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WO2018062360A1 - Procédé de fabrication d'un matériau hybride et matériau hybride - Google Patents

Procédé de fabrication d'un matériau hybride et matériau hybride Download PDF

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WO2018062360A1
WO2018062360A1 PCT/JP2017/035135 JP2017035135W WO2018062360A1 WO 2018062360 A1 WO2018062360 A1 WO 2018062360A1 JP 2017035135 W JP2017035135 W JP 2017035135W WO 2018062360 A1 WO2018062360 A1 WO 2018062360A1
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Prior art keywords
metal
ion
hydroxide
metal substrate
trivalent
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Japanese (ja)
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暁 福垣内
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Ehime University NUC
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Ehime University NUC
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Priority to JP2018542834A priority Critical patent/JP6949375B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—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
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00

Definitions

  • the present invention relates to a method for producing a hybrid material in which a layered double hydroxide classified as a kind of clay mineral is formed on the surface of a base material, and the hybrid material.
  • Layered double hydroxide is a basic layer consisting of octahedral hydroxides composed of divalent or trivalent metal ions and hydroxide ions, and an intermediate composed of anions and water. It has a structure in which layers are alternately stacked. Since LDH has anion exchange capacity, it has been conventionally used as a catalyst, an adsorbent, a filter material, a halogen scavenger for molecular materials, and the like. It is also attracting attention as a material that conducts hydroxide ions, and its use in alkaline fuel cell electrolytes and zinc-air battery catalyst layers is being studied.
  • Patent Documents 1 and 2 disclose a method of depositing LDH on the surface of a ceramic porous substrate in order to use LDH as a solid electrolyte separator of an alkaline secondary battery.
  • the porous substrate is heated under high temperature and high pressure. Is treated (hydrothermal treatment) in an aqueous solution containing a constituent element of LDH to form an LDH thin film on the surface of the porous substrate.
  • JP 2016-084263 A JP2016-084264
  • a uniform and dense LDH thin film is formed on the surface of the porous substrate by interposing a surfactant between the porous substrate and the LDH thin film.
  • the LDH thin film is only physically bonded to the surface of the porous substrate, for example, when the porous substrate and the LDH thin film expand or contract due to temperature changes, the difference in thermal expansion coefficient between the two. Therefore, the bonding surface between the porous substrate and the LHD thin film may be distorted, and the LDH thin film may be peeled off from the porous substrate. Note that the above problem is caused not only by the difference in thermal expansion coefficient between the substrate and LDH, but also by the difference in chemical resistance, the difference in rigidity, and the like.
  • the problem to be solved by the present invention is to increase the bonding strength of the boundary surface between the LDH layer and the substrate in the hybrid material composed of the substrate and the LDH layer formed on the surface thereof.
  • the manufacturing method of the hybrid material which has a layered double hydroxide layer on the surface based on the 1st mode of the present invention made in order to solve the above-mentioned subject, a) contacting a basic solution containing hydroxide ions with at least part of the surface of the metal substrate containing the first metal that can be divalent ions; b) An aqueous solution containing a trivalent ion of a second metal that is the same as or different from the first metal and an anion other than a hydroxide ion at a position of the surface of the metal substrate that is in contact with the basic solution. It has the process made to contact, It is characterized by the above-mentioned.
  • the manufacturing method of the hybrid material which has a layered double hydroxide layer on the surface based on the 2nd aspect of this invention comprised in order to solve the said subject, a) contacting a basic solution containing hydroxide ions with at least a portion of the surface of the metal substrate containing the first metal that can be a trivalent ion; b) An aqueous solution containing a divalent ion of a second metal that is the same as or different from the first metal, and an anion other than a hydroxide ion at a portion of the surface of the metal substrate that is in contact with the basic solution. It has the process made to contact, It is characterized by the above-mentioned.
  • the manufacturing method of the hybrid material which has the layered double hydroxide layer on the surface based on the 3rd aspect of this invention made in order to solve the said subject, a) A basic solution containing hydroxide ions on at least a part of the surface of a metal substrate containing a first metal that can be a divalent ion and a second metal different from the first metal that can be a trivalent ion.
  • the location is washed with water (distilled water, ion exchange water, industrial water, etc.).
  • the aqueous solution may be contacted after washing with. By doing so, since the basic solution on the surface of the metal substrate is washed away, the influence of the basic solution on the reaction of ions contained in the aqueous solution can be reduced or eliminated.
  • a hybrid material composed of a metal and an LDH layer is formed by forming a layered double hydroxide (LDH) layer on the surface of a metal substrate through a plurality of steps. It is a manufacturing method. In the production methods according to the first to third aspects, any of the steps can be performed at room temperature. In the manufacturing methods according to the first to third aspects, it is presumed that an LDH layer is formed on the surface of the metal substrate, probably by the reaction described below.
  • LDH layered double hydroxide
  • a basic solution is brought into contact with at least a part of the surface of the metal substrate, so that the first metal present in the location becomes divalent ions, and hydroxide ions (OH) -) reacts with changes hydroxide.
  • OH hydroxide ions
  • the composite hydroxide represented by the following general formula (1) is formed by the fact that the plurality of octahedral complexes share a ridge, and the crystallization of the composite hydroxide proceeds, A laminated structure of composite hydroxide is formed. Since the trivalent metal ion hydroxide is mixed with the divalent metal ion hydroxide, each layer of the composite hydroxide has a positive charge, and the electrical neutrality of each layer of the composite hydroxide is maintained. Therefore, the anion contained in the aqueous solution is taken into the space between the composite hydroxide layer and the composite hydroxide layer.
  • a hydrate represented by formula (2) is formed.
  • an LDH layer represented by the following general formula (3) is formed in which the basic layer made of the composite hydroxide and the intermediate layer made of the hydrate are alternately laminated.
  • M 2+ is a divalent metal ion (cation)
  • M 3+ is a trivalent metal ion (cation).
  • the divalent metal ions are Mg 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , Zn 2+
  • the trivalent metal ions are Al 3+ , Cr 3+ , Fe 3+ , Co 3 3+ , In 3+ .
  • a n ⁇ is an arbitrary anion, and is typically CO 3 2 ⁇ , OH ⁇ , Cl ⁇ , SO 4 2 ⁇ , SiO 4 4 ⁇ . .
  • LDH is a non-stoichiometric compound represented by the above general formula (3).
  • the number of divalent metal ions (1-x), the number of trivalent metal ions (x), the number of anions (x / n) and the number m of water molecules vary depending on the reaction conditions.
  • LDH has a minimum unit of a structure composed of two basic layers and one intermediate layer sandwiched between them.
  • a natural mineral hydrotalcite having a composition of Mg 6 Al 2 (OH) 16 CO 3 .4H 2 O is known. Therefore, LDH is also called a hydrotalcite-like compound.
  • a basic solution is brought into contact with at least a part of the surface of the metal substrate, so that the first metal existing in the location becomes trivalent ions and hydroxide ions. Reacts and changes to hydroxide.
  • divalent ions of trivalent ions and a second metal of the first metal is OH - in the surrounded by octahedra
  • a complex hydroxide represented by the above general formula (1) is formed by a plurality of octahedral complexes sharing a ridge.
  • the subsequent reaction is the same as in the manufacturing method according to the first aspect, and finally, the LDH layer represented by the general formula (3) is formed on the surface of the metal substrate.
  • the step of bringing the basic solution into contact with the metal substrate and the step of bringing the aqueous solution into contact can be combined into one.
  • a basic aqueous solution containing a trivalent or divalent metal ion and an anion is brought into contact with the metal substrate.
  • a basic solution is brought into contact with at least a part of the surface of the metal substrate, so that the first metal and the second metal present in the location are divalent ions and trivalent, respectively. It becomes an ion and is surrounded by hydroxide ions to form an octahedral complex structure.
  • a plurality of octahedral complexes share a ridge so that the composite represented by the above general formula (1) A hydroxide is formed, and the crystallization of the composite hydroxide proceeds to form a laminated structure of the composite hydroxide.
  • the composite hydroxide has a positive charge because a hydroxide of a trivalent metal ion and a hydroxide of a divalent metal ion are mixed. For this reason, by bringing an aqueous solution containing anions into contact with the same portion, in the space between the composite hydroxide layer and the composite hydroxide layer, other than hydroxide ions or hydroxide ions contained in the aqueous solution An anion and a water molecule are taken in, and these combine to form a hydrate represented by the above general formula (2). As a result, an LDH layer represented by the above general formula (3) is formed in which a basic layer made of a composite hydroxide and an intermediate layer made of a hydrate are alternately laminated.
  • the divalent ions of the first metal and the trivalent ions of the second metal contained in the metal substrate are water contained in the basic solution.
  • the base layer is formed by reacting with oxide ions, and at the same time, hydroxide ions contained in the basic solution are directly taken in between the base layer and the base layer to form an intermediate layer.
  • the basic solution contains an anion other than the hydroxide ion, the divalent ion of the first metal contained in the metal substrate when the basic solution is brought into contact with the metal substrate.
  • the intermediate layer may be formed by being taken in between the basic layer. In such a case, the step of contacting the aqueous solution becomes unnecessary.
  • Examples of the method of bringing the surface of the metal substrate into contact with the basic solution include a method of applying the basic solution to the surface of the metal substrate or immersing the metal substrate in the basic solution.
  • examples of the method of bringing an aqueous solution containing an anion into contact include a method of applying an aqueous solution to the surface of a metal substrate or a method of immersing a metal substrate in an aqueous solution. If the time for contacting the metal substrate with the basic solution and the time for contacting the metal substrate with the aqueous solution are lengthened, the reaction between the metal ions and the hydroxide ions proceeds accordingly, so the number of stacked basic layers increases.
  • the thickness of the LDH layer also changes by changing the reaction temperature, the pH of the basic solution, the concentration of the aqueous solution, and the like.
  • the crystallization from the composite hydroxide to LDH does not proceed, and the composite hydroxide is formed on the surface of the metal substrate, or the composition is the same as the above-described formula (3).
  • an amorphous LDH-like material a material like an LDH precursor
  • a material in which a composite hydroxide or an amorphous LDH-like substance is formed on the surface of a metal substrate is also included in a hybrid material having an LDH layer on the surface.
  • the aqueous solution may further contain a divalent ion of the same or different metal as the first metal.
  • the aqueous solution is the first metal. It may contain trivalent ions of the same or different metal.
  • the aqueous solution may further contain a divalent ion of the same or different metal as the first metal and a trivalent ion of the same or different metal as the second metal.
  • the basic layer may contain not only divalent metal ions and trivalent metal ions but also monovalent metal ions and tetravalent metal ions.
  • the LDH layer includes a mixture of basic layers having various configurations.
  • the metal contained in the metal substrate is ionized and simultaneously hydroxideized by bringing a basic solution into contact with the surface of the metal substrate.
  • the ionization treatment and the hydroxide treatment can be performed in separate steps.
  • By the treatment of incorporating anions and water molecules between the metal hydroxides A hybrid material having a layered double hydroxide layer on the surface of the metal substrate is produced.
  • the metal contained in the metal substrate is ionized.
  • a basic solution having a pH of about 9 is brought into contact with the metal substrate, metal ions are converted into hydroxides.
  • the metal substrate contains only one of a metal that can be a divalent ion and a metal that can be a trivalent ion, a basic solution containing the other metal ion and an anion is used.
  • a basic layer made of a metal hydroxide (a composite hydroxide) having a divalent metal ion and a trivalent metal ion is formed, and at the same time, an intermediate made of a hydrate of an anion and a water molecule.
  • a layer is formed, and an LDH layer is formed on the surface of the metal substrate.
  • the metal located on the surface of the metal substrate needs to be ionized and hydroxideized while remaining on the surface. Therefore, the ionizing treatment is preferably performed by applying or immersing hydrochloric acid on the surface of the metal substrate, and the hydroxideizing treatment is preferably performed by applying or immersing the basic solution on the surface of the metal substrate.
  • another aspect of the present invention is a method for producing a hybrid material having a single hydroxide layer on the surface, wherein at least one of a first metal that can be a divalent ion and a second metal that can be a trivalent ion It has the process of making the basic solution containing a hydroxide ion contact at least one part of the surface of the metal base material containing this.
  • the metal present at the location becomes ions, which react with the hydroxide ions to change into hydroxides, and the single hydroxide layer Form.
  • the metal present at the location becomes ions, which react with the hydroxide ions to change into hydroxides, and the single hydroxide layer Form.
  • sodium hydroxide is brought into contact with the surface of an aluminum metal substrate
  • an aluminum hydroxide layer is formed on the surface of the metal substrate.
  • the surface form of aluminum hydroxide varies depending on the reaction conditions (temperature, pH, etc.) at this time. Since aluminum hydroxide (Al (OH) 3 ) has a large specific surface area, a hybrid material in which an aluminum hydroxide layer is formed on the surface of a metal substrate can be used as an adsorbent.
  • the steps included in the manufacturing method according to this aspect correspond to step a) of the manufacturing method according to the first to third aspects. Therefore, the hybrid material obtained by the manufacturing method according to this aspect is subjected to the process b) of the manufacturing method according to the first to third aspects, thereby manufacturing a hybrid material having an LDH layer on the surface. be able to.
  • the hybrid material according to the present invention includes a metal base material containing at least one of a metal that can be a divalent ion and a metal that can be a trivalent ion; A basic layer formed by bonding divalent metal ions, trivalent metal ions, and hydroxide ions formed on the surface of the metal base; and an intermediate layer formed by bonding anions and water molecules.
  • a hybrid material having a layered double hydroxide layer formed by alternately laminating At least one of a divalent metal ion and a trivalent metal ion constituting the basic layer is a metal ion obtained by ionizing a part of the metal contained in the metal substrate. This hybrid material is obtained by the manufacturing method according to the present invention described above.
  • the boundary portion between the metal base material and the LDH layer is in a state where the metal base material and the LDH layer are mixed with each other, or the transition layer in the middle of changing from the metal base material to LDH at the boundary portion Compared with the conventional method in which the base material and the LDH layer are physically joined because the metal base material and the LDH layer are chemically joined due to the presence of (single hydroxide, double hydroxide). Thus, the bonding strength between the metal substrate and the LDH layer can be increased.
  • the conceptual diagram which shows the flow of the manufacturing method which concerns on this invention.
  • the figure which shows the specific example of a process of each process of the manufacturing method which concerns on this invention.
  • the schematic diagram which shows the structure of a single hydroxide.
  • the schematic diagram which shows the structure of a composite hydroxide.
  • the schematic diagram which shows the structure of a layered double hydroxide.
  • the SEM image of the porous structure which is an example of the surface structure of a hybrid material.
  • the SEM image of the plate-shaped structure which is an example of the surface structure of a hybrid material.
  • the SEM image of the nanoparticle structure which is an example of the surface structure of a hybrid material.
  • SEM image of the surface of the sample of Example 2 4 is an SEM image of a cross section of the sample of Example 2.
  • FIG. 10 is an SEM image of the surface of the sample of Example 8. The SEM image of the surface of the sample of Example 10.
  • FIG. The SEM image of the surface of the sample of Example 13 The SEM image of the surface of the sample of Example 15.
  • the SEM image of the surface of the sample of Example 16 The SEM image of the surface of the sample of Example 20.
  • FIG. 4 is a SEM image of the surface of the sample of Example 32.
  • FIG. 4 The SEM image of the surface of the sample of Example 33.
  • the figure which shows the scratch test result of the sample of Example 2, and a comparative example. 4 is an SEM image of a cross section near the surface of the sample of Example 2.
  • the present invention relates to a hybrid material having a single hydroxide layer on the surface and a manufacturing method thereof, and a hybrid material having a layered double hydroxide (LDH) layer on the surface and a manufacturing method thereof.
  • LDH layered double hydroxide
  • the metal substrate used for the production of the hybrid material only needs to contain at least one of a metal that can be a divalent ion (divalent metal) and a metal that can be a trivalent ion (trivalent metal).
  • the base material include base materials made of aluminum (Al), zinc (Zn), brass (CuZn), Al—Mg alloy, Al—Cu alloy, and the like.
  • the metal base material may have any shape such as a plate shape, a spherical shape, a granular shape, and a mesh plate shape, and can have an appropriate shape according to the intended use of the hybrid material.
  • a hybrid material having a single hydroxide layer on the surface is obtained by changing a part or all of the metal present on the surface of the metal base material to a single hydroxide. Further, the single hydroxide layer of the hybrid material is changed to a composite hydroxide, and further, the composite hydroxide is changed to LDH, whereby a hybrid material having an LDH layer on the surface can be obtained. Therefore, the shape and size of the metal substrate are almost the same as the shape and size of the hybrid material.
  • hybrid material which has a single hydroxide layer on the surface is obtained in the middle of the manufacturing process of the hybrid material which has an LDH layer on the surface. Therefore, in the following description, a hybrid material having a single hydroxide layer on the surface is referred to as a hybrid intermediate material in order to distinguish it from a hybrid material having an LDH layer on the surface.
  • FIG. 1A and 1B are explanatory views showing a basic procedure of a manufacturing method according to the present invention.
  • the shape of the metal substrate is a rectangular plate shape, but is not limited thereto.
  • a metal substrate is first prepared, and a predetermined basic solution is brought into contact with at least a part of the surface of the metal substrate (step A).
  • the contact between the surface of the metal substrate and the basic solution is performed, for example, by applying the basic solution to the surface of the metal substrate or immersing the metal substrate in the basic solution.
  • the hydroxide ions contained in the basic solution react with the divalent or trivalent metal present in the portion having a predetermined thickness from the outermost surface of the metal base material to form a metal hydroxide, and the metal water A hybrid intermediate material having an oxide layer on the surface is obtained.
  • the metal hydroxide on the surface of the hybrid intermediate material is a single hydroxide composed of one kind of metal ion and hydroxide ion.
  • a predetermined aqueous solution is brought into contact with the metal hydroxide layer (single hydroxide layer) of the hybrid intermediate material (step C).
  • This is done by immersing the hybrid intermediate in an aqueous solution containing, for example, anions and metal ions.
  • the metal hydroxide reacts with the metal ions to form a composite hydroxide that is a composite of a divalent metal hydroxide and a trivalent metal hydroxide, and further, crystals of the composite hydroxide.
  • LDH is formed.
  • cleaning water may be added, and the process D which wash
  • the composite hydroxide is composed of a plurality of types of metal ions and hydroxide ions.
  • the LDH has a plurality of basic layers crystallized from the composite hydroxide.
  • the intermediate layer is composed of a hydrate of water molecules and anions incorporated between the basic layer and the basic layer.
  • the degree of crystallization and the crystal shape of the composite hydroxide vary depending on the reaction conditions such as the temperature and the ion concentration contained in the aqueous solution or basic solution. Therefore, not only LDH but also a composite hydroxide may be formed on the surface of the hybrid material obtained by the process C, and the surface structure of the hybrid material becomes porous, plate-like, nano-particle, etc. .
  • 3A to 3C show scanning electron microscope (SEM) images in which a porous structure, a plate-like structure, and a nanoparticle structure are observed as examples of the surface structure of the hybrid material.
  • the LDH layer formed on the surface of the hybrid material is obtained by changing a part of the metal substrate. For this reason, usually, the combined length of the LDH layer and the unreacted metal base is substantially the same as the thickness of the original metal base or the thickness of the original metal base. Slightly bigger. For example, when the thickness of the metal oxide formed by the process A is larger than the thickness of the original part, the total length of the LDH layer and the unreacted metal base is It becomes larger than the thickness of the metal substrate.
  • a hybrid material having a desired shape and size can be manufactured by accurately setting the shape and size of the metal substrate according to the type of the first metal contained in the metal substrate.
  • FIG. 3D is an SEM image of the surface structure of the hybrid intermediate material obtained when ammonia water (NH 3 water) is brought into contact with the surface of the metal substrate. An amorphous porous structure was formed on the surface of the hybrid intermediate material.
  • LDH generally has lower electrical conductivity and thermal conductivity than metal
  • insulation and heat resistance can be imparted to the metal substrate.
  • porous and nanoparticulate LDH has fine irregularities on its surface
  • a hybrid material having such an LDH layer is cured by an adhesive or paint entering the irregularities on the surface of the LDH layer. By doing so, the anchor effect that the bonding strength with the adhesive or paint is increased can be obtained.
  • the LED layer colored gold, brown, white, etc. can be obtained according to the conditions of the process A and the process C.
  • titanium oxide (TiO 2 ) particles into the LDH layer, a hybrid material having a photocatalytic action can be obtained.
  • the LDH layer can be colored by incorporating inorganic particles such as pigments into the LDH layer.
  • the thickness of the LDH layer can be increased by increasing the pH in step C or by increasing the thickness of the single hydroxide layer of the hybrid intermediate material obtained in step A.
  • the production method according to the present invention comprises a reaction between a metal ion and a hydroxide ion (hydration) by simply contacting a basic solution and an aqueous solution with a metal substrate at room temperature (20 ° C. to 30 ° C.), a basic layer, Incorporation of anions and water molecules into the space between the basic layers and the binding (hydration) of the anions and water molecules proceed. Therefore, the hybrid intermediate material and the hybrid material can be manufactured by a simple method.
  • the manufacturing method which concerns on this invention can be performed at room temperature, when it is performed at temperature higher than room temperature, reaction of the process A and the process C can be accelerated, or the crystallinity of LDH can be raised.
  • the basic solution examples include sodium hydroxide (NaOH) solution, potassium hydroxide (KOH) solution, lithium hydroxide (LiOH) solution, ammonia (NH 3 ) aqueous solution, hydrochloric acid (HCl), nitric acid (HNO 3 ), sulfuric acid. (H 2 SO 4 ) and the like can be mentioned as long as they contain OH ⁇ and H + .
  • the metal contained in the metal substrate is aluminum (trivalent)
  • the aqueous solution containing anions includes divalent metal ions such as MgCl 2 , Zn (NO 3 ) 2 , and Cu (NO 3 ) 2.
  • the metal is zinc or brass (divalent)
  • those containing trivalent metal ions such as Al (NO 3 ) 2 and Fe (Cl) 3 are exemplified.
  • the pH of the aqueous solution used in the production method according to the present invention is preferably 7 to 11, but an aqueous solution having a pH of less than 7 can be used depending on conditions.
  • the hybrid material manufacturing method according to the present invention has the following four modes. Basically, the first to fourth aspects include step A and step C. Hereinafter, Step A and Step C in each embodiment will be described in detail.
  • Process A A basic solution is made to contact at least one part of the surface of the metal base material containing the 1st metal which can become a bivalent ion.
  • Step C An aqueous solution containing a second metal that can be a trivalent ion and an anion is brought into contact with a portion of the surface of the metal substrate that has been brought into contact with the basic solution.
  • Process A A basic solution is made to contact at least one part of the surface of the metal base material containing the 1st metal which can become a trivalent ion.
  • Step C An aqueous solution containing a second metal that can be a divalent ion and an anion is brought into contact with a portion of the surface of the metal substrate that has been brought into contact with the basic solution.
  • Process A A basic solution is made to contact at least one part of the surface of the metal base material containing the 1st metal which can become a bivalent ion, and the 2nd metal which can become a trivalent ion.
  • Process C The aqueous solution containing an anion is made to contact the location which contacted the basic solution among the surfaces of a metal base material.
  • a composite hydroxide represented by the following general formula (1) is formed by Step A and Step C in the third embodiment, and in Step A in the third embodiment.
  • the basic layer is formed.
  • an intermediate layer of LHD represented by the following general formula (2) is formed by the step C, and thus represented by the following general formula (3).
  • LDH is completed. [(A n ⁇ ) x / n ⁇ mH 2 O] (2)
  • [M 2+ 1-x M 3+ x (OH) 2 ] [(A n ⁇ ) x / n ⁇ mH 2 O] (3)
  • Step a An acidic solution is brought into contact with at least a part of the surface of the metal substrate including at least one of a first metal that can be a divalent ion and a second metal that can be a trivalent ion.
  • Process C The aqueous solution containing an anion (and a bivalent metal ion or a trivalent metal ion) is made to contact the location which contacted the acidic solution among the surfaces of the metal base material.
  • an acidic solution is used in step a instead of the basic solution, whereby the metal contained in the metal substrate is ionized.
  • the metal ions are converted into hydroxides to form a composite hydroxide represented by the general formula (1).
  • an LDH basic layer (general formula (1)) is formed.
  • an intermediate layer (general formula (2)) and an LDH layer (general formula (3)) are formed. It is formed.
  • Example 1 shows the types of the metal substrate, basic solution, and aqueous solution used in each example.
  • Examples 1 to 22, 24 to 29 are the first aspect
  • Examples 30 and 31 are the second aspect
  • Examples 32 and 33 are the third aspect
  • Example 23 is the fourth aspect. It corresponds.
  • the concentration, pH, temperature, and reaction time all indicate the concentration, pH, temperature, and time of immersion in the aqueous solution. Specific contents of each embodiment will be described later.
  • the obtained XRD profile was analyzed with reference to the X-ray diffraction intensity database, and the surface structure was identified.
  • the X-ray diffraction intensity database is a database compiled by the Joint Committee on Powder Diffraction Standards (JCPDS) of the International Data Center for Diffraction Data (ICDD) (“JCPDS Card”). Called).
  • ⁇ Functional test 1 insulation> The continuity test of the sample was performed with a tester (customized, MC-01U).
  • ⁇ Functional test 2 Dye adsorption> The sample was immersed in a red remazole dye solution (manufactured by Sigma Aldrich Japan LLC) for 30 minutes to confirm the adsorptivity of the dye.
  • Examples 1 to 22 and 24 to 29 of the first aspect [No. 1-8, 11-13, 15-21] An aluminum foil having a purity of 99% (vertical 20 mm ⁇ width 20 mm ⁇ thickness 0.1 mm) was used as the metal substrate, and the metal substrate was immersed in a basic solution of sodium hydroxide (NaOH). Thereafter, the metal substrate was taken out of the NaOH solution, washed with distilled water, and immersed in an aqueous MgCl 2 solution. [No. 24] A 99% pure aluminum foil (vertical 20 mm ⁇ width 20 mm ⁇ thickness 0.1 mm) was used as a metal substrate, and a basic solution sodium hydroxide (NaOH) solution was applied to the surface.
  • NaOH sodium hydroxide
  • the metal substrate was washed with distilled water and immersed in an aqueous Zn (NO 3 ) 2 solution.
  • a 99% purity aluminum foil (vertical 20 mm ⁇ width 20 mm ⁇ thickness 0.1 mm) was used as a metal substrate, and ammonia (NH 3 ) water as a basic solution was applied to the surface.
  • the metal substrate was washed with distilled water and immersed in an aqueous MgCl 2 solution.
  • a 99% purity aluminum foil (vertical 20 mm ⁇ width 20 mm ⁇ thickness 0.1 mm) was used as a metal substrate, and ammonia (NH 3 ) water as a basic solution was applied to the surface.
  • the metal substrate was washed with distilled water and immersed in an aqueous Zn (NO 3 ) 2 solution.
  • a 99% purity aluminum foil vertical 20 mm ⁇ width 20 mm ⁇ thickness 0.1 mm was used as a metal substrate, and ammonia (NH 3 ) water as a basic solution was applied to the surface.
  • the metal substrate was washed with distilled water and immersed in an aqueous Cu (NO 3 ) 2 solution.
  • Example of No. 2 A 99% pure zinc (Zn) plate (vertical 150 mm ⁇ width 45 mm ⁇ thickness 0.3 mm) was used as a metal substrate, and a basic solution NaOH solution was applied to this surface. Thereafter, the metal substrate was washed with distilled water and immersed in an Al (NO 3 ) 3 aqueous solution.
  • Brass (Cu—Zn alloy) foil (vertical 150 mm ⁇ width 45 mm ⁇ thickness 0.3 mm) made of 60% copper and 39% zinc was used as the metal substrate, and a basic solution sodium hydroxide (NaOH) was used on this surface. ) The solution was applied. Thereafter, the metal substrate was washed with distilled water and immersed in an Al (NO 3 ) 3 aqueous solution.
  • Example of the third aspect Al-Mg alloy (A5052) (Vertical 150mm x Width 45mm x Thickness 0.3mm) with 95% Aluminum and 3% Magnesium is used as the metal substrate, and the basic solution is sodium hydroxide (NaOH) The solution was applied. Thereafter, the metal substrate was washed with distilled water and immersed in water (H 2 O).
  • Al-Cu alloy (A2017) (Vertical 150mm x Width 45mm x Thickness 0.3mm) with 91% aluminum and 4.5% copper is used as the metal substrate, and the basic solution is sodium hydroxide (NaOH) The solution was applied. Thereafter, the metal substrate was washed with distilled water and immersed in water (H 2 O).
  • Example of the fourth aspect An aluminum foil of 99% purity (vertical 20 mm ⁇ width 20 mm ⁇ thickness 0.1 mm) was used as a metal substrate, and an acidic solution of hydrochloric acid (HCl) was applied to this surface. Thereafter, the metal substrate was washed with distilled water and immersed in an aqueous MgCl 2 solution.
  • HCl hydrochloric acid
  • Examples 8, 10 to 12 and 20 are examples in which the reaction time (time of immersion in an aqueous solution) was set to 5 minutes, and the immersion time was shorter than in other examples. Therefore, although a porous material is generated in a reaction time of 5 minutes, the porous material is not uniformly formed on the surface of the metal substrate, and since the amount of generation is small, insulation and dye adsorption It seems that it was not shown.
  • the diffraction peak of LDH is the diffraction peak of LDH in a state where the crystallinity is low (amorphous) even if the substance represented by the general formula (3) is formed on the surface of the metal substrate. Not confirmed. Therefore, although the diffraction peak of LDH was not confirmed by XRD analysis, in the example in which the insulating property and the dye adsorptivity were improved compared to before the reaction, an amorphous material having the same composition as LDH was formed on the surface of the metal substrate. It was speculated that a substance (LDH-like substance) was formed.
  • Example 2 (4) SEM observation of surface structure About some Examples, the surface structure of the sample was observed by SEM. 4A and 4B show SEM images of the surface and cross section of Example 2.
  • a portion having a thickness of about 10 ⁇ m from the surface of the metal substrate had a different cross-sectional structure from the other portions, and an LDH layer having a thickness of about 10 ⁇ m was formed.
  • Examples 8, 10, 12, 13, 15, 16, 20, 22, 23, 32, and 33 show SEM images of the surfaces of the samples of Examples 8, 10, 12, 13, 15, 16, 20, 22, 23, 32, and 33, respectively.
  • a porous structure was observed on the entire surface of the metal substrate.
  • Example 13 long fibrous materials were intertwined to form a porous structure, but in other cases, the porous structure was composed of divided short fibrous materials.
  • Example 22 a porous structure was present inside, and part of the porous structure was exposed on the surface.
  • Examples 32 and 33 a porous material in which a large number of granular materials were connected to the surface of the metal substrate was observed.
  • Friction force measurement About the sample of Example 2, and the untreated metal base material (aluminum), the friction force of those surfaces was measured.
  • the measurement of the frictional force was performed by preparing two measurement objects and arranging them in the state shown in FIG. Specifically, one of the two objects to be measured is placed on the experimental bench so that the surface thereof faces upward, and the other is placed on the object to be measured with the surface facing down. .
  • the other object to be measured was fixed to the lower surface of the weight, and the static friction force and dynamic friction force were measured by fixing the tip of the thread attached to the weight to a tensile tester.
  • a tensile tester manufactured by A & D Co., Ltd. was used for the measurement.
  • Table 2 As can be seen from Table 2, the sample of Example 2 was lower in both static friction force and dynamic friction force than the untreated metal substrate.
  • the surface structure of the sample is separate from the metal substrate, and if the sample is peeled off from the metal substrate, the scratch load decreases, the load-friction force relationship does not become a continuous straight line, and discontinuities occur. .
  • FIG. 17 a continuous linear load-friction force relationship was obtained for both the sample of Example 2 and the untreated metal substrate. From this, it was estimated that the surface structure of the sample of Example 2 was integral with the metal substrate.
  • 18 is an SEM image of a cross section near the surface of the sample of Example 2. FIG. This SEM image also confirms that the surface structure of Example 2 is in close contact with the lower structure (that is, it is integral with the metal substrate).
  • the surface structure of the sample of Example 34 was observed with an electron microscope. As a result, it was found that a plate-like structure was formed on the surface of the sample as shown in FIG.
  • the surface structure of the sample of Example 34 was measured using an X-ray photoelectron spectroscopy (XPS) apparatus and an X-ray diffraction (XRD) apparatus.
  • 20 shows an XPS profile
  • FIG. 21 shows an XRD profile. From FIG. 20, it was found that the elements constituting the surface structure of the sample of Example 34 contained zinc (Zn) and aluminum (Al). Further, in the XRD profile shown in FIG. 21, a slight LDH peak was confirmed.
  • Example 34 was subjected to a continuity test using the tester. As a result, it was found that electricity flows in the sample of Example 34.
  • the hybrid material is expected to be applied to, for example, a battery material utilizing the conductivity. Moreover, it can utilize for example, a bearing material taking advantage of smoothness.
  • Example 36 Aluminum having a purity of 99% (length 20 mm ⁇ width 20 mm ⁇ thickness 0.3 mm) was used as a metal substrate, and this was immersed in a NaOH solution. Subsequently, the metal substrate was taken out from the NaOH solution, washed with distilled water, and then immersed in an aqueous zinc nitrate solution having a concentration of 0.1 M at 50 ° C. for 6 hours. When the sample of Example 36 was observed with the naked eye, the surface was white. Moreover, when the surface of the sample of Example 36 was observed with the electron microscope, the porous structure was formed (refer FIG. 23).
  • This porous structure has larger pores than the porous structure formed on the sample surface of Examples 1 to 33 described above, and the sample of Example 36 can be coated with a pigment or the like on the surface. It seemed.
  • XRD X-ray diffraction
  • Example 37 Aluminum having a purity of 99% (length 20 mm ⁇ width 20 mm ⁇ thickness 0.3 mm) was used as a metal substrate, and this was immersed in a NaOH solution. Subsequently, the metal substrate was taken out from the NaOH solution, washed with distilled water, and then immersed in an aqueous solution of zinc nitrate having a concentration of 0.1 M to which a yellow dye (Remazol Yellow) was added at 50 ° C. for 6 hours. When the product of Example 37 was observed with the naked eye, the surface was yellow and transparent. Thus, since the sample of Example 37 can color the base material of aluminum in arbitrary colors, the application to a decoration is anticipated.
  • Modified Example a modified example in which the surface of the metal substrate is treated only with the basic solution will be described.
  • Modification 3 Aluminum having a purity of 99% (length 20 mm ⁇ width 20 mm ⁇ thickness 0.3 mm) was used as a metal substrate, and this was immersed in a NaOH solution. After removing the metal substrate from the NaOH solution and washing with distilled water, a titanium oxide sol (TS-S4110 manufactured by Sumitomo Chemical Co., Ltd.) was applied to the surface of the metal substrate and dried. Subsequently, the metal substrate on which the titanium oxide sol was applied was immersed in an aqueous solution of zinc nitrate having a concentration of 0.1 M at 50 ° C. for 6 hours.
  • a titanium oxide sol T-S4110 manufactured by Sumitomo Chemical Co., Ltd.
  • titanium oxide (TiO 2 ) has a photocatalytic action, if titanium oxide particles are attached to an organic base material, the base material is decomposed.
  • a base material made of an inorganic substance such as a metal it is not decomposed by titanium oxide, but since the surface of the base material is smooth, it is necessary to use an adhesive to attach titanium oxide. The effect of the titanium oxide photocatalyst is reduced.
  • a porous structure can be formed on the surface of the metal substrate, and titanium oxide particles can be taken into the porous structure, so that the effect of the photocatalyst can be maintained.
  • Reference Example 8 A reference example in which a metal base material made of aluminum was surface-treated according to the procedure described in paragraphs [0052], [0054], and [0055] of Patent Document 2 described in the background art section of this specification. Produced. However, in Patent Document 2, hydrothermal treatment is performed at 70 ° C. for 168 hours, but in this reference example, hydrothermal treatment was performed at 70 ° C. for 24 hours for comparison with the above-described example.
  • a sulfone group is generated on the surface of the material, and bivalent and trivalent metal ions are attracted by the sulfone group to generate LDH on the surface of the substrate.
  • an aluminum base material is used, and even if such a metal base material is immersed in a mixed solution of an anionic surfactant and ion exchange water, a sulfone group is not generated on the surface thereof.
  • Patent Document 2 describes a method of sulfonating the surface of a polystyrene base material using concentrated sulfuric acid (paragraph [0047]), but when an aluminum base material is immersed in concentrated sulfuric acid. It will dissolve. That is, with the method of Patent Document 2, an LDH layer cannot be formed on the surface of the metal substrate.
  • the present invention is not limited to the above-described embodiments, and various modifications can be made within the scope of the gist of the present invention.
  • the metal substrate was washed with distilled water between Step 1 and Step 2, but this may be omitted. Moreover, it may replace with washing
  • the combination of the concentration, pH, temperature, reaction time of the aqueous solution, the first metal, the second metal, and the anion is not limited to the above-described embodiments.
  • the hybrid material of the present invention has a catalyst, an adsorbent, a filter material, a halogen scavenger, a fuel cell separator, etc. due to the dye adsorption property, insulation property, thermal conductivity, anchor effect, etc. of the LDH layer formed on the surface thereof. It is useful as various functional materials.

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Abstract

Un matériau hybride selon la présente invention comprend : un substrat métallique qui comprend au moins un métal pouvant devenir un ion divalent et un métal capable de devenir un ion trivalent; et une couche d'hydroxyde double couches qui est formée sur une surface du substrat métallique et est obtenue par stratification alternée d'une couche de base et d'une couche intermédiaire. Ladite couche de base est obtenue par liaison d'ions métalliques divalents, d'ions métalliques trivalents et d'ions hydroxyde, et ladite couche intermédiaire est obtenue par liaison d'ions négatifs et de molécules d'eau. Ledit matériau hybride est caractérisé en ce qu'au moins l'un des ions métalliques divalents et les ions métalliques trivalents constituant la couche de base sont des ions métalliques qui ont été ionisés par une partie du métal inclus dans le substrat métallique.
PCT/JP2017/035135 2016-09-28 2017-09-28 Procédé de fabrication d'un matériau hybride et matériau hybride Ceased WO2018062360A1 (fr)

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JP7727282B2 (ja) 2019-12-06 2025-08-21 貴和化学薬品株式会社 金属表面前処理剤
WO2022050173A1 (fr) * 2020-09-01 2022-03-10 協和化学工業株式会社 Hydrotalcite traitée en surface, suspension de celle-ci, et système de distribution de molécule fonctionnelle l'utilisant
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WO2022113434A1 (fr) * 2020-11-24 2022-06-02 日本碍子株式会社 Batterie secondaire au zinc
JPWO2022113434A1 (fr) * 2020-11-24 2022-06-02
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WO2022113433A1 (fr) * 2020-11-30 2022-06-02 日本碍子株式会社 Batterie utilisant un composé de type hydroxyde double lamellaire
JP7037002B1 (ja) * 2020-11-30 2022-03-15 日本碍子株式会社 層状複水酸化物様化合物を用いた電池
JP7048830B1 (ja) * 2020-12-01 2022-04-05 日本碍子株式会社 Ｌｄｈ様化合物セパレータ及び亜鉛二次電池
WO2022118503A1 (fr) * 2020-12-01 2022-06-09 日本碍子株式会社 Séparateur composite de type ldh et batterie secondaire au zinc
WO2022118504A1 (fr) * 2020-12-01 2022-06-09 日本碍子株式会社 Séparateur composite de type ldh et batterie secondaire au zinc
JP7048831B1 (ja) * 2020-12-01 2022-04-05 日本碍子株式会社 Ｌｄｈ様化合物セパレータ及び亜鉛二次電池
JP2022161389A (ja) * 2021-04-09 2022-10-21 国立研究開発法人物質・材料研究機構 層状複水酸化物を表面に有する金属板の製造方法
JP7669028B2 (ja) 2021-04-09 2025-04-28 国立研究開発法人物質・材料研究機構 層状複水酸化物を表面に有する金属板の製造方法

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