JPS6178585A - Zirconium and zirconium alloy clad steel and its manufacture - Google Patents

Abstract

PURPOSE:To obtain a zirconium clad steel at a cost and safely by one process, by interposing a specified inserting material between zirconium and steel. CONSTITUTION:Ti2, Mo4 and Ni5 are inserted as inserting materials in said order from the side of Zr or a Zr alloy 3, between Zr or the Zr alloy 3 and a steel material 1. The which has been prepared in this way is set into a diffusing welder 6, and an oxygen absorbent of a shape of plate, foil, rod, wire, etc. consisting of one kind or two kinds or more of Mg, Zr and T, and alloys having them as main components is placed in its periphery. The whole of them is heated and pressed in a vacuum or an inert gas atmosphere, and a desired clad steel is manufactured by diffusion welding in one process, in a state that it remains a solid phase.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to zirconium and zirconium alloy crund steel that can be applied to chemical reaction vessels, modules for gas and oil plants, and a method for producing the same.

[Conventional technology]

Zirconium (Zr) and zirconium alloys (Zr alloys) have excellent corrosion resistance and heat resistance, so they are often used in chemical reaction vessels, nuclear reactor materials, etc. However, due to their high prices, they are used only in the necessary parts. It was required to use Zr and Zr alloy for the parts, and to use inexpensive carbon steel etc. for the other parts. In order to meet this demand, explosive bonded Zr clad steel has been developed and put into practical use.
This is a 5iC, manufactured in two steps as shown in FIG. That is, in the first step [Ni) → 03)], titanium (T1) 2 is bonded onto the base material steel 1 by explosive bonding, and the surface is polished, and then the second step [Stem] → (C )] on which Zr or Zr alloy 3 is bonded by explosion bonding.

This method had five drawbacks: the explosion bonding process was repeated twice, which increased the number of man-hours and cost, and it was dangerous because it utilized the explosive power of gunpowder.

[Problem that the invention seeks to solve]

An object of the present invention is to provide Zr and Zr gland steels that can be produced inexpensively and safely in one process.

[Failure to solve the problem]

The present invention interposes an insert material between zirconium or zirconium alloy and steel, which includes titanium, molybdenum, and nickel in this order from the zirconium or zirconium alloy side. The present invention relates to zirconium and zirconium alloy crund steel characterized by being joined by diffusion welding.

In addition, in producing a cladding of zirconium or zirconium alloy and steel, the present invention stacks titanium, molybdenum, and nickel as insert materials from the zirconium or zirconium alloy side, and surrounds it with Mg, Zr. , 'ri, and alloys containing these as main components, and diffusion welding of the metals is performed while reducing the oxygen concentration in the atmosphere to form a joined body. The present invention relates to a method for producing zirconium and zirconium alloy crund steel.

The present invention will be explained below based on the drawings.

FIG. 1 shows the construction of Zr and Zr gland steel according to the invention. In the figure, zr or Zr alloy 5 and steel material 1
Ti 2 , Mo4. Insert in the order of Ni5. These insert materials may be inserted by inserting foil of each insert material, or by vapor deposition, plating,
The surface of the steel material 1 or Zr or Zr alloy may be coated by a coating method such as thermal spraying. T1 used as an insert material is 0.05 to 10+a, M.

The thickness of α01 to 10 and N1 is preferably α01 to 10. If the values are below the lower limit values, it is impossible to manufacture by rolling, and coatings such as plating and thermal spraying do not provide uniform film thickness, leading to variations in joint strength during diffusion welding. rice bowl Further, although it is possible to manufacture a steel having a thickness greater than the upper limit, it is not possible to provide an inexpensive rad steel, which is one of the objects of the present invention. As shown in FIG. 2, the material prepared in this way is placed in a diffusion welding machine 6, and ~Ig,
An oxygen absorber 7 in the form of a plate, foil, rod, wire, etc. made of one or more of Zr, Ti, and alloys thereof as χ generating components is arranged. The entire structure is heated and pressurized in a vacuum or in an inert gas atmosphere, and a desired glue 2-piece steel is produced in one step by diffusion welding while it remains in a solid state.

In addition, in FIG. 2, 8 is a heater, 9 is an upper pressure body, 1
0 indicates a lower pressurizing body, 11 indicates a valve, and 12 indicates a vacuum pump.

[Effect]

The present invention features a five-layer insert method of Ti, Mo, and Nλ;

Considering the combination of atoms at each interface of Ti-Mo, Mo-Ni, and Ni-Fe, it has the effect of forming a good metallurgical bond without forming brittle intermetallic compounds. In addition, Mg and Zr are placed around the periphery.

Since active metals such as T1 have a strong affinity for oxygen, they absorb acid Xt in the atmosphere during expansion welding and have the effect of lowering the oxygen concentration.

〔Effect of the invention〕

Previously, Zr clad steel could only be produced by explosion bonding, but the present invention has made it possible to produce it by diffusion welding. In other words, it is impossible to join ZR and steel materials directly because they generate brittle intermetallic compounds, but the Ti-blo-Ni three-layer insert method prevents the formation of intermetallic compound layers. , a strong metallurgical bond is formed. Since these insert materials are used in a foil or surface coating method, the Zr-insert material-steel material bond is completed simultaneously in one step by simply laminating them one after another on top of the Zr or steel material. Compared to the conventional two-step gA layer deposition method, the number of man-hours is significantly reduced, and it is now possible to supply low-cost crund steel.

In addition, since ZR is a metal with a strong affinity for oxygen, when it is heated in vacuum during diffusion bath welding, a small amount of oxygen present in the atmosphere oxidizes the bonding surface and reduces the bonding strength. The arranged Mg, Zr, Ti, and their alloys have an affinity for oxygen equal to or greater than that of Zr or Zr alloy, which is the material to be joined.
What's in the atmosphere? Absorption and chlorine concentration? By lowering the bonding strength, oxidation of the materials to be joined is prevented and sufficient joining strength is ensured.

Next, examples will be shown.

Example 1 As a material to be joined, a plate thickness of 2 m and a size of 100 x 100 mm
Zr and 5S with plate thickness 6m and size 1100X100
41, and in the middle, as an insert material, from the Zr side, T1 with a plate thickness of 0.1 gourd, MO1 plate thickness α with a plate thickness of 05 m
The size is 100x100m each with N1 of 05m.
The foils were sequentially laminated. A combination of traps like this,
Diffusion welding was performed by heating to 850°C in a vacuum of 5X 10' Torr and applying pressure at a pressure of 2 kg/m for 2 hours.After joining, the joint strength was investigated and it was found to be 17 kg in a shear test. /■2 was obtained, and microstructural observation revealed that a good joined body with no defects was obtained.

Example 2 The materials to be joined were a Zr plate with a thickness of 4 mm and a size of 150 x 100 pieces, on one side of which was vacuum-deposited Tifa to a thickness of 02 m, and a plate with a thickness of 10 mm and a size of 150 x 100 pieces.
m 5US410, with Ni fj (α02m
I used a piece that had been peeled to a thickness of . T1 vapor deposited surface and N
The 1Y side? Facing each other, insert V and O foils of thickness Q and size 05 + 50 x 100 as insert material in the middle, overlap them, surround them with Tl plate of thickness 1, and perform diffusion welding. Ta. The bonding conditions are
Degree of vacuum: 5 x 10-4 Torr, humidity: 800°C,
The pressing force was 15 kg/as'' and the bonding time was 1 hour.

After bonding, ultrasonic flaw detection was performed and no defects were found (
Example 6 It was found that a good joined body having a shear strength of 22 Y/2 was obtained.The material to be joined was C, Zircaloy-2 (Zr-15%).

Sn-α1%, Fe-0.1%, Cr-0.05%N1
Plate thickness α5III111 size 50X100+a
s+ one and 5US with 20μ of IcNI deposited on one side.
504, a plate thickness of 12 pieces, and a size of 50 x 100 pieces was used.

In the middle, as an insert material, from the Zircaloy side, a plate thickness of 0.2 ■, size 50 x 100 T1, plate thickness 0.11
1II11 MOs with a thickness of 50×100+m were sequentially laminated. Mg foil having a thickness of α1 was placed around this, and diffusion welding was performed. The bonding conditions were Ar, 1 atm, bonding temperature of 850°C, pressurizing force of 2 klil/as'', and bonding time of 2 hours.As in Examples 1 and 2, a good bonded body with no defects was obtained. Ta.

In addition, instead of Mg foil in the above b example, a trap, Zr,
Similar results were obtained when a Ti foil was used.

[Brief explanation of drawings]

FIG. 1 shows the structure of Zr and Zr alloy crush steel according to the present invention, and FIG.
This figure shows the configuration of a diffusion welding machine used to weld alloy crund steel. FIG. 5 is an explanatory diagram of a process for manufacturing conventional Zr clad steel. Sub-agents 1) Meifuku agent Ryo Hagiwara -

Claims (2)

[Claims] (1) Zirconium or zirconium alloy and steel are joined by diffusion welding by interposing an insert material of titanium, molybdenum, and nickel in this order from the zirconium or zirconium alloy side between the zirconium or zirconium alloy and the steel. Zirconium and zirconium alloy clad steel. (2) When manufacturing clad steel made of zirconium or zirconium alloy and steel, titanium, titanium,
Molybdenum and nickel are laminated in this order, and M
An oxygen absorber made of one or more of g, Zr, Ti, and alloys containing these as main components is placed, and the metals are joined by diffusion welding while reducing the oxygen concentration in the atmosphere. A method for producing zirconium and zirconium alloy clad steel, characterized by obtaining a zirconium and zirconium alloy clad steel.