CN101295563A - Production method of MgB2 block material doped with organic matter - Google Patents

Production method of MgB2 block material doped with organic matter Download PDF

Info

Publication number
CN101295563A
CN101295563A CNA200810115718XA CN200810115718A CN101295563A CN 101295563 A CN101295563 A CN 101295563A CN A200810115718X A CNA200810115718X A CN A200810115718XA CN 200810115718 A CN200810115718 A CN 200810115718A CN 101295563 A CN101295563 A CN 101295563A
Authority
CN
China
Prior art keywords
powder
mgb2
mgb
mixed
block
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CNA200810115718XA
Other languages
Chinese (zh)
Other versions
CN101295563B (en
Inventor
张子立
索红莉
马麟
张腾
刘敏
高培阔
王朝
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenchuang Superconductor Shenzhen Technology Co ltd
Original Assignee
Beijing University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing University of Technology filed Critical Beijing University of Technology
Priority to CN200810115718XA priority Critical patent/CN101295563B/en
Publication of CN101295563A publication Critical patent/CN101295563A/en
Application granted granted Critical
Publication of CN101295563B publication Critical patent/CN101295563B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E40/00—Technologies for an efficient electrical power generation, transmission or distribution
    • Y02E40/60—Superconducting electric elements or equipment; Power systems integrating superconducting elements or equipment

Landscapes

  • Inorganic Compounds Of Heavy Metals (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

A preparation method for an MgB2 block mixed with organics belongs to the preparation filed of MgB2 superconducting material. The existing nanometer particles are mixed with MgB2 which has a high cost and is not beneficial to industrialization manufacture. The invention obtains the MgB2 block mixed with organics by adding boron metal powder with mixed powders into de-ionized water and stirring for one hour; drying the water and then fully mixing the MgB2 block mixed with organics with magnesium powder in a glove box; wherein, the mol ratio of the magnesium power to the boron metal powder is 1 to 1.1: 2; the powers of the adulterants account for 10 to 30 percent of the weight of precursor powder; then the precursor powder is pressed into a block with a pressure of 6 to 14MPa and kept for 5 minutes; finally, the temperature of the block is raised to the temperature between 600 to 900 DEG C at a temperature-raising speed of 6 DEG C/min under floating Argon gas and the temperature is persevered for one hour, and then furnace cooling is carried out to obtain the MgB2 block mixed with organics. The block of the invention has high critical current density and lower manufacture cost and is beneficial to industrialization manufacture.

Description

A kind of MgB of doped with organic matter 2The preparation method of bulk
Technical field
The invention belongs to MgB 2The superconductor preparation field is specifically related to a kind of MgB of improvement 2The method of superconductor high-field performance.
Background technology
MgB 2Be a kind of simple binary compound, be found in calendar year 2001 and have superconductivity that because its critical transition temperature is 39K, this temperature can use refrigeration machine to reach, thereby avoid using expensive liquid helium; While MgB 2There is not weak connection between crystal boundary, is easy to prepare big current delivery lead; Raw material are cheap for manufacturing cost in addition, by each superconduction research group extensive concern of the world.Use under 20～30K temperature range, low externally-applied magnetic field condition, its superconductivity has has met and exceeded the ripe at present traditional low temperature superconducting material Nb that uses 3Sn.In medical field, MgB 2Superconductor very likely replaces the Nb that the core magnet in present stage Magnetic resonance imaging (MRI) equipment uses 3The Sn superconductor, and reduce use cost greatly, have very strong competitiveness.Yet pure MgB 2Its critical current density of superconductor (J c) increasing the phenomenon that quick decline occurs with externally-applied magnetic field, this problem has greatly hindered MgB 2Superconductor application in practice.Through discovering, to MgB 2Carry out doping vario-property, artificial introduces defective and forms pinning center in superconductor, stop moving of magnetic flux line, can effectively improve MgB 2The high-field performance of superconductor improves the critical current density under its High-Field.
At present, the material that is used to mix mainly contains: 1) nano scale metal simple substance particle, as Ti, Zr, Zn and Cu etc.; 2) compound between nano level metal is as Ho 2O 3, ZrSi, ZrB 2And Si 3N 4Deng; 3) nano-scale carbon simple substance particle and carbide particle are as diamond particles, SiC, B 4C and TiC etc.Discover that nano-scale particle is compared micron particles can better improve MgB 2Therefore the critical current density of superconductor is widely used in the laboratory development.But nano-scale particle costs an arm and a leg, and can significantly improve manufacturing cost in the large-scale production of factory, can not adapt to industrial production requirement.
Summary of the invention
The objective of the invention is to solve the deficiencies in the prior art, and a kind of MgB of doped with organic matter is provided 2The preparation method of bulk.The present invention can effectively improve MgB 2The high-field performance of superconductor reduces production costs simultaneously.
The present invention adopts the polyacrylic acid zinc of non-nano level or polyacrylic acid magnesium dust and magnesium and boron powder to mix, then by forcing press with mixed-powder compression moulding, the sintering of annealing again makes the MgB of doped with organic matter 2Bulk specifically may further comprise the steps:
1) boron powder and organic blended thing powder are added in the deionized water, after stirring 1h, the oven dry transpiring moisture, obtain the mixed-powder of boron and organic blended thing, again with mixed-powder and magnesium powder in glove box, the Ar protective atmosphere is fully mixed down to obtain forerunner's powder, wherein, the mol ratio of magnesium powder and boron powder is 1～1.1: 2, and organic blended thing powder accounts for 10～30% of forerunner's powder weight;
2) the forerunner's powder that obtains in the step 1) is packed in the mould, compression moulding obtains bulk, and pressure is 6～14Mpa, keeps 5min;
3) with step 2) bulk that the obtains sintering of under mobile Ar protective atmosphere, annealing, sintering process is: be warmed up to 600～900 ℃ from room temperature, heating rate is 6 ℃/min, and temperature retention time is 1h, obtains the MgB of doped with organic matter with the stove cooling 2Bulk.
Wherein, the organic blended thing described in the step 1) is polyacrylic acid zinc or magnesium polyacrylate.
Compared with prior art, the present invention has following beneficial effect:
The present invention adopts the organic blended thing powder of non-nano level to MgB 2Superconductor mixes, and compares product with the sample that do not mix, and can increase substantially MgB 2The critical current density of bulk under 5K, under 7T, the critical current density value of doped samples is 5～9 times of doped samples not, and greatly reduces production cost.
Below in conjunction with the drawings and the specific embodiments the present invention is further described.
Description of drawings
The MgB of the polyacrylic acid zinc doping of Fig. 1, embodiment 1 preparation 2The XRD figure spectrum of bulk.
The MgB of the polyacrylic acid zinc doping of Fig. 2, embodiment 1 preparation 2The SEM picture of bulk fracture.
The MgB of the polyacrylic acid zinc doping of Fig. 3, embodiment 1 preparation 2The relation curve of critical current density and externally-applied magnetic field.
The MgB of the polyacrylic acid zinc doping of Fig. 4, embodiment 1 preparation 2The relation curve of ac magnetic susceptibility and temperature.
The MgB that the magnesium polyacrylate of Fig. 5, embodiment 2 preparations mixes 2The XRD figure spectrum of bulk.
The MgB that the magnesium polyacrylate of Fig. 6, embodiment 2 preparations mixes 2The relation curve of critical current density and externally-applied magnetic field.
The MgB of the polyacrylic acid zinc doping of Fig. 7, embodiment 3 preparations 2The relation curve of critical current density and externally-applied magnetic field.
The XRD figure stave is bright, MgB of the present invention 2Bulk has good phase composition.ESEM (SEM) is observed and is shown MgB of the present invention 2Bulk granular size homogeneous.The relation curve of critical current density and externally-applied magnetic field shows, MgB of the present invention 2Bulk has critical current density value preferably.The relation curve of ac magnetic susceptibility and temperature shows, MgB of the present invention 2Bulk has suiperconducting transition preferably.
Below in conjunction with drawings and the specific embodiments the present invention is carried out concrete description.
Embodiment
Embodiment 1
1) take by weighing Mg powder 2.764359g, B powder 2.235641g and polyacrylic acid zinc powder 0.5g respectively, boron powder and polyacrylic acid zinc powder are added in the deionized water, stir 1h, with baking oven solvent is evaporated fully subsequently, and fully mixed under the Ar protective atmosphere with the magnesium powder;
2) powder that mixes is packed in the mould, obtain bulk with forcing press compression moulding, pressure is 14Mpa, keeps 5min;
3) bulk that the obtains sintering of annealing is obtained polyacrylic acid zinc doping MgB under the Ar protective atmosphere 2Bulk, sintering process is: be warmed up to 800 ℃ from room temperature with the heating rate of 6 ℃/min, behind the insulation 1h, obtain the MgB of polyacrylic acid zinc doping with the stove cooling 2Bulk.
MgB 2The XRD figure spectrum of sample has mainly generated MgB as shown in Figure 1 as can be seen in reaction 2Phase.MgB 2The fracture apperance of sample as shown in Figure 2, SEM photo MgB as can be seen thus 2The granular size homogeneous.Fig. 3 is MgB 2The sample critical current density is with the variation of temperature curve, and the critical current density of extrapolating this wire rod by the magnetic measurement method is: 1.14 * 10 4A/cm 2(7T, 5K).Fig. 4 is MgB 2The ac magnetic susceptibility of sample and the relation curve of temperature, visible MgB 2Sample has suiperconducting transition preferably, and its superconducting transition temperature is 36.8K.
Embodiment 2
1) take by weighing Mg powder 2.646047g, B powder 2.353953g and polyacrylic acid zinc-magnesium 1g respectively, boron powder and polyacrylic acid magnesium dust are added in the deionized water, stir 1h, with baking oven solvent is evaporated fully subsequently, and fully mixed under the Ar protective atmosphere with the magnesium powder;
2) powder that mixes is packed in the mould, obtain bulk with forcing press compression moulding, pressure is 14Mpa, keeps 5min;
3) bulk that the obtains sintering of annealing is obtained magnesium polyacrylate doped with Mg B under the Ar protective atmosphere 2Bulk, sintering process is: be warmed up to 900 ℃ from room temperature with the heating rate of 6 ℃/min, behind the insulation 1h, obtain the MgB that magnesium polyacrylate mixes with the stove cooling 2Bulk.
MgB 2The XRD figure spectrum of sample has mainly generated MgB as shown in Figure 5 as can be seen in reaction 2Phase.Fig. 6 is MgB 2The sample critical current density is with the variation of temperature curve, and the critical current density of extrapolating this wire rod by the magnetic measurement method is: 9700A/cm 2(7T, 5K).
Embodiment 3
1) take by weighing Mg powder 2.764359g, B powder 2.235641g and polyacrylic acid zinc powder 1.5g respectively, boron powder and polyacrylic acid zinc powder are added in the deionized water, stir 1h, with baking oven solvent is evaporated fully subsequently, and fully mixed under the Ar protective atmosphere with the magnesium powder;
2) powder that mixes is packed in the mould, use forcing press compression moulding, pressure is 14Mpa, keeps 5mi;
3) bulk that the obtains sintering of annealing is obtained polyacrylic acid zinc doping MgB under the Ar protective atmosphere 2Bulk, sintering process is: be warmed up to 600 ℃ from room temperature with the heating rate of 6 ℃/min, behind the insulation 1h, obtain the MgB of polyacrylic acid zinc doping with the stove cooling 2Bulk.
Fig. 7 is MgB 2The sample critical current density is with the variation of temperature curve, and the critical current density of extrapolating this wire rod by the magnetic measurement method is: 5640A/cm 2(7T, 5K).

Claims (2)

1, a kind of MgB of doped with organic matter 2The preparation method of bulk is characterized in that, may further comprise the steps:
1) boron powder and organic blended thing powder are added in the deionized water, after stirring 1h, the oven dry transpiring moisture, obtain the mixed-powder of boron and organic blended thing, again with mixed-powder and magnesium powder in glove box, the Ar protective atmosphere is fully mixed down to obtain forerunner's powder, wherein, the mol ratio of magnesium powder and boron powder is 1～1.1: 2, and organic blended thing powder accounts for 10～30% of forerunner's powder weight;
2) the forerunner's powder that obtains in the step 1) is packed in the mould, compression moulding obtains bulk, and pressure is 6～14Mpa, keeps 5min;
3) with step 2) bulk that the obtains sintering of under mobile Ar protective atmosphere, annealing, sintering process is: be warmed up to 600～900 ℃ from room temperature, heating rate is 6 ℃/min, and temperature retention time is 1h, obtains the MgB of doped with organic matter with the stove cooling 2Bulk.
2, method according to claim 1 is characterized in that, the organic blended thing described in the step 1) is polyacrylic acid zinc or magnesium polyacrylate.
CN200810115718XA 2008-06-27 2008-06-27 Production method of MgB2 block material doped with organic matter Active CN101295563B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN200810115718XA CN101295563B (en) 2008-06-27 2008-06-27 Production method of MgB2 block material doped with organic matter

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN200810115718XA CN101295563B (en) 2008-06-27 2008-06-27 Production method of MgB2 block material doped with organic matter

Publications (2)

Publication Number Publication Date
CN101295563A true CN101295563A (en) 2008-10-29
CN101295563B CN101295563B (en) 2010-12-08

Family

ID=40065761

Family Applications (1)

Application Number Title Priority Date Filing Date
CN200810115718XA Active CN101295563B (en) 2008-06-27 2008-06-27 Production method of MgB2 block material doped with organic matter

Country Status (1)

Country Link
CN (1) CN101295563B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101989472A (en) * 2010-12-06 2011-03-23 西北有色金属研究院 Method for preparing core-reinforced multi-core MgB2 superconducting wires/strips
CN104774013A (en) * 2015-03-13 2015-07-15 西北工业大学 Y2O3:Eu3+ illuminant doped MgB2 superconductor with high critical transition temperature
CN105541338A (en) * 2016-01-13 2016-05-04 天津大学 Method for increasing superconducting critical current density of ex-situ magnesium diboride block through self reaction
CN106205861A (en) * 2016-06-29 2016-12-07 西北有色金属研究院 A kind of preparation method of graphene-supported multi-element doping magnesium diboride superconductive bulk
CN110229005A (en) * 2019-07-16 2019-09-13 史玉成 A kind of superconduction new material and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1988058B (en) * 2006-12-30 2010-04-14 中国科学院电工研究所 Magnesium diboride super conductive material and its preparing method

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101989472A (en) * 2010-12-06 2011-03-23 西北有色金属研究院 Method for preparing core-reinforced multi-core MgB2 superconducting wires/strips
CN104774013A (en) * 2015-03-13 2015-07-15 西北工业大学 Y2O3:Eu3+ illuminant doped MgB2 superconductor with high critical transition temperature
CN105541338A (en) * 2016-01-13 2016-05-04 天津大学 Method for increasing superconducting critical current density of ex-situ magnesium diboride block through self reaction
CN106205861A (en) * 2016-06-29 2016-12-07 西北有色金属研究院 A kind of preparation method of graphene-supported multi-element doping magnesium diboride superconductive bulk
CN106205861B (en) * 2016-06-29 2017-05-10 西北有色金属研究院 Preparation method for graphene-loaded multielement-doped magnesium diboride superconducting bulk material
CN110229005A (en) * 2019-07-16 2019-09-13 史玉成 A kind of superconduction new material and preparation method thereof
CN111943681A (en) * 2019-07-16 2020-11-17 史玉成 Method for preparing novel superconducting material
CN111943681B (en) * 2019-07-16 2022-07-22 苏州鱼得水电气科技有限公司 Method for preparing novel superconducting material

Also Published As

Publication number Publication date
CN101295563B (en) 2010-12-08

Similar Documents

Publication Publication Date Title
CN101295563B (en) Production method of MgB2 block material doped with organic matter
WO2013056526A1 (en) Method for improving upper critical field and critical current density of iron-based superconductor
CN101265099B (en) Preparation method of high-temperature superconducting material
CN102255041B (en) Preparation method of YBCO (Yttrium Barium Copper Oxide) superconducting thin film
JP2005529832A (en) Superconducting material and synthesis method
CN101279847A (en) Preparation for YBCO Superconducting bulk doped with trace rare-earth element
CN101168442B (en) High-performance MgB2 superconducting material and preparation method thereof
EP2062302A1 (en) Superconducting materials and methods of synthesis
CN104774013B (en) Y2O3:Eu3+ illuminant doped MgB2 superconductor with high critical transition temperature
CN110229005B (en) Novel superconducting material and preparation method thereof
CN114182123B (en) Fast Nb preparation method 3 Method for producing Al superconductor
CN106336220B (en) High-density MgB2Method for producing superconductor
CN102531610B (en) Glycine-doped MgB2 superconductor with high critical current density and preparation method thereof
CN101250060A (en) Method for preparing MgB2 superconductive material by using spherical magnesium powder
CN102992771A (en) Method for producing magnesium diboride-based superconducting block
CN101508571B (en) Method for producing carbon doped MgB2 cryogenic conductor by step-by-step sintering reaction
CN1264749C (en) Method for preparing MgB2 superconductive material
Jiang et al. Phase formation and superconductive properties of Cu doped MgB2 sintered with milled B powder
Yang et al. Improved superconducting properties in Ti-doped MgB2 prepared by two-step reaction method and high-energy ball milling
CN101450804A (en) Method for preparing metallic nickel nano granule doped MgB2 superconduction material by reduction method
CN102982889B (en) MgB 2superconducting line and manufacture method thereof
CN105272203A (en) Preparation method of LAO (LaAlO3) doped composite YBCO film
CN101314544A (en) Method for quickly producing MgB2 cryogenic conductor at low-temperature
CN101319380B (en) Method for rare earth 242 phase control component for growing superconducting block material
CN103021563A (en) Preparation method of Nb3Sn superconductive bulk

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20170719

Address after: 530000 Guangxi Nanning city Shuangyong Road No. 32 South Lake Garden 4-2004

Patentee after: Guo Fuliang

Address before: 100124 Chaoyang District, Beijing Ping Park, No. 100

Patentee before: Beijing University of Technology

TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20221020

Address after: A1501, Innovation Plaza, No. 2007, Pingshan Avenue, Liulian Community, Pingshan Street, Pingshan District, Shenzhen, Guangdong 518118

Patentee after: Shenchuang Superconductor (Shenzhen) Technology Co.,Ltd.

Address before: 4-2004, Nanhu Jingyuan, No. 32, Shuangyong Road, Nanning, Guangxi 530000

Patentee before: Guo Fuliang