CN102351571A - Preparation method of nanosilver-doped yttrium barium copper oxide film - Google Patents
Preparation method of nanosilver-doped yttrium barium copper oxide film Download PDFInfo
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Abstract
The invention discloses a preparation method of a nanosilver-doped yttrium barium copper oxide film, which comprises the following steps: 1. preparing a nanosilver sol by electrochemical reaction, adding the nanosilver sol into a yttrium barium copper oxide precursor liquid to prepare a precursor sol; 2. evenly applying the precursor sol on a CeO2/YSZ/Y2O3/NiW substrate to obtain a wet film; 3. carrying out low-temperature pyrolysis to obtain a precursor film; 4. crystallizing to obtain the nanosilver-doped yttrium barium copper oxide film. The electrochemical reaction for preparing nanosilver particles does not need dispersant, reducer or other complex compounds, and can easily obtain the high-purity impurity-free nanosilver sol; the nanosilver particles in the prepared precursor sol are distributed uniformly, do not aggregate, and have high stability, and the dimension of the nanosilver particles is smaller than 20 nm; the nanosilver-doped yttrium barium copper oxide film obtained by applying the precursor sol has the advantages of low phase formation temperature and uniform nucleation, and has a superconductive layer which is 400-600nm thick and has excellent superconductivity.
Description
Technical field
The invention belongs to the thin-film material technical field, be specifically related to a kind of preparation method of nanometer silver doping yttrium barium copper oxide film.
Background technology
Coating conductor becomes one of focus of present practical high temperature superconducting materia research with high-field performance superior under its 77K.People's successful development chemical solution deposition technique prepare the YBCO superconducting film, wherein be the emphasis of research for the forming core in the crystallization process and crystal grain advantage oriented growth.Adopting chemical solution deposition technique to prepare in the process of coating conductor, nanometer silver joins in the superconducting film, helps reducing the one-tenth phase temperature of superconducting layer, promotes its homogeneous nucleation growth.
Prepare in the process in REBCO (RE represents REE) bulk, mix through silver and reduce the fusing point of REBCO base substrate, impel cold seed crystal to induce the growth of bulk, it is not high for the purity and the dimensional requirement of silver particles.And prepare in the process at coating conductor, require silver particles at nano-scale and have good homogeneity and dispersiveness.Adulterated nano silver particles all adopts mechanical ball milling technology or chemical reduction method preparation in the coating conductor at present, adopts silver particles out-of-shape, the particle diameter of mechanical ball milling prepared big, causes forerunner's colloidal sol of silver-doped unstable; And the nano silver particles that adopts chemical reduction method to prepare is introduced impurity easily in colloid, makes the superconducting layer performance of preparation reduce.
Summary of the invention
Technical problem to be solved by this invention is the deficiency to above-mentioned prior art, and a kind of preparation method of nanometer silver doping yttrium barium copper oxide film is provided.Adopt the nanometer silver doping yttrium barium copper oxide film of this method preparation to become the phase temperature low, forming core is even, has excellent superconductivity.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is: a kind of preparation method of nanometer silver doping yttrium barium copper oxide film is characterized in that this method may further comprise the steps:
The preparation of step (1) forerunner's colloidal sol:
Step 101, Silver Nitrate being dissolved in the mixed solvent of second alcohol and water, being mixed with the solution that silver nitrate concentration is 0.01mol/L～0.5mol/L, is reaction solution with the solution of being prepared; With the argon gas stream is negative electrode; Silver foil is an anode, and energized is carried out electrochemical reaction, obtains nano silver colloidal sol; The volume ratio of second alcohol and water is 1: 1～10 in the said mixed solvent;
Step 102, with trifluoroacetic acid yttrium, trifluoroacetic acid barium and cupric benzoate by yttrium: barium: the atomic ratio of copper=1: 2: 3 is dissolved in the ethanol, obtains the yttrium barium copper oxide precursor liquid; The total concn of yttrium, barium and copper metal ion is 0.5mol/L～2.5mol/L in the said yttrium barium copper oxide precursor liquid;
Step 103, the underpressure distillation under 50 ℃ of conditions of nano silver colloidal sol described in the step 101 is concentrated; Adopt ethanol to disperse the nano silver colloidal sol after concentrating; In yttrium barium copper oxide precursor liquid described in the nano silver colloidal sol adding step 102 after disperseing, mix and obtain forerunner's colloidal sol; The quality percentage composition of Nano silver grain is 0.5%～5% in said forerunner's colloidal sol;
Step (2) applies: adopt dip coating that the colloidal sol of forerunner described in the step 103 evenly is coated on CeO
2/ YSZ/Y
2O
3On/NiW the substrate, obtaining thickness is the wet film of 10 μ m～50 μ m, and wherein, said YSZ is the stable zirconium white of yttrium;
Step (3) pyrolysis: wet film described in the step (2) is carried out low temperature pyrogenation in tube furnace, obtain precursor film;
Step (4) crystallization: precursor film described in the step (3) is carried out crystallization handle, obtain nanometer silver doping yttrium barium copper oxide film.
Above-mentioned a kind of nanometer silver doping yttrium barium copper oxide membrane preparation method, described in the step 101 in the mixed solvent volume ratio of second alcohol and water be 1: 2～5.
Above-mentioned a kind of nanometer silver doping yttrium barium copper oxide membrane preparation method; In the electrochemical reaction process, adopt the stainless steel needle tubing in reaction solution, to feed argon gas stream described in the step 101, the stainless steel needle tubing is placed on the above 2mm～5mm in reaction solution surface; The gas flow of control argon gas stream is 200mL/min～1000mL/min; Electrochemical reaction voltage is 0.5KV～2KV, and electric current is 1mA～20mA, and the reaction times is 10min～60min.
Above-mentioned a kind of nanometer silver doping yttrium barium copper oxide membrane preparation method, the preferred 500mL/min of the gas flow of said argon gas stream, the preferred 1KV of electrochemical reaction voltage, the preferred 10mA of electric current.
Above-mentioned a kind of nanometer silver doping yttrium barium copper oxide membrane preparation method, the preferred 1.5mol/L of total concn of yttrium, barium and copper metal ion in the precursor liquid of yttrium barium copper oxide described in the step 102.
Above-mentioned a kind of nanometer silver doping yttrium barium copper oxide membrane preparation method, the quality percentage composition of Nano silver grain is preferred 1%～3% in the colloidal sol of forerunner described in the step 103, and the Nano silver grain in said forerunner's colloidal sol is sphere or cylindricality.
Above-mentioned a kind of nanometer silver doping yttrium barium copper oxide membrane preparation method; The process of low temperature pyrogenation is described in the step (3): the speed of tube furnace with 2 ℃/min～10 ℃/min is heated up;, temperature in the stove in stove, introduces the steam dividing potential drop when being higher than 200 ℃ and is 2%～2.5% wet oxygen; Continue to heat up, reaction finishes when temperature in the stove rises to 400 ℃, stops the furnace cooling of ventilating.
Above-mentioned a kind of nanometer silver doping yttrium barium copper oxide membrane preparation method, the preferred 5 ℃/min of said temperature rise rate, the steam dividing potential drop preferred 2.3% of said wet oxygen.
Above-mentioned a kind of nanometer silver doping yttrium barium copper oxide membrane preparation method; The process that crystallization described in the step (4) is handled is: the speed with 15 ℃/min～35 ℃/min is warming up to 710 ℃～740 ℃; And under wet argon oxygen gas mixture atmosphere constant temperature 2h, furnace cooling under exsiccant argon oxygen gas mixture atmosphere is replaced by oxygen atmosphere with atmosphere when temperature is reduced to 525 ℃ then; Constant temperature 3h when temperature is reduced to 450 ℃, furnace cooling under oxygen atmosphere at last; The steam dividing potential drop of said wet argon oxygen gas mixture atmosphere is 2.5%～3.5%, and oxygen quality content is 100ppm in the wet argon oxygen gas mixture atmosphere, and surplus is an argon gas; Oxygen quality content is 100ppm in the said exsiccant argon oxygen gas mixture atmosphere, and surplus is an argon gas.
Above-mentioned a kind of nanometer silver doping yttrium barium copper oxide membrane preparation method, the preferred 25 ℃/min of said temperature rise rate, the steam dividing potential drop preferred 3.1% of said wet argon oxygen gas mixture atmosphere.
The present invention compared with prior art has the following advantages:
1, the present invention adopts electrochemical reaction to prepare nano silver colloidal sol, adopts the negative electrode of hollow, introduces electronics through air-flow; Substitute solid state cathode with plasma (orifice) gas; Make and realize current lead-through that electrode is contactless, thereby prepare Nano silver grain at negative electrode; This method does not need complex compounds such as dispersion agent, reductive agent, obtains high-purity pure nano silver colloidal sol easily.
2, nano silver particles is evenly distributed in forerunner's colloidal sol of the present invention, does not reunite, and size has high stability less than 20nm, and the nanometer silver doping yttrium barium copper oxide film that adopts this forerunner's colloidal sol to apply the back preparation becomes the phase temperature low, and forming core is even.
3, the adulterated yttrium barium copper oxide film of nanometer silver of the present invention's preparation has the superconducting layer that thickness is 400nm～600nm, and the superconductivity of superconducting layer is excellent, and Jc reaches 1MA/cm
2～2MA/cm
2
Through accompanying drawing and embodiment, technical scheme of the present invention is done further detailed description below.
Description of drawings
Fig. 1 is transmission electron microscope (TEM) figure of nano silver particles in forerunner's colloidal sol of the embodiment of the invention 1 preparation.
Fig. 2 is the x diffraction θ-2 θ scintigram of the nanometer silver doping yttrium barium copper oxide film of the embodiment of the invention 1 preparation.
Fig. 3 is ESEM (SEM) figure of surface topography of the nanometer silver doping yttrium barium copper oxide film of the embodiment of the invention 1 preparation.
Embodiment
Embodiment 1
The preparation of step (1) forerunner's colloidal sol:
Step 101, Silver Nitrate being dissolved in the mixed solvent of second alcohol and water, being mixed with the solution that silver nitrate concentration is 0.15mol/L, is reaction solution with the solution of being prepared; Adopt the stainless steel needle tubing in reaction solution, to feed argon gas stream as negative electrode, the stainless steel needle tubing is placed on the above 3mm in reaction solution surface, the pilot-gas flow is 500mL/min; With the silver foil is anode; Energized is carried out electrochemical reaction, and control electrochemical reaction voltage is 1KV, and electric current is 10mA; Reaction times is 60min, obtains nano silver colloidal sol; The volume ratio of second alcohol and water is 1: 2 in the said mixed solvent;
Step 102, with trifluoroacetic acid yttrium, trifluoroacetic acid barium and cupric benzoate by yttrium: barium: the atomic ratio of copper=1: 2: 3 is dissolved in the ethanol, obtains the yttrium barium copper oxide precursor liquid; The total concn of yttrium, barium and copper metal ion is 1.5mol/L in the said yttrium barium copper oxide precursor liquid;
Step 103, the underpressure distillation under 50 ℃ of conditions of nano silver colloidal sol described in the step 101 is concentrated; Adopt ethanol to disperse the nano silver colloidal sol after concentrating; Nano silver colloidal sol after disperseing is added described in 102 in the yttrium barium copper oxide precursor liquid, and mixing and obtaining nano grain of silver protonatomic mass percentage composition is forerunner's colloidal sol of 5%; Nano silver grain in said forerunner's colloidal sol is spherical;
Step (2) applies: adopt dip coating that the colloidal sol of forerunner described in the step 103 evenly is coated on CeO
2/ YSZ/Y
2O
3On/NiW the substrate, obtain the wet film that thickness is 20 μ m, wherein, said YSZ is the stable zirconium white of yttrium;
Step (3) pyrolysis: wet film described in the step (2) is carried out low temperature pyrogenation in tube furnace, obtain precursor film; The process of said low temperature pyrogenation is: the speed of tube furnace with 5 ℃/min is heated up;, temperature in the stove in stove, introduces the steam dividing potential drop when being higher than 200 ℃ and is 2.3% wet oxygen; Continue to heat up, reaction finishes when temperature in the stove rises to 400 ℃, stops the furnace cooling of ventilating;
Step (4) crystallization: precursor film described in the step (3) is carried out crystallization handle, obtain nanometer silver doping yttrium barium copper oxide film; The process that said crystallization is handled is: the speed with 25 ℃/min is warming up to 740 ℃; And be 3.1% in the steam dividing potential drop; Oxygen quality content is constant temperature 2h under the wet argon oxygen gas mixture atmosphere of 100ppm, is furnace cooling under the exsiccant argon oxygen gas mixture atmosphere of 100ppm at oxygen quality content then, when temperature is reduced to 525 ℃, atmosphere is replaced by oxygen atmosphere; Constant temperature 3h when temperature is reduced to 450 ℃, furnace cooling under oxygen atmosphere at last.
Fig. 1 is transmission electron microscope (TEM) figure of nano silver particles in forerunner's colloidal sol of present embodiment preparation; Wherein Nano silver grain is of a size of 10nm; Nano silver grain is well-dispersed in the precursor liquid, in the heat treatment process in later stage, can effectively reduce the one-tenth phase temperature of superconducting layer.Fig. 2 is the x diffraction θ-2 θ scintigram of the nanometer silver doping yttrium barium copper oxide film of present embodiment preparation; As can be seen from the figure the nanometer silver doping yttrium barium copper oxide film of preparation has YBCO (001) peak; And there is not the dephasign peak basically; Show sharp keen cubic texture, explain that adulterated nanometer silver has promoted the homogeneous nucleation and the growth of superconducting layer.Fig. 3 is ESEM (SEM) figure of surface topography of the nanometer silver doping yttrium barium copper oxide film of present embodiment preparation, as can be seen from the figure the nanometer silver doping yttrium barium copper oxide film surface compact of preparation.
Nano silver particles is evenly distributed in forerunner's colloidal sol of present embodiment, does not reunite, and has high stability; The nanometer silver doping yttrium barium copper oxide film of preparation becomes the phase temperature low, and forming core is even, the thickness 400nm of superconducting layer in the nanometer silver doping yttrium barium copper oxide film; Superconductivity is excellent, and Jc reaches 2MA/cm
2
The preparation of step (1) forerunner's colloidal sol:
Step 101, Silver Nitrate being dissolved in the mixed solvent of second alcohol and water, being mixed with the solution that silver nitrate concentration is 0.2mol/L, is reaction solution with the solution of being prepared; Adopt the stainless steel needle tubing in reaction solution, to feed argon gas stream as negative electrode, the stainless steel needle tubing is placed on the above 5mm in reaction solution surface, the pilot-gas flow is 1000mL/min; With the silver foil is anode; Energized is carried out electrochemical reaction, and control electrochemical reaction voltage is 2KV, and electric current is 20mA; Reaction times is 10min, obtains nano silver colloidal sol; The volume ratio of second alcohol and water is 1: 10 in the said mixed solvent;
Step 102, with trifluoroacetic acid yttrium, trifluoroacetic acid barium and cupric benzoate by yttrium: barium: the atomic ratio of copper=1: 2: 3 is dissolved in the ethanol, obtains the yttrium barium copper oxide precursor liquid; The total concn of yttrium, barium and copper metal ion is 0.5mol/L in the said yttrium barium copper oxide precursor liquid;
Step 103, the underpressure distillation under 50 ℃ of conditions of nano silver colloidal sol described in the step 101 is concentrated; Adopt ethanol to disperse the nano silver colloidal sol after concentrating; Nano silver colloidal sol after disperseing is added described in the step 102 in the yttrium barium copper oxide precursor liquid, and mixing and obtaining nano grain of silver protonatomic mass percentage composition is forerunner's colloidal sol of 1%; Nano silver grain in said forerunner's colloidal sol is a cylindricality;
Step (2) applies: adopt dip coating that the colloidal sol of forerunner described in the step 103 evenly is coated on CeO
2/ YSZ/Y
2O
3On/NiW the substrate, obtain the wet film that thickness is 50 μ m, wherein, said YSZ is the stable zirconium white of yttrium;
Step (3) pyrolysis: wet film described in the step (2) is carried out low temperature pyrogenation in tube furnace, obtain precursor film; The process of said low temperature pyrogenation is: the speed of tube furnace with 10 ℃/min is heated up;, temperature in the stove in stove, introduces the steam dividing potential drop when being higher than 200 ℃ and is 2.5% wet oxygen; Continue to heat up, reaction finishes when temperature in the stove rises to 400 ℃, stops the furnace cooling of ventilating;
Step (4) crystallization: precursor film described in the step (3) is carried out crystallization handle, obtain nanometer silver doping yttrium barium copper oxide film; The process that said crystallization is handled is: the speed with 35 ℃/min is warming up to 730 ℃; And be 3.5% in the steam dividing potential drop; Oxygen quality content is constant temperature 2h under the wet argon oxygen gas mixture atmosphere of 100ppm, is furnace cooling under the exsiccant argon oxygen gas mixture atmosphere of 100ppm at oxygen quality content then, when temperature is reduced to 525 ℃, atmosphere is replaced by oxygen atmosphere; Constant temperature 3h when temperature is reduced to 450 ℃, furnace cooling under oxygen atmosphere at last.
Nano silver particles is evenly distributed in forerunner's colloidal sol of present embodiment, does not reunite, and has high stability; Size is less than 20nm; The nanometer silver doping yttrium barium copper oxide film of preparation becomes the phase temperature low, and forming core is even, the thickness 500nm of superconducting layer in the nanometer silver doping yttrium barium copper oxide film; Superconductivity is excellent, and Jc reaches 1.5MA/cm
2
The preparation of step (1) forerunner's colloidal sol:
Step 101, Silver Nitrate being dissolved in the mixed solvent of second alcohol and water, being mixed with the solution that silver nitrate concentration is 0.5mol/L, is reaction solution with the solution of being prepared; Adopt the stainless steel needle tubing in reaction solution, to feed argon gas stream as negative electrode, the stainless steel needle tubing is placed on the above 2mm in reaction solution surface, the pilot-gas flow is 200mL/min; With the silver foil is anode; Energized is carried out electrochemical reaction, and control electrochemical reaction voltage is 0.5KV, and electric current is 1mA; Reaction times is 30min, obtains nano silver colloidal sol; The volume ratio of second alcohol and water is 1: 1 in the said mixed solvent;
Step 102, with trifluoroacetic acid yttrium, trifluoroacetic acid barium and cupric benzoate by yttrium: barium: the atomic ratio of copper=1: 2: 3 is dissolved in the ethanol, obtains the yttrium barium copper oxide precursor liquid; The total concn of yttrium, barium and copper metal ion is 2.5mol/L in the said yttrium barium copper oxide precursor liquid;
Step 103, the underpressure distillation under 50 ℃ of conditions of nano silver colloidal sol described in the step 101 is concentrated; Adopt ethanol to disperse the nano silver colloidal sol after concentrating; Nano silver colloidal sol after disperseing is added described in the step 102 in the yttrium barium copper oxide precursor liquid, and mixing and obtaining nano grain of silver protonatomic mass percentage composition is forerunner's colloidal sol of 0.5%; Nano silver grain in said forerunner's colloidal sol is spherical;
Step (2) applies: adopt dip coating that the colloidal sol of forerunner described in the step 103 evenly is coated on CeO
2/ YSZ/Y
2O
3On/NiW the substrate, obtain the wet film that thickness is 10 μ m, wherein, said YSZ is the stable zirconium white of yttrium;
Step (3) pyrolysis: wet film described in the step (2) is carried out low temperature pyrogenation in tube furnace, obtain precursor film; The process of said low temperature pyrogenation is: the speed of tube furnace with 2 ℃/min is heated up;, temperature in the stove in stove, introduces the steam dividing potential drop when being higher than 200 ℃ and is 2% wet oxygen; Continue to heat up, reaction finishes when temperature in the stove rises to 400 ℃, stops the furnace cooling of ventilating;
Step (4) crystallization: precursor film described in the step (3) is carried out crystallization handle, obtain nanometer silver doping yttrium barium copper oxide film; The process that said crystallization is handled is: the speed with 15 ℃/min is warming up to 710 ℃; And be 2.5% in the steam dividing potential drop; Oxygen quality content is constant temperature 2h under the wet argon oxygen gas mixture atmosphere of 100ppm, is furnace cooling under the exsiccant argon oxygen gas mixture atmosphere of 100ppm at oxygen quality content then, when temperature is reduced to 525 ℃, atmosphere is replaced by oxygen atmosphere; Constant temperature 3h when temperature is reduced to 450 ℃, furnace cooling under oxygen atmosphere at last.
Nano silver particles is evenly distributed in forerunner's colloidal sol of present embodiment, does not reunite, and has high stability; Size is less than 20nm; The nanometer silver doping yttrium barium copper oxide film of preparation becomes the phase temperature low, and forming core is even, the thickness 600nm of superconducting layer in the nanometer silver doping yttrium barium copper oxide film; Superconductivity is excellent, and Jc reaches 1MA/cm
2
Embodiment 4
The preparation of step (1) forerunner's colloidal sol:
Step 101, Silver Nitrate being dissolved in the mixed solvent of second alcohol and water, being mixed with the solution that silver nitrate concentration is 0.01mol/L, is reaction solution with the solution of being prepared; Adopt the stainless steel needle tubing in reaction solution, to feed argon gas stream as negative electrode, the stainless steel needle tubing is placed on the above 4mm in reaction solution surface, the pilot-gas flow is 600mL/min; With the silver foil is anode; Energized is carried out electrochemical reaction, and control electrochemical reaction voltage is 1KV, and electric current is 5mA; Reaction times is 20min, obtains nano silver colloidal sol; The volume ratio of second alcohol and water is 1: 5 in the said mixed solvent;
Step 102, with trifluoroacetic acid yttrium, trifluoroacetic acid barium and cupric benzoate by yttrium: barium: the atomic ratio of copper=1: 2: 3 is dissolved in the ethanol, obtains the yttrium barium copper oxide precursor liquid; The total concn of yttrium, barium and copper metal ion is 2mol/L in the said yttrium barium copper oxide precursor liquid;
Step 103, the underpressure distillation under 50 ℃ of conditions of nano silver colloidal sol described in the step 101 is concentrated; Adopt ethanol to disperse the nano silver colloidal sol after concentrating; Nano silver colloidal sol after disperseing is added described in the step 102 in the yttrium barium copper oxide precursor liquid, and mixing and obtaining nano grain of silver protonatomic mass percentage composition is forerunner's colloidal sol of 3%; Nano silver grain in said forerunner's colloidal sol is a cylindricality;
Step (2) applies: adopt dip coating that the colloidal sol of forerunner described in the step 103 evenly is coated on CeO
2/ YSZ/Y
2O
3On/NiW the substrate, obtain the wet film that thickness is 30 μ m, wherein, said YSZ is the stable zirconium white of yttrium;
Step (3) pyrolysis: wet film described in the step (2) is carried out low temperature pyrogenation in tube furnace, obtain precursor film; The process of said low temperature pyrogenation is: the speed of tube furnace with 6 ℃/min is heated up;, temperature in the stove in stove, introduces the steam dividing potential drop when being higher than 200 ℃ and is 2.2% wet oxygen; Continue to heat up, reaction finishes when temperature in the stove rises to 400 ℃, stops the furnace cooling of ventilating;
Step (4) crystallization: precursor film described in the step (3) is carried out crystallization handle, obtain nanometer silver doping yttrium barium copper oxide film; The process that said crystallization is handled is: the speed with 20 ℃/min is warming up to 720 ℃; And be 2.8% in the steam dividing potential drop; Oxygen quality content is constant temperature 2h under the wet argon oxygen gas mixture atmosphere of 100ppm, is furnace cooling under the exsiccant argon oxygen gas mixture atmosphere of 100ppm at oxygen quality content then, when temperature is reduced to 525 ℃, atmosphere is replaced by oxygen atmosphere; Constant temperature 3h when temperature is reduced to 450 ℃, furnace cooling under oxygen atmosphere at last.
Nano silver particles is evenly distributed in forerunner's colloidal sol of present embodiment, does not reunite, and has high stability; Size is less than 20nm; The nanometer silver doping yttrium barium copper oxide film of preparation becomes the phase temperature low, and forming core is even, the thickness 450nm of superconducting layer in the nanometer silver doping yttrium barium copper oxide film; Superconductivity is excellent, and Jc reaches 1.8MA/cm
2
Embodiment 5
The preparation of step (1) forerunner's colloidal sol:
Step 101, Silver Nitrate being dissolved in the mixed solvent of second alcohol and water, being mixed with the solution that silver nitrate concentration is 0.3mol/L, is reaction solution with the solution of being prepared; Adopt the stainless steel needle tubing in reaction solution, to feed argon gas stream as negative electrode, the stainless steel needle tubing is placed on the above 3mm in reaction solution surface, the pilot-gas flow is 400mL/min; With the silver foil is anode; Energized is carried out electrochemical reaction, and control electrochemical reaction voltage is 1.5KV, and electric current is 15mA; Reaction times is 40min, obtains nano silver colloidal sol; The volume ratio of second alcohol and water is 1: 4 in the said mixed solvent;
Step 102, with trifluoroacetic acid yttrium, trifluoroacetic acid barium and cupric benzoate by yttrium: barium: the atomic ratio of copper=1: 2: 3 is dissolved in the ethanol, obtains the yttrium barium copper oxide precursor liquid; The total concn of yttrium, barium and copper metal ion is 1mol/L in the said yttrium barium copper oxide precursor liquid;
Step 103, the underpressure distillation under 50 ℃ of conditions of nano silver colloidal sol described in the step 101 is concentrated; Adopt ethanol to disperse the nano silver colloidal sol after concentrating; Nano silver colloidal sol after disperseing is added described in the step 102 in the yttrium barium copper oxide precursor liquid, and mixing and obtaining nano grain of silver protonatomic mass percentage composition is forerunner's colloidal sol of 2%; Nano silver grain in said forerunner's colloidal sol is spherical;
Step (2) applies: adopt dip coating that the colloidal sol of forerunner described in 103 evenly is coated on CeO
2/ YSZ/Y
2O
3On/NiW the substrate, obtain the wet film that thickness is 40 μ m, wherein, said YSZ is the stable zirconium white of yttrium;
Step (3) pyrolysis: wet film described in the step (2) is carried out low temperature pyrogenation in tube furnace, obtain precursor film; The process of said low temperature pyrogenation is: the speed of tube furnace with 5 ℃/min is heated up;, temperature in the stove in stove, introduces the steam dividing potential drop when being higher than 200 ℃ and is 2.4% wet oxygen; Continue to heat up, reaction finishes when temperature in the stove rises to 400 ℃, stops the furnace cooling of ventilating;
Step (4) crystallization: precursor film described in the step (3) is carried out crystallization handle, obtain nanometer silver doping yttrium barium copper oxide film; The process that said crystallization is handled is: the speed with 30 ℃/min is warming up to 740 ℃; And be 3.1% in the steam dividing potential drop; Oxygen quality content is constant temperature 2h under the wet argon oxygen gas mixture atmosphere of 100ppm, is furnace cooling under the exsiccant argon oxygen gas mixture atmosphere of 100ppm at oxygen quality content then, when temperature is reduced to 525 ℃, atmosphere is replaced by oxygen atmosphere; Constant temperature 3h when temperature is reduced to 450 ℃, furnace cooling under oxygen atmosphere at last.
Nano silver particles is evenly distributed in forerunner's colloidal sol of present embodiment, does not reunite, and has high stability; Size is less than 20nm; The nanometer silver doping yttrium barium copper oxide film of preparation becomes the phase temperature low, and forming core is even, the thickness 550nm of superconducting layer in the nanometer silver doping yttrium barium copper oxide film; Superconductivity is excellent, and Jc reaches 1.2MA/cm
2
The above; It only is preferred embodiment of the present invention; Be not that the present invention is done any restriction, every according to inventing technical spirit to any simple modification, change and equivalent structure variation that above embodiment did, all still belong in the protection domain of technical scheme of the present invention.
Claims (10)
1. the preparation method of a nanometer silver doping yttrium barium copper oxide film is characterized in that this method may further comprise the steps:
The preparation of step (1) forerunner's colloidal sol:
Step 101, Silver Nitrate being dissolved in the mixed solvent of second alcohol and water, being mixed with the solution that silver nitrate concentration is 0.01mol/L～0.5mol/L, is reaction solution with the solution of being prepared; With the argon gas stream is negative electrode; Silver foil is an anode, and energized is carried out electrochemical reaction, obtains nano silver colloidal sol; The volume ratio of second alcohol and water is 1: 1～10 in the said mixed solvent;
Step 102, with trifluoroacetic acid yttrium, trifluoroacetic acid barium and cupric benzoate by yttrium: barium: the atomic ratio of copper=1: 2: 3 is dissolved in the ethanol, obtains the yttrium barium copper oxide precursor liquid; The total concn of yttrium, barium and copper metal ion is 0.5mol/L～2.5mol/L in the said yttrium barium copper oxide precursor liquid;
Step 103, the underpressure distillation under 50 ℃ of conditions of nano silver colloidal sol described in the step 101 is concentrated; Adopt ethanol to disperse the nano silver colloidal sol after concentrating; In yttrium barium copper oxide precursor liquid described in the nano silver colloidal sol adding step 102 after disperseing, mix and obtain forerunner's colloidal sol; The quality percentage composition of Nano silver grain is 0.5%～5% in said forerunner's colloidal sol;
Step (2) applies: adopt dip coating that the colloidal sol of forerunner described in the step 103 evenly is coated on CeO
2/ YSZ/Y
2O
3On/NiW the substrate, obtaining thickness is the wet film of 10 μ m～50 μ m, and wherein, said YSZ is the stable zirconium white of yttrium;
Step (3) pyrolysis: wet film described in the step (2) is carried out low temperature pyrogenation in tube furnace, obtain precursor film;
Step (4) crystallization: precursor film described in the step (3) is carried out crystallization handle, obtain nanometer silver doping yttrium barium copper oxide film.
2. the preparation method of a kind of nanometer silver doping yttrium barium copper oxide film according to claim 1 is characterized in that, described in the step 101 in the mixed solvent volume ratio of second alcohol and water be 1: 2～5.
3. the preparation method of a kind of nanometer silver doping yttrium barium copper oxide film according to claim 1 is characterized in that, described in the step 101 in the electrochemical reaction process; Adopt the stainless steel needle tubing in reaction solution, to feed argon gas stream; The stainless steel needle tubing is placed on the above 2mm～5mm in reaction solution surface, and the gas flow of control argon gas stream is 200mL/min～1000mL/min, and electrochemical reaction voltage is 0.5KV～2KV; Electric current is 1mA～20mA, and the reaction times is 10min～60min.
4. the preparation method of a kind of nanometer silver doping yttrium barium copper oxide film according to claim 3 is characterized in that the gas flow of said argon gas stream is 500mL/min, and electrochemical reaction voltage is 1KV, and electric current is 10mA.
5. the preparation method of a kind of nanometer silver doping yttrium barium copper oxide film according to claim 1 is characterized in that the total concn of yttrium, barium and copper metal ion is 1.5mol/L in the precursor liquid of yttrium barium copper oxide described in the step 102.
6. the preparation method of a kind of nanometer silver doping yttrium barium copper oxide film according to claim 1; It is characterized in that; The quality percentage composition of Nano silver grain is 1%～3% in the colloidal sol of forerunner described in the step 103, and the Nano silver grain in said forerunner's colloidal sol is sphere or cylindricality.
7. the preparation method of a kind of nanometer silver doping yttrium barium copper oxide film according to claim 1; It is characterized in that; The process of low temperature pyrogenation is described in the step (3): the speed of tube furnace with 2 ℃/min～10 ℃/min is heated up, when temperature in the stove is higher than 200 ℃, in stove, introduce the steam dividing potential drop and be 2%～2.5% wet oxygen, continue to heat up; Reaction finishes when temperature in the stove rises to 400 ℃, stops the furnace cooling of ventilating.
8. the preparation method of a kind of nanometer silver doping yttrium barium copper oxide film according to claim 7 is characterized in that said temperature rise rate is 5 ℃/min, and the steam dividing potential drop of said wet oxygen is 2.3%.
9. a kind of nanometer silver doping yttrium barium copper oxide membrane preparation method according to claim 1; It is characterized in that the process that crystallization described in the step (4) is handled is: the speed with 15 ℃/min～35 ℃/min is warming up to 710 ℃～740 ℃, and under wet argon oxygen gas mixture atmosphere constant temperature 2h; Furnace cooling under exsiccant argon oxygen gas mixture atmosphere then; When temperature is reduced to 525 ℃, atmosphere is replaced by oxygen atmosphere, constant temperature 3h when temperature is reduced to 450 ℃, furnace cooling under oxygen atmosphere at last; The steam dividing potential drop of said wet argon oxygen gas mixture atmosphere is 2.5%～3.5%, and oxygen quality content is 100ppm in the wet argon oxygen gas mixture atmosphere, and surplus is an argon gas; Oxygen quality content is 100ppm in the said exsiccant argon oxygen gas mixture atmosphere, and surplus is an argon gas.
10. a kind of nanometer silver doping yttrium barium copper oxide membrane preparation method according to claim 9 is characterized in that said temperature rise rate is 25 ℃/min, and the steam dividing potential drop of said wet argon oxygen gas mixture atmosphere is 3.1%.
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