YBCO (Yttrium Barium Copper Oxide) high-temperature superconducting filter and preparation method thereof
By mixing photosensitive resin with YBCO precursor powder and using photopolymerization 3D printing technology, the high cost problem in the fabrication of YBCO high-temperature superconducting filters has been solved, realizing a high-precision and low-cost fabrication method suitable for the precise fabrication of YBCO high-temperature superconducting filters.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-01-23
- Publication Date
- 2026-04-07
AI Technical Summary
The fabrication process of existing YBCO high-temperature superconducting filters is costly in terms of both economy and time.
A photosensitive resin was prepared by mixing resin, dispersant and cosolvent, and YBCO precursor powder was prepared by mixing it with barium carbonate powder, nano-yttrium oxide and nano-copper oxide. YBCO high-temperature superconducting filter was prepared by combining photopolymerization 3D printing technology through printing, cleaning, curing and sintering steps.
It achieves higher printing accuracy and lower manufacturing cost, meeting the application requirements of YBCO high-temperature superconducting filters. It has micron-level accuracy and fine detail, reducing the threshold for use and time cost.
Smart Images
Figure CN121812915A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of light-cured 3D printing, and relates to a YBCO high-temperature superconducting filter and a preparation method thereof. BACKGROUND
[0002] A filter is a frequency selection device that can pass specific frequency components in a signal while greatly attenuating other components. It is mainly a frequency-selective two-port network composed of inductors, capacitors, resistors or ferrite devices, and is mainly used to filter out or weaken noise, interference and other signals in the input signal to extract useful signals. It is widely used in interference elimination and frequency spectrum analysis. Superconducting filters are an important type of filter. Under certain conditions, the resistance of the superconducting film surface is very small. In the high-frequency range of mobile communication, the microwave surface resistance of the superconducting film is only one thousandth of that of normal metal. Based on this property, superconducting filters have better filtering performance and filter out more stray signals. The superconducting transition temperature of superconducting materials is an important factor limiting the application of superconducting materials. The high superconducting transition temperature of high-temperature superconducting materials reduces the application threshold of superconducting filters. Yttrium barium copper oxide (YBCO) as a typical high-temperature superconducting material is one of the important materials for preparing high-temperature superconducting filters.
[0003] As an important representative of the first microwave electronic device to make a breakthrough, high-temperature superconducting filters have received widespread attention from the scientific research community. Since 2000, the research on superconducting filters has made great progress. Various types of filters such as narrowband, broadband and multi-band have emerged and are widely used in mobile communication, radar, deep space exploration and satellite communication, etc. YBCO, as a high-temperature superconducting material, has excellent superconducting performance and increasingly diverse preparation methods, making YBCO an excellent raw material for preparing high-temperature superconducting filters.
[0004] Yttrium barium copper oxide (YBCO) ceramic, as a high-temperature superconducting material, has excellent current carrying capacity under high magnetic fields, as shown by high critical current density, high irreversible field and low ac loss. Because of its excellent superconducting performance and high superconducting transition temperature, research on YBCO high-temperature superconducting materials is increasingly widespread. Currently, the main preparation method for YBCO high-temperature superconducting filters is to first deposit a superconducting film on a single crystal substrate, and then perform photolithography and etching to meet the precision requirements of superconducting filters. The precision is very high, but the economic and time costs are relatively high. SUMMARY
[0005] The purpose of the present application is to provide a YBCO high-temperature superconducting filter and a preparation method thereof, which solves the problem of high economic and time costs in the preparation process of existing YBCO high-temperature superconducting filters.
[0006] To achieve the above object, the application adopts the following technical solutions to achieve the above object: A preparation method of a YBCO high-temperature superconducting filter, comprising: The resin, dispersant and cosolvent are mixed uniformly, a photoinitiator is added, and water bath heating is carried out in the dark to obtain a photosensitive resin; The barium carbonate powder, nano yttrium oxide and nano copper oxide are mixed uniformly, dried, and YBCO precursor powder is obtained; The photosensitive resin with different proportions is mixed with the YBCO precursor powder to prepare high-temperature superconducting filter slurry and positioning frame slurry; The positioning frame slurry is distributed on the 3D printing platform, and the positioning frame slurry is solidified by emitting laser to print an embryo positioning frame with a thickness consistent with that of the single crystal substrate; The single crystal substrate is placed in the embryo positioning frame, the high-temperature superconducting filter slurry is used to print and solidify one side of the single crystal substrate, the solidified single crystal substrate and positioning frame are cleaned and dried, and then turned over, and printing is carried out on the other side of the single crystal substrate according to the designed high-temperature superconducting filter pattern model to form a superconducting filter structure embryo; The superconducting filter structure embryo is cleaned and solidified, and after the degreasing and sintering treatment, a YBCO high-temperature superconducting filter is obtained.
[0007] Further, the resin includes two or three of dipropylene glycol diacrylate, 1,6-hexanediol diacrylate, dipropylene glycol diacrylate and bistrimethylolpropane acrylate; The dispersant is one or two of BYK-110, Tween 80 and gamma-glycidoxypropyltrimethoxysilane; The cosolvent is triethylene glycol; The photoinitiator is one or two of 2,4,6-trimethylbenzoyl phenyl ethyl phosphonate and 1-hydroxycyclohexyl phenyl ketone.
[0008] Further, in the preparation process of the photosensitive resin, the resin is added in an amount of 85 wt% to 92 wt%, the dispersant is added in an amount of 0.8 wt% to 3 wt%, the cosolvent is added in an amount of 0.8 wt% to 2 wt%, and the photoinitiator is added in an amount of 4 wt% to 8 wt%.
[0009] Further, in the preparation process of the YBCO precursor powder, the element ratio of Y:Ba:Cu in the added barium carbonate powder, nano yttrium oxide and nano copper oxide is 1:2:3.
[0010] Further, in the high-temperature superconducting filter slurry, the mass ratio of the YBCO precursor powder to the photosensitive resin is 55 wt% to 65 wt%: 35 wt% to 45 wt%. The mass ratio of the YBCO precursor powder to the photosensitive resin in the positioning frame slurry is 45-55 wt%: 45-55 wt%.
[0011] Further, the printing parameters are as follows: the laser power is 65%-90%, the single-layer repetition number is 1-4 times, the solid scanning speed is 1000-4500 mm / s, the contour scanning speed is 3500-5000 mm / s, and the slurry temperature is -5-0 DEG C.
[0012] Further, the cleaning process of the superconducting filter structure embryo is as follows: The superconducting filter structure embryo is placed in a cleaning liquid, and after being cleaned by ultrasonic waves for 2-4 min, the embryo is taken out, and then the un-solidified slurry remaining on the surface and details of the embryo is cleaned by using a spray gun with anhydrous ethanol as a cleaning agent; The cleaning liquid is 1,6-hexanediol diacrylate, water or alcohol.
[0013] Further, the process of the degreasing treatment is as follows: Air is introduced at a flow rate of 200-300 sccm, and the superconducting filter structure embryo is preliminarily shaped by being heated at a temperature increasing rate of 12 DEG C / h from room temperature to 200 DEG C and being kept at 200 DEG C for 60 min; The temperature is increased to 350 DEG C at a rate of 6 DEG C / h, and the embryo is kept at 350 DEG C for 200 min; The temperature is further increased to 450 DEG C at a rate of 6 DEG C / h, and the embryo is kept at 450 DEG C for 120 min; The temperature is further increased to 550 DEG C at a rate of 6 DEG C / h, and the embryo is kept at 550 DEG C for 120 min; The temperature is kept at 550 DEG C until no photosensitive resin component is left.
[0014] Further, the process of the sintering treatment is as follows: Oxygen is introduced at a flow rate of 200-250 sccm, and the shape of the superconducting filter structure embryo is further solidified by being heated at a temperature increasing rate of 30 DEG C / h to 850 DEG C and being kept at 850 DEG C for 100 min; The temperature is increased to 920 DEG C at a rate of 6 DEG C / h, and the embryo is kept at 920 DEG C for 25 h to grow crystals; The temperature is decreased to room temperature at a rate of 3 DEG C / min.
[0015] A YBCO high-temperature superconducting filter prepared by the preparation method.
[0016] Compared with the prior art, the application has the following beneficial effects: The application provides a preparation method of a YBCO high-temperature superconducting filter, which comprises the following steps: preparing a photosensitive resin by using resin, dispersant and cosolvent and adding a photoinitiator, preparing YBCO precursor powder by using barium carbonate powder, nano yttrium oxide and nano copper oxide, mixing the photosensitive resin with different proportions and the YBCO precursor powder to prepare photocured 3D printing slurry, high-temperature superconducting filter structure design, positioning frame printing, YBCO thin film and structure printing, cleaning, curing, debinding and sintering, and using photocured 3D printing technology to prepare the YBCO high-temperature superconducting filter. The YBCO high-temperature superconducting material is combined with the photocured 3D printing technology, the shape of the material can be more accurately controlled, higher printing precision is realized, and the YBCO high-temperature superconducting filter can be accurately prepared and the shape can be controlled. Different from traditional photoetching and etching processes, the application has lower use threshold, time cost and price cost, meanwhile, the photocured 3D printing technology has the advantages of rapid prototyping and high precision, so that the prepared YBCO high-temperature superconducting filter has the characteristics of micron-level precision, fine detail description and low preparation cost, and fully meets the use requirement, and provides a new idea and feasible method for the preparation of the high-temperature superconducting filter. BRIEF DESCRIPTION OF DRAWINGS
[0017] In order to more clearly illustrate the technical solutions of the embodiments of the application, the following will briefly introduce the drawings needed to be used in the embodiments, and it should be understood that the following drawings only show some embodiments of the application, and therefore should not be regarded as a limitation to the scope, and for those skilled in the art, other related drawings can also be obtained without creative labor on the basis of these drawings.
[0018] Figure 1 The flow chart of the photocured 3D printing YBCO superconducting material of the application.
[0019] Figure 2 The schematic diagram of the photocured 3D printing YBCO superconducting material device of the application.
[0020] Figure 3 The schematic diagram of the YBCO high-temperature superconducting filter model of the application.
[0021] Figure 4 The schematic diagram of the single crystal substrate of the application.
[0022] Figure 5 The superconducting filter structure blank figure printed in embodiment 1 of the application.
[0023] Figure 6 The YBCO high-temperature superconducting filter line width characterization figure prepared in embodiment 1 of the application.
[0024] Figure 7XRD test pattern of the filter prepared for Example 1 of the present application. DETAILED DESCRIPTION
[0025] To enable persons skilled in the art to understand the features and effects of the present application, the following is a general explanation and definition of the terms and phrases mentioned in the specification and claims. Unless otherwise specified, all technical and scientific words used herein have the usual meaning understood by those skilled in the art of the present application, and in the event of a conflict, the definition in the specification shall prevail.
[0026] Theories and mechanisms described and disclosed herein, whether correct or not, should not be considered limiting on the scope of the present application, which can be practiced without regard to any particular theory or mechanism.
[0027] Herein, all features defined by numerical ranges or percentage ranges, such as numerical values, amounts, contents and concentrations, are for the sake of brevity and convenience. Accordingly, the description of numerical ranges or percentage ranges should be considered to have encompassed and specifically disclosed all possible sub-ranges and individual numerical values within the range (including integers and fractions).
[0028] Herein, unless otherwise specified, "comprise", "include", "contain", "have" or similar words encompass the meaning of "consist of" and "consist essentially of", for example, "A comprises a" encompasses the meaning of "A comprises a and other" and "A comprises only a".
[0029] Herein, for the sake of brevity, all possible combinations of the technical features in each embodiment or example are not described. Accordingly, as long as the combinations of the technical features do not contradict each other, the technical features in each embodiment or example can be combined arbitrarily, and all possible combinations should be considered to fall within the scope of the present specification.
[0030] The present application will be further clarified by the following specific examples. It should be understood that these examples are intended to illustrate the present application and are not intended to limit the scope of the present application. Furthermore, it should be understood that various modifications can be made to the present application by those skilled in the art, and such equivalent forms are intended to fall within the scope of the appended claims.
[0031] The following examples use apparatus and equipment that are conventional in the art. The experimental methods in the following examples, unless otherwise specified, are generally performed according to conventional conditions, or according to the conditions recommended by the manufacturer. The following examples use various raw materials, unless otherwise specified, all of which are conventional commercially available products, and the specifications thereof are conventional in the art. In the specification of the present application and in the following examples, unless otherwise specified, "%" means weight percent, "parts" means weight parts, and the ratio means weight ratio.
[0032] The present application will be further described in detail below with reference to the accompanying drawings: The present application provides a preparation method of YBCO high-temperature superconducting filter. First, a usable superconducting filter model is designed, as shown in Figure 3 The YBCO slurry is solidified on a single crystal substrate (such as MgO) using a photocuring 3D printing method, and a YBCO high-temperature superconducting filter is obtained after debinding and sintering, as shown in Figure 1 The basic printing method is as follows: the printing process first prepares the printing slurry by mixing the photosensitive resin with the YBCO powder. The main functional device of 3D printing is as shown in Figure 2 The thickness of the YBCO superconducting film is ensured by moving the printing platform. The printing slurry is laid on the printing platform by a scraper. The slurry is solidified by emitting laser, and a positioning frame with a thickness consistent with the single crystal substrate is printed. Then the single crystal substrate is placed, and a layer of slurry is laid. The laser is emitted multiple times according to the path to print the superconducting filter structure. The completed model is cleaned to ensure no excess slurry residue, vacuum dried at room temperature, and then placed in a ultraviolet curing box for overall curing. Then the single crystal substrate is reversed, and a layer is solidified by emitting laser according to the set route. The cleaning and overall curing are repeated again. Finally, after debinding and crystal growth, a YBCO superconducting structure with fine shape, regular arrangement and high critical current is obtained, ensuring the accuracy of line width and line spacing, with an error of not more than 60 μm. Specifically, the following steps are included: Step one: configure photosensitive resin and precursor powder: the photosensitive resin needs to be configured within one week before use for the best effect. The composition of the photosensitive resin mainly includes resin, photoinitiator, dispersant and cosolvent. The main components are commercial resins, mainly including tripropylene glycol diacrylate (TPGDA), and one or two of 1,6-hexanediol diacrylate (HDDA), dipropylene glycol diacrylate (DPGDA), and bistrimethylolpropane acrylate (Di-TMPTA). The photoinitiator uses one or both of 2,4,6-trimethylbenzoyl phenyl phosphonic acid ethyl ester (TPO-L) and 1-hydroxycyclohexyl phenyl ketone (photoinitiator 184). The dispersant uses one or both of BYK-110, Tween 80 and γ-glycidyl ether oxypropyl trimethoxysilane (kh560). The cosolvent uses triethylene glycol. Other auxiliary components can be used in combination with the effect, and other auxiliary components can be added as appropriate.
[0033] The configuration step of the photosensitive resin and the content of each component: first, 85 wt%-92 wt% of the resin is placed in a beaker, wherein TPGDA is 35 wt%-45 wt%, after stirring and mixing, 0.8 wt%-2 wt% of the cosolvent, 0.8 wt%-3 wt% of the dispersant are added, and the mixture is uniformly mixed by mechanical stirring for 10-15 min. 4 wt%-8 wt% of the photoinitiator is added, wherein TPO-L is 3 wt%-6 wt%, 184 is 1 wt%-2 wt%, TPO-L is mainly used, and 184 is auxiliary, and ultrasonic dispersion is performed for 30 min. Finally, the temperature is kept at 55-65℃, and water bath stirring is performed for 30-40 min. In addition, the step after adding the photoinitiator needs to be carried out in the dark.
[0034] Secondly, the YBCO precursor powder is treated, using nano yttrium oxide, barium carbonate and nano copper oxide as the material, and the barium carbonate powder is pretreated, the barium carbonate is mixed with anhydrous ethanol, ball milling for 1-2 h, dried and filtered through a 1400 mesh screen to obtain smaller size barium carbonate powder. According to the element ratio of Y:Ba:Cu being 1:2:3, accurately add the three powders in the ball milling tank, the mass error of single powder is controlled within ±0.005 g, add anhydrous ethanol, ball mill at a speed of 350 r / min for 30 min to ensure the uniformity of the precursor powder, then dry and use an ultrasonic sifter to break the agglomerated powder to obtain dry and uniform YBCO precursor powder.
[0035] Step two: preparation of photocured 3D printing paste: the present application is mainly applied to the preparation of high-temperature superconducting filters, but before printing the high-temperature superconducting filter, the YBCO embryo positioning frame needs to be printed on the magnetic sticker in advance, and different resin and powder ratios will obtain more stable results. The paste used to prepare the high-temperature superconducting filter is the high-temperature superconducting filter paste, and the paste used to prepare the positioning frame is the positioning frame paste. In the high-temperature superconducting filter paste, the mass ratio of YBCO precursor powder to photosensitive resin is 55 wt%-65 wt%:35 wt%-45 wt%; in the positioning frame paste, the mass ratio of YBCO precursor powder to photosensitive resin is 45-55 wt%:45-55 wt%. The configuration of the two pastes is consistent: The photosensitive resin is mixed with the YBCO precursor powder to configure a photocuring 3D printing paste. In a light-proof environment, the YBCO precursor powder is slowly added to the photosensitive resin, a glass rod is used to stir slowly during the process to avoid the agglomeration of the YBCO precursor powder, and then a stirrer is used for mechanical stirring for 30-60 min to obtain a premix, and then the premix is ball milled in a ball mill at a speed of 300 r / min for 20-40 min for further mixing, and finally a vacuum drying oven is used to remove bubbles at a temperature of 50°C for 1 h, and finally a uniform and bubble-free photocuring 3D printing paste is obtained.
[0036] Step three: photocuring 3D printing YBCO high-temperature superconducting filter: the photocuring 3D printer used in the application is Cerabulider 60s produced by Wuhan Inveio Technology Co., Ltd., the wavelength of the laser is 405 nm, the power is 3 W, and the laser power is adjusted in the range of 1%-100% through an external laser controller. The printing platform is a circular platform with a diameter of 60 mm, the printer can realize automatic feeding and recycling of the paste, the laser precision is 35 μm, and the up-down movement precision of the platform is not less than the printing precision.
[0037] Part of the photocuring 3D printing paste is laid on the printing platform, and the laser power is adjusted to 75%. Turn on the laser to scan and solidify a layer to determine the solidification depth of the paste, which is affected by factors such as photosensitive resin ratio and environment, and there is fluctuation. The above steps are repeated 5-10 times, and the average value is taken to obtain the average solidification depth of the current batch of paste.
[0038] A high-temperature superconducting filter model is established, the model size is adjusted according to actual needs, and attention is paid to the details. The model is adjusted in size and position using Materialise Magics 21.0 software, and a No. 1 printing path file is output; a model with the same size as the substrate is established according to the substrate size, and the thickness is slightly higher than the design thickness, and a No. 2 path file is output, which is used to print the YBCO high-temperature superconducting material layer on the back of the high-temperature superconducting filter; a hollow square frame is designed as a positioning frame based on the size of the substrate, so that the substrate can be placed in the center of the positioning frame, ensuring that the structure is accurately printed on the substrate, and the thickness of the positioning frame is referenced from the thickness of the substrate. The printing thickness required by the high-temperature superconducting filter is generally small, which can be manually determined, and then a layer is solidified, so the designed structure thickness has no effect on the actual printing result, but the thickness of the positioning frame needs to be designed with emphasis. The thickness of the single crystal substrate is measured several times to obtain the average thickness of the single crystal substrate, and the thickness of the thin film required for printing the high-temperature superconducting filter is considered comprehensively, and the sum of the two is the thickness of the positioning frame.
[0039] According to different slice thickness, the printing parameters are modified according to the actual performance. The printing path file is input to the print list of the master software, and the model is placed in the center of the platform. First, make the printing platform zero, and place the magnet sticker to facilitate the removal of the printed model for subsequent processing; move the scraper to the top of the printing platform, then lower the scraper, adjust the distance from the magnet sticker through the screw on the scraper, and keep the bottom of the scraper horizontal.
[0040] When using the light-cured 3D printing method to prepare a high-temperature superconducting filter, first print a positioning frame, then place a single crystal substrate in the positioning frame to start printing the two sides of the superconducting filter. When printing the positioning frame, the platform does not need to be lowered, only the scraper needs to be leveled, and the distance between the scraper and the "magnet sticker" mentioned below should be less than 1 / 2 of the solidification depth of the slurry. After the positioning frame is printed, the scraper returns to the initial position in the horizontal direction, the platform is zeroed, and the positioning frame is fixed on the "magnet sticker". At this time, together with the magnet sticker, it is taken out for cleaning, drying and curing in the curing box. Then put it back on the platform as a whole. At this time, according to the thickness of the positioning frame, the distance from the scraper to the surface of the magnet sticker, and the thickness that needs to be printed on the single crystal, control the platform to lower a certain distance, and start printing the superconducting filter.
[0041] First, place a magnet sticker consistent with the size of the printing platform on the printing platform, and print the base positioning frame according to the general printing steps. For this printing process, the parameter settings are as follows: Set the laser power to 65%~90%, the single-layer repetition number to 1~4 times, the solid scanning speed to 1000~4500 mm / s, and the contour scanning speed to 3500~5000 mm / s. Use an external cooling device (ordinary single-chip microcomputer cooling device) to keep the positioning frame slurry temperature at -5~0 ℃, maintaining a viscous state. Turn on the positioning frame slurry automatic supply, pre-coat the positioning frame slurry on the printing platform to ensure complete coverage, and then start the printing program to automatically print the specified model.
[0042] The main process of the printing program is as follows: the peristaltic pump starts, a certain amount of positioning frame slurry is extracted from the slurry box to the printing platform; the scraper is lowered and moved from the starting position to the end, so that the positioning frame slurry is evenly distributed, and the excess positioning frame slurry is scraped back into the slurry box; the laser is started, and the pattern and parameters set by the program are scanned and solidified on the platform; after solidification is completed, the printing platform is lowered by a certain distance, which is the set slice thickness; the scraper returns to the original position. Repeat the process, and after the specified model is printed, end the printing program and the platform returns to the initial position. The machine light blocking glass should be closed throughout the printing process to avoid external light affecting the printing process.
[0043] Clean and dry the printed positioning frame part, especially ensure that the inside of the frame is clean and dry, to prevent the substrate from being uneven due to residual slurry, which will affect subsequent printing. Place the single crystal substrate such as YBCO on the positioning frame, and start printing the superconducting filter according to the general printing steps. Figure 4As shown, place in the positioning frame, lower the platform, the thickness of the lower is the sum of the positioning frame thickness and the target layer thickness, and appropriate consideration of the error caused by the scraper height.
[0044] Since the high-temperature superconducting filter usually needs to prepare superconducting thin film on both sides of the single crystal substrate, the printing process needs to turn over the single crystal substrate. In order to ensure the integrity of the printed film, after printing is completed, it needs to be cleaned and ultraviolet cured, and then the other side is printed. Because this printing process only needs to print one layer, the process is manual. First, print the back YBCO high-temperature superconducting film, place the high-temperature superconducting filter slurry on the magnetic surface, cover the substrate or add on the left side of the platform, lower the scraper from the magnetic surface, and make the high-temperature superconducting filter slurry completely cover the substrate, then emit laser according to path 2, print, and repeat the laser scanning process 2~3 times; After printing is completed, clean and dry the single crystal substrate and the positioning frame. Then turn over, and then repeat the above steps to print the superconducting filter structure surface on the other blank side. After this process is completed, the YBCO ceramic embryo is obtained, and subsequent material preparation is performed.
[0045] Step four: cleaning, drying and curing: the embryo is taken out from the printing platform as a whole, and direct contact with the embryo is avoided as much as possible. The model is cleaned by clamping the magnetic sticker (HDDA is the best cleaning liquid, followed by water or alcohol). First, place the YBCO high-temperature superconducting filter embryo in a special cleaning liquid, and clean it with ultrasonic waves. After 2~4 min, take it out, then use anhydrous ethanol as a cleaning agent, and use a spray gun to clean the embryo surface and the details of the residual uncured slurry. After cleaning, naturally dry for 20~30 min, then use a vacuum drying box to dry the embryo at 30℃ for 60~80 min to obtain a complete YBCO ceramic embryo with a clean and dry surface without residue. Arrange the YBCO embryo neatly in the ultraviolet curing box, set the temperature to 50~60℃, and irradiate the whole body for 30~60 min to completely cure the embryo and obtain a YBCO high-temperature superconducting material embryo.
[0046] Step five: debinding and crystal growth: place the YBCO high-temperature superconducting material embryo in a dry and clean crucible, and the distance between adjacent embryos is at least 2 cm to ensure that the resin in each embryo is fully decomposed and will not stick together.
[0047] The defatting and sintering processes both use a three-temperature zone tube furnace produced by Hefei Kexing Material Co., Ltd. A crucible containing a YBCO high-temperature superconducting material embryo is placed in the middle position of the tube furnace, and a temperature rising program is set to defat the embryo. The defatting is carried out in an air atmosphere, and air is introduced at a flow rate of 200-300 sccm throughout the process; the temperature rising is set as follows: the embryo is preliminarily shaped by heating from room temperature to 200℃ at a heating rate of 12℃ / h and keeping the temperature for 60 min; the embryo is heated to 350℃ at a heating rate of 6℃ / h and kept for 200 min; the embryo is continuously heated to 450℃ at a heating rate of 6℃ / h and kept for 120 min; the embryo is continuously heated to 550℃ at a heating rate of 6℃ / h and kept for 120 min, to complete the temperature rising process in the defatting stage. The process refers to the decomposition temperature of different components in the photosensitive resin, and different components are decomposed at different temperatures. Finally, the temperature is heated to 550℃ to ensure that there is no photosensitive resin component (organic component) left. This step can ensure that the sample is completely defatted and the shape is maintained.
[0048] The sintering process introduces oxygen at a flow rate of 200-250 sccm, which is connected to the defatting process. The embryo is further solidified by heating to 850℃ at a heating rate of 30℃ / h and keeping the temperature for 100 min, to prepare for the sintering process; then the embryo is slowly heated to the crystal growth temperature range by heating to 920℃ at a heating rate of 6℃ / h and keeping the temperature for 25 h, to reduce the uneven shrinkage and shape damage caused by high heating rate and to fully carry out the crystal growth process; finally, the temperature is reduced to room temperature at a cooling rate of 3℃ / min, to complete the entire defatting and sintering process, and to obtain a YBCO high-temperature superconducting filter with a dense and smooth surface and good shape retention.
[0049] The technical solutions of the present application are further described in detail through specific embodiments as follows: Embodiment 1: 35 wt% of TPGDA, 20 wt% of HDDA, 15 wt% of DPGDA and 20.5 wt% of Di-TMPTA are taken in a beaker, and after stirring and mixing, 2 wt% of triethylene glycol is added as a cosolvent, 1.5 wt% of kh560 is added as a dispersant, and mechanical stirring is carried out for 12 min to mix uniformly. 4 wt% of TPO-L and 2 wt% of photoinitiator 184 are added as photoinitiators, and ultrasonic dispersion is carried out for 30 min. Finally, a water bath stirring is carried out at a temperature of 60℃ for 30 min to prepare a photosensitive resin.
[0050] Barium carbonate and anhydrous ethanol were mixed, ball-milled for 1.5 h, filtered using a 1400-mesh screen after drying, to obtain barium carbonate powder of smaller size. In a ball-milling tank, 40 g of nano yttrium oxide, 139.828 g of barium carbonate, and 84.56 g of nano copper oxide were accurately added, anhydrous ethanol was added, and ball-milling was performed at a speed of 350 r / min for 30 min to ensure uniformity of the precursor powder, followed by drying and crushing the agglomerated powder using an ultrasonic sifter, to obtain dry and uniform YBCO precursor powder.
[0051] 55 g of YBCO precursor powder was slowly added to 45 g of photosensitive resin, with a glass rod being used to slowly stir to avoid agglomeration of the YBCO precursor powder, followed by mechanical stirring using a blender for 45 min to obtain a premix, and then the premix was ball-milled in a ball mill at a speed of 300 r / min for 40 min for further mixing, and finally vacuum degassing was performed using a vacuum drying oven at a temperature of 50°C for 1 h, to finally obtain a uniform and bubble-free high-temperature superconducting filter slurry.
[0052] 60 g of YBCO precursor powder was slowly added to 40 g of photosensitive resin, with a glass rod being used to slowly stir to avoid agglomeration of the YBCO precursor powder, followed by mechanical stirring using a blender for 45 min to obtain a premix, and then the premix was ball-milled in a ball mill at a speed of 300 r / min for 40 min for further mixing, and finally vacuum degassing was performed using a vacuum drying oven at a temperature of 50°C for 1 h, to finally obtain a uniform and bubble-free positioning frame slurry.
[0053] The laser power was set to 75%, the single-layer repetition number was set to 2 times, the solid scanning speed was set to 3000 mm / s, the contour scanning speed was set to 4500 mm / s, a general single-chip microcomputer cooling device was used to keep the slurry temperature at 0°C, and the printing was performed on a superconducting filter structure blank. Figure 5 The printed superconducting filter structure blank is shown in
[0054] The superconducting filter structure blank was placed in a cleaning solution and removed after being cleaned using ultrasonic waves for 4 min, and then anhydrous ethanol was used as a cleaning agent to clean the surface and details of the blank. After cleaning, the blank was naturally dried for 26 min, and then a vacuum drying oven was used to vacuum dry the blank at 30°C for 65 min to obtain a complete YBCO ceramic blank with a dry and clean surface and no residue. The YBCO blanks were arranged in a UV curing box, the temperature was set to 55°C, and the entire surface was irradiated for 60 min to completely cure the blanks, to obtain a YBCO high-temperature superconducting material blank.
[0055] The crucible containing the YBCO high-temperature superconducting material embryo is placed in the middle of the tube furnace, and air is supplied at a flow rate of 280 sccm throughout the process; the temperature is raised from room temperature to 200°C at a rate of 12°C / h, and the embryo is preliminarily shaped after being kept at 200°C for 60 min; the temperature is raised to 350°C at a rate of 6°C / h, and the embryo is kept at 350°C for 200 min; the temperature is further raised to 450°C at a rate of 6°C / h, and the embryo is kept at 450°C for 120 min; the temperature is further raised to 550°C at a rate of 6°C / h, and the embryo is kept at 550°C for 120 min, completing the temperature rising process of the debinding stage. Finally, the temperature is kept at 550°C to ensure that there is no photosensitive resin component left.
[0056] The sintering process is carried out by supplying oxygen at a flow rate of 220 sccm, which is connected to the debinding process. The temperature is raised to 850°C at a rate of 30°C / h, and the embryo is kept at 850°C for 100 min to further solidify the shape of the embryo; then the temperature is raised to 920°C at a rate of 6°C / h, and the embryo is kept at 920°C for 25 h; finally, the temperature is reduced to room temperature at a rate of 3°C / min, completing the entire debinding and sintering process, and obtaining a YBCO high-temperature superconducting filter with a smooth and compact surface and good shape retention.
[0057] Example 2: 40 wt% of TPGDA, 20 wt% of HDDA, 12.5 wt% of DPGDA, and 18 wt% of Di-TMPTA are placed in a beaker, and after stirring and mixing, 2.5 wt% of triethylene glycol is added as a cosolvent, 2 wt% of kh560 is added as a dispersant, and the mixture is stirred uniformly for 15 min. 3 wt% of TPO-L and 2 wt% of photoinitiator 184 are added as photoinitiators, and ultrasonic dispersion is performed for 30 min. Finally, a water bath is stirred at 65°C for 35 min to prepare the photosensitive resin.
[0058] Barium carbonate is mixed with absolute ethanol and ball milled for 1 h. After drying, the smaller size barium carbonate powder is obtained by filtering through a 1400 mesh screen. In a ball milling tank, 40 g of nano yttria, 139.828 g of barium carbonate, and 84.56 g of nano copper oxide are accurately added, absolute ethanol is added, and ball milling is performed at a speed of 350 r / min for 30 min to ensure uniformity of the precursor powder. Then, the powder is dried and broken up by an ultrasonic sifter to obtain dry and uniform YBCO precursor powder.
[0059] 50 g YBCO precursor powder was slowly added to 50 g photosensitive resin, a glass rod was used to stir slowly during the process to avoid the agglomeration of YBCO precursor powder, then a mechanical stirrer was used to stir for 30 min to obtain a premix, then the premix was ball milled in a ball mill at a speed of 300 r / min for 35 min to further mix uniformly, finally a vacuum drying oven was used to remove bubbles at a temperature of 50 °C for 1 h, and finally a uniform and bubble-free high-temperature superconducting filter slurry was obtained.
[0060] 50 g YBCO precursor powder was slowly added to 50 g photosensitive resin, a glass rod was used to stir slowly during the process to avoid the agglomeration of YBCO precursor powder, then a mechanical stirrer was used to stir for 30 min to obtain a premix, then the premix was ball milled in a ball mill at a speed of 300 r / min for 35 min to further mix uniformly, finally a vacuum drying oven was used to remove bubbles at a temperature of 50 °C for 1 h, and finally a uniform and bubble-free positioning frame slurry was obtained.
[0061] The laser power was set to 90%, the single-layer repetition number was set to 1 time, the entity scanning speed was set to 1000 mm / s, the contour scanning speed was set to 3500 mm / s, a general single-chip microcomputer cooling device was used to keep the slurry temperature at -2 °C, and the printing superconducting filter structure blank was kept in a viscous state.
[0062] The superconducting filter structure blank was placed in a cleaning solution and cleaned using ultrasonic waves for 3 min, then anhydrous ethanol was used as a cleaning agent to clean the surface and details of the blank. After cleaning, the blank was naturally dried for 30 min, then a vacuum drying oven was used to vacuum dry the blank at 30 °C for 60 min to obtain a complete YBCO ceramic blank with a clean and dry surface. The YBCO blanks were arranged neatly in a UV curing oven, the temperature was set to 60 °C, and the blanks were irradiated for 30 min to completely cure the blanks, and a YBCO high-temperature superconducting material blank was obtained.
[0063] The crucible containing the YBCO high-temperature superconducting material blank was placed in the middle of the tube furnace, and air was supplied at a flow rate of 200 sccm throughout the process; the temperature was raised from room temperature to 200 °C at a rate of 12 °C / h, and the blank was kept at this temperature for 60 min to preliminarily shape the blank; the temperature was raised to 350 °C at a rate of 6 °C / h, and the blank was kept at this temperature for 200 min; the temperature was further raised to 450 °C at a rate of 6 °C / h, and the blank was kept at this temperature for 120 min; the temperature was further raised to 550 °C at a rate of 6 °C / h, and the blank was kept at this temperature for 120 min to complete the temperature rising process of the debinding stage. Finally, the temperature was kept at 550 °C to ensure that there was no photosensitive resin component left.
[0064] The sintering process is carried out by introducing oxygen with a flow rate of 200 sccm, and the debinding process is carried out. The temperature is raised to 850°C at a rate of 30°C / h, and the temperature is kept for 100 min to further solidify the shape of the green body; then the temperature is raised to 920°C at a rate of 6°C / h and kept for 25 h; finally, the temperature is reduced to room temperature at a rate of 3°C / min, and the entire debinding and sintering process is completed, obtaining a YBCO high-temperature superconducting filter with a smooth and dense surface and good shape retention.
[0065] Example 3: Take 45 wt% of TPGDA, 25 wt% of HDDA and 20.5 wt% of Di-TMPTA in a beaker, stir and mix, then add 2 wt% of triethylene glycol as a cosolvent, 1.5 wt% of Tween 80 as a dispersant, and mechanically stir for 10 min to mix evenly. Add 5 wt% of TPO-L and 1 wt% of photoinitiator 184 as a photoinitiator, and ultrasonic dispersion for 30 min. Finally, keep the temperature at 55°C, and stir in a water bath for 40 min to prepare the photosensitive resin.
[0066] Mix barium carbonate with absolute ethanol, ball mill for 2 h, dry and filter through a 1400 mesh screen to obtain smaller size barium carbonate powder. In the ball mill tank, accurately add 40 g of nano yttria, 139.828 g of barium carbonate and 84.56 g of nano copper oxide, add absolute ethanol, and ball mill at a speed of 350 r / min for 30 min to ensure uniformity of the precursor powder, then dry and use an ultrasonic sifter to break up the agglomerated powder to obtain dry and uniform YBCO precursor powder.
[0067] Slowly add 60 g of YBCO precursor powder to 40 g of photosensitive resin, stirring slowly with a glass rod during the process to prevent clumping of the YBCO precursor powder, then mechanically stir the premix with a blender for 60 min, then ball mill the premix in a ball mill at a speed of 300 r / min for 20 min to further mix evenly, and finally use a vacuum drying oven to vacuum degassing at a temperature of 50°C for 1 h, finally obtaining a uniform and bubble-free high-temperature superconducting filter slurry.
[0068] Slowly add 40 g of YBCO precursor powder to 60 g of photosensitive resin, stirring slowly with a glass rod during the process to prevent clumping of the YBCO precursor powder, then mechanically stir the premix with a blender for 60 min, then ball mill the premix in a ball mill at a speed of 300 r / min for 20 min to further mix evenly, and finally use a vacuum drying oven to vacuum degassing at a temperature of 50°C for 1 h, finally obtaining a uniform and bubble-free positioning frame slurry.
[0069] The laser power is set to 65%, the single layer repetition number is set to 4 times, the entity scanning speed is set to 4500 mm / s, the contour scanning speed is set to 5000 mm / s, the ordinary single-chip cooling device is used, the slurry temperature is kept at-5 DEG C, the viscous state is kept, and the superconducting filter structure blank is printed.
[0070] The superconducting filter structure blank is placed in a cleaning liquid, taken out after being cleaned by ultrasonic waves for 2 minutes, then the residual unsolidified slurry on the surface and details of the blank is cleaned by using a spray gun with anhydrous ethanol as a cleaning agent. After cleaning, the blank is naturally dried for 20 minutes, then the vacuum drying box is used, the blank is vacuum dried at 30 DEG C for 80 minutes to obtain a complete YBCO ceramic blank with a clean and dry surface without residues. The YBCO blanks are arranged in the ultraviolet curing box, the temperature is set to 50 DEG C, the whole is irradiated for 45 minutes, so that the blanks are completely cured, and the YBCO high-temperature superconducting material blank is obtained.
[0071] The crucible containing the YBCO high-temperature superconducting material blank is placed in the middle position of the tube furnace, air is introduced at a flow rate of 300 sccm during the whole process; the temperature is increased to 200 DEG C from room temperature at a heating rate of 12 DEG C / h, and the blank is preliminarily shaped by keeping the temperature for 60 minutes; the temperature is increased to 350 DEG C at a heating rate of 6 DEG C / h, and the blank is kept for 200 minutes; the temperature is continuously increased to 450 DEG C at a heating rate of 6 DEG C / h, and the blank is kept for 120 minutes; the temperature is continuously increased to 550 DEG C at a heating rate of 6 DEG C / h, and the blank is kept for 120 minutes, so that the temperature increasing process of the debinding stage is completed. Finally, the temperature is kept at 550 DEG C to ensure that there is no photosensitive resin component left.
[0072] The sintering process is carried out by introducing oxygen at a flow rate of 250 sccm. The temperature is increased to 850 DEG C at a heating rate of 30 DEG C / h, and the blank is kept for 100 minutes to further solidify the shape of the blank; then the temperature is increased to 920 DEG C at a heating rate of 6 DEG C / h, and the blank is kept for 25 hours; finally, the temperature is decreased to room temperature at a cooling rate of 30 DEG C / min, so that the whole debinding and sintering process is completed, and the YBCO high-temperature superconducting filter with a dense and smooth surface and a good shape is obtained.
[0073] The high-temperature superconducting filter prepared in Example 1 of the present application is characterized, and the feasibility of preparing the YBCO high-temperature superconducting filter by the present application is demonstrated. As shown in Figure 6 the line width of the printed filter structure is basically consistent with the designed size, is uniformly distributed, the error is within ± 20 μm, and the material surface is uniform and smooth. As shown in Figure 7 the XRD curve of the material, it can be seen from the figure that the YBCO high-temperature superconducting material prepared by the present application has good superconducting performance.
[0074] The above merely describes the preferred embodiments of the present application, and is not used to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims
1. A method for fabricating a YBCO high-temperature superconducting filter, characterized in that, include: A photosensitive resin is obtained by uniformly mixing resin, dispersant and cosolvent, adding photoinitiator and heating in a water bath in the dark. Barium carbonate powder, nano-yttrium oxide, and nano-copper oxide are mixed evenly and dried to obtain YBCO precursor powder. Different ratios of photosensitive resin were mixed with YBCO precursor powder to prepare high-temperature superconducting filter slurry and positioning frame slurry. The positioning frame slurry is distributed on the 3D printing platform, and a laser is emitted to solidify the positioning frame slurry, printing a preform positioning frame with the same thickness as the single crystal substrate. The single crystal substrate is placed in the preform positioning frame. One side of the single crystal substrate is printed and cured using high-temperature superconducting filter paste. After the single crystal substrate and positioning frame are cleaned and dried, they are flipped over. According to the designed high-temperature superconducting filter graphic model, the other side of the single crystal substrate is printed to form the superconducting filter structure preform. The superconducting filter structure preform was cleaned and solidified, and then degreased and sintered to obtain the YBCO high-temperature superconducting filter.
2. The method for fabricating a YBCO high-temperature superconducting filter according to claim 1, characterized in that, The resin includes dipropylene glycol diacrylate, and two or three of 1,6-hexanediol diacrylate, dipropylene glycol diacrylate and bis(trimethylolpropane) acrylate; The dispersant is one or two of BYK-110, Tween 80 and γ-glycidoxypropyltrimethoxysilane; The cosolvent is triethylene glycol; The photoinitiator is one or both of ethyl 2,4,6-trimethylbenzoylphenylphosphonate and 1-hydroxycyclohexylphenyl ketone.
3. The method for fabricating a YBCO high-temperature superconducting filter according to claim 1, characterized in that, In the preparation of photosensitive resin, the amount of resin added is 85 wt%~92 wt%, the amount of dispersant added is 0.8 wt%~3 wt%, the amount of cosolvent added is 0.8 wt%~2 wt%, and the amount of photoinitiator added is 4 wt%~8 wt%, by mass percentage.
4. The method for fabricating a YBCO high-temperature superconducting filter according to claim 1, characterized in that, In the preparation of YBCO precursor powder, the elemental ratio of Y:Ba:Cu in the added barium carbonate powder, nano-yttrium oxide, and nano-copper oxide is 1:2:
3.
5. The method for fabricating a YBCO high-temperature superconducting filter according to claim 1, characterized in that, By mass percentage, the ratio of YBCO precursor powder to photosensitive resin in the high-temperature superconducting filter slurry is 55 wt%~65 wt%: 35 wt%~45 wt%. In the positioning frame slurry, the mass ratio of YBCO precursor powder to photosensitive resin is 45~55 wt%:45~55 wt%.
6. The method for fabricating a YBCO high-temperature superconducting filter according to claim 1, characterized in that, The printing parameters are as follows: laser power is 65%~90%, single-layer repetition is 1~4 times, solid scanning speed is 1000~4500 mm / s, contour scanning speed is 3500~5000 mm / s, and slurry temperature is -5~0 ℃.
7. The method for fabricating a YBCO high-temperature superconducting filter according to claim 1, characterized in that, The cleaning process for the superconducting filter structure blank is as follows: The superconducting filter structure preform was placed in the cleaning solution and ultrasonically cleaned for 2-4 minutes. Then, anhydrous ethanol was used as the cleaning agent, and a spray gun was used to clean the uncured slurry remaining on the surface and details of the preform. The cleaning solution is 1,6-hexanediol diacrylate, water, or alcohol.
8. The method for fabricating a YBCO high-temperature superconducting filter according to claim 1, characterized in that, The degreasing process is as follows: Air was introduced at a flow rate of 200~300 sccm, and the temperature was increased from room temperature to 200℃ at a heating rate of 12℃ / h, and held for 60 minutes to initially shape the superconducting filter structure. Heat to 350℃ at a heating rate of 6℃ / h and hold for 200 min; Continue heating at a rate of 6℃ / h to 450℃ and hold for 120 min; Continue heating at a rate of 6℃ / h to 550℃ and hold for 120 min; Heat at 550℃ until no photosensitive resin residue remains.
9. The method for fabricating a YBCO high-temperature superconducting filter according to claim 1, characterized in that, The sintering process is as follows: Oxygen was introduced at a flow rate of 200~250 sccm, and the temperature was increased to 850℃ at a heating rate of 30℃ / h. The temperature was held for 100 min to further solidify the shape of the superconducting filter structure preform. The temperature was increased to 920℃ at a heating rate of 6℃ / h and held for 25 h to grow crystals. The temperature was reduced to room temperature at a rate of 3℃ / min.
10. A YBCO high-temperature superconducting filter prepared by the method according to any one of claims 1 to 9.