2006 International Conference on

Nanotechnology, April 26-28, 2006

Atlanta, GA

Synthetic Layered Silicates for Paper and Polymeric Nanocomposites Applications

Platy Magadiite a Novel Pigment & Nanofiller

Authors: Juan M. Garcés *, Jamel Attal** * Consultant, Retired from:**The Dow Chemical Company Your logo here

PRESENTED BY

Juan M. Garcés

Consultant, LLC

Garces45@aol.com

Outline• Polymer nanocomposites: a new frontier

• Nanocomposites for automotive applications

• Need for new synthetic nanofillers

• Platy magadiite: High aspect ratio silicate

• Platy magadiite in paper coating formulations

• Platy magadiite a surprisingly good pigment

• Challenges

Composites and NanocompositesDifferent Levels of Dispersion in Polymer Matrix

1000 nm 100 nm

Clay CompositeClay Nanocomposite:

less clay, more interface

NANOCOMPOSITES OPPORTUNITYLow Cost - High Performance

• Higher Stiffness/Toughness At Lower Weight

– Automotive, Appliances, Aircraft

• Stiffness With Clarity

– Coatings, Films, Packaging

• Enhanced Melt/Solution Behavior

– Fibers, Cosmetics, Paints

• Increased Ion/Electron Transport

– Batteries, Conductive Polymers

• Superior Barrier For Small Molecules

– Flame Retardant Applications, Packaging

Automotive OpportunitiesATP: TPO Goal

• Fascia target ( 250,000 psi , 0.95 g/cc, 10 ft-lb/in @ 0C)• Hypothesized benefits

– Higher modulus = wall thickness reduction = 25% improvement– Lower specific gravity over current “filled” materials = 5% improvement– Lower CLTE = advantages of improved fit with fewer fasteners

Material Synthesis by DesignPolymer-Clay Nanocomposites

High Aspect Ratio Fillers

Synthetic PlatyMaterials

Plates Dispersedin Polymer

Modeling Performanceand Structure

Modeling an Ideal NanocompositeModulus, CLTE, Permeability, Orientation, etc.

1.0

1.5

2.0

2.5

3.0

3.5

0 0.01 0.02 0.03 0.04 0.05

Mod

ulus

Enh

ance

men

t Rat

io

Nanofiller Volume Fraction

1

10

100

25

50

Filler AspectRatio = 20

200

500

10,000

1,000

Modulus Ratio (Filler/Matrix) = 73.5

Source: LITAC Model / J. Bice

0

2

4

6

8

10

12

0 0.1 0.2 0.3

Volume fraction of filler

CLT

E (m

/m/K

x10-

5)

aspect ratio 200aspect ratio 50aspect ratio 10aspect ratio 5aspect ratio 1

J. Bicerano, J. F. Douglas and D. A. Brune, J. Macromol. Sci. - Reviews, C39, 561-642 (1999).D. A. Brune and J. Bicerano, Polymer, 43, 369-387 (2002).

Synthetic Magadiite G. Lagaly, K. Beneke, A. Weiss: Proc. Internat. Clay Conf. Madrid

1972. Madrid (1973) 663-673

QuickTime™ and aTIFF (Uncompressed) decompressor

are needed to see this picture.

Na2O. 14SiO2. 9H2O = Na2O. 14SiO2. H2O + 8H2O [13.53%]

Na2O. 14SiO2. H2O = Na2O. 14SiO2+ H2O [1.69%]

d001 = 15.5 Ao

Synthetic Platy MagadiiteNa2O. 14SiO2. 9H2O

proposed structure

Magadiite: Na2O. 14SiO2.9H2O

NaO ONaONa NaO

ONaNaO ONa NaO

proposed structure

NaO ONaONa NaO

ONaNaO ONa NaO

d = 15 oA

Aspect Ratio: 10-1000

Platy MagadiiteNovel Paper Pigment?

• Platy morphology: very flat and smooth surface

• Synthetic platy magadiite: very white and bright

• Composition: sodium silicate hydrate

• Crystal size and composition controllable

• Tunable Surface Chemistry: Si-O-Na+, Si-OH, or Si-OR sites

• Chemistry and morphology: compatible with paper coatings

• Potentially a low-cost material

Latex Description

-202000Carboxylated Styrene/Butadiene/Acrylontrile

Latex C

101250Carboxylated Styrene/ButadieneLatex B

21250Carboxylated Styrene/Butadiene/Acrylontrile

Latex A

TgoC

Particle Size oA

Composition

Paper Coating Formulation

51%51%51%51%51%51%51%51%51%51%% Solids

Aim Points:

0.50.50.50.50.50.50.50.50.50.5Finnfix 10

66666Latex B

66666Latex A

Dry Parts per 100 parts PigmentBINDERS/ADDITIVES

252525152515Platy Magadiite

7510075100Hydrocarb 90 Ground Calcium

Carbonate

75851007585100Hydraprint Clay (delaminated

Clay)

10987654321PIGMENTS

Coat Weight = 4.5 lbs/3300 sq. ft

Tappi OpacityPlaty magadiite: Impact on formulations

80.0

80.5

81.0

81.5

82.0

82.5

83.0R

un 1

(A+C

lay

Ctl) Run

2(A

+15M

ag)

Run

3(A

+25M

ag)

Run

4 (B

+Cla

yC

tl) Run

5(B

+15M

ag)

Run

6(B

+25M

ag)

Run

7 (A

+Car

b)

Run

8(A

+25M

ag)

Run

9 (B

+Car

b)

Run

10

(B+2

5Mag

)

Tapp

i Opa

city

Sheet Gloss

35

40

45

50

55

60R

un 1

(A+C

lay

Ctl) Run

2(A

+15M

ag)

Run

3(A

+25M

ag)

Run

4 (B

+Cla

yC

tl) Run

5(B

+15M

ag)

Run

6(B

+25M

ag)

Run

7 (A

+Car

b)

Run

8(A

+25M

ag)

Run

9 (B

+Car

b)

Run

10

(B+2

5Mag

)

Shee

t Glo

ss (7

5 D

eg)

Print Gloss

65

70

75

80

85

90

95R

un 1

(A+C

lay

Ctl) Run

2(A

+15M

ag)

Run

3(A

+25M

ag)

Run

4 (B

+Cla

yC

tl) Run

5(B

+15M

ag)

Run

6(B

+25M

ag)

Run

7 (A

+Car

b)

Run

8(A

+25M

ag)

Run

9 (B

+Car

b)

Run

10

(B+2

5Mag

)

Prin

t Glo

ss

Brightness

65.0

66.0

67.0

68.0

69.0

70.0

71.0

72.0

73.0R

un 1

(A+C

lay

Ctl)

Run

2 (A

+15M

ag)

Run

3 (A

+25M

ag)

Run

4 (B

+Cla

yC

tl)

Run

5 (B

+15M

ag)

Run

6 (B

+25M

ag)

Run

7 (A

+Car

b)

Run

8 (A

+25M

ag)

Run

9 (B

+Car

b)

Run

10

(B+2

5Mag

)

Bri

ghtn

ess

Helio – Roto Printability

0

10

20

30

40

50

60

70

80

Run

1 (A

+Cla

y C

tl)

Run

2 (A

+15M

ag)

Run

3 (A

+25M

ag)

Run

4 (B

+Cla

y C

tl)

Run

5 (B

+15M

ag)

Run

6 (B

+25M

ag)

Run

7 (A

+Car

b)

Run

8 (A

+25M

ag)

Run

9 (B

+Car

b)

Run

10

(B+2

5Mag

)

Hel

io (m

to 2

0 m

issi

ng d

ots)

Roughness (mm)

0.7

0.9

1.1

1.3

1.5

1.7

1.9

Run

1 (A

+Cla

yC

tl)

Run

2 (A

+15M

ag)

Run

3 (A

+25M

ag)

Run

4 (B

+Cla

yC

tl)

Run

5 (B

+15M

ag)

Run

6 (B

+25M

ag)

Run

7 (A

+Car

b)

Run

8 (A

+25M

ag)

Run

9 (B

+Car

b)

Run

10

(B+2

5Mag

)

Rou

ghne

ss

Whiteness

35

37

39

41

43

45

47

49

51R

un 1

(A+C

lay

Ctl) Run

2(A

+15M

ag)

Run

3(A

+25M

ag)

Run

4 (B

+Cla

yC

tl) Run

5(B

+15M

ag)

Run

6(B

+25M

ag)

Run

7 (A

+Car

b)

Run

8(A

+25M

ag)

Run

9 (B

+Car

b)

Run

10

(B+2

5Mag

)

AST

M W

hitn

ess

B-Value

5.5

6.0

6.5

7.0

7.5

8.0

Run

1 (A

+Cla

yC

tl) Run

2(A

+15M

ag)

Run

3(A

+25M

ag)

Run

4 (B

+Cla

yC

tl) Run

5(B

+15M

ag)

Run

6(B

+25M

ag)

Run

7 (A

+Car

b)

Run

8(A

+25M

ag)

Run

9 (B

+Car

b)

Run

10

(B+2

5Mag

)

CIE

B-V

alue

Coating Strength – IGT Pick

0

50

100

150

200

250

300R

un 1

(A+C

lay

Ctl) Run

2(A

+15M

ag)

Run

3(A

+25M

ag)

Run

4 (B

+Cla

yC

tl) Run

5(B

+15M

ag)

Run

6(B

+25M

ag)

Run

7 (A

+Car

b)

Run

8(A

+25M

ag)

Run

9 (B

+Car

b)

Run

10

(B+2

5Mag

)

Dry

Pic

k

Run 3

(A + 25 Parts Magadiite)

Run 1 A + Clay Control

SEM – Coated Surfaces

Pilot Coater RunnabilityDow Pilot Coater

Speed = 4000 ft/min

Results CommentsPositives– Excellent Hellio for Roto Printability– Excellent Ink Gloss– Improved Brightness and Opacity– Excellent smoothness– Pilot run successful Challenges

– Higher binder demand– Rheology control– Platy magadiite synthesis

Formulation

Pigment 1 2 3 4 5 6 7 8Delam Hydraprint Cla 100 50 50 78 78 70Hydracrab 90 100 50Ansilex 15 15 15

Platy Magadiite 50 50 50 7 15TiO2 7

Latex C 6 6 5 6 6 6 6 6

Finfix 10 1 1 1 1 1 1 1

PG 280 2

Solids, % 55% 55% 55% 55% 55% 55% 55% 55%

Typical Negative Ctrl

TiO2 Replacement

Helio Distance to 20 missing Dots

5

25

45

65

85

105

125

Dis

tanc

e to

20

Mis

sing

Dot

s

Clay Ctl Clay/50Magadiite

Clay/50Magadiite/LS

Carb Ctl Carb/50Magadiite

Clay/ 7 TiO2 Ctl Clay/ 7Magadiite

Clay/ 15Magadiite

Clay Carbonate Clay/TiO2

Image AnalysisMissing Dots

0

50

100

150

200

250

300

350

400

450

Imag

e A

naly

sis

(Mis

sing

Dot

s)

Clay Ctl Clay/50Magadiite

Clay/50Magadiite/LS

Carb Ctl Carb/50Magadiite

Clay/ 7 TiO2Ctl

Clay/ 7Magadiite

Clay/ 15Magadiite

CarbonateClay Clay/TiO2

Roughness

0.6

0.7

0.8

0.9

1.0

1.1

1.2

1.3

1.4

Rou

ghne

ss (M

icro

ns)

Clay Ctl Clay/50Magadiite

Clay/50Magadiite/LS

Carb Ctl Carb/50Magadiite

Clay/ 7 TiO2Ctl

Clay/ 7Magadiite

Clay/ 15Magadiite

Clay

CarbonateClay/TiO2

Brightness

67.0

69.0

71.0

73.0

75.0

77.0

Brig

htne

ss

Clay Ctl Clay/50Magadiite

Clay/50Magadiite/LS

Carb Ctl Carb/50Magadiite

Clay/ 7 TiO2 Ctl Clay/ 7Magadiite

Clay/ 15Magadiite

Clay

Carbonate

Clay/TiO2

Opacity

77.0

79.0

81.0

83.0

85.0

87.0

89.0

Opa

city

Clay Ctl Clay/50Magadiite

Clay/50Magadiite/LS

Carb Ctl Carb/50Magadiite

Clay/ 7 TiO2 Ctl Clay/ 7Magadiite

Clay/ 15Magadiite

ResultsPlaty magadiite: a new paper pigment

• Positives– Excellent Hellio for Roto Printability– Excellent Ink Gloss– Improved Brightness and Opacity– Excellent smoothness– Platy Magadiite: Clay, CaCO3, TiO2 all in one!

• Challenges– Higher binder demand– Rheology control– Cost and supply of Platy Magadiite

Acknowledgements

• The Dow Chemical Company

• NIST (Department of Commerce)Advanced Technology

Program, Cooperative Agreement # 70NANB7H3028

• Platy Magadiite synthesis team

• Paper coating team