoxy is widely
used. Developments are currently well advanced for performing in situ pipe repairs on such
pipes using fresh thermoset with appropriate application techniques and approved procedures.
58
Some thermosets cure at ambient temperature, for example, epoxy-based adhesives.
15
16
4 ELASTOMER TYPES TO RESIST FLUID EFFECTS
4.1 INTRODUCTION TO FLUID COMPATIBILITY
Elastomers are more prone to fluid uptake than thermoplastics; however, the arguments still
apply to the amorphous regions of semi-crystalline thermoplastics, but the effects are usually
smaller due to constraints from surrounding crystalline regions.
Progressive degradation is very dependent on the nature of the fluids contacting a seal and on
the thermal environment. It may also be influenced by pressure. Additionally, gas pressure is a
major factor influencing extent of explosive decompression damage when that applies. The
fundamental processes described below are involved in the failure modes listed in section 6,
some in more than one. An appreciation of these processes aids the understanding of such
failures.
It is important to consider all the details of the local fluid environment of a seal, on the low
pressure side as well as on the fluid side - including possible variations around the periphery due
to fluid stratification. In particular, atmospheric oxygen can diffuse into a seal and contribute to
ageing. It is also important to distinguish physico-chemical effects, such as swelling or
leaching, from purely chemical effects, for example, the aforementioned oxidation.
Chemical reactions most commonly occur if two contacting species interact with each other to
change to the molecular structure of one or both of them. The influence of increasing
temperature is to accelerate chemical reaction rates: hence testing at elevated temperatures is
commonly employed in the laboratory as a means of compressing a multi-year material design
life to a realistic testing period, to enable life prediction calculations.
Two basic forms of chemical ageing can exist for elastomers – (i) continuation of curing
reactions at elevated temperatures due to unstable cure systems, and (ii) exposure to hostile
fluids (the latter occurring initially at the elastomer surface, depending on diffusion to access the
bulk unless surface cracking provides a more rapid route). In the oilfield industry, hostile fluids
can include hydrogen sulphide (produced in some wells), various amines and amides used as
corrosion inhibitors, certain brines used in well completion, etc. Hydrogen sulphide will readily
attack unsaturated sealing elastomers such as nitriles, so that use of hydrogenated nitrile rubbers
(and FKMs) can be beneficial here. Some FKMs are prone to attack by amines at high
temperatures, a process accelerated by application of stress (presumably the increase in stored
energy also increasing chemical potential). This is an instance of environmental stress cracking
(ESC, a common example of this elsewhere in the rubber industry being ozone cracking, which
is now controlled well by incorporating suitable antidegradent additives in the elastomer
compound). ESC can involve chemical or physico-chemical attacks; some FKMs are attacked
by methanol by a process which can be shown to be reversible - and the application of stress
again exacerbates it.
Fluids which contact seals are of the following types:

• liquid
- may contain one or more chemical species
- multi-component liquids; may or may not be miscible
• gas
- may contain one or more chemical species
17
• gas/liquid mixtures
- each phase may contain one or more chemical species
- multi-component liquid phase; may or may not be miscible.
As mentioned above, the affinity a polymer has for a fluid depends on the chemical nature of the
polymer repeat unit. Other factors are relevant, in particular, fluid uptake by an elastomer can
be limited if there is relatively little free space (free volume) between chains. The efficiency of
chain packing, albeit in a disordered array and within the framework of local density
fluctuations arising thermally, again depends on detailed molecular structure. Thus, a high glass
transition temperature is associated with a low level of free space, a fact which is reflected in the
relatively high Tg of many oil resistant polymers.
Fluids absorbed by a polymer can be either chemically hostile or benign. In the latter,
mechanical and physical properties may be degraded by the mere physical presence of fluid
molecules between polymer chains. Removing the fluid, for example, by evaporation, can
largely restore original property levels. However, if the contacting fluid is chemically
aggressive, the chemical structure of the elastomer can be essentially59 irreversibly altered by
degradation reactions, and its properties permanently deteriorated. Molecular chain backbone
unsaturation offers particular sites for chemical attack, for example, by oxygen during thermal
aerobic ageing. Elastomers with considerable levels of unsaturation include the nitrile rubbers.
The premium oilfield elastomers have little (e.g., HNBR) or no unsaturation (fluoroelastomers),
but some are susceptible to chemical degradation in other ways. For instance, the acrylonitrile
functional group (which imparts oil resistance) in nitrile rubbers can be attacked by H2S at high
temperatures. In many fluoroelastomers containing vinylidene fluoride and hexafluoropropylene
monomers, dehydrofluorination occurs in particular environments, which results in the
development of unsaturation in the polymer backbone; thus a potential crosslinking site is
formed.
4.2 LIQUID INTERACTIONS WITH ELASTOMERS
4.2.1 Solubility parameters
Any liquid or elastomer possesses a “solubility parameter”, δ. This is a thermodynamic

property which is related to the energy of attraction between molecules. Thus if two chemical
species have the same, or similar, solubility parameter values, when intermixed they are likely
to have a strong affinity for one another. Hence an elastomer will possess a drive to absorb a
liquid of similar δ, and be swollen by it. As the difference between the solubility parameter
values of species increases, so their affinity for each other decreases. Other factors, discussed
below, can inhibit the extent of swelling of an elastomer in a compatible liquid. However, for
those elastomers which are prone to significant swelling in some liquids, then a good indication
of which liquids will swell a particular elastomer can be gained from a knowledge of their
respective solubility parameters. The commonest units for δ in the literature are (cal/cm3)1/2; to
convert to MPa multiply by 2.05.
59
Unlike physical interactions, chemical reactions are usually deemed irreversible. In fact, this is not always really the
case – an equilibrium can exist between the chemical reactants, products and factors such as volume, temperature and
pressure. Whether products or reactants dominate depends on the surrounding environment, Le Chatelier’s principle
observing that the equilibrium balance will alter to counteract any change in one of the participant-variables in the
equilibrium. For instance, if a product is removed (e.g. as often occurs when it is a gas), the “forward” reaction is
favoured in a thermodynamically-driven attempt to replace the removed species.
18
Thermodynamically, intermixing as above arises from achieving a negative free energy from the
process; in turn, this arises by balancing a contribution from enthalpy (heat content) with
another from entropy (involving structural aspects). The solubility parameter reflects the
enthalpic term.
Solubility parameter spectroscopy (SPS) is a means of determining the δ value of an elastomer.

Replicate elastomer samples are immersed in a series of carefully selected liquids or miscible
liquid mixtures, each of known δ, and a plot (spectrum) of swelling vs. liquid solubility
parameter thus developed. The δ value coinciding with the maximum of the plot is taken as the
δ value for the elastomer. The width of the solubility parameter peak in SPS indicates the δ
range across which substantial swelling of an elastomer can occur in low viscosity solvents. As
solvent viscosity increases, the width and height of the peak are reduced.
Intermediate liquid δ values are obtained by mixing liquids of known solubility parameter. The
δ value of the mixture is equal to the volume-weighted sum of the individual component liquid
δ values. This phenomenon can have important consequences in some applications. Thus the
mass uptake of a miscible liquid mixture by an elastomer may be very much greater than
the swelling which would occur in the presence of either one of the component liquids
alone. The mixture could of course comprise more than two liquid components, and an
analogous situation would apply.
The technique of reverse solubility parameter spectroscopy (RSPS) was developed60 to

determine the δ value for a liquid (e.g., an oil), from a series of swelling measurements using a
range of elastomers of known δ. In this way, δ for crude Brent oil has been found to be 8.2
(cal/cm3)1/2.
Solubility parameters are perhaps not listed as frequently as many other properties: Table 5 lists
the δ values of a number of common solvents, including some associated with oil production.
Also included in the table are the solubility parameter values for the elastomers tabulated in
Table3; these were determined using solubility parameter spectroscopy.
60
Developed by MERL personnel
19
Table 5 Solubility parameters61 for a range of solvents and elastomers
Solvent δ62 Solvent δ62 Solvent δ62

iso-octane 6.90 Toluene 8.97 propanol 12.0
hexane 7.33 o-xylene 9.03 ethanol 12.9
octane 7.60 ethyl acetate 9.10 methanol 14.5
diethylether 7.74 Benzene 9.22 ethylene glycol 14.5
decane 7.77 MEK 9.56 water 23.2
p-xylene 8.83 Acetone 9.74
m-xylene 8.87 1,2-dichloroethane 9.96
Elastomer δ62 δ range63 Elastomer δ62 δ range2

EPDM 8.25 7.5 - 9.0 ECO 10.7 9.0 - 12.5
FEPM 9.0 8.5 - 10.0 FKM I 10.9 9.0 - 12.5
LOW NBR 9.3 8.5 - 11.0 HIGH NBR 11.0 9.0 - 12.0
HNBR 9.6 8.5 - 11.5 FKM III 64

(10.5 - 11.5)65
64 64
FKM II 10.7 9.0 - 12.0 FFKM
4.2.2 Other factors which influence liquid uptake
A number of variables can be used to exert a degree of “control” over the level of liquid
absorbed by sealing elastomers. These are structural aspects, thermodynamically arising from
the entropic contribution to the free energy equation (see section 4.2.1).
If the δ difference between liquid and polymer are significantly different there is no chance of
swelling but if they are similar, swelling may occur. The following structural considerations
then become important:
• Glass transition temperature: swelling will be reduced in an elastomer with a high

Tg, that is, in a polymer with little free volume available for absorbed liquid.
• Crosslinking: since crosslinks provide a constraint against swelling, swelling is
reduced by high levels of crosslinking (see Figure 4).
• Filler: swelling is reduced by the use of high filler loadings; there is less elastomer
available to absorb fluid.
In these last two cases the benefits of reduced volume swell may need to be offset against
reductions in desirable physical properties, such as tear strength, and operational issues, such as
ease of installation.
In addition, the following points are relevant

• Increasing liquid viscosity lowers the rate of absorption and the level of equilibrium
mass uptake.
• Increasing temperature may increase swelling by a modest amount.
• During liquid immersion, soluble non-bound ingredients in the elastomer can be
removed by leaching; this is usually (but not always) a small effect (see Figure 5).
61
Allen, Gee, and Nicholson, Polymer, 1, 56 (1960).
62
units (cal/cm3)1/2
63
indicates where low viscosity uptake is above about 70% of peak value
64
swelling not measurable
65
based on low measured levels of volume swell
20
• An elastomer exposed to an immiscible liquid mixture will eventually swell as if
exposed to the more compatible liquid (i.e., the one with the nearest δ), even if the
sample does not directly contact that liquid in a pure form.
• Volume swell is a useful measurement to apply when considering tolerances for housing
design.
The effect of increasing crosslink density on reducing the solvent swelling of an HNBR
compound is shown in Figure 4. The unaged material absorbs ca 90wt% toluene at equilibrium.
After ageing samples of the HNBR for various times in an aggressive environment, which
causes the rubber to form additional chemical crosslinks; the rate of solvent uptake and the
equilibrium level of absorption are reduced.
To illustrate the influence of leaching, Figure 4 shows an (extreme) example. Here, the polymer
is a thermoplastic (plasticized nylon 11), rather than an elastomer, immersed in methanol. The
lower curve is the as-received material; it passes through an absorption peak before eventually
losing mass after an extended immersion period. Two processes are occurring here – leaching of
plasticizer (which is present in the polymer at ca15wt%) from the plastic, and absorption of
methanol. If the plasticizer is first extracted from the nylon and then the material immersed in
the alcohol, a classic uptake curve obtained is obtained – where an equilibrium plateau is
attained.
Figure 4 The effect of increasing crosslink density of the toluene absorption of an
100
80
%Mass uptake
60
40
20
0
0 1 2 3
Time (hrs1/2)
HNBR compound. The unaged material is represented by the upper curve.
21
16
14
12
10
%Mass uptake
0
0 4 8 12 16 20 24 28 32 36
-2
Time (hrs 1/2)
Figure 5 Nylon 11 in methanol at room temperature. Lower curve is plasticized

material, upper curve is de-plasticized polymer.
4.2.3 Kinetics and swelling
The rate of liquid uptake is controlled by diffusion, itself dependent on a concentration gradient.
The appropriate integrated solution to Fick's laws of diffusion show the proportionality constant
to be the diffusion coefficient, D (units, for example, cm2/second). A convenient means of
measuring D is on an average basis for 50% mass uptake, when, using sheet66 elastomer
samples,
0.5 = (2/h)(Dt/π)1/2
where t is the time to 50% uptake (i.e., one half the final equilibrium value), and 2h is sample
thickness. If D is first measured from simple tests, it can be re-applied to another, service-
appropriate, geometry such as a hollow-cylinder where relevant different equation exists to
estimate liquid breakthrough time or uptake. For other more complex component geometries, a
numerical approach can provide concentration profiles at different times or, alternatively, an
approximation using a simple equation can be used to estimate how much liquid uptake has
occurred.
D increases with temperature, following an “Arrhenius-type” relationship, useful for making

long-time predictions for low temperature service from tests at several elevated temperatures.
For details of the Arrhenius approach, see Appendix 4.
4.2.3.1 A kinetic effect of swelling on stress relaxation
Because sealing relies on maintaining a sufficient stress throughout the service life, the stress
relaxation rate of the sealing material should be considered at the design stage. However, fluid
(especially liquid) absorption can cause additional changes in sealing stress. Absorption of
liquid by a compressed seal can, potentially, have two physical effects. Firstly, the sealing force
may be raised because the swelling force is added to that already present due to compression.
Secondly, the absorbed liquid may separately act as a plasticizer, thereby lowering the existing
66
Other equations apply for different testpiece shapes.
22
sealing force. The two effects are in competition - which dominates depends upon
circumstances such as seal housing dimensions, degree of compression etc. However, the
kinetics of each process will apply during this competition, as indicated in a laboratory
quantification of this observation outlined in Appendix 2.
Case study
In the work discussed in Appendix 2, it was seen that absorption of the liquid results in
a large rise in sealing stress, at a rate separately found to follow the laws of diffusion.
On removal of the liquid, the stress decreases, eventually reaching a level significantly
below the level that would have been attained had no swelling occurred. This
observation suggests that some physical damage could have been suffered by the
sealing material.
Further effects can also arise. Considering first low amounts of volume swell, it has been
shown that the ingress of seawater has no significant effect on rates of stress relaxation. This
conclusion is based on MERL results for HIGH (acrylonitrile) NBR, (equilibrium mass uptake
4.2%), and ECO (equilibrium mass uptake 7.6%).
These findings confirm the view commonly held in the sealing industry, that a small amount
of positive swell is generally beneficial in assisting sealing Excessive swell, on the other
hand, should be avoided, as this may lead to weakening and eventual extrusion or
fracturing/tearing of the seal; the latter is particularly relevant where the extrusion gap is
significant and/or non-uniform.
4.2.4 Hostile liquid environments
A number of liquid environments are met by seals in the offshore oil and gas industry. Some
examples are briefly discussed below; the list is in no way comprehensive.
4.2.4.1 Treatment fluids – Methanol
Excessive swelling of FKM I when immersed in methanol is a well known phenomenon. This
is a reversible and unstable situation, as long-term immersion can result in a reduction of
swelling (thought by MERL to be due to hydrogen bonding interactions between methanol and
the fluoroelastomer, which bring molecular chains into closer proximity with one another). If
the seal is subsequently dried out, any later exposure to methanol results in a repetition of this
phenomenon. Although the solvent-polymer interaction is reversible, it produces a situation
hostile to stable sealing. See Table 4. However, most oilfield treatments using methanol mix it
with water, with much-reduced swelling then resulting67. The reason is that the solubility
parameters of these mixtures is higher than methanol, moving away from the FKM values. This
is illustrated graphically in Figure 6, which shows the dramatic reduction in fluid uptake upon
diluting methanol with small amounts of water.
67
Steve Groves paper: Project guidelines for selecting seals for high pressure gas duty and other oilfield service; see
Bibliography.
23
35
28
21
%Mass change
14
0
0 5 10 15 20 25 30 35 40
1/2
Root time (hrs )
Figure 6 Mass uptake curves at room temperature for FKM in methanol/water

mixtures. From top, 100/0 methanol/water, 99/1, 98/2, 97/3, 96/4, 95/5, 90/10.
The degree of methanol swelling can be useful for identifying a particular FKM type;
compounding aspects can alter absorption substantially, so this approach should be used as a
rough guide only.
Methanol has also been found to have a substantial effect on stress relaxation rates (see section
4.2.3). For FKM I, two other FKM elastomers and FEPM, rates of stress relaxation increased
several-fold when they contact methanol. It is particularly surprising that so large an effect is
found for FEPM, a material which swells very little in methanol (<<5%). These tests followed
the first 25-35% loss in sealing stress; it is not known whether the influence of methanol contact
extends beyond this range.
4.2.4.2 Water at high temperature
Water uptake by an elastomer compound at ambient temperature involves the normal physico
chemical processes plus, on occasions, physical absorption by filler or curing additive particles.
At higher temperatures, specific instances of exceptional behaviour have been documented. For
example, any FKM I formulation which contains a combination of magnesium oxide and
calcium hydroxide is subject to delayed degradation after long periods in water at 150 °C and
above. Replacing these ingredients by lead oxide in the cure recipe yields an elastomer which
effectively resists this type of degradation.
4.2.4.3 Corrosion inhibitors
Speciality chemicals are often added at low concentrations (ppm up to a few per cent) to liquids
being transported through steel pipes in order to inhibit corrosion of the pipes. These corrosion
inhibitors are known in some cases to degrade elastomeric seals. Studies on the elastomers
tabulated previously indicate that different mechanisms may apply for different
elastomer/inhibitor combinations. The three different types of chemical attack proposed by
MERL are:
24
• Ionic: attack by amines in sea water or other aqueous media (seen chiefly for HIGH
NBR and HNBR), possibly involving the acrylonitrile group; high pH amines (high
amine nos.) are the most hostile;
• Free radical: attack by these amines in either aqueous or hydrocarbon liquids
(observed in FKM I);
• Less hostile attack by phosphate esters and other minor additives, observed
generally.
The consequence of such chemical attack is a permanent reduction in elastomer property levels,
with increased temperature increasing the rate of any degradative reactions. At worst (e.g., high
pH amines and FKM I), the seal can disintegrate. However, effective corrosion inhibitors which
are claimed not to attack elastomers are now commercially available. Their manufacturers can
advise on choice of inhibitor for preventing corrosion in particular applications, especially at
high temperatures. In seal selection, it should be remembered that FKM I, NBR, and HNBR are
susceptible to high pH inhibitors. As always, the best defence against catastrophe is appropriate
compatibility testing prior to service. Material suppliers have developed grades of
fluoroelastomer which are resistant to high pH environments; for example, Viton ETP (DuPont
Dow Elastomers).
The most common outcome of interaction between a sealing elastomer and a hostile chemical
species is the formation of additional crosslinks within the elastomer structure; for example,
FKM contacting high pH fluids at elevated temperatures, NBR exposed to amines or oxygen at
high temperature. The elastomer stiffens and may eventually embrittle, with loss of material
compromising sealing function. The opposite type of degradation involves breakdown of the
elastomer network (chain scission), resulting in the softening of the material.
4.2.4.4 Well stimulation fluids – acids
Because an acid might chemically attack ingredients within the elastomer as well as, in some
cases, the elastomer itself, it is recommended that verification data of a selected material’s
compatibility in the acid is requested from the component supplier. If unavailable, service-
realistic testing should be performed.
Acetic acid, formic acid and hydrochloric acid/hydrofluoric acid (HCl/HF) mixtures are the
more commonly-used treatment acids used offshore. Regarding handling, avoiding splashing
into eyes etc is the main issue with the first two types, as these are weak acids, but HCl/HF is
highly corrosive to personnel as well as to metals etc; stoppered glass containers, suitably
cushioned, should be used for transporting this acid mixture. Regarding procedures, one
becoming popular offshore with such fluids is to localise the treatment to the relevant part of the
well etc – which will minimise the number of seals etc liable to become in contact with these
acids. Each of these acids can be resisted by some elastomers, but not all – and the
combinations will vary. It is therefore strongly advisable to provide exact details of the acids to
be used to the supplier, to check carefully that the specified elastomer seals etc are fit-for-
purpose.
4.2.5 Summary of liquid effects on seal elastomers
• Liquids dissolve into the surface of an elastomer, with diffusion carrying them into
the bulk polymer.
• Different elastomers and liquids have different solubility parameter values.
• Maximum absorption of fluid by an elastomer depends on the difference in δ values;
the closer they are, the more likely is fluid absorption.
25
• Other factors such as glass transition temperature, filler loading, degree of

crosslinking, and liquid viscosity also affect maximum concentration.
• Volume swell is important for housing tolerance considerations.
• Dissolved fluids diffuse into the elastomer bulk over a period of time depending on
- the value of the diffusion coefficient (which depends on the fluid and the
elastomer)
- the seal section and geometry.
• Diffusion is driven by concentration gradient, not by pressure.

• Liquid uptake by elastomers results in swell:
- swell < 20% by volume is not usually a problem in static applications
- swell > 20% can result in:
* overfill of the seal housing groove

* seal extrusion damage
* extremely high stresses in the seal and in the housing
* occasionally, metal components being fractured
* progressive degradation, such as a loss in physical and mechanical properties.

• Leaching effects are usually more than compensated for by swelling - but note that the
leaching of protective agents, for example, antioxidants, has a knock-on effect on
durability.
• Methanol can be particularly hostile to some elastomers, but for physico-chemical reasons
only.
• Corrosion inhibitors, especially those of high pH, can chemically degrade some elastomers.
• A small degree of positive swell is beneficial for the retention of sealing force.
4.3 GAS INTERACTIONS WITH ELASTOMERS
• Gases dissolve into the surface of an elastomer (adsorption):

- gas concentration at the surface is the product of the applied gas pressure
(partial pressure of each gas in a mixture) and the solubility coefficient.
• Gases diffuse from the surface into the interior of the elastomer
- the diffusion coefficient relates diffusion rate with concentration gradient.
- diffusion of gases is ca 1-2 orders of magnitude faster than liquid diffusion.
• If geometrical considerations allow, gases will pass right through the elastomer by
dissolving, diffusing, and evaporating. The combination of these processes is permeation.
• Diffusion and solubility coefficients, D and s, are evaluated from permeation
measurements.
4.3.1 Gas permeation
In permeation through a sheet, a linear concentration gradient exists between the contact and
exit surfaces. The flat sheet is therefore a convenient geometry for evaluating D and s. For the
steady-state diffusion of adsorbed gas from one surface of a plane sheet of elastomer through to
the other, integration of Fick's laws of diffusion gives
(1/A)(q/t) = D(c1 - c2 )/h
where gas volume q (at STP) diffuses across area A, and through thickness h, in time t. D is the
diffusion coefficient and c1 and c2 are the initial (“high”) and final (“low”) concentrations. If P1
and P2 are the initial and final pressures, then from Henry's law
c1 = sP1 and c2 = sP2
26
where s is the solubility coefficient. If the product Ds is defined as Q, termed the permeation
coefficient, combining the above equations gives the general permeation equation for a
membrane:
(1/A) (q/t) = Q (P1 - P2)/h
Hence Q - numerically the permeation rate through a unit cube brought about by unit pressure
difference - can be obtained experimentally from the linear plot for q/t (all other factors being
known). D is measured separately, and equals h2/6τ, where τ is the time lag by which the
steady state permeation back-extrapolated to zero permeation is delayed from the test-start
origin. Once Q and D are quantified, s and c1 are obtained using the equations above.
One use for these equations when performing HP permeation testing is to find the best
conditions (low concentration, high diffusion coefficient) for avoiding potential explosive
decompression failure68. As an example, in a series of tests three elastomers (FKM II, FKM III
and FEPM) showed equally high gas permeation rates. However, the high permeation rates of
FKM II and FEPM are mainly the result of a high rate of diffusion, with their solubility
coefficients (and thus concentration of dissolved gas) being relatively low. For FKM III the
reverse is true. Hence for these three elastomers the lower potential for explosive
decompression damage is associated with FKM II and FEPM, although other material factors
can also contribute to the extent of damage. The final choice would depend on these other
factors.
Other pointers associated with HP gas in elastomers:

• If an elastomer is completely surrounded by gas, or if there is no exit route from the
seal housing, the high surface concentration will eventually be attained throughout the
elastomer bulk: saturation will be achieved.
• Below its Critical Temperature, a gas can become a liquid at elevated pressures, and
behave accordingly. Carbon dioxide often displays this phenomenon in applications
below 31°C.
• Solubility parameter can become relevant for gases at high pressures, that is, when
liquid-like densities are achieved.
• At high pressures, the dissolved gas volume (relative to STP) in a seal can be more
than 100 times the volume of the seal, that is, the gas concentration is greater than 100
cm3 of gas per cm3 of elastomer.
• Consequently, since reducing pressure rapidly allows gas to come out of solution
inside the elastomer,
- the original concentration/pressure balance no longer applies,
- gas bubbles may form in the elastomer, causing internal fractures and/or surface
blistering. This is “explosive decompression” - see later for details.
4.3.2 Pressure, time and temperature effects
It might be thought that, from Henry's law, the concentration adsorbed at the high pressure
surface could be increased indefinitely by increasing pressure. This is not so. At high
pressures, when gas densities approach liquid densities, the adsorbed concentration tends to a
constant value (analogous to the equilibrium mass uptake for liquids). The solubility coefficient
is no longer a constant, but decreases with increasing pressure. For example, during permeation
through HIGH ACN NBR at 195°C, carbon dioxide reaches an equilibrium concentration in the
region of 100 cm3 of gas per cm3 of elastomer at about 7000 psi.
68
Review, section 4.4
27
Material effects also occur at high pressures. Permeation coefficients can change (normally
reduce) with time and with the application of additional pressure. A major reason for the
change is the hydrostatic compaction (densification) of the elastomer at high pressure; polymer
chains are forced into closer proximity and the material density rises. Eventually, Q values
probably level out. An example of the measurement of this phenomenon follows (Figure 7).
-2 0 5 10 15 20 25 30 35 40
% Thickness Change
-4
-6
-8
-10
-12
-14
-16
Time (hours)
Figure 7 Schematic representation of an HP gas test for elastomer thickness

measurement, showing compaction upon gas pressure application and subsequent
swelling as gas is absorbed
Sequence of high-pressure-induced thickness changes (cf Figure 7)

In a diagnostic experiment, an EPDM elastomer was compacted thus by a high pressure inert gas and
taken though a regime of temperature and associated pressure changes using a high pressure steel cell
designed for measuring material volume changes. It possessed features for cooling, heating, and
dimensional measurement using a pointed probe (akin to a sharp pencil in shape) for measuring a sheet
sample thickness. The probe hung from a fine thread of exact pitch 1mm: a dial indicator gauge then
allows thickness changes of 0.005mm to be read, which was 0.6% of the EPDM thickness. An electrical
contact system operating via a metal “table” permanently attached to the top sample surface allowed the
precise position where the probe touches the sample to be identified, by illuminating a neon bulb; the
table did not inhibit pressure application to the sample. Each sheet sample was moulded and bonded
during cure into a holder which could then be securely fitted into the cell, prior to assembly of the probe
and contact systems. After suitable initial calibrations, a comprehensive series of tests were conducted
across a wide temperature and pressure range.
In one typical test, it was found that an initial increase in pressure at 23°C from 0 to 8300 psi/58 MPa
resulted a compaction of 14% (Stage 1); this is illustrated schematically in Figure 6. With the pressure
staying constant at 8300 psi/58 MPa, the sample subsequently began to swell (exhibiting a typical
diffusion-type profile) until a constant thickness was reached, when the system was thought to be in
equilibrium (Stage 2). The swelling caused about a 30% reduction of the compacted value. A decrease in
the temperature to –29°C and associated decrease in pressure to 5700psi/39 MPa resulted in thermal
shrinkage of the sample of 3%. Following this, no swelling was evidenced while the temperature and
pressure were kept constant. With a temperature increase to 54°C and accompanying pressure rise to
10,000 psi/69 MPa (Stage 3), the sample swelled to its greatest value following initial compaction, but did
not reach its original, pre-test, thickness. A temperature and pressure reduction back to 23°C and 8300
psi/58 MPa (Stage 4) resulted in shrinkage back to the equilibrium (swollen) Stage 1 value at the same
temperature and pressure.
28
The exercise above shows that compaction and swelling effects should be heeded when sealing
high pressure oilfield fluids. Housing and/or seal design should be such that these effects are
minimised.
4.3.2.1 Temperature effects at high pressure over long periods
At low pressures, where the permeation coefficient is independent of time and pressure,
Arrhenius-type relationships, linearly linking logarithmic reciprocal time to reciprocal absolute
temperature, apply. However, high pressures and long timescales can cause the coefficient to
vary so that bands of data, rather than a single straight-line plot, apply in an Arrhenius manner.
Diffusion coefficients D, and solubility coefficients s, at different temperatures can also give
rise to similar Arrhenius bands. Because Q = Ds, these are inter-related. See Appendix 4 for
details about the Arrhenius approach.
4.3.3 Hostile gas environments
Gases can not only damage elastomers by their physical presence (e.g., in explosive
decompression), but can be chemically hostile to certain polymer types.
4.3.3.1 Hydrogen Sulphide
H2S is a chemically aggressive gas, present in numerous offshore situations, which may cause
seal degradation. It will enter the elastomer according to the physico-chemical rules discussed
above, but additionally it may attack the elastomers chemically. Hence, increasing the
temperature will increase the rate of chemical attack.
In tests at 120 °C on a range of the elastomers discussed above, it has been shown that the
presence of a small amount of H2S (e.g., 0.5%) in a gas mixture has little or no effect, and that
other factors such as temperature, time of ageing, or decompression rate, are more important.
Increasing the time of exposure at this concentration level also had no effect. The role of small
amounts of H2S on elastomers therefore needs to be kept in proportion. If high levels (>10%) of
H2S are present (e.g., very sour reservoir fluids, sour/acid gas re-injection operations), a
concentration effect exists: that is, the increased amount of hydrogen sulphide present increases
the probability of degradative reaction occurring where the gas contacts certain polymeric
materials. This situation does not apply in the North Sea, where the level of H2S is generally
low. However, it should be noted that many sealing elastomer types do react with H2S; these
include NBR, HNBR and several FKMs. Fortunately, a small number of elastomer types are
little affected by sour gas, even at very high temperatures – these include TFE/P and FFKM.
4.3.3.2 Oxygen
The oxygen in air is potentially hostile at elevated temperatures. Usually it is found only at low
pressures (i.e., on the air-exposed side of many seals) and in speciality applications (e.g., seals
in regulators for compressed gas tanks) not relevant offshore. Hence the oxygen concentration
may not be high, as it is driven by its partial pressure (Henry's law). However, the oxidative
attack may cause skin effects such as embrittlement, perhaps accompanied by cracking
especially for NBR elastomers. These may be of sufficient significance to impair sealing. FKM
elastomers tend to be oxidation resistant to temperatures as high as 200°C. Certain sealing
materials may contact air; for example, the nitrile component of a wellhead piston seal
assembly.
29
4.3.3.3 Hydrocarbons
Hydrocarbon gases such as methane and ethane are found in production fluids but are not
chemically aggressive to elastomers. They might become involved physico-chemically with
sealing materials at high pressures, when at liquid-like densities, a small amount of swelling
might result from contact with some elastomers (e.g., Aflas). As with other gases, hydrocarbon
types will cause explosive decompression damage in seals if the host polymer is saturated and
the pressure drop is sufficiently rapid.
4.4 EXPLOSIVE DECOMPRESSION
4.4.1 Nature of the problem and mechanisms
Explosive decompression (ED) is the name given to the phenomenon which results in the
formation of microvoids and, subsequently, growth of larger cracks within sealing elastomers
when the gas pressure is rapidly reduced (see discussion on rate of decompression below)
subsequent to a period long enough to allow the polymer to reach equilibrium saturation. As
Figure 8 indicates, when an elastomer is in a situation where ED can occur, thicker sections are
more affected than thinner ones; with the latter, a greater proportion of the gas absorbed in the
sample or component can escape by diffusion/evaporation during the decompression period.
Figure 8 ED failure for 3 specimens of an oilfield elastomer after unconstrained

exposure in same cell to high pressure gaseous conditions and rapid depressurisation.
Note less damage with thin strip.
If a seal is incorrectly specified, ED is can be met under severe conditions in sealing situations,
Figure 9 showing an extreme example; cracks may grow and blisters form and burst,
irreversibly damaging the sealing elastomer. It can also occur within hose linings.
30
Figure 9 A severe split induced in a seal by realistic ED testing at severe conditions,

after removal from its housing
The mechanism of ED is thought to involve these points:

1. gas dissolution in the elastomer under high applied pressure;
2. when the hydrostatic effect of high external gas pressure is removed, the gas comes
out of solution and inflates small bubbles at nucleation sites; these may harmlessly
deflate if the gas can escape the bulk elastomer by diffusion and evaporation;
3. if not, above a critical bubble size, irreversible crack growth occurs, and such cracks
may rupture the seal.
Appropriate external constraints can limit the degree of inflation and hence the internal damage;
such damage may not always be visible in an external seal inspection, so that in assessing ED
fully, seal sections need to be cut through and examined under magnification. The problem can
manifest itself in similar severe conditions with thermoplastic seals but is less likely for
morphological reasons (see earlier comments on crack growth resistance). PTFE has the
additional microstructural feature of porosity. For specific reasons like this and that at the end
of section 4.4.2, ED tests should be carried out in service-realistic conditions.
4.4.2 Explosive decompression summary
Explosive decompression ED damage is increased……
……STRONGLY by
• high gas pressures (especially > 2000 psi)
• high gas concentrations in the elastomer
• high decompression rates ( > 10 psi/min)
and less strongly by

• temperature
• multiple decompressions.
Explosive decompression damage is decreased…..
…….STRONGLY by
• low gas pressures (e.g., < 900 psi)
• low gas concentration in the polymer
• high gas diffusion rates
• high seal constraint (e.g., back-up rings)
• high degree of groove fill (e.g., > 90%)
31
• slow decompression rates (> 5 days)
and less strongly by

• high elastic modulus (but individual cracks may be larger if failure does occur)
• high rubber tear strength.
(these increasing with decreasing temperature).
Note Because concentration is a large factor in bringing about ED-induced fractures,

accelerated tests should not take the approach of using CO2 as test gas instead of a service gas.
The very high concentration of CO2 in elastomers means that the “ acceleration” brings about
failures that probably will not arise at all with the service gas. Any acceleration is best brought
about by using elevated pressures and temperature changes as appropriate to speed up the time
to saturate the elastomer prior to the decompression stage. Similarly, correct housings should be
employed to constrain the seals during testing as, during service, these provide support in
resisting ED failure, in effect by increasing the elastomer’s modulus; if tested unconstrained,
the lack of this support is a departure from service-reality.
As a caveat, it should be noted that extrapolation of test results is not yet possible with ED; that
is, performance at low pressure/small seal section/high temperature cannot be used to indicate
performance at high pressure/large seal section/low temperature. Qualification testing at (or
close to) service conditions is desirable. However, for thick section seals, time aspects of the
gas absorption stage can be accelerated if values of all permeation-related coefficients for the
system are known.
4.5 LIFE PREDICTION TECHNIQUE
For applications with components exposed to fluids where design criteria are used to set limits
the criteria being based on a property which will change with time for a service-related reason
then residual life becomes zero when one or the other limit is reached. Service life prediction is
ideally based on predicting when this stage is reached. One caveat required that a prediction
based on a selected property assumes no other failure mechanism becomes dominant instead
during service.
Example
For instance, a seal may have a 10 year life from a prediction based on stress
relaxation or stiffness changes, but if it is unexpectedly exposed to the
explosive decompression phenomenon it could suffer damage and fail
immediately. All possibilities must be considered, and the determining factor
identified for all stages of service life.
At constant temperature, if laboratory testing can be performed for the full service life, then the
response of a critical property (e.g. modulus, stiffness) for an elastomer to, for instance,
exposure to a particular fluid can be checked in full before the application is started. In addition
with unchanging temperature, the behaviour of properties such as stress relaxation which follow
well established rules can be extrapolated with confidence to much beyond testing times (care
only being taken that the relative contributions of physical and chemical stress relaxation have
been properly resolved). The complications introduced where temperatures can vary are
considered later.
Empirical extrapolation of other properties to longer service times at one temperature is possible
if a clear pattern is established for the property level (or its logarithm) against time, but any
associated competing chemical reactions can cause some confusion in these patterns.
32
As increases in temperature cause increases in reaction rates, a means of conducting laboratory

testing at temperatures well above service temperature (provided no transition or degradation
temperature is surpassed) is highly desirable. These can be empirical; however, a more
reasoned approach can also be possible, the “Arrhenius approach” being detailed in Appendix 4.
A warning - it should be noted that, if the upper service temperature is high (e.g. 180 °C), the
scope for timely acceleration is reduced using thermal means. Experience may then be a factor
in making judgement about likely performance, (e.g. by using an increase in concentration
instead).
33
34
5 QA/QC
QA/QC is only treated in outline here. For Quality Assurance (QA), the purchaser should
obtain from the supplier technical evidence that the materials selected will meet specification.
This information should be in the form of appropriate mechanical and fluid resistance
(compatibility) data, ideally including ageing information and, for high pressure gas
applications, explosion decompression results from service-realistic testing procedures (or,
failing that, well-established Standard tests). More detail is provided when discussing the
Standard test methods that can be employed for obtaining this information (see section 7, and
Table 1).
Regarding Quality Control (QC), ideally, the purchaser will obtain as a minimum from each
batch of seal products a typical hardness value obtained from five seals chosen at random, and a
copy of a test plot from a curemeter showing that the cure characteristics of the batch are within
prescribed limits. Ideally, other data for specific behaviour relevant to particular applications
could be included – e.g. from methanol absorption testing if FKM seals are to be located in
service such that they may be exposed to methanol treatments.
35
36
6 SEAL FAILURE
(Further to the comments in Guidelines sections 2.2. and 2.3.)
Material deterioration (physical or chemical) can bring about failure of its own accord, or can
weaken the elastomer so that other factors manifest themselves more easily. As an example of
the first statement, explosive decompression fracture (section 4.4) - if reaching right through the
seal - could easily lead to significant or drastic leakage; regarding the second point, liquid
absorption with associated swelling and weakening (section 4.2) can increase the rate of
extrusion damage. However, other less dramatic forms of failure are possible, as discussed
below.
6.1 SEAL LEAKAGE MODES
Basically, a sealing system functions successfully for its full service life (the most likely case if
design and material selection points are correct) or it fails by allowing leakage – at some rate
between the extremes of seepage or catastrophic failure.
Clearly if a seal is damaged for whatever reason, leakage might occur, perhaps at a considerable
rate. However, the more fundamental modes of leakage are (largest first):
• fluid flow between a seal and its steel counterface through lack of sealing force between the
seal and the counterface
• molecular diffusion through the body of the material – one part of the permeation
phenomenon
• molecular diffusion along the interface between seal and counterface.
The first mode is usually the important one. In applications at high pressure the second mode
may be sufficiently significant that it should be allowed for; however, in a particular HP test
comparison performed at MERL, appropriate measurements led to the estimation that gas
permeation rate was at most 2% of the rate of the smallest leak that could be measured. If there
is good contact, then the third mode is unlikely to be significant. Only first mode leakage is
considered for the remainder of this section.
Leakage can arise from deficiencies in design, housing or seal manufacture, or operational
factors.
6.2 DESIGN, MANUFACTURING AND OPERATIONAL FACTORS IN LEAKAGE
6.2.1 Design factors
If poor design allows excessive deflections of the supporting structure, the housings can be
stretched outside tolerance as a result, in the worst case thus allowing leakage. If the design
requires anti-extrusion rings, these can be solid or spiral. A spiral ring can be made of PTFE or
some other flexible material, and they are easy to fit on a housing containing permanently-
machined grooves and rims. When the seal is activated, the step in the back-up ring disappears,
to give essentially a flat profile. Solid anti-extrusion rings are more reliable under more extreme
conditions, but can only be fitted if the design is such that the housing has one rim only (on the
low pressure side) or if any high pressure-side rim is removable (probably threaded).
The use of seal stacks, outlined previously, is based on the concept that, if the first set of seals
fails, the following sets in the sequence will continue the overall sealing; however, the
37
following important question needs to be answered in resolving whether this indeed is the case.
If the first set initially operates successfully but then leaks, does its presence allow the second
set to energise properly when called upon to do so?
6.2.2 Housing factors and seal quality
Housing-manufacturing quality and seal manufacturing issues are also factors. A poorly located
O-ring can allow leakage, for instance, due to the inner shaft’s not being located centrally, or an
off-centre housing. Properly applied QA and QC procedures applied to the seal manufacture
should mean that seals are of the correctly-specified material type, cured to the correct degree,
with no flaws or weaknesses.
6.2.3 Seal damage during installation
Installation should be conducted with care, to avoid damaging seal and/or housing - clearly, any
such damage might increase any leakage rate, either initially or later in the seal’s life.
Specifically, overstretching or cutting the seal, scratching the housing, or scoring the rim could
all lead to unpredictable leakage.
6.2.4 Loss of sealing force (stress relaxation or thermal effects)
The loss of sealing stress by the process of stress relaxation (section 3.4.2 and Appendix 2)
should not lead to complete loss of sealing stress providing that correct design and material
choice has been made. Laboratory test methods for measuring this property’s magnitudes exist
(Appendix 2). However, it is strongly suspected that absolute predictions are not yet possible –
there are too many variables which could change relaxation rate (Appendix 2). Relative
material performance can be obtained by the laboratory testing - the ranking obtained should be
used to select the best material. Then selection material will also be very strongly dependent on
experience. Using back-up rings will help resist stress relaxation.
Thermal effects are threefold:

• influence on stress relaxation
• thermal shrinkage/expansion
• cooling through Tg.
The first two effects are discussed briefly in Appendix 2. The variations arising from the first
can be significant, being one reason why the time to reach a complete loss of sealing stress by
this ongoing fundamental time-dependent property is difficult to predict.
Regarding the second, the coefficients of expansion of elastomers vary by perhaps 50% between
different elastomers, but more importantly, as a class elastomers possess coefficients 10x greater
than that of steel. Hence, if extreme temperature decreases occur, a seal in a badly-designed
housing could become too small for the groove – thus clearly losing sealing stress. An increase
in temperature could enhance the likelihood of extrusion taking place – especially if a high
groove-fill is used (for instance, to combat the possibility of ED damage).
If the temperature change on cooling passes through the Tg of the elastomer, it will become
glassy as well as shrink, and could well lose sealing force in this state. Even if re-warmed, a
compression set feature might apply, the elastomer (remembering its compressed configuration,
so that once again being prone to leakage).
38
6.2.5 Extrusion
Extrusion may lead to fracture, because of the stress concentration where the seal comes into
contact with the sharp edge of the housing; if the fracture is large enough, leakage can result.
However, there is a ‘Catch 22’ situation, as excessive rounding of this edge to reduce the stress
concentration and hence the possibility of fracture may have the effect of making extrusion
easier! Using back-up rings will help resist extrusion by limiting access to the extrusion gap.
6.2.6 ED with HP gas
ED will only take place in a fluid with gas present after a depressurisation, probably a rather
rapid one. This form of fracture is discussed in section 4.4. As cracks and blisters can arise if it
occurs, clearly seal leakage can follow.
6.2.7 Fluid swelling (mainly liquids)
Swelling can occur in circumstances covered in section 4.2, or if the seal material is constrained,
the associated build-up of stress is outlined in Appendix 2. Excessive swelling can lead to a
weakening of the material allowing fracture/tear or failure by extrusion.
6.2.8 Chemical ageing
Chemical attack due to mechanisms such as those discussed throughout sections 4.2 and 4.3 can
result in failure due to specifications being exceeded or, more randomly, to eventual material
failure such as surface embrittlement with associated cracking or crumbling.
39
40
7 FAILURES FOR OTHER COMPONENTS
7.1 HOSE FAILURE AND LEAKAGE
Fluid leakage is the main overall failure mode, but various sub-modes exist. Correct design and
quality control should ensure the absence of manufacturing flaws or the like, to preclude early
failure; in the absence of such flaws, elastomer-deterioration by ageing and/or fluid
permeation/diffusion become the likely causes by which long term failure might eventually
occur. A table such as Table 6, applying here for 15°C service, should be completed at the
onset of service or before, using (i) diffusion data from accelerated laboratory testing and (ii)
estimations arising from inserting these in appropriate permeation/diffusion equations or
models. It is also possible that fatigue aspects eventually become relevant, if the hose location
allows motions from tides, waves, winds, internal pressure fluctuation, etc.
Table 6 Years at 15°C to migrate outwards through hose layers indicated
Layer Best case69 Worst case*

NBR liner TBC TBC
Change over compound, e.g. NBR/SBR blend TBC TBC
Various SBR/NR blend filling layers TBC TBC
NR or CR subcover TBC TBC
NR or CR cover TBC TBC
TBC - to be completed by the tester (following initial laboratory testing)
Pointers
• Ageing of the hose liner, especially if a nitrile rubber, during long term storage, can take the
material out of specification. For hose stiffness (as opposed to liner material stiffness), the
reinforcing wires could well dominate this feature.
• Certain factors influencing potential failure might become important, with failure then
occurring within a relatively-short time frame. These include the possible onset of end-
fitting failure, fatigue failure, or pitting corrosion – but the chances of these are not thought
to be high (see later items).
• Other more insidious processes will happen in the fullness of time, but the periods involved
could probably be considered too long to matter.
• The second effect might exacerbate factors in the first; again it is likely that times for this
would be long.
• The insidious effects which must eventually happen involve diffusion of the crude oil/gas
radially outwards through the hose wall structure, with accompanying weakening of some of
the rubber layers and/or the development of considerable swelling forces due to the greater
ability to swell in oil possessed by some elastomer layers outside the inner liner. However,
estimated times for these processes are probably such that very long times will probably
apply at the hose service conditions before they manifest themselves. (Table 6 would need
to be completed to quantify this statement.)
• Hoses are large enough to be visually inspected at intervals for incipient failures arising
from slow processes such as those above, by remote travelling camera or divers if
appropriate.
• The swelling forces mentioned in the pointer above can be roughly estimated for an
elastomer by comparison with plots such as that in Appendix 2, providing its extent of
69
Accumulative
41
unconstrained swelling is known from simple laboratory test work. Such plots can be
established for different elastomers; MERL has such data for several oilfield elastomer
types.
• However, it is unlikely that swelling forces will become high enough to be important for
some years longer than the times estimated in the summary table above, which is based
solely on times to reach the various regions by the liquid diffusion process. Swelling will
have its own slower time frame.
• Fatigue aspects could also apply if continual movements are associated with the hose
service. Unless these conditions are severe, fatigue onset will probably be far off – it cannot
be quantified; one factor which could affect this is if diffusion to outer hose regions cause
rubber deterioration which allows crack initiation to occur. However, from the pointers
above, long times would be expected before this occurred.
• Fatigue could also make an existing crack (split) grow, but regular inspections should
monitor its rate It is unlikely to grow uncontrollably between inspections of once or twice a
year.
• It is thought that end-fitting debonding issues are not likely to be great. The bonded
interfacial region is thin (tens of micrometres) so that it displays only a tiny cross-sectional
area to crude oil internally and sea water externally. Hence only very small amounts of
liquid would be able to diffuse into the dried cured adhesive at the interface. Because of the
hugely-greater liner inner surface area, more oil would enter liner regions near the end-
fittings to cause swelling if sufficiently unconstrained; as these regions must be heavily
constrained, being compressed by the tightly-wrapped end-fitting holding (fixing) wires, this
attempted swelling will transpose to an associated swelling force which would realistically
acting radially inwards. This would lead to a compression of the interfacial adhesive region,
which would inhibit potential failure modes. It is not thought that the rubber-to-steel
adhesive interface is a likely failure path.
• Repeated inspections (annually or more frequent) are recommended to observe whether
cracks are initiated or if there is evidence of hose swelling; inspection at the end-fitting can
reassure on the debonding point above. (The possibility of whether a permanent painted
grid is possible on the hose to assist in these assessments can be considered.)
Sea water is not seen as a general hazard, as it causes minimal elastomer deterioration
throughout. However, if the existing split provides a short-cut route of seawater to the
embedded support wires, pitting corrosion is a possibility. Hence special inspection should be
made of any existing split region (if relevant), to include checking for local swelling, evidence
of rust etc.
7.2 FLEXIBLE JOINTS
For these components (see section 2.3), as well as the types of failures evidenced by elastomers
used as seals, elastomer-to-metal debonding can again be an issue to resolve at the design and
QA stage. Fatigue issues can also be important, as the application is a dynamic one.
7.3 DELUGE SLEEVE VALVE DIAPHRAGMS
Deluge sleeves (section 2.3) during development in their original form initially exhibited fatigue
failures brought about by a monthly testing routine demanded by the end-users to gain
confidence they would function if called upon in the event of a potential disaster. A material
42
development and change solved this problem. This is an unusual situation where the failure was
actually brought about by the QA testing deemed necessary to ensure that a component would
function whenever called upon to do so.
7.4 ROOT CAUSE ANALYSIS FOR COMPONENT- FAILURE GENERALLY
If a failure incident occurs, root cause analysis (RCA) can be used to identify the most basic
cause. If this cause is within management control, then steps can be taken to control it. If the
cause is design, then a re-design may be the only option. RCA will involve a sequence of
defining the problem and collecting data, charting events and causal factors, identifying the
critical or direct causes, and the root causes from which effective solutions can be identified and
implemented. Barriers to avoid unwanted outcomes may also need to be reviewed. A variety of
techniques is available for RCA, detailed description of which is beyond the scope of this
document. The following is a discussion of the specific aspects that may need to be considered
as part of an RCA of an incident involving elastomeric materials and components used offshore.
7.4.1 Gathering data
At this stage as much information as possible is required as input to the later stages. Things to
be considered include:
• the history of the conditions that the component has experienced – including storage,
installation and operation (e.g. temperatures, pressures, pressure changes, fluids, UV, ozone
levels, exceptional weather or storm events etc)
• details of the design specifications
• details of the design and materials selected and the methodology employed
• details of design verification and performance verification and validation
• quality records relating to the manufacture of the component and factory acceptance
(traceability of the rubber component should go back to the manufacturers moulding
records)
• procedures for transportation, installation and installation records
• maintenance and inspection procedures and records
• previous or similar incidents
• examination/analysis of failed components/material (see Guidelines section 9).
7.4.2 Barriers
Barriers to prevent incidents will be in place as part of work-place precautions and a risk control
system. Barriers are not only physical, but will also include documentation and procedures
involving:
• design review
• design verification and validation studies
• risk assessment
• quality assurance and inspection
• preventative maintenance
• training and supervision etc.
7.4.3 Charting events and causal factors
As part of an investigation, a sequence diagram that charts all the events chronologically,
together with their relationships, is produced. Generally, this will include equipment, personnel
and other factors, e.g. natural phenomena such as storms. Failure of a barrier can be a causal
43
factor but a root cause will generally lie within the management system that is responsible for
policy, organisation, planning and implementing, measuring and reviewing performance.
Causal factors for rubber materials will be related to a loss of function, e,g, the ability to
maintain an adequate sealing force in the case of a seal or the ability to contain in the case of a
hose. The failure of an elastomeric component will often result in leakage or the threat of
leakage; thus contributory factors to the performance of the elastomer will often need to be
considered in any incident involving a leakage. To identify causal factors, possible failure
modes should be considered. Some possible causal factors for elastomers are listed in Table 7.
Table 7 Possible causal factors for elastomeric components
Aspect Possible causal factors

Design specification LTA definition of the operating environment - functional requirements,
fluids, temperatures, pressures, loads decompressions etc).
Design (for seals) LTA selection of material - incompatible with fluids, insufficient strength,
excessive creep, stress relaxation, ageing, thermal expansion/contraction
etc).
LTA geometry i.e. seal size, groove size, tolerances - leading to groove
overfill or underfill.
Design (for hoses) LTA selection of material - incompatible with fluids, insufficient
strength/fatigue resistance, excessive creep, ageing, thermal
expansion/contraction etc.
Manufacture LTA quality assurance (mixing, processing, moulding, curing, bonding of
the elastomer not sufficiently controlled and/or measured) – leading to
variability in component performance.
LTA traceability of component manufacture.
Design verification LTA verification testing/analysis - acceleration factors inappropriate for
ageing and fatigue loading, fluid compatibility, loading and temperature
extremes not adequately accounted for.
Acceptance LTA factory acceptance test - inappropriate tests for the function of the
component or inappropriate acceleration factors for load, environmental
ageing, fluid interaction.
Installation LTA quality assurance - incorrect seal installed.
LTA procedures, training, supervision – resulting in damaged seal
housing, damaged seal, seal incorrectly installed.
Operations LTA monitoring (recording of operating environment, decompression

events etc.) - environment outside original specification, not compared
with specification).
LTA inspection (visible signs of deterioration).
LTA preventative maintenance (e.g. planned replacement of seals after
periods or decompression).
LTA procedures and training.
LTA – less than acceptable
7.4.4 Identifying the root cause
Various graphical techniques are used to identify root causes. One such technique is fault tree
analysis. Using the events and causal factors chart, the fault tree aims to work back from the
incident (e.g. a leakage) to a point usually in the management system where remedial action can
44
be taken to prevent repetition. A simple example of part of a fault tree is shown in Figure 10.
It is based on the report of an actual event where O-ring failure occurred as a result of contact
with an acid that was part of the well stimulation fluids. This is only a part of a bigger fault tree
that would be required to consider all possible contributions to the failures. There are clearly
further steps to follow down to explain why the stimulation fluids were in the process area and
why a different kind of acid was being used. Eventually this will lead down to root causes
within the management system.
Leakage
and
High pressure Deterioration of

o-rings
and
Acid present Acid incompatible

with elastomer
Stimulation fluids Different kind of acid used

entered processing than on other TLPs
area
Figure 10 Part of possible fault tree analysis for in-service seal failures
45
46
8 INDUSTRY STANDARDS
Tables and comments showing the designation of Standards concerning coding of elastomer
types, appropriate general mechanical properties, and chemical analysis to identify most aspects
about elastomers, are given in sections 3.4.3, 3.4.1 and 3.4.6 respectively. The comments below
address other Standards associated with elastomeric component upstream O&G performance.
Ageing behaviour is followed by observing changes in mechanical properties such as tensile

modulus and other tensile properties, compression set, tear strength (see Table 1).
8.1 NORSOK M-710 REV 2
This specific Standard for seals is designed to qualify “critical non-metallic (polymer) sealing,
seal and back-up materials for permanent use subsea” by addressing two aspects of performance
– chemical ageing and rapid gas decompression (RGD) resistance. NORSOK Standards are
administered and issued by the Norwegian Technology Centre.
For elastomers, the relevant sections of the Standard are 7.2 (and Annex A) and 7.3 (and Annex
B). The first provides guidance for evaluating chemical (including sour) ageing of elastomers,
the second to assess their resistance to rapid gas decompression (RGD) (or ED) events – testing
being conducted with housing jigs which constrain the seals in a service-realistic manner.
Clearly, the RGD test is only applicable if the seals contact pressurised gas during service. For
thermoplastics, only chemical ageing is listed (section 8 and Annex C in the Standard).
For the most part, NORSOK M-710 rev. 2 allows specimens and test conditions to be selected
which are service-relevant for primary seals, including the model test liquids to be used. For
sealing applications involving high pressure gas, it is crucial to replicate service conditions as
closely as possible when qualifying elastomers. However, NORSOK is rather restrictive about
the choice of gas mixtures that can be used in RGD testing. Findings from this work should
probably be tempered with regard to secondary seal situations as here, in practice, fluid
conditions at the seal will not reach the severity of the well conditions until primary seal failure.
Hence, NORSOK M-710 is highly relevant, although it is not perfect.
8.1.1 Detailed comments
The key word in this Standard is “shall”, defined in section 3.1 as follows:
“Verbal form used to indicate requirements strictly to be followed in order to

conform to the Standard and from which no deviation is permitted, unless
accepted by all involved parties.”
This means, for instance, that other O-ring sizes from the BS300 series, such as BS312, could,
with mutual agreement between interested parties, be used if a suitable argument for this change
could be made: for instance, valve seals may have thicker section than the 5.33 mm of the
BS300 series. In RGD testing at blowdown, O-ring section diameter governs gas diffusion rate
out of the seal, and the related housing geometry will govern how much reinforcement is applied
to the seal, to bolster elastomer strength levels. Hence, results should be the same after testing
any BS300 series O-ring, all other factors (temperature, pressure, blowdown rate, etc) being the
same.
47
NORSOK M-710 Rev.2 is relatively broad, allowing conditions and testpieces to be selected
according to particular needs.
Chemical ageing
Table 8 lists the important variables for elastomer ageing testing and gives the NORSOK
requirements, with other comments separately.
Table 8 Variables and comments on NORSOK M-710 requirements for chemical

ageing
Variable NORSOK Comment

Specimen BS325 (or other BS300-series - see Tensile testpieces from moulded sheet preferred;
text above) O-rings shall be used, constraint not necessary for ageing of sheet; O-rings
constrained; fluid access both sides necessary for compression set measurements – all BS300
series would give same result
Replication Three Five preferred for tensile testpieces
Fluid Shall be representative of seal If reservoir fluid unavailable, simulated sour production
application environment; sample fluid acceptable (Table A.1 in the Standard)
shall be exposed in the oil phase
Temperature Run tests at three temperatures For accelerated ageing, example test temperatures are
above service temperature 185, 195 and 205°C, if the service level is 150°C
Pressure 100 ±10 bar, or higher shall be used 100 bar sufficient, although pressure will not contribute
significantly to acceleration of chemical ageing
Duration Shall take account of time to reach Time to saturation usually short relative to that necessary
saturation for significant ageing; regular sampling of the highest
temperature exposure test will help determine exposure
duration for the lower temperature tests
Properties Mass/volume, hardness, tensile Tensile data for use in Arrhenius relationship, if
strength, elongation, E-modulus, applicable, to estimate life
compression set
Provided there is agreement between parties to the qualification testing, the above variables can
be altered to suit particular service conditions and testing requirements. Elastomer mechanical
properties for the purposes of reliable life prediction (and future use of the data) are best
obtained from 2 mm thick moulded sheet, from which tensile specimens are be die-cut and
tested to an appropriate Standard. O-rings for measuring tensile properties are very much a
second choice but have the advantage of being the actual part, incorporating any moulding
idiosyncrasies, etc. In using sheet specimens the assumption is that material properties are the
same as moulded sheet; although usually acceptable, this may not always be the case, especially
for thick parts and items where directional and/or memory effects may be introduced as a
consequence of the processing method used. O-rings are necessary to measure compression set.
The use of actual (or representative) seals is much more important in RGD testing.
The level of acceleration achievable will depend upon the maximum service temperature of
each sealing material. The chemical change (if it occurs at all) will be brought about by
interaction of the H2S with the exposed elastomers; hence the higher the level of H2S, the
greater the extent of ageing within a given time at a particular temperature. The H2S level in the
NORSOK sour simulation fluid is 2% (20,000 ppm).
Rapid gas decompression
48
Table 9 lists the important variables for elastomer RGD testing and gives the NORSOK position
and MERL comments in separate columns. There is no NORSOK provision for testing of
thermoplastics. Where such materials are used in sealing systems (e.g., to provide anti-extrusion
support to elastomer seals) they should be included when testing the elastomer(s), to ensure
realism. Thermoplastics in general are much more resistant to decompression damage than
elastomers, mainly because they are stiffer and have lower free volume. In the experience of
MERL, PEEK and PTFE perform well in RGD tests to at least 10,000 psi.
Table 9 Variables and comments on NORSOK M-710 requirements for RGD testing
Variable NORSOK Comment

Specimen Shall be BS325 O-ring Should be actual (or representative section) seal,
constrained realistically
Constraint 20% compression, parallel plates Use service compression and housing, if known;
otherwise plate or spigot/sleeve housing
acceptable
Replication Three 2 or 4 for O-rings, usually mounted in pairs, is
convenient
Fluid Three options are provided If service gas mixture unavailable, select closest
match; 90/10 CH4/CO2
Temperature Shall be conducted at 100, 150 or Test temperature should be maximum service
200 °C temperature, with perhaps supporting testing at
lowest temperature
Pressure Shall be conducted at 150, 200 or Test pressure should be maximum service
300 bar pressure
Duration Shall be 72 hrs Sufficient to ensure sample saturation; can
estimate given knowledge of diffusion
coefficients
Decompression Standard shall be 20-40 bar/min Rate should be that of service; if unknown, use
rate standard rate
Cycles 10 cycles with inspection at end Samples at 1, 3 or 5, 10 cycles for inspection
and rating
It is worth bearing in mind that the NORSOK M-710 RGD test pass/fail is based on inspection
of sectioned seals: in other words, it is not a leak test. It is not unknown for seals to continue to
function long after sustaining significant gas decompression damage.
More importantly, the Standard does not appear to recognise the importance of seal section. It is
pointless testing seals with a smaller section than those which will be employed in service as
simple extrapolation of performance is not possible. The specimen recommended is the BS325
O-ring (section diameter 5.33 mm). However, if the service section is only 3.53 mm, there is no
point in using BS325 seals as seal cord diameter is an important performance variable. Also, if
the seal section is not circular (e.g., a T-seal), or contains embedded springs (e.g., a spring seal),
no guidance is given on how the rating system should be applied. To re-iterate, there is little
point in testing seals of larger section than service, and no point in testing O-rings which are of
smaller section than that specified for service.
Test temperature and pressure should reflect service requirements. An elastomer qualified at
300 bar is not qualified at 1000 bar, but the reverse is true. Specimens are soaked in the
appropriate gas mixture until equilibrium saturation has been achieved, and then decompressed.
The Standard requires 10 cycles to be undertaken before the seals are inspected. MERL strongly
recommend that additional samples are removed for inspection after the first and (third or) fifth
cycles. Again, these will provide valuable performance information beyond the minimum
49
required by the Standard. This is particularly relevant in the case of the sealing materials to be
used in temporary operations.
Chemically aged specimens, if available, should be included in the RGD tests. Where ageing
has stiffened the elastomer, ED resistance is likely to improve.
The rating system given in NORSOK M-710 is useful for comparing seal ED performance. The
system ranks the four exposed sections of an O-ring according to the number and length of
cracks visible under magnification of at least 10X. A section which is visible intact is rated “0”,
one with a small number of short cracks “1” and so on. A rating of “5” indicates a seal splitting
crack and/or fragmentation of the seal. NORSOK states that ratings of 4 and 5 are unacceptable:
in other words, if any tested seal of a particular material has a 4 or 5 rating, the seal is
considered to have failed NORSOK, for the conditions employed. Examples of the sort of
fracture damage which attracts these ratings are shown in Figure 11.
Figure 11 Exposed sections of ED-damaged seals showing the range of fracture

damage for NORSOK rating 4 (top two) and 5 (lower two). The arrows indicate the
pressure direction across the seal during testing.
Clearly, any seal which splits completely or fragments is a poor performer and a 5 rating (the
worst case) should not be ignored. The 4 rating covers a range of fracture damage: >8 internal
cracks or one of more cracks longer than 80% of the seal cross section. In neither example for
this rating in Figure 11 is a path formed for gas to pass through the O-ring. However, the seals
are clearly badly damaged, and this may well increase with additional cycling; hence the 4
rating is considered by NORSOK to constitute failure.
8.2 API 17K
Specific Standard for hoses. It is largely concerned with ensuring that purchasers provide
sufficient information on service requirements and conditions when specifying, and that hose
manufacturers design to meet these specifications. One approach is that the manufacturers
provide the purchaser beforehand appropriate technical data previously obtained for their
elastomers by an independent laboratory testing against a range of fluids at different conditions.
50
8.3 NACE
Many Standards, for specific elastomer duties. As examples, ageing issues due to H2S
exposures in sour liquid and gas environments are covered in NACE Standards TM0296-96
(Item no. 21227) and TM0187-98 (Item no. 21220) respectively. (These Standards are seen as
supporting NACE Standard MR0175, which concerns “Sulfide stress cracking resistant metallic
materials for oilfield equipment”.)
Other examples for elastomer usage are two explosive decompression NACE Standard tests
TM0192 –98 (Item no. 21222) for moderate temperatures and TM0297-97 (Item no. 21229) for
high temperatures; a considerable weakness with these two Standards is that CO2 is specified,
ostensibly to accelerate testing times but in reality bringing about failure damage that might not
occur at all in real service conditions as dissolved gas concentrations are unrealistically high
with this gas (see section 4.4).
8.4 CORPORATE
Most, if not all, oil companies will have their own standard procedures associated with the use
of elastomers; some organisations have many, other fewer. Their usage will be the basis for
one-to-one contact with the supplier. In a few isolated cases, tests exist which have been
developed by an oil company and published, and which potential suppliers use to indicate the
good quality of their products; these tests may be undertaken by an independent laboratory.
But a warning on this; in one such case, involving ED testing, it was found necessary to make
the supplier aware that (i) a test developed and publicised by an oil company did not, in fact,
form part of the official standard procedures for that oil company, and (ii) even if the product
passed the test, this did not mean that the oil company would definitely use this product.
Potential suppliers should ascertain from each end-user the exact requirements to be formally
accepted as a supplier and to validate their goods.
51
52
9 BIBLIOGRAPHY FOR REVIEW

Design
“Seals and Sealing Handbook”, publ. DuPont de Nemours International S.A., Switzerland
(1985).
“Recommended Practice RP-F106: Factory Applied External Pipeline Coatings for Corrosion
Control” - see:
<http://exchange.dnv.com/BxWmWeb/TaskManager.asp?WCI=MenuArea&WCE=PMA_6_81
2!816!818&uid=ID20041021710580657197>
Guideline papers
S Groves, “Project Guidelines for Selecting Seals for High Pressure Gas Duty and other Oilfield
Service”, Proceedings “17th International Conference on Fluid Sealing”, York, UK, publ. BHR
Group, Cranfield, Beds, UK, (8 – 10 April 2003).
N Page and P Embury, “Elastomeric Seal Failure Analysis and Diagnosis”, Energy Rubber
Group Educational Symposium, Galveston, Texas, USA (1998)
Others
J Cowie, “Polymers: Chemistry and Physics of Modern Materials”, Blackie, Glasgow (1991).
J Brydson, “Plastics Materials”, Butterworth-Heinemann, Oxford (1996).
C Blow and C Hepburn (Eds), “Rubber Technology and Manufacture”, Butterworths, London
(1985).
F Eirich (Ed), “Science and Technology of Rubber”, Academic Press, New York (1978).
D Morton-Jones, “Polymer Processing”, Chapman and Hall, London (1989).
R Campion, “Permeation through Polymers for Processing Industry Applications”, Materials
Technology Institute of the Chemical Process Industries, St Louis, USA; distributed by Elsevier
Science, Amsterdam, The Netherlands (2000).
53
APPENDIX 1 ELASTOMER COMPOUNDING ISSUES
Compounding is the process of formulating a recipe from the above ingredients such that, when
all constituents are mixed and subsequently cured, the resulting elastomer has properties
suitable for a specific (sealing) application. Achieving the correct balance is complex and relies
very much the expertise of the seal manufacturer. The fine details may be commercially
confidential but the user should understand the basic principles in order to carry out a
meaningful technical dialogue with the manufacturer.
Many elastomers are compounded for general-purpose use, but particular duties may require
more specific combinations of properties. For such situations, particular compounds can be
formulated and their suitability established by appropriate tests. It is seldom sufficient to
specify an elastomer by generic type alone.
The compounding ingredients are normally supplied to the seal manufacturer by specialist
chemical companies. The seal manufacturer then mechanically mixes these additives with the
base polymer and cures the resultant material to form a stable vulcanized elastomer. Most seals
are made by curing the mix in a mould, which determines ultimate seal shape and dimensions.
Due to varying amounts of shrinkage during this process the tolerances on moulded elastomeric
parts are usually wider than for machined metal components. Individual classes of compound
ingredient are discussed below.
A1.1 Base polymer
The base polymer (elastomer) comprises long chain molecules whose chemical nature
determines the basic chemical and physical characteristics of the elastomer (see later). The
choice of elastomer is mainly determined by fluid resistance, chemical resistance and thermal
performance considerations. Usually, carbon atoms form the backbone of polymer molecules,
with other atoms such as hydrogen or fluorine or larger chemical groupings (pendant groups)
attached at regular intervals. The chemical nature of both the main chain and the side groups
give rise to the affinity or otherwise of a polymer for other chemical species. The degree of
affinity is roughly expressed thermodynamically in terms of polarity. For a better approach to
determining the compatibility of polymers with fluids, the solubility parameter approach is very
useful (see later).
A1.2 Cure system
The function of the cure system is to produce chemical crosslinks between neighbouring
polymer chains. In relation to the length of the polymer chains there are only a few crosslinks,
but these confer physical stability on the network. Curing is a chemical process and it generally
takes place in a mould under the action of heat, required to break down the curatives to instigate
the required reactions. Pressure is applied concurrently so that the correct product shape is
achieved, and porosity within the elastomer (due to the volatilization of certain ingredients and
cure by-products at early stages of cure) is avoided. Crosslinking agents include:
Organic peroxides - these usually introduce crosslinks directly between polymer backbones,
Amines - these introduce crosslinks between polymer chains via an organic section with amino
groups either end (an “amine bridge”),
Sulphur - commonly used in general purpose rubbers; the crosslink is formed from one or more
sulphur atoms,
Bisphenols - commonly used vulcanizing agents in FKM compounds; the crosslink is formed
from a derivative of the bisphenol.
54
Elastomers for sealing applications should be fully cured (i.e., all of the crosslinking agent
consumed), and have sufficient crosslink density to ensure material stability, particularly with
respect to temperature. Use of inadequately cured material could have serious consequences as
the curing reaction will continue in service resulting in massive compression set. The cure time
and temperature are established by rheometric measurements. A rheometer monitors compound
stiffness (torque) as curing proceeds at a particular temperature; from the resulting trace the
optimum cure time can be determined. Good quality control procedures are essential to ensure
consistent full cure of elastomer compounds.
NB. Different classes of curing systems should not be mixed; for instance, the presence of
sulphur inhibits the curing activity of peroxides.
A1.3 Post-cure
The majority70 of seals based on FKM, FFKM and FEPM elastomers must be post-cured, that is,
after removal from the mould articles are subjected to a secondary cure for a number of hours
(typically 16 to 24) at atmospheric pressure and a temperature above the original cure
temperature. Post-curing operations are invariably carried out in an oven. The process allows
gaseous by-products to escape from the elastomer by diffusion, and aids consolidation of the
crosslinked elastomer network. Other elastomers (e.g., NBR and HNBR) may, for some
applications, also require a post-cure.
A1.4 Fillers
Fillers are particulate inorganic materials added to an elastomer primarily to modify its
properties. They can change the
Tensile strength,
Elastic modulus, or hardness,
Tear strength,
Abrasion resistance,
Fluid-swell resistance,
Chemical resistance,
of an elastomer compound. Filler materials include
Carbon black (by far the most common filler type – and of several different particle sizes,
leading to different elastomer property levels),
Calcium silicate,
Treated calcium carbonate,
Finely divided silica,
Talc,
Barytes,
Whiting
Magnesium carbonate.
Fillers are generally referred to as “reinforcing” or “non-reinforcing”. These terms are not well
defined but, generally, reinforcement of an elastomer refers to an increase in modulus and/or
abrasion resistance. For most elastomers the addition of a reinforcing filler will increase its
tensile strength, and indeed many elastomers can only reach practical levels of tensile strength
70
There are now some fluoroelastomers on the market which, according to their manufacturers, do not require a post-
cure.
55
through the addition of such fillers. Carbon black and silica are the primary reinforcing fillers;
larger particle size materials such as whiting do not reinforce. The ability of a filler to reinforce
depends on its ability to bond to itself and to the elastomer - determined by such factors as size
(surface area), shape, and the physical and chemical nature of the filler surface.
A1.5 Antidegradents
In static seal elastomers the function of antidegradents (or protective agents) is to inhibit
Oxidation,
Ozone attack,
Light (including uv) and thermal degradation,
Flex-cracking (in dynamic applications).
Antidegradants are typically complex organic chemicals or waxes. As protection may be
required against more than one of the degradation sources listed, blends of chemicals are often
used: this procedure lessens the chance of individual antidegredants exceeding their solubilities
in the elastomer, and consequently migrating to the surface to cause an effect known as
“bloom”. Selection of suitable antidegradents is complex because the effects which the
chemicals may have on the vulcanization of the elastomer has to be taken into account.
A1.6 Plasticisers
Plasticizers include
Mineral oils,
Waxes,
Organic esters.
The function of a plasticiser in high quality components is to enhance the low temperature
properties of the elastomer. By separating the molecular chains, plasticisers lower the glass
transition temperature of the base polymer. However, this can come at the expense of high
temperature ageing resistance. A secondary function of plasticiser is to ease mixing and
moulding operations. Plasticisers may also be used as extenders to allow the incorporation of
higher levels of filler. This is usually carried out to reduce costs, and may be difficult to detect,
but it will lead to lower physical and chemical properties in almost any circumstances.
Comparisons between apparently identical products require caution.
56
APPENDIX 2 STRESS RELAXATION VERSUS SWELLING

FORCES FROM LIQUID ABSORPTION OF CONSTRAINED
ELASTOMER, AND TEMPERATURE EFFECTS
Figure A1 shows initially a typical linear plot of applied load relaxing in a linear mode with log
time for a size 312 (BS1806) EPDM O-ring located in the housing region of a specially-
developed stress relaxometer used for testing seals. After some 20 minutes, hydrocarbon
solvent was added to contact fully the seal’s inner surface – this being possible by design with
this relaxometer. (This material/liquid high-swelling combination was chosen to illustrate the
point being made.) Over successive decades of time the early feature of stress relaxation in the
absence of solvent is overcome by swelling forces after its addition – because the elastomeric
seal is driven to attempt to swell in contact with the solvent, but cannot, being constrained by
the housing, it instead produces extra stress – “swelling stress”. This phenomenon can be
beneficial in the early stages of swelling, by opposing stress relaxation and maintaining sealing
stress. However, if it continues to high values as shown, it can increase the possibility of
extrusion damage – especially as the elastomer modulus gradually reduces as solvent is
absorbed. More reasonable sealing elastomers for hydrocarbons will display this phenomenon
but to a lesser extent – the risk of eventual overswelling is less.
solvent removed
2000
1500
with solvent
solvent added
load (N)
1000
dry
500
0
1 10 100 1000 10000 100000
time (mins)
Figure A1 Seal swelling force taking over from stress relaxation on addition of solvent
Turning to temperature effects, a compressed elastomeric seal will lose sealing force
significantly when the temperature is reduced, due to a mixture of thermal contraction,
geometric, and thermodynamic effects, as illustrated for a cycling situation in Figure A2 –
actual test data being shown.
57
Figure A2 Cyclic temperature effects on stress relaxation
58
APPENDIX 3 HIGH PERFORMANCE THERMOPLASTIC

DEVELOPMENT
The five major-use engineering thermoplastics comprise polyamide (PA), acetal (POM),
polycarbonate (PC), modified PPO and polybutylene terephthalate (PBT). Acetal, for instance,
can be used continuously in air at temperatures around 100 °C; if the material contacts fluids in
service, the continuous use temperature will be lowered. Above this on the property scale are
the (so called) super-engineering plastics (e.g., PEEK, PEK, PEKK, PPS, PES, PSU, PI, PAI,
PAR, LCP, PEI, fluoroplastics). These are produced in lower volumes for specific demanding
applications in the aerospace, automotive, electrical, chemical processing and offshore oil and
gas industries. Of this group the fluoroplastics (particularly the perfluoroplastics71) possess the
ultimate combination of heat stability and chemical resistance, and they are chosen for these
qualities rather than mechanical performance per se: the latter has to be optimized as well as
possible in the quest for utmost chemical resistance. Others such as PEEK have generally very
good chemical and thermal resistance, combined with superb mechanical properties, which in
themselves might be the reason for their choice. A good example would be the widespread use
of PEEK as a back-up ring material, an application which demands exceptional strength and
dimensional stability as well as good chemical and fluid resistance. Although a soft material
compared to PEEK, PTFE is also widely specified for back-up rings, a role which can exploit its
outstanding thermal and chemical resistance. PTFE is also used as a primary seal, but must be
energised, usually via an embedded metallic spring or an elastomer. Polyurethanes are similar in
a many of ways to polyamides but are little used as a thermoplastic moulding material due to
their high cost. Polyurethane elastomers (and fibres), on the other hand, are very versatile and
widely used [2], but not commonly in sealing applications. The development of polymers to
replace metal as an engineering material has brought many benefits, the reduction in weight
being especially important in the aerospace industry.
Two main strategies have evolved for the development of high performance engineering
thermoplastics. The first seeks to stiffen the polymer chain, usually by the introduction of
aromatic rings to the backbone. In this way, Tg is raised, as is Tm if the stiffer chains have a
linear symmetrical structure and are sufficiently mobile to form ordered arrays with
neighbouring macromolecules during processing. Taken to extremes, this approach results in
materials which are extremely heat resistant but impossible to process by conventional means.
In the case of the polyimides, this intractability has been overcome with the development and
commercialisation of thermoplastic polyimides. These incorporate ether-containing units in the
polymer backbone which greatly improves its flexibility, but at the expense of some thermal
stability.
The other general approach to raising performance, particularly chemical and thermal
resistance, has entailed the “replacement” of the (relatively) weak C-H bonds in the polymer
structure with significantly stronger C-F links. The best known perfluoroplastic is undoubtedly
poly(tetrafluoroethylene)72, the fluorinated analogue of PE. With PTFE however, high thermal
stability arises from the combination of (1) high crystallinity and (2) the absence of C-H bonds;
a jacket of fluorine atoms surrounds the all-carbon backbone. The high crystallinity is a direct
result of the linear chain growth (no branching) during synthesis. While this is desirable for
chain packing, it is also responsible for the poor cold flow of PTFE, which in turn explains the
extremely high MW necessary for commercial PTFE: in general, chains must be sufficiently
branched or long to entangle and ensure reasonable mechanical properties so that, for PTFE,
very long macromolecules are necessary. However, high MW means high melt viscosity, hence
71
Polymers in which all C-H bonds which can be “replaced” are fluorinated.
72
More commonly known as Teflon (DuPont tradename), Teflon PTFE, or just PTFE.
59
the impossibility of processing PTFE by conventional means: special techniques such as
compression moulding, paste extrusion and ram extrusion are required. In all three methods,
PTFE particles are sintered, that is, fused above Tm (an inter-surface phenomenon). In
compression moulding PTFE powder is compacted in a mould at room temperature into a
preform prior to a sintering, usually in an air-circulating oven. In ram extrusion the die is
continuously charged with free-flowing PTFE powder, which is compressed and forced into the
sintering zone of the extruder. Paste extrusion requires the addition of a processing aid,
allowing a cylindrical preform to be fabricated. This is then forced through a heated die where,
within the sintering region, the extrusion aid is vaporised and the PTFE fused; the lubricant is
completely removed during the process. In all PTFE processing methods, incomplete fusion
leaves microvoids in the polymer bulk and these can affect properties73, particularly permeation
behaviour. This is used to advantage for some filtering applications. This feature has been
highlighted as a possible starting point for explosive (rapid gas) decompression failure of
PTFE.
It was in order to overcome the difficulties of processing PTFE that many years ago impetus
was given to the development of numerous TFE-based co- and terpolymers; commoner choices
include HFP, PPVE, PMVE, VDF and E. The major commercial polymers resulting from these
developments are ECTFE, ETFE, FEP, PFA and MFA. The copolymers have improved
mechanical properties since the asymmetric commoner allows increased chain entanglement,
which reduces slippage under loading. An important consequence of copolymerization is the
reduction in MW it allows, enabling the modified polymers to be melt processed using
conventional equipment. Polymers synthesized from partially fluorinated monomers (PVDF,
PVF, PCTFE) are more easily processed than PTFE, but none has its superior thermal and
chemical resistance.
Some high performance polymers are completely amorphous but have a high Tg, so that they
function below this temperature; examples include PES, PPSU, PSU and PAI. By and large
these materials are functional as long as the service temperature remains below Tg but
mechanical properties degenerate rapidly at this transition. Because they are glasses, with more
free volume than semi-crystalline thermoplastics, the amorphous engineering plastics tend to
have a lower resistance to chemical attack and dissolution. In some applications their optical
clarity is a desirable attribute, but this varies according to polymer type; for example, Teflon
AF is colourless, Ultem PEI is amber brown.
73
The incorporation of small (<1 mole%) amounts of a second fluorinated monomer during TFE polymerization, to
produce “modified PTFE”, has resulted in some marked property improvements.
60
APPENDIX 4 DETAILS OF ARRHENIUS APPROACH, & OTHER
FACTORS
It has become an established practice over recent years to apply the Arrhenius equation, derived
from physical chemistry, to property changes. The equation has been applied to two general
areas:
(a) Chemical ageing effects on a mechanical property, where k = A exp (-Ea/RT)

(b) Permeation, diffusion, solubility, where e.g. D = D0 exp (-Ea/RT)
where k is reaction rate, D is diffusion coefficient, A and D0 are frequency-associated constants,

T is absolute temperature, R is the gas constant, and Ea for each is the activation energy of that
process. In standard physical chemistry, k is measured by considering concentration changes,
wheras for the diffusion-related properties, the coefficients represent rate per unit cube. From
these equations, for both chemical and diffusion-related situations, the plotting of log k or log D
against 1/T (°Kelvin) should give straight lines, of slope – Ea/R. This has been shown to apply
for numerous situations.
The –Ea/RT term is a statistically-derived term, associated with

• the amount of reaction occurring (numbers of molecules attaining an energy level greater
than Ea) for (a)
• the probability governing the number of big enough holes (between the rubber molecular
chain segments as they continually move kinetically) capable of accepting diffusing
molecules of another species for (b).
Solubility also follows a similar equation (using the solubility coefficient s). As permeation
involves both diffusion and solubility (see section 4.3.1), its temperature dependence also
follows an analogous Arrhenius equation.
A convenient way of doing this is by defining rate as being reciprocal time, the time in question
being the duration of ageing to a specified stiffness (etc) loss or gain. This is repeated after
exposures at other temperatures, and Arrhenius plots developed. Figure A3 shows a schematic
of three typical tensile-modulus versus time plots that have been observed as an elastomer is
aged in a hostile fluid at three high temperatures (well above service temperature for the
application in mind). In reality, each plot had several individual points on it, each being the
average of three measurements. An initial physical softening due to fluid absorption was
followed by two chemical stages – crosslinking, then degradation. Taking the reciprocal of the
time to each maximum value as a rate associated with good performance for each temperature,
the Arrhenius plot shown in Figure A4 is obtained. An extrapolation to service temperature
could then be carried out. (Alternatively, rates k can be quantified by the local gradient
applying for any stage.)
61
Mechanical
Property
Level
Decreasing
Temperature
Exposure Time
Figure A3 Changes in e.g. modulus level versus exposure time at three temperatures
Some related points:

• if other properties (tensile strength, tear strength) are dominated by stiffness aspects, they
could also be treated in this way.
• if flaws dominate the measured value, clearly they will not be governed by stiffness factors
so that the Arrhenius approach may not then apply.
• sometimes in these tests there is insufficient time at the lower exposure temperatures to
reach the specified stiffness change. By making a significant number of measurements at
shorter times, it may be possible to extrapolate the property/time plot until the specified
stiffness change is reached, to give a predicted time which can then be used in an Arrhenius
plot.
• applying the stiffness-for-concentration argument to chemical kinetic equations, it is strictly
most appropriate to plot the logarithm of the property against time when making the initial
extrapolation; however, experience has shown that this procedure does not alter the rate
calculated as outlined earlier for inclusion in Arrhenius plots such as shown in Figure A4.
ln(1/ts) • 225°C Elastomer exposures to

aggressive fluid
• 210°C
Short-time
tests at 195°C
high •
temperatures
service
ts = time to 160°C temperature
reach
specified 5 years
stiffness.
rate k = 1/ts
1/T
2.0 2.3
x10-3
Figure A4 Extrapolation to service temperature using an Arrhenius plot
62
A fair criticism of the example just discussed is that a three-point Arrhenius plot gives a poor
statistical basis for a subsequent extrapolation. This is undeniable; however, this example was
deliberately chosen to illustrate the paucity of data that are sometimes available to engineers
when making predictions of this type. These tests were for an oilfield application, where the
seals were to be made from a chemically resistant elastomer. The ageing exposures were
conducted for several months at temperatures between 200°C and 300°C, and at fluid pressures
of 15,000psi (ca. 100MPa); hence the ageing durations were long, and experimentation was
difficult. Moreover, the oilfield engineers required the data as soon as possible for offshore
operational reasons, as they had a “window” of opportunity for putting the appropriate
equipment in place. In these conditions, the data shown represented a prediction for the
engineers to employ, adding their own safety factor as thought necessary. One approach to help
this is to use a statistical assessment of the data plotted, and hence derive the “worst case”
extrapolation.
Another extrapolation possibility exists for some cases where circumstances decree that only a
few aged property magnitudes can be obtained. If the chemical mechanism of the appropriate
ageing-induced deterioration is known and can be followed in a relatively-easy way by a
suitable chemical analytical technique, giving many data, a reliable activation energy so-derived
could be applied to the few property data obtained, to give confidence to any extrapolation to
service temperature.
A4.1 Permeation/diffusion etc at high pressures
Arrhenius-type plots of permeation, diffusion and solubility can be in the form of series of
bands rather then a line, as both time and high pressure can cause values to decrease (by
allowing physical compaction of the polymer to occur. This has been verified for elastomers
and thermoplastics at high gas pressures.
A4.1.2 Factors which can override predictions.
Attempts to predict when failure will occur due to other factors such as swelling require extra
stages, i.e. (loss of) stiffness might be used to quantify the swelling meaningfully by an
Arrhenius approach, but less predictable factors such as extrusion might also intervene.
Validation testing is required in such a case. Predicting the onset of explosive decompression
damage can be equally difficult - the usual approach is to design housings, etc, that experience
has shown will limit damage (and maintain sealing, etc) to the greatest extent, and perform
multicycle tests at higher pressures and temperatures than service ones to determine the best
materials. In a similar way, crack growth fatigue issues may be changed during ageing and
these may override other factors.
63
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Printed and published by the Health and Safety Executive
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ISBN 0-7176-2969-4
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Elastomers for fluid containment in offshore oil and gas production: Guidelines and review
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Elastomers for fluid containment in offshore oil

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RESEARCH REPORT 320

Elastomers for fluid containment in offshore oil

Dr R P Campion, Dr B Thomson and Dr J A Harris

First published 2005

ISBN 0 7176 2969 4

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(ii) Development of a review document relating to the use of elastomers on offshore

ELASTOMERS FOR FLUID CONTAINMENT IN OFFSHORE OIL &

1.1 STRUCTURE OF GUIDELINES ................................................................................2

2 FUNCTIONAL PROPERTIES AND DETERIORATION MODES OF

2.1 FUNCTIONAL PROPERTIES ....................................................................................5

2.2 FUNCTIONAL PERFORMANCE FACTORS .................................................................5

2.3 MODES OF DETERIORATION..................................................................................7

3 DESIGN ASPECTS ...........................................................................................11

3.1 MATERIAL SELECTION ........................................................................................11

3.2 SEAL DESIGN ....................................................................................................11

3.3 DESIGN ASPECTS FOR OTHER COMPONENTS .......................................................12

6 QUALITY CONTROL/QUALITY ASSURANCE DURING MANUFACTURE......19

8 OPERATION AND MONITORING/INSPECTION ..............................................23

9 FAILURE ANALYSIS ........................................................................................25

9.1 ROOT CAUSE ANALYSIS......................................................................................26

10.2 TECHNICAL .......................................................................................................29

11 BIBLIOGRAPHY FOR GUIDELINES ................................................................33

ELASTOMERS FOR FLUID CONTAINMENT IN OFFSHORE OIL &

Figure 1 Schematic of an O-ring seal in operation, with some possible deterioration

(1) carcass; not fluid-containing. Has other duties.*

1.1 STRUCTURE OF GUIDELINES

Figure 3 Structure of guidelines – key stages

2 FUNCTIONAL PROPERTIES AND DETERIORATION MODES

2.1 FUNCTIONAL PROPERTIES

Elastomers (also termed rubbers) are:

The behaviour of an elastomer can be characterised by property magnitudes. Mechanical

2.2 FUNCTIONAL PERFORMANCE FACTORS

2.2.1 Viscoelastic effects

For more details, see the indicated sections in Part 2 (Review):

Property magnitudes depend on temperature; elastomers expand on heating, accompanied by a

2.2.3 Fluid absorption

For more details, see the indicated sections in Part 2 (Review):

Regarding long term performance, rates of fluid-induced deterioration of elastomers, whether

Figure 4 Schematic of a spigot/sleeve fixture used to house O-rings for realistic ED

2.3 MODES OF DETERIORATION

See also Guidelines section 9

Although an infinitestimal amount of deterioration can be taking place in an elastomer as soon

For more details, see the indicated sections in Part 2 (Review):

Failure mode Description

For more details, see the indicated sections in Part 2 (Review):

In general terms, deterioration could arise from:

3.1 MATERIAL SELECTION

3.2 SEAL DESIGN

For more details, see the indicated sections in Part 2 (Review):

3.3 DESIGN ASPECTS FOR OTHER COMPONENTS

For deluge sleeve valve diaphragms, fatigue considerations must be included.33

Shaft/piston OD _ Material _

Bore/housing ID _ Material _

Production gases CO2 H2S Other