3M TM Specialty Additives Energy & Advanced Materials Division People Technology - Future Dynamar TM Polymer Processing Additives (PPA s) 1 Dyneon 2012
What are Dynamar TM PPA s? Dynamar TM polymer processing additives (PPA s) are fluoropolymer based additives designed to improve the processing of polyolefins and other polymers 2
Dynamar MKT Breakdown by Application Pipes 15% Cable 1% BM 1% BOPP 2% Others 6% Core 75% 3 Volume
EMEA Dynamar Ways to market 4
Dynamar PPA Mechanism PPA exists as immiscible droplets in polyolefin matrix PPA has high affinity for metal die wall Forms low surface energy, dynamic coating Allows melt to slip through Extruder PPA Extruder Polymer Flow Die Wall Die Wall Photomicrograph of PPA in LLDPE 5
Capillary Rheo-optics Sapphire 6 K.B. Migler - NIST C. Lavallée - 3M Canada Company C.L. Gettinger - 3M Company
Flow Visualization 250X Frame Width: 500mm 7
Fluoropolymer-based PPAs How to add? Typical end-use levels: 50 1000 ppm Addition via masterbatch is recommended: To facilitate right dosage To achieve homogenious distribution Typical masterbatch concentration: 1 5 % MFI of carrier resin =or> MFI of application Carrier resin should be properly stabilized 8
Processes that Benefit from PPA Blown Film Pipe/Tubing Cast Film Extrusion Extrusion Blow Molding Concentrate compounding Fiber Extrusion Wire & Cable Sheets Extrusion 9
Benefits in Blown film 10
PPA Benefits Elimination of melt fracture Alleviate die build-up Reduce production down time Improve processing of lower MI resins Reduction in gel formation Extrusion through narrower die gaps less machine direction drawing better balance of properties less cooling requirements improved gauge control 11
PPA Benefits Reduce operating pressures and amperage draw increase output // energy savings Operate at lower processing temperature decrease degradation // energy savings Faster color change Increase gloss Improve surface smoothness Reduce (or eliminate) LDPE blending 12
Melt Fracture Remaining (%) Energy & Advanced Materials Division Melt Fracture Elimination 0 min 15 min 30 min 45 min 120 Typical Melt Fracture Elimination Curve 100 80 60 40 20 13 0 0 10 20 30 40 50 60 70 80 90 100 Time (minutes)
Reduction in Interfacial Stability 3- layer film (mlldpe/mdpe/mlldpe) Without PPA Containing PPA 14
Die Build-Up Reduction High Filled HDPE photograph after 30 min photograph after 60 min Without with PPA 15
PPA Reduces Gels Types of Gels Gels formed during extrusion: cross-linked Gels oxidized Gels unmixed/unmelted Gels Contaminants - fibers, other resins Agglomerates - inorganic additives Gels formed during polymerization 16
PPAs for Gel Reduction Mechanism for Gel Formation Die Wall Cross-linked and Oxidized Gel Reduction with PPA Oxidized species stick to die wall Act as a site for other oxidation to occur - to the polymer Causes a localized high concentration of oxidized species Leads to cross-linking 17
PPAs for Gel Reduction Mechanism for Gel Formation Cross-linked and Oxidized Gel Reduction with PPA PPA coats the die wall and prevents build-up PPA Die Wall Fluoropolymer is thermally stable unlike the low MW components 18
PPA Reduces Gels Experiment: blown film extrusion Materials: VLDPE base resin, 0.9 MI, 0.91 density PPA-1, PPA-2, PPA-3 Measurement: optical detection of gels 19
Gel Count (weighted average) Energy & Advanced Materials Division PPA Reduces Gels 20
PPA improves resin blending Experiment Resins: LDPE LLDPE 0.9 MI; 0.920 density 0.8 MI; 0.925 density Extruder: Blown Film Line Die gap: 0.6 mm Measure: Pressure, Output, Temperature 21
Blown Film Line Experiment: Constant Output 22
Blown Film Line Experiment: Constant Output 23
Blown Film Line Experiment: Constant Pressure & Output 24
Improve processing of lower MI resins Capillary rheometer Rheology Evaluation @ 230 C with 500 ppm Dynamar TM FX 5911 in HDPE 25
Improve processing of lower MI resins Capillary rheometer Rheology Evaluation @ 230 C with 500 ppm Dynamar TM FX 5911 in HDPE Shear rate (s-1) /Product 650 800 950 1100 1250 1400 1550 HDPE (0.6 MFI) HDPE (0.95 MFI) same density HDPE (0.6 MFI) + 500 ppm FX 5911 26
Applications other than Blown film Pipe/Tubing Cast Film Extrusion Extrusion Blow Molding Concentrate compounding Fiber Extrusion Wire & Cable Sheets Extrusion 27
Cast Film Improving Gauge uniformity Elimination of die build up Improved gauge uniformity Pressure reduction 28
Cast Film Die build Up Reduction No PPA With PPA 29
Pipes In HDPE Pipes Extrusion PPAs and LTHS (Long Term Hoop Stress) Property Tests used ASTM D 2837, ISO TR 9080 Tests have been carried out on pipes produced with and without PPAs Stress and crack propagation properties of HDPE pipes are not affected by using PPAs After 10.000 hours testing no differences in property were reported between formulations with and without PPAs Benefits Using Dynamar PPAs Elimination of surface defects Consistent surface finish Reduction of extrusion pressure Reduction of processing temperature Reduction of die lines Improved output 30
Pipes Effect of PPA on Surface Appearance Note: Long Term Hydrostatic Stress Properties of HDPE are NOT affected by using PPAs No PPA With PPA 31
Pipes 32
RPM Pressure (bar) RPM Energy & Advanced Materials Division Pipes Dynamar TM PPA evaluation protocol No PPA Contineous addition of 500 ppm PPA via masterbatch 130 50 125 Reference Capillary Rheometry 210 C 120 P melt drop @ 210 C P melt reduction @ 190 C P melt reduction @ 170 C 45 40 35 30 25 115 110 105 130 125 120 T die 210 C Further stabilization of PPA slip layer T die 190 C 20 PPA effect on Capillary Rheometry 15 210 C 190 C 170 C 10 T die 170 C 0 20 40 60 Time 80 (min) 100 120 140 160 Phase 1 Phase 2 Phase 3 Phase 4 Start-up Melt Pressure reduction Output increase Temperature reduction Time (min) 0 20 40 60 80 100 120 140 160 5 0 50 45 40 115 110 105 Measure Output increase 35 30 25 33 Increase extruder Speed Reduce extruder Speed