JP3456876B2 - Titanium-based metal clad steel and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a titanium-based metal in which a base metal selected from various steels such as carbon steel and low-alloy steel and a titanium-based metal selected from various pure titanium and titanium alloys are joined as a joining material. The present invention relates to a clad steel and a manufacturing method thereof.

[0002]

2. Description of the Related Art The above-described titanium-based metal clad steel has been manufactured by stacking a steel slab as a base material and a titanium-based metal slab as a laminated material into an assembled slab, and hot rolling the slab. . The assembled slab has been manufactured by joining both slabs by an explosive bonding method or by covering both slabs that have been superposed 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 both slabs to improve the joint strength of the product clad steel.

For example, in JP-A-63-56371, a low carbon steel having a C content of 0.01% by weight or less is interposed as the intermediate material, and Cu, N is further added.
It has been proposed to interpose any one of i and Cu-Ni alloys together. Also, JP-A-63-30603
Japanese Patent Laid-Open No. 1-2004 proposes to interpose a Fe—Zn alloy.

[0004]

In the above-mentioned prior art, in order to manufacture an assembled slab, special equipment such as explosive deposition equipment, steel plate coating equipment and exhaust equipment is required, and excessive labor, time and cost are required. Was. Further, in the hot rolling, normal equipment for steel plates or titanium plates can be used, but due to the difference in deformation resistance between steel and titanium-based metal, there are problems such as non-crimped parts. Had. Further, even if the intermediate material proposed in the above publications is interposed, the obtained clad steel product is
It did not necessarily have sufficient bonding strength.

The present invention is a titanium-based metal clad steel in which a base metal selected from various steels such as carbon steel and low alloy steel is joined with a titanium-based metal selected from various pure titanium and titanium alloys as a joining material, and It is a manufacturing method thereof, has stable and sufficient bonding strength, can be manufactured by general-purpose equipment, and aims to reduce labor, time, and manufacturing cost.

[0006]

The present invention for achieving the above-mentioned object is to provide Ti, Zr,
10 to 50 atomic% of at least one of Hf is contained,
An amorphous alloy whose balance consists of Cu and inevitable impurities, or, if necessary, in addition to the above alloy elements, V,
A layer mainly composed of steel, containing 0.1 to 10 atomic% of at least one of Nb, Cr, Mo, Mn, and Ni, and the balance being diffusion bonded with an amorphous alloy of Cu and unavoidable impurities interposed therebetween, A layer mainly consisting of elements other than Cu among the constituent elements of the amorphous alloy and Fe,
The titanium-based metal clad steel is characterized in that four layers of a layer mainly composed of constituent elements of an amorphous alloy and a layer mainly composed of titanium-based metal are sequentially formed. The layer mainly composed of the constituent elements of the amorphous alloy is preferably densely mixed with a plurality of phases different from each other.

Further, according to the present invention for achieving the above object, 10 to 50 atomic% of at least one of Ti, Zr, and Hf is contained between steel and a titanium-based metal, and the balance is C.
Amorphous alloy consisting of u and inevitable impurities, or V, Nb, Cr, M in addition to the above alloy elements as necessary.
It is characterized in that at least one of O, Mn, and Ni is contained in an amount of 0.1 to 10 atomic%, and the balance is an amorphous alloy consisting of Cu and inevitable impurities, and heating is performed while applying pressure to perform diffusion bonding. This is a method for producing titanium-based metal clad steel. And the above heating is 10 kPa in the atmosphere.
It can be performed under the condition that the temperature is kept at 800 ° C. or higher for 30 seconds or more while being pressurized with the above pressure.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The titanium-based metal clad steel of the present invention comprises at least one of Ti, Zr, and Hf as an intermediate material to be interposed between the base steel and the titanium-based metal of the composite material.
Amorphous alloy containing 10 to 50 atomic% of seeds and the balance of Cu and inevitable impurities, or Ti, Z
10 to 50 atomic% of at least one of r and Hf, and 0.1 to 10 atomic% of at least one of V, Nb, Cr, Mo, Mn, and Ni, and the balance Cu and unavoidable One of the amorphous alloys consisting of specific impurities is used, and the base material and the joining material are diffusion-bonded by an intervening intermediate material. A schematic view of a cross section of the diffusion bonding portion shows that
As shown in FIG. 1, a layer 1 mainly composed of steel, a layer 2 mainly composed of elements other than Cu among constituent elements of an amorphous alloy and Fe, a layer 3 mainly composed of constituent elements of an amorphous alloy, Four layers 4 of titanium-based metal are sequentially formed.

As the base steel, various steels such as carbon steel and low alloy steel are targeted, and as the titanium-based metal for the composite material, various industrial pure titanium specified by JIS H 4600 and 6Al- Various titanium alloys such as 4V-Ti can be targeted. Intermediate materials are Ti, Zr, H
It is a Cu-based alloy containing at least one of f, and contains 10 to 50 atomic% of at least one of Ti, Zr, and Hf in order to rapidly solidify from the molten metal to become amorphous. Furthermore, in order to realize a lower melting point of this amorphous alloy, this amorphous alloy can further contain at least one of V, Nb, Mo, Mn, and Ni in the range of 0.1 to 10 atomic%. .
An amorphous alloy is used in the present invention because it is desirable that the intermediate material used for diffusion bonding has a low melting point. However, by using the above composition, it is possible to further lower the melting point and further enhance the function as an intermediate material. It becomes possible.

The layer 1 mainly composed of steel of the titanium-based metal clad steel of the present invention is mainly composed of the steel component and structure of the base material, and is usually on one side or both of the composition and the structure on the titanium-based metal side of the laminated material. Change is seen. In addition, the layer 4 mainly composed of titanium-based metal is mainly composed of components and structure of various industrial pure titanium or titanium alloy of the composite material, and on the steel side of the base metal, a change is usually found in one or both of the component and structure. To be The layer 2 is mainly composed of at least one of Ti, Zr and Hf and Fe.

In the clad steel of the present invention, the layer 3 mainly composed of the constituent elements of the amorphous alloy is
As shown in FIG. 2, it is preferable that a plurality of phases are densely mixed and configured. When the layer 3 is observed in detail in such a preferred embodiment, as shown in the layer 3 of FIG. 2, the dark-looking portion and the bright-looking portion are intricately intertwined with each other, which are the main elements of the amorphous alloy. The contents of Ti, Zr, Hf and Cu elements are different. Then, as shown in FIG. 3, the Vickers hardness of the layer 3 gradually decreases from the layer 2 side to the layer 4 side.

The titanium-based metal clad steel of the present invention as described above can be obtained by interposing an intermediate material of an amorphous alloy between the base material and the composite material, and heating the material while applying pressure for diffusion bonding. The above amorphous alloy is easily melted, and since the constituent elements of the amorphous alloy are easily diffused, it is possible to perform diffusion bonding by heating for a short time, without requiring high temperature and long time heating in vacuum as in the conventional case, It can be manufactured using a general-purpose heating equipment that does not have an exhaust device for creating a vacuum atmosphere or an atmosphere adjusting device for creating a non-oxidizing atmosphere.

The base material in the clad steel of the present invention can be a tube or a shape member of any shape in addition to a plate, and a bonding material matched to the surface shape is diffusion bonded with a foil-shaped intermediate material interposed. it can. Moreover, the obtained clad steel has a strong joint strength and can be made into a product as it is or after being subjected to processing such as rolling.

Next, according to the method of the present invention, as shown in FIG. 4, Ti, Zr, H as an intermediate material 7 is provided between the base material 5 and the laminated material 6.
an amorphous alloy containing 10 to 50 atomic% of at least one of f and the balance Cu and unavoidable impurities;
Alternatively, at least one of Ti, Zr, and Hf is 10
Contains 50 atomic% and contains V, Nb, Cr, Mo, Mn,
An amorphous alloy containing 0.1 to 10 atomic% of at least one of Ni and the balance of Cu and unavoidable impurities is interposed, and heating is performed while applying pressure to perform diffusion bonding. The base material 5 is made of various steels such as carbon steel and low alloy steel, and the composite material 6 is a titanium-based metal.
Various industrial pure titanium specified by 600 etc., and Ti
-6Al-4V or the like can be targeted.

In the diffusion bonding, the pressure is 10 kPa or more,
The temperature is 800 ° C or higher at which the intermediate material 7 melts, and the holding time is 3
It may be 0 seconds or more. Since it does not require heating at high temperature for a long time as in the past, there is no need to use a vacuum or non-oxidizing atmosphere,
It can be heated in the atmosphere. Pressurization is performed by placing a weight made of refractory material such as refractory bricks, but if the base material is thick, arrange it so that the base material is on the upper side and pressurize by the self-weight of the base material. You can also

In the method of the present invention, the heating atmosphere for diffusion bonding can be atmospheric air as described above, a conventional vacuum furnace is not required, and an exhaust device for creating a vacuum atmosphere and a non-oxidizing atmosphere are used. It is possible to use various general-purpose heating equipment that does not have an atmosphere adjusting device for creating an atmosphere. Specifically, the heating in the atmosphere is intended for heating in which the atmosphere is not adjusted by an air-releasing electric resistance heating furnace, an induction heating furnace, or the like.

Further, in the present invention, heating can be carried out 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 that maximizes the heating efficiency. 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 while suppressing oxidation may be performed by using an inert gas atmosphere.

The amorphous alloy of the intermediate material 7 is Ti, Zr, Hf because it is rapidly solidified from the molten metal to become amorphous.
The content of at least one of them is set in the range of 10 to 50 atom%. Further, in order to further lower the melting point of this amorphous alloy, at least one of V, Nb, Mo, Mn, and Ni is contained in the range of 0.1 to 10 atomic%. In diffusion bonding, it is desirable that the intermediate material to be used has a low melting point in order to minimize the influence of heat on the base material. In the present invention, an amorphous alloy having a melting point lower than that of the base steel or titanium-based metal is used from this point, but at least one of Ti, Zr, and Hf is 10
In an amorphous alloy containing up to 50 atomic% and the balance Cu and unavoidable impurities, V, Nb,
0.1-10 at least one of Mo, Mn, and Ni
By adding at%, the melting point can be further lowered. By further lowering the melting point, the function as an intermediate material can be further enhanced. It should be noted that the metal structure of the intermediate material 7 may be mostly amorphous, and may contain a crystalline material having a volume ratio of about 30% or less. Such an amorphous alloy can be manufactured by being rapidly cooled and solidified by injecting a molten metal onto the peripheral surface of a rotating cooling roll, and has a thickness of about 100 μm or less.

In order to produce a clad steel plate by the method of the present invention, a steel plate is used as a base material 5, a titanium metal plate is used as a bonding material 6, and the flat foil-shaped amorphous alloy is used as an intermediate material 7.
It can be diffusion bonded. In order to manufacture a clad steel pipe, the steel pipe is used as the base material 5, the flat foil-shaped amorphous alloy is interposed as the intermediate material 7 on the inner or outer circumference of the base material 5, and the above-mentioned mating material 6 is fitted. Can be diffusion bonded. Further, various shapes of shapes can be manufactured by stacking the base material 5 and the bonding material 6 having the matched shapes with the intermediate material 7 interposed therebetween and by diffusion bonding. After joining, hot rolling or cold rolling can be performed.

[0020]

【Example】

[Invention Example 1] The base material 5 is a steel plate having a thickness of 5 mm of carbon steel SS400 specified in JIS G 3192, and the laminated material 6 is J
It is a 1.2 mm thick plate of two types of industrial pure titanium specified in ISH 4600, and the amorphous alloy foil shown in Table 1 is interposed as an intermediate material 7, and the layers are stacked as shown in FIG. After placing it under pressure at a predetermined pressure, it is inserted into an electric resistance heating furnace open to the atmosphere, heated to a predetermined temperature at a heating rate of about 5 ° C./sec, and held at the temperature for a predetermined time. , Left to cool in the atmosphere.

With respect to the obtained clad steel, the joint strength between the base material 5 and the laminated material 6 was determined, and the result was JIS G 06.
As shown in Table 1, the shear strength of No. 01 was 340 MPa or more in all the samples. The shear strength was obtained by preparing the test piece shown in FIG. 5, applying pressure as shown by the arrow, and measuring the breaking stress. As a result of observing and analyzing the joint portion by EPMA, all the samples were composed of four layers as shown in the schematic view of FIG. The thickness of each of these layers is, for example, No. 1 in Table 1. In the case of the sample No. 1, the layer 1 mainly made of steel is about 5 mm, the layer 2 mainly made of elements other than Cu and Fe among the constituent elements of the amorphous alloy is about 20 μm, and the constituent element of the mainly interposed amorphous alloy is about 5 mm. The layer 3 made of Qin is about 0.2 mm, the layer 4 mainly made of titanium metal is about 0.8 mm,
The other samples had almost the same thickness. The layer 3 mainly composed of the constituent elements of the amorphous alloy
The organization of Table 1 No. The case of 1 is shown in FIG. 2 as an example.
A plurality of phases having different compositions were densely mixed, and the same tendency was confirmed in other samples.

[0022]

[Table 1]

[Invention Example 2] The base material 5 is the same steel plate as in Invention Example 1, and the laminated material 6 is 6Al-4V-Ti having a thickness of 1.2 mm.
No. 1 in Table 1 as the intermediate material 7 1 to
Diffusion bonding was performed with the amorphous alloy foil of No. 5 interposed.
The other joining conditions are the same as No. 1 of the invention example 1. The same conditions as 1 to 5 were set.

The clad steel thus obtained was tested and observed in the same manner as in Example 1 of the present invention. As a result, the shear strength was 320 MPa or more in all the samples. In addition, the joint portion was composed of the same four layers in all the samples, and the thickness of each layer was about 5 mm for layer 1, about 30 μm for layer 2, about 0.3 mm for layer 3, and about 0. It was 9 mm. Then, the layer 3 had a composition substantially similar to that of the first example of the present invention.

[Comparative Example] The base material 5 and the composite material 6 were the same as in the present invention example 1, and a Cu foil having a thickness of 50 μm was interposed as the intermediate material 7, and pressure and heating were performed under the same conditions as in the present invention example. . The shear strength of the obtained clad steel measured in the same manner as in Inventive Example 1 was as low as 180 MPa.

[0026]

The titanium-based metal clad steel of the present invention has a stable and sufficient joint strength, and its production requires special equipment such as conventional bombing equipment, steel sheet coating equipment, and vacuum exhaust equipment. Instead, it can be manufactured by general equipment, reducing labor, time, and manufacturing cost.

[Brief description of 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 an EP showing a cross-sectional structure of a joint in the example of the present invention.
It is an MA secondary electron image.

FIG. 3 is a graph showing a change in hardness of a Ti-side cross section of a joint portion in an example of the present invention.

FIG. 4 is a perspective view showing an example of the method of the present invention.

FIG. 5 is an explanatory diagram of a method for measuring the shear strength of clad steel.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Layer 2 which consists mainly of steel 1 ... Layer 3 which consists mainly of elements other than Cu among the constituent elements of the amorphous alloy which intervened, and Fe ... Layer 4 which consists mainly of the constituent elements of the amorphous alloy which intervened ... Mainly titanium-based metal Layer 5 ... Base material 6 ... Laminated material 7 ... Intermediate material

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI B32B 15/01 B32B 15/01 K (72) Inventor Mitsuo Ishii 20-1 Shintomi, Futtsu-shi, Chiba Nippon Steel Co., Ltd. (56) References JP-A-57-171569 (JP, A) JP-A-5-131279 (JP, A) JP-A-4-182079 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B23K 20/00-20/227

Claims (6)

(57) [Claims] 1. Ti, Z is present between steel and titanium-based metal.
Constitution of 10 to 50 atomic% of at least one of r and Hf, the remainder being diffusion bonded with an amorphous alloy consisting of Cu and unavoidable impurities interposed, a layer mainly consisting of steel, and a structure of an amorphous alloy mainly interposed Among the elements, a titanium-based metal characterized in that four layers, that is, a layer composed of an element other than Cu and Fe, a layer mainly composed of constituent elements of an amorphous alloy, and a layer mainly composed of a titanium-based metal are sequentially formed. Clad steel. 2. Between the steel and the titanium-based metal, Ti, Z
10 to 50 atomic% of at least one of r and Hf, and 0.1 to 10 atomic% of at least one of V, Nb, Cr, Mo, Mn, and Ni, and the balance Cu and unavoidable Layer diffusion-bonded by interposing an amorphous alloy consisting of specific impurities, a layer mainly consisting of steel, a layer mainly consisting of elements other than Cu among constituent elements of the amorphous alloy and Fe, and a constituent element mainly constituting the amorphous alloy A titanium-based metal clad steel characterized in that four layers, that is, a layer made of, and a layer mainly made of titanium-based metal are sequentially formed. 3. The titanium-based material according to claim 1, wherein the layer mainly composed of constituent elements of the amorphous alloy is densely mixed with a plurality of phases having different compositions. Metal clad steel. 4. Ti, Z between the steel and the titanium-based metal
A titanium-based metal clad containing at least one of r and Hf in an amount of 10 to 50 atomic% and the remainder being an amorphous alloy consisting of Cu and unavoidable impurities, which is heated and pressurized for diffusion bonding. Steel manufacturing method. 5. Ti and Z between the steel and the titanium-based metal
10 to 50 atomic% of at least one of r and Hf, and 0.1 to 10 atomic% of at least one of V, Nb, Cr, Mo, Mn, and Ni, and the balance Cu and unavoidable A method for producing a titanium-based metal clad steel, characterized in that an amorphous alloy made up of specific impurities is interposed, and heating and diffusion are performed to perform diffusion bonding. 6. The titanium-based metal clad according to claim 4 or 5, wherein the titanium-based metal clad is heated in the atmosphere at a pressure of 10 kPa or more while being stored at a temperature of 800 ° C. or more for 30 seconds or more. Steel manufacturing method.