Polyketone very versatile! Agenda I. What is Polyketone? II. Characteristics III. Applications IV. Present & Future V. Summary 3 K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe I. What is Polyketone? Chemical Structure – aliphatic Polyketonee The following monomers are the basic components for Polyketone: o Ethylene o Propylene o Carbon monoxide (chemical formula terpolymer Polyketonee) 4 K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe I. What is Polyketone? History Hyosung 50kt/yr production plant running since Q2 2015 5 K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe I. What is Polyketone? Polyketonee’s broad range of performance properties make it “natural” engineering thermoplastic Mechanical properties are similar to PA 12; the melting point is 40 °C higher (220 °C) Permanent use temperature up to 120 °C High resilience and minor creep Good chemical resistance and superior barrier performance Good flow behavior Short cycle times Low moisture absorption 0,4 % at 23 °C 50 % rel. humidity Quite high elongation at break Excellent tribological properties 6 K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe I. What is Polyketone? Polyketone can easily be reinforced with flame retardarant qualities excellent weld ability: laser welding, vibration welding etc. gamma sterilization possible outstanding reproducibility of dimension and tolerances Attention during processing (POM; PA; retention time)! 7 K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe Agenda I. What is Polyketone? II. Characteristics III. Applications IV. Present & Future V. Summary 8 K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe II. Characteristics New Green Polymeric Material based on CO o New green polymeric material made of the monomer CO, one major air-pollution source o AT full plant capacity (50,000 mt/yr) 25,000 mt of harmful CO are atng converted. In order to purify a similar amount of CO, ~3.8 mln pine trees would be required! (30yr. Pine tree purify 6.6 Kg/yr CO2) 9 K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe II. Characteristics High Impact Strength o More than 230% higher impact strength compared to PA, PBT (dry, at room temperature) o No deterioration due to good hydrolysis resistance. 10 K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe II. Characteristics Tensile Properties (unreinforced) 90 PA 6.6 dry 80 Yield Stress [MPa] 70 PA 6.12 Polyketone,PK-HM average Viscosity POM 60 PA6.6 cond. PBT 50 RM-D PA 12 40 30 20 10 0 0 5 10 15 20 25 30 35 Elongation at yield [%] 11 K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe II. Characteristics Stress strain diagram for different temperatures (reinforced) 140 30% GF reinforced Polyketone, average Viscosity, 23°C 120 PA 6, 30% GF reinforced, 23°C kond. Stress [MPa] 100 30% GF reinforced Polyketone, average viscosity, 80°C 30% GF reinforced Polyketone, average viscosity, 120°C 80 PA 6, 30% GF reinforced, 80°C kond. PA 6, 30% GF reinforced, 120°C kond. 60 30% GF reinforced Polyketone, average viscosity, 150°C 40 20 0 0 12 1 2 Strain [%] 3 4 5 6 7 K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe II. Characteristics Creep Curve 7000 creep strain [MPa] 6000 5000 4000 3000 A3 GF 30 1 schwarz bei 120°C PA 6.6, 30% GF reinforced, black at 120°C C3 GF 30 1 schwarz (4363) bei 120°C PA 6.6.6, 30% GF reinforced, black at 120°C B3 GF30% 30 1GFschwarz bei black 120°Cat 120°C PA 6, reinforced, PK-HM GF 30 natur (4709) beiat120°C Polyketone, 30% GF reinforced 120°C Polyketone, 30% GF reinforced 80°C PK-HM GF 30 natur (4709) beiat80°C 2000 1000 0 Creeplast: 0,00 13 20 MPa 0,01 0,10 1,00 log10 time [h] 10,00 100,00 1.000,00 K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe II. Characteristics creep strain 0,45 0,40 CreepStrain [mm] 0,35 0,30 0,25 0,20 PA 6.6, 30% GF reinforced, black at 120°C A3 GF 30 1 schwarz bei 120°C PA 6.6.6, GF reinforced, at 120°C C3 GF 3030% 1 schwarz (4363) black bei 120°C PA 6, reinforced, B3 GF30% 30 1GFschwarz bei black 120°Cat 120°C Polyketone, 30% GF reinforced 120°C PK-HM GF 30 natur (4709) beiat120°C Polyketone, 30% GF reinforced 80°C PK-HM GF 30 natur (4709) beiat80°C 0,15 0,10 0,05 Creeplast: 0,00 1,00E-06 14 1,00E-05 1,00E-04 1,00E-03 1,00E-02 1,00E-01 log10 time [h] 1,00E+00 1,00E+01 20 MPa 1,00E+02 1,00E+03 K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe II. Characteristics Creep Characteristics PA6.6 - PK 300 200 creep strain [kpsi] PK @ 21 °C PK @ 60 ° C 100 PA6.6 @ 21 ° C 50 PA6.6 @ 60 ° C 30 1 15 3 10 30 100 time [h] 300 1,000 3,000 10,000 Source: Shell K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe II. Characteristics Excellent Chemical Resistance o POK’s chemical resistance is the top level among the plastics. o No drops in properties due to the resistance to acidic/basic solutions. Chemical resistance (80 °C Exposure for 25 Days) 70 60 50 40 PK 30 PA6.6 20 10 0 Control Referenz (0 Tage) 16 Water Wasser 1 % NaOH 1 % HCl 5 % CaCl₂ 50 % ZnCl₂ Ethylenglycol Source: Shell K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe II. Characteristics Excellent Chemical Resistance 17 K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe II. Characteristics Excellent Chemical Resistance o Zinkchlorid at 200 hrs. according to SAE 2044 Polyketone (50% glass fibrereinforced, average Viscosity) Polyketone (30% glass fibrereinforced, average Viscosity) for comparison: PA6.6 PA66 (30% glass fibre-reinforced) nach 2 hrs. storage 18 K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe II. Characteristics Excellent Chemical Resistance o Calciumchlorid (CaCl₂) according to DBL 5416 Test average Viscosity, black Polyketone 50% glass fibre-reinforced, average Viscosity, black for comparison: PA6 30% glass fibre-reinforced, black 19 K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe II. Characteristics Excellent Chemical Resistance o Battery Acid(38 % H₂SO₄) After30 hrs. After48 hrs. PA 6.6 (30% glass fibre reinforced) 20 After 35 Days Polyketone (50% glass fibre reinforced, average Viscosity, K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe II. Characteristics Excellent Fuel Resistance o Polyketone shows small change even after 3,000 hrs test o 2 times superior to the PA12, current material for automotive fuel tube Property (Flexural Modulus) after treated in Diesel for 3.000 hrs 21 Property (Flexural Modulus) after treated in Gasoline for 3.000 hrs (60°C) K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe II. Characteristics High Heat Deflection Temperature (HDT) o Polyketone’s HDT is 210℃, superior to other material, possible to use at high temperature circumstance. 22 K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe II. Characteristics Excellent Tribological Property o Polyketone has 14 times higher anti-abrasion property than that of POM, currently the most stiff material. It helps almost permanent use without change. POK base resin POK base resin POK base resin . with 1% Additiv 23 > POM > POM with 1% Additiv e > POM with 3% Additive → 14 times higher. → 1,7 times higher. → 10-times higher K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe II. Characteristics Excellent Tribological Property Polyketone and POM is the best known combination in terms of low wear!! In 20 hrs no wear was measurable! PK POM PA PK POM PA +++ + +++ --+ + + -- Experimental setup: relative wear factor pin on disc (speed 0,25 m/s, pressure 5 MPa) 24 K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe II. Characteristics Excellent Tribological Property Universal tribometer Pin-Disc Pin-Disc at RT Load: 2,5 Mpa Hub: 1,8 mm Disc: 100Cr6 Sliding speed: 46 Hz Ra=0,42 [Source: KuK Fachhochschule Lübeck] 25 Dynamic Coeeficient [-] Specific Wear Rate k * 10-6 [mm³/Nm] Polyketone, average Viscosity 0,52 34 Polyketone, low Viscosity 0,33 0,8 Polyketone, average Viscosity, 30% glass fibre reinforced 0,50 14,5 0,44 3,9 0,44 60 Polyketone, average Viscosity, 30% glass fibre reinforced POM Copolymer K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe II. Characteristics High Oxygen Barrier Property o Same level of EVOH, top class of food packaging material due to the gas barrier property 26 K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe II. Characteristics High Hydrocarbon Barrier Property o Polyketone has excellent barrier property to the hydrocarbon, with good chemical resistance Permeation Coefficient at 23°C, 50% RH (g.mm/m², day) Gasoline Ottokraftstoff Gasoline Ottokraftstoff C + 15% MeOH 35 35 HDPE PA12 EVOH POK 27 0,067 12,2 0,002 2,5 0,005 2 K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe II. Characteristics High Hydrocarbon Barrier Property Permeability to unleaded Gasoline at 93℃ [g] g Gewichtsverlust Weight Change, 0 Polyketone -1 TEFLON -2 -3 -4 NYLON 12 -5 measured by GM Spec 9061.P -6 0 2 4 6 8 Auslagerungstimedays [Tage] Exposure, 28 10 12 14 Source: Shell K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe II. Characteristics General Barrier Characteristics Polymer Oxygen Steam 0,06 11 EVOH 0,01 – 0,09 1,4 – 3,8 PA 6 3,6 22 HDPE 150 0,4 MXD6 0,32 - PK oxygen permeability coefficient : Water vapor permeability: (cc mil/100in² day atm) at 0%RH / 23°C (g mil/100in² day) at 90-0%RH / 38°C [Source: Shell] 29 K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe II. Characteristics Excellent flame retardant Phosphor flame retardant (Metal Phosphinat) Test results for UL-V0 Rate Content % 30 POK PA66 8 17 K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe II. Characteristics Well Balanced Product Characteristics o Generally Nylon has high tensile property but impact strength and elongation is low. o Polyketone has a good impact strength and elongation with enough tensile property. 31 K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe II. Characteristics High Productivity o Sealing Point for Polyketone is achieved faster resulting in shorter cycle times Polyketone, average PK-HM Viscosity natur (4773) 44,5 99.5 % 44 Part weight [g) PA6.6 A3 natur 43,5 99.5 % 43 42,5 42 41,5 41 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Holding pressure time [s] 32 K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe II. Characteristics Flowability PAGF 6, 50 50% GF reinforced B3 natur (2475) B3 natur (2471) PAGF 6, 30 30% GF reinforced 0 300 600 Fließspirale [mm] Melt temperature Mould temperature Pressure Cross Section 33 Polyketone, average Viscosity, PK-VM GFreinforced 50 natur (4905) 50% GF Polyketone, Viscosity, PK-VM GF 30 average natur (4706) 30% GF reinforced 900 1200 B3PAnatur 6 (2500) Polyketone, low PK-VM natur (4774) Viscosity 0 500 A3PAnatur 6.6 (2414) Polyketone, PK-HM natur (4773) average Viscosity 1000 Fließspirale [mm] 1500 Polyketone 245 °C PA 6.6 320 °C PA 6 270 °C 80 °C 750 bar 7 * 3,5 [mm²] 100 °C 750 bar 7 * 3,5 [mm²] 80 °C 750 bar 7 * 3,5 [mm²] 2000 K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe II. Characteristics IR-welding – Strength IR-welding Zugfestigkeit IR Schweißen Basic material Grundmaterialfestigkeit 140 Processing principle 120 Infraredradiator 100 Stremgth [MPa] Festigkeit [MPa] Part A 80 60 40 Part B 20 0 34 Polyketone, 6.6 Polyketone, PK-HM schwarz (4953) PK-HM GF 30 schwarz (4952) PA6PA GF30 average Viscosity, 30% GF-reinforced average Viscosity 30% GF-reinforced K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe II. Characteristics Laser Welding- Strenth 1600 Beam source: Diode laser Pressure Laser transparent Plastic 1400 1200 [N] Scherkraft[MPa] Stremgth Processing Principle 1000 800 600 400 Absorbing Plastic 200 0 PK-HM natur (4773) Polyketone, + PK-HMViscosity schwarz average (4953) 35 PK-HM GF 30 natur B3 GF 30 Polyketone, PA natur 6 (4709) + B3 GF 30 1 schwarz average Viscosity, 30% GF-reinforced + PK-HM GF 30 30% GF-reinforced schwarz (4952) K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe II. Characteristics Processing of Polyketone Extrusion parameters 36 Feed section 𝝑𝑬 60 – 100 °C Extruder Zones 𝝑𝒁 225 – 240 °C Melt Temperature 𝝑𝑺 230 -245 °C Dying 𝝑𝝉 60 – 80 °C (up to 4 hrs.) K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe II. Characteristics Water uptake 500 h 70 °C / 62 % rel. humidity 3,000 Moisture absorption [%] [%] Feuchtezunahme PA 6.6, black A3 GF 30 1 schwarz 30% GF-reinforced Polyketone, average Visc., PK-HM GF 30 natur (4709) 30% GF-reinforced Polyketone, average Visc., PK-HM GF 50 natur (4741) 50% GF-reinforced PA 6.6, black A3 GF 50 1 schwarz 50% GF-reinforced 2,500 2,000 1,500 1,000 0,500 0,000 0 50 100 150 200 250 300 350 400 450 500 Auslagerungstime [hrs.] Time [h] 37 K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe II. Characteristics Summary: Polyketones is a new green polymer material based on carbon monoxide. It features : • • • • • excellent impact resistance excellent chemical resistance very good tribological Characteristics high gas barrier Characteristics excellent flame retardant and can be applied as an engineering plastic in a broad spectrum due to its unique characteristics. 38 K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe II. Characteristics Summary: o Comparison of PA* and Polyketone Mech. Characteristics 39 Test Specifications Test Method Unit Polyketone, Polyketone, low Viscosity average Viscosity PA 12 PA 6.6 dry kond. dry kond. dry kond. dry kond. Tensile Modulus 1 mm/min ISO 527-1/2 MPa 3100 1100 1500 1500 1450 1400 1400 1100 Tensile stress at yield 5 mm/min ISO 527-1/2 MPa 85 50 60 60 60 60 45 40 Elongation at yield 5 mm/min ISO 527-1/2 % 4,5 20 29 - 32 32 5 12 Elongation at break 5 mm/min ISO 527-1/2 MPa >25 >50 >200 >200 >300 >300 >50 >50 Charpy Impact Strength 23 ℃ ISO 179-1/1eU kJ/m² o.b. o.b. o.b. o.b. o.b. o.b. o.b. o.b. Charpy notched Impact Strength 23 ℃ ISO 179-1/1eA kJ/m² 3 13 10 10 17 17 6 7 K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe II. Characteristics Summary: o Comparison of 50%-glass fibre reinforced Polyketone and PA 12, PA 612 & PBT* Polyketone Mech. Characteristics PA 6, PA 12, PA 6.12, average 50% glass fibre- 50% glass fibre- 50% glass fibreViscosity, reinforced reinforced reinforced 50% glass fibrereinforced dry kond. dry kond. dry kond. dry kond. Test Specifications Test Method Unit Tensile Modulus 1 mm/min ISO 527-1/2 MPa Tensile stress at break 5 mm/min ISO 527-1/2 MPa 140 130 230 145 155 135 5 mm/min ISO 527-1/2 MPa 2 2 2,5 4,5 5 23 ℃ ISO 179-1/1eU kJ/m² 65 50 100 110 23 ℃ ISO 179-1/1eA kJ/m² 20 20 20 26 1,8 MPa ISO 75-2 °C Properties Elongation at break Charpy Impact Strength Charpy notched Impact Strength HDT-A 40 12500 11500 17000 10300 12000 11500 16500 220 220 PBT 50% glass fibrereinforced 12000 16000 200 145 160 6 2,0 2,5 2,5 90 80 70 72 50 19 20 13 16 10 165 205 210 K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe Agenda I. What is Polyketone? II. Characteristics III. Applications IV. Present & Future V. Summary 41 K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe III. Applications Overview: Electro/ Electronic Automotive Industrial • Gear-wheels • Valves • Connectors • Fuel tank • Fuse holders • Switches • Sockets • Fuel line • Fuel filter • Connectors • Injection rails • Inlet manifolds • Wheel covers 42 • Gear-wheels • Clips • Bearings • Conveyor systems • Hoses • Liners K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe III. Applications Realised Applications Gear by Öchsler AG, Ansbach 43 Flatfilm by LITE GmbH (200 µm) K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe III. Applications Realised Applications Raw Stock SUSTAKON by Röchling Sustaplast KG 44 K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe III. Applications Realised Applications Water Pipe produced by IKV Aachen 45 K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe Agenda I. What is Polyketone? II. Characteristics III. Applications IV. Present & Future V. Summary 46 K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe IV. Present & Future 2004 • Start Lab. Scale Development • Bench scale Polymerization Equipment setup (10 MT/Yr, R&D Lab) 2006 2008 2011 • Start ENPLA materials development • Start Fiber Development 1,000 MT/yr Plant (Ulsan, Korea) • 1st Polymerization Plant start 2012 • ( 1,000 MT/Y, Ulsan, Korea) 2013 • Finish engineering for 50,000 MT/Yr Plant • B2nd Polymerization Plant start (50,000 MT/Y, Ulsan, Korea) 2015 47 50,000 MT/yr Plant (Ulsan, Korea) K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe IV. Present & Future Packaging of the product 25kg bagged cargo 48 1 FCL : 14MT on palett[ 875 kg (25 kg x 35 bags) / palett K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe IV. Present & Future base resin grades: High Flow M230A Medium Flow M330A High Impact M630A Method Unit M230A M330A M630A ASTM D792 g/cm³ 1,24 1,24 1,24 ASTM D570 % 0,45 0,5 0,5 Melting Temperature ASTM D1525 °C 220 220 200 Melt Flow Rate (240°C, 2.16kg) ASTM D1238 g/10min 150 60 6 Deflection Temperature : HDT 0.45 Mpa (4.6 kg/cm²) ASTM D648 °C 205 210 210 Mechanical Tensile Strength Normal Strain at Break ASTM D638 ASTM D638 kg/cm² % 700 >25 700 >250 700 >300 Flexural Strength Flexural Modulus ASTM D790 ASTM D790 kg/cm² kg/cm² 700 18.000 700 18.000 700 18.000 Charpy Notched Impact Strength ASTM D256 kg - cm/cm 5 12 18 ASTM D257 ASTM D149 Ωcm KV/mm 20 17 17 Item Physical Density Water Content (23°C, 60% RH, Eq.) Thermal Electrical Volume Resistivity Di-electric Strength 49 K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe Agenda I. What is Polyketone? II. Characteristics III. Applications IV. Present & Future V. Summary 50 K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe V. Summary Polyketones are true engineering polymers with a broad and very attractive range of performance properties o o o o o o o o o Excellent impact performance over a broad temperature range Outstanding chemical resistance and barrier performance Excellent fuel resistance High heat distortion temperature Good friction and wear characteristic Superior resilience and snapability Excellent hydrolytic stability Short molding cycles extremely small tolerances possible (high crystalisation speed) Total market potential is broad and large to very large 50KT/Y new commercial plant came on stream in 2015, 2Q by Hyosung’s proprietary catalyst and production technology. 51 K.D. Feddersen Ueberseegesellschaft mbH Ein Unternehmen der Feddersen-Gruppe Vielen für your Ihre Aufmerksamkeit! ThankDank you for kind attention!