WO2017018513A1 - チタン複合材および熱間圧延用チタン材 - Google Patents

チタン複合材および熱間圧延用チタン材 Download PDF

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WO2017018513A1
WO2017018513A1 PCT/JP2016/072335 JP2016072335W WO2017018513A1 WO 2017018513 A1 WO2017018513 A1 WO 2017018513A1 JP 2016072335 W JP2016072335 W JP 2016072335W WO 2017018513 A1 WO2017018513 A1 WO 2017018513A1
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titanium
layer
alloy
slab
hot rolling
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PCT/JP2016/072335
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English (en)
French (fr)
Japanese (ja)
Inventor
吉紹 立澤
知徳 國枝
森　健一
一浩 ▲高▼橋
藤井　秀樹
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新日鐵住金株式会社
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Priority to JP2017530939A priority Critical patent/JP6515358B2/ja
Publication of WO2017018513A1 publication Critical patent/WO2017018513A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
    • B21B1/38—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling sheets of limited length, e.g. folded sheets, superimposed sheets, pack rolling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K15/00—Electron-beam welding or cutting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F1/00—Shielding characterised by the composition of the materials
    • G21F1/02—Selection of uniform shielding materials
    • G21F1/08—Metals; Alloys; Cermets, i.e. sintered mixtures of ceramics and metals
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F3/00—Shielding characterised by its physical form, e.g. granules, or shape of the material

Definitions

  • the present invention relates to a titanium composite material and a titanium material for hot rolling.
  • Titanium material has excellent properties such as corrosion resistance, oxidation resistance, fatigue resistance, hydrogen embrittlement resistance, and neutron blocking properties. These properties can be achieved by adding various alloying elements to titanium.
  • neutron beam shielding plates that can shield thermal neutrons are used.
  • the neutron shielding effect is highest for boron 10 ( 10 B), which is 19.9% of natural B.
  • Stainless steel containing B is generally used as a material for the neutron beam shielding plate.
  • Patent Document 1 Japanese Examined Patent Publication No. 58-6704 includes Kuna Copite (2MgO.3B 2 O 2 .13H 2 O), Meyerhot Ferrite (3CaO.3B 2 O 2 .7H 2 O), Colemanite (2CaO.3B). 2 O 2 ⁇ 5H 2 O), a cured molded body obtained by kneading and molding a borate aggregate containing crystal water such as hemihydrate gypsum and calcium aluminate cement with water, and containing 5 mass of B A neutron beam blocking material containing at least% is disclosed.
  • the neutron beam shielding material disclosed in Patent Document 1 is made of cement, there is a problem in terms of corrosion resistance, manufacturability, and workability.
  • Patent Document 2 uses a hot-rolled sheet of boron-containing titanium alloy containing B by 0.1 to 10% by mass and the balance being titanium and inevitable impurities. It is disclosed.
  • Patent Document 3 describes a boron-containing material (NaB 4 O 7 , B 2 O 3 , PbO, Fe 2 O 3, etc.) in a hollow metal casing, A radiation shielding material filled with a metal oxide mixed therein to be solidified is disclosed. According to Patent Document 3, neutron beams are mainly blocked by boron and hydrogen, and gamma rays are blocked by a casing and metal therein.
  • the titanium material is usually manufactured by the method shown below.
  • the raw material titanium oxide is chlorinated to titanium tetrachloride by the crawl method, and then reduced with magnesium or sodium to produce a lump-like sponge-like metal titanium (sponge titanium).
  • This sponge titanium is press-molded to form a titanium consumable electrode, and a titanium ingot is manufactured by vacuum arc melting using the titanium consumable electrode as an electrode.
  • an alloy element is added as necessary to produce a titanium alloy ingot.
  • the titanium alloy ingot is divided, forged and rolled into a titanium slab, and the titanium slab is further subjected to hot rolling, annealing, pickling, cold rolling, and vacuum heat treatment to produce a titanium thin plate.
  • titanium ingot is smashed, hydroground, dehydrogenated, powder crushed, and classified to produce titanium powder, and titanium powder is powder-rolled, sintered, and cold-rolled.
  • the manufacturing method is also known.
  • Patent Document 4 discloses that a titanium powder is produced directly from sponge titanium, not a titanium ingot, and a titanium thin plate is produced from the obtained titanium powder.
  • Sintered compacts are manufactured by sintering pre-sintered compacts made of viscous compositions containing agents and solvents into thin sheets, and sintered compacts are manufactured by compacting the sintered compacts.
  • a method is disclosed in which the fracture elongation of the sintered thin plate is 0.4% or more, the density ratio is 80% or more, and the density ratio of the sintered compacted plate is 90% or more. ing.
  • Patent Document 5 discloses a composite powder obtained by adding an appropriate amount of iron powder, chromium powder or copper powder to titanium alloy powder using titanium alloy scrap or titanium alloy ingot as a raw material. After extruding the carbon steel capsule, the capsule on the surface of the obtained round bar is dissolved and removed, and further solution treatment or solution treatment and aging treatment are performed to produce a titanium alloy with excellent quality by the powder method A method is disclosed.
  • Patent Document 6 describes a method in which a sponge capsule is filled with a sponge titanium powder and then subjected to warm extrusion at an extrusion ratio of 1.5 or more and an extrusion temperature of 700 ° C. or less.
  • a method for producing a titanium molded body in which 20% or more of the total length of the grain boundary of the molded body is in metal contact is performed by performing outer peripheral processing excluding copper.
  • a pack rolling method is known as a technique for rolling the sheet.
  • the pack rolling method is a method in which a core material such as a titanium alloy having poor workability is covered with a cover material such as inexpensive carbon steel having good workability and hot rolling is performed.
  • a release agent is applied to the surface of the core material, and at least two upper and lower surfaces thereof are covered with a cover material, or the four peripheral surfaces are covered with a spacer material in addition to the upper and lower surfaces, and the surroundings are welded. Assembled and hot rolled.
  • a core material which is a material to be rolled, is covered with a cover material and hot rolled. Therefore, the core material surface does not directly contact a cold medium (atmosphere or roll), and the temperature drop of the core material can be suppressed, so that even a core material with poor workability can be manufactured.
  • Patent Document 7 discloses a method for assembling a hermetically sealed box
  • Patent Document 8 discloses a degree of vacuum of 10 ⁇ 3 torr order or more.
  • a method of manufacturing a hermetically sealed box by sealing the cover material is disclosed, and further, Japanese Patent Application Laid-Open No. 11-057810 (Patent Document 9) discloses a method in which the cover material is covered with carbon steel (cover material) on the order of 10 ⁇ 2 torr.
  • a method for producing a hermetic coated box by sealing by high energy density welding under the following vacuum is disclosed.
  • Patent Document 10 steel is used as a base material and titanium or a titanium alloy is used as a base material, and the joint surface between the base material and the base material is evacuated and then welded and assembled.
  • a method for manufacturing a titanium clad steel sheet in which an assembly slab for rolling is joined by hot rolling is disclosed.
  • Patent Document 11 discloses that pure nickel, pure iron, and carbon content are 0.01% by mass or less on the surface of a base steel material containing 0.03% by mass or more of carbon. After the titanium foil material is laminated by interposing an insert material made of any one of the above-mentioned low carbon steels with a thickness of 20 ⁇ m or more, a laser beam is irradiated from either side of the lamination direction, A method of manufacturing a titanium-coated steel material by melting and joining at least the vicinity of the edge with a base steel material over the entire circumference is disclosed.
  • Patent Document 12 the surface of a porous titanium raw material (sponge titanium) formed into an ingot shape is melted using an electron beam under vacuum to make the surface layer portion dense titanium.
  • the titanium ingot is manufactured and hot rolled and cold rolled to form a porous portion in which the porous titanium raw material is formed into an ingot shape, and the entire surface of the porous portion composed of dense titanium.
  • a method for producing a dense titanium material (titanium ingot) having a dense coating portion for coating with very little energy is exemplified.
  • Patent Document 13 Japanese Patent Application Laid-Open No. 62-270277 describes that surface effect treatment of an engine member for automobiles is performed by thermal spraying.
  • the hot-rolled sheet disclosed in Patent Document 2 has a high B content, and thus cannot be inevitably increased in cost, has poor workability, and is actually difficult to use as a neutron beam shielding plate.
  • the radiation shielding material disclosed in Patent Document 3 is a metal casing material filled with a boron-containing material, and is difficult to process after the boron-containing material is filled.
  • sponge titanium is press-molded to form a titanium consumable electrode, and a titanium ingot is manufactured by vacuum arc melting using the titanium consumable electrode as an electrode.
  • the titanium slab was forged and rolled into a titanium slab, and the titanium slab was manufactured by hot rolling, annealing, pickling, and cold rolling.
  • a process of dissolving titanium and producing a titanium ingot was always added.
  • a method of producing titanium powder by powder rolling, sintering, and cold rolling is also known, but in the method of producing titanium powder from a titanium ingot, a step of dissolving titanium is also added.
  • the core material covered with the cover material is slab or ingot to the last, and has undergone a melting process or is made of expensive titanium powder, and the manufacturing cost cannot be reduced.
  • a dense titanium material can be produced with very little energy, but the surface of the titanium sponge formed into an ingot shape is dissolved, and the dense titanium surface layer portion and the internal components are the same kind of pure titanium. Or it is prescribed
  • thermal spraying is a method in which a film is formed by melting a metal, ceramics, or the like and spraying it on the surface of a titanium material.
  • thermal spraying is performed while shielding with an inert gas in order to avoid oxidation of the film.
  • inert gases are entrained in the pores of the coating.
  • Such pores containing the inert gas are not pressed by hot working or the like.
  • vacuum heat treatment is generally carried out, but during this treatment, the inert gas in the pores may expand and the film may be peeled off.
  • the abundance ratio (porosity) of pores generated by thermal spraying is several vol. % Or more and 10 vol. % May be exceeded.
  • a titanium material having a high porosity in the film has a risk of peeling in the manufacturing process, and there is a risk that a defect such as a crack during processing may occur.
  • melt resolidification process As a process for melting and resolidifying the surface layer of the slab using an electron beam. Usually, the melted and re-solidified surface layer is removed in a pickling step after hot rolling. For this reason, in the conventional melt resolidification treatment, no consideration is given to the segregation of the alloy components in the surface layer portion.
  • the present inventors specify the material for hot rolling at a low price by attaching a titanium plate containing a specific alloy element to the surface of a slab made of industrial pure titanium or titanium alloy. We considered obtaining a titanium material with excellent performance.
  • the present invention reduces the content of alloying elements to be added to improve neutron blocking properties (the amount of specific alloying elements that express target characteristics), and suppresses the production cost of titanium materials,
  • An object is to obtain a titanium composite material having a desired neutron blocking property and a titanium material for hot rolling at low cost.
  • the present invention has been made to solve the above-described problems, and the gist of the present invention is the following titanium composite material and titanium material for hot rolling.
  • an inner layer made of industrial pure titanium or titanium alloy A surface layer having a chemical composition different from that of the inner layer formed on at least one rolling surface of the inner layer; An intermediate layer formed between the inner layer and the surface layer and having a different chemical composition from the inner layer;
  • a titanium composite comprising: The surface layer has a thickness of 2 ⁇ m or more, and the proportion of the total thickness is 40% or less per side, The chemical composition of the surface layer part is mass%, B: 0.1-3.0% balance: titanium and impurities, The intermediate layer has a thickness of 0.5 ⁇ m or more. Titanium composite material.
  • Another surface layer is formed on a surface other than the rolled surface of the inner layer,
  • the other surface layer has the same chemical composition as the surface layer,
  • a base material made of pure industrial titanium or a titanium alloy; A surface layer material joined to at least one rolling surface of the base material; A titanium material for hot rolling comprising a welded portion that joins the periphery of the base material and the surface layer material, The surface layer material has a chemical composition different from that of the base material, and in mass%, B: 0.1-3.0% The balance: titanium and impurities The welded portion shields the interface between the base material and the surface material from outside air; Titanium material for hot rolling.
  • the base material comprises a direct cast slab.
  • the directly cast slab is obtained by forming a melt-resolidified layer on at least a part of the surface.
  • the chemical composition of the melt-resolidified layer is different from the chemical composition of the center portion of the thickness of the direct cast slab, (6) Titanium material for hot rolling.
  • the titanium composite material according to the present invention includes an inner layer made of industrial pure titanium or a titanium alloy and a surface layer having a chemical composition different from that of the inner layer, the whole is compared with a titanium material made of the same titanium alloy. Thus, it has the same neutron blocking property, but can be manufactured at low cost.
  • FIG. 1 is an explanatory view showing an example of the configuration of a titanium composite material according to the present invention.
  • FIG. 2 is an explanatory view showing an example of the configuration of the titanium composite material according to the present invention.
  • FIG. 3 is an explanatory view schematically showing that the titanium rectangular slab and the titanium plate are bonded together by welding in a vacuum.
  • FIG. 4 is an explanatory view schematically showing bonding by welding a titanium plate not only on the surface of the titanium rectangular cast piece but also on the side surface.
  • FIG. 5 is an explanatory view showing a method of melt re-solidification.
  • FIG. 6 is an explanatory view showing a method of melt re-solidification.
  • FIG. 7 is an explanatory view showing a method of melt re-solidification.
  • the present inventors reduced the amount of a specific alloy element that exhibits neutron blocking properties by alloying only the surface layer of the titanium plate of the final product, and the titanium material
  • the interface between the base material made of industrial pure titanium or titanium alloy and the surface layer material having a different chemical composition from the base material is blocked from the outside air.
  • the titanium material for hot rolling which welded the circumference
  • the titanium composite obtained by hot working this titanium material for hot rolling becomes a titanium material having excellent neutron blocking properties at low cost.
  • Titanium composite 1-1 The surface layers 3 and 4 which have a composition, and the intermediate
  • a surface layer is formed on one or both rolling surfaces of the inner layer 5, but a surface other than the rolling surface of the inner layer 5 (side surface in the example shown in FIGS. 1 and 2).
  • the surface layer, the inner layer, and the intermediate layer will be sequentially described.
  • the thickness is 2 ⁇ m or more, and the proportion of the total thickness is 40% or less per side.
  • the thickness of the surface layer is preferably 5 ⁇ m or more, and more preferably 10 ⁇ m or more.
  • the ratio of the thickness of the surface layer to the total thickness of the titanium composite is 40% or less per side, and more preferably 30% or less. In particular, it should be 5 to 40%.
  • B 0.1-3.0% In B, 19.9% of 10 B exists, but this 10 B has a large absorption cross section of thermal neutrons and a large shielding effect of neutron beams. If the B content is less than 0.1%, a sufficient neutron beam shielding effect cannot be obtained. If the B content exceeds 3.0%, cracking during hot rolling and deterioration of workability may occur.
  • the titanium alloy containing B can be produced by adding a boride such as B or TiB 2 to titanium.
  • a boride such as B or TiB 2
  • a 10 B enriched boron-containing material 10 B content is approximately 90% or more
  • H 3 10 BO 3 , 10 B 2 O 10 B 4 C is used, neutron beams even if the B content is small Since the shielding effect is large, it is extremely effective.
  • H and O are also concentrated in the alloy layer. However, if H is removed from the material during heat treatment such as vacuum annealing, it is a problem. If O and C are 0.4 mass% O or less and 0.1 mass% C or less, which are below the upper limit contained in industrial pure titanium, they can be produced without any problem.
  • Impurities can be contained within a range that does not impair the neutron blocking properties, and other impurities are mainly impurity elements mixed from scrap such as Cr, Ta, Al, V, Cr, Nb, Si, Sn, Mn, Mo. And Cu, etc., together with general impurity elements C, N, Fe, O and H, a total amount of 5% or less is acceptable.
  • Inner layer 5 is made of industrial pure titanium or a titanium alloy.
  • industrial pure titanium is used for the inner layer 5
  • the processability at room temperature is excellent as compared with a titanium material made entirely of the same titanium alloy.
  • the industrial pure titanium mentioned here is an industry defined by JIS standards 1 to 4 and ASTM standards Grades 1 to 4 and DIN standards 3, 7025, 3, 7035, and 37055. Contains pure titanium. That is, the industrial pure titanium targeted in the present invention is, for example, C: 0.1% or less, H: 0.015% or less, O: 0.4% or less, N: 0.07% or less, Fe: It consists of 0.5% or less and the balance Ti.
  • a titanium alloy may be used for the inner layer 5.
  • the alloy cost can be significantly reduced and high strength can be obtained.
  • any of an ⁇ -type titanium alloy, an ⁇ + ⁇ -type titanium alloy, and a ⁇ -type titanium alloy can be used according to a required application.
  • the ⁇ -type titanium alloy for example, a high corrosion resistance alloy (ASTM Grade 7, 11, 16, 26, 13, 30, 33, or a titanium material containing a small amount of JIS species corresponding thereto and various elements).
  • Examples of ⁇ + ⁇ type titanium alloys include Ti-6Al-4V, Ti-6Al-6V-2Sn, Ti-6Al-7V, Ti-3Al-5V, Ti-5Al-2Sn-2Zr-4Mo-4Cr, Ti-6Al. -2Sn-4Zr-6Mo, Ti-1Fe-0.35O, Ti-1.5Fe-0.5O, Ti-5Al-1Fe, Ti-5Al-1Fe-0.3Si, Ti-5Al-2Fe, Ti-5Al -2Fe-0.3Si, Ti-5Al-2Fe-3Mo, Ti-4.5Al-2Fe-2V-3Mo, or the like can be used.
  • ⁇ -type titanium alloy for example, Ti-11.5Mo-6Zr-4.5Sn, Ti-8V-3Al-6Cr-4Mo-4Zr, Ti-10V-2Fe-3Mo, Ti-13V-11Cr-3Al Ti-15V-3Al-3Cr-3Sn, Ti-6.8Mo-4.5Fe-1.5Al, Ti-20V-4Al-1Sn, Ti-22V-4Al, and the like can be used.
  • the titanium and titanium alloy used for the inner layer 5 desirably have a 0.2% proof stress of 1000 MPa or less.
  • the titanium composite material of the present invention includes an intermediate layer between the inner layer and the surface layer. That is, a titanium material for hot rolling, which will be described later, is a material in which a surface layer material is attached to a base material and the periphery thereof is welded. During the subsequent hot rolling and heat treatment processes after cold rolling, the base material and the surface layer When diffusion occurs at the interface with the material and the titanium composite material is finally finished, an intermediate layer is formed between the inner layer derived from the base material and the surface layer derived from the surface material. This intermediate layer has a chemical composition different from the chemical composition of the base material. This intermediate layer bonds the inner layer and the surface layer to each other and bonds them firmly. Further, since a continuous element gradient is generated in the intermediate layer, the difference in strength between the inner layer and the surface layer can be reduced, and cracks during processing can be suppressed.
  • the thickness of the intermediate layer can be measured using EPMA or GDS. If GDS is used, more detailed measurement is possible. In the case of GDS, after removing the surface layer to some extent by polishing, the thickness of the intermediate layer can be measured by performing GDS analysis in the depth direction from the surface.
  • the intermediate layer is the increased content from the base material (in the case of an element not included in the base material, its content, in the case of an element also included in the base material, the increase in content from the base material) ) Is C MID, and the average of the increased content in the surface layer portion is C AVE , it means a region of 0 ⁇ C MID ⁇ 0.8 ⁇ C AVE .
  • the thickness of this intermediate layer is 0.5 ⁇ m or more. On the other hand, if the thickness of the intermediate layer becomes too large, the surface alloy layer may become thin by that amount, and the effect may not be exhibited. Therefore, the upper limit is preferably 15 ⁇ m.
  • Titanium material for hot rolling is a material (slab of slab, bloom, billet, etc.) used for hot working, and after hot working, it can be cooled if necessary. It is processed into a titanium composite material by performing inter-processing, heat treatment, etc.
  • the titanium material for hot rolling according to the present invention will be described with reference to the drawings.
  • “%” regarding the content of each element means “mass%”.
  • FIG. 3 is an explanatory view schematically showing that the base material (titanium rectangular cast, slab) 6 and the surface layer material (titanium plate) 7 are bonded together in a vacuum, and FIG. It is typical to bond the surface materials (titanium plates) 7 and 8 not only to the surface (rolled surface) of the base material (titanium rectangular cast slab, slab) but also to the side surfaces (surfaces other than the rolled surface). It is explanatory drawing shown in.
  • titanium plates 7 and 8 containing an alloy element that exhibits neutron blocking properties are bonded to the surface of a slab 6 that is a base material, and then bonded by hot rolling cladding. As a result, the surface layers of the titanium composite materials 1 and 2 are alloyed.
  • a titanium plate 7 may be bonded to only one side of the slab 6 in a vacuum as shown in FIG. 3, and the titanium plate 7 is attached to the other side of the slab 6. You may hot-roll without sticking.
  • a titanium plate 7 may be bonded to one side of the slab 6 as well as the other side. Thereby, generation
  • a plate containing an alloy element may be bonded to both rolling surfaces of the slab 6 as shown in FIG.
  • the same standard titanium plate 8 may be bonded together in a vacuum and welded to the side surface of the slab 6 that becomes the edge side during hot rolling.
  • the amount of the side surface of the slab 6 that wraps around during hot rolling varies depending on the manufacturing method, but is usually about 20 to 30 mm. Therefore, it is not necessary to attach the titanium plate 8 to the entire side surface of the slab 6, and the manufacturing method is not limited. It is only necessary to attach the titanium plate 8 only to the portion corresponding to the sneak amount.
  • titanium composites 1 and 2 are manufactured, they are manufactured through a shot-pickling process after hot rolling in order to remove the oxide layer formed by hot rolling. However, if the surface layer formed by the hot-rolled cladding is removed during this step, the neutron blocking characteristics cannot be expressed.
  • the thickness of the surface layer of the titanium composites 1 and 2 becomes too thin, the targeted neutron blocking characteristics will not be exhibited. On the other hand, if the thickness of the surface layer is too thick, the manufacturing cost increases accordingly. Since the titanium composite materials 1 and 2 only have to have a surface layer thickness suitable for the purpose of use, the thickness of the titanium plates 7 and 8 used as the material is not particularly limited, but the thickness of the slab 6 It is preferably in the range of 5 to 40%.
  • titanium plate As the surface layer material (titanium plate), a titanium plate having the predetermined chemical composition described in the section of the surface layer of the titanium composite material is used. In particular, it is desirable to adjust the chemical composition of the titanium plate to a component containing a predetermined element in the same component as the base material in order to suppress the plate breakage during hot rolling. . In particular, the following points should be noted.
  • a titanium alloy plate containing 0.1% or more and 3% or less of B is used as the surface layer material.
  • the chemical composition of the surface layer material is based on the same components as the above-mentioned base material in order to suppress plate breakage during hot rolling, and the component contains B in the range of 0.1% to 3%. It is desirable to adjust to. Further, in order to maintain good workability in hot and cold conditions, a Ti-0.1 to 3% B alloy may be used.
  • This B-containing titanium alloy plate can be produced by adding a boride such as B or TiB 2 to titanium.
  • a boride such as B or TiB 2
  • B addition amount of the surface layer 3 and 4 At least the titanium composites 1 and 2 are extremely effective because they have a large neutron shielding effect.
  • H, O, and C will also be concentrated in the alloy layer, but H is a problem because it escapes from the material during heat treatment such as vacuum annealing.
  • O and C can be produced without problems as long as they are 0.4% O or less and 0.1% C or less, which are below the upper limit contained in industrial pure titanium.
  • Base material As the base material, the industrial pure titanium or titanium alloy described in the section of the inner layer of the titanium composite is used. In particular, it is preferable to use a direct casting slab as a base material.
  • the direct cast slab may be one in which a melt resolidified layer is formed on at least a part of the surface.
  • a predetermined element was added to the surface of the direct casting slab when the melt resolidification process was performed, and a melt resolidification layer having a chemical composition different from that of the center portion of the direct casting slab was formed. May be.
  • the slab 6 and the titanium plates 7 and 8 are welded at least around the welded portion 9 in a vacuum vessel.
  • the slab 6 and the titanium plates 7 and 8 are bonded together by sealing with a vacuum, blocking the outside air, and rolling.
  • the welded portion to be joined after the titanium plates 7 and 8 are bonded to the slab 6 is shielded from the atmosphere at the interface between the slab 6 and the titanium plates 7 and 8. Weld.
  • Titanium is an active metal and forms a strong passive film on the surface when left in the atmosphere. It is impossible to remove the oxidized layer on the surface. However, unlike stainless steel, etc., oxygen easily dissolves in titanium. Therefore, when heated in a vacuum and sealed without external oxygen supply, oxygen on the surface diffuses into the solid solution. Therefore, the passive film formed on the surface disappears. Therefore, the slab 6 and the titanium plates 7 and 8 on the surface thereof can be completely adhered by the hot rolling cladding method without generating any inclusions between them.
  • the slab 6 when an as-cast slab is used as the slab 6, surface defects occur in the subsequent hot rolling process due to coarse crystal grains generated during solidification.
  • the titanium plates 7 and 8 are bonded to the rolled surface of the slab 6 as in the present invention, the bonded titanium plate 7 has a fine structure, so that surface defects in the hot rolling process can be suppressed. .
  • a base material of a titanium material for hot rolling is usually manufactured by cutting and refining an ingot after making it into a slab or billet shape by breakdown. In recent years, rectangular slabs that can be hot-rolled directly at the time of ingot production are sometimes produced and used for hot-rolling. When manufactured by breakdown, since the surface is relatively flat by breakdown, it is easy to disperse the material containing the alloy element relatively uniformly, and it is easy to make the element distribution of the alloy phase uniform.
  • an ingot directly manufactured in the shape of a hot-rolling material during casting (direct casting slab)
  • the cutting and refining process can be omitted, so that it can be manufactured at a lower cost.
  • the ingot is manufactured and then used after the surface is cut and refined, the same effect can be expected when it is manufactured through breakdown.
  • an alloy layer may be stably formed on the surface layer, and an appropriate material may be selected according to the situation.
  • the slab and welding the surroundings After assembling the slab and welding the surroundings, it is heated to 700 to 850 ° C. and subjected to 10-30% joint rolling, and then heated at the ⁇ -zone temperature for 3 to 10 hours to diffuse the base material components to the surface layer. It is preferable to perform hot rolling later. This is because by performing hot rolling at a ⁇ -region temperature, the deformation resistance becomes low and rolling becomes easy.
  • the direct cast slab used as the base material may be one in which a melt resolidification layer is formed on at least a part of the surface.
  • a predetermined element was added to the surface of the direct casting slab when the melt resolidification process was performed, and a melt resolidification layer having a chemical composition different from that of the center portion of the direct casting slab was formed. May be.
  • the melt resolidification process will be described in detail.
  • FIGS. 5 to 7 are explanatory diagrams showing the method of melt re-solidification.
  • a method for melting and resolidifying the surface of the base material of the titanium material for hot rolling there are laser heating, plasma heating, induction heating, electron beam heating, etc., and any method may be used.
  • electron beam heating since it is performed in a high vacuum, even if a void or the like is formed in this layer during the melt resolidification treatment, it can be made harmless by pressure bonding in subsequent rolling because it is a vacuum.
  • the degree of vacuum in the case of melting in a vacuum is desirably higher than 3 ⁇ 10 ⁇ 3 Torr.
  • the processing time becomes longer and the cost increases.
  • the melt resolidification method of the surface layer is carried out as shown in FIG. 5 in the case of a rectangular slab. That is, among the outer surfaces of the rectangular slab 10, at least two wide surfaces 10A and 10B that become the rolling surfaces (surfaces in contact with the hot rolling roll) in the hot rolling process are irradiated with an electron beam, and the surfaces on the surfaces are irradiated. Only melt the layer.
  • the surface 10A is one of the two surfaces 10A and 10B.
  • the area of the electron beam irradiation region 14 by the single electron beam irradiation gun 12 on the surface 10A of the rectangular slab 10 is compared with the total area of the surface 10A to be irradiated.
  • the electron beam irradiation is actually performed while continuously moving the electron beam irradiation gun 12 or continuously moving the rectangular slab 10. It is normal.
  • the shape and area of this irradiation area can be adjusted by adjusting the focus of the electron beam or by using an electromagnetic lens to oscillate a small beam at a high frequency (oscillation Oscillation) to form a beam bundle. can do.
  • the moving direction of the electron beam irradiation gun is not particularly limited, it is generally continuous along the length direction (usually the casting direction D) or the width direction (usually the direction perpendicular to the casting direction D) of the rectangular slab 10.
  • the irradiation region 14 is continuously irradiated in a band shape with a width W (in the case of a circular beam or beam bundle, a diameter W).
  • the electron beam irradiation is performed in a belt shape while continuously moving the irradiation gun 12 in the reverse direction (or the same direction) in the adjacent unirradiated belt region.
  • a plurality of irradiation guns may be used to simultaneously perform electron beam irradiation on a plurality of regions.
  • FIG. 5 the case where a rectangular beam is continuously moved along the length direction (usually casting direction D) of the rectangular slab 10 is shown.
  • the surface (surface 10A) of the rectangular titanium cast piece 10 is irradiated with an electron beam by such a surface heat treatment step and heated to melt the surface, the rectangular titanium as shown in the left side of the center of FIG.
  • the surface layer of the surface 10A of the slab 10 is melted at the maximum by a depth corresponding to the heat input.
  • the depth from the direction perpendicular to the irradiation direction of the electron beam is not constant as shown in FIG. 7, and the depth becomes the largest at the central part of the electron beam irradiation, and the thickness increases toward the strip-shaped end part. Decreases, resulting in a downwardly convex curved shape.
  • the surface layer is melted and re-solidified with a material composed of the target alloy element, whereby the surface layer of the material for hot rolling can be alloyed to form an alloy layer having a chemical composition different from that of the base material.
  • a material used in this case one or more of powder, chip, wire, thin film, cutting powder, and mesh may be used.
  • the component and amount of the material to be arranged before melting are determined so that the component in the element concentration region after melting and solidifying together with the material surface becomes the target component.
  • the melt resolidification treatment After the melt resolidification treatment, it is preferable to hold at a temperature of 100 ° C. or higher and lower than 500 ° C. for 1 hour or longer. If it is cooled rapidly after melting and resolidification, fine cracks may occur in the surface layer due to strain during solidification. In the subsequent hot rolling process and cold rolling process, this fine crack may be the starting point, causing surface layer peeling, or a part where the alloy layer is partially thin, which may deteriorate the neutron blocking performance. . Further, if the inside is oxidized due to fine cracks, it is necessary to remove in the pickling process, and the thickness of the alloy layer is further reduced. By maintaining at the above temperature, fine cracks on the surface can be suppressed. At this temperature, atmospheric oxidation hardly occurs even if the temperature is maintained.
  • a titanium material for hot rolling can be manufactured by attaching a titanium plate containing a predetermined alloy component to the surface of a base material provided with a surface layer portion formed by melt resolidification treatment.
  • the titanium material for hot rolling is preferably bonded to the slab 6 and the titanium plates 7 and 8 which are welded in advance by the hot rolled clad method.
  • the surface layer of the titanium composite material is bonded by hot rolling cladding. Is alloyed. That is, after the titanium plate 7 containing the alloy element is bonded to the surface corresponding to the rolling surface of the slab 6, the slab 6 and the titanium plate 7 are preferably welded at least around the welded portion 9 in a vacuum vessel. The space between the slab 6 and the titanium plate 7 is bonded together by vacuum sealing and rolling. In welding for bonding the titanium plate 7 to the slab 6, for example, as shown in FIGS. 3 and 4, the entire circumference is welded so that air does not enter between the slab 6 and the titanium plate 7.
  • Titanium is an active metal and forms a strong passive film on the surface when left in the atmosphere. It is impossible to remove the oxidized layer on the surface. However, unlike stainless steel, etc., oxygen easily dissolves in titanium. Therefore, when heated in a vacuum and sealed without external oxygen supply, oxygen on the surface diffuses into the solid solution. Therefore, the passive film formed on the surface disappears. For this reason, the slab 6 and the titanium plate 7 on the surface thereof can be completely adhered by the hot rolling cladding method without generating any inclusions between them.
  • the slab 6 when an as-cast slab is used as the slab 6, surface defects occur in the subsequent hot rolling process due to coarse crystal grains generated during solidification.
  • the titanium plate 7 when the titanium plate 7 is bonded to the rolled surface of the slab 6 as in the present invention, the bonded titanium plate 7 has a fine structure, so that surface defects in the hot rolling process can be suppressed.
  • titanium plates 7 may be bonded to both sides of the slab 6 instead of just one side. Thereby, generation
  • hot rolling at least a part of the side surface of the slab 6 usually wraps around the surface side of the hot-rolled sheet by being rolled down by the slab 6. Therefore, if the structure of the surface layer on the side surface of the slab 6 is coarse or a large number of defects exist, surface flaws may occur on the surface near both ends in the width direction of the hot-rolled sheet.
  • the same standard titanium plate 8 is preferably bonded and welded to the side surface of the slab 6 on the edge side during hot rolling as well as the rolled surface. Thereby, generation
  • This welding is preferably performed in a vacuum.
  • the amount of the side surface of the slab 6 that wraps around during hot rolling varies depending on the manufacturing method, but is usually about 20 to 30 mm. Therefore, it is not necessary to attach the titanium plate 8 to the entire side surface of the slab 6, and the manufacturing method is not limited. It is only necessary to attach the titanium plate 8 only to the portion corresponding to the sneak amount.
  • the base material-derived component can be contained in the titanium composite material. For example, heat treatment at 700 to 900 ° C. for 30 hours is exemplified.
  • Methods for welding the slab 6 and the titanium plates 7 and 8 in vacuum include electron beam welding and plasma welding.
  • the electron beam welding can be performed under a high vacuum
  • the space between the slab 6 and the titanium plates 7 and 8 can be made a high vacuum, which is desirable.
  • the degree of vacuum when the titanium plates 7 and 8 are welded in a vacuum is desirably a higher degree of vacuum of 3 ⁇ 10 ⁇ 3 Torr or less.
  • the slab 6 and the titanium plate 7 are not necessarily welded in a vacuum vessel.
  • a vacuum suction hole is provided in the titanium plate 7 and the titanium plate 7 is overlapped with the slab 6. Later, the slab 6 and the titanium plate 7 may be welded while evacuating the slab 6 and the titanium plate 7 using a vacuum suction hole, and the vacuum suction hole may be sealed after welding.
  • the thickness and chemical composition of the surface layer are as follows: It depends on the thickness of the titanium plates 7 and 8 before bonding and the distribution of alloy elements.
  • the annealing treatment is performed in a vacuum atmosphere or the like in order to obtain the finally required strength and ductility.
  • a concentration gradient is generated in the depth direction.
  • the diffusion distance of the element generated in the final annealing process is about several ⁇ m, and the entire thickness of the alloy layer is not diffused. In particular, it affects the concentration of the alloy element in the vicinity of the surface layer, which is important for neutron blocking. do not do.
  • titanium plates 7 and 8 the uniformity of the alloy components in the entire titanium plates 7 and 8 leads to stable expression of the characteristics.
  • titanium plates 7 and 8 manufactured as products it is possible to use titanium plates 7 and 8 manufactured as products, so it is easy to control the segregation of alloy components as well as the plate thickness accuracy, and have a uniform thickness and chemical properties after manufacturing. Titanium composite materials 1 and 2 having a surface layer having components can be produced, and stable characteristics can be expressed.
  • Hot rolling process Also in the hot rolling process, if the surface temperature is too high, a large amount of scale is generated during sheet passing, and the scale loss increases. On the other hand, if it is too low, the scale loss is reduced, but surface flaws are likely to occur. Therefore, it is necessary to remove by surface pickling, and it is desirable to perform hot rolling in a temperature range in which surface flaws can be suppressed. . Therefore, it is desirable to perform rolling in the optimum temperature range. In addition, since the surface temperature of the titanium material decreases during rolling, it is desirable to minimize roll cooling during rolling and suppress the decrease in the surface temperature of the titanium material.
  • the hot-rolled plate has an oxide layer on its surface
  • the oxide layer is generally removed by pickling with a nitric hydrofluoric acid solution.
  • the surface may be ground by grinding with a grindstone after pickling.
  • a two-layer or three-layer structure including an inner layer and a surface layer derived from the base material and the surface layer portion of the titanium material for hot rolling may be used.
  • a shot blast treatment is performed as a pretreatment for the pickling treatment to remove a part of the scale on the surface, and at the same time, cracks are formed on the surface, and in the subsequent pickling step The liquid penetrates into the cracks and removes part of the base material.
  • the neutron beam shielding plates shown in FIGS. 1 and 2 and Table 1 were manufactured by the hot rolling cladding shown below using the slab 6 and the titanium plates 7 and 8 shown in FIGS.
  • a titanium ingot 6 as a material was manufactured using a rectangular mold by electron beam melting (EB melting) or plasma arc melting (plasma melting), or using a cylindrical mold by VAR melting.
  • EB melting electron beam melting
  • plasma melting plasma arc melting
  • the cylindrical ingot 6 has a diameter of 1200 mm ⁇ length of 2500 mm
  • the rectangular ingot 6 has a thickness of 100 mm ⁇ width of 1000 mm ⁇ length of 4500 mm.
  • the titanium plate 7 is bonded by superimposing (covering) Ti-B alloy plates of various sizes and thicknesses equivalent to the rolling surface of the ingot or slab 6 and electron beam welding (about 3 ⁇ ). 10 -3 Torr or less degree of vacuum) by welding, and between the titanium plate 7 and the ingot (or slab) 6 is sealed in a vacuum state.
  • Bonding of the alloy plate was mainly performed on the rolled surface, and two types of a two-layer structure in which only one side surface was performed and a three-layer structure in which both side surfaces were performed were produced.
  • the ratio per one side of the total thickness in the final product is shown in Table 1, and in the three-layer structure, the B-concentrated layers on both surfaces have the same thickness. It was adjusted to become.
  • a Ti-B alloy plate is used for the titanium plate 7 used for bonding the plates, and B is added in advance by TiB 2 or 10 B enriched boron (H 3 10 BO 3 , 10 B 2 O 10 B 4 C). The ingot melted in this manner was produced by hot rolling.
  • the Ti—B alloy plate is descaled by passing through a continuous pickling line made of nitric hydrofluoric acid after hot rolling.
  • the slab 6 was heated at 800 ° C. for 240 minutes and then hot-rolled to produce strip coils (titanium composite materials) 1 and 2 having a thickness of about 4 mm. By this hot rolling, the surface layers of the titanium composites 1 and 2 were made into Ti-0.1 to 3.8% B alloy.
  • a titanium alloy may be used for the slab 6, but in this case, the titanium plate 7 to be bonded was a Ti-0.1 to 3.8% B alloy containing only Ti and B.
  • the strip coils 1 and 2 after hot rolling were passed through a continuous pickling line made of nitric hydrofluoric acid, descaled, and then visually observed for the occurrence of cracks.
  • the measuring method of the depth of the surface layers 3 and 4 (B concentrating layer) is a part of the hot-rolled sheet (collected from the central part in the width direction at three points of the front end, the center, and the rear end in the longitudinal direction).
  • the cut and polished material was subjected to SEM / EDS analysis, and the ratio of the B-concentrated layer to the plate thickness and the B concentration of the B-concentrated layer were determined (the average value in the observed portion was adopted).
  • a total of 20 bending specimens in the L direction were collected from the central part in the width direction at three points, the front, center and rear ends in the longitudinal direction, and bent according to JIS Z 2248 (metal material bending test method).
  • JIS Z 2248 metal material bending test method
  • a specimen having a thickness of 500 mm ⁇ 500 mm ⁇ 4 mm was fixed at a position 200 mm from the radiation source using Am-Be (4.5 MeV) as a radiation source.
  • the detector is installed at a position of 300 mm from the radiation source, and the peak value of the target energy is measured for each of the radiation equivalents of the industrial test pure titanium JIS type 1 and the test piece of the control test piece.
  • the shielding effect was evaluated (industrial pure titanium JIS type 1 neutron beam shielding effect is 1, and the value of each test piece is described).
  • the comparative example and Example shown in 8 are the cases where the EB melt
  • the comparative example 1 is a case where the same kind of pure titanium JIS as the slab 6 is used as the titanium plate 7. No cracks occurred in the hot-rolled sheet, and no cracks occurred in the bending test.
  • the comparative example 2 is a case where the intermediate layer is thin.
  • the hot-rolled sheet was partially cracked, and the crack generation rate was high even in the bending test.
  • No. 3 is a case where the thickness ratio of the surface layers 3 and 4 exceeds 40%.
  • the hot-rolled sheet was partially cracked, and the crack generation rate was high even in the bending test.
  • Examples 4 to 7 are cases in which the evaluation was made by changing the type of the inner five, the layer structure, the thickness ratio of the surface layers 3 and 4, and the B content. Since the thickness ratio of the surface layers 3 and 4 is in the range of 5 to 40% and the B content in the surface layers 3 and 4 is in the range of 0.1 to 3.0%, both are hot-rolled sheets. No cracks occurred, and no cracks occurred in the bending test.
  • Example 8 is a case where the alloy plate is bonded not only to the rolling surface but also to the side surface in the longitudinal direction. Since the thickness ratio of the surface layers 3 and 4 is in the range of 5 to 40% and the B content in the surface layers 3 and 4 is in the range of 0.1 to 3.0%, both are hot-rolled sheets. No cracks occurred, and no cracks occurred in the bending test. In addition, since the alloy plate is bonded to the side surface in the longitudinal direction, surface wrinkles at the end in the width direction due to the wraparound of the side surface are reduced.
  • Examples 9 to 11 are cases in which an as-cast plasma melted ingot is used, and evaluation is performed by changing the type of the inner 5, the layer structure, the thickness ratio of the surface layers 3 and 4, and the B content. Since the thickness ratio of the surface layers 3 and 4 is in the range of 5 to 40% and the B content in the surface layers 3 and 4 is in the range of 0.1 to 3.0%, both are hot-rolled sheets. No cracks occurred, and no cracks occurred in the bending test.
  • the cast skin surface of the EB melting ingot is cut and used, and evaluation is made by changing the type of the inner 5 layer, the layer structure, the thickness ratio of the surface layers 3 and 4 and the B content. It is. Since the thickness ratio of the surface layers 3 and 4 is in the range of 5 to 40% and the B content in the surface layers 3 and 4 is in the range of 0.1 to 3.0%, both are hot-rolled sheets. No cracks occurred, and no cracks occurred in the bending test.
  • Example 18 to 20 various ingots were used after being ingot-rolled, and the surface was cut and used. Evaluation was made by changing the type of inner 5 layer, the layer structure, the thickness ratio of the surface layers 3 and 4, and the B content. This is the case. Since the thickness ratio of the surface layers 3 and 4 is in the range of 5 to 40% and the B content in the surface layers 3 and 4 is in the range of 0.1 to 3.0%, both are hot-rolled sheets. No cracks occurred, and no cracks occurred in the bending test.
  • the surface is cut and used after the VAR ingot is ingot-rolled, and various titanium alloys are used as the internal 5 types, and the layer structure, the thickness ratio of the surface layers 3 and 4, It is a case where B content is changed and evaluated. Since the thickness ratio of the surface layers 3 and 4 is in the range of 5 to 40% and the B content in the surface layers 3 and 4 is in the range of 0.1 to 3.0%, both are hot-rolled sheets. No cracks occurred, and no cracks occurred in the bending test.
  • the alloy used for the interior 5 in the example of the present invention was subjected to a tensile test with a JIS13B test piece having a thickness of 1.5 mm in advance, and the 0.2% proof stress was 1000 MPa or less.
  • the neutron shielding effect is 23.7 in the stainless steel plate (4 mm thickness) having a B content of 0.5% used in the nuclear fuel storage rack.
  • a higher neutron beam shielding effect was obtained than this stainless steel plate.
  • the neutron shielding plate shown in Table 2 as each example (example of the present invention) was manufactured by the following method.
  • the slab 6 subjected to plate bonding in the same procedure as in Example 1 was heated at 800 ° C. for 240 minutes using a steel facility, and then hot-rolled to form a strip coil (titanium composite) 1 having a thickness of about 20 mm. , 2 were produced.
  • the surface layers of the titanium composites 1 and 2 were made into Ti-0.1 to 3.8% B alloy.
  • the strip coils 1 and 2 after hot rolling were passed through a continuous pickling line made of nitric hydrofluoric acid, descaled, and then visually observed for the occurrence of cracks.
  • the measuring method of the depth of the surface layers 3 and 4 is a part of the hot-rolled sheet (collected from the central part in the width direction at three points of the front end, the center, and the rear end in the longitudinal direction).
  • the cut and polished material was subjected to SEM / EDS analysis, and the ratio of the B-concentrated layer to the plate thickness and the B concentration of the B-concentrated layer were determined (the average value in the observed portion was adopted).
  • a total of 20 bending specimens in the L direction were collected from the central part in the width direction at three points, the front, center and rear ends in the longitudinal direction, and bent according to JIS Z 2248 (metal material bending test method).
  • JIS Z 2248 metal material bending test method
  • a test piece having a thickness of 500 mm ⁇ 500 mm ⁇ 20 mm was fixed at a position 200 mm from the radiation source using Am-Be (4.5 MeV) as a radiation source.
  • the detector is installed at a position of 300 mm from the radiation source, and the peak value of the target energy is measured for each of the radiation equivalents of the industrial test pure titanium JIS type 1 and the test piece of the control test piece.
  • the shielding effect was evaluated (industrial pure titanium JIS type 1 neutron beam shielding effect is 1, and the value of each test piece is described).
  • the comparative example of 42 and an Example are the cases where the EB melt
  • the comparative example of 38 is a case where the same kind of pure titanium JIS type 1 as the slab 6 is used as the titanium plate 7. No cracks occurred in the hot-rolled sheet, and no cracks occurred in the bending test.
  • the intermediate layer is thin.
  • the hot-rolled sheet was partially cracked, and the crack generation rate was high even in the bending test.
  • Examples 40 to 42 evaluation was made by changing the type of the inner 5 layer, the layer structure, the thickness ratio of the surface layers 3 and 4, and the B content. Since the thickness ratio of the surface layers 3 and 4 is in the range of 5 to 40% and the B content in the surface layers 3 and 4 is in the range of 0.1 to 3.0%, both are hot-rolled sheets. No cracks occurred, and no cracks occurred in the bending test.
  • Examples 43 to 45 as-cast plasma melted ingots were used, and evaluation was performed by changing the type of the inner 5 layer, the layer structure, the thickness ratio of the surface layers 3 and 4, and the B content. Since the thickness ratio of the surface layers 3 and 4 is in the range of 5 to 40% and the B content in the surface layers 3 and 4 is in the range of 0.1 to 3.0%, both are hot-rolled sheets. No cracks occurred, and no cracks occurred in the bending test.
  • Example 46 to 48 the surface of the cast surface of the EB melting ingot is cut and used, and evaluation is made by changing the type of the inner 5 layer, the layer structure, the thickness ratio of the surface layers 3 and 4, and the B content. It is. Since the thickness ratio of the surface layers 3 and 4 is in the range of 5 to 40% and the B content in the surface layers 3 and 4 is in the range of 0.1 to 3.0%, both are hot-rolled sheets. No cracks occurred, and no cracks occurred in the bending test.
  • Example 49 to 51 the casting surface of the plasma melting ingot was cut and used, and the evaluation was made by changing the type of the inner 5 layer, the layer structure, the thickness ratio of the surface layers 3 and 4 and the B content. It is. Since the thickness ratio of the surface layers 3 and 4 is in the range of 5 to 40% and the B content in the surface layers 3 and 4 is in the range of 0.1 to 3.0%, both are hot-rolled sheets. No cracks occurred, and no cracks occurred in the bending test.
  • Examples 52 to 54 various ingots were used after being ingot-rolled, and the surface was cut and used. Evaluation was made by changing the type of the inner 5 layer, the layer structure, the thickness ratio of the surface layers 3 and 4, and the B content. This is the case. Since the thickness ratio of the surface layers 3 and 4 is in the range of 5 to 40% and the B content in the surface layers 3 and 4 is in the range of 0.1 to 3.0%, both are hot-rolled sheets. No cracks occurred, and no cracks occurred in the bending test.
  • Examples 55 to 57 various ingots are forged and then used after cutting the surface.
  • the inner 5 varieties, the layer structure, the thickness ratio of the surface layers 3 and 4 and the B content are changed, the results are evaluated. It is. Since the thickness ratio of the surface layers 3 and 4 is in the range of 5 to 40% and the B content in the surface layers 3 and 4 is in the range of 0.1 to 3.0%, both are hot-rolled sheets. No cracks occurred, and no cracks occurred in the bending test.
  • the neutron shielding plate shown in Table 3 as each example (example of the present invention) was manufactured by the following method.
  • the slab 6 bonded to the plate in the same procedure as in Example 1 was heated at 800 ° C. for 240 minutes using a steel facility and then hot-rolled to obtain a strip coil (titanium composite) 1 having a thickness of about 5 mm. , 2 were produced. Further, cold rolling was performed to obtain a titanium plate having a thickness of 1 mm, and as an annealing treatment, heat treatment was performed by heating to 600 to 750 ° C. in a vacuum or an inert gas atmosphere and holding for 240 minutes. The cold-rolled sheet was visually observed for cracking in the surface inspection process after annealing.
  • the measuring method of the depth of the surface layers 3 and 4 is a part of the cold-rolled plate (collected from the central portion in the width direction at three locations, the front end, the center, and the rear end in the longitudinal direction).
  • the cut and polished material was subjected to SEM / EDS analysis, and the ratio of the B-concentrated layer to the plate thickness and the B concentration of the B-concentrated layer were determined (the average value in the observed portion was adopted).
  • a total of 20 bending specimens in the L direction were collected from the central part in the width direction at three points, the front, center and rear ends in the longitudinal direction, and bent according to JIS Z 2248 (metal material bending test method).
  • JIS Z 2248 metal material bending test method
  • a specimen having a thickness of 500 mm ⁇ 500 mm ⁇ 1 mm was fixed at a position 200 mm from the radiation source using Am-Be (4.5 MeV) as a radiation source.
  • the detector is installed at a position of 300 mm from the radiation source, and the peak value of the target energy is measured for each of the radiation equivalents of the industrial test pure titanium JIS type 1 and the test piece of the control test piece.
  • the shielding effect was evaluated (industrial pure titanium JIS type 1 neutron beam shielding effect is 1, and the value of each test piece is described).
  • the comparative example of 63 and an Example are the cases where the EB melt
  • the comparative example of 58 is a case where the same kind of pure titanium JIS as the slab 6 is used as the titanium plate 7. No cracks occurred in the cold-rolled sheet, and no cracks occurred in the bending test.
  • No. 59 is a case where the B content of the surface layers 3 and 4 exceeds 3.0%.
  • the cold-rolled sheet was partially cracked, and the rate of cracking was high in the bending test.
  • the comparative example of 60 is a case where the thickness ratio of the surface layers 3 and 4 exceeds 40%.
  • the cold-rolled sheet was partially cracked, and the rate of cracking was high in the bending test.
  • Examples 61 to 63 the evaluation was made by changing the type of the inner five, the layer structure, the thickness ratio of the surface layers 3 and 4, and the B content. Since the thickness ratio of the surface layers 3 and 4 is in the range of 5 to 40% and the B content in the surface layers 3 and 4 is in the range of 0.1 to 3.0%, both are cold-rolled sheets. No cracks occurred, and no cracks occurred in the bending test.
  • Examples 64-66 an as-cast plasma melted ingot was used, and evaluation was performed by changing the type of the inner 5, the layer structure, the thickness ratio of the surface layers 3 and 4, and the B content. Since the thickness ratio of the surface layers 3 and 4 is in the range of 5 to 40% and the B content in the surface layers 3 and 4 is in the range of 0.1 to 3.0%, both are cold-rolled sheets. No cracks occurred, and no cracks occurred in the bending test.
  • Examples 67 and 68 the cast skin surface of the EB melting ingot or the plasma melting ingot is cut and used, and the type of the inner five, the layer structure, the thickness ratio of the surface layers 3 and 4, and the B content are changed. It is a case where it evaluates. Since the thickness ratio of the surface layers 3 and 4 is in the range of 5 to 40% and the B content in the surface layers 3 and 4 is in the range of 0.1 to 3.0%, both are cold-rolled sheets. No cracks occurred, and no cracks occurred in the bending test.
  • Examples 69 to 71 various ingots were used after being ingot-rolled and the surface was cut and used, and the evaluation was made by changing the type of the inner 5 layer, the layer structure, the thickness ratio of the surface layers 3 and 4, and the B content. This is the case. Since the thickness ratio of the surface layers 3 and 4 is in the range of 5 to 40% and the B content in the surface layers 3 and 4 is in the range of 0.1 to 3.0%, both are cold-rolled sheets. No cracks occurred, and no cracks occurred in the bending test.
  • Examples 72 to 74 various ingots are forged and then used after cutting the surface.
  • the evaluation is made. It is. Since the thickness ratio of the surface layers 3 and 4 is in the range of 5 to 40% and the B content in the surface layers 3 and 4 is in the range of 0.1 to 3.0%, both are cold-rolled sheets. No cracks occurred, and no cracks occurred in the bending test.
  • a neutron beam shielding plate 1 which is a titanium composite material having a two-layer structure according to the present invention is hot-rolled after melting and re-solidifying one side surface of a base material, so Formed.
  • the neutron beam shielding plate 2 having a three-layer structure according to the present invention shown in FIG. 2 is obtained by hot rolling after melting and re-solidifying the both side surfaces of the base material, so It is formed.
  • the manufacturing method of the neutron beam shielding plates 1 and 2 will be specifically described.
  • the neutron beam shielding plates 1 and 2 shown as examples (examples of the present invention) in Table 4 are manufactured by the following method.
  • a titanium ingot as a material was manufactured using a rectangular mold by electron beam melting (EB melting) and plasma arc melting (plasma melting) or using a cylindrical mold by VAR melting.
  • EB melting electron beam melting
  • plasma melting plasma arc melting
  • the size of the ingot was a cylindrical ingot of diameter 1200 mm ⁇ length 2500 mm, a rectangular ingot 100 mm thick ⁇ width 1000 mm ⁇ length 4500 mm, and the varieties were pure titanium JIS type 1, JIS type 2 and JIS type 3.
  • the melt resolidification treatment was performed on at least one of the rolling surfaces, and was also performed on the side surface in the longitudinal direction as necessary. This treatment is performed by electron beam welding in a vacuum atmosphere of about 3 ⁇ 10 ⁇ 3 Torr, and TiB 2 powder (100 ⁇ m or less), Ti—B alloy tip (2 mm square, 1 mm thickness), Ti—B alloy at the time of melting. A wire ( ⁇ 5 mm or less), Ti—B alloy thin film (20 ⁇ m or less), or Ti—B alloy mesh ( ⁇ 1 mm combined in a lattice shape) is added, and the molten re-solidified layer is Ti-0.1-3 By using a 5% B alloy, a titanium slab having a two-layer structure or a three-layer structure was obtained. For the surface layers 3 and 4 (B-concentrated layer), the ratio per one side of the total thickness of the titanium composite materials 1 and 2 is shown in Table 4, and in the three-layer structure, B-concentration on both surfaces The layers were adjusted to have the same thickness.
  • the material containing B was uniformly dispersed over the entire rolling surface of the titanium cast slab so as to be uniformly added to the entire slab, and then melted and re-solidified. In addition, it hold
  • the melted and re-solidified titanium slab was heated at 800 ° C. for 240 minutes using a steel facility, and then hot-rolled to produce a strip coil having a thickness of about 4 mm.
  • the strip-like coil after hot rolling was passed through a continuous pickling line made of nitric hydrofluoric acid, descaled, and then visually observed for the occurrence of cracks.
  • the measuring method of the depth of the surface layers 3 and 4 is a part of the hot-rolled sheet after pickling (from the center in the width direction for three portions of the front end, center, and rear end in the longitudinal direction) Each sampled) was cut out and polished, and subjected to SEM / EDS analysis to determine the ratio of the surface layers 3 and 4 (B concentrated layer) to the plate thickness and the B concentration of the surface layers 3 and 4 (B concentrated layer) ( The average value among the observation points was adopted).
  • a total of 20 bending specimens in the L direction were collected from the central part in the width direction at three points, the front, center and rear ends in the longitudinal direction, and bent according to JIS Z 2248 (metal material bending test method).
  • JIS Z 2248 metal material bending test method
  • a specimen having a thickness of 500 mm ⁇ 500 mm ⁇ 4 mm was fixed at a position 200 mm from the radiation source using Am-Be (4.5 MeV) as a radiation source.
  • the detector is installed at a position of 300 mm from the radiation source, and the peak value of the target energy is measured for each of the radiation equivalents of the industrial test pure titanium JIS type 1 and the test piece of the control test piece.
  • the shielding effect was evaluated (industrial pure titanium JIS type 1 neutron beam shielding effect is 1, and the value of each test piece is described).
  • the comparative example of 75 is a case where the raw material containing B was not added at the time of melt re-solidification. No cracks occurred in the hot-rolled sheet, and no cracks occurred in the bending test.
  • a comparative example of 76 is a case where the B concentration of the surface layers 3 and 4 exceeds 3.0%.
  • the hot-rolled sheet was partially cracked, and the crack generation rate was high even in the bending test.
  • the comparative example of 77 is a case where the thickness ratio of the surface layers 3 and 4 exceeds 40%.
  • the hot-rolled sheet was partially cracked, and the crack generation rate was high even in the bending test.
  • Examples 78-83 (examples of the present invention) were evaluated by changing the B-containing material to TiB 2 powder, Ti—B alloy tip, Ti—B alloy wire, Ti—B alloy thin film, and Ti—B alloy mesh. This is the case. In both cases, the thickness ratio of the surface layers 3 and 4 is in the range of 5 to 40%, and the B concentration of the surface layers 3 and 4 is in the range of 0.1 to 3.0%. No cracks occurred in the plate, and no cracks occurred in the bending test.
  • Examples 84-88 use as-cast plasma melting ingots, and B-containing materials are TiB 2 powder, Ti—B alloy tip, Ti—B alloy wire, Ti—B alloy thin film, This is a case where the evaluation is performed by changing to a Ti-B alloy mesh. In both cases, the thickness ratio of the surface layers 3 and 4 is in the range of 5 to 40%, and the B concentration of the surface layers 3 and 4 is in the range of 0.1 to 3.0%. No cracks occurred in the plate, and no cracks occurred in the bending test.
  • Example 89 to 93 the cast skin surface of the EB melting ingot was cut and used, and the B-containing material was TiB 2 powder, Ti—B alloy tip, Ti—B alloy wire, This is a case where the evaluation was performed by changing the Ti—B alloy thin film and the Ti—B alloy mesh.
  • the melt re-solidification treatment is performed on the side surface in the longitudinal direction as well as the rolled surface. Since the thickness ratio of the surface layers 3 and 4 is in the range of 5 to 40% and the B concentration of the surface layers 3 and 4 is in the range of 0.1 to 3.0%, both are hot-rolled sheets. No cracks occurred, and no cracks occurred in the bending test.
  • Examples 94 to 98 are obtained by cutting the cast skin surface of a plasma melting ingot and using a B-containing material as TiB 2 powder, Ti—B alloy tip, Ti—B alloy wire, This is a case where the evaluation was performed by changing the Ti—B alloy thin film and the Ti—B alloy mesh.
  • the melt re-solidification treatment is performed on the side surface in the longitudinal direction as well as the rolled surface. Since the thickness ratio of the surface layers 3 and 4 is in the range of 5 to 40% and the B concentration of the surface layers 3 and 4 is in the range of 0.1 to 3.0%, both are hot-rolled sheets. No cracks occurred, and no cracks occurred in the bending test.
  • Examples 99 to 101 are cases in which various ingots are subjected to ingot rolling and the surface is cut and used, and TiB 2 powder is used as a B-containing material at the time of melt resolidification. . Since the thickness ratio of the surface layers 3 and 4 is in the range of 5 to 40% and the B concentration of the surface layers 3 and 4 is in the range of 0.1 to 3.0%, both are hot-rolled sheets. No cracks occurred, and no cracks occurred in the bending test.
  • Examples 102-104 examples of the present invention
  • various ingots were forged and the surface was cut and used, and TiB 2 powder was used as a B-containing material at the time of re-solidification. Since the thickness ratio of the surface layers 3 and 4 is in the range of 5 to 40% and the B concentration of the surface layers 3 and 4 is in the range of 0.1 to 3.0%, both are hot-rolled sheets. No cracks occurred, and no cracks occurred in the bending test.
  • the alloy used for the interior 5 in the example of the present invention was subjected to a tensile test with a JIS13B test piece having a thickness of 1.5 mm in advance, and the 0.2% proof stress was 1000 MPa or less.
  • the neutron shielding effect was 1 or more, and the neutron beam shielding effect could be confirmed.
  • the stainless steel plate (4 mm thickness) to which 0.5% by mass of B used in the nuclear fuel storage rack is added has a neutron shielding effect of 23.7.
  • Examples 86, 93, 106, and 108 a higher neutron beam shielding effect was obtained than this stainless steel plate.
  • the neutron beam shielding plates 1 and 2 shown in Table 5 as examples (examples of the present invention) are manufactured by the following method.
  • Example 4 In the same procedure as in Example 4, the melted and re-solidified titanium slab was heated at 800 ° C. for 240 minutes using a steel facility, and then hot-rolled to produce a strip coil having a thickness of about 20 mm.
  • the strip-like coil after hot rolling was passed through a continuous pickling line made of nitric hydrofluoric acid, descaled, and then visually observed for the occurrence of cracks.
  • the measuring method of the depth of the surface layers 3 and 4 is a part of the hot-rolled sheet after pickling (from the center in the width direction for three portions of the front end, center, and rear end in the longitudinal direction) Each sampled) was cut out and polished, and subjected to SEM / EDS analysis to determine the ratio of the surface layers 3 and 4 (B concentrated layer) to the plate thickness and the B concentration of the surface layers 3 and 4 (B concentrated layer) ( The average value among the observation points was adopted).
  • a total of 20 bending specimens in the L direction were collected from the central part in the width direction at three points, the front, center and rear ends in the longitudinal direction, and bent according to JIS Z 2248 (metal material bending test method).
  • JIS Z 2248 metal material bending test method
  • a test piece having a thickness of 500 mm ⁇ 500 mm ⁇ 20 mm was fixed at a position 200 mm from the radiation source using Am-Be (4.5 MeV) as a radiation source.
  • the detector is installed at a position of 300 mm from the radiation source, and the peak value of the target energy is measured for each of the radiation equivalents of the industrial test pure titanium JIS type 1 and the test piece of the control test piece.
  • the shielding effect was evaluated (industrial pure titanium JIS type 1 neutron beam shielding effect is 1, and the value of each test piece is described).
  • the comparative example of 105 is a case where the raw material containing B was not added at the time of melt re-solidification. No cracks occurred in the hot-rolled sheet, and no cracks occurred in the bending test.
  • No. 106 is a case where the B concentration of the surface layers 3 and 4 exceeds 3.0%.
  • the hot-rolled sheet was partially cracked, and the crack generation rate was high even in the bending test.
  • a comparative example 107 is a case where the thickness ratio of the surface layers 3 and 4 exceeds 40%. The hot-rolled sheet was partially cracked, and the crack generation rate was high even in the bending test.
  • Examples 108 to 112 were evaluated by changing the B-containing material to TiB 2 powder, Ti—B alloy chip, Ti—B alloy wire, Ti—B alloy thin film, and Ti—B alloy mesh, respectively. This is the case. In both cases, the thickness ratio of the surface layers 3 and 4 is in the range of 5 to 40%, and the B concentration of the surface layers 3 and 4 is in the range of 0.1 to 3.0%. No cracks occurred in the plate, and no cracks occurred in the bending test.
  • Examples 113 to 117 use as-cast plasma melting ingots, and B-containing materials are TiB 2 powder, Ti-B alloy chip, Ti-B alloy wire, Ti-B alloy thin film, This is a case where the evaluation is performed by changing to a Ti-B alloy mesh. In both cases, the thickness ratio of the surface layers 3 and 4 is in the range of 5 to 40%, and the B concentration of the surface layers 3 and 4 is in the range of 0.1 to 3.0%. No cracks occurred in the plate, and no cracks occurred in the bending test.
  • Example 118 and 119 the cast skin surface of an EB melting ingot or a plasma melting ingot is cut and used, and TiB 2 powder is used as a B-containing material at the time of melt resolidification. It is. Since the thickness ratio of the surface layers 3 and 4 is in the range of 5 to 40% and the B concentration of the surface layers 3 and 4 is in the range of 0.1 to 3.0%, both are hot-rolled sheets. No cracks occurred, and no cracks occurred in the bending test.
  • Examples 120 to 122 are cases in which various ingots are subjected to ingot rolling and the surface is cut and used, and TiB 2 powder is used as a B-containing material at the time of melt resolidification. . Since the thickness ratio of the surface layers 3 and 4 is in the range of 5 to 40% and the B concentration of the surface layers 3 and 4 is in the range of 0.1 to 3.0%, both are hot-rolled sheets. No cracks occurred, and no cracks occurred in the bending test.
  • Examples 123 to 125 examples of the present invention
  • various ingots were forged and the surface was cut and used, and TiB 2 powder was used as a B-containing material at the time of re-solidification. Since the thickness ratio of the surface layers 3 and 4 is in the range of 5 to 40% and the B concentration of the surface layers 3 and 4 is in the range of 0.1 to 3.0%, both are hot-rolled sheets. No cracks occurred, and no cracks occurred in the bending test.
  • the neutron beam shielding plates 1 and 2 shown in Table 6 as examples (examples of the present invention) are manufactured by the following method.
  • the melted and re-solidified titanium slab was heated at 800 ° C. for 240 minutes using a steel facility and then hot-rolled to produce a strip coil having a thickness of about 5 mm.
  • the strip coil after hot rolling was descaled through a continuous pickling line made of nitric hydrofluoric acid.
  • cold rolling was performed to obtain a titanium plate having a thickness of 1 mm, and as an annealing treatment, heat treatment was performed by heating to 600 to 750 ° C. in a vacuum or an inert gas atmosphere and holding for 240 minutes. The cold-rolled sheet was visually observed for cracking in the surface inspection process after annealing.
  • the measuring method of the depth of the surface layers 3 and 4 is a part of the cold-rolled plate (collected from the central portion in the width direction at three locations, the front end, the center, and the rear end in the longitudinal direction).
  • the SEM / EDS analysis was performed on the cut and polished material, and the ratio of the surface layers 3 and 4 (B concentrated layer) to the plate thickness and the B concentration of the surface layers 3 and 4 (B concentrated layer) were obtained (in the observed portion). Was used).
  • a total of 20 bending specimens in the L direction were collected from the central part in the width direction at three points, the front, center and rear ends in the longitudinal direction, and bent according to JIS Z 2248 (metal material bending test method).
  • JIS Z 2248 metal material bending test method
  • a specimen having a thickness of 500 mm ⁇ 500 mm ⁇ 1 mm was fixed at a position 200 mm from the radiation source using Am-Be (4.5 MeV) as a radiation source.
  • the detector is installed at a position 300 mm from the radiation source, and the peak value of the target energy is measured for each of the radiation equivalents of the industrial test pure titanium JIS type 1 (1 mm thickness) and the test piece (1 mm thickness). From the ratio of the values, the neutron beam shielding effect was evaluated (the value of each test piece was described with the neutron beam shielding effect of 1 type of industrial pure titanium JIS being 1).
  • the comparative example of 126 is a case where the raw material containing B was not added at the time of melt re-solidification. No cracks occurred in the cold-rolled sheet, and no cracks occurred in the bending test.
  • the B concentration of the surface layers 3 and 4 exceeds 3.0%.
  • the cold-rolled sheet was partially cracked, and the rate of cracking was high in the bending test.
  • a comparative example of 128 is a case where the thickness ratio of the surface layers 3 and 4 exceeds 40%.
  • the cold-rolled sheet was partially cracked, and the rate of cracking was high in the bending test.
  • Examples 129 to 131 are cases in which the B-containing material is evaluated by changing to TiB 2 powder, Ti—B alloy tip, and Ti—B alloy wire, respectively.
  • the thickness ratio of the surface layers 3 and 4 is in the range of 5 to 40%, and the B concentration of the surface layers 3 and 4 is in the range of 0.1 to 3.0%. No cracks occurred in the plate, and no cracks occurred in the bending test.
  • Examples 132-134 examples of the present invention
  • the B-containing material was evaluated by changing to TiB 2 powder, Ti-B alloy thin film, and Ti-B alloy mesh, respectively. It is.
  • the thickness ratio of the surface layers 3 and 4 is in the range of 5 to 40%
  • the B concentration of the surface layers 3 and 4 is in the range of 0.1 to 3.0%. No cracks occurred in the plate, and no cracks occurred in the bending test.
  • Example 135 and 136 the cast skin surface of an EB melting ingot or a plasma melting ingot is cut and used, and TiB 2 powder is used as a B-containing material at the time of melting and resolidification. It is. Since the thickness ratio of the surface layers 3 and 4 is in the range of 5 to 40% and the B concentration of the surface layers 3 and 4 is in the range of 0.1 to 3.0%, both are cold-rolled sheets. No cracks occurred, and no cracks occurred in the bending test.
  • Examples 137 to 139 are cases in which various ingots are subjected to ingot rolling and the surface is cut and used, and TiB 2 powder is used as a B-containing material at the time of melt resolidification. . Since the thickness ratio of the surface layers 3 and 4 is in the range of 5 to 40% and the B concentration of the surface layers 3 and 4 is in the range of 0.1 to 3.0%, both are cold-rolled sheets. No cracks occurred, and no cracks occurred in the bending test.
  • Example 140 to 142 examples of the present invention
  • various ingots were forged and the surface was cut and used, and TiB 2 powder was used as a B-containing material at the time of melting and re-solidification. Since the thickness ratio of the surface layers 3 and 4 is in the range of 5 to 40% and the B concentration of the surface layers 3 and 4 is in the range of 0.1 to 3.0%, both are cold-rolled sheets. No cracks occurred, and no cracks occurred in the bending test.

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CN112824498A (zh) * 2019-11-21 2021-05-21 江苏和成显示科技有限公司 一种液晶组合物及其应用
CN112824491A (zh) * 2019-11-21 2021-05-21 江苏和成显示科技有限公司 一种液晶组合物及其应用
CN112824495A (zh) * 2019-11-21 2021-05-21 江苏和成显示科技有限公司 一种液晶组合物及其应用
CN114346512A (zh) * 2021-12-29 2022-04-15 西安理工大学 合金钢-不锈钢复合材料过渡层用焊丝及其制备方法

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CN112824498A (zh) * 2019-11-21 2021-05-21 江苏和成显示科技有限公司 一种液晶组合物及其应用
CN112824491A (zh) * 2019-11-21 2021-05-21 江苏和成显示科技有限公司 一种液晶组合物及其应用
CN112824495A (zh) * 2019-11-21 2021-05-21 江苏和成显示科技有限公司 一种液晶组合物及其应用
CN112824491B (zh) * 2019-11-21 2022-12-30 江苏和成显示科技有限公司 一种液晶组合物及其应用
CN112824498B (zh) * 2019-11-21 2022-12-30 江苏和成显示科技有限公司 一种液晶组合物及其应用
CN112824495B (zh) * 2019-11-21 2023-01-24 江苏和成显示科技有限公司 一种液晶组合物及其应用
CN114346512A (zh) * 2021-12-29 2022-04-15 西安理工大学 合金钢-不锈钢复合材料过渡层用焊丝及其制备方法

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