CN1188822A - Method for preparing neodymium barium copper oxygen superconductive monocrystal - Google Patents
Method for preparing neodymium barium copper oxygen superconductive monocrystal Download PDFInfo
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- CN1188822A CN1188822A CN 97121888 CN97121888A CN1188822A CN 1188822 A CN1188822 A CN 1188822A CN 97121888 CN97121888 CN 97121888 CN 97121888 A CN97121888 A CN 97121888A CN 1188822 A CN1188822 A CN 1188822A
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Abstract
A process for preparing superconducting Nd-Ba-Cu-O monocrystal is especially suitable to prepare the inoculating crystal for growing Nd-Ba-Cu-O monosrystal, and features that the gram atomic ratio of Nd : Ba :Cu is 1 : (2+x) : 3, where x=0.2-0.8, and the monocrystal is grown by peritectic reaction and fusion growing, that is, the pressed mixture block is heated in Ba-enriching condition. Its advantages include no need of crucible, other crystal seeds and mechanical system, growing crystal in ordinary sinter furnace, low cost and high reliability.
Description
A kind of preparation method of neodymium barium copper oxygen superconductive monocrystal relates to a kind of growth method of oxide superconductor, particularly is applicable to the manufacturing of growth Nd-Ba-Cu oxygen single crystal seed crystal.
At present, prepare Nd-Ba-Cu oxygen (NdBCO) single crystal both at home and abroad and generally adopt flux growth method.The equipment complexity that these class methods are used involves great expense, and mostly needs high-purity crucible, and operating system complexity, production cost and difficulty are all very big.As in mobile melt float zone growth method, need a seed crystal rod, charging rod and flux, need an infrared radiation stove and special speculum, but also need under the low oxygen pressure condition, grow, also to control the rotating speed and the pull rate of seed crystal, operation easier is very big.In addition, in flux method for growth, often be in the Nd123 of standard proportioning, to keep excessive liquid phase, its mixture is put into high-quality crucible, melt and single crystal growing, after growth finishes, because the single crystal embedding of growth is applied on refrigerative grower and sidewall of crucible, be difficult to separate, be difficult for bonding crystalline purity like this, be difficult to grow high-quality neodymium barium copper oxygen superconductive monocrystal.The more important thing is when the seed crystal of preparation growth Yt-Ba-Cu-O superconductor, mostly take, and then it is carried out cutting, the seed crystal that the Yt-Ba-Cu-O superconductor that obtains being suitable for growing is used with the neodymium barium copper oxygen superconductive body that has prepared.On the one hand cutting technology has certain degree of difficulty, on the other hand owing to use the cutting of neodymium barium copper oxygen superconductive body crystal also to cause the raising of production cost, makes to obtain the Yt-Ba-Cu-O superconductor growth and become a technical barrier with seed crystal.
The object of the invention is to overcome the above-mentioned shortcoming that exists among the neodymium barium copper oxygen superconductive monocrystal preparation method that has, provide that a kind of preparation method is simple, production cost is low, the Nd-Ba-Cu oxygen monocrystalline superconductor of can growing effectively, particularly be applicable to the preparation method of growth Yt-Ba-Cu-O superconductor with a kind of neodymium barium copper oxygen superconductive monocrystal of seed crystal.
The objective of the invention is to be achieved through the following technical solutions.
A kind of preparation method of neodymium barium copper oxygen superconductive monocrystal comprises Nd
2O
3, BaCO
3, the CuO raw material powder mixes, calcining, grind the preparation powder, the mixed powder briquetting, crystal growth, the crystal separation process, it is characterized in that: preparation contains neodymium, barium, copper during mixed powder in the proportion material ratio (grammeatom than) is Nd: Ba: Cu=1: (2+x): 3, and x=0.2～0.8 wherein; Crystal growing process is that the mixture block behind the briquetting is heated under rich barium condition, carries out Peritectic Reaction, the melt growth crystal, and following skill condition is: mixture block is heated to 940 ℃, constant temperature sintering 10～24 hours; Be warmed up to 1150 ℃～1200 ℃ again, be incubated 0.5～3 hour; Cool the temperature to 1070 ℃～1090 ℃ then, its rate of temperature fall is 50 ℃～180 ℃/hour; Cool the temperature to 980 ℃～1040 ℃ again, its rate of temperature fall is 0.5～3/ hour; Cool the temperature to room temperature then, its rate of temperature fall is 120 ℃～300 ℃/hour and reduces to room temperature; The separation of its growing single-crystal body is at room temperature, and is from reacted mixture block, broken automatically and isolating with it by the material piece.
Because the preparation method of a kind of neodymium barium copper oxygen superconductive monocrystal of the present invention, adopt the melt growth method of barium enriched raw material proportioning, directly will prepare the honest material piece and carry out the melting growth heat treatment, do not need crucible and other seed crystal and mechanical system, in common sintering oven, can finish crystal growing process, simple to operate, economic and reliable.One secondary growth, the separable high quality neodymium copper oxygen single crystal that obtains obtaining many 2～8mm, the directly seed crystal of conduct growth big farmland district Yt-Ba-Cu-O superconductor.If it is carried out the atmosphere calcining, adjust its oxygen level, also can be used as laboratory study neodymium copper oxygen single crystal material, very economical practicality.Thereby method of the present invention is a kind of preparation method of very practical and effective neodymium barium copper oxygen superconductive monocrystal.
Below in conjunction with example to method further instruction of the present invention.
A kind of preparation method of neodymium barium copper oxygen superconductive monocrystal is at first with high-purity Nd
2O
3, BaCO
3With the CuO raw material powder, press NdBa
2+xCu
3The nominal set of dispense ratio of O, proportion material proportioning when promptly mixed powder prepares (grammeatom than) is: Nd: Ba: Cu=1: (2+x): 3, x=0.2～0.8 wherein; After ground and mixed was even, 940 ℃ of calcinings 24 hours, the powder ground and mixed of burning is even, and in air or oxygen, sintering was 24 hours in the time of 980 ℃ again in air or oxygen, got required powder after the grinding.Then the powder for preparing is pressed into bulk.Crystal growing process is that the mixture block behind the pre-briquetting is heated under rich barium condition, carries out Peritectic Reaction, the melt growth crystal, and processing condition are: mixture block is heated to 940 ℃, constant temperature sintering 10～24 hours; Be warmed up to 1150 ℃～1200 ℃ again, be incubated 0.5～3 hour; Cool the temperature to 1070 ℃～1090 ℃ then, its rate of temperature fall is 50 ℃～180 ℃/hour; Cool the temperature to 980 ℃～1040 ℃ again, its rate of temperature fall is 0.5～3/ hour; Cool the temperature to room temperature then, its rate of temperature fall is 120 ℃～300 ℃/hour and reduces to room temperature; The separation of its growing single-crystal body is at room temperature, and is from reacted mixture block, broken automatically and isolating with it by the material piece.This process is carried out in air.
Embodiment 1
With high-purity N d
2O
3, BaCO
3Prepare burden in the ratio of Nd: Ba: Cu (grammeatom than)=1: 2.5: 3 with CuO, mixing the back calcined 24 hours under 940 ℃ in air, after grinding, calcined 24 hours down at 980 ℃ again, after the grinding of the powder behind the sintering, be pressed into the bulk of 20 * 10mm, this bulk is placed on the MgO substrate, put into stove in the lump, be warming up to 950 ℃ of constant temperature 24 hours, be warming up to 1150 ℃ with 120 ℃/hour temperature rise rate again with 120/ hour speed, constant temperature 1 hour, be cooled to 1080 ℃ of constant temperature 1 hour with 60/ hour speed again, be cooled to 1000 ℃ with 1 ℃/hour speed again, be cooled to room temperature with 120 ℃/hour speed at last.After the automatic fragmentation of sample after waiting at room temperature to grow, obtained the neodymium barium copper oxygen superconductive monocrystal of 2～5mm.
Embodiment 2
With high-purity N d
2O
3BaO and CuO prepare burden in the ratio of Nd: Ba: Cu (grammeatom than)=1: 2.6: 3, mix the back in air 940 ℃ the calcining 24 hours, after grinding, calcined 24 hours down at 980 ℃ again, after the grinding of the powder behind the sintering, be pressed into the bulk of 20 * 10mm, this bulk is placed on the MgO substrate, put into stove in the lump, be warming up to 950 ℃ of constant temperature 24 hours, be warming up to 1180 ℃ with 120 ℃/hour temperature rise rate again with 120 ℃/hour speed, constant temperature 1 hour, be cooled to 1080 ℃ of constant temperature 1 hour with 60 ℃/hour speed again, be cooled to 1020 ℃ with 1 ℃/hour speed again, be cooled to room temperature with 120 ℃/hour speed at last.After the automatic fragmentation of sample after waiting at room temperature to grow, obtained the neodymium barium copper oxygen superconductive monocrystal of 2～8mm.
Embodiment 3
With the pure NdBa of X-x ray diffraction analysis x
2Cu
3O
7Prepare burden with the ratio of 1: 0.8 (mole ratio) with BaO, mixing the back calcined 24 hours in air, after grinding, calcined 24 hours down at 980 ℃ again, after the grinding of the powder behind the sintering, be pressed into the bulk of 20 * 10mm, this bulk is placed on the MgO substrate, put into stove in the lump, be warming up to 950 ℃ of constant temperature 24 hours, be warming up to 1180 ℃ with 120 ℃/hour temperature rise rate again with 120 ℃/hour speed, constant temperature 1 hour, be cooled to 1070 ℃ of constant temperature 1 hour with 60 ℃/hour speed again, be cooled to 1000 ℃ with 0.5 ℃/hour speed again, be cooled to room temperature with 120 ℃/hour speed at last.After the automatic fragmentation of sample after waiting at room temperature to grow, obtained the neodymium barium copper oxygen superconductive monocrystal of 2～8mm.
The neodymium barium copper oxygen superconductive monocrystal that the foregoing description obtained does not need any cutting, and size is to carry out physical property research and the fabulous seed crystal of single YBCO bulky crystal of growing about 2～8mm, experimental results show that very reliable.
The method has the following advantages.
(1) its crystal growth equipment only need have single heating function stove and a high temperature resistant pad Sheet does not need crucible and other mechanical system such as the MgO pad, can finish the growth of crystal Process, easy and simple to handle, with low cost.
(2) changed in the past in the technology growth of Nd BCO monocrystal in liquid phase, adopted simple Melt growth technology.
(3) monocrystal with the method preparation can natural separation go out, and quantity is many, size uniform, Be particularly suitable for doing seed crystal, growth single domain bulk YBCO superconductor.
(4) cost is low, and use properties is good, once can prepare a large amount of little cun NdBCO monocrystalline, very economical practicality.
Claims (1)
1. the preparation method of a neodymium barium copper oxygen superconductive monocrystal comprises Nd
2O
3, BaCO
3, the CuO raw material powder mixes, calcining, grind the preparation powder, the mixed powder briquetting, crystal growth, the crystal separation process is characterized in that:
The ratio (grammeatom than) that contains neodymium, barium, copper when a. preparing mixed powder in the proportion material is Nd: Ba: Cu=1: (2+x): 3, and x=0.2～0.8 wherein;
B. crystal growing process is that the mixture block behind the briquetting is heated under rich barium condition, carries out Peritectic Reaction, the melt growth crystal, and technological process and condition are: mixture block is heated to 940 ℃, constant temperature sintering 10～24 hours; Be warmed up to 1150 ℃～1200 ℃ again, be incubated 0.5～3 hour; Cool the temperature to 1070 ℃～1090 ℃ then, its rate of temperature fall is 50 ℃～180 ℃/hour; Cool the temperature to 980 ℃～1040 ℃ again, its rate of temperature fall is 0.5 ℃～3 ℃/hour; Cool the temperature to room temperature then, its rate of temperature fall is 120 ℃～300 ℃/hour and reduces to room temperature;
C. the separation of its growing single-crystal body is at room temperature, and is from reacted mixture block, broken automatically and isolating with it by the material piece.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97121888A CN1064723C (en) | 1997-12-11 | 1997-12-11 | Method for preparing neodymium barium copper oxygen superconductive monocrystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97121888A CN1064723C (en) | 1997-12-11 | 1997-12-11 | Method for preparing neodymium barium copper oxygen superconductive monocrystal |
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|---|---|
| CN1188822A true CN1188822A (en) | 1998-07-29 |
| CN1064723C CN1064723C (en) | 2001-04-18 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101861237A (en) * | 2007-11-15 | 2010-10-13 | 弗赖贝格化合物原料有限公司 | Method for dividing monocrystals |
| CN103198900A (en) * | 2012-01-05 | 2013-07-10 | 李忠让 | Preparation method of superconducting materials |
| CN105063754A (en) * | 2015-09-28 | 2015-11-18 | 天津师范大学 | Preparation method of magnesium-doped neodymium-barium-copper-oxygen large seed crystal |
| CN109943890A (en) * | 2019-03-21 | 2019-06-28 | 上海交通大学 | A method of REBCO high-temperature superconductive crystal is grown using novel precursor component |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU600156B2 (en) * | 1987-08-06 | 1990-08-02 | University Of Arkansas, The | Meltable high temperature superconductor |
-
1997
- 1997-12-11 CN CN97121888A patent/CN1064723C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101861237A (en) * | 2007-11-15 | 2010-10-13 | 弗赖贝格化合物原料有限公司 | Method for dividing monocrystals |
| US8723288B2 (en) | 2007-11-15 | 2014-05-13 | Freiberger Compound Materials Gmbh | Method of cutting single crystals |
| CN101861237B (en) * | 2007-11-15 | 2015-06-24 | 弗赖贝格化合物原料有限公司 | Method for dividing monocrystals |
| CN103198900A (en) * | 2012-01-05 | 2013-07-10 | 李忠让 | Preparation method of superconducting materials |
| CN103198900B (en) * | 2012-01-05 | 2016-05-18 | 李忠让 | A kind of preparation method of conductor material |
| CN105063754A (en) * | 2015-09-28 | 2015-11-18 | 天津师范大学 | Preparation method of magnesium-doped neodymium-barium-copper-oxygen large seed crystal |
| CN109943890A (en) * | 2019-03-21 | 2019-06-28 | 上海交通大学 | A method of REBCO high-temperature superconductive crystal is grown using novel precursor component |
| CN109943890B (en) * | 2019-03-21 | 2021-02-12 | 上海交通大学 | Method for growing REBCO high-temperature superconducting crystal by using precursor component |
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|---|---|
| CN1064723C (en) | 2001-04-18 |
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