New Ingeo products offer structure and property

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

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

Quiescent crystallization

•Generally spherulitic •Follows Avrami kinetics

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)

34 NGk π=

nktex −−=1

Radial crystal growth rate, G(T) for PLLA (generally 0-0.3% D)

60 80 100 120 140 160 180

Temp (C)

Collected G(T) for PLLA (scaled)

DiLorenzo

Miyata-high

Data from Runt, DiLorenzo,Miyata, Abe, and Vasanthakumari. All adjusted with Go (only 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.

60 80 100 120 140 160 180

Temperature (C)

Di Lorenzo data

Runt-data

Miyata-low mw

Miyata-mid

Miyata-high mw

Vasanthakumari-D-dataVasanthakumari-C-dataAbe-C

Raw data from literature

Scaled data (at 130°C) for MW and experiment differences

Melting point is a function of crystallization temperature (Tc) Shown for random poly(L-lactide-co-D-lactides)*

100 110 120 130 140 150 160 170

Tc (˚C)

Tm (̊ C

PD0.015L0.985LA

PD0.03L0.97LA

PD0.06L0.94LA

*from Runt, et al. (2001)

Increasing Stereo Purity

In summary, increasing %D isomer results in… • 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

Ingeo Technology Platforms

3000 series injection Molding

7000 series bottles - ISBM

6000 series fibers & nonwovens

4000 series films

2000 series thermoforming

8000 series foam

Lactide monomer

Basic Design Table – Ingeo Grades

4032D 2003D 4043D 7001D

3001D 6201D 6202D

3052D 6752D 8052D

3251D 6252D

Increasing Level of D- isomer

Fiber and Injection Molding Grades

Extrusion Grades

Expanded Design Table – Ingeo Grades

In Development 4032D

2003D 4043D 7001D

3100HP 6100D

3001D 6201D 6202D

3052D 6752D 8052D

3260HP 6260D

3251D 6252D

Increasing Level of D- isomer

Fiber and Injection Molding Grades

Extrusion Grades

Properties of New High %L Ingeo Grade Offering

High %L Crystal Growth Rate Results Hot stage microscopy measuring lineal crystal growth rate

Crystal radial growth shows > 2x increase as f(T) over today’s product offering

110 115 120 125 130 135 140 145 150 155 160 165

th (µ

Temperature (°C)

Radial Crystal Growth Rate at Various Temperatures

6100D6201D

# %D RV 6100D 0.3 3.1 6201D 1.5 3.1

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

Bulk Crystallization by Flash DSC 1 from Mettler

“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

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)

Specifications - Flash DSC 1 - Flash Differential Scannng Calorimeter

Isothermal Methods

0 5 10 15

time (sec)

0 5 10 15

time (sec)

Isotherm after quench x = 5 – 600 s Measure changes at 100°C/s

Isotherm after melt x = 5 – 600 s Measure changes at 100°C/s

Dynamic Methods

0 10 20 30

time (sec)

0 10 20 30

time (sec)

Varied heating rates 0.333 to 2000°C/s Measure crystallization and melting during heating

Varied cooling rates -0.333 to -2000°C/s Measure cooling history at 100°C/s reheat

Flash DSC example of collected data 1: Reheat at 100°C/sec after annealing 5-600 seconds at 130°C from quenched state (30°C)

Increasing crystallization time

Ingeo 6201D + 1% LAK-301 Sample size = 0.00151 mg by calculation

•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

Experiment: 793-75-04 130C quench isotherms, 29.09.2011 16:16:15Performed 29.09.2011 16:41:44

°C30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200

793-75-04 130C quench isotherms

12.10.2011 15:12:07

STARe SW 10.00

Lab: METTLER

Increasing crystallization time

Effect of impingement and secondary crystallization processes on crystallinity

Simulation showing free growth, Avrami, and effect of secondary crystallization

0 10 20 30 40 50 60

Time (minutes)

linity

Free growth Avrami Avrami +secondary

Free growth, no impingement

Avrami kinetics

Secondary crystallization

Crystallization ½ time

Isothermal Crystallization Temperature Effects Ingeo 6201D (~1.5%D) vs. 6100D (~0.3%D) at equal MW

6201D + 1% LAK-301 5-600 seconds at varied temp. From the quench state (30°C)

6100D + 1% LAK-301 5-600 seconds at varied temp. From the quench state (30°C)

10876 1007050403020 200 300 400 600

isotherm time (s)

isotherm

10876543 1007050403020 200 300 500

isotherm time (s)

isotherm

Tested using 1% LAK-301 Nucleant from Takemoto Oil & Fat 100% PLA crystal = -93 J/g

Neat polymer (no nucleant) crystallized from the melt and quenched states

100 110 120 130

isotherm temp

Polymerisotherm from melt

isotherm from quench

experiment

Bivariate Fit of cryst 1/2 time [s] By isotherm temp Nucleant=neat

Fastest temp. is about 110°C and 6100D ~ 4x faster than 6201D

1.0% LAK-301 nucleant crystallized from the melt and quenched states

100 105 110 115 120 125 130

isotherm temp

experiment

Bivariate Fit of cryst 1/2 time [s] By isotherm temp Nucleant=1% LAK-301

LAK-301 supplied by Takemoto Oil & Fat

Rate is fastest up to 130°C and 6100D ~ 3.5x faster than 6201D

1.0% Ecopromote nucleant crystallized from the melt and quenched states

100 110 120 130

isotherm temp

experiment

Bivariate Fit of cryst 1/2 time [s] By isotherm temp Nucleant=1% Ecopromote

Ecopromote supplied by Nissan Chemical

Rate is fast at high temps 6100D ~ 2.5x faster than 6201D

0.5% talc nucleant crystallized from the melt and quenched states

100 110 120 130

isotherm temp

experiment

Bivariate Fit of cryst 1/2 time [s] By isotherm temp Nucleant=0.5% Talc

Ultratalc 609 supplied Specialty Minerals

Rate fast at cool temps but slows at high temps.

0.5% EBS nucleant crystallized from the melt and quenched states

100 110 120 130

isotherm temp

experiment

Bivariate Fit of cryst 1/2 time [s] By isotherm temp Nucleant=0.5% EBS

EBS supplied by Crompton

Rate fast at cool temps, but slow at high temps. Quench improves rate

Flash DSC example of collected data 2: Crystallization during rapid heating

Increasing heating rate

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

20°C/min

50°C/s

Crystallization During Varied Heating Rates Ingeo 6201D (~1.5%D) vs. 6100D (~0.3%D) at equal MW with Four Nucleants Analysis of % Crystallinity During Heating

6201D + nucleants heating at 0.5-100°C/sec second From the quenched state (30°C)

6100D + nucleants heating at 0.5-100°C/sec second From the quenched state (30°C)

10.80.60.4 108765432 17050403020

heating rate (°Cs^-1)

0.5% EBS

0.5% Talc

1% Ecopromote

1% LAK-301

Nucleant

10.80.60.4 108765432 17050403020

heating rate (°Cs^-1)

0.5% EBS

0.5% Talc

1% Ecopromote

1% LAK-301

Nucleant

Crystallization During Varied Cooling Rates Ingeo 6201D (~1.5%D) vs. 6100D (~0.3%D) at equal MW with Four Nucleants Analysis of % Crystallinity During Reheat at 100°C/sec

6201D + nucleants cooling at 0.5-20°C/sec second From the molten state (210°C)

6100D + nucleants cooling at 0.5-20°C/sec second From the molten state (210°C)

10.80.60.5 108765432 20

prior cooling rate (- °Cs^-1)

0.5% EBS

0.5% Talc

1% Ecopromote

1% LAK-301

Nucleant

10.80.60.5 108765432 20

prior cooling rate (- °Cs^-1)

0.5% EBS

0.5% Talc

1% Ecopromote

1% LAK-301

Nucleant

E’ Modulus(T) Results: Hot molded bars with nucleant, 3 point bend geometry to measure E’

1.00E+01

1.00E+02

1.00E+03

1.00E+04

0 50 100 150 200

Temperature [C]

6100D + 1% LAK-301 6201D + 1% LAK-301

66 psi HDT estimate

~15°C HDT improvement

% crystallinity and Tm vs. isotherm time (s) for Polymer=6100D, experiment=isotherm from melt

Tm (°

10876543 1007050403020 200 300 500

isotherm time (s)

isotherm

temp 0.5% EBS

0.5% Talc

1% Ecopromote

1% LAK-301

Nucleant

10876543 1007050403020 200 300 500

isotherm time (s)

isotherm

temp 0.5% EBS

0.5% Talc

1% Ecopromote

1% LAK-301

Nucleant

First examination of the raw data showed incredible variations in observed melting point. Heating rate = 100°C/s Large differences in crystallization kinetics and final crystallinity

Making Sense of Melting Point

Tm (°

0 10 20 30 40 50 60 70

% crystallinity

isotherm

temp 0.5% EBS

0.5% Talc

1% Ecopromote

1% LAK-301

Nucleant

Bivariate Fit of Tm (°C) By % crystallinity Polymer=6100D

Compiled data of crystallinity developed during isotherms from both quenched and melt states

Tm (°

0 10 20 30 40 50 60

% crystallinity

isotherm

temp 0.5% EBS

0.5% Talc

1% Ecopromote

1% LAK-301

Nucleant

Bivariate Fit of Tm (°C) By % crystallinity Polymer=6201D

Analysis of variance on final crystallinity*:

• 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

Tm (°

150 155 160 165 170 175 180

Tm (°C) Predicted P<.0001

RSq=0.97 RMSE=1.1916

35 40 45 50 55 60 65 70

% crystallinity Predicted

P<.0001 RSq=0.88 RMSE=2.2237

*Data selected for Avrami 1-X < 0.05

Nonwoven Fabrics Demonstrations 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

Melt Blown Extrusion Line

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 extruder

Nonwovens Research Lab at The University of Tennessee, under direction of Gajanan Bhat

Melt blown fibers optimized results

sample direction

Fiber Diameters

100°C hot air shrink

[%]Peak

Force [lb]

Peak Elongation

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

Conditions 0.6 g/min/hole 240°C melt temp., ~250 psi melt press. 260°C air temp., ~20 psi air press. 200-220 mm distance from die to collector 30 g/m2 basis weight

Spunbond Process

Spun bond simulation

NatureWorks’ custom modified Hills Fiber line with Lurgi fiber attenuator

Spun bond fiber shrinkage

60 80 100 120 140Boili

Air draw pressure [psi]6251D 6260D lab scale

Lurgi Gun spun bond simulation 144 holes at 0.3mm diameter 0.75 g/min/hole Draw down range = 18-21 Filament velocity range = 2800-3800 m/min 220°C melt temperature, 800-900 psi

Increasing velocity and cost Increasing asset age

6260D processes with lower shrinkage at lower air draw pressures compared to 6251D standard material

60 110 160

Air draw pressure [psi]

6251D 6260D lab scale

Spun bond fiber strength

Lurgi Gun spun bond simulation 144 holes at 0.3mm diameter 0.75 g/min/hole Draw down range = 18-21 Filament velocity range = 2800-3800 m/min 220°C melt temperature, 800-900 psi

6260D processes has similar strength characteristics as 6251D standard material

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

Advantages of expanded offering for the Durable & 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

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.

New Ingeo products offer structure and property

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