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New High Performance Ingeo Grades from NatureWorks

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New Ingeo biopolymer high performance grades offer structure and property capabilities that enhance performance in fiber/nonwovens, injection molding, and durables markets. Presented by Jed Randall of NatureWorks at Innovation Takes Root 2012 - February 21, 2012.

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New High Performance Ingeo Grades from NatureWorks

  1. 1. New Ingeo products offer structure and property capabilities that enhance performance in fiber / nonwovens,injection molding and durables markets Jed Randall NatureWorks LLC Innovation Takes Root 2012 1 © 2012 NatureWorks LLC
  2. 2. Outline • Review of PLA crystallization properties as a function of stereo composition • NatureWorks future Ingeo grade offerings • Crystallization properties of Ingeo new grades • Melt blown fiber research • Spun bond fiber research • Injection molding and durables opportunities • Timeline for commercialization 2 © 2012 NatureWorks LLC
  3. 3. Quiescent crystallization •Generally spherulitic •Follows Avrami kinetics 4 − kt n k = πNG x = 1 − e 3 3 Where x = fraction of crystallinity and n=3 •Dominated by slow crystal growth, G •Enhanced by nucleation, N •Size of spherulites after impingement is dominated by N •Applied when crystallizing pellets or annealing processes •Highly sensitive to optical comp. and T •∆H of pure crystal = -93.1 J/g*from Pyda, et al. (2002) 3 © 2012 NatureWorks LLC
  4. 4. Radial crystal growth rate, G(T) for PLLA (generally 0-0.3% D) 12 Di Lorenzo data 10 Runt-dataRadial growth rate (um/min) 8 Miyata-low mw 6 Miyata-mid Raw data from literature Miyata-high mw 4 Vasanthakumari- 2 D-data Vasanthakumari- Collected G(T) for PLLA (scaled) 0 C-data Abe-C 7 Data from Runt, DiLorenzo,Miyata, Abe, and 60 80 100 120 140 160 180 Vasanthakumari. All adjusted with Go (only Temperature (C) 6 term needed for mol wt) to match Runt (4.6- 4.8 um/min) at peak. Abe fot T<145C only. Thirteen PLLA samples total. 5 Runt G(T)- scaled um/min 4 DiLorenzo Scaled data (at 130°C) for 3 Miyata-high MW and experiment 2 differences 1 0 60 80 100 120 140 160 180 Temp (C) 4 © 2012 NatureWorks LLC
  5. 5. Melting point is a function of crystallization temperature (Tc)Shown for random poly(L-lactide-co-D-lactides)* 200 190 180 PLLA PD0.015L0.985LA 170 160 PD0.03L0.97LA C) Tm ( ˚ 150 140 PD0.06L0.94LA Increasing 130 Stereo Purity 120 110 100 110 120 130 140 150 160 170 *from Runt, et al. (2001) Tc (˚C) 5 © 2012 NatureWorks LLC
  6. 6. In summary, increasing %D isomer resultsin…• Depression of the melting point• Reduction in the level of attainable crystallinity• Reduction in the rate of crystallization• Change stress-strain behavior between Tg and Tm• Reduction in modulus above Tg when crystalline• Above ~10%D polymer does not crystallize in most practical processes 6 © 2012 NatureWorks LLC
  7. 7. Ingeo Technology Platforms8000 seriesfoam7000 seriesbottles - ISBM6000 seriesfibers & nonwovens4000 seriesfilms3000 seriesinjection Molding2000 seriesthermoformingLactide monomer 7 © 2012 NatureWorks LLC
  8. 8. Basic Design Table – Ingeo Grades 2003D Increasing Molecular Weight 4032D 4043D 4060D Extrusion Grades 7001D 3001D 3052D 6201D 6752D 6302D 6202D 8052D Fiber and Injection Molding Grades 3251D 6252D Increasing Level of D- isomer 8 © 2012 NatureWorks LLC
  9. 9. Expanded Design Table – Ingeo Grades 2003D Increasing Molecular Weight In Development 4032D 4043D 4060D Extrusion Grades 7001D 3001D 3052D 3100HP 6201D 6752D 6302D 6100D 6202D 8052D Fiber and Injection Molding Grades 3260HP 3251D 6260D 6252D Increasing Level of D- isomer 9 © 2012 NatureWorks LLC
  10. 10. Properties of New High %L Ingeo Grade Offering 10 © 2012 NatureWorks LLC
  11. 11. High %L Crystal Growth Rate ResultsHot stage microscopy measuring lineal crystal growth rate # %D RV 6100D 0.3 3.1 Radial Crystal Growth Rate at Various Temperatures 6201D 1.5 3.1 10.0 9.0 6100D 6201D 8.0 7.0 Crystal radial growth 6.0 shows > 2x increaseRadial Growth (µM/min) 5.0 as f(T) over today’s 4.0 product offering 3.0 2.0 1.0 0.0 110 115 120 125 130 135 140 145 150 155 160 165 Temperature (°C) 11 © 2012 NatureWorks LLC
  12. 12. Bulk crystallization: nucleation study• Crompton, Kemamide EBS at 0.5 wt% – ethylene-bis-stearamide – 140°C Tm, flash point 280°C• Nissan Chemical, Ecopromote at 1.0 wt% – phenylphosphonic acid, zinc salt – decomposition >500°C• Takemoto Oil & Fat, LAK-301 at 1.0 wt% – aromatic sulfonate derivative• Specialty Minerals, Ultratalc 609 at 0.5 wt% – 0.9 µm mean particle size Montana talc, untreated 12 © 2012 NatureWorks LLC
  13. 13. Bulk Crystallization by Flash DSC 1 from Mettler Specifications - Flash DSC 1 - Flash Differential Scannng Calorimeter Temperature range Air cooling (Room temperature + 5 K) … 500 °C IntraCooler (1-stage) -35 °C … 450 °C IntraCooler (2-stage) -95 °C … 420 °C Cooling rates (typical) -6 K/min. (-0.1 K/s) … -240 000 K/min (-4 000 K/s) Heating rates (typical) 30 K/min. (0.5 K/s) … 2 400 000 K/min (40 000 K/s) Sensor material Ceramic Thermocouples 16 Sample size 10 ng … 1 μg Sampling rate Max. 10 kHz (10 000 points per second) “Flash DSC is a novel technique, a quantum leap in DSC technology that opens up new frontiers. The Flash DSC 1 revolutionizes rapid-scanning DSC thanks to its ultra-high heating and cooling rates. The state-of-the-art instrument can easily analyze reorganization and crystallization processes which were previously difficult or impossible to measure. The Flash DSC 1 is the ideal complement to conventional DSC for characterizing modern materials and optimizing production processes by thermal analysis.” -Mettler web site 13 © 2012 NatureWorks LLC
  14. 14. Isothermal 250 Methods 200Temperature (°C) 150 ( )x 100 Isotherm after quench x = 5 – 600 s 50 Measure changes at 100°C/s 0 0 5 10 15 time (sec) 250 200Temperature (°C) 150 ( )x 100 Isotherm after melt 50 x = 5 – 600 s Measure changes at 100°C/s 0 0 5 time (sec) 10 15 14 © 2012 NatureWorks LLC
  15. 15. Dynamic Methods 250 200Temperature (°C) 150 100 Varied heating rates 0.333 to 2000°C/s 50 0 Measure crystallization and 0 10 time (sec) 20 30 melting during heating 250Temperature (°C) 200 150 Varied cooling rates 100 -0.333 to -2000°C/s 50 0 Measure cooling history 0 10 20 30 at 100°C/s reheat time (sec) 15 © 2012 NatureWorks LLC
  16. 16. Flash DSC example of collected data 1: Reheat at 100°C/sec afterannealing 5-600 seconds at 130°C from quenched state (30°C) ^exo 793-75-04 130C quench isotherms 12.10.2011 15:12:07 Experiment: 793-75-04 130C quench isotherms, 29.09.2011 16:16:15 Performed 29.09.2011 16:41:44 Increasing crystallization time 0.5 mW Increasing crystallization time Ingeo 6201D + 1% LAK-301 Sample size = 0.00151 mg by calculation 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 °C Lab: METTLER STAR SW 10.00 e •Heating rate is fast enough to prevent cold crystallization during measurement •Melting peak enthalpy and temperature increase with time •Glass transition delta Cp shrinks with time 16 © 2012 NatureWorks LLC
  17. 17. Effect of impingement and secondary crystallization processes on crystallinity Simulation showing free growth, Avrami, and effect of secondary crystallization 50 45 Free growth, no Secondary crystallization impingement 40 35 Avrami kineticsCrystallinity (J/g) 30 25 20 Crystallization ½ time 15 10 5 0 0 10 20 30 40 50 60 Time (minutes) Free growth Avrami Avrami +secondary 17 © 2012 NatureWorks LLC
  18. 18. Isothermal Crystallization Temperature EffectsIngeo 6201D (~1.5%D) vs. 6100D (~0.3%D) at equal MW isotherm 50 temp 100 40 105 6201D + 1% LAK-301 110 5-600 seconds at varied temp. % crystallinity 30 115 20 130 From the quench state (30°C) 10 °C 0 6 7 8 10 20 30 40 50 70 100 200 300 400 600 isotherm time (s) 70 isotherm 60 temp 105 50 110 6100D + 1% LAK-301 115 5-600 seconds at varied temp. % crystallinity 40 130 30 From the quench state (30°C) 20 °C 10 0 3 4 5 6 7 8 10 20 30 40 50 70 100 200 300 500 isotherm time (s) Tested using 1% LAK-301 Nucleant from Takemoto Oil & Fat 100% PLA crystal = -93 J/g 18 © 2012 NatureWorks LLC
  19. 19. Neat polymer (no nucleant) crystallized from themelt and quenched states Bivariate Fit of cryst 1/2 time [s] By isotherm temp Nucleant=neat 50 Polymer experiment 6100D isotherm from melt 40 6201D isotherm from quench 30 cryst 1/2 time [s] 20 Fastest temp. is 10 about 110°C and 6100D ~ 4x 0 100 110 120 130 faster than isotherm temp 6201D 19 © 2012 NatureWorks LLC
  20. 20. 1.0% LAK-301 nucleant crystallized from the meltand quenched states Bivariate Fit of cryst 1/2 time [s] By isotherm temp Nucleant=1% LAK-301 19 Polymer experiment 6100D isotherm from melt 17 6201D isotherm from quench 15 13 cryst 1/2 time [s] 11 90 70 Rate is fastest 50 up to 130°C and 30 6100D ~ 3.5x 10 100 105 110 115 120 125 130 faster than isotherm temp 6201D LAK-301 supplied by Takemoto Oil & Fat 20 © 2012 NatureWorks LLC
  21. 21. 1.0% Ecopromote nucleant crystallized from themelt and quenched states Bivariate Fit of cryst 1/2 time [s] By isotherm temp Nucleant=1% Ecopromote 19 Polymer experiment 6100D isotherm from melt 17 6201D isotherm from quench 15 13 cryst 1/2 time [s] 11 90 70 Rate is fast at 50 high temps 30 6100D ~ 2.5x 10 100 110 120 130 faster than isotherm temp 6201D Ecopromote supplied by Nissan Chemical 21 © 2012 NatureWorks LLC
  22. 22. 0.5% talc nucleant crystallized from the melt andquenched states Bivariate Fit of cryst 1/2 time [s] By isotherm temp Nucleant=0.5% Talc 19 Polymer experiment 6100D isotherm from melt 17 6201D isotherm from quench 15 13 cryst 1/2 time [s] 11 90 70 Rate fast at cool 50 temps but slows 30 at high temps. 10 100 110 120 130 isotherm temp Ultratalc 609 supplied Specialty Minerals 22 © 2012 NatureWorks LLC
  23. 23. 0.5% EBS nucleant crystallized from the melt andquenched states Bivariate Fit of cryst 1/2 time [s] By isotherm temp Nucleant=0.5% EBS 20 Polymer experiment 18 6100D isotherm from melt 16 6201D isotherm from quench 14 12 cryst 1/2 time [s] 10 80 60 Rate fast at cool 40 temps, but slow 20 at high temps. 0 100 110 120 130 Quench isotherm temp improves rate EBS supplied by Crompton 23 © 2012 NatureWorks LLC
  24. 24. Flash DSC example of collected data 2: Crystallization during rapidheating Increasing 20°C/min heating rate 50°C/s Ingeo 6201D + 1% LAK-301 Sample size = 0.00151 mg by calculation •Signal from material transitions is much stronger at faster rates •Cold-crystallization is completely supressed at high rates 24 © 2012 NatureWorks LLC
  25. 25. Crystallization During Varied Heating RatesIngeo 6201D (~1.5%D) vs. 6100D (~0.3%D) at equal MW with Four NucleantsAnalysis of % Crystallinity During Heating 60 Nucleant 50 0.5% EBS 0.5% Talc 40 1% Ecopromote 6201D + nucleants heating at 1% LAK-301 0.5-100°C/sec second% crystallinity 30 20 From the quenched state (30°C) 10 0 -10 0.4 0.6 0.8 1 2 3 4 5 6 7 8 10 20 30 40 50 70 1 heating rate (°Cs^-1) 60 Nucleant 50 0.5% EBS 0.5% Talc 40 1% Ecopromote 1% LAK-301 6100D + nucleants heating at % crystallinity 30 20 0.5-100°C/sec second 10 From the quenched state (30°C) 0 -10 0.4 0.6 0.8 1 2 3 4 5 6 7 8 10 20 30 40 50 70 1 heating rate (°Cs^-1) 25 © 2012 NatureWorks LLC
  26. 26. Crystallization During Varied Cooling RatesIngeo 6201D (~1.5%D) vs. 6100D (~0.3%D) at equal MW with Four NucleantsAnalysis of % Crystallinity During Reheat at 100°C/sec 70 Nucleant 60 0.5% EBS 0.5% Talc 50 1% Ecopromote 6201D + nucleants cooling at 40 1% LAK-301 0.5-20°C/sec second% crystallinity 30 20 From the molten state (210°C) 10 0 -10 0.5 0.6 0.8 1 2 3 4 5 6 7 8 10 20 prior cooling rate (- °Cs^-1) 70 Nucleant 60 0.5% EBS 0.5% Talc 50 1% Ecopromote 40 1% LAK-301% crystallinity 30 6100D + nucleants cooling at 20 0.5-20°C/sec second 10 From the molten state (210°C) 0 -10 0.5 0.6 0.8 1 2 3 4 5 6 7 8 10 20 prior cooling rate (- °Cs^-1) 26 © 2012 NatureWorks LLC
  27. 27. E’ Modulus(T) Results: Hot molded bars with nucleant,3 point bend geometry to measure E’ 1.00E+04 ~15°C HDT 1.00E+03 improvement E [MPa] 66 psi HDT estimate 1.00E+02 1.00E+01 0 50 100 150 200 Temperature [C] 6100D + 1% LAK-301 6201D + 1% LAK-301 27 © 2012 NatureWorks LLC
  28. 28. Making Sense of Melting Point% crystallinity and Tm vs. isotherm time (s) for Polymer=6100D, experiment=isotherm from melt isotherm Nucleant 18 temp 0.5% EBS 95 0.5% Talc 17 First examination of the raw 100 1% Ecopromote 17 105 1% LAK-301 Tm (°C) 16 110 115 neat data showed incredible 16 130 variations in observed melting 15 point. Heating rate = 100°C/s 3 4 5 6 7 8 10 20 30 40 50 70 100 200 300 500 isotherm time (s) 70 isotherm Nucleant 60 temp 0.5% EBS Large differences in crystallization kinetics and final 95 0.5% Talc 50 100 1% Ecopromote 40 105 1% LAK-301 crystallinity % crystallinity 110 neat 30 115 20 130 10 0 3 4 5 6 7 8 10 20 30 40 50 70 100 200 300 500 isotherm time (s) 28 © 2012 NatureWorks LLC
  29. 29. Compiled data of crystallinity developed duringisotherms from both quenched and melt states Bivariate Fit of Tm (°C) By % crystallinity Polymer=6100D isotherm Nucleant 18 temp 0.5% EBS 17 95 0.5% Talc 100 1% Ecopromote 17 105 1% LAK-301 Tm (°C) 110 neat 16 115 16 130 15 15 0 10 20 30 40 50 60 70 % crystallinity 29 © 2012 NatureWorks LLC
  30. 30. Compiled data of crystallinity developed duringisotherms from both quenched and melt states Bivariate Fit of Tm (°C) By % crystallinity Polymer=6201D isotherm Nucleant 17 temp 0.5% EBS 17 95 0.5% Talc 16 100 1% Ecopromote 105 1% LAK-301 Tm (°C) 16 110 neat 15 115 130 15 14 14 0 10 20 30 40 50 60 % crystallinity 30 © 2012 NatureWorks LLC
  31. 31. 70 18 65 17 60 17 Tm (°C) Actual % crystallinity 55Analysis of variance Actual 16 50 45 16 15on final crystallinity*: 40 35 15 35 40 45 50 55 60 65 70 150 155 160 165 170 175 180 % crystallinity Predicted Tm (°C) Predicted P<.0001 P<.0001 RSq=0.88 RMSE=2.2237 RSq=0.97 RMSE=1.1916 • Isotherm temperature has a strong influence on both % crystallinity and Tm +0.57% absolute crystallinity increase per °C anneal T +0.71°C Tm increase per °C anneal T • 6100D had 11% relative crystallinity increase and 3°C Tm increase over 6201D • All nucleants showed similar Tm and % crystallinity to within 1 °C and 3% abs. crystallinity at the end of annealing *Data selected for Avrami 1-X < 0.05 31 © 2012 NatureWorks LLC
  32. 32. Nonwoven FabricsDemonstrations with New Grades • Melt Blown – Fine fibers (2-7 micron diameter) – Low porosity (filtration) – Softness – Low orientation (low strength) • Spunbond – High strength to weight ratio – Higher fiber diameter (15-35 micron diameter) – Geotextile, medical, automotive – High degree of orientation 32 © 2012 NatureWorks LLC
  33. 33. Melt Blown Extrusion Line 33 33 © 2012 NatureWorks LLC
  34. 34. Melt blown fibers Equipment 6 inch die width 120 holes at 0.245mm (0.010 in) diameter 0.06 inch air gap 0.06 inch setback 30° die angle 15 L/D extruderNonwovens Research Lab at The University of Tennessee, under direction of Gajanan Bhat 34 © 2012 NatureWorks LLC
  35. 35. Conditions 0.6 g/min/holeMelt blown fibers 240°C melt temp., ~250 psi melt press. 260°C air temp., ~20 psi air press.optimized results 200-220 mm distance from die to collector 30 g/m2 basis weight Fiber 100°C hot Peak Diameters air shrink Peak Elongation sample direction [µm] [%] Force [lb] [%] 6251D MD 3.5 27.2 3.1 2.9 6251D CD 41.3 1.9 25.2 6260D MD 4.0 4.1 2.7 19.7 6260D CD 3.5 1.5 31.6 35 © 2012 NatureWorks LLC
  36. 36. Spunbond Process 36 36 © 2012 NatureWorks LLC
  37. 37. Spun bond simulation NatureWorks’ custom modified Hills Fiber line with Lurgi fiber attenuator 37 © 2012 NatureWorks LLC
  38. 38. Lurgi Gun spun bond simulation 144 holes at 0.3mm diameter 0.75 g/min/hole Spun bond fiber Draw down range = 18-21 Filament velocity range = 2800-3800 m/min shrinkage 220°C melt temperature, 800-900 psi 100 Boiling Water Shrinkage 80 6260D processes with 60 lower shrinkage at 40 lower air draw [%] 20 pressures compared to 6251D standard 0 material 60 80 100 120 140 Air draw pressure [psi] 6251D 6260D lab scale Increasing velocity and costIncreasing asset age 38 © 2012 NatureWorks LLC
  39. 39. Lurgi Gun spun bond simulation 144 holes at 0.3mm diameter 0.75 g/min/holeSpun bond fiber Draw down range = 18-21 Filament velocity range = 2800-3800 m/minstrength 220°C melt temperature, 800-900 psi 2.8 Tenacity [g/den] 2.6 6260D processes has similar strength 2.4 characteristics as 2.2 6251D standard material 2 60 110 160 Air draw pressure [psi] 6251D 6260D lab scale 39 © 2012 NatureWorks LLC
  40. 40. Advantages of expanded offering in fibers • Broad range of applications, with lower shrinkage expected across the board – Nonwovens – Drawn and heat set fibers • Higher modulus above Tg • More hydrolysis resistant • Heat setting at higher temperatures leads to higher melting / sticking points during processing and use • Higher Tm has advantages in bicomponent systems, broadending process windows 40 © 2012 NatureWorks LLC
  41. 41. Advantages of expanded offering for theDurable & Semi-Durable Market • Compounders can produce more competitive materials – Higher productivity during molding – Wider processing window – Simpler & more cost effective formulations – Improves base performance the Ingeo 3801X • Potential for higher bio-content in formulations • Higher modulus above Tg, higher HDT • Higher hydrolysis resistance • Improved performance in extruded & thermoformed durable applications 41 © 2012 NatureWorks LLC
  42. 42. Timeline for commercialization • Ingeo 6100D, 3100HP, 6262D and 3262HP are scheduled to be available 2Q2013 • Expect further publications and process guides from NatureWorks throughout the year *Note all data shown for Ingeo 6100D and Ingeo 6260D in this presentation were from product development samples, and some changes are expected with large scale commerciallization. No descriptions or results shown are specifications for these materials. 42 © 2012 NatureWorks LLC

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