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transcript
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
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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