PE原料及PE管道发展现状及趋势

Gustaaf SUYS Total Petroch. Research Feluy (formerly ATOFINA) WHERE, WHEN, WHY and WHICH HDPE for PIPES CHINA NATIONAL STANDARDS Seminar Beijing, 26-27 June 2005 Gustaaf SUYS Total Petroch. Research Feluy GOLDEN JUBILEE 50 Years HDPE Gustaaf SUYS Total Petroch. Research Feluy SOME APPLICATIONS Cable Blow Molding Film, Sheet, ProfileRotomolding Gustaaf SUYS Total Petroch. Research Feluy PIPE and FITTING APPLICATION Gustaaf SUYS Total Petroch. Research Feluy MANUFACTURING ETHYLENEPOLYETHYLENE -CH2CH2n-n CH2=CH2 CATALYST COMONOMER Gustaaf SUYS Total Petroch. Research Feluy Gustaaf SUYS Total Petroch. Research Feluy COMONOMER SYSTEMS C / C C / C C / C C / C C / C C / C C / C C / C C / C C / C C / C C / C C / C C - C / / C C - C / C C / C C / C C / C C / C C C / / C C - C / C - C / C C / C C / C HomopolymerButene CopolymerHexene CopolymerOctene Copolymer Gustaaf SUYS Total Petroch. Research Feluy Gustaaf SUYS Total Petroch. Research Feluy CRYSTALLINITY Amorphous structure, e.g. PVC, ABS, Semi-crystalline structure, e.g. PE, PP, PA, PC, Gustaaf SUYS Total Petroch. Research Feluy Gustaaf SUYS Total Petroch. Research Feluy CRYSTALLISATION PRINCIPLE The comonomer branches disturb the crystallisation. Hexene has a much higher efficiency than butene Gustaaf SUYS Total Petroch. Research Feluy Gustaaf SUYS Total Petroch. Rh F l Gustaaf SUYS Total Petroch. Research Feluy DUCTILE FAILURE MECHANISM Re: Arnold LUSTIGER 1 2 1Failure by break : tensile test failure Failure by splitting : pressure testing2 Gustaaf SUYS Total Petroch. Research Feluy BRITTLE FAILURE MECHANISM Re: Arnold LUSTIGER 1 1 Intercrystalline failure by SCG Gustaaf SUYS Total Petroch. Research Feluy MWD : MONOMODAL Comonomer The highest content of comonomer is in the lowest molecular weight portion, which is not the optimal condition for high strength material Gustaaf SUYS Total Petroch. Research Feluy Gustaaf SUYS Total Petroch. Research Feluy MWD : BIMODAL MWD AMWD B MWD AB Comonomer in B Comonomer in AB As only portion B is copolymer, it will lead to high comonomer branching in the high molecular weight part of AB Gustaaf SUYS Total Petroch. Research Feluy Gustaaf SUYS Total Petroch. Research Feluy HDPE PIPES IN EUROPE Although the European HDPE pipe market started over 40 years, and can be considered as a mature market to-day, there is still a very substantial growth expected in the coming years 0 200 400 600 800 1000 1200 1400 1600 1980198519901995200020052010 kTON Gustaaf SUYS Total Petroch. Research Feluy Gustaaf SUYS Total Petroch. Research Feluy PE100 vs. PE80 market P E / P E 100 P ipes m arket E urope by P roduct C lass 0 100 200 300 400 500 600 700 800 19961997199819992000200120022003 KMT PE 80PE 100 PE80 / PE100 Pipes market Europe by Product Class 0 100 200 300 400 500 600 700 800 19961997199819992000200120022003 KMT PE80 WEPE80 EEPE100 WEPE100 EE In West Europe, where most PE100 is sold, the PE80 market is expected to shrink at 3% per year. PE100, which grows at 15%-20% per year, takes the entire growth of the PE pipes market. Gustaaf SUYS Total Petroch. Research Feluy HDPE PIPES IN THE US-CANADA Decreasing share for PE pipes Possible reasons: -Lower performance rating -MOP for PE3408 and PE2406 lower than PE80 -No PE100 type yet -Discriminating design -Gas, water and sewage is only 20% (in Europe about 70%) -PVC quite popular Gustaaf SUYS Total Petroch. Research Feluy TIME DEPENDENT PROPERTIES PE is a visco-elastic material: most properties are time dependent LONG TERM: - STRENGTH: resistance to internal pressure (MRS) - STIFFNESS: resistance to deformation by top load - FLEXIBILITY: stress release by limited deformation SHORT TERM: - TOUGHNESS: impact and rapid crack propagation resistance (RCP) - FLEXIBILITY: ease of coiling, handling and installing SHORT and LONG TERM: - STRESS CRACKING RESISTANCE: - environmental (ESCR) - mechanical (MSCR) Gustaaf SUYS Total Petroch. Research Feluy Gustaaf SUYS Total Petroch. Research Feluy INTERNAL PRESSURE RESISTANCE LONG TERM PERFORMANCE Gustaaf SUYS Total Petroch. Research Feluy INTERNAL PRESSURE TESTING METHOD: EN 921 ISO 1167 Reference pipe: 32x3 mm Temperature: 20,40,60,80C Pressure: f.(failure times) Failure times: 10 - 9000 h Data: minimum 30/temperature Extrapolation: ISO 9080 Gustaaf SUYS Total Petroch. Research Feluy FAILURE MODES DUCTILE FAILURE: - large deformation -“fish mouth” failure - mechanical overloading of the test piece BRITTLE FAILURE: - no deformation -“slit” failure - result of fatigue Gustaaf SUYS Total Petroch. Research Feluy STRESS-TIME FAILURE CURVE DUCTILE FAILURE MODE FAILURE DATA BRITTLE FAILURE MODE 97.5 % lcl CURVE AVERAGE CURVE KNEE-POINT 1 2 3 1 2 3 . . . . . . . . . . . . x Log HOOP STRESS (MPa) Log FAILURE TIME (h) DUCTILE failure line : measure for maximum stress loading BRITTLE failure line : measure for expected service life Gustaaf SUYS Total Petroch. Research Feluy EXTRAPOLATION PRINCIPLE Log FAILURE TIME (h) Log HOOP STRESS (MPa) 20C 40C 60C 80C 100 50 6 Re: ISO EN50 y Gustaaf SUYS Total Petroch. Research Feluy PE 80 Class MD HD Minimum requirements Typical performance EN ISO HD MD HD MD 4.5 NPT 4.0 8.0 9.0 10.0 100 W 165 G 500 1000 50 y 100 y Failure time (h) Hoop stress (MPa) PE 63 PE 80 PE 100 20C 80C Gustaaf SUYS Total Petroch. Research Feluy PE 100 Class Minimum requirements - Typical performance 50 y 20C 40C 60C 80C 12.4 5.4 5.0 NPT 4.6 G 500 W 165 Hoop stress (MPa) Failure time (h) Some already brittle failure 100 Y 10.0 100 1000 PE 125 (PE 112) PE 100 PE 80 PE 63 Gustaaf SUYS Total Petroch. Research Feluy RESISTANCE TO SLOW CRACK GROWTH - SCG Gustaaf SUYS Total Petroch. Research Feluy POSSIBLE SURFACE DEFECTS Undue care during transporting,handling and installing may lead to scratching and notching the outside pipe surface Squeeze-off to stop the flow may leave hair cracks at the edges on the inside pipe surface Gustaaf SUYS Total Petroch. Research Feluy NOTCHES BY THE SYSTEM Bead roll-over in butt fusion jointing Cold zones in electrofusion joints Gustaaf SUYS Total Petroch. Research Feluy POINT LOADING EFFECTS Damage inside-wall by point-loading Re: GASTEC Re: HESSEL Gustaaf SUYS Total Petroch. Research Feluy REAL FACTS Slow Crack Growth failure by rock impingment Courtesy Dr J.HESSEL Gustaaf SUYS Total Petroch. Research Feluy NOTCHED PIPE TESTING (NPT) Re: WAVIN Ltd METHOD: EN ISO 13479 Reference pipe: 110/125 mm SDR11 Temperature: 80C Pressure: PE 80: 8 bar PE 100: 9.2 bar Failure time: 165 h (500 h) Gustaaf SUYS Total Petroch. Research Feluy Notched Pipe Testing Results 5000 h 0 2000 4000 6000 8000 10000 12000 Failure time in hours F.HP401 F.3802 PE100(a) F.XS10 PE100 (c) F.XSC50 1 F.XSC50 2 F.XSC50 3 F.XSC50 4 Gustaaf SUYS Total Petroch. Research Feluy FULL NOTCH CREEP TEST (FNCT) Kg METHOD: ISO DIS16770.3 Test specimen: - square bar - 6 or 10 mm - 50% ligament Temperature: 80,95C Stress: - 4.5 MPa at 95C - 4 or 4.6 at 80C Medium: 2% aq.Arkopal N110 SUYS - ATOFINA Research 2002-1 Gustaaf SUYS Total Petroch. Research Feluy FNCT Results 0 1000 2000 3000 4000 5000 Failure time in hours F.HP401 F.3802 PE100(a) F.XS10 PE100(c) F.XSC50 2 F.XSC50 3 F.XSC50 4 5000 h Gustaaf SUYS Total Petroch. Research Feluy Point loading simulation test A metal ball is pressed on the outside surface to create a flat segment perpendicular to the pipe radius on the inside wall Constant position 5mm flat d = 10 mm Re: Dr HESSEL Gustaaf SUYS Total Petroch. Research Feluy Point loading testing Inside surface Outside surface Failures Re: Dr Hessel Re: Dr Hessel METHOD: Dr HESSEL Pipe : 110 mm SDR 11 Ball point : 10 mm Controlled deformation Temperature : 80C Pressure : 8 bar Water outside - 2% Arkopal inside Loading area Gustaaf SUYS Total Petroch. Research Feluy Point Loading Test Results 5000 h 0 1000 2000 3000 4000 5000 6000 7000 Failure time in hours F.HP401 F.3802 PE100(a) F.XS10 F.XSC50 2 F.XSC50 3 Gustaaf SUYS Total Petroch. Research Feluy RESISTANCE TO RAPID CRACK PROPAGATION - RCP Gustaaf SUYS Total Petroch. Research Feluy REAL FACTS Slow Crack Growth failure by rock impingment Courtesy Dr J.HESSEL Gustaaf SUYS Total Petroch. Research Feluy RCP, NOT ONLY IN PE RCP initiation pipe Re: ADVANTICA Re: BG Corp Steel pipe 25 mm thick wall Gustaaf SUYS Total Petroch. Research Feluy REAL FACTS Belgium July 2004 Belgium February 1994 Gustaaf SUYS Total Petroch. Research Feluy Rapid Crack Propagation S4 TEST (Small Scale Steady State - ISO 13477) Impact speed of falling knife = 15 m/s Internal baffles and external cage limit the decompression of the pipe during the propagation of the crack. Gustaaf SUYS Total Petroch. Research Feluy RCP FS TEST Finathene XS 10 H, 500mmSDR11 Pipe at 3C filled to 90%, 24 barDeep cooling of initiation zone Crack initiation blade Re: ADVANTICARe: ADVANTICARe: ADVANTICA Re: ADVANTICA Gustaaf SUYS Total Petroch. Research Feluy RCP FS TEST Finathene XS 10 H, 500mmSDR11 Low resistance initiation pipe failureCrack lengths in test pipes 69 mm 80 mm Re: ADVANTICARe: ADVANTICARe: ADVANTICA Re: ADVANTICA Gustaaf SUYS Total Petroch. Research Feluy Relative Performance of PE Compounds Rapid Crack Propagation Resistance PE100 PE80 MDPE HDPE Bimodal Monomodal Butene Hexene LowHigh Low High Slow Crack Growth Resistance Gustaaf SUYS Total Petroch. Research Feluy PIPE DESIGN: NETWORK ECONOMICS ECONOMICS : COMPARISON PE63 - PE80 - PE100 PE 63PE80PE100 SERVICE FACTOR1.251.251.25 DESIGN STRESS (MPa)56.38 MAX. OPERATING PRESSURE (bar)101010 EXTERNAL DIAMETER (mm)250250250 SDR1113.617 INTERNAL DIAMETER (mm)204.5213.2220.6 WALL THICKNESS (mm)22.7518.414.7 PIPE WEIGHT (kg/dm)1.6251.3351.083 RELATIVE WEIGHT ( - )1.51.231 INTERNAL PIPE SECTION (dm)3.283.573.82 RELATIVE MATERIAL COST 0.90.951 RELATIVE PRODUCTION COST0.950.91 ECONOMIC FACTOR *0.420.320.283 RELATIVE ECONOMIC FACTOR ( - )1.51.131 * : ECONOMIC FACTOR = (WEIGHTxCOSTxCOST) / SECTION Gustaaf SUYS Total Petroch. Research Feluy ECONOMICS: COMPOUND or NATURAL+MASTERBATCH? All ISO and EN Standards impose the use of compound for gas, water and pressure sewerage pipe production USA and Japan Standards allow Natural+Masterbatch European pipe manufacturers also experimented 20 years ago with Natural+MB: Standard pipe extrusion lines do not mix well enough End-products do not fulfil the same requirements Substantial additional cost in mixing equipment and lower output Much higher cost for Approval and Quality Control testing Modern extrusion equipment is designed for high output and require pre-compounded material CONCLUSION: use of Natural+MB is not economical for production of QUALITY PRODUCTS Gustaaf SUYS Total Petroch. Research Feluy DISPERSION AND APPE