CN106825104B - A kind of high intensity nickel-tungsten alloy base-band of strong cubic texture and preparation method thereof - Google Patents

A kind of high intensity nickel-tungsten alloy base-band of strong cubic texture and preparation method thereof Download PDF

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CN106825104B
CN106825104B CN201710056689.3A CN201710056689A CN106825104B CN 106825104 B CN106825104 B CN 106825104B CN 201710056689 A CN201710056689 A CN 201710056689A CN 106825104 B CN106825104 B CN 106825104B
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nickel
tungsten
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tungsten alloy
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CN106825104A (en
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唐亚楠
晋争
陈卫光
李成刚
潘立军
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Zhengzhou Normal University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B21MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21CMANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C37/00Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
    • B21C37/04Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of bars or wire
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/01Layered products comprising a layer of metal all layers being exclusively metallic
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • C22C1/023Alloys based on nickel
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00Electroplating characterised by the article coated
    • C25D7/06Wires; Strips; Foils
    • C25D7/0614Strips or foils

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Abstract

A kind of high intensity nickel-tungsten alloy base-band of strong cubic texture and preparation method thereof, which is:Nickel block and tungsten block are matched according to the atomic percentage content of tungsten for 5.0%~7.5%, mixing material after proportioning is placed in melting in vacuum induction melting furnace, nickel tungsten ingot casting is obtained, forging is then carried out at high temperature to alloy cast ingot and hot rolling obtains the initial billet before cold rolling;Hot rolled ingot surface scale is removed, then carries out being cold-rolled to 70~100 μ m-thicks, total deformation 88%;By above-mentioned cold rolling nickel-tungsten alloy base-band upper and lower surface electro-deposition nickel-tungsten alloy plating, the atomic percentage content of tungsten is 15%~18% in coating;Nickel-tungsten alloy base-band after electro-deposition is subjected to recrystallization annealing, concrete technology is:Heating temperature is 1120 DEG C~1170 DEG C, keeps the temperature 100~180 minutes, and heating rate is 1000 DEG C/S or more, and protective atmosphere is pure hydrogen.Product of the present invention can get strong cubic texture, and preparation process is simple, and in liquid nitrogen temperature without ferromagnetism, yield strength is higher, be convenient for following process, be suitble to industrialized production.

Description

A kind of high intensity nickel-tungsten alloy base-band of strong cubic texture and preparation method thereof
Technical field
The present invention relates to composite basebands more particularly to high intensity nickel-tungsten alloy base-band and preparation method thereof.
Background technology
Since being found as the high temperature coating superconductor of representative using YBCO, a variety of toughness gold have had been studied Belong to the based belt material as high temperature coating superconductor.In the research of second generation high temperature coating superconductor, Ni-5at.%W alloys Base band is widely used as the base material of high temperature coating superconducting tape, and epitaxial growth transition zone and superconducting layer, has been had at present More units can commercially produce Ni-5at.%W alloy base bands, since its yield strength is relatively low, has iron in liquid nitrogen temperature The shortcomings of magnetic, cannot fully meet the requirement of more application fields.
Studies have shown that when the atomic percentage content of tungsten is more than 9.3at.%, nickel-tungsten alloy base-band is in liquid nitrogen temperature iron-free Magnetism, and its yield strength at room temperature is higher, it can be difficult to being obtained in this alloy by traditional base band preparation route Obtain strong cubic texture.Then the Chinese patent application of publication number CN 1844430A prepares initial alloy billet using powder metallurgy It carries out cold rolling and annealing obtains the composite baseband of cubic texture, but base band surface quality prepared by powder metallurgy is poor, no Conducive to subsequently preparing high performance transition zone and superconducting layer, and in powder metallurgy powder preparation time it is longer, tedious process, It is also not suitable for industrialized production.
Therefore, how to obtain strong cubic texture without ferromagnetism high-strength nickel tungsten alloy base band, and how to make high intensity Nickel-tungsten alloy base-band is convenient for following process, has important practical significance and industrialized production textured metal base band faces One new challenge.
Invention content
One of the object of the invention is to provide a kind of nickel tungsten base of the strong cubic texture of no ferromagnetism, high-yield strength Band.
Another object of the present invention is to provide a kind of nickel-tungsten alloy base-band of strong cubic texture, is convenient for following process.
Another object of the present invention is to provide a kind of preparation method of the high intensity nickel-tungsten alloy base-band of strong cubic texture, with system For the nickel-tungsten alloy base-band of no ferromagnetism, high-yield strength, while base band surface being made to obtain strong cubic texture.
Another object of the present invention is to provide a kind of preparation method of the high intensity nickel-tungsten alloy base-band of strong cubic texture, makes The high intensity nickel-tungsten alloy base-band obtained is convenient for following process.
The present invention provides a kind of high intensity nickel-tungsten alloy base-band of strong cubic texture comprising upper epidermis, layer and core Layer, wherein
The upper epidermis and the layer are that tungsten atom percentage composition is 15%~18% nickel tungsten layer, and thick Degree is 5~20 μm;
The sandwich layer be cold rolling nickel-tungsten alloy base-band, tungsten atom percentage composition be 5.0%~7.5% nickel tungsten layer, And the thickness of the cold rolling nickel-tungsten alloy base-band is 70~100 μm;And
The upper epidermis and the layer are respectively in the nickel tungsten of the upper and lower surface electro-deposition of cold rolling nickel-tungsten alloy base-band Alloy layer, to which the upper epidermis, the sandwich layer and the layer are sequentially stacked to form the high-strength nickel tungsten alloy base Band.
It is preferred that the nickel-tungsten alloy base-band is carried out again after the upper epidermis described in electro-deposition and the layer The concrete technology of the nickel-tungsten alloy base-band of recrystallization annealing, the recrystallization annealing is:Heating temperature is 1120 DEG C~1170 DEG C, Heat preservation 100~180 minutes, heating rate are 1000 DEG C/S or more, and protective atmosphere is pure hydrogen.
It is preferred that the upper epidermis and the tungsten atom percentage composition of the layer are 15%.
It is preferred that the upper epidermis and the tungsten atom percentage composition of the layer are 18%.
The present invention also provides a kind of preparation methods of the high intensity nickel-tungsten alloy base-band of strong cubic texture comprising following step Suddenly:
Step 1: preparing initial nickel tungsten billet:
Nickel block and tungsten block are matched according to the atomic percentage content of tungsten for 5.0%~7.5%, by the mixing after proportioning Material is placed in melting in vacuum induction melting furnace, obtains nickel tungsten ingot casting, is then forged at high temperature to alloy cast ingot And hot rolling obtains the initial billet before cold rolling;
Step 2: carrying out cold rolling to the alloy billet after aforementioned hot rolling:
Hot rolled ingot surface scale is removed, then carries out being cold-rolled to 70~100 μ m-thicks, total deformation 88% obtains To cold rolling nickel-tungsten alloy base-band;
Step 3: to cold rolling nickel-tungsten alloy base-band surface electro-deposition nickel-tungsten alloy plating:
By the upper and lower surface electro-deposition nickel-tungsten alloy plating of the cold rolling nickel-tungsten alloy base-band, the electricity upper and lower surfaces of The thickness for depositing nickel-tungsten alloy plating is 5~20 μm, and tungsten in the electro-deposition nickel-tungsten alloy plating upper and lower surfaces of Atomic percentage content is 15%~18%;
Step 4: carrying out recrystallization annealing to the nickel-tungsten alloy base-band after aforementioned electro-deposition:
Nickel-tungsten alloy base-band after aforementioned electro-deposition is subjected to recrystallization annealing, concrete technology is:Heating temperature is 1120 DEG C~1170 DEG C, 100~180 minutes are kept the temperature, heating rate is 1000 DEG C/S or more, and protective atmosphere is pure hydrogen.
It is preferred that the purity of the nickel block and tungsten block is at least 99.99%.
It is preferred that the tungsten atom percentage composition of the electro-deposition nickel-tungsten alloy plating upper and lower surfaces of is 15%.
It is preferred that the tungsten atom percentage composition of the electro-deposition nickel-tungsten alloy plating upper and lower surfaces of is 18%.
It is preferred that concrete technology is in step 4:Heating temperature is 1150 DEG C, keeps the temperature 150 minutes, heating rate For 1000 DEG C/S or more, protective atmosphere is pure hydrogen.
It is preferred that concrete technology is in step 4:Heating temperature is 1120 DEG C, keeps the temperature 140 minutes, heating rate For 1000 DEG C/S or more, protective atmosphere is pure hydrogen.
The nickel-tungsten alloy base-band of the present invention passes through the nickel tungsten belt surface electro-deposition high W content in 70~100 μ m-thicks Nickel tungsten layer composite construction, and combine specific recrystallization annealing, formed strong cubic texture, to obtained without ferromagnetism, The nickel-tungsten alloy base-band of high-yield strength, also, the nickel-tungsten alloy base-band is convenient for subsequently preparing high performance transition zone and superconduction Layer.
Core of the invention thought is:In the nickel tungsten surface electro-deposition high W content for being easy to get strong cubic texture Nickel tungsten thin layer, during last recrystallization annealing, cube be orientated crystal grain preferentially in matrix nickel tungsten forming core and It grows up, and quickly annexes non-cubic orientation crystal grain in the alloy of outer layers deposition and further grow up, while making coating middle and high concentration Wolfram element spread into matrix alloy base band, the final strong cubic texture nickel-tungsten alloy base-band for obtaining whole high W content.
Present invention process is simple, is easy to control, and in liquid nitrogen temperature without ferromagnetism, yield strength is higher, is suitble to industrialization Production.
Description of the drawings
It will be briefly described attached drawing used in this application below, it should be apparent that, these attached drawings are only used for explaining the present invention Design.
Fig. 1 is (111) face pole figure on the alloy base band surface obtained using the preparation method of example 1 of the present invention.
Fig. 2 is (111) face pole figure on the alloy base band surface obtained using the preparation method of example 2 of the present invention.
Specific implementation mode
The embodiment of high intensity nickel-tungsten alloy base-band of strong cubic texture of the present invention and preparation method thereof is described below.
The embodiment recorded herein is the specific specific implementation mode of the present invention, for illustrating design of the invention, It is explanatory and illustrative, should not be construed as the limitation to embodiment of the present invention and the scope of the invention.Except what is recorded herein Outside embodiment, those skilled in the art can also based on the application claims and specification disclosure of that using aobvious and The other technical solutions being clear to, these technical solutions include to the embodiment recorded herein make it is any it is obvious replacement and The technical solution of modification.
The nickel-tungsten alloy base-band of the present invention includes upper epidermis, layer and sandwich layer, and upper epidermis and layer are tungsten atom Percentage composition is 15%~18% nickel tungsten layer, and thickness is 5~20 μm, and sandwich layer is that tungsten atom percentage composition is 5.0%~7.5% nickel tungsten layer, upper epidermis and layer are respectively in the upper and lower surface of cold rolling nickel-tungsten alloy base-band electricity The nickel-tungsten alloy plating of deposition, to which upper epidermis, sandwich layer and layer are sequentially stacked the high-strength nickel tungsten to form strong cubic texture Alloy base band.
Also, in the present invention, it is preferred that, the nickel-tungsten alloy base-band is the upper epidermis described in electro-deposition and institute The nickel-tungsten alloy base-band for carrying out recrystallization annealing after layer again is stated, the concrete technology of the recrystallization annealing is:Heating temperature It is 1120 DEG C~1170 DEG C, keeps the temperature 100~180 minutes, heating rate is 1000 DEG C/S or more, and protective atmosphere is pure hydrogen.
The example of the preparation method of the present invention is described below.
Example 1
The step of example 1, is as follows:
Nickel block and tungsten block are matched according to the atomic percentage content of tungsten for 5.0%, the mixing material after proportioning is set The melting in vacuum induction melting furnace obtains nickel tungsten ingot casting, then carries out forging and hot rolling at high temperature to alloy cast ingot Obtain the initial billet before cold rolling;
Hot rolled ingot surface scale is removed, then carries out being cold-rolled to 70~100 μ m-thicks, total deformation 88%;
Thickness by above-mentioned cold rolling nickel-tungsten alloy base-band upper and lower surface electro-deposition nickel-tungsten alloy plating, coating is 5~20 μ M, and the atomic percentage content of tungsten is 18% in coating;And
Nickel-tungsten alloy base-band after electro-deposition is subjected to recrystallization annealing, concrete technology is:Heating temperature is 1150 DEG C, is protected Temperature 150 minutes, heating rate are 1000 DEG C/S or more, and protective atmosphere is pure hydrogen.
Preferably, the purity of the nickel block and tungsten block is at least 99.99%, for example, 99.999%.
(111) the face pole figure on the exemplary alloy base band surface as shown in Figure 1, its to illustrate that the base band surface obtains strong Cubic texture, and yield strength at room temperature has reached 300MPa, is suitble to the application in more areas.
Example 2
The step of example 2, is as follows:
Nickel block and tungsten block are matched according to the atomic percentage content of tungsten for 7.5%, the mixing material after proportioning is set The melting in vacuum induction melting furnace obtains nickel tungsten ingot casting, then carries out forging and hot rolling at high temperature to alloy cast ingot Obtain the initial billet before cold rolling;
Hot rolled ingot surface scale is removed, then carries out being cold-rolled to 70~100 μ m-thicks, total deformation 88%;
Thickness by above-mentioned cold rolling nickel-tungsten alloy base-band upper and lower surface electro-deposition nickel-tungsten alloy plating, coating is 5~20 μ M, and the atomic percentage content of tungsten is 18% in coating;And
Nickel-tungsten alloy base-band after electro-deposition is subjected to recrystallization annealing, concrete technology is:Heating temperature is 1120 DEG C, is protected Temperature 140 minutes, heating rate are 1000 DEG C/S or more, and protective atmosphere is pure hydrogen.
Preferably, the purity of the nickel block and tungsten block is at least 99.99%, for example, 99.999%.
(111) the face pole figure on the exemplary alloy base band surface is as shown in Fig. 2, illustrate that the base band surface obtains strong stand Square texture, and yield strength at room temperature has reached 330MPa, is suitble to the application in more areas.
In high temperature coating superconductor field, that there are yield strengths is relatively low for Ni-5at.%W alloy base bands, has in liquid nitrogen temperature There is ferromagnetism.Although composite baseband prepared by powder metallurgy can obtain cubic texture, base band surface quality is poor, no Conducive to subsequently preparing high performance transition zone and superconducting layer, and in powder metallurgy powder preparation time it is longer, tedious process, It is also not suitable for industrialized production.
The present invention is optimized the alloying component of upper epidermis, layer and sandwich layer and devises special composite junction Structure, designing specific alloying component and specific structure can preferably utilize atoms permeating to realize better interface binding power, and And the formation of cubic texture is more advantageous to by the interfacial effect between ectonexine under special component, it is functional to obtain Nickel-tungsten alloy base-band, and create new nickel-tungsten alloy base-band manufacturing process.
Specifically, nickel-tungsten alloy base-band of the invention is high by the nickel tungsten belt surface electro-deposition at 70~100 μm The nickel tungsten layer composite construction of W content, and specific recrystallization annealing is combined, strong cubic texture is formed, to obtain nothing The nickel-tungsten alloy base-band of ferromagnetism, high-yield strength, also, the nickel-tungsten alloy base-band is convenient for subsequently preparing high performance transition zone And superconducting layer.
On the other hand, method of the invention is in the nickel tungsten surface electro-deposition high W content for being easy to get strong cubic texture Nickel tungsten thin layer cube be orientated the preferential forming core in matrix nickel tungsten of crystal grain during last recrystallization annealing And grow up, and quickly annex non-cubic orientation crystal grain in the alloy of outer layers deposition and further grow up, while making highly concentrated in coating The wolfram element of degree is spread into matrix alloy base band, the final strong cubic texture nickel-tungsten alloy base-band for obtaining whole high W content.
Above to the embodiment of the high intensity nickel-tungsten alloy base-band of strong cubic texture and preparation method thereof of the present invention into Explanation is gone.It should be understood that the above-mentioned specific implementation mode of the present invention is used only for exemplary illustration or explains the present invention Principle, but not to limit the present invention.Therefore, that is done without departing from spirit and scope of the present invention appoints What modification, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.In addition, appended claims of the present invention Whole variations for being intended to cover to fall into attached claim scope and boundary or this range and the equivalent form on boundary and Modification.

Claims (10)

1. a kind of high intensity nickel-tungsten alloy base-band of strong cubic texture, which includes upper epidermis, layer and core Layer, wherein
The upper epidermis and the layer are that tungsten atom percentage composition is 15%~18% nickel tungsten layer, and thickness is equal It is 5~20 μm;
The sandwich layer be cold rolling nickel-tungsten alloy base-band, tungsten atom percentage composition be 5.0%~7.5% nickel tungsten layer, and The thickness of the cold rolling nickel-tungsten alloy base-band is 70~100 μm;And
The upper epidermis and the layer are respectively in the nickel tungsten of the upper and lower surface electro-deposition of cold rolling nickel-tungsten alloy base-band Coating, to which the upper epidermis, the sandwich layer and the layer are sequentially stacked to form the high intensity nickel-tungsten alloy base-band.
2. high intensity nickel-tungsten alloy base-band according to claim 1, wherein the nickel-tungsten alloy base-band is in electro-deposition institute State the nickel-tungsten alloy base-band for carrying out recrystallization annealing after upper epidermis and the layer again, the concrete technology of the recrystallization annealing For:Heating temperature is 1120 DEG C~1170 DEG C, keeps the temperature 100~180 minutes, and heating rate is 1000 DEG C/S or more, protective atmosphere For pure hydrogen.
3. high intensity nickel-tungsten alloy base-band according to claim 1, wherein the upper epidermis and the tungsten of the layer are former Sub- percentage composition is 15%.
4. high intensity nickel-tungsten alloy base-band according to claim 1, wherein the upper epidermis and the tungsten of the layer are former Sub- percentage composition is 18%.
5. a kind of preparation method of the high intensity nickel-tungsten alloy base-band of strong cubic texture, includes the following steps:
Step 1: preparing initial nickel tungsten billet:
Nickel block and tungsten block are matched according to the atomic percentage content of tungsten for 5.0%~7.5%, by the mixing material after proportioning It is placed in melting in vacuum induction melting furnace, obtains nickel tungsten ingot casting, then carries out forging and heat at high temperature to alloy cast ingot Roll the initial billet before obtaining cold rolling;
Step 2: carrying out cold rolling to the alloy billet after aforementioned hot rolling:
Hot rolled ingot surface scale is removed, then carries out being cold-rolled to 70~100 μ m-thicks, total deformation 88% obtains cold Roll nickel-tungsten alloy base-band;
Step 3: to cold rolling nickel-tungsten alloy base-band surface electro-deposition nickel-tungsten alloy plating:
By the upper and lower surface electro-deposition nickel-tungsten alloy plating of the cold rolling nickel-tungsten alloy base-band, the electro-deposition upper and lower surfaces of The thickness of nickel-tungsten alloy plating is 5~20 μm, and in the electro-deposition nickel-tungsten alloy plating upper and lower surfaces of tungsten atom Percentage composition is 15%~18%;
Step 4: carrying out recrystallization annealing to the nickel-tungsten alloy base-band after aforementioned electro-deposition:
Nickel-tungsten alloy base-band after aforementioned electro-deposition is subjected to recrystallization annealing, concrete technology is:Heating temperature be 1120 DEG C~ 1170 DEG C, 100~180 minutes are kept the temperature, heating rate is 1000 DEG C/S or more, and protective atmosphere is pure hydrogen.
6. the preparation method of high intensity nickel-tungsten alloy base-band according to claim 5, wherein the nickel block and the tungsten block Purity be at least 99.99%.
7. the preparation method of high intensity nickel-tungsten alloy base-band according to claim 5, wherein the electricity upper and lower surfaces of The tungsten atom percentage composition for depositing nickel-tungsten alloy plating is 15%.
8. the preparation method of high intensity nickel-tungsten alloy base-band according to claim 5, wherein the electricity upper and lower surfaces of The tungsten atom percentage composition for depositing nickel-tungsten alloy plating is 18%.
9. the preparation method of high intensity nickel-tungsten alloy base-band according to claim 5, wherein concrete technology in step 4 For:Heating temperature is 1150 DEG C, keeps the temperature 150 minutes, and heating rate is 1000 DEG C/S or more, and protective atmosphere is pure hydrogen.
10. the preparation method of high intensity nickel-tungsten alloy base-band according to claim 5, wherein concrete technology in step 4 For:Heating temperature is 1120 DEG C, keeps the temperature 140 minutes, and heating rate is 1000 DEG C/S or more, and protective atmosphere is pure hydrogen.
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CN108385135B (en) * 2018-05-03 2020-03-13 北京工业大学 Method for preparing high-tungsten alloy base band billet for coated conductor through electrochemical deposition
CN109576644A (en) * 2018-12-14 2019-04-05 北京工业大学 A kind of method of prepares coating conductor high-tungsten alloy base band
CN109576744B (en) * 2018-12-14 2020-09-25 北京工业大学 Method for preparing texture nickel-based high-tungsten alloy base band for coated conductor by diffusion method
CN109576749B (en) * 2018-12-17 2021-02-02 河南师范大学 Novel strong cubic texture metal base band and preparation method thereof
CN109371284B (en) * 2018-12-17 2020-11-03 河南师范大学 High-performance cubic texture metal base band and preparation method thereof
CN111139505A (en) * 2019-12-30 2020-05-12 河南师范大学 Preparation method of nickel-tungsten composite base band with cubic texture
CN111180134A (en) * 2020-01-16 2020-05-19 河南城建学院 Preparation method of strong cubic texture metal composite strip

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