New High Performance Ingeo Grades from NatureWorks

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

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


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


Radial crystal growth rate, G(T) for PLLA
(generally 0-0.3% D)
12
Di Lorenzo data
10 Runt-data
Radial 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


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


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

6


Ingeo Technology Platforms

8000 series
foam

7000 series
bottles - ISBM

6000 series
fibers & nonwovens

4000 series
films

3000 series
injection Molding

2000 series
thermoforming

Lactide monomer

7


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


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


Properties of New High %L
Ingeo Grade Offering

10


High %L Crystal Growth Rate Results
Hot 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 increase
Radial 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


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


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


Isothermal
250 Methods
200
Temperature (°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
200
Temperature (°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


Dynamic Methods
250
200
Temperature (°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

250
Temperature (°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


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)
^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


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 kinetics
Crystallinity (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


Isothermal Crystallization Temperature Effects
Ingeo 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


Neat polymer (no nucleant) crystallized from the
melt 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


1.0% LAK-301 nucleant crystallized from the melt
and quenched states
Bivariate Fit of cryst 1/2 time [s] By isotherm temp Nucleant=1% LAK-301

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


1.0% Ecopromote nucleant crystallized from the
melt and quenched states
Bivariate Fit of cryst 1/2 time [s] By isotherm temp Nucleant=1% Ecopromote

17
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


0.5% talc nucleant crystallized from the melt and
quenched states
Bivariate Fit of cryst 1/2 time [s] By isotherm temp Nucleant=0.5% Talc

17
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


0.5% EBS nucleant crystallized from the melt and
quenched 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


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

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


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
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


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
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


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


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


Compiled data of crystallinity developed during
isotherms 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


Compiled data of crystallinity developed during
isotherms 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


70
18
65
17
60
17

Tm (°C) Actual
% crystallinity
55

Analysis of variance

Actual
16
50

45 16

15

on 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


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

32


Melt Blown Extrusion Line

33
33

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

34


Conditions
0.6 g/min/hole
Melt 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


Spunbond Process

36
36

Spun bond simulation

NatureWorks’ custom modified Hills
Fiber line with Lurgi fiber attenuator

37


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 cost
Increasing asset age

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
strength 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


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


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

41


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


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