RILSAN® Polyamide 11

in Oil & Gas

Off-shore Fluids
Compatibility Guide

ATOFINA Chemicals, Inc. 2000 Market Street Philadelphia, PA 19103-3222 Telephone: (215) 419-7000
ATOFINA Canada, Ltd. 700 Third Line Oakville, Ontario L6J5A3 Canada, Telephone: (905) 827-9841
www.AtofinaChemicals.com
After 14 years of research in a program
launched in 1958 by the French Institut de
Petrole, polyamide 11 was chosen as the
best material out of several hundred
tested. Today RILSAN® polyamide 11, the
unique polyamide from ATOFINA, looks
back at a service history of over 30 years
in the petroleum industry. The combined
qualities of flexibility, excellent impact
resistance even at low temperatures, high
resistance to aging and good compatibility
with products common to the petroleum
industry environment have made RILSAN
polyamide 11 an unequaled standard.
For even higher demands, especially at
higher temperatures or when the
combined high temperature and high
water content requirements are too
severe, ATOFINA proposes its unique
KYNAR® off-shore grade. KYNAR is a
thermoplastic fluoropolymer resin
developed by ATOFINA. Outstanding
thermomechanical properties combined
with exceptional chemical and aging
resistance enable KYNAR to meet the
most stringent demands.

The data given in this brochure describe the material performance of RILSAN® polyamide 11 in applications such as
pneumatic or hydraulic tubes. For large diameter pipes or sheaths such as in flexible pipe the data give indications
of lifetime limits, but further considerations might have to be taken into account. Hence this data may be inapplica-
ble where lifetime and design specifications established by flexible pipe manufacturers or joint industry efforts have
resulted in new recommended practices or industry specifications.
The statements, technical information and recommendations contained herein are believed to be accurate as of the date hereof. As the condition and methods of use of
the products and of the information referred to herein are beyond our control, ATOFINA expressly disclaims any and all liability as to any results obtained or arising from
any use of the product or reliance on such information; NO WARRANTY OF FITNESS FOR ANY PARTICULAR PURPOSE, WARRANTY OF MERCHANTABILITY, OR ANY OTHER WAR-
RANTY, EXPRESS OR IMPLIED, IS MADE CONCERNING THE GOODS DESCRIBED OR THE INFORMATION PROVIDED HEREIN. The information provided herein relates only to the
specific product designated and may not be applicable when such product is used in combination with other materials or in any process. The user should thoroughly test
any application before commercialization. Nothing contained herein should be taken as an inducement to infringe any patent and the user is advised to take appropriate
steps to be assured that any proposed use of the product will not result in patent infringement.

BEFORE HANDLING THIS MATERIAL, READ AND UNDERSTAND THE MSDS (MATERIAL SAFETY DATA SHEET) FOR ADDITIONAL INFORMATION ON PERSONAL PROTECTIVE EQUIP-
MENT AND FOR SAFETY, HEALTH AND ENVIRONMENTAL INFORMATION.
 PA11 CONTENTS

1 1 General introduction and material overview Page 2

1.1 Introduction to thermoplastic polymers 3
1.2 General guide for the use of polyamide 11 3

2 2 Technical data: RILSAN® BESNO P40 TLO resin 5

2.1 Mechanical properties and design parameters 5
2.2 Thermal properties 5

3
3 Overview of aging properties and chemical compatibility 7
3.1 Heat aging 7
3.2 UV aging 8
3.3 Chemical aging 9
3.4 Chemical resistance tables – RILSAN® BESNO P40 resin grades 10
3.5 Aging in water and acidic solutions – hydrolysis 15
3.6 Influence of methanol on aging and mechanical
properties, permeability data 17
3.7 Influence of monoethyleneglycol and ethyleneglycol
based hydraulic liquids on mechanical properties 19
®
3.8 Compatibility of RILSAN BESNO P40 TLX and BESNO P40 TLO
resins with various offshore fluids and chemicals 21
3.8.1 Demulsifiers 22
3.8.2 Corrosion inhibitors – oil soluble 22
3.8.3 Corrosion inhibitors – water soluble 23
3.8.4 Corrosion inhibitors – oil soluble and water dispersible 24
3.8.5 Oxygen scavengers 24
3.8.6 Biocides 25
3.8.7 Paraffin inhibitors 26
3.8.8 Scale inhibitors 27
3.8.9 Overview of chemical compatibility of RILSAN® BESNO P40 TLX
and BESNO P40 TLO resins with common offshore chemicals 27
3.9 Compatibility with crude oil, natural gas,
carbon dioxide (CO2 ) and hydrogen sulfide (H2S) 29
3.9.1 Compatibility with crude oil 29
3.9.2 Compatibility with natural gas 29
3.9.3 Compatibility with carbon dioxide (CO2) 30
3.9.4 Compatibility with hydrogen sulfide (H2S) 30
3.10 Data on permeability of polyamide 11 30
3.11 Blistering resistance 31
2
1
General introduction and
material overview
The term umbilical is applied to
connective systems between underwater
equipment such as wellheads, subsea
manifolds or remote operated vehicles
(ROVs).
An umbilical generally consists of a group
of hydraulic lines, injection lines and/or
electrical cables bundled together in a
flexible arrangement, sheathed and
sometimes armored for mechanical
strength and/or a specific buoyancy.
Related information describing
recommended practice can be found in
the API documents 17R, but also in
API 17B and API 17J on flexible pipes.
Specific examples of structures are given
below.
Fig.1 Umbilical cross sections
PA11 hydraulic PA11 hydraulic
hose 1/2” hose 1”
PP fillers
Tape binder PE sheath
PP separator
Steel armor wires and outer sheath
A range of materials comes into play to
make up the entire structure:
• carbon steel for the armor
• metals for electrical wire
• cable sheathing
• different thermoplastics for the
injection and hydraulic lines
• fiber reinforcement, often aramid
fibers are used
• outer sheathing of umbilical, often
polyethylene or polyurethane
• duplex steel for hydraulic lines
Extruded pipe made from polyamide 11,
in combination with an aramid braiding
and subsequently sheathed with another
layer of polyamide, provides a very
reliable hose possessing high flexibility,
very high pressure performance, unlimit-
ed seamless tube length and long life in
harsh offshore environments.
Power cables Outer sheath
PP fillers
PA11 hydraulic
Steel armor wires hose 1/2”
 3

Fig. 2 Morphology of a semicrystalline polymer The following table gives an outline of the scope of properties of thermoplastic
a. b. polymers which can be found in offshore applications today.
● ●
● ● ● lc
● ●
●
● ● Lp
● ● ●
● ●
la COMPARISON OF DIFFERENT THERMOPLASTIC POLYMERS USED IN OFFSHORE SERVICE
● ● ●
● ●
PVC HDPE PA11 PVDF
d. c.
Density (g cm-3) 1.38 – 1.40 0.95 – 0.98 1.03 1.78

Melting Point (°C) 80 130 – 135 188 160 – 170

Flexural modulus (MPa) 1100 – 2700 700 – 1000 300 – 1300 800 – 2000
a. repeat unit cell b. crystalline (lc) and amorphous
(la) domains within the long period Lp (lamellar Tensile strength (MPa) 50 – 75 20 – 30 25 – 30 37 – 48
structure) c. a stack of lamelle d. the spherolite.
Shore D hardness 55 – 70 32 – 61 75 – 77
1.1 Introduction to thermoplastic
polymers LOI (%) 42 5.7 26 44

Thermoplastic polymers are a class of

materials with a wide range of flexibility,
a medium range of elasticity and a wide
range of upper temperature limits. For 1.2 General guide for the use of polyamide 11
semicrystalline materials, their maximum
Polyamide 11 is a specialty nylon. It combines high ductility, excellent aging resistance
use temperatures are limited by the
and high barrier properties with mechanical strength and resistance to creep and fatigue.
melting point of the crystalline phase.
It thus compares advantageously to standard nylons such as 6 and 66. Notably its signifi-
An image of the general structure of a cantly lower water absorption results in better aging resistance, higher chemical resist-
semicrystalline thermoplastic material is ance and less property fluctuation due to plasticization by water.
given above. The properties of such a
material are governed by the interplay of
the crystalline phase giving strength and COMPARISON OF DIFFERENT POLYAMIDES
temperature resistance and the amor-
PA 66 PA 6 PA 11 PA 11
phous phase rendering the material plasticized
tough and flexible. Typical examples of
Melting point (°C) 255 215 188 184
semicrystalline polymers are high density
polyethylene (HDPE), polyamide 11 or Density 1.14 1.13 1.03 1.05
nylon 11 (PA11) and polyvinylidene
fluoride (PVDF). Flexural modulus (MPa)
50% RH (23°C) 2800 (1200) 2200 1300 300

Water absorption
50% RH (23°C) 2.5 2.7 1.1 1.2
in water immersion 8.5 9.5 1.9 1.9

Charpy notched impact

ISO 180/1A (kJ/m2)
23°C 5.3 (24) 8 (30) 23 N.B.
- 40°C X X 13 7

ISO 527
Tensile stress (MPa) 87 (77) 85 (70) 36 21
Tensile elongation (%) 5 (25) 22 –
Elongation at rupture (%) 60 (300) 15 – 200 360 380

N.B. = no break, values in parentheses at elevated humidities, RH = relative humidity

4

The excellent properties of polyamides
and in particular polyamide 11 are a result
of the amide linkages in the chain which
allow a strong interaction between the
chains by hydrogen bonds. Low creep,
high abrasion resistance, good resistance
to fatigue and high barrier properties are
a direct result of these strong inter-chain
links.
Molecules which can create hydrogen
bonds such as water, methanol, ethanol,
ethylene glycol can penetrate polyamide
11 and lead to plasticization. They can
interfere in inter-chain hydrogen bonds
thus weakening the hydrogen bond net-
work. Especially methanol has a signifi-
cant absorption rate and must be consid-
ered in certain applications. Please refer
to section 3.6.
PA CHAINS WITH H-BONDING
Although polyamide 11 is highly resistant A range of RILSAN® polyamide 11 grades
to aging and chain breakdown, the reac- has been developed to correspond to the
tion of water with amide bonds creates a specific needs of the oil and gas industry.
limit to the use of polyamide at higher
BESNO P40 TL
temperatures and in the presence of
A high viscosity and plasticized grade
water. The specific reaction induced by
developed for pipe extrusion.
water, called hydrolysis, can be accelerat-
ed in the presence of acids. At continuous
BESNO P40 TLX
service temperatures of 65°C and below,
A high viscosity and plasticized grade
the impact of hydrolysis on polyamide 11
developed for pipe extrusion especially
in a neutral medium such as water can be
for the inner pressure layer of flexible
neglected. Under these conditions, the
pipe.
material can have a service life of 20 years
or more. The use at higher continuous
BESNO P40 TLO
service temperatures depends on the per-
A high viscosity and plasticized grade
formance requirements and more precise
developed for pipe extrusion with a low
conditions. The reader should refer to
extractable content especially adapted for
data on temperature – lifetime correla-
hydraulic hoses in umbilicals.
tions in section 3.5.
The blooming of oligomers has clogged
valves or filters in subsea installations.
REACTION: HYDROLYSIS Oligomeric molecules present in the
polymerized PA11 resin are extracted and
O
the material is compounded with a
=

vvvvv C–N vvvvv +H2O →

← vvvvv CO2H + vvvvv NH2
H–N plasticizer and heat additives.
–

C=O IIIIIII H–N H

C=O IIIIIII H–N BESNO P20 TL
C=O
A special molecule, butyl-benzene-sulfon- A medium plasticized, high viscosity extru-
amide or BBSA, has been chosen as a sion grade for pipe and sheath extrusion.
O=C
N–H IIIIIII O=C plasticizer. It has very low volatility and
N–H IIIIIII O=C leads to an efficient plastification of the BESNO TL
H–N resin. Questions related to its extraction A high viscosity unplasticized grade
or its influence on material properties are adapted for pipe extrusion.
discussed in section 3.7.
H–N BMNO TLD
C=O IIIIIII H-N An injection molding grade.
C=O IIIIIII H–N BUTYL-BENZENE-SULFONAMIDE OR BBSA
C=O These grades are all of natural color.
O Certain colored grades or color master
O=C II batches are also available.
N–H IIIIIII O=C
N–H IIIIIII O=C S N
II
O H
 5

FLEXURAL TESTS ACCORDING TO ISO 178 : 93

Temperature °C -40 -20 23 80

Flexural modulus MPa 1950 1350 320 165

(dry material)

Flexural modulus MPa 2050 1150 280 160

(after conditioning 15
days at 23°C, 50% R.H.)

FLEXURAL TESTS ACCORDING TO ASTM D790

Temperature °C 23 80

2 Flexural modulus
(dry material)
MPa 330 170

Technical data: BESNO P40 TLO

BESNO P40 TLO is a plasticized and IMPACT TESTS ACCORDING TO ISO 179 (type 1)
washed polyamide 11 grade. The
Temperature °C -40 23
methanol washing process eliminates
low molecular weight extractables Unnotched KJ.m-2 N.B. N.B.
(chemical name: oligomers) which can
lead to fouling or clogging of the filters Notched KJ.m-2 8 N.B.
or needle valves. N.B. = no break

2.1 Mechanical properties and

design parameters IMPACT TESTS ACCORDING TO ISO 179 :93 CA
DENSITY
Temperature °C -40 -20 0 23
ASTM D792 1.05 g/cm3
Notched KJ.m-2 6.8 9.9 52.9 N.B.
HARDNESS
ISO 2039/2 (R SCALE) 75
ISO 868 (D SCALE) 61

COMPRESSION STRENGTH
ASTM D695 (23°C) 50 MPa

ABRASION RESISTANCE
ISO 9352 : 1995(F)
(loss in weight after 1000 rev under
500g H18 wheel) 22 mg 2.2 Thermal properties

THERMAL CONDUCTIVITY

Temperature (°C) 39 61 82 102 122 142 163 182 202 223

K (W/m°K) 0.21 0.24 0.24 0.24 0.24 0.24 0.25 0.25 0.25 0.25

THERMAL EXPANSION HEAT DISTORTION TEMPERATURE SOFTENING POINT

ASTM E 821 ASTM D648 ASTM D1525

from -30°C to +50°C 11x10-5 °K-1 ISO 75 (0.46 Mpa) 130 °C under 1 daN 170 °C
from +50°C to +120°C 23x10-5 °K-1 ISO 75 (1.85 Mpa) 45 °C under 5 daN 140 °C
6

HEAT CAPACITY

Measured by D.S.C.
Temperature (°C) 20 50 80 120 160 200 230 260

cal/g.°C 0.40 0.50 0.6 0.6 0.65 0.65 0.65 0.65

GLASS TRANSITION TEMPERATURE

D.M.A. 0-10 °C

DYNAMIC MECHANICAL ANALYSIS flexibility. This softening is due to the

(full curve) onset of motion, the glass transition, in
the amorphous regions. From 40 to 160°C,
The DMA curve obtained is characteristic the PA11 modulus remains very stable
for semicrystalline polymers. Essentially due to the crystalline phase with its
four different temperature zones can be onset of melting starting only around
described which are related to character- 160°C. The fine distribution of the crys-
istic relaxational transitions. talline phase and its constant modulus,
The first zone is a low temperature high largely independent of temperature,
modulus zone which starts to soften guarantee very stable mechanical
around –20°C. Due to efficient low tem- properties over a very wide temperature
perature relaxations (centered around range and a high resistance to creep.
–80°C) PA11 is tough even at these very For a textbook on the comprehensive
low temperatures. analysis of DMA data refer to Anelastic
Between –20 and 40°C the material soft- and Dielectric Effects in Polymer Solids by
ens gradually to attain its characteristic N.G. McCrum, B.E. Read, G. Williams;
Dover Publication, New York, 1991.

1.00E+10
STORAGE MODULUS E' (Pa) LOSS MODULUS E" (Pa)

E'
E"

1.00E+09

1.00E+08

1.00E+07
-140 -120 -100 - 80 -60 -40 -20 0 20 40 60 80 100 120 140 160 180
TEMPERATURE ( °C)

Fig. 3 BESNO P40 TL – plasticized PA11 Measurement in a 3-point bending flexural mode at 10 rad/s
 7

3.1 Heat aging

Heat in the presence of oxygen causes oxidative degradation. For the reaction of
oxygen with an organic polymer to take place, oxygen molecules must diffuse into the
bulk polymer from the outside. Reactions occur first on the surface, leading to surface
embrittlement.

Oxidative degradation can be efficiently suppressed by anti-oxidants. All RILSAN® PA11

grades used in offshore applications have specially suited anti-oxidant packages. In
the grade nomenclature, this is notified by a suffix “TL.”

Heat aging performance has been established based on accelerated tests in a ventilat-
ed oven. In most cases the performance is monitored by tensile experiments. An

3 example of a typical test series is given in the figure below.

Overview of aging properties of

polyamide 11 500
• mean values
Polyamide 11 is subject to aging phe- 450
nomena. These phenomena are rather • •
400
ELONGATION AT BREAK (%)

varied and depend on the specific envi-

ronment. The most important factors 350
• •
inducing aging and subsequent loss of •
properties for polyamides are: 300

• Heat 250

• UV light 200
• Chemicals
150
All data given in the following chapters
100
refer to BESNO grades. The suffix “P40”
signifies a plasticized grade. 50 •
“TL” and “TLX” signify various heat and •
light stabilizer packages. 0 50 100 150 200 250 300 350
TIME (HOURS)
The suffix “TLO” signifies an oligomer
extracted grade which is heat and light Fig. 4 Reduction of elongation at break: BESNO P40 TLX aged at 155°C
stabilized.
8

Fig. 5 Laboratory aging as a function of temperature – half times from elongation at break 3.2. UV aging
are taken from injection-molded and machined samples – material is BESNO P40 TLX. The
influence of poorer surface quality on aging performance is demonstrated.
UV light in conjunction with oxygen leads
4 to similar surface degradation effects as
■■■ 20 YEARS ■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■

heat degradation. Effective anti-UV light

3.5 ■■■ 10 YEARS ■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■
stabilizing packages are routinely
■■■ 5 YEARS ■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■
employed to protect the resin (marked by
3 suffix “TL”). Different tests have been
developed to simulate the impact of UV-
■■■ 1 YEAR ■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■■
light combined with natural weathering.
LOG TIME (DAYS)

2.5
These tests include cycles where the sam-
ples are alternatively subject to moist heat
2 and UV light.

1.5 The UV resistance is measured under

accelerated conditions on a standardized
Machined machine, XENOTEST 1200, according to
1 Injected the RENAULT standard no. 1380. Results
+ are shown in Figure 6.
Linear (machined)
.5 Linear (injected)
Conditions:
Xenon lamps with filters eliminating radia-
0 + + + + + + + + tion with wave lengths less than to 300 nm.
150 140 130 120 110 100 90 80
TEMPERATURE ( °C) Intermittent exposure – equal periods of
light and darkness.
Fig. 6 Laboratory aging of BESNO P40 TLX: Xenotest 1200 During a 20 minute cycle, the specimens
400 are exposed to 3 minutes of distilled
• water spray and 17 minutes of exposure
350
• without spraying. The relative humidity of
ELONGATION AT BREAK (%)

300 the cabinet during period without spray is

• approximately 65%.
250

200 Black panel temperature in the measure-

ment cabinet:
150
65°C ± 2°C before spraying
100 45°C ± 2°C after spraying
•
50 The specimens are dumbells according to
•
ISO/NFT 51034 cut from a film of 1 mm
0 500 1000 1500 2000 2500 thickness. Tensile tests are carried out at
TIME (HOURS) 50 mm/minute.

TIME (h) 0 500 1000 1400 2000

EB (%) 380 330 275 85 33

EB/EB0 1 0.87 0.72 0.22 0.09

MB (MPa) 72 61 47 34 25

YI 6 14 16 13 13

EB = elongation at break, MB = modulus at break, YI = yellowness index

 9

3.3 Chemical aging Fig. 6A Evolution of Yellowness Index (YI) in Xenotest aging

40
In offshore applications, certain offshore
fluids and chemicals can have a detrimental 35

ELONGATION AT BREAK (%)

effect on polyamide 11 performance. For 30
each application, the specific chemicals
should be reviewed in order to estimate 25
service life. YI 20

Polyamides, and in particular polyamide 15 •

11, are very resistant to many types of • • •
10
chemicals. Polyamide 11 is very resistant
to oils and hydrocarbons as well as to a 5•
large variety of solvents. In contrast to
standard polyamides 6 and 66; polyamide
0 500 1000 1500 2000 2500
11 shows only little absorption of water
TIME (HOURS)
and is also resistant to diluted acids and
bases. Due to its increased flexibility and
molecular structure, it is also highly resistant
to stress cracking, unlike most other thermo-
plastics. EQUILIBRIUM SWELLING AND CHEMICAL COMPATIBILITY
OF COMMON SOLVENTS AND OFF SHORE FLUIDS
Polyamide 11 can be used in conjunction
with a great variety of standard offshore Solvent Swelling at 20°C in % weight Compatibility
chemicals. A detailed description of compat-
ibilities is given in sections 3.8 and 3.9. Benzene 7.5 good up to 70°C / swelling

Because chemical species attack thermo- Toluene 7 good up to 90°C / swelling

plastic resins when they are absorbed,
Cyclohexane 1 good
diffusion and solubility play important roles
in the assessment of chemical compatibility. Petrol ether 1.5 good
There are two effects induced by absorbed
species – an influence on the mechanical Decaline <1 good
properties due to plasticization, and a
Gasoline depends on type, mostly < 2% good
chemical effect leading to loss of material
performance. Kerosene depends on type, mostly < 2% good

Specific examples of absorption and Ethylene glycol 2.5 good up to 60°C / swelling
plasticizer extraction are given in sections
3.6 and 3.7 on methanol-and glycol-based Glycerol 1 good up to 60°C
hydraulic liquids.

The main chemical effect is reduction in

polymer molecular weight due to hydroly-
sis. Hydrolysis is the reverse reaction of the
chain-forming polycondensation reaction.
It can be induced by water at elevated
temperatures and is accelerated by acids
and, to some extent, also by bases. Due to
the importance of hydrolysis in aging relat-
ed to offshore applications, section 3.5
describes the phenomenon in detail.
10

3.4. Chemical resistance table – BESNO P40 grades

The following tables give a first impression of chemical

resistance of PA11 extrusion resins.

G: good
L: limited (important swelling or dissolution)
P: poor
Index * denotes swelling, index b denotes discoloration
(brownish or yellowish)

Concentration 20°C 40°C 60°C 90°C

Inorganic Salts

calcium arsenate Concentrated or paste G G G

sodium carbonate Concentrated or paste G G L P

barium chloride Concentrated or paste G G G G

potassium nitrate Concentrated or paste Gb Lb P P

diammonium phosphate Concentrated or paste G G L

trisodium phosphate Concentrated or paste G G G G

aluminium sulphate Concentrated or paste G G G G

ammonium sulphate Concentrated or paste G G L

copper sulphate Concentrated or paste G G G G

potassium sulphate Concentrated or paste G G G G

sodium sulphide Concentrated or paste G G L

calcium chloride Concentrated or paste G G G G

magnesium chloride 50% G G G G

sodium chloride saturated G G G G

zinc chloride saturated G G L P

iron trichloride saturated G G G

barium formate saturated G L P

sodium acetate saturated G L P

 11

Concentration 20°C 40°C 60°C 90°C

Other Inorganic Materials

water See section 3.5 G G G G

sea water G G G G

carbonated water G G G G

bleach L P P P

hydrogen peroxide 20% G L

oxygen G G L P

hydrogen G G G G

ozone L P P P

sulphur G G

mercury G G G G

fluorine P P P P

chlorine P P P P

bromine P P

potassium permanganate 5% P P

agricultural sprays G G

Organic Bases

aniline Pure L P P P

pyridine Pure L P P P

urea G G L L

diethanolamine 20% G G* G* L

Inorganic Bases

sodium hydroxide 50% G L P P

potassium hydroxide 50% G L P P

ammonium hydroxide concentrated G G G G

ammonia liquid or gas G G

12

Concentration 20°C 40°C 60°C 90°C

Inorganic Acids

hydrochloric acid 1% G L P P

10% G L P P

sulphuric acid 1% G L L P

10% G L P P

phosphoric acid 50% G L P P

nitric acid P P P P

chromic acid 10% P P P P

sulphur dioxide L P P P

Halogenated solvents

methyl bromide G P

methyl chloride G P

trichloroethylene L P

perchloroethylene L P

carbon tetrachloride P

trichloroethane L P

Freon G

Phenols P P P P

Esters and Ethers

methyl acetate G G G

ethyl acetate G G G

butyl acetate G G G L

amyl acetate G G G L

tributylphosphate G G G L

dioctylphosphate G G G L

dioctylphthalate G G G L

diethyl ether G

fatty acid esters G G G G

methyl sulphate G L
 13

Concentration 20°C 40°C 60°C 90°C

Various Organic Compounds

anethole G

ethylene chlorohydrin P P L

ethylene oxide G G P P

carbon disulphide G L L

furfuryl alcohol G G

tetraethyl lead G

diacetone alcohol G G L P

glucose G G G G

Organic Acids and Anhydrides

acetic acid refer to section 3.5 – role of acidity in hydrolysis L P P P

acetic anhydride L P P P

citric acid G G L P

formic acid P P P P

lactic acid G G G L

oleic acid G G G L

oxalic acid G G L P

picric acid L P P P

stearic acid G G G L

tartaric acid G G G L

uric acid G G G L
14

Concentration 20°C 40°C 60°C 90°C

Hydrocarbons

methane G G G G

propane G G G G

butane G G G G

acetylene G G G G

benzene G G L P

toluene G G L L

xylene G G L L

styrene G G

cyclohexane G G G L

naphthalene G G G L

decalin G G G L

crude oil G G G L

Alcohols

methanol Pure G L P

ethanol Pure G L P

butanol G L P

glycerine pure G G L P

glycol G G L P

benzyl alcohol L P P P

Aldehydes and Ketones

acetone Pure G G L P

acetaldehyde G L P

formaldehyde G L P

cyclohexanone G L P

methylethylketone G G L P

methylisobutylketone G G L P

benzaldehyde G L P
 15

3.5 Aging in water and acid solutions – hydrolysis

In many offshore conditions, the performance loss for polyamide 11 has been linked to
a chain scission mechanism due to a reaction with water. Polyesters, polyamides and
polyurethanes are created by polycondensation. The polycondensation reaction creating
the long chains is reversible and the opposite reaction is called hydrolysis. Among the
cited polymers, polyamide 11 is particularly resistant to hydrolysis due to its low
moisture absorption (~2% water at saturation).

=
vvvvv CO2H + vvvvv NH2 →
← vvvvv C – N vvvvv +H2O

–
H
polycondensation => <= hydrolysis

The hydrolysis chain scission reaction is not significant in ordinary use at ambient tem-
peratures. Polycondensates are formed at temperatures between 200 and 350°C. The
reverse reaction rate at, or slightly above, room temperature is insignificant. Only the
use of PA11 continuously over many years at a maximum temperature of 65°C or higher
makes hydrolysis a prevailing degradation mechanism.

In oilfield use, PA11 is rarely exposed to pure water but rather to oil/water mixtures. It
has been shown that the hydrolysis mechanism operates in exactly the same way
whether only water is present or a water phase is present alongside an oil phase.

Fig. 7 Lifetime estimation of PA11 in water contact with pure water (pH 7) as a function of temperature
150

140
1 month
----------------------------------------------

130
AGING TEMPERATURE (°C)

1 year
120
----------------------------------------------

5 years
-----------------------------------

110

100 10 years
----------------------------

20 years
90
-----------------------

80

70

60

0 10 100 1000 10000 100000

AGING TIME (DAYS)
16

Fig. 8 Hydrolysis resistance as a function of pH

100000

■
10000
■■■ 20 YEARS ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■
■■■ 10 YEARS ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■■■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■
5 YEARS ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■

LIFETIME (DAYS)
■■■
■
1000
▲
■■■ 1 YEAR ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ▲
■ •
■■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■

100 ■ •
■
▲
■
• ■ pure water pH=7
An aggravating factor for the hydrolysis 10
■ ▲ pH=5 CO2 liquid
process is the presence of acids – either ■
▲ ■ pH=4 CO2 gas
carbonic acid produced under CO2 pres- • • pH=4 CO2 liquid
sure or naphthenic acids possibly present
in crude oil. 1
140 130 120 110 100 90 80 70
Carbonic acid formed by the dissolution
TEMPERATURE ( °C)
of carbon dioxide in water under pressure
causes a more severe polymer perform-
ance loss than gaseous carbon dioxide. Fig. 9 Aging behavior as a function of pH
In the case of naphthenic acids, the larger 100000
molecule size slows its diffusion into the
polymer. In this case, a distinct surface
attack or a gradient over the sample thick- ■

ness can be observed. 10000

■■■ 20 YEARS ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■
■
■■■ 10 YEARS ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■
5 YEARS ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■
LIFETIME (DAYS)

■■■
■
1000

■■■ •
1 YEAR ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■■■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■

100 ■ • ◆
◆
■

•
10
◆ ■ pure water pH=7
■ • pH=4 CO2 liquid
• ◆ Strong organic acid

1
140 130 120 110 100 90 80 70
TEMPERATURE ( °C)
 17

3.6 Influence of methanol on aging and mechanical The effect of methanol absorption on mechanical properties is
properties, permeability data outlined in the figure below.

Methanol is a widely used injection fluid. For example, it is effi- 60

cient in dissolving gas hydrates formed during a gas production •

50

STRESS AT RUPTURE (MPa)

pipe shut-down. Methanol, due to its small molecule size and its
high solubility, has a high permeation rate through PA11. It is 40
also an efficient solvent for plasticizer extraction. In spite of • •
30 ••
these unfavorable factors, methanol can be successfully used in
conjunction with PA11 hydraulic tubes.
20

Methanol affects the material performance of PA11 in

10
several ways:
• A swelling effect accompanied by plasticization. At temperatures
0 5 10 15 20 25 30 35 40 45
of 140°C and above, methanol becomes a solvent for PA11.
TIME (DAYS)
• Plasticizer extraction.
Fig. 11 Methanol aging: Stress at rupture in time at 40°C
• A methanolysis reaction which leads to a loss of
polymer molecular weight. A rapid drop in strength as measured by stress at rupture is
observed due to deplasticization. The resin strength then equili-
O O brates in methanol leading to stable properties.
=

CH3OH + vvvvv N – H2 – C vvvvv →

← vvvvv NH2 + vvvvv C – OCH3 Extraction of plasticizer and swelling due to methanol change
–

H the modulus, but this is not an aging effect. Once the modulus
after methanol conditioning is attained, it remains stable. The
long-term stability of polyamide 11 in methanol is further
50 demonstrated in experiments outlined below.
45

40 Long term aging data of PA11, BESNO P40 TLO in methanol

METHANOL ABSORPTION WT. %

35 Small dogbone samples are immersed at a given temperature in

30 • methanol in an autoclave. After a given time, five samples are
25 retrieved and tensile tests are performed.
20
• DATA AT 40°C
15
•
10 • •
• Time (days) Stress at rupture (MPa) Elongation at rupture (%)
5
0 53 ± 0.86 438 ± 13
0 20 40 60 80 100 120 140 160
TEMPERATURE (°C) 40 42.2 ± 2.63 597 ± 34

Fig.10 Methanol absorption of BESNO P40 grades 100 42.9 ± 0.9 646 ± 22.6

150 42.8 ± 2.71 667 ± 31.7

250 40.6 ± 1.94 591 ± 46

300 39.7 ± 1.4 603 ± 51

360 43.2 ± 1.4 646 ± 28.8

410 37.4 ± 2.2 561 ± 32.5

At 40°C, the plasticizer is extracted after 2 days. The initial

decrease of the stress at rupture is due to a plasticization effect
of absorbed methanol.
18

DATA AT 70°C

Time (days) Stress at rupture (MPa) Elongation at rupture (%)

0 53 ± 0.86 438 ± 13

1 31.9 ± 2.58 419 ± 25.1

2 32.8 ± 3.43 419 ± 32.8

8 33.7 ± 2.48 432 ± 19.6

42 34.9 ± 3.02 440 ± 22.7

120 33.8 ± 4.3 460 ± 44

160 33.1 ± 3.8 442 ± 30

2000 (5 1/2 years) 32 ± 5 320 ± 40

The plasticizer is extracted after 2 hours at 70°C. The strong plastification effect of
methanol more than compensates for the plasticizer loss. The material becomes more
flexible. At 70°C, Rilsan® PA11 is not significantly degraded.

All these factors lead to the following picture for a service life – temperature relationship:

Fig. 12 Polyamide 11, BESNO P40 grades – lifetime in methanol contact

100000

10000
■■■ 20 YEARS ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■
LIFETIME (DAYS)

1000

100

water, pH=7
methanol

10

1
120 110 100 90 80 70 60 50
TEMPERATURE ( °C)
 19

METHANOL PERMEATION
METHANOL PERMEATION DATA
DATA
Temperature in °C 4 23
PA11 unplasticized 6 18
PA11 plasticized 13.5 40
units: g mm/m2 day atm
The activation energies for the unplasticized and plasticized
grades are respectively:
39.4 kJ mol-1 and 43.1 kJ mol-1.
3.7 Influence of monoethylene glycol and ethylene
40 50
glycol-based hydraulic liquids on mechanical
properties
Monoethylene glycol and other ethylene glycols mixed in
115 190 different ratios with water are used as constituents of hydraulic
liquids in offshore applications. These liquids can extract plasti-
cizer from polyamide resin because the plasticizer has a rather
high solubility in glycol/water mixtures. This effect is shown in
the graph below. The tensile yield shifts to higher
modulus with the departure of the plasticizer.

Fig. 13 Methanol permeability To some extent glycol/water mixtures act as plasticizer them-
selves when absorbed by polyamide 11 resin.
1000

All these phenomena are well known today and experience has
shown that they do not cause any particular problem in the
• BESNO TL
functioning of the subsea installation under ordinary working
PERMEABILITY (G.MM/M2.DAY)

■ BESNO P40TL
■
conditions.
■
100
In the following, the phenomena are described in detail so that a
thorough understanding of the prevailing material behavior can
■
be developed.

• ■
10

Fig. 14 Evolution of tensile stress of BESNO P40 TL 12mm bore

hoses in water/glycol 60/40
1
50°C 40°C 30°C 20°C 10°C 0°C 40
1/TEMPERATURE
35

30
STRESS AT YIELD (MPa)

Pressure effects on permeability have been observed. As a 25

general rule, a tenfold increase in pressure results in a three-fold
20
increase in methanol permeation.
15 40°C
Conclusions: 70°C

• Methanol has a finite permeation rate through PA11 which has 10

to be taken into account in design.
5
• Liquid methanol efficiently extracts the plasticizer from PA11
plasticized grade “P40”. For umbilicals, this extraction has no 0 200 400 600 800 1000
consequence on the integrity of the pipe. TIME (DAYS)

• Methanol induces a softening and also polymer breakdown at

higher temperatures. We suggest 70°C as the maximum contin-
uous use temperature and 90°C for occasional temperature
peaks in the case of hydraulic hoses. For offshore flexible
pipes, the extraction of plasticizer and the modification of the
flexiblity can further reduce the continuous use temperature.
20

14
The physical picture of the interactions

In a physical description of the ensemble 12 60°C

“umbilical filled with control fluid,” we 22°C
have to consider a closed system with

BBSA SOLUBILITY (G/L)

10
two phases, PA11 and control fluid, and
several components which, in time, can
8
interdiffuse between the two phases.
These components are the plasticizer
BBSA and constituents of the control 6
fluid, mainly glycols.
4
Control Fluid PA11
2

BBSA BBSA
0 5 10 15 20 25 30 35 40 45
GLYCOL CONTENT ( %)
The effects can be described when the
Fig. 15 The solubility of BBSA in glycol-based control fluids and its temperature
solubility parameters of the diffusing dependence
species and the diffusion kinetics are
known. The mathematics of diffusion in a The maximum extractable amount of plasticizer adds up to approximately 6% by
plane sheet are well described (Crank). weight. For a hydraulic fluid containing 45% glycol, the maximum plasticizer solubility
We will use some simple forms to illus- at ambient temperature is close to 6%. For a hydraulic fluid containing 25% glycol, the
trate the effects in a semiquantitative solubility limit is 2.2 – 2.5%. At temperatures over 60°C, the plasticizer will be extract-
manner. ed as it will become soluble in such a fluid.
For a particular umbilical, the ratio 22°C 60°C
between the two phases may be different
due to the particular tube dimensions. pure water based, eg., Oceanic* HW 500 0.1 - 1 1.5 – 2.5
The approach is best described in a
approx 25% glycol, eg., Oceanic HW 525 2.2 – 2.5 6.8 – 7.4
worked example.
approx 40% glycol, eg., Oceanic HW 540 4.0 – 5.0 12.0 – 13.6
Standard 1/2’’ hydraulic tube *Hydraulic fluid manufactured by MacDermid Canning, PLC
ID = 12 mm WS = 1.5 mm
OD = 15 mm L = 100 mm

...................
...................

OD ID
...................
...................

We calculate:
Fluid volume: 11.3 ml
Weight of tube (r = 1.05 mm): 5.4 g

The plasticizer content is on average

12.5% by weight of the resin.

BBSA content in a tube

with L = 100 mm: 675 mg
 21

3.8 Compatibility of RILSAN® BESNO P40 TLX and
BESNO P40 TLO resin with various offshore fluids
and chemicals
A variety of offshore fluids have specific functions in the explo-
ration and production process in offshore installations:
• Demulsifiers to break oil/water emulsions
• Corrosion inhibitors to slow corrosion of steel
• Bactericides to suppress the formation of acid-creating
bacteria
For convenience, the results of the tests of typical offshore fluids
are summarized in a final subsection 3.8.9.
For the screening tests, small dogbone samples were autoclaved
at a given temperature immersed in the chosen offshore fluid.
After a given time, 5 samples were retrieved on which tensile
tests were performed, weight changes monitored, and the
molecular weight changes analyzed.
All compatibility tests were performed at 60°C. Testing periods
were generally 2 years.

• Paraffin inhibitors which prevent the crystallization of
paraffins leading to a blocking of the pipes
• Scale inhibitors which prevent the formation of salt scales
capable of blocking of the pipes
• Oxygen scavengers which help prevent corrosion
Given the typical activation energy for the chemical degradation
processes, a good behavior after 2 years at 60°C should give a
service life over 20 years at temperatures around 20°C.

Numerous formulations exist depending on the producer and

specific adaptions. However, the nature of the ingredients
remain essentially the same. Often even the compounds remain
the same and given formulations differ only in the amounts of
the constituents. The aim of this chapter is to analyze the behav-
ior of PA11 when exposed to the specific chemicals used in off-
shore applications. It supplements the information in the more
general chemical resistance table in section 3.4.
22

3.8.1 Demulsifiers

Chemicals Comments
• oxypropylated and/or oxyethylated alkylphenol None of these chemicals have adverse effect on PA11.
• ethylene oxide/propylene oxide copolymers Aromatic solvents exert slight swelling at temperatures above 40°C.
• glycol esters
• condensates of modified propylene oxide/ethylene oxide
• aromatic solvents, C7 to C10
(benzene, toluene, xylene, ethylbenzene)

TEST: PROCHINOR 2948 (AROMATIC SOLVENTS, NON-IONIC SURFACTANT)

Immersion time at 60°C Ultimate tensile Elongation at break Weight Inherent viscosity
strength % change % change % change % change

1 week - 2.7 -0 + 1.26

1 month + 5.3 0 - 0.43

3 months + 85 + 2.7 - 2.37

6 months + 0.4 - 4.5 – 2.9

12 months + 10.5 +0

18 months -4 - 7.2 - 3.16

24 months + 1.4 - 1.2 - 3.26 no change

3.8.2 Corrosion inhibitors – oil soluble

Chemicals
• fatty amines
• imidazoline derivatives
• aromatic solvents

TEST: NORUST® PA23 (FATTY AMINES, IMIDAZOLINE DERIVATIVES, AROMATIC SOLVENT)

Immersion time at 60°C Ultimate tensile stress Elongation at break Weight Inherent viscosity
(% change) (% change) (% change) (% change)

1 week + 3.6 - 3.6 - 1.13

1 month + 3.4 - 6.3 - 2.0

3 months + 8.7 - 3.3 - 3.17

6 months + 1.8 - 9.0 - 4.07

12 months + 9.7 - 7.5

18 months + 1.0 - 6.0 - 5.37

24 months + 5.15 - 10.2 - 5.85 + 1.6

 23

3.8.3 Corrosion inhibitors – water soluble

Chemicals
• fatty amines
• imidazoline derivatives
• sulphite derivatives
• water/glycol mixtures

TEST: NORUST® 743D (FATTY AMINES, IMIDAZOLINE DERIVATIVES, WATER/GLYCOL MIXTURES)

Immersion time at 60°C Ultimate tensile stress Elongation at Weight Inherent viscosity
(% change) break (% change) (% change) (% change)

1 week - 6.7 - 4.2 - 1.04

1 month + 0.2 - 2.4 - 3.06

3 months + 4.5 - 0.6 - 5.02

6 months + 2.0 - 3.3 - 5.82

12 months + 4.2 - 2.1

18 months + 5.0 + 2.4

24 months + 3.0 - 3.3 - 6.79 0

TEST: NORUST 720 (FATTY AMINES, IMIDAZOLINE DERIVATIVES, WATER)

1 week - 1.4 + 2.7 - 1.03

1 month + 2.2 + 0.9 - 3.22

3 months + 5.9 + 4.8 - 5.7

6 months - 5.7 - 3.0 - 6.63

12 months - 4.7 - 7.8 - 7.54

18 months - 3.0 - 3.6

24 months + 2.6 - 0.6 - 7.55 + 0.8

TEST: NORUST CR486 (FATTY AMINES, SULPHITE DERIVATIVES, WATER/GLYCOL MIXTURE)

1 week - 8.9 - 6.0 - 1.0

1 month - 5.7 - 10.0 - 2.86

3 months + 2.6 - 0.9 - 5.1

6 months - 4.5 - 3.3 - 5.89

12 months - 15 - 12.7

18 months - 36.6 - 38.4 - 6.33

24 months - 42.7 - 50.1 - 5.98 - 38

24

3.8.4 Corrosion inhibitors (oil soluble and water dispersible)

TEST: NORUST® PA23D (FATTY AMINES, IMIDAZOLINE DERIVATIVES, AROMATIC SOLVENT, ALCOHOL)

Immersion time at 60°C Ultimate tensile stress Elongation at break Weight Inherent viscosity
(% change) (% change) (% change) (% change)

1 week + 5.1 - 1.8 - 0.74

1 month + 5.1 - 5.1 - 1.31

3 months + 9.1 + 0.3 - 2.37

6 months + 0.4 - 8.4 - 4.4

12 months + 6.5 - 5.1

18 months + 3.0 - 1.5 – 4.67

24 months + 8.3 - 2.7 - 6.02 + 4.0

3.8.5 Oxygen scavengers

Chemicals
• sodium bisulphite

NORUST SC45

Immersion time at 60°C Ultimate tensile stress Elongation at break Weight Inherent viscosity
(% change) (% change) (% change) (% change)

1 week - 13.6 - 5.4 + 4.23

1 month - 10.3 - 1.5 + 5.78

3 months - 10.5 + 2.1 + 3.94

6 months - 13.9 + 3.6 + 4.67

12 months - 23.2 + 0.9

18 months - 80.2 - 97 + 5.22 - 65

24 months
 25

3.8.6 Biocides

Chemicals
• ammonium quarternary salts
• ammonium salts
• aldehydes
• water/glycol mixtures

TEST: BACTIRAM® C85 (AMMONIUM QUARTERNARY SALTS, WATER)

Immersion time at 60°C Ultimate tensile stress Elongation at break Weight Inherent viscosity
(% change) (% change) (% change) (% change)

1 week + 0.6 + 1.5 - 0.73

1 month + 8.7 + 5.1 - 2.79

3 months + 7.5 + 0.9 - 4.86

6 months + 7.3 - 0.6 - 5.32

12 months + 3.1 - 3.3

18 months - 6.8

24 months - 3.0 - 7.5 - 8.07 + 5.6

TEST: BACTIRAM CD30 (AMMONIUM SALTS, WATER/GLYCOL MIXTURE)

1 week - 15.8 - 0.6 - 0.09

1 month - 15.4 - 1.8 - 1.87

3 months - 9.3 + 5.7 - 2.44

6 months - 7.9 + 3.6 + 0.48

12 months -12.3 0.0

18 months - 18.8 - 8.8 - 1.59

24 months - 21.8 - 1.5 - 3.19 -4

TEST: BACTIRAM 3084 (ALDEHYDES, WATER)

1 week - 3.2 - 1.8 + 0.77

1 month + 2.2 + 0.3 - 2.23

3 months + 0.2 - 5.4 - 3.53

6 months 0.0 - 5.4 - 4.1

12 months + 2.4 + 3.6

18 months - 8.9 - 9.4 + 0.65

24 months - 9.1 - 3.9 - 2.02 - 22.6

26

3.8.7 Paraffin inhibitors

Chemicals
• non-ionic surfactants
• polyacrylate
• aromatic solvents

TEST: PROCHINOR® AP 104 (NON-IONIC SURFACTANT, AROMATIC SOLVENTS)

Immersion time at 60°C Ultimate tensile Elongation at break Weight Inherent viscosity
stress (% change) (% change) (% change) (% change)

1 week + 1.4 - 1.5 + 0.8

1 month + 3.2 - 1.2 - 0.43

3 months + 7.5 + 1.2 - 2.44

6 months - 5.9 - 9.4 - 2.9

12 months + 3.0 - 4.8

18 months + 3.0 - 0.6 - 3.38

24 months + 4.9 - 0.1 - 4.35 +8

TEST: PROCHINOR AP 270 (POLYACRYLATE. AROMATIC SOLVENTS)

1 week - 3.7 + 0.6 + 3.07

1 month + 0.6 - 1.5 - 0.04

3 months + 6.3 + 4.2 - 0.28

6 months + 2.0 + 1.5 + 1.37

12 months + 4.0 + 4.2

18 months - 1.0 + 6.0 - 1.84

24 months - 3.2 - 2.7 + 0.2 - 13.7

 27

3.8.8 Scale inhibitors

Chemicals
• phosphonate
• polyacrylate

TEST: INIPOL® AD100 (POLYACRYLATE, WATER)

Immersion time at 60°C Ultimate tensile stress Elongation at break Weight Inherent viscosity
(% change) (% change) (% change) (% change)

1 week - 0.6 + 2.7 - 0.58

1 month + 2.6 + 1.8

3 months + 11.5 + 9.4 - 3.83

6 months + 0.8 - 0.3 - 5.64

12 months - 4.9 - 0.9

18 months - 6.9 - 4.5 - 5.48

24 months - 9.7 - 3.6 - 5.5 - 16

TEST: INIPOL AD20 (PHOSPHONATE, WATER)

1 week - 3.4 + 4.5 + 1.88

1 month - 3.6 + 6.0 + 1.98

3 months - 82.2 - 97.8 + 2.5 - 48

6 months

12 months

18 months

24 months

3.8.9 Overview of chemical compatibility of RILSAN® To quickly assess the compatibility of a given offshore fluid, it is
BESNO P40 TLX and BESNO P40 TLO with useful to examine the active constituents which are most often
common offshore chemicals given in the safety data sheet. Concentrations of the active
chemical species in the concentrated offshore fluid range
Offshore fluids are complex mixtures of several functional between 3 and 30%. In order to estimate the chemical compati-
chemicals which are either bility, the most aggressive species must be identified. Its given
• water based temperature limit can be taken as the limit for the given offshore
• glycol/water mixture based fluid. In the given list, no two chemicals have a synergistic
• hydrocarbon based degradative effect, but some have antagonistic effects.
Furthermore, the pH value should be noted when it is given.
28

100000 Fig. 16 Overview: compatibility

between PA11 grades BESNO
Water P40 TLO, TL and TLX and different
Class 1 Class 2 Class 3 chemical classes
10000
■■■ 20 YEARS ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■
■■■ 10 YEARS ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■
■■■ 5 YEARS ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■Class
■■■■■4■■■
LIFETIME (DAYS)

1000

■■■ 1 YEAR ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■

100

10

1
120 110 100 90 80 70 80 50 40 30 20
TEMPERATURE ( °C)

Chemical Liquid base Functions Compatibility class

oxypropylated and/or oxyethylated hydrocarbon demulsifier < water

alkylphenols “non ionic surfactants” water/glycol

ethylene oxide/propylene oxide copolymers hydrocarbon demulsifier < water

glycol esters hydrocarbon demulsifier < water

fatty amines hydrocarbon corrosion inhibitor class 1

water
water/glycol

imidazoline derivatives hydrocarbon corrosion inhibitor class 1

water
water/glycol

sulphite derivatives water corrosion inhibitor class 1

water/glycol

bisulphite salts water oxygen scavenger class 2

quaternary ammonium salts, water

“quats”, ammonium salts water/glycol biocides < water

aldehydes water biocides class 2

water/glycol

polyacrylates water paraffine inhibitors class 1

water/glycol scale inhibitors

organic phosphonates water scale inhibitors class 3

water/glycol corrosion inhibitors

organic sulfonates water scale inhibitors class 3

water/glycol corrosion inhibitors

hydrochloric acid, 15% water well stimulation class 4

hydrofluoric acid, 15% water well stimulation class 4

The sign “< water” means that the chemical is less agressive than water.
 29

3.9 Compatibility with crude oil, CRUDE OIL EXPOSURE

natural gas, carbon dioxide (CO2)
and hydrogen sulfide (H2S) Solvent Swelling at 20°C in % weight Compatibility

3.9.1 Compatibility with crude oil Benzene 7.5 good up to 70°C / swelling

Toluene 7 good up to 90°C / swelling

Polyamide 11 is not chemically attacked
by hydrocarbons. Aliphatic hydrocarbons Cyclohexane 1 good
have a very low solubility in polyamide
11, so that barrier properties are very Petrol ether 1.5 good
high. Low molecular weight aromatic Decaline <1 good
hydrocarbons can lead to some swelling
at higher temperatures as shown in the Gasoline depends on type, mostly < 2% good
following table.
Kerosene depends on type, mostly < 2% good
The low solubility of hydrocarbons and
the high cohesive energy of polyamide
METHANE OR NATURAL GAS EXPOSURE AT 20° C
11 result in an excellent blistering
resistance (see section 3.11). Time Flexural modulus Yield strength Elongation Stress at rupture
Whereas polyamide 11 is highly resistant (hours) (MPa) (MPa) at break (%) (MPa)
to hydrocarbons, certain other con-
0 350 27 325 45
stituents of crude oil can lead to perform-
ance limitations. These constituents are 100 350 32.5 345 53
water, organic acids, often referred to as
250 500 30.5 325 57
naphthenic acids, carbon dioxide and, to
a lesser extent, hydrogen sulfide. All 500 600 34.5 375 60.5
these chemicals create different acidities
depending on pressure, concentration 1000 400 28 360 63
and overall fluid composition. Their
2000 480 32 335 43
effects are described in the correspon-
ding chapters. 5000 460 34.5 430 55

3.9.2 Compatibility with natural gas

Fig. 17 Polyamide 11, BESNO TL in natural gas - Evolution of elongation at break
Polyamide 11 is perfectly resistant to 500
methane, ethane, propane and butane as 450
well as higher hydrocarbons. Chemical •
degradation can only be induced by acid 400
ELONGATION AT BREAK (%)

species, that is carbon dioxide and/or • •

350
hydrogen sulfide in combination with • •
300
• •
water vapor.

The following test demonstrates the 250

chemical resistance:
200
Sheets of BESNO P40 TL with 2mm
thickness are immersed in natural gas at 150
100°C and 120 bar pressure for a given
100
time. Mechanical properties are checked.
Composition of the natural gas: 93% 50
hydrocarbon, 4% hydrogen sulfide, and
3% carbon dioxide and moisture.
0 1000 2000 3000 4000 5000 6000
TIME (HOURS)
30

TABLE COMPARING INITIAL AND AGED MECHANICAL PROPERTIES

Elongation Stress at Stress at Elongation at Tensile

at break (%) rupture (Mpa) yield (Mpa) yield (%) modulus (Gpa)

Aged sample 315 ± 38 46.7 ± 8,3 27.7 ± 0.5 42.4 ± 0.6 2.82 ± 0.02

Initial sample 359 ± 48 42.0 ± 3,0 – – 2.78 ± 0.008

No chemical degradation was observed. Fluctuations in the 3.10 Data on permeability of polyamide 11
mechanical properties are caused by the loss of plasticizer and
changes in moisture content of the gas. The following data were obtained from a detailed study on 6 mm
extruded sheet.
In a typical field experience, polyamide 11 grade BESNO P40 TL
used as a lining for carbon steel pipe was aged in the following RILSAN® BESNO P40 TL
conditions: P (bar) T (°C) Permeability Diffusion Solubility
Temperature: 65°C /f (bar) cm3.cm/cm2.s.bar cm2/s cm3/cm3.bar
10-8 10-7
Natural gas: moist, with some condensate, H2S 17%, pH 5.5.
CH4 96 99 3.8 7.3 0.05
A sample was retrieved after 5 years of service. A chemical
analysis revealed no polymer degradation. Of the initial plasti- 99 99 4.4 6.1 0.07
cizer, 30% was lost. 103 78 2 2.8 0.07

As a conclusion, polyamide 11 grades BESNO TL, BESNO P40 TL, 97 80 2 3.3 0.06
BESNO P40 TLX and BESNO P40 TLO are compatible with hydro-
101 61 0.8 2.6 0.03
gen sulfide.
103 61 0.9 2.2 0.04
3.9.3. Compatibility with carbon dioxide (CO2)
102 41 0.4

Polyamide 11 is quite resistant to dry carbon dioxide. However, 101 60 0.8 2.2 0.03
carbonic acid formed by dissolution of carbon dioxide in water
under pressure can lead to chain degradation due to hydrolysis. CO2 40 79 10 4.5 0.22
The rate of hydrolysis, as a function of acidity, is relatively well 39 80 9.4 4.7 0.2
known and described in section 3.5.
39 60 4.5 1.9 0.23

3.9.4. Compatibility with hydrogen sulfide (H2S) 39 61 4.4 2.3 0.19

Polyamide 11 is also resistant to hydrogen sulfide. As with car- 41 41 1.5 0.9 0.16
bon dioxide, only aqueous solutions which are acidic can lead to H2S 100/47.5 80 67 7.6 0.88
chain degradation. Due to the low acidity and generally low par-
tial pressures of hydrogen sulfide in crude oil or natural gas, 103/48 80 66 8.2 0.8
degradation via hydrolysis seldom occurs. 92/47 80 77 9.2 0.84
For a series of tests, please refer to the preceeding section 3.9.2 41/33 80 43 4.2 1.04
“Compatibility with natural gas.”
40/33 80 46 5.1 0.9

39/33 80 38 4.5 0.85

 31

Complementary data can be obtained from the literature. 3.11. Blistering resistance
PLASTICIZED POLYAMIDE 11
The blistering resistance of a polymer material is directly related
Fluid Conditions Permeation value/ to the solubility of gases in the material and its cohesive
cm3.cm/cm2.s.bar
strength. The blistering effect has its origin in the gas bubbles
CH4 70°C, 100 bars 9x10-9 formed when gas dissolved in the polymer material under high
pressure is expelled on a rapid decompression.
CO2 70°C, 100 bars 50x10-9
An extensive study has been performed at IFP (French Petroleum
H2O 70°C, 50 to 100 bars 2x10-6 to 7x10-6 Institute) which confirms the excellent blister resistance of
H2S 70°C, 100 bars 1.5x10-7
plasticized polyamide 11 according to the procedures outlined
in API 17J.
METHANOL 23°C, 1 bar 3.7x10-9
The following grades were tested on samples cut from an
data from IFP/ COFLEXIP OTC 5231
extruded pipe, thickness 8 mm:
BESNO P40 TLX
PLASTICIZED POLYAMIDE 11
BESNO P40 TLOS
Fluid Permeation value/cm3.cm/cm2.s.bar
Test conditions:
70°C, 25 bar 70°C, 50 bar 70°C, 75 bar 70°C, 100 bar
medium: 85% CH4 + 15% CO2
CH4 0.53x10-7 1.4x10-7 1.9x10-7 1.8x10-7 temperature: 90°C
pressure: 1000 bar
CO2 2.3x10-7 5.8x10-7 7.8x10-7 7.8x10-7
The decompression rate was explosive. The soak time was more
H2O 3.6x10-6 6.5x10-6 3.4x10-6 1.9x10-6 than 30 hours.
data from NACE publication, Jan Ivar Skar (Norsk Hydro)
Result:
After 20 pressure/decompression cycles, no blister was
Some differences exist in reported values which can be
observed.
explained by different conditioning of the measured samples. For
example, some plasticizer loss leads to high barrier and lower The same result is obtained when the samples were
permeation. preconditioned in oil or diesel fuel.
 ADDRESSES OF REGIONAL SALES OFFICES

EUROPE
ATOFINA NORDEN ATOFINA UK Ltd. ATOFINA
(Danmark) Colthrop Way - Thatcham Technical Polymers Division
Herlev Hovegarde 195 Newbury - Berkshire 4/8 cours Michelet
2730 Herlev RG 13 4 LW 92800 Puteaux, France
Tel: 44 503 939 Tel: (01635) 87 0000 Tel: +33 149008080
Fax: 44 503 940 Fax: (01635) 86 1212 Fax: +33 149008044

ATOFINA NEDERLAND BV ATOFINA KIMYA SAN ATOFINA BELGIUM N.V.

Otto Heldringstraat 41 Ihlamur Rue de Stalle 63 - Bte 1
1066 XT Amsterdam Yildiz Cad. Kessaf Sok n° 4 1180 Bruxelles
Tel: (20) 614 25 11 Besiktas 80700 Tel: (2) 370 20 32
Fax: (20) 669 2231 Istanbul Fax: (2) 332 12 84
Tel: (212) 227 6384
Fax: (212) 227 6386

ATOFINA DEUTSCHLAND GmbH ATOFINA SCHWEIZ AG ATOFINA ÖSTERREICH

Tersteegenstr. 28, Postfach 300152 Luegisland 2/4 Handelsges. m. b. H.
40474 Düsseldorf 8143 Stallikon Karlsplatz 1/Steige 1/Büro n°8
Tel: (0211) 4552 00 Tel: (1) 701 8121 A 1010 Wien
Fax: (0211) 4552 112 Fax: (1) 700 3921 Tel: (1) 503 5055
Fax: (1) 503 505520

ATOFINA ITALIA SRL ATOFINA PORTUGAL LDA ATOFINA ESPANA SA

Degli Artigianelli 10 Rua Artilharia UM 63 Poligon Industrial Pratenc
20159 Milano 4’ Dto Lisboa Calle 100s/n Acesso A
Tel: (02) 668 111 Tel: 113 806 004 08820 - El Prat De Llobregat
Fax: (02) 668 03 607 Fax: 113 862 281 Barcelone
Tel: (3) 403 9500
Fax: (3) 337 94307

AMERICAS
ATOFINA Chemicals, Inc. ATOFINA BRASIL QUIMICA Ltda
Technical Polymers Avenida Ibirapuerra, 2033
2000 Market Street 8° andar
Philadelphia CEP 04029 901
PA 19103 – 3222 Sao Paulo
U.S.A. Tel: +55 11 5051 0622
Tel: +1 215 419 7400 Fax: +55 11 5051 4780
Fax: +1 215 419 7497

FAR EAST
ATOFINA CHINA ATOFINA S.E.A. ATOFINA JAPAN
Room 1410 53, Tuas Crescent Engineering Plastics Division
China World Tower Singapour 638732 Bungei shunju Annex 2F
1, Jianguomenwaidajie Tel: +65 86 90 268 3-23 Kioi-cho
Beijing 100004 Fax: +65 86 90 341 Chiyoda-Ku
China Tokyo 102
Tel: +86 10 650 52 291 Tel: +81 3 32 88 71 21
Fax: +86 10 6505 55 17 Fax: +81 3 32 88 71 30

Inipol®, NoRust®, Prochinor® and Bactiram® are registered trademarks of CECA, S.A.
Rilsan® is a registered trademark of Atofina.

ATOFINA S.A. - Société Anonyme au capital de 2 953 089 200 F - RCS Nanterre B 319 632 790
4, cours Michelet - La Défense 10 - Cedex 42 - 92091 Paris La Défense (France) - Tél. 149 00 80 80 - Téléfax 149 00 83 96

© 2003 ATOFINA Chemicals, Inc. All rights reserved.

After 14 years of research in a program
launched in 1958 by the French Institut de
Petrole, polyamide 11 was chosen as the
best material out of several hundred
tested. Today RILSAN® polyamide 11, the
unique polyamide from ATOFINA, looks
back at a service history of over 30 years
in the petroleum industry. The combined
qualities of flexibility, excellent impact
resistance even at low temperatures, high
resistance to aging and good compatibility
with products common to the petroleum
industry environment have made RILSAN
polyamide 11 an unequaled standard.
For even higher demands, especially at
higher temperatures or when the
combined high temperature and high
water content requirements are too
severe, ATOFINA proposes its unique
KYNAR® off-shore grade. KYNAR is a
thermoplastic fluoropolymer resin
developed by ATOFINA. Outstanding
thermomechanical properties combined
with exceptional chemical and aging
resistance enable KYNAR to meet the
most stringent demands.

The data given in this brochure describe the material performance of RILSAN® polyamide 11 in applications such as
pneumatic or hydraulic tubes. For large diameter pipes or sheaths such as in flexible pipe the data give indications
of lifetime limits, but further considerations might have to be taken into account. Hence this data may be inapplica-
ble where lifetime and design specifications established by flexible pipe manufacturers or joint industry efforts have
resulted in new recommended practices or industry specifications.
The statements, technical information and recommendations contained herein are believed to be accurate as of the date hereof. As the condition and methods of use of
the products and of the information referred to herein are beyond our control, ATOFINA expressly disclaims any and all liability as to any results obtained or arising from
any use of the product or reliance on such information; NO WARRANTY OF FITNESS FOR ANY PARTICULAR PURPOSE, WARRANTY OF MERCHANTABILITY, OR ANY OTHER WAR-
RANTY, EXPRESS OR IMPLIED, IS MADE CONCERNING THE GOODS DESCRIBED OR THE INFORMATION PROVIDED HEREIN. The information provided herein relates only to the
specific product designated and may not be applicable when such product is used in combination with other materials or in any process. The user should thoroughly test
any application before commercialization. Nothing contained herein should be taken as an inducement to infringe any patent and the user is advised to take appropriate
steps to be assured that any proposed use of the product will not result in patent infringement.

BEFORE HANDLING THIS MATERIAL, READ AND UNDERSTAND THE MSDS (MATERIAL SAFETY DATA SHEET) FOR ADDITIONAL INFORMATION ON PERSONAL PROTECTIVE EQUIP-
MENT AND FOR SAFETY, HEALTH AND ENVIRONMENTAL INFORMATION.
 RILSAN® Polyamide 11
in Oil & Gas

Off-shore Fluids
Compatibility Guide

ATOFINA Chemicals, Inc. 2000 Market Street Philadelphia, PA 19103-3222 Telephone: (215) 419-7000
ATOFINA Canada, Ltd. 700 Third Line Oakville, Ontario L6J5A3 Canada, Telephone: (905) 827-9841
www.AtofinaChemicals.com