CN101181750A - Method for in-situ preparation of carbon coated nickel-particle doped MgB2 superconductive material - Google Patents
Method for in-situ preparation of carbon coated nickel-particle doped MgB2 superconductive material Download PDFInfo
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- CN101181750A CN101181750A CNA2007101510355A CN200710151035A CN101181750A CN 101181750 A CN101181750 A CN 101181750A CN A2007101510355 A CNA2007101510355 A CN A2007101510355A CN 200710151035 A CN200710151035 A CN 200710151035A CN 101181750 A CN101181750 A CN 101181750A
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- superconductor
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Abstract
The invention discloses an in-situ prepared MgB2 superconductor material doped with carbon-coated nickel particles. The invention is characterized by the following steps: MgB2 and Ni(NO3)2 are weighted at the weight ratio of 4-25 : 1 between MgB2 and Ni, added with distilled water, stirred, titrated with NaOH solution, and precipitated at room temperature for 3 to 12 hours; the precipitation is dried, put into a tube furnace, calcined in the protection of argon, filled with H2, heated to 500 to 700 DEG C, thermal insulated for 1 to 3 hours, filled with CH2, thermal insulated for 2 hours, and finally cooled to room temperature. The method of the invention prepares carbon and coats carbon around the nickel spheres, and equally dopes nickel into MgB2 matrix, the obtained sample has stable components and is hard to form agglomerate with obvious morphological characteristics; Ni nano-phase is in-situ introduced while C particles are introduced, and the particles can be taken as an effective magnetic-flux pinning center that is beneficial to enhancing critical current density.
Description
Technical field
The invention belongs to the superconductor technology field, relate to a kind of original position carbon doping and strengthen MgB
2The method of composite.
Background technology
People such as calendar year 2001 Japan scientist J.Nagamatsu have found a kind of new superconduction material---magnesium diboride (MgB of the 39K of having critical transition temperature
2) (J.Nagamatsu et al.Nature 410 (2001) 63), its superconducting transition temperature is the highest in the compound between simple metal up to now, this has caused the great interest of people.Compare MgB with high temperature superconducting materia
2Superconducting characteristic be not subjected to the weak influence that connects of crystal boundary, promptly high-angle boundary also can make electric current pass through that (A.Gurevichet al.Supercond.Sci.Technol 17 (2004) 278; S.X.Dou et al.J.Appl.Phys 96 (2004) 7549; Y.Zhao et al.Appl Phy Lett 79 (2001) 1154; G.Grasso et al.Appl.Phy.Lett.79 (2001) 230), therefore, can bear higher critical current density (J
c).But MgB
2The irreversible magnetic field of superconductor lower (J.H.Kim et al.Physica C 449 (2006) 133), critical current density sharply reduces with the increase of magnetic field intensity, has had a strong impact on its practical application aspect magnet.At present, the focus of people's research is exactly how to improve MgB
2The critical current density value of superconductor under the highfield.
Scientist by metallurgical technology to MgB
2Mix, to form pinning center, stop the motion of magnetic flux line, improve irreversible magnetic field, improve the physical property of material, make superconductor under certain externally-applied magnetic field, still have higher critical current density (C.H.Hsieh et al.Solid State Communications 137 (2006) 97).Wherein mainly comprising element doping and nano-particle doped, for element doping, mainly is in order to make metal simple-substance particle replacement Mg atom, still their pinning DeGrain under the highfield.Along with deepening continuously of research, the researcher finds that the nano-particle doped of non-metal simple-substance, compound and oxide can improve MgB under higher magnetic field condition
2Superconductivity.Carbide mixes and is considered in these particles MgB
2J
cValue is improved the most significant.
People such as S.X.Dou adopt the nano-particle doped MgB of SiC first
2Superconductor (S.X.Dou et al.Supercond.Sci.Technol.15 (2002) 1587), its critical current density is up to 1.4 * 10
5A/cm
2(5K, 4T).After this, people for the understanding of mixing gradually deeply explore through constantly making great efforts, and scientists finds why carbide has so high critical current density value if mixing, be because carbon atom can replace MgB
2The position of B in the lattice, thus distortion of lattice caused, and these distorted regions just can be used as the center of electron scattering, therefore can effectively improve J
c(S.X.Dou et al.Phys.Rev.Lett.98 (2007) 097002).
In general, in order to guarantee that these nano particles can guarantee that it is crucial that nano particle is evenly distributed on matrix inside as effective flux pinning center.Present doping way mainly is a mechanical mixture: grind (S.X.Dou et al.J.Appl.Phys.94 (2003) 1850), ball milling, ultrasonic dispersion (W.K.Yeoh et al.Supercond.Sci.Technol.19 (2006) L5).But owing to exist very strong Van der Waals force between nano particle, therefore be easy to form and reunite, can not be evenly distributed in the matrix mutually, do not reach the purpose of doping thereby nanoscale is mixed.On the other hand, with regard to practical application, the particle of nano-scale costs an arm and a leg, and is not suitable for large-scale industrial production.
Therefore, people want to seek a kind of effective carbon doping method, and nano particle is evenly distributed on the matrix.At present, people attempt to generate by original position the method doped with Mg B of carbon
2Superconductor, its advantage is as follows: 1. uniformity; 2. course of reaction is violent; 3. atom level doped interface cleaning, pollution-free.The Australia scientist adopts glucose to coat the B precursor powder first, is mixed with carbon doping sample MgB with the Mg powder then
2(Sihai Zhou et al.Adv.Mater.19 (2007) 1373).This method has been opened in-situ doped new page, but people's research still is in the elementary step, need constantly explore.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, a kind of in-situ preparation of carbon coated nickel-particle doped MgB is provided
2The method of superconductor.
Technical scheme of the present invention is summarized as follows:
A kind of in-situ preparation of carbon coated nickel-particle doped MgB
2The method of superconductor is made up of following step: press MgB
2: the Ni weight ratio is that 4～25: 1 ratio takes by weighing MgB
2Powder and Ni (NO
3)
26H
2The O powder is a raw material; 40～60 times the distilled water that adds described raw material weight stirs, with NaOH solution or the titration of KOH solution; after titration is intact; under room temperature, precipitate 3～12 hours, will precipitate drying, put into tube furnace; under nitrogen or argon shield; in 300～600 ℃ of calcinings 1～5 hour, reduce to room temperature, feed H again
2, flow is 10-15L/min, is warming up to 500～700 ℃, insulation 1-3h, logical CH
4Gas, flow are 10-15L/min, and insulation 2h is cooled to room temperature.
Preferably described MgB
2: the Ni weight ratio is 19: 1.
The described sedimentation time is preferably 4 hours.
Described calcining heat is preferably 400 ℃.
Described logical CH
4Temperature retention time is preferably 1 hour behind the gas.
A kind of in-situ preparation of carbon coated nickel-particle doped MgB of the present invention
2The method of superconductor, owing to be that reaction is mixed, so gained mixes that to be evenly distributed in matrix mutually inner mutually, and the gained sample constituents is stable, agglomeration can not take place, and morphological feature is obvious.Coat B doped with Mg B with glucose
2Matrix is compared, and when introducing the C particle, original position has been introduced the Ni nanophase again, and the nickel particle size of mixing is a nanoscale, can be used as effective flux pinning center; Be coated on the circumgranular carbon-coating of nickel simultaneously and can replace MgB effectively
2B atom in the matrix causes distortion of lattice, thereby can be equally as the center of flux pinning, and the influence of double action can help MgB
2The raising of superconductivity.
The present invention is by in-situ chemical method doped with Mg B
2Matrix, method is simple, and preparation cost is low, and gained mixes and is evenly distributed mutually, and size is single.Compare with traditional mechanical mixing, nano particle is evenly distributed, and does not have and reunites, for obtaining to have created precondition than high critical current densities.
Description of drawings
Fig. 1 is the prepared carbon coated nickel-particle doped MgB of method of the present invention
2The X ray diffracting spectrum of superconductor.
Fig. 2 is the prepared carbon coated nickel-particle doped MgB of method of the present invention
2The transmission photo of superconductor.
Fig. 3 is the prepared carbon coated nickel-particle doped MgB of method of the present invention
2The high-resolution transmission photo of superconductor.(Fig. 2 is the same with Fig. 3, is the multiplication factor difference, and we see except nanosphere in the drawings, and matrix is exactly MgB mutually
2Powder)
Fig. 4 is the enlarged photograph of one of them ball among Fig. 3.
The specific embodiment
The present invention is further illustrated below in conjunction with specific embodiment.
Embodiment 1
A kind of in-situ preparation of carbon coated nickel-particle doped MgB
2The method of superconductor is made up of following step: with MgB
2: Ni is 4: 1 ratio weighing MgB by weight
2Powder and Ni (NO
3)
26H
2The O powder is a raw material, and the powder after the weighing is poured in the large beaker, pours 50 times distilled water of suitable raw material weight simultaneously into, beaker is placed in the magnetic stirring apparatus stirs, and with the titration of NaOH solution, the reaction that takes place in this process is:
Ni (NO
3)
26H
2O+2NaOH=Ni (OH)
2(precipitation)+2NaNO
3
After titration is intact, beaker was placed under the room temperature precipitation 5 hours, precipitation is separated with the aqueous solution, the remaining aqueous solution is poured out, deposit MgB
2And Ni (OH)
2Be placed on the dry excessive moisture of removing in the drying box, then precipitation put into tube furnace, under nitrogen protection,, reduce to room temperature, make Ni (OH) in 400 ℃ of calcinings 2 hours
2Decompose and generate NiO;
Material after the calcining is fed H in tube furnace
2, flow is 12L/min, is incubated 1h after being warming up to 500 ℃ again, reacting in this process is NiO+H
2=H
2O+Ni, therefore the Ni as catalyst just is separated, logical then CH
4, flow is 12L/min, insulation 2h, and bolt down procedure is chilled to room temperature with stove, CH in this process
4Can under the effect of Ni, decompose generation C simple substance, thereby be coated on around the Ni, mix MgB simultaneously
2A kind of in-situ preparation of carbon coated nickel-particle doped MgB is promptly made in matrix inside
2Superconductor.
With in-situ preparation of carbon coated nickel-particle doped MgB
2Superconductor carries out X-ray diffraction analysis and finds MgB
2Still be principal phase, the while, we found the diffraction maximum of Ni owing to catalyst mixes, and a spot of MgO is inevitable.But we do not find the existence at C peak, and this is not generate carbon, but because the carbon of this moment is amorphous state, therefore do not observe in X ray.
The nickel of successfully having observed the reaction generation under transmission electron microscope is the nano particle phase, and all is no more than the spheric granules of 5nm for diameter, is distributed on the matrix this explanation matrix MgB uniformly
2The nano particle phase has been mixed in inside, and this particle can improve MgB as the center of effective flux pinning
2Superconductivity.Simultaneously by Fig. 3 we as can be seen, the dizzy existence of a circle white is all arranged, by the high-resolution photo (Fig. 4) that amplifies around each nickel ball, as can be seen, from level to level atom is arranged around the Ni ball, by measuring the interplanar distance of this material, we can be defined as carbon.C simple substance be in the effect deposit of catalyst spheres in matrix inside, and all be distributed in catalyst around, so just can judge that it is successful that original position carbon mixes.
MgB
2Can buy, also can oneself prepare, the preparation method is: is Mg: B=1 with magnesium powder (purity 99.5%) and amorphous boron powder (purity 99%) according to atomic ratio: 2 mix, and grinding mixed it in 1 hour in agate mortar, compression moulding under the pressure of 5Mpa then, compressing tablet is the cylinder of φ 4 * 2mm, the sample that suppresses is put into tube furnace, feed argon gas, the design temperature program is then: heating rate 20K/min, rise to 721 ℃, directly reduce to room temperature, promptly make the very high MgB of a kind of purity with the cooling velocity of 40K/min
2
Embodiment 2
A kind of in-situ preparation of carbon coated nickel-particle doped MgB
2The method of superconductor is made up of following step: with MgB
2: Ni is 19: 1 ratio weighing MgB by weight
2Powder and Ni (NO
3)
26H
2The O powder is a raw material; powder after the weighing is poured in the large beaker; pour 50 times distilled water of suitable raw material weight simultaneously into; beaker is placed in the magnetic stirring apparatus stirs; and with the titration of KOH solution (can also with other alkaline solution titration); after titration is intact; place under the room temperature precipitation after 3 hours in beaker; precipitation is separated with the aqueous solution; the remaining aqueous solution is poured out, precipitation is placed in the drying box puts into tube furnace behind the dry removal excessive moisture, under nitrogen protection; reduce to room temperature in 400 ℃ of calcinings after 2 hours, the material after will calcining then feeds H in tube furnace
2, flow is 10L/min, is incubated 1h after being warming up to 500 ℃ again, logical then CH
4, flow is 10L/min, insulation 2h, and bolt down procedure is chilled to room temperature with stove, promptly makes a kind of in-situ preparation of carbon coated nickel-particle doped MgB
2Superconductor.
Embodiment 3
A kind of in-situ preparation of carbon coated nickel-particle doped MgB
2The method of superconductor is made up of following step: with MgB
2: Ni is 4: 1 ratio weighing MgB by weight
2Powder and Ni (NO
3)
26H
2The O powder is a raw material; powder after the weighing is poured in the container; pour 40 times distilled water of suitable raw material weight simultaneously into; stir; and with the titration of NaOH solution; after titration is intact; place under the room temperature precipitation after 12 hours in container; precipitation is separated with the aqueous solution; the remaining aqueous solution is poured out, precipitation is placed on the dry excessive moisture of removing in the drying box, deposit is put into tube furnace under nitrogen protection; reduce to room temperature in 400 ℃ of calcinings after 2 hours, the material after will calcining then feeds H in tube furnace
2, flow is 15L/min, is incubated 1h after being warming up to 500 ℃ again, logical then CH
4, flow is 15L/min, insulation 2h, and bolt down procedure is chilled to room temperature with stove, promptly makes a kind of in-situ preparation of carbon coated nickel-particle doped MgB
2Superconductor.
Embodiment 4
A kind of in-situ preparation of carbon coated nickel-particle doped MgB
2The method of superconductor is made up of following step: with MgB
2: Ni is 4: 1 ratio weighing MgB by weight
2Powder and Ni (NO
3)
26H
2The O powder is a raw material; powder after the weighing is poured in the container; pour 60 times distilled water of suitable raw material weight simultaneously into; stir; and with or the titration of KOH solution; after titration is intact; place under the room temperature precipitation after 4 hours in container; precipitation is separated with the aqueous solution, the remaining aqueous solution is poured out, deposit is placed on the dry excessive moisture of removing in the drying box; deposit is put into tube furnace; under argon shield, reduce to room temperature in 600 ℃ of calcinings after 1 hour, the material after will calcining then feeds H in tube furnace
2, flow is 13L/min, is incubated 3h after being warming up to 700 ℃ again, logical then CH
4Flow is 13L/min, insulation 1h, and bolt down procedure is chilled to room temperature with stove, promptly makes a kind of in-situ preparation of carbon coated nickel-particle doped MgB
2Superconductor.
Embodiment 5
A kind of in-situ preparation of carbon coated nickel-particle doped MgB
2The method of superconductor is made up of following step: with MgB
2: Ni is 4: 1 ratio weighing MgB by weight
2Powder and Ni (NO
3)
26H
2The O powder is a raw material; powder after the weighing is poured in the container; pour 40 times distilled water of suitable raw material weight simultaneously into; stir; and with the titration of NaOH solution; after titration is intact; place under the room temperature precipitation after 12 hours in container; precipitation is separated with the aqueous solution, the remaining aqueous solution is poured out, deposit is placed on the dry excessive moisture of removing in the drying box; then deposit is put into tube furnace; under nitrogen protection, reduce to room temperature in 300 ℃ of calcinings after 5 hours, the material after the calcining is fed H in tube furnace
2, flow is 15L/min, is incubated 2h after being warming up to 500 ℃ again, logical then CH
4, flow is 15L/min, insulation 1h, and bolt down procedure is chilled to room temperature with stove, promptly makes a kind of in-situ preparation of carbon coated nickel-particle doped MgB
2Superconductor.
Embodiment 6
A kind of in-situ preparation of carbon coated nickel-particle doped MgB
2The method of superconductor is made up of following step: with MgB
2: Ni is 25: 1 ratio weighing MgB by weight
2Powder and Ni (NO
3)
26H
2The O powder is a raw material; powder after the weighing is poured in the container; pour 50 times distilled water of suitable raw material weight simultaneously into; stir; and with or the titration of KOH solution; after titration is intact; place under the room temperature precipitation after 6 hours in container; precipitation is separated with the aqueous solution, the remaining aqueous solution is poured out, deposit is placed on the dry excessive moisture of removing in the drying box; deposit is put into tube furnace; under argon shield, reduce to room temperature in 400 ℃ of calcinings after 2 hours, the material after will calcining then feeds H in tube furnace
2, flow is 15L/min, is incubated 2h after being warming up to 500 ℃ again, logical then CH
4, flow is 15L/min, insulation 1h, and bolt down procedure is chilled to room temperature with stove, promptly makes a kind of in-situ preparation of carbon coated nickel-particle doped MgB
2Superconductor.
Claims (5)
1. in-situ preparation of carbon coated nickel-particle doped MgB
2The method of superconductor is characterized in that being made up of following step: press MgB
2: the Ni weight ratio is that 4～25: 1 ratio takes by weighing MgB
2Powder and Ni (NO
3)
26H
2The O powder is a raw material; 40～60 times the distilled water that adds described raw material weight stirs, with NaOH solution or the titration of KOH solution; after titration is intact; under room temperature, precipitate 3～12 hours, will precipitate drying, put into tube furnace; under nitrogen or argon shield; in 300～600 ℃ of calcinings 1～5 hour, reduce to room temperature, feed H again
2, flow is 10-15L/min, is warming up to 500～700 ℃, insulation 1-3h, logical CH
4Gas, flow are 10-15L/min, and insulation 2h is cooled to room temperature.
2. a kind of in-situ preparation of carbon coated nickel-particle doped MgB according to claim 1
2The method of superconductor is characterized in that described MgB
2: the Ni weight ratio is 19: 1.
3. a kind of in-situ preparation of carbon coated nickel-particle doped MgB according to claim 1
2The method of superconductor is characterized in that the described sedimentation time is 4 hours.
4. a kind of in-situ preparation of carbon coated nickel-particle doped MgB according to claim 1
2The method of superconductor is characterized in that described calcining heat is 400 ℃.
5. a kind of in-situ preparation of carbon coated nickel-particle doped MgB according to claim 1
2The method of superconductor is characterized in that described logical CH
4Temperature retention time is 1 hour behind the gas.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101510355A CN100558489C (en) | 2007-12-14 | 2007-12-14 | In-situ preparation of carbon coated nickel-particle doped MgB 2The method of superconductor |
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|---|---|---|---|
| CNB2007101510355A CN100558489C (en) | 2007-12-14 | 2007-12-14 | In-situ preparation of carbon coated nickel-particle doped MgB 2The method of superconductor |
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| Publication Number | Publication Date |
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| CN101181750A true CN101181750A (en) | 2008-05-21 |
| CN100558489C CN100558489C (en) | 2009-11-11 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105788752A (en) * | 2016-04-05 | 2016-07-20 | 西北工业大学 | MgB2-based superconductor with increased critical transition temperature through electroluminescent excitation and preparation method thereof |
-
2007
- 2007-12-14 CN CNB2007101510355A patent/CN100558489C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105788752A (en) * | 2016-04-05 | 2016-07-20 | 西北工业大学 | MgB2-based superconductor with increased critical transition temperature through electroluminescent excitation and preparation method thereof |
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