WO2012075309A1 - Systèmes et procédés d'assemblage couche par couche à pulvérisation en rotation - Google Patents

Systèmes et procédés d'assemblage couche par couche à pulvérisation en rotation Download PDF

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Publication number
WO2012075309A1
WO2012075309A1 PCT/US2011/062919 US2011062919W WO2012075309A1 WO 2012075309 A1 WO2012075309 A1 WO 2012075309A1 US 2011062919 W US2011062919 W US 2011062919W WO 2012075309 A1 WO2012075309 A1 WO 2012075309A1
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Prior art keywords
layer
substrate
disc
spinning
nozzle
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PCT/US2011/062919
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English (en)
Inventor
Andre D. Taylor
David Kohn
Forrest Gittleson
Xiaokai Li
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Yale University
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Publication of WO2012075309A1 publication Critical patent/WO2012075309A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
    • H01M8/1013—Other direct alcohol fuel cells [DAFC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/08—Fuel cells with aqueous electrolytes
    • H01M8/083—Alkaline fuel cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/002—Processes for applying liquids or other fluent materials the substrate being rotated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • B05D1/38—Successively applying liquids or other fluent materials, e.g. without intermediate treatment with intermediate treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
    • B05D3/0406—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases the gas being air
    • B05D3/0413—Heating with air
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present disclosure is directed to systems and methods for efficiently and effectively undertaking layer-by-layer assembly of nanostructures.
  • the present disclosure further relates to advantageous apparatus/systems for layer-by-layer assembly and processing modalities that achieve high quality nanostructures in a more time effective manner.
  • Layer-by-layer (LBL) assembly has emerged out of a range of disciplines including biology, chemistry, chemical engineering, materials science, mechanical engineering, electrical engineering, and applied physics. This interdisciplinary area is promising for a wide variety of industries, especially for energy conversion and storage (e.g., fuel cells, solar cells and batteries).
  • layer-by-layer assembly techniques are not limited in potential applicability to energy/storage; rather, there are diverse applications in other industries/technologies, e.g., the pharmaceutical industry (e.g., to achieve desired time release parameters), defense industry applications, membrane separation technologies, sensor technology, etc.
  • FIG. 1 shows a schematic illustration of cycle times for a conventional dipping LBL assembly process for a PEO PAA film.
  • the film stays in contact with the polyelectrolyte solutions and rinsing fluids for sufficiently long periods of time to achieve a thermodynamic equilibrium at each stage.
  • the cycle time for a conventional dipping LBL process is 26 minutes or 45 hours for a 100 bilayer film.
  • the amount of the material deposited onto the substrate is thus determined by the adsorption/desorption equilibrium conditions. Exploration of integrative membrane-electrode assembly methods as well as a comprehensive assessment of materials for DAFCs is critical for rapid nanomanufacturing and transformative progress in this field.
  • the present disclosure provides a spin spray layer-by-layer apparatus/system and associated processing methods/techniques that advantageously reduce traditional layer-by-layer processing times by 2-3 orders of magnitude.
  • the disclosed spin spray layer-by-layer (SSLBL) assembly
  • apparatus/system and associated method offer an integrated approach to the formation of self- assembled polyelectrolyte composites.
  • Exemplary embodiments of the disclosed apparatus/system utilize a plurality of atomizing nozzles to deliver desired constituents, e.g., polyanionic and polycationic polymer systems, to a spinning substrate.
  • the disclosed apparatus/system also advantageously delivers rinse fluid, e.g., from one or more separate atomizing nozzles, between constituent delivery.
  • a source of heat is also generally provided so as to control/promote drying of individual layers.
  • fixed volume water based processing may be performed to generate alkaline direct alcohol fuel cells (e.g., methanol and ethanol).
  • the disclosed apparatus/systems and associated methods may also be employed to generate a range of fuel cell systems (e.g., hydrogen, hydrazine, or other hydrocarbons) and composite applications (e.g., drug delivery, solar cells and the like).
  • the disclosed spray spin layer-by- layer assembly apparatus/systems and associated methods may be used to generate ultra thin (submicron) films, e.g., through the alteration of polyanionic and polycationic polymer systems. These molecular level blends would be difficult to achieve using conventional means of fabricating materials composites.
  • Assembly and processing parameters may be selected according to the present disclosure to achieve desired results, e.g., parameters such as polyelectrolyte selection, ionic strength, pH, and solution concentration (nanocolloids and poiyions) may be varied to nanomanufacture a series of functional thin film membranes with tunable porosity, strength, and conductivity.
  • parameters such as polyelectrolyte selection, ionic strength, pH, and solution concentration (nanocolloids and poiyions) may be varied to nanomanufacture a series of functional thin film membranes with tunable porosity, strength, and conductivity.
  • a system for layer-by-layer assembly of a thin film, catalyst, and/or membrane includes a spinning substrate, atomizing nozzles, and a heat source.
  • the atomizing nozzles are directed to the spinning substrate.
  • Each of the nozzles are in communication with a source of fluid.
  • the heat source directed to the spinning substrate for delivering heat energy to the spinning substrate.
  • a method for layer-by-layer assembly of a thin film, catalyst, membrane includes providing a plurality of atomizing nozzles and a spinning disc or substrate, delivering constituents to the spinning disc or substrate from the plurality of atomizing nozzles in an alternating sequence so as to form a product in a layer-by-layer manner, and delivering heat energy to the spinning disc or substrate so as to influence the drying cycle of the product on a layer-by- layer basis.
  • a system for layer-by-layer assembly of a thin film, catalyst, or membrane includes a spinning disc; a first nozzle, a second nozzle, and a control system.
  • the first nozzle is directed to the spinning disc and is in communication with a first polyelectrolyte.
  • a first solenoid controls ejection of the first polyelectrolyte from the first nozzle.
  • the second nozzle is directed to the spinning disc and is in communication with a second polyelectrolyte.
  • a second solenoid controls ejection of the second polyelectrolyte from the second nozzle.
  • the control system operates the first and second solenoids to control a quantity of the first and second polyelectrolytes being disposed on the disc and further controls a speed at which the spinning disc rotates.
  • the disclosed spray spin layer-by-layer assembly apparatus/system and associated method may be employed to achieve material properties that are comparable ⁇ if not superior ⁇ to traditional layer- by-layer films with the added advantages of high throughput and increased material utilization.
  • Thin film materials assembled according to the present disclosure may be used to generate thicker (e.g., 10 ⁇ ) freestanding catalyst layers having substantial industrial utility.
  • the cycle time for the SSLBL process can be about 2 seconds (e.g., about 3 minutes for a 100 bilayer or about 30 minutes for a free standing 1000 bilayer film).
  • FIG. 1A shows a schematic illustration of cycle times for a conventional dipping LBL assembly process for a PEO/PAA film.
  • FIG. IB shows a schematic illustration of cycle times for a spray spin LBL assembly process for a PEO/PAA film.
  • FIG. 2 is a schematic illustration of an exemplary SSLBL apparatus/system according to the present disclosure in which atomized droplets form a lamella phase are spread across the top of a rotating substrate.
  • Various polyelectrol te conformations are dependent on solution conditions.
  • FIGS. 3 and 4 are additional schematic illustrations of exemplary SSLBL apparatus/systems according to the present disclosure.
  • FIG. 5 provides plots of the angular evolution of a rod-like particle tumbling in shear flow in a parallel-wall channel as calculated using applicable algorithms. In particular, evolution of linear chains of spears undergoing tumbling motion in a parallel wall channel are shown.
  • FIG. 6 provides SEM images comparing a traditional polyethylene oxide/polyacrlylic acid (PEO/PAA) LBL film to an SSLBL film with similar striation patterns. Insets -100-bilayer LBL film, 1000 bilayer SSLBL. Fabrication times as set forth in FIGS. I A and IB.
  • PEO/PAA polyethylene oxide/polyacrlylic acid
  • Exemplary embodiments of the SSLBL apparatus/system and related methods can use an aqueous based processing technique.
  • the aqueous based processing technique can utilize a fixed volume electrostatic assembly.
  • LBL layer-by-layer assembly involves repeated, sequential exposure of a substrate to one or more constituents.
  • catalyst development for direct alcohol fuel cells has been generally elusive. This can be attributed to the high cost and poor utilization of the materials used in developing these catalysts. The majority of the cost typically arises from the precious metal based catalysts (i.e., Platinum,
  • Supported metal particles on carbon nanotubes offer advantages over traditional carbon black materials due to improved access to triple phase boundary regions, higher electrical conductivity of the support, and electrochemical stability. It has been demonstrated that these nanocolloids can be dispersed with functional polyelectroiytes to create freestanding films via LBL assembly. While these films exhibited an order of magnitude higher Pt utilization compared to conventional catalysts, diffusion limited LBL construction of these films required 5 days of continuous processing according to conventional LBL techniques.
  • exemplary embodiments of the present disclosure can be implemented in various fields of technology.
  • applications of exemplary embodiments of the SSLBL apparatus/systems can range from sensors to electrochemical devices to biomedical applications or to organic electronics.
  • Using the disclosed apparatus/sy stems and associated methods to rapidly generate LBL assemblies it is possible to effectively study a range of issues/parameters, e.g., the interactions of new nanocolloids with new polyelectrolyte LBL systems. In this way, a fundamental understanding can be developed on how these materials can be strategically arranged to control film conductivity, porosity, and morphology.
  • the interfacial fuel cell catalyst materials for this study are particularly interesting because similar interfacial challenges are being investigated for solar cells, batteries, water purification, or ion selective membranes.
  • an exemplary SSLBL apparatus/system 100 according to the present disclosure is depicted that offers several elements of control that could be advantageous for film growth, including solution volume, flow rate, concentration, and rinse.
  • apparatus/system 100 includes a plurality of atomizing nozzles:
  • Nozzle 110 which is in communication with a supply of polyelectrolyte 1 12 and is adapted to deliver atomized droplets 1 14 of polyelectrolyte to a centrally located spinning disc/substrate 102;
  • Nozzle 120 which is in communication with a supply of deionized water 122 (i.e., rinse solution) and is adapted to deliver atomized droplets of DI water to the centrally located spinning disc/substrate 102; and
  • Nozzle 130 which is in communication with a supply of polyelectrolyte 132 and is adapted to deliver atomized droplets of polyelectrolyte to the centrally located spinning disc/substrate 102.
  • the exemplary SSLBL apparatus/system 100 of FIG. 2 shows three nozzles 1 10, 120, 130, but the present disclosure is not limited to the disclosed arrangement. Rather, a greater number of nozzles may be provided, e.g., if it is desired to introduce more than two constituents to the LBL assembly. In addition, elimination of the "rinse" nozzle 120 may be feasible, e.g., if each constituent layer is permitted and/or induced to form a layer of desired thickness and to sufficiently dry prior to delivery of the next constituent layer.
  • a heat source 140 e.g., a blower for delivery of heated air/gas to the substrate surface may be advantageously included in the exemplary apparatus/system.
  • the source of heat could be adapted to deliver heat to the substrate surface at predetermined times and for predetermined periods of time, or may be adapted to deliver heat to the substrate surface on a continuous basis.
  • the disc/substrate 102 is adapted to spin to establish desired shear forces and to facilitate formation of distinct layers 104 of desired thickness on the disc/substrate 102.
  • the sprayed droplets are dispersed substantially uniformly across the disc/substrate surface (or atop the previously deposited layer) and any excess material is removed from the disc/substrate 102 through applicable centrifugal forces.
  • the spin rate, cycle time for atomization nozzle operations, solution concentrations, constituent selection, and temperature/flow rate of the heat source are among the variables that may be controlled to achieve desired LBL assembly using the disclosed SSLBL apparatus/system 100 and associated methods.
  • the timing of the rinse application during hydration of the underlying film could affect the bond between the recently deposited materials with the underlying layer. If the film is too dry, this could allow too much entanglement, preventing the removal of the excess material, thus again affecting the quality of the film.
  • Operation of the nozzles 110, 120, 130 is generally controlled by solenoid valves 116, 126, 128, respectively, that are, in turn, controlled by a processor 162 of a control system 160 that is programmed to control the cycle time and cycle sequence of droplet delivery to the spinning disc/substrate 102. Additionally, the heat source 140 and rotation of the substrate/disc 102 can be controlled by the processor 162.
  • the apparatus/system is generally designed for automated control, whereby variables such as cycle time, rinse time, spinning speed, hot air temperature and/or flow rate, are controlled by the programmed processor.
  • the processing variables may be modified with ease, thereby allowing rapid modification of operating conditions to achieve desired results.
  • the apparatus/system 200 includes three spaced atomizing nozzles 210, 220, 230 positioned above and pointed at a centrally located disc/substrate region 202.
  • the nozzles 210, 220, 230 are in communication with discrete sources of materials 212, 222, 232, respectively, and may be repositioned, as desired, to ensure accurate delivery of atomized droplets to the spinning disc/substrate 202.
  • a motor (not shown) can drive rotation of the
  • disc/substrate 202 can be positioned below the base of the apparatus housing 250.
  • a heat source (not shown) is generally positioned above the disc/substrate to deliver heated air/gas to the disc/substrate 202 so as to enhance drying of individual layers, e.g., a hot air blower.
  • the operation of the atomizing nozzles 210, 220, 230 is generally controlled by solenoid valves that are, in turn, controlled by a processor that is programmed to control the cycle time and cycle sequence of droplet delivery to the spinning disc/substrate 202.
  • the apparatus/system 200 is generally designed for automated control, whereby variables such as cycle time, rinse time, spinning speed, hot air temperature and/or flow rate, are controlled by the programmed processor.
  • the processing variables may be modified with ease, thereby allowing rapid modification of operating conditions to achieve desired results.
  • the concentration and volume of constituent delivery from each atomizing nozzle may be advantageously selected so as to deliver only so much material as is necessary to form the desired layer thickness on the disc/substrate.
  • the disclosed SSLBL apparatus/system 100 and/or 200 and associated methods dramatically increase the efficiency of the LBL process by minimizing material waste.
  • the disclosed SSLBL significantly increases the speed with which LBL assembly is achieved relative to previous LBL systems/techniques.
  • Exemplary embodiments of the systems 100, 200 provide an integrated approach to the formation of self-assembled polyelectrolyte composites by utilizing, for example, an atomized fixed volume water based processing method such that ultrathin (e.g., submicron) films having molecular level blends are generated through the alteration of polyanionic and polycationic polymer systems
  • ultrathin e.g., submicron
  • DAFCs Direct Alcohol Fuel Cells.
  • liquid fuels have attracted enormous attention as power sources for portable electronic devices and fuel -cell vehicles due to the much higher energy density of liquid fuels than gaseous fuels such as hydrogen.
  • gaseous fuels such as hydrogen.
  • ethanol is particularly attractive because it is less toxic than methanol, is readily available, and can be produced from renewable sources (i.e., biofuel).
  • alkaline fuel cells can have faster kinetics associated with the oxygen reduction reaction and can be implemented using less expensive non-precious metals, such as silver catalysts and/or perovskite type oxides.
  • Alkaline Fuel Cells One of the challenges with alkaline fuel cells is the need to prevent the formation of carbonates created at the anode by the reaction of OH " with the CO and/or C0 2 resulting from the electro-oxidation reaction. These salt precipitates (i.e., Na 2 C0 3 or K 2 C0 3 , depending on the electrolyte chemistry) would greatly decrease the power and long term performance of the alkaline cells by fouling the electrode catalysts and blocking the pores of the electrolyte. Previous methods used to circumvent this issue required the use of very expensive ultra pure hydrogen and oxygen.
  • AEM Anion Exchange Membrane
  • Catalyst Layer One of the most desirable properties of an ionomer for use in the catalyst layer is high water solubility and a low boiling point (such as ethanol and (n- or 2-) propanol), due to ease of handling and removal during electrode preparation.
  • a low boiling point such as ethanol and (n- or 2-) propanol
  • the mechanical properties (hence durability) of the films are penalized.
  • the pore sizes of the films are too large due to increased swelling, fuel crossover of polar molecules becomes an issue.
  • the disclosed SSLBL apparatus/systems and associated methods offer advantageous opportunities to address the limitations described above with respect to the highlighted potential applications, e.g., by utilizing polyelectrolyte complexation to generate highly stable ionically conductive media for hydroxide ion transport through the membrane and catalyst layer.
  • Polyelectrolyte multilayer assembly typically involves the formation of thin films through the alternating adsorption of positively and negatively charged polymer species under ambient conditions.
  • the disclosed SSLBL method allows the fine-tuning of polyanions and polycations to create ionically crosslinked continuous films.
  • the disclosed SSLBL methods also have utility for microelectrochemical devices, including organic solar cells and battery applications. Recent work in this area has been focused on hydrogen fuel cells, particularly in the formation of the catalyst layers that incorporate high performance nanostructured materials. According to the present disclosure, this nanoscale blend approach to the formation of ultrathin functional nano-assemblies using SSLBL permits development of high performance nanomaterial catalysts and permits such nanomaterials to be incorporated into an alkaline direct ethanol fuel cell architecture.
  • the apparatus/systems and associated methods of the present disclosure may be used to develop (i) high performance nanomaterial catalysts that are active for ethanol oxidation and oxygen reduction in alkali mediums, e.g., by decorating carbon nanotubes and nanofibers with selected transition metals using supercritical fluids, (ii) rapid nanomanufacturing of high performance nanomaterials and polyelectrolyte polymers into functional thin film catalyst layers, such rapid manufacturing benefiting from swift film growth, precise use of materials, materials in one cycle are not dependent on the specific composition of previous cycles, and increased flexibility of layered films built with different materials in different layers, and (iii) variation of polycationic basic polymers with polyanions coupled with nanocolloids to create a new generation of high performance functional thin films.
  • Film growth modulation can be achieved by changing a variety of deposition parameters, such as solution pH, salt content, rinse times, and drying times.
  • the disclosed SSLBL process involves many parameters (e.g., the delivered amount of material, flow strength, and drying time), which control not only the time required to produce a nanocomposite film, but also affect the film microstructure and macroscopic properties.
  • parameters e.g., the delivered amount of material, flow strength, and drying time
  • a fundamental understanding of physical phenomena that govern the growth dynamics and the microstructure of the film are desired. Modeling efforts may be employed to gain a better understanding of these issues, e.g., (i) hydrodynamic modeling of the drying liquid layer on the spinning disk; (ii) an analysis of the effect of the fluid flow on the deposition process; and (iii) an investigation of the effect of layer adsorption conditions on the properties of the LBL films.
  • hydrodynamic modeling of the spin/dry process may aid development of the optimal SSLBL protocol by directly evaluating the amount of material retained in the film after the completion of a given spray/spin/dry step. Determination of the time-dependent concentration profile in the fluid film covering the spinning substrate is also valuable. Information obtained from such calculations may be used to establish which key factors control the properties of the nanocomposite film. For example, the role of the amount of material deposited in each step, deposition time, concentration of the solution, and the flow rate during the deposition process may be ascertained. The dynamics of a layer of the polyelectrolyte solution on the spinning disk may be determined using lubrication approximation.
  • FIG. 5 provides plots of the angular evolution of a rod-like particle tumbling in shear flow in a parallel-wall channel as calculated using applicable algorithms.
  • evolution of linear chains of spears undergoing tumbling motion in a parallel wall channel are shown.
  • the upper graph shows normalized period of motion versus distance from a channel wall for different chain lengths N.
  • the lower graph shows evolution of the orientation of the chain.
  • a set of numerical simulations of the dynamics of macromolecules and nanotubes in shear flow in the presence of a planar substrate may be performed.
  • the nanotubes may be modeled as linear conglomerates of spheres. It has been shown that such models faithfully capture hydrodynamic interactions of rod-like particles.
  • hydrodynamic interactions between the particles and the substrate may be described applying Cartesian-representation algorithms. Using such algorithms, the angular evolution of a rod-like particle tumbling in shear flow in a parallel-wall channel has been established, as illustrated in FIG. 3.
  • the nanotubes may be solubilized using PSS or Nafion polyelectrolyte.
  • nanotube-polyelectrolyte complexes may be described using a coarse-grained bead-spring model for the polyelectrolyte and a rigid chain of spheres for the nanotube.
  • the orientational evolution of nanotube-polyelectrolyte complexes in shear flow may be investigated in the presence of a planar substrate.
  • adsorption of such complexes on the substrate may be studied.
  • Numerical simulations allow an assessment of feasibility of fabrication of nanostructured films with nanotubes aligned by the flow, e.g., for potential photovoltaic and nanoelectronic applications.
  • PEO/PAA Oxide/Polyacrylic Acid

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Abstract

La présente invention concerne un appareil/système et un procédé associé pour la formation de matériaux couche par couche, comprenant un disque ou substrat en rotation, une pluralité de buses d'atomisation dirigées vers le disque ou le substrat en rotation, chaque buse de la pluralité de buse étant en communication avec une source de fluide, et une source de chaleur dirigée vers le disque ou le substrat en rotation pour libérer une énergie thermique vers le disque ou le substrat en rotation. L'appareil/système de l'invention et le procédé associés possèdent des applications industrielles et de recherche étendues, et augmentent fortement la vitesse de formation des matériaux LBL (couche par couche).
PCT/US2011/062919 2010-12-01 2011-12-01 Systèmes et procédés d'assemblage couche par couche à pulvérisation en rotation WO2012075309A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014043286A1 (fr) * 2012-09-17 2014-03-20 Svaya Nanotechnologies, Inc. Procédés, matériaux et appareil permettant d'améliorer le réglage et l'efficacité de processus de dépôt couche par couche
US9393589B2 (en) 2011-02-15 2016-07-19 Eastman Chemical Company Methods and materials for functional polyionic species and deposition thereof
US9395475B2 (en) 2011-10-07 2016-07-19 Eastman Chemical Company Broadband solar control film
US9453949B2 (en) 2014-12-15 2016-09-27 Eastman Chemical Company Electromagnetic energy-absorbing optical product and method for making
US9817166B2 (en) 2014-12-15 2017-11-14 Eastman Chemical Company Electromagnetic energy-absorbing optical product and method for making
CN107639848A (zh) * 2017-10-28 2018-01-30 南京汇龙橡胶制品有限公司 一种橡胶制品搭接的截断注胶装置
US9891347B2 (en) 2014-12-15 2018-02-13 Eastman Chemical Company Electromagnetic energy-absorbing optical product and method for making
US9891357B2 (en) 2014-12-15 2018-02-13 Eastman Chemical Company Electromagnetic energy-absorbing optical product and method for making
EP3502346A1 (fr) * 2017-12-19 2019-06-26 Centre National De La Recherche Scientifique Procédé de préparation de films assemblés sur des textiles tissés et non tissés, sur des papiers ou sur des objets perméables souples par pulverisation et centrifugation à l'interieur un tambour perforé en rotation
US10338287B2 (en) 2017-08-29 2019-07-02 Southwall Technologies Inc. Infrared-rejecting optical products having pigmented coatings
WO2019136160A1 (fr) 2018-01-04 2019-07-11 Massachusetts Institute Of Technology Particules stabilisées par micronutriments hydrosolubles et liposolubles avec barrière de polymère entérique
US10613261B2 (en) 2018-04-09 2020-04-07 Southwall Technologies Inc. Selective light-blocking optical products having a neutral reflection
US10627555B2 (en) 2018-04-09 2020-04-21 Southwall Technologies Inc. Selective light-blocking optical products having a neutral reflection
WO2021079106A1 (fr) 2019-10-24 2021-04-29 University Of Newcastle Upon Tyne Procédé et appareil pour la fabrication de couches minces
KR20210097376A (ko) * 2020-01-30 2021-08-09 주식회사 한국농산식품 농산물 또는 포장재 내피에 코팅막을 형성하는 방법
EP3956335A4 (fr) * 2019-04-18 2022-12-28 North Carolina State University Revêtements de substrat, systèmes, procédés et techniques
US11541017B2 (en) 2013-12-16 2023-01-03 Massachusetts Institute Of Technology Fortified micronutrient salt formulations
US11747532B2 (en) 2017-09-15 2023-09-05 Southwall Technologies Inc. Laminated optical products and methods of making them

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5942035A (en) * 1993-03-25 1999-08-24 Tokyo Electron Limited Solvent and resist spin coating apparatus
US20050076831A1 (en) * 2001-05-30 2005-04-14 Allen Gilliard Method and apparatus for applying a coating to an ophthalmic lens
US20100003499A1 (en) * 2006-09-08 2010-01-07 Krogman Kevin C Automated layer by layer spray technology
US20100062155A1 (en) * 2007-04-11 2010-03-11 Yukitoshi Tajima Spin coater, temperature controlling method of the same, optical disc production apparatus, and optical disc production method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5942035A (en) * 1993-03-25 1999-08-24 Tokyo Electron Limited Solvent and resist spin coating apparatus
US20050076831A1 (en) * 2001-05-30 2005-04-14 Allen Gilliard Method and apparatus for applying a coating to an ophthalmic lens
US20100003499A1 (en) * 2006-09-08 2010-01-07 Krogman Kevin C Automated layer by layer spray technology
US20100062155A1 (en) * 2007-04-11 2010-03-11 Yukitoshi Tajima Spin coater, temperature controlling method of the same, optical disc production apparatus, and optical disc production method

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9393589B2 (en) 2011-02-15 2016-07-19 Eastman Chemical Company Methods and materials for functional polyionic species and deposition thereof
US9395475B2 (en) 2011-10-07 2016-07-19 Eastman Chemical Company Broadband solar control film
RU2659525C2 (ru) * 2012-09-17 2018-07-02 Истман Кемикал Компани Способы, материалы и устройство для улучшения управляемости и эффективности послойных процессов
CN104704145A (zh) * 2012-09-17 2015-06-10 伊士曼化工公司 用于提高叠层过程的控制和效率的方法、材料和设备
US9387505B2 (en) 2012-09-17 2016-07-12 Eastman Chemical Company Methods, materials and apparatus for improving control and efficiency of layer-by-layer processes
WO2014043286A1 (fr) * 2012-09-17 2014-03-20 Svaya Nanotechnologies, Inc. Procédés, matériaux et appareil permettant d'améliorer le réglage et l'efficacité de processus de dépôt couche par couche
US11541017B2 (en) 2013-12-16 2023-01-03 Massachusetts Institute Of Technology Fortified micronutrient salt formulations
US9453949B2 (en) 2014-12-15 2016-09-27 Eastman Chemical Company Electromagnetic energy-absorbing optical product and method for making
US9817166B2 (en) 2014-12-15 2017-11-14 Eastman Chemical Company Electromagnetic energy-absorbing optical product and method for making
US9891357B2 (en) 2014-12-15 2018-02-13 Eastman Chemical Company Electromagnetic energy-absorbing optical product and method for making
US9891347B2 (en) 2014-12-15 2018-02-13 Eastman Chemical Company Electromagnetic energy-absorbing optical product and method for making
US10338287B2 (en) 2017-08-29 2019-07-02 Southwall Technologies Inc. Infrared-rejecting optical products having pigmented coatings
US11747532B2 (en) 2017-09-15 2023-09-05 Southwall Technologies Inc. Laminated optical products and methods of making them
CN107639848A (zh) * 2017-10-28 2018-01-30 南京汇龙橡胶制品有限公司 一种橡胶制品搭接的截断注胶装置
EP3502346A1 (fr) * 2017-12-19 2019-06-26 Centre National De La Recherche Scientifique Procédé de préparation de films assemblés sur des textiles tissés et non tissés, sur des papiers ou sur des objets perméables souples par pulverisation et centrifugation à l'interieur un tambour perforé en rotation
WO2019136160A1 (fr) 2018-01-04 2019-07-11 Massachusetts Institute Of Technology Particules stabilisées par micronutriments hydrosolubles et liposolubles avec barrière de polymère entérique
US10613261B2 (en) 2018-04-09 2020-04-07 Southwall Technologies Inc. Selective light-blocking optical products having a neutral reflection
US10627555B2 (en) 2018-04-09 2020-04-21 Southwall Technologies Inc. Selective light-blocking optical products having a neutral reflection
EP3956335A4 (fr) * 2019-04-18 2022-12-28 North Carolina State University Revêtements de substrat, systèmes, procédés et techniques
WO2021079106A1 (fr) 2019-10-24 2021-04-29 University Of Newcastle Upon Tyne Procédé et appareil pour la fabrication de couches minces
KR20210097376A (ko) * 2020-01-30 2021-08-09 주식회사 한국농산식품 농산물 또는 포장재 내피에 코팅막을 형성하는 방법
KR102391440B1 (ko) * 2020-01-30 2022-04-27 양상일 농산물 또는 포장재 내피에 코팅막을 형성하는 방법

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