Synthetic Layered Silicates for Paper and Polymeric Nanocomposites Applications

Transcription

1 2006 International Conference on Nanotechnology, April 26-28, 2006 Atlanta, GA Synthetic Layered Silicates for Paper and Polymeric Nanocomposites Applications Platy a Novel Pigment & Nanofiller Authors: Juan M. Garcés *, Jamel Attal** * Consultant, Retired from: **The Dow Chemical Company Your logo here

2 PRESENTED BY Juan M. Garcés Consultant, LLC

3 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

4 Composites and Nanocomposites Different Levels of Dispersion in Polymer Matrix 1000 nm 100 nm Clay Composite Clay Nanocomposite: less clay, more interface

5 NANOCOMPOSITES OPPORTUNITY Low 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

6 Automotive Opportunities ATP: TPO Goal Fascia target ( 250,000 psi, 0.95 g/cc, 10 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

7 Material Synthesis by Design Polymer-Clay Nanocomposites High Aspect Ratio Fillers Synthetic Platy Materials Plates Dispersed in Polymer Modeling Performance and Structure

8 Modeling an Ideal Nanocomposite Modulus, CLTE, Permeability, Orientation, etc. 3.5 Modulus Ratio (Filler/Matrix) = Modulus Enhancement Ratio ,000 1, Filler Aspect Ratio = CLTE (m/m/kx10-5) Volume fraction of filler aspect ratio 200 aspect ratio 50 aspect ratio 10 aspect ratio 5 aspect ratio 1 Nanofiller Volume Fraction Source: LITAC Model / J. Bice J. Bicerano, J. F. Douglas and D. A. Brune, J. Macromol. Sci. - Reviews, C39, (1999). D. A. Brune and J. Bicerano, Polymer, 43, (2002).

9 Synthetic G. Lagaly, K. Beneke, A. Weiss: Proc. Internat. Clay Conf. Madrid Madrid (1973) QuickTime and a TIFF (Uncompressed) decompressor are needed to see this picture.

10 : Na 2 O. 14SiO 2.9H 2 O Synthetic Platy Na 2 O. 14SiO 2. 9H 2 O NaO ONa NaO ONa Na 2 O. 14SiO 2. 9H 2 O = Na 2 O. 14SiO 2. H 2 O + 8H 2 O [13.53%] NaO ONa NaO ONa NaO ONa NaO ONa d = 15 o A proposed structure NaO ONa NaO ONa Na 2 O. 14SiO 2. H 2 O = Na 2 O. 14SiO 2 + H 2 O [1.69%] proposed structure Aspect Ratio: d 001 = 15.5 A o

11 Platy Novel 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

12 Latex Description Composition Particle Size o A Tg o C Latex A Carboxylated Styrene/Butadiene/Acryl ontrile Latex B Carboxylated Styrene/Butadiene Latex C Carboxylated Styrene/Butadiene/Acryl ontrile

13 Paper Coating Formulation PIGMENTS Hydraprint Clay (delaminated Clay) Hydrocarb 90 Ground Calcium Carbonate Platy BINDERS/ADDITIVES Dry Parts per 100 parts Pigment Latex A Latex B Finnfix Aim Points: % Solids 51% 51% 51% 51% 51% 51% 51% 51% 51% 51% Coat Weight = 4.5 lbs/3300 sq. ft

14 Tappi Opacity Platy magadiite: Impact on formulations Tappi Opacity Run 1 (A+Clay Ctl) Run 2 (A+15Mag) Run 3 (A+25Mag) Run 4 (B+Clay Ctl) Run 5 (B+15Mag) Run 6 (B+25Mag) Run 7 (A+Carb) Run 8 (A+25Mag) Run 9 (B+Carb) Run 10 (B+25Mag)

15 Sheet Gloss Sheet Gloss (75 Deg) Run 1 (A+Clay Ctl) Run 2 (A+15Mag) Run 3 (A+25Mag) Run 4 (B+Clay Ctl) Run 5 (B+15Mag) Run 6 (B+25Mag) Run 7 (A+Carb) Run 8 (A+25Mag) Run 9 (B+Carb) Run 10 (B+25Mag)

16 Print Gloss Print Gloss Run 1 (A+Clay Ctl) Run 2 (A+15Mag) Run 3 (A+25Mag) Run 4 (B+Clay Ctl) Run 5 (B+15Mag) Run 6 (B+25Mag) Run 7 (A+Carb) Run 8 (A+25Mag) Run 9 (B+Carb) Run 10 (B+25Mag)

17 Brightness Brightness Run 1 (A+Clay Ctl) Run 2 (A+15Mag) Run 3 (A+25Mag) Run 4 (B+Clay Ctl) Run 5 (B+15Mag) Run 6 (B+25Mag) Run 7 (A+Carb) Run 8 (A+25Mag) Run 9 (B+Carb) Run 10 (B+25Mag)

18 Helio Roto Printability Helio (m to 20 missing dots) Run 1 (A+Clay Ctl) Run 2 (A+15Mag) Run 3 (A+25Mag) Run 4 (B+Clay Ctl) Run 5 (B+15Mag) Run 6 (B+25Mag) Run 7 (A+Carb) Run 8 (A+25Mag) Run 9 (B+Carb) Run 10 (B+25Mag)

19 Roughness (mm) Roughness Run 1 (A+Clay Ctl) Run 2 (A+15Mag) Run 3 (A+25Mag) Run 4 (B+Clay Ctl) Run 5 (B+15Mag) Run 6 (B+25Mag) Run 7 (A+Carb) Run 8 (A+25Mag) Run 9 (B+Carb) Run 10 (B+25Mag)

20 Whiteness ASTM Whitness Run 1 (A+Clay Ctl) Run 2 (A+15Mag) Run 3 (A+25Mag) Run 4 (B+Clay Ctl) Run 5 (B+15Mag) Run 6 (B+25Mag) Run 7 (A+Carb) Run 8 (A+25Mag) Run 9 (B+Carb) Run 10 (B+25Mag)

21 B-Value CIE B-Value Run 1 (A+Clay Ctl) Run 2 (A+15Mag) Run 3 (A+25Mag) Run 4 (B+Clay Ctl) Run 5 (B+15Mag) Run 6 (B+25Mag) Run 7 (A+Carb) Run 8 (A+25Mag) Run 9 (B+Carb) Run 10 (B+25Mag)

22 Coating Strength IGT Pick Dry Pick Run 1 (A+Clay Ctl) Run 2 (A+15Mag) Run 3 (A+25Mag) Run 4 (B+Clay Ctl) Run 5 (B+15Mag) Run 6 (B+25Mag) Run 7 (A+Carb) Run 8 (A+25Mag) Run 9 (B+Carb) Run 10 (B+25Mag)

23 SEM Coated Surfaces Run 1 A + Clay Control Run 3 (A + 25 Parts )

24 Pilot Coater Runnability Dow Pilot Coater Speed = 4000 ft/min

25 Results Comments Positives 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

26 Formulation Typical Negative Ctrl TiO2 Replacement Pigment Delam Hydraprint Cla Hydracrab Ansilex Platy TiO2 7 Latex C Finfix PG Solids, % 55% 55% 55% 55% 55% 55% 55% 55%

27 Helio Distance to 20 missing Dots Clay Carbonate Clay/ TiO2 Distance to 20 Missing Dots Clay Ctl Clay/50 Clay/50 /LS Carb Ctl Carb/50 Clay/ 7 TiO2 Ctl Clay/ 7 Clay/ 15

28 Image Analysis Missing Dots Image Analysis (Missing Dots) Clay Carbonate Clay/ TiO Clay Ctl Clay/50 Clay/50 /LS Carb Ctl Carb/50 Clay/ 7 TiO2 Ctl Clay/ 7 Clay/ 15

29 Roughness 1.4 Carbonate Clay Clay/ TiO2 Roughness (Microns) Clay Ctl Clay/50 Clay/50 /LS Carb Ctl Carb/50 Clay/ 7 TiO2 Ctl Clay/ 7 Clay/ 15

30 Brightness Clay Carbonate Clay/ TiO2 Brightness Clay Ctl Clay/50 Clay/50 /LS Carb Ctl Carb/50 Clay/ 7 TiO2 Ctl Clay/ 7 Clay/ 15

31 Opacity Opacity Clay Ctl Clay/50 Clay/50 /LS Carb Ctl Carb/50 Clay/ 7 TiO2 Ctl Clay/ 7 Clay/ 15

32 Positives Results Platy magadiite: a new paper pigment Excellent Hellio for Roto Printability Excellent Ink Gloss Improved Brightness and Opacity Excellent smoothness Platy : Clay, CaCO 3, TiO 2 all in one! Challenges Higher binder demand Rheology control Cost and supply of Platy

33 Acknowledgements The Dow Chemical Company NIST (Department of Commerce)Advanced Technology Program, Cooperative Agreement # 70NANB7H3028 Platy synthesis team Paper coating team