JPH11286069A - Titanium metal-clad stainless steel and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To have stable, sufficient bond strength, to enable production by general purpose equipment, and to reduce labor, time, and production costs in titanium metal-clad stainless steel and its production method in which stain less steel is used as a base material, and a titanium metal selected from pure titanium and titanium alloys is bonded as a mating material. SOLUTION: An amorphous alloy which contains 10-50 atom % of at least one element selected from Ti, Zr, and Hf and the rest of Cu and inevitable impurities is placed between stainless steel and a titanium metal and diffusion- bonded, and a layer 1 mainly comprising stainless steel, a layer 2 mainly comprising the elements of the amorphous alloy excluding Cu and the elements of the stainless steel such as Fe, a layer 3 mainly comprising the element of the amorphous alloy, a layer 4 mainly comprising titanium metals are formed in turn.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a titanium-based metal-clad stainless steel in which a stainless steel is used as a base material and a titanium-based metal selected from various pure titanium and titanium alloys is joined as a bonding material, and a method for producing the same. Is,

[0002]

2. Description of the Related Art Titanium-based metal-clad stainless steel
It has been manufactured by laminating a stainless steel slab as a base material and a titanium-based metal slab as a joining material into an assembled slab, and hot rolling the slab. The assembled slab has been manufactured by joining both slabs by a bombardment method, or covering the superposed slabs with a cover such as a steel plate and degassing.
In the latter, a method is known in which an intermediate material is interposed between the two slabs to improve the joining strength of the product clad stainless steel.

For example, Japanese Patent Application Laid-Open No. 63-56371 proposes interposing any one of Cu, Ni and Cu-Ni alloy as the intermediate material. JP-A-63-306031 discloses Fe.
-It has been proposed to interpose a Zn alloy.

[0004]

In the above prior art, first, special equipment such as explosive equipment, steel sheet coating equipment, and exhaust equipment is required to manufacture an assembled slab, and excessive labor, time and cost are required. Was. In hot rolling, ordinary equipment for steel sheets or titanium sheets can be used. However, there is a problem that a part that is not pressed is generated due to a difference in deformation resistance between stainless steel and titanium-based metal. Had. Furthermore, even if an intermediate material proposed in the above-mentioned publications is interposed, the obtained product of titanium clad stainless steel does not always have a sufficient bonding strength.

The present invention is a titanium-based metal-clad stainless steel in which a stainless steel is used as a base material and a titanium-based metal selected from various pure titanium and titanium alloys is joined as a composite material, and a method for producing the same. An object of the present invention is to have high bonding strength, to be able to be manufactured by general-purpose equipment, and to reduce labor, time and manufacturing cost.

[0006]

SUMMARY OF THE INVENTION The present invention is to solve the above-mentioned object, and its gist is as follows. (1) Ti, between stainless steel and titanium-based metal
A layer mainly composed of stainless steel, containing at least one of Zr and Hf in an amount of 10 to 50 atomic%, and the balance being an amorphous alloy composed of Cu and unavoidable impurities. Four layers are formed in this order: a layer composed of elements other than Cu and a constituent element of stainless steel such as Fe among the elements, a layer composed mainly of an amorphous alloy constituent element interposed, and a layer composed mainly of a titanium-based metal. A titanium-based metal-clad stainless steel characterized by the following.

(2) At least one of Ti, Zr and Hf is added between stainless steel and titanium-based metal
V, Nb, Cr, Mo, Mn,
A layer mainly composed of stainless steel, containing at least one kind of Ni in an amount of 0.1 to 10 atomic% and the balance being an amorphous alloy composed of Cu and unavoidable impurities. Four layers are formed in this order: a layer composed of elements other than Cu and a constituent element of stainless steel such as Fe among the elements, a layer composed mainly of an amorphous alloy constituent element interposed, and a layer composed mainly of a titanium-based metal. A titanium-based metal-clad stainless steel characterized by the following.

(3) At least one of Ti, Zr and Hf is added between the stainless steel and the titanium-based metal.
A method for producing a titanium-based metal-clad stainless steel, characterized in that an amorphous alloy containing 50 atomic% and the balance consisting of Cu and unavoidable impurities is interposed, and is heated and press-bonded for diffusion bonding.

(4) Between the stainless steel and the titanium-based metal, at least one of Ti, Zr and Hf is
V, Nb, Cr, Mo, Mn,
Titanium-based metal-clad stainless steel characterized in that at least one kind of Ni is contained in an amount of 0.1 to 10 atomic% and the balance is made of an amorphous alloy comprising Cu and unavoidable impurities, and is heated and press-bonded for diffusion bonding. Steel production method.

(5) The method according to the above (3) or (4), wherein heating is performed in the atmosphere while maintaining the temperature at 800 ° C. or more for 30 seconds or more while applying a pressure of 10 kPa or more in the atmosphere. Manufacturing method for titanium metal clad stainless steel.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The titanium-based metal-clad stainless steel according to the present invention is an intermediate material containing 10 to 50 atomic% Ti, between a base stainless steel and a composite titanium-based metal.
An amorphous alloy containing Zr and Hf and the balance being Cu and unavoidable impurities, or containing at least one of Ti, Zr and Hf in an amount of 10 to 50 atomic%, and
At least one of V, Nb, Cr, Mo, Mn, Ni
It is diffusion-bonded with an amorphous alloy containing 0.1 to 10 atomic% of a seed and the balance being Cu and unavoidable impurities. The cross-section is schematically shown in FIG. , A layer 2 mainly composed of elements other than Cu among the elements constituting the amorphous alloy and stainless steel, a layer 3 mainly composed of the elements of the amorphous alloy, and a layer 4 mainly composed of the titanium-based metal. Are formed in order.

JIS G is used as the base material stainless steel.
Various industrial stainless steels such as austenitic stainless steel such as SUS304 and ferritic stainless steel such as SUS430 specified in 4303 and the like.
Various industrial pure titanium specified by 600 etc., and 6A
Various titanium alloys such as l-4V-Ti can be used.

The intermediate material is 10 to 50 atomic% of Ti, Zr,
An amorphous alloy containing Hf and a balance of Cu and unavoidable impurities, or at least one of Ti, Zr, and Hf in an amount of 10 to 50 atomic% and V, N
b, Cr, Mo, Mn, Ni An amorphous alloy containing 0.1 to 10 atomic% of at least one of Ni and the balance being Cu and unavoidable impurities. At least one of Zr and Hf is contained in an amount of 10 to 50 atomic%. further,
In order to reduce the melting point of the amorphous alloy, the amorphous alloy contains at least one of V, Nb, Mo, Mn, and Ni in a range of 0.1 to 10 atomic%. Since the intermediate material used for diffusion bonding desirably has a low melting point, an amorphous alloy is used in the present invention,
By further lowering the melting point, the function as an intermediate material can be further enhanced.

The layer 1 mainly composed of stainless steel of the titanium-based metal-clad stainless steel of the present invention mainly comprises the stainless steel component and the structure of the base metal, and usually one of the component and the structure on the titanium-based metal side of the composite material. Or both have changed. The layer 4 mainly composed of a titanium-based metal is
Mainly the composition and structure of various industrial pure titanium or titanium alloys of the composite material, one or both of the composition and the structure usually change on the stainless steel side of the base material.

Such a titanium-metal-clad stainless steel of the present invention can be obtained by interposing an intermediate material of an amorphous alloy between the base material and the composite material, and performing diffusion bonding by heating while applying pressure. Since the amorphous alloy is easily melted, and the constituent elements of the amorphous alloy are easily diffused, diffusion bonding by short-time heating is possible, without requiring high-temperature long-time heating in a vacuum as in the related art. It can be manufactured using general-purpose heating equipment without an exhaust device for creating a vacuum atmosphere or an atmosphere adjusting device for creating a non-oxidizing atmosphere.

The base material of the titanium-clad stainless steel of the present invention can be a plate, a pipe, or a profile of any shape, in addition to a plate. Diffusion bonding is possible. Moreover, the obtained titanium-clad stainless steel has a strong bonding strength, and can be made into a product in the same shape or by processing such as rolling.

Next, according to the method of the present invention, as shown in FIG. 2, between the base material 5 and the composite material 6, 10 to 50 atomic% of Ti, Zr, Hf is contained as the intermediate material 7 and the balance is Cu and Amorphous alloy consisting of unavoidable impurities, or Ti, Z
At least one of r and Hf is contained in an amount of 10 to 50 at.%, and at least one of V, Nb, Cr, Mo, Mn and Ni is contained in an amount of 0.1 to 10 at. And diffusion bonding by heating while pressurizing with an amorphous alloy made of natural impurities. Base material 5 is JI
Various stainless steels specified by SG4303 etc. are targeted, and Laimura 6 is a titanium-based metal.
Various industrial pure titanium specified by H4600 and the like, and titanium alloys such as Ti-6Al-4V can be targeted.

In the diffusion bonding, the pressure may be 10 kPa or more, the temperature may be 800 ° C. or more at which the intermediate material 7 melts, and the holding time may be 30 seconds or more. Since heating at a high temperature for a long time as in the conventional case is not required, it is not necessary to use a vacuum or a non-oxidizing atmosphere, and heating can be performed in the atmosphere. Pressing is performed by placing a weight made of a refractory material such as a refractory brick, for example.If the base material is thick, arrange so that the base material is on the upper side and pressurize by the own weight of the base material. Can also.

In the method of the present invention, the heating atmosphere for diffusion bonding can be in the atmosphere as described above, and a conventional vacuum furnace is unnecessary. Various general-purpose heating equipment having no atmosphere adjusting device for setting the atmosphere can be used. Specifically, the heating in the atmosphere is intended for heating without adjusting the atmosphere by an open-to-air type electric resistance heating furnace, induction heating furnace, or the like.

In the present invention, heating can be performed in various combustion furnaces provided with burners. The atmosphere in that case does not need to be particularly considered, and may be an air ratio at which the heating efficiency is the best. Of course, in order to suppress oxidation, a combustion atmosphere with an air ratio of less than 1.0 may be used, and radiant heating in which oxidation is suppressed can be performed by an atmosphere using an inert gas.

The amorphous alloy of the intermediate material 7 is made of Ti, Zr, Hf in
At least one of them has a content of 10 to 50 atomic%. In order to further lower the melting point of the amorphous alloy, at least one of V, Nb, Mo, Mn, and Ni can be contained in a range of 0.1 to 10 atomic%. In diffusion bonding, it is desired that the intermediate material used has a low melting point from the viewpoint of minimizing the influence of heat on the base material. In the present invention, an amorphous alloy having a lower melting point than the melting point of the base metal such as stainless steel and titanium-based metal is used in the present invention, and contains at least one of Ti, Zr, and Hf in an amount of 10 to 50 atomic%. In an amorphous alloy containing Cu and unavoidable impurities, the melting point can be further reduced by adding at least one of V, Nb, Mo, Mn, and Ni in an amount of 0.1 to 10 atomic%. . By further lowering the melting point, the function as an intermediate material can be further enhanced. It is sufficient that the metal structure of the intermediate material 7 is mostly amorphous as long as it contains a crystalline material having a volume ratio of about 30% or less. Such an amorphous alloy can be manufactured by rapidly solidifying by injecting a molten metal around a rotating cooling roll, and has a thickness of about 100 μm or less.

In order to produce a titanium clad stainless steel sheet by the method of the present invention, the steel sheet is used as the base material 5, the titanium-based metal sheet is used as the composite material 6, and the amorphous alloy in the form of a flat foil is used as the intermediate material 7, and diffusion bonding is performed. be able to. In order to manufacture a clad steel pipe, the steel pipe is used as the base material 5, and the flat box-shaped amorphous alloy is interposed as an intermediate material 7 on the inner circumference or the outer circumference of the base material 5, and the joining material 6 is fitted. Diffusion bonding. Further, with respect to the shaped members having various shapes, the base material 5 and the combined material 6 having the same shape can be combined with the intermediate material 7.
And can be manufactured by diffusion bonding. Then, after joining, hot or cold rolling can be performed.

[0023]

[Example of the present invention-1] Base material 5 is JIS G43.
Austenitic steel SUS304 specified in No. 03, stainless steel plate with a thickness of 6 mm, composite material 6 is JIS H4
Two types of industrial pure titanium specified in 600, 1.2 m thick
m in Table 1 as an intermediate material 7. 2 with the amorphous alloy foils shown in FIGS. 1 to 6 interposed therebetween, refractory bricks are placed on top of the foils and pressurized at a predetermined pressure, and inserted into an open air electric resistance heating furnace at about 5 ° C. The temperature was raised to a predetermined temperature at a heating rate of / sec, maintained at that temperature for a predetermined time, and then allowed to cool in the air.

With respect to the obtained titanium clad stainless steel, the joining strength between the base material 5 and the joining material 6 was determined.
As shown in Table 1, the shear strength according to JIS G0601 was 320 MPa or more in all samples. The shear strength was determined by preparing a test piece shown in FIG. 3, applying pressure as indicated by an arrow, and measuring the breaking stress. Further, as a result of observing and analyzing the joint by EPMA, all the samples were composed of four layers as shown in the schematic diagram of FIG. The thickness of each of these layers is, for example, as shown in Table 1 No. In the case of the sample No. 1, the layer 1 mainly made of stainless steel is approximately 6 m.
m, a layer 2 mainly composed of elements other than Cu among the constituent elements of the amorphous alloy interposed and stainless steel constituent elements of Fe, Cr, and Ni is about 20 μm, and a layer 3 mainly composed of the interposed amorphous alloy constituent elements is The thickness was about 0.2 mm, and the layer mainly composed of titanium-based metal was about 0.8 mm. The thickness of the other samples was almost the same.

[0025]

[Table 1]

[Invention Example-2] Base material 5 is JIS G4
Ferritic stainless steel SUS4 specified in 303
30 stainless steel plate with a thickness of 6 mm, composite material 6 is 6Al
No. 4 in Table 1 was used as an intermediate material 7 as a titanium alloy plate having a thickness of 1.2 mm of -4V-Ti. Diffusion bonding was carried out with amorphous alloy foils 7 to 12 interposed therebetween. The other joining conditions were the same as in No. 1 of the present invention-1. The same tests and observations as in Example 1 were performed on the obtained clad steel under the same conditions as in Examples 1 to 6, and as a result, the shear strength was 330 MPa or more in all samples. In addition, the joint portion consists of the same four layers in all the samples, and the thickness of each layer is also about 6 mm in the layer 1 mainly made of stainless steel in all the samples. The layer 2 composed of the element and the stainless steel constituent element of Fe and Cr is about 25 μm, the layer 3 mainly composed of the amorphous alloy constituent element interposed is about 0.3 mm, and the layer mainly composed of the titanium-based metal is about 0.8 mm. , And the other samples had almost the same thickness.

The same tests and observations as in Example 1 were carried out on the obtained clad steel, and as a result, the shear strength was 320 MPa or more in all samples. In addition, the joints consisted of the same four layers in all samples, and the thickness of each layer was about 5 mm for layer 1 and layer 2 for all samples.
Was about 30 μm, layer 3 was about 0.3 mm, and layer 4 was about 0.9 mm. Then, the layer 3 is the present invention example-1
And almost the same composition.

[Comparative Example 2] The base material 5 and the composite material 6 were the same as in Example 1 of the present invention, and the intermediate material 7 was 100 μm thick.
, And pressurized and heated under the same conditions as in the example of the present invention. About the obtained clad steel, the present invention example-1
The shear strength measured in the same manner as described above showed a low value of 180 MPa.

[0029]

The titanium-based metal-clad stainless steel of the present invention has a stable and sufficient bonding strength. In manufacturing the same, special equipment such as conventional explosion equipment, steel sheet coating equipment, and vacuum exhaust equipment are used. It is not required and can be manufactured with general-purpose equipment, reducing labor, time and manufacturing cost.

[Brief description of the drawings]

FIG. 1 is a schematic view showing a cross section of a joint portion of an example of the present invention.

FIG. 2 is a perspective view showing an example of the method of the present invention.

FIG. 3 is an explanatory diagram of a method for measuring the shear strength of a titanium-based metal-clad stainless steel,

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Layer mainly consisting of stainless steel 2 ... Layer mainly consisting of stainless constituent elements such as Ti and Fe 3 ... Layer mainly consisting of Ti and Cu 4 ... Layer mainly consisting of titanium-based metal 5 ... Base metal 6 ... Composite material 7 ... Intermediate material

Claims (5)

[Claims] 1. A method according to claim 1, wherein the stainless steel and the titanium-based metal are
A layer mainly composed of stainless steel, and a layer mainly composed of stainless steel, and an amorphous alloy mainly composed of Ti, Zr, and Hf, which contain at least one kind of Ti, Zr, and Hf in an amount of 10 to 50 atomic% and the balance is an amorphous alloy including Cu and unavoidable impurities. Among these constituent elements, four layers are formed in this order: a layer consisting of elements other than Cu and a constituent element of stainless steel such as Fe, a layer mainly consisting of constituent elements of an amorphous alloy interposed, and a layer mainly consisting of a titanium-based metal. A titanium-based metal-clad stainless steel. 2. Between a stainless steel and a titanium-based metal,
At least one of Ti, Zr, and Hf is contained in an amount of 10 to 50 at%, and at least one of V, Nb, Cr, Mo, Mn, and Ni is contained in an amount of 0.1 to 10 at%, with the balance being Cu and A layer mainly made of stainless steel, which is diffusion-bonded with an amorphous alloy composed of unavoidable impurities interposed therebetween, and a layer mainly composed of elements other than Cu and constituent elements of stainless steel such as Fe among the constituent elements of the amorphous alloy interposed therebetween. A titanium-based metal-clad stainless steel, wherein four layers, that is, a layer mainly composed of an amorphous alloy constituent element and a layer mainly composed of a titanium-based metal are sequentially formed. 3. A method according to claim 1, wherein the stainless steel and the titanium-based metal are
Titanium-based metal containing at least one of Ti, Zr, and Hf in an amount of 10 to 50 at% and the balance being an amorphous alloy containing Cu and unavoidable impurities, and heating while applying pressure to perform diffusion bonding. Manufacturing method of clad stainless steel. 4. A method according to claim 1, wherein the stainless steel and the titanium-based metal are
At least one of Ti, Zr, and Hf is contained in an amount of 10 to 50 at%, and at least one of V, Nb, Cr, Mo, Mn, and Ni is contained in an amount of 0.1 to 10 at%, with the balance being Cu and A method for producing a titanium-based metal-clad stainless steel, characterized in that an amorphous alloy comprising unavoidable impurities is interposed and diffusion bonding is performed while heating under pressure. 5. The titanium-based metal clad according to claim 3, wherein the titanium-based metal clad is heated at a temperature of 800 ° C. or more for 30 seconds or more while being pressurized in the atmosphere at a pressure of 10 kPa or more. Manufacturing method of stainless steel.