WO2018236785A1 - Procédé de formation de nanostructures d'oxyde métallique de grande superficie et ses applications - Google Patents

Procédé de formation de nanostructures d'oxyde métallique de grande superficie et ses applications Download PDF

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WO2018236785A1
WO2018236785A1 PCT/US2018/038165 US2018038165W WO2018236785A1 WO 2018236785 A1 WO2018236785 A1 WO 2018236785A1 US 2018038165 W US2018038165 W US 2018038165W WO 2018236785 A1 WO2018236785 A1 WO 2018236785A1
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metallic material
hot water
metal oxide
metallic
nano
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Tansel Karabacak
Nawzat Saeed Saadi
Laylan Bapper Hassan
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Board Of Trustees Of The University Of Arkansas
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/80—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/10—Oxidising
    • C23C8/16—Oxidising using oxygen-containing compounds, e.g. water, carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/02—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/04—Treatment of selected surface areas, e.g. using masks
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/40—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/40—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions
    • C23C8/42—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions only one element being applied

Definitions

  • the invention relates generally to nanomaterials, and more particularly, to method of forming high surface area metal oxide nano structures by a hot water process and applications of the same.
  • One of the objectives of this invention is to develop a hot water process nanostructure growth mechanism for forming a high surface area metal oxide on almost any given metallic substrate.
  • the hot water process can form nano structured metal oxides on different types of metals and their alloys/compounds.
  • the invention relates to a method of forming metal oxide nano structures on a metallic material, comprising applying a hot water process to the metallic material, which includes treating the metallic material with hot water under a treatment condition for a period of time so as to form metal oxide nano structures on a surface of the metallic material, where the treated metallic material with metal oxide nano structures under the hot water process has a high surface area that is higher than its pristine surface area of the metallic material.
  • the hot water is a liquid phase of water, a gas phase of water, or a combination thereof.
  • the hot water is stirred at various flow patterns, flown at a direction, or in the steam applied at an angle relative to the surface of the metallic material.
  • the hot water comprises a type of water with different levels of purity, resistivity, dissolved oxygen, or mineral content.
  • the metallic material comprises one or more metallic compositions including elemental metals, alloys, compounds, a combination thereof, or a combination of metallic and non-metallic materials.
  • the metallic material comprises a one-dimensional (ID), two- dimensional (2D), or three-dimensional (3D) metallic material.
  • ID metallic material has a fiber, wire or rod geometry
  • 2D metallic material has a plate, foil or thin film geometry
  • 3D metallic material has a powder, pipe, mesh or foam geometry.
  • the metallic material is in a form of substrate being electrically charged or neutral.
  • the treatment condition comprises a temperature in a variety of ranges such that the hot water is liquid water at ambient temperatures, warm water below boiling point, boiling water, or steam at much higher temperatures.
  • the treatment condition further comprises a variety of environmental pressures including different atmospheric pressures at different altitudes and high or low pressures achieved in a special container, and a variety of dissolved oxygen levels.
  • the method further comprises controlling the treatment condition to determine sizes, morphology, stoichiometry, composition, and phase of the metal oxide nano structures.
  • the phase of the metal oxides nano structures comprises thermally stable stoichiometric oxides and hydroxides.
  • the step of treating the metallic material with the hot water comprises immersing the metallic material the hot water, or applying a steam of the hot water at the metallic material.
  • the step of treating the metallic material with the hot water is assisted by external physical and chemical factors including radiation, applied electric or magnetic fields, mechanical vibrations, and chemical additives.
  • the radiation includes microwave, laser, ultraviolet and infrared light
  • the chemical additives include metal salt and metal salt solution.
  • the method further comprises heating the water, the metallic material, or both of them.
  • the method further comprises activating the surface of the metallic material with a pretreatment physical method and/or a pretreatment chemical method so as to enhance formation kinetics of the metal oxide nano structures during the hot water process.
  • the pretreatment chemical method includes acid dipping, or plasma exposure
  • the pretreatment physical method includes roughening the surface of the metallic material by polishing, abrasive blasting, and/or a mechanical erosion process.
  • the method further comprises, prior to the step of treating the metallic material with the hot water, performing surface patterning and/or roughening on the metallic material, so as to form a hierarchically micro-nano-structured metallic material with a surface area that is substantially higher than the high surface area of the treated metallic material.
  • the hot water process produces a solution containing metal oxide molecules, useable for other purposes in addition to metal oxide nanostructure growth.
  • the invention relates to a nano structured metallic material formed by the above method.
  • the invention in yet another aspect, relates to a method of depositing metal oxide nano structures on a target material, comprising applying a hot water process to a source metallic material and the target material, which includes treating the source metallic material and the target material with hot water under a treatment condition for a period of time so as to form metal oxide nano structures on a surface of the target material.
  • the source metallic material comprises one or more metallic compositions including elemental metals, alloys, compounds, a combination thereof, or a combination of metallic and non- metallic materials.
  • the target material is a non-metallic material, a metallic material, or a combination thereof.
  • the step of treating the source metallic material with the hot water comprises immersing the source metallic material and the target material in the hot water.
  • the step of treating the source metallic material with the hot water is assisted by external physical and chemical factors including radiation, applied electric or magnetic fields, mechanical vibrations, and chemical additives.
  • the radiation includes microwave, laser, ultraviolet and infrared light
  • the chemical additives include metal salt and metal salt solution.
  • the method further comprises activating the surface of the target material with a pretreatment physical method and/or a pretreatment chemical method so as to enhance formation kinetics of the metal oxide nano structures during the hot water process.
  • the pretreatment chemical method includes acid dipping, or plasma exposure
  • the pretreatment physical method includes roughening the surface of the metallic material by polishing, abrasive blasting, and/or a mechanical erosion process.
  • the method further comprises, prior to the step of treating the source metallic material with the hot water, performing surface patterning and/or roughening on the target material, so as to form a hierarchically micro-nano-structured metallic material with a surface area that is substantially higher than the high surface area of the treated target material.
  • the hot water process produces a solution containing metal oxide molecules, useable for other purposes in addition to metal oxide nanostructure growth.
  • the formation of the metal oxide nano structures on the surface of the target material metal comprises metal oxide formation on a surface of source metallic material, release of metal oxide molecules from the source metallic material, migration of the metal oxide molecules through water, and deposition of the metal oxide molecules on the surface of the target material, and surface diffusion of the metal oxide molecules so as to form the metal oxide nano structures with smooth crystal facets on the surface of the target material.
  • FIG. 1A shows schematically a hot water process utilized to produce high surface area metal oxide nano structures according to one embodiment of the present invention.
  • FIG. IB shows schematically a hot water process utilized to produce high surface area metal oxide nano structures according to another embodiment of the present invention.
  • FIG. 1C shows nano structured morphology by the hot water process according to one embodiment of the present invention, where the SEM image of Zn metal after the hot water process shows the formation of nano structures.
  • FIGS. 2A-2D show SEM images of several metals after the hot water process according to embodiments of the present invention, which show the formation of nano structures.
  • FIGS. 3A-3B show AFM topography and roughness values for flat-control (FIG. 3 A) and hot water processed nano-rough Cu substrate (FIG. 3B) according to embodiments of the present invention.
  • FIGS. 4A-4B show schematically a hot water process and steps involved in the formation of MONSTRs according to embodiments of the present invention.
  • FIG. 4A shows the hot water process and the metal oxide formation during the hot water process at metal/water interface
  • FIG. 4B shows steps involved in the formation of MONSTR during the hot water process.
  • the nanostructure formation mechanism includes "plugging" and surface diffusion.
  • FIG. 5 shows schematically the steps of 'plugging' and surface diffusion in MONSTRs formation by the hot water process as metal oxide nano structures deposition method according to embodiments of the present invention.
  • FIG. 6 shows schematically a sandblasting and a hot water process utilized to produce hierarchical micro-nano-structures of high surface areas according to one embodiment of the present invention.
  • FIGS. 7A-7H show SEM images of several metals after the sandblasting and the hot water process according to embodiments of the present invention, which show the formation of hierarchical micro-nanostructures. These metals have been chosen for demonstration purposes; and hierarchical surface fabrication by the sandblasting and the hot water process can apply to a wide variety of metallic materials.
  • FIG. 8 shows schematically a sandblasting and a hot water process utilized to produce hierarchical micro-nano-structures of high surface areas according to another embodiment of the present invention.
  • FIGS. 9A-9D show SEM images of several metals after the sandblasting and the hot water process according to embodiments of the present invention, which show the formation of hierarchical micro-nanostructures. These metals have been chosen for demonstration purposes; and hierarchical surface fabrication by the sandblasting and the hot water process can apply to a wide variety of metallic materials.
  • FIGS. 10A-10D show schematically a flowchart of fabricating patterned micro- nano structures using the sandblasting and the hot water process according to one embodiment of the present invention.
  • FIGS. 11 A- l lC show schematically nano structured morphology of a metal substrate after the hot water process, micro structured morphology of a metal substrate after sandblasting, and hierarchical micro-nano-structured surfaces fabricated by the sandblasting and the hot water process, respectively, according to embodiments of the present invention.
  • first, second, third etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer or section from another element, component, region, layer or section. Thus, a first element, component, region, layer or section discussed below could be termed a second element, component, region, layer or section without departing from the teachings of the invention.
  • relative terms such as “lower” or “bottom” and “upper” or “top,” may be used herein to describe one element's relationship to another element as illustrated in the figures. It will be understood that relative terms are intended to encompass different orientations of the device in addition to the orientation depicted in the figures. For example, if the device in one of the figures is turned over, elements described as being on the “lower” side of other elements would then be oriented on “upper” sides of the other elements. The exemplary term “lower”, can therefore, encompasses both an orientation of “lower” and “upper,” depending of the particular orientation of the figure.
  • the phrase "at least one of A, B, and C" should be construed to mean a logical (A or B or C), using a non-exclusive logical OR.
  • high surface area material refers to the material after the treatments according to this invention having “higher surface area” compared to its starting
  • a nano structured metal oxide layer formed on the surface of a metal foam will increase the overall surface area of the metal foam and make it even a higher surface area of the metallic materials.
  • Another example can be a metal plate having small nano structures grown on its surface, which will also have a "higher" surface area compared to the starting flat topography of the metal plate.
  • the term "metallic materials" for the hot water process is not limited to specific chemical compositions such as elemental metals, alloys, compounds or any combination of them, or a combination of metallic and none-metallic materials or any physical dimension such as sheet, foil, plate, mesh and powder.
  • the term also includes an ionic compound that can be formed by the neutralization reaction of an acid and a base, or composed of numbers of cations and anions so that the product is electrically neutral such as metals salt and metal salt solutions.
  • a combination of metal salt or metal salt solution with other elemental metals, alloys, compounds or any combination of them, or a combination of metallic and none-metallic materials is covered by the term "metallic materials”.
  • hot water refers to water having a temperature higher than the freezing temperature of water.
  • the hot water can be in a liquid phase of water, a gas phase of water, or a combination thereof.
  • the description below is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses.
  • the broad teachings of the invention can be implemented in a variety of forms. Therefore, while this invention includes particular examples, the true scope of the invention should not be so limited since other modifications will become apparent upon a study of the drawings, the specification, and the following claims.
  • the same reference numbers will be used in the drawings to identify similar elements. It should be understood that one or more steps within a method may be executed in different order (or concurrently) without altering the principles of the invention.
  • Nano structured metallic materials offer the advantage of having high surface-to-volume ratios, which allows the maximum utilization of atoms to be positioned on the surface instead of in the bulk of a metallic material.
  • a nano structured catalyst can reach superior chemical activity due to the active participation of catalyst atoms available at the high surface provided.
  • hierarchical micro-nano- structured metallic materials which are composed of micronized features with nanostructures, possess not only the high surface area and activity of nano materials, but also the structural stability and robustness of the bulk material. Thus, they combine the advantages of both nano structured and bulk metallic materials.
  • hierarchical micro-nano-structured metallic materials can achieve even higher surface areas compared to a nano structured surface alone.
  • this invention relates to methods of producing high surface area metal oxide materials by using simple, low-cost, scalable, high-throughput, and eco-friendly hot water process.
  • the approach operates in low-temperature and does not require any special environments/steps such as vacuum, acidic, alkaline solutions, or lithographical processing.
  • the high surface area metal oxide materials produced by the hot water process include a nano structured metal oxide layer on a base metal.
  • the methods are applicable to a wide variety of metallic materials including elemental, alloy, or compound metals or combination of them with other non-metallic materials.
  • the methods are applicable to almost any geometry including ID (e.g., wire, rod), 2D (e.g., plate, foil, thin film), and 3D (e.g., powder, pipe, mesh, and foam) metallic materials.
  • the hot water process is a metal oxide nanostructure (MONSTR) growth technique that results in materials with a high surface area by introducing nano scale surface roughness.
  • the process involving reaction between hot water (deionized (DI), distilled, or purified) and metallic materials surface.
  • DI deionized
  • This invention utilizes the principle of oxidizing the metallic surface and their respond to hot water to form metal oxides.
  • MONSTRs metal oxide nano structures
  • the nanoscale dimension of metal oxide features grew on the surface by these processes considered as physical modification which introduce surface roughness after the treatment processes. Because metal oxides formed by these processes have different chemical properties from the surface of the base metal, it undergoes the chemical modification.
  • these process results in physical and chemical surface modifications on the metal surface that can be utilized in several applications.
  • the growth of MONSTRs on a surface results in the development of rough surface that is in nanoscale (nano roughness), thus increasing the surface area of the treated materials comparing to the starting surface of the materials.
  • the fabrication of metal oxide can take place at either relatively low water temperature (e.g., between 50-95 C) for liquid water at atmospheric pressure conditions) or at higher temperatures when steam (gas phase of water) is used instead of liquid water. Notwithstanding of the used methods, the treated surface is covered with nano structures that increase the surface area.
  • Hot water processed-metals form metal oxide surfaces with features in the nanoscale (nano structured metal oxide) approximately in the range of 25-500 nm on top of the base metal surface.
  • the geometry and size of nano structures depend on treatment conditions, such as treatment time, water temperature, dissolved oxygen (DO) in water, and the initial surface roughness of the metal.
  • Nano structures formed by hot water process provide significantly higher surface areas compared to a pristine metal.
  • the process has mainly been used to fabricate metal oxide thin films, e.g., MgO, ZnO, CuO, and AI 2 O 3 [1-6].
  • the hot water process is a simple and eco-friendly technique. Since no complicated fabrication processes are involved in the hot water process, such as the need for vacuum environment or plasma, the process is low-cost, scalable, and high-throughput. With almost no restrictions on metal types and their compounds, e.g., alloys or composites, or their geometry, e.g., ID, 2D or 3D, the process promises an ideal technique to fabricate metallic materials with high surface areas for several applications.
  • water with high resistivity, low conductivity, and high purity is preferred.
  • water of poorer qualities of these properties such as mineral water or even water from lakes, rivers, and sea can be used to practice the invention.
  • FIGS. 1A and IB show the hot water process according to two different embodiments of the invention, respectively.
  • a base metal substrate is disposed in hot water, which involves a reaction between metals and water, such as deionized (DI), distilled, or purified, at temperatures higher than room temperature (usually between 50-95 C).
  • DI deionized
  • the hot water process results in metal oxide surfaces with features in the nanoscale (nano structured metal oxide) approximately in the range of 25-500 nm on top of the base metal surface.
  • the geometry and size of nano structures depend on treatment conditions such as treatment time, water temperature, dissolved oxygen (DO) in water, and also the initial surface roughness of the base metal substrate. Nano structures formed by the hot water treatment provide significantly higher surface areas compared to a pristine metal.
  • the hot water process does not involve any chemicals, such as surfactants, reductants, oxidation agents, additives or any byproducts, and also takes place at relativity low temperatures, the hot water process is a simple and eco-friendly technique. Since no complicated fabrication processes are involved in the hot water process, such as the need for vacuum environment or plasma, the process is low-cost, scalable, and high- throughput.
  • a metal substrate is treated with steam (gas phase) of water.
  • Steam treatment can effectively form high surface area metal oxide nano structures on a base metal.
  • FIG. 1A which is limited to the maximum boiling temperature of water
  • water is delivered to the metal surface in the form of vapor that can acquire almost any temperature. Higher temperatures of the steam can allow much faster nanostructure formation kinetics.
  • Steam also does not require the use high purity or DI water. Regular tap water can be evaporated to produce a steam that is free from impurities.
  • mechanisms of the hot water process include the effects of dissolved oxygen, which enhances metal oxide nanostructure formation.
  • molecular oxygen from ambient environment can be easily incorporated to the steam that further increases the nanostructure formation kinetics.
  • the steam treatment can allow spatial control on nano structuring and easy patterning. For example, using a beam of steam coming out of nozzle, one can do the steam treatment on select regions of a given metal and form a heterogeneous pattern incorporating untreated metal and the steam treated metal oxide nano structures.
  • the steam treatment has all the advantages and similar nano structures formed on the surface of the metal substrate under the hot water treatment shown in FIG. 1A.
  • the surface of a given metal substrate reacts with water at temperatures higher than room temperature to form high surface
  • nano structured metal oxides In order to introduce a nano structured layer onto a metal surface, a native oxide layer and potential contamination on the surface are removed, which can enhance the reactions during hot water process. This is followed by a cleaning process such as ultrasonicating the samples first with acetone, isopropanol, and then DI water cleaned metallic materials are then followed by the hot water process. Treatment time may vary depending on the metal. In certain embodiments, it ranges between a couple of minutes up to several hours. The morphology and porosity of the nano structured layer on a metal can be tuned by varying the process time (from a few minutes up to several hours). FIGS.
  • FIGS. 3A-3B show the AFM topography and roughness values for control (pristine Cu) and nano structured surfaces and a similar morphology of Cu sample (FIG. 2A) can be observed.
  • R a 97 nm (FIG. 3B).
  • a hot water process is used to generate high surface area nano structured metal oxides.
  • the process is facile, low-cost, scalable, and eco-friendly.
  • the mechanisms of nanostructure formation on metal surfaces to produce high surface nano structured materials are the same process involving water-metal reaction.
  • FIG. 4A illustrates the steps of MONSTR formation during the hot water process according to the invention.
  • the first step involves the formation of metal oxide molecules on the surface of a metallic substrate ("1- Metal oxide" shown in FIG.
  • FIG. 4B which follows a reaction similar to the steps of metal oxide film formation described above (FIG. 4A).
  • metal oxide molecules can diffuse on the surface. However, the surface diffusion is not believed to be the dominant mechanism that explains the nano structure formation at the relatively low temperature conditions.
  • a more likely next step is a dissolution-precipitation process called "plugging” [36] that has been used to describe the corrosion of metals. It involves the release of the metal oxide molecule ("2- Release”) from the surface into the liquid followed by transportation through water (“3- Migration”) and precipitation (“4- Re-deposition”) onto another surface position. Re- deposited molecules can initiate the formation of isolated nano structures.
  • the random nature of plugging might not be sufficient to explain smooth crystalline surfaces observed in hot water process nano structures.
  • the re-deposited metal oxide molecules can diffuse on the surface, which may help in forming smooth individual nano structures observed in the SEM images of FIGS. 2A-2D.
  • the release step can become easier and make the plugging process more dominant.
  • such plugging process can lead to the formation of fractal- like rough nano structures.
  • initial substrate surface chemistry can play a critical role in the nucleation of metal oxide nano structures.
  • metal oxide molecules may preferentially stick to defect sites, e.g., voids or grain boundaries with dangling bonds, which can act as nucleation regions. Migration and re-deposition may also depend on external factors such as liquid flow patterns, substrate morphology, mechanical vibrations, or even external magnetic and electric fields.
  • defect sites e.g., voids or grain boundaries with dangling bonds
  • Migration and re-deposition may also depend on external factors such as liquid flow patterns, substrate morphology, mechanical vibrations, or even external magnetic and electric fields.
  • several factors can enhance the formation of metal oxide nano structures and speed-up the reaction between water-metal. Such factors can incorporate the kinetics and dynamics of the hot water process.
  • the factors such as the concentration of reactants, temperature, pressure, the physical state of reactants and their dispersion, the water, and the presence of a catalyst, may influence the reaction rates of chemical reactions in the hot water process.
  • the hot water process can be enhanced by the assist of thermal effects of radiations, such as microwave, laser, and Infrared (IR) radiation, named as an assisted hot water treatment.
  • radiations such as microwave, laser, and Infrared (IR) radiation
  • the assisted-hot water processes can be achieved by physical factors such as the enhancements generate from radiation, applying electric or magnetic fields, the presence of mechanical factors. Radiation-assisted (such as microwave-assisted) processing attracted a great deal of attention due to its advantages to supply higher synthesis rate, resulting superior to traditional heating. The ability to elevate the temperature of a reaction above the boiling point of the solution increases the speed of reactions by a factor of 10-1000. In certain embodiments, the typical hot water process is performed in temperatures higher room
  • the hot water process may take several hours for most metals to forms metal oxide nano structures.
  • the steam treatment can speed up the formation of metal oxide nano structures.
  • the microwave-assisted hot water process can also speed up the synthesis of metal oxide
  • the synthesis of metal oxide nano structures for metals is completed in minutes or even seconds.
  • radiations of different wavelengths such as ultraviolet (UV), laser, and infrared (IR)
  • UV ultraviolet
  • IR infrared
  • UV ultraviolet
  • IR infrared
  • the radiation reaction with water-metal results in increasing of the thermal conditions of the process, and thus increases the kinetic of metal oxide synthesis.
  • an electric or magnetic field voltage may also be applied in speeding up the fabrication process.
  • the chemical conditions at which the hot water process performs can also enhance the formation MONSTRs.
  • the hot water process only water and metallic materials surface are usually involved in the process to synthesize metal oxide nano structures.
  • several chemical conditions such as the presence of chemical additives in the process can enhance the kinetics and dynamics of the hot water process.
  • Metal salts additive can speed-up the MONSTR formation since the metal salts results in increasing the rate of metal cation in the process, thus higher metal oxide rate formation.
  • Nano structure formation kinetics can be enhanced by activating the surface with pretreatment methods such as acid dipping (e.g., HF, HCL, and HN0 3 ) or plasma exposure.
  • pretreatment methods such as acid dipping (e.g., HF, HCL, and HN0 3 ) or plasma exposure.
  • Chemically modified metallic surfaces can incorporate higher number of metal ions that can speed up the fabrication process.
  • physical pretreated surface such as roughened surface mechanically or chemically can enhance the MONSTRs formation in the hot water process.
  • the hot water process can be used to deposit a large variety of MONSTR materials on almost any type of substrate material or geometry.
  • the hot water process simply involves a source metallic material and a target substrate that are both immersed into hot water.
  • a growth mechanism that includes the processes of "plugging" and surface diffusion, as shown in FIG. 5. The plugging involves the steps of metal oxide formation on metal- source surface, release of metal oxide molecules from the source, migration through water, and deposition on the target surface. This is followed by surface diffusion of metal oxide molecules that help forming MONSTRs with smooth crystal facets.
  • hierarchical topographies that incorporate multi-scale features with different sizes can further increase the surface area beyond one can achieve with single-length-scale structures.
  • Two-tier hierarchical roughness with micro- and nano-scale components is an ideal example of high surface area materials.
  • an abrasive blasting process such as sandblasting (SB) is used to fabricate micro-scale features.
  • Sandblasting is used for a wide variety of purposes like smoothing a rough surface, roughening a smooth surface, shaping a surface, and removing surface contaminants.
  • Sandblasting involves a stream of abrasive material propelled against a surface under high pressure.
  • the contact area is plastically deformed due to the high compressive and shear stresses involved.
  • the large tensile stress produced by sandblasting due to the impact results in lateral cracks on material surface causing material removal. Based on material removal rates, surfaces get rougher due to micro-structures being formed.
  • micro-scale features typically enhance the roughness formation up to a certain limit.
  • Such simple technique can be effectively used to form materials with micro-scale features of surface area higher than that of the starting material.
  • the features are not in very regular shapes or sizes, which can be controlled by masking the surface and blasting time during the sandblasting process, the micro-sized features can effectively serve as the bases of hierarchical micro-nano-structures with a high surface area.
  • a combination of the SB process and the hot water process is used to fabricate metallic materials with hierarchical micro-nano-structures that acquire superior surface areas compared to either of a micro-rough surface by the SB process or a nano-rough by the hot water process alone.
  • the SB process is a facile, low-cost, environment-friendly, robust, and scalable surface processing method.
  • the combination of the SB process and the hot water process is still a simple and low-cost fabrication process that combine the advantages of both nano structured and bulk metallic materials, which gives the metallic materials not only the high surface area and activity of nano materials, but also the structural stability and robustness of the bulk.
  • a clean metal surface is first sandblasted with abrasive particles followed by the hot water treatment to obtain a hierarchical, micro-nano- structured surface.
  • the sandblasting step is used to engrave the metallic materials surface and gain micro-sized features (micro-structures).
  • the size and geometry of micro-structures can be controlled typically in the range of few to tens of micrometers by changing the abrasive particle size and shape.
  • a variety of micro structures of different lateral sizes and depth that the abrasive digs into the surface
  • the micro-rough metal surface is cleaned using conventional chemical cleaning processes (e.g., with acetone, isopropanol, and then DI water each for 5 min then dried by N 2 gas) to remove the sandblasting residuals and potential contamination on the surface.
  • a clean sandblasted metal surface is then immersed in hot DI water for the hot water treatment, which is described above.
  • the hot water treatment introduces a nano structured roughness onto the previously imparted micro-structures, which results in a hierarchical micro- nano-roughness of higher surface area than that of the micro -structured surface.
  • FIGS. 7A-7H SEM images of different metals processed by the sandblasting and the hot water treatment to form surfaces with hierarchical micro-nano-structured structures with high surface areas are shown in FIGS. 7A-7H.
  • Cu, Al, Zn and Pb metal substrates were sandblasted and then exposed to hot water for 24hrs, 10 min, 2 hrs and 15 min, respectively.
  • the SEM images show the surfaces gained hierarchical micro-nano scaled features compare to pristine metal surface.
  • FIGS. 7 A, 7C, 7E, and 7H show the micro-structures of the hierarchical surfaces formed by the sandblasting for Cu, Al, Zn and Pb metal substrates, respectively.
  • 7B, 7D, 7F, and 7G show that the micro -structured SB metal surfaces have nano structures formed on the top of micro-structures after the hot water treatment for Cu, Al, Zn and Pb metal substrates, respectively, which also show different shapes and size of metal oxides for different metals formed after the hot water treatment, e.g., nanoplates, nanograss, nanorods, and thick nanoplates for Cu, Al, Zn and Pb, respectively.
  • the sandblasting can also be combined with the steam treatment to fabricate metallic materials with hierarchical micro-nano-structures of superior surface areas compared to either a micro-rough surface by the sandblasting or a nano-rough by the steam treatment alone.
  • a sandblasted surface of high surface area can easily gain more surface area and have the activity of nanomaterials when it is combined with the steam treatment. The successful combination of the sandblasting and the steam treatment makes the fabrication of hierarchical surface even simpler and lower cost.
  • a clean metal substrate is first sandblasted with abrasive particles to produce a micro -structured surface of the metal substrate.
  • FIGS. 9A-9D show the fabrication of hierarchical micro-nano-structured surfaces of high surface areas by the sandblasting and the steam treatment, where FIGS. 9A and 9C show the micro-structures of the hierarchical structured surface by the sandblasting for Mg and Zn, respectively, and FIGS. 9B and 9D show the nano-scaled metal oxide nano structures (MgO and ZnO) of the high surface areas formed by the steam treatment for Mg and Zn, respectively.
  • the sandblasting and the hot water process can be further extended to generating patterned surfaces incorporating micro-nano-rough regions of different height.
  • FIGS. 10A-10D illustrate the process of using the sandblasting and the hot water process to form plateaus and valleys of hierarchical roughness.
  • a shadow mask e.g., a pre-patterned piece of metal with openings that abrasive particles can pass through, is placed on the top of the metallic material before the sandblasting in order to introduce a desired pattern of micro-rough valleys with smooth plateaus (FIGS. 10A-10B).
  • the shadow mask is removed and the whole surface is gently sandblasted for a short amount of time in order to introduce a micro-roughness to the plateaus that were shadowed under the mask (FIG. IOC). Then, the sample can go through the hot water process that results in a hierarchically micro- nano-rough patterned surface (FIG. 10D).
  • FIG. 10D One skilled in the art would appreciate that other types of patterning strategies can also be used to fabricate hierarchically rough surfaces of different patterns by the sandblasting and the hot water process.
  • High surface area materials can serve either as an active material or support for others to attain enhanced chemical and physical properties.
  • Materials with high surface-to-volume ratios can utilize most of the atoms positioned on the surface that can increase a wide range of properties such as catalysis, adhesion, mass transport, electronic conductivity, and optical absorption.
  • the hot water process can be used can be used effectively to fabricate nano structured materials of high surface-to-volume ratios that can lead to an increase in the surface areas, as schematically shown in FIG. 11 A.
  • the interaction of liquid water or vapor (steam) with a metallic material at high temperatures leads to the formation of metal oxide nano-structures and hence significantly increases the surface area.
  • the sandblasting can be successfully used to engrave the material surface and form features in micro-scale, as schematically shown in FIG. 11B, which can further increase the surface area or serve as a template for applications sensitive to micro-features. Therefore, to generate high surface area hierarchical micro-nano-structured materials, a metallic material is first engraved with micro-structures by the sandblasting. Then, the hot water process can be used to pair the base micro-structures with metal oxide nano structures that lead to superior high surface area materials, as schematically shown in FIG. 11C. The resultant material of hierarchical micro-nano-structures owns higher surface areas compared to the initial flat surface or a surface with only nano structures.
  • the methods described above are applicable to a wide variety of metallic materials including elemental, alloy, or compound metals or combination of them with other non-metallic materials.
  • the methods are applicable to almost any geometry including ID (e.g., wire, rod), 2D (e.g., plate, foil, thin film), and 3D (e.g., powder, pipe, mesh, and foam) metallic materials.
  • High surface area materials are desired for numerous applications such as catalysis, photonics, optical devices, energy storage, sensors, cooling systems, drinking water generation from air, water production for agriculture, self-cleaning surfaces, semiconductor devices, cooling systems, drinking water generation from air, water production for agriculture, self-cleaning surfaces, semiconductor devices and biotechnology.
  • Increased surface area can drastically enhance chemical and physical properties that can improve the functionality, productivity, and permanence of those applications. The following is a few pf examples of such potential applications.
  • Nano structured materials can be used to control surface wettability.
  • a surface with hydrophilic (water-attracting) properties can be tuned to become superhydrophilic when nano structures are imparted on the surface [37].
  • a nano structured material can attain superhydrophobicity (highly water-repellant) when coated with low- surface-energy layers. All the models explaining the wetting behavior of liquids on rough surfaces incorporate surface area as a critical parameter. Overall, the higher the surface area is, the more hydrophilic or hydrophobic the material gets [38].
  • such a control on the surface wettability can be used in anti- fouling surfaces acting as protectors against the adhesion of unwanted biological species to the hull of boats, ships, or to off-shore platforms.
  • Superhydrophobic surfaces can also impart self-cleaning properties, especially useful on everyday products like home appliances, paint, or clothes.
  • Another example of the application of hydrophilic/hydrophobic surfaces is in devices that function based on heat-transfer between a liquid and solid surface such as heat-pipes and heat-sinks.
  • anti-fogging and anti- freezing properties can also be introduced by generating high surface area hydrophobic materials by the methods described above.
  • Photocatalyst materials can initiate chemical reactions such as the production of hydrogen and oxygen through water splitting or killing harmful biological species for water purification with the absorption of light and corresponding oxidation/reduction reactions.
  • Metal oxide semiconducting materials like titanium oxide and tungsten oxide are few examples of oxide photocatalyst materials. Therefore, introducing nano- roughness or hierarchical micro-nano-roughness to such oxides using the methods described above can increase their surface area and therefore significantly enhance the catalyst activity, which is directly proportional to the exposed surface area to the external environment. In addition, rough surface can increase the optical absorption that can further enhance photocatalyst activity. Overall, high surface area metal oxide photocatalyst materials of this invention can lead to higher reaction rates and functional efficiency.
  • High-response sensors Most gas sensors rely on chemical reactions taking place at their surface. Therefore, having high surface area metal oxides can offer opportunities for advanced sensors with enhanced response even to minute amounts of external stimulus.
  • a gas sensor incorporating zinc oxide nano structures made by HWT or ST can provide enhanced sensitivity over a wide range of dynamic response to gasses like C0 2 , CO, S0 2 , 0 2 , 0 3 , H 2 , Ar, N 2 , NH 3 .
  • most of the conduction electrons are trapped in the surface states. Therefore, due to the high surface to volume ratio of nanostructures, these electrons can be helped to achieve enhanced response for surface reactions.
  • Hierarchical micro- nano-structures of this invention can further increase such sensor activity due to their enhanced surface area.
  • Advanced storage devices Batteries and capacitors are few of the most commonly known examples of electrochemical energy storage devices.
  • Several state-of-the-art and advanced battery and capacitor materials utilize metal oxides as active electrodes. Therefore, high surface area metal oxide electrodes of this invention can provide enhanced electrochemical reaction rates that can significantly improve energy storage in such applications.
  • Li- ion batteries involve cathode materials made of metal oxides like cobalt oxide and vanadium oxide, which can be engineered to have nano- or micro-nano-morphologies using the methods of this invention. Having high surface area can help increase the electrochemical reactions for lithium ions during charging/discharging and therefore improve charge storage.
  • porous nature of the nano structured and micro-nano-structured cathode surface can enhance the mechanical durability of the electrode against volumetric changes in the electrode due to charging/discharging.
  • capacitors made of high surface area materials such as nickel oxide nano structures or micro-nano-structures using the methods of this invention can significantly enhance double layer formation at the solid/liquid interface and therefore increase the faradaic charge storage.
  • Optoelectronic devices include optical-to-electrical or electrical- to-optical response in their operation.
  • this invention can produce high surface area semiconducting metal oxides for energy conversion applications such as solar cells.
  • Modern solar cell devices that are under development can incorporate p- or n-type metal oxides (e.g., copper oxide as p-type or zinc oxide as n-type) that act as critical components in converting solar energy to electricity.
  • Nano structured semiconducting materials can offer the advantage of smaller dimensions with higher interface that can allow the development of core-shell type nano structured solar cells. Such geometry can enhance both light trapping and charge carrier collection and significantly improve the solar cell efficiency.
  • a photodetector which is another example of an optoelectronic device, can benefit from the similar nano structured metal oxide geometry explained for solar cells and produce superior photo-response.
  • the invention relates to a method of forming metal oxide nano structures on a metallic material, comprising applying a hot water process to the metallic material, which includes treating the metallic material with hot water under a treatment condition for a period of time so as to form metal oxide nano structures on a surface of the metallic material, where the treated metallic material with metal oxide nano structures under the hot water process has a high surface area that is higher than its pristine surface area of the metallic material.
  • the hot water is a liquid phase of water, a gas phase of water, or a combination thereof.
  • the hot water is stirred at various flow patterns, flown at a direction, or in the steam applied at an angle relative to the surface of the metallic material.
  • the hot water comprises a type of water with different levels of purity, resistivity, dissolved oxygen, or mineral content.
  • the metallic material comprises one or more metallic compositions including elemental metals, alloys, compounds, a combination thereof, or a combination of metallic and non-metallic materials.
  • the metallic material comprises a one-dimensional (ID), two- dimensional (2D), or three-dimensional (3D) metallic material.
  • ID metallic material has a fiber, wire or rod geometry
  • 2D metallic material has a plate, foil or thin film geometry
  • 3D metallic material has a powder, pipe, mesh or foam geometry.
  • the metallic material is in a form of substrate being electrically charged or neutral.
  • the treatment condition comprises a temperature in a variety of ranges such that the hot water is liquid water at ambient temperatures, warm water below boiling point, boiling water, or steam at much higher temperatures.
  • the treatment condition further comprises a variety of environmental pressures including different atmospheric pressures at different altitudes and high or low pressures achieved in a special container, and a variety of dissolved oxygen levels.
  • the method further comprises controlling the treatment condition to determine sizes, morphology, stoichiometry, composition, and phase of the metal oxide nano structures.
  • the phase of the metal oxides nano structures comprises thermally stable stoichiometric oxides and hydroxides.
  • the step of treating the metallic material with the hot water comprises immersing the metallic material the hot water, or applying a steam of the hot water at the metallic material.
  • the step of treating the metallic material with the hot water is assisted by external physical and chemical factors including radiation, applied electric or magnetic fields, mechanical vibrations, and chemical additives.
  • the radiation includes microwave, laser, ultraviolet and infrared light
  • the chemical additives include metal salt and metal salt solution.
  • the method further comprises heating the water, the metallic material, or both of them.
  • the method further comprises activating the surface of the metallic material with a pretreatment physical method and/or a pretreatment chemical method so as to enhance formation kinetics of the metal oxide nano structures during the hot water process.
  • the pretreatment chemical method includes acid dipping, or plasma exposure
  • the pretreatment physical method includes roughening the surface of the metallic material by polishing, abrasive blasting, and/or a mechanical erosion process.
  • the method further comprises, prior to the step of treating the metallic material with the hot water, performing surface patterning and/or roughening on the metallic material, so as to form a hierarchically micro-nano-structured metallic material with a surface area that is substantially higher than the high surface area of the treated metallic material.
  • the hot water process produces a solution containing metal oxide molecules, useable for other purposes in addition to metal oxide nanostructure growth.
  • the invention relates to a nano structured metallic material formed by the above method.
  • the invention in yet another aspect, relates to a method of depositing metal oxide nano structures on a target material, comprising applying a hot water process to a source metallic material and the target material, which includes treating the source metallic material and the target material with hot water under a treatment condition for a period of time so as to form metal oxide nano structures on a surface of the target material.
  • the source metallic material comprises one or more metallic compositions including elemental metals, alloys, compounds, a combination thereof, or a combination of metallic and non- metallic materials.
  • the target material is a non-metallic material, a metallic material, or a combination thereof.
  • the step of treating the source metallic material with the hot water comprises immersing the source metallic material and the target material in the hot water.
  • the step of treating the source metallic material with the hot water is assisted by external physical and chemical factors including radiation, applied electric or magnetic fields, mechanical vibrations, and chemical additives.
  • the radiation includes microwave, laser, ultraviolet and infrared light
  • the chemical additives include metal salt and metal salt solution.
  • the method further comprises activating the surface of the target material with a pretreatment physical method and/or a pretreatment chemical method so as to enhance formation kinetics of the metal oxide nano structures during the hot water process.
  • the pretreatment chemical method includes acid dipping, or plasma exposure
  • the pretreatment physical method includes roughening the surface of the metallic material by polishing, abrasive blasting, and/or a mechanical erosion process.
  • the method further comprises, prior to the step of treating the source metallic material with the hot water, performing surface patterning and/or roughening on the target material, so as to form a hierarchically micro-nano-structured metallic material with a surface area that is substantially higher than the high surface area of the treated target material.
  • the hot water process produces a solution containing metal oxide molecules, useable for other purposes in addition to metal oxide nanostructure growth.
  • the formation of the metal oxide nano structures on the surface of the target material metal comprises metal oxide formation on a surface of source metallic material, release of metal oxide molecules from the source metallic material, migration of the metal oxide molecules through water, and deposition of the metal oxide molecules on the surface of the target material, and surface diffusion of the metal oxide molecules so as to form the metal oxide nano structures with smooth crystal facets on the surface of the target material.
  • Khedir R Khedir, Z.S.S., TahaDemirkan, Rosure B. Abdulrahman, and TanselKarabacak Growth of ZnONanorod and Nano flower Structures by Facile Treatment of Zinc Thin Films in Boiling De-Ionized Water. Nano Communications, in-print.

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Abstract

Cette invention concerne un procédé de formation de nanostructures d'oxyde métallique sur un matériau métallique, comprenant l'application d'un traitement à l'eau chaude au matériau métallique, qui comprend le traitement du matériau métallique avec de l'eau chaude sous une condition de traitement pendant une période de temps de façon à former des nanostructures d'oxyde métallique sur une surface du matériau métallique, le matériau métallique traité avec des nanostructures d'oxyde métallique par le traitement à l'eau chaude ayant une grande superficie qui est supérieure à la superficie vierge du matériau métallique. L'invention concerne en outre un procédé de dépôt de nanostructures d'oxyde métallique sur un matériau cible, comprenant l'application d'un traitement à l'eau chaude à un matériau métallique source et au matériau cible, qui comprend le traitement du matériau métallique source et du matériau cible avec de l'eau chaude sous une condition de traitement pendant une période de temps de façon à former des nanostructures d'oxyde métallique sur une surface du matériau cible.
PCT/US2018/038165 2017-06-20 2018-06-19 Procédé de formation de nanostructures d'oxyde métallique de grande superficie et ses applications WO2018236785A1 (fr)

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