CN108727026B - Method for improving electric transport performance of polycrystalline ceramic - Google Patents

Method for improving electric transport performance of polycrystalline ceramic Download PDF

Info

Publication number
CN108727026B
CN108727026B CN201810498672.8A CN201810498672A CN108727026B CN 108727026 B CN108727026 B CN 108727026B CN 201810498672 A CN201810498672 A CN 201810498672A CN 108727026 B CN108727026 B CN 108727026B
Authority
CN
China
Prior art keywords
sintering
temperature
mno
process object
substance
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201810498672.8A
Other languages
Chinese (zh)
Other versions
CN108727026A (en
Inventor
刘翔
刘阳
孙涛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kunming University of Science and Technology
Original Assignee
Kunming University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kunming University of Science and Technology filed Critical Kunming University of Science and Technology
Priority to CN201810498672.8A priority Critical patent/CN108727026B/en
Publication of CN108727026A publication Critical patent/CN108727026A/en
Application granted granted Critical
Publication of CN108727026B publication Critical patent/CN108727026B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3213—Strontium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/422—Carbon
    • C04B2235/425—Graphite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

The invention discloses a method for improving La1‑xCaxSryMnO3The method for improving the electric transport performance of the polycrystalline perovskite ceramic improves the electric transport performance of the polycrystalline perovskite ceramic through the excellent electric conductivity of the graphene. The method comprises the following steps: la1‑xCaxSryMnO3Matrix powder synthesis, synthetic phase material preparation, and polycrystalline ceramic preparation. The polycrystalline ceramics prepared by the invention have reduced resistance, thereby causing the Temperature Coefficient of Resistance (TCR) to be increased and the metal-insulator transition temperature (T)p) The temperature is closer to room temperature, and the device can be widely applied to near-room temperature magnetoelectronic devices, ultra-giant magnetoresistance bolometers (Bolometers), infrared detectors and other devices.

Description

Method for improving electric transport performance of polycrystalline ceramic
Technical Field
The invention relates to a method for improving the electric transport performance of polycrystalline ceramic, in particular to a method for improving La1- xCaxSryMnO3A method for electric transport performance of polycrystalline ceramics belongs to the technical field of electronic ceramics.
Background
Perovskite-structured manganese oxide R1-xAxMnO3Has the giant magnetoresistance effect (CMR) and other excellent physical properties, and has important application value in sensitive devices such as resistance sensors, spintronic equipment, magnetic recording and bolometer, etc. La1-xCaxMnO3And La1-xSrxMnO3As R1-xAxMnO3Important members of the system, respectively, have a high TCR (temperature coefficient of resistance) and a low Tp(metal-insulation transition temperature) and high TpThe low TCR profile makes it economically advantageous to use sensitive devices.
However, the prior art has the following disadvantages: (1) la1-xCaxSryMnO3The range of the regulation temperature of the base polycrystalline ceramic is relatively low and cannot be close to the range of the room temperature which can be applied in a large scale, and the TCR and the TPThe regulation and control effect is general; (2) to make La1- xCaxSryMnO3The regulation and control effect of the polycrystalline ceramics is stable, the regulation and control range is improved, a large amount of elements with low cost performance are required to be doped, and therefore, the transition to pilot production or even subsequent mass production is not facilitated, and the polycrystalline ceramics cannot be commercializedAnd the second time, the phase structure in the ceramic is changed or unstable due to large doping amount, so that the service life of the ceramic is shortened, and even the product quality cannot be guaranteed.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for improving La1-xCaxSryMnO3The method for realizing the electric transport performance of the polycrystalline ceramic specifically comprises the following steps:
1、La1-xCaxSryMnO3synthesizing matrix powder:
1.1 calculating and weighing La (NO) according to x and y values3)3、Ca(NO3)2、Sr(NO3)2、Mn(NO3)2And citric acid, sequentially pouring into deionized water, and synchronously stirring to obtain process material I in liquid state, wherein citric acid is used as chelating agent in the colloid preparation reaction process, and citric acid and Mn (NO) are added3)2The molar ratio of (A) to (B) is 3-6: 1;
1.2, dripping ethylene glycol into the process product I obtained in the step 1.1 to obtain a process product II, wherein the process product II is in a liquid state, the ethylene glycol is used as a dispersing agent in a colloid preparation reaction process, so that raw materials in the liquid process product I can be uniformly mixed, flocculation precipitation is not generated, and the uniformly mixed process product II is obtained, and the volume ratio of the ethylene glycol to the process product I is 3-6%;
1.3, carrying out high-temperature evaporation treatment on the process substance II obtained in the step 1.2 to obtain a process substance III in a non-flowing gel state, wherein the flowing state of the process substance III is used as a reaction stopping criterion, and the step is used for removing macroscopic moisture;
1.4, performing high-temperature drying treatment on the process substance III obtained in the step 1.3 to obtain a dry gel-state process substance IV, wherein the drying treatment temperature is 120-170 ℃, the drying treatment time is 6-24 hours, and the step is used for removing crystallization moisture;
1.5, fully ball-milling and crushing the process material IV obtained in the step 1.4 to obtain a process material V, wherein the process material V is powdery, the particle size range of the process material V is 0.1-1 mm, and if the particle size is larger than the range, the subsequent protective sintering is influenced because of insufficient contact;
1.6 protective sintering treatment of the process product V obtained in the step 1.5 to obtain La1-xCaxSryMnO3The protective sintering treatment can ensure that the process object V is not oxidized and the surface oxidation layer is less, so that the graphene cannot be doped due to the blocking of the oxidation layer in the subsequent operation;
2. preparation of synthetic phase material:
2.1 pouring multilayer graphene weighed into La obtained in step 1.61-xCaxSryMnO3Carrying out ball milling and stirring on the base powder to obtain a process object VI, wherein the process object VI is powder, the ball milling and stirring speed is 200-400 r/min, and the ball milling and stirring time is 5-10 h;
2.2, sequentially packaging the process object VI obtained in the step 2.1 by using a film and sealing rubber, and then putting the packaged process object VI into a cold isostatic press for extrusion operation to obtain a process object VII, wherein the process object VII is powdery, the extrusion operation pressure is 150-200 MPa, and the extrusion operation time is 2-4 h, and the step is to ensure that the graphene and the matrix powder are extruded and permeated under high pressure and are tightly adhered together, and meanwhile, a surface oxidation layer cannot be generated or has no area;
2.3, carrying out tabletting operation on the process object VII obtained in the step 2.2 to obtain a process object VIII, wherein the process object VIII is a block material, the pressure intensity of tabletting operation is 15-25 MPa, and the duration of tabletting operation is 15-30 min;
2.4, performing synthetic sintering treatment on the process object VIII obtained in the step 2.3 to obtain a synthetic phase material, wherein the synthetic phase material is a block material, and the step is to perform high-temperature infiltration doping on graphene and matrix powder in an oxygen-free environment to generate a required ceramic phase;
3. preparing polycrystalline ceramics:
3.1 mashing the synthetic phase material obtained in the step 2.4, and then crushing the synthetic phase material into a powdery process substance IX by adopting ball milling crushing operation, wherein the ball milling crushing operation lasts for 10-20 hours, and the particle size range of the process substance IX is 100-500 nm;
3.2 carrying out oxygen-enriched sintering on the process IX obtained in the step 3.1 to obtain a process X, wherein the process X is powdery, the sintering oxygen pressure is 0.02-0.05 MPa, and the sintering time is 6-10 h; the powdery process object X is fully oxidized through oxygen-enriched sintering, so that the oxygen content of a subsequent product reaches the standard to the target polycrystalline ceramic, and a preferential growth effect can be achieved;
3.3, carrying out tabletting operation on the process object X obtained in the step 3.2 to obtain a process object XI, wherein the process object XI is a block material, the tabletting operation pressure is 15-25 MPa, and the tabletting operation time is 15-30 min;
3.4 sequentially packaging the process substance XI obtained in the step 3.3 by using a film and sealing rubber, then putting the packaged process substance XI into a cold isostatic press to perform extrusion operation to obtain a process substance XII, wherein the process substance XII is a block, the extrusion operation pressure is 200-250 MPa, the extrusion operation time is 1-2 h, and the cold isostatic pressing process ensures that the block of the process substance XII is extruded in all directions, so that the block of the process substance XII is more compact, and the defects of the block of the process substance XII are reduced;
3.5, performing oxygen-enriched sintering on the process product XII obtained in the step 3.4 to obtain polycrystalline ceramic, wherein the polycrystalline ceramic is a block material, the sintering oxygen pressure is 0.04-0.08 MPa, and the sintering time is 8-14 h; fully oxidizing the tightly compacted process product XII through oxygen-enriched sintering, strengthening the preferential growth effect and further ensuring the oxygen content;
preferably, La1-xCaxSryMnO3Wherein x is 0.05-0.8 and y is 0.01-0.15.
Preferably, the protective sintering treatment in the step 1.6 is vacuum sintering treatment, the vacuum degree is less than or equal to 10Pa, the sintering temperature is 500-600 ℃, the sintering time is 8-10 h, and the temperature is respectively kept at the sintering temperature nodes of 200 ℃ and 400 ℃ for 0.5-1 h.
Preferably, La in step 2.11-xCaxSryMnO3The mass ratio of the matrix powder to the multilayer graphene is 1: 0.0001-1: 0.1, if the doping amount of the graphene exceeds the upper limit of the range, the self-aggregation phenomenon of the graphene is aggravated, the doping effect is poor, and if the doping amount of the graphene exceeds the lower limit of the range, no obvious performance optimization effect exists.
Preferably, the thickness of the multilayer graphene in step 2.1 is less than or equal to 10nm, and if the thickness exceeds the thickness range, multilayer stacking of graphene is easily caused to cover the base powder, which may cause uneven composition of subsequent products.
Preferably, the synthetic sintering treatment in step 2.4 is atmospheric pressure sintering in an atmosphere of N2The atmosphere pressure is 1.5-2 MPa, the sintering temperature is 600-1000 ℃, and the sintering time is 0.5-5 h.
Preferably, the sintering temperature of the oxygen-enriched sintering in the step 3.2 is 1000-1100 ℃, because the sintering temperature required by the powder can be lower than the sintering temperature of the bulk material, and self-agglomeration is easily caused by too high sintering temperature.
Preferably, the sintering temperature of the oxygen-enriched sintering in the step 3.5 is 1250-1450 ℃.
The invention has the beneficial effects that:
the invention mixes the graphene into the La1-xCaxSryMnO3A polycrystalline ceramic whose temperature range is increased to a room temperature range suitable for large-scale application, and TCR and TPThe regulation and control effect of (2) is improved; la1-xCaxSryMnO3The polycrystalline ceramic is regulated and controlled to the room temperature range with stable effect and large-scale application, only a small amount of graphene needs to be doped, so that the transition to pilot plant production or even subsequent mass production is facilitated, the cost is low, the popularization and the commercial use are facilitated, and the object phase structure in the ceramic can not be changed or unstable due to the small doping amount, so that the service life of the ceramic is prolonged, the product quality is guaranteed, and the requirements of users are better met.
Drawings
FIG. 1 is a plot of the rho-T test for the polycrystalline ceramic bulk of example 1;
FIG. 2 is a plot of the rho-T test for the polycrystalline ceramic bulk of example 2;
FIG. 3 is a plot of the rho-T test for the polycrystalline ceramic bulk of example 3;
FIG. 4 is a plot of the rho-T test for the polycrystalline ceramic bulk of example 4;
FIG. 5 is a plot of the rho-T test for the polycrystalline ceramic bulk material of the comparative example;
FIG. 6 is a graph showing electrical characteristics of the polycrystalline ceramic bulk material of example 1;
FIG. 7 is a graph showing electrical characteristics of the polycrystalline ceramic bulk material according to example 2;
FIG. 8 is a graph showing electrical characteristics of the polycrystalline ceramic bulk material according to example 3;
FIG. 9 is a graph showing electrical characteristics of the polycrystalline ceramic bulk material according to example 4;
FIG. 10 is a graph showing the electrical characteristics of the polycrystalline ceramic bulk material in the comparative example.
Detailed Description
The invention will be described in more detail with reference to the following figures and examples, but the scope of the invention is not limited thereto.
Example 1
Improve La1-xCaxSryMnO3A method for providing electrical transport properties to a polycrystalline ceramic, comprising the steps of:
1、La0.95Ca0.05Sr0.01MnO3synthesizing matrix powder:
1.1 weighing 0.95mol La (NO)3)3、0.05mol Ca(NO3)2、0.01mol Sr(NO3)2、1mol Mn(NO3)2And 3mol of citric acid, sequentially pouring into deionized water, and synchronously stirring to obtain a process product I;
1.2, dripping 6mL of glycol (the volume ratio of the glycol to the process I is 3%) into the process I obtained in the step 1.1 to obtain a process II;
1.3, carrying out high-temperature evaporation treatment on the process substance II obtained in the step 1.2 to obtain a process substance III in a non-flowing gel state;
1.4, performing high-temperature drying treatment on the process substance III obtained in the step 1.3 to obtain a dry gel-state process substance IV, wherein the drying treatment temperature is 120 ℃, and the drying treatment time is 6 hours;
1.5, fully ball-milling and crushing the process object IV obtained in the step 1.4 to obtain a process object V with the particle size of 0.1 mm;
1.6 protective sintering treatment of the process product V obtained in the step 1.5 to obtain La0.95Ca0.05Sr0.01MnO3A base powder; the protective sintering treatment is vacuum sintering treatment, and the vacuum degreeLess than or equal to 10Pa, the sintering temperature is 500 ℃, the sintering time is 8 hours, and the temperature is respectively kept at the sintering temperature nodes of 200 ℃ and 400 ℃ for 0.5 hour;
2. preparation of synthetic phase material:
2.1 weighing multilayer graphene (0.5 nm) and pouring the multilayer graphene into the La obtained in the step 1.60.95Ca0.05Sr0.01MnO3Base powder, La0.95Ca0.05Sr0.01MnO3The mass ratio of the matrix powder to the multilayer graphene is 1:0.0001, the process object VI is obtained by performing ball milling and stirring on the matrix powder and the multilayer graphene, the ball milling and stirring speed is 200r/min, and the ball milling and stirring time is 5 hours;
2.2, sequentially packaging the process object VI obtained in the step 2.1 by using a film and sealing rubber, and then putting the packaged process object VI into a cold isostatic press for extrusion operation to obtain a process object VII, wherein the process object VII is powdery, the extrusion operation pressure is 150MPa, and the extrusion operation time is 2 h;
2.3, carrying out tabletting operation on the process object VII obtained in the step 2.2 to obtain a process object VIII, wherein the process object VIII is a block material, the tabletting operation pressure is 15MPa, and the tabletting operation time is 15 min;
2.4, performing synthetic sintering treatment on the process object VIII obtained in the step 2.3 to obtain a synthetic phase material, wherein the synthetic phase material is a block material, the synthetic sintering treatment is atmosphere pressurization sintering, and the atmosphere is N2The atmosphere pressure is 1.5MPa, the sintering temperature is 600 ℃, and the sintering time is 0.5 h;
3. preparing polycrystalline ceramics:
3.1 mashing the synthetic phase material obtained in the step 2.4, and then crushing the synthetic phase material into a powdery process substance IX by adopting ball milling crushing operation, wherein the ball milling crushing operation lasts for 10 hours, and the particle size of the process substance IX is 100 nm;
3.2 oxygen-enriched sintering is carried out on the process IX obtained in the step 3.1 to obtain a process X, the sintering oxygen pressure is 0.02MPa, the sintering time is 6h, and the sintering temperature is 1000 ℃;
3.3, carrying out tabletting operation on the process substance X obtained in the step 3.2 to obtain a process substance XI, wherein the process substance XI is a block material, the tabletting operation pressure is 15MPa, and the tabletting operation time is 15 min;
3.4 sequentially packaging the process object XI obtained in the step 3.3 by using a film and sealing rubber, and then putting the packaged product XI into a cold isostatic press for extrusion to obtain a process object XII, wherein the extrusion pressure is 200MPa, and the extrusion time is 1 h;
3.5, performing oxygen-enriched sintering on the process product XII obtained in the step 3.4 to obtain polycrystalline ceramic, wherein the polycrystalline ceramic is a block material, the sintering oxygen pressure is 0.04MPa, the sintering time is 8 hours, and the sintering temperature is 1250 ℃;
4. and (4) adopting a four-probe test method to carry out electric transport performance test.
Example 2
Improve La1-xCaxSryMnO3A method for providing electrical transport properties to a polycrystalline ceramic, comprising the steps of:
1、La0.85Ca0.15Sr0.03MnO3synthesizing matrix powder:
1.1 weighing 0.85mol La (NO)3)3、0.15mol Ca(NO3)2、0.03mol Sr(NO3)2、1mol Mn(NO3)2And 4mol of citric acid, sequentially pouring into deionized water, and synchronously stirring to obtain a process product I;
1.2, dripping 8mL of glycol (the volume ratio of the glycol to the process I is 4%) into the process I obtained in the step 1.1 to obtain a process II;
1.3, carrying out high-temperature evaporation treatment on the process substance II obtained in the step 1.2 to obtain a process substance III in a non-flowing gel state, wherein the flowing state of the process substance III is used as a reaction stopping criterion;
1.4, performing high-temperature drying treatment on the process substance III obtained in the step 1.3 to obtain a dry gel-state process substance IV, wherein the drying treatment temperature is 140 ℃, and the drying treatment time is 12 hours;
1.5, fully ball-milling and crushing the process object IV obtained in the step 1.4 to obtain a process object V with the particle size of 0.2 mm;
1.6 protective sintering treatment of the process product V obtained in the step 1.5 to obtain La0.85Ca0.15Sr0.03MnO3A base powder; the protective sintering treatment is vacuum sintering treatment, and the vacuum degree is less than or equal to10Pa, the sintering temperature is 550 ℃, the sintering time is 9h, and the temperature is respectively kept at the sintering temperature nodes of 200 ℃ and 400 ℃ for 0.8 h;
2. preparation of synthetic phase material:
2.1 weighing multilayer graphene (1 nm) and pouring the multilayer graphene into the La obtained in the step 1.60.85Ca0.15Sr0.03MnO3Base powder, La0.85Ca0.15Sr0.03MnO3The mass ratio of the matrix powder to the multilayer graphene is 1:0.001, the process object VI is obtained by performing ball milling and stirring on the matrix powder and the multilayer graphene, the ball milling and stirring speed is 300r/min, and the ball milling and stirring time is 8 hours;
2.2, sequentially packaging the process object VI obtained in the step 2.1 by using a film and sealing rubber, and then putting the packaged process object VI into a cold isostatic press for extrusion operation to obtain a process object VII, wherein the process object VII is powdery, the extrusion operation pressure is 160MPa, and the extrusion operation time is 3 h;
2.3, carrying out tabletting operation on the process object VII obtained in the step 2.2 to obtain a process object VIII, wherein the process object VIII is a block material, the tabletting operation pressure is 16MPa, and the tabletting operation time is 20 min;
2.4, performing synthetic sintering treatment on the process object VIII obtained in the step 2.3 to obtain a synthetic phase material, wherein the synthetic phase material is a block material, the synthetic sintering treatment is atmosphere pressurization sintering, and the atmosphere is N2The atmosphere pressure is 1.6MPa, the sintering temperature is 800 ℃, and the sintering time is 2 h;
3. preparing polycrystalline ceramics:
3.1 mashing the synthetic phase material obtained in the step 2.4, and then crushing the synthetic phase material into a powdery process substance IX by adopting ball milling crushing operation, wherein the ball milling crushing operation lasts for 15 hours, and the particle size of the process substance IX is 200 nm;
3.2 oxygen-enriched sintering is carried out on the process substance IX obtained in the step 3.1 to obtain a process substance X, the sintering oxygen pressure is 0.03MPa, the sintering time is 8h, and the sintering temperature is 1050 ℃;
3.3, carrying out tabletting operation on the process object X obtained in the step 3.2 to obtain a process object XI, wherein the process object XI is a block material, the tabletting operation pressure is 16MPa, and the tabletting operation time is 20 min;
3.4 sequentially packaging the process object XI obtained in the step 3.3 by using a film and sealing rubber, and then putting the packaged product XI into a cold isostatic press for extrusion to obtain a process object XII, wherein the extrusion pressure is 220MPa, and the extrusion time is 1.5 h;
3.5, performing oxygen-enriched sintering on the process product XII obtained in the step 3.4 to obtain polycrystalline ceramic, wherein the polycrystalline ceramic is a block material, the sintering oxygen pressure is 0.05MPa, the sintering time is 10 hours, and the sintering temperature of the oxygen-enriched sintering is 1300 ℃;
4. and (4) adopting a four-probe test method to carry out electric transport performance test.
Example 3
Improve La1-xCaxSryMnO3A method for providing electrical transport properties to a polycrystalline ceramic, comprising the steps of:
1、La0.685Ca0.315Sr0.06MnO3synthesizing matrix powder:
1.1 weighing 0.685mol La (NO)3)3、0.315mol Ca(NO3)2、0.06mol Sr(NO3)2、1mol Mn(NO3)2And 5mol of citric acid, sequentially pouring into deionized water, and synchronously stirring to obtain a process product I;
1.2, dripping 10mL of glycol (the volume ratio of the glycol to the process I is 5%) into the process I obtained in the step 1.1 to obtain a process II;
1.3, carrying out high-temperature evaporation treatment on the process substance II obtained in the step 1.2 to obtain a process substance III in a non-flowing gel state, wherein the flowing state of the process substance III is used as a reaction stopping criterion;
1.4, performing high-temperature drying treatment on the process substance III obtained in the step 1.3 to obtain a dry gel-state process substance IV, wherein the drying treatment temperature is 150 ℃, and the drying treatment time is 18 h;
1.5, fully ball-milling and crushing the process object IV obtained in the step 1.4 to obtain a process object V with the particle size of 0.3 mm;
1.6 protective sintering treatment of the process product V obtained in the step 1.5 to obtain La0.685Ca0.315Sr0.06MnO3A base powder; the protective sintering treatment is trueCarrying out air sintering treatment, wherein the vacuum degree is less than or equal to 10Pa, the sintering temperature is 550 ℃, the sintering time is 9h, and the temperature is respectively kept at the sintering temperature nodes of 200 ℃ and 400 ℃ for 0.8 h;
2. preparation of synthetic phase material:
2.1 weighing multilayer graphene (5 nm) and pouring the multilayer graphene into the La obtained in the step 1.60.685Ca0.315Sr0.06MnO3Base powder, La0.685Ca0.315Sr0.06MnO3The mass ratio of the matrix powder to the multilayer graphene is 1:0.01, the process object VI is obtained by performing ball milling and stirring on the matrix powder and the multilayer graphene, the ball milling and stirring speed is 350r/min, and the ball milling and stirring time is 9 hours;
2.2, sequentially packaging the process object VI obtained in the step 2.1 by using a film and sealing rubber, and then putting the packaged process object VI into a cold isostatic press for extrusion operation to obtain a process object VII, wherein the process object VII is powdery, the extrusion operation pressure is 180MPa, and the extrusion operation time is 3.5 h;
2.3, carrying out tabletting operation on the process object VII obtained in the step 2.2 to obtain a process object VIII, wherein the process object VIII is a block material, the tabletting operation pressure is 20MPa, and the tabletting operation time is 25 min;
2.4, performing synthetic sintering treatment on the process object VIII obtained in the step 2.3 to obtain a synthetic phase material, wherein the synthetic phase material is a block material, the synthetic sintering treatment is atmosphere pressurization sintering, and the atmosphere is N2The atmosphere pressure is 1.8MPa, the sintering temperature is 900 ℃, and the sintering time is 4 h;
3. preparing polycrystalline ceramics:
3.1 mashing the synthetic phase material obtained in the step 2.4, and then crushing the synthetic phase material into a powdery process substance IX by adopting ball milling crushing operation, wherein the ball milling crushing operation lasts for 18 hours, and the particle size of the process substance IX is 300 nm;
3.2 oxygen-enriched sintering is carried out on the process substance IX obtained in the step 3.1 to obtain a process substance X, the sintering oxygen pressure is 0.04MPa, the sintering time is 9h, and the sintering temperature is 1050 ℃;
3.3, carrying out tabletting operation on the process object X obtained in the step 3.2 to obtain a process object XI, wherein the process object XI is a block material, the tabletting operation pressure is 20MPa, and the tabletting operation time is 25 min;
3.4 sequentially packaging the process object XI obtained in the step 3.3 by using a film and sealing rubber, and then putting the packaged product XI into a cold isostatic press for extrusion to obtain a process object XII, wherein the extrusion pressure is 240MPa, and the extrusion time is 1.8 h;
3.5, performing oxygen-enriched sintering on the process product XII obtained in the step 3.4 to obtain polycrystalline ceramic, wherein the polycrystalline ceramic is a block material, the sintering oxygen pressure is 0.06MPa, the sintering time is 12 hours, and the sintering temperature of the oxygen-enriched sintering is 1400 ℃;
4. and (4) adopting a four-probe test method to carry out electric transport performance test.
Example 4
Improve La1-xCaxSryMnO3A method for providing electrical transport properties to a polycrystalline ceramic, comprising the steps of:
1、La0.2Ca0.8Sr0.15MnO3synthesizing matrix powder:
1.1 weighing 0.2mol La (NO)3)3、0.8mol Ca(NO3)2、0.15mol Sr(NO3)2、1mol Mn(NO3)2And 6mol of citric acid, sequentially pouring into deionized water, and synchronously stirring to obtain a process product I;
1.2, dripping 12mL of glycol (the volume ratio of the glycol to the process I is 6%) into the process I obtained in the step 1.1 to obtain a process II;
1.3, carrying out high-temperature evaporation treatment on the process substance II obtained in the step 1.2 to obtain a process substance III in a non-flowing gel state, wherein the flowing state of the process substance III is used as a reaction stopping criterion;
1.4, performing high-temperature drying treatment on the process substance III obtained in the step 1.3 to obtain a dry gel-state process substance IV, wherein the drying treatment temperature is 170 ℃, and the drying treatment time is 24 hours;
1.5, fully ball-milling and crushing the process object IV obtained in the step 1.4 to obtain a process object V with the particle size of 1 mm;
1.6 protective sintering treatment of the process product V obtained in the step 1.5 to obtain La0.2Ca0.8Sr0.15MnO3A base powder; the protective burnThe sintering treatment is vacuum sintering treatment, the vacuum degree is less than or equal to 10Pa, the sintering temperature is 600 ℃, the sintering time is 10 hours, and the temperature is respectively kept for 1 hour at the sintering temperature nodes of 200 ℃ and 400 ℃;
2. preparation of synthetic phase material:
2.1 weighing multilayer graphene (10 nm) and pouring the multilayer graphene into the La obtained in the step 1.60.2Ca0.8Sr0.15MnO3Base powder, La0.2Ca0.8Sr0.15MnO3The mass ratio of the matrix powder to the multilayer graphene is 1:0.1, and the process object VI is obtained by performing ball milling and stirring on the matrix powder and the multilayer graphene, wherein the ball milling and stirring speed is 400r/min, and the ball milling and stirring time is 10 hours;
2.2, sequentially packaging the process object VI obtained in the step 2.1 by using a film and sealing rubber, and then putting the packaged process object VI into a cold isostatic press for extrusion operation to obtain a process object VII, wherein the process object VII is powdery, the extrusion operation pressure is 200MPa, and the extrusion operation time is 4 h;
2.3, carrying out tabletting operation on the process object VII obtained in the step 2.2 to obtain a process object VIII, wherein the process object VIII is a block material, the tabletting operation pressure is 25MPa, and the tabletting operation time is 30 min;
2.4, performing synthetic sintering treatment on the process object VIII obtained in the step 2.3 to obtain a synthetic phase material, wherein the synthetic phase material is a block material, the synthetic sintering treatment is atmosphere pressurization sintering, and the atmosphere is N2The atmosphere pressure is 2MPa, the sintering temperature is 1000 ℃, and the sintering time is 5 h;
3. preparing polycrystalline ceramics:
3.1 mashing the synthetic phase material obtained in the step 2.4, and then crushing the synthetic phase material into a powdery process substance IX by adopting ball milling crushing operation, wherein the ball milling crushing operation lasts for 20 hours, and the particle size of the process substance IX is 500 nm;
3.2 oxygen-enriched sintering is carried out on the process substance IX obtained in the step 3.1 to obtain a process substance X, the sintering oxygen pressure is 0.05MPa, the sintering time is 10h, and the sintering temperature is 1100 ℃;
3.3, carrying out tabletting operation on the process object X obtained in the step 3.2 to obtain a process object XI, wherein the process object XI is a block material, the tabletting operation pressure is 25Mpa, and the tabletting operation time is 30 min;
3.4 sequentially packaging the process object XI obtained in the step 3.3 by using a film and sealing rubber, and then putting the packaged product XI into a cold isostatic press for extrusion to obtain a process object XII, wherein the extrusion pressure is 250MPa, and the extrusion time is 2 h;
3.5, performing oxygen-enriched sintering on the process product XII obtained in the step 3.4 to obtain polycrystalline ceramic, wherein the polycrystalline ceramic is a block material, the sintering oxygen pressure is 0.08MPa, the sintering time is 14h, and the sintering temperature of the oxygen-enriched sintering is 1450 ℃;
4. and (4) adopting a four-probe test method to carry out electric transport performance test.
Comparative example
1、La0.685Ca0.315Sr0.06MnO3Synthesizing matrix powder:
1.1 weighing 0.685mol La (NO)3)3、0.315mol Ca(NO3)2、0.06mol Sr(NO3)2、1mol Mn(NO3)2And 5mol of citric acid, sequentially pouring into ionized water, and synchronously stirring to obtain a process product I;
1.2, dripping 10mL of glycol (the volume ratio of the glycol to the process I is 5%) into the process I obtained in the step 1.1 to obtain a process II;
1.3, carrying out high-temperature evaporation treatment on the process substance II obtained in the step 1.2 to obtain a process substance III in a non-flowing gel state;
1.4, performing high-temperature drying treatment on the process substance III obtained in the step 1.3 to obtain a dry gel-state process substance IV, wherein the drying treatment temperature is 150 ℃, and the drying treatment time is 18 h;
1.5, fully ball-milling and crushing the process object IV obtained in the step 1.4 to obtain a process object V with the particle size of 0.1 mm;
1.6 protective sintering treatment of the process product V obtained in the step 1.5 to obtain La0.685Ca0.315Sr0.06MnO3A base powder; the protective sintering treatment is vacuum sintering treatment, the vacuum degree is less than or equal to 10Pa, the sintering temperature is 550 ℃, the sintering time is 9 hours, and the temperature is respectively kept at the sintering temperature nodes of 200 ℃ and 400 ℃ for 0.8 hour;
2. preparing polycrystalline ceramics:
2.1 vs. La obtained in step 1.60.685Ca0.315Sr0.06MnO3Carrying out oxygen-enriched sintering to obtain a process object VI, wherein the sintering oxygen pressure is 0.04MPa, the sintering time is 9h, and the sintering temperature is 1050 ℃;
2.2, carrying out tabletting operation on the process object VI obtained in the step 2.1 to obtain a process object VII, wherein the process object VII is a block material, the tabletting operation pressure is 20MPa, and the tabletting operation time is 25 min;
2.3, sequentially packaging the process object VII obtained in the step 2.2 by using a film and sealing rubber, and then putting the packaged process object VII into a cold isostatic press for extrusion operation to obtain a process object VIII, wherein the extrusion operation pressure is 240MPa, and the extrusion operation time is 1.8 h;
2.4, performing oxygen-enriched sintering on the process object VIII obtained in the step 2.3 to obtain polycrystalline ceramic, wherein the polycrystalline ceramic is a block material, the sintering oxygen pressure is 0.06MPa, the sintering time is 12h, and the sintering temperature is 1400 ℃;
3. and (4) adopting a four-probe test method to carry out electric transport performance test.
FIGS. 1-4 are rho-T curves for polycrystalline ceramic blocks made according to examples 1-4, and FIG. 5 is a rho-T curve for polycrystalline ceramic blocks made according to a comparative example. It can be seen from the graph that the resistivity of the polycrystalline ceramic bulk material is significantly reduced and the metal-insulator transition temperature (T) is significantly reduced as the amount of doped graphene is increasedp) Remains unchanged, i.e. the phase of the polycrystalline ceramic is not changed. When the amount of doped graphene is increased to a certain limit, the resistivity of the sample is rather increased. The reason for this is probably that a new conductive channel is formed between the crystal boundaries by the graphene, so that the resistivity of the sample is reduced, and when the doping amount of the graphene reaches a certain limit, the graphene is agglomerated and flocculent and cannot be uniformly mixed with the matrix powder, so that the crystal boundary obstruction is increased, and the resistivity is increased.
FIGS. 6 to 9 are TCR curves of the polycrystalline ceramic blocks produced in examples 1 to 4, and FIG. 10 is a TCR curve of the polycrystalline ceramic block produced in a comparative example. It can be seen from the figure that T is increased along with the increase of the doping amount of the graphenek(TCR Curve Peak temperature) and TCR value increase to some extent (T, FIG. 8 as an example)kIs 300.96K leftRight, TCR 31.57% K-1Left and right) then begins to decrease. When La1- xCaxSryMnO3The TCR of the sample is the largest when the matrix powder to graphene mass ratio is 1:0.01, which indicates that the moderate addition of graphene contributes to the improvement of the TCR of the sample, which can be attributed to the improvement of the connectivity between the sample particles by the graphene, but increases the morphological defects inside the sample as the amount of graphene continues to increase, having a negative effect on the TCR value.

Claims (8)

1. Improve La1-xCaxSryMnO3The method for realizing the electric transport performance of the polycrystalline ceramic is characterized by comprising the following steps:
(1)La1-xCaxSryMnO3synthesizing matrix powder:
①La1-xCaxSryMnO3wherein x is 0.05-0.8, y is 0.01-0.15, and La (NO) is weighed according to the calculation of x and y3)3、Ca(NO3)2、Sr(NO3)2、Mn(NO3)2Sequentially pouring citric acid and deionized water, and synchronously stirring to obtain a process product I;
dropping ethylene glycol into the process product I to obtain a process product II;
thirdly, carrying out high-temperature evaporation treatment on the process substance II to obtain a process substance III in a non-flowing gel state;
fourthly, drying the process substance III at a high temperature to obtain a dry gel-state process substance IV, wherein the drying temperature is 120-170 ℃, and the drying time is 6-24 hours;
fully ball-milling and crushing the process material IV to obtain a process material V with the particle size of 0.1-1 mm;
sixthly, the process material V is subjected to protective sintering treatment to obtain La1-xCaxSryMnO3A base powder;
(2) preparation of synthetic phase material:
①La1-xCaxSryMnO3the mass ratio of the matrix powder to the multilayer graphene is 10.0001-1: 0.1, weighing multilayer graphene, and pouring the multilayer graphene into La1-xCaxSryMnO3The process VI is obtained by performing ball milling and stirring on the base powder, wherein the ball milling and stirring speed is 200-400 r/min, and the ball milling and stirring time is 5-10 h;
sequentially packaging the process object VI by using a film and sealing rubber, and then putting the packaged process object VI into a cold isostatic press for extrusion operation to obtain a process object VII, wherein the extrusion operation pressure is 150-200 MPa, and the extrusion operation time is 2-4 h;
tabletting the process object VII to obtain a process object VIII, wherein the pressure of tabletting operation is 15-25 MPa, and the duration of tabletting operation is 15-30 min;
fourthly, synthetic sintering treatment is carried out on the process substance VIII to obtain a synthetic phase material;
(3) preparing polycrystalline ceramics:
firstly, smashing a synthetic phase material, and then crushing the synthetic phase material into a powdery process substance IX by adopting ball milling crushing operation, wherein the ball milling crushing operation lasts for 10-20 hours, and the particle size of the process substance IX is 100-500 nm;
secondly, oxygen-enriched sintering is carried out on the process IX to obtain a process X, the sintering oxygen pressure is 0.02-0.05 MPa, and the sintering time is 6-10 h;
tabletting the process X to obtain a process XI, wherein the pressure of the tabletting operation is 15-25 MPa, and the duration of the tabletting operation is 15-30 min;
sequentially packaging the process object XI by using a film and sealing rubber, and then putting the packaged process object XI into a cold isostatic press for extrusion operation to obtain a process object XII, wherein the extrusion operation pressure is 200-250 MPa, and the extrusion operation time is 1-2 h;
fifthly, oxygen-enriched sintering is carried out on the process object XII to obtain polycrystalline ceramic, the sintering oxygen pressure is 0.04-0.08 MPa, and the sintering time is 8-14 hours.
2. The method of claim 1, wherein: in the step (1) (-) citric acid and Mn (NO)3)2The molar ratio of (A) to (B) is 3-6: 1.
3. The method of claim 1, wherein: in the step (1) and the step (II), the volume ratio of the ethylene glycol to the process I is 3-6%.
4. The method of claim 1, wherein: in the step (1), the protective sintering treatment is vacuum sintering treatment, the vacuum degree is less than or equal to 10Pa, the sintering temperature is 500-600 ℃, the sintering time is 8-10 h, and the temperature is respectively kept at the sintering temperature nodes of 200 ℃ and 400 ℃ for 0.5-1 h.
5. The method of claim 1, wherein: in the step (2), the thickness of the multilayer graphene is less than or equal to 10 nm.
6. The method of claim 1, wherein: the synthetic sintering treatment in the step (2) is atmosphere pressurization sintering, and the atmosphere is N2The atmosphere pressure is 1.5-2 MPa, the sintering temperature is 600-1000 ℃, and the sintering time is 0.5-5 h.
7. The method of claim 1, wherein: in the step (3) and the step (2), the sintering temperature of the oxygen-enriched sintering is 1000-1100 ℃.
8. The method of claim 1, wherein: and (4) in the step (3), the sintering temperature of the oxygen-enriched sintering is 1250-1450 ℃.
CN201810498672.8A 2018-05-23 2018-05-23 Method for improving electric transport performance of polycrystalline ceramic Active CN108727026B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810498672.8A CN108727026B (en) 2018-05-23 2018-05-23 Method for improving electric transport performance of polycrystalline ceramic

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810498672.8A CN108727026B (en) 2018-05-23 2018-05-23 Method for improving electric transport performance of polycrystalline ceramic

Publications (2)

Publication Number Publication Date
CN108727026A CN108727026A (en) 2018-11-02
CN108727026B true CN108727026B (en) 2021-05-14

Family

ID=63935056

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810498672.8A Active CN108727026B (en) 2018-05-23 2018-05-23 Method for improving electric transport performance of polycrystalline ceramic

Country Status (1)

Country Link
CN (1) CN108727026B (en)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101550003A (en) * 2009-04-22 2009-10-07 湖南大学 Nano-graphite alkenyl composite wave-absorbing material and method of preparing the same
CN102096262A (en) * 2009-12-09 2011-06-15 中国科学院物理研究所 Photoelectric device including lithium titanate membrane electrode and application thereof
CN102891316A (en) * 2012-10-11 2013-01-23 中国科学院过程工程研究所 Lithium iron vanadium manganese phosphate nano oxide compound anode material and preparation method thereof
CN106672945A (en) * 2016-12-23 2017-05-17 武汉理工大学 Method for preparing metal self-doped graphene by performing partial chlorination on two-dimensional metal carbide crystal
CN107119214A (en) * 2017-04-19 2017-09-01 安徽固齐线路器材有限公司 A kind of power cable Al-alloy material
CN107285769A (en) * 2017-05-03 2017-10-24 昆明理工大学 A kind of preparation method of high TCR polycrystalline ceramics
CN106365661B (en) * 2016-09-12 2019-02-26 中国科学院兰州化学物理研究所 A kind of multilayered structure alumina composite ceramic and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101701237B1 (en) * 2013-05-21 2017-02-03 한양대학교 산학협력단 Lare-size Single-crystal Monolayer Graphene and Manufacturing Method Thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101550003A (en) * 2009-04-22 2009-10-07 湖南大学 Nano-graphite alkenyl composite wave-absorbing material and method of preparing the same
CN102096262A (en) * 2009-12-09 2011-06-15 中国科学院物理研究所 Photoelectric device including lithium titanate membrane electrode and application thereof
CN102891316A (en) * 2012-10-11 2013-01-23 中国科学院过程工程研究所 Lithium iron vanadium manganese phosphate nano oxide compound anode material and preparation method thereof
CN106365661B (en) * 2016-09-12 2019-02-26 中国科学院兰州化学物理研究所 A kind of multilayered structure alumina composite ceramic and preparation method thereof
CN106672945A (en) * 2016-12-23 2017-05-17 武汉理工大学 Method for preparing metal self-doped graphene by performing partial chlorination on two-dimensional metal carbide crystal
CN107119214A (en) * 2017-04-19 2017-09-01 安徽固齐线路器材有限公司 A kind of power cable Al-alloy material
CN107285769A (en) * 2017-05-03 2017-10-24 昆明理工大学 A kind of preparation method of high TCR polycrystalline ceramics

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Ag 掺杂对La2/3A1/3MnO3(A=Ca、Sr、Ba)多晶陶瓷材料电学性能的影响";刘翔等;《无机材料学报》;20131231;第28卷(第12期);第1308页左栏第3段至右栏第1段 *

Also Published As

Publication number Publication date
CN108727026A (en) 2018-11-02

Similar Documents

Publication Publication Date Title
JPH0530905B2 (en)
TWI429771B (en) Zno vapor deposition material and zno film thereof
CN101851745B (en) Indium zinc gallium oxide (IZGO) sputtering target for transparent conductive film and manufacturing method
JP5376117B2 (en) ZnO sputtering target and manufacturing method thereof
Muchuweni et al. Physical properties of gallium and aluminium co-doped zinc oxide thin films deposited at different radio frequency magnetron sputtering power
WO2014097963A1 (en) Zinc oxide-based transparent conductive film
JP2009537426A5 (en)
CN103787653A (en) Preparation method of carbon-modified CaCu3Ti4O12 high dielectric material
CN114560700B (en) Non-doped conductive zinc telluride target and preparation method thereof
CN107759215A (en) The method for preparing huge dielectric constant low-loss ceramic capacitor
Yuan et al. Preparation of BaTiO3-based X7R ceramics with high dielectric constant by nanometer oxides doping method
CN108727026B (en) Method for improving electric transport performance of polycrystalline ceramic
Zhang et al. Study of high-density AZO ceramic target
JP5732978B2 (en) Barium silicide polycrystal, method for producing the same, and barium silicide sputtering target
JP5082927B2 (en) Method for producing ZnO vapor deposition material
CN107935585A (en) A kind of preparation method of pressure sensitive for ceramic electrical resistance body
KR100960222B1 (en) Zinc oxide based sputtering target, method for mamufacturing the same and zinc oxide based thin film manufactured by using the same
Sedghi et al. Comparison of electrical properties of zinc oxide varistors manufactured from micro and nano ZnO powder
CN107285769B (en) Preparation method of high TCR polycrystalline ceramic
CN107459347B (en) Lead-free ceramic material with high energy storage density and high energy storage efficiency and preparation method thereof
CN103693954A (en) High conductivity zinc oxide ceramic and preparation method thereof
CN112216783B (en) Preparation method of Ga-Ti doped ZnO block thermoelectric material
CN102560391A (en) Conducting film, and preparation method and application thereof
CN102650035B (en) Method for producing silicon doping zinc oxide film, produced film and application thereof
CN112725752A (en) Magnesium-doped zinc oxide magnetron sputtering target material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant