CN1472368A - Post-treating method and apparatus for rareearth barium-copper superconductive blocks under high pressure oxygen condition - Google Patents
Post-treating method and apparatus for rareearth barium-copper superconductive blocks under high pressure oxygen condition Download PDFInfo
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- CN1472368A CN1472368A CNA021258775A CN02125877A CN1472368A CN 1472368 A CN1472368 A CN 1472368A CN A021258775 A CNA021258775 A CN A021258775A CN 02125877 A CN02125877 A CN 02125877A CN 1472368 A CN1472368 A CN 1472368A
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Abstract
A post-treating method for the large-domain RE-BaCuO superconductor block features use of high-pressure oxygen at 300-700 deg.C under 1-2.5 MPa. Its high-pressure oxygen treating apparatus is composed of the heating furnace with heater and sealed furnace cavity which has feeding inlet, sealing door, gas inlet and its valve, thermocouple, and gas outlet, the temp controller, and the protector. Its advantages are high superdoncutor performance, short time and low oxygen consumption.
Description
Technical field
The present invention relates to the post-treating method and the using appts thereof of the big farmland of a kind of RE, Ba and Cu oxide superconductive block.
Background technology
RE, Ba and Cu oxide (REBaCuO, RE=Nd, Sm, Gd, Eu, Ho ...) big farmland (comprising single domain and non-single domain) superconductive block is the critical material of making super-conductive magnetic suspension device and superconductive permanent magnet.It adopts melting texture growing technology and the preparation of top seed product technology, is a kind monocrystal material.Because the oxygen loss under the high temperature, the material that has just grown out has tetragonal phase structure, does not have supraconductivity, must handle by the follow-up oxygen under the 300-600 ℃ of temperature to make it reach suitable oxygen level, and be that quadrature obtains superconductivity mutually from tetragonal phase converting.Usually, this aftertreatment is to carry out in the oxygen that flows.Because the density (near its theoretical value) of this big farmland superconduction piece is much higher than the material of powder sintering process preparation, the diffusion of oxygen supply brings very big difficulty.For example, need reach 200 hours treatment time, its critical transition temperature is reached about 90K the superconduction piece of 30mm diameter.And along with the increase of superconduction piece size, the time also will prolong.Simultaneously, keep oxygen atmosphere for a long time, also have a large amount of oxygen depletions in the mobile mode.This has not only prolonged the manufacturing cycle, and has increased the manufacturing cost of product.In addition, under the situation that adopts the oxygen that flows, can have the dead angle of oxygen flow, thereby furnace chamber should not be too big, limited the processing quantity of each superconduction piece.
Summary of the invention
It is short to the purpose of this invention is to provide a kind of aftertreatment time, and the oxygen depletion amount is low, cheaply the post-treating method of the big farmland of RE, Ba and Cu oxide superconductive block.
Another object of the present invention provides a kind of employed hyperbaric oxygen treatment unit of post-treating method of efficient, the safe big farmland of RE, Ba and Cu oxide superconductive block.
For achieving the above object, the present invention takes following technical scheme: the post-treating method of this RE, Ba and Cu oxide single domain superconductive block is that various improved melting texture growing technologies of employing and/or top seed crystal method prepare the post-treating method in the superconductive block of the big farmland of RE, Ba and Cu oxide.Aftertreatment is carried out in hyperbaric oxygen atmosphere, and pressure is 1-2.5Mpa, and temperature is 300-700 ℃.Adopt hyperbaric oxygen to replace the oxygen that flows, in batch the big farmland of processing RE, Ba and Cu oxide superconductive block under the pressure of 1-2.5Mpa has not only significantly shortened the treatment time, and has saved oxygen greatly, thereby has reduced the manufacturing cost of material.
Described RE, Ba and Cu oxide is to be the multiple oxide superconducting materials of principal element with rare earth (RE), barium (Ba) and copper (Cu).In REBaCuO, RE is one or more in the rare earth element.Its composition is roughly REBa
2Cu
3O
7-δ+ (0-40mol%) RE
2BaCuO
5, also contain a spot of other element usually, as in the elements such as Ag, Pt, Ce, Sn, Zn, B one or more.
In the method for the invention, the optimizing technology parameters of aftertreatment is: in the described aftertreatment, pressure is 1.5-2Mpa, and temperature is 350-500 ℃.
The pressure and temperature of aftertreatment influences the hyperbaric oxygen treatment time, in addition, the size of handled superconduction piece, and what of quantity also directly influence the hyperbaric oxygen treatment time, therefore the present invention does not do concrete qualification to the hyperbaric oxygen treatment time, but the hyperbaric oxygen treatment time generally was not less than 24 hours.
The employed hyperbaric oxygen treatment unit of post-treating method of the big farmland of RE, Ba and Cu oxide of the present invention superconductive block material; this device includes process furnace; be provided with the furnace chamber of heating member and sealing in the process furnace; furnace chamber is provided with opening for feed and hermatic door thereof; and the air outlet that is provided with inlet mouth and intake valve thereof, the thermopair that is connected with temperature controller, is connected with protector; this protector is a closed container, is provided with venting port and purging valve thereof, pressure-regulator.Adopt this device to carry out the aftertreatment of the big farmland of RE, Ba and Cu oxide superconductive block, under the situation of hyperbaric oxygen, oxygen can be full of whole cavity equably, thereby has increased the treatment capacity of superconduction piece, further reduces manufacturing cost.This hyperbaric oxygen treatment unit that has protector is the hyperbaric oxygen treatment unit of first kind of structure.
In the hyperbaric oxygen treatment unit of first kind of structure of the present invention, described heating stove furnace chamber is provided with tensimeter.
In the hyperbaric oxygen treatment unit of first kind of structure of the present invention, described protector is provided with safety valve.
In the hyperbaric oxygen treatment unit of first kind of structure of the present invention, described intake valve is connected with oxygen cylinder by pressure reducer.Intake valve also can be connected with other oxygen generating plant by pressure reducer.
In the hyperbaric oxygen treatment unit of first kind of above-mentioned structure; pressure-regulator; venting port and purging valve thereof are provided in a side of on the protector; also can not adopt protector; with pressure-regulator; venting port and purging valve thereof are directly arranged on the furnace chamber; this is not the hyperbaric oxygen treatment unit of second kind of structure with protector; its structure is as follows: this device includes process furnace; be provided with the furnace chamber of heating member and sealing in the process furnace; furnace chamber is provided with opening for feed and hermatic door thereof, and is provided with inlet mouth and intake valve thereof; the thermopair that is connected with temperature controller; venting port and purging valve thereof; pressure-regulator.
In the hyperbaric oxygen treatment unit of second kind of structure of the present invention, described heating stove furnace chamber is provided with tensimeter.
In the hyperbaric oxygen treatment unit of second kind of structure of the present invention, described heating stove furnace chamber is provided with safety valve.
In the hyperbaric oxygen treatment unit of second kind of structure of the present invention, described intake valve is connected with oxygen cylinder by pressure reducer.
Description of drawings
Fig. 1 is a hyperbaric oxygen treatment unit synoptic diagram of the present invention
Fig. 2 is the graph of relation in critical transition temperature of the present invention and oxygen treatment time
Fig. 3 is the graph of relation in critical current density of the present invention and oxygen treatment time
Fig. 4 is the graph of relation in magnetic suspension force of the present invention and oxygen treatment time
Embodiment
Hyperbaric oxygen treatment unit of the present invention as shown in Figure 1, in process furnace 8, be provided with the furnace chamber 9 of heating member 10 and sealing, furnace chamber 9 is provided with opening for feed and hermatic door thereof (with ring flange as hermatic door, scheme not shown), and be provided with inlet mouth and intake valve 2 thereof, tensimeter 3, the thermopair that is connected with temperature controller (thermopair is contained in the conduit 4), and the air outlet, the inlet mouth of furnace cavity 9 leads to the bottom (scheming not shown) of furnace chamber 9 by interconnecting pipe.The air outlet of furnace chamber 9 is connected with protector 11 by pipeline, and this protector 11 is provided with blow-off valve 5, safety valve 6, pressure-regulator 7.Intake valve 2 is connected with oxygen cylinder 12 by pressure reducer 2.This device is made with high temperature steel, furnace chamber 9 internal diameter 100mm, and authorized pressure reaches 2.5Mpa under 700 ℃ maximum operation (service) temperature.For safety operation, this device is provided with pressure protective device 11.In use, set required pressure, and make in the container of protector 11 the pressure all-the-time stable on setting pressure by pressure-regulator 7; When pressure surpassed allowed band, safety valve 6 can be opened release automatically.In the experiment, at first will wait and handle the temperature homogeneity range that layers of material is put into furnace chamber 9 equably, keep that certain space is arranged between each block of material, and material not contact with the furnace wall.Compress upper flange plate and make furnace chamber 9 sealings.Open the valve of oxygen cylinder 12, adjust pressure reducer 1 to a little more than setting pressure, adjust pressure-regulator 7 simultaneously to setting pressure, open intake valve 2 then, by interconnecting pipe gas is sent into furnace chamber 9 bottoms, close intake valve 2 when observing indication on the tensimeter 3, open purging valve 5 releases venting to about 0.5Mpa.Inflation and deflation course repeat 3-4 time, to reduce the air content in the furnace chamber 9.Open intake valve 2 again, the indication of observing tensimeter 3 is inflated to setting pressure, and (this set(ting)value must consider that pressure Yin Wendu raises and the amplitude of increase, pressure when making the arrival design temperature is no more than the maximum allowble pressure of device), close intake valve 2 and oxygen cylinder valve then successively, and unclamp pressure reducer 1.Thermopair inserts the furnace chamber uniform temperature zone by conduit 4, and is connected on the temperature controller, by temperature control furnace temperature is heated up by setup program, insulation and cooling.
As shown in Figure 1, the big farmland superconduction of the YBaCuO of 22 30mm diameters piece divides 2 layers to be placed in the uniform temperature zone of sending into furnace chamber 9 on the specimen holder made from stainless steel, and the sealing furnace chamber, adjusts intake valve 2 to 1.1Mpa, adjusts pressure-regulator 7 to 1.0Mpa; After charging and discharging gas, pressure given at 1.0Mpa, and is closed intake valve and oxygen cylinder through 3 times; Open temperature controller, setting program is warming up to 470 ℃ (this moment, the indication of furnace chamber internal pressure increased with the rising of temperature, reached 2Mpa in the time of 470 ℃) with 200 ℃/hour speed, 470 ℃ of insulations after 72 hours stove be chilled to room temperature; Open purging valve 5 releases, the hermatic door of opening furnace chamber then takes out the superconduction piece.
The structure that the X-ray diffraction result confirms the superconduction piece is from the tetragonal phase converting phase that is orthogonal.The superconductivity test result shows: critical transition temperature T
cReach 91K, the critical magnetzation current density J under the 77K temperature
CmReach 10
4A/cm
2Magnitude; Magnetic suspension force under 77K temperature and the 0.5T magnetic field is at 12N/cm
2More than.
Utilize device of the present invention, we have carried out the experiment of the relation of superconduction piece performance and pressure, temperature and time, and handle with mobile oxygen and to compare.What the oxygen that flows was handled use is the quartzy tube furnace of internal diameter 65mm.Adopt SQUID magnetometer survey dc magnetizing strength M and temperature T and the relation that adds magnetic induction density B.The initial critical transition temperature Tc of superconducting material, onset (Tc) is determined by the initial transition point on the M-T curve; Critical magnetzation current density Jcm is by the magnetic hysteresis loop of M-B, by the Bean critical state model J of expansion
Cm=30 Δ M/d calculate, and the Δ M in the formula rises the field and the difference of M when falling, and d is the size (equaling the diameter of superconduction piece for single domain superconduction piece d, for the diameter of non-single domain superconduction piece d less than the superconduction piece) of superconduction circulation.
Fig. 2 has shown the critical transition temperature T through the superconduction piece of hyperbaric oxygen and the processing of mobile oxygen
cRelation with treatment time t.As can be seen, the single domain YBaCuO superconduction block of 11mm diameter is after (pressure is 0.1Mpa) handled through 8 days mobile oxygen, T
cReached maximum; And under the hyperbaric oxygen condition of 1Mpa pressure, through 1 day processing T
cJust reached maximum.Fig. 3 has shown the critical current density J through the superconduction piece of hyperbaric oxygen and the processing of mobile oxygen
cRelation with treatment time t.Significantly be higher than the superconduction piece of handling through the oxygen that flows through 24 hours critical current densities equally through hyperbaric oxygen processing superconduction piece.
Fig. 4 has provided magnetic suspension force f
0Relation with the oxygen treatment time.Equally as can be seen, for the single domain YBaCuO superconduction block of 11mm diameter, reaching the needed time of maximum magnetic flux buoyancy has significantly shortened along with increasing of pressing of oxygen.The hyperbaric oxygen processing of 1.0Mpa and the mobile oxygen of 0.1Mpa are handled, and the time is respectively 40 and 100 hours, and the maximum magnetic flux buoyancy value that reaches is suitable.
Embodiment 2
Utilize device of the present invention, diameter 30mm YBaCuO single domain superconduction piece is carried out aftertreatment, 470 ℃ of treatment temps, pressure 1MPa, 72 hours time, 22 of the quantity of processing superconduction piece.Can find out clearly that by the result who lists in the table adopt hyperbaric oxygen to handle with the oxygen processing of flowing and compare, gas has been saved about 20 times, used time decreased to three/one, handling quantity has increased nearly 3 times.
Table 1 adopts the comparison of flow oxygen and hyperbaric oxygen processing 30mm diameter YBaCuO single domain superconduction piece
| The access times of every bottle of oxygen | Every stove is handled the quantity of superconduction piece | Treatment time (hour) | Average magnetic buoyancy (N/cm 2) | |
| The 1Mpa hyperbaric oxygen is handled | ????＞50 | ????22 | ????72 | ????12 |
| Oxygen is handled 0.1Mpa flow | ????2-3 | ????8 | ????200 | ????12 |
Embodiment 3
Utilize device of the present invention, the big farmland superconduction of diameter 20mm SmBaCuO piece has been carried out aftertreatment.350 ℃ of treatment temps, pressure 1MPa, 40 hours time.Handle the T of back superconduction piece
cReach 93K, J
cReach 10
4A/cm
2
The post-treating method and the use equipment thereof of the big farmland of RE, Ba and Cu oxide of the present invention superconductive block have the following advantages:
1, for the big farmland superconduction of YBaCuO piece, the superconductivity (critical transition temperature, critical current density and magnetic suspension force) that adopts the hyperbaric oxygen aftertreatment not only can obtain, and obviously shortened the aftertreatment time.
2, hyperbaric oxygen is handled and not only can be shortened the treatment time, and greatly reduces the consumption of oxygen, thereby has reduced the manufacturing cost of material.
3, the present invention is not only applicable to the big farmland of YBaCuO superconducting material, and is applicable to other big farmland of RE BaCuO superconducting material.
4, the present invention also is applicable to the aftertreatment of various oxide superconducting monocrystalline.
Claims (10)
1, the post-treating method of the big farmland of a kind of RE, Ba and Cu oxide superconductive block, be that employing melting texture growing technology and top seed crystal method prepare the post-treating method in the superconductive block of the big farmland of RE, Ba and Cu oxide, it is characterized in that: aftertreatment is carried out in hyperbaric oxygen atmosphere, pressure is 1-2.5Mpa, and temperature is 300-700 ℃.
2, the post-treating method of the big farmland of RE, Ba and Cu oxide according to claim 1 superconductive block is characterized in that: in the described aftertreatment, pressure is 1.5-2Mpa, and temperature is 400-500 ℃.
3, a kind of claim 1 or the used hyperbaric oxygen treatment unit of 2 described post-treating methods; it is characterized in that: this device includes process furnace; be provided with the furnace chamber of heating member and sealing in the process furnace; furnace chamber is provided with opening for feed and hermatic door thereof; and the air outlet that is provided with inlet mouth and intake valve thereof, the thermopair that is connected with temperature controller, is connected with protector; this protector is a closed container, is provided with venting port and purging valve thereof, pressure-regulator.
4, hyperbaric oxygen treatment unit according to claim 3, it is characterized in that: described heating stove furnace chamber is provided with tensimeter.
5, hyperbaric oxygen treatment unit according to claim 4, it is characterized in that: described protector is provided with safety valve.
6, hyperbaric oxygen treatment unit according to claim 5, it is characterized in that: described intake valve is connected with oxygen cylinder by pressure reducer.
7, a kind of claim 1 or the used hyperbaric oxygen treatment unit of 2 described post-treating methods, it is characterized in that: this device includes process furnace, be provided with the furnace chamber of heating member and sealing in the process furnace, furnace chamber is provided with opening for feed and hermatic door thereof, and is provided with inlet mouth and intake valve, the thermopair that is connected with temperature controller, venting port and purging valve thereof, pressure-regulator.
8, hyperbaric oxygen treatment unit according to claim 7, it is characterized in that: described heating stove furnace chamber is provided with tensimeter.
9, hyperbaric oxygen treatment unit according to claim 7, it is characterized in that: described heating stove furnace chamber is provided with safety valve.
10, hyperbaric oxygen treatment unit according to claim 7, it is characterized in that: described intake valve is connected with oxygen cylinder by pressure reducer.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100392157C (en) * | 2005-03-25 | 2008-06-04 | 北京有色金属研究总院 | Poly-seed crystal preparation method for YBaCuO single domain superconductor |
| CN103014873A (en) * | 2012-09-18 | 2013-04-03 | 苏州四海常晶光电材料有限公司 | Pure-oxygen-atmosphere annealing device and method |
-
2002
- 2002-08-01 CN CN 02125877 patent/CN1230577C/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100392157C (en) * | 2005-03-25 | 2008-06-04 | 北京有色金属研究总院 | Poly-seed crystal preparation method for YBaCuO single domain superconductor |
| CN103014873A (en) * | 2012-09-18 | 2013-04-03 | 苏州四海常晶光电材料有限公司 | Pure-oxygen-atmosphere annealing device and method |
| CN103014873B (en) * | 2012-09-18 | 2017-07-14 | 苏州四海常晶光电材料有限公司 | A kind of pure oxygen atmosphere annealing device and method for annealing |
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Effective date of registration: 20190628 Address after: 101407 No. 11 Xingke East Street, Yanqi Economic Development Zone, Huairou District, Beijing Patentee after: YOUYAN ENGINEERING TECHNOLOGY RESEARCH INSTITUTE Co.,Ltd. Address before: 100088, 2, Xinjie street, Beijing Patentee before: General Research Institute for Nonferrous Metals |
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