MPWT19-14451

Advanced Functional Testing for Non-Metallics in HPHT Conditions

Rod Martin, Vice President Technology

Element Materials Technology
10 Lower Grosvenor Road
London, SW1W 0EN
United Kingdom

ABSTRACT

As the service conditions for non-metallics becomes ever more challenging, their reliability and fitness
for service evaluation requires more refined levels of testing. For elastomers used in HPHT sour
conditions, the need to evaluate their ability to continue to seal requires testing that closer represents
them as an elastomer seal and not as an elastomer material. This paper discusses new methods to test
new techniques for the use of sour gas to conduct rapid decompression testing and new functional testing
techniques to measure their ability to seal. The increased use of composite materials in more aggressive
service has required new evaluation approaches to be developed and new standards written to match.
This paper also discusses these new test methods for testing at a material and a pipe level within these
standards.

Keywords: Elastomers, composites, sour service, functional testing, sour gas service, regression testing,
burst testing.

INTRODUCTION

While non-metallics comprise a fraction of the materials used in oil field production compared to metallics,
their performance in service is as critical as any steel-based component. Non-metallics are generally
classified as elastomers used primarily for sealing, thermoplastics used primarily for insulation and
pressure barriers and composite materials (or fiber reinforced plastics) used primarily for tubulars. The
new horizons for oil production require operators to produce from high pressure high temperature (HPHT)
reservoirs. Downhole temperatures in excess of 200C and pressures in excess of 20,000 psi provide
challenges for non-metallics in terms of their ability to withstand the operating conditions where gases
such as CO2 and H2S are supercritical.

Elastomers function as seals, packers, barriers etc. by deforming against surfaces to prevent passage of
fluids. Their elasticity allows them to accommodate changes in temperature, pressure and movement in
ways that are impractical for ‘harder’ materials. However, at very low and very high temperatures this
elasticity may be compromised particularly when also under pressurized conditions causing the
component to lose its rubbery capabilities and cease to function as expected. In addition, operation in a
sour gas environment, creates degradation issues that interact with its function to seal and not split under
rapid gas decompression events. This paper presents some test methods and observations for testing in
these environments.

In 2007 a technology gap review of composites in the UK oil and gas industry1 was published that listed
a number of existing and potential uses of composites and their barriers to growth in the oil and gas
industry. In 2013 a paper was published2 demonstrating the growth of composites as an enabling material
in risers and other tubulars and in 2018 DNV-GL published a very detailed standard based on its previous
recommended practice for thermoplastic composite pipes (TCP) to meet the significant increase of this
material type3. This growth in these materials over the past 10 years arise from these materials being
lighter, stiffer (in the fiber direction), stronger and more corrosion resistant than carbon steel. The
willingness of the industry to accept components fabricated from composite materials is directly related
to the operational risks for that component and experience in their use. This paper also discusses some
of the new approaches of testing composite materials for these applications.

FUNCTIONAL TESTING OF ELATOMERS

Elastomers have a long history in critical applications in the oil and gas industry with many instances of
successful operation for decades at high and low temperatures, high pressures and in potentially
aggressive media4. But there are also examples of failure such as leakage from the elastomer failing to
service its function. Some of these setbacks can be linked to inadequate materials, poor design or
misunderstanding of the operational requirements or capabilities of the elastomer involved. One such
issue is the behavior of elastomers at extremes of temperature, both high and low. More and more oil
and gas fields are being developed where low temperatures are common (cold environments or blow-
down events) or higher temperature production. The inclusion of rapid decompression events also
requires additional qualification steps.

For extremes of temperature a typical ISO 10423 F.1.11 (API 6A)5 test might involve subjecting a sealing
arrangement to pressure and temperature cycling between -18 and +121°C with pressure differentials of
690 bar; the seals must not leak during a set of pre-determined hold points of pressure and temperature.
Seals made of elastomers with theoretical low temperature capabilities well below -18°C have been found
to fail at the final test phase when pressurized which needs to be better understood.

Sealing at Cold Temperatures

Pressurizing an elastomer raises its glass transition temperature (Tg) by way of reducing internal free
volume and hence increasing stiffness. Therefore, particularly at low temperatures, there is potential for
seals to lose elasticity when at high pressure due to a Tg shift. The measurement of Tg with pressure is
a critical measurement to quantify. Recent developments have led to a differential scanning calorimeter
(DSC) being used at high pressures in the oil and gas industry for gas hydrate research and wax
appearance temperatures in oil industry.

To demonstrate this, an FKM Type 3 was investigated based on Viton® GLT which has a relatively low
Tg4. This was tested in nitrogen at 1 bar, 250 bar, 500 bar, 750 bar and 1,000 bar using an HP-MicroDSC.
The resultant Tg versus pressure plot and its linear trend with the equation relating the two variables is
shown in Figure 1 confirming the often-considered rule of thumb that 50 bar ≡ 1°C shift in Tg. In practice
this means that 1,000 bar pressure is capable of increasing Tg by 20°C which when combined with
contraction and housing/seal design could explain why seal leakage has been observed at temperatures
well above what Tg alone would suggest is expected. This leads to the observation that a measure of Tg
is an effective measure or predictor of seal performance at low temperatures. However, there may be a
limit to this relationship if all free volume is eliminated from an elastomer.
 0

-5

-10
y = 0.0198x - 33.372
-15 R² = 0.9973

Tg (°C)
-20

-25

-30

-35
0 200 400 600 800 1000 1200
applied pressure (bar)

Figure 1: Shift in Tg of an FKM Type 3 with pressure (in nitrogen)4

As more oil and gas fields are developed under HPHT conditions, so these considerations will become
ever important – 1,400 bar testing of materials has already been undertaken and this may increase to
2,000 bar in the near future.

Sealing at High Temperature

At higher temperatures, several elastomer failure mechanisms become more prevalent, especially when
in conjunction with high pressures and aggressive media. Amongst these is extrusion, where elevated
temperatures make materials weaker and softer and easier to tear. Also affected by temperature is gas
decompression resistance; higher temperatures make the diffusion process faster and solubility lower
which are compensated for by the weaker material which cannot resist bubble formation. Thirdly,
chemical attack is accelerated at higher temperatures for such species as H2S, corrosion inhibitors and
other treatment chemicals resulting in hardening (or softening), increased stiffness, loss of elongating
properties and loss of sealing properties through compression set and sealing force issues.

A test to look at the measure of sealing force as a measure of the function of a seal to continue to seal4.
O-rings were used as face seals with pressurized treatment chemicals on the inner diameter with the
whole assembly heated to high temperature. The test used a load cell arrangement to measure the total
force generated by the seal and the environment and to monitor how this changed with ageing of the
seal. To do this, a constant dimension of extrusion gap was required that could be reproduced. In this
test, the extrusion gap was large and significant extrusion occurred unexpectedly, Figure 2. Although the
seal force was seen to change, any extrusion was unwelcome and complicated the measure of force
from ageing and environment.
Figure 2: Badly extruded O-ring at High Temperature Figure 3: Less extruded O-ring

A second test was performed at a lower temperature in the same fixture showing far less extrusion with
the result seen in Figure 3.

Rapid Gas Decompression in Sour Gas

Damage to seals caused by rapid gas decompression (RGD) events has been a problem for many years
but several compounds have been introduced in that time which are resistant to the phenomenon and
have established service histories. However, as the pressures and temperatures of exploration and
production continue to increase, so the number of effective compounds will decrease. Testing for RGD
resistance often takes the form of seals in custom-built hardware (Figure 4) designed so that several
materials can be tested simultaneously, with the best material progressing to further service-specific
testing or marketed as qualified to certain standards such as NORSOK M-7106 or ISO 23936-27.

Figure 4: RGD fixture and examples of RGD damage

The usual inspection routine for RGD damage involves disassembling the fixture and observing internal
and external damage features such as shown in Figure 4, which shows a range of splits, blisters and
cracks, all of which become more prevalent as temperature is increased. In a development of the
inspection process, a still-assembled metal fixture containing a pair of tested O-rings and subjected it to
X-ray CT scanning and the internal damage show is visible as dark patches, Figure 64. These were later
confirmed after disassembly illustrating that the CT scan is a viable a NDT approach for inspecting valves
etc. in-situ without the need for disassembly.
sleeve O-ring

bolt

spigot damage –
dark areas

Figure 6: CT scan image of inside O-ring assembled in its metal RGD fixture

As given in ISO 23936-2 standard, Annex F7 for safety reasons, RGD testing described above is rarely
undertaken with H2S (or gas mixtures containing H2S) in test laboratories even if the service conditions
will be sour. Currently, CO2 is considered as a suitable substitute gas because it is more soluble than
methane and is believed to give more conservative results. While Element has undertaken sour RGD
tests for several years, the conditions ranged from a few per cent H2S at moderate pressures to very low
levels of H2S at high pressures. The level of H2S was insufficiently high to have a measurable influence
on O-ring RGD resistance. However, there is evidence that H2S is absorbed more readily and in greater
quantities at equilibrium than is carbon dioxide. Hence, there is a possibility that H2S is the more hostile
gas in terms of elastomer RGD resistance; in addition, there may be an additional ageing aspect
introduced.

In Reference 8, HNBR and fluoroelastomer grades were selected for the program with the HNBR chosen
because it is less resistance to chemical deterioration for the study. Higher levels of H2S were used with
a small free volume in the pressure vessel but still requiring dedicated boosting, scrubbing and gas
detection equipment. The sour test gas mixture was specified as 25/75 mol% H2S/CH4. With this mixture,
200 bar was achieved. A four-cycle test at 200 bar and 100 °C, with venting at 20 bar/minute, was used.
The results were compared with a base case of RGD with methane.

The results from the testing is that H2S is more soluble in HNBR than CO2 and this situation is believed
to apply to fluoroelastomers generally. The H2S caused a significant increase in RGD fracturing in
susceptible elastomers, when compared with CO2. The conclusion was that substitution of H2S by CO2
when running “sour” RGD tests is too conservative and future qualification RGD tests should include
running with a sour gas component or increasing the level of CO2 used. More R&D in this area is required.

COMPOSITE MATERIALS

Composite materials are not new to the oil and gas industry with glass reinforced epoxy and vinylester
filament wound pipes having been used extensively onshore in processing plants to transport water (fire
systems, deluge, drilling and processed water), crude oil and gases. In the Middle East, thousands of
kilometers are in use and some lines are over twenty years old. Filament wound composite pipes are
also routinely used to line steel pipe providing corrosion protection for the pipe bore by acting as a barrier
to the passage of transported fluids. Composite materials are also now commonly used to repair corroded
steelwork, including pipes, decks, structural members and caissons.

To meet some of the future challenges, the industry is beginning to look at new types of composite
materials moving on to glass and carbon reinforced thermoplastics that offer high temperature capability,
and high load capacity and stiffness. These are known as TCPs (Thermoplastic composites). To qualify
these materials news standards are being introduced such as ISO 23936-4 (Draft)9 and DNVGL-ST-F119
requirements for flexible TCPs3. The following section describes some of the work to look at screening
and also for full qualification of composite materials in these new applications conducted at Element
Hitchin.

Short Term Screening Tests

Early work on these new applications before these standards were written looked at screening of
materials. In Reference 10 a screening test program on a wide range of reinforced thermoplastic
materials was conducted with the aim of selecting different materials that could be used in spoolable
composite pipes. Thermoplastic resins including POM, PA11, PEEK, PPS, PVDF, and Polypropylene
were reinforced with either continuous glass or carbon fibers depending on the resin system and the end
use environment. Three wet environments were specified, salt water, hydrocarbon, and sour fluid, all at
representative temperatures and pressures. With composite materials the angle of the fibers at different
depths through the pipe wall is one of the design requirements and allows the stress and stiffness to be
optimized for the application. For pressurized pipe, the optimized lay-up is (approximately) +55o/-55o. As
part of the screening, mechanical tests were conducted before and after exposure to the three conditions
on laminates fabricated at those angles. The tests chosen for the screening were tensile, flexure and
interlaminar shear tests. These reflect a range of properties of the composite that are dominated either
by the fiber or the thermoplastic matrix to give a high level of understanding of the level of degradation.
The tensile properties of PPS/Carbon after one-week exposure in a hydrocarbon are shown in Figure
showing that all materials appear suitable in these short-term conditions.

Tensile Property Levels

1.6
Maximum stress Maximum strain Young's modulus
1.4

Normalised Property Level

1.2

0.8

0.6

0.4

0.2

0
Unaged 100°C 120°C 140°C
Exposure Temperature

Figure 7 PPS/Carbon: Effect of one-week hydrocarbon exposure using tensile coupons

The specimens for these tests, shown in Figure 7 follow very much the same test standards as other
composite materials tests, e.g. ASTM D3039, but the panels have to be fabricated as flat panels for these
tests. It is assumed manufacturing flat panels gives representative data laminated manufactured by the
winding process.

Long term thickness degradation considerations

For any long term study, a detailed investigation is needed into the techniques for gradual ageing starting
from the surface that is exposed to the corrosive media. In Reference 2 the effect of gradual degradation
or ageing through the thickness was modeled to look at the effect of the inner layer degradation effect on
the overall properties of the pipe. This is analogous to corrosion in metals which is a surface effect and
is permitted to a certain depth or corrosion rate. A test method was developed as shown in Figure 8
where fluid was added to the internal pipe and the arrangement set to different temperatures. Test
coupons were also placed in the pipe and aged at the same condition to determine degradation at coupon
level and from coupons cut from the pipe to determine any difference. To prevent the cut edges of the
pipe being affected by the test fluid, they can be coated in a resin that is resistant to the fluid as shown
in Figure 8. These tests are still ongoing.
 Figure 8 Single sided exposure samples

Figure 9 Example ring test at elevated temperature and pipe ring test under compression

The publication of DNVGL-ST-F1193 gives a very thorough methodology for qualifying spoolable TCPs
from a material level to full-scale and includes fatigue and stress rupture testing that Element have set
up to test. An example of ring testing at temperature and compression testing of pipe testing are given in
Figure 9. For these tests a stress rupture test can be performed up to 1000 hours and illustrative data
are shown in Figure 10 allowing extrapolation to longer service durations.
 Figure 10: Indicative data for stress rupture testing

Another long-term regression test investigates burst pressures. A facility was developed at Element that
can test several pipes at one time at different internal pressures, Figure 11. The test pipes are placed in
a containment vessel that contains heated water. Internal pressure is applied and monitored using a Data
acquisition system to identify the burst event for times up to 1000 hours. The water temperature up and
down the containment vessel is maintained by … The current facility allows for six pipes to be tested at
one time with pressures up to 10,000 psi. Example of different configurations of post pipe burst tests are
shown in Figure 1211.

CONCLUSIONS

This work described some of the current test techniques for two types of non-metallics (elastomers and
composites) in aggressive oil field production conditions. For elastomers, under low temperatures, an
understanding of the change of properties with temperature needs to be understood to ensure that the
material will continue to seal under such cold temperatures. At high elevated temperatures with the
material softening, extrusion of the material needs to be avoided by fully understanding the gaps allowed
between the two sealing faces. This paper also reviewed the work done on resistance to rapid
decompression where not using sour gas during the test may lead to unconservative results. Finally, test
methods for qualifying composites, particularly the thermoplastic composites (TCPs) are presented
illustrating that qualifying these materials to the new DNV standard is available with growing knowledge.
 Figure 11: Long term TCP burst facility

a) Glass reinforced POM (b) Kevlar reinforced pipe

Figure 12: Qualification/Development burst tests of reinforced thermoplastic pipe
 ACKNOWLEDGEMENTS

The author acknowledges the colleagues in Element Materials Technology Hitchin who conducted the
work described in this paper. The project leads for this work include Amir Hajdaei, Luke Shield, Glyn
Morgan and Barry Thomson.

REFERENCES

1. R. H. Martin, A Technology Gap Review of Composites in the UK Oil and Gas Industry, MERL
Technical Report C1889 1 March 2007, Hitchin UK.
2. R. H. Martin, Composite Materials: An Enabling Material for Offshore Piping Systems, OTC Paper
23925 MS,
3. DNVGL-ST-F119 Composite TCP Standard
4. G. Morgan et al, Challenges of Temperature Extremes for Elastomer Materials, API Paper High
Performance Polymers for Oil and Gas Conference, Edinburgh, 2014
5. ISO 10423:2009 Petroleum and natural gas industries — Drilling and Production Equipment —
Wellhead and Christmas Tree Equipment.
6. NORSOK M-710 Qualification of non-metallic sealing materials and manufacturers Rev 2 2001
7. ISO 23936-2:2011 Petroleum, petrochemical and natural gas industries — Non-Metallic Materials
in Contact with Media Related to Oil and Gas Production Part 2: Elastomers
8. B. Thomson, M. Lewan, K. Somani, RGD Tests Involving Hydrogen Sulphide, Element Materials
Conference, London, April 2016
9. ISO 23936-4, “Petroleum and natural gas industries - Non-metallic Materials in Contact with
Media Related to Oil and Gas Production; Part 4: Fibre reinforced composites”
10. R. H. Martin, Ageing of Composites, Woodhead Publishing London, 2008
11. EPL Composite Solutions project coordinator; Element (MERL), Chevron, Hess, Subsea 7
(Acergy), Ticona, PERA partners. TSB project No: TP/MHP/6/I/22341