CN102615280A - Method for manufacturing iron-based superconductor by using SPS (Spark Plasma Sintering) technology - Google Patents
Method for manufacturing iron-based superconductor by using SPS (Spark Plasma Sintering) technology Download PDFInfo
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- CN102615280A CN102615280A CN2012100823885A CN201210082388A CN102615280A CN 102615280 A CN102615280 A CN 102615280A CN 2012100823885 A CN2012100823885 A CN 2012100823885A CN 201210082388 A CN201210082388 A CN 201210082388A CN 102615280 A CN102615280 A CN 102615280A
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Abstract
The invention discloses a method for manufacturing an iron-based superconductor by using an SPS (Spark Plasma Sintering) technology and belongs to the technical field of high-temperature superconductive materials. The method comprises the following steps of: carrying out thermal treatment on rare earth powder Ln and As powder according to the ratio being 1:(1-1.1) in a high vacuum quartz tube to prepare initial powder LnAs; carrying out ball milling on LnAs and Fe powder, Fe2O3 powder and FeF3 powder according to mol ratio being 3:(1+x):(1-x):x; placing a die filled with powder into sintering equipment; manufacturing the iron-based superconductor by adopting a spark plasma sintering technology; and pressurizing and sintering at a sintering pressure of 30-50Mpa and the sintering temperature of 900-1100DEG C for 5-60 minutes under vacuum conditions. According to the method disclosed by the invention, the sintering time is short, so that the loss of component elements is reduced and the compactness of the material is reduced, thus the high-performance iron-based superconductor is obtained.
Description
Technical field
The present invention relates to a kind of preparation method of iron-based superconductor, belong to the high temperature superconducting materia preparing technical field.
Background technology
Iron-based superconductor has higher critical transition temperature, quite high upper critical field and irreversible field, thereby be expected to have the forceful electric power field in magnetic field to realize its application at superconducting transformer, superconducting motor, superconductive current limiter etc.At present; The preparation method that iron-based superconductor is commonly used is a conventional solid state reaction; This method needs quite long heat treatment time when the preparation iron-based superconductor; Heat treatment causes some of units to have a large amount of loss (as: As and F) for a long time, has reduced the quality of preparation material, and then has influenced its performance; The iron-based superconductor compactness of traditional in addition heat treatment method preparation is not high to contain more hole, causes it to transport poor-performing.Therefore need a kind of method when the preparation iron-based superconductor, sintering that can the short time reduces the loss of composition element, and can improve the compactness of material, thereby obtains high performance iron-based superconductor.
Summary of the invention
The objective of the invention is to propose a kind of easy-formation, high density, high-performance iron base super conductor preparation method.
A kind of preparation method of iron-based superconductor is characterized in that, adopts the method for discharge plasma sintering, may further comprise the steps:
(1) preparation of initial powder
Under high-purity Ar (being not less than 99.9%) protective atmosphere, with the rare earth powder (Ln) of needs and As powder in molar ratio 1: the ratio of (1～1.1) is carried out weighing, fully mixes; The raw material that mixes is encapsulated in high vacuum 10
-5～10
-6In the quartz ampoule of Pa, heat-treat then, heat treatment process is followed successively by: room temperature～400 ℃, and heating rate is 3～5 ℃/min; 400 ℃～600 ℃ heating rates are 1～3 ℃/min; 600 ℃ are incubated 3～10 hours; 600 ℃～900 ℃ heating rates are 1～3 ℃/min; 900 ℃ are incubated 10～20 hours; Last stove is chilled to room temperature.
(2) preparation of iron-based superconductor LnO1-xFxFeAs (La, Ce, Pr, Nd, Sm, Eu etc.):
In the glove box of high-purity argon gas (being not less than 99.9%) protection, with the initial powder LnAs for preparing in the first step and Fe powder, Fe
2O
3Powder, FeF
3Powder in molar ratio 3: (1+x): (1-x): x carries out proportioning (0＜x＜0.6); Adopt ball mill to carry out ball milling then, drum's speed of rotation is 150～300 rev/mins, and ball milling total time is 0.5-2 hour, after treating fully to mix, mixed powder is packed in the mould; Adopt the discharge plasma sintering technology to prepare iron-based superconductor then, the mould of having filled powder is put into agglomerating plant, pressure sintering under vacuum condition; It is 30～50Mpa that sintering is pressed; Sintering temperature is 900～1100 ℃, and the time is 5～60min, obtains a kind of iron-based superconductor.
The iron-based superconductor that makes through method of the present invention has following characteristics:
1, because the present invention adopts the heat treatment of short time, therefore pair element loss is less in course of reaction, helps improving the performance of iron-based superconductor;
2, than traditional solid-phase sintering technology commonly used now; Discharge plasma sintering technique is in the heat treatment process of preparation iron-based superconductor, and its raw material is in the state of fusion, and in heat treatment process, applies bigger pressure; Help the abundant reaction of various elements, and improve its density.
Description of drawings
Fig. 1 is the SmO of preparation among the embodiment 1
0.8F
0.2The image of FeAs;
Fig. 2 is the SmO of preparation among the embodiment 1
0.8F
0.2The SEM image in the section cross section of FeAs;
Fig. 3 is the SmO of preparation among the embodiment 1
0.8F
0.2The resistance temperature transition curve of FeAs;
Fig. 4 is the SmO of preparation among the embodiment 1
0.8F
0.2The J of FeAs
cWith the outfield change curve.
The specific embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is done further detailed description, but the present invention is not limited to following examples.
Embodiment 1:SmO
0.8F
0.2The preparation of FeAs superconductor
Step 1: the preparation of initial powder
With the Sm powder and the As powder carries out weighing according to mol ratio at 1: 1.03 and mixed under the Ar protective atmosphere.The Sm powder that mixes and As powder be encapsulated in carry out sintering in the quartz ampoule, vacuum is 10
-6Pa, heat treatment process is followed successively by: room temperature～400 ℃, heating rate is 5 ℃/min; 400 ℃～600 ℃, heating rate is 1 ℃/min; 600 ℃ are incubated 5 hours; 600 ℃～900 ℃ heating rates are 1 ℃/min; 900 ℃ are incubated 10 hours; Last stove is chilled to room temperature.
Step 2: SmO
0.8F
0.2The preparation of FeAs superconductor
In the glove box of high-purity argon gas protection, with the initial powder SmAs powder for preparing in the first step, Fe powder, Fe
2O
3Powder, FeF
3Powder 30: 12: 8 in proportion: 2 proportionings; Adopt ball mill to carry out ball milling then, drum's speed of rotation is 150 rev/mins, and ball milling total time is 0.5 hour, after treating fully to mix, mixed powder is packed in the mould; Adopt the discharge plasma sintering technology to prepare iron-based superconductor then, the mould of having filled powder is put into agglomerating plant, pressure sintering under vacuum condition; Sintering pressure is 30Mpa; Sintering temperature is 1000 ℃, and the time is 10min, obtains a kind of iron-based superconductor.
Fig. 1 is the SmO of embodiment preparation for this reason
0.8F
0.2The appearance images of FeAs superconductor.Fig. 2 is the SmO of embodiment preparation for this reason
0.8F
0.2The SEM image in the section cross section of FeAs superconductor; The pore quantity that can observe among the figure in the sample of SPS method preparation is few; Single crystal grain in the sample has sizable size, and the raising of density and the increase of single crystallite dimension will cause the raising of its performance.Fig. 3 is the SmO of embodiment preparation for this reason
0.8F
0.2The resistance of FeAs superconductor is with the change curve of temperature T, by SmO
0.8F
0.2The resistance of FeAs is with finding out in the variation of temperature curve, and the starting point of its critical transition temperature is 54K, and the temperature of zero resistance is 52K, and the sample that the method is prepared has SmO
0.8F
0.2Higher critical transition temperature in the FeAs system, its narrow width of transition shows to have higher purity in the sample.Fig. 4 is the SmO of embodiment preparation for this reason
0.8F
0.2The FeAs superconductor is at 10K and 30K temperature lower critical current density (J
c) temperature variant curve.Can find out by figure, under the temperature of 10K, SmO during external magnetic field 0T
0.7F
0.3FeAs sample critical current density is 2.6 * 10
5A/cm
2, this result is near copper oxygen compound superconductor.Can find out its have similar two generation superconductor the good electrical application prospect.Particularly importantly, when temperature is 10K, in the external magnetic field 3T-9T scope, SmO
0.8F
0.2The influence that the critical current density of FeAs superconductor is raise by hardly in the outfield, this shows that sample has good high-field performance under the low temperature, this point is superior to copper oxide superconductor.When temperature is 30K, hang down after the match SmO
0.8F
0.2The critical current density of FeAs superconductor acutely descends with the rising in outfield, in the 3T-9T scope, and the influence that the sample critical current density is changed by hardly in the outfield.This superconductivity that shows sample is at high temperature very responsive to the outfield.
Embodiment 2:CeO
0.8F
0.2The preparation of FeAs superconductor
Step 1: the preparation of initial powder
With the Ce powder and the As powder carries out weighing according to mol ratio at 1: 1 and mixed under the Ar protective atmosphere.The Ce powder that mixes and As powder be encapsulated in carry out sintering in the high vacuum quartz ampoule, quartz ampoule vacuum is 10
-4Pa, heat treatment process is followed successively by: room temperature～400 ℃, heating rate is 5 ℃/min; 400 ℃～600 ℃, heating rate is 3 ℃/min; 600 ℃ are incubated 10 hours; 600 ℃～900 ℃ heating rates are 3 ℃/min; 900 ℃ are incubated 20 hours; Last stove is chilled to room temperature.
Step 2: CeO
0.8F
0.2The preparation of FeAs superconductor
In the glove box of high-purity argon gas protection, with the initial powder CeAs powder for preparing in the first step, Fe powder, Fe
2O
3Powder, FeF
3Powder 30: 12: 8 in proportion: 2 proportionings; Adopt ball mill to carry out ball milling then, drum's speed of rotation is 150 rev/mins, and ball milling total time is 0.5 hour, after treating fully to mix, mixed powder is packed in the mould; Adopt the discharge plasma sintering technology to prepare iron-based superconductor then, the mould of having filled powder is put into agglomerating plant, add the flanging sintering in vacuum condition bottom; Sintering pressure is 30Mpa; Sintering temperature is about 1000 ℃, and the time is about 10min, prepares CeO
0.8F
0.2The FeAs superconductor.
Embodiment 3:NdO
0.8F
0.2The preparation of FeAs superconductor
Step 1: the preparation of initial powder
With the Nd powder and the As powder carries out weighing according to mol ratio at 1: 1.1 and mixed under the Ar protective atmosphere; The Nd powder that mixes and As powder be encapsulated in the high vacuum quartz ampoule heat-treat, quartz ampoule vacuum is 10
-5Pa.Heat treatment process is followed successively by: room temperature～400 ℃, and heating rate is 5 ℃/min; 400 ℃～600 ℃, heating rate is 3 ℃/min; 600 ℃ are incubated 5 hours; 600 ℃～900 ℃ heating rates are 3 ℃/min; 900 ℃ are incubated 20 hours; Last stove is chilled to room temperature.
Step 2: NdO
0.8F
0.2The preparation of FeAs superconductor
In the glove box of high-purity argon gas protection, with the initial powder NdAs powder for preparing in the first step, Fe powder, Fe
2O
3Powder, FeF
3Powder 30: 12: 8 in proportion: 2 proportionings; Adopt ball mill to carry out ball milling then, drum's speed of rotation is 150 rev/mins, and ball milling total time is 0.5 hour, after treating fully to mix, mixed powder is packed in the mould; Adopt the discharge plasma sintering technology to prepare iron-based superconductor then, the mould of having filled powder is put into agglomerating plant, add the flanging sintering in vacuum condition bottom, sintering pressure is 30Mpa, and sintering temperature is about 1000 ℃, and about 10min of time prepares NdO
0.8F
0.2The FeAs superconductor.
Claims (1)
1. the technological method for preparing iron-based superconductor of SPS is characterized in that, adopts the method for discharge plasma sintering, may further comprise the steps:
(1) preparation of initial powder
Under the high-purity Ar protective atmosphere, with rare earth powder Ln and As powder in molar ratio 1: the ratio of (1～1.1) is carried out weighing, fully mixes; The raw material that mixes is encapsulated in high vacuum 10
-5～10
-6In the quartz ampoule of Pa, heat-treat then, heat treatment process is followed successively by: room temperature～400 ℃, and heating rate is 3～5 ℃/min; 400 ℃～600 ℃ heating rates are 1～3 ℃/min; 600 ℃ are incubated 3～10 hours; 600 ℃～900 ℃ heating rates are 1～3 ℃/min; 900 ℃ are incubated 10～20 hours; Last stove is chilled to room temperature;
(2) preparation of iron-based superconductor LnO1-xFxFeAs:
In the glove box of high-purity argon gas protection, with the initial powder LnAs for preparing in the first step and Fe powder, Fe
2O
3Powder, FeF
3Powder in molar ratio 3: (1+x): (1-x): x carries out proportioning, wherein 0＜x＜0.6; Adopt ball mill to carry out ball milling then, drum's speed of rotation is 150～300 rev/mins, and ball milling total time is 0.5-2 hour, after treating fully to mix, mixed powder is packed in the mould; Adopt the discharge plasma sintering technology to prepare iron-based superconductor then, the mould of having filled powder is put into agglomerating plant, pressure sintering under vacuum condition; It is 30～50Mpa that sintering is pressed; Sintering temperature is 900～1100 ℃, and the time is 5～60min, obtains a kind of iron-based superconductor.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106735177A (en) * | 2017-01-23 | 2017-05-31 | 江苏顺通管业有限公司 | A kind of manufacture method of reducing pipe mold |
| CN108666045A (en) * | 2017-04-01 | 2018-10-16 | 中国科学院大连化学物理研究所 | A kind of method that discharge plasma sintering technology prepares iron selenium superconductor |
| WO2021044871A1 (en) * | 2019-09-03 | 2021-03-11 | 国立研究開発法人産業技術総合研究所 | Polycrystalline bulk body and method for producing same |
| CN112692281A (en) * | 2020-11-23 | 2021-04-23 | 北京理工大学 | Preparation method of secondary hardening ultrahigh-strength steel by utilizing SPS sintering and deformation |
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| US20040086412A1 (en) * | 2002-10-25 | 2004-05-06 | Yasuyoshi Suzuki | Method for producing a soft magnetic material |
| JP2005068526A (en) * | 2003-08-27 | 2005-03-17 | Fuji Electric Holdings Co Ltd | Method of producing composite magnetic particle powder molded body |
| CN1740357A (en) * | 2005-09-23 | 2006-03-01 | 北京工业大学 | Prepn process of high temperature superconductive Ni-W alloy |
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| US20040086412A1 (en) * | 2002-10-25 | 2004-05-06 | Yasuyoshi Suzuki | Method for producing a soft magnetic material |
| JP2005068526A (en) * | 2003-08-27 | 2005-03-17 | Fuji Electric Holdings Co Ltd | Method of producing composite magnetic particle powder molded body |
| CN1740357A (en) * | 2005-09-23 | 2006-03-01 | 北京工业大学 | Prepn process of high temperature superconductive Ni-W alloy |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106735177A (en) * | 2017-01-23 | 2017-05-31 | 江苏顺通管业有限公司 | A kind of manufacture method of reducing pipe mold |
| CN108666045A (en) * | 2017-04-01 | 2018-10-16 | 中国科学院大连化学物理研究所 | A kind of method that discharge plasma sintering technology prepares iron selenium superconductor |
| CN108666045B (en) * | 2017-04-01 | 2020-06-09 | 中国科学院大连化学物理研究所 | Method for preparing iron selenium superconducting material by spark plasma sintering technology |
| WO2021044871A1 (en) * | 2019-09-03 | 2021-03-11 | 国立研究開発法人産業技術総合研究所 | Polycrystalline bulk body and method for producing same |
| JP2021038435A (en) * | 2019-09-03 | 2021-03-11 | 国立研究開発法人産業技術総合研究所 | Polycrystalline bulk body and method for producing the same |
| JP7360123B2 (en) | 2019-09-03 | 2023-10-12 | 国立研究開発法人産業技術総合研究所 | Polycrystalline bulk body and manufacturing method thereof |
| CN112692281A (en) * | 2020-11-23 | 2021-04-23 | 北京理工大学 | Preparation method of secondary hardening ultrahigh-strength steel by utilizing SPS sintering and deformation |
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Application publication date: 20120801 |