Nanocomposite metal material and method for producing nanocomposite metal material

Abstract

A metal nanocomposite material 10 according to the present invention is composed of: a carrier 12 that is formed of Zr; and two-element metal particles 14 that are supported by the carrier 12. The two-element metal particles 14 are formed of Cu and Ni; and the degree of oxidation of the carrier 12 is more than 31% but not more than 100%. Alternatively, the two-element metal particles 14 are formed of Pd and Ni; and the degree of oxidation of the carrier 12 is from 3% to 100%.

Description

Technical Field

[0001] Embodiments of the present invention relate to a nano-composite metal material and a method for manufacturing the nano-composite metal material.

Background Art

[0002] Techniques for using metal nanoparticles in an exothermic reaction with hydrogen have been disclosed. For example, a technique for causing an exothermic reaction by supplying hydrogen gas to a reactant having a plurality of metal nano-protrusions made of a hydrogen storage metal formed on the surface has been disclosed.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, in the prior art, it has been difficult to increase the amount of heat generated by an exothermic reaction with hydrogen.

[0005] The present invention has been made in view of the above, and an object thereof is to provide a nano-composite metal material and a method for manufacturing the nano-composite metal material, which can increase the amount of heat generated by an exothermic reaction with hydrogen.

Means for Solving the Problems

[0006] The nano-composite metal material of the embodiment comprises a carrier made of Zr, and binary metal particles made of Cu and Ni supported on the carrier. The atomic number ratio of Cu to Ni is in the range of 1:7 or more and 1:15 or less, and the atomic number ratio of Ni to Zr is in the range of 1:2 or more and 1:4 or less. The degree of oxidation of the carrier is greater than 31% and 100% or less. A nano-composite metal material, wherein when the nano-composite metal material is placed in the reaction furnace of a thermal reaction device, the inside of the reaction furnace is evacuated, and at least one of hydrogen gas and deuterium gas is supplied into the reaction furnace while heating the inside of the reaction furnace to a temperature range of 250°C or more and 350°C or less by a heating mechanism provided in the thermal reaction device, the excess heat of the nano-composite metal material calculated by comparing with the calorimetric calibration test data obtained by loading a non-heating blank sample of zirconia beads into the reaction furnace is 100 W / kg or more. .

[0007] The nano-composite metal material of the embodiment comprises a carrier made of Zr, and binary metal particles made of Pd and Ni supported on the carrier.The atomic number ratio of Pd to Ni is in the range of 1:7 or more and 1:15 or less, and the atomic number ratio of Ni to Zr is in the range of 1:2 or more and 1:4 or less. The degree of oxidation of the carrier is 3% or more and 100% or less. A nano-composite metal material, wherein when the nano-composite metal material is placed in the reaction furnace of a thermal reaction device, the inside of the reaction furnace is evacuated, and at least one of hydrogen gas and deuterium gas is supplied into the reaction furnace while heating the inside of the reaction furnace to a temperature range of 250°C or more and 350°C or less by a heating mechanism provided in the thermal reaction device, the excess heat of the nano-composite metal material calculated by comparing with the calorimetric calibration test data obtained by loading a non-heating blank sample of zirconia beads into the reaction furnace is 40 W / kg or more. 。

Brief Description of the Drawings

[0008]

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Mode for Carrying Out the Invention

[0009] Hereinafter, embodiments of the present invention will be described.

[0010] The nano composite metal material of the present embodiment is a metal composite material comprising a carrier made of ceramics and binary metal particles supported on the carrier and composed of Cu or palladium (Pd) and nickel (Ni).

[0011] FIG. 1 is a schematic diagram showing an example of the nano composite metal material 10 of the present embodiment.

[0012] For example, the nano composite metal material 10 has a configuration in which the binary metal particles 14 are supported inside and on the surface of the carrier 12. Note that being supported on the carrier 12 means a state in which the binary metal particles 14 are adhered or fused to the inside and surface of the carrier 12 by a chemical treatment such as firing. Also, being supported inside the carrier 12 means being supported on the surface of the pores of the carrier 12.

[0013] The carrier 12 is composed of ceramics. Specifically, the carrier 12 is ceramics having nano-sized pores on the inside and surface. In the present embodiment, nano-sized means a range of 2 nm or more and 50 nm or less.

[0014] The ceramics constituting the carrier 12 are, for example, zirconium (Zr), zirconia (ZrO2), mesoporous silica, zeolite, carbon nanotube, and the like.

[0015] The outer shape of the carrier 12 is not limited. The outer shape of the carrier 12 may be any shape such as spherical, elliptical, polygonal, etc.

[0016] The binary metal particles 14 are supported inside and on the surface of the carrier 12. Specifically, the binary metal particles 14 are in a state of being supported in the pores inside and on the surface of the carrier 12.

[0017] The binary metal particles 14 are metal nanoparticles composed of two elements of Cu and Ni, or Pd and Ni. Specifically, the binary metal particles 14 are particles having a core-shell structure with Ni as the core and Cu or Pd as the shell.

[0018] The outer shape of the binary metal particles 14 is not limited. The outer shape of the binary metal particles 14 may be any of, for example, spherical, elliptical, polygonal, linear, string shape with at least a part being twisted, etc.

[0019] The volume average particle diameter of the nano composite metal material 10 includes at least the range of 0.01 mm or more and 1 mm or less. It is more preferable that the volume average particle diameter of the nano composite metal material 10 includes at least the range of 0.05 mm or more and 0.3 mm or less. Note that the volume average particle diameter of the nano composite metal material 10 may further include the range of 0.05 mm or more and 0.5 mm or less.

[0020] Specifically, it is preferable that the volume average particle diameter of the nano composite metal material 10 composed of the carrier 12 made of Zr supporting the binary metal particles 14 composed of two elements of Cu and Ni includes at least the range of 0.1 mm or more and 1.0 mm or less. Also, it is preferable that the volume average particle diameter of the nano composite metal material 10 composed of the carrier 12 made of Zr supporting the binary metal particles 14 composed of two elements of Pd and Ni includes at least the range of 0.05 mm or more and 1.0 mm or less.

[0021] The volume average particle diameter of the nano composite metal material 10 indicates the volume average particle diameter of the carrier 12 (refer to the particle diameter L1) when the structure of the nano composite metal material 10 is the structure shown in FIG. 1.

[0022] The volume average particle diameter of the binary metal particles 14 is preferably in the range of, for example, 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.

[0023] The volume average particle diameters of the nano composite metal material 10 and the binary metal particles 14 are measured, for example, by the following method.

[0024] Specifically, using a measurement device manufactured by NEC Corporation, product name: STEM / EDS, by measuring an element distribution map under the condition of 200 keV electron beam scanning, the volume average particle diameter and shape of each of the nano composite metal material 10 and the binary metal particles 14 are image-analyzed with a resolution of 1 nm or less to measure the volume average particle diameter.

[0025] The nano composite metal material 10 of the present embodiment is classified into eight types: nano composite metal material 10A, nano composite metal material 10B, nano composite metal material 10C, nano composite metal material 10D, nano composite metal material 10E, nano composite metal material 10F, nano composite metal material 10G, and nano composite metal material 10H by the manufacturing method described later. These nano composite metal materials 10A, 10B, 10C, 10D, 10E, 10F, 10G, and 10H have different manufacturing methods. In the present embodiment, when the nano composite metal materials 10A, 10B, 10C, 10D, 10E, 10F, 10G, and 10H are collectively described, they are simply described as the nano composite metal material 10.

[0026] The nano-composite metal material 10 of the present embodiment can increase the calorific value by being used in an exothermic reaction with hydrogen. Hereinafter, each of the nano-composite metal materials 10A, 10B, 10C, 10D, 10E, 10F, 10G, and 10H will be described in detail.

[0027] <Nano-composite metal material 10A> First, the nano-composite metal material 10A and the manufacturing method of the nano-composite metal material 10A will be described.

[0028] The nano-composite metal material 10A is composed of a carrier 12 made of Zr, and binary metal particles 14 made of Cu and Ni supported on the carrier 12, and is a nano-composite metal material 10 in which the degree of oxidation of the carrier 12 made of Zr is greater than 31% and 100% or less. Hereinafter, the carrier 12 made of Zr may sometimes be simply referred to as the carrier 12 for explanation.

[0029] It is essential that the degree of oxidation of the carrier 12 of the nano-composite metal material 10A is greater than 31% and 100% or less, but it is preferably 50% or more and 100% or less, more preferably 80% or more and 100% or less, and particularly preferably 90% or more and 100% or less.

[0030] The method for measuring the degree of oxidation of the nano-composite metal material 10A will be described later.

[0031] The nano-composite metal material 10A has a firing step of firing 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 nano-composite metal material 10A.

[0032] FIG. 2 is an explanatory diagram of an example of the firing step of the nano-composite metal material 10A and the nano-composite metal material 10B described later.

[0033] The case where Zr is used as the carrier 12 will be described as an example. In addition, when using ceramics other than Zr as the carrier 12, the same firing process may be performed.

[0034] First, an amorphous metal 18 is produced by melting and rapidly cooling a Cu-Ni-Zr alloy by the melt spinning method (melt quenching method). The melt spinning method is a method of obtaining an amorphous (non-crystalline) metal by spraying a high-temperature molten alloy onto the surface of a roll-shaped member rotating at high speed, thereby rapidly cooling in a time shorter than the crystallization time.

[0035] Specifically, the Cu-Ni-Zr alloy is melted by heating in a heating furnace 22A, and the molten liquid is supplied to a rotating cooling roll 22B. The molten liquid solidifies by contacting the rotating cooling roll 22B, and a ribbon-shaped amorphous metal 18 is produced. The thickness of the ribbon-shaped amorphous metal 18 is adjusted to a range of, for example, 5 μm or more and 50 μm or less by adjusting the supply amount to the cooling roll 22B and the rotation speed of the cooling roll 22.

[0036] Then, the amorphous metal 18 is oxidized in the air. For example, the amorphous metal 18 is put into a crucible 24 and heated at a temperature of 400°C or more and 600°C or less for 100 hours or more and 200 hours or less to oxidize the amorphous metal 18. By this oxidation treatment, ZrO2 in which Zr is oxidized is obtained.

[0037] Then, fine metal particles 20A are obtained by performing a pulverization treatment of pulverizing the amorphous metal 18 after the oxidation treatment. The pulverization treatment is performed by automatic mortar treatment. 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.

[0038] Next, the fine metal particles 20A are fired at 300°C or more and 600°C or less to obtain a nano-composite metal material 10A. In addition, the firing temperature in this firing step must be in the range of 300°C or more and 600°C or less, but the range of 400°C or more and 500°C or less is preferable, the range of 450°C or more and 500°C or less is more preferable, and 450°C is particularly preferable. The firing time is preferably in the range of 120 hours or more and 180 hours or less.

[0039] As described above, the degree of oxidation of the carrier 12 of the nano-composite metal material 10A manufactured by the above manufacturing method is greater than 31% and 100% or less.

[0040] The degree of oxidation of the nano-composite metal material 10A may be adjusted by adjusting the firing temperature and firing time in the firing process.

[0041] In the present embodiment, the ratio of the weight of the nano-composite 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 nano-composite metal material 10A. Specifically, 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 nano-composite metal material 10A after firing with respect to before firing was measured. This weight increase rate was calculated as the degree of oxidation, which is the increase rate of the amount of oxygen added by firing.

[0042] The composition of the nano-composite metal material 10A manufactured by the above manufacturing method, when the carrier 12 is composed of Zr which is ceramics, the atomic ratio (Cu:Ni) of Cu and Ni is in the range of 1:7 or more and 1:15 or less, and the atomic ratio of Ni and Zr is in the range of 1:2 or more and 1:4 or less.

[0043] Note that the composition of the nano-composite metal material 10A is preferably in the above range, but the atomic ratio (Cu:Ni) of Cu and Ni is preferably in the range of 1:7 or more and 1:12 or less. Also, the atomic ratio of Ni and Zr may be in the range of 1:2 or more and 1:4 or less, or in the range of 1:2 or more and 1:3 or less.

[0044] The composition of the nano-composite metal material 10A is adjusted by adjusting the atomic ratio (mass ratio) of the Cu-Ni-Zr alloy, which is the charged amount at the time of producing the fine metal particles 20A.

[0045] <Nano-composite metal material 10B> The nano-composite metal material 10B and the manufacturing method of the nano-composite metal material 10B will be described.

[0046] The nano-composite metal material 10B consists of a carrier 12 made of Zr and binary metal particles 14 carried on the carrier 12 and made of Pd and Ni, and is a nano-composite metal material 10 in which the degree of oxidation of the carrier 12 made of Zr is 3% or more and 100% or less.

[0047] Although it is essential that the degree of oxidation of the carrier 12 made of Zr in the nano-composite metal material 10B is 3% or more and 100% or less, it is preferably 20% or more and 100% or less, and more preferably 25% or more and 100% or less.

[0048] The nano-composite metal material 10B has a firing step of firing 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 nano-composite metal material 10B.

[0049] This will be described with reference to FIG. 2. Note that the case where Zr is used as the carrier 12 will be described as an example. The same firing process may be performed when using ceramics other than Zr as the carrier 12.

[0050] The nano-composite metal material 10B is produced by the same firing process as the nano-composite metal material 10A, except that a Pd-Ni-Zr alloy is used instead of a Cu-Ni-Zr alloy.

[0051] First, an amorphous metal 18 is produced by melting and rapidly cooling a Pd-Ni-Zr alloy by the melt spinning method.

[0052] Specifically, the Pd-Ni-Zr alloy is melted by heating in a heating furnace 22A, and the melted liquid is supplied to a rotating cooling roll 22B. The melted liquid solidifies by contacting the rotating cooling roll 22B, and a ribbon-shaped amorphous metal 18 is produced. The thickness of the ribbon-shaped amorphous metal 18 is adjusted to a thickness range of, for example, 2 μm or more and 50 μm or less by adjusting the supply amount to the cooling roll 22B and the rotation speed of the cooling roll 22.

[0053] Then, the amorphous metal 18 is oxidized in the atmosphere. For example, the amorphous metal 18 is put into the crucible 24 and heated at a temperature of 400°C or higher and 600°C or lower for 100 hours or longer and 200 hours or shorter to oxidize the amorphous metal 18. By this oxidation treatment, ZrO2 obtained by oxidizing Zr is obtained.

[0054] Then, by performing a pulverization treatment of pulverizing the amorphous metal 18 after the oxidation treatment, fine metal particles 20B are obtained. The pulverization treatment is performed by automatically processing in a mortar. The volume average particle diameter of the fine metal particles 20B preferably includes at least the range of 0.05 mm or more and 0.5 mm or less.

[0055] Next, the fine metal particles 20B are fired at 300°C or higher and 600°C or lower to obtain the nano composite metal material 10B. In this firing step, the firing temperature in the range of 300°C or higher and 600°C or lower is essential, but the range of 450°C or higher and 600°C or lower is preferable, the range of 450°C or higher and 500°C or lower is more preferable, and 450°C is particularly preferable. The firing time is preferably in the range of 120 hours or longer and 180 hours or shorter.

[0056] As described above, the degree of oxidation of the nano composite metal material 10B manufactured by the above manufacturing method is 3% or more and 100% or less.

[0057] The degree of oxidation of the nano composite metal material 10B may be adjusted by adjusting the firing temperature and the firing time in the firing step.

[0058] In the present embodiment, similar to the degree of oxidation of the nano composite metal material 10A, the ratio of the weight of the nano composite metal material 10B, which is the fine metal particles 20B after firing, to the weight of the fine metal particles 20B before firing is used as the degree of oxidation of the carrier 12 made of Zr in the nano composite metal material 10B. The measurement of the degree of oxidation of the carrier 12 made of Zr in the nano composite metal material 10B may be performed in the same manner as the measurement of the degree of oxidation of the nano composite metal material 10A.

[0059] When the carrier 12 of the nano-composite metal material 10B is composed of Zr which is a ceramic, the atomic ratio (Pd:Ni) of Pd and Ni is in the range of 1:7 or more and 1:15 or less, and the atomic ratio of Ni and Zr is in the range of 1:2 or more and 1:4 or less.

[0060] Although the composition of the nano-composite metal material 10B is preferably within the above range, the atomic ratio (Pd:Ni) of Pd and Ni is more preferably in the range of 1:7 or more and 1:12 or less. Further, the atomic ratio of Ni and Zr may be in the range of 1:2 or more and 1:3 or less.

[0061] The composition of the nano-composite metal material 10B is adjusted by adjusting the atomic ratio (mass ratio) of the Pd-Ni-Zr alloy, which is the charged amount during the production of the fine metal particles 20B.

[0062] <Nano-composite metal material 10C> Next, the nano-composite metal material 10C and the manufacturing method of the nano-composite metal material 10C will be described.

[0063] The nano-composite metal material 10C is composed of a carrier 12 made of Zr and binary metal particles 14 made of Cu and Ni supported on the carrier 12, and is a nano-composite metal material 10 manufactured by a manufacturing method different from that of the nano-composite metal material 10A which is a nano-composite metal material 10 containing Cu.

[0064] The manufacturing method of the nano-composite metal material 10C includes a hydrogen storage step and a heating step.

[0065] The hydrogen storage step in the manufacturing method of the nano-composite metal material 10C is a step of supplying hydrogen gas to the fine metal particles 20A and storing hydrogen in the fine metal particles 20A. The fine metal particles 20A are the same as those 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 a reactor in a vacuum state. The hydrogen gas to be supplied may be either deuterium gas or light hydrogen gas.

[0066] In the heating step of the method for manufacturing the nano-composite metal material 10C, the fine metal particles 20A occluding hydrogen are heated to 200°C or higher and 300°C or lower under a vacuum state to obtain the nano-composite metal material 10C. This heating step may be referred to as baking.

[0067] The temperature range of this heating step is preferably in the range of 200°C or higher and 450°C or lower, but may also be in the range of 200°C or higher and 500°C or lower, or in the range of 250°C or higher and 400°C or lower. The selection of the temperature range may be appropriately selected according to the material composition and the degree of oxidation. Specifically, the temperature range of this heating step (baking) only needs to be within the range where 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. It should be noted that the period from the start to the end is maintained within the temperature range from the lowest temperature of 200°C or higher and 250°C or lower to the highest temperature of 350°C or higher and 450°C or lower.

[0068] Also, the heating time in this heating step may be adjusted according to the heating temperature, the released gas pressure, etc. For example, 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.

[0069] It should be noted that this heating step (baking) is preferably performed multiple times. The multiple heating steps refer to counting 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 vacuum degree reaches 1 Pa or less as one time, and indicating the number of repetitions of this series of steps. The temperature in the heating step may vary within the above range according to the gas pressure at the start and the gas release amount during baking.

[0070] In the first heating step, phenomena such as the evaporation of moisture in the fine metal particles 20A occluding hydrogen and the generation of impurity gases (such as nitrogen) from the fine metal particles 20A are considered to occur. Therefore, it is preferable to use the nano-composite metal material 10 manufactured by performing the heating step two or more times as the nano-composite metal material 10C.

[0071] The heating process (baking) heats the inside of the reactor in a vacuum state within the range of 200°C or higher and 450°C or lower. Next, as the hydrogen storage process, hydrogen gas is set to 0.5 MPa - 1 MPa at room temperature to store hydrogen. The second heating process (baking) is carried out by raising the temperature to 200°C or higher and 450°C or lower while exhausting the hydrogen gas present in the reactor. In addition, when baking is performed three or more times, it may be repeated in the same manner.

[0072] It is considered that the following phenomena occur due to these hydrogen storage processes and heating processes.

[0073] Specifically, it is considered that at least a part of Cu of the fine metal particles 20A used in the hydrogen storage process is in an oxidized state due to the oxidation treatment of the amorphous metal 18 during the production of the fine metal particles 20A. Regarding Ni, it is considered that almost no oxidation has occurred. By storing hydrogen in these fine metal particles 20A, it is considered that the oxygen atoms of copper oxide react 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 detachment of oxygen atoms.

[0074] Then, when the fine metal particles 20A are heated by the heating process, it is considered that at least a part of the stored hydrogen is desorbed. At the time of this hydrogen desorption, the binary metal particles 14 having a core-shell structure with Ni as the core and Cu as an incomplete covering shell are supported on the carrier 12 in a pulverized state, and it is considered that the nano-composite metal material 10C is obtained. It is theoretically speculated that heat generation sites due to hydrogen clusters are formed on the surface of the complete shell and the Ni core. It is estimated that an increase in the number of heat generation sites is brought about by baking and re-firing of the nano-composite metal material, increasing the excess heat generation power. Re-firing corresponds to the baking process described above for obtaining the nano-composite metal material 10A by baking the fine metal particles 20A or the fine metal particles 20B at 300°C or higher and 600°C or lower.

[0075] The nano-composite metal material 10C is manufactured, for example, by passing through the hydrogen storage step and the heating step using a thermal reaction device.

[0076] Figure 3 is a schematic diagram showing an example of the thermal reaction device 30.

[0077] The thermal reaction device 30 includes a reaction furnace 32 for holding a sample such as fine metal particles 20A inside. The reaction furnace 32 is disposed inside a housing 33. The reaction furnace 32 and the housing 33 are made of, for example, stainless steel (SUS306 or SUS316).

[0078] The reaction furnace 32 has a hollow and sealed shape, and is, for example, a cylindrical member with both end faces in the longitudinal direction sealed.

[0079] A gas supply unit 34 and a vacuum mechanism 36 are communicated with the reaction furnace 32 via a pipe 34B.

[0080] The gas supply unit 34 includes a gas cylinder 34A, a pipe 34B, valves 34C and 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 reaction furnace 32 via the pipe 34B. The valves 34C and 34D are provided on the pipe 34B and are used for supplying hydrogen gas and adjusting the pressure. The tank 34E is communicated with the reaction furnace 32 via the pipe 34B. The tank 34E is a mechanism for adjusting the pressure inside the reaction furnace 32. The pressure measurement unit 34F measures the pressure of the reaction furnace 32.

[0081] The vacuum mechanism 36 is a mechanism for evacuating the inside of the reaction furnace 32. The vacuum mechanism 36 includes a vacuum pump 36A, a valve 36B, a pipe 36C, and a pressure measurement unit 36D. One end of the pipe 36C is communicated with the reaction furnace 32 via the pipe 34B, and the other end is communicated with the vacuum pump 36A via the valve 36B. By operating the vacuum pump 36A, the inside of the reaction furnace 32 is adjusted to a vacuum state. The pressure measurement unit 36D measures the pressure inside the reaction furnace 32.

[0082] The reactor 32 is provided with a heating mechanism 38. In this embodiment, the thermal reaction device 30 includes a heating unit 38A and a heating unit 38B as the heating mechanism 38. The heating unit 38A heats the reactor 32 from the outside. The heating unit 38B is provided inside the reactor 32 and directly heats the inside of the reactor 32.

[0083] Further, the reactor 32 is provided with a temperature sensor 40. The temperature sensor 40 is a sensor that measures the temperature inside the reactor 32. In this embodiment, four temperature sensors 40, namely a temperature sensor 40A, a temperature sensor 40B, a temperature sensor 40C, and a temperature sensor 40D, are provided inside the reactor 32. Note that the number of temperature sensors 40 is not limited to four. These multiple temperature sensors 40 (temperature sensors 40A to 40D) are arranged at different positions at the bottom of the reactor 32. Also, these multiple temperature sensors 40 (temperature sensors 40A to 40D) are arranged at positions where they can measure the temperatures at different positions in the longitudinal direction of the reactor 32 inside the reactor 32.

[0084] Further, the thermal reaction device 30 includes a circulation mechanism 42. The circulation mechanism 42 is a mechanism for transferring the heat generated inside the reactor 32 to a fluid by heat exchange between them and using it for hot water supply, heat supply, power generation, etc.

[0085] In this embodiment, the circulation mechanism 42 includes a water circulation temperature controller 42A, an oil circulation temperature controller 42B, a fluid 42C, a pipe 42D, an adjustment unit 42E, a water bath 42F, a pipe 42H, a pump 42I, a pipe 42J, a pipe 42K, a valve 42L, a storage unit 42M, a pump 42P, a pipe 42Q, and a valve 42R.

[0086] The heat transfer pipe 42X is a tubular member and is spirally wound along the outer wall of the reactor 32. A fluid 42C flows in the heat transfer pipe 42X. One longitudinal end of the heat transfer pipe 42X communicates with a water circulation temperature controller 42A and an oil circulation temperature controller 42B via a pipe 42K. The water circulation temperature controller 42A and the oil circulation temperature controller 42B are devices for circulating the circulating fluid oil (hereinafter referred to as fluid 42C). After the fluid 42C is supplied to a flow meter 42O, it flows into a water bath 42F via a pipe 42D and an adjustment unit 42E. The flow meter 42O is a known device that measures the flow rate of the fluid 42C based on the number of droplets.

[0087] The fluid 42C supplied to the water bath 42F is cooled by a liquid 42G stored in the water bath 42F and then supplied again to the pipe 42X wound around the reactor 32 via a pipe 42H, a pump 42I, and a pipe 42J. After recovering the heat quantity, it is supplied to the pipe 42K.

[0088] The storage unit 42M is a mechanism for storing the fluid 42C and is communicated with the flow meter 42O via a valve 42L. The pump 42P is connected to the main body of the thermal reaction device 30 via a pipe 42Q and a valve 42R.

[0089] The thermal reaction device 30 is provided with a control unit 50 for controlling the electronic devices of the thermal reaction device 30, and the thermal reaction device 30 is controlled by the control of the control unit 50.

[0090] When manufacturing the nano composite metal material 10C using the thermal reaction device 30, for example, the following method is used.

[0091] For example, first, a hydrogen storage step is performed. In the hydrogen storage step, first, after supplying the fine metal particles 20A into the reactor 32, the inside of the reactor 32 is evacuated by driving the vacuum mechanism 36 under the control of the control unit 50. Then, while maintaining the evacuated state, hydrogen gas is supplied into the reactor 32. The supply of hydrogen gas is performed under the control of the control unit 50.

[0092] By supplying hydrogen gas into the reactor 32, hydrogen is occluded in the fine metal particles 20A, resulting in a state where hydrogen is occluded in the fine metal particles 20A.

[0093] Next, a heating process is executed. In the heating process, the supply of hydrogen gas into the reactor 32 is stopped. Then, while maintaining the hydrogen gas state in the reactor 32, by controlling the heating mechanism 38, the inside of the reactor 32 is heated so that, for example, the material temperature distribution during heating is at least 200°C or more and 250°C or less, and at most 350°C or more and 450°C or less. The control of the heating mechanism 38 may be performed by the control unit 50. By this heating process, the nano composite metal material 10C is manufactured.

[0094] The composition of the nano composite metal material 10C is such that the atomic ratio (Cu:Ni) of Cu and Ni is in the range of 1:7 or more and 1:15 or less, and the atomic ratio of Ni and Zr is in the range of 1:2 or more and 1:4 or less.

[0095] Note that although the composition of the nano composite metal material 10C is preferably within the above range, the atomic ratio (Cu:Ni) of Cu and Ni is preferably in the range of 1:7 or more and 1:12 or less. Also, the atomic ratio of Ni and Zr may be in the range of 1:2 or more and 1:35 or less, or in the range of 1:2 or more and 1:2.5 or less.

[0096] The composition of the nano composite metal material 10C is adjusted by adjusting the atomic ratio (mass ratio) of the Cu-Ni-Zr alloy, which is the charged amount during the production of the fine metal particles 20A.

[0097] <Nano composite metal material 10D> Next, the nano composite metal material 10D and the manufacturing method of the nano composite metal material 10D will be described.

[0098] The nano composite metal material 10D is composed of a carrier 12 made of ceramics and binary metal particles 14 composed of Pd and Ni supported on the carrier 12, and is a nano composite metal material 10 manufactured by a manufacturing method different from that of the nano composite metal material 10B, which is a nano composite metal material 10 containing Pd.

[0099] The manufacturing method of the nano-composite metal material 10D has a hydrogen storage step and a heating step.

[0100] The hydrogen storage step in the manufacturing method of the nano-composite metal material 10D is a step of supplying hydrogen gas to the fine metal particles 20B at room temperature. Hydrogen is stored in the fine metal particles 20B, and after heat treatment is performed for 3 days or more and 7 days or less under heating conditions with a temperature increase from 250°C or more to 350°C or less, 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 a reactor in a vacuum state at room temperature. The hydrogen gas to be supplied may be either deuterium gas or light hydrogen gas.

[0101] The heating step in the manufacturing method of the nano-composite metal material 10D is a step of obtaining the nano-composite metal material 10D by heating the fine metal particles 20B storing hydrogen to 200°C or more and 450°C or less under a vacuum state.

[0102] The temperature range of this heating step is preferably in the range of 200°C or more and 450°C or less, but may also be in the range of 300°C or more and 450°C or less, or in the range of 350°C or more and 450°C or less. Specifically, the temperature range of this heating step (baking) only needs to be such that the material temperature distribution during heating falls within the range of at least 200°C or more and 250°C or less, and at most 350°C or more and 450°C or less.

[0103] Also, the heating time in this heating step may be adjusted according to the heating temperature (from 250°C to 450°C), etc. For example, in the case of the condition of 300°C, 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.

[0104] It is considered that the following phenomena occur due to these hydrogen storage step and heating step.

[0105] When the fine metal particles 20B are heated by the heating process, it is considered that the process of desorbing at least a part of the occluded hydrogen and the process of absorbing from the outside compete on the surface of the Ni core. It is considered that at least a part of the occluded hydrogen is desorbed when the fine metal particles 20B are heated by the heating process. It is theoretically speculated that heat generation sites due to hydrogen clusters are formed on the surfaces of the Pd complete shell and the Ni core. It is estimated that an increase in the number of heat generation sites is brought about by baking and re-firing of the nano-composite metal material, increasing the excess heat generation power induced by hydrogen clusters.

[0106] Note that, similar to the nano-composite metal material 10C, the heating process in the production of the nano-composite metal material 10D is preferably carried out multiple times. The definition of the multiple heating processes is the same as above.

[0107] In the first heating process, it is considered that phenomena such as evaporation of moisture in the fine metal particles 20B occluding hydrogen and generation of impurity gases (such as nitrogen) from the fine metal particles 20B occur. Therefore, it is preferable to use the nano-composite metal material 10 produced by performing the heating process two or more times as the nano-composite metal material 10D.

[0108] For example, the nano-composite metal material 10D is produced by undergoing the above hydrogen occlusion process and the above heating process using a thermal reaction device. For example, a thermal reaction device 30 is used in the production of the nano-composite metal material 10D (see FIG. 3).

[0109] When producing the nano-composite metal material 10D using the thermal reaction device 30, for example, the following method is used.

[0110] For example, first, the hydrogen occlusion process is performed. In the hydrogen occlusion process, first, after supplying the fine metal particles 20B into the reaction furnace 32, the vacuum mechanism 36 is driven under the control of the control unit 50 to make the inside of the reaction furnace 32 in a vacuum state. Then, while maintaining the vacuum state, hydrogen gas is supplied into the reaction furnace 32. The supply of hydrogen gas is performed under the control of the control unit 50.

[0111] By supplying hydrogen gas into the reactor 32, hydrogen is occluded in the fine metal particles 20B, resulting in a state where hydrogen is occluded in the fine metal particles 20B.

[0112] Next, a heating step is performed. In the heating step, the supply of hydrogen gas into the reactor 32 is stopped. Then, while maintaining the hydrogen gas state in the reactor 32, by controlling the heating mechanism 38, the inside of the reactor 32 is heated to 200°C or higher and 300°C or lower. The control of the heating mechanism 38 may be performed by the control unit 50. By this heating step, the nano-composite metal material 10D is manufactured.

[0113] The composition of the nano-composite metal material 10D is such that the atomic ratio (Pd:Ni) of Pd to Ni is in the range of 1:7 or more and 1:15 or less, and the atomic ratio of Ni to Zr is in the range of 1:2 or more and 1:4 or less.

[0114] Although it is preferable that the composition of the nano-composite metal material 10D is within the above range, the atomic ratio (Pd:Ni) of Pd to Ni is more preferably in the range of 1:7 or more and 1:12 or less. Also, the atomic ratio of Ni to Zr may be in the range of 1:2 or more and 1:3 or less, or in the range of 1:2 or more and 1:2.5 or less.

[0115] The composition of the nano-composite metal material 10D is adjusted by adjusting the atomic ratio (mass ratio) of the Pd-Ni-Zr alloy, which is the charged amount during the production of the fine metal particles 20B.

[0116] <Nano-composite metal material 10E> Next, the nano-composite metal material 10E and the method for manufacturing the nano-composite metal material 10E will be described.

[0117] The nano-composite metal material 10E is composed of a carrier 12 made of ceramics and binary metal particles 14 composed of Cu and Ni supported on the carrier 12, and is a nano-composite metal material 10 that is manufactured by a manufacturing method different from that of the nano-composite metal materials 10A and 10C, which are nano-composite metal materials 10 containing Cu.

[0118] The manufacturing method of the nano composite metal material 10E includes a firing step of firing fine metal particles 20A obtained by pulverizing an amorphous metal 18 composed of Cu, Ni, and ceramics at 300°C or higher and 600°C or lower, a hydrogen storage step of supplying hydrogen gas to the fired fine metal particles 20A to store hydrogen, and a heating step of heating the hydrogen-stored fine metal particles 20A at 200°C or higher and 300°C or lower under a vacuum state to obtain the nano composite metal material 10E.

[0119] That is, the manufacturing method of the nano composite metal material 10E corresponds to the manufacturing method of the nano composite metal material 10C, in which the nano composite metal material 10A obtained by the manufacturing method of the nano composite metal material 10A is used as the fine metal particles 20A.

[0120] Therefore, the firing step in the manufacturing method of the nano composite metal material 10E is the same as the firing step in the manufacturing method of the nano composite metal material 10A.

[0121] Also, the hydrogen storage step and the heating step in the manufacturing method of the nano composite metal material 10E are the same as the hydrogen storage step and the heating step in the manufacturing method of the nano composite metal material 10C, except that in the hydrogen storage step, the nano composite metal material 10A obtained by the firing step is used instead of the fine metal particles 20A.

[0122] When the carrier 12 is composed of Zr which is a ceramic, the composition of the nano composite metal material 10E is such that the atomic number ratio of Cu to Ni (Cu:Ni) is in the range of 1:7 or more and 1:15 or less, and the atomic number ratio of Ni to Zr is in the range of 1:2 or more and 1:4 or less.

[0123] Although the composition of the nano composite metal material 10E is preferably within the above range, 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. Also, the atomic number ratio of Ni to Zr may be in the range of 1:2 or more and 1:3 or less, or in the range of 1:2 or more and 1:2.5 or less.

[0124] The composition of the nano-composite metal material 10E is adjusted by adjusting the atomic ratio (mass ratio) of the Cu-Ni-Zr alloy, which is the charged amount during the production of the fine metal particles 20A.

[0125] <Nano-composite metal material 10F> Next, the nano-composite metal material 10F and the manufacturing method of the nano-composite metal material 10F will be described.

[0126] The nano-composite metal material 10F consists of a carrier 12 made of ceramics and binary metal particles 14 composed of Pd and Ni supported on the carrier 12, and is a nano-composite metal material 10 different from the nano-composite metal materials 10B and 10D, which are nano-composite metal materials 10 containing Pd, manufactured by different manufacturing methods.

[0127] The manufacturing method of the nano-composite metal material 10F includes a firing step of firing fine metal particles 20B obtained by pulverizing an amorphous metal 18 composed of Pd, Ni, and ceramics at 300°C or higher and 600°C or lower, a hydrogen storage step of supplying hydrogen gas to the fired fine metal particles 20B to store hydrogen, and a heating step of heating the hydrogen-stored fine metal particles 20B at 200°C or higher and 300°C or lower under a vacuum state to obtain the nano-composite metal material 10F.

[0128] That is, the manufacturing method of the nano-composite metal material 10F corresponds to the manufacturing method of the nano-composite metal material 10D, using the nano-composite metal material 10B obtained by the manufacturing method of the nano-composite metal material 10B as the fine metal particles 20B.

[0129] Therefore, the firing step in the manufacturing method of the nano-composite metal material 10F is the same as the firing step in the manufacturing method of the nano-composite metal material 10B.

[0130] Also, the hydrogen storage step and the heating step in the manufacturing method of the nano-composite metal material 10F are the same as the hydrogen storage step and the heating step in the manufacturing method of the nano-composite metal material 10D, except that in the hydrogen storage step, the nano-composite metal material 10B obtained by the firing step is used instead of the fine metal particles 20B.

[0131] When the carrier 12 is composed of Zr which is a ceramic, the composition of the nano composite metal material 10F is such that the atomic ratio (Pd:Ni) of Pd to Ni is in the range of 1:7 or more and 1:15 or less, and the atomic ratio of Ni to Zr is in the range of 1:2 or more and 1:4 or less.

[0132] Note that although the composition of the nano composite metal material 10F is preferably within the above range, the atomic 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 ratio of Ni to Zr may be in the range of 1:2 or more and 1:3 or less, or in the range of 1:2 or more and 1:2.5 or less.

[0133] The composition of the nano composite metal material 10F is adjusted by adjusting the atomic ratio (mass ratio) of the Pd-Ni-Zr alloy, which is the charged amount during the production of the fine metal particles 20A.

[0134] <Reaction process> Next, the exothermic reaction between the above-adjusted nano composite metal material 10 (nano composite metal materials 10A to 10F) and hydrogen will be described.

[0135] The nano composite metal material 10 is placed in a reaction furnace, and after evacuating the inside of the reaction furnace, hydrogen gas is supplied into the reaction furnace. The hydrogen gas to be supplied may be either deuterium gas or light hydrogen gas. Then, the inside of the reaction furnace is heated within the range of 250°C or more and 450°C or less. Specifically, the material temperature distribution during heating is such that the minimum is 200 - 250°C and the maximum is 350 - 450°C. Then, due to the thermal reaction between the nano composite metal material 10 and hydrogen, an exothermic phenomenon due to this thermal reaction occurs. This exothermic phenomenon may be referred to as an abnormal exothermic phenomenon.

[0136] It has been clarified that the nano composite metal material 10 of the present embodiment can achieve an increase in the amount of heat generated in the above exothermic phenomenon compared to a conventional composite metal material manufactured by a manufacturing method other than the above-described manufacturing method.

[0137] The reason for the above effects has not been clarified, but it is presumed as follows. However, the present invention is not limited by the following presumption. The number of sites of the nano-catalyst pitting structure (referred to as sub-nano holes and theoretical models) formed on the Ni core surface of the incomplete shell of Cu-Ni and Pd-Ni - Ni core is greatly increased by the treatment combining the re-annealing and baking of the present invention, and the exothermic reaction induced by hydrogen clusters formed at the sites is presumed to greatly increase under the dynamic balance of the temperature rise during the hydrogen desorption and absorption. It is considered that the heat generation amount can be increased by such a mechanism.

[0138] <Nano composite metal material 10G> Next, the nano composite metal material 10G and the manufacturing method of the nano composite metal material 10G will be described.

[0139] The nano composite metal material 10G is composed of a carrier 12 made of ceramics and binary metal particles 14 made of Cu and Ni supported on the carrier 12, and is a nano composite metal material 10 manufactured by a manufacturing method different from that of the nano composite metal materials 10A, 10C, and 10E which are nano composite metal materials 10 containing Cu.

[0140] The manufacturing method of the nano composite metal material 10G uses fine metal particles 20A as a starting material and has a heating step, a hydrogen storage step, a reaction step, and a re-annealing step.

[0141] The heating step of the manufacturing method of the nano composite metal material 10G is the same as the heating step used in the manufacturing methods of the above-mentioned nano composite metal materials 10C and 10E, and any condition can be selected from the conditions of the heating step listed above.

[0142] The hydrogen storage step of the manufacturing method of the nano composite metal material 10G is the same as the hydrogen storage step used in the manufacturing methods of the above-mentioned nano composite metal materials 10C and 10E, and any condition can be selected from the conditions of the hydrogen storage step listed above.

[0143] The reaction process of the method for manufacturing the nano composite metal material 10G is the same as the reaction process which is the exothermic reaction of the above-described nano composite metal materials 10A to 10F and hydrogen, and any conditions can be selected from among the conditions of the reaction process listed above.

[0144] The re-firing process of the method for manufacturing the nano composite metal material 10G is the same as the firing process used in the method for manufacturing the above-described nano composite metal material 10A, and any conditions can be selected from among the conditions of the firing process listed above. However, the re-firing process in the nano composite metal material 10G is a firing process performed after the above-described hydrogen storage process, heating process, and reaction process, and is distinguished from the firing process for manufacturing the nano composite metal material 10A from the above-described fine metal particles 20A.

[0145] The method for manufacturing the nano composite metal material 10G will be described with reference to FIG. 4. FIG. 4 is a flowchart showing an example of the procedure of the method for manufacturing the nano composite metal material 10G according to the embodiment.

[0146] As shown in FIG. 4, fine metal particles 20A are produced from a Cu-Ni-Zr alloy using the above-described method (step S110).

[0147] Next, the heating process (baking) (step S1211), hydrogen storage process (step S1221), and reaction process (step S1231) are repeatedly performed on the fine metal particles 20A in this order until a predetermined number of times is reached (step S1201). The number of times of performing these processes can be one or more times.

[0148] Next, a re-firing process is performed on the fine metal particles 20A (step S1301). At this time, the fine metal particles 20A are taken out from the reaction furnace used in the above process and re-fired in another system. Thereby, the calorific value obtained from the nano composite metal material 10G increases dramatically.

[0149] Up to the process of step S1301 above, the nano-composite metal material 10G1 is manufactured. Note that taking the processes of step S120 (steps S121 to S123) and step S130 as one cycle, these processes can be repeated multiple times.

[0150] The nano-composite metal material 10 obtained by performing the processes of step S120 and step S130 once is referred to as the nano-composite metal material 10G1 as described above. The nano-composite metal material 10 obtained by performing the processes of step S120 and step S130 twice is referred to as the nano-composite metal material 10G2. As shown in FIG. 4, the one that has gone through the processes of the nth step S120n (steps S121n to S123n) and step S130n is referred to as the nano-composite metal material 10Gn. The larger the number n of the nano-composite metal material 10Gn, that is, the more the number of times of the hydrogen storage process, the heating process, and the re-firing process after the reaction process increases, the more the calorific value obtained from the nano-composite metal material 10Gn tends to increase.

[0151] <Nano-composite metal material 10H> Next, the nano-composite metal material 10H and the manufacturing method of the nano-composite metal material 10H will be described.

[0152] The nano-composite metal material 10H is composed of a carrier 12 made of ceramics and binary metal particles 14 made of Pd and Ni supported on the carrier 12, and is a nano-composite metal material 10 containing Pd, which is manufactured by a manufacturing method different from that of the nano-composite metal materials 10B, 10D, and 10F.

[0153] The manufacturing method of the nano-composite metal material 10H uses fine metal particles 20B as a starting material and has a heating process, a hydrogen storage process, a reaction process, and a re-firing process.

[0154] The heating process in the manufacturing method of the nano-composite metal material 10H is the same as the heating process used in the manufacturing methods of the above-described nano-composite metal materials 10D and 10F, and any conditions can be selected from the conditions of the heating process listed above.

[0155] The hydrogen storage process in the manufacturing method of the nano-composite metal material 10H is the same as the hydrogen storage process used in the manufacturing methods of the above-described nano-composite metal materials 10D and 10F, and any conditions can be selected from the conditions of the hydrogen storage process listed above.

[0156] The reaction process in the manufacturing method of the nano-composite metal material 10H is the same as the reaction process which is the exothermic reaction between the above-described nano-composite metal materials 10A to 10F and hydrogen, and any conditions can be selected from the conditions of the reaction process listed above.

[0157] The re-firing process in the manufacturing method of the nano-composite metal material 10H is the same as the firing process used in the manufacturing method of the above-described nano-composite metal material 10B, and any conditions can be selected from the conditions of the firing process listed above. However, the re-firing process in the nano-composite metal material 10H is a firing process performed after the above hydrogen storage process, heating process, and reaction process, and is distinguished from the firing process for manufacturing the nano-composite metal material 10B from the above-described fine metal particles 20B.

[0158] The manufacturing method of the nano-composite metal material 10H will be described with reference to FIG. 5. FIG. 5 is a flowchart showing an example of the procedure of the manufacturing method of the nano-composite metal material 10H according to the embodiment.

[0159] As shown in FIG. 5, fine metal particles 20B are produced from a Pd-Ni-Zr alloy using the above-described method (step S210).

[0160] Next, for the fine metal particles 20B, a heating process (baking) (step S2211), a hydrogen storage process (step S2221), and a reaction process (step S2231) are repeated in this order until a predetermined number of times is reached (step S2201). The number of times these processes are performed can be one or more times.

[0161] Next, a re-firing process is performed on the fine metal particles 20B (step S2301). At this time, the fine metal particles 20B are taken out from the reaction furnace used in the above process and re-fired in another system. As a result, the calorific value obtained from the nano-composite metal material 10H increases dramatically.

[0162] As described above, the nano-composite metal material 10H1 is manufactured by the processing up to step S2301. Note that the processing of step S220 (steps S221 to S223) and step S230 is regarded as one cycle, and these processes can be repeated a plurality of times.

[0163] The nano-composite metal material 10 obtained by performing the processing of step S220 and step S230 once is referred to as the nano-composite metal material 10H1 as described above. The nano-composite metal material 10 obtained by performing the processing of step S220 and step S230 twice is referred to as the nano-composite metal material 10H2. As shown in FIG. 5, the product that has undergone the processing of the nth step S220n (steps S221n to S223n) and step S230n is referred to as the nano-composite metal material 10Hn. As the number n of the nano-composite metal material 10Hn increases, that is, as the number of times of the re-firing process after the hydrogen storage process, the heating process, and the reaction process increases, the calorific value obtained from the nano-composite metal material 10Hn tends to increase.

Example

[0164] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[0165] <Adjustment of fine metal particles 20> The following fine metal particles 20 (fine metal particles 20A, fine metal particles 20B) were prepared. · Fine metal particles 20A: CNZ7 · Fine metal particles 20B: PNZ10

[0166] 〔Fine metal particles 20A: CNZ7〕 CNZ7 is an example of the fine metal particles 20A produced using the above Cu-Ni-Zr alloy. The atomic ratio of CNZ7 was Cu:Ni:Zr = 1:7:14.

[0167] CNZ7 was produced as follows.

[0168] An Cu-Ni-Zr alloy with an atomic ratio of Cu:Ni:Zr = 1:7:14 was melted by heating in a heating furnace 22A (see Fig. 2), and the molten liquid was supplied to a rotating cooling roll 22B. The molten liquid solidified by contacting the rotating cooling roll 22B, and ribbon-shaped amorphous metal 18 was produced. The thickness of the ribbon-shaped amorphous metal 18 was 10 μm or more and 20 μm or less.

[0169] Then, 1000 g of this amorphous metal 18 was put into a crucible 24 and heated at a temperature of 450 °C for 120 hours in the air. 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. When the volume average particle diameter of this 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. Also, when the degree of oxidation of CNZ7 was measured by measuring the weight increase rate after firing, it was 31%.

[0170] 〔Fine metal particles 20B: PNZ10〕 PNZ10 is an example of the fine metal particles 20B produced using the above Pd-Ni-Zr alloy. The atomic ratio of PNZ10 was Pd:Ni:Zr = 1:10:20.

[0171] PNZ10 was produced as follows.

[0172] The Pd-Ni-Zr alloy with an atomic ratio of Pd:Ni:Zr = 1:10:20 was melted by heating in a heating furnace 22A (see Fig. 2), and the molten liquid was supplied to a rotating cooling roll 22B. The molten liquid solidified by contacting the rotating cooling roll 22B, and ribbon-shaped amorphous metal 18 was produced. The thickness of the ribbon-shaped amorphous metal 18 was 10 μm or more and 50 μm or less.

[0173] Then, 1000 g of this amorphous metal 18 was put into a crucible 24 and heated at a temperature of 450°C for 80 hours in the air. Then, the heated amorphous metal 18 was pulverized using an automatic mortar to produce PNZ10, which is an example of fine metal particles 20B. When the volume average particle diameter of this PNZ10 was measured with an optical microscope under the condition of a resolution of 0.01 mm, it was 0.05 mm or more and 0.1 mm or less. Also, when the degree of oxidation of PNZ10 was measured by the weight increase rate after firing, it was 2.44%.

[0174] <Adjustment of nano composite metal material 10> The following nano composite metal materials 10 were adjusted as nano composite metal materials 10A to nano composite metal materials 10H. · Nano composite metal material 10A: CNZ7r · Nano composite metal material 10B: PNZ10r · Nano composite metal material 10C: CNZ7♯1-1, CNZ7♯2-1 · Nano composite metal material 10D: PNZ10♯1-1, PNZ10♯2-1 · Nano composite metal material 10E: CNZ7r♯1-1, CNZ7r♯1-2, CNZ7r♯2-1, CNZ7r♯2-2, CNZ7r♯2-4 · Nano composite metal material 10F: PNZ10r♯1-1, PNZ10r♯1-4, PNZ10r♯2-1, PNZ10r♯2-2 · Nano composite metal material 10G: CNZ7R, CNZ7RR, CNZ7RRR · Nano composite metal material 10H: PNZ10R, PNZ10RR, PNZ10RRR

[0175] 〔Nanocomposite Metal Material 10A: CNZ7r〕 CNZ7r is an example of the nanocomposite metal material 10A fabricated using the CNZ7 (fine metal particles 20A) adjusted as described above. The lowercase "r" means that the firing process of the nanocomposite metal material 10A was carried out once.

[0176] CNZ7r was fabricated as follows.

[0177] 1000 g of the CNZ7 (fine metal particles 20A) fabricated as described above was put into an electric furnace (reactor 32) and fired at 450 °C for 120 hours in the air. Through this firing process, CNZ7r (nanocomposite metal material 10A) was fabricated.

[0178] Figure 6 is an electron micrograph of CNZ7r. The atomic ratio of CNZ7r was the same as that of the initial amorphous ribbon after melt spinning, with Cu:Ni:Zr = 1:7:14. Also, when the volume average particle diameter of CNZ7r (nanocomposite metal material 10A) was measured by the method described above, it was 0.1 mm or more and 1 mm or less. Further, when the degree of oxidation of the carrier 12 which is Zr in CNZ7r was measured by the method described above, it was 35.6% by weight ratio.

[0179] 〔Nanocomposite Metal Material 10B: PNZ10r〕 PNZ10r is an example of the nanocomposite metal material 10B fabricated using the PNZ10 (fine metal particles 20B) adjusted as described above. The lowercase "r" means that the firing process of the nanocomposite metal material 10B was carried out once.

[0180] PNZ10r was fabricated as follows.

[0181] 600 g of the PNZ10r (fine metal particles 20B) fabricated as described above was put into an electric furnace (reactor 32) and fired at 450 °C for 120 hours in the air. Through this firing process, PNZ10r (nanocomposite metal material 10B) was fabricated.

[0182] The atomic ratio of PNZ10r was the same as that of the initial melt-spun ribbon, Pd:Ni:Zr = 1:10:20. Also, when the volume average particle diameter of PNZ10r (nano composite metal material 10B) was measured by the method described above, it was 0.05 mm or more and 1 mm or less. Further, when the degree of oxidation of PNZ10r was measured by the method described above, it was 14.9% by weight ratio.

[0183] 〔Nano composite metal material 10C: CNZ7♯1-1, CNZ7♯2-1〕 As the nano composite metal material 10C, CNZ7♯1-1 and CNZ7♯2-1 were produced. CNZ7♯1-1 and CNZ7♯2-1 are an example of the nano composite metal material 10C produced using the CNZ7 (fine metal particles 20A) adjusted above.

[0184] The number immediately after “♯” indicates the number of heating steps (baking) in the nano composite metal material 10C. That is, ♯1 means that the heating step (baking) was carried out once after the hydrogen storage step. Also, ♯2 means that the heating step (baking) was carried out twice after the hydrogen storage step.

[0185] CNZ7♯1-1 and CNZ7♯2-1 were produced as follows.

[0186] Using the thermal reaction apparatus 30 shown in FIG. 3, CNZ7♯1-1 and CNZ7♯2-1 were produced.

[0187] Specifically, 1000 g of CNZ7 was supplied into the reactor 32. Then, the vacuum mechanism 36 was driven under the control of the control unit 50 to make the inside of the reactor 32 in a vacuum state. And in the state where the vacuum state was maintained, hydrogen gas was supplied from the gas supply unit 34 into the reactor 32 (hydrogen storage step). And after maintaining this state for 48 hours, while maintaining the hydrogen gas state in the reactor 32, the supply of hydrogen gas was stopped. And the exhaust in the reactor 32 was carried out, and while maintaining the vacuum state, the reactor 32 was heated by the heating mechanism 38 to control the material temperature distribution in the reactor 32 within a temperature range of at least 200 °C and at most 450 °C and heated for 64 hours (heating step (baking)). By this heating step, CNZ7♯1-1 was produced.

[0188] Also, after executing the heating step (baking) of heating for 64 hours within the above temperature range (the first baking), light hydrogen gas was charged so as to have a pressure of 0.2 Mpa or more and 0.6 Mpa or less, and the reactor 32 was heated from 200 °C to 450 °C and a heating test was carried out for two weeks. Then, again, instead of the above vacuum exhaust, by executing the heating step (baking) of heating for 24 hours (the second baking), CNZ7♯2-1 was produced.

[0189] [Nanocomposite metal material 10D: PNZ10♯1-1, PNZ10♯2-1] As the nanocomposite metal material 10D, PNZ10♯1-1 and PNZ10♯2-1 were produced. PNZ10♯1-1 and PNZ10♯2-1 are an example of the nanocomposite metal material 10D produced using the PNZ10 (fine metal particles 20B) adjusted above.

[0190] The number immediately after "♯" indicates the number of times of the heating step (baking) in the nanocomposite metal material 10D. That is, ♯1 means that the heating step (baking) was executed once after the hydrogen storage step. Also, ♯2 means that the heating step (baking) was executed twice after the hydrogen storage step.

[0191] PNZ10♯1-1 and PNZ10♯2-1 were produced using the thermal reaction device 30 shown in Figure 3.

[0192] Specifically, 600 g of PNZ10 was supplied into the reactor 32. Then, the vacuum mechanism 36 was driven under the control of the control unit 50 to make the inside of the reactor 32 in a vacuum state. And while maintaining the vacuum state, hydrogen gas was supplied from the gas supply unit 34 into the reactor 32 (hydrogen storage step). And after maintaining this state for 48 hours, while maintaining the hydrogen gas state in the reactor 32, the supply of hydrogen gas was stopped. And the exhaust in the reactor 32 was carried out, and while maintaining the vacuum state, the reactor 32 was heated by the heating mechanism 38 to control the material temperature distribution in the reactor 32 within the temperature range of at least 200°C and at most 450°C or less and heated for 48 hours (heating step (baking)). By this heating step, PNZ10#1-1 was produced.

[0193] Also, after the hydrogen gas storage at the above room temperature, the temperature was raised to 200°C or more and 450°C or less to conduct a heat generation test. Then, it was switched to vacuum exhaust and baking was executed under the same conditions as the first baking above (second baking), thereby producing PNZ10#2-1.

[0194] 〔Nano composite metal material 10E: CNZ7r#1-1, CNZ7r#1-2, CNZ7r#2-1, CNZ7r#2-2, CNZ7r#2-4〕 As the nano composite metal material 10E, CNZ7r#1-1, CNZ7r#1-2, CNZ7r#2-1, CNZ7r#2-2, CNZ7r#2-4 were produced.

[0195] CNZ7r#1-1, CNZ7r#1-2, CNZ7r#2-1, CNZ7r#2-2, CNZ7r#2-4 are an example of the nano composite metal material 10E produced using the above-adjusted CNZ7 (fine metal particles 20A).

[0196] Similar to the above, the number immediately after “#” indicates the number of times of the heating step (baking) in the nano composite metal material 10E.

[0197] CNZ7r♯1-1, CNZ7r♯1-2, CNZ7r♯2-1, CNZ7r♯2-2, and CNZ7r♯2-4 were fabricated using the thermal reaction apparatus 30 shown in FIG. 3.

[0198] Specifically, 505 g of CNZ7r, which is the nano-composite metal material 10A generated above, was supplied into the reaction furnace 32. Then, the vacuum mechanism 36 was driven under the control of the control unit 50 to make the inside of the reaction furnace 32 in a vacuum state. And while maintaining the vacuum state, hydrogen gas was supplied from the gas supply unit 34 into the reaction furnace 32 (hydrogen storage step). And after maintaining this state for 24 hours, while maintaining the hydrogen gas state in the reaction furnace 32, the supply of hydrogen gas was stopped. And while maintaining the hydrogen gas state in the reaction furnace 32, the reaction furnace 32 was heated by the heating mechanism 38 to control the material temperature distribution in the reaction furnace 32 within a temperature range of at least 200°C and at most 450°C or less, and the overheating measurement test was carried out for several weeks. Then, it was switched to vacuum exhaust and heated for 24 hours (heating step (baking)). By this heating step, CNZ7r♯1-2 was fabricated by the same process as CNZ7r♯1-1.

[0199] Also, in the heating step (baking) in the fabrication of the above CNZ7r♯1-1, the heating step of heating for 24 hours in the temperature range of 200°C or more and 350°C or less was executed (the first baking), and then, it was switched to vacuum exhaust and the heating step (baking) was executed under the same conditions as the first baking (the second baking) to fabricate CNZ7r♯2-1.

[0200] Also, after hydrogen gas storage at room temperature was carried out for 24 hours, it was heated to 200°C or more and 350°C or less and the overheating generation test was carried out for several days. Further, again, the heating step (baking) of controlling the material temperature distribution during heating within the range of at least 200°C and at most 450°C or less and heating for 24 hours was executed (the second baking) to fabricate CNZ7r♯2-2.

[0201] 〔Nano-composite metal material 10F: PNZ10r♯1-1, PNZ10r♯1-4, PNZ10r♯2-1, PNZ10r♯2-2〕 As the nano-composite metal materials 10F, PNZ10r♯1-1, PNZ10r♯1-4, PNZ10r♯2-1, and PNZ10r♯2-2 were fabricated.

[0202] PNZ10r♯1-1, PNZ10r♯1-4, PNZ10r♯2-1, and PNZ10r♯2-2 are examples of the nano-composite metal materials 10F fabricated using the PNZ10 (fine metal particles 20B) adjusted as described above. Similar to the above, the number immediately after "♯" indicates the number of times of the heating process (baking) in the nano-composite metal material 10E.

[0203] PNZ10r♯1-1, PNZ10r♯1-4, PNZ10r♯2-1, and PNZ10r♯2-2 were fabricated using the thermal reaction device 30 shown in FIG. 3.

[0204] Specifically, 450 g of PNZ10r, which is the nano-composite metal material 10B generated as described above, was supplied into the reaction furnace 32. Then, the vacuum mechanism 36 was driven under the control of the control unit 50 to make the inside of the reaction furnace 32 in a vacuum state. And while maintaining the vacuum state, hydrogen gas was supplied from the gas supply unit 34 into the reaction furnace 32 (room temperature hydrogen storage process). And after maintaining this state for 48 hours, while maintaining the state inside the reaction furnace 32, the supply of hydrogen gas was stopped. And while maintaining the hydrogen gas state inside the reaction furnace 32, the reaction furnace 32 was heated to 250°C - 350°C by the heating mechanism 38 to conduct an overheating test for several days. Then, it was switched to vacuum exhaust and the material temperature distribution inside the reaction furnace 32 was heated at a minimum of 200°C and a maximum of 450°C or less for 24 hours (heating process (baking)). By this heating process, PNZ10r♯1-1 was fabricated. Then, hydrogen storage at room temperature (♯1-2) and heating to 300°C were carried out to fabricate PNZ10r♯1-4.

[0205] After the above PNZ10r#1-4 heating overheat test, the heating process (baking) in the production, i.e., the heating process of heating the material temperature distribution at a minimum of 200°C and a maximum of 450°C or less for 24 hours (the second baking) was performed. After that, PNZ10r#2-1 was produced. Following the hydrogen storage at room temperature (#2-1), a heating test (#2-2) was performed at a temperature of 300°C or higher and 350°C or lower.

[0206] Also, after producing PNZ10r#2-2, the same processes of room temperature hydrogen storage, heating overheat test to 300°C, and baking were repeated to produce PNZ10r#3-1.

[0207] 〔Nano-composite metal material 10G: CNZ7R, CNZ7RR, CNZ7RRR〕 As the nano-composite metal material 10G, CNZ7R, CNZ7RR, and CNZ7RRR were produced.

[0208] CNZ7R, CNZ7RR, and CNZ7RRR are examples of the nano-composite metal material 10G produced using the above-adjusted CNZ7 (fine metal particles 20A). The capital letter "R" attached after CNZ7 means the nano-composite metal material 10G for which the heating process, hydrogen storage process, and re-firing process after the reaction process were performed once. That is, CNZ7R is an example of the nano-composite metal material 10G1, CNZ7RR is an example of the nano-composite metal material 10G2, and CNZ7RRR is an example of the nano-composite metal material 10G3.

[0209] 〔Nano-composite metal material 10H: PNZ10R, PNZ10RR, PNZ10RRR〕 As the nano-composite metal material 10H, PNZ10R, PNZ10RR, and PNZ10RRR were produced.

[0210] PNZ10R, PNZ10RR, and PNZ10RRR are examples of the nano-composite metal material 10H fabricated using the above-adjusted PNZ10 (fine metal particles 20B). The capital letter "R" appended to PNZ10 means the nano-composite metal material 10H for which the heating process, hydrogen storage process, and post-reaction re-firing process were carried out once. That is, PNZ10R is an example of the nano-composite metal material 10H1, PNZ10RR is an example of the nano-composite metal material 10H2, and PNZ10RRR is an example of the nano-composite metal material 10H3.

[0211] <Evaluation> Hydrogen gas was supplied to the above-fabricated nano-composite metal materials 10A to 10H, and the calorific value of the exothermic reaction with hydrogen was evaluated.

[0212] Specifically, each of the above-fabricated nano-composite metal materials 10, weighing 450 g or more and 505 g or less, was placed in the reaction furnace 32 of the thermal reaction apparatus 30 shown in Fig. 3. After evacuating the inside of the reaction furnace 32, the supply of deuterium gas into the reaction furnace 32 was started. Then, while continuously supplying deuterium gas, the inside of the reaction furnace 32 was heated to a temperature range of 250°C or more and 350°C or less by controlling the heating mechanism 38. Then, the supply of deuterium gas and the heating of the reaction furnace 32 were continued for 150 hours or more, and the change in the calorific value due to the thermal reaction between the nano-composite metal material 10 and hydrogen was measured.

[0213] The average value of the temperature measurement results of each of the temperature sensors 40A to 40D, which are temperature sensors 40 installed in the reaction furnace 32, was calculated by comparing with the calorimetric calibration test data obtained by loading a non-exothermic blank sample of 1300 g of zirconia beads into the reaction furnace, and the result was measured as the excess heat power amount.

[0214] [Evaluation of the calorific values of CNZ7, CNZ7r, PNZ10, and PNZ10r] Fig. 7 shows the measurement results indicating the relationship between the calorific value and the degree of oxidation of the fine metal particles 20 and the nano-composite metal material 10.

[0215] Note that Fig. 7 shows the calorific value calculated using the average value of the temperature measurement results by the temperature sensor 40 for several weeks after 24 hours from the start of heating the above reactor 32 to 300 °C and supplying deuterium gas.

[0216] Fig. 7 shows the diagram 60 and the diagram 62.

[0217] The diagram 60 is a diagram passing through the plot 60A and the plot 60B. The plot 60A shows the correspondence between the oxidation degree (2.44%) of the fine metal particles 20B which is PNZ10 and the calorific value (10.4 W / Kg). The plot 60B shows the relationship between the oxidation degree (14.9%) of the nano composite metal material 10B which is PNZ10r and the calorific value (62.5 W / Kg). As shown in the diagram 60, compared with the fine metal particles 20B which is PNZ10, the nano composite metal material 10B which is PNZ10r has a significantly increased calorific value.

[0218] Also, the diagram 62 is a diagram passing through the plot 62A and the plot 62B. The plot 62A shows the correspondence between the oxidation degree (31%) of the fine metal particles 20A which is CNZ7 and the calorific value (9.67 W / Kg). The plot 62B shows the relationship between the oxidation degree (35.6%) of the nano composite metal material 10A which is CNZ7r and the calorific value (104.9 W / Kg). As shown in the diagram 62, compared with the fine metal particles 20A which is CNZ7, the nano composite metal material 10A which is CNZ7r has a significantly increased calorific value.

[0219] 〔Evaluation of the calorific values of CNZ7, CNZ7♯1-1, CNZ7♯2-1, PNZ10♯1-1, PNZ10♯2-1, CNZ7r♯1-1, CNZ7r♯2-1, PNZ10r♯1-1, PNZ10r♯2-1〕 Fig. 8 shows the measurement results of the calorific values of the fine metal particles 20 and the nano composite metal material 10.

[0220] Note that Fig. 8 shows the calorific value calculated using the average value of the temperature measurement results by the temperature sensor 40 at the time point of several weeks after 24 hours from the start of heating the above reactor 32 to 300 °C and supplying deuterium gas.

[0221] FIG. 8 shows diagrams 64, 66, 68, and 70.

[0222] Diagram 70 is a diagram passing through plots 70A, 70B, and 70C. Plot 70A shows the correspondence between the baking times and the calorific values of CNZ7 which is fine metal particles 20A. Plot 70B shows the correspondence between the baking times and the calorific values of CNZ7♯1-1 which is nano-composite metal material 10C. Plot 70C shows the correspondence between the baking times and the calorific values of CNZ7♯2-1 which is nano-composite metal material 10C.

[0223] Diagram 68 is a diagram passing through plots 68A, 68B, and 68C. Plot 68A shows the correspondence between the baking times and the calorific values of PNZ10 which is fine metal particles 20B. Plot 68B shows the correspondence between the baking times and the calorific values of PNZ10♯1-1 which is nano-composite metal material 10D. Plot 68C shows the correspondence between the baking times and the calorific values of PNZ10♯2-1 which is nano-composite metal material 10D.

[0224] Diagram 66 is a diagram passing through plots 66A, 66B, and 66C. Plot 66A shows the correspondence between the baking times and the calorific values of CNZ7r which is nano-composite metal material 10A. Plot 66B shows the correspondence between the baking times and the calorific values of CNZ7r♯1-1 which is nano-composite metal material 10E. Plot 66C shows the correspondence between the baking times and the calorific values of CNZ7r♯2-1 which is nano-composite metal material 10E.

[0225] Diagram 64 is a diagram passing through plots 64A, 64B, and 64C. Plot 64A shows the correspondence between the baking times and the calorific values of PNZ10r which is nano-composite metal material 10B. Plot 64B shows the correspondence between the baking times and the calorific values of PNZ10r♯1-1 which is nano-composite metal material 10F. Plot 64C shows the correspondence between the baking times and the calorific values of PNZ10♯r2-1 which is nano-composite metal material 10F.

[0226] As shown in diagrams 64, 66, 68, and 70 of FIG. 8, the amount of heat generated increased upon baking. Also, the greater the number of baking times, the greater the amount of heat generated. Further, for any of the nano-composite metal materials 10, an increase in the amount of heat generated was confirmed compared to the fine metal particles 20.

[0227] 〔Evaluation of the amount of heat generated for CNZ7r♯1-2, CNZ7r♯2-2, CNZ7r♯2-4, PNZ10r♯1-4, PNZ10r♯2-1, and PNZ10r♯2-2〕 FIG. 9 is a diagram showing the change in the amount of heat generated for CNZ7r♯1-2, which is the nano-composite metal material 10E. Diagram 80A is a diagram showing the change in the amount of heat generated for CNZ7r♯1-2. Diagram 80B is a diagram showing the transition of the average value of the measurement results of the four temperature sensors 40 (temperature sensors 40A to 40D) in the thermal reaction device 30. Diagram 80C is a diagram showing the number of moles of hydrogen atoms absorbed by the thermal reaction.

[0228] FIG. 10 is a diagram showing the change in the amount of heat generated for CNZ7r♯2-2, which is the nano-composite metal material 10E. Diagram 82A is a diagram showing the change in the amount of heat generated for CNZ7r♯2-2. Diagram 82B is a diagram showing the transition of the average value of the measurement results of the four temperature sensors 40 (temperature sensors 40A to 40D) in the thermal reaction device 30. Diagram 82C is a diagram showing the number of moles of hydrogen atoms absorbed by the thermal reaction.

[0229] FIG. 11 is a diagram showing the change in the amount of heat generated for CNZ7r♯2-4, which is the nano-composite metal material 10E. Diagram 84A is a diagram showing the change in the amount of heat generated for CNZ7r♯2-4. Diagram 84B is a diagram showing the transition of the average value of the measurement results of the four temperature sensors 40 (temperature sensors 40A to 40D) in the thermal reaction device 30. Diagram 84C is a diagram showing the number of moles of hydrogen atoms desorbed by the thermal reaction.

[0230] FIG. 12 is a diagram showing the change in the calorific value of PNZ10r♯1-4 which is the nano-composite metal material 10F. Diagram 86A is a diagram showing the change in the calorific value of PNZ10r♯1-4. Diagram 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. Diagram 86C is a diagram showing the number of moles of hydrogen atoms desorbed by the thermal reaction.

[0231] FIG. 13 is a diagram showing the change in the calorific value of PNZ10r♯2-2 which is the nano-composite metal material 10F. Diagram 88A is a diagram showing the change in the calorific value of PNZ10r♯2-2. Diagram 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. Diagram 88C is a diagram showing the number of moles of hydrogen atoms desorbed by the thermal reaction.

[0232] As shown in FIGS. 9 to 13, a high calorific value was measured for any of the nano-composite metal materials 10.

[0233] 〔Evaluation of Calorific Value of CNZ7 and PNZ10 by Number of Annealing Cycles〕 FIG. 14 shows the measurement results of the relationship between the calorific value and the number of annealing cycles of CNZ7 which is an example of the fine metal particles 20A, and CNZ7R, CNZ7RR, CNZ7RRR which are nano-composite metal materials 10G produced from the fine metal particles 20A.

[0234] FIG. 14 shows the calorific value (also referred to as excess heat) of CNZ7, CNZ7R, CNZ7RR, CNZ7RRR when the input power to the heating mechanism 38 of the reactor 32 is 200 W and 235 W.

[0235] As shown in FIG. 14, regardless of whether the input power to the heating mechanism 38 is 200 W or 235 W, the calorific value increases substantially proportionally up to CNZ7RR which has been annealed twice. However, for CNZ7RRR which has been annealed three times, the calorific value seems to be approximately the same as or rather lower than that of CNZ7RR.

[0236] Also, when the input power to the heating mechanism 38 was 200 W and 235 W, the result was that the heat generation amount was generally larger when it was 235 W.

[0237] As described above, when manufacturing the nano-composite metal material 10G from the fine metal particles 20A, it was found that there was a tendency that a larger heat generation amount could be obtained by increasing the number of re-firing times.

[0238] However, in the example of FIG. 14 above, in the case of CNZ7RRR with three re-firing times, the increasing tendency of the heat generation amount seems to level off. Also, when the input power to the heating mechanism 38 is 200 W and 235 W, the magnitude relationship of the heat generation amount may be reversed. Therefore, there seems to be room for improvement in the conditions of the re-firing process and the like.

[0239] FIG. 15 shows the measurement results of the relationship between the heat generation amount and the number of re-firing times of PNZ10, which is an example of the fine metal particles 20B, and PNZ10R, PNZ10RR, and PNZ10RRR, which are nano-composite metal materials 10H produced from the fine metal particles 20B.

[0240] FIG. 15 shows the heat generation amounts (also referred to as excess heat) of PNZ10, PNZ10R, PNZ10RR, and PNZ10RRR when the input power to the heating mechanism 38 of the above reactor 32 is 200 W and 235 W.

[0241] As shown in FIG. 15, regardless of whether the input power to the heating mechanism 38 is 200 W or 235 W, the heat generation amount increases as the number of re-firing times increases. In particular, up to PNZ10RR with two re-firing processes, the heat generation amount increases proportionally. On the other hand, in the case of PNZ10RRR with three re-firing processes, the increase in the heat generation amount seems to be slightly dulled.

[0242] Also, when the input power to the heating mechanism 38 was 200 W and 235 W, the result was that the heat generation amount was generally larger when it was 235 W.

[0243] As described above, when manufacturing the nano composite metal material 10B from the fine metal particles 20B, it was found that by increasing the number of re-firing times, there is a tendency to obtain a larger amount of heat generation.

[0244] However, in the example of Fig. 15 above, in PNZ10RRR with 3 re-firing times, the tendency for the amount of heat generation to increase seems to have slowed down. Therefore, it is considered that there is room for improvement in the conditions of the re-firing process and the like.

[0245] As described above, the embodiments of the present invention have been described. However, the above embodiments are presented as examples and are not intended to limit the scope of the invention. The above novel embodiments can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the gist of the invention. These embodiments are included in the scope and gist of the invention, and are included in the invention described in the claims and its equivalent scope.

Explanation of Reference Numerals

[0246] 10, 10A, 10B, 10C, 10D, 10E, 10F nano composite metal materials 12 carrier 14 binary metal particles

Claims

1. It consists of a carrier made of Zr, and binary metal particles composed of Cu and Ni supported on the carrier, The atomic ratio of Cu to Ni is in the range of 1:7 or more and 1:15 or less, and the atomic ratio of Ni to Zr is in the range of 1:2 or more and 1:4 or less, A nano composite metal material in which the degree of oxidation of the carrier is greater than 31% and 100% or less, When the nano composite metal material is placed in the reaction furnace of a thermal reaction device, the inside of the reaction furnace is evacuated, and at least one of hydrogen gas and deuterium gas is supplied into the reaction furnace, and the reaction furnace is heated to a temperature range of 250°C or more and 350°C or less by the heating mechanism provided in the thermal reaction device, the excess heat of the nano composite metal material calculated by comparing with the calorimetric calibration test data of a non-heating blank sample of zirconia beads loaded in the reaction furnace is 100 W / kg or more, Nano composite metal material.

2. It consists of a carrier made of Zr, and binary metal particles composed of Pd and Ni supported on the carrier, The atomic ratio of Pd to Ni is in the range of 1:7 or more and 1:15 or less, and the atomic ratio of Ni to Zr is in the range of 1:2 or more and 1:4 or less, A nano composite metal material in which the degree of oxidation of the carrier is 3% or more and 100% or less, When the nano composite metal material is placed in the reaction furnace of a thermal reaction device, the inside of the reaction furnace is evacuated, and at least one of hydrogen gas and deuterium gas is supplied into the reaction furnace, and the reaction furnace is heated to a temperature range of 250°C or more and 350°C or less by the heating mechanism provided in the thermal reaction device, the excess heat of the nano composite metal material calculated by comparing with the calorimetric calibration test data of a non-heating blank sample of zirconia beads loaded in the reaction furnace is 40 W / kg or more, Nano composite metal material.

3. It includes at least a range where the volume average particle size is 0.01 mm or more and 1 mm or less, The nano-composite metal material according to claim 1 or claim 2.

4. having a volume average particle size in the range of 0.01 mm or more and 1 mm or less, The nano-composite metal material according to claim 1 or claim 2.

5. A hydrogen storage step of supplying at least one of hydrogen gas and deuterium gas to fine metal particles obtained by pulverizing an amorphous metal composed of Cu, Ni, and Zr, and storing at least one of hydrogen and deuterium; A reaction step of heating the fine metal particles storing at least one of hydrogen and deuterium to 200 ° C or higher and 450 ° C or lower to obtain a nano-composite metal material; A method for producing a nano-composite metal material having the above.

6. A hydrogen storage step of supplying at least one of hydrogen gas and deuterium gas to fine metal particles obtained by pulverizing an amorphous metal composed of Pd, Ni, and Zr, and storing at least one of hydrogen and deuterium; A reaction step of heating the fine metal particles storing at least one of hydrogen and deuterium to 200 ° C or higher and 450 ° C or lower to obtain a nano-composite metal material; A method for producing a nano-composite metal material having the above.

7. A heating step of heating the fine metal particles at 200 ° C or higher and 450 ° C or lower, The method for producing a nano-composite metal material according to claim 5 or claim 6 having the above.

8. Repeating the heating step, the hydrogen storage step, and the reaction step in this order a predetermined number of times, The method for producing a nano-composite metal material according to claim 7.

9. A re-firing step of re-firing the fine metal particles at 300 ° C or higher and 600 ° C or lower after repeating the heating step, the hydrogen storage step, and the reaction step the predetermined number of times, The method for producing a nano-composite metal material according to claim 8 having the above.

10. After repeating the heating step, the hydrogen storage step, and the reaction step the predetermined number of times, performing the re-firing step is defined as one cycle, and repeating the cycle the predetermined number of times. The method for producing a nano composite metal material according to claim 9.

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