CN103243383B - A kind of cooling rate controls the growth method of high-temperature superconductor block material - Google Patents

A kind of cooling rate controls the growth method of high-temperature superconductor block material Download PDF

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CN103243383B
CN103243383B CN201310172563.4A CN201310172563A CN103243383B CN 103243383 B CN103243383 B CN 103243383B CN 201310172563 A CN201310172563 A CN 201310172563A CN 103243383 B CN103243383 B CN 103243383B
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temperature
cooling rate
powder
growth
phase
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CN103243383A (en
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姚忻
庄宇峰
彭波南
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Shanghai Jiaotong University
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Shanghai Jiaotong University
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Abstract

Cooling rate controls a growth method for high-temperature superconductor block material, comprises following operation: powder a) preparing LRE123 phase and LRE211 phase; B) presoma is prepared; C) seed crystal is placed on the upper surface of described presoma; D) described presoma and seed crystal are placed in growth furnace, are warming up to top temperature, and be incubated; E) fast temperature is reduced to Peritectic Reaction temperature, then with the speed of 0.5 DEG C ~ 1.0 DEG C per hour cooling 20-40 hour, the obtained superconduction bulk material of finally quenching.The present invention is by controlling in the cooling rate of superconductor bulk in process of growth, component in adjustment process of growth melt, the light rare earths occurred in effective suppression Peritectic Reaction process and the alternative case of barium element, the superconductivity of the LREBCO superconductor prepared under improving air.

Description

A kind of cooling rate controls the growth method of high-temperature superconductor block material
Technical field
The present invention relates to high-temperature superconductor block Material Field, more specifically, relate to the growth method that a kind of cooling rate controls high-temperature superconductor block material.
Background technology
Melting texture method (MTG) is generally considered a kind of preparation method preparing barium copper oxygen high-temperature superconductor block material of great potential.This kind of superconduction bulk material has many potential application, as can be used for the aspects such as magnetic suspension force, magnetic bearing, flywheel energy storage and permanent magnet.And be generally in the requirement of application to bulk and there is larger size, higher superconducting transition temperature (T c) and higher after the match outside critical current density (J c).Research finds, compared 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, there is 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 the melt, therefore the preparation of this two classes superconductive block has the higher speed of growth, this for preparation large volume bulk advantageously.But in atmosphere in melting texture growing SmBCO and NdBCO bulk process, due to Nd ion, Sm ion is similar with the atomic radius of Ba ion, very easily there is substituting of rare earth ion and barium ion, form Sm (or Nd) 1+xba 2-xcu 3o 7solid solution, the appearance of this Solid solution has very adverse influence for the superconducting transition temperature of block materials and other superconductivity.In order to address this problem, general adopt two kinds of methods: the first, oxygen partial pressure controls growth method (OCMG), by introducing low oxygen partial pressure in process of growth, effectively can suppress substituting of rare earth ion and barium ion, and then effectively suppressing the formation of sosoloid.The second, precursor component control method, by introducing rich barium phase in pioneer's powder, reaches the object reducing solid solubility.For the former, oxygen partial pressure controls growth method required equipment costly, and operate more complicated.For the latter, synthesize single rich barium pure phase under needing to utilize solid-state sintering high temperature, cost increase.The present invention suppresses substituting of light rare earth ion and barium ion under aiming to provide a kind of air, obtain the preparation method of large size and high performance light RE, Ba and Cu oxide high-temperature superconductor block material.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, provide a kind of cooling rate to control the growth method of high-temperature superconductor block material, melting texture method prepares large single domain, high-performance LRE-BCO superconduction bulk material fast in atmosphere.
The thinking that the present invention solves the problems of the technologies described above is: by controlling the cooling rate of superconductive block between vitellarium, realizes the component in adjustment process of growth melt, suppresses the alternative case of light rare earths and the barium element occurred in Peritectic Reaction process, prevent LRE 1+xba 2-xcu 3o 7the formation of (LRE-BCO or LRE123) Solid solution, the superconductivity of the LRE-BCO superconductor prepared under improving air.
This is because compared to slower cooling rate, when adopt faster cooling rate time, the crystal growth time of block reduces, then the oxygen in melt and air reduces action time.Chemical valence due to light rare earths (LRE) is+3 valencys, and the chemical valence of barium (Ba) is+divalent, and the chemical valence of oxygen (O) is-divalent, then compared to slower cooling rate, the content of oxygen reduces, and from the angle of valency conservation, the now ratio regular meeting of LRE and Ba reduces.Namely correspond to light rare earths to be suppressed the alternative of barium element, thus in 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 barium copper melts is large, be easy to occur spontaneous nucleation in melting texture growing process, general solution is for inducing slow cooling to grow (cooling rate is less than 0.3 DEG C per hour) by seed crystal.But, in the present invention, by introducing dystectic thin film seed material, effectively can expand 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 adopted technical scheme:
Grow the method that cooling rate control group divides growth superconducting block material, mainly comprise following operation:
A) powder of LRE123 phase and LRE211 phase is prepared;
B) presoma is prepared;
C) seed crystal is placed on the upper surface of described presoma;
D) described presoma and seed crystal are placed in growth furnace and carry out melting texture growing high-temperature superconductor block;
It is characterized in that, described operation d) in melting texture growing comprise the following steps:
E) make the temperature in described growth furnace rise to top temperature, and be incubated; Wherein said top temperature is the Peritectic Reaction temperature 30-80 DEG C higher than LRE123 phase.
F) with the first cooling rate, the temperature in described growth furnace is reduced to the Peritectic Reaction temperature of described high-temperature superconductor block, then with the speed of 0.5 DEG C ~ 1.0 DEG C per hour cooling 20-40 hour, finally quenches.
In technique scheme, described operation a) comprising:
According to the ratio of LRE:Ba:Cu=1:2:3 by LRE 2o 3and BaCO 3, CuO powder mixes, and obtains the Precursor Powder of described LRE123 phase; According to the ratio of LRE:Ba:Cu=2:1:1 by LRE 2o 3and BaCO 3, CuO powder mixes, and obtains the Precursor Powder of described LRE211 phase;
After described Precursor Powder grinding evenly, about 900 DEG C sinter 48 hours in atmosphere; Then gained sintered powder is again ground, sintered, this process repeats 3 times altogether, to obtain LRE123 and the LRE211 powder of pure phase.
In technique scheme, described operation b) be: the LRE123 powder described operation a) obtained and LRE211 powder are by LRE123+(10 ~ 30) mol%LRE211+(0.3 ~ 1.5) wt%CeO 2ratio mix, be pressed into columniform presoma, wherein, the mol ratio that the Precursor 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 technique scheme, described operation e) be: make the temperature in described growth furnace within the very first time, rise to the first temperature; Be incubated 2 ~ 5 hours; Make the temperature in described growth furnace rise to the second temperature within the second time, be incubated 1 ~ 2 hour;
The described very first time is 3 ~ 8 hours; Described first temperature is lower than described Peritectic Reaction temperature 20-100 DEG C; Described second time is 1 ~ 2 hour; Described second temperature is higher than described Peritectic Reaction temperature 30-80 DEG C
In technique scheme, described operation f) in the first cooling rate be: in 25 minutes, the temperature in described growth furnace is reduced to described Peritectic Reaction temperature.
In technique scheme, described operation f) in quenching be: by described high-temperature superconductor block furnace cooling.
In technique scheme, described seed crystal is the REBCO/MgO square film of c-axis orientation.
In 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 process of growth, the performance of superconductive block is not had a negative impact;
2. prepare environment without the need to special atmosphere, technique is simple, low for equipment requirements, easy to operate;
3. under air ambient, light rare earths barium copper oxygen can have the higher speed of growth, is therefore applicable to prepare the high-performance high-temperature superconductor LRE-BCO block materials with large one-domain structure.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is further described.Following examples do not form limitation of the invention.
The present invention adopts cooling rate to control to control the method for component to grow LRE-BCO superconductive block, by the cooling rate adjustment bath component in blocks process of growth, the light rare earths occurred in effective suppression 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 that melting texture legal system is standby under raising air.
Realize this kind of growth, first will according to LRE123+(10 ~ 30) mol%LRE211+(0.3 ~ 1.5) LRE123 and the LRE211 powder sintering phase in advance into mixes and carries out component batching by the ratio of wt%CeO2, after being pressed into forerunner's body piece, put corresponding seed crystal material at its top, obtain the accurate single domain block materials of LRE-BCO by heat temperature raising program.
Embodiment 1: control cooling rate growth samarium barium copper oxygen (Sm123) block materials
1, BaCO is used 3, CuO and Sm 2o 3powder is according to the component ratio preparation original powder of Sm123 and Sm211.
2, original powder is fully ground evenly, then powder is sintered 48 hours at about 900 DEG C, for ensureing finally to obtain less Sm123 and the Sm211 pure phase of particle, the powder after sintering is again ground, sinters, same process altogether in triplicate, obtains the pure phase of Sm123 and Sm211.
3, by obtain pure phase powder according to Sm123+(10 ~ 30) mol%Sm211+(0.3 ~ 1.5) and wt%CeO2 component batching, ground powder compression after sintering is become each a slice of the circular forerunner's body piece of φ 20mm × 10mm and φ 5mm × 2mm, be placed in by small pieces directly over sheet, top central region 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 in growth furnace.
5, within 5 hours, be warming up to 950 DEG C, be incubated 3 hours; Continue heating, within 1.5 hours, be warming up to 1110 DEG C, be incubated 1.5 hours.
6, in 25 minutes, temperature is reduced to 1065 DEG C, then lowers the temperature 30 hours with the speed of 0.5 DEG C ~ 1.0 DEG C per hour, the obtained superconduction Sm123 block materials of finally quenching.
Embodiment 2: control cooling rate growth Nd-Ba-Cu oxygen (Nd123) block materials
1, BaCO is used 3, CuO and Nd 2o 3powder is according to the component ratio preparation original powder of Nd123 and Nd422.
2, original powder is fully ground evenly, then powder is sintered 48 hours at about 900 DEG C; For ensureing finally to obtain less Nd123 and the Nd211 pure phase of particle, the powder after sintering is again ground, sintered, and same process altogether in triplicate, obtains the pure phase of Nd123 and Nd211.
3, by obtain pure phase powder according to Nd123+(10 ~ 30) mol%Nd211+(0.3 ~ 1.5) and wt%CeO2 component batching, ground powder compression after sintering is become each a slice of the circular forerunner's body piece of φ 20mm × 10mm and φ 5mm × 2mm, be placed in by small pieces directly over sheet, 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 in growth furnace
5, within 5 hours, be warming up to 950 DEG C, be incubated 3 hours; Continue heating, within 1.5 hours, be warming up to 1115 DEG C, be incubated 1.5 hours.
6, in 25 minutes, temperature is reduced to 1085 DEG C, then lowers the temperature 30 hours with the speed of 0.5 DEG C ~ 1.0 DEG C per hour, the obtained superconduction Nd123 block materials of finally quenching.
More than describe preferred embodiment of the present invention in detail.Should be appreciated that the ordinary skill of this area just design according to the present invention can make many modifications and variations without the need to creative work.Therefore, all technician in the art, all should by the determined protection domain of 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 (5)

1. cooling rate controls a growth method for high-temperature superconductor block material, comprises following operation:
A) powder of LRE123 phase and LRE211 phase is prepared;
B) presoma is prepared;
C) seed crystal is placed on the upper surface of described presoma;
D) described presoma and seed crystal are placed in growth furnace and carry out melting texture growing high-temperature superconductor block;
It is characterized in that, described operation d) in melting texture growing comprise the following steps:
E) make the temperature in described growth furnace within the very first time, rise to the first temperature; Be incubated 2 ~ 5 hours; Make the temperature in described growth furnace rise to the second temperature within the second time, be incubated 1 ~ 2 hour;
The described very first time is 3 ~ 8 hours; Described first temperature is lower than the Peritectic Reaction temperature 20-100 DEG C of described high-temperature superconductor block; Described second time is 1 ~ 2 hour; Described second temperature is higher than described Peritectic Reaction temperature 30-80 DEG C;
F) with the first cooling rate, the temperature in described growth furnace is reduced to the Peritectic Reaction temperature of described high-temperature superconductor block, then with the speed of 0.5 DEG C ~ 1.0 DEG C per hour cooling 20-40 hour, finally quenches; Described first cooling rate is: in 25 minutes, the temperature in described growth furnace is reduced to described Peritectic Reaction temperature; Described quenching is: by described high-temperature superconductor block furnace cooling.
2. cooling rate according to claim 1 controls the growth method of high-temperature superconductor block material, and it is characterized in that, described operation a) comprising:
According to the ratio of LRE:Ba:Cu=1:2:3 by LRE 2o 3, BaCO 3with the mixing of CuO powder, obtain the Precursor Powder of LRE123 phase; According to the ratio of LRE:Ba:Cu=2:1:1 by LRE 2o 3, BaCO 3with the mixing of CuO powder, obtain the Precursor Powder of LRE211 phase;
Respectively by after the grinding of the Precursor Powder of described LRE123 phase and LRE211 phase, 900 DEG C of sintering 48 hours repeat 3 these grindings, sintering process in atmosphere.
3. cooling rate according to claim 1 controls the growth method of high-temperature superconductor block material, it is characterized in that, described operation b) be: the LRE123 powder described operation a) obtained and LRE211 powder are by LRE123+ (10 ~ 30) mol%LRE211+ (0.3 ~ 1.5) wt%CeO 2ratio mix, be pressed into columniform presoma.
4. cooling rate according to claim 1 controls the growth method of high-temperature superconductor block material, and it is characterized in that, described seed crystal is the REBCO/MgO square film of c-axis orientation.
5. cooling rate according to claim 1 controls the growth method of high-temperature superconductor block material, and it is characterized in that, described LRE is Sm or Nd.
CN201310172563.4A 2013-05-10 2013-05-10 A kind of cooling rate controls the growth method of high-temperature superconductor block material Expired - Fee Related CN103243383B (en)

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CN104233455B (en) * 2014-08-06 2017-03-08 上海交通大学 A kind of method preparing high-temperature superconductor doped crystal
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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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
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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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

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* Cited by examiner, † Cited by third party
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
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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