CN102409298B - Continuous rapid laser coating method of superconducting layer in second-generation high-temperature superconducting strip - Google Patents
Continuous rapid laser coating method of superconducting layer in second-generation high-temperature superconducting strip Download PDFInfo
- Publication number
- CN102409298B CN102409298B CN 201110367810 CN201110367810A CN102409298B CN 102409298 B CN102409298 B CN 102409298B CN 201110367810 CN201110367810 CN 201110367810 CN 201110367810 A CN201110367810 A CN 201110367810A CN 102409298 B CN102409298 B CN 102409298B
- Authority
- CN
- China
- Prior art keywords
- coating
- laser
- superconducting
- target
- temperature
- 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.)
- Active
Links
Images
Landscapes
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
The invention provides a continuous rapid laser coating method of a superconducting layer in a second-generation high-temperature superconducting strip. According to the invention, through a method of bi-dimensionally scanning a superconducting target along an x-y axle, the whole surface of the target can be utilized and a laser evaporation coating process can be stably and sustainably carried out; coating intervals are increased through a method of scanning along the motion direction of the strip by use of laser spots; and the width of the coating interval vertical to the motion direction of the strip is increased through a method of twining the strip on a belt roller above a heater multiple times. By using the method provided by the invention, evaporated substances are fully collected on a metal base band to the greatest extend, thereby effectively improving the preparation speed of the strip, increasing the utilization rates of the target and the evaporated substances, greatly improving the production efficiency and reducing the production cost of the strip. According to the method provided by the invention, the rapid coating of the second-generation high-temperature superconducting strip suitable for large-scale industrial production can be realized.
Description
Technical field
The present invention relates to the new oxide belt material of high temperature superconduct and manufacture field, relate in particular to the serialization fast laser film coating method of superconducting layer in a kind of s-generation belt material of high temperature superconduct.
Background technology
Superconducting material always was subject to the showing great attention to of scientific circles and industry member by Dutch scientist Ang Neisi in unexpected 100 years of finding so far from 1911.Scientist strives to find normal temperature (room temperature or approach room temperature) superconductor always, so that large-scale application is brought benefit to the mankind.Traditional superconducting material is generally metal and alloy, and the highest superconducting transition temperature of this class material is 23.2K, mainly take niobium titanium alloy as representative in the application in the fields such as Magnetic resonance imaging at present, and the refrigeration cycle medium is liquid helium, is called traditionally low temperature superconducting material.
1986, the laboratory reported first lanthanum barium copper oxygen oxide compound that IBM Corporation is positioned at Zurich, SUI had the supraconductivity of 35K.The traditional concept of " oxide ceramic material can only be isolator " has been broken in this discovery, thereby has opened up new research approach for exploring the superconducting material with higher temperature, greatly open many field scientists' the visual field.The discoverer Miao Le of high-temperature superconductor phenomenon and Bednorz have just obtained Nobel prize for physics at Second Year (1987), have created the Nobel prize in history from obtaining achievement in research to the fastest prize-winning historical record.The yttrium barium copper oxide with higher superconducting temperature of finding has subsequently been broken through liquid nitrogen " temperature barrier " superconducting transition temperature has been brought up to liquid nitrogen temperature (77K) first on human history more than.Because liquid nitrogen is compared with liquid helium, the cost of the resource cost that still freezes itself is all much lower, so the discovery of liquid nitrogen temperature superconducting material can be rated as on the Materials history, so the important breakthrough on science and technology developing history, for the large-scale commercial application of superconducting material, lay a good foundation first.Traditionally the rare earth oxide superconducting material is called to high temperature superconducting materia.
Superconducting material, owing to having superior and unique conductivity and magnetic performance, has attracted numerous scientists' attention since superconducting phenomenon at the beginning of last century is found always.The huge applications prospect of its without hindrance, complete diamagnetic characteristic in fields such as industry, national defence, scientific research, medical science makes national governments all very pay attention to the research and development of superconductor technology.Especially there is irreplaceability in Application Areass such as medical science and magnetic confinement nuclear fusion reactors.
Traditional low temperature superconducting material is generally the metal or alloy material, has good mechanical property, easily is processed into the required wire rod of various application or band.But, because superconducting transition temperature is positioned at the liquid helium warm area, the working temperature of low-temperature superconducting device also can only be positioned at the liquid helium warm area, so expensive refrigeration cost has limited its range of application greatly.Be mainly used at present the irreplaceable fields of other material such as Magnetic resonance imaging and high field magnet.High temperature superconducting materia not only can greatly reduce thermal losses in production, transmission and the Application Areas of electric power, improve the effective rate of utilization of the energy, and can not cause environmental pollution, so the research and development of high temperature superconducting materia not only have scientific value with production, also there is huge social and economic benefits.But, after high-temperature superconductor heat in a few years, along with going deep into of research work, find that the practical application of high temperature superconducting materia is more much more difficult than original expection.This is main relevant with microtexture and the mechanical property of high temperature superconducting materia.With traditional metal low temp superconductor, compare, high-temperature superconductor belongs to oxide material, with regard to its mechanical property, belong to " oxide ceramics " series, so, compare and be difficult for being processed into the required wire rod of various application or band with traditional low temperature superconducting material, therefore can't be in the energy, electric power, medical treatment and military industry field large-scale application.
Be difficult for being processed into this difficult problem of wire rod in order to solve high temperature superconducting materia, the method that at first scientists adopts is " silver-colored jacket " method, is referred to as first-generation belt material of high temperature superconduct.First-generation belt material of high temperature superconduct be take bismuth system (bismuth-strontium-calcium-copper-oxygen) high temperature superconducting materia as main.The principle of " silver-colored jacket " method is that the Bi-based high-temperature superconductive powder is poured in the hollow silver sleeve, and the processes such as stretched and pressurization becomes the silver-colored jacket belt material of high temperature superconduct of 4 mm wide 0.2 mm thick.Belt material of high temperature superconduct through the processing of " silver-colored jacket " method has good flexibility, can be used for manufacturing the various devices such as high-temperature superconductive cable, superconducting coil, superconductive generator, superconducting motor, superconducting transformer, superconductive current limiter.First-generation hts tape can transmit the electric current of 150-210 ampere left and right.Joint length is over 1000 meters.First-generation belt material of high temperature superconduct is through the research and development of more than ten years, and production technology is mature on the whole, and has built production line.Although first-generation belt material of high temperature superconduct has started to commercially produce, due to the obstacle that has the aspects such as cost performance, at present still can't large-scale promotion application.Its major cause is as follows: the first-generation belt material of high temperature superconduct that the bi tape of the first, take is representative can't be compared with the yttrium barium copper oxide belt material of high temperature superconduct with regard to its Superconducting Current Density and electric current transmission performance.And through the research and development of more than ten years, further improved limited space.The second, bi tape its supercurrent decay in magnetic field is very fast, that is, in externally-applied magnetic field, after magneticstrength surpasses certain value, can lose its supraconductivity.Yet the application of most of energy, power domain is often relevant with high-intensity magnetic field, so first-generation belt material of high temperature superconduct can't be applied under the magnetic field more than most of medium tenacitys.Three, because silver as noble metal, material cost is higher, therefore adopt the cost of the first-generation Bi-based high-temperature superconductive strip of " silver-colored jacket " law technology production to be difficult to be reduced to the price with the competition of traditional copper conductor.At present still in 150-200 dollar/kiloampere rice ($ 150-200/kAm) scope.According to the estimation of USDOE, the ratio of performance to price of belt material of high temperature superconduct large-scale commercial application should be better than the copper conductor cost performance, is about 20-50 dollar/kiloampere rice ($ 20-50/kAm).Only have after the ratio of performance to price of belt material of high temperature superconduct reaches this index, just likely substitute on a large scale traditional copper conductor material.
Since nineteen ninety, the states such as U.S., day, moral have started the R&D work of s-generation belt material of high temperature superconduct, have set up the research and development route map of s-generation belt material of high temperature superconduct and related application.So-called s-generation belt material of high temperature superconduct, adopt various plated film means to arrive the rare earth oxide high-temperature superconducting thin film of several micron thick at the upper plating of conventional metals base band (alloys such as nickel-base alloy or the stainless steel) one deck about 1 of very thin (40-100 micron) exactly.With the first-generation belt material of high temperature superconduct of " silver-colored jacket " law technology development, compare, s-generation belt material of high temperature superconduct has more superior superconductivity, because the yttrium barium copper oxide belt material of high temperature superconduct that adopts film coating method to form has almost ideal single crystal structure, so have very strong supercurrent transmittability.And the cost of metal base band is very low, therefore, along with the raising of R & D Level, the cost of s-generation belt material of high temperature superconduct will reduce greatly.Due to the sharp rising of the prices of raw and semifnished materials such as oil, precious metal, non-ferrous metal, the cost objective of s-generation belt material of high temperature superconduct is more easily realized in recent years.The research work of s-generation belt material of high temperature superconduct starts from the nineties in last century in the world.Especially since U.S. Los Alamos (Los Alamos National Laboratory, being abbreviated as LANL) after at first National Laboratory adopt the laser coating technology to succeed in developing the yttrium barium copper oxide belt material of high temperature superconduct that 1 meter magnitude length, supercurrent are 100 amperes in 1996, s-generation belt material of high temperature superconduct has generally caused the great attention of the states such as U.S., day, moral.And emphasis progressively is transitioned into to the research and development aspect of s-generation belt material of high temperature superconduct from the research of first-generation belt material of high temperature superconduct.
Since two thousand eight, under the support of the Department of Science and Technology and the Shanghai City State Scientific and Technological Commission, Shanghai Superconducting Technology Co., Ltd. cooperates with the Shanghai Communications University, the research and development pattern that adopts industries, universities and research institutors to combine, " the long band of the s-generation high-temperature superconductor Study on manufacturing technology that be suitable for serialization production " project, as Shanghai City innovation research platform construction project, is carried out to s-generation belt material of high temperature superconduct industrialization R&D work.Research and develop the s-generation belt material of high temperature superconduct coating process that successfully has independent intellectual property right the end of the year 2010, the superconduction current capacity has reached 194 amperes.And the technological difficulties such as stability, repeatability and reliability of the coating process that transfer must overcome from the laboratory study achievement to industrialization have thoroughly been solved.Thereby lay a good foundation for follow-up industrialization production.
The oxide compound rare earth superconductor that the yttrium barium copper oxide of take is representative, because its superconductivity is very responsive to the microstructure of material, so the powder metallurgical technique that is difficult to adopt first-generation belt material of high temperature superconduct to use prepares band.In order to form the crystalline network of almost Perfect, superconducting layer adopts various coating techniques usually in order to realize epitaxy on cheap metal base band.The preparation technology of s-generation belt material of high temperature superconduct can be divided into metal base band, compound insulation layer and superconducting layer three parts.Wherein superconducting layer is core.
Base band preparation technology can be divided into two large classes: ion beam assisted deposition (Ion Beam Assited Deposition, be abbreviated as IBAD) and auxiliary biaxial texture technology (the Rolling Assisted Biaxially Textured Substrates of rolling, be abbreviated as RABiTS), its multilayered structure schematic diagram is as shown in Figure 1.The IBAD technology does not have particular requirement to the selection of metal base band material, and Ni alloy and the stainless steel capital can be used as the base band material.In IBAD technique, according to the difference of selected material, its technological process also respectively has characteristics.Material commonly used comprises YSZ(yttrium-stabile zirconium dioxide, Y-ZrO at present
2), GZO(Gd
2zr
2o
7) and MgO.Japan ISTEC and Fujikura company have higher IBAD base band and prepare level.FUJIKURA has built large-scale IBAD equipment, can go out 1000 meters long base band by continuous production.U.S. Los Alamos National Laboratories (LANL) cooperate also possess the ability that preparation surpasses 1000m length IBAD-MgO base band with SuperPower company.
The IBAD technology is to take high-vacuum technology as basis, and for the IBAD technology, the RABiTS technology has advantages of that efficiency is high, equipment is simple and be with low cost.Ni-5at%W and the Ni-3at%W alloy of the low magnetic of tool are the main raws of current RABiTS base band.Germany Evico company is the long Ni-5at%W base band of 100-200 rice for sale, thickness of strip 40-80 micron, and width 4-20 millimeter, face interscan (Ф scanning) halfwidth is less than 8
o, the rough degree of surperficial rootmean-square Rms is less than 5 nanometers.The invention unit U.S. Oak Ridge National Laboratory of RABiTS technology (Oak Ridge National Laboratory, be abbreviated as ORNL) still maintains the leading position in this field.ORNL is that 1000 grades of clean rooms have been built in the preparation of RABiTS base band, can prepare the single Ni-5at%W base band that surpasses 1000 meters.AMSC can prepare 4 centimetres wide, the RABiTS base band of 1000 meters long.Typical base band is characterized as face interscan halfwidth and is less than 7
o, r.m.s. roughness is 3 nanometers.
With IBAD technique, compare, the relative merits of RABiTS technique are as follows: advantage: rolling technology is comparatively ripe, if adopt broadband (being greater than 10 centimetres) rolling technology, is applicable to scale operation.Shortcoming: mechanical property is poor, has faint magnetic; In addition, the easy oxidation of high temperature lower surface, therefore increased difficulty and the complexity of epitaxy sealing coat.On the RABiTS base band, if seed layer thickness (CeO
2) surpass 100 nanometers, easily form tiny crack.
On the preparation method of compound insulation layer on the RABiTS metal base band (Seed Layer, sealing coat and cap layer) and IBAD base band, the preparation method of compound insulation layer comprises: laser coating method (Pulsed Laser Deposition, be abbreviated as PLD), the method such as magnetron sputtering method, coevaporation method (Thermal Co-evaporation, be abbreviated as TCE) and ion beam sputtering.Due to the compound buffer layer very thin thickness, so that material cost almost can be ignored is too late, prime cost derives from coating process and controls (yield rate).On the IBAD base band, the preparation of buffer layer is more complicated comparatively speaking.And on the RABiTS base band, there is certain difficulty (Ni base band surface oxidation problem under high temperature) in the preparation of Seed Layer.
The preparation method of the rare earth oxide superconducting layer that the yttrium barium copper oxide of take is representative comprises: the methods such as laser coating method, coevaporation method, metal organic chemical vapor deposition method (MOCVD) and solution method (MOD).The growth of yttrium barium copper oxide superconducting layer is the key of manufacturing s-generation belt material of high temperature superconduct.Because the quality of superconducting layer determined superconducting tape can transmission current size, and the size of supercurrent is directly relevant to the ratio of performance to price of superconducting tape, so can prepare the key that the band with very high supercurrent transmittability is the large-scale commercial application.Above the relative merits of several film coating method as follows:
In the laser coating route plan, because the many target systems of laser coating not only can be used to prepare superconducting layer, but sealing coat etc. also can greatly be saved facility investment intensity so compare with other method, and improve the effective rate of utilization of investment in fixed assets.
The laser coating technological advantage comprises: the speed of becoming a useful person is high, can accurately control by laser pulse frequency the thickness of nanometer scale.Good stability, the technique degree of controllability is high.Target is oxide powder sintering target, and cost is low and utilization ratio is high.The laser coating method has good stability and repeatability, has best superconductivity with the yttrium barium copper oxide superconducting tape of laser coating technology growth at present.The advantage of the method maximum is exactly accurately to control the component of growing film, thereby can obtain correct yttrium, barium, copper (123) phase chemistry proportioning.Yield rate is more than 95%, far away higher than other method.So have more competitive power on overall cost performance.
Metal organic chemical vapor deposition method (MOCVD) route plan: in the MOCVD route plan, due to the MOCVD system only for the preparation of the yttrium barium copper oxide superconducting layer, need other PVD(laser coating or magnetron sputtering) filming equipment growth Seed Layer, sealing coat and cap layer etc., so, in the MOCVD scheme, facility investment intensity is larger.In addition, need synthetic special Y, Ba, Cu organic compound source, and the organic source of MOCVD cost is high, so material cost is also higher.MOCVD technique relate to chemical reaction and relate to again the film growth dynamic process, with laser coating technique, compares, and technology stability is poor, yield rate lower (<50%).
Chemical solution method (MOD) route plan: MOD technique belongs to antivacuum coating process, and the equipment threshold of being engaged in static preparation MOD-YBCO sample is low.In the world, combination with the auxiliary biaxial texture technology (RABiTS) of antivacuum rolling/metal organic deposit (MOD) technology is considered to one of striving direction cheaply, and American Superconductor Corp. has realized the band mass production of hundred meters magnitudes based on this technology.But the MOD route plan is not broken through thick-film technique at present yet.Because the yttrium barium copper oxide speed of growth is very slow, so the approach of enhancing productivity is to adopt the broadband coating technique, with regard to current result, the yield rate of broadband route plan is lower.In addition, although it is very low to be engaged in the equipment threshold of static preparation MOD-YBCO sample, be transitioned into dynamic difficulty from static state larger, improved the investment threshold of equipment.
Multi-source coevaporation route plan: thought in the past that multi-source coevaporation method was difficult to accurately to control yttrium barium copper oxide chemical element proportioning, therefore German Theva company has abandoned the method after effort in a few years.But Korea S SuNAM company has obtained breakthrough recently.Although obtained achievement more than hundred meters, still had the difficult points such as technology stability is poor, yield rate (<50%) is low.
Laser evaporation is similar to electron beam evaporation on principle, and the key distinction is that the former uses the laser beam heats target, and the latter heats target with electron beam.In industrial production and the Laser Devices that medically obtain application with YAG, CO
2laser apparatus and various miniature laser are main.Excimer laser is as a kind of novel tunable laser device, there is the advantages such as radiation wave length (wavelength is at ultraviolet band), high gain, high-level efficiency and superpower, and can also under high repetition frequency, work, so more and more be subject to people's favor, be particularly suitable for applying in the fields such as materials processing and plated film.Due to the radiation frequency of excimer laser in ultraviolet band, not only easily by many materials such as metal, oxide compound, pottery, glass, macromolecular material and plastics, absorbed, but also beam spot size can be controlled to even sub-micrometer scale of micron, can greatly improve the energy density of bundle spot, this processing to various materials and evaporation are very favourable.Common laser coating device mainly is comprised of excimer laser, vacuum chamber, well heater, target etc.Laser beam incides the target surface by quartz window, owing to absorbing energy, the temperature of target material surface, more than the utmost point is elevated to boiling point in the short period of time, just has a large amount of atoms, molecule to be evaporated from target surface thereupon, and be directly injected on base band and condense into film with very high speed, see Fig. 2.Because being oval row, laser evaporation target material out distributes, so, in the single passage laser coating system shown in Fig. 2, only less than 50% evaporated material, be deposited on metal base band.Thereby the utilization ratio and the band that have greatly limited laser energy prepare speed.Be not suitable for scale operation.
If the target transfixion, in high-energy, high frequency situation, LASER SPECKLE very fast (several minutes) will form a pit at target material surface, even punches target, thereby makes coating process can't continue to go on.In order to increase target utilization and to extend the plated film time, adopt the way of rotation target body, the area for laser evaporation on whole target surface can be become to the endless belt shown in Fig. 3 like this.Even use the large size superconducting target of diameter more than 10 centimetres, the method also can only make the laser evaporation coating process maintain the steady time of 1-5 hour.So the method can only meet the preparation of the short belt transect material of laboratory study type, can't realize meeting the preparation of the kilometer level s-generation belt material of high temperature superconduct of requirement on industrial application.Moreover, at superconducting target, only adopting under rotary mode, LASER SPECKLE only is incident in target surface endless belt as shown in Figure 3, and target utilization is very low, causes the superconducting target consumptive material to increase, and is unfavorable for realizing the desired low-cost target of industrialization production.
Summary of the invention
The invention provides the serialization fast laser film coating method of superconducting layer in a kind of s-generation belt material of high temperature superconduct, greatly improved laser utilization ratio and band and prepared speed, reduced cost, realized serialization, the sustainable stably manufactured of kilometer level band.
In order to achieve the above object, the invention provides the serialization fast laser film coating method of superconducting layer in a kind of s-generation belt material of high temperature superconduct, the method includes the steps of:
Step 1, by the metal base band that has plated compound insulation layer and soon need to the prepare superconducting layer plated film chamber of packing into, repeatedly be wrapped on the band roller II of sheet metal strip transmission mechanism of multi-channel laser filming equipment;
Step 2, start well heater, heater temperature is raised to the coating temperature of setting;
Step 3, actuator temperature to be heated are opened oxygen channel after stablizing;
After coating temperature and stable gas pressure in step 4, chamber to be coated, start the rare earth oxide superconducting target, laser coating target Manipulators and laser beam spot scanning device start along the x-direction of rare earth oxide superconducting target and y-scanning direction and rotatablely move;
After step 6, prevapourising process complete, start the sheet metal strip transmission mechanism, by the coating speed of setting, start the superconducting layer coating process;
After step 7, coating process finish, close the light path window of laser apparatus, close well heater, after waiting the metal base band I of all plated films all to lead to cutting belt roller II to be wrapped on reel, stop drawing the stepper-motor of metal base band I transmission;
Step 8, etc. heater temperature be reduced to 50
owhen C is following, open the nitrogen valve, make in the vacuum plating chamber to fill nitrogen to 1 normal atmosphere, open plated film chamber door, take out the band that has plated superconducting layer;
Step 9, cleaning plated film chamber, start coating process next time.
In described step 1, metal base band is nickel-tungsten, Hastelloy or stainless steel metal base band.
In described step 2, press 10-30
othe heat-up rate of C/ minute; Coating temperature is 750-850
oc.
In described step 3,
The flow of oxygen is controlled by mass-flow gas meter, and oxygen flow is in the 10-20SCCM scope;
Oxygen partial pressure during plated film is controlled by the molecular pump flashboard valve, and oxygen partial pressure is 5 * 10
-2-3 * 10
-1in the Torr scope.
In described step 4, the molecular formula of rare earth oxide superconducting material is Re
1ba
2cu
3o
7, wherein, Re is rare earth element y, Gd, Sm, Nd, Ho, Dy, Yb, Er.
In described step 5,
The time of prevapourising is 10-30 minute;
The laser apparatus output frequency is the 100-300 hertz.
In described step 6,
During plated film, the output energy of laser apparatus is the 400-700 millijoule;
Coating speed is 50-200 m/h;
The superconducting layer membrane component is: Re
1ba
2cu
3o
7, wherein, Re is rare earth element y, Gd, Sm, Nd, Ho, Dy, Yb, Er etc., superconducting layer thickness is the 1-5 micron.
Before plated film starts, the background vacuum pressure in the plated film chamber is 5 * 10
-7-5 * 10
-6torr.
In multi-channel laser film coating method of the present invention, the method scanned along the precession of x-y axle two dimension by superconducting target is all utilized the whole surface of target target, and can make the laser evaporation coating process can stablize lasting going on.Increased the plated film interval along the ribbon motion direction by LASER SPECKLE along the way of ribbon motion scanning direction.By above well heater with roller on repeatedly be wound around the way of band, increased the plated film sector width perpendicular to the ribbon motion direction.Fully evaporated material has been collected on metal base band to greatest extent, effectively improved band prepare speed, increased target and evaporated material utilization ratio, greatly improved production efficiency, reduced the band manufacturing cost.Thereby solved the quick plated film problem of s-generation belt material of high temperature superconduct superconducting layer that is suitable for large-scale industrial production.
The accompanying drawing explanation
Fig. 1 is the belt structure schematic diagram that utilizes ion beam assisted deposition and the auxiliary biaxial texture technology of rolling to form in background technology;
Fig. 2 is the principle schematic of single passage laser coating in background technology;
Fig. 3 is superconducting target rotary mode principle schematic in background technology;
Fig. 4 is that the present invention adopts the multi-channel laser plated film to prepare the principle schematic of superconducting layer;
Fig. 5 is superconducting target motion principle schematic diagram of the present invention;
Fig. 6 is the superconduction tunic that utilizes the present invention to prepare
the ray diffraction spectrogram;
Fig. 7 is in the superconduction tunic a-b plane that utilizes the present invention to prepare
the X-ray diffraction spectrogram of scanning;
Fig. 8 is the current-voltage characteristic curve of the superconduction tunic that utilizes the present invention to prepare.
Embodiment
Following according to Fig. 4～Fig. 8, illustrate preferred embodiment of the present invention.
As shown in Figure 4, adopted the multi-channel laser film coating method to prepare the rare earth oxide superconducting layer in s-generation belt material of high temperature superconduct, this serialization fast laser film coating method comprises following steps:
Step 1, by the metal base band that has plated compound insulation layer and soon need to the prepare superconducting layer plated film chamber of packing into, repeatedly be wrapped on the band roller II of sheet metal strip transmission mechanism of multi-channel laser filming equipment;
Metal base band is nickel-tungsten, Hastelloy or stainless steel metal base band;
Step 2, start well heater, heater temperature is raised to the coating temperature of setting;
Press 10-30
othe heat-up rate of C/ minute;
Coating temperature is 750-850
oc;
Step 3, actuator temperature to be heated are opened oxygen channel after stablizing;
The flow of oxygen is controlled by mass-flow gas meter, and oxygen flow is in the 10-20SCCM scope;
Oxygen partial pressure during plated film is controlled by the molecular pump flashboard valve, and oxygen partial pressure is 5 * 10
-2-3 * 10
-1in the Torr scope;
After coating temperature and stable gas pressure in step 4, chamber to be coated, start the rare earth oxide superconducting target, laser coating target Manipulators and laser beam spot scanning device start along the x-direction of rare earth oxide superconducting target and y-scanning direction and rotatablely move; Laser coating target Manipulators is by the step motor control of below, along parameters such as x-direction and y-scanning direction and the speed rotatablely moved, step-lengths, by system operating software, sets; Laser beam spot is realized by quick swing laser mirror input angle in the scanning motion of target surface;
The molecular formula of rare earth oxide superconducting material is Re
1ba
2cu
3o
7, wherein, Re is rare earth element y, Gd, Sm, Nd, Ho, Dy, Yb, Er etc.;
The time of prevapourising is 10-30 minute;
The laser apparatus output frequency is the 100-300 hertz;
After step 6, prevapourising process complete, start the sheet metal strip transmission mechanism, by the coating speed of setting, start the superconducting layer coating process;
During plated film, the output energy of laser apparatus is the 400-700 millijoule;
Coating speed is 50-200 m/h;
The superconducting layer membrane component is: Re
1ba
2cu
3o
7, wherein, Re is rare earth element y, Gd, Sm, Nd, Ho, Dy, Yb, Er etc., superconducting layer thickness is the 1-5 micron;
After step 7, coating process finish, close the light path window of laser apparatus, close well heater, after waiting the metal base band I of all plated films all to lead to cutting belt roller II to be wrapped on reel, stop drawing the stepper-motor of metal base band I transmission;
Step 8, etc. heater temperature be reduced to 50
owhen C is following, open the nitrogen valve, make inflated with nitrogen to 1 normal atmosphere in the vacuum plating chamber, open plated film chamber door, take out the band that has plated superconducting layer;
Step 9, cleaning plated film chamber, start coating process next time.
Before plated film starts, the background vacuum pressure in the plated film chamber is 5 * 10
-7-5 * 10
-6torr.
Prepare speed and reduce costs in order to increase band, the present invention has adopted the multi-channel laser film coating method to prepare the rare earth oxide superconducting layer in s-generation belt material of high temperature superconduct, by adopting the multi-channel laser film coating method can make the evaporated material more than 90% be deposited on metal base band, thereby the utilization ratio and the band that have greatly improved laser energy prepare speed, have reduced cost.
In addition, as shown in Figure 5, in order to realize serialization, the sustainable stably manufactured of kilometer level band, the present invention adopts the method for superconducting target along x-y axle two dimension precession scanning.Under this pattern, in the laser coating process, target drives along x-axle and y-axle and carries out planar scanning by stepper-motor.Can guarantee that by scanning LASER SPECKLE is incident on whole target surface, thereby increase target utilization, can make target utilization bring up to more than 90%.And in coating process, make target surface remain smooth, 20 centimetres of such diameters, the target that thickness is 1 centimetre can prepare the band of 10-20 kilometer.Thereby greatly reduce the band manufacturing cost.
In a word, in multi-channel laser film coating method of the present invention, the method scanned along the precession of x-y axle two dimension by superconducting target is all utilized the whole surface of target target, and can make the laser evaporation coating process can stablize lasting going on.Increased the plated film interval along the ribbon motion direction by LASER SPECKLE along the way of ribbon motion scanning direction.By above well heater with roller on repeatedly be wound around the way of band, increased the plated film sector width perpendicular to the ribbon motion direction.Fully evaporated material has been collected on metal base band to greatest extent, effectively improved band prepare speed, increased target and evaporated material utilization ratio, greatly improved production efficiency, reduced the band manufacturing cost.Thereby solved the quick plated film problem of s-generation belt material of high temperature superconduct superconducting layer that is suitable for large-scale industrial production.
As shown in Figure 6, be the Re prepared
1ba
2cu
3o
7the superconduction tunic
the ray diffraction spectrogram, Fig. 7 is the Re prepared
1ba
2cu
3o
7in superconduction tunic a-b plane
the X-ray diffraction spectrogram of scanning.
The present invention adopts the multi-channel laser plating method, has not only overcome little this shortcoming of coating film area of single passage laser coating method, has greatly improved coating speed, and has given full play to every advantage of laser coating method.The superconducting thin film that the results show adopts the multi-channel laser plating method to prepare has following microstructure and current transfer performance: it is single-orientated that (1) superconducting film has very pure c-axle, and X-ray diffraction is measured proof Re
1ba
2cu
3o
7film only exists (00
l) diffraction peak, without a-axle orientation crystal grain.(2) highly crystalline, X-ray diffraction only the analysis showed that in the a-b plane that the diffraction peak every 90 degree occurs, proves Re
1ba
2cu
3o
7superconducting film has single-orientated quadruple symmetrical structure.(3) superconduction transports the performance measurement proof and adopts the standby Re of laser evaporation legal system
1ba
2cu
3o
7superconducting tape has superior superconduction current capacity.Figure 8 shows that and adopt the standby Re of laser evaporation legal system
1ba
2cu
3o
7the current-voltage characteristic curve of superconducting film.Test condition is: temperature 77K, and without externally-applied magnetic field.Strip width is 1 centimetre; Base band thickness is the 50-80 micron; Superconducting layer thickness is 1 micron.The superconduction critical electric current of sample shown in Fig. 8 is 300 amperes.This numerical value is more than 200 times of same cross-sectional area traditional copper wire current capacity.The quench judging criterion is: 1 microvolt/centimetre.Under superconducting state, because band resistance is almost nil, so voltage is less than and receives volt (voltmeter noise signal magnitude).
Although content of the present invention has been done detailed introduction by above preferred embodiment, will be appreciated that above-mentioned description should not be considered to limitation of the present invention.After those skilled in the art have read foregoing, for multiple modification of the present invention with to substitute will be all apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (2)
1. the serialization fast laser film coating method of superconducting layer in a s-generation belt material of high temperature superconduct, is characterized in that, the method includes the steps of:
Step 1, by the metal base band that has plated compound insulation layer and soon need to the prepare superconducting layer plated film chamber of packing into, repeatedly be wrapped on the band roller II of sheet metal strip transmission mechanism of multi-channel laser filming equipment;
Step 2, start well heater, heater temperature is raised to the coating temperature of setting;
Step 3, actuator temperature to be heated are opened oxygen channel after stablizing;
After coating temperature and stable gas pressure in step 4, chamber to be coated, start the rare earth oxide superconducting target, laser coating target Manipulators and laser beam spot scanning device start along the x-direction of rare earth oxide superconducting target and y-scanning direction and rotatablely move;
Step 5, start laser apparatus, open the light path window of laser apparatus, start the rare earth oxide superconducting target is carried out to prevapourising;
After step 6, prevapourising process complete, start the sheet metal strip transmission mechanism, by the coating speed of setting, start the superconducting layer coating process;
After step 7, coating process finish, close the light path window of laser apparatus, close well heater, after waiting the metal base band I of all plated films all to lead to cutting belt roller II to be wrapped on reel, stop drawing the stepper-motor of metal base band I transmission;
Step 8, etc. heater temperature be reduced to 50
owhen C is following, open the nitrogen valve, make inflated with nitrogen to 1 normal atmosphere in the vacuum plating chamber, open plated film chamber door, take out the band that has plated superconducting layer;
Step 9, cleaning plated film chamber, start coating process next time;
In described step 1, metal base band is nickel-tungsten, Hastelloy or stainless steel metal base band;
In described step 2, press 10-30
oit is temperature required that the heat-up rate of C/ minute is elevated to plated film by heater temperature from room temperature; Coating temperature is 750-850
oc;
In described step 3,
The flow of oxygen is controlled by mass-flow gas meter, and oxygen flow is in the 10-20SCCM scope;
Oxygen partial pressure during plated film is controlled by the molecular pump flashboard valve, and oxygen partial pressure is 5 * 10
-2-3 * 10
-1in the Torr scope;
In described step 4, the molecular formula of rare earth oxide superconducting material is Re
1ba
2cu
3o
7, wherein, Re is rare earth element y, or Gd, or Sm, or Nd, or Ho, or Dy, or Yb, or Er;
In described step 5,
The time of prevapourising is 10-30 minute;
The laser apparatus output frequency is the 100-300 hertz;
In described step 6,
During plated film, the output energy of laser apparatus is the 400-700 millijoule;
Coating speed is 50-200 m/h;
The superconducting layer membrane component is: Re
1ba
2cu
3o
7, wherein, Re is rare earth element y, or Gd, or Sm, or Nd, or Ho, or Dy, or Yb, or Er, superconducting layer thickness is the 1-5 micron.
2. the serialization fast laser film coating method of superconducting layer in s-generation belt material of high temperature superconduct as claimed in claim 1, is characterized in that, before plated film starts, the background vacuum pressure in the plated film chamber is 5 * 10
-7-5 * 10
-6torr.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110367810 CN102409298B (en) | 2011-11-18 | 2011-11-18 | Continuous rapid laser coating method of superconducting layer in second-generation high-temperature superconducting strip |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110367810 CN102409298B (en) | 2011-11-18 | 2011-11-18 | Continuous rapid laser coating method of superconducting layer in second-generation high-temperature superconducting strip |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102409298A CN102409298A (en) | 2012-04-11 |
| CN102409298B true CN102409298B (en) | 2013-12-25 |
Family
ID=45911635
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110367810 Active CN102409298B (en) | 2011-11-18 | 2011-11-18 | Continuous rapid laser coating method of superconducting layer in second-generation high-temperature superconducting strip |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102409298B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110205602B (en) * | 2019-06-20 | 2021-10-19 | 上海超导科技股份有限公司 | Coating method for growing second-generation high-temperature superconducting tape barrier layer composite film |
| CN110791745B (en) * | 2019-12-12 | 2024-02-13 | 上海超导科技股份有限公司 | Orthogonal radiation auxiliary conduction heating equipment suitable for roll-to-roll continuous strip |
| CN111785443B (en) * | 2020-07-15 | 2021-09-21 | 上海超导科技股份有限公司 | Method for producing high-temperature superconducting strip by multi-source ion jet source ex-situ deposition |
| CN112599300B (en) * | 2021-03-04 | 2021-05-11 | 上海超导科技股份有限公司 | Apparatus and method for coating superconducting tape and superconducting tape |
| CN113463045B (en) * | 2021-06-11 | 2022-10-14 | 华中科技大学 | Laser pulse deposition system and processing method |
| CN114184399B (en) * | 2021-12-09 | 2022-11-18 | 上海超导科技股份有限公司 | Device and method for testing turning diameter of reel-to-reel superconducting strip |
| CN114934308B (en) * | 2022-06-30 | 2024-03-26 | 东部超导科技（苏州）有限公司 | High-temperature superconducting strip copper electroplating device and method based on insoluble anode |
| CN117821906A (en) * | 2024-01-21 | 2024-04-05 | 江苏康美达光学有限公司 | Optical lens coating method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050005846A1 (en) * | 2003-06-23 | 2005-01-13 | Venkat Selvamanickam | High throughput continuous pulsed laser deposition process and apparatus |
-
2011
- 2011-11-18 CN CN 201110367810 patent/CN102409298B/en active Active
Non-Patent Citations (4)
| Title |
|---|
| Fast Growth Process of Long-Length YBCO Coated Conductor With High Critical Current Density;Yijie Li, et al.;《IEEE TRANSACTIONS ON APPLIED SUPERCONDUCTIVITY》;20050630;第15卷(第2期);第2771-2774页 * |
| The Influence of Temperature Distribution on YBCO Coated Conductor Deposited by Reel-to-Reel PLD Method;Xiaokun Song, et al.;《Journal of Superconductivity and Novel Magnetism》;20110731;第24卷(第5期);第1793-1796页 * |
| Xiaokun Song, et al..The Influence of Temperature Distribution on YBCO Coated Conductor Deposited by Reel-to-Reel PLD Method.《Journal of Superconductivity and Novel Magnetism》.2011,第24卷(第5期),第1793-1796页. |
| Yijie Li, et al..Fast Growth Process of Long-Length YBCO Coated Conductor With High Critical Current Density.《IEEE TRANSACTIONS ON APPLIED SUPERCONDUCTIVITY》.2005,第15卷(第2期),第2771-2774页. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102409298A (en) | 2012-04-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102409298B (en) | Continuous rapid laser coating method of superconducting layer in second-generation high-temperature superconducting strip | |
| Foltyn et al. | High-T/sub c/coated conductors-performance of meter-long YBCO/IBAD flexible tapes | |
| Goyal et al. | The RABiTS approach: Using rolling-assisted biaxially textured substrates for high-performance YBCO superconductors | |
| Watanabe et al. | Progress and future prospects of research and development on coated conductors in Japan | |
| CN103985479B (en) | A kind of preparation method of conductor of high-temperature superconductor coat band | |
| CN103695859B (en) | The two-sided LaMnO of superconducting tape 3the preparation method of buffer layer | |
| CN102610322B (en) | High-temperature superconductive coating conductor dual-layer buffering layer structure and dynamic deposition method thereof | |
| Kakimoto et al. | Fabrication of long-Y123 coated conductors by combination of IBAD and PLD | |
| CN102306702B (en) | Method suitable for continuously preparing high-temperature superconductive belt material | |
| CN100469940C (en) | Prepn process of metal oxide film | |
| CN110205602B (en) | Coating method for growing second-generation high-temperature superconducting tape barrier layer composite film | |
| JP4316070B2 (en) | High strength oriented polycrystalline metal substrate and oxide superconducting wire | |
| US11488746B2 (en) | Superconductor with improved flux pinning at low temperatures | |
| JP4398582B2 (en) | Oxide superconducting wire and method for producing the same | |
| WO2007040567A2 (en) | Method for improving performance of high temerature superconductors within a magnetic field | |
| CN102251219B (en) | Multichannel laser deposition method for preparing YSZ buffer layer | |
| JP2003206134A (en) | High temperature superconducting thick film member and method for producing the same | |
| Izumi et al. | All Japan efforts on R&D of HTS coated conductors for future applications | |
| JP2002075079A (en) | High-temperature superconducting thick-layer material and method for manufacturing the same | |
| Kakimoto et al. | Development of Y-123 coated conductors by ion-beam-assisted deposition | |
| CN110257792B (en) | Film coating mechanism and device for growing second-generation high-temperature superconducting strip barrier layer composite film | |
| CN102286711A (en) | Multi-passage fast in-situ annealing method for biaxial textured nickel-tungsten metal base band | |
| EP4258298A1 (en) | Method for manufacturing superconducting coils and device | |
| Tachikawa et al. | New A15 Nb3 (Al, Ge) tape prepared from σ-phase powder | |
| CN102690114B (en) | Method for preparing YBCO superconducting composite film |
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 |