CN106498470B - B4C-Al neutron absorber material surface protection film generation methods - Google Patents
B4C-Al neutron absorber material surface protection film generation methods Download PDFInfo
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- CN106498470B CN106498470B CN201610924045.7A CN201610924045A CN106498470B CN 106498470 B CN106498470 B CN 106498470B CN 201610924045 A CN201610924045 A CN 201610924045A CN 106498470 B CN106498470 B CN 106498470B
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- neutron absorber
- material surface
- protection film
- surface protection
- ultrasonic cleaning
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- 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
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- 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
- C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
Abstract
B provided by the invention4C Al neutron absorber material surface protection film generation methods are by the way of constant voltage in B4C Al neutron absorber material Surface Creation protective films, by B4C Al neutron absorber materials remove the impurity and oxide layer on surface; it is sequentially placed into sodium hydroxide solution, nitric acid and hydrofluoric acid mixed solution and impregnates again; then using material as anode; graphite cake or stereotype are as cathode; immerse sulfuric acid solution; voltage is kept constant, in material surface growth protecting film, is finally putting into high temperature deionized water and carries out sealing of hole.This method control parameter is easy, and the protective film of generation can eliminate the microdefect of material surface, covers boron carbide particles.Uniform, fine and close, the dimmed protective film that material surface is formed, can effectively improve B4Corrosion resistance of the C Al neutron absorber materials in hydro-thermal, aqueous vapor environment.This method may be used on the fields such as the neutron absorber material of the transport of nuclear power station fresh fuel, spentnuclear fuel transhipment, wet method storage and Dry storage, pile neutron shielding.
Description
Technical field
The invention belongs to material science corrosion and protection technical fields, and in particular to a kind of B4C-Al neutron absorber material tables
Surface protective film generation method.
Background technology
B4C-Al neutron absorber materials are by B4C ceramic particle even dispersions are distributed in Al metallic matrixes, and pass through pressure
System, sintering, squeeze and a series of process such as hot rolling and the uniformity that obtains is good, consistency is high and excellent in mechanical performance is answered
Close object material.Because larger containing thermal neutron absorption cross section in material10B nucleic, can be as neutron absorber material extensive use
In fields such as reactor, nuclear power stations.B4B in C-Al neutron absorber materials4C exists usually in the form of ceramic particle, due to
B4The difference of chemical property between C and Al results in corrosion resistance when such material uses in the environment such as hydro-thermal, aqueous vapor
It is poor.When material surface is there are when impurity or defect, and regional area will generate etch pit, corrosion product aggregation, fall off phenomena such as,
The security reliability of materials'use process will be jeopardized when serious.Therefore, in order to improve B4C-Al neutron absorber materials it is anticorrosive
Performance avoids and reduces the generation of corrosion, needs to carry out surface modification to material to improve the corrosion resistance of material.
Invention content
The B of the present invention4C-Al neutron absorber material surface protection film generation methods include the following steps：
A. use the method for mechanical polishing or shot-peening by B4The impurity and oxide layer on C-Al neutron absorber materials surface remove,
Then ultrasonic cleaning obtains material I in deionized water；The B4The volume hundred of boron carbide in C-Al neutron absorber materials
It is 5.3% ~ 36.6% to divide than content；
B. material I is put into alkaline solution and is impregnated, then ultrasonic cleaning obtains material II in deionized water；It is described
Alkaline solution be mass percent be 60g/L ~ 120g/L NaOH solution, soaking temperature be room temperature ~ 60 DEG C；
C. material II is put into mixed acid solution and is impregnated, then ultrasonic cleaning obtains material III in deionized water；
The mixed acid solution is the mixed acid of nitric acid and hydrofluoric acid, and nitric acid percent by volume is 45% ~ 55%, hydrofluoric acid volume percentage
Than being 5% ~ 15%, remaining is water, and soaking temperature is room temperature；
D. by material III as anode, graphite cake or stereotype as cathode, in sulfuric acid solution, control anode and cathode it
Between voltage be steady state value, so that the surface protection film of material III is grown to balance, then ultrasonic cleaning obtains in deionized water
To material IV；The steady state value of the voltage is 4V ~ 15V, and sulfuric acid solution percent by volume is 14% ~ 20%, remaining is water, processing
The temperature of solution is less than 20 DEG C in the process；
E. material IV is put into deionized water and is impregnated, until the surface protection film of material IV completes sealing of hole, i.e. B4C-Al
The growth of neutron absorber material surface protection film terminates.
In step a, mechanical polishing is polished using sand paper, and sand paper contents is the mesh of 200 mesh ~ 1200, and shot-peening is using bead spray
Ball or steel ball shot-peening, ultrasonic cleaning time are 2min ~ 10min.
Soaking time is 2min ~ 15min in step b, and the ultrasonic cleaning time is 2min ~ 10min.
Soaking time is 1min ~ 5min in step c, and the ultrasonic cleaning time is 2min ~ 10min.
In step d, the surface area of cathode:Surface area >=1.5 of anode, the distance between cathode and anode be 2cm ~
15cm, growth time are 10min ~ 60min, and the ultrasonic cleaning time is 2min ~ 5min.
Deionized water temperature is higher than 80 DEG C in step e, and soaking time is more than 60min.
The B of the present invention4C-Al neutron absorber material surface protection film generation methods are by the way of constant voltage in B4C-Al
Neutron absorber material surface growth protecting film, this method control parameter is easy, the B of generation4C-Al neutron absorber materials surface
Protective film can eliminate B4The microdefect on C-Al neutron absorber materials surface covers B4The carbon on C-Al neutron absorber materials surface
Change boron particles, it can be in B4C-Al neutron absorber materials surface forms one layer of uniform, fine and close, dimmed protective film, can effectively carry
High B4Corrosion resistance of the C-Al neutron absorber materials in hydro-thermal, aqueous vapor environment may be used on nuclear power station fresh fuel and transport, be weary
The fields such as fuel transhipment, the neutron absorber material of wet method storage and Dry storage, pile neutron shielding.
Specific implementation mode
The B of the present invention4C-Al neutron absorber material surface protection film generation methods include the following steps：
A. use the method for mechanical polishing or shot-peening by B4The impurity and oxide layer on C-Al neutron absorber materials surface remove,
Then ultrasonic cleaning obtains material I in deionized water；The B4The volume hundred of boron carbide in C-Al neutron absorber materials
It is 5.3% ~ 36.6% to divide than content；
B. material I is put into alkaline solution and is impregnated, then ultrasonic cleaning obtains material II in deionized water；It is described
Alkaline solution be mass percent be 60g/L ~ 120g/L NaOH solution, soaking temperature be room temperature ~ 60 DEG C；
C. material II is put into mixed acid solution and is impregnated, then ultrasonic cleaning obtains material III in deionized water；
The mixed acid solution is the mixed acid of nitric acid and hydrofluoric acid, and nitric acid percent by volume is 45% ~ 55%, hydrofluoric acid volume percentage
Than being 5% ~ 15%, remaining is water, and soaking temperature is room temperature；
D. by material III as anode, graphite cake or stereotype as cathode, in sulfuric acid solution, control anode and cathode it
Between voltage be steady state value, so that the surface protection film of material III is grown to balance, then ultrasonic cleaning obtains in deionized water
To material IV；The steady state value of the voltage is 4V ~ 15V, and sulfuric acid solution percent by volume is 14% ~ 20%, remaining is water, processing
The temperature of solution is less than 20 DEG C in the process；
E. material IV is put into deionized water and is impregnated, until the surface protection film of material IV completes sealing of hole, i.e. B4C-Al
The growth of neutron absorber material surface protection film terminates.
In step a, mechanical polishing is polished using sand paper, and sand paper contents is the mesh of 200 mesh ~ 1200, and shot-peening is using bead spray
Ball or steel ball shot-peening, ultrasonic cleaning time are 2min ~ 10min.
Soaking time is 2min ~ 15min in step b, and the ultrasonic cleaning time is 2min ~ 10min.
Soaking time is 1min ~ 5min in step c, and the ultrasonic cleaning time is 2min ~ 10min.
In step d, the surface area of cathode:Surface area >=1.5 of anode, the distance between cathode and anode be 2cm ~
15cm, growth time are 10min ~ 60min, and the ultrasonic cleaning time is 2min ~ 5min.
Deionized water temperature is higher than 80 DEG C in step e, and soaking time is more than 60min.
Embodiment 1：
Select B4The B that C percents by volume are 21.1%4C-Al neutron absorber materials, successively contents be 200 mesh, 500 mesh and
The impurity particle and oxide layer of polishing removal surface attachment, the mode that shot-peening can also be used carry out surface on the sand paper of 1200 mesh
Cleaning, and it is cleaned by ultrasonic 5min in deionized water, 5min is impregnated in the sodium hydroxide solution that mass percent is 90g/L,
And it is cleaned by ultrasonic 3min in deionized water.It is put into percent by volume nitric acid:Hydrofluoric acid:Water is 5:1:In 4 mixed acid solution
2min is impregnated, and is cleaned by ultrasonic 2min in deionized water.By B4C-Al neutron absorber materials are as anode, and graphite cake is as cloudy
Pole can also use stereotype as cathode, the wherein surface area of cathode:The distance of surface area=2.0 of anode, cathode and anode
For 3cm, in the sulfuric acid solution that percent by volume is 15%, voltage constant is that 6.5V carries out protective film growth, and growth time is
20min is then cleaned by ultrasonic 3min in deionized water.It is then placed in sealing pores in the deionized water that temperature is 100 DEG C
65min finally obtains dark gray protective film in material surface.
Specific control parameter is shown in Table 1, B4C-Al neutron absorber material surface protection film film thickness test results are shown in Table 2.
Embodiment 2：
The present embodiment and the embodiment of embodiment 1 are essentially identical, and the main distinction is：Select B4C percents by volume are
5.3% B4C-Al neutron absorber materials, cathode and the surface area that anode distance is 10cm and cathode:Surface area=1.5 of anode,
Sulfuric acid solution percent by volume is 16%, and protective film growth course voltage constant is 4.8V and growth time is 31min, specific to control
Parameter processed is shown in Table 1, B4C-Al neutron absorber material surface protection film film thickness test results are shown in Table 2.
Embodiment 3：
The present embodiment and the embodiment of embodiment 1 are essentially identical, and the main distinction is：Select B4C percents by volume are
15.9% B4C-Al neutron absorber materials, sulfuric acid solution percent by volume are 18%, and protective film growth course voltage constant is
5.2V and growth time are 60min, and specific control parameter is shown in Table 1, B4C-Al neutron absorber material surface protection film film thickness is tested
It the results are shown in Table 2.
Embodiment 4：
The present embodiment and the embodiment of embodiment 1 are essentially identical, and the main distinction is：Nitric acid in mixed acid:Hydrofluoric acid:
Water is 9:3:8 and soaking time be 3min, protective film growth course voltage constant is 8.0V and growth time is 45min, in temperature
Degree is sealing of hole 120min in 85 DEG C of deionized water, and specific control parameter is shown in Table 1, B4C-Al neutron absorber material surface protection films
Film thickness test result is shown in Table 2.
Embodiment 5：
The present embodiment and the embodiment of embodiment 1 are essentially identical, and the main distinction is：Select B4C percents by volume are
26.3% B4C-Al neutron absorber materials, sulfuric acid solution percent by volume are 20%, and protective film growth course voltage constant is
10.0 V and growth time are 35min, and specific control parameter is shown in Table 1, B4C-Al neutron absorber material surface protection film film thickness is surveyed
Test result is shown in Table 2.
Embodiment 6：
The present embodiment and the embodiment of embodiment 1 are essentially identical, and the main distinction is：Select B4C percents by volume are
32.7% B4C-Al neutron absorber materials, sulfuric acid solution percent by volume are 14%, and protective film growth course voltage constant is 4.0
V and growth time are 25min, and specific control parameter is shown in Table 1, B4C-Al neutron absorber material surface protection film film thickness test results
It is shown in Table 2.
Embodiment 7：
The present embodiment and the embodiment of embodiment 1 are essentially identical, and the main distinction is：Select B4C percents by volume are
36.6% B4C-Al neutron absorber materials, protective film growth course voltage constant is 7.5 V and growth time is 37min, specifically
Control parameter is shown in Table 1, B4C-Al neutron absorber material surface protection film film thickness test results are shown in Table 2.
Embodiment 8：
The present embodiment and the embodiment of embodiment 1 are essentially identical, and the main distinction is：Hydroxide in sodium hydroxide solution
Sodium mass percent is 60g/L and soaking time is 15min, nitric acid in mixed acid:Hydrofluoric acid:Water is 9:1:10 and soaking time
For 5min, protective film growth course voltage constant is 15.0 V and growth time is 16min, and specific control parameter is shown in Table 1, B4C-
Al neutron absorber material surface protection film film thickness test results are shown in Table 2.
Embodiment 9：
The present embodiment and the embodiment of embodiment 1 are essentially identical, and the main distinction is：Hydroxide in sodium hydroxide solution
Sodium mass percent is 120g/L and soaking time is 2min, nitric acid in mixed acid:Hydrofluoric acid:Water is 11:3:6 and soaking time
For 1min, protective film growth course voltage constant is 5.0 V and growth time is 10min, and specific control parameter is shown in Table 1, B4C-
Al neutron absorber material surface protection film film thickness test results are shown in Table 2.
Pass through corresponding obtained B in control parameter in table 1 and table 24The film of C-Al neutron absorber material surface protection films
Thick test result, it is recognised that B using the present invention4C-Al neutron absorber material surface protection film generation methods, control parameter
To B4The B that C percents by volume are 5.3% ~ 36.6%4C-Al neutron absorber materials are pervasive.Sodium hydroxide in sodium hydroxide solution
Mass percent is bigger, and required soaking time is shorter.Nitric acid and hydrofluoric acid volume percentage are higher in mixed acid solution, required leaching
It is shorter to steep the time.Voltage value is bigger in anodic oxidation growth course, and protection layer-growth rate is faster, the longer protective film of growth time
It is thicker.Deionized water temperature is higher during sealing of hole, soaking time is longer, and the protective film obtained is finer and close.Described in embodiment 3
Technique be growth B4The optimum process of C-Al neutron absorber material surface protection films, the protective film obtained under the technique is most
It is thick.The thickness of material surface protective film, consistency can be carried out by the structure adjusting to protective film growth technique corresponding
Control, and obtain the protective film for meeting certain corrosion resistance.
Table 1
Table 2
Claims (6)
1.B4C-Al neutron absorber material surface protection film generation methods, which is characterized in that the method includes the following steps：
A. use the method for mechanical polishing or shot-peening by B4The impurity and oxide layer on C-Al neutron absorber materials surface remove, then
Ultrasonic cleaning obtains material I in deionized water；The B4The percent by volume of boron carbide in C-Al neutron absorber materials
Content is 5.3% ~ 36.6%；
B. material I is put into alkaline solution and is impregnated, then ultrasonic cleaning obtains material II in deionized water；The alkali
Property solution be mass percent be 60g/L ~ 120g/L NaOH solution, soaking temperature be room temperature ~ 60 DEG C；
C. material II is put into mixed acid solution and is impregnated, then ultrasonic cleaning obtains material III in deionized water；It is described
Mixed acid solution be nitric acid and hydrofluoric acid mixed acid, nitric acid percent by volume is 45% ~ 55%, and hydrofluoric acid volume percentage is
5% ~ 15%, remaining is water, and soaking temperature is room temperature；
D. it is used as anode, graphite cake or stereotype as cathode material III, in sulfuric acid solution, between control anode and cathode
Voltage is steady state value, so that the surface protection film of material III is grown to balance, then ultrasonic cleaning obtains material in deionized water
Material IV；The steady state value of the voltage is 4V ~ 15V, and sulfuric acid solution percent by volume is 14% ~ 20%, remaining is water, processing procedure
The temperature of middle solution is less than 20 DEG C；
E. material IV is put into deionized water and is impregnated, until the surface protection film of material IV completes sealing of hole, i.e. B4C-Al neutrons are inhaled
The growth of material surface protective film is received to terminate.
2. B according to claim 14C-Al neutron absorber material surface protection film generation methods, it is characterised in that：Step a
In, mechanical polishing is polished using sand paper, and sand paper contents is the mesh of 200 mesh ~ 1200, and shot-peening uses bead shot-peening or steel ball shot-peening,
The ultrasonic cleaning time is 2min ~ 10min.
3. B according to claim 14C-Al neutron absorber material surface protection film generation methods, it is characterised in that：Step b
Middle soaking time is 2min ~ 15min, and the ultrasonic cleaning time is 2min ~ 10min.
4. B according to claim 14C-Al neutron absorber material surface protection film generation methods, it is characterised in that：Step c
Middle soaking time is 1min ~ 5min, and the ultrasonic cleaning time is 2min ~ 10min.
5. B according to claim 14C-Al neutron absorber material surface protection film generation methods, it is characterised in that：Step d
In, the surface area of cathode:Surface area >=1.5 of anode, the distance between cathode and anode are 2cm ~ 15cm, and growth time is
10min ~ 60min, ultrasonic cleaning time are 2min ~ 5min.
6. B according to claim 14C-Al neutron absorber material surface protection film generation methods, it is characterised in that：Step e
Middle deionized water temperature is higher than 80 DEG C, and soaking time is more than 60min.
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| 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 |
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| CN102094132B (en) * | 2010-12-28 | 2012-07-11 | 中国工程物理研究院核物理与化学研究所 | Method for preparing B4C-Al composite material |
| CN103668382B (en) * | 2012-09-05 | 2016-08-03 | 安徽应流久源核能新材料科技有限公司 | B4C-Al composite material surface processing method |
| CN104264201A (en) * | 2014-09-26 | 2015-01-07 | 清华大学深圳研究生院 | Method for preparing B4C/Al composite material corrosion-resistance film and neutron absorption material |
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