Luận án tiến sĩ: Công nghệ đồng đùn nanolớp polymer - Nghiên cứu cơ bản và ứng dụng

FUNDAMENTAL AND APPLIED RESEARCH ENABLED BY POLYMER NANOLAYER COEXTRUSION TECHNOLOGY by YI JIN Submitted in partial fulfillment of the requirements For the degree of Doctor of Philosophy Dissertation Advisers: Dr. Anne Hiltner and Dr. Eric Baer Department of Macromolecular Science and Engineering CASE WESTERN RESERVE UNIVERSITY May 2007 UMI Number: 3241778 UMI Microform 3241778 Copyright 2007 by ProQuest Information and Learning Company. All rights reserved.

This microform edition is protected against unauthorized copying under Title 17, United States Code. ProQuest Information and Learning Company 300 North Zeeb Road P. Box 1346 Ann Arbor, MI 48106-1346 CASE WESTERN RESERVE UNIVERSITY SCHOOL OF GRADUATE STUDIES We hereby approve the dissertation of Yi Jin ______________________________________________________ candidate for the Ph. Anne Hiltner (signed)_______________________________________________ (chair of the committee) David Schiraldi ________________________________________________ Peter N.

Pintauro ________________________________________________ Eric Baer ________________________________________________ ________________________________________________ ________________________________________________ 12/15/06 (date) _______________________ *We also certify that written approval has been obtained for any proprietary material contained therein. To dad (金公度) and mom (程金秀) To sister (金鑫) and brother (金大祥) To husband (傅朝阳) iii TABLE OF CONTENTS Page LIST OF TABLES. vi LIST OF FIGURES. STRUCTURE OF POLYPROPYLENE CRYSTALLIZED IN CONFINED NANOLAYERS.

FORMATION AND TRANSFORMATION OF SMECTIC POLYPROPYLENE NANOPARTICLES. FRACTIONATED CRYSTALLIZATION OF POLYPROPYLENE PARTICLES PRODUCED BY NANOLAYER BREAKUP. EFFECT OF AN ORGANIC DICARBOXYLIC ACID SALT ON FRACTIONATED CRYSTALLIZATION OF POLYPROPYLENE PARTICLES. EFFECT OF A SORBITOL NUCLEATING AGENT ON FRACTIONATED CRYSTALLIZATION OF POLYPROPYLENE PARTICLES.

BIO-INSPIRED POLYMER GRIN LENSES BY NANOLAYER FORCED-ASSEMBLY. A NEW CLASS OF BIO-INSPIRED LENSES WITH GRADIENT REFRACTIVE INDEX. ACHIEVE HIGH QUALITY GRIN LENSES. SUPERIOR GRIN LENS.

226 v LIST OF TABLES Table Page 1.1 Comparison of PP layer thickness measured from AFM images with PP layer thickness calculated from processing parameters .2 Thermal properties of polypropylene in films .3 Long period measured from the SAXS pattern.1 Thermal analysis of PP nanoparticles .1 Thermal analysis of PP nanoparticles .2 Melting Enthalpies of PP particles from different PP nanolayers .1 Crystallization enthalpies of PP nanolayers.2 Crystallization enthalpies of PP particles from 12 nm layers .3 Melting enthalpies of PP particles from 12 nm layers.4 Crystallization enthalpies of PP particles from 20 nm layers .5 Crystallization enthalpies of PP particles from 40 nm layers .6 Crystallization enthalpies of PP particles from 200 nm layers .1 Melting enthalpies of PP nanolayers.2 Crystallization enthalpies of PP particles .3 Melting enthalpies of PP particles from 12 nm layers. 150 vi LIST OF FIGURES Figure Page 1.1 AFM phase images of cross-sections from layered PP/PS films: (a) PP/PS 90/10 250 μm thick film; (b) PP/PS 20/80 250 μm thick film; (c) PP/PS 10/90 250 μm thick film; and (d) PP/PS 10/90 40 μm thick film.2 Polarized light micrographs: (a) PP control film; (b) film with 460 nm PP layers; (c) film with 108 nm PP layers; (d) film with 65 nm PP layers; and (e) film with 10 nm PP layers.3 AFM height images: (a) a typical PP spherulite at a free film surface; (b) a discoid in a 460 nm PP layer; (c) a discoid in a 108 nm PP layer; (d) a discoid in a 65nm PP layer; and (e) a smooth 10 nm PP layer.4 AFM phase images showing lamellar morphology: (a) PP control film; (b) a 460 nm PP layer; (c) a 108 nm PP layer; (d) a 65 nm PP.5 SAXS patterns in the flow direction (F): (a) PP control film; (b) film with 460 nm PP layers; (c) film with 108 nm layers; (d) film with 65 nm PP layers; and (e) film with 10 nm PP layers. The transverse direction (T) is vertical and the film normal direction (N) is horizontal.6 Reflection WAXS 2θ scans of the PP control film and layered films.7 Transmission WAXS 2θ scans of the (-113) reflection of polypropylene α crystals.8 Two dimensional transmission diffraction patterns of the PP control and films with 460 nm, 108 nm, 65 nm, and 10 nm PP layers in the normal (N), transverse (T), and flow (F) directions.9 Pole figures of α crystals in films with 460 nm PP layers: (a) normals to (110) planes; (b) normals to (040) planes; and (c) normals to ( 113) planes.10 Schematic showing an edge on radial or mother lamella that nucleated at the interface with (010) planes flat on. The cross hatched lamella formed by secondary nucleation on the (010) plane.

The width of the radial lamella and the amount of cross- vii hatched overgrowth are limited by the thickness of the PP layer. In 65 nm layers and 10 nm layers, a second crystal population nucleates at the interface with (110) planes flat on.1 AFM phase images of the coextruded nanolayer assembly with 257 layers and PP/PS 10/90 (vol/vol) composition: (a) The cross- section of the layered assembly with arrows identifying the very thin PP layers; and (b) the surface of a PP nanolayer after it was exposed by peeling the layers apart.2 The WAXD curves of the coextruded PP/PS assembly, the PS control, and the PP nanolayers. The latter was obtained by weighted subtraction of the PS contribution.3 Heating thermograms of the coextruded PP/PS assembly, the PS control, and the PP nanolayers. The latter was obtained by weighted subtraction of the PS contribution.4 The PP particles formed by nanolayer beakup: (a) AFM phase image of the film cross-section; and (b) SEM image of the isolated particles.5 Thermograms of the PP/PS assembly, the PS control, and the PP nanoparticles obtained by weighted subtraction: (a) Cooling from 230 ºC at 10 ºC min -1; and (b) subsequent heating at 40 ºC min -1.6 WAXD curves of the coextruded PP/PS assembly after heating to 230 ºC for 10 min, the PS control, and the PP nanoparticles.

The latter was obtained by weighted subtraction of the PS contribution.7 Effect of annealing at various temperatures for 10 min on the WAXD pattern: (a) Before subtraction of the PS contribution; and (b) after subtraction of the PS contribution.8 Effect of annealing at various temperatures for 10 min on the heating thermogram of PP nanoparticles. The PS contribution has been subtracted.1 AFM phase images of the cross-sections from coextruded nanolayer assemblies: (a) 75 μm film with 12 nm PP layers; (b) 125 μm film with 20 nm PP layers; (c) 250 μm film with 40 nm PP layers; and (d) 1.25mm film with 200 nm PP layers .2 OM images of the particles from various layer thicknesses: (a) 12 nm layers; (b) 20 nm layers; (c) 40 nm layers; and (d) 200 nm layers.3 AFM images of the particles from various layer thicknesses: (a) from 12 nm layers; and (b) from 20 nm layers.4 Particle size distributions: (a) Submicron particles from 12 nm layers taken from AFM images; (b) large particles from 12 nm layers taken from OM images; (c) submicron particles from 20 nm layers taken from AFM images; and (d) large particles from 20 nm layers taken from OM images.5 Large particle size distribution from OM images: (a) particles from 40 nm layers; and (b) particles from 200 nm layers.6 Particle volume distributions: (a) from 12 nm layers; (b) from 20 nm layers; (c) from 40 nm layers; and (d) from 200 nm layers.7 Schematic of the envisaged layer breakup proces .8 Cooling thermograms of the PP/PS assembly after heating to 230 ºC for various PP layer thicknesses. The PS contribution was subtracted.9 Heating thermograms of the PP particles from various PP layer thicknesses after subtraction of the PS contribution.10 Dependence of crystallization enthalpy on initial layer thicknesses.11 The WAXD curves of the PP particles from various PP layer thicknesses: (a) before subtraction of the PS contribution; and (b) after subtraction of the PS contribution.12 Effect of breakup time and temperature on the crystallization thermogram of PP particles from 100 nm layers: (a) Breakup time at 230 ºC; and (b) Breakup temperature for 3 min.13 AFM phase images of the film cross section after breakup at different temperatures: (a) 3 min at 250 ºC; and (b) 3 min at 350 ºC.1 AFM images of PP with 2 % HPN after the microtomed surface was etched to remove the HPN particles.2 AFM phase images of the cross-sections from coextruded nanolayer assemblies: (a) 75 μm film with 12 nm PP layers; (a) 75 μm film with 12 nm PP layers containing 0.6 % HPN; (c) 125 μm film with 20 nm PP layers; (d) 125 μm film with 20 nm PP layers containing 0.6 % HPN; (e) 250 μm film with 40 nm PP layers; and (f) 250 μm film with 40 nm PP layers with 0.3 Heating thermograms of the coextruded nanolayer assemblies.4 OM images of the particles from: (a) 12 nm layers; (b) 12 nm layers with 1.0 % HPN; (c) 40 nm layers; (d) 40 nm layers with 1.0 % HPN; (e) 200 nm layers; and (f) 200 nm layers with 1.5 AFM images of the particles from: (a) 12 nm layers; and (b) 12 nm layers with 1.6 Particle size distributions from 12 nm layers: (a) Submicron PP particles from AFM images; (b) large PP particles from OM; (c) submicron PP particles with 1.0 % HPN from AFM; and (d) large PP particles with 1.0 % HPN from OM.7 Large particle size distributions from OM images from: (a) 40 nm PP layers; (b) 40 nm PP layers with 1.0 % HPN; (c) 200 nm PP layers; and (d) 200 nm layers with 1.8 Particle volume distributions: (a) From 12 nm layers; (b) from 12 nm layers with 1 % HPN; (c) from 40 nm layers; (d) from 40 nm with 1 % HPN; (e) from 200 nm layers; and (f) from 200 nm layers with 1 % HPN.9 Thermograms of the PP/PS assembly with 12 nm PP layers containing various concentrations of HPN after heating to 230 ºC: (a) Cooling thermograms; and (b) subsequent heating thermograms. The PS contribution was subtracted.10 The WAXD curves of the PP particles from 12 nm PP layers with various concentrations of HPN: (a) before subtraction of the PS contribution; and (b) after subtraction of the PS contribution.11 Cooling thermograms of the PP/PS assembly with various concentrations of HPN in the PP layer after heating to 230 ºC: (a) 20 nm layers; (b) 40 nm layers; and (c) 200 nm layers.

The PS contribution was subtracted.12 Comparison of the crystallization thermograms of particles from 12, 20, 40 and 200 nm layers with 1 % HPN.1 AFM phase images of the cross-sections from coextruded nanolayer assemblies: (a) 75 μm film with 12 nm PP layers; and (b) 75 μm film with 12 nm PP layers containing 1.2 Heating thermograms of the coextruded nanolayer assemblies with various concentrations of MD.3 OM images of the particles from 12 nm layers: (a) 0 % MD; (b) 0.3 % MD; and (c) 1 % MD.4 AFM images of particles from 12 nm layers: (a) 0 % MD; (b) 0. and (d) the PS control with 2.5 Particle size distributions from 12 nm layers: (a) 0 % MD; (b) 0.6 Thermograms of the PP/PS assembly with 12 nm PP layers containing various concentrations of MD after heating to 230 ºC: (a) Cooling thermograms; and (b) subsequent heating thermograms. The PS contribution was subtracted.7 The WAXD curves of the PP particles from 12 nm PP layers with various concentrations of MD: (a) before subtraction of the PS contribution; and (b) after subtraction of the PS contribution.8 Dependence of crystallization enthalpy on MD concentration.9 Schematic phase diagram for the binary system in the low MD concentration region.1 The structure of our synthetic gradient index (GRIN) lens is inspired by the layering found in the human lens.* Forced- assembly is used to create transparent films with thousands of alternating nanolayers of two polymers where the relative concentration of the polymers specifies the refractive index. The films are assembled into a GRIN material.

A method of molding and cutting the layered GRIN material introduces radial components to the index gradient and forms the biomimetic lens. *Reference 33, by permission.