CN108264350B - Preparation method of anisotropic lanthanum calcium manganese oxygen-based ceramic target - Google Patents

Preparation method of anisotropic lanthanum calcium manganese oxygen-based ceramic target Download PDF

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CN108264350B
CN108264350B CN201810250897.1A CN201810250897A CN108264350B CN 108264350 B CN108264350 B CN 108264350B CN 201810250897 A CN201810250897 A CN 201810250897A CN 108264350 B CN108264350 B CN 108264350B
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张辉
李之昱
刘翔
陈清明
杨盛安
李陵
梁国威
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Kunming University of Science and Technology
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Abstract

The invention discloses a preparation method of an anisotropic lanthanum calcium manganese oxygen-based ceramic target, belonging to the technical field of ceramic preparation. The method specifically comprises the following steps: sol process, gel process, dry glue process, primary crushing process, primary calcining process, silver doping process, powder static pressing process, secondary calcining process, secondary crushing process, pre-mold pressing process, final mold static pressing process and tertiary calcining process; according to the method, the Ag doping effect can be improved through liquid phase mixing and infiltration sintering, the doping loss is greatly reduced, the actual doping proportion is close to the calculated amount, and the anisotropy of the ceramic target is further enhanced; combined with a non-oxidizing sintering process to enable La to be formed x1‑Ca x MnO3The matrix and the Ag element are not oxidized before the doping is not finished, so that the doping effect is improved; the combination of the cold isostatic pressing process generates multidirectional stress in the permeation and pressing processes, which is beneficial to the preferential growth of the target material and greatly eliminates the defective tissue, thereby enabling the ceramic target to have strong anisotropy.

Description

Preparation method of anisotropic lanthanum calcium manganese oxygen-based ceramic target
Technical Field
The invention relates to a preparation method of an anisotropic lanthanum calcium manganese oxygen-based ceramic target, belonging to the technical field of ceramic preparation.
Background
La1-xCaxMnO3 is a rare earth doped manganese oxide with a perovskite structure. The material has giant magnetoresistance effect and laser induced voltage effect, can be used for manufacturing giant magnetoresistance bolometers, photoelectric conversion devices, high-density storage magnetic heads, non-contact magnetoresistive switches, magnetic sensitive sensors, thermoelectric devices and the like, thereby arousing the research interest of broad scholars and becoming another research hotspot of strongly-associated material systems after high-temperature superconduction. The research of the current La1-xCaxMnO3 system focuses on the synthesis preparation of doped Ag, so that the ceramic target can be assisted to grow preferentially in the growth process, the anisotropy of the target is further enhanced, and the electrical property of the target is greatly improved; and secondly, the electrical temperature-sensitive performance of the material can be greatly improved due to the enhancement of anisotropy. However, the current preparation process has the following common diseases in most aspects: (1) in the prior art, most of granulated silver powder is adopted for mixed sintering, the purpose of doping is achieved through solid-phase reaction, although the effect can be improved by controlling the particle size of the silver powder, the defect of the solid-phase reaction still exists, the doping effect is poor, the doping amount loss is too large, and the doping proportion is far lower than the calculated amount; (2) no matter what method is adopted for doping, no anti-oxidation measure is provided in the prior art, firstly, after the La1-xCaxMnO3 matrix material is oxidized to form a stable state, Ag element is not easy to dope, and secondly, Ag factor is oxidized, so that the doping effect is poor and the Ag element cannot effectively enter the matrix material; (3) in the existing process operation, a conventional pressing means is adopted, and generally directional stress is generated, so that the target material is not favorable for preferential growth in subsequent sintering, and the defects cannot be greatly eliminated. Therefore, in order to solve the problems, the design and development of a preparation process of the ceramic target with strong anisotropy (LaxCa1-xMnO 3). Agy is in urgent need.
Disclosure of Invention
In view of the problems of the prior art, it is an object of the present invention to provide an anisotropic ceramic target (La)xCa1-xMnO3)·AgyThe preparation method specifically comprises the following steps:
(1) and (3) sol process: lanthanum nitrate, calcium nitrate, manganese nitrate and citric acid are mixed according to the formula (La)xCa1-xMnO3)·AgyThe transition compound I is obtained after mixing by weighing according to the stoichiometric proportion and pouring into a mixing container by adopting methanol as a mixed solvent carrier and ethylene glycol as a dispersing agent; wherein the content of the first and second substances, X0.66 to 0.75, and y is 0.1 to 0.3.
(2) And (3) a gel process: and (2) putting the transition object I obtained in the step (1) into an environment with the temperature of 75-90 ℃ for drying and steaming to obtain a transition object II.
(3) And (3) a glue drying process: and (3) placing the transition substance II obtained in the step (2) in an environment of 110-130 ℃ for dehydration and foaming to obtain a transition substance III.
(4) A primary crushing process: performing ball milling and crushing treatment on the transition object III obtained in the step (3) to obtain a transition object IV; the particle size of the product is small enough through fragmentation, so that the non-component impurities can be completely volatilized during the subsequent one-time calcination, and enough volatilization channels can be formed.
(5) The primary calcination process comprises the following steps: calcining the transition substance IV obtained in the step (4) for the first time to obtain a transition substance V; impurity components in the transition substance IV can be completely volatilized by non-oxidation sintering, and meanwhile, an oxide layer is not generated, so that subsequent silver elements cannot be doped into a material system.
(6) The silver doping process comprises the following steps: uniformly coating silver paste on grinding small balls of a ball mill and the inner side of the wall of a ball milling tank, and pouring the transition substance V obtained in the step (5) into the ball milling tank to start ball milling to obtain a transition substance VI; by the process, sufficient silver paste can be coated on the transition object V, and the overall coating surface area can be maximized by coating and crushing.
(7) Powder static pressure process: carrying out cold isostatic pressing on the transition object VI obtained in the step (6) to obtain a transition object VII; the step can ensure that the transition object VI is subjected to omnibearing extrusion force, a permeation interface is formed under the condition of long-time high pressure, and a foundation is laid for subsequent secondary calcination.
(8) And (3) secondary calcination process: carrying out secondary calcination on the transition object VII obtained in the step (7) to obtain a transition object VIII; through the sintering in the step, the permeation layer with the silver element with extremely thin thickness can be ensured to enter the base material, and the silver element can be ensured not to be oxidized in a large amount in a vacuum state, so that the silver element is really doped.
(9) And (3) secondary crushing process: performing ball milling on the transition object VIII obtained in the step (8) by using a ball mill to obtain a transition object IX; and products with complete components are refined and mixed, so that the overall components of the subsequent ceramic target are ensured to be uniform.
(10) And (3) a pre-mold pressing process: pressing the transition substance IX obtained in the step (9) into a premoulded target.
(11) And (3) final die static pressure process: performing cold isostatic pressing on the pre-molded target obtained in the step (10) to obtain a final molded target; the step can ensure that the ceramic target is subjected to omnibearing extrusion force, greatly improves the density, reduces the probability of defect generation, and lays a foundation for preferential growth in the subsequent three times of calcination.
(12) And (3) a tertiary calcination process: oxygen-enriched sintering is carried out on the final die target obtained in the step (11), and anisotropy (La) is obtainedxCa1-xMnO3)·AgyA ceramic target; the ceramic target with anisotropy is obtained by preferential growth.
Preferably, the particle size of the transition material IV obtained by ball milling in the step (4) of the present invention is less than 0.1 mm.
Preferably, the conditions of the primary calcination in step (5) of the present invention are: the vacuum degree is less than 500Pa, the sintering temperature is 480-500 ℃, and the sintering time is 6-8 h.
Preferably, the using amount of the silver paste in the step (6) is 105% -107% of the real calculated amount, and the viscosity of the silver paste is 1.5 CPS-2.5 CPS; the ball milling conditions are as follows: the ball milling speed is 300 r/min-600 r/min, and the ball milling time is 6-8 h.
Preferably, the cold isostatic pressing in step (7) of the present invention comprises the following specific processes: pouring the obtained transition object VI on a preservative film, vibrating and flatly paving the transition object VI through an ultrasonic plate, folding and wrapping the transition object VI, sequentially packaging the transition object VI with the preservative film and a thin rubber bag, vacuumizing the packaged thin rubber bag, and immersing the vacuum thin rubber bag into a cold isostatic press oil tank for static pressure; the static pressure process is a step pressure maintaining operation, the pressure value is 170-210 MPa, and the total pressure time is 40-180 min.
Preferably, the conditions of the secondary calcination in step (8) of the present invention are: the vacuum degree is less than 500Pa, the sintering temperature is 400-450 ℃, and the sintering time is 12-15 h.
Preferably, the particle size of the transition compound IX obtained in step (9) of the present invention is less than 0.5 mm.
Preferably, in the step (10), the pressure in the pressing process is 8-13 MPa, and the total pressing time is 10-20 min.
Preferably, the cold isostatic pressing in step (11) of the present invention comprises the following specific processes: the method comprises the steps of sequentially packaging a preservative film and a thin rubber bag, vacuumizing the packaged thin rubber bag through a drawing press, immersing the vacuum thin rubber bag into a cold isostatic pressing engine oil tank for static pressure operation, wherein the static pressure process is step-type pressure maintaining operation, the pressure value is 230 Mpa-250 Mpa, and the total pressure duration is 15 min-20 min.
Preferably, the oxygen-enriched sintering conditions in step (12) of the present invention are: the sintering temperature is 1350-1450 ℃, the sintering time is 12-16 h, and the flowing oxygen pressure is 0.01-0.07 Mpa.
Compared with the prior art, the invention has the advantages that:
(1) the process can improve the Ag doping effect and greatly reduce the doping loss through liquid phase mixing and infiltration sintering, so that the actual doping proportion is close to the calculated amount, and the anisotropy of the ceramic target is further enhanced.
(2) The process can be combined with a non-oxidation sintering process to ensure that the La is prepared x1-Ca x MnO3The matrix and the Ag element are not oxidized before the doping is not finished, so that the doping effect is improved.
(3) The process combines the cold isostatic pressing process, generates multidirectional stress in the permeation and pressing processes, can be favorable for the preferential growth of the target material and greatly eliminates the defective tissue, thereby leading the ceramic target to have strong anisotropy.
Drawings
FIG. 1 is a graph illustrating electrical property measurements of the target of example 1;
FIG. 2 is a graph showing the electrical properties of the target of comparative example 1;
FIG. 3 is a graph showing the electrical properties of the target of comparative example 2;
fig. 4 is a graph showing the electrical properties of the target of comparative example 3.
The specific implementation mode is as follows:
the invention is described in detail below with reference to the drawings and examples, which are for illustrative purposes only and are not intended to limit the invention.
Example 1
Strong anisotropy (La)0.7Ca0.3MnO3)·Ag0.2Ceramic target preparation process and deviceThe method comprises the following steps:
(1) and (3) sol process: lanthanum nitrate, calcium nitrate, manganese nitrate and citric acid are poured into a mixing container according to the mass ratio of 6:1:6:19, methanol is used as a mixed solvent carrier, glycol is used as a dispersing agent, and the mixture is mixed to obtain a transition substance I.
(2) And (3) a gel process: and (2) putting the transition substance I obtained in the step (1) in an environment of 80 ℃ for drying and steaming to obtain a transition substance II.
(3) And (3) a glue drying process: and (3) placing the transition substance II obtained in the step (2) in an environment of 120 ℃ for dehydration foaming to obtain a transition substance III.
(4) A primary crushing process: and (4) performing ball milling on the transition substance III obtained in the step (3) by using a ball mill to obtain a transition substance IV (the particle size is less than 0.1 mm).
(5) The primary calcination process comprises the following steps: calcining the transition substance IV obtained in the step (4) for the first time through a vacuum sintering furnace to obtain a transition substance V; the vacuum degree of the primary calcination is required to be less than 500Pa, the sintering temperature is 490 ℃, and the sintering time is 7 h.
(6) The silver doping process comprises the following steps: uniformly coating the planned amount of silver paste on the grinding small balls of the ball mill and the inner side of the wall of the ball milling tank, and pouring the transition substance V obtained in the step (5) into the ball milling tank for ball milling operation to obtain a transition substance VI; the planned amount is 106% of the real calculated amount, the viscosity range of the silver paste is 2.0 CPS, the ball milling rotation speed of the ball milling operation is 450 r/min, and the ball milling time is 7 h.
(7) Powder static pressure process: pouring the transition object VI obtained in the step (6) on a preservative film, vibrating and tiling the transition object VI through an ultrasonic plate, folding and wrapping the transition object VI, sequentially packaging the transition object VI with the preservative film and a thin rubber bag, performing vacuum operation on the packaged thin rubber bag through a drawing press, and immersing the thin rubber bag in a vacuum state into a cold isostatic press oil tank for static pressure operation to obtain a transition object VII; the static pressure operation can be carried out in a step-type pressure maintaining mode, the range of the pressure value is 190Mpa, and the total pressure-bearing duration range is 100 min.
(8) And (3) secondary calcination process: pouring the transition object VII obtained in the step (7) out of the package, and carrying out secondary calcination on the transition object VII through a vacuum sintering furnace to obtain a transition object VIII; the vacuum degree of the secondary calcination needs to be less than 500Pa, the sintering temperature is 430 ℃, and the sintering time is 14 h.
(9) And (3) secondary crushing process: and (5) performing ball milling on the transition substance VIII obtained in the step (8) by using a ball mill to obtain a transition substance IX (the particle size is less than 0.5 mm).
(10) And (3) a pre-mold pressing process: pressing the transition substance IX obtained in the step (9) into a premoulded target by a mechanical tablet press; the range of the pressure value adopted by pressing is 10Mpa, and the total pressing duration range is 15 min.
(11) And (3) final die static pressure process: sequentially packaging the pre-molded target obtained in the step (10) by using a preservative film and a thin rubber bag, performing vacuum operation on the packaged thin rubber bag by using a drawing press, and immersing the vacuum thin rubber bag into a cold isostatic pressing engine oil tank for static pressure operation to obtain a final molded target; the static pressure operation can be carried out in a stepped pressure maintaining mode, the pressure value is 240Mpa, and the total pressure-bearing time range is 18 min.
(12) And (3) a tertiary calcination process: performing oxygen-enriched sintering on the final die target obtained in the step (11) by using an atmosphere sintering furnace to obtain the strong anisotropy (La)0.7Ca0.3MnO3)·Ag0.2A ceramic target. The sintering temperature of the oxygen-enriched sintering is 1400 ℃, the sintering time is 14h, and the flowing oxygen pressure is 0.04 Mpa.
The electrical property test of the target material prepared in this example 1 is shown in fig. 1, and it can be seen from the graph that the TCR value of the target material is 33.67% at 256.68K in the magnetic field environment perpendicular to the target, and 46.35% at 257.21K in the magnetic field environment horizontal to the target. It can be known that, under the condition that the difference of the electrical sensitivity temperature points is not large, the electrical properties are greatly improved, and the electrical sensitivity difference, namely the TCR difference, is improved to 12.68 percent, so that the ceramic target can be judged to have strong anisotropy.
Example 2
Strong anisotropy (La)0.7Ca0.3MnO3)·Ag0.2The preparation process of the ceramic target specifically comprises the following steps:
(1) and (3) sol process: lanthanum nitrate, calcium nitrate, manganese nitrate and citric acid are poured into a mixing container according to the mass ratio of 6:1:6:19, methanol is used as a mixed solvent carrier, glycol is used as a dispersing agent, and the mixture is mixed to obtain a transition substance I.
(2) And (3) a gel process: and (2) placing the transition substance I obtained in the step (1) in an environment of 75 ℃ for drying and steaming to obtain a transition substance II.
(3) And (3) a glue drying process: and (3) placing the transition substance II obtained in the step (2) in an environment of 110 ℃ for dehydration foaming to obtain a transition substance III.
(4) A primary crushing process: and (4) performing ball milling on the transition substance III obtained in the step (3) by using a ball mill to obtain a transition substance IV (the particle size is less than 0.1 mm).
(5) The primary calcination process comprises the following steps: calcining the transition substance IV obtained in the step (4) for the first time through a vacuum sintering furnace to obtain a transition substance V; the vacuum degree of the primary calcination is required to be less than 500Pa, the sintering temperature is 480 ℃, and the sintering time is 6 h.
(6) The silver doping process comprises the following steps: uniformly coating the planned amount of silver paste on the grinding small balls of the ball mill and the inner side of the wall of the ball milling tank, and pouring the transition substance V obtained in the step (5) into the ball milling tank for ball milling operation to obtain a transition substance VI; the planned amount is 105% of the real calculated amount, the viscosity range of the silver paste is 1.5CPS, the ball milling rotation speed of the ball milling operation is 300r/min, and the ball milling time is 6 h.
(7) Powder static pressure process: pouring the transition object VI obtained in the step (6) on a preservative film, vibrating and tiling the transition object VI through an ultrasonic plate, folding and wrapping the transition object VI, sequentially packaging the transition object VI with the preservative film and a thin rubber bag, performing vacuum operation on the packaged thin rubber bag through a drawing press, and immersing the thin rubber bag in a vacuum state into a cold isostatic press oil tank for static pressure operation to obtain a transition object VII; the static pressure operation can be carried out in a step-type pressure maintaining mode, the range of the pressure value is 170Mpa, and the total pressure-bearing duration range is 40 min.
(8) And (3) secondary calcination process: pouring the transition object VII obtained in the step (7) out of the package, and carrying out secondary calcination on the transition object VII through a vacuum sintering furnace to obtain a transition object VIII; the vacuum degree of the secondary calcination needs to be less than 500Pa, the sintering temperature is 400 ℃, and the sintering time is 12 h.
(9) And (3) secondary crushing process: and (5) performing ball milling on the transition substance VIII obtained in the step (8) by using a ball mill to obtain a transition substance IX (the particle size is less than 0.5 mm).
(10) And (3) a pre-mold pressing process: pressing the transition substance IX obtained in the step (9) into a premoulded target by a mechanical tablet press; the range of the pressure value adopted by the pressing is 8Mpa, and the range of the total duration of the pressing is 10 min.
(11) And (3) final die static pressure process: sequentially packaging the pre-molded target obtained in the step (10) by using a preservative film and a thin rubber bag, performing vacuum operation on the packaged thin rubber bag by using a drawing press, and immersing the vacuum thin rubber bag into a cold isostatic pressing engine oil tank for static pressure operation to obtain a final molded target; the static pressure operation can be carried out in a stepped pressure maintaining mode, the pressure value is 230Mpa, and the total pressure-bearing time range is 15 min.
(12) And (3) a tertiary calcination process: performing oxygen-enriched sintering on the final die target obtained in the step (11) by using an atmosphere sintering furnace to obtain the strong anisotropy (La)0.7Ca0.3MnO3)·Ag0.2A ceramic target. The sintering temperature of the oxygen-enriched sintering is 1350 ℃, the sintering time is 12 hours, and the flowing oxygen pressure is 0.01 Mpa.
The target material prepared in this example 2 has an electrical property of 25.66% in the magnetic field environment perpendicular to the target, and 37.53% in the magnetic field environment horizontal to the target. It is known that the difference of the electrical sensitivity, i.e., the difference of the TCR, is increased to 11.87%, and it can be judged that the ceramic target has strong anisotropy.
Example 3
Strong anisotropy (La)0.7Ca0.3MnO3)·Ag0.2The preparation process of the ceramic target specifically comprises the following steps:
(1) and (3) sol process: lanthanum nitrate, calcium nitrate, manganese nitrate and citric acid are poured into a mixing container according to the mass ratio of 6:1:6:19, methanol is used as a mixed solvent carrier, glycol is used as a dispersing agent, and the mixture is mixed to obtain a transition substance I.
(2) And (3) a gel process: and (2) placing the transition substance I obtained in the step (1) in an environment of 90 ℃ for drying and steaming to obtain a transition substance II.
(3) And (3) a glue drying process: and (3) placing the transition substance II obtained in the step (2) in an environment of 130 ℃ for dehydration foaming to obtain a transition substance III.
(4) A primary crushing process: and (4) performing ball milling on the transition substance III obtained in the step (3) by using a ball mill to obtain a transition substance IV (the particle size is less than 0.1 mm).
(5) The primary calcination process comprises the following steps: calcining the transition substance IV obtained in the step (4) for the first time through a vacuum sintering furnace to obtain a transition substance V; the vacuum degree of the primary calcination is required to be less than 500Pa, the sintering temperature is 500 ℃, and the sintering time is 8 h.
(6) The silver doping process comprises the following steps: uniformly coating the planned amount of silver paste on the grinding small balls of the ball mill and the inner side of the wall of the ball milling tank, and pouring the transition substance V obtained in the step (5) into the ball milling tank for ball milling operation to obtain a transition substance VI; the planned amount is 107% of the real calculated amount, the viscosity range of the silver paste is 2.5 CPS, the ball milling rotation speed of the ball milling operation is 600 r/min, and the ball milling time is 8 hours.
(7) Powder static pressure process: pouring the transition object VI obtained in the step (6) on a preservative film, vibrating and tiling the transition object VI through an ultrasonic plate, folding and wrapping the transition object VI, sequentially packaging the transition object VI with the preservative film and a thin rubber bag, performing vacuum operation on the packaged thin rubber bag through a drawing press, and immersing the thin rubber bag in a vacuum state into a cold isostatic press oil tank for static pressure operation to obtain a transition object VII; the static pressure operation can be carried out in a step-type pressure maintaining mode, the range of the pressure value is 210Mpa, and the total pressure-bearing duration range is 180 min.
(8) And (3) secondary calcination process: pouring the transition object VII obtained in the step (7) out of the package, and carrying out secondary calcination on the transition object VII through a vacuum sintering furnace to obtain a transition object VIII; the vacuum degree of the secondary calcination needs to be less than 500Pa, the sintering temperature is 450 ℃, and the sintering time is 15 h.
(9) And (3) secondary crushing process: and (5) performing ball milling on the transition substance VIII obtained in the step (8) by using a ball mill to obtain a transition substance IX (the particle size is less than 0.5 mm).
(10) And (3) a pre-mold pressing process: pressing the transition substance IX obtained in the step (9) into a premoulded target by a mechanical tablet press; the range of the pressure value adopted by the pressing is 13Mpa, and the range of the total pressed time is 20 min.
(11) And (3) final die static pressure process: sequentially packaging the pre-molded target obtained in the step (10) by using a preservative film and a thin rubber bag, performing vacuum operation on the packaged thin rubber bag by using a drawing press, and immersing the vacuum thin rubber bag into a cold isostatic pressing engine oil tank for static pressure operation to obtain a final molded target; the static pressure operation can be carried out in a stepped pressure maintaining mode, the pressure value is 250Mpa, and the total pressure-bearing time range is 20 min.
(12) And (3) a tertiary calcination process: performing oxygen-enriched sintering on the final die target obtained in the step (11) by using an atmosphere sintering furnace to obtain the strong anisotropy (La)0.7Ca0.3MnO3)·Ag0.2A ceramic target. The sintering temperature of the oxygen-enriched sintering is 1450 ℃, the sintering time is 16h, and the flowing oxygen pressure is 0.07 Mpa.
The target material prepared in this example 3 has an electrical property of 27.56% in the magnetic field environment perpendicular to the target, and 38.45% in the magnetic field environment horizontal to the target. It is known that the difference in the electrical sensitivity, i.e., the difference in the TCR, is increased to 10.89%, and it can be determined that the ceramic target has strong anisotropy.
It can be seen from the processes of examples 1, 2, and 3 that the Ag element is a silver paste medium, which is uniformly mixed with the substrate material and tightly bonded, and the bonding layer is thin enough to be infiltrated and doped by non-oxidation sintering, and generates a multidirectional stress by a cold isostatic pressing process during the target pressing process, thereby facilitating the preferential growth of the target while substantially eliminating the defective tissue, and finally completing the preparation by oxygen-enriched sintering.
Comparative example 1
This comparative example was prepared using the following procedure (La)0.7Ca0.3MnO3)·Ag0.2Ceramic target:
(1) and (3) sol process: lanthanum nitrate, calcium nitrate, manganese nitrate and citric acid are poured into a mixing container according to the mass ratio of 6:1:6:19, methanol is used as a mixed solvent carrier, glycol is used as a dispersing agent, and the mixture is mixed to obtain a transition substance I.
(2) And (3) a gel process: and (2) putting the transition substance I obtained in the step (1) in an environment of 80 ℃ for drying and steaming to obtain a transition substance II.
(3) And (3) a glue drying process: and (3) placing the transition substance II obtained in the step (2) in an environment of 120 ℃ for dehydration foaming to obtain a transition substance III.
(4) A primary crushing process: and (4) performing ball milling on the transition substance III obtained in the step (3) by using a ball mill to obtain a transition substance IV, wherein the particle size of the transition substance IV is 0.08 mm.
(5) The primary calcination process comprises the following steps: and (3) calcining the transition substance IV obtained in the step (4) for one time by using a conventional sintering furnace to obtain a transition substance V, wherein the sintering temperature is 490 ℃, and the sintering time is 7 hours.
(6) The silver doping process comprises the following steps: silver powder (specifically 0.26 g) with the particle size of 200 meshes is doped into the transition substance V and is ground and mixed to obtain a transition substance VI.
(7) The pressing process comprises the following steps: and (3) pressing the transition object VI obtained in the step (6) into a target by a mechanical tablet press, wherein the pressure value adopted by pressing is 12Mpa, and the total pressing duration range is 18 min.
(8) And (3) secondary calcination process: sintering the target obtained in the step (7) through a conventional sintering furnace to obtain (La)0.7Ca0.3MnO3)·Ag0.2The ceramic target is sintered at 1400 ℃ for 14 h.
This comparative example 1 was prepared using current conventional techniques (La)0.7Ca0.3MnO3)·Ag0.2As shown in FIG. 2, the TCR value of FIG. 2 is a feedback of the electrical sensitivity of the ceramic target under the mutually perpendicular magnetic field conditions, and it can be seen that the TCR value of the ceramic target is 17.27% at 266.85K in the magnetic field environment perpendicular to the target, and is 19.87% at 268.5K in the magnetic field environment horizontal to the target. It can be known that the difference of the electrical sensitivity performance, i.e. the difference of the TCR, is only 2.6% when the difference of the electrical sensitivity temperature points is not large. Therefore, the ceramic target can be judged to have low anisotropy.
Comparative example 2
This comparative example was prepared using the following procedure (La)0.7Ca0.3MnO3)·Ag0.2Ceramic target:
(1) and (3) sol process: lanthanum nitrate, calcium nitrate, manganese nitrate and citric acid are poured into a mixing container according to the mass ratio of 6:1:6:19, methanol is used as a mixed solvent carrier, glycol is used as a dispersing agent, and the mixture is mixed to obtain a transition substance I.
(2) And (3) a gel process: and (2) putting the transition substance I obtained in the step (1) in an environment of 80 ℃ for drying and steaming to obtain a transition substance II.
(3) And (3) a glue drying process: and (3) placing the transition substance II obtained in the step (2) in an environment of 120 ℃ for dehydration foaming to obtain a transition substance III.
(4) A primary crushing process: and (4) performing ball milling on the transition substance III obtained in the step (3) by using a ball mill to obtain a transition substance IV, wherein the particle size of the transition substance IV is 0.08 mm.
(5) The primary calcination process comprises the following steps: and (3) calcining the transition substance IV obtained in the step (4) for one time by using a vacuum sintering furnace to obtain a transition substance V, wherein the sintering temperature is 490 ℃, the sintering time is 7h, and the vacuum degree is 450 Pa.
(6) The silver doping process comprises the following steps: and (3) uniformly coating the planned amount of silver paste on the grinding small balls of the ball mill and the inner side of the wall of the ball milling tank, and pouring the transition object V obtained in the step (5) into the ball milling tank for ball milling operation to obtain a transition object VI, wherein the planned amount is 106%, and the viscosity range of the silver paste is 2 CPS. The ball milling speed of the ball milling operation is 450 r/min, and the ball milling time is 7 h.
(7) Powder static pressure process: and (3) pouring the transition object VI obtained in the step (6) on a preservative film, vibrating and tiling the transition object VI through an ultrasonic plate, folding and wrapping the transition object VI, sequentially packaging the transition object VI by using the preservative film and a thin rubber bag, performing vacuum operation on the packaged thin rubber bag through a suction compressor, immersing the thin rubber bag in a vacuum state into a cold isostatic press oil tank for static pressure operation to obtain a transition object VII, performing step type pressure maintaining operation on the static pressure operation, wherein the range of the pressure value is 190MPa, and the total pressure-bearing duration range is 110 min.
(8) And (3) secondary calcination process: and (4) pouring the transition object VII obtained in the step (7) out of the package, and carrying out secondary calcination on the transition object VII through a vacuum sintering furnace to obtain the transition object VIII, wherein the sintering temperature is 425 ℃, the sintering time is 13.5h, and the vacuum degree is 450 Pa.
(9) And (3) secondary crushing process: and (5) performing ball milling on the transition substance VIII obtained in the step (8) by using a ball mill to obtain a transition substance IX, wherein the particle size of the transition substance IX is 0.4 mm.
(10) The pressing process comprises the following steps: and (3) pressing the transition substance IX obtained in the step (9) into a target by a mechanical tablet press, wherein the pressure value adopted by pressing is 12Mpa, and the total pressing time range is 18 min.
(11) And (3) a tertiary calcination process: performing oxygen-enriched sintering on the target obtained in the step (10) by using an atmosphere sintering furnace to obtain strong anisotropy (La)xCa1-xMnO3)·AgyThe ceramic target is sintered at 1400 ℃ for 14h and has a flowing oxygen pressure of 0.04 MPa.
The comparative example 2 is prepared by combining the processes of solid-liquid mixing, non-oxidation infiltration sintering and the like on the basis of the prior art0.7Ca0.3MnO3)·Ag0.2The ceramic target is prepared by the steps of uniformly mixing Ag element with a base material and tightly bonding the Ag element with the base material, wherein the bonding layer is thin enough, and is subjected to infiltration doping through non-oxidation sintering, and finally, oxygen-enriched sintering; the electrical performance of the target material is shown in fig. 3, and it can be seen from fig. 3 that the TCR value of the target material is 29.37% at 260.76K in the perpendicular magnetic field environment, and 33.7% at 261.4K in the horizontal magnetic field environment. It can be known that, under the condition that the difference of the electrical sensitivity temperature points is not large, not only the electrical properties are improved, but also the electrical sensitivity difference, namely the TCR difference, is improved to 4.33%, and the ceramic target anisotropy can be judged to be improved compared with the conventional process.
Comparative example 3
This example step was carried out according to the process of example 1, but the total length of time the pressure was applied in step (11) was outside the upper range. The electrical performance of the target material is shown in fig. 4, and it can be seen from fig. 4 that the TCR value of the target material is 48.06% at 244.79K in the perpendicular to the targeted magnetic field environment, and 49.95% at 245.88K in the horizontal to the targeted magnetic field environment. It can be known that, although the electrical properties are greatly improved under the condition that the difference between the electrical sensitivity temperature points is not large, the difference between the electrical sensitivity properties, namely the TCR difference, is reduced to 1.89%, because the target density can be enhanced by maintaining the pressure for a long time under the high-pressure state. The defects are reduced, the electrical performance is improved, but the glass phase on the cell interface inside the ceramic target is increased, the subsequent preferential growth is hindered, and strong anisotropy can not be formed, so that the anisotropy of the ceramic target can be judged to be low.
The results of the anisotropic comparison of the ceramic targets of examples 1, 2 and 3 and comparative examples 1, 2 and 3 are shown in Table 1, and it can be seen from Table 1 that the present invention combines the solid-liquid mixing, cold isostatic pressing and non-oxidation infiltration sintering processes based on the sol-gel process to prepare the highly anisotropic (La) targetxCa1-xMnO3)·AgyThe ceramic target is characterized by large directional differences in electrical properties.
TABLE 1 anisotropy comparison of ceramic targets of various examples and comparative examples
Figure 868725DEST_PATH_IMAGE002

Claims (10)

1. A preparation method of an anisotropic lanthanum calcium manganese oxygen-based ceramic target is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) and (3) sol process: lanthanum nitrate, calcium nitrate, manganese nitrate and citric acid are mixed according to the formula (La)xCa1-xMnO3)·AgyThe transition compound I is obtained after mixing by weighing according to the stoichiometric proportion and pouring into a mixing container by adopting methanol as a mixed solvent carrier and ethylene glycol as a dispersing agent; wherein the content of the first and second substances, X0.66 to 0.75, y is 0.1 to 0.3;
(2) and (3) a gel process: putting the transition object I obtained in the step (1) into an environment with the temperature of 75-90 ℃ for drying and steaming to obtain a transition object II;
(3) and (3) a glue drying process: placing the transition substance II obtained in the step (2) in an environment of 110-130 ℃ for dehydration and foaming to obtain a transition substance III;
(4) a primary crushing process: performing ball milling and crushing treatment on the transition object III obtained in the step (3) to obtain a transition object IV;
(5) the primary calcination process comprises the following steps: calcining the transition substance IV obtained in the step (4) for the first time to obtain a transition substance V;
(6) the silver doping process comprises the following steps: uniformly coating silver paste on grinding small balls of a ball mill and the inner side of the wall of a ball milling tank, and pouring the transition substance V obtained in the step (5) into the ball milling tank to start ball milling to obtain a transition substance VI;
(7) powder static pressure process: carrying out cold isostatic pressing on the transition object VI obtained in the step (6) to obtain a transition object VII;
(8) and (3) secondary calcination process: carrying out secondary calcination on the transition object VII obtained in the step (7) to obtain a transition object VIII;
(9) and (3) secondary crushing process: performing ball milling on the transition object VIII obtained in the step (8) by using a ball mill to obtain a transition object IX;
(10) and (3) a pre-mold pressing process: pressing the transition substance IX obtained in the step (9) into a pre-molded target;
(11) and (3) final die static pressure process: performing cold isostatic pressing on the pre-molded target obtained in the step (10) to obtain a final molded target;
(12) and (3) a tertiary calcination process: oxygen-enriched sintering is carried out on the final die target obtained in the step (11), and anisotropy (La) is obtainedxCa1- xMnO3)·AgyA ceramic target.
2. The method of preparing an anisotropic lanthanum calcium manganese oxygen-based ceramic target according to claim 1, wherein: and (4) grinding the balls in the step (4) to obtain a transition substance IV with the particle size of less than 0.1 mm.
3. The method of preparing an anisotropic lanthanum calcium manganese oxygen-based ceramic target according to claim 1, wherein: the conditions of the primary calcination in the step (5) are as follows: the vacuum degree is less than 500Pa, the sintering temperature is 480-500 ℃, and the sintering time is 6-8 h.
4. The method of preparing an anisotropic lanthanum calcium manganese oxygen-based ceramic target according to claim 1, wherein: in the step (6), the using amount of the silver paste is 105% -107% of the real calculated amount, and the viscosity of the silver paste is 1.5 CPS-2.5 CPS; the ball milling conditions are as follows: the ball milling speed is 300 r/min-600 r/min, and the ball milling time is 6-8 h.
5. The method of preparing an anisotropic lanthanum calcium manganese oxygen-based ceramic target according to claim 1, wherein: the cold isostatic pressing in the step (7) comprises the following specific processes: pouring the obtained transition object VI on a preservative film, vibrating and flatly paving the transition object VI through an ultrasonic plate, folding and wrapping the transition object VI, sequentially packaging the transition object VI with the preservative film and a thin rubber bag, vacuumizing the packaged thin rubber bag, and immersing the vacuum thin rubber bag into a cold isostatic press oil tank for static pressure; the static pressure process is a step-type pressure maintaining operation, the pressure value is 170 MPa-210 MPa, and the total pressure-bearing time is 40 min-180 min.
6. The method of preparing an anisotropic lanthanum calcium manganese oxygen-based ceramic target according to claim 1, wherein: the conditions of the secondary calcination in the step (8) are as follows: the vacuum degree is less than 500Pa, the sintering temperature is 400-450 ℃, and the sintering time is 12-15 h.
7. The method of preparing an anisotropic lanthanum calcium manganese oxygen-based ceramic target according to claim 1, wherein: and (4) the particle size of the transition substance IX obtained in the step (9) is less than 0.5 mm.
8. The method of preparing an anisotropic lanthanum calcium manganese oxygen-based ceramic target according to claim 1, wherein: the pressure of the pressing process in the step (10) is 8-13 MPa, and the total pressing time is 10-20 min.
9. The method of preparing an anisotropic lanthanum calcium manganese oxygen-based ceramic target according to claim 1, wherein: the cold isostatic pressing in the step (11) comprises the following specific processes: the method comprises the steps of sequentially packaging a preservative film and a thin rubber bag, vacuumizing the packaged thin rubber bag through a drawing press, immersing the vacuum thin rubber bag into a cold isostatic pressing machine oil tank for static pressure operation, wherein the static pressure process is step-type pressure maintaining operation, the pressure value is 230-250 MPa, and the total pressure duration is 15-20 min.
10. The method of preparing an anisotropic lanthanum calcium manganese oxygen-based ceramic target according to claim 1, wherein: the oxygen-enriched sintering conditions in the step (12) are as follows: the sintering temperature is 1350-1450 ℃, the sintering time is 12-16 h, and the flowing oxygen pressure is 0.01-0.07 MPa.
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