ELASTOMERS USED IN THE

OIL AND GAS INDUSTRY AT

EXTREMES OF TEMPERATURE
AND PRESSURE

Glyn Morgan, Dr Sabine Munch &

Philip Clarke

Element Materials Technology

Hitchin, UK

RIEG Meeting, Elastomers in Extreme

Environments, London,
December 2014
What we do in Hitchin

• In-service realistic synergistic effects (pressure, temperature, fluids, time)

• High pressure, high temperature fluid exposures (accelerated ageing, fluid
compatibility)
• Produced (sweet, sour), completion, control, kill, muds, inhibitors, biocides,
stimulation acids, solvents, methanol, salt water, ...
• High pressure gas permeation
Non Metallic materials in Oil & Gas applications

Elastomers

Composites

Thermoplastics
Introduction

• Low Temperatures
• Visual Monitoring of Seals
• High Pressures
• High Temperatures
• Extrusion
• Rapid Gas Decompression (RGD)
• Chemical ageing
Low Temperature Functional Testing

• ISO 10423 and API 6A detail

pressure/temperature cycling tests to be
performed to qualify seals for defined
service conditions 16000 140
• Seals quite often leak at low
14000 120
temperatures well in excess of their
Tg 12000 100

temperature ('C)
pressure (psi)
10000 80

8000 60

6000 40

4000 20

2000 0

0 -20
0 20 40 60 80 100 120 140 160 180
pressure
time (hours)
temperature
Low Temperature Functional Testing

40
20
30
• Methodology developed in JIPs
20
(COLD, COLDX....COLDHP?)
10 15
• Automated test with housed seal
0 (O-ring, PTFE, T-Seal ...)
0 5 10 15 20 25 30 35 40 45
RE-SEAL • Established low temperature

PRESSURE
-10
TEMP

SEAL
-20
10 sealing factors for sealing and
leaking
-30

-40
LEAK 5
-50

-60

-70 0
TIME

Cool under pressure

Current LT performance test
Low Temperature Functional Testing

• Unaged seals:
10
• Tg correlates with low 0
temperature functional limits
-10

Functional limit (°C)

• 15 elastomers
-20
• Swollen seals:
-30
• Tg and low temperature limit
both decrease -40 seal
• Thermally aged seals: -50 leak

• Tg unchanged -60
-70
• Low temperature limit
increased -80
-80 -70 -60 -50 -40 -30 -20 -10 0 10
Tg (DMA °C)
Tg alone not sufficient to explain all
behaviour
Low Temperature High Pressure

• Elastomers contain free volume

• This helps to make them elastomeric
• It can be reduced by high pressure
• This will affect stiffness (modulus)
• Seals won’t be able to accommodate movement or ‘change’
• Is there an empirical relation between pressure and stiffness?
• Historically: 50 bar 1oC rise in glass transition temperature
Low Temperature High Pressure

• DMA Dynamic Properties Elastomer vs Temperature

2.00E+10

1.75E+10

1.50E+10

1.25E+10
Modulus /Pa

1.00E+10

7.50E+09

5.00E+09

2.50E+09

0.00E+00
-80.0 -60.0 -40.0 -20.0 0.0 20.0
Temperature /°C
High Pressure Tg Effects

• HP DSC
0
y = 0.0198x - 33.372
-5 R² = 0.9973
Tg (°C)
-10
-15
-20
-25
-30
-35
0 500 1000 1500
applied pressure (bar)
High Pressure Tg Effects

• Tested with nitrogen and FKM

• Test with methane, carbon
dioxide
• Nitrile, Aflas, (FFKM)
• Is the 50 bar 1oC rise in Tg
‘universal’?
forced close

permeation rate
• 2,000 bar? packing

limit of proportionality
pressure
Low Temperature Visual Observation

• Being able to see what is happening to a seal as it

functions or leaks is worth a thousand hours ‘in the
dark’
• Developed two sapphire-windowed pressure
vessels
• One with an O-ring squashed and sealed
against one window
• One with windows at both ends to observe
material samples
• Swell/contract thermally and with applied
pressure
• Swell/blister on decompression
Low Temperature Visual Observation

Pressure up to 350 bar

Temperature up to 150ºC
2 s to 100 min sampling rate

Camera Pressure Light

cell with source
sapphire
windows
Low Temperature Visual Observation
Seal ID

Contact
width
Low Temperature Visual Observation

Observations:
• Pressurized seals remain ‘locked’ in their
energized shape when cooled, even when leakage
occurs – no movement or loss of contact area is
observed
• Without pressure, there is a reduction in contact
width during cooling but this does not reduce to
zero
• When cold, unpressurised seals function (re-seal)
when the temperature allows low-level movement
at the seal ID
Low Temperature Visual Observation

Observations:
• Seal movement under the influence of applied
pressure is a primary factor in sealing capability
• Tg is a reliable (conservative) basis for seal
selection, provided that significant thermal ageing
does not occur during service
Visual Observation

• What else can we see directly?

• Unconstrained material sample
• Super critical CO2
• Swelling/decompression damage

gas gas
Supercritical
Fluid
liquid liquid
Visual Observation

Front lighting Back lighting

• Surface changes (cracks, • Polymer swelling/compaction in

blisters, chemical ageing...) HPHT conditions
• Absorption/desorption rates
• Diffusion coefficient
• Thermal expansion
Visual Observation

FKM @100ºC and 300 bar pure carbon dioxide

  




 - Start of the test
 - Thermal expansion
 - End of pressurisation
 - Equilibrium swelling

 - Dwell period (no
changes) 1012
pixel



High Temperature - extrusion
Predicted Strain Distribution in the Seal at failure
Extrusion of Seal

Maximum strain 129-

143%

12
23C
10 50C
100C
150C
8

Stress (MPa)
6

Strain to failure
2 at 100C = 100%

0
0 50 100 150 200 250
Strain (%)
High Temperature – gas decompression

• NORSOK M-710/ISO 23936-2

• NACE TM0192, TM0297
•
7000

Shell RGD rig 6000

• TOTALFINA SP-TCS-142 5000

4000

• Service 3000

2000

1000

API 17J (ISO 13628-2)

High Temperature – gas decompression

• Service envelope below which

damage-free operation
• Differentiate elastomers, seal types
and boundaries
400
unsafe – possible
RGD damage
300
pressure (bar)

200

safe to use –
100
no damage

0
0 50 100 150 200
temperature (°C)
High Temperature – gas decompression

• X-ray CT scan (screenshot from

video)
sleeve
O-ring

bolt

spigot damage –
dark areas
High Temperature – chemical ageing

• Does this form of damage matter?

• Yes because the material is degraded

• BUT it might still continue to seal for a while
longer
High Temperature – chemical ageing
High Temperature – chemical ageing

• Why – because we are measuring material

performance and not seal performance

35 200

30

150
25
50% modulus (MPa)

Elongation at Break (%)

20
160 C 100 160 C
15 170 C 170 C
180 C 180 C

10
50

0 0
0 10 20 30 40 50 0 10 20 30 40 50 60

Time (days) Time (days)

High Temperature – chemical ageing

• Which we use to estimate material life from

the Arrhenius approach

-2.6

ln(1/time to 50% change in modulus) -2.8

-3.0

-3.2

-3.4 y = -7325.4x + 13.379

R² = 0.9991
-3.6

-3.8

-4.0
0.0022 0.00225 0.0023 0.00235
1/Temperature (K)
Concluding remarks

Cold temperatures + high pressures = raised Tg

and unexpected seal leakage

T/P cycling standards – too severe or

unrepresentative?

High temperatures = extrusion, RGD, ageing.

Reduce by design and new materials

Material + functional testing + visual observation

+ FEA = greater confidence in reliability
New Facility

Double capacity
30 sour
90 non-sour
20 specials

10 staff to run
Operational Q4
New Facility

SOA DAQ
Capability in Houston 2015
Thank you

Glyn Morgan
[Link]@[Link]