Utilitarian Polymer Blends: A General Approach for the Design of Optical Materials with Tailored Properties .


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Functional Polymer Blends: A General Approach for the Design of Optical Materials with Tailored Properties. Christoph Weder Department of Macromolecular Science and Engineering. Functional Polymer Blends. Summary. Approach:
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Practical Polymer Blends: A General Approach for the Design of Optical Materials with Tailored Properties Christoph Weder Department of Macromolecular Science and Engineering

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Functional Polymer Blends Summary Approach: Blending of "passive" polymers with minor divisions of "active" visitor particles, which present chose functionalities . Inspiration: Rather than growing new materials frameworks \'without any preparation\', the approach endeavors to join the property networks and handling conventions of surely understood polymers with the uncommon, promptly customized properties of utilitarian natural atoms . Challenges: Characterize and control supramolecular models.

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Functional Polymer Blends Outline Light-Polarizing Photoluminescent Systems Excimer Probes Functional Multilayer Films Conclusions

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Linear Polarization of Light Introduction Linearly captivated light is typically produced by the utilization of dichroic polarizers Applications: Liquid precious stone presentations , shades, optical channels Dichroic Polarizer: Uniaxially situated retaining colors, straightly spellbound retention, proficiency < 45 % Photoluminescent (PL) Polarizer: Uniaxially arranged luminescent particles, directly enraptured outflow, Combination of polarizer and "dynamic" shading channel

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Light-Polarizing PL Polymers PL LCDs Science 1998 , 279 , 835. PCT IB98/00998 (1998)

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Light-Polarizing PL Polymers PL LCDs Science 1998 , 279 , 835. WO 9901792 (1999)

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Light-Polarizing PL Polymers Security Features WO 0019016 (2001)

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Light-Polarizing PL Polymers Processing Adv. Mater. 1997 , 9 , 1035. J. Mater. Chem. 1999 , 9 , 2221.

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Light-Polarizing PL Polymers Properties

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Light-Polarizing PL Polymers Properties Polarized ingestion and outflow of situated (  = 80) 2 % w/w EHO-OPPE/UHMW PE mix movies DR A = 57 DR E = 72

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Light-Polarizing PL Polymers Orientation Mechanism Synth. Met. 2001, 124 , 113.

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Light-Polarizing PL Polymers Orientation Mechanism

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Light-Polarizing PL Polymers Orientation Mechanism J. Phys. Chem. 2000 , 104 , 5221.

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Light-Polarizing PL Polymers Patterning Polarizer unpolarized 0° 90°

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Nature 1998 , 392 , 261. Macromolecules 1999 , 32 , 4677 . Phys. Chem. Chem. Phys. 1999 , 1, 5697.

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Cyano-OPVs Excimer Formation upon p - p stacking 1,4-bis (a - cyano-4-methoxystyryl)- 2,5-dimethoxybenzene BCMDB: 644 506/538 Synthesis 2002 , 1185. US Patent Appl. recorded.

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Cyano-OPVs Excimer Formation upon p - p stacking 1,4-bis (a - cyano-4-methoxystyryl)- benzene BCMB: 561 459/485

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Cyano-OPVs Excimer Formation upon p - p stacking Birks, J. Photophysics of Aromatic Molecules, Wiley, New York 1970.

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Cyano-OPVs Synthesis R1 R2 Yield BCMDB: MeO MeO 89% BCMB: MeO H 90% BCEHODB: 2-Ethylhexyloxy MeO 83% Synthesis 2002 , 1185. US Patent Appl. documented.

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Excimers as Molecular Probes Diffusion Dyeing Polymer film Dye Solvent (toluene, CHCl 3 ) Diffusion coloring Rinsing, drying

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Excimers as Molecular Probes Diffusion-Dyed Polymer Blends PL spectra of LLDPE/BCMDB mix film ( ~ 0.1 % w/w) - Influence of elastic misshapening: PL spectra of LLDPE/BCMDB mix movies: [dye] (% w/w): ( — ) ~0.02, ( — ) ~0.06, ( — ) ~0.1, ( — ) ~0.3 Adv. Mater. 2002 , 22 , 1625-1629 . ; US Patent Appl. Documented.

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Excimers as Molecular Probes Diffusion-Dyed Polymer Blends PL lifetime of LLDPE/BCMDB mix movies (ex 481 nm): [dye]/% w/w: ● ~ 0.02, ● ~ 0.1, ■ ~ 0.1 extended to 200 % 530 nm 650 nm

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Excimers as Molecular Probes Melt Processing of Blends Polymer Dye Extrusion Polymers: LLDPE, PP; Film thickness ~100 m; Dye focus 0.01 – 0.40 % w/w

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Melt-Processed BCMBD/LLDPE Blends Properties PL spectra of crisply extinguished LLDPE/BCMDB mix movies: [dye]/% w/w: ( — ) 0.01, ( — ) ~0.05, ( — ) ~0.1, ( — ) ~0.20, ( — ) ~0.40

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Melt-Processed BCMBD/LLDPE Blends Properties PL spectra of LLDPE/BCMDB mix film ( ~ 0.18 % w/w) Influence of molding at room temperature: Polym. Mater. Sci. Eng. 2003 , In Press.

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Melt-Processed Blends Phase Behavior

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Melt-Processed BCMBD/LLDPE Blends Conditioning PL spectra of a LLDPE/BCMDB mix film ( ~ 0.18 % w/w) before/in the wake of molding at room temperature: PL spectra of a LLDPE/BCMDB mix film ( ~ 0.18 % w/w) before/in the wake of molding at room temperature:

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Melt-Processed Blends Mechanical Deformation PL spectra of an adapted LLDPE/BCMDB mix film ( ~ 0.18 % w/w) before/after disfigurement to l = (l-l 0 )/l 0 = 300 % PL spectra of a molded LLDPE/BCMB mix film ( ~ 0.18 % w/w) before/after misshapening to l = (l-l 0 )/l 0 = 300 %

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Excimers as Molecular Probes Application Anti - Tampering Films Security Features/Brand Protection Integrated Failure Indicators - Protective Gear - Load-bearing Structures - Adhesives . . .

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AB Feedblock Extruder An Extruder B Melt Pump B Melt Pump A Multipliers Exit Die Cross-Section of Layer Multiplier Flow Direction Layer Multiplier Functional Multilayer Films Process of Multilayering E. Baer et al. Preparing and Properties of Polymer Microlayered Systems in Polymer Process Engineering 97 ; Coates, P.D. Ed.; The Institute of Materials, London:1997, 137-157.

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n 1 n 2 n 1 n 2 Functional Multilayer Films Reflective Films with substituting layers of two polymers of various refractive files are profoundly intelligent.

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n 1 n 1 n 2 n 2/n 3/n 2 n 1 n 1 n 2 n 2/n 3/n 2 n 1 n 1 Functional Multilayer Films Photoreactive Films A B C Incorporation of photoreactive components in intelligent multilayer movies Multilayer movies with rotating "inactive" and "photoreactive" layers Exposure of movies changes RI of exchange photoreactive layers By specifically uncovering certain ranges of a film to UV radiation, examples can be created because of the RI change in substitute layers Low-cost, tuneable optical components (dielectric mirrors, security highlights,… )

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Functional Multilayer Films Photoreactive Films Polymers utilized for photoreactive multilayer movies Photodimerization response of cinnamic corrosive Cinnamic corrosive dimerizes in a 2+2 cycloaddition response to shape truxillic corrosive upon introduction to high-vitality UV light ( λ = 278 nm) Upon dimerization the refractive record is lessened from 1.555 to 1.523

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Effect of piece on T g Phase Behavior of PMMA-CA Blends T g of mixes abatements with grouping of CA  CA has a plasticizing impact on PMMA Homogeneous blends of PMMA-CA are acquired up to a centralization of 20% CA w/w

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Photoreaction Photophysical Behavior of PMMA-CA Blends Change of the UV retention range of a PMMA-CA mix upon presentation to a 100 W air-cooled Hg light (higher power)

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Refractive Index Photophysical Behavior of PMMA-CA Blends RI of mixes increments directly with organization RI of mixes reductions upon introduction to UV; The relative RI change increments with the convergence of CA

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PMMA/PMMA-CA Photopatterning of Multilayer Films PMMA/PMMA multilayer film PMMA-CA solid film 100 µ m PMMA/PMMA-CA (15 % w/w) 1024 layers, d = 50 nm US Prov. Appl. documented

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PC/PMMA-BZPO Photopatterning of Multilayer Films PC/PMMA-BZPO (0.1 % w/w) 1024 layers, d = 75 nm J. Mater. Chem. 2002 , 12 , 2620-2626 .

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New Concepts Functional Multilayer Films < 5 nm Orientation Integration of PL colors in reflecting cavity: Optically invigorated lasing? "Constrained gathering" of PL colors: Spatially determined (polarizing) vitality exchange "Constrained get together" of p-and n-sort polymer semiconductors: Efficient charge detachment?

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Conclusions Functional Polymer Blends The mixing of "inactive" network polymers with minor measures of "dynamic" visitor particles speaks to an alluring, general idea for the outline of practical polymer frameworks. Sufficient portrayal and control of supramolecular structures – at different levels – is vital.

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Acknowledgments CWRU Weder Group CWRU Macro Science Brent Crenshaw Ximei Sun Dr. Eric Baer Akshay Kokil Ravisubash Tangirala Dr. Anne Hiltner Christian Huber Eric Hittinger Dr. Christiane L öwe Dr. Christoph Kocher CWRU Physics Dr. Michael Schroers Dr. Quinghui Chu Dr. Kenneth Singer ETHZ Materials ETHZ Chemistry Dr. Cees Bastiaansen Dr. Bert Hecht Dr. Walter Caseri Dr. Alois Renn Dr. Christoph Kocher Dr. Werner Trabesinger Dr. Andrea Montali Prof. Urs Wild Dr. Anja Palmans Dr. Paul Smith Dr. Theo Tervoort Funding 3M Nontenured Faculty Award National Science Foundation DMR-0215342 DuPont Aid to Education Grant Sumitomo Bakelite Co. DuPont Young Professor Grant The Goodyear Tire and Rubber Company Hayes Foundation Equipment Grant The Petroleum Research Foundation Landqart Co.

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