CN103243383A - Growth method with cooling speed control of high-temperature superconducting block material - Google Patents
Growth method with cooling speed control of high-temperature superconducting block material Download PDFInfo
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- CN103243383A CN103243383A CN2013101725634A CN201310172563A CN103243383A CN 103243383 A CN103243383 A CN 103243383A CN 2013101725634 A CN2013101725634 A CN 2013101725634A CN 201310172563 A CN201310172563 A CN 201310172563A CN 103243383 A CN103243383 A CN 103243383A
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Abstract
The invention relates to a growth method with cooling speed control of a high-temperature superconducting block material. The method comprises the following steps of: (a) preparing LRE123 phase powder and LRE211 phase powder; (b) preparing a precursor; (c) placing a seed crystal on the upper surface of the precursor; (d) heating the precursor and the seed crystal in a growth furnace to a highest temperature, and performing heat preservation on the precursor and the seed crystal; and (e) rapidly cooling the precursor and the seed crystal to a peritectic reaction temperature, cooling the precursor and the seed crystal for 20h to 40h at a speed of 0.5 to 1.0 DEG C per hour, and finally quenching the precursor and the seed crystal to obtain the superconducting block material. By controlling the cooling speed of the superconducting block material in a growth process, components in a melt in the growth process are adjusted, the substitution situation of light rare earth elements and barium elements in the peritectic reaction process can be effectively inhibited, and the superconducting property of an LREBCO superconductor prepared in air can be improved.
Description
Technical field
The present invention relates to high-temperature superconductor block material field, more specifically, relate to a kind of growth method of cooling rate control high-temperature superconductor block material.
Background technology
Melting texture method (MTG) is generally believed it is a kind of preparation barium copper oxygen high-temperature superconductor block preparation methods that has potentiality.This class superconduction bulk material has many potential application, as can be used for aspects such as magnetic suspension force, magnetic bearing, flywheel energy storage and permanent magnet.Has bigger size, higher superconducting transition temperature (T and at application the requirement of bulk is generally
c) and higher critical current density (J after the match outside
c).Discover, compare with traditional yttrium barium copper oxide (YBCO) superconductor, light rare earths barium copper oxygen (LRE-BCO) superconductor, mainly comprise Nd-Ba-Cu oxygen (NdBCO) and samarium barium copper oxygen (SmBCO) superconductor, has more excellent flux pinning ability, higher critical magnetic field strength and the critical current density under High-Field.In addition, because neodymium and samarium have the high characteristic of solubleness in melt, so the preparation of this two classes superconductive block has the higher speed of growth, and this is more favourable for preparation large volume bulk.But in melting texture growing SmBCO and the NdBCO bulk process, because the Nd ion, the Sm ion is similar with the atomic radius of Ba ion in air, substituting of rare earth ion and barium ion very easily occur, forms Sm (perhaps Nd)
1+xBa
2-xCu
3O
7Solid solution, the appearance of this Solid solution has very adverse influence for superconducting transition temperature and other superconductivity of block materials.In order to address this problem, generally adopt two kinds of methods: the first, oxygen partial pressure control growth method (OCMG) by introduce low oxygen partial pressure in process of growth, can effectively suppress substituting of rare earth ion and barium ion, and then effectively suppress the formation of sosoloid.The second, precursor component control method by introduce rich barium phase in pioneer's powder, reaches the purpose that reduces solid solubility.For the former, oxygen partial pressure control growth method required equipment is relatively more expensive, and more complicated operates.For the latter, need utilize synthetic single rich barium pure phase under the solid-state sintering high temperature, cost rises.The present invention aims to provide and suppresses substituting of light rare earth ion and barium ion under a kind of air, obtains large size and high-performance light rare earths barium copper oxygen high-temperature superconductor block preparation methods.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of growth method of cooling rate control high-temperature superconductor block material is provided, the melting texture method prepares big single domain, high-performance LRE-BCO superconduction bulk material fast in air.
The thinking that the present invention solves the problems of the technologies described above is: by the cooling rate of control superconductive block between the vitellarium, realize adjusting the component in the process of growth melt, the light rare earths that occurs in the inhibition Peritectic Reaction process and the alternative case of barium element prevent LRE
1+xBa
2-xCu
3O
7The formation of (LRE-BCO or LRE123) Solid solution, the superconductivity of the LRE-BCO superconductor for preparing under the raising air.
This is because compared to slower cooling rate, when adopting faster cooling rate, and the crystalline growth time decreased of block, then melt and minimizing action time of airborne oxygen.Because the chemical valence of light rare earths (LRE) be+3 valencys, the chemical valence of barium (Ba) be+divalent, and the chemical valence of oxygen (O) be-divalent, then than slower cooling rate, and the reduction of the content of oxygen, from the angle of valency conservation, the ratio regular meeting of LRE and Ba reduction at this moment.Namely corresponding to light rare earths the alternative of barium element is suppressed, thereby in the Peritectic Reaction process, the LRE of formation
1+xBa
2-xCu
3O
7The solid solubility x of Solid solution can reduce.
In addition, in the preparation technology of traditional preparation LRE-BCO superconduction bulk material, consider that the solubleness of LRE in the barium copper melts is big, be easy to occur spontaneous nucleation in the melting texture growing process, general solution is for being induced slow cooling growth (cooling rate is less than per hour 0.3 ℃) by seed crystal.Yet, in the present invention, by introducing dystectic thin film seed material, can effectively enlarge the growth window of LRE123 phase, under the speed of growth faster, still can suppress the appearance of spontaneous nucleation, realize the preparation of large size LRE-BCO single domain bulk.
The present invention solves the problems of the technologies described above the technical scheme that adopts:
A kind of method of the cooling rate control component growth superconducting block material of growing mainly comprises following operation:
A) preparation LRE123 phase and LRE211 powder mutually;
B) preparation presoma;
C) seed crystal is placed on the upper surface of described presoma;
D) place growth furnace to carry out melting texture growing high-temperature superconductor block described presoma and seed crystal;
It is characterized in that described operation d) in melting texture growing may further comprise the steps:
E) make the temperature in the described growth furnace rise to top temperature, and insulation; Wherein said top temperature is 30-80 ℃ of the Peritectic Reaction temperature that is higher than the LRE123 phase.
F) with first cooling rate temperature in the described growth furnace is reduced to the Peritectic Reaction temperature of described high-temperature superconductor block, with per hour 0.5 ℃～1.0 ℃ speed cooling 20-40 hour, quenches at last then.
In the technique scheme, described operation a) comprising:
According to the ratio of LRE:Ba:Cu=1:2:3 with LRE
2O
3And BaCO
3, the CuO powder mixes obtains forerunner's powder of described LRE123 phase; According to the ratio of LRE:Ba:Cu=2:1:1 with LRE
2O
3And BaCO
3, the CuO powder mixes obtains forerunner's powder of described LRE211 phase;
After grinding described forerunner's powder evenly, 900 ℃ of left and right sides sintering are 48 hours in air; With gained sintered powder regrinding, sintering, this process repeats 3 times altogether then, to obtain LRE123 and the LRE211 powder of pure phase.
In the technique scheme, described operation b) be: LRE123 powder and LRE211 powder that described operation a) obtains are pressed LRE123+(10～30) mol%LRE211+(0.3～1.5) wt%CeO
2Mixed even, be pressed into columniform presoma, wherein, the mol ratio that forerunner's powder of compacting presoma can be regarded as LRE123 and LRE211 is 1:(10～30) %, CeO
2Quality be (0.3～1.5) % of LRE123 and LRE211 total mass.
In the technique scheme, described operation e) be: make the temperature in the described growth furnace in the very first time, rise to first temperature; Be incubated 2～5 hours; Make the temperature in the described growth furnace in second time, rise to second temperature, be incubated 1～2 hour;
The described very first time is 3～8 hours; Described first temperature is lower than 20-100 ℃ of described Peritectic Reaction temperature; Described second time is 1～2 hour; Described second temperature is higher than 30-80 ℃ of described Peritectic Reaction temperature
In the technique scheme, described operation f) first cooling rate in is: the temperature in the described growth furnace is reduced to described Peritectic Reaction temperature in 25 minutes.
In the technique scheme, described operation f) quenching in is: with described high-temperature superconductor block furnace cooling.
In the technique scheme, described seed crystal is the REBCO/MgO square film of c axle orientation.
In the technique scheme, described LRE is Sm or Nd.
Beneficial effect of the present invention is as follows:
1. do not introduce other element impurity in the process of growth, the performance of superconductive block is not had a negative impact;
2. need not the preparation environment of special atmosphere, technology is simple, and is low for equipment requirements, easy to operate;
3. light rare earths barium copper oxygen can have the higher speed of growth under air ambient, is applicable to that therefore preparation has the high-performance high-temperature superconductor LRE-BCO block materials of big one-domain structure.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is further described.Following examples do not constitute limitation of the invention.
The method that the present invention adopts cooling rate the to control component LRE-BCO superconductive block of growing, adjust bath component by the cooling rate in the controll block bulk-growth process, effectively the light rare earths that occurs in the inhibition Peritectic Reaction process and the alternative case of barium element prevent LRE
1+xBa
2-xCu
3O
7The formation of Solid solution, the superconductivity of the LREBCO superconductor of melting texture method preparation under the raising air.
Realize this class growth, at first will be according to LRE123+(10～30) mol%LRE211+(0.3～1.5) ratio of wt%CeO2 LRE123 and the LRE211 powder mixes that will sinter phase in advance into carry out the component batching together, after being pressed into the presoma sheet, put corresponding seed crystal material at its top, obtain the accurate single domain block materials of LRE-BCO by the heat temperature raising program.
Embodiment 1: control cooling rate growth samarium barium copper oxygen (Sm123) block materials
1, uses BaCO
3, CuO and Sm
2O
3Powder is prepared original powder according to the component ratio of Sm123 and Sm211.
2, original powder is fully ground evenly, then with powder 900 ℃ of left and right sides sintering 48 hours, for guaranteeing finally to obtain the less Sm123 of particle and Sm211 pure phase, with powder regrinding, the sintering behind the sintering, same process is triplicate altogether, obtains the pure phase of Sm123 and Sm211.
3, with the pure phase powder that obtains according to Sm123+(10～30) mol%Sm211+(0.3～1.5) the component batching of wt%CeO2, powder compression ground behind the sintering is become φ 20mm * 10mm and each a slice of the circular presoma sheet of φ 5mm * 2mm, small pieces are placed directly over the sheet, and the center of top zone is placed seed crystal and is controlled orientation.
4, forerunner's block and the square REBCO/MgO thin film seed of 2mm * 2mm are placed growth furnace.
5, be warming up to 950 ℃ in 5 hours, be incubated 3 hours; Continue heating, be warming up to 1110 ℃ in 1.5 hours, be incubated 1.5 hours.
6, in 25 minutes temperature is reduced to 1065 ℃, lowered the temperature 30 hours with per hour 0.5 ℃～1.0 ℃ speed then, quenching at last makes superconduction Sm123 block materials.
Embodiment 2: control cooling rate growth Nd-Ba-Cu oxygen (Nd123) block materials
1, uses BaCO
3, CuO and Nd
2O
3Powder is prepared original powder according to the component ratio of Nd123 and Nd422.
2, original powder is fully ground evenly, then with powder 900 ℃ of left and right sides sintering 48 hours; For guaranteeing finally to obtain the less Nd123 of particle and Nd211 pure phase, with powder regrinding, the sintering behind the sintering, same process is triplicate altogether, obtains the pure phase of Nd123 and Nd211.
3, with the pure phase powder that obtains according to Nd123+(10～30) mol%Nd211+(0.3～1.5) the component batching of wt%CeO2, powder compression ground behind the sintering is become φ 20mm * 10mm and each a slice of the circular presoma sheet of φ 5mm * 2mm, small pieces are placed directly over the sheet, and the top is placed seed crystal and is controlled orientation.
4, forerunner's block and the square REBCO/MgO thin film seed of 2mm * 2mm are placed growth furnace
5, be warming up to 950 ℃ in 5 hours, be incubated 3 hours; Continue heating, be warming up to 1115 ℃ in 1.5 hours, be incubated 1.5 hours.
6, in 25 minutes temperature is reduced to 1085 ℃, lowered the temperature 30 hours with per hour 0.5 ℃～1.0 ℃ speed then, quenching at last makes superconduction Nd123 block materials.
More than describe preferred embodiment of the present invention in detail.The ordinary skill that should be appreciated that this area need not creative work and just can design according to the present invention make many modifications and variations.Therefore, all technician in the art all should be in the determined protection domain by claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (8)
1. the growth method of cooling rate control high-temperature superconductor block material comprises following operation:
A) preparation LRE123 phase and LRE211 powder mutually;
B) preparation presoma;
C) seed crystal is placed on the upper surface of described presoma;
D) place growth furnace to carry out melting texture growing high-temperature superconductor block described presoma and seed crystal;
It is characterized in that described operation d) in melting texture growing may further comprise the steps:
E) make the temperature in the described growth furnace rise to top temperature, and insulation;
F) with first cooling rate temperature in the described growth furnace is reduced to the Peritectic Reaction temperature of described high-temperature superconductor block, with per hour 0.5 ℃～1.0 ℃ speed cooling 20-40 hour, quenches at last then.
2. cooling rate according to claim 1 is controlled the growth method of high-temperature superconductor block material, it is characterized in that described operation a) comprising:
According to the ratio of LRE:Ba:Cu=1:2:3 with LRE
2O
3, BaCO
3With the CuO powder mixes, obtain forerunner's powder of LRE123 phase; According to the ratio of LRE:Ba:Cu=2:1:1 with LRE
2O
3, BaCO
3With the CuO powder mixes, obtain forerunner's powder of LRE211 phase;
Respectively with described LRE123 mutually and after LRE211 forerunner's powder grinding mutually, 900 ℃ of sintering 48 hours and repeat 3 these grindings, sintering process in air.
3. cooling rate according to claim 1 is controlled the growth method of high-temperature superconductor block material, it is characterized in that described operation b) be: LRE123 powder and LRE211 powder that described operation a) obtains are pressed LRE123+(10～30) mol%LRE211+(0.3～1.5) wt%CeO
2Mixed even, be pressed into columniform presoma.
4. the growth method of cooling rate control high-temperature superconductor block material according to claim 1 is characterized in that described operation e) be: make the temperature in the described growth furnace in the very first time, rise to first temperature; Be incubated 2～5 hours; Make the temperature in the described growth furnace in second time, rise to second temperature, be incubated 1～2 hour;
The described very first time is 3～8 hours; Described first temperature is lower than 20-100 ℃ of described Peritectic Reaction temperature; Described second time is 1～2 hour; Described second temperature is higher than 30-80 ℃ of described Peritectic Reaction temperature.
5. the growth method of cooling rate according to claim 1 control high-temperature superconductor block material is characterized in that described operation f) in first cooling rate be: in 25 minutes, the temperature in the described growth furnace is reduced to described Peritectic Reaction temperature.
6. the growth method of cooling rate according to claim 1 control high-temperature superconductor block material is characterized in that described operation f) in quenching be: with described high-temperature superconductor block furnace cooling.
7. the growth method of cooling rate control high-temperature superconductor block material according to claim 1 is characterized in that described seed crystal is the REBCO/MgO square film of c axle orientation.
8. the growth method of cooling rate control high-temperature superconductor block material according to claim 1 is characterized in that described LRE is Sm or Nd.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104233455A (en) * | 2014-08-06 | 2014-12-24 | 上海交通大学 | Method for preparing high-temperature superconductor doped crystal |
| CN110373717A (en) * | 2019-07-12 | 2019-10-25 | 上海交通大学 | A method of REBCO high-temperature superconducting block is grown using component hierarchical control method |
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|---|---|---|---|---|
| CN1706994A (en) * | 2005-04-14 | 2005-12-14 | 上海交通大学 | Homoepitaxial superconductor lump material growing process with RE, Ba and Cu oxide film as crystal seed |
| CN101319379A (en) * | 2008-05-15 | 2008-12-10 | 上海交通大学 | Method for 45 degree rare earth barium copper oxygen thin film seed high speed growth superconducting block material |
| CN102747416A (en) * | 2012-07-13 | 2012-10-24 | 上海交通大学 | Method of oriented induced growth of REBCO superconductive block from multiple seed crystals in asymmetric(110)/(110) manner |
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2013
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1706994A (en) * | 2005-04-14 | 2005-12-14 | 上海交通大学 | Homoepitaxial superconductor lump material growing process with RE, Ba and Cu oxide film as crystal seed |
| CN101319379A (en) * | 2008-05-15 | 2008-12-10 | 上海交通大学 | Method for 45 degree rare earth barium copper oxygen thin film seed high speed growth superconducting block material |
| CN102747416A (en) * | 2012-07-13 | 2012-10-24 | 上海交通大学 | Method of oriented induced growth of REBCO superconductive block from multiple seed crystals in asymmetric(110)/(110) manner |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104233455A (en) * | 2014-08-06 | 2014-12-24 | 上海交通大学 | Method for preparing high-temperature superconductor doped crystal |
| CN104233455B (en) * | 2014-08-06 | 2017-03-08 | 上海交通大学 | A kind of method preparing high-temperature superconductor doped crystal |
| CN110373717A (en) * | 2019-07-12 | 2019-10-25 | 上海交通大学 | A method of REBCO high-temperature superconducting block is grown using component hierarchical control method |
| CN110373717B (en) * | 2019-07-12 | 2021-07-20 | 上海交通大学 | Method for growing REBCO high-temperature superconducting block by using component layering control method |
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