CN102409298A - 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
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- CN102409298A CN102409298A CN2011103678107A CN201110367810A CN102409298A CN 102409298 A CN102409298 A CN 102409298A CN 2011103678107 A CN2011103678107 A CN 2011103678107A CN 201110367810 A CN201110367810 A CN 201110367810A CN 102409298 A CN102409298 A CN 102409298A
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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 make the field, relate in particular to the quick laser coating method of serialization of superconducting layer in a kind of s-generation belt material of high temperature superconduct.
Background technology
Superconducting material always received 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 near 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 type material is 23.2K, and the application in fields such as zeugmatographys mainly is representative with the niobium titanium alloy at present, and the refrigeration cycle medium is a liquid helium, is called low temperature superconducting material traditionally.
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 an isolator " has been broken in this discovery, thereby has opened up new research approach for exploring the superconducting material with higher temperature, open greatly many field scientists' the visual field.The discoverer Miu Le of high-temperature superconductor phenomenon and Bednorz have just obtained Nobel prize for physics 1 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 of finding subsequently with higher superconducting temperature is being brought up to superconducting transition temperature more than the liquid nitrogen temperature (77K) on the human history first, has broken through liquid nitrogen " temperature barrier ".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 material development history, so the important breakthrough on the science and technology developing history, lay a good foundation for the large-scale commercial applications application of superconducting material first.Traditionally the rare earth oxide superconducting material is called high temperature superconducting materia.
Superconducting material has attracted numerous scientists' attention owing to have superior and unique conductivity and magnetic performance always since superconducting phenomenon at the beginning of last century is found.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 has 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, is processed into required wire rod of various application or band easily.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, thus the expensive big limitations of refrigeration cost its range of application.Be mainly used in the irreplaceable fields of other material such as zeugmatography and high field magnet at present.High temperature superconducting materia not only can reduce thermal losses greatly 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, also have huge social, economic benefit so the research and development of high temperature superconducting materia not only have scientific value with production.But after high-temperature superconductor heat in a few years,, find that the practical application of high temperature superconducting materia is tired more much more difficult than original expection along with going deep into of research work.This is main relevant with the microtexture and the mechanical property of high temperature superconducting materia.Compare with traditional metal cryogenic superconductor; High-temperature superconductor belongs to oxide material; With regard to its mechanical property, belong to " oxide ceramics " series, so; Compare with traditional low temperature superconducting material and to be difficult for being processed into required wire rod of various application or band, so 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 scientists at first 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 is main with bismuth system (bismuth-strontium-calcium-copper-oxygen) high temperature superconducting materia.The principle of " silver-colored jacket " method is that the Bi-based high-temperature superconductive powder is poured in the hollow silver sleeve, and processes such as stretched and pressurization becomes the silver-colored jacket belt material of high temperature superconduct of 4 mm wides, 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 making 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 about the 150-210 ampere.Joint length is above 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 up production line.Though first-generation belt material of high temperature superconduct has begun to commercially produce, because the obstacle of aspects such as existence price ratio, at present still can't large-scale promotion application.Its major cause is following: the first-generation belt material of high temperature superconduct that the first, with the bi tape 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 space is limited.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 used under the magnetic field more than most of medium tenacitys.Three, because silver as noble metal, material cost is higher, so 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 of competing with traditional copper conductor.At present still at 150-200 dollar/KA rice ($150-200/kAm) in the scope.According to the estimation of USDOE, the ratio of performance to price of belt material of high temperature superconduct large-scale commercial applications application should be superior to the copper conductor cost performance, is about 20-50 dollar/KA rice ($20-50/kAm).Have only after the ratio of performance to price of belt material of high temperature superconduct reaches this index, just might substitute traditional copper conductor material on a large scale.
Since nineteen ninety, states such as U.S.A, day, moral have begun 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 adopts various plated film means to go up the rare earth oxide high-temperature superconducting thin film of plating one deck about 1 to several micron thick in the traditional metal base band (alloys such as nickel-base alloy or stainless steel) of very thin (40-100 micron) exactly.Compare with the first-generation belt material of high temperature superconduct of " silver-colored jacket " law technology development; 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, thus along with research and development level raising, the cost of s-generation belt material of high temperature superconduct will reduce greatly.In recent years because sharp rising of the prices of raw and semifnished materials such as oil, precious metal, non-ferrous metal realizes the cost objective of s-generation belt material of high temperature superconduct more easily.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) at first to adopt the laser coating technology to succeed in developing 1 meter magnitude length, supercurrent in 1996 be that s-generation belt material of high temperature superconduct has generally caused the great attention of states such as U.S.A, day, moral behind 100 amperes the yttrium barium copper oxide belt material of high temperature superconduct in National Laboratory.And emphasis progressively carried out the transition 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 is carried out s-generation belt material of high temperature superconduct industrialization R&D work with " 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.2010 s-generation belt material of high temperature superconduct coating process that the end of the year, successful development had independent intellectual property right, the superconduction current capacity has reached 194 amperes.And thoroughly solved from the laboratory study achievement to industrialization shift the technological difficulties such as stability, repeatability and safety of the coating process that must overcome.Thereby lay a good foundation for follow-up industrialization production.
With the yttrium barium copper oxide is the oxide compound rare earth superconductor of representative, because its superconductivity is very responsive to the microstructure of material, so be difficult to adopt the employed powder metallurgical technique of first-generation belt material of high temperature superconduct to prepare band.Be close to perfect crystalline network in order to form, superconducting layer adopts various coating techniques usually so that on the metal base band of cheapness, realize epitaxy.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 the core.
Base band preparation technology can be divided into two big types: ion beam assisted deposition (Ion Beam Assited Deposition; Be abbreviated as IBAD) and rolling auxiliary biaxial texture technology (Rolling Assisted Biaxially Textured Substrates; Be abbreviated as RABiTS), its multilayered structure synoptic diagram is as shown in Figure 1.The IBAD technology does not have particular requirement to the metal base band material chosen, and the Ni alloy and the stainless steel capital can be used as the base band material.In the IBAD technology, according to the difference of selecting for use material, its technological process also respectively has characteristics.Material commonly used at present comprises YSZ (yttrium-stabile zirconium dioxide, Y-ZrO
2), GZO (Gd
2Zr
2O
7) and MgO.Japan ISTEC and Fujikura company have higher IBAD base band and prepare level.FUJIKURA has built up large-scale IBAD equipment, can prepare 1000 meters long base band continuously.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 be the basis with the high-vacuum technology, and for the IBAD technology, the RABiTS technology has efficient height, equipment advantage simple and with low cost.The Ni-5at%W and the Ni-3at%W alloy of the low magnetic of tool are the main raws of present RABiTS base band.The long Ni-5at%W base band of Germany's Evico company 100-200 rice for sale, thickness of strip 40-80 micron, 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 (Oak Ridge National Laboratory is abbreviated as ORNL) of RABiTS technology still maintains the leading position in this field.ORNL has built 1000 grades of clean rooms for 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, 1000 meters long RABiTS base band.Typical base band is characterized as face interscan halfwidth less than 7
o, r.m.s. roughness is 3 nanometers.
Compare with IBAD technology, the relative merits of RABiTS technology are following: advantage: rolling technology is comparatively ripe, if adopt broadband (greater than 10 centimetres) rolling technology, is fit to scale operation.Shortcoming: mechanical property is relatively poor, has faint magnetic; In addition, the high temperature lower surface is prone to oxidation, so increased the difficulty and the complexity of epitaxy sealing coat.On the RABiTS base band, if seed layer thickness (CeO
2) surpass 100 nanometers, form tiny crack easily.
The preparation method of compound insulation layer comprises on the preparation method of compound insulation layer on the RABiTS metal base band (Seed Layer, sealing coat and cap layer) and the IBAD base band: laser coating method (Pulsed Laser Deposition; Be abbreviated as PLD), method such as magnetron sputtering method, coevaporation method (Thermal Co-evaporation is abbreviated as TCE) and ion beam sputtering.Because the compound buffer layer very thin thickness, so that material cost almost can be ignored is too late, prime cost derives from coating process control (yield rate).The preparation of impact plies is more complicated on the IBAD base band comparatively speaking.And there is certain difficulty (Ni base band surface oxidation problem under the high temperature) in the preparation of Seed Layer on the RABiTS base band.
The preparation method who with the yttrium barium copper oxide is the rare earth oxide superconducting layer of representative comprises: laser coating method, coevaporation method, metal organic chemical vapor deposition method (MOCVD) and solution method methods such as (MOD).The growth of yttrium barium copper oxide superconducting layer is a key of making s-generation belt material of high temperature superconduct.Because the quality of superconducting layer determined superconducting tape can transmission current size; Can and the size of supercurrent be directly relevant with the ratio of performance to price of superconducting tape, be the large-scale commercial applications key in application so prepare the band with very high supercurrent transmittability.Above the relative merits of several kinds of film coating method following:
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 be practiced thrift facility investment intensity greatly 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 height, can accurately control the thickness of nanometer scale through laser pulse frequency.Good stability, the technology degree of controllability is high.Target is an oxide powder sintering target, and cost is low and utilization ratio is high.The laser coating method has good stability and repeatability, and the yttrium barium copper oxide superconducting tape with the laser coating technology growth has best superconductivity at present.This method biggest advantage is exactly the accurate component of control growing film, thereby can obtain correct yttrium, barium, copper (123) phase chemistry proportioning.Yield rate is higher than other method far away more than 95%.So on the bulking property price ratio, have more competitive power.
Metal organic chemical vapor deposition method (MOCVD) route plan: in the MOCVD route plan; Because the MOCVD system only is used to prepare the yttrium barium copper oxide superconducting layer; Need other the growth of PVD (laser coating or magnetron sputtering) filming equipment Seed Layer, sealing coat and cap layer etc.; So in the MOCVD scheme, facility investment intensity is bigger.In addition, need synthetic special Y, Ba, Cu organic cpds source, and the organic source of MOCVD cost is high, so material cost is also higher.MOCVD technology promptly relates to chemical reaction and relates to the film growth dynamic process again, with laser coating technology relatively, technology stability is poor, yield rate lower (< 50%).
Chemical solution method (MOD) route plan: MOD technology 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 antivacuum rolling auxiliary biaxial texture technology (RABiTS)/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 present result, the yield rate of broadband route plan is lower.In addition, though it is very low to be engaged in the equipment threshold of static preparation MOD-YBCO sample, it is bigger to carry out the transition to dynamic difficulty from static state, has improved the investment of devices threshold.
Multi-source coevaporation route plan: thought in the past that multi-source coevaporation method was difficult to accurately control yttrium barium copper oxide chemical element proportioning, so German Theva company has abandoned this method after effort in a few years.But Korea S SuNAM company has obtained breakthrough recently.Though obtained achievement more than hundred meters, have still that technology stability is poor, a difficult point such as yield rate (< 50%) is low.
Laser evaporation is similar to electron beam evaporation on principle, the key distinction is that the former uses the laser beam heats target, and the latter then heats target with electron beam.In industrial production and the Laser Devices of medically using with YAG, CO
2Laser apparatus and various miniature laser are main.Excimer laser is as a kind of novel tunable laser device; Have 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 receive people's favor, be particularly suitable in fields such as materials processed and plated film, using.Because the radiation frequency of excimer laser is in ultraviolet band; Not only absorbed by many materials such as metal, oxide compound, pottery, glass, macromolecular material and plastics easily; But also can beam spot size be controlled to micron even sub-micrometer scale; Can improve the energy density of bundle spot greatly, this processing and evaporation to various materials is very favourable.Common laser coating device mainly is made up of excimer laser, vacuum chamber, well heater, target etc.Laser beam incides the target surface through quartz window; Because absorb energy, the temperature of target material surface is elevated in the short period of time more than the boiling point at the utmost point, just has a large amount of atoms, molecule to be evaporated from target surface thereupon; And be directly injected to very high speed and condense into film on the base band, see Fig. 2.Because being oval row, the target material that laser evaporation comes out distributes, so, in single passage laser coating system shown in Figure 2, only be deposited on the metal base band less than 50% evaporated material.Thereby big limitations the utilization ratio and the band of laser energy prepare speed.Be not suitable for scale operation.
If the target transfixion, under 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 prolong the plated film time, adopt the way of rotation target body, can the area that be used for laser evaporation on the whole target surface be become endless belt shown in Figure 3 like this.Even use the large size superconduction target of diameter more than 10 centimetres, this method also can only make the laser evaporation coating process keep 1-5 hour steady time.So this method can only satisfy the preparation of the short belt transect material of laboratory study type, can't realize satisfying the preparation of the kilometer level s-generation belt material of high temperature superconduct of requirement on industrial application.Moreover, only adopting under the rotary mode at the superconduction target, LASER SPECKLE only is incident in the target surface endless belt as shown in Figure 3, and target utilization is very low, causes superconduction target consumptive material to increase, and is unfavorable for realizing that industrialization produces desired low-cost target.
Summary of the invention
The present invention provides the serialization of superconducting layer in a kind of s-generation belt material of high temperature superconduct quick laser coating method, has improved laser utilization ratio and band greatly and has prepared speed, reduced cost, has realized serialization, the Sustainable Stability production of kilometer level band.
In order to achieve the above object, the present invention provides the serialization of superconducting layer in a kind of s-generation belt material of high temperature superconduct quick laser coating method, and the method includes the steps of:
Step 1, the metal base band that will plate compound insulation layer and be about to need the preparation superconducting layer plated film chamber of packing into repeatedly is 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;
After step 3, actuator temperature to be heated are stablized, open oxygen channel;
Behind the coating temperature and stable gas pressure in step 4, the chamber to be coated, start rare earth oxide superconduction target, laser coating target effector and laser beam spot scanning device begin along the x-direction of rare earth oxide superconduction target and y-scanning direction and rotatablely move;
After step 6, prevapourising process are accomplished, start the sheet metal strip transmission mechanism, begin the superconducting layer coating process by the coating speed of setting;
After step 7, coating process finish, close the light path window of laser apparatus, close well heater, after waiting all the metal base band I of plated film having led to cutting belt roller II and is wrapped on the reel, stop to draw 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 and fill 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 begin coating process next time.
In the described step 1, metal base band is nickel-tungsten, Hastelloy or stainless steel metal base band.
In the described step 2, press 10-30
oC/ minute heat-up rate; Coating temperature is 750-850
oC.
In the 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 by the control of molecular pump flashboard valve, and oxygen partial pressure is 5 * 10
-2-3 * 10
-1In the Torr scope.
In the 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 the described step 5,
The time of prevapourising is 10-30 minute;
The laser apparatus output frequency is the 100-300 hertz.
In the described step 6,
During plated film, the output energy of laser apparatus is the 400-700 millijoule;
Coating speed be 50-200 rice/hour;
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 began, the background vacuum pressure in the plated film chamber was 5 * 10
-7-5 * 10
-6Torr.
In the multi-channel laser film coating method that the present invention adopted, make the whole surface of target target all obtain utilizing through the superconduction target along x-y axle two dimension precession method for scanning, and can make the laser evaporation coating process can stablize lasting going on.Increased along the plated film of ribbon motion direction interval through LASER SPECKLE along the way of ribbon motion scanning direction.Through the way of on the band roller above the well heater, repeatedly twining band, increased plated film sector width perpendicular to the ribbon motion direction.Fully will be evaporated material collected to greatest extent on the metal base band, 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.
Description of drawings
Fig. 1 is the belt structure synoptic diagram that utilizes ion beam assisted deposition and rolling auxiliary biaxial texture technology to form in the background technology;
Fig. 2 is the principle schematic of single passage laser coating in the background technology;
Fig. 3 is a superconduction target rotary mode principle schematic in the 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 a superconduction target motion principle synoptic diagram of the present invention;
Fig. 6 is
the XRD X spectrogram that utilizes the superconduction tunic that the present invention prepares;
Fig. 7 is the X-ray diffraction spectrogram that utilizes
scanning in the superconduction tunic a-b plane that the present invention prepares;
Fig. 8 is the current-voltage characteristic curve that utilizes the superconduction tunic that the present invention prepares.
Embodiment
Following according to Fig. 4～Fig. 8, specify 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 the s-generation belt material of high temperature superconduct, the quick laser coating method of this serialization comprises following steps:
Step 1, the metal base band that will plate compound insulation layer and be about to need the preparation superconducting layer plated film chamber of packing into repeatedly is 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
oC/ minute heat-up rate;
Coating temperature is 750-850
oC;
After step 3, actuator temperature to be heated are stablized, open oxygen channel;
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 by the control of molecular pump flashboard valve, and oxygen partial pressure is 5 * 10
-2-3 * 10
-1In the Torr scope;
Behind the coating temperature and stable gas pressure in step 4, the chamber to be coated, start rare earth oxide superconduction target, laser coating target effector and laser beam spot scanning device begin along the x-direction of rare earth oxide superconduction target and y-scanning direction and rotatablely move; Laser coating target effector is by the step motor control of below, sets through system operating software along parameters such as x-direction and y-scanning direction and the speed that rotatablely moves, step-lengths; Laser beam spot is realized through 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 are accomplished, start the sheet metal strip transmission mechanism, begin the superconducting layer coating process by the coating speed of setting;
During plated film, the output energy of laser apparatus is the 400-700 millijoule;
Coating speed be 50-200 rice/hour;
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 all the metal base band I of plated film having led to cutting belt roller II and is wrapped on the reel, stop to draw 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 begin coating process next time.
Before plated film began, the background vacuum pressure in the plated film chamber was 5 * 10
-7-5 * 10
-6Torr.
Prepare speed and reduce cost 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 the s-generation belt material of high temperature superconduct; Through employing multi-channel laser film coating method the evaporated material more than 90% is deposited on the metal base band, thereby the utilization ratio and the band that have improved laser energy greatly prepare speed, have reduced cost.
In addition, as shown in Figure 5, in order to realize serialization, the Sustainable Stability production of kilometer level band, the present invention adopts the superconduction target along x-y axle two dimension precession method for scanning.Under this pattern, in the laser coating process, target carries out planar scanning through step motor drive along x-axle and y-axle.Can guarantee that through scanning LASER SPECKLE is incident on the whole target surface, thereby increase target utilization, target utilization is brought up to more than 90%.And it is smooth that target surface is remained, 20 centimetres of such diameters, and 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 the multi-channel laser film coating method that the present invention adopted, make the whole surface of target target all obtain utilizing through the superconduction target along x-y axle two dimension precession method for scanning, and can make the laser evaporation coating process can stablize lasting going on.Increased along the plated film of ribbon motion direction interval through LASER SPECKLE along the way of ribbon motion scanning direction.Through the way of on the band roller above the well heater, repeatedly twining band, increased plated film sector width perpendicular to the ribbon motion direction.Fully will be evaporated material collected to greatest extent on the metal base band, 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 for preparing
1Ba
2Cu
3O
7The superconduction tunic
XRD X spectrogram, Fig. 7 are the Re for preparing
1Ba
2Cu
3O
7In the 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 improved coating speed greatly, and has given full play to each item advantage of laser coating method.The experimental result proof adopts the superconducting thin film of multi-channel laser plating method preparation to have 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, no a-axle orientation crystal grain.(2) highly crystalline property has only every diffraction peak at a distance from 90 degree to occur in the X-ray diffraction analysis revealed a-b plane, prove Re
1Ba
2Cu
3O
7Superconducting film has single-orientated quadruple symplex structure.(3) superconduction transport property energy measurement proof adopts the Re of laser evaporation method preparation
1Ba
2Cu
3O
7Superconducting tape has superior superconduction current capacity.Shown in Figure 8 for adopting the Re of laser evaporation method preparation
1Ba
2Cu
3O
7The current-voltage characteristic curve of superconducting film.Test condition is: temperature 77K, no 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 lead current capacity.The quench judgement criteria is: 1 microvolt/centimetre.Under superconducting state, because band resistance is almost nil, so voltage is less than receiving volt (voltmeter noise signal magnitude).
Although content of the present invention has been done detailed introduction through above-mentioned 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 all will be conspicuous.Therefore, protection scope of the present invention should be limited appended claim.
Claims (8)
1. the quick laser coating method of serialization of superconducting layer in the s-generation belt material of high temperature superconduct is characterized in that the method includes the steps of:
Step 1, the metal base band that will plate compound insulation layer and be about to need the preparation superconducting layer plated film chamber of packing into repeatedly is 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;
After step 3, actuator temperature to be heated are stablized, open oxygen channel;
Behind the coating temperature and stable gas pressure in step 4, the chamber to be coated, start rare earth oxide superconduction target, laser coating target effector and laser beam spot scanning device begin along the x-direction of rare earth oxide superconduction target and y-scanning direction and rotatablely move;
Step 5, start laser apparatus, open the light path window of laser apparatus, begin rare earth oxide superconduction target is carried out prevapourising;
After step 6, prevapourising process are accomplished, start the sheet metal strip transmission mechanism, begin the superconducting layer coating process by the coating speed of setting;
After step 7, coating process finish, close the light path window of laser apparatus, close well heater, after waiting all the metal base band I of plated film having led to cutting belt roller II and is wrapped on the reel, stop to draw 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 begin coating process next time.
2. the quick laser coating method of the serialization of superconducting layer is characterized in that in the s-generation belt material of high temperature superconduct as claimed in claim 1, and in the described step 1, metal base band is nickel-tungsten, Hastelloy or stainless steel metal base band.
3. the quick laser coating method of the serialization of superconducting layer is characterized in that in the s-generation belt material of high temperature superconduct as claimed in claim 1, in the described step 2, presses 10-30
oIt is temperature required that C/ minute heat-up rate is elevated to plated film with heater temperature from room temperature; Coating temperature is 750-850
oC.
4. the quick laser coating method of the serialization of superconducting layer is characterized in that in the s-generation belt material of high temperature superconduct as claimed in claim 1, in the 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 by the control of molecular pump flashboard valve, and oxygen partial pressure is 5 * 10
-2-3 * 10
-1In the Torr scope.
5. the quick laser coating method of the serialization of superconducting layer is characterized in that in the s-generation belt material of high temperature superconduct as claimed in claim 1, and in the 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.
6. the quick laser coating method of the serialization of superconducting layer is characterized in that in the s-generation belt material of high temperature superconduct as claimed in claim 1, in the described step 5,
The time of prevapourising is 10-30 minute;
The laser apparatus output frequency is the 100-300 hertz.
7. the quick laser coating method of the serialization of superconducting layer is characterized in that in the s-generation belt material of high temperature superconduct as claimed in claim 1, in the described step 6,
During plated film, the output energy of laser apparatus is the 400-700 millijoule;
Coating speed be 50-200 rice/hour;
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.
8. the quick laser coating method of the serialization of superconducting layer is characterized in that in the s-generation belt material of high temperature superconduct as claimed in claim 1, and before plated film began, the background vacuum pressure in the plated film chamber was 5 * 10
-7-5 * 10
-6Torr.
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