CN110817957B - Method for preparing Bi-2212 precursor powder by suspension sintering method - Google Patents
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Abstract
The invention discloses a method for preparing Bi-2212 precursor powder by a suspension sintering method, which comprises the following specific steps: adding Bi2O3、Ca(OH)2、SrCO3Mixing with CuO, preparing oxalate mixed powder by adopting an oxalate coprecipitation method, and then sequentially carrying out heating and heat preservation, primary sintering, high-temperature sintering and phase-forming sintering to obtain Bi-2212 precursor powder. According to the invention, the oxalate mixed powder is prepared by adopting a coprecipitation method as raw material powder, so that the quality purity of the Bi-2212 phase in the Bi-2212 precursor powder is effectively improved, the complete phase formation is effectively promoted by combining a step-by-step suspension sintering method, the powder segregation problem caused by melting of a low-melting-point phase is prevented, the problem of incomplete final phase formation caused by excessively low local temperature due to the fact that the Bi-2212 phase directly generated from oxide powder absorbs heat greatly is avoided, the uniformity and quality of the Bi-2212 precursor powder are greatly improved, and the method is suitable for mass production.
Description
Technical Field
The invention belongs to the technical field of preparation of Bi-2212 superconducting wire strips, and particularly relates to a method for preparing Bi-2212 precursor powder by a suspension sintering method.
Background
Bi-2212 high-temperature superconductor (Bi)2Sr2CaCu2Ox) Is the most important branch in high-temperature superconducting materials. Because of its easy processing and high current-carrying property, the Bi-2212 wire becomes one of the most promising high-temperature superconducting materials at present. The Bi-2212 precursor powder has a determining effect on the current-carrying performance of the Bi-2212 wire. The criteria for high performance precursor powders are: the powder is a high-purity Bi-2212 phase, has small and uniform particle size, and contains few impure phases and impurities. The high-quality Bi-2212 precursor powder puts high requirements on the powder preparation technology.
For five-membered compounds Bi2Sr2CaCu2OxThe difficulty of preparing a high purity phase of the pentanary compound is greater due to the complex reaction. The method has the main problems that most of compounds containing Bi are low-melting-point compounds, and the generation of the low-melting-point compounds is difficult to avoid in the conventional static sintering process, so that the problem of macro segregation of powder is easy to occur, and the quality of the powder is influenced. The conventional spray pyrolysis method has the disadvantages that the original body (fog drops) prepared by the conventional spray pyrolysis method contains a large amount of high specific heat water, the original body enters a high-temperature furnace, the furnace temperature is obviously reduced, therefore, in order to ensure the decomposition temperature, the adding speed of the original body needs to be controlled to be small, the yield of powder is greatly limited, in addition, the spray pyrolysis powder also needs to adopt the conventional static sintering, and the part of residual Bi-containing low-specific heat water can be causedMelting of the melting point phase affects the quality of the final powder.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing Bi-2212 precursor powder by a suspension sintering method aiming at the defects of the prior art. The method adopts a coprecipitation method to prepare oxalate mixed powder as raw material powder, effectively improves the quality purity of Bi-2212 phase in the Bi-2212 precursor powder, combines a step-by-step suspension sintering method, effectively promotes complete phase formation, prevents the problem of powder segregation caused by melting of a low-melting-point phase, avoids the problem of incomplete final phase formation caused by excessively low local temperature due to the fact that the Bi-2212 phase directly generated from oxide powder absorbs heat greatly, and greatly improves the uniformity and quality of the Bi-2212 precursor powder.
In order to solve the technical problems, the invention adopts the technical scheme that: a method for preparing Bi-2212 precursor powder by a suspension sintering method is characterized by comprising the following steps:
step one, adding Bi2O3、Ca(OH)2、SrCO3And CuO are mixed according to the mass ratio of Bi, Sr, Ca, Cu (1.95-2.2), 1.95-2.2, 0.9-1 and 1.95-2.2) to prepare a nitrate mixed solution, and then an oxalate coprecipitation method is adopted to prepare oxalate mixed powder;
step two, putting the oxalate mixed powder obtained in the step one into a box-type furnace for heating and heat preservation, cooling along with the furnace, taking out for grinding, then putting into a continuous rotating automatic sintering furnace for primary sintering, taking out and grinding to obtain primary sintering powder;
step three, loading the primary sintering powder obtained in the step two into a first raw material powder storage tank of a high-temperature powder suspension sintering furnace, heating and preserving heat of the high-temperature powder suspension sintering furnace, then opening a first air inlet switch and a first powder adding motor, adjusting air inlet speed, then opening a first air hammer, allowing the primary sintering powder in the first raw material powder storage tank to enter a first furnace tube under the action of gas carrier for high-temperature sintering, and then allowing the primary sintering powder to enter a first powder collecting tank through a first collecting cloth bag to obtain high-temperature sintering powder;
and step four, loading the high-temperature sintering powder obtained in the step three into a second raw material powder storage tank of the powder suspension phase-forming sintering furnace, heating and preserving heat of the powder suspension phase-forming sintering furnace, then opening a second air inlet switch and a second powder adding motor, adjusting air inlet speed, opening a second air hammer, enabling the high-temperature sintering powder in the second raw material powder storage tank to enter a second furnace tube under air carrying to perform phase-forming sintering, and then entering a second powder collection tank through a second collection cloth bag to obtain the Bi-2212 precursor powder.
According to the invention, the raw material powder is mixed to prepare a nitrate mixed solution, the oxalate mixed powder is prepared by adopting an oxalate coprecipitation method, and under the action of oxalate, Bi, Sr, Ca and Cu metal ions rapidly form precipitates at the same time, so that the element proportion of each oxalate mixed powder particle is very close to that of Bi-2212, and a Bi-2212 phase with high quality and purity can be formed by a subsequent sintering process; then, the oxalate mixed powder is heated, kept warm and then ground, a continuous rotary automatic sintering furnace is adopted for primary sintering and then grinding, and through static sintering at the temperature lower than the melting point of the Bi-rich phase, on the premise of ensuring that the quality of the primary sintered powder is not affected, the full decomposition of water, nitrate and oxalate in the oxalate mixed powder is promoted, the preparation efficiency of the primary sintered powder is improved, the equipment cost is reduced, and the preparation efficiency of the Bi-2212 precursor powder is improved; and then sequentially carrying out high-temperature powder suspension sintering and powder suspension phase-forming sintering at the temperature higher than the melting point of the Bi-rich phase, so that the primary sintering powder forms a Bi-2201 phase and a calcium-copper phase, and then the Bi-2201 phase reacts with the calcium-copper phase to generate a Bi-2212 phase, thereby avoiding the problem that the final phase forming is not complete due to too low local temperature caused by the fact that the Bi-2212 phase directly generated from the oxide powder absorbs heat greatly, preventing the problem of powder segregation caused by melting of a low-melting-point phase, and greatly improving the uniformity and quality of the Bi-2212 precursor powder.
The method for preparing the Bi-2212 precursor powder by the suspension sintering method is characterized in that the specific process of heating and heat preservation in the step two is as follows: firstly, heating to 200-250 ℃ at the speed of 40-80 ℃/h, preserving heat for 2-5 h, then heating to 450-500 ℃ at the speed of 40-80 ℃/h, and preserving heat for 2-5 h. The preferred heat-holding process effectively removes water from the oxalate mixed powder and promotes the decomposition of nitrates and oxalates in the oxalate mixed powder.
The method for preparing the Bi-2212 precursor powder by the suspension sintering method is characterized in that the temperature rise rate of the primary sintering in the second step is 40-80 ℃/h, the sintering temperature is 450-500 ℃, and the heat preservation time is 2-5 h. This preferred preliminary sintering process has guaranteed that oxalate mixed powder decomposes into the oxide completely, obtains the even low water of composition, low nitrogen's primary sintering powder, has improved preliminary sintering efficiency through controlling rate of rise of temperature simultaneously, has effectively prevented that the powder that rate of rise of temperature caused from splashing.
The method for preparing the Bi-2212 precursor powder by the suspension sintering method is characterized in that in the third step, the high-temperature powder suspension sintering furnace is heated to 700-750 ℃ and is kept warm for more than 30min, and the air inlet rate is 20-50L/min. The heated temperature and the air inlet rate effectively ensure that the primary sintering powder can be completely sintered at high temperature to form Bi2Sr2CuOXPhase (i.e., Bi-2201 phase) and Ca2The CuO phase (namely the calcium copper phase) improves the quality of the high-temperature sintering powder.
The method for preparing the Bi-2212 precursor powder by the suspension sintering method is characterized in that the powder is suspended in a phase sintering furnace and heated to 830-850 ℃ and is kept warm for more than 30min in the fourth step, and the air inlet rate is 20-50L/min. The heated temperature and air inlet rate effectively ensure Bi in the high-temperature sintering powder2Sr2CuOXPhase of Ca2The CuO phase is sintered into the Bi-2212 phase, so that the completeness of the phase formation is improved, and the quality of the Bi-2212 precursor powder is further improved.
The method for preparing the Bi-2212 precursor powder by the suspension sintering method is characterized in that the rate of the primary sintering powder entering the first furnace tube in the third step under the action of gas load and the rate of the high-temperature sintering powder entering the second furnace tube in the fourth step under the action of gas load are both 10 g/min-20 g/min, and the time of the gas entering and passing through the first furnace tube and the second furnace tube is more than 0.1 s. The preferred rate and time for the gas to enter and pass through the furnace tube further promotes the uniformity and thoroughness of the high temperature sintering and phase forming sintering processes, and reduces powder segregation.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, firstly, the oxalate mixed powder is prepared by adopting a coprecipitation method as the raw material powder, so that the element proportion of the raw material powder particles is close to that of Bi-2212, the quality purity of the Bi-2212 phase in the Bi-2212 precursor powder is effectively improved, the preparation efficiency of the Bi-2212 precursor powder is improved by combining heating and heat preservation and continuous rotary preliminary sintering, then, the step-by-step suspension sintering method is adopted, the thorough phase formation is effectively promoted, the problem of powder segregation caused by melting of a low-melting-point phase is prevented, and the uniformity and quality of the Bi-2212 precursor powder are greatly improved.
2. The method adopts a coprecipitation method to prepare the raw material powder, improves the yield of the raw material powder, then adopts static sintering with large treatment capacity to effectively remove residual water, nitrate and oxalate in the raw material powder, improves the quality and yield of primary sintered powder, reduces the equipment pressure of subsequent suspension sintering, reduces the equipment cost and sintering cost, and is beneficial to realizing the mass production of the Bi-2212 precursor powder.
3. The invention adopts a step-by-step suspension sintering method, sequentially passes through high-temperature powder suspension sintering and powder suspension phase-forming sintering, firstly leads primary sintering powder to form a Bi-2201 phase and a calcium-copper phase, and then reacts to generate a Bi-2212 phase, effectively promotes the phase formation, improves the quality of the Bi-2212 precursor powder, and simultaneously greatly improves the preparation efficiency of the Bi-2212 precursor powder.
4. The preparation method has the advantages of simple preparation process, reasonable design, low preparation cost and large popularization range, and is suitable for the industrial production of the Bi-2212 precursor powder.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
FIG. 1 is a schematic structural diagram of a high-temperature powder suspension sintering furnace and a powder suspension phase-forming sintering furnace adopted by the invention.
Description of reference numerals:
1-a first raw material powder storage tank; 1-2-a first powder feeder; 1-3 — a first intake pipe;
1-4-a first furnace tube; 1-5-a first heating body; 1-6-a first collection cloth bag;
1-7-a first induced draft fan; 1-8-first air hammer; 1-9-a first powder collection tank;
1-10-first air intake switch; 1-11-a first powdering motor; 2-1-a second raw material powder storage tank;
2-a second powder adding device; 2-3-a second air inlet pipe; 2-4-a first furnace tube;
2-5-second heating body; 2-6-second collecting cloth bag; 2-7, a second induced draft fan;
2-8-second air hammer; 2-9 — a second powder collection tank; 2-10-second air inlet switch;
2-11-second powdering motor.
Detailed Description
As shown in figure 1, the high-temperature powder suspension sintering furnace adopted by the invention comprises a first furnace tube 1-4 and a first heating body 1-5 arranged on the periphery of the first furnace tube 1-4, wherein the feeding end of the first furnace tube 1-4 is connected with a first raw material powder storage tank 1-1 through a first powder adding device 1-2, the first powder adding device 1-2 is connected with a first powder adding motor 1-11, the feeding end of the first furnace tube 1-4 is connected with a first air inlet pipe 1-3, a first air inlet switch 1-10 is arranged between the feeding end of the first furnace tube 1-4 and the first air inlet pipe 1-3, the discharging end of the first furnace tube 1-4 is connected with a powder collector through a pipeline, a first collecting cloth bag 1-6 is arranged in the powder collector, a first air hammer 1-8 is arranged around the first collecting cloth bag 1-6, the upper part of the powder collector is connected with a first induced draft fan 1-7, and the lower end of the powder collector is provided with a first powder collecting tank 1-9 for connection.
The powder suspension phase-forming sintering furnace adopted by the invention comprises a second furnace tube 2-4 and a second heating body 2-5 arranged at the periphery of the second furnace tube 2-4, wherein the feeding end of the second furnace tube 2-4 is connected with a second raw material powder storage tank 2-1 through a second powder adding device 2-2, the second powder adding device 2-2 is connected with a second powder adding motor 2-11, the feeding end of the second furnace tube 2-4 is connected with a second air inlet tube 2-3, a second air inlet switch 2-10 is arranged between the feeding end of the second furnace tube 2-4 and the second air inlet tube 2-3, the discharging end of the second furnace tube 2-4 is connected with a powder collector through a pipeline, a second collecting cloth bag 2-6 is arranged in the powder collector, and a second air hammer 2-8 is arranged around the second collecting cloth bag 2-6, the upper part of the powder collector is connected with a second draught fan 2-7, and the lower end of the powder collector is provided with a second powder collecting tank 2-9 for connection.
The processes for preparing the Bi-2212 precursor powder by the coprecipitation method in the embodiments 1 to 5 of the invention are disclosed in the literature (hokuaib, preparation and performance research of a high-current-carrying Bi-2212 high-temperature superconducting wire, northeast university, doctor academic thesis 2018), and the details of the processes for preparing the Bi-2212 precursor powder by the spray thermal decomposition method are disclosed in the literature (the effect of the collection mode on the spray thermal decomposition of the Bi-2223 precursor powder in bang of liu, qing shui, No. 1 st stage 59-63 of 2018).
Example 1
The embodiment comprises the following steps:
step one, adding Bi2O3、Ca(OH)2、SrCO3Mixing CuO and Sr according to the mass ratio of Bi to Sr to Ca to Cu of 1.95 to 0.9 to 1.95, preparing a nitrate mixed solution, and preparing oxalate mixed powder by adopting an oxalate coprecipitation method;
step two, putting the oxalate mixed powder obtained in the step one into a box-type furnace for heating and heat preservation, cooling along with the furnace, taking out for grinding, then putting into a continuous rotating automatic sintering furnace for primary sintering, taking out and grinding to obtain primary sintering powder; the specific process of heating and heat preservation is as follows: firstly, heating to 200 ℃ at the speed of 40 ℃/h and preserving heat for 2h, then heating to 450 ℃ at the speed of 40 ℃/h and preserving heat for 2 h; the temperature rise rate of the primary sintering is 40 ℃/h, the sintering temperature is 450 ℃, and the heat preservation time is 2 h;
step three, loading the primary sintering powder obtained in the step two into a first raw material powder storage tank 1-1 of a high-temperature powder suspension sintering furnace, heating the furnace temperature of the high-temperature powder suspension sintering furnace to 700 ℃, keeping the temperature for 30min, then opening a first air inlet switch 1-10 and a first powder adding motor 1-11, controlling the air inlet speed to be 20L/min, then opening a first air hammer 1-8, enabling the primary sintering powder in the first raw material powder storage tank 1-1 to enter a first furnace pipe 4-1 at the speed of 10g/min under the action of air load for high-temperature sintering, and then entering a first powder collecting tank 9-1 through a first collecting cloth bag 6-1 to obtain high-temperature sintering powder;
step four, loading the high-temperature sintering powder obtained in the step three into a second raw material powder storage tank 1-2 of the powder suspension phase-forming sintering furnace, raising the temperature of the powder suspension phase-forming sintering furnace to 830 ℃, keeping the temperature for 40min, then opening a second air inlet switch 2-10 and a second powder adding motor 2-11, controlling the air inlet rate to be 20L/min, then opening a second air hammer 2-8, enabling the high-temperature sintering powder in the second raw material powder storage tank 2-1 to enter a second furnace tube 2-4 at the rate of 10g/min under the action of air load to perform phase-forming sintering, and then entering a second powder collection tank 2-9 through a second collection cloth bag 2-6 to obtain the Bi-2212 precursor powder.
The Bi-2212 precursor powder prepared by the implementation and the Bi-2212 precursor powder prepared by the coprecipitation method and the spray thermal decomposition method in the prior art are observed and compared by adopting a scanning electron microscope (multiplied by 100), and the result shows that the probability of one non-Bi-2212 phase particle appearing in the scanning electron microscope (multiplied by 100) picture of the Bi-2212 precursor powder prepared by the implementation is 0.3 per piece, the probability of one non-Bi-2212 phase particle appearing in the scanning electron microscope (multiplied by 100) picture of the Bi-2212 precursor powder prepared by the coprecipitation method in the prior art is 3 per piece, and the probability of one non-Bi-2212 phase particle appearing in the scanning electron microscope (multiplied by 100) picture of the Bi-2212 precursor powder prepared by the spray thermal decomposition method is 1 per piece; the Bi-2212 precursor powder is prepared by adopting the process of the embodiment and a coprecipitation method and a spray thermal decomposition method in the prior art respectively under the same production period condition, and the preparation efficiency of the embodiment is 80 kg/month which is far higher than the preparation efficiency of the coprecipitation method in the prior art by 5 kg/month and the preparation efficiency of the spray thermal decomposition method by 20 kg/month through calculation, so that the preparation process effectively promotes the phase formation, improves the quality of the Bi-2212 precursor powder and simultaneously improves the preparation efficiency of the Bi-2212 precursor powder.
Example 2
The embodiment comprises the following steps:
step one, adding Bi2O3、Ca(OH)2、SrCO3Mixing CuO and Sr, Ca and Cu according to the mass ratio of Bi to Sr to Ca to Cu of 2.2 to 1 to 2.2, preparing a nitrate mixed solution, and preparing oxalate mixed powder by adopting an oxalate coprecipitation method;
step two, putting the oxalate mixed powder obtained in the step one into a box-type furnace for heating and heat preservation, cooling along with the furnace, taking out for grinding, then putting into a continuous rotating automatic sintering furnace for primary sintering, taking out and grinding to obtain primary sintering powder; the specific process of heating and heat preservation is as follows: firstly, heating to 250 ℃ at the speed of 80 ℃/h and preserving heat for 5h, and then heating to 500 ℃ at the speed of 80 ℃/h and preserving heat for 5 h; the temperature rise rate of the primary sintering is 80 ℃/h, the sintering temperature is 500 ℃, and the heat preservation time is 5 h;
step three, loading the primary sintering powder obtained in the step two into a first raw material powder storage tank 1-1 of a high-temperature powder suspension sintering furnace, raising the furnace temperature of the high-temperature powder suspension sintering furnace to 750 ℃, keeping the temperature for 40min, then opening a first air inlet switch 1-10 and a first powder adding motor 1-11, controlling the air inlet speed to be 50L/min, then opening a first air hammer 1-8, enabling the primary sintering powder in the first raw material powder storage tank 1-1 to enter a first furnace pipe 4-1 at the speed of 20g/min under the action of air load for high-temperature sintering, and then entering a first powder collecting tank 9-1 through a first collecting cloth bag 6-1 to obtain high-temperature sintering powder;
step four, loading the high-temperature sintering powder obtained in the step three into a second raw material powder storage tank 1-2 of the powder suspension phase-forming sintering furnace, raising the temperature of the powder suspension phase-forming sintering furnace to 830 ℃, keeping the temperature for 30min, then opening a second air inlet switch 2-10 and a second powder adding motor 2-11, controlling the air inlet speed to be 50L/min, then opening a second air hammer 2-8, enabling the high-temperature sintering powder in the second raw material powder storage tank 2-1 to enter a second furnace tube 2-4 at the speed of 20g/min under the action of air load to perform phase-forming sintering, and then entering a second powder collection tank 2-9 through a second collection cloth bag 2-6 to obtain the Bi-2212 precursor powder.
The Bi-2212 precursor powder prepared by the implementation and the Bi-2212 precursor powder prepared by the coprecipitation method and the spray thermal decomposition method in the prior art are observed and compared by adopting a scanning electron microscope (multiplied by 100), and the result shows that the probability of one non-Bi-2212 phase particle appearing in the scanning electron microscope (multiplied by 100) picture of the Bi-2212 precursor powder prepared by the implementation is 0.2 per sheet, the probability of one non-Bi-2212 phase particle appearing in the scanning electron microscope (multiplied by 100) picture of the Bi-2212 precursor powder prepared by the coprecipitation method in the prior art is 2 per sheet, and the probability of one non-Bi-2212 phase particle appearing in the scanning electron microscope (multiplied by 100) picture of the Bi-2212 precursor powder prepared by the spray thermal decomposition method is 1 per sheet; the Bi-2212 precursor powder is prepared by adopting the process of the embodiment and a coprecipitation method and a spray thermal decomposition method in the prior art respectively under the same production period condition, and the preparation efficiency of the embodiment is 160 kg/month and is far higher than the preparation efficiency of the coprecipitation method in the prior art by 5 kg/month and the preparation efficiency of the spray thermal decomposition method by 20 kg/month through calculation, which shows that the preparation process of the invention effectively promotes phase formation, improves the quality of the Bi-2212 precursor powder and simultaneously improves the preparation efficiency of the Bi-2212 precursor powder.
Example 3
The embodiment comprises the following steps:
step one, adding Bi2O3、Ca(OH)2、SrCO3Mixing CuO and Bi, Sr, Ca and Cu according to the mass ratio of 2:2:0.95:2, preparing a nitrate mixed solution, and preparing oxalate mixed powder by adopting an oxalate coprecipitation method;
step two, putting the oxalate mixed powder obtained in the step one into a box-type furnace for heating and heat preservation, cooling along with the furnace, taking out for grinding, then putting into a continuous rotating automatic sintering furnace for primary sintering, taking out and grinding to obtain primary sintering powder; the specific process of heating and heat preservation is as follows: firstly, heating to 230 ℃ at the speed of 60 ℃/h and preserving heat for 3h, and then heating to 470 ℃ at the speed of 60 ℃/h and preserving heat for 3 h; the temperature rise rate of the primary sintering is 60 ℃/h, the sintering temperature is 470 ℃, and the heat preservation time is 3 h;
step three, loading the primary sintering powder obtained in the step two into a first raw material powder storage tank 1-1 of a high-temperature powder suspension sintering furnace, heating the furnace temperature of the high-temperature powder suspension sintering furnace to 700 ℃, keeping the temperature for 30min, then opening a first air inlet switch 1-10 and a first powder adding motor 1-11, controlling the air inlet speed to be 30L/min, then opening a first air hammer 1-8, allowing the primary sintering powder in the first raw material powder storage tank 1-1 to enter a first furnace pipe 4-1 at the speed of 15g/min under the action of air load for high-temperature sintering, and then allowing the primary sintering powder to enter a first powder collecting tank 9-1 through a first collecting cloth bag 6-1 to obtain high-temperature sintering powder;
step four, loading the high-temperature sintering powder obtained in the step three into a second raw material powder storage tank 1-2 of the powder suspension phase-forming sintering furnace, raising the temperature of the powder suspension phase-forming sintering furnace to 830 ℃, keeping the temperature for 30min, then opening a second air inlet switch 2-10 and a second powder adding motor 2-11, controlling the air inlet rate to be 30L/min, then opening a second air hammer 2-8, enabling the high-temperature sintering powder in the second raw material powder storage tank 2-1 to enter a second furnace tube 2-4 at the rate of 15g/min under the action of air load to perform phase-forming sintering, and then entering a second powder collection tank 2-9 through a second collection cloth bag 2-6 to obtain the Bi-2212 precursor powder.
The Bi-2212 precursor powder prepared by the implementation and the Bi-2212 precursor powder prepared by the coprecipitation method and the spray thermal decomposition method in the prior art are observed and compared by adopting a scanning electron microscope (multiplied by 100), and the result shows that the probability of one non-Bi-2212 phase particle appearing in the scanning electron microscope (multiplied by 100) picture of the Bi-2212 precursor powder prepared by the implementation is 0.15 per piece, the probability of one non-Bi-2212 phase particle appearing in the scanning electron microscope (multiplied by 100) picture of the Bi-2212 precursor powder prepared by the coprecipitation method in the prior art is 2 per piece, and the probability of one non-Bi-2212 phase particle appearing in the scanning electron microscope (multiplied by 100) picture of the Bi-2212 precursor powder prepared by the spray thermal decomposition method is 1 per piece; the Bi-2212 precursor powder is prepared by adopting the process of the embodiment and a coprecipitation method and a spray thermal decomposition method in the prior art respectively under the same production period condition, and the preparation efficiency of the embodiment is calculated to be 120 kg/month which is far higher than the preparation efficiency of the coprecipitation method in the prior art by 5 kg/month and the preparation efficiency of the spray thermal decomposition method by 20 kg/month, so that the preparation process effectively promotes the phase formation, improves the quality of the Bi-2212 precursor powder and simultaneously improves the preparation efficiency of the Bi-2212 precursor powder.
Example 4
The embodiment comprises the following steps:
step one, adding Bi2O3、Ca(OH)2、SrCO3Mixing CuO and Sr, Ca and Cu according to the mass ratio of 2.1:2.1:0.95:2.1, preparing a nitrate mixed solution, and preparing oxalate mixed powder by adopting an oxalate coprecipitation method;
step two, putting the oxalate mixed powder obtained in the step one into a box-type furnace for heating and heat preservation, cooling along with the furnace, taking out for grinding, then putting into a continuous rotating automatic sintering furnace for primary sintering, taking out and grinding to obtain primary sintering powder; the specific process of heating and heat preservation is as follows: firstly, heating to 240 ℃ at the speed of 70 ℃/h and preserving heat for 4h, and then heating to 490 ℃ at the speed of 70 ℃/h and preserving heat for 4 h; the temperature rise rate of the primary sintering is 70 ℃/h, the sintering temperature is 490 ℃, and the heat preservation time is 4 h;
step three, loading the primary sintering powder obtained in the step two into a first raw material powder storage tank 1-1 of a high-temperature powder suspension sintering furnace, heating the furnace temperature of the high-temperature powder suspension sintering furnace to 700 ℃, keeping the temperature for 30min, then opening a first air inlet switch 1-10 and a first powder adding motor 1-11, controlling the air inlet speed to be 40L/min, then opening a first air hammer 1-8, allowing the primary sintering powder in the first raw material powder storage tank 1-1 to enter a first furnace pipe 4-1 at the speed of 15g/min under the action of air load for high-temperature sintering, and then allowing the primary sintering powder to enter a first powder collecting tank 9-1 through a first collecting cloth bag 6-1 to obtain high-temperature sintering powder;
step four, loading the high-temperature sintering powder obtained in the step three into a second raw material powder storage tank 1-2 of the powder suspension phase-forming sintering furnace, raising the temperature of the powder suspension phase-forming sintering furnace to 830 ℃, keeping the temperature for 30min, then opening a second air inlet switch 2-10 and a second powder adding motor 2-11, controlling the air inlet speed to be 40L/min, then opening a second air hammer 2-8, enabling the high-temperature sintering powder in the second raw material powder storage tank 2-1 to enter a second furnace tube 2-4 at the speed of 15g/min under the action of air load to perform phase-forming sintering, and then entering a second powder collection tank 2-9 through a second collection cloth bag 2-6 to obtain the Bi-2212 precursor powder.
The Bi-2212 precursor powder prepared by the implementation and the Bi-2212 precursor powder prepared by the coprecipitation method and the spray thermal decomposition method in the prior art are observed and compared by adopting a scanning electron microscope (multiplied by 100), and the result shows that the probability of one non-Bi-2212 phase particle appearing in the scanning electron microscope (multiplied by 100) picture of the Bi-2212 precursor powder prepared by the implementation is 0.15 per piece, the probability of one non-Bi-2212 phase particle appearing in the scanning electron microscope (multiplied by 100) picture of the Bi-2212 precursor powder prepared by the coprecipitation method in the prior art is 2 per piece, and the probability of one non-Bi-2212 phase particle appearing in the scanning electron microscope (multiplied by 100) picture of the Bi-2212 precursor powder prepared by the spray thermal decomposition method is 1 per piece; the Bi-2212 precursor powder is prepared by adopting the process of the embodiment and a coprecipitation method and a spray thermal decomposition method in the prior art respectively under the same production period condition, and the preparation efficiency of the embodiment is calculated to be 120 kg/month which is far higher than the preparation efficiency of the coprecipitation method in the prior art by 5 kg/month and the preparation efficiency of the spray thermal decomposition method by 20 kg/month, so that the preparation process effectively promotes the phase formation, improves the quality of the Bi-2212 precursor powder and simultaneously improves the preparation efficiency of the Bi-2212 precursor powder.
Example 5
The embodiment comprises the following steps:
step one, adding Bi2O3、Ca(OH)2、SrCO3Mixing CuO and Sr, Ca and Cu according to the mass ratio of 1.9:2.1:0.95:2.1, preparing a nitrate mixed solution, and preparing oxalate mixed powder by adopting an oxalate coprecipitation method;
step two, putting the oxalate mixed powder obtained in the step one into a box-type furnace for heating and heat preservation, cooling along with the furnace, taking out for grinding, then putting into a continuous rotating automatic sintering furnace for primary sintering, taking out and grinding to obtain primary sintering powder; the specific process of heating and heat preservation is as follows: firstly, heating to 230 ℃ at the speed of 50 ℃/h and preserving heat for 3h, and then heating to 460 ℃ at the speed of 50 ℃/h and preserving heat for 3 h; the temperature rise rate of the primary sintering is 60 ℃/h, the sintering temperature is 460 ℃, and the heat preservation time is 3 h;
step three, loading the primary sintering powder obtained in the step two into a first raw material powder storage tank 1-1 of a high-temperature powder suspension sintering furnace, heating the furnace temperature of the high-temperature powder suspension sintering furnace to 700 ℃, keeping the temperature for 50min, then opening a first air inlet switch 1-10 and a first powder adding motor 1-11, controlling the air inlet speed to be 30L/min, then opening a first air hammer 1-8, allowing the primary sintering powder in the first raw material powder storage tank 1-1 to enter a first furnace pipe 4-1 at the speed of 15g/min under the action of air load for high-temperature sintering, and then allowing the primary sintering powder to enter a first powder collecting tank 9-1 through a first collecting cloth bag 6-1 to obtain high-temperature sintering powder;
step four, loading the high-temperature sintering powder obtained in the step three into a second raw material powder storage tank 1-2 of the powder suspension phase-forming sintering furnace, raising the temperature of the powder suspension phase-forming sintering furnace to 830 ℃, keeping the temperature for 30min, then opening a second air inlet switch 2-10 and a second powder adding motor 2-11, controlling the air inlet rate to be 30L/min, then opening a second air hammer 2-8, enabling the high-temperature sintering powder in the second raw material powder storage tank 2-1 to enter a second furnace tube 2-4 at the rate of 15g/min under the action of air load to perform phase-forming sintering, and then entering a second powder collection tank 2-9 through a second collection cloth bag 2-6 to obtain the Bi-2212 precursor powder.
The Bi-2212 precursor powder prepared by the implementation and the Bi-2212 precursor powder prepared by the coprecipitation method and the spray thermal decomposition method in the prior art are observed and compared by adopting a scanning electron microscope (multiplied by 100), and the result shows that the probability of one non-Bi-2212 phase particle appearing in the scanning electron microscope (multiplied by 100) picture of the Bi-2212 precursor powder prepared by the implementation is 0.15 per piece, the probability of one non-Bi-2212 phase particle appearing in the scanning electron microscope (multiplied by 100) picture of the Bi-2212 precursor powder prepared by the coprecipitation method in the prior art is 2 per piece, and the probability of one non-Bi-2212 phase particle appearing in the scanning electron microscope (multiplied by 100) picture of the Bi-2212 precursor powder prepared by the spray thermal decomposition method is 1 per piece; the Bi-2212 precursor powder is prepared by adopting the process of the embodiment and a coprecipitation method and a spray thermal decomposition method in the prior art respectively under the same production period condition, and the preparation efficiency of the embodiment is 80 kg/month which is far higher than the preparation efficiency of the coprecipitation method in the prior art by 5 kg/month and the preparation efficiency of the spray thermal decomposition method by 20 kg/month through calculation, so that the preparation process effectively promotes the phase formation, improves the quality of the Bi-2212 precursor powder and simultaneously improves the preparation efficiency of the Bi-2212 precursor powder.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (6)
1. A method for preparing Bi-2212 precursor powder by a suspension sintering method is characterized by comprising the following steps:
step one, adding Bi2O3、Ca(OH)2、SrCO3And CuO are mixed according to the mass ratio of Bi to Sr to Ca to Cu = (1.95-2.2) to (0.9-1) to (1.95-2.2), then a nitrate mixed solution is prepared, and an oxalate coprecipitation method is adopted to prepare oxalate mixed powder;
step two, putting the oxalate mixed powder obtained in the step one into a box-type furnace for heating and heat preservation, cooling along with the furnace, taking out for grinding, then putting into a continuous rotating automatic sintering furnace for primary sintering, taking out and grinding to obtain primary sintering powder; the specific process of heating and heat preservation is as follows: firstly heating to 200-250 ℃ for heat preservation, and then heating to 450-500 ℃ for heat preservation; the sintering temperature of the primary sintering is 450-500 ℃;
step three, loading the primary sintering powder obtained in the step two into a first raw material powder storage tank (1-1) of a high-temperature powder suspension sintering furnace, heating the high-temperature powder suspension sintering furnace to 700-750 ℃, preserving heat, then opening a first air inlet switch (1-10) and a first powder adding motor (1-11), adjusting air inlet rate, then opening a first air hammer (1-8), allowing the primary sintering powder in the first raw material powder storage tank (1-1) to enter a first furnace tube (1-4) under the action of gas to perform high-temperature sintering, and allowing the primary sintering powder to enter a first powder collection tank (1-9) through a first collection cloth bag (1-6) to obtain high-temperature sintering powder;
and step four, filling the high-temperature sintering powder obtained in the step three into a second raw material powder storage tank (2-1) of the powder suspension phase-forming sintering furnace, heating the powder suspension phase-forming sintering furnace to 830-850 ℃, keeping the temperature, then opening a second air inlet switch (2-10) and a second powder adding motor (2-11) and adjusting the air inlet rate, then opening a second air hammer (2-8), allowing the high-temperature sintering powder in the second raw material powder storage tank (2-1) to enter a second furnace tube (2-4) under the action of gas to perform phase-forming sintering, and then allowing the high-temperature sintering powder to enter a second powder collection tank (2-9) through a second collection cloth bag (2-6) to obtain Bi-2212 precursor powder.
2. The method for preparing the Bi-2212 precursor powder by the suspension sintering method according to claim 1, wherein the specific process of heating and heat preservation in the second step is as follows: firstly, heating to 200-250 ℃ at the speed of 40-80 ℃/h, and preserving heat for 2-5 h, then heating to 450-500 ℃ at the speed of 40-80 ℃/h, and preserving heat for 2-5 h.
3. The method for preparing the Bi-2212 precursor powder by the suspension sintering method according to claim 1, wherein the temperature rise rate of the primary sintering in the second step is 40-80 ℃/h, and the heat preservation time is 2-5 h.
4. The method for preparing the Bi-2212 precursor powder by the suspension sintering method according to claim 1, wherein the high-temperature powder suspension sintering furnace is heated to 700-750 ℃ and is kept at the temperature for more than 30min in the third step, and the air inlet rate is 20-50L/min.
5. The method for preparing the Bi-2212 precursor powder by the suspension sintering method according to claim 1, wherein the powder is heated to 830-850 ℃ in the suspension phase sintering furnace and is kept at the temperature for more than 30min in the fourth step, and the air inlet rate is 20-50L/min.
6. The method for preparing Bi-2212 precursor powder by using the suspension sintering method according to claim 1, wherein the rate of the primary sintering powder entering the first furnace tube (1-4) in the third step under the action of gas load and the rate of the high-temperature sintering powder entering the second furnace tube (2-4) in the fourth step under the action of gas load are both 10 g/min-20 g/min, and the time of the gas entering and passing through the first furnace tube (1-4) and the second furnace tube (2-4) is more than 0.1 s.
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