CN104264201A - Method for preparing B4C/Al composite material corrosion-resistance film and neutron absorption material - Google Patents
Method for preparing B4C/Al composite material corrosion-resistance film and neutron absorption material Download PDFInfo
- Publication number
- CN104264201A CN104264201A CN201410505927.0A CN201410505927A CN104264201A CN 104264201 A CN104264201 A CN 104264201A CN 201410505927 A CN201410505927 A CN 201410505927A CN 104264201 A CN104264201 A CN 104264201A
- Authority
- CN
- China
- Prior art keywords
- matrix material
- preparation
- resistance film
- solution
- film layer
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21C—NUCLEAR REACTORS
- G21C7/00—Control of nuclear reaction
- G21C7/06—Control of nuclear reaction by application of neutron-absorbing material, i.e. material with absorption cross-section very much in excess of reflection cross-section
- G21C7/24—Selection of substances for use as neutron-absorbing material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
Abstract
The invention discloses a method for preparing a B4C/Al composite material corrosion-resistance film. The method comprises the following steps: a, pre-treating the surface of a B4C/Al composite material; b, anodizing the surface of the B4C/Al composite material to generate a porous alumina film; c, putting the anodized B4C/Al composite material into a nickel salt or cobalt salt solution, and carrying out hole sealing treatment to obtain a uniform and compact protective film on the surface of the B4C/Al composite material. The invention further discloses a method for preparing a neutron absorption material by adopting the method for preparing the B4C/Al composite material corrosion-resistance film. According to the methods, the hole sealing speed of an oxidation film can be improved, and the hole sealing quality can be improved.
Description
Technical field
The present invention relates to a kind of B
4the preparation method of C/Al matrix material wear-resistance film layer, and a kind of this B of use
4the preparation method of the neutron absorber material of C/Al matrix material wear-resistance film layer preparation method.
Background technology
In reactor, nuclear fuel " burning " in nuclear reactor does not allow once to burnout as fossil oil, has the danger that certain radioactivity, toxicity and existence generation core are critical after using, the health existence of the entail dangers to mankind and environment.The present installed capacity of China's nuclear energy is less than 10000MW, expect the year two thousand twenty, China's nuclear power can will reach 40000MW, positive nuclear power developing planning has all been formulated in countries in the world, " third generation " Nuclear power plants makes substantial progress, the business of input had transports or is about to project verification, and irradiated fuel store amount will be increasing.In order to reduce environment protection cost and storage cost, irradiated fuel store will towards densification, long life future development.
International advanced spent fuel storage system mainly adopts BORAL
tMand METAMIC
tMbe used as neutron absorber material etc. aluminum-based composites, it can be used as the reaction that storage screen work material can effectively control in irradiated fuel store process.B
4c/Al matrix material can adopt the method for stirring casting, is prepared by grinding, refining slagging-off, machinery and induction stirring, the several step of hot pressing roll forming.
B
4b in C/Al matrix material
4the mass percentage of C is 20% ~ 40%, B
4c namely
10the content of B determines the neutron absorption performance of material, wherein B
4c even particle distribution, disperse, dense structure, does not have the casting flaws such as obvious pore, and the mechanical mechanics property of material is very excellent.But, meanwhile, B
4the introducing of wild phase in C particle enhanced aluminum-based composite material, make the corrosion behavior of matrix material complicated, its corrosion behavior is much more complicated than matrix alloy, and this will limit the application of this material in the environment of etching condition harshness.The film of non-crystal structure has isotropy, the surperficial feature without crystal boundary, therefore not easily forms corrosion microbattery in corrosive medium, reduces and galvanic corrosion possibility occurs, have good solidity to corrosion.At B
4the erosion resistance that amorphous nickel/phosphorus/aluminium oxide composite film is expected to improve this material is prepared on the surface of C/Al matrix material.
Relevant B
4the report of C/Al composite material surface Corrosion Resistant Film preparation technology is few, and its process means prepares pellumina at material surface, then carries out sealing pores to it.A kind of known B
4the surface treatment method of C/Al matrix material comprises: by matrix material machinery polishing also ultrasonic cleaning in acetone, then alkali cleaning and ultrasonic cleaning, pickling and ultrasonic cleaning successively, then in Sulfuric Acid Solution oxidation, finally in boiling water, makes sealing pores.But above-mentioned preparation method exists following problem: 1, adopt single sulfuric acid electrolyte, in reaction process, solution warms is fast, and too high solution temperature often causes coating mass to decline, and affects the solidity to corrosion of rete.If installation refrigerating unit, required cost can increase greatly.Therefore need to explore more suitably anodic oxidation electrolyte or find out the additive widening anodizing temperature.2, aluminum matrix composite forms nonuniform film in anode oxidation process, even film forming difficulty on nonconducting Second Phase Particle, and B
4the film forming situation of C/Al interface is also unclear.[Wang Xi, the fabricated in situ TiB such as Wang Xi
2the research of-6351Al composite material anode oxidation, material protection, 2007,40 (10): 61 ~ 63] propose inhibition due to matrix material enhanced granule, the condition obtaining even rete is harsh, Al and TiB
2the thicknesses of layers that particle is formed is different, and then makes overall film forming thickness limited, causes the oxidation film corrosion resistance that matrix material is formed to reduce.The reason of thicknesses of layers inequality is caused to be TiB
2electroconductibility not as Al.By that analogy, at B
4in C/Al matrix material, wild phase B
4c particle does not have electroconductibility, makes B
4the composite material anode oxidation filming of C particle reinforce is more difficult, than general aluminium alloy and the TiB having certain electroconductibility
2the more difficult oxidation filming of matrix material Deng particle reinforce, makes its practical application be restricted.3, adopt boiling water sealing hole, sealing of hole temperature is higher, and sealing of hole speed is low, and energy consumption is high, and the sealing quality of oxide film is low, the B obtained
4c/Al matrix material resistance to corrosion is not strong, and the closing process therefore after anodic oxidation has to be optimized.
Summary of the invention
Main purpose of the present invention is, for above the deficiencies in the prior art, to provide a kind of B
4the preparation method of C/Al matrix material wear-resistance film layer, prepares amorphous nickel/phosphorus/aluminium oxide film at composite material surface, greatly improves oxide film sealing of hole speed, improves sealing quality.
Further, the present invention also aims under the prerequisite not reducing coating mass, reduce the impact of reaction heat effect in anode oxidation process.
The present invention also provides a kind of and adopts this B
4the preparation method of the neutron absorber material of the preparation method of C/Al matrix material wear-resistance film layer.
For achieving the above object, the present invention is by the following technical solutions:
A kind of B
4the preparation method of C/Al matrix material wear-resistance film layer, comprises the following steps:
A. to B
4c/Al composite material surface carries out pre-treatment;
B. to the described B through step a process
4c/Al composite material surface carries out anodic oxidation, generates multiaperture pellumina;
C. by the described B after anodic oxidation
4c/Al matrix material puts into nickel salt or cobalt salt hole sealing solution, carries out sealing pores, makes described B
4c/Al composite material surface obtains the protective membrane of even compact.
Further, described hole sealing solution is the mixing solutions of nickel salt or cobalt salt and boric acid.
Described nickel salt or cobalt salt are the acetate of nickel or cobalt, molybdate, vanadate or tungstate, be preferably nickelous acetate or cobaltous acetate, nickelous acetate or cobaltous acetate and boric acid mixing solutions is adopted in step c, the stoichiometric ratio of nickelous acetate is 5.0 ~ 8.0g/L, the mass percent of cobaltous acetate is 2.1% ~ 6.4%, and the stoichiometric ratio of boric acid is 40 ~ 60g/L, and sealing of hole temperature is 70 ~ 95 DEG C, the pH of pore-sealing liquid is 5.0 ~ 6.0, and the sealing of hole time is 15 ~ 25min.
In step b, anodic oxidation solution is the glycerine of the sulfuric acid of massfraction 15% ~ 30%, the oxalic acid solution of 1 ~ 5% and 3 ~ 5g/L, and current density is 0.5 ~ 2.5A/dm
2, treatment temp is 15 DEG C ~ 30 DEG C, and the treatment time is 0.5 ~ 1.5h.
In step b, anodic oxidation is with stereotype or graphite for negative electrode, and cathodic surface area: anode surface area=2 ~ 6, the distance of anode and negative electrode is 2.5cm ~ 4cm.
Step a comprises:
(1) adopt the method for mechanical polishing medium sand paper polishing by described B
4c/Al composite material surface polishes, and removes surface scratch, zone of oxidation and impurity particle, then does mechanical polishing, then wash with deionized water;
(2) material in step (1) is put into basic solution alkali cleaning, use washed with de-ionized water subsequently;
(3) material in step (2) is put into acidic solution pickling, use washed with de-ionized water subsequently;
(4) material in step (3) is carried out mechanical polishing again, use washed with de-ionized water subsequently.
In described step (1) and/or described step (4), what mechanical polishing adopted is sand paper polishing, and sand paper contents is 150 ~ 1200 orders, preferably also adopts granularity to be 2.5 μm of diamond polishing cream.
In described step (2), described basic solution is NaOH solution, and the massfraction of NaOH is 5 ~ 15%, and alkali cleaning temperature is 50 ~ 60 DEG C, and the alkali cleaning time is 20 ~ 60s.
In described step (3), described acidic solution is H
2sO
4solution, H
2sO
4massfraction be 5 ~ 15%, pickling temperature is 60 ~ 70 DEG C, and pickling time is 2 ~ 4min.
A preparation method for neutron absorber material, comprises preparation B
4the step of C/Al matrix material, also comprises and uses described B
4the preparation method of C/Al matrix material wear-resistance film layer is at described B
4c/Al composite material surface forms B
4the step of C/Al matrix material wear-resistance film layer.
Beneficial effect of the present invention:
Nickel salt or cobalt salt solution is adopted to carry out sealing pores to oxide film, sealing of hole temperature is lower than boiling water sealing hole, compared with boiling water sealing hole, there is heat-sealing hole and cold seal hole in this sealing of hole process, sealing of hole speed is far above boiling water sealing hole, and technique is simple simultaneously, energy consumption is low, bath life is long, and sealing quality is excellent, greatly can improve B
4c/Al matrix material resistance to corrosion, improves B
4the work-ing life of C/Al matrix material under spent fuel wet method storage environment.The present invention particularly preferably adopts and implements sealing pores according to the nickelous acetate of certain ratio mixing or the mixing solutions of cobaltous acetate and boric acid, is aided with specific temperature and pH value range simultaneously, makes sealing of hole speed and best results.
In preferred scheme, the present invention adds organic acid oxalic acid in sulfuric acid electrolyte, under the prerequisite not reducing coating mass, can reduce the impact of reaction heat effect in anode oxidation process, prepare amorphous nickel/phosphorus/aluminium oxide film at composite material surface.Best, adopt the sulfuric acid of special proportioning, oxalic acid and glycerine solution, be aided with specific current density, temperature and treatment time scope simultaneously, effectively widen anodic oxidation and allow operating temperature range and reduce the temperature of electrolytic solution, become coating mass good.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the pure aluminum-based boron carbide surface film oxide prepared according to the embodiment of the present invention;
Fig. 2 is the B without anodic oxidation treatment and sealing pores
4c/Al neutron absorber material (left side) and the B prepared according to the embodiment of the present invention
4c/Al neutron absorber material (right side) comparison diagram.
Embodiment
Below embodiments of the present invention are elaborated.It is emphasized that following explanation is only exemplary, instead of in order to limit the scope of the invention and apply.
According to embodiments of the invention, mechanical sand paper can be adopted B
4c/Al matrix material does the pre-treatment such as polishing, by pretreated B
4c/Al matrix material adopts mixed acid anodic oxidation electrolytic solution; the oxidation of wide temperature is carried out to matrix material and prepares amorphous nickel/phosphorus/aluminium oxide film; afterwards; pellumina is immersed in nickel salt or cobalt salt hole sealing solution; utilize the hydration reaction of aluminum oxide and nickel hydroxide or the deposition of cobaltous hydroxide in pellumina micropore; fast and effeciently seal the porous-film of pellumina, greatly improve the compactness extent that material surface generates protective membrane.Nickel salt in hole sealing solution or cobalt salt can be the acetate of nickel or cobalt, molybdate, vanadate or tungstate, preferably adopt the nickelous acetate of certain proportioning or cobaltous acetate and boric acid mixing solutions.B
4c/Al matrix material can be prepared by stirring casting method, B
4b in C/Al matrix material
4the mass percent of C can be 20% ~ 40%.
In certain embodiments, B
4the surface treatment method of C/Al matrix material can comprise the following steps:
(1) adopt the method for mechanical polishing medium sand paper polishing and diamond polishing by B
4c/Al composite material surface polishes, and then washes with deionized water;
(2) material in step (1) is put into NaOH solution alkali cleaning, use washed with de-ionized water subsequently twice;
(3) material in step (2) is put into H
2sO
4pickling in solution, uses washed with de-ionized water twice subsequently;
(4) material sand paper in step (3) is carried out mechanical polishing, use washed with de-ionized water subsequently twice;
(5) using the material after polishing in step (4) as anode, stereotype or graphite are negative electrode, in mixed acid solution, adopt D.C. regulated power supply, control current density, carry out anodic oxidation, generate protective membrane at material surface, use a large amount of flowing water and washed with de-ionized water successively subsequently;
(6) material after step (5) Anodic Oxidation is put into nickel or cobalt salt solution, carry out sealing pores, at B
4c/Al composite material surface obtains the protective membrane of even compact.
After material surface process, fine and close in the protective membrane good insulating of Surface Creation.Boric acid soak test shows, the material after anodic oxidation treatment can significantly improve its corrosion resistance under boric acid environment and spent fuel wet method storage environment, is likely applied to the screen work material of pressurized-water reactor Spent fuel pit.
In a further embodiment, in step (1), what mechanical polishing adopted is sand paper polishing, and sand paper contents is 150 orders, 500 orders, 800 orders, 1200 orders, and polishing contents from low to high, removes surface scratch, zone of oxidation and impurity particle; Mechanical polishing adopts diamond polishing cream.
In step (2), soda-wash solution is NaOH solution, and the massfraction of NaOH is 5 ~ 15%, and alkali cleaning temperature is 50 ~ 60 DEG C, and the alkali cleaning time is 20 ~ 60s, material surface dirt and natural oxide film can be removed.
In step (3), Acidwash solution is H
2sO
4solution, H
2sO
4massfraction be 5 ~ 15%, pickling temperature is 60 ~ 70 DEG C, and pickling time is 2 ~ 4min, can by alkaline cleaning procedure material surface formed oxide film removing and material surface attachment debris neutralization, in order to avoid pollution electrolytic solution.
In step (4), material sand paper carries out mechanical polishing, and sand paper contents until 1200 orders, uses washed with de-ionized water twice from 150 orders subsequently.
In step (5), anodic oxidation solution is the glycerine of the sulfuric acid of massfraction 15% ~ 30%, the oxalic acid solution of 1 ~ 5% and 3 ~ 5g/L, stereotype or graphite are negative electrode, cathodic surface area: anode surface area=2 ~ 6, the distance of anode and negative electrode is 2.5cm ~ 4cm, and current density is 0.5 ~ 2.5A/dm
2, treatment temp is 15 DEG C ~ 30 DEG C, and the treatment time is 0.5 ~ 1.5h.This process is the critical process generating protective membrane at composite material surface, can form the protective membrane of densification, good insulating;
In step (6), sealing of hole adopts nickel or cobalt salt solution, wherein one is nickelous acetate and boric acid mixing solutions, the stoichiometric ratio of nickelous acetate is 5.0 ~ 8.0g/L, the stoichiometric ratio of boric acid is 40 ~ 60g/L, sealing of hole temperature is 70 ~ 95 DEG C, and the pH of pore-sealing liquid is 5.0 ~ 6.0, and the sealing of hole time is 15 ~ 25min.Another kind is cobaltous acetate and boric acid mixing solutions, and the mass percent of cobaltous acetate is 2.1% ~ 6.4%, and other conditions are identical.PH relies on the acetic acid of 10% or ammoniacal liquor to regulate.By sealing pores, the further densification of protective membrane that can will be formed in step (5), improves the corrosion resisting property of material.
For B
4c/Al matrix material carries out surface protection process, can form the dimmed fine and close protective membrane of macroscopic view at material surface.By the corrosion test at boric acid environment and pressurized-water reactor Spent fuel pit environment, materials'use all increases weight early stage, and in surperficial use procedure, surface film oxide is by further densification.Visible, after surface treatment, the solidity to corrosion of material significantly improves, and is likely applied as the neutron absorber material of spent fuel wet method storage screen work.
Be described below by way of example more specifically.
B
4the preparation method of C/Al composite material surface wear-resistance film layer comprises the following steps: (1) adopts sand paper by B
4c/Al composite board carries out mechanical polishing, and sand paper contents is 150 orders, 500 orders, 800 orders, 1200 orders, and polishing order carries out from low to high successively, carries out mechanical polishing subsequently with polishing cloth, and rumbling compound is diamond polishing cream; (2) material after step (1) polishing is put into basic solution alkali cleaning, soda-wash solution is NaOH solution, and the massfraction of NaOH is 5 ~ 15%, and alkali cleaning temperature is 50 ~ 60 DEG C, and the alkali cleaning time is 30s, uses washed with de-ionized water twice subsequently; (3) material after step (2) alkali cleaning is put into acidic solution pickling, Acidwash solution is H
2sO
4solution, H
2sO
4massfraction be 5 ~ 15%, pickling temperature is 60 ~ 70 DEG C, and pickling time is 2 ~ 4min, uses washed with de-ionized water subsequently; (4) adopt sand paper to carry out mechanical polishing the material after step (3) pickling, sand paper contents is 150 order ~ 1200 orders; (5) using the material after step (4) mechanical polishing as anode, stereotype or graphite are negative electrode, D.C. regulated power supply is as external source, anodic oxidation is carried out in the glycerine of the sulfuric acid of 15% ~ 30%, the oxalic acid solution of 1 ~ 5% and 3 ~ 5g/L, control current density, wherein cathodic surface area: anode surface area=2 ~ 6, the distance of anode and negative electrode is 2.5cm ~ 4cm, and constant current density is 0.5 ~ 2.5A/dm
2, anodic oxidation solution is, treatment temp is 15 DEG C ~ 30 DEG C, and the treatment time is 0.5 ~ 1.5h, uses flowing water, deionized water and alcohol washes successively subsequently, dries up at cold wind; (6) material after step (5) anodic oxidation is put into nickel or cobalt salt and boric acid solution, sealing pores is carried out at 70 ~ 95 DEG C of temperature, wherein a kind of optional nickel salt or cobalt salt are nickelous acetate or cobaltous acetate, the stoichiometric ratio of nickelous acetate is 5.0 ~ 8.0g/L, the mass percent of cobaltous acetate is 2.1% ~ 6.4%, and the stoichiometric ratio of boric acid is 40 ~ 60g/L, and the pH of pore-sealing liquid is 5.0 ~ 6.0, the sealing of hole time is that 15 ~ 20min, pH rely on the acetic acid of 10% or ammoniacal liquor to regulate.This B
4the protective membrane even compact that C/Al composite material surface obtains, can significantly improve its solidity to corrosion under irradiated fuel store environment, is likely applied as the neutron absorber material of Nuclear Power Station's Exhausted Fuels wet method storage screen work.Experimental result can be shown in Figure 1 pure aluminum-based boron carbide surface film oxide SEM figure, wherein thickness 20 ~ 30 μm, satisfactory thickness is at twenties microns.
Demonstration example 1
Select B
4c mass percent is the B of 31%
4c-Al matrix material, carries out mechanical polishing, then is the diamond polishing agent polishing of 2.5 μm by granularity, and be 55 DEG C in temperature, massfraction is alkali cleaning 30s in the NaOH of 9.8%.Putting into pickling temperature is 65 DEG C, and massfraction is 9.8%H
2sO
4soak 3min in solution, then use sand paper polishing, sand paper contents is followed successively by 150 orders, 400 orders, 800 orders, 1200 orders.Using the material after polishing as anode, stereotype is as negative electrode, cathodic surface area: anode surface area=2, the distance of anode and negative electrode is 2.5cm, D.C. regulated power supply is as external source, anodic oxidation is carried out in the glycerine of the sulfuric acid of 15%, the oxalic acid solution of 3% and 3g/L, oxidation voltage is 25V, treatment time is 60min, then puts into nickelous acetate and boric acid solution, carries out sealing pores at 80 DEG C of temperature, the stoichiometric ratio of nickelous acetate is 5.5g/L, the stoichiometric ratio of boric acid is 50g/L, and the pH of pore-sealing liquid is 5.7, and the sealing of hole time is 20min.Finally obtain Dark grey protective membrane at material surface.Experimental result can be shown in Figure 2, illustrated therein is the B without anodic oxidation treatment and sealing pores
4c/Al neutron absorber material (left side) and the B after processing
4c/Al neutron absorber material (right side).
Demonstration example 2
Select B
4c mass percent is the B of 31%
4c-Al matrix material is 55 DEG C in temperature, and massfraction is alkali cleaning 30s in the NaOH solution of 9.8%.Putting into pickling temperature is 65 DEG C, and massfraction is 9.8%H
2sO
43min is soaked in solution.Use sand paper polishing again, sand paper contents is followed successively by 150 orders, 400 orders, 800 orders, 1200 orders.Using the material after polishing as anode, graphite is as negative electrode, cathodic surface area: anode surface area=2, the distance of anode and negative electrode is 2.5cm, D.C. regulated power supply is as external source, at the sulfuric acid of 15%, anodic oxidation is carried out in the oxalic acid solution of 3% and the glycerine of 3g/L, oxidation voltage is 20V, treatment time is 70min, then nickelous acetate is put into, in cobaltous acetate and boric acid solution, sealing pores is carried out at 80 DEG C of temperature, the stoichiometric ratio of nickelous acetate is 5.5g/L, the massfraction of cobaltous acetate is 3.0%, the stoichiometric ratio of boric acid is 50g/L, the pH of pore-sealing liquid is 5.6, the sealing of hole time is 20min.
Above content combines concrete/preferred embodiment further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention; without departing from the inventive concept of the premise; its embodiment that can also describe these makes some substituting or modification, and these substitute or variant all should be considered as belonging to protection scope of the present invention.
Above content combines concrete/preferred embodiment further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention; without departing from the inventive concept of the premise; its embodiment that can also describe these makes some substituting or modification, and these substitute or variant all should be considered as belonging to protection scope of the present invention.
Claims (10)
1. a B
4the preparation method of C/Al matrix material wear-resistance film layer, is characterized in that, comprise the following steps:
A. to B
4c/Al composite material surface carries out pre-treatment;
B. to the described B through step a process
4c/Al composite material surface carries out anodic oxidation, generates multiaperture pellumina;
C. by the described B after anodic oxidation
4c/Al matrix material puts into nickel salt or cobalt salt hole sealing solution, carries out sealing pores, makes described B
4c/Al composite material surface obtains the protective membrane of even compact.
2. B as claimed in claim 1
4the preparation method of C/Al matrix material wear-resistance film layer, is characterized in that, described hole sealing solution is the mixing solutions of nickel salt or cobalt salt and boric acid.
3. B as claimed in claim 2
4the preparation method of C/Al matrix material wear-resistance film layer, it is characterized in that, described nickel salt or cobalt salt are the acetate of nickel or cobalt, molybdate, vanadate or tungstate, be preferably nickelous acetate or cobaltous acetate, nickelous acetate or cobaltous acetate and boric acid mixing solutions is adopted in step c, the stoichiometric ratio of nickelous acetate is 5.0 ~ 8.0g/L, the mass percent of cobaltous acetate is 2.1% ~ 6.4%, the stoichiometric ratio of boric acid is 40 ~ 60g/L, sealing of hole temperature is 70 ~ 95 DEG C, the pH of pore-sealing liquid is 5.0 ~ 6.0, and the sealing of hole time is 15 ~ 25min.
4. the B as described in any one of claims 1 to 3
4the preparation method of C/Al matrix material wear-resistance film layer, is characterized in that, in step b, anodic oxidation solution is the glycerine of the sulfuric acid of massfraction 15% ~ 30%, the oxalic acid solution of 1 ~ 5% and 3 ~ 5g/L, and current density is 0.5 ~ 2.5A/dm
2, treatment temp is 15 DEG C ~ 30 DEG C, and the treatment time is 0.5 ~ 1.5h.
5. B as claimed in claim 4
4the preparation method of C/Al matrix material wear-resistance film layer, is characterized in that, in step b, anodic oxidation is with stereotype or graphite for negative electrode, and cathodic surface area: anode surface area=2 ~ 6, the distance of anode and negative electrode is 2.5cm ~ 4cm.
6. the B as described in any one of claims 1 to 3
4the preparation method of C/Al matrix material wear-resistance film layer, it is characterized in that, step a comprises:
(1) adopt the method for mechanical polishing medium sand paper polishing by described B
4c/Al composite material surface polishes, and removes surface scratch, zone of oxidation and impurity particle, then does mechanical polishing, then use washed with de-ionized water;
(2) material in step (1) is put into basic solution alkali cleaning, use washed with de-ionized water subsequently;
(3) material in step (2) is put into acidic solution pickling, use washed with de-ionized water subsequently;
(4) material in step (3) is carried out mechanical polishing again, use washed with de-ionized water subsequently.
7. B as claimed in claim 6
4the preparation method of C/Al matrix material wear-resistance film layer, it is characterized in that, in described step (1) and/or described step (4), what mechanical polishing adopted is sand paper polishing, sand paper contents is 150 ~ 1200 orders, preferably also adopts granularity to be 2.5 μm of diamond polishing cream.
8. B as claimed in claim 6
4the preparation method of C/Al matrix material wear-resistance film layer, is characterized in that, in described step (2), described basic solution is NaOH solution, and the massfraction of NaOH is 5 ~ 15%, and alkali cleaning temperature is 50 ~ 60 DEG C, and the alkali cleaning time is 20 ~ 60
s.
9. B as claimed in claim 6
4the preparation method of C/Al matrix material wear-resistance film layer, is characterized in that, in described step (3), described acidic solution is H
2sO
4solution, H
2sO
4massfraction be 5 ~ 15%, pickling temperature is 60 ~ 70 DEG C, and pickling time is 2 ~ 4min.
10. a preparation method for neutron absorber material, comprises preparation B
4the step of C/Al matrix material, is characterized in that, also comprises and uses method described in any one of claim 1 to 9 at described B
4c/Al composite material surface forms B
4the step of C/Al matrix material wear-resistance film layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410505927.0A CN104264201A (en) | 2014-09-26 | 2014-09-26 | Method for preparing B4C/Al composite material corrosion-resistance film and neutron absorption material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410505927.0A CN104264201A (en) | 2014-09-26 | 2014-09-26 | Method for preparing B4C/Al composite material corrosion-resistance film and neutron absorption material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104264201A true CN104264201A (en) | 2015-01-07 |
Family
ID=52155769
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410505927.0A Pending CN104264201A (en) | 2014-09-26 | 2014-09-26 | Method for preparing B4C/Al composite material corrosion-resistance film and neutron absorption material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104264201A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106498470A (en) * | 2016-10-24 | 2017-03-15 | 中国工程物理研究院核物理与化学研究所 | B4C Al neutron absorber material surface protection film generation methods |
| CN108179451A (en) * | 2017-12-06 | 2018-06-19 | 安徽应流久源核能新材料科技有限公司 | A kind of surface treatment method of aluminum-based boron carbide composite material |
| CN113904039A (en) * | 2021-09-30 | 2022-01-07 | 蜂巢能源科技有限公司 | Anodic oxidation liquid, battery shell, and insulation protection method and application thereof |
| US11643715B2 (en) | 2021-09-07 | 2023-05-09 | Industrial Technology Research Institute | Composite structure with aluminum-based alloy layer containing boron carbide and manufacturing method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101019742A (en) * | 2007-03-23 | 2007-08-22 | 严卫星 | Making process of antiwear nonstick cooker |
| CN101205616A (en) * | 2006-12-20 | 2008-06-25 | 深圳富泰宏精密工业有限公司 | Surface treating method for metal workpieces |
| CN103060877A (en) * | 2013-01-08 | 2013-04-24 | 嘉兴中科亚美合金技术有限责任公司 | Electrolyte for aluminum alloy micro-plasma electrolytic oxidation and treating process thereof |
| CN103668382A (en) * | 2012-09-05 | 2014-03-26 | 中国工程物理研究院核物理与化学研究所 | Surface treatment method of B4C-Al composite material |
-
2014
- 2014-09-26 CN CN201410505927.0A patent/CN104264201A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101205616A (en) * | 2006-12-20 | 2008-06-25 | 深圳富泰宏精密工业有限公司 | Surface treating method for metal workpieces |
| CN101019742A (en) * | 2007-03-23 | 2007-08-22 | 严卫星 | Making process of antiwear nonstick cooker |
| CN103668382A (en) * | 2012-09-05 | 2014-03-26 | 中国工程物理研究院核物理与化学研究所 | Surface treatment method of B4C-Al composite material |
| CN103060877A (en) * | 2013-01-08 | 2013-04-24 | 嘉兴中科亚美合金技术有限责任公司 | Electrolyte for aluminum alloy micro-plasma electrolytic oxidation and treating process thereof |
Non-Patent Citations (1)
| Title |
|---|
| 姚寿山等: "《表面科学与技术》", 31 January 2005 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106498470A (en) * | 2016-10-24 | 2017-03-15 | 中国工程物理研究院核物理与化学研究所 | B4C Al neutron absorber material surface protection film generation methods |
| CN108179451A (en) * | 2017-12-06 | 2018-06-19 | 安徽应流久源核能新材料科技有限公司 | A kind of surface treatment method of aluminum-based boron carbide composite material |
| US11643715B2 (en) | 2021-09-07 | 2023-05-09 | Industrial Technology Research Institute | Composite structure with aluminum-based alloy layer containing boron carbide and manufacturing method thereof |
| CN113904039A (en) * | 2021-09-30 | 2022-01-07 | 蜂巢能源科技有限公司 | Anodic oxidation liquid, battery shell, and insulation protection method and application thereof |
| CN113904039B (en) * | 2021-09-30 | 2023-08-08 | 蜂巢能源科技有限公司 | Anodic oxidation liquid, battery shell, and insulation protection method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104264201A (en) | Method for preparing B4C/Al composite material corrosion-resistance film and neutron absorption material | |
| CN102758234B (en) | Method for preparing aluminum alloy anti-corrosion layer and electrolyte used in method | |
| CN102080248A (en) | Preparation method of magnesium alloy micro-arc oxidation film | |
| CN106350849B (en) | The oxidation film electro-deposition preparation method of aluminium surface high-selenium corn and low transmitting solar spectrum | |
| CN104947141A (en) | Method for manufacturing energy-saving stainless steel electrolytic electrode with titanium dioxide coating | |
| CN104973662B (en) | Oxide anode for treatment of ship domestic sewage and preparation method thereof | |
| CN103215614A (en) | Preparation method of metallic oxide anode containing cold spraying tantalum intermediate layer | |
| CN107557789B (en) | A kind of optical anode material and its preparation and application | |
| CN105088309A (en) | Efficient energy-saving anodic oxidation treatment method for die-cast aluminum alloy | |
| CN103280611B (en) | A kind of lithium iron phosphate battery negative electrode waste paper recovery method | |
| CN103668382A (en) | Surface treatment method of B4C-Al composite material | |
| CN105648516A (en) | Method for obtaining ultra-hard surface modification layers of zirconium alloy | |
| CN103334143A (en) | Microarc oxidation method for quickly preparing wear-proof zirconia and alumina mixed coating on surface of zirconium alloy | |
| CN105386061A (en) | Method for preparing Bi2S3/TiO2 nanorod composite-film photo-anodes | |
| CN105846007A (en) | Method for preparing electrode active materials for lead storage battery in pairs by electrochemical process | |
| CN106319558B (en) | A kind of MoS of high-efficiency multiple2- Zn hydrogen-precipitating electrodes and preparation method thereof | |
| CN102899703A (en) | Silicate electrolyte and application of silicate electrolyte in magnesium alloy micro-arc oxidation film preparation | |
| CN105063715A (en) | Preparation method for anodic oxide film on B4C-A1-based composite surface and oxide film prepared through preparation method | |
| CN109735847A (en) | AgInS for photoproduction cathodic protection2/ graphene/TiO2Nano composite membrane light anode and preparation and application | |
| CN103147112A (en) | Electrolyte as well as application and method for preparing micro-arc oxidation film on zirconium alloy cladding of nuclear fuel rod by an electrolyte | |
| CN106521494B (en) | Ni, S codope TiO2 films and its application and preparation method | |
| CN103273062A (en) | High-temperature metal phase change heat storage material and preparation method | |
| CN105887148A (en) | Ni-B/SiC CMMA coating for marine equipment and preparation method thereof | |
| CN105543926A (en) | Preparation method of corrosion-resistant wear-resistant synergistic coating for surfaces of light alloy and composite material | |
| CN101230475A (en) | Aluminum alloy differential arc oxidation batch production technique |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| CB03 | Change of inventor or designer information |
Inventor after: Wang Aosong Inventor after: Li Qiulin Inventor after: Liu Wei Inventor after: Shu Guogang Inventor after: Liu Feihua Inventor after: Zeng Qingfang Inventor before: Li Qiulin Inventor before: Liu Wei Inventor before: Zeng Qingfang |
|
| COR | Change of bibliographic data | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20160624 Address after: 518000 No. 69 Shennan Middle Road, Shenzhen, Guangdong, Futian District Applicant after: China Nuclear Power Engineering Co., Ltd. Applicant after: Graduate School at Shenzhen, Tsinghua University Address before: 518055 Guangdong city of Shenzhen province Nanshan District Xili of Tsinghua Applicant before: Graduate School at Shenzhen, Tsinghua University |
|
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150107 |