new ingeo products offer structure and property

1

© 2012 NatureWorks LLC

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

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

3


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)

3

34 NGk π=

nktex −−=1

4


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

0

1

2

3

4

5

6

7

60 80 100 120 140 160 180

G(T

)-sc

aled

um

/min

Temp (C)

Collected G(T) for PLLA (scaled)

Runt

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.

0

2

4

6

8

10

12

60 80 100 120 140 160 180

Rad

ial g

row

th ra

te (u

m/m

in)

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

5


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

110

120

130

140

150

160

170

180

190

200

100 110 120 130 140 150 160 170

Tc (˚C)

Tm (̊ C

)

PLLA

PD0.015L0.985LA

PD0.03L0.97LA

PD0.06L0.94LA

*from Runt, et al. (2001)

Increasing Stereo Purity

6


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

7


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

8


Basic Design Table – Ingeo Grades

4032D 2003D 4043D 7001D

4060D

3001D 6201D 6202D

3052D 6752D 8052D

6302D

3251D 6252D

Increasing Level of D- isomer

Incr

easi

ng M

olec

ular

Wei

ght

Fiber and Injection Molding Grades

Extrusion Grades

9


Expanded Design Table – Ingeo Grades

In Development 4032D

2003D 4043D 7001D

4060D

3100HP 6100D

3001D 6201D 6202D

3052D 6752D 8052D

6302D

3260HP 6260D

3251D 6252D

Increasing Level of D- isomer

Incr

easi

ng M

olec

ular

Wei

ght

Fiber and Injection Molding Grades

Extrusion Grades

10


Properties of New High %L Ingeo Grade Offering

11


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

0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

9.0

10.0

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

Rad

ial G

row

th (µ

M/m

in)

Temperature (°C)

Radial Crystal Growth Rate at Various Temperatures

6100D6201D

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

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

13


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

14


Isothermal Methods

0

50

100

150

200

250

0 5 10 15

Tem

pera

ture

(°C)

time (sec)

0

50

100

150

200

250

0 5 10 15

Tem

pera

ture

(°C)

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

( )x

( )x

15


Dynamic Methods

0

50

100

150

200

250

0 10 20 30

Tem

pera

ture

(°C)

time (sec)

0

50

100

150

200

250

0 10 20 30

Tem

pera

ture

(°C)

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

16


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

mW0.5

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

^exo

793-75-04 130C quench isotherms

12.10.2011 15:12:07

STARe SW 10.00

Lab: METTLER

Increasing crystallization time

17


Effect of impingement and secondary crystallization processes on crystallinity

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

0

5

10

15

20

25

30

35

40

45

50

0 10 20 30 40 50 60

Time (minutes)

Cry

stal

linity

(J/g

)

Free growth Avrami Avrami +secondary

Free growth, no impingement

Avrami kinetics

Secondary crystallization

Crystallization ½ time

18


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)

0

10

20

30

40

50

% c

ryst

allin

ity

10876 1007050403020 200 300 400 600

isotherm time (s)

100

105

110

115

130

isotherm

temp

0

10

20

30

40

50

60

70

% c

ryst

allin

ity

10876543 1007050403020 200 300 500

isotherm time (s)

105

110

115

130

isotherm

temp

°C

°C

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

19


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

0

10

20

30

40

50

crys

t 1/2

time

[s]

100 110 120 130

isotherm temp

6100D

6201D

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

20


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

10

30

50

70

90

11

13

15

17

19

crys

t 1/2

time

[s]

100 105 110 115 120 125 130

isotherm temp

6100D

6201D



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

21


1.0% Ecopromote nucleant crystallized from the melt and quenched states

10

30

50

70

90

11

13

15

17

19

crys

t 1/2

time

[s]

100 110 120 130

isotherm temp

6100D

6201D



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

22


0.5% talc nucleant crystallized from the melt and quenched states

10

30

50

70

90

11

13

15

17

19

crys

t 1/2

time

[s]

100 110 120 130

isotherm temp

6100D

6201D



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.

23


0.5% EBS nucleant crystallized from the melt and quenched states

0

20

40

60

80

10

12

14

16

18

20

crys

t 1/2

time

[s]

100 110 120 130

isotherm temp

6100D

6201D



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

24


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

25


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

0

10

20

30

40

50

60

% c

ryst

allin

ity

10.80.60.4 108765432 17050403020

heating rate (°Cs^-1)

0.5% EBS

0.5% Talc

1% Ecopromote

1% LAK-301

Nucleant

-10

0

10

20

30

40

50

60

% c

ryst

allin

ity

10.80.60.4 108765432 17050403020

heating rate (°Cs^-1)

0.5% EBS

0.5% Talc

1% Ecopromote

1% LAK-301

Nucleant

26


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

0

10

20

30

40

50

60

70

% c

ryst

allin

ity

10.80.60.5 108765432 20

prior cooling rate (- °Cs^-1)

0.5% EBS

0.5% Talc

1% Ecopromote

1% LAK-301

Nucleant

-10

0

10

20

30

40

50

60

70

% c

ryst

allin

ity

10.80.60.5 108765432 20

prior cooling rate (- °Cs^-1)

0.5% EBS

0.5% Talc

1% Ecopromote

1% LAK-301

Nucleant

27


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

E' [M

Pa]

Temperature [C]

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

66 psi HDT estimate

~15°C HDT improvement

28


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

15

16

16

17

17

18

Tm (°

C)

10876543 1007050403020 200 300 500

isotherm time (s)

95

100

105

110

115

130

isotherm

temp 0.5% EBS

0.5% Talc

1% Ecopromote

1% LAK-301

neat

Nucleant

0

10

20

30

40

50

60

70

% c

ryst

allin

ity

10876543 1007050403020 200 300 500

isotherm time (s)

95

100

105

110

115

130

isotherm

temp 0.5% EBS

0.5% Talc

1% Ecopromote

1% LAK-301

neat

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

29


15

15

16

16

17

17

18

Tm (°

C)

0 10 20 30 40 50 60 70

% crystallinity

95

100

105

110

115

130

isotherm

temp 0.5% EBS

0.5% Talc

1% Ecopromote

1% LAK-301

neat

Nucleant

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

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

30


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

14

14

15

15

16

16

17

17

Tm (°

C)

0 10 20 30 40 50 60

% crystallinity

95

100

105

110

115

130

isotherm

temp 0.5% EBS

0.5% Talc

1% Ecopromote

1% LAK-301

neat

Nucleant

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

31


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

15

15

16

16

17

17

18

Tm (°

C) A

ctua

l

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

% c

ryst

allin

ity

Act

ual

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

32


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

33


Melt Blown Extrusion Line

33

http://www.kasen.co.jp/english/index.html

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 extruder

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

35


Melt blown fibers optimized results

sample direction

Fiber Diameters

[µm]

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

36


Spunbond Process

36

http://www.kasen.co.jp/english/index.html

37


Spun bond simulation

NatureWorks’ custom modified Hills Fiber line with Lurgi fiber attenuator

38


Spun bond fiber shrinkage

0

20

40

60

80

100

60 80 100 120 140Boili

ng W

ater

Shr

inka

ge

[%]

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

39


2

2.2

2.4

2.6

2.8

60 110 160

Tena

city

[g/d

en]

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

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

41


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

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.

new ingeo products offer structure and property

Documents