WO2021045230A1 - ナノ複合金属材料、および、ナノ複合金属材料の製造方法 - Google Patents

ナノ複合金属材料、および、ナノ複合金属材料の製造方法 Download PDF

Info

Publication number
WO2021045230A1
WO2021045230A1 PCT/JP2020/033824 JP2020033824W WO2021045230A1 WO 2021045230 A1 WO2021045230 A1 WO 2021045230A1 JP 2020033824 W JP2020033824 W JP 2020033824W WO 2021045230 A1 WO2021045230 A1 WO 2021045230A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal material
nanocomposite
nanocomposite metal
metal particles
heating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2020/033824
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
亮人 高橋
蜂須賀　譲二
雄一 古山
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Technova Inc
Kobe University NUC
Original Assignee
Technova Inc
Kobe University NUC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=74852366&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2021045230(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Technova Inc, Kobe University NUC filed Critical Technova Inc
Priority to EP20859758.3A priority Critical patent/EP4008453A4/en
Priority to CN202080062306.3A priority patent/CN114787401B/zh
Priority to US17/640,736 priority patent/US12091732B2/en
Priority to JP2021544074A priority patent/JP7694386B2/ja
Publication of WO2021045230A1 publication Critical patent/WO2021045230A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C16/00—Alloys based on zirconium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/08—Metallic powder characterised by particles having an amorphous microstructure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/18—Non-metallic particles coated with metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/002—Making metallic powder or suspensions thereof amorphous or microcrystalline
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/023—Hydrogen absorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/16—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer formed of particles, e.g. chips, powder or granules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/0005—Reversible storage of hydrogen, e.g. by hydrogen getters or electrodes
    • C01B3/001—Reversible storage of hydrogen, e.g. by hydrogen getters or electrodes characterised by the uptaking media; Treatment thereof
    • C01B3/0018—Inorganic elements or compounds, e.g. oxides, nitrides, borohydrides or zeolites; Solutions thereof
    • C01B3/0031—Intermetallic compounds; Metal alloys
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/0005—Reversible storage of hydrogen, e.g. by hydrogen getters or electrodes
    • C01B3/001—Reversible storage of hydrogen, e.g. by hydrogen getters or electrodes characterised by the uptaking media; Treatment thereof
    • C01B3/0078—Composite solid storage media, e.g. mixtures of polymers and metal hydrides, coated solid compounds or structurally heterogeneous solid compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/17—Metallic particles coated with metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/049—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by pulverising at particular temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2201/00—Treatment under specific atmosphere
    • B22F2201/01—Reducing atmosphere
    • B22F2201/013—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/10—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/15—Nickel or cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/20—Refractory metals
    • B22F2301/205—Titanium, zirconium or hafnium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2303/00—Functional details of metal or compound in the powder or product
    • B22F2303/01—Main component
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps

Definitions

  • An embodiment of the present invention relates to a nanocomposite metal material and a method for producing a nanocomposite metal material.
  • a technique for using metal nanoparticles for an exothermic reaction with hydrogen is disclosed. For example, a technique for causing an exothermic reaction by supplying hydrogen gas to a reactant in which a plurality of metal nano-convex portions made of a hydrogen storage metal are formed on the surface is disclosed.
  • the present invention has been made in view of the above, and an object of the present invention is to provide a nanocomposite metal material and a method for producing a nanocomposite metal material, which can increase the calorific value by an exothermic reaction with hydrogen. And.
  • the nanocomposite metal material of the embodiment comprises a carrier made of Zr and two-element metal particles supported on the carrier and made of Cu and Ni, and the degree of oxidation of the carrier is greater than 31% and less than 100%. is there.
  • the nanocomposite metal material of the embodiment is composed of a carrier made of Zr and two-element metal particles supported on the carrier and made of Pd and Ni, and the degree of oxidation of the carrier is 3% or more and 100% or less. Is.
  • FIG. 1 is a schematic view showing an example of the nanocomposite metal material according to the embodiment.
  • FIG. 2 is an explanatory diagram of an example of the nanocomposite metal material and the firing step of the nanocomposite metal material according to the embodiment.
  • FIG. 3 is a schematic view showing an example of the thermal reactor according to the embodiment.
  • FIG. 4 is a flow chart showing an example of a procedure of a method for manufacturing a nanocomposite metal material according to an embodiment.
  • FIG. 5 is a flow chart showing an example of a procedure of a method for manufacturing a nanocomposite metal material according to an embodiment.
  • FIG. 6 is an electron micrograph of CNZ7r according to an example.
  • FIG. 7 is a diagram showing measurement results showing the relationship between the calorific value and the degree of oxidation of the fine metal particles and the nanocomposite metal material according to the examples.
  • FIG. 8 is a diagram showing measurement results showing the calorific value of the fine metal particles and the nanocomposite metal material according to the examples.
  • FIG. 9 is a diagram showing changes in the calorific value of CNZ7r # 1-2 according to the embodiment.
  • FIG. 10 is a diagram showing changes in the calorific value of CNZ7r # 2-2 according to the embodiment.
  • FIG. 11 is a diagram showing changes in the calorific value of CNZ7r # 2-4 according to the embodiment.
  • FIG. 12 is a diagram showing changes in the calorific value of PNZ10r # 1-4 according to the embodiment.
  • FIG. 13 is a diagram showing changes in the calorific value of PNZ10r # 2-2 according to the embodiment.
  • FIG. 14 is a diagram showing measurement results showing the relationship between the calorific value of CNZ7, CNZ7R, CNZ7RR, and CNZ7RRR and the number of firings according to the embodiment.
  • FIG. 15 is a diagram showing measurement results showing the relationship between the calorific value of PNZ10, PNZ10R, PNZ10RR, and PNZ10RRR and the number of firings according to the embodiment.
  • the nanocomposite metal material of the present embodiment is a metal composite material composed of a carrier made of ceramics and two-element metal particles supported on the carrier and made of Cu or palladium (Pd) and nickel (Ni).
  • FIG. 1 is a schematic view showing an example of the nanocomposite metal material 10 of the present embodiment.
  • the nanocomposite metal material 10 has a structure in which two-element metal particles 14 are supported on the inside and the surface of the carrier 12.
  • the term "supported on the carrier 12" means a state in which the two-element metal particles 14 are adhered or fused to the inside and the surface of the carrier 12 by a chemical treatment such as firing. Further, being supported inside the carrier 12 means that it is supported on the surface of the pores of the carrier 12.
  • the carrier 12 is made of ceramics. Specifically, the carrier 12 is a ceramic having nano-sized pores inside and on the surface. In the present embodiment, the nano size means a range of 2 nm or more and 50 nm or less.
  • the ceramics constituting the carrier 12 are, for example, zirconium (Zr), zirconia (ZrO 2 ), mesoporous silica, zeolite, carbon nanotubes, and the like.
  • the outer shape of the carrier 12 is not limited.
  • the outer shape of the carrier 12 may be any shape such as a spherical shape, an elliptical shape, a polygonal shape, or the like.
  • the two-element metal particles 14 are supported on the inside and the surface of the carrier 12. Specifically, the two-element metal particles 14 are supported on the pores inside and on the surface of the carrier 12.
  • the two-element metal particles 14 are metal nanoparticles composed of two elements, Cu and Ni, or Pd and Ni. Specifically, the two-element metal particles 14 are particles having a core-shell structure having Ni as a core and Cu or Pd as a shell.
  • the outer shape of the two-element metal particles 14 is not limited.
  • the outer shape of the two-element metal particles 14 may be, for example, spherical, elliptical, polygonal, linear, or at least a partially twisted string shape.
  • the volume average particle size of the nanocomposite metal material 10 includes at least a range of 0.01 mm or more and 1 mm or less. It is more preferable that the volume average particle diameter of the nanocomposite metal material 10 includes at least a range of 0.05 mm or more and 0.3 mm or less. The volume average particle diameter of the nanocomposite metal material 10 may further include a range of 0.05 mm or more and 0.5 mm or less.
  • the volume average particle diameter of the nanocomposite metal material 10 made of the carrier 12 made of Zr, which supports the two-element metal particles 14 made of two elements of Cu and Ni is 0.1 mm or more and 1.0 mm or less. It is preferable to include at least the range of. Further, the volume average particle diameter of the nanocomposite metal material 10 made of the carrier 12 made of Zr, which supports the two-element metal particles 14 made of two elements of Pd and Ni, is in the range of 0.05 mm or more and 1.0 mm or less. Is preferably contained at least.
  • the volume average particle size of the nanocomposite metal material 10 indicates the volume average particle size of the carrier 12 (see particle size L1) when the structure of the nanocomposite metal material 10 is as shown in FIG.
  • the volume average particle diameter of the two-element metal particles 14 is, for example, preferably in the range of 2 nm or more and 50 nm or less, more preferably in the range of 2 nm or more and 20 nm or less, and particularly preferably in the range of 2 nm or more and 10 nm or less. preferable.
  • the volume average particle diameter of the nanocomposite metal material 10 and the two-element metal particles 14 is measured by, for example, the following method.
  • each of the nanocomposite metal material 10 and the binary metal particles 14 was measured by measuring the element distribution map under the condition of 200 keV electron beam scan using NEC's product name: STEM / EDS as the measuring device.
  • the volume average particle size was measured by image analysis of the volume average particle size and shape of the above with a resolution of 1 nm or less.
  • the nanocomposite metal material 10 of the present embodiment has a nanocomposite metal material 10A, a nanocomposite metal material 10B, a nanocomposite metal material 10C, a nanocomposite metal material 10D, a nanocomposite metal material 10E, and a nanocomposite metal according to a manufacturing method described later. It is classified into eight types: material 10F, nanocomposite metal material 10G, and nanocomposite metal material 10H.
  • nanocomposite metal materials 10A, nanocomposite metal materials 10B, nanocomposite metal materials 10C, nanocomposite metal materials 10D, nanocomposite metal materials 10E, nanocomposite metal materials 10F, nanocomposite metal materials 10G, and nanocomposite metal materials 10H are different in manufacturing method from each other.
  • nanocomposite metal material 10H When the nanocomposite metal material 10H is generically described, it is simply referred to as the nanocomposite metal material 10.
  • the nanocomposite metal material 10 of the present embodiment can be used for an exothermic reaction with hydrogen to increase the calorific value.
  • nanocomposite metal material 10A, nanocomposite metal material 10B, nanocomposite metal material 10C, nanocomposite metal material 10D, nanocomposite metal material 10E, nanocomposite metal material 10F, nanocomposite metal material 10G, and nanocomposite metal material 10H Each of the above will be described in detail.
  • Nanocomposite metal material 10A First, a method for producing the nanocomposite metal material 10A and the nanocomposite metal material 10A will be described.
  • the nanocomposite metal material 10A is composed of a carrier 12 made of Zr, two-element metal particles 14 made of Cu and Ni supported on the carrier 12, and the degree of oxidation of the carrier 12 made of Zr is more than 31% and 100. % Or less nanocomposite metal material 10.
  • the carrier 12 made of Zr may be simply referred to as the carrier 12.
  • the degree of oxidation of the carrier 12 of the nanocomposite metal material 10A is essential to be greater than 31% and 100% or less, but is preferably 50% or more and 100% or less, more preferably 80% or more and 100% or less, and 90%. % To 100% is particularly preferable.
  • the nanocomposite metal material 10A has a calcining step of calcining fine metal particles obtained by pulverizing an amorphous metal composed of Cu, Ni, and Zr at 300 ° C. or higher and 600 ° C. or lower to obtain the nanocomposite metal material 10A.
  • FIG. 2 is an explanatory diagram of an example of a firing process of the nanocomposite metal material 10A and the nanocomposite metal material 10B described later.
  • an amorphous metal 18 is produced by melting and quenching a Cu—Ni—Zr alloy by a melt spinning method (melt quenching method).
  • the melt spinning method is a method of obtaining an amorphous metal by spraying an alloy melted at a high temperature on the surface of a roll-shaped member that rotates at high speed and quenching it in a shorter time than the crystallization time.
  • the Cu—Ni—Zr alloy is melted by heating in the heating furnace 22A, and the melted liquid is supplied to the rotating cooling roll 22B.
  • the molten liquid solidifies when it comes into contact with the rotating cooling roll 22B to produce a ribbon-shaped amorphous metal 18.
  • the thickness of the ribbon-shaped amorphous metal 18 is adjusted to, for example, a thickness range of 5 ⁇ m or more and 50 ⁇ m or less by adjusting the supply amount to the cooling roll 22B, the rotation speed of the cooling roll 22, and the like.
  • the amorphous metal 18 is oxidized in the atmosphere.
  • the amorphous metal 18 is oxidized by putting it into the crucible 24 and heating it at a temperature of 400 ° C. or higher and 600 ° C. or lower for 100 hours or more and 200 hours or less.
  • ZrO 2 obtained by oxidizing Zr is obtained.
  • fine metal particles 20A are obtained by performing a pulverization treatment for pulverizing the amorphous metal 18 after the oxidation treatment.
  • the crushing process is performed by automatic mortar processing.
  • the volume average particle diameter of the fine metal particles 20A preferably includes at least a range of 0.05 mm or more and 0.3 mm or less.
  • the fine metal particles 20A are calcined at 300 ° C. or higher and 600 ° C. or lower to obtain a nanocomposite metal material 10A.
  • the firing temperature in this firing step is indispensable in the range of 300 ° C. or higher and 600 ° C. or lower, but is preferably in the range of 400 ° C. or higher and 500 ° C. or lower, more preferably 450 ° C. or higher and 500 ° C. or lower, and 450 ° C. Especially preferable.
  • the firing time is preferably in the range of 120 hours or more and 180 hours or less.
  • the degree of oxidation of the carrier 12 of the nanocomposite metal material 10A produced by the above production method is greater than 31% and less than 100%.
  • the degree of oxidation of the nanocomposite metal material 10A may be adjusted by adjusting the firing temperature and firing time in the firing step.
  • the ratio of the weight of the nanocomposite metal material 10A, which is the fine metal particles 20A after firing, to the weight of the fine metal particles 20A before firing is used as the degree of oxidation of the carrier 12 in the nanocomposite metal material 10A.
  • firing was performed under firing conditions of firing at 450 ° C. for 120 hours or more and 180 hours or less, and the weight increase rate of the nanocomposite metal material 10A after firing was measured with respect to that before firing. This weight increase rate was calculated as the degree of oxidation, which is the rate of increase in the amount of oxygen added by firing.
  • the composition of the nanocomposite metal material 10A produced by the above production method is such that when the carrier 12 is composed of Zr, which is ceramic, the atomic number ratio (Cu: Ni) of Cu and Ni is 1: 7 or more and 1:15.
  • the range is as follows, and the atomic number ratio of Ni and Zr is in the range of 1: 2 or more and 1: 4 or less.
  • the composition of the nanocomposite metal material 10A is preferably in the above range, but the atomic number ratio of Cu to Ni (Cu: Ni) is preferably in the range of 1: 7 or more and 1:12 or less. Further, the atomic number ratio of Ni and Zr may be in the range of 1: 2 or more and 1: 4 or less, or 1: 2 or more and 1: 3 or less.
  • composition of the nanocomposite metal material 10A is adjusted by adjusting the atomic ratio (mass ratio) of the Cu—Ni—Zr alloy, which is the amount charged at the time of producing the fine metal particles 20A.
  • Nanocomposite metal material 10B A method for producing the nanocomposite metal material 10B and the nanocomposite metal material 10B will be described.
  • the nanocomposite metal material 10B is composed of a carrier 12 made of Zr, two-element metal particles 14 made of Pd and Ni supported on the carrier 12, and the degree of oxidation of the carrier 12 made of Zr is 3% or more.
  • the nanocomposite metal material 10 is 100% or less.
  • the degree of oxidation of the carrier 12 made of Zr of the nanocomposite metal material 10B is 3% or more and 100% or less, but it is preferably 20% or more and 100% or less, and 25% or more and 100% or less. More preferred.
  • the nanocomposite metal material 10B has a calcining step of calcining fine metal particles obtained by pulverizing an amorphous metal composed of Pd, Ni, and Zr at 300 ° C. or higher and 600 ° C. or lower to obtain the nanocomposite metal material 10B.
  • the nanocomposite metal material 10B is produced by the same firing process as the nanocomposite metal material 10A except that a Pd—Ni—Zr alloy is used instead of the Cu—Ni—Zr alloy.
  • the amorphous metal 18 is produced by melting and quenching the Pd-Ni—Zr alloy by the melt spinning method.
  • the Pd-Ni—Zr alloy is melted by heating in the heating furnace 22A, and the melted liquid is supplied to the rotating cooling roll 22B.
  • the molten liquid solidifies when it comes into contact with the rotating cooling roll 22B to produce a ribbon-shaped amorphous metal 18.
  • the thickness of the ribbon-shaped amorphous metal 18 is adjusted to, for example, a thickness range of 2 ⁇ m or more and 50 ⁇ m or less by adjusting the supply amount to the cooling roll 22B, the rotation speed of the cooling roll 22, and the like.
  • the amorphous metal 18 is oxidized in the atmosphere.
  • the amorphous metal 18 is oxidized by putting it into the crucible 24 and heating it at a temperature of 400 ° C. or higher and 600 ° C. or lower for 100 hours or more and 200 hours or less.
  • ZrO 2 obtained by oxidizing Zr is obtained.
  • the fine metal particles 20B are obtained by performing a pulverization treatment for pulverizing the amorphous metal 18 after the oxidation treatment.
  • the crushing process is performed by automatic mortar processing.
  • the volume average particle diameter of the fine metal particles 20B preferably includes at least a range of 0.05 mm or more and 0.5 mm or less.
  • the fine metal particles 20B are calcined at 300 ° C. or higher and 600 ° C. or lower to obtain a nanocomposite metal material 10B.
  • the firing temperature in this firing step is indispensable in the range of 300 ° C. or higher and 600 ° C. or lower, but is preferably in the range of 450 ° C. or higher and 600 ° C. or lower, more preferably 450 ° C. or higher and 500 ° C. or lower, and 450 ° C. is preferable. Especially preferable.
  • the firing time is preferably in the range of 120 hours or more and 180 hours or less.
  • the degree of oxidation of the nanocomposite metal material 10B produced by the above production method is 3% or more and 100% or less.
  • the degree of oxidation of the nanocomposite metal material 10B may be adjusted by adjusting the firing temperature and firing time in the firing step.
  • the ratio of the weight of the nanocomposite metal material 10B which is the fine metal particles 20B after firing to the weight of the fine metal particles 20B before firing is set to the nanocomposite. It is used as the degree of oxidation of the carrier 12 made of Zr in the metal material 10B.
  • the measurement of the degree of oxidation of the carrier 12 made of Zr in the nanocomposite metal material 10B may be performed in the same manner as the measurement of the degree of oxidation of the nanocomposite metal material 10A.
  • the composition of the nanocomposite metal material 10B is such that when the carrier 12 is composed of Zr, which is a ceramic, the atomic number ratio (Pd: Ni) of Pd to Ni is in the range of 1: 7 or more and 1:15 or less. , The atomic number ratio of Ni and Zr is in the range of 1: 2 or more and 1: 4 or less.
  • the composition of the nanocomposite metal material 10B is preferably in the above range, but the atomic number ratio (Pd: Ni) of Pd to Ni is more preferably in the range of 1: 7 or more and 1:12 or less. Further, the atomic number ratio of Ni and Zr may be in the range of 1: 2 or more and 1: 3 or less.
  • composition of the nanocomposite metal material 10B is adjusted by adjusting the atomic ratio (mass ratio) of the Pd—Ni—Zr alloy, which is the amount charged at the time of producing the fine metal particles 20B.
  • Nanocomposite metal material 10C ⁇ Nanocomposite metal material 10C> Next, a method for producing the nanocomposite metal material 10C and the nanocomposite metal material 10C will be described.
  • the nanocomposite metal material 10C is a nanocomposite metal material 10A composed of a carrier 12 made of Zr and two-element metal particles 14 made of Cu and Ni supported on the carrier 12, and is a nanocomposite metal material 10 containing Cu.
  • the nanocomposite metal material 10 is manufactured by a manufacturing method different from that of the above.
  • the method for producing the nanocomposite metal material 10C includes a hydrogen storage step and a heating step.
  • the hydrogen storage step in the method for producing the nanocomposite metal material 10C is a step of supplying hydrogen gas to the fine metal particles 20A and causing the fine metal particles 20A to occlude hydrogen.
  • the fine metal particles 20A are the same as described above.
  • the storage of hydrogen in the fine metal particles 20A is realized by supplying hydrogen gas to the fine metal particles 20A arranged in the reaction furnace in a vacuum state.
  • the hydrogen gas to be supplied may be either deuterium gas or light hydrogen gas.
  • the heating step in the method for producing the nanocomposite metal material 10C is a step of obtaining the nanocomposite metal material 10C by heating the fine metal particles 20A occluded with hydrogen to 200 ° C. or higher and 300 ° C. or lower under a vacuum state. .. This heating process is sometimes referred to as baking.
  • the temperature range of this heating step is preferably 200 ° C. or higher and 450 ° C. or lower, but may be 200 ° C. or higher and 500 ° C. or lower, or 250 ° C. or higher and 400 ° C. or lower.
  • the temperature range may be appropriately selected according to the material composition and the degree of oxidation.
  • the temperature range of this heating step (baking) may be within a range in which the material temperature distribution during heating is at least 200 ° C. or higher and 250 ° C. or lower, and at least 350 ° C. or higher and 450 ° C. or lower.
  • the period from the start to the end shall be maintained in the temperature range from the minimum temperature of 200 ° C. or higher and 250 ° C. or lower to the maximum temperature of 350 ° C. or higher and 450 ° C. or lower. ..
  • the heating time in this heating step may be adjusted according to the heating temperature, the released gas pressure, and the like.
  • the heating time is preferably in the range of 10 hours or more and 72 hours or less, and more preferably in the range of 24 hours or more and 72 hours or less.
  • this heating step is executed a plurality of times.
  • the plurality of heating steps is a series of steps from the start of heating to 200 ° C. or higher and 300 ° C. or lower under a vacuum state until the degree of vacuum reaches 1 Pa or lower, and this series of steps is counted as one step. The number of repetitions of the number of steps is shown.
  • the temperature in the heating step may change within the above range depending on the gas pressure at the start and the amount of gas released during baking.
  • the first heating step it is considered that phenomena such as evaporation of water in the fine metal particles 20A occluded with hydrogen and generation of impurity gas (nitrogen, etc.) from the fine metal particles 20A occur. Therefore, it is preferable to use the nanocomposite metal material 10 produced by executing the heating step twice or more as the nanocomposite metal material 10C.
  • the heating step (baking) the inside of the reaction furnace in a vacuum state is heated within the range of 200 ° C. or higher and 450 ° C. or lower.
  • hydrogen storage is performed by setting the hydrogen gas to 0.5 MPa-1 MPa at room temperature.
  • the second heating step (baking) is performed by raising the temperature to 200 ° C. or higher and 450 ° C. or lower while exhausting the hydrogen gas existing in the reactor.
  • baking is performed three times or more, it may be repeated in the same manner.
  • the fine metal particles 20A used in the hydrogen storage step are in a state in which at least a part of Cu is oxidized by the oxidation treatment of the amorphous metal 18 at the time of producing the fine metal particles 20A. It is considered that Ni is hardly oxidized. It is considered that when hydrogen is occluded in the fine metal particles 20A, the oxygen atom of copper oxide reacts with hydrogen gas, and oxygen is discharged as water or heavy water. Therefore, it is considered that holes are formed on the surface of the carrier 12 due to the departure of oxygen atoms.
  • the two-element metal particles 14 having a core-shell structure having Ni as a core and Cu as an incompletely covered shell are supported on the carrier 12 in a pulverized state, and are nanocomposite. It is considered that the metal material 10C can be obtained. It is theoretically speculated that heat generation sites due to hydrogen clusters are formed on the surface of the complete shell and Ni core. It is estimated that the increase in the number of exothermic sites is brought about by the baking and recalcination of the nanocomposite metal material, which increases the excess exothermic power.
  • the refiring corresponds to the above-mentioned firing step of firing the fine metal particles 20A or the fine metal particles 20B at 300 ° C. or higher and 600 ° C. or lower to obtain the nanocomposite metal material 10A.
  • the nanocomposite metal material 10C is produced by, for example, using a thermal reactor and undergoing the hydrogen storage step and the heating step.
  • FIG. 3 is a schematic view showing an example of the thermal reactor 30.
  • the thermal reaction apparatus 30 includes a reaction furnace 32 for holding a sample such as fine metal particles 20A inside.
  • the reaction furnace 32 is arranged in the housing 33.
  • the reactor 32 and the housing 33 are made of, for example, stainless steel (SUS306 or SUS316).
  • the reactor 32 has a hollow and closed shape, and is, for example, a cylindrical member in which both end faces in the longitudinal direction are sealed.
  • the gas supply unit 34 and the vacuum mechanism 36 are communicated with the reaction furnace 32 via the pipe 34B.
  • the gas supply unit 34 includes a gas cylinder 34A, a pipe 34B, a valve 34C, a valve 34D, a tank 34E, and a pressure measurement unit 34F.
  • the gas cylinder 34A stores hydrogen gas such as deuterium gas or light hydrogen gas.
  • the hydrogen gas stored in the gas cylinder 34A is supplied into the reactor 32 via the pipe 34B.
  • the valve 34C and the valve 34D are provided in the pipe 34B and are used for supplying hydrogen gas and adjusting the pressure.
  • the tank 34E communicates with the reactor 32 via the pipe 34B.
  • the tank 34E is a mechanism for adjusting the pressure in the reactor 32.
  • the pressure measuring unit 34F measures the pressure of the reactor 32.
  • the vacuum mechanism 36 is a mechanism for evacuating the inside of the reactor 32.
  • the vacuum mechanism 36 includes a vacuum pump 36A, a valve 36B, a pipe 36C, and a pressure measuring unit 36D.
  • One end of the pipe 36C communicates with the reactor 32 via the pipe 34B, and the other end communicates with the vacuum pump 36A via the valve 36B.
  • the pressure measuring unit 36D measures the pressure in the reactor 32.
  • the reaction furnace 32 is provided with a heating mechanism 38.
  • the heat reaction device 30 includes a heating unit 38A and a heating unit 38B as a heating mechanism 38.
  • the heating unit 38A heats the reaction furnace 32 from the outside.
  • the heating unit 38B is provided in the reaction furnace 32 and directly heats the inside of the reaction furnace 32.
  • the reaction furnace 32 is provided with a temperature sensor 40.
  • the temperature sensor 40 is a sensor that measures the temperature inside the reactor 32.
  • the number of temperature sensors 40 is not limited to four.
  • These plurality of temperature sensors 40 are arranged at different positions on the bottom of the reactor 32. Further, these plurality of temperature sensors 40 (temperature sensors 40A to 40D) are arranged in the reaction furnace 32 at positions where the temperatures at different positions in the longitudinal direction of the reaction furnace 32 can be measured.
  • the thermal reaction device 30 includes a circulation mechanism 42.
  • the circulation mechanism 42 is a mechanism for transferring the heat generated in the reactor 32 to the fluid by exchanging heat with the fluid, and using it for hot water supply, heat supply, power generation, and the like.
  • the circulation mechanism 42 includes a water circulation temperature controller 42A, an oil circulation temperature controller 42B, a fluid 42C, a pipe 42D, an adjusting unit 42E, a water bath 42F, a pipe 42H, a pump 42I, a pipe 42J, a pipe 42K, and a valve. It includes 42L, a storage section 42M, a pump 42P, a pipe 42Q, and a valve 42R.
  • the heat transport pipe 42X is a tubular member, and is spirally wound along the outer wall of the reactor 32.
  • the fluid 42C is flowing in the heat transport pipe 42X.
  • One end of the heat transport pipe 42X in the longitudinal direction is communicated with the water circulation temperature controller 42A and the oil circulation temperature controller 42B via the pipe 42K.
  • the water circulation temperature controller 42A and the oil circulation temperature controller 42B are devices that circulate the oil of the circulating fluid (hereinafter referred to as the fluid 42C).
  • the fluid 42C After being supplied to the flow rate measuring instrument 42O, the fluid 42C is flowed to the water bath 42F via the pipe 42D and the adjusting unit 42E.
  • the flow rate measuring instrument 42O is a known device that measures the flow rate of the fluid 42C based on the number of droplets.
  • the fluid 42C supplied to the water bath 42F is cooled by the liquid 42G stored in the water bath 42F, and then again wound around the reactor 32 via the pipe 42H, the pump 42I, and the pipe 42J. After recovering the amount of heat, it is supplied to the pipe 42K.
  • the storage unit 42M is a mechanism for storing the fluid 42C, and communicates with the flow rate measuring instrument 42O via the valve 42L.
  • the pump 42P is connected to the main body of the thermal reactor 30 via the pipe 42Q and the valve 42R.
  • the heat reaction device 30 is provided with a control unit 50 that controls the electronic devices of the heat reaction device 30, and the heat reaction device 30 is controlled by the control of the control unit 50.
  • the following method is used.
  • the hydrogen storage process is executed.
  • the fine metal particles 20A are supplied into the reaction furnace 32, and then the vacuum mechanism 36 is driven under the control of the control unit 50 to put the inside of the reaction furnace 32 into a vacuum state.
  • hydrogen gas is supplied into the reactor 32 while maintaining the vacuum state. The hydrogen gas is supplied under the control of the control unit 50.
  • the heating process is executed.
  • the supply of hydrogen gas into the reactor 32 is stopped.
  • the heating mechanism 38 by controlling the heating mechanism 38 while maintaining the hydrogen gas state in the reactor 32, for example, the material temperature distribution during heating in the reactor 32 is at least 200 ° C. or higher and 250 ° C. or lower, and at the highest 350 ° C. Heat so that the temperature is 450 ° C or lower.
  • the heating mechanism 38 may be controlled by the control unit 50.
  • the nanocomposite metal material 10C is produced.
  • the composition of the nanocomposite metal material 10C has an atomic number ratio of Cu to Ni (Cu: Ni) in the range of 1: 7 or more and 1:15 or less, and an atomic number ratio of Ni to Zr of 1: 2. The range is 1: 4 or less.
  • the composition of the nanocomposite metal material 10C is preferably in the above range, but the atomic number ratio of Cu to Ni (Cu: Ni) is preferably in the range of 1: 7 or more and 1:12 or less. Further, the atomic number ratio of Ni and Zr may be in the range of 1: 2 or more and 1:35 or less, or 1: 2 or more and 1: 2.5 or less.
  • composition of the nanocomposite metal material 10C is adjusted by adjusting the atomic ratio (mass ratio) of the Cu—Ni—Zr alloy, which is the amount charged at the time of producing the fine metal particles 20A.
  • Nanocomposite metal material 10D ⁇ Nanocomposite metal material 10D> Next, a method for producing the nanocomposite metal material 10D and the nanocomposite metal material 10D will be described.
  • the nanocomposite metal material 10D is composed of a carrier 12 made of ceramics, two-element metal particles 14 made of Pd and Ni supported on the carrier 12, and the nanocomposite metal material 10B which is a nanocomposite metal material 10 containing Pd.
  • the nanocomposite metal material 10 is manufactured by a manufacturing method different from that of the above.
  • the method for producing the nanocomposite metal material 10D includes a hydrogen storage step and a heating step.
  • the hydrogen storage step in the method for producing the nanocomposite metal material 10D is a step of supplying hydrogen gas to the fine metal particles 20B at room temperature. Hydrogen is occluded in the fine metal particles 20B, and heat generation treatment is performed for 3 days or more and 7 days or less under a temperature rising condition of 250 ° C. or higher and 350 ° C. or lower, and then heating is performed under vacuum.
  • the fine metal particles 20B are the same as described above.
  • the storage of hydrogen in the fine metal particles 20B is realized by supplying hydrogen gas to the fine metal particles 20B arranged in the reaction furnace in a vacuum state at room temperature.
  • the hydrogen gas to be supplied may be either deuterium gas or light hydrogen gas.
  • the heating step in the method for producing the nanocomposite metal material 10D is a step of obtaining the nanocomposite metal material 10D by heating the fine metal particles 20B occluded with hydrogen to 200 ° C. or higher and 450 ° C. or lower under a vacuum state. ..
  • the temperature range of this heating step is preferably 200 ° C. or higher and 450 ° C. or lower, but may be 300 ° C. or higher and 450 ° C. or lower, or 350 ° C. or higher and 450 ° C. or lower.
  • the temperature range of this heating step (baking) may be within a range in which the material temperature distribution during heating is at least 200 ° C. or higher and 250 ° C. or lower, and at the highest 350 ° C. or higher and 450 ° C. or lower.
  • the heating time in this heating step may be adjusted according to the heating temperature (250 ° C to 450 ° C) and the like.
  • the heating time is preferably in the range of 24 hours or more and 64 hours or less, and most preferably in the range of 48 hours or more and 64 hours or less.
  • the heating step in the production of the nanocomposite metal material 10D is preferably executed a plurality of times.
  • the definition of the multiple heating steps is the same as above.
  • the first heating step it is considered that phenomena such as evaporation of water in the fine metal particles 20B occluded with hydrogen and generation of impurity gas (nitrogen, etc.) from the fine metal particles 20B occur. Therefore, it is preferable to use the nanocomposite metal material 10 produced by executing the heating step twice or more as the nanocomposite metal material 10D.
  • the nanocomposite metal material 10D is produced by passing through the hydrogen storage step and the heating step using a thermal reactor.
  • a thermal reactor 30 is used in the production of the nanocomposite metal material 10D (see FIG. 3).
  • the following method is used.
  • the hydrogen storage process is executed.
  • the fine metal particles 20B are supplied into the reaction furnace 32, and then the vacuum mechanism 36 is driven under the control of the control unit 50 to put the inside of the reaction furnace 32 into a vacuum state.
  • hydrogen gas is supplied into the reactor 32 while maintaining the vacuum state. The hydrogen gas is supplied under the control of the control unit 50.
  • the heating process is executed.
  • the supply of hydrogen gas into the reactor 32 is stopped.
  • the inside of the reaction furnace 32 is heated to 200 ° C. or higher and 300 ° C. or lower by controlling the heating mechanism 38 while maintaining the hydrogen gas state in the reaction furnace 32.
  • the heating mechanism 38 may be controlled by the control unit 50.
  • the composition of the nanocomposite metal material 10D has an atomic number ratio of Pd to Ni (Pd: Ni) in the range of 1: 7 or more and 1:15 or less, and an atomic number ratio of Ni to Zr of 1: 2.
  • the range is 1: 4 or less.
  • the composition of the nanocomposite metal material 10D is preferably in the above range, but the atomic number ratio (Pd: Ni) of Pd to Ni is more preferably in the range of 1: 7 or more and 1:12 or less. Further, the atomic number ratio of Ni and Zr may be in the range of 1: 2 or more and 1: 3 or less, or 1: 2 or more and 1: 2.5 or less.
  • composition of the nanocomposite metal material 10D is adjusted by adjusting the atomic ratio (mass ratio) of the Pd—Ni—Zr alloy, which is the amount charged at the time of producing the fine metal particles 20B.
  • Nanocomposite metal material 10E Next, the nanocomposite metal material 10E and the method for producing the nanocomposite metal material 10E will be described.
  • the nanocomposite metal material 10E is a nanocomposite metal material 10A composed of a carrier 12 made of ceramics and two-element metal particles 14 made of Cu and Ni supported on the carrier 12, and is a nanocomposite metal material 10 containing Cu.
  • the nanocomposite metal material 10 is manufactured by a manufacturing method different from that of the nanocomposite metal material 10C.
  • the method for producing the nanocomposite metal material 10E includes a firing step of firing fine metal particles 20A obtained by crushing an amorphous metal 18 made of Cu, Ni, and ceramics at 300 ° C. or higher and 600 ° C. or lower, and the fired fine metal particles.
  • the method for producing the nanocomposite metal material 10E corresponds to the method for producing the nanocomposite metal material 10C using the nanocomposite metal material 10A obtained by the method for producing the nanocomposite metal material 10A as the fine metal particles 20A.
  • the firing step in the manufacturing method of the nanocomposite metal material 10E is the same as the firing step in the manufacturing method of the nanocomposite metal material 10A.
  • the nano-composite metal material 10A obtained by the firing step is used instead of the fine metal particles 20A in the hydrogen storage step. This is the same as the hydrogen storage step and the heating step of the method for producing the composite metal material 10C.
  • the composition of the nanocomposite metal material 10E is such that when the carrier 12 is composed of Zr, which is ceramic, the atomic number ratio (Cu: Ni) of Cu and Ni is in the range of 1: 7 or more and 1:15 or less. , The atomic number ratio of Ni and Zr is in the range of 1: 2 or more and 1: 4 or less.
  • the composition of the nanocomposite metal material 10E is preferably in the above range, but the atomic number ratio of Cu to Ni (Cu: Ni) is more preferably in the range of 1: 7 or more and 1:12 or less. Further, the atomic number ratio of Ni and Zr may be in the range of 1: 2 or more and 1: 3 or less, or 1: 2 or more and 1: 2.5 or less.
  • composition of the nanocomposite metal material 10E is adjusted by adjusting the atomic ratio (mass ratio) of the Cu—Ni—Zr alloy, which is the amount charged at the time of producing the fine metal particles 20A.
  • Nanocomposite metal material 10F ⁇ Nanocomposite metal material 10F> Next, a method for producing the nanocomposite metal material 10F and the nanocomposite metal material 10F will be described.
  • the nanocomposite metal material 10F is composed of a carrier 12 made of ceramics, two-element metal particles 14 made of Pd and Ni supported on the carrier 12, and the nanocomposite metal material 10B which is a nanocomposite metal material 10 containing Pd.
  • the nanocomposite metal material 10 is manufactured by a manufacturing method different from that of the nanocomposite metal material 10D.
  • the method for producing the nanocomposite metal material 10F is a firing step of firing fine metal particles 20B obtained by crushing an amorphous metal 18 composed of Pd, Ni, and ceramics at 300 ° C. or higher and 600 ° C. or lower, and the fired fine metal particles.
  • the method for producing the nanocomposite metal material 10F corresponds to the method for producing the nanocomposite metal material 10D using the nanocomposite metal material 10B obtained by the method for producing the nanocomposite metal material 10B as the fine metal particles 20B.
  • the firing step in the manufacturing method of the nanocomposite metal material 10F is the same as the firing step in the manufacturing method of the nanocomposite metal material 10B.
  • the nano-composite metal material 10B obtained by the firing step is used instead of the fine metal particles 20B in the hydrogen storage step. This is the same as the hydrogen storage step and the heating step of the method for producing the composite metal material 10D.
  • the composition of the nanocomposite metal material 10F is such that when the carrier 12 is composed of Zr, which is a ceramic, the atomic number ratio (Pd: Ni) of Pd to Ni is in the range of 1: 7 or more and 1:15 or less. , The atomic number ratio of Ni and Zr is in the range of 1: 2 or more and 1: 4 or less.
  • the composition of the nanocomposite metal material 10F is preferably in the above range, but the atomic number ratio (Pd: Ni) of Pd to Ni is more preferably in the range of 1: 7 or more and 1:12 or less. Further, the atomic number ratio of Ni and Zr may be in the range of 1: 2 or more and 1: 3 or less, or 1: 2 or more and 1: 2.5 or less.
  • composition of the nanocomposite metal material 10F is adjusted by adjusting the atomic ratio (mass ratio) of the Pd—Ni—Zr alloy, which is the amount charged at the time of producing the fine metal particles 20A.
  • the nanocomposite metal material 10 is placed in the reaction furnace, the inside of the reaction furnace is evacuated, and hydrogen gas is supplied into the reaction furnace.
  • the hydrogen gas to be supplied may be either deuterium gas or light hydrogen gas.
  • the inside of the reaction furnace is heated within the range of 250 ° C. or higher and 450 ° C. or lower, specifically, the material temperature distribution at the time of heating is 200-250 ° C. at the lowest and 350-450 ° C. at the highest.
  • the thermal reaction between the nanocomposite metal material 10 and hydrogen causes an exothermic phenomenon due to the thermal reaction. This heat generation phenomenon may be referred to as an abnormal heat generation phenomenon.
  • the nanocomposite metal material 10 of the present embodiment can realize an increase in the calorific value of the heat generation phenomenon as compared with the conventional composite metal material manufactured by a manufacturing method other than the above-mentioned manufacturing method. It was.
  • the present invention is not limited by the following speculation. Incomplete shell of Cu-Ni, Pd-Ni-The number of nanocatalytic dented structures (called sub-nanoholes in the theoretical model) on the surface of the Ni core of the Ni core combined the refiring and baking of the present invention. It is presumed that the treatment causes a large increase in the hydrogen cluster-induced exothermic reaction formed at the site, with a dynamic balance between hydrogen storage and occlusion under elevated temperature. It is considered that the calorific value can be increased by such a mechanism.
  • Nanocomposite metal material 10G ⁇ Nanocomposite metal material 10G> Next, a method for producing the nanocomposite metal material 10G and the nanocomposite metal material 10G will be described.
  • the nanocomposite metal material 10G is a nanocomposite metal material 10A composed of a carrier 12 made of ceramics and two-element metal particles 14 made of Cu and Ni supported on the carrier 12, and is a nanocomposite metal material 10 containing Cu. , The nanocomposite metal material 10C, and the nanocomposite metal material 10 manufactured by a manufacturing method different from that of the nanocomposite metal material 10E.
  • the method for producing the nanocomposite metal material 10G uses fine metal particles 20A as a starting material, and includes a heating step, a hydrogen storage step, a reaction step, and a refiring step.
  • the heating step included in the method for producing the nanocomposite metal material 10G is the same as the heating step used in the method for producing the nanocomposite metal material 10C and the nanocomposite metal material 10E described above, and is the same as the heating step used in the method for producing the nanocomposite metal material 10E. Any condition can be selected from the conditions.
  • the hydrogen storage step of the method for producing the nanocomposite metal material 10G is the same as the hydrogen storage step used in the method for producing the nanocomposite metal material 10C and the nanocomposite metal material 10E described above, and is the same as the hydrogen storage step used in the method for producing the nanocomposite metal material 10E. Any condition can be selected from the storage process conditions.
  • the reaction step of the method for producing the nanocomposite metal material 10G is the same as the reaction step which is an exothermic reaction between the nanocomposite metal material 10A to the nanocomposite metal material 10F and hydrogen described above, and is the reaction described above. Any condition can be selected from the process conditions.
  • the refiring step of the method for producing the nanocomposite metal material 10G is the same as the firing step used in the method for producing the nanocomposite metal material 10A described above, and is arbitrary from the conditions of the firing step described above. Conditions can be selected.
  • the re-firing step in the nano-composite metal material 10G is a firing step performed after the above-mentioned hydrogen storage step, heating step, and reaction step, and the nano-composite metal material 10A is produced from the above-mentioned fine metal particles 20A. It is distinguished from the firing process for.
  • FIG. 4 is a flow chart showing an example of the procedure of the manufacturing method of the nanocomposite metal material 10G according to the embodiment.
  • fine metal particles 20A are produced from a Cu—Ni—Zr alloy using the above method (step S110).
  • step S121 1 the heating step (baking) (step S121 1 ), the hydrogen storage step (step S122 1 ), and the reaction step (step S123 1 ) are repeated in this order for the fine metal particles 20A until a predetermined number of times is reached (step).
  • step S120 1 The number of times these steps are performed can be one or more.
  • step S130 1 a refiring step is carried out on the fine metal particles 20A (step S130 1 ).
  • the fine metal particles 20A are taken out from the reaction furnace used in the above step and refired in another system.
  • the calorific value obtained from the nanocomposite metal material 10G is dramatically increased.
  • the nanocomposite metal material 10G 1 is manufactured by the processing up to step S130 1.
  • the processes of steps S120 (steps S121 to S123) and steps S130 can be regarded as one cycle, and these processes can be repeated a plurality of times.
  • the nanocomposite metal material 10 obtained by performing the treatments of step S120 and step S130 once is referred to as the nanocomposite metal material 10G 1 as described above.
  • the nanocomposite metal material 10 obtained by performing the treatments of step S120 and step S130 twice is referred to as nanocomposite metal material 10G 2.
  • the nth step S120n (steps S121n to S123n) and the process up to the treatment of step S130n are referred to as nanocomposite metal material 10Gn.
  • the calorific value obtained from the nanocomposite metal material 10Gn tends to increase. is there.
  • Nanocomposite metal material 10H ⁇ Nanocomposite metal material 10H> Next, a method for producing the nanocomposite metal material 10H and the nanocomposite metal material 10H will be described.
  • the nanocomposite metal material 10H is composed of a carrier 12 made of ceramics, two-element metal particles 14 made of Pd and Ni supported on the carrier 12, and the nanocomposite metal material 10B which is a nanocomposite metal material 10 containing Pd. , The nanocomposite metal material 10D, and the nanocomposite metal material 10 manufactured by a manufacturing method different from that of the nanocomposite metal material 10F.
  • the method for producing the nanocomposite metal material 10H uses fine metal particles 20B as a starting material, and includes a heating step, a hydrogen storage step, a reaction step, and a refiring step.
  • the heating step included in the manufacturing method of the nanocomposite metal material 10H is the same step as the heating step used in the manufacturing method of the nanocomposite metal material 10D and the nanocomposite metal material 10F described above, and is the same step as the heating step used in the manufacturing method of the nanocomposite metal material 10F described above. Any condition can be selected from the conditions.
  • the hydrogen storage step of the method for producing the nanocomposite metal material 10H is the same as the hydrogen storage step used in the method for producing the nanocomposite metal material 10D and the nanocomposite metal material 10F described above, and is the same as the hydrogen storage step used in the method for producing the nanocomposite metal material 10F. Any condition can be selected from the storage process conditions.
  • the reaction step of the method for producing the nanocomposite metal material 10H is the same as the reaction step which is an exothermic reaction between the nanocomposite metal material 10A to the nanocomposite metal material 10F and hydrogen described above, and is the reaction described above. Any condition can be selected from the process conditions.
  • the refiring step of the method for producing the nanocomposite metal material 10H is the same as the firing step used in the method for producing the nanocomposite metal material 10B described above, and is arbitrary from the conditions of the firing step described above. Conditions can be selected.
  • the re-firing step in the nano-composite metal material 10H is a firing step performed after the above-mentioned hydrogen storage step, heating step, and reaction step, and the nano-composite metal material 10B is produced from the above-mentioned fine metal particles 20B. It is distinguished from the firing process for.
  • FIG. 5 is a flow chart showing an example of the procedure of the manufacturing method of the nanocomposite metal material 10H according to the embodiment.
  • fine metal particles 20B are produced from the Pd—Ni—Zr alloy using the above method (step S210).
  • step S221 1 the heating step (baking) (step S221 1 ), the hydrogen storage step (step S222 1 ), and the reaction step (step S223 1 ) are repeated in this order for the fine metal particles 20B until a predetermined number of times is reached (step).
  • step S220 1 The number of times these steps are performed can be one or more.
  • step S230 1 a refiring step is performed on the fine metal particles 20B (step S230 1 ).
  • the fine metal particles 20B are taken out from the reaction furnace used in the above step and refired in another system.
  • the calorific value obtained from the nanocomposite metal material 10H is dramatically increased.
  • the nanocomposite metal material 10H 1 is manufactured by the treatment up to step S230 1.
  • the processes of steps S220 (steps S221 to S223) and steps S230 can be regarded as one cycle, and these processes can be repeated a plurality of times.
  • nanocomposite metal material 10H 1 The nanocomposite metal material 10 obtained by performing the treatments of steps S220 and S230 once is referred to as the nanocomposite metal material 10H 1 as described above.
  • the nanocomposite metal material 10 obtained by performing the treatments of steps S220 and S230 twice is referred to as nanocomposite metal material 10H 2.
  • nanocomposite metal material 10Hn those that have undergone the nth step S220n (steps S221n to S223n) and the treatment of step S230n are referred to as nanocomposite metal material 10Hn.
  • the calorific value obtained from the nanocomposite metal material 10Hn tends to increase. is there.
  • fine metal particles 20 fine metal particles 20A, fine metal particles 20B
  • fine metal particles 20A fine metal particles 20A, fine metal particles 20B
  • -Fine metal particles 20A CNZ7
  • -Fine metal particles 20B PNZ10
  • CNZ7 is an example of the fine metal particles 20A produced by using the above-mentioned Cu—Ni—Zr alloy.
  • CNZ7 was prepared as follows.
  • this amorphous metal 18 was put into the crucible 24 and heated in the air at a temperature of 450 ° C. for 120 hours. Then, the heated amorphous metal 18 was pulverized using an automatic mortar to produce CNZ7, which is an example of the fine metal particles 20A.
  • CNZ7 is an example of the fine metal particles 20A.
  • the volume average particle diameter of CNZ7 was measured with an optical microscope at a resolution of 0.01 mm, the volume average particle diameter was 0.1 mm to 0.2 mm or less.
  • the degree of oxidation of CNZ7 was 31% when the weight increase rate after firing was measured.
  • PNZ10 is an example of the fine metal particles 20B produced by using the above-mentioned Pd—Ni—Zr alloy.
  • PNZ10 was prepared as follows.
  • this amorphous metal 18 was put into the crucible 24 and heated in the air at a temperature of 450 ° C. for 80 hours. Then, the heated amorphous metal 18 was pulverized using an automatic mortar to prepare PNZ10, which is an example of the fine metal particles 20B.
  • PNZ10 is an example of the fine metal particles 20B.
  • the volume average particle diameter of PNZ10 was measured with an optical microscope under the condition of 0.01 mm resolution, it was 0.05 mm or more and 0.1 mm or less. Further, the degree of oxidation of PNZ10 was measured by the weight increase rate after firing and found to be 2.44%.
  • nanocomposite metal material 10 The following nanocomposite metal materials 10 were prepared as the nanocomposite metal material 10A to the nanocomposite metal material 10H.
  • -Nanocomposite metal material 10A CNZ7r -Nanocomposite metal material 10B: PNZ10r -Nanocomposite metal material 10C: CNZ7 # 1-1, CNZ7 # 2-1 -Nanocomposite metal material 10D: PNZ10 # 1-1, PNZ10 # 2-1 -Nanocomposite metal material 10E: CNZ7r # 1-1, CNZ7r # 1-2, CNZ7r # 2-1, CNZ7r # 2-2, CNZ7r # 2-4 -Nanocomposite metal material 10F: PNZ10r # 1-1, PNZ10r # 1-4, PNZ10r # 2-1 and PNZ10r # 2-2 -Nanocomposite metal material 10
  • CNZ7r is an example of a nanocomposite metal material 10A produced by using CNZ7 (fine metal particles 20A) prepared above.
  • the lowercase “r” means that the firing step of the nanocomposite metal material 10A was performed once.
  • CNZ7r was prepared as follows.
  • CNZ7 fine metal particles 20A
  • reaction furnace 32 an electric furnace
  • CNZ7r nanocomposite metal material 10A
  • FIG. 6 is an electron micrograph of CNZ7r.
  • the volume average particle diameter of CNZ7r nanocomposite metal material 10A
  • the degree of oxidation of the carrier 12 which is Zr of CNZ7r was measured by the method described above, it was 35.6% by weight.
  • PNZ10r is an example of the nanocomposite metal material 10B produced by using the PNZ10 (fine metal particles 20B) prepared above.
  • the lowercase “r” means that the firing step of the nanocomposite metal material 10B was performed once.
  • PNZ10r was prepared as follows.
  • PNZ10r fine metal particles 20B prepared above was put into an electric furnace (reaction furnace 32) and calcined in the atmosphere at 450 ° C. for 120 hours. By this firing step, PNZ10r (nanocomposite metal material 10B) was produced.
  • Nanocomposite metal material 10C CNZ7 # 1-1, CNZ7 # 2-1] CNZ7 # 1-1 and CNZ7 # 2-1 were prepared as the nanocomposite metal material 10C.
  • CNZ7 # 1-1 and CNZ7 # 2-1 are examples of nanocomposite metal material 10C prepared by using CNZ7 (fine metal particles 20A) prepared above.
  • the number immediately after "#" indicates the number of heating steps (baking) in the nanocomposite metal material 10C. That is, # 1 means that the heating step (baking) was executed once after the hydrogen storage step. Further, # 2 means that the heating step (baking) was executed twice after the hydrogen storage step.
  • CNZ7 # 1-1 and CNZ7 # 2-1 were prepared as follows.
  • CNZ7 # 1-1 and CNZ7 # 2-1 were produced using the thermal reactor 30 shown in FIG.
  • CNZ7 # 2-1 was produced by performing a heating step (baking) of heating for 24 hours (second baking) again by changing to the above vacuum exhaust.
  • Nanocomposite metal material 10D PNZ10 # 1-1, PNZ10 # 2-1
  • PNZ10 # 1-1 and PNZ10 # 2-1 were prepared as the nanocomposite metal material 10D.
  • PNZ10 # 1-1 and PNZ10 # 2-1 are examples of the nanocomposite metal material 10D produced using the PNZ10 (fine metal particles 20B) prepared above.
  • the number immediately after "#" indicates the number of heating steps (baking) in the nanocomposite metal material 10D. That is, # 1 means that the heating step (baking) was executed once after the hydrogen storage step. Further, # 2 means that the heating step (baking) was executed twice after the hydrogen storage step.
  • PNZ10 # 1-1 and PNZ10 # 2-1 were produced using the thermal reactor 30 shown in FIG.
  • PNZ10 # 1-1 was produced by this heating step.
  • PNZ10 # 2-1 was produced by switching to vacuum exhaust and performing baking under the same conditions as the first baking (second baking).
  • Nanocomposite metal material 10E CNZ7r # 1-1, CNZ7r # 1-2, CNZ7r # 2-1 and CNZ7r # 2-2, CNZ7r # 2-4
  • CNZ7r # 1-1, CNZ7r # 1-2, CNZ7r # 2-1 and CNZ7r # 2-2, CNZ7r # 2-4 were prepared.
  • CNZ7r # 1-1, CNZ7r # 1-2, CNZ7r # 2-1 and CNZ7r # 2-2, CNZ7r # 2-4 are nanocomposite metals prepared using CNZ7 (fine metal particles 20A) prepared above. This is an example of the material 10E.
  • the number immediately after "#" indicates the number of heating steps (baking) in the nanocomposite metal material 10E.
  • CNZ7r # 1-1, CNZ7r # 1-2, CNZ7r # 2-1 and CNZ7r # 2-2, CNZ7r # 2-4 were produced using the thermal reactor 30 shown in FIG.
  • CNZ7r which is the nanocomposite metal material 10A produced above
  • the vacuum mechanism 36 was driven by the control of the control unit 50 to put the inside of the reaction furnace 32 into a vacuum state.
  • hydrogen gas was supplied from the gas supply unit 34 into the reactor 32 while maintaining the vacuum state (hydrogen storage step).
  • the supply of hydrogen gas was stopped while maintaining the hydrogen gas state in the reactor 32.
  • the material temperature distribution in the reaction furnace 32 is controlled in a temperature range of a minimum of 200 ° C. and a maximum of 450 ° C. or less.
  • CNZ7r # 1-2 was produced by the same step as CNZ7r # 1-1.
  • a heating step (first baking) of heating to the temperature range of 200 ° C. or higher and 350 ° C. or lower which is a heating step (baking) in the production of CNZ7r # 1-1, is executed (first baking), and then vacuum exhaust is performed.
  • CNZ7r # 2-1 was produced by switching to and executing the heating step (baking) under the same conditions as the first baking (second baking).
  • Nanocomposite metal material 10F PNZ10r # 1-1, PNZ10r # 1-4, PNZ10r # 2-1 and PNZ10r # 2-2
  • PNZ10r # 1-1, PNZ10r # 1-4, PNZ10r # 2-1 and PNZ10r # 2-2 were prepared.
  • PNZ10r # 1-1, PNZ10r # 1-4, PNZ10r # 2-1 and PNZ10r # 2-2 are examples of nanocomposite metal material 10F produced using PNZ10 (fine metal particles 20B) prepared above. .. Similar to the above, the number immediately after “#” indicates the number of heating steps (baking) in the nanocomposite metal material 10E.
  • PNZ10r # 1-1, PNZ10r # 1-4, PNZ10r # 2-1 and PNZ10r # 2-2 were produced using the thermal reactor 30 shown in FIG.
  • PNZ10r which is the nanocomposite metal material 10B produced above
  • the vacuum mechanism 36 was driven by the control of the control unit 50 to put the inside of the reaction furnace 32 into a vacuum state.
  • hydrogen gas was supplied from the gas supply unit 34 into the reaction furnace 32 while maintaining the vacuum state (room temperature hydrogen storage step).
  • the supply of hydrogen gas was stopped while maintaining the state inside the reactor 32.
  • the reaction furnace 32 was heated to 250 ° C.-350 ° C. by the heating mechanism 38 to generate excessive heat for several days and perform a test.
  • PNZ10r # 1-1 was produced.
  • PNZ10r # 1-4 was prepared by storing hydrogen at room temperature (# 1-2) and raising the temperature to 300 ° C.
  • PNZ10r # 1-4 heating overheating test a heating step of heating for 24 hours with the material temperature distribution set to a minimum of 200 ° C. and a maximum of 450 ° C., which is a heating step (baking) in production, is executed (2).
  • PNZ10r # 2-1 was prepared, and following hydrogen storage (# 2-1) at room temperature, a temperature rise test (# 2-2) was performed at a temperature of 300 ° C. or higher and 350 ° C. or lower. Executed.
  • Nanocomposite metal material 10G CNZ7R, CNZ7RR, CNZ7RRR] CNZ7R, CNZ7RR, and CNZ7RRR were prepared as the nanocomposite metal material 10G.
  • CNZ7R, CNZ7RR, and CNZ7RRR are examples of nanocomposite metal material 10G prepared by using CNZ7 (fine metal particles 20A) prepared above.
  • the capital letter "R" after CNZ7 means the nanocomposite metal material 10G that has undergone one heating step, hydrogen storage step, and refiring step after the reaction step. That is, CNZ7R is an example of the nanocomposite metal material 10G 1 , CNZ7RR is an example of the nanocomposite metal material 10G 2 , and CNZ7RRR is an example of the nanocomposite metal material 10G 3 .
  • Nanocomposite metal material 10H PNZ10R, PNZ10RR, PNZ10RRR] PNZ10R, PNZ10RR, and PNZ10RRR were prepared as the nanocomposite metal material 10H.
  • PNZ10R, PNZ10RR, and PNZ10RRR are examples of the nanocomposite metal material 10H produced by using the PNZ10 (fine metal particles 20B) prepared above.
  • the capital letter "R" after PNZ10 means the nanocomposite metal material 10H that has undergone one heating step, hydrogen storage step, and refiring step after the reaction step. That is, PNZ10R is an example of the nanocomposite metal material 10H 1 , PNZ10RR is an example of the nanocomposite metal material 10H 2 , and PNZ10RRR is an example of the nanocomposite metal material 10H 3 .
  • each of the nanocomposite metal materials 10 produced above is placed in the reaction furnace 32 of the thermal reaction apparatus 30 shown in FIG. 3 in an amount of 450 g or more and 505 g or less, and the inside of the reaction furnace 32 is evacuated.
  • the supply of deuterium gas into the reactor 32 was started.
  • the inside of the reaction furnace 32 was heated to a temperature range of 250 ° C. or higher and 350 ° C. or lower by controlling the heating mechanism 38.
  • the supply of deuterium gas and the heating of the reaction furnace 32 were continued for 150 hours or more, and the change in calorific value due to the thermal reaction between the nanocomposite metal material 10 and hydrogen was measured.
  • a calorific value calibration test in which the average value of the temperature measurement results of the temperature sensors 40A to 40D, which are the temperature sensors 40 installed in the reactor 32, is loaded into the reactor with a non-heating blank sample of 1300 g of zirconia beads. The result calculated by comparing with the data was measured as the amount of excess heat generation power.
  • FIG. 7 is a measurement result showing the relationship between the calorific value and the degree of oxidation of the fine metal particles 20 and the nanocomposite metal material 10.
  • FIG. 7 is calculated using the average value of the temperature measurement results by the temperature sensor 40 for several weeks from 24 hours after the start of heating the reactor 32 to 300 ° C. and the supply of deuterium gas. The calorific value was shown.
  • FIG. 7 shows a diagram 60 and a diagram 62.
  • the diagram 60 is a diagram passing through the plot 60A and the plot 60B.
  • Plot 60A shows the correspondence between the degree of oxidation (2.44%) of PNZ10, which is the fine metal particles 20B, and the calorific value (10.4 W / Kg).
  • Plot 60B shows the relationship between the degree of oxidation (14.9%) and the calorific value (62.5 W / Kg) of PNZ10r, which is a nanocomposite metal material 10B.
  • the calorific value of PNZ10r which is the nanocomposite metal material 10B, is significantly increased as compared with PNZ10, which is the fine metal particles 20B.
  • the diagram 62 is a diagram passing through the plot 62A and the plot 62B.
  • Plot 62A shows the correspondence between the degree of oxidation (31%) and the calorific value (9.67 W / Kg) of CNZ7, which is the fine metal particles 20A.
  • Plot 62B shows the relationship between the degree of oxidation (35.6%) and the calorific value (104.9 W / Kg) of CNZ7r, which is a nanocomposite metal material 10A.
  • the calorific value of CNZ7 which is the nanocomposite metal material 10A, is significantly increased as compared with CNZ7, which is the fine metal particles 20A.
  • FIG. 8 is a measurement result showing the calorific value of the fine metal particles 20 and the nanocomposite metal material 10.
  • FIG. 8 shows a diagram 64, a diagram 66, a diagram 68, and a diagram 70.
  • the diagram 70 is a diagram passing through the plot 70A, the plot 70B, and the plot 70C.
  • Plot 70A shows the correspondence between the number of bakings of CNZ7, which is the fine metal particles 20A, and the calorific value.
  • Plot 70B shows the correspondence between the number of baking times and the calorific value of CNZ7 # 1-1, which is the nanocomposite metal material 10C.
  • Plot 70C shows the correspondence between the number of baking times and the calorific value of CNZ7 # 2-1 which is the nanocomposite metal material 10C.
  • Diagram 68 is a diagram passing through plot 68A, plot 68B, and plot 68C.
  • Plot 68A shows the correspondence between the number of bakings of PNZ10, which is the fine metal particles 20B, and the calorific value.
  • Plot 68B shows the correspondence between the number of baking times and the calorific value of PNZ10 # 1-1, which is the nanocomposite metal material 10D.
  • Plot 68C shows the correspondence between the number of baking times and the calorific value of PNZ10 # 2-1 which is the nanocomposite metal material 10D.
  • the diagram 66 is a diagram passing through the plot 66A, the plot 66B, and the plot 66C.
  • Plot 66A shows the correspondence between the number of baking times and the calorific value of CNZ7r, which is a nanocomposite metal material 10A.
  • Plot 66B shows the correspondence between the number of baking times and the calorific value of CNZ7r # 1-1, which is the nanocomposite metal material 10E.
  • Plot 66C shows the correspondence between the number of baking times and the calorific value of CNZ7r # 2-1 which is the nanocomposite metal material 10E.
  • the diagram 64 is a diagram passing through the plot 64A, the plot 64B, and the plot 64C.
  • Plot 64A shows the correspondence between the number of baking times and the calorific value of PNZ10r, which is a nanocomposite metal material 10B.
  • Plot 64B shows the correspondence between the number of baking times and the calorific value of PNZ10r # 1-1, which is the nanocomposite metal material 10F.
  • Plot 64C shows the correspondence between the number of baking times and the calorific value of PNZ10 # r2-1 which is the nanocomposite metal material 10F.
  • the amount of heat generated increased due to the execution of baking. Moreover, as the number of bakings increased, the calorific value increased. Further, it was confirmed that the calorific value of each of the nanocomposite metal materials 10 was increased as compared with that of the fine metal particles 20.
  • FIG. 9 is a diagram showing changes in the calorific value of CNZ7r # 1-2, which is a nanocomposite metal material 10E.
  • FIG. 80A is a diagram showing changes in the calorific value of CNZ7r # 1-2.
  • FIG. 80B is a diagram showing the transition of the average value of the measurement results of the four temperature sensors 40 (temperature sensor 40A to temperature sensor 40D) in the thermal reaction device 30.
  • FIG. 80C is a diagram showing the number of moles of hydrogen atoms absorbed by the thermal reaction.
  • FIG. 10 is a diagram showing changes in the calorific value of CNZ7r # 2-2, which is a nanocomposite metal material 10E.
  • FIG. 82A is a diagram showing a change in the calorific value of CNZ7r # 2-2.
  • FIG. 82B is a diagram showing the transition of the average value of the measurement results of the four temperature sensors 40 (temperature sensor 40A to temperature sensor 40D) in the thermal reaction device 30.
  • FIG. 82C is a diagram showing the number of moles of hydrogen atoms absorbed by the thermal reaction.
  • FIG. 11 is a diagram showing changes in the calorific value of CNZ7r # 2-4, which is a nanocomposite metal material 10E.
  • FIG. 84A is a diagram showing a change in the calorific value of CNZ7r # 2-4.
  • FIG. 84B is a diagram showing the transition of the average value of the measurement results of the four temperature sensors 40 (temperature sensor 40A to temperature sensor 40D) in the thermal reaction device 30.
  • FIG. 84C is a diagram showing the number of moles of hydrogen atoms desorbed by the thermal reaction.
  • FIG. 12 is a diagram showing changes in the calorific value of PNZ10r # 1-4, which is a nanocomposite metal material 10F.
  • FIG. 86A is a diagram showing changes in the calorific value of PNZ10r # 1-4.
  • FIG. 86B is a diagram showing the transition of the average value of the measurement results of the four temperature sensors 40 (temperature sensor 40A to temperature sensor 40D) in the thermal reaction device 30.
  • FIG. 86C is a diagram showing the number of moles of hydrogen atoms desorbed by a thermal reaction.
  • FIG. 13 is a diagram showing changes in the calorific value of PNZ10r # 2-2, which is a nanocomposite metal material 10F.
  • FIG. 88A is a diagram showing a change in the calorific value of PNZ10r # 2-2.
  • FIG. 88B is a diagram showing the transition of the average value of the measurement results of the four temperature sensors 40 (temperature sensor 40A to temperature sensor 40D) in the thermal reaction device 30.
  • FIG. 88C is a diagram showing the number of moles of hydrogen atoms desorbed by the thermal reaction.
  • FIG. 14 shows the measurement results showing the relationship between the calorific value of CNZ7, which is an example of the fine metal particles 20A, and the calorific value of CNZ7R, CNZ7RR, and CNZ7RRR, which are nanocomposite metal materials 10G made from the fine metal particles 20A, and the number of recalculations. is there.
  • FIG. 14 shows the calorific value (also referred to as excess heat) of CNZ7, CNZ7R, CNZ7RR, and CNZ7RRR when the input power to the heating mechanism 38 of the reactor 32 is 200 W and 235 W.
  • the calorific value increases in a substantially proportional manner up to CNZ7RR in which the re-baking step is performed twice.
  • the calorific value of CNZ7RRR which has undergone the re-baking step three times, seems to be substantially the same as or rather lower than that of CNZ7RR.
  • FIG. 15 shows the measurement results showing the relationship between the calorific value of PNZ10, which is an example of the fine metal particles 20B, and the calorific value of PNZ10R, PNZ10RR, and PNZ10RRR, which are nanocomposite metal materials 10H prepared from the fine metal particles 20B, and the number of recalculations. is there.
  • FIG. 15 shows the calorific value (also referred to as excess heat) of PNZ10, PNZ10R, PNZ10RR, and PNZ10RRR when the input power to the heating mechanism 38 of the reactor 32 is 200 W and 235 W.
  • the amount of heat generated increases as the number of re-baking increases.
  • the calorific value increases proportionally up to PNZ10RR in which the re-baking step is performed twice.
  • the increase in calorific value seems to be slightly slowed down.
  • Nanocomposite metal material 12 Carrier 14 Two-element metal particles

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
PCT/JP2020/033824 2019-09-06 2020-09-07 ナノ複合金属材料、および、ナノ複合金属材料の製造方法 Ceased WO2021045230A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP20859758.3A EP4008453A4 (en) 2019-09-06 2020-09-07 METAL NANOCOMPOSITE MATERIAL AND PRODUCTION METHOD OF METAL NANOCOMPOSITE MATERIAL
CN202080062306.3A CN114787401B (zh) 2019-09-06 2020-09-07 纳米复合金属材料和纳米复合金属材料的制造方法
US17/640,736 US12091732B2 (en) 2019-09-06 2020-09-07 Nanocomposite metal material and method for manufacturing nanocomposite metal material
JP2021544074A JP7694386B2 (ja) 2019-09-06 2020-09-07 ナノ複合金属材料、および、ナノ複合金属材料の製造方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2019-163326 2019-09-06
JP2019163326 2019-09-06
JP2019172247 2019-09-20
JP2019-172247 2019-09-20

Publications (1)

Publication Number Publication Date
WO2021045230A1 true WO2021045230A1 (ja) 2021-03-11

Family

ID=74852366

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/033824 Ceased WO2021045230A1 (ja) 2019-09-06 2020-09-07 ナノ複合金属材料、および、ナノ複合金属材料の製造方法

Country Status (5)

Country Link
US (1) US12091732B2 (https=)
EP (1) EP4008453A4 (https=)
JP (1) JP7694386B2 (https=)
CN (1) CN114787401B (https=)
WO (1) WO2021045230A1 (https=)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2023085111A (ja) * 2021-12-08 2023-06-20 株式会社テクノバ 発熱反応装置および過剰熱発生方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004253385A (ja) * 2003-02-19 2004-09-09 Samsung Sdi Co Ltd 燃料電池のカソード用触媒
JP2006517172A (ja) * 2003-01-21 2006-07-20 シエル・インターナシヨナル・リサーチ・マートスハツペイ・ベー・ヴエー ジルコニア押出し品
JP2009263796A (ja) * 2003-08-05 2009-11-12 Nippon Mining & Metals Co Ltd スパッタリングターゲット及びその製造方法
JP2013215701A (ja) * 2012-04-12 2013-10-24 Toyota Motor Corp コアシェル触媒の製造方法、及び、膜電極接合体の製造方法
WO2015008859A2 (ja) 2013-07-18 2015-01-22 水素技術応用開発株式会社 反応体、発熱装置及び発熱方法
JP2018521844A (ja) * 2015-07-15 2018-08-09 アーチャー−ダニエルズ−ミッドランド カンパニー 改良された銅含有多元金属触媒およびバイオベースの１，２−プロパンジオールを製造するためにこれを使用する方法

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1198325B (it) 1980-06-04 1988-12-21 Getters Spa Struttura e composizione getteranti,particolarmente adatti per basse temperature
US5654246A (en) 1985-02-04 1997-08-05 Lanxide Technology Company, Lp Methods of making composite ceramic articles having embedded filler
US4839085A (en) 1987-11-30 1989-06-13 Ergenics, Inc. Method of manufacturing tough and porous getters by means of hydrogen pulverization and getters produced thereby
JP2834165B2 (ja) * 1988-12-29 1998-12-09 松下電器産業株式会社 水素吸蔵合金の製造法および電極
DE68909590T2 (de) * 1989-06-13 1994-01-27 Getters Spa Verfahren zur Herstellung von zähen und porösen Gettern durch Zerkleinerung mit Wasserstoff sowie damit hergestellte Getter.
JP2002057003A (ja) 2000-08-10 2002-02-22 Nippon Soken Inc 耐還元性サーミスタ素子とその製造方法および温度センサ
EP1328035A1 (fr) * 2002-01-09 2003-07-16 HTceramix S.A. - High Technology Electroceramics PEN de pile à combustible à oxydes solide
CA2705769A1 (en) 2007-11-20 2009-05-28 Exxonmobil Research And Engineering Company Bimodal and multimodal dense boride cermets with low melting point binder
CA2780575C (en) * 2009-11-24 2015-09-22 Shell Internationale Research Maatschappij B.V. Process for catalytic hydrotreatment of a pyrolysis oil
US9403157B2 (en) * 2013-04-29 2016-08-02 Ford Global Technologies, Llc Three-way catalyst comprising mixture of nickel and copper
CN106423171B8 (zh) * 2016-08-01 2019-02-22 中南民族大学 一种用于催化甲醇合成反应的Ni/Cu/M催化剂及其制备方法
CN109174120A (zh) * 2018-09-06 2019-01-11 南京理工大学 负载型Pd-Ni双金属纳米颗粒催化剂及其制备方法和应用

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006517172A (ja) * 2003-01-21 2006-07-20 シエル・インターナシヨナル・リサーチ・マートスハツペイ・ベー・ヴエー ジルコニア押出し品
JP2004253385A (ja) * 2003-02-19 2004-09-09 Samsung Sdi Co Ltd 燃料電池のカソード用触媒
JP2009263796A (ja) * 2003-08-05 2009-11-12 Nippon Mining & Metals Co Ltd スパッタリングターゲット及びその製造方法
JP2013215701A (ja) * 2012-04-12 2013-10-24 Toyota Motor Corp コアシェル触媒の製造方法、及び、膜電極接合体の製造方法
WO2015008859A2 (ja) 2013-07-18 2015-01-22 水素技術応用開発株式会社 反応体、発熱装置及び発熱方法
JP2018521844A (ja) * 2015-07-15 2018-08-09 アーチャー−ダニエルズ−ミッドランド カンパニー 改良された銅含有多元金属触媒およびバイオベースの１，２−プロパンジオールを製造するためにこれを使用する方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4008453A4

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2023085111A (ja) * 2021-12-08 2023-06-20 株式会社テクノバ 発熱反応装置および過剰熱発生方法

Also Published As

Publication number Publication date
CN114787401B (zh) 2023-09-12
CN114787401A (zh) 2022-07-22
JP7694386B2 (ja) 2025-06-18
JPWO2021045230A1 (https=) 2021-03-11
US12091732B2 (en) 2024-09-17
EP4008453A1 (en) 2022-06-08
EP4008453A4 (en) 2023-10-11
US20220339698A1 (en) 2022-10-27

Similar Documents

Publication Publication Date Title
JP5553080B2 (ja) カーボンナノチューブ集合体
EP2148754B1 (en) Method of production of transition metal nanoparticles
US20090191352A1 (en) Combustion-Assisted Substrate Deposition Method For Producing Carbon Nanosubstances
US6743500B2 (en) Hollow carbon fiber and production method
TW201134782A (en) Low thermal expansion doped fused silica crucibles
WO2021045230A1 (ja) ナノ複合金属材料、および、ナノ複合金属材料の製造方法
JP4534016B2 (ja) 高純度窒化ホウ素ナノチューブの製造方法
CN113912074B (zh) 一种高纯超细无定形硼粉及其制备方法
TW201008641A (en) Method for making glass frit powders using aerosol decomposition
JP2001048507A (ja) カーボンナノチューブの製造方法およびカーボンナノチューブ膜の製造方法
CN102745977B (zh) 一种快速制备高致密度氧化镁纳米陶瓷的方法
WO2007122684A1 (ja) 低酸素金属粉末の製造方法
WO2006095663A2 (en) Method for producing high purity silicon
JP4473183B2 (ja) 中空金属体の製造方法
JPWO2021045230A5 (https=)
CN109179466B (zh) 一种金属铝制备超细刚玉粉的方法
RU2530070C1 (ru) СПОСОБ СИНТЕЗА ПОЛЫХ НАНОЧАСТИЦ γ-Al2O3
JP4724828B2 (ja) ホウ素ドープ２層カーボンナノチューブ、連結２層カーボンナノチューブおよびその製造方法
Han et al. Active chemical furnace‐assisted combustion synthesis of SiC nanoparticles with in situ spontaneous granulation
Reger et al. Combustion synthesis and characterization of porous β‐SiAlON fiber‐reinforced foam filters
CN111253938A (zh) 一种钬镱离子共掺红外上转换材料及其制备方法
US20230250999A1 (en) Exothermic reaction apparatus and method for generating excessive heat
CN117701050B (zh) 一种乙烯裂解炉炉管外壁使用的复合结晶膜浆料
JP2005164268A (ja) 評価試料の作製方法、分析方法、電子部品材料の生産方法、電子部品及び評価試料作製装置
JP7359037B2 (ja) カーボンナノチューブ分散液の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20859758

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2021544074

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2020859758

Country of ref document: EP

Effective date: 20220303