New VESTAMID (Polyamide 12) grades to manufacture products with large geometrical dimensions for oil and gas applications

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1 New VESTAMID (Polyamide 12) grades to manufacture products with large geometrical dimensions for oil and gas applications Andreas Dowe, Dr. Christian Baron, Reinhard Buessing

2 Agenda: (Evonik) Degussa GmbH and BU High Performance Polymers Innovative PA12 grades create new possibilities PA 12 for large diameter gas pipes PA 12 for large diameter oil pipes

3 Agenda: (Evonik) Degussa GmbH and BU High Performance Polymers Innovative PA12 grades create new possibilities PA 12 for large diameter gas pipes PA 12 for large diameter oil pipes

Today Degussa GmbH is a multinational group dedicated to specialty chemicals. Historically the company developed from the strategic merger of important national and international chemical companies.

4 Today Degussa GmbH is a multinational group dedicated to specialty chemicals. Historically the company developed from the strategic merger of important national and international chemical companies. - third-largest chemical company in Europe - global market leader in specialty chemicals Degussa GmbH offers innovative products and system solutions for the success of the customers in accordance with the guiding principle creating essentials

5 RAG Aktiengesellschaft Energy Chemicals Real Estate STEAG Degussa RAG Immobilien Mining Deutsche Steinkohle RAG Coal International

7 Facts & Figures Corporate Center: Duesseldorf Sales: 1,9 bn Operating Result: 879 m Equity Ratio: 34 % Business Units: 12 Sites: more than 3 Employees: 36, as of December 31, 26

8 Business Unit High Performance Polymers One of the Degussa Divisions Building Blocks Feed Additives Coatings & Colorants Eclusive Synthesis Superabsorber High Performance Polymers Aerosil & Silanes Care & Surface Specialties Specialty Acrylics Advanced Fillers & Pigments C4-Chemistry Methacrylates

9 Largest production side in Marl, Germany Produktion F&E Marketing 2,5 km

10 Agenda: Degussa GmbH and BU High Performance Polymers Innovative PA12 grades create new possibilities PA 12 for large diameter gas pipes PA 12 for large diameter oil pipes

11 High risk application e. g. fuel line and air brake systems Mono layer tubes Multi layer tubes with barrier layers for low hydrocarbon emissions

12 High risk application With approvals worldwide. Car Manufacturer. Region AUDI BMW DAIMLERCHRYSLER FIAT FORD LAND ROVER MCC MG ROVER NEDCAR OPEL / SAAB PORSCHE VOLKSWAGEN VOLVO DAIMLERCHRYSLER FORD GM ISUZU MITSUBISHI DAIMLERCHRYSLER GM PSA DAEWOO HONDA HYUNDAI KIA MAZDA MITSUBISHI NISSAN TOYOTA. Europe Europe Europe Europe Europe Europe Europe Europe Europe Europe Europe Europe Europe North-America North-America North-America North-America North-America South-America South-America South-America Asia Asia Asia Asia Asia Asia Asia Asia Specification acc. to VW TL B QV 16 6 SAE J /1 WSS-M98D33-A3/-A4 FS1 Blueprint FS1 TR GME 8 1 PTL acc. to VW TL TR PF-8813 SAE J226 WSS-M98D33-A3/-A4 GM213M GM646M GM213M GM646M ES-X6625 ES-X6628 PF-8813 SAE J226 GME 8 1 STE EDS-M-519 MS Blueprint ZL XE ES-X6625 ES-X6628 MLT Status in production in production in production in production in production in production in production in production in production in production in production in production in production in production in production in production in production in production in production in production in production in production in production in production in production in production in production in production in production

13 New PA12 platform Rheological behavior Naturally, PA 12 has a low melt viscosity. Even higher molecular etrusion grades are not suitable for manufacturing of big tubes or for blow molding Degussa has developed new PA 12 grades which increase their molecular weight during processing remarkably, but in a controlled manor. In terms of relative solution viscosity (m-cresol): 2.1 (granules) 2.4 (or higher if requested)

14 New PA12 platform Rheological behavior 2 C ma. pull force in cn Increase of mel t stiffness ofpa 12 meter measured with a strain viscosi 7 22 C 24 C Standard PA 12 High viscous PE New PA 12

15 New PA12 platform Rheological behavior Etrusion of a yellow PA 12 pipe, size 11 mm SDR-11, for natural gas installation

16 Agenda: Degussa GmbH and BU High Performance Polymers Innovative PA12 grades create new possibilities PA 12 for large diameter gas pipes PA 12 for large diameter oil pipes

17 Gas pipe application Technical positioning vs. PE carbonamidegroup hydrogen bonds (bridges) Polyethylen - CH2-CH2-CH2 - Polyamide 12 (- CH2)11-NH-CO- Property Melting point( C) Tensile strength atyield (MPa) Tensile elongation atbreak (%) FleuralModulus (MPa) Charpy impactstrength (kj/m2) Hardness, Shore D Permeability *) under investigation PA 12 PE 1 PE >2 12 no break > > for methane <.5 for hydrogen <.1 *) *),24,7

18 Gas pipe application Technical positioning vs. PE PA 12 allows higher maimum operation pressures and temperatures (including design safety factor of 2, for SDR-11 pipes) MOP 1) in bar 23 C 6 C 8 C PE PE PA ) Maimum Operation pressures to be applied including safety factors (design coefficients)

19 Gas pipe application Feasibility study in USA Conclusions of the GTI report: Based on the cumulative results of the testing, it can be reasonable inferred that the PA12 material is a suitable material for high pressure gas distribution piping applications. The results of the comprehensive testing demonstrate the PA12 piping material conforms to all of the requirements contained with ASTM D2513 and its respective Annees. First test installations of 6 SDR11 pipes including electro fusion fittings are done in USA. Installations were completed in October 26. The Operation pressure is 17 bar (25 psi). Total length: Several 1 meter

20 Gas pipe application Test installation at EON Ruhrgas Installation of a 6 m test pipe 11 mm SDR-11 delivered on a coil to be equipped with: Butt fusion joint Electro fusion joint and end-caps Detection of permeation Running time of 2 years with a operation pressure of 24 bar

21 PA 12 on PE etruder! Coiling of 11mm SDR-11 pipe on 2.7 m drum! quick burst at 93 bar!

22 Gas pipe application Technical positioning vs. PE Installations are operating at 24 and 36 bar for 2 years 6 m 11mm SDR-11 pipe, two butt fusion and two electro-fusion joints, electro-fused endcaps

23 Agenda: Degussa GmbH and BU High Performance Polymers Innovative PA12 grades create new possibilities PA 12 for large diameter gas pipes PA 12 for large diameter oil pipes

24 Fleible pipe application Fleible riser with LX92 Flowlines with LX92

25 Fleible pipe application Required Tests, API 17J, ISO MATERIAL PROPERTIES Mechanical Properties Stress at yield Strain at yield Stress at break Strain at break Poisson's ratio Modulus of elasticity Hardness Compressive strength Impact strength Fracture toughness Abrasion resistance Long-term Mechanical Properties Creep resistance Stress relaation Fatigue Resistance Fatigue crack propagation Physical Properties Density Thermal Properties Thermal conductivity coefficient Thermal epansion coefficient Softening point (Vicat) Heat distortion temperature Heat capacity vs temperature Heat of fusion, melting point Brittleness temperature or glass transition temperature Permeation Characteristics Permeability Blistering resistance Compatibility and Aging Fluid compatibility Aging tests Weathering resistance Heat aging tests air Water absorption required Standard used Standard ISO API W/S ASTM D638 ASTM D638 ASTM D638 ASTM D638 ASTM D638 ASTM D638 ASTM D638 ASTM D638 ASTM D638 ASTM D638 ASTM D224 ISO 64 ASTM D256 ISO ISO 9352 s s s s s s ASTM D299 ASTM E 328 ASTM D671 ASTM D299 ASTM E 328 BS 3518 part3 ISO CD 1585 ASTM D792 ASTM D792 ASTM C177 ASTM E831 ASTM D1525 ASTM D648 ASTM E1269 ASTM D3418 ASTM D746 ASTM E1356 ASTM C177 ASTM E831 ASTM D1525 ASTM D648 ASTM E1269 ASTM D3418 ASTM E1356 API 17J, Sect API 17J, Sect API 17J, Sect API 17J, Sect API 17J, Sect API 17J, Sect ASTM G151 API 17J, Sect API 17J, Sect s s ASTM D57 ASTM D57 ASTM D638 ASTM D224, D2583 ASTM D695, ISO 64 ASTM D256 ASTM D1242, D46, D144 or E DIN ISO s - only outer sheath

26 Fleible pipe application PA12 VESTAMID LX92 (since Jan. 26) vs. PA11 material used since 2

27 Fleible pipe application Test Laboratories ICI Measurement Science Group (Fatigue, Crack Propagation) UKAS Material Engineering Laboratory (MERL) (Blistering) ISO 91:2 Shell Global Solutions (Chemical ageing) ISO 91:2 Degussa Polymer Testing (All other tests) ISO 91:2 QS 9 ISO 1725

28 Fleible pipe application Mechanical Properties Tensile Test acc. ASTM D638 4 Strain at break in % PA12 PA Temperature in C 2 4

29 Fleible pipe application Longterm Mechanical Properties

30 Fleible pipe application Longterm Mechanical Properties

31 Fleible pipe application Compatibility and Aging Nomenclature CIV Corrected Inherent Viscosity [dl/g]. A measure of the molecular weight of the polymer. TAN Total Acid Number [mg KOH/g]. A measure of acidity in oil caused by organic acids.

32 Fleible pipe application Compatibility and Aging TAN = 1.1 mg KOH/g Test is ongoing Ageing in Cruide Oil at 8 C PA12 (Low TAN) Mass-Change [%] -1 PA11 (Low TAN) Ageing time [d] 2 25

33 Fleible pipe application Compatibility and Aging TAN = 1.1 mg KOH/g Test is ongoing Ageing in Cruide Oil at 8 C Elongation at break in % PA12 (Low TAN) 5 PA11 (Low TAN) Ageing time [d] 2 25

34 Fleible pipe application Compatibility and Aging TAN = 1.1 mg KOH/g Test is ongoing Ageing in Cruide Oil at 8 C 2.2 CIV in dl/g PA12 (Low TAN) 1.2 PA11 (Low TAN) Ageing time [d] 2 25

35 Fleible pipe application Compatibility and Aging Chemical ageing in water (Shell Global Solutions) Testing is performed according to API 17TR2 The ageing tests have been etended: tma > 125 days! Ageing tests follow Appendi B Medium: de-ionised water with pp CO2 = bar, T = 8 C, 1 C, 12 C, tma = 818 days pp CO2 = 1 bar, T = 8 C, 1 C, 12 C, tma = 818 days After ageing the following properties are measured: Corrected inherent viscosity (CIV) as per Appendi D Dimensional and density changes Tensile properties

36 Fleible pipe application Compatibility and Aging Chemical ageing (Shell Global Solutions)

37 Fleible pipe application Compatibility and Aging Aging in water with 1 bar CO2 1 9 Strain at break [%] PA 12 CO2 8 C PA 12 CO2 1 C PA 12 CO2 12 C PA 11 CO2 8 C PA 11 CO2 1 C PA 11 CO2 12 C ageing time [days]

38 Fleible pipe application Compatibility and Aging Ageing in water with 1 bar CO2 2.2 PA 12 CO2 12 C PA 12 CO2 1 C PA 12 CO2 8 C acceptance criterion PA 11 CO2 12 C PA 11 CO2 1 C PA 11 CO2 8 C 2. CIV [dl/g] ageing time [days]

39 Fleible pipe application Compatibility and Aging Mechanical vs. chemical properties 1 8 C 9 Strain at break [%] d d d d CIV [dl/g]

40 Fleible pipe application Compatibility and Aging Mechanical vs. chemical properties 1 8 C 9 1 C Strain at break [%] CIV [dl/g]

41 Fleible pipe application Compatibility and Aging Mechanical vs. chemical properties 1 8 C 1 C 9 12 C 8 Strain at break [%] CIV [dl/g]

42 Fleible pipe application Compatibility and Aging 2. acceptance criterion PA 12 CO2 12 C fit PA 12 CO2 1 C fit PA 12 CO2 8 C PA 11 CO2 12 C fit PA 11 CO2 1 C fit PA 11 CO2 8 C 1.8 CIV [dl/g] ageing time [days] 1

43 Fleible pipe application Compatibility and Aging 1 bar CO2, Arrhenius curves Time to reachinitial acceptance criterion of CIV = 1.2 dl/g[years] ph=5 (API 17TR2) ph=4 (API 17TR2).1 PA 11 H2O/1 bar CO2 fit [years] PA 11 H2O/1 bar CO2 [years] PA 12 H2O/1 bar CO2 fit [years] PA 12 H2O/1 bar CO2 [years] T [ C]

44 Fleible pipe application Compatibility and Aging 1 bar N2, Arrhenius curves Time to reach initial acceptance criterion of CIV = 1.2 dl/g [years] API RP 17B "Saturated" ph=7 (API 17TR2).1 PA 11 H2O/no CO2 fit [years] PA 11 H2O/no CO2 [years] PA 12 H2O/no CO2 fit [years] PA 12 H2O/no CO2 [years] T [ C]

45 Fleible pipe application Compatibility and Aging Ageing in air (oidation) 4 PA 12, T = 12 C PA 12, T = 14 C PA 11, T = 12 C PA 11, T = 14 C strain at break [%] ageing time [days] 2

46 Fleible pipe application Compatibility and Aging Ageing in air (oidation) 4 PA 12, T = 8 C PA 12, T = 1 C PA 11, T = 8 C PA 11, T = 1 C strain at break [%] ageing time [days] 4

47 Fleible pipe application Compatibility and Aging Ageing in air (oidation) time to reach 5 % strain at break [years] API RP 17B "Saturated" PA 11 air.1 PA 11 air (fit) PA 12 air PA 12 air (fit) T [ C]

48 PA12 for liner application e. g. TitelinerTM process

49 PA12 for liner application Elastic memory after compression PA 11plasticized Initial Compression % Initial Compression Remaining Compressi on after 24 h in % 9, 4,9 2,,6 Remaining Compressi on after 1 h in % 1,2 5,6 2,4,7 PE 1 VESTAMI D LX92 Remaining Compressi on after 24 h in % 16,4 1,5 4,8 1,5 Remaining Compressi on after 1 h in % 17,2 12,2 5,8 1,7 Remaining Compression after 24 h in % 14,4 9,3 4,8 1,7 Remaining Compression after 1 h in % 15,3 9,7 5, 1,7

50 PA12 for liner application TitelinerTM process First roll down trial with a 3 PA12 liner Material behaves like PE

51 PA12 for liner application Compatibility and Aging Swelling behaviour in several oils 6 MDPE / 6 C / RM 93 5 / Dieselöl Length swelling [%] MDPE / Rohöl Low TAN 4 BS 942 / 8 C / IRM 93 / Dieselöl / Rohöl Low TAN 3 LX92 / 8 C / IRM 93 / Dieselöl 2 / Rohöl Low TAN VESTAMID LX93 1 VESTAMID LX Time [h] 3 4 5

52 PA12 for liner application Advantages of PA12 Advantages of PA12 Higher MOT than PE Outstanding swelling behavior Lower cost compared to PVDF Better processability compared to PA11 Longer lifetime compared to PA11

53 Summary Key Messages New PA12 grades with high melt stiffness for large diameter tubes Easy to process First approval for the oil industry Longer lifetime with PA12 than PA11 MOT for PA12 is app. 6 C higher than for PA11 Low swelling in oil Easy to install

54 Back up slides

55 PA12 for liner application Design 1. Grooved Liner Window of application: 2. Perforated Liner PE: < 6 C, low cost PA11/12: up to 8 C, medium cost PVDF: < 13 C, high cost

56 In terms of dynamic shear viscosity: Increase of PA 12 melt viscosity mesured acc. to ASTM D444 in a mechanical spectrometer Shear viscosity in Pa s s 1 E+6 22 C 24 C 1 E+5 New PA 12 grade 22 C 24 C T=2 C PE standard etrusion grades 1 E+4 PA 12 standard etrusion grades 1 E+3 1 E-1 1 E+ Shear rate [1/s] 1 E+1 1 E+2

57 Fleible pipe application Mechanical Properties Tensile Test acc. ASTM D E-Module [Mpa] PA12 PA Temperature [ C] 6 8 1

58 Fleible pipe application Thermal Properties Property Test Method Standard Specimen PA12 PA11 Unit W/(m K) μm/(m K) C C C C J/(g.K) C 1 Thermal Conductivity Coefficient ASTM C177 Thermal Epansion Coefficient (23 55 C) ASTM E831 Softening Point Vicat A (1N) Softening Point Vicat B (5N) Heat Distortion Temp. (HDT A.45 MPa) Heat Distortion Temp (HDT A 1.8 MPa) Heat capacity DSC (23 C) Glass Transition Temp. DSC Melt Temperature DSC Heat of fusion DSC Heat of fusion (1% crystalline) crystallinity ASTM D1525 ASTM D1525 ASTM D648 ASTM D648 ASTM E1269 ASTM E1356 Plate Thickn.: 4mm Diam.: 6mm Derived from ASTM D638/I Derived from ASTM D638/I Derived from ASTM D638/I Derived from ASTM D638/I Derived from ASTM D638/I Derived from ASTM D638/I Derived from ASTM D638/I ASTM D3418 Derived from ASTM D638/I C ASTM D3418 Derived from ASTM D638/I J/g theoretical DSC / theoretical Degussa van Krevelen.3.23 J/g 1 - Specimen derived from a mm injection moulded plate

59 Fleible pipe application Thermal Properties Thermal Epansion Coefficient ASTM E831 Term Ep. Coeff.in um/(m * K) Temperaturein C 5 75 PA12 1 PA11

60 Fleible pipe application Compatibility and Aging Chemical ageing in crude oil (Degussa Polymer Testing) Medium: crude oil low TAN = 1,1 mg KOH/g, T = 8 C, tma = 1. h high TAN = 8,9 mg KOH/g, T = 8 C, tma = 1. h After ageing the following properties are measured: Corrected inherent viscosity (CIV) as per Appendi D of API 17 TR2 Dimensional and density changes Tensile properties

61 Fleible pipe application Compatibility and Aging 2. PA 11 N2 12 C fit PA 11 N2 1 C fit PA 11 N2 8 C PA 12 N2 12 C fit PA 12 N2 1 C fit PA 12 N2 8 C acceptance criterion 1.8 CIV [dl/g] ageing time [days] 1

62 PA12 for liner application Compatibility and Aging 1 bar CO2, Arrhenius curves Time to reach initial acceptance criterion of CIV = 1.1 dl/g [years] 1, 1, 1, PA 11 H2O/1 bar CO2 fit [years] CIV=1.1,1 PA 11 H2O/1 bar CO2 [years] CIV=1.1 PA 12 H2O/1 bar CO2 fit [years] CIV=1.1 PA 12 H2O/1 bar CO2 [years] CIV=1.1, T [ C]

63 PA12 for liner application Compatibility and Aging 1 bar N2, Arrhenius curves Time to reach initial acceptance criterion of CIV = 1.1 dl/g [years] 1, 1, 1, API RP 17B "Saturated",1 PA 11 H2O/no CO2 fit [years] CIV=1.1 PA 11 H2O/no CO2 [years] CIV=1.1 PA 12 H2O/no CO2 fit [years] CIV=1.1 PA 12 H2O/no CO2 [years] CIV=1.1, T [ C]

64 Fleible pipe application Compatibility and Aging Chemical ageing in methanol UV - Resistance (Degussa Polymer testing) Methanol T = 8 C, tma = 1. h T = 8 C, tma = 1. h UV ATLAS Ci 5 Xenon Wheather-Ometer, tma = 1. h After ageing the following properties are measured: Corrected inherent viscosity (CIV) as per Appendi D Dimensional and density changes Tensile properties

65 Fleible pipe application Compatibility and Aging Methanol at 8 C Test is ongoing 35 strain at break [%] PA11 PA ageing time [h] 4 5 6

66 Fleible pipe application Compatibility and Aging Methanol at 8 C Test is ongoing 22 2 CIV [ml/g] 18 PA12 PA ageing time [h] 4 5 6

67 Fleible pipe application Compatibility and Aging UV Resistance of PA12 and PA11 35 Strain at break in % PA12 (black) PA11 (black) Time in h 8 1

68 Fleible pipe application Compatibility and Aging UV Resistance of PA12 and PA CIV in ml/g 18 PA12 (black) 16 PA11 (black) Time in h

69 Fleible pipe application Lloyd s Certificate Certificate of Material Qualification for use of Polyamide 12 Grade - VESTAMID LX92 in Wellstream manufactured non-bonded Fleible Pipes (API 17J and ISO )

70 PA12 for liner application Processability Melt temperature 248 C etrusionsvideo

71 PA12 for liner application First eperiences with LX92 GPS (Glynwed Pipe Systems) produced 9 mm pipes. Statement: LX92 shows an outstanding processability Georg Fischer produced 3 mm thin wall liner. Statement: The material is suitable for much larger dimensions Egeplast produced 11 mm pipes for gas application Statement: The melt stiffness is even higher than of PE

72 Fleible pipe application Samples PA 11 PA 12 From 4 inch Wellstream etruded pipes ASTM D638 Type V tensile specimens have been machined

73 Fleible pipe application Mechanical Properties Property Test Method Standard Specimen PA12 PA11 Unit Yield stress (23 C) Yield strain (23 C) ASTM D638 ASTM D638 Type I Type I n.a. n.a. MPa % Stress at break (23 C) Strain at break (23 C) Tensile Modulus (23 C) Poisson ratio (23 C) Shore Hardness A (1s) ASTM D638 ASTM D638 ASTM D638 ASTM D638 ASTM D224 Type I Type I Type I Type I Obtained from ASTM D638/I MPa % MPa Shore Hardness A (15s) Shore Hardness D (1s) Shore Hardness D (15s) Compressive Modulus (23 C) ASTM D224 ASTM D224 ASTM D224 ISO 64 Obtained from ASTM D638/I Obtained from ASTM D638/I Obtained from ASTM D638/I 5*14 mm MPa Type A Width: 6,7 mm J/m IZOD (23 C) Impact Strength ASTM D695 ASTM D256

74 Fleible pipe application Compatibility and Aging TAN = 8.9 mg KOH/g Ageing in Cruide Oil at 8 C Test is ongoing Elongation at break in % PA12 (High TAN) 5 PA11 (High TAN) Ageing time [d] 2 25

75 Fleible pipe application Compatibility and Aging TAN = 8.9 mg KOH/g Ageing in Cruide Oil at 8 C Test is ongoing 2.2 CIV in dl/g PA12 (High TAN) 1.2 PA11 (High TAN) Ageing time [d] 2 25

76 Fleible pipe application Longterm Mechanical Properties

77 Fleible pipe application Longterm Mechanical Properties Comp ressi on Stress Rel Compressi aati on acc. AST M E 328 (Str ai n: 1%) on Stress Relaati on acc. ASTM E 328 (Strai n: 25%) P A12 (RT ) P A12 (4 C) P A1 1 ( RT) 25 MPa P A12 (RT ) P A12 (4 C) P A1 1 (RT ) P A1 1 (4 C) Stress in Stress i n MPa 2 2 P A1 1 ( 4 C) Ti me i n sec Ti me i n sec 8 1

78 Fleible pipe application Thermal Properties The rmal Conductivity Coefficient acc ASTM C177 The rm. Cond. in W/m*K,35,3,25,2,15,1, Tempe rat ur e in C PA11 PA12

79 HP has a Well Established Organization and Network in Europe, NAFTA and Asia Headquarters in Marl, Germany Production sites in Germany, USA, Austria, China Research centre in Germany Sales offices and representatives in over 3 countries Direct contact to over 7 customers Sales Offices Manufacturing plants Daicel-Degussa

Andreas DOWE, Dr. Christian BARON, Reinhardt BÜSSING**

Andreas DOWE*, Dr. Christian BARON*, Reinhardt BÜSSING** X Międzynarodowa Konferencja Techniczna: 2-21 września, 27, Płock Zarządzanie Ryzykiem w Eksploatacji Rurociągów New VESTAMID (Polyamide 12) grades to manufacture products with large geometrical dimensions