JP2003286524A - METHOD FOR MANUFACTURING (Ni, Al)-V ALLOY MATERIAL - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a V-based alloy material which can be a material for producing a large area of a hydrogen separation and refinement film with an arbitrary form, in order to treat a large quantity of hydrogen. <P>SOLUTION: This manufacturing method is characterized by diffusing and infiltrating V, or V and Al into a Ni substrate to form the alloy phase, or diffusing and infiltrating one or more of Ni and Al in a V substrate to form the alloy phase. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The invention of this application is (Ni, A
l) -V alloy material manufacturing method. More specifically, the invention of this application makes it possible to manufacture a (Ni, Al) -V alloy material, which is useful as a member for hydrogen separation and purification, in an arbitrary shape, and enables separation and purification of hydrogen at a large flow rate. The present invention relates to a new manufacturing method of a (Ni, Al) -V alloy material that can be manufactured.

[0002]

2. Description of the Related Art V-based alloys containing Ni or Al have a high hydrogen permeability and are less expensive than Pd alloys currently in practical use as hydrogen permeable membranes. I have V with such characteristics
With respect to the base alloy, the inventors of the present application have made detailed studies for practical use as a hydrogen separation / purification membrane (for example, Materials Tran).
sactions, JIM, Vol.32, No.5 (1991), pp.501-507;
Journal of Alloys and Compounds 330-332 (2002) 902-
906).

However, since these alloys are easily oxidized and the melting point of the oxide is low, hot rolling is difficult,
There is also a problem that it is actually difficult to directly cold-roll an ingot because cracks are likely to occur.

Therefore, conventionally, in order to obtain a thin plate-shaped product, the ingot is cut and then thinned by polishing.
Moreover, there is a problem that it cannot be made a large area.

Therefore, the invention of the present application solves the conventional problems as described above, and is large so that it can be used as a hydrogen separation and purification membrane in any shape and with a large flow rate of hydrogen. It is an object of the present invention to provide a new method for producing a V-based alloy material that can have an area.

[0006]

Means for Solving the Problems In order to solve the above problems, the invention of the present application is as follows. First, V or V and Al are diffused and permeated into a Ni base material to form an alloy phase. And a second method for forming an alloy phase by diffusing and permeating at least one of Ni and Al into a V base material. A method of manufacturing a (Ni, Al) -V alloy material is provided.

The third aspect of the invention of the present application is the above method, wherein a gaseous metal halide is brought into contact with a substrate to diffuse and permeate (Ni, Al).
Fourth, the method for producing a -V alloy material is characterized by including a process of producing a gaseous metal halide and its chemical transport on a temperature gradient, and a contact with a substrate (N.
Fifth, the base material is a thin plate or a pipe-shaped body (Ni, Al) -V alloy material (Ni,
An Al) -V alloy material manufacturing method is provided.

In the invention of this application as described above, since the alloy material is manufactured by utilizing the vapor phase diffusion infiltration method,
It is possible to alloy a pure metal of Ni or V, which is easier to process than an alloy material that is difficult to process, into a predetermined shape by cold rolling or the like in advance. For this reason,
Of any shape, including complicated shapes,
Further, it is easy to manufacture a large area.

Since it is a diffusion infiltration method, it is possible to precisely control the composition of the alloy by selecting and changing the conditions such as temperature, pressure and gas concentration, and also to obtain a graded composition. It is possible.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The invention of this application has the characteristics as described above, and the embodiments thereof will be described below.

In the invention of this application, a V-base alloy material is produced, which has a main use as a membrane for separating and refining hydrogen. Its composition is Ni-V alloy, Ni-Al-V.
Either the alloy or the Al-V alloy.

As a means for producing these alloy materials, a diffusion permeation method in which a gas (gas) is brought into contact with a substrate is adopted. As the base material, a pure metal of Ni or V is used, and these base materials may be previously formed into a predetermined shape, for example, a thin plate, a cylindrical body, or another complicated shape.

The gas that is contacted with these substrates for diffusional permeation is either V or a compound of V and Al in the case of Ni substrates and Ni in the case of V substrates. , Al
One or more compounds of These compounds may be various compounds as long as they can exist in a gaseous state at a predetermined temperature level, and halides such as chlorides and iodides, carbonyl compounds and the like are considered. When using these gaseous metal compounds, it is also conceivable to carry out their production, chemical transport on a temperature gradient and contact with the substrate as a continuous process.

In fact, the inventor of this application has found that metals V, N
In the chemical transport reaction in which gaseous chloride or iodide formed by heating i and Al in the presence of hydrogen chloride, iodine, etc. is decomposed after being transported along a temperature gradient and precipitated as the original metal. Paying attention, install a source of metal V, Ni, Al and hydrogen chloride in one place on the temperature gradient furnace, install a V or Ni base material in a place apart from this, and heat each to a different temperature. According to the above, it has been found that a chloride produced by the reaction between a metal and hydrogen chloride is chemically transported on a temperature gradient, decomposes on a base material and diffuses and permeates to form an alloy layer. The composition of the formed alloy differs depending on the temperature difference between the transport raw material and the base material, and it has been confirmed that the alloy composition can be precisely controlled by changing the reaction conditions. It is also possible to obtain a composition with a gradient composition. By subjecting pure V and Ni, which are extremely easy to process, to an arbitrary shape by cold rolling or the like and then performing the above-mentioned treatment, a V-based alloy film having a complicated shape, which is difficult to manufacture by the conventional method, can be obtained. It becomes possible to manufacture.

Metals that can be used as raw materials for hydrogen separation alloys have only a very low vapor pressure as a single metal, and in order to deposit them through the gas phase, physical methods such as vapor deposition and sputtering, or chemical transport. Either of the reactions needs to be used. However, the former method requires extremely expensive equipment, is not suitable for mass production of hydrogen separation alloy membranes, and is difficult to uniformly deposit on a substrate having a complicated shape such as a pipe shape. On the other hand, when the chemical transport reaction is used, the raw materials are easily available, and chloride, iodide, etc.
Since it has a high vapor pressure even at a relatively low temperature of 000 ° C. or less, it is practically effective to use hydrogen chloride or iodine as a transport agent.

The invention of this application will now be described in more detail with reference to the following examples. Of course, the invention is not limited to the following examples.

[0017]

EXAMPLE An apparatus having the configuration illustrated in FIG. 1 was used. The reference numerals in the figure indicate the following. 1: Temperature gradient furnace, 2: Quartz tube, 3: Ni base material, 4: Alumina boat, 5: Chemical transport raw material (metal V, platinum chloride, ammonium chloride) First, a 10 mm × 10 mm × 0.2 mm Ni plate was prepared. Both sides were mirror-polished by mechanical polishing. A mixture of 0.0733 g of platinum chloride and 0.0098 g of ammonium chloride as a source of HCl was wrapped in Ni foil, and a chemical transport material (5) was attached to one end of the quartz tube (2) that was sealed together with the bulk V metal that was the transport material.
I put it as. Ni about 6 cm away from there
The plate (3) was placed. The quartz tube (2) was connected to a vacuum line, and the other end was sealed while being pulled up to the level of 10 ⁻⁶ Torr. As shown in FIG. 1, a temperature gradient was set such that the lowest temperature was 900 ° C. and the highest temperature was 924 ° C. in an electric furnace having a plurality of independent heating parts and capable of setting the temperature gradient. The quartz tube (2) was placed in an electric furnace so that the raw material part (5) of the quartz tube (2) was 900 ° C and the Ni plate (3) was 924 ° C. After 8 days, the quartz tube (2) was taken out and cooled. The sample weight of the Ni plate (3) increased from 0.158 g to 0.200 g by 0.032 g. The thickness of the sample is 0.11 from 0.20mm to 0.31mm.
mm increased. FIG. 2 is an X-ray diffraction pattern of the Ni base material before and after the diffusion and penetration experiment. Almost no peaks other than the peaks based on Ni were observed in the base material before the experiment, whereas the Ni peaks disappeared in the base material after the experiment and peaks based on the fcc phase and the σ phase appeared. The fcc phase has the same structure as Ni,
The whole peak is shifted to the lower angle side, and the calculated lattice constant is 3.638, which is larger than the lattice constant of Ni, 3.5238. Therefore, V has a large atomic radius as compared with Ni, and the lattice expands. Judged as something. It is the case where V is 39 to 55 at% that the two-phase region of the fcc phase and the σ phase is taken from the Ni-V binary system phase diagram at the base material temperature of 924 ° C.
The line diffraction results show that an equivalent amount of V diffused and penetrated into the Ni substrate in the 8 day experiment.

[0018]

As described above in detail, according to the invention of this application, it is possible to manufacture a V-Ni alloy film having an arbitrary shape and an arbitrary composition. This makes it possible to fabricate a hydrogen separation device using a V-Ni alloy and efficiently purify a large amount of hydrogen at low temperatures.

The price of Pd, which is known as a hydrogen separation membrane material, has risen 2 to 4 times as much as that of gold in the past year, and it is difficult to use it as a membrane material in terms of cost. On the other hand, Ni and Al are extremely inexpensive, and the price of V per gram is 1/10 or less of Pd. It is possible to reduce the price. The alloy material of the invention of this application is also applicable as a hydrogen production device for fuel cell vehicles, and is considered to contribute to the spread of fuel cell vehicles.

[Brief description of drawings]

FIG. 1 is a diagram illustrating the configuration of an experimental device for diffusion osmosis.

FIG. 2 is an X-ray diffraction pattern of a Ni base material, (a)
Before the experiment, (b) after the diffusion and penetration experiment at 924 ° C. for 192 hours is shown.

[Explanation of symbols]

1 Temperature gradient furnace 2 Quartz tube 3 Ni base material 4 Alumina boat 5 Transport materials (metal V, platinum chloride, ammonium chloride)

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Claims (5)

[Claims] 1. An alloy phase is formed by diffusing and permeating V or V and Al into a Ni base material (Ni, A).
l) -V alloy material manufacturing method. 2. An alloy phase is formed by diffusing and permeating at least one of Ni and Al into a V base material (N.
i, Al) -V alloy material manufacturing method. 3. The method for producing a (Ni, Al) -V alloy material according to claim 1, wherein the gaseous metal halide is brought into contact with the base material to diffuse and permeate. 4. The (Ni, Al)-of claim 3, characterized in that it comprises the process of the production of the gaseous metal halide and its chemical transport over a temperature gradient and the contact with the substrate.
V alloy material manufacturing method. 5. The substrate (Ni, A) according to claim 1, wherein the substrate is a thin plate or a pipe.
l) -V alloy material manufacturing method.