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Thermoplastic Polymers for OFF-SHORE Flexible Pipes

KYNAR

®

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RILSAN, the unique polyamide from ATOFINA, today looks back at a service history of 30 years in the petrol industry. After 14 years of research in a program launched in 1958 by the French Institut de Petrole, PA11 was chosen as the best material out of several hundred tested. The combined qualities of flexibility, excellent impact resistance even at low temperatures, high resistance to ageing and good compatibility to products common to the petrol industry environment have made RILSAN an unequaled standard. For even higher demands, especially when the temperature or 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 initially developped by ATOFINA. Its outstanding thermomechanical properties combined with exceptional chemical and ageing resistance made it possible for KYNAR to meet the highest demands.

This document is intended to provide detailed technical information on the properties of ATOFINAs thermoplastic polymers for flexible pipe use. The scope of the technical details is defined in the “ Specification for Unbonded Flexible Pipe ” - API Specification API 17J effective since March 1st 1997. The diffusion of this document is controlled, that is, the document is available to costumers of ATOFINA, the flexible pipe manufacturers, and their costumers; the petrol industry. The data given in this document based on trials carried out in our Research Centres and data selected from litterature are given to the best of our knowledge and do not contribute or imply any warranty, undertaking, express or implied commitment from our part. Our formal specifications define the limit of our commitment. For specific questions on this document please contact : M. Michael Werth Tel +33 232466874 M. Patrick Dang Tel +33 232466882

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Contents
1. 1.1 1.2 1.3 1.4 1.5 1.6 1.7 API 17J - Property Requirements for Extruded Polymer materials Mechanical/physical properties Thermal properties Permeation characteristics, compatibility and ageing Fluid permeability Blistering resistance Fluid compatibility Ageing tests page 4 4 4 5 5 5 5 6 7 8 8 8 8 8 8 8 8 8 9 12 13 14 14 14 17 18 20 20 20 20 20 20 20 21 22 23 23 25 28 28 30 31 32

BESNO P40 TLX and BESNO P40 TLXOS 2. Mechanical/physical properties 2.1 Density 2.2 Hardness 2.3 Compression strength 2.4 Abrasion resistance 2.5 Flexural test according to ISO 178-93 2.6 Flexural test according to ASTM D790 2.7 Impact test according to ISO 179 (type II) 2.8 Impact test according to ISO 179-93 CA 2.9 Tensile creep 2.10 Stress relaxation 2.11 Fatigue 2.12 Tensile tests according to ISO 527-93 BA 2.13 Tensile tests according to ASTM D638 type II 2.14 Poisson ratio 2.15 Compression test 2.16 Creep in compression mode 3. 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 4. 4.1 4.2 4.3 4.4 4.5 4.6 4.7 Thermal properties Thermal conductivity Thermal expansion Heat deflection temperature ASTM D648 Softening point ASTM D1525 Heat capacity Glass transition temperature Dynamic mechanical analysis Differential Scanning Calorimetry (DSC) Ageing behaviour, compatibility and permeation Lifetime models and end-of-life criteria based on polyamide hydrolysis Evolution of properties during ageing Compatibility with offshore fluids and gases Permeation characteristics Blistering resistance Weathering resistance Water absorption

Annexes : Magnified plots

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1.

API 17J - PROPERTY REQUIREMENTS FOR EXTRUDED POLYMER MATERIALS

The API specification 17 J “ Specification for unbonded flexible pipe ” was edited in december 1996 and is effective since 1st of march 1997. The intention of this specification is the harmonization of current practice in the off-shore industry with the particular aim of obtaining high safety standards and a common reference basis for all suppliers to the off-shore industry. The API specification 17 J contains a specific chapter 6.1.2 dealing with polymer materials. ATOFINA, a supplier of polymer materials to the off-shore industry, is adressing the specified properties in this given document.

1.1

MECHANICAL/PHYSICAL PROPERTIES

Internal pressure sheath : A, Intermediate sheath / Anti-Wear layer : B, Outer sheath : C A X X X X X B X X X X C X X X X X X X X X X X X X X X Test Procedure ASTM D2990 ASTM D638 (ISO 527 93.1 BA) ASTM D638 ASTM E328 ASTM D790 (ISO 178 :39) ASTM D2240 (ISO 2039/2 et 868) ASTM 695 ASTM D25 (ISO 179 type1 et ISO 179 :93CA6 ASTM D4060 (ISO 9352 :1995F) ASTM D792 ASTM D671 ASTM D256 Comments due to temperature and pressure

Resistance to creep Yield strength/elongation Ultimate strenth/elongation Stress relaxation properties Modulus of elsticity Hardness Compression strenth Impact strength Abrasion resistance Density Fatigue Notch sensitivity

at design minimum temperatures or ASTM D1044 ASTM D1505 dynamic applications only

1.2

THERMAL PROPERTIES

Internal pressure sheath : A, Intermediate sheath / Anti-Wear layer : B, Outer sheath : C A X X X B X X X X X C X X X X X X Test Procedure ASTM C177 ASTM E831 ASTM D648 (ISO 75) ASTM D1525 ASTM E1269 ASTM D746 Comments

Coefficient of thermal conductivity Coefficient of thermal expansion Heat distortion temperatures Softening point Heat capacity Brittleness (or temperature

Method A

glass

X X transition) X

or ASTM E1356

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Tests shall be based on the design conditions of temperature. b) Soak time .Use design pressure as a minimum.If available. pressure and strain. CO2.If available.After each depressurization the sample shall be examined at a magnification of × 20 for signs of blistering. Sufficient tests at different temperatures to allow for linear interpolation should be performed. 1. e) Thickness .4 a) b) c) d) e) 1. No blister formation or slitting shall be observed.6 FLUID COMPATIBILITY All components shall be evaluated in the environments to which the polymer is exposed. c) Test cycles .Internal pressure sheath wall thickness as a minimum. The diameter is 70 mm as a minimum. or else use as a minimum 70 bar per minute.5 FLUID PERMEABILITY The sample shall be taken from an extruded polymer sheath. 1. g) Pressure . elongation at break.Use sufficient to ensure stauration. use expected decompression rate. h) Procedure .Use gas components of specified environment as documented in the test procedure. visual appearance and fluid absorption (weight gain) and desorption (weight loss) shall be measured and evaluated in the tests. COMPATIBILITY AND AGING Fluid permeability Blistering resistance Fluid compatibility Aging tests Environmental stress cracking weathering resistance Water absorption A X X X X X B X C X Test Procedure details in API 17J details in API 17J details in API 17J details in API 17J ASTM D1693 Comments CH4. H2S and methanol at design conditions X X X X X X X X X ASTM D570 Effectiveness of UV stabilizer Insulation material only For the characteristics listed in the last table API 17J recommends the following test requirements.. The thickness is 1 mm as a minimum. d) Decompression rate . Sufficient tests at different pressures to allow for linear interpolation should be performed.Use the expected decompression temperature. use expected number of decompressions.0 26/08/02 5 . As a minimum tensile strength.document with controlled diffusion .ATO-API version 3. f) Temperature . or else use 20 cycles as a minimum.3 PERMEATION CHARACTERISTICS. BLISTERING RESISTANCE a) Fluid mixtures . © ATOFINA Technical Polymers . swelling and slitting.1.

Special attention should be given to deplastification.1. chemicel environment and mechanical load. For PVDF materials the assessment of aging shall include the effect of temperature.document with controlled diffusion . The aging models may include accumulated damage concepts based on blocks of time or operational cycles of temperature/pressure under different exposure conditions. Creep.0 26/08/02 6 . water cut and pH. fluid absorption and changes of dimensions.7 AGEING TESTS Polymer aging models shall be based on testing and experience and shall predict the aging or deterioration of the polymer under the influence of environmental and load conditions that have benn identified to be relevant through testing. As a minimum.ATO-API version 3. cyclic strain and relaxation shall be investigated on aged and unaged samples. Aging may be determined by change in either specific mechanical properties or in specified physico-chemical characteristics which includes reduction in the plasticizer content of the material. © ATOFINA Technical Polymers . polymer aging models for PA-11 shall consider temperature.

ATO-API version 3.document with controlled diffusion .0 26/08/02 7 . In general and in case it is not specifically stated. Such extruded sheet gives similar experimental results as the extruded flexible pipe.BESNO P40 TLX BESNO P40 TLX OS DATA BESNO P40 TLX and BESNO P40 TLX OS are both plasticized PA11 grades destinated for off-shore flexible pipe use. © ATOFINA Technical Polymers . experiments were conducted on extruded sheet material. Th difference between the two grades lies in different granules’ conditioning for shipment. Their respective compositions are strictly the same as well as their properties.

7 IMPACT TESTS ACCORDING TO ISO 179 (type 1) Temperature Unnotched Notched °C -40 -2 KJ.H.8 IMPACT TESTS ACCORDING TO ISO 179 :93 CA Temperature Notched °C KJ.9 23 N.m N. KJ.B.ATO-API version 3.05 2. © ATOFINA Technical Polymers .1 2. N.5 2.B.m-2 8 23 N.2.9 0 52.B. 2. 2.2 MECHANICAL/PHYSICAL PROPERTIES DENSITY ASTM D792 HARDNESS ISO 2039/2 (R SCALE) ISO 868 (D SCALE) 75 63 50 MPa 1.B.4 COMPRESSION STRENGTH ASTM D695 (23°C) ABRASION RESISTANCE ISO 9352 : 1995(F) (loss in weight after 1000 rev under 500g load with H18 abrasive wheel) 22 mg FLEXURAL TESTS ACCORDING TO ISO 178 : 93 Temperature Flexural modulus (dry material) Flexural modulus (after conditionning 15 days 23°C 50% R.) °C MPa MPa -40 1950 2050 -20 1350 1150 23 320 280 80 165 160 2.m-2 -40 6.3 2.document with controlled diffusion .6 FLEXURAL TESTS ACCORDING TO ASTM D790 Temperature Flexural modulus (dry material) °C MPa 23 330 80 170 2.8 -20 9.0 26/08/02 8 .

014 0.document with controlled diffusion .strain data 0.002 0 1 10 100 TIME (s) STRAIN (mm/mm) 1000 10000 100000 23°C 30°C 40°C 50°C 60°C 80°C 100°C Master plot at 2 MPa obtained using the time .006 0.ATO-API version 3.01 0.2.012 0.008 0.002 0 1 100 10000 1000000 1E+08 1E+10 1E+12 1E+14 STRAIN(mm/mm) TIME (s) 23°C 30°C 40°C 50°C 60°C 80°C 100°C modele © ATOFINA Technical Polymers .9 TENSILE CREEP . From the different curves a creep master curve was constructed by applying the time temperature superposition principle. Creep curves at 2 MPa for different temperatures .016 0.TRACTION MODE Tensile creep tests according to ASTM D2990 were performed under 2 MPa at different temperatures rangeing from 23°C to 80°C. The creep modulus can then be modeled by a linear function on a log-log scale.temperature shifting principle scaled to 23°C 0.012 0.008 0. Tensile specimens were of ISO R 527 injected type and a MTS 810 servohydraulic machine is used.014 0.006 0.0 26/08/02 9 .004 0.004 0.01 0.016 0.

stress data 1000 MODULUS(MPa) 100 1 10 100 TIME (s) 1000 10000 100000 23°C 30°C 40°C 50°C 60°C 80°C 100°C © ATOFINA Technical Polymers .document with controlled diffusion .0035 Creep curves at 2 MPa for different temperatures .0 26/08/02 10 .0031 0.Plot of the shifting factor αΤ used to obtain the maste plot 10 9 8 7 6 5 4 3 2 1 0 0.0033 0.0027 0.0025 log(aT) 0.ATO-API version 3.0029 1/T K-1 0.

ATO-API version 3. 50°C and 80°C for both injection molded and extruded specimen © ATOFINA Technical Polymers . Tensile creep curves under 5 Mpa at 23°C.Tensile creep master curve constructed for 23°C 1000 MODULUS(MPa) 100 1 100 10000 1000000 1E+08 1E+10 1E+12 1E+14 TIME (s) 23°C 30°C 40°C 50°C 60°C 80°C 100°C All these creep studies have been done on ISO R 527 injection molded samples for purpose of simplicity but we have checked that there is merely no difference in the creep behaviour between injection molded or extruded samples.0 26/08/02 11 .document with controlled diffusion .

The imposed strain was 1%.ATO-API version 3. but using ISO R 527 tensile specimens.86. Stress relaxation curves for different temperatures at 1% strain MODULUS(MPa) 1000 100 1 10 23°C 50°C Puissance (30°C) Puissance (60°C) 100 1000 10000 100000 Time(sec) 30°C 60°C Puissance (40°C) 40°C Puissance (23°C) Puissance (50°C) Master plot : Evolution of E Modulus during stress relaxation under 1% strain at 23°C 1000 MODULUS(MPa) 100 1 100 10000 1000000 Temps(sec) 1E+08 1E+10 1E+12 23°C 30°C 40°C 60°C 80°C 50°C © ATOFINA Technical Polymers .temperature superposition principle.log plot.2.0 26/08/02 12 .document with controlled diffusion . A stress relaxation master curve was built using time .10 STRESS RELAXATION Stress relaxation measurements were performed according to ASTM standard E 328. The stress relaxation modulus is seen to decrease linearly in time in a log .

We chose this standard which measures fatigue at constant deformation in contrast to the ASTM standard which measures at constant stress.00 7.ATO-API version 3.document with controlled diffusion . To our knowledge the constant amplitude mode is more representative to the actual situation in a flexible riser.00 8.00 2. the constant stress mode would result in a considerable increase of deformation during the fatigue experiment due to stress relaxation of the material.00 1. FATIGUE TEST OF BESNOP40TLX WITH AN END OF LIFE CRITERIA OF 20% REDUCTION OF THE INITIAL STRESS 10.00 INITIAL STRESS (MPa) 9.00 6.00 4.00 1000 10000 100000 1000000 10000000 N cycles © ATOFINA Technical Polymers .11 FATIGUE Measured according to NF T51-120 in replacement to the norm ASTM D671.Comparison between the creep master plot and the stress relaxation master plot at 23°C 1000 MODULUS(MPa) CREEP STRESS RELAXATION 100 1 100 10000 1000000 1E+08 1E+10 1E+12 1E+14 TIME (s) 2.00 0.00 5. Furthermore.0 26/08/02 13 .00 3.

8 37.13 TENSILE TESTS ASTM D638 type II Samples cut from extruded sheaths TEMPERATURE Yield strength MPa 64 46 36 26 20 20 13 11 9 -40°C -20°C 0°C 20°C 40°C 60°C 80°C 100°C 120°C Elongation at Ultimate strength yield % MPa 16 33 30 > 39 40 > 39 44 > 27 46 > 26 46 > 26 44 > 17 42 > 15 38 > 13 Elongation break % 128 > 230 > 230 > 230 > 230 > 230 > 230 > 230 > 230 at Apparatus limited in size to reach maximum elongation 2. This is due to loss of plasticizer which exerts a slight influence on dimensional change.7 Elongation break % 75 90 202 231 263 260 260 262 282 323 at 2.3 34 31.1BA Samples injection moulded TEMPERATURE Yield strength MPa 93.45 The poisson ratio at 100°C is decreasing contrary to theoretical prediction.3 49.document with controlled diffusion .14 POISSON RATIO Temperature (°C) Poisson ratio -40 0. © ATOFINA Technical Polymers .9 32.385 23 0.8 21 59.2 33.2.8 48.47 100 0.2 56.0 26/08/02 14 .4 77.8 43.12 TENSILE TESTS ISO 527 93.1 36.ATO-API version 3.5 11 60.4 - -60°C -40°C -20°C 0°C 23°C 40°C 60°C 80°C 100°C 120°C Elongation at Ultimate strength yield % MPa 10 65.

Tensile test according ISO R 527-93 1BA 120 100 80 -60°C -20°C 0°C -40°C 60 20°C 40°C 40 60°C 80°C 120°C 20 0 0 50 100 150 200 250 300 350 Strain(%) note : Curve fluctuations at lower temperatures are a consequence of temperature fluctuations.0 26/08/02 15 .document with controlled diffusion . © ATOFINA Technical Polymers .ATO-API version 3.

ATO-API version 3.Tensile tests according ASTMD 638 type II 70 -40°C -20°C 0°C 60 20°C 40°C 60°C 50 80°C 100°C Stress (MPa) 40 120°C 30 20 10 0 0 50 100 150 200 250 300 Strain (%) © ATOFINA Technical Polymers .0 26/08/02 16 .document with controlled diffusion .

15 COMPRESSION TESTS Compression tests were done on 10*10*5 mm specimen machined in an extruded pipe. The compression is applied along the thickness on an MTS 810 servohydraulic machine.ATO-API version 3.document with controlled diffusion .0 26/08/02 17 .2. Compression tests on BESNO P40 TLX at 1 mm/min 180 160 140 120 Stress (MPa) 100 80 60 40 20 0 0 10 20 30 40 Strain(%) 60°c 50 60 70 80 23°c 40°c 80°c 100°c © ATOFINA Technical Polymers . The compression speed is 1mm/min.

2.0 26/08/02 18 .ATO-API version 3.document with controlled diffusion . Creep in compression mode of BESNO P40 TLX under 10 MPa 12 10 8 Strain(%) 6 4 2 0 1 10 100 1000 10000 100000 Time(s) 20°C 30°C 40°C 60°C 80°C © ATOFINA Technical Polymers .16 CREEP IN COMPRESSION MODE Creep tests in compression were done on 10*10*5 mm specimen machined in an extruded pipe. The compression is applied along the thickness on an MTS 810 servohydraulic machine.

document with controlled diffusion .Creep in compression mode of BESNO P40 TLX under 15 MPa 25 20 Strain(%) 15 10 5 0 1 10 100 1000 10000 100000 Time(s) 23°c 30°c 40°c 60°c 80°c 100°c © ATOFINA Technical Polymers .ATO-API version 3.0 26/08/02 19 .

document with controlled diffusion .4 SOFTENING POINT ASTM D1525 under 1daN under 5 daN 3. Temperature (°C) cal/g.6 GLASS TRANSITION TEMPERATURE D.C.A.3 HEAT DISTORSION TEMPERATURE ASTM D648 130 45 °C °C ISO 75 (0.24 0.25 0.40 0.50 0.2 THERMAL EXPANSION 11x10-5 23x10-5 °K-1 °K-1 ASTM E 821 from -30°C to +50°C from +50°C to +120°C 3.24 0.°C 20 50 80 120 160 200 230 260 0.S. 0-10 °C © ATOFINA Technical Polymers .85 Mpa) 3.21 0.21 0.46 Mpa) ISO 75 (1.66 0.66 0.25 Temperature (°C) K (W/m°K) 3.1 THERMAL PROPERTIES THERMAL CONDUCTIVITY 39 61 82 102 122 142 163 182 202 223 0.0 26/08/02 20 .3 3.6 0.25 0.25 0.56 0.63 0.5 HEAT CAPACITY 170 140 °C °C Measured by D.M.ATO-API version 3.24 0.24 0.67 3.

00E+10 1.00E+08 1. denominated β. Essentially four different relaxational transitions can be detected.0 26/08/02 21 180 -80 -60 -40 -20 . For a textbook on the comprehensive analysis of DMA data refer to “ Anelastic and dielectric effects in polymer solids ” by N. Williams Dover Publication New York 1991.relaxation. © ATOFINA Technical Polymers .3.7 DYNAMIC MECHANICAL ANALYSIS (full curve) Measurement in a 3-point bending flexural mode at 10 rad/s STORAGE MODULUS E' (Pa) . The intermittent low temperature relaxation.00E+07 0 20 40 60 80 100 120 140 160 -140 -120 -100 Temperature(°C) The DMA curve obtained is characteristic for semicristalline polymers. G. The γ transition at the lowest temperature (-130°C) is commonly attributed to localized motion of methylene segments. It implies large segmental motion of the polymer chains enabling diffusion processes to take place . B. Read.document with controlled diffusion .00E+09 E' E'' 1. LOSS MODULUS E''(Pa) 1.E.ATO-API version 3. Finally the last transition with an onset at 140°C is linked to the melting of the cristalline phase. is attributed to localized motion of H-bonded groups like the amide functions and its amplitude varies depending on water content. McCrum.G. The α-relaxation around -10°C is also called the glass transition.

8 DSC CURVE OF BESNO P40 TLX The DSC curve is obtained on a PERKIN ELMER DSC 7 calorimeter at a heating rate of 20°C/min.ATO-API version 3. one can easily observe the melting zone and the melting peak that gives the melting temperature.0 26/08/02 22 .3. 50 Heating rate : 20°C/min Heat Flow (mW) 45 40 35 30 25 -80 -40 0 40 80 120 160 200 240 Temperature(°C) © ATOFINA Technical Polymers . On the thermogram.document with controlled diffusion .

Also the preparation of test samples and factors such as the weigth ratio testing medium / samples are important parameters.Brunet. “Lifetime prediction of PA11 and PVDF thermoplastics in oilfield service– a synthetic approach” Patrick Dang. 3. October 1998. the reader should refer to API TB 17 RUG. Bernard Jacques. R. For further information. London. 1997 © ATOFINA Technical Polymers . COMPATIBILITY AND PERMEATION LIFETIME MODELS AND FAILURE CRITERIA BASED ON POLYAMIDE HYDROLYSIS From a point of view of material evolution due to ageing the following effects have been demonstrated in plasticized PA11 : . The reference of this document is API Technical Bulletin 17 RUG. Special attention is drawn to the necessity of appropriate procedures for ageing experiments.plasticizer loss . Yves Germain.1 AGEING BEHAVIOUR. Serpe.absorption of oil components. B. The kinetics of molecular weight loss are known in detail and can rather well be correlated with material performance [1 2 3 4]. Michael R. in particular lifetime estimations and Arrhenius curves based on above acceptance and failure criteria. "Ageing of polyamide 11 in acid solutions". 1911-1917. Driancourt.document with controlled diffusion . American Chemical Society Rubber Division meeting in Dallas. Werth. Vol 38 n°8. 1.annealing which leads to a higher crystalline content. Polymer.20 dl/g which includes a safety factor. For detailed information please refer to API TB 17 RUG. Hydrolysis has been reckognized as the most important ageing phenomenon in PA11. Jarrin. However. A. Guidelines how to measure CIV are given in detail in API TB 17 RUG and refer to standards ASTM D2857-95 and ISO 307:1994. The main result of the industry working group is a document which states specifically the end-of-life criteria and typical lifetime curves for environments of different acidity. 4. Communication at MERL Oilfield engineering with polymers. Chaupart. The oxygen content in long term ageing experiments must be tightly controlled and kept below a minimum to avoid a significant increase in ageing severity. gases and moisture . The failure criterion for PA11 in flexible pipes has been determined as CIV = 1. G. "Durability of polyamide 11 for offshore flexible pipe applications".05 dl/g. J.molecular weight loss due to a hydrolysis reaction in the presence of water . The reference ageing criterion defined is based on average molecular weight as expressed in Corrected Inherent Viscosity (CIV). Pierre. The importance and the complexity of the PA11 ageing behaviour have resulted in a combined industry effort. The process is well understood due to intense recent research.0 26/08/02 23 . The initial acceptance criterion has been defined as 1. special procedures not outlined in the ASTM or ISO standards apply.G.ATO-API version 3. 3/04/2000 2. J. N.4. James Mason. Verdu.

n° 3570 8.ATO-API version 3. Verdu. D. 2nd edition 1998 6. "Durability of polyamide 11 for offshore flexible pipe applications". Dang. Proceedings of Oilffield Engineering with polymers 2001. “The Rilsan User Group and APUI TR 17RUG” S. R. June 23 – 28 2002 Oslo 16. Groves. Serpe. Verdu. MERL Conference 28-29/11/2002-03-18 14. Polymer. “Accelerated ageing of polyamide 11 : evidence of physical ageing playing a role in the end-of-life criteria” H. "Improved thermoplastic materials for offshore flexible pipes". 1375-1380. Serpe. 9. “Lifetime prediction of PA11 and PVDF thermoplastics in oilfield service– a synthetic approach” Patrick Dang. "Molecular weight distribution and mass changes during polyamide hydrolysis". Chaupart. Fell. Chedozeau. N. F. P. M.J. 1375-1380. Polymer. Thompson. revised edition 1997 7. Jacques. Lefevre. J.G. Michael R. 1911-1917. “Polyamide 11 – a high tenacity thermoplastic. Rigaud. 1986. James Mason. J. B. Verdu. Dawans. Serpe. Werth. E. 1997 12. Kranbuehl. "Ageing of polyamide 11 in acid solutions". Belcher. Werth. OTC 14062 6 – 9 may 2002 15. October 1998. N. J. Hochstetter. J. Communication OTC 5231. G. Chaupart. Groves Proceedings of OMAE’01. “Progress towards a better understanding of the performances of Polyaminde 11 in flexible pipe applications” S. G. London. Chaupart.H. API TB 17 RUG © ATOFINA Technical Polymers . its material properties and the influence of ageing in offshore conditions” M? Werth. OMAE ’02 –28570 . Jarrin. Oeren. T. Yves Germain. B. Communication at MERL Oilfield engineering with polymers. Bernard Jacques. Pelisson. J. Driancourt. “Recommended practice for flexible pipe” API 17B. R. Vol 39 n°6-7. M. J. N. Buchner.document with controlled diffusion . Chang. J. A. Pierre. Vol 38 n°8. G. K. M. Ottoy. J. N. 1998 13.0 26/08/02 24 . S. Jarrin. American Chemical Society Rubber Division meeting in Dallas. “Specification for unbonded flexible pipe” API Specification 17J. Ottoy. 3/04/2000 10. Polymer. Caveny. 11. Vol 39 n°6-7.4. 1998 5. G. M. "Molecular weight distribution and mass changes during polyamide hydrolysis".Brunet.

This method is very sensitive for material changes due to ageing effects. Ageing conditions and durations were similar to the tensile tests.97 dl/g.G. after 19 days a considerable reduction in elongation is observed. the ageing performance and CIV are well correlated .2 EVOLUTION OF PROPERTIES DURING AGEING Tensile properties For demonstration purposes the evolution of tensile properties in an accelerated ageing experiment at 120°C in diluted sulfuric acid (pH = 4) are given. This type of test reveals a more gradual properties’ transition upon ageing than the tensile test. However. The K1c values thus obtained are well correlated with the CIV values. after 19 days the CIV = 0. ISO R527 samples with 3 mm thickness are machined out of extruded sheath and tesile tests performed at 23°C and 50 mm/min traction speed. The material can be considered brittle and not fit for purpose. The data presented shows a limited performance reduction for samples aged for “ and 10 days.document with controlled diffusion . Such rather steep transitions between slightly affected aged material and a strong drop in tensile properties is characteristic of polyamide 11 behaviour upon ageing. in particular at lower temperatures. BESNO P 40TL Influence du vieillissement H2SO4/120°C Traction 50mm/min 23°C Haltère ISO R257 épaisseur 3mm usinée dans tube Coflexip 40 35 30 Ecart-type en pointillés Contrainte (MPa) 25 20 15 10 5 0 0 20 40 60 80 100 120 140 160 180 200 Allongement rupture (%) non vieilli 3 jours 10 jours 19 jours 29 jours 40 jours Fracture toughness A pertinent property for the flexible application is fracture toughness.0 26/08/02 25 . Moreover. Following the protocols developed by the J.ATO-API version 3.4. Williams research team. © ATOFINA Technical Polymers . notched Compact test (CT) specimen with a thickness of 8 mm were tractioned at 5°C and a high speed of 85 mm/s.

5 2 2.0 2.5 1 0.0 26/08/02 26 .5 2.5 4 3.5 1 CIV (dl/g) 1.5 Viscosité corrigée ISO (dl/g) H2SO4/120°C pH=4 Haltères ISO R527 épaisseur 3mm Eau/140°C Haltères 53448A Visco cœur Eau/140°C Haltères DIN53448A Visco peau © ATOFINA Technical Polymers .0 1.5 CT tensile H2SO4/120°C CT tensile water/140°C bars charpy water/140°C BESNO P40TL Traction 23°C et 50mm/min 200 180 Allongement rupture (%) 160 140 120 100 80 60 40 20 0 0.ATO-API version 3.√m) 3 2.5 1.document with controlled diffusion .0 0.5 0 0 0.5 K1c (MPa.Comparison of K1c values obatined on compact test specimen and charpy bars aged in H2SO4 pH 4 at 120°C and water at 140°C 5 4.5 2 1.

Williams. Williams testing Protocol.G.3 1.document with controlled diffusion .2 1.1998 : Determination of Fracture Toughness (Gc and Kc) Linear Fracture Mechanics (LEFM) Approach - J.5 1.0 26/08/02 27 . some cut from retrived pipes presenting a viscosity gradient. 15 (1990) J. Chichester (1984) ISO/TC61 N5015 : Plastics.0 0.J.9 1. Test method for Tension-Tension Fatigue Crack Propagation © ATOFINA Technical Polymers . London ASTM E 399-81 Standatd test method for plane strain Fracture Toughness of metallic materials J.5 MPa.8 CIV (dl/g) pipe 864N sheath 864N The bars indicate viscosity gradients over the sheath thickness.Fatigue experiments Fatigue experiments have been performed on strips cut from aged pressure sheath in the extrusion direction and thus including the interior extrusion band on the specimen and also on strips cut from smooth bore pipes. Imperial College. Testing.7 0.8 0. The specimens are aged to different levels.0 1. Williams “Fracture Mechanics of Polymers” Ellis Horwood Ltd. The imposed starting strain is 4 % corresponding to 12. Mech. The fatigue experiments demonstrate good performance for sheath material above CIV = 1. Eng.G.6 1. 9. M. ISO/DIS 13586-2.1 0. march 1990.7 1.6 0.G. The fatigue cycles are stress controlled and oscillate at 1 Hz (maximum frequency without self heating) between 10 and 100 % of imposed maximum stress. Polym. Literature on fracture mechanics with references on methodology : .5 0.2 0.1 1.0 dl/g.4 1. Cawood. Tensile fatigue : samples cut from pipe and sheath aged in benzoic acid at 120°C 450000 400000 Number of cycles to rupture 350000 300000 no break 250000 200000 150000 100000 50000 0 0.ATO-API version 3. Dept.3 0.4 0.ISO task group working on the compact test K1C method : ISO/TC61/SC2 n° 572.

5 10 200 . 100 bars 80°C. © ATOFINA Technical Polymers . Dodge. information is given relative to diverse injection fluids used in combination with thermoplastic umbilicals.4.s.D. BESNO P40 TLO.R. 100 bars 70°C 50 to 100 bars 80°C. BESNO P40 TL is specified in detail in a separate document : RILSAN® Polyamide 11 in Oil & Gas OFF-SHORE Applications Reference © 2001/11/08. D. Details are described in the confidential report n° 52 735.ATO-API version 3.700 51 CO2 H2O H2S The data correlates well with data published elsewhere. I. 40 bars Permeation value / 10-8 cm3.4. 100 bars 100°C. The dimensions were 2 mm thickness and 70 mm diameter. Stables.document with controlled diffusion . This document gives comprehensive information on ageing of polyamide 11 in all offshore environments. MacRaild OTC 7272 1993 4. Circular samples were cut from extruded sheath. 100 bars 60°C. Reference “A more realistic method for predicting the compatibility of thermoplastic hoses when used in subsea umbilical systems” J. 100 bars 60°C. Fluid CH4 Conditions 40°C.3 COMPATIBILITY The compatibility of RILSAN® offshore grades BESNO P40 TLX. octobre 1999 issued by IFP.4 PERMEATION CHARACTERISTICS Permeability of gases Gas permeabilities were measured at the Institut de Pétrole (IFP) France following the “time-lag” method. Furthermore.5 4. 100 bars 80°C.cm/cm2. 100 bars 40°C.bar 0.8 2 4 1. 0.0 26/08/02 28 .

T. Klopffer.5 23 18 40 115 190 40 50 units : g mm/m2 day atm The activation energies for the unplasticized and plasticized grades are respectively 39. M. "Improved thermoplastic materials for offshore flexible pipes".ATO-API version 3.H. Taravel-Condat. Eurocorr Congress 99. Proceedings of Oilffield Engineering with polymers 2001. Communication OTC 5231. 1986.4 kJ mol-1 and 43. C. M. F. Dawans. Flaconneche. Hansteen. J. Andersen.1 kJ mol-1.0 26/08/02 29 . C. Lefevre.document with controlled diffusion . Pelisson. Jarrin. “Permeability of methane. n°410 18. carbin dioxide and water in PA11 and PVDF for flexible pipes” T. J.I. MERL Conference 28-29/11/2002-03-18 19. “High pressure permeation of gases in semicrystalline polymers : measurement method and experimental data” B. 1000 Permeability (g mm/m2 day atm) BESNO TL BESNO P40 TL 100 10 1 50°C 40°C 30°C 20°C 10°C 0°C 1/Temperature Litterature 17. Skar.Permeability of PA11 to methanol Temperature in °C PA11 unplastizised PA11 plastizised 4 6 13. © ATOFINA Technical Polymers .R.

samples taken from extruded pipe (8 mm thickness) Conditions : Sample size Test medium Test temperature Test pressure Soak time Decompression rate 35× 45 × 8 mm 85 % CH4 + 15 % CO2 90°C 1000 bar > 30 h explosive .ATO-API version 3.document with controlled diffusion .0 26/08/02 30 . Material tested : BESNOP40TLX. > 70 bars/min Conclusion : No blister and no slitting have been observed after 20 cycles of compression – decompression.5 BLISTERING RESISTANCE A blistering resistance study was performed at Institut Français du Pétrole (Solaize France). the RILSAN® BESNOP40TLX saturated by Diesel type II is qualified at 90°C / 1000 bar toward blistering according to the IFP’s test procedure issued from the API 17 J specification. © ATOFINA Technical Polymers .4.

22 34 13 2000 33 0. Intermittent exposure -è equal periods of light and darkness. The specimens are dumbells according to ISO/NFT 51034 cut from a film of 1 mm thickness. During a 20 minute cycle the specimens are exposed to 3 minutes of distillated water spray and 17 minutes of exposure without spraying.document with controlled diffusion . Black panel temperature in the measurement cabinet : 65°C ± 2°C before spraying 45°C ± 2°C after spraying.6 WEATHERING RESISTANCE The UV resistance is measured under accelerated conditions on a standardized machine XENOTEST 1200 according to the RENAULT standard n° 1380.ATO-API version 3.09 25 13 UV ageing : loss of elongation at break 400 350 300 EB (%) 250 200 150 100 50 0 0 500 1000 1500 2000 2500 time (h) © ATOFINA Technical Polymers . Tensile tests are carried out at 50 mm/minute.0 26/08/02 31 . Conditions : Xenon lamps with filters eliminating radiation with wave lengths inferior to 300 nm. The relative humidity of the cabinet during period without spray is approximately 65%. time (h) EB (%) EB / EB0 MB (MPa) YI 0 380 1 72 6 500 330 0.72 47 16 1400 85 0.4.87 61 14 1000 275 0.

7 WATER ABSORPTION ASTM D570 0.5 1 0.5 2 23°C 80°C 60°C 100°C Abs (%) 1.4.0 26/08/02 32 .5 0 0 200 400 600 800 1000 1200 1400 1600 1800 2000 rac t / L (min^0.H.5/cm) © ATOFINA Technical Polymers .cinetics 3 2.) 1.6% (23°C saturation) Water Absorption of BESNO P40 TLX at different temperatures .ATO-API version 3.document with controlled diffusion .8% (23°C 50%R.

016 0.006 0.TENSILE CREEP OF RILSAN BESNOP40TLX UNDER 2 MPa 0.008 0.018 0.004 0.document with controlled diffusion .002 0 1 10 100 TIME (s) 1000 10000 100000 23°C 30°C 40°C 50°C 60°C 80°C 100°C © ATOFINA Technical Polymers division .01 0.012 STRAIN (mm/mm) 0.0 26/08/02 33 .ATO-API version version 3.014 0.

004 0.014 0.0 26/08/02 34 .CREEP MASTER CURVE OF BESNOP40TLX UNDER 2 MPa 0.008 0.ATO-API version version 3.012 0.document with controlled diffusion .018 0.01 0.006 0.002 0 1 100 10000 1000000 100000000 1E+10 1E+12 1E+14 TIME (s) 23°C 30°C 40°C 50°C 60°C 80°C 100°C modele © ATOFINA Technical Polymers division .016 0.

ATO-API version version 3.document with controlled diffusion .0 26/08/02 35 .TENSILE CREEP OF RILSAN BESNO P40 TLX UNDER 2 MPa 1000 100 1 10 100 TIME (s) 1000 10000 100000 23°C 30°C 40°C 50°C 60°C 80°C 100°C © ATOFINA Technical Polymers division .

TENSILE CREEP MASTER CURVE OF RILSAN BESNOP40TLX UNDER 2 MPa 1000 MODULUS(MPa) 100 1 100 10000 1000000 100000000 1E+10 1E+12 1E+14 TIME (s) 23°C 30°C 40°C 50°C 60°C 80°C 100°C © ATOFINA Technical Polymers division .ATO-API version version 3.0 26/08/02 36 .document with controlled diffusion .

SHIFT FACTOR FOR THE CREEP MASTER CURVE OF BESNO P40 TLX 12 10 8 6 4 2 0 0.0029 0.0 26/08/02 37 .0034 0.0026 0.0035 © ATOFINA Technical Polymers division .0031 0.document with controlled diffusion .ATO-API version version 3.0032 0.0028 0.0033 0.003 1/T K-1 0.0025 0.0027 0.

ATO-API version version 3.0 26/08/02 38 .BESNO P40 TLX .document with controlled diffusion .10 MPa 1000 10000 100000 © ATOFINA Technical Polymers division .COMPRESSION CREEP UNDER 10 MPa 12 10 8 6 4 2 0 1 10 100 Time(s) 23°c .10 MPa 80°c -10 MPa 30°c-10 MPa 23°c .10 MPa 40°c -10 MPa 60°c.

document with controlled diffusion .CREEP COMPRESSION OF BESNO P40 TLX UNDER 10 MPa 12 10 8 Strain(%) 6 4 2 0 1 10 100 1000 Time(s) 23°C 30°C 40°C 60°C 80°C 10000 100000 1000000 © ATOFINA Technical Polymers division .0 26/08/02 39 .ATO-API version version 3.

0 26/08/02 40 .CREEP IN COMPRESSION UNDER 15 MPa 25 20 15 10 5 0 1 10 100 Time(s) 23°c 30°c 40°c 60°c 80°c 100°c 1000 10000 100000 © ATOFINA Technical Polymers division .BESNO P40 TLX .ATO-API version version 3.document with controlled diffusion .

document with controlled diffusion .0 26/08/02 41 .ATO-API version version 3.COMPRESSION CREEP OF BESNOP40TLX UNDER 15MPa 25 20 15 Strain(%) 10 5 0 1 10 100 1000 Time(s) 23°C 30°C 40°C 60°C 80°C 100°C 10000 100000 1000000 © ATOFINA Technical Polymers division .

00E+08 1.00E+09 1.0 26/08/02 42 .DYNAMIC MECHANICAL ANALYSIS OF BESNOP40TLX (3 POINT BENDING FLEXURAL MODE AT 10rad/s) 1.document with controlled diffusion .00E+07 -140 -120 -100 -80 -60 -40 -20 0 20 40 60 80 100 120 140 160 180 Temperature(°C) © ATOFINA Technical Polymers division . LOSS MODULUS E''(Pa) E' E'' 1.ATO-API version version 3.00E+10 STORAGE MODULUS E' (Pa) .

ATO-API version version 3.DSC curve of BESNO P40 TLX 50 Heating rate : 20°C/min 45 Heat Flow (mW) 40 35 30 25 -80 -60 -40 -20 0 20 40 60 80 100 120 140 160 180 200 220 240 Temperature(°C) © ATOFINA Technical Polymers division .0 26/08/02 43 .document with controlled diffusion .