PolymerClay Nanobrick Wall Thin Films as Foil Replacements

Polymer-Clay Nanobrick Wall Thin Films as Foil Replacements Morgan A. Priolo, Kevin M. Holder, Laura Bolling, Jaime C. Grunlan* CHEMICAL & MECHANICAL ENGINEERING TEXAS A&M UNIVERSITY COLLEGE STATION, TX 77843 AICh. E Annual meeting, Pittsburg, PA– November 1 st, 2012 *jgrunlan@tamu. edu

Acknowledgements POLYMER NANO COMPOSITES NANOCOMPOSITES. TAMU. EDU

Applications Food Packaging Flexible Electronics cryovac. com Pressurized Systems mitsubishicars. com Separation Membranes ornl. gov Eichie, F. E. et al. , J. Appl. Polym. Sci. 2006, 99, 725. Grunlan, J. C. et al. J. Appl. Polym. Sci. 2004, 93, 1102. Graff, G. L. et al. Flexible Flat Panel Displays, Crawford, G. P. , Ed. John Wiley & Sons, Ltd. : 2005. 3

Motivation Metallized Plastic Thin metal films have been deposited onto polymeric webs for gas barrier since the 1970 s. In 2001 alone, 11 billion sq. meters were used for packaging. Only 10– 100 nm imparts 1000 x reduction in permeability. Major drawbacks: o Not microwavable o Not recyclable × 2, 000 o Completely opaque Graff et. al. In Flexible Flat Panel Displays; Crawford, G. P. , Ed. ; John Wiley & Sons, Ltd. : 2005, p 57. 4

Background Silicon Oxide (Si. Ox) Barrier Film o Transparency, microwavability o Cracking, poor adhesion to polymer Roberts et. al. J. Membr. Sci. 2002, 208, 75. Leterrier, Y. Prog. Mater. Sci. 2003, 48, 1. Polymer Multilayer (PML) o Packaging solution for electronics o Complicated processing, cracking (better than Si. Ox) Affinito et. al. Thin Solid Films 1996, 291, 63. Graff et. al. In Flexible Flat Panel Displays; Crawford, G. P. , Ed. ; John Wiley & Sons, Ltd. : 2005, p 57. Bulk Composite o Poor transparency o Relatively low barrier Nazarenko et. al. J. Polym. Sci. B: Polym. Phys. 2007, 45, 1733. 5

Background Property comparison of Si. Ox, polymer multilayer and layer-by-layer films Layer-by-layer assembly can produce super gas barrier films without any of the drawbacks of previously mentioned techniques! Inagaki, N. ; Tasaka, S. ; Hiramatsu, H. , Journal of Applied Polymer Science 1999, 71, 2091. Affinito, J. D. ; Gross, M. E. ; Coronado, C. A. ; Graff, G. L. ; Greenwell, E. N. ; Martin, P. M. , Thin Solid Films 1996, 291, 63. 3 Jang, W. S. ; Rawson, I. ; Grunlan, J. C. , Thin Solid Films 2008, 516, 4819. 1 2 6

Thin Film Materials Sodium Montmorrilonite Clay (MMT): (Cloisite-Na+ from Southern Clay) § Platelet structure (~1 nm thick) § Aspect ratio (ℓ/d) of 100– 1000 § 1. 0 wt. % suspension § Negatively charged in water Ploehn, H. J. ; Liu, C. Y. , Ind. Eng. Chem. Res. 2006, 45, 7025. Branched Polyethylenimine (PEI): (Purchased from Sigma–Aldrich) § Mw = 25, 000 g/mol § 0. 1 wt. % at p. H = 10 § Positively charged in water Poly(acrylic acid) (PAA): (Purchased from Sigma–Aldrich) § Mw = 100, 000 g/mol § 0. 2 wt. % at p. H = 4 § Negatively charged in water Priolo, M. A. ; Gamboa, D. ; Holder, K. M. ; Grunlan, J. C. , Nano Letters 2010, 4970. 7

Layer-by-Layer Assembly Repeat until desired # of layers are deposited 1 Bilayer Substrate + + + + Ambient Processing Rinse Dry Tunable Properties Nanoparticle Control Priolo, M. A. ; Gamboa, D. ; Grunlan, J. C. ACS Applied Materials & Interfaces 2010, 2, 312. Decher, G. Science 1997, 277, 1232. 8

Layer-by-Layer Assembly 2 D Robot 3 D Robot Gamboa, D. ; Priolo, M. A. ; Ham, A. ; Grunlan, J. C. , Rev Sci Instrum 2010, 81, 036103. Jang, W. S. ; Grunlan, J. C. , Rev Sci Instrum 2005, 76, 103904. 9

Film Thickness Priolo, M. A. ; Gamboa, D. ; Holder, K. M. ; Grunlan, J. C. , Nano Letters 2010, 4970. 10

Film Composition 26. 2% MMT 36. 7% MMT 48. 6% MMT 53. 7% MMT Priolo, M. A. ; Gamboa, D. ; Holder, K. M. ; Grunlan, J. C. , Nano Letters 2010, 4970. 11

Optical Clarity > 95% Transparent Priolo, M. A. ; Gamboa, D. ; Holder, K. M. ; Grunlan, J. C. , Nano Letters 2010, 4970. 12

9 Bare PET Super Gas Barrier 8, 169 OTR (cc/(m 2·day·atm)) 8 QLs 7 2 3 4 5 6 5 OTR Film Thickness 2 (cc/(m ·day·atm)) (nm) 8. 169 2. 341 ≤ 0. 005 <0. 005 Film Permeability (10 -16 cc·cm/(cm 2·s·Pa)) 16. 1 28. 3 50. 9 82. 6 0. 065859 0. 002082 ≤ 0. 000005 <0. 000009 Without PAA, this level of barrier Lowest reported permeability for a requires at least 24 PEI/MMT polymer – clay thin film! BLs. 4 Morgan A. Priolo, Kevin M. Holder, Daniel Gamboa, and Jaime C. Grunlan Langmuir 2011 27 (19), 12106 3 2, 341 2 1 0 2 3 ≤ 0. 005 <0. 005 4 5 Number of Quadlayers Priolo, M. A. ; Gamboa, D. ; Holder, K. M. ; Grunlan, J. C. , Nano Letters 2010, 4970. 13

80 nm Nanobrick Wall Structure 20 nm 5 QL on 5 -mil PS Priolo, M. A. ; Gamboa, D. ; Holder, K. M. ; Grunlan, J. C. , Nano Letters 2010, 4970. 14

Humidity & Crosslinking (7 QL) OTR (cc/(m 2·day·atm)) 0, 16 0, 14 0, 1395 Neat Thin Film Heated 2 hr at 80 C 0, 12 0, 10 0, 08 0, 06 0, 09300000001 Thermal cross-linking improves humid barrier performance of neat thin film by 33% 0, 04 0, 02 <0. 005 0, 00 0 Relative Humidity (%) 100 Priolo, M. A. ; Gamboa, D. ; Holder, K. M. ; Grunlan, J. C. , Nano Letters 2010, 4970. 15

Conclusion & Future Work • Transparent QL films made using Lb. L deposition • 4 QL film has lowest reported permeability for a clay-polymer film • Need to evaluate gas separation • Will work to eliminate humidity sensitivity 16

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