CN1029885C - High-temp. superconductor containing boronic oxide and preparation method thereof - Google Patents

High-temp. superconductor containing boronic oxide and preparation method thereof Download PDF

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CN1029885C
CN1029885C CN92111618A CN92111618A CN1029885C CN 1029885 C CN1029885 C CN 1029885C CN 92111618 A CN92111618 A CN 92111618A CN 92111618 A CN92111618 A CN 92111618A CN 1029885 C CN1029885 C CN 1029885C
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oxide
high temperature
crucible
boracic
superconductor
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CN1086341A (en
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朱文杰
赵忠贤
黄玉珍
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Institute of Physics of CAS
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Abstract

The present invention relates to a superconductor, more specifically high-temperature superconductors containing boronic oxide and a preparation method thereof, which is improved and has high critical temperatures (Tc) and high stability. The present invention provides the superconductors containing boronic oxide having the high critical temperatures, and the oxide has a composition formula (B<x>Cu<1-x>) (Sr<2-z>Ba<z>) RCu<2>O<y>), wherein the R in the formula is Y, La, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb. The present invention also provides a solid phase reaction method for preparing the high-temperature superconductors containing the boronic oxide; the critical transition temperature of the superconductors prepared by the method can reach from 30 to 50 k, and the superconductors prepared by the method have high stability; the diffraction analysis of x-ray is in an obvious 123 phase, and the crystal structures have layer-shaped characteristics.

Description

High-temp. superconductor containing boronic oxide and preparation method thereof
The present invention relates to a kind of superconductor.Specifically, the present invention relates to a kind of after improving, possess high-critical temperature (Tc) and high stability contain oxide superconductor of B and preparation method thereof.
Research to the superconductivity of concrete material starts from 1911, finds that at that time mercury becomes superconductor under the transition temperature of about 4 ° of K.Nineteen twenty finds that for the later stage NbC becomes superconductor at higher temperature under promptly up to about 10.5 ° of K.Tested other compound afterwards again, the superconducting transition temperature of finding various Nb compositions improves gradually but amplitude is very little.The transition temperature of observing NbN in 1940 in early days is about 14 ° of K; Then in nineteen fifty for early detection Nb 3The superconducting temperature of Sn, the later stage sixties is found Nb 3(Al-Ce) superconducting temperature, and in early detection seventies Nb 3The superconducting temperature of Ge all is about 17 ° of K, optimizes Nb meticulously 3The Ge film can improve its critical temperature, makes it reach 23.3 ° of K.Carry out though this is operated in constantly, since 3/4th century began one's study in the past, the maximum temperature that superconductivity occurs still only rose to 23.3 ° of K.Existing theory can be explained the superconductivity of these materials, but does not have to predict the superconductivity that is higher than 40 ° of K.Up to 1986, reported poly-right reduction of resistivity of special co-precipitation that makes and heat treated lanthanum, barium, copper composite oxides, found be higher than Nb 3Become superconductor under the Ge film transition temperature.
In February, 1987, we successfully prepared with M in the laboratory XR 5-XA 5O 5(3-Y)The superconductor of system, its initial transition temperature 110K, zero-resistance temperature 78.5K, mid point transition temperature 92.8K, the Ba of width of transition 4K XY 5-XCu 5O 5(3-Y)The liquid nitrogen temperature superconductor.As seen list of references (1) KEXVETONGBAO, VOl.32, NO.10(1987) 661-4; (2) number of patent application 87100997, March 2 87 year applying date.After this, reported that in the world the superconducting transition temperature that professor Zhu Jingwu of houston, u.s.a university makes superconductor is 98K.
Superconductivity is the very large phenomenon of a kind of potential using value.In the electric energy transition process, at magnet, in buoyancy monorail train and other many modem devices, this phenomenon can make thermal losses reduce to zero.So each state is all in the superconduction new material and the preparation method that make great efforts to explore higher world's transition temperature in the world.
The objective of the invention is to seek prepare transition temperature surpass above-mentioned superconduction composition critical transition temperature have a better new superconductor of superconductivity.
The object of the present invention is to provide a kind of have a high-critical temperature contain the B oxide high temperature superconductor.
Second purpose of the present invention provide a kind of can with practical methods production and have a good reproducibility contain the B oxide high temperature superconductor.
The 3rd purpose of the present invention provides a kind of being easy to by mixing behind the B-high stability oxide high temperature superconductor that easily formation contains Cu again and has layered crystal structure.
High-temperature superconductor composition of the present invention: comprising formula
(B xCu 1-X) (Sr 2-Z, Ba 2) R Cu 2The oxide of Oy.
Wherein " R " is Y, La, and Nd, Sm, Eu, Gd, Yb, Dy, Ho, Er, Tm, and be preferably Y, Er, Tm, Dy, Ho; R is 1; " X " is 0.1-0.9; " Z " is 0.0-2.0.Y ≠ 0, y is by X, and Z comes fixed.During preparation, can select the corresponding oxide of these elements for use, carbonate, nitrate, acetate are raw material as CuO, Cu(AC) 2, Cu(NO 3) 2, Sr(NO 3) 2, SrCO 3, SrO, Sr(AC) 2, Ba(NO 3) 2, BaCO 3, BaO, Ba(AC) 2, B 2O 3, H 3BO 3; R 2O 3; R is a rare earth element.And be preferably Cu:CuO;
Sr：SrCO 3;
Ba：BaCO 3
B：H 3BO 3，B 2O 3;
R：Y 2O 3，Er 2O 3，Dy 2O 3，Ho 2O 3，Tm 2O 3。
The present invention also provides a kind of solid phase reaction to prepare the solid phase reaction method that this class contains the B oxide high temperature superconductor, below describes one of its embodiment in detail, selects for use material purity more than 98.00%, to contain B, Cu, Sr by what form metering, Ba, the solid state powder compound of R, and be preferably Y 2O 3, CuO, SrCO 3, BaCO 3And H 3BO 3Abundant ground and mixed.Mixing can be carried out in sign indicating number brain mortar or ball mill, afterwards, powder is pressed into the garden sheet, and pressure is 1 ton/centimetre 2, can use stainless steel mould, when being to make the compound sintering, the compressing tablet effect fully reacts completely, and the sheet that presses is put into aluminium oxide or platinum pincers crucible, and it is interior under 900 ℃ to 1100 ℃ temperature to put Muffle furnace, and sintering is 24 hours in the air atmosphere.Heating rate is 200 ℃/hour.React completely for making, take out that the garden sheet is pulverized again, grinding, compressing tablet, put into aluminium oxide pincers crucible again, in air in 900 ℃ to 1100 ℃ following sintering 24 hours, afterwards, material annealing 12 hours in 500 ℃ of-600 ℃ of oxygen atmospheres again.
Below in conjunction with embodiment and accompanying drawing 1,2,3,4, table 1 couple the present invention be described in further detail:
Fig. 1 is sample (B 0.5Cu 0.5) Sr 2Y Cu 2O 7X-ray diffraction pattern.
Fig. 2 is sample (B xCu 1-x) Sr 2Y Cu 2O 7Lattice parameter and B content X relation.
Fig. 3 sample (B 0.5Cu 0.5) Sr 2Y Cu 2O 7Crystal structure figure.
Fig. 4 is sample (B 0.5Cu 0.5) Sr 2-ZBa zY Cu 2O 7The susceptibility curve of (Z=0.6,0.8,1.0,2.0).
Embodiment 1
Proportioning is (B 0.1Cu 0.9) Sr 1.5Ba 0.5Y Cu 2O 7, selecting commercially available purity for use is 98% Y 2O 3, CuO, SrCO 3, BaCO 3And H 3BO 3Be raw material, weight is respectively 1.354,2.766, and 2.655,1.184,0.074 gram is put and fully ground compressing tablet (φ 1cm) in yard brain mortar.The garden sheet places aluminium oxide pincers crucible, puts into Muffle furnace again.Be warming up to 950 ℃ with 200 ℃ of/hour speed, constant temperature is 24 hours in air atmosphere, take out to pulverize the compressing tablet of refacing afterwards, and sintering 24 hours in 1000 ℃ of air atmospheres cools to room temperature with the furnace again.X-ray diffraction the analysis showed that obviously has 123 to form mutually, and magnetic measurement shows that sample is superconductivity at 31K.
Embodiment 2
Proportioning is (B 0.9Cu 0.1) Sr 1.5Ba 0.5YCu 2O 7, select raw material for use, technology is with example 1, and diffraction analysis shows: sample is mainly 123 phase compositions.Showing superconducting transition temperature is 15K.
Embodiment 3
Proportioning is (B 0.5Cu 0.5) Sr 2YCu 2O 7, select raw material for use, technology is with example 1, and diffraction analysis shows, is 123 pure phases as Fig. 1 sample, not assorted peak.Magnetic measurement shows that this sample do not have a superconductivity.
Embodiment 4
Proportioning is (B 0.5Cu 0.5) Ba 2YCu 2O 7, selecting purity for use is 99% raw material Y 2O 3, CuO, BaCO 3, and H 3BO 3Match well 2 gram material by metering.Sintering process is with example 1, and sample is mainly 123 phases.But do not show superconductivity.
Embodiment 5
Proportioning is (B 0.5Cu 0.5) SrBaYCu 2O 7, selecting purity for use is 99% raw material Y 2O 3, CuO, SrCO 3, BaCO 3, H 3BO 3Preparation technology is with example 1, and just sample is at last again 600 ℃ of oxygen atmosphere annealings 12 hours.X-ray analysis shows that sample is 123 single-phase, and magnetic measurement results shows that superconducting transition temperature is 35K.(see figure 4)
Embodiment 6
Proportioning is (B 0.3Cu 0.7) Sr 0.8Ba 1.2YCu 2O 7, select raw material for use, sintering process is with example 5.X-ray analysis shows that sample is single-phase.Magnetic measurement shows that transition temperature is 50K.
Embodiment 7
The crystal structure determination of the sample of embodiment 3 is 123 phases of three layers of Ca-Ti ore type.See Fig. 3.
Embodiment 8
The sample of embodiment 5, is handled without oxygen atmosphere annealing with the stove cooling through 1000 ℃ of air atmosphere sintering, and superconducting transition temperature and original basically identical are 34K, good stability.
Embodiment 9
Proportioning is (B 0.5Cu 0.5) SrBaTmCu 2O 7, selecting raw material for use is the Tm of purity 98% 2O 3, CuO, SrCO 3, BaCO 3, H 3BO 3Sintering process is with example 5.X-ray analysis shows that sample is single-phase.Magnetic measurement show sample transition temperature is 33K.
Embodiment 10
Proportioning is (B 0.5Cu 0.5) SrBaGdCu 2O 7, selecting raw material for use is the Gd of purity 98% 2O 3, CuO, SrCO 3, BaCO 3, H 3BO 3Sintering process is with example 5.X-ray analysis shows that sample is closely for single-phase.Show significant diamagnetism at the 30K place.
Embodiment 11
Proportioning is (B 0.5Cu 0.5) SrBaHo Cu 2O 7, selecting raw material for use is the Ho of purity 98% 2O 3, CuO, SrCO 3, BaCO 3, H 3BO 3Sintering process is with example 5.X-ray analysis shows that sample is 123 single-phase.Magnetic measurement shows that sample is superconductivity at 28K.
Superconductor provided by the invention replaces the position of copper with B, and crystal structure is layer structure, and single phase property is good.The high superconducting transition temperature of material reach can 30 to 50K, and have the high stable performance, it is as shown in the table.
The method of the oxide of the high superconducting transition temperature of preparation provided by the invention is simple, is easy to repeat to produce again, and the material property of preparing is good, and is represented as accompanying drawing.
The Tc of table 1, some proportioning samples and phase composition
Composition Tc(K) magnetic transition phase composition
（B 0.1Cu 0.9）Sr 1.5Ba 0.5YCu 2O 731 123 phases, the part dephasign
（B 0.9Cu 0.1）Sr 1.5Ba 0.5YCu 2O 715 are mainly 123 phases
（B 0.5Cu 0.5）Sr 2YCu 2O 7/ 123 phases
（B 0.5Cu 0.5）Sr 2BaYCu 2O 735 123 phases
（B 0.5Cu 0.5）Sr 0.8Ba 1.2YCu 2O 738 123 phases
（B 0.3Cu 0.7）Sr 0.8Ba 1.2YCu 2 O 750 123 phases
（B 0.5Cu 0.5）Ba 2YCu 2O 7/ be mainly 123 phases
（B 0.5Cu 0.5）SrBaTmCu 2O 733 123 phases

Claims (5)

1, a kind of boracic oxide high temperature superconductor is characterized in that: comprise a kind of layered crystal structure that has, its superconducting transition temperature is 30 to 50K the boron oxide compound that contains, and composition formula is: (B xCu 1-x) (Sr 2-xBa x) RCu 2O y, wherein " R " is Y, La, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb;
R=1，
X=0.1-0.9，
Z=0.0-2.0，
Y ≠ 0, it is by X, and Z comes fixed.
2, by the described boracic oxide high temperature superconductor of claim 1, it is characterized in that: " R " is Y, La, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb in the described composition formula, and is preferably: Y, Er, Tm, Dy, Ho.
3, a kind of solid phase reaction method for preparing the described boracic oxide high temperature superconductor of claim 1 is characterized in that: select Ba, B, Cu, the corresponding oxide of Sr element for use, carbonate, nitrate, acetate are raw material, press composition formula (B xCu 1-x) (Sr 2-zBa z) RCu 2O y, R=1 wherein, X=0.1-0.9, Z=0.0-2.0; Mix earlier weighing up material, grinding, compression moulding, then the slice, thin piece of compression moulding is put into crucible, one is put in the high temperature furnace, is warmed up under 900 ℃-1100 ℃ with 200 ℃/hour programming rates, sintering is 24 hours in air atmosphere, cooling back is taken out material garden sheet and pulverized again and grind, and repressed again slabbing is put into crucible in high temperature furnace, and is another inferior to 900 ℃ of-1100 ℃ of following sintering 24 hours, afterwards, material was annealed 12 hours in 500-600 ℃ of oxygen atmosphere.
4, by the solid phase reaction method of the described preparation boracic of claim 3 oxide high temperature superconductor, it is characterized in that: the described Ba of selecting for use, B, Cu, the corresponding oxide of Sr element, carbonate, nitrate, acetate are CuO, Cu(AC) 2, Cu(NO 3) 2, Sr(NO 3) 2, SrCO 3, SrO, Sr(AC) 2, Ba(NO 3) 2, BaCO 3, BaO, Ba(AC) 2, B 2O 3, H 3BO 3; R 2O 3; R is Y 2O 3, Er 2O 3, Dy 2O 3, Ho 2O 3, Tm 2O 3
5, by the solid phase reaction method of the described preparation boracic of claim 3 oxide high temperature superconductor, it is characterized in that: described crucible is an alumina crucible, platinum crucible.
CN92111618A 1992-10-24 1992-10-24 High-temp. superconductor containing boronic oxide and preparation method thereof Expired - Fee Related CN1029885C (en)

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CN102272070B (en) * 2008-12-25 2014-12-17 株式会社根本研究所 Light-transmissive polycrystalline material and method for producing the same
RU2470864C2 (en) * 2011-03-02 2012-12-27 федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Нижегородский государственный архитектурно-строительный университет" Method of producing oxide melts having superconducting liquid properties
CN105845269A (en) * 2016-05-05 2016-08-10 成都君禾天成科技有限公司 High temperature superconducting material and method for preparing high temperature superconducting material

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