CN1844429A - Ni-based alloy composite substrate and its melting preparation method - Google Patents

Abstract

This invention relates to a Ni radical alloy compound strip and smelt preparation method, which belongs to the high temperature coat super conduct intensified tenacity strip technique filed. The W atom percent of the surface and core of the Ni alloy compound strip are 3-7% and 9.3-12% separately. The method as follows: coldly pressing NiW alloy casting ingot whose W atom percent are 3-7% and 9.3-12% separately into one according to B-contiguous layer-A-contiguous layer-B order, in the Ar/H2 and under 750-900deg C agglomerating them for 3-8h to obtain the compound ingot, wherein B and A thickness ratio is 1: 1 to 1:4, the total thickness is 6-18mml; coldly rolling the compound ingot to obtain the radical strip whose thickness is 60-200 mum , wherein the deformation quantum is 5-20%, the total deformation quantum is more than 95%; operating anneal with the radical strip under Ar/H2 or vacuum and under 1000-1300deg C; or operating anneal under 700deg C, then rising temperature up to 1100deg C, and then operating anneal for 30-60min to obtain the Ni radical alloy compound strip. The surface and core of the radical strip is not easy to crack, it has high mechanical strength, low magnetism, and it has strong biaxial cubic organization.

Description

Ni base alloy composite baseband and smelting preparation method thereof

Technical field

The invention belongs to the high temperature coat super conduct intensified tenacity strip technique filed.

Background technology

Yttrium barium copper oxide (is YBa₂Cu₃O₇-x is abbreviated as YBCO usually) the coating high-temp superconducting tape is to be prepared from by being grown on the biaxial texture metal base band that has sealing coat.Because metal Ni is easy to form the twin shaft cubic texture, at the coating superconducting research initial stage base band materials that adopt the pure Ni of metal as the YBCO band, but pure Ni has ferromegnetism more, and yield strength is low, can not satisfy the requirement of YBCO coating superconducting base-band application fully.Chinese patent CN1740357 (open day: 2006.3.1) disclose in Ni a certain amount of W element of solid solution to address the above problem, when the atomic percentage conc of W is lower than 5% (being abbreviated as Ni5W), obtain easily strong twin shaft cubic texture, but the physical strength of base band and magnetic still can not satisfy belt material of high temperature superconduct at High-Field with the requirement of application under exchanging; And the atomic percentage conc of working as W is higher than 9.3% (being abbreviated as Ni9.3W), although the magnetic completely dissolve of base band, mechanical property also increases substantially, but the volume fraction of cubic texture sharply descends in the recrystallization texture, is difficult for the NiW alloy base band of the strong twin shaft cubic texture of preparation.In order to solve above-mentioned contradiction, Germany adopts Ni3W or Ni4.5W as outer tube respectively at 2003 (referring to document Acta Materialia 51 (2003) 4919-4927), the Ni15%Cr or Ni10%Cr1.5%Al (the being atomic percentage conc) rod that insert high strength, low magnetic therein form compound starting-ingot just as core, make composite baseband through forge hot and hot rolling then, form cubic texture by annealing at Ni3W or Ni4.5W skin at last.Although comparing pure its intensity of Ni5W alloy base band and magnetic all makes moderate progress, but this composite ingot will finally form mechanical compound alloy base band by hot rolling, just simple physics combination between the top layer of this base band and the internal layer, in the rolling and last handling process in later stage, be easy to layering and cracking, the use of hot rolling technology has had a strong impact on rolling texture in addition, the percentage composition that forms the required copper type rolling texture of recrystallize cubic texture is seriously descended, so be difficult to prepare the composite baseband of strong twin shaft cubic texture by this complex method.

Summary of the invention

The objective of the invention is Ni base alloy composite baseband by the preparation multilayered structure, solve in the existing composite baseband preparation process, top layer and sandwich layer ftracture easily, be difficult for obtaining the problem of strong twin shaft cubic texture, improve the physical strength of Ni base alloy baseband simultaneously, reduce base band magnetic, for YBCO coating superconducting band provides a kind of high strength, low magnetic, has strong twin shaft cubic texture Ni base alloy composite baseband and smelting preparation method thereof.

Ni base alloy composite baseband provided by the present invention is composited by top layer and sandwich layer, and top layer and sandwich layer are the NiW alloy that the atomic percentage conc of W is respectively 3-7% and 9.3-12%.

The smelting preparation method of Ni base alloy composite baseband provided by the present invention may further comprise the steps:

(1) proportioning raw materials and the melting of starting-ingot just

With the atomic percentage conc of W is that the atomic percentage conc of the NiW mixing pieces of 3-7% and W is that the NiW mixing pieces of 9.3-12% is smelted into NiW alloy solid solution body in 1500 ℃ respectively under vacuum condition, casting then can obtain the first starting-ingot of the Ni alloy (code name is B) of the Ni alloy (code name is A) of high W content and low W content after the forge hot;

(2) structure design and the preparation of Ni base alloy composite ingot

Is 1 with first starting-ingot B and A in the thickness ratio: 1-1: 4 ratio cuts into certain thickness fritter, according to structure as shown in Figure 1: the order of B-articulamentum-A-articulamentum-B is colded pressing and is obtained composite ingot together, the thickness of composite ingot is 6-18mm, the structure of articulamentum is: Cu paper tinsel (50 μ m)-Ag paper tinsel (150 μ m)-Cu paper tinsel (50 μ m), with the coarctate composite ingot of above-mentioned machinery at Ar/H₂In 750-900 ℃ of following sintering 3-8h, can obtain agglomerating Ni base alloy composite ingot in the mixed gas protected atmosphere;

(3) thermomechanical rolling of agglomerating composite ingot

Ni behind sintering base alloy composite ingot is carried out cold rolling, pass deformation is 2-20%, and total deflection is greater than 95%, and obtaining thickness is the cold rolling base band of 60-200 μ m;

(4) the recrystallize thermal treatment of cold rolling base band

Cold rolling base band is at Ar/H₂Under the mixed gas protected or vacuum condition in 1000-1300 ℃ of annealing 0.5-2h down; Perhaps descend annealing 30-60min, and then be warming up to 1100 ℃ of annealing 30-60min, obtain having the Ni base alloy composite baseband of twin shaft cubic texture at 700 ℃.

The present invention is an articulamentum with Cu paper tinsel-Ag paper tinsel-Cu paper tinsel, forms the chemical reaction layer by chemically sintered between the different inside and outside NiW alloy pig of W content, and they are closely adhered to together.Because the Ag fusing point is low, easy and Cu formation eutectic during low temperature, and Cu and Ni easily form sosoloid, can reduce the sintering temperature of composite ingot like this, can make between the ectonexine again and combine closely by chemical bond, solve the drawback of mechanical-physical combining method in the prior art, avoided the delamination splitting phenomenon that in follow-up thermomechanical rolling process, occurs.Can find out that from the cross section shape appearance figure (Fig. 2) of composite baseband be combined into one fully between each layer, responding layer and ectonexine interface are very clear, do not observe any cracking, show with having good binding between this composite baseband skin and the internal layer.

The present invention adopts the top layer of the NiW alloy of low W content (atomic percentage conc is less than 7.0%) as composite baseband, by having formed strong twin shaft cubic texture after the recrystallization annealing, as Fig. 3-Fig. 6, four diffraction peaks of concentrating have very much all been shown in (111) crystal face phi-scanning result on composite baseband surface, its FWHM (halfwidth degree value) shows and adopts the Ni base alloy composite baseband of the inventive method preparation to have strong twin shaft cubic texture between 7-9 °.

The present invention adopts the NiW alloy of the high W content (atomic percentage conc is greater than 9.3%) with high strength, nonmagnetic characteristics to increase the physical strength of composite baseband as sandwich layer, the yield strength value of this composite baseband sees Table 1, as shown in Table 1, the physical strength of comparing pure Ni base band and this composite baseband of Ni5W alloy base band is improved largely, yield strength value reaches as high as 225MPa, being 5.5 times of pure Ni base band yield strength value, is 1.5 times of Ni5W alloy base band yield strength value.

Adopt the magnetic hysteresis loop of the composite baseband of the inventive method preparation to the results are shown in Figure 7, as seen from the figure, under thetemperature 77K that the YBCO belt material of high temperature superconduct is used, than the also reduction greatly of magnetic of pure Ni base band and this composite baseband of Ni5W alloy base band.

Description of drawings

The multilayered structure design diagram of Fig. 1: Ni base alloy composite ingot.

The scanning electronic microscope shape appearance figure in the cross section of composite baseband among Fig. 2: theembodiment 1.

(111) face Phi-scintigram on composite baseband surface among Fig. 3: theembodiment 1.

(111) face Phi-scintigram on composite baseband surface among Fig. 4: the embodiment 2.

(111) face Phi-scintigram on composite baseband surface among Fig. 5: theembodiment 3.

(111) face Phi-scintigram on composite baseband surface among Fig. 6: the embodiment 4.

Fig. 7: composite baseband and pure Ni among the embodiment 1-4, Ni5W, the magnetic hysteresis loop of Ni9.3W alloy base band.

Embodiment

Below in conjunction with drawings and Examples the present invention is described in further details.

Embodiment 1

With the atomic percentage conc of W is that the atomic percentage conc of 5% NiW mixing pieces and W is that 9.3% NiW mixing pieces is smelted into NiW alloy solid solution body in 1500 ℃ respectively under vacuum condition, casting then, forging can obtain the initial ingot casting of the Ni alloy (code name is B) of the Ni alloy (code name is A) of high W content and low W content; Is that 1: 1 ratio cuts into certain thickness fritter with initial ingot casting B and A in the thickness ratio, and cold pressing according to the order of B-articulamentum-A-articulamentum-B obtains composite ingot together, and the thickness of composite ingot is 6mm.With the coarctate composite ingot of above-mentioned machinery at Ar/H₂In 750 ℃ of following sintering 8h, can obtain agglomerating Ni base alloy composite ingot in the mixed gas protected atmosphere; Ni behind sintering base alloy composite ingot is carried out cold rolling, pass deformation is 10-20%, and total deflection is greater than 95%, and obtaining thickness is the cold rolling base band of 160 μ m; Cold rolling base band is at Ar/H₂700 ℃ of 30min that anneal down in mixed gas protected, and then be warming up to 1100 ℃ of annealing 60min down, can obtain the Ni base alloy composite baseband.The shape appearance figure in this Ni base alloy composite baseband cross section is seen Fig. 2; (111) crystal face Phi-scanning result on surface is seen Fig. 3, and its FWHM is 7.08 °; This base band yield strength value at room temperature is 195MPa, is 4.9 times of pure Ni, 1.3 times of Ni5W.The magnetic hysteresis loop of this composite baseband is seen Fig. 7, and as seen from the figure, than pure Ni base band and Ni5W alloy base band, the magnetic of this composite baseband reduces greatly.

Embodiment 2

With the atomic percentage conc of W is that the atomic percentage conc of 5% NiW mixing pieces and W is that 12% NiW mixing pieces is smelted into NiW alloy solid solution body in 1500 ℃ respectively under vacuum condition, casting then, forging can obtain the initial ingot casting of the Ni alloy (code name is B) of the Ni alloy (code name is A) of high W content and low W content; Is that 1: 2 ratio cuts into certain thickness fritter with initial ingot casting B and A in the thickness ratio, and cold pressing according to the order of B-articulamentum-A-articulamentum-B obtains composite ingot together, and the thickness of composite ingot is 12mm.With the coarctate composite ingot of above-mentioned machinery at Ar/H₂In 900 ℃ of following sintering 3h, can obtain agglomerating Ni base alloy composite ingot in the mixed gas protected atmosphere; Ni behind sintering base alloy composite ingot is carried out cold rolling, pass deformation is 8-15%, and total deflection is greater than 95%, and obtaining thickness is the cold rolling base band of 180 μ m; Cold rolling base band is at Ar/H₂Mixed gas protected down in 1200 ℃ of 0.5h that anneal down, can obtain the Ni base alloy composite baseband.(111) crystal face Phi-scanning result on this Ni base alloy composite baseband surface is seen Fig. 4, and its FWHM is 8.42 °; This base band yield strength value at room temperature is 315MPa, is 8.0 times of pure Ni, 2.0 times of Ni5W; The magnetic hysteresis loop of this composite baseband is seen Fig. 7, and as seen from the figure, than pure Ni base band and Ni5W alloy base band, the magnetic of this composite baseband reduces greatly.

Embodiment 3

With the atomic percentage conc of W is that the atomic percentage conc of 7% NiW mixing pieces and W is that 10% NiW mixing pieces is smelted into NiW alloy solid solution body in 1500 ℃ respectively under vacuum condition, casting then, forging can obtain the initial ingot casting of the Ni alloy (code name is B) of the Ni alloy (code name is A) of high W content and low W content; Is that 1: 1 ratio cuts into certain thickness fritter with initial ingot casting B and A in the thickness ratio, and cold pressing according to the order of B-articulamentum-A-articulamentum-B obtains composite ingot together, and the thickness of composite ingot is 6mm.With the coarctate composite ingot of above-mentioned machinery at Ar/H₂In 850 ℃ of following sintering 4h, can obtain agglomerating Ni base alloy composite ingot in the mixed gas protected atmosphere; Ni behind sintering base alloy composite ingot is carried out cold rolling, pass deformation is 2-12%, and total deflection is greater than 95%, and obtaining thickness is the cold rolling base band of 200 μ m; Cold rolling base band is at Ar/H₂700 ℃ of 60min that anneal down in mixed gas protected, and then be warming up to 1100 ℃ of annealing 30min down, can obtain the Ni base alloy composite baseband.(111) crystal face Phi-scanning result on this Ni base alloy composite baseband surface is seen Fig. 5, and its FWHM is 8.63 °; This base band yield strength value at room temperature is 240MPa, is 6.0 times of pure Ni, 1.6 times of Ni5W; The magnetic hysteresis loop of this composite baseband is seen Fig. 7, and as seen from the figure, than pure Ni base band and Ni5W alloy base band, the magnetic of this composite baseband reduces greatly.

Embodiment 4

With the atomic percentage conc of W is that the atomic percentage conc of 3% NiW mixing pieces and W is that 9.3% NiW mixing pieces is smelted into NiW alloy solid solution body in 1500 ℃ respectively under vacuum condition, casting then, forging can obtain the initial ingot casting of the Ni alloy (code name is B) of the Ni alloy (code name is A) of high W content and low W content; Is that 1: 4 ratio cuts into certain thickness fritter with initial ingot casting B and A in the thickness ratio, and cold pressing according to the order of B-articulamentum-A-articulamentum-B obtains composite ingot together, and the thickness of composite ingot is 18mm.With the coarctate composite ingot of above-mentioned machinery at Ar/H₂In 800 ℃ of following sintering 6h, can obtain agglomerating Ni base alloy composite ingot in the mixed gas protected atmosphere; Ni behind sintering base alloy composite ingot is carried out cold rolling, pass deformation is 5-13%, and total deflection is greater than 95%, and obtaining thickness is the cold rolling base band of 60 μ m; Cold rolling base band is at Ar/H₂Mixed gas protected down in 1000 ℃ of 2h that anneal down, can obtain the Ni base alloy composite baseband.(111) crystal face Phi-scanning result on this Ni base alloy composite baseband surface is seen Fig. 6, and its FWHM is 8.20 °; This base band yield strength value at room temperature is 225MPa, is 5.5 times of pure Ni, 1.5 times of Ni5W; The magnetic hysteresis loop of this composite baseband is seen Fig. 7, and as seen from the figure, than pure Ni base band and Ni5W alloy base band, the magnetic of this composite baseband reduces greatly.

Table 1: composite baseband yield strength at roomtemperature

Embodiment	Embodiment

1	Embodiment 2	Embodiment 3	Embodiment 4
				Composite baseband yield strength/MPa at room temperature	195	315	240	225
It is the multiple of pure Ni base band yield strength	4.9	8.0	6.0						5.5
				It is the multiple of Ni5W alloy base band yield strength	1.3	2.1	1.6	1.5
Yield strength value/the MPa of pure Ni base band	40
		Yield strength value/the MPa of Ni5W alloy base band	150

Claims (2)

Translated fromChinese

1、一种Ni基合金复合基带，由表层和芯层复合而成，表层和芯层为W的原子百分含量分别为3-7％和9.3-12％的NiW合金。1. A Ni-based alloy composite substrate, which is composed of a surface layer and a core layer, the surface layer and the core layer are NiW alloys with W atomic percentages of 3-7% and 9.3-12% respectively.2、一种Ni基合金复合基带的熔炼制备方法，包括以下步骤：2, a kind of smelting preparation method of Ni-based alloy composite substrate, comprising the following steps:(1)原料配比与初始锭的熔炼(1) Raw material ratio and initial ingot smelting将W的原子百分含量为3-7％的NiW混合块及W的原子百分含量为9.3-12％的NiW混合块分别在真空条件下于1500℃熔炼成NiW合金固溶体，然后浇铸，热锻后即可获得高W含量的Ni合金(代号为A)和低W含量的Ni合金(代号为B)的初始锭；The NiW mixed block with 3-7 atomic percent of W and the NiW mixed block with 9.3-12 atomic percent of W were smelted under vacuum conditions at 1500° C. to form NiW alloy solid solution, and then cast, heated Initial ingots of Ni alloy with high W content (code named A) and Ni alloy with low W content (code named B) can be obtained after forging;(2)Ni基合金复合铸锭的结构设计与制备(2) Structural design and preparation of Ni-based alloy composite ingot将初始锭B和A按厚度比为1∶1-1∶4的比例切割成一定厚度的小块，按照B-连接层-A-连接层-B的顺序冷压在一起获得复合锭，复合锭的厚度是6-18mm，连接层的结构为：Cu箔(50μm)-Ag箔(150μm)-Cu箔(50μm)，将上述机械压在一起的复合锭在Ar/H₂混合气体保护气氛中于750-900℃下烧结3-8h，即可获得烧结的Ni基合金复合锭；The initial ingots B and A are cut into small pieces of a certain thickness according to the thickness ratio of 1:1-1:4, and cold pressed together in the order of B-connecting layer-A-connecting layer-B to obtain a composite ingot. The thickness of the ingot is 6-18mm, and the structure of the connection layer is: Cu foil (50μm)-Ag foil (150μm)-Cu foil (50μm), the composite ingot that is pressed together by the above machinery is placed in an Ar/H₂ mixed gas protective atmosphere Sintering at 750-900°C for 3-8h to obtain a sintered Ni-based alloy composite ingot;(3)烧结的复合锭的形变轧制(3) Deformation rolling of sintered composite ingot将烧结后的Ni基合金复合锭进行冷轧，道次变形量为2-20％，总的变形量大于95％，得到厚度为60-200μm的冷轧基带；Cold-rolling the sintered Ni-based alloy composite ingot with a deformation amount of 2-20% per pass and a total deformation amount greater than 95%, to obtain a cold-rolled base strip with a thickness of 60-200 μm;(4)冷轧基带的再结晶热处理(4) Recrystallization heat treatment of cold-rolled base strip冷轧基带在Ar/H₂混合气体保护或真空条件下于1000-1300℃下退火0.5-2h；或者在700℃下退火30-60min，然后再升温至1100℃退火30-60min，得到具有双轴立方织构的Ni基合金复合基带。The cold-rolled base strip is annealed at 1000-1300°C for 0.5-2h under the protection of Ar/H₂ mixed gas or under vacuum; or annealed at 700°C for 30-60min, and then heated to 1100°C for 30-60min to obtain a double Ni-based alloy composite substrate with axial cubic texture.

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