CN109811385A - Aluminium and aluminum alloy surface polyvinylidene fluoride/aluminum oxide composite membrane and preparation method thereof - Google Patents
Aluminium and aluminum alloy surface polyvinylidene fluoride/aluminum oxide composite membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of aluminium and aluminum alloy surface polyvinylidene fluoride/aluminum oxide composite membrane and preparation method thereof, introduce zirconates in the solution using differential arc oxidation, zirconium oxide is generated in ceramic membrane；It is introduced into Kynoar and generates polyvinylidene fluoride coating in ceramic membrane, to close the micropore in ceramic coating formed by micro-arc oxidation, change the section and surface tension/infiltration angle of ceramic membrane and corrosive medium, improve the performances such as the alkaline-resisting and acid corrosion-resistant of coating, resulting aluminium and the resistance to neutrality NaCl salt air corrosion of aluminum alloy surface polyvinylidene fluoride/aluminum oxide composite membrane are up to 500h or more, microhardness is up to 950Hv, pressure-resistant 1000V, insulation resistance is up to 495M Ω, alkali drips etching time and reaches 227s or more, to the material of aluminum or aluminum alloy, shape and size etc. are without particular/special requirement, with wide applicability.
Description
Technical field
The present invention relates to technical field of metal material surface treatment, and in particular to a kind of aluminium and aluminum alloy surface polyvinylidene fluoride
Alkene/alumina composite film and preparation method thereof.
Background technique
Aluminium alloy is in modern industry alloy with one of widest alloy.It is a certain amount of by being added in aluminum substrate
Copper, silicon, aluminium, zinc, the elements such as manganese and a small amount of nickel, iron, titanium, chromium, lithium make aluminium alloy keep fine aluminium light weight etc. excellent
While point, moreover it is possible to which there is relatively high intensity.Make its " specific strength " to surpass many steel alloys in this way, becomes ideal structure
Material is widely used in Aeronautics and Astronautics, automobile, machine-building, ship and chemical industry etc., such as fuselage, the illiteracy of aircraft
Skin, compressor etc. are often manufactured with aluminium alloy, to mitigate self weight.The welding of steel plate materials is replaced using aluminium alloy, construction weight can
Mitigate 50% or more.Since aluminium alloy density is low, but intensity is relatively high, and near or above high-quality steel, plasticity is good, can be processed into each
Kind profile；Meanwhile having many advantages, such as excellent electric conductivity, thermal conductivity and rotproofness.
Micro-arc oxidation process is a kind of non-ferrous metal developed in recent years (such as aluminium, aluminium, titanium) process of surface treatment,
Especially since nineteen nineties, which has become the research hotspot of domestic academic, and is gradually produced
The approval of industry.Especially micro-arc oxidation of aluminum alloy surface handle, due to the higher hardness of micro-arc oxidation ceramic layer, anti scuffing and
The abilities such as anticorrosive, make the technology be widely used in the surface treatment of alloy product.
When at present to aluminum alloy differential arc oxidation, silicate, phosphate and meta-aluminate solution system, the pottery of preparation are mostly used
Porcelain film hardness, in terms of significantly improved；However, the ceramic membrane in aluminum alloy surface preparation is both sexes oxidation
Object, neither acid corrosion-resistant nor alkali corrosion resistance.
Summary of the invention
Aiming at the problems existing in the prior art, the purpose of the present invention is to provide a kind of aluminium and aluminum alloy surface to gather inclined fluorine
Ethylene/alumina composite film and preparation method thereof, introduces zirconates using differential arc oxidation in the solution, and oxidation is generated in ceramic membrane
Zirconium；It is introduced into Kynoar and generates polyvinylidene fluoride coating in ceramic membrane, so that the micropore in ceramic coating formed by micro-arc oxidation is closed,
The section and surface tension/infiltration angle for changing ceramic membrane and corrosive medium, improve the performances such as the alkaline-resisting and acid corrosion-resistant of coating,
Resulting aluminium and the resistance to neutrality NaCl salt air corrosion of aluminum alloy surface polyvinylidene fluoride/aluminum oxide composite membrane are up to 500h or more, show
Microhardness is up to 950Hv, pressure-resistant 1000V, and insulation resistance is up to 495M Ω, and alkali drips etching time and reaches 227s or more.
In order to achieve the above object, the present invention is achieved by the following scheme.
(1) a kind of aluminium and aluminum alloy surface polyvinylidene fluoride/aluminum oxide composite membrane, including following raw material: Kynoar
Solution, ammonium fluozirconate, sodium dihydrogen phosphate, calgon, borax and water.
Preferably, the solvent of the Kynoar solution is dimethyl sulfoxide.
Preferably, the dosage of the raw material are as follows: 100-250 parts of Kynoar solution, 5-50 parts of ammonium fluozirconate, di(2-ethylhexyl)phosphate
20-30 parts of hydrogen sodium, 14-20 parts of calgon and 15-25 parts of borax.
Preferably, the volume ratio of the Kynoar solution and water are as follows: (0.1-0.25): 1.
Preferably, the concentration of Kynoar is 10-50g/L in the Kynoar solution.
(2) preparation method of a kind of aluminium and aluminum alloy surface polyvinylidene fluoride/aluminum oxide composite membrane, comprising the following steps:
Step 1, Kynoar is dissolved in dimethyl sulfoxide, obtains Kynoar solution；
Step 2, ammonium fluozirconate, Kynoar solution, sodium dihydrogen phosphate, calgon and borax are added to the water,
It stirs evenly, adjusts pH value to 6~7, obtain zirconates system solution；
Step 3, ultrasonic disperse is carried out to the zirconates system solution, differential arc oxidation, obtains aluminium and aluminum alloy surface gathers inclined fluorine
Ethylene/alumina composite film.
Preferably, in step 2, the adjusting pH value is adjusted using sodium citrate.
Preferably, in step 3, the frequency of the ultrasonic disperse is 40KHZ, and the temperature of ultrasonic disperse is 15~25 DEG C, is surpassed
The time of sound dispersion is 30min.
Preferably, in step 3, the method for the differential arc oxidation are as follows: zirconates system solution is placed in micro-arc oxidation treatment slot
It is middle to be used as micro-arc oxidation electrolyte, aluminum or aluminum alloy is placed in micro-arc oxidation electrolyte as anode, stainless steel plate is placed in
It is used as cathode in micro-arc oxidation electrolyte, is 100~2000Hz, duty ratio in pulse frequency using the differential arc oxidation pulse power
Differential arc oxidation is carried out under conditions of being 5~50%.
It is further preferred that the pulse frequency of the differential arc oxidation is 500~700Hz, and differential arc oxidation accounts in step 3
Sky is than being 15~30%.
Preferably, in step 3, the temperature of the differential arc oxidation is 10~50 DEG C, the time of differential arc oxidation is 15~
65min。
It is further preferred that in step 3, by first differential arc oxidation under conditions of voltage is 50~250V of aluminum or aluminum alloy
5min continues differential arc oxidation 10min~60min after voltage is then risen to 300~450V.
Compared with prior art, the invention has the benefit that
1) in the preparation method of the resulting aluminium of the present invention and aluminum alloy surface polyvinylidene fluoride/aluminum oxide composite membrane, pass through
Add zirconium ion in micro-arc oxidation electrolyte, and micro-arc oxidation process optimized, by Kynoar organic matter with
Differential arc oxidation combines, to grow polyvinylidene fluoride/aluminum oxide (Al in aluminum or aluminum alloy surface in situ2O3) composite ceramic film,
Make full use of ZrO2Excellent corrosion resistance, the sealing of hole effect of Kynoar, improves the corrosion resistance of ceramic membrane.Resulting aluminium and
The resistance to neutrality NaCl salt air corrosion of aluminum alloy surface polyvinylidene fluoride/aluminum oxide composite membrane is up to 500h or more, and microhardness is up to
950Hv or more, pressure-resistant 1000V, insulation resistance are up to 495M Ω, and alkali drips etching time and reaches 227s.
And use the aluminium and aluminum alloy surface of the preparations such as traditional microarc oxidation solution such as silicate, aluminate, phosphate
The resistance to neutrality NaCl salt air corrosion time of ceramic membrane is less than 300h, and alkali drips etching time and is less than 30s, thus pressure-resistant 500V illustrates
Kynoar/Al after micro-arc oxidation treatment of the present invention2O3The excellent effect of composite membrane.
(2) present invention can obtain smooth and fine and close Kynoar/Al on aluminum or aluminum alloy surface2O3Composite ceramics
Film.When within 30 μm, the surface roughness (Ra) of ceramic membrane not will increase the ceramics film thickness under normal conditions less than 1 μm
The surface roughness of aluminum or aluminum alloy workpiece；Show the average diameter of the ceramic membrane surface micropore less than 2 through microscopic examination
μm, and micro-pore diameter reduces with the increase of ceramic film thickness, ceramic membrane growth has self-enclosed trend.
And the table for the aluminium and aluminum alloy surface ceramic film for using traditional microarc oxidation solution and micro-arc oxidation process to prepare
Surface roughness and micro-pore diameter increase with the increase of ceramic film thickness.
(3) zirconates system solution used in the present invention, continuous use service life are up to 6 months or more；And the system is molten
Generate the metal ion seriously polluted, in addition long service life, therefore the system solution in liquid to environment without containing high valence chrome etc.
Has the advantages that long stable effect, environmentally protective.
(4) present invention to material, shape and size of aluminum or aluminum alloy etc. without particular/special requirement, it is all to be immersed in zirconates
Aluminum or aluminum alloy in system solution can obtain uniform and fine and close ceramics after micro-arc oxidation treatment of the present invention on surface
Film, therefore the present invention has wide applicability.
Detailed description of the invention
The present invention is described in further details in the following with reference to the drawings and specific embodiments.
Fig. 1 is the outside drawing of the aluminium alloy of embodiment 1；Wherein, figure (a) is the appearance of the aluminium alloy before micro-arc oxidation treatment
Figure；Figure (b) is the outside drawing of aluminium alloy after being not added with Kynoar solution micro-arc oxidation treatment；Scheming (c) is at differential arc oxidation
The outside drawing of aluminium alloy after reason；
Fig. 2 is the infiltration angle figure of 1 aluminium alloy of embodiment；Wherein, figure (a) is the infiltration of the aluminium alloy before micro-arc oxidation treatment
Angle figure；Figure (b) is the infiltration angle figure of aluminium alloy after being not added with Kynoar solution micro-arc oxidation treatment；Scheming (c) is differential of the arc oxygen
The infiltration angle figure of aluminium alloy after change processing；
Fig. 3 is the preceding figure of alkali drop corrosion of 1 aluminium alloy of embodiment；Wherein, figure (a) is the aluminium alloy before micro-arc oxidation treatment
Figure before alkali drop corrosion；Figure (b) is the preceding figure of alkali drop corrosion of aluminium alloy after being not added with Kynoar solution micro-arc oxidation treatment；Figure
It (c) is figure before the alkali drop corrosion of aluminium alloy after micro-arc oxidation treatment；
Fig. 4 is to scheme after the alkali drop of 1 aluminium alloy of embodiment is corroded；Wherein, figure (a) is the aluminium alloy before micro-arc oxidation treatment
Scheme after alkali drop corrosion；Figure (b) is to scheme after the alkali drop of aluminium alloy after being not added with Kynoar solution micro-arc oxidation treatment is corroded；Figure
(c) the alkali drop for aluminium alloy after micro-arc oxidation treatment is schemed after corroding；
Fig. 5 is that the section SEM of 1 aluminium alloy of embodiment schemes, and amplification factor is 1000 times；Wherein, figure (a) is at differential arc oxidation
Manage the section SEM figure of the polyvinylidene fluoride/aluminum oxide composite membrane generated；Figure (b) is to be not added with Kynoar solution differential of the arc oxygen
Change the section SEM figure for the ceramic membrane that processing generates；
Fig. 6 is that the surface SEM of 1 aluminium alloy of embodiment schemes, and amplification factor is 500 times；Wherein, figure (a) is aluminum alloy differential arc
The surface SEM figure for the polyvinylidene fluoride/aluminum oxide composite ceramic film that oxidation processes generate, figure (b) are to be not added with Kynoar
The surface SEM figure for the ceramic membrane that solution micro-arc oxidation treatment generates；
Fig. 7 is that the surface SEM of 1 aluminium alloy of embodiment schemes, and amplification factor is 1000 times and 1500 times；Scheming (a) is differential of the arc oxygen
Change the surface SEM figure for the polyvinylidene fluoride/aluminum oxide composite membrane that processing generates；Figure (b) is micro- to be not added with Kynoar solution
The surface SEM figure for the ceramic membrane that arc oxidation processes generate；
Fig. 8 is that the line of 1 aluminium alloy of embodiment scans EDS spectrogram；Wherein, figure (a) is aluminium alloy table after micro-arc oxidation treatment
The line of face polyvinylidene fluoride/aluminum oxide composite membrane scans EDS spectrogram；Figure (b) is to be not added with Kynoar solution differential arc oxidation
The ceramic membrane line that processing generates scans EDS spectrogram；
Fig. 9 is aluminum alloy surface polyvinylidene fluoride/aluminum oxide composite membrane after the processing of 1 aluminum alloy differential arc oxidation of embodiment
XRD spectra.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
It will be appreciated that the following example is merely to illustrate the present invention, and it is not construed as limiting the scope of the invention.
Embodiment 1
A kind of preparation method of aluminium and aluminum alloy surface polyvinylidene fluoride/aluminum oxide composite membrane, comprising the following steps:
Step 1, Kynoar is dissolved in dimethyl sulfoxide, obtaining concentration is 50g/L Kynoar solution.
Step 2, deionization is added in ammonium fluozirconate, Kynoar solution, sodium dihydrogen phosphate, calgon and borax
It in water, stirs evenly, sodium citrate is added and adjusts pH value to 6~7, obtains zirconates system solution；Wherein, fluorine in zirconates system solution
The concentration of zirconic acid ammonium is 25g/L, and the concentration of sodium dihydrogen phosphate is 20g/L, and the concentration of calgon is 14g/L, borax it is dense
Degree is 15g/L, and the concentration of Kynoar solution is 100mL/L.
Step 3, zirconates system solution is placed in ultrasonic dispersing machine under the conditions of frequency is 40KHZ, temperature is 25 DEG C
Ultrasonic disperse 30min is subsequently placed in micro-arc oxidation treatment slot as micro-arc oxidation electrolyte, 2A12 aluminium alloy plate is placed in micro-
It is used as anode in arc oxidation electrolyte, stainless steel plate is placed in micro-arc oxidation electrolyte as cathode, differential of the arc oxygen is then used
Change the pulse power, is 600Hz in pulse frequency, duty ratio 15%, temperature carries out aluminium alloy plate under conditions of being 30 DEG C micro-
Arc oxidation processes, and first voltage be 200V under conditions of differential arc oxidation 5min, then voltage is risen to after 450V continue it is micro-
Arc aoxidizes 30min, obtains polyvinylidene fluoride/aluminum oxide (Al on aluminium alloy plate surface2O3) composite membrane.
Embodiment 2
A kind of preparation method of aluminium and aluminum alloy surface polyvinylidene fluoride/aluminum oxide composite membrane, comprising the following steps:
Step 1, Kynoar is dissolved in dimethyl sulfoxide, obtaining concentration is 40g/L Kynoar solution.
Step 2, deionization is added in ammonium fluozirconate, Kynoar solution, sodium dihydrogen phosphate, calgon and borax
It in water, stirs evenly, sodium citrate is added and adjusts pH value to 6~7, obtains zirconates system solution；Wherein, fluorine in zirconates system solution
The concentration of zirconic acid ammonium is 25g/L, and the concentration of sodium dihydrogen phosphate is 20g/L, and the concentration of calgon is 14g/L, borax it is dense
Degree is 15g/L, and the concentration of Kynoar solution is 100mL/L.
Step 3, zirconates system solution is placed in ultrasonic dispersing machine under the conditions of frequency is 40KHZ, temperature is 20 DEG C
Ultrasonic disperse 30min is subsequently placed in micro-arc oxidation treatment slot as micro-arc oxidation electrolyte, 2A12 aluminium alloy plate is placed in micro-
It is used as anode in arc oxidation electrolyte, stainless steel plate is placed in micro-arc oxidation electrolyte as cathode, differential of the arc oxygen is then used
Change the pulse power, is 600Hz in pulse frequency, duty ratio 15%, temperature carries out aluminium alloy plate under conditions of being 30 DEG C micro-
Arc oxidation processes, and first voltage be 200V under conditions of differential arc oxidation 5min, then voltage is risen to after 450V continue it is micro-
Arc aoxidizes 30min, obtains polyvinylidene fluoride/aluminum oxide (Al on aluminium alloy plate surface2O3) composite membrane.
Embodiment 3
A kind of preparation method of aluminium and aluminum alloy surface polyvinylidene fluoride/aluminum oxide composite membrane, comprising the following steps:
Step 1, Kynoar is dissolved in dimethyl sulfoxide, obtaining concentration is 30g/L Kynoar solution.
Step 2, deionization is added in ammonium fluozirconate, Kynoar solution, sodium dihydrogen phosphate, calgon and borax
It in water, stirs evenly, sodium citrate is added and adjusts pH value to 6~7, obtains zirconates system solution；Wherein, fluorine in zirconates system solution
The concentration of zirconic acid ammonium is 25g/L, and the concentration of sodium dihydrogen phosphate is 30g/L, and the concentration of calgon is 14g/L, borax it is dense
Degree is 19g/L, and the concentration of Kynoar solution is 100mL/L.
Step 3, zirconates system solution is placed in ultrasonic dispersing machine under the conditions of frequency is 40KHZ, temperature is 20 DEG C
Ultrasonic disperse 30min is subsequently placed in micro-arc oxidation treatment slot as micro-arc oxidation electrolyte, 2A12 aluminium alloy plate is placed in micro-
It is used as anode in arc oxidation electrolyte, stainless steel plate is placed in micro-arc oxidation electrolyte as cathode, differential of the arc oxygen is then used
Change the pulse power, is 600Hz in pulse frequency, duty ratio 15%, temperature carries out aluminium alloy plate under conditions of being 30 DEG C micro-
Arc oxidation processes, and first voltage be 200V under conditions of differential arc oxidation 5min, then voltage is risen to after 450V continue it is micro-
Arc aoxidizes 30min, obtains polyvinylidene fluoride/aluminum oxide (Al on aluminium alloy plate surface2O3) composite membrane.
Embodiment 4
A kind of preparation method of aluminium and aluminum alloy surface polyvinylidene fluoride/aluminum oxide composite membrane, comprising the following steps:
Step 1, Kynoar is dissolved in dimethyl sulfoxide, obtaining concentration is 20g/L Kynoar solution.
Step 2, deionization is added in ammonium fluozirconate, Kynoar solution, sodium dihydrogen phosphate, calgon and borax
It in water, stirs evenly, sodium citrate is added and adjusts pH value to 6~7, obtains zirconates system solution；Wherein, fluorine in zirconates system solution
The concentration of zirconic acid ammonium is 25g/L, and the concentration of sodium dihydrogen phosphate is 30g/L, and the concentration of calgon is 14g/L, borax it is dense
Degree is 19g/L, and the concentration of Kynoar solution is 100mL/L.
Step 3, zirconates system solution is placed in ultrasonic dispersing machine under the conditions of frequency is 40KHZ, temperature is 25 DEG C
Ultrasonic disperse 30min is subsequently placed in micro-arc oxidation treatment slot as micro-arc oxidation electrolyte, 2A12 aluminium alloy plate is placed in micro-
It is used as anode in arc oxidation electrolyte, stainless steel plate is placed in micro-arc oxidation electrolyte as cathode, differential of the arc oxygen is then used
Change the pulse power, is 600Hz in pulse frequency, duty ratio 15%, temperature carries out aluminium alloy plate under conditions of being 30 DEG C micro-
Arc oxidation processes, and first voltage be 200V under conditions of differential arc oxidation 5min, then voltage is risen to after 450V continue it is micro-
Arc aoxidizes 30min, obtains polyvinylidene fluoride/aluminum oxide (Al on aluminium alloy plate surface2O3) composite membrane.
Embodiment 5
A kind of preparation method of aluminium and aluminum alloy surface polyvinylidene fluoride/aluminum oxide composite membrane, comprising the following steps:
Step 1, Kynoar is dissolved in dimethyl sulfoxide, obtaining concentration is 20g/L Kynoar solution.
Step 2, deionization is added in ammonium fluozirconate, Kynoar solution, sodium dihydrogen phosphate, calgon and borax
It in water, stirs evenly, sodium citrate is added and adjusts pH value to 6~7, obtains zirconates system solution；Wherein, fluorine in zirconates system solution
The concentration of zirconic acid ammonium is 25g/L, and the concentration of sodium dihydrogen phosphate is 30g/L, and the concentration of calgon is 14g/L, borax it is dense
Degree is 19g/L, and the concentration of Kynoar solution is 150mL/L.
Step 3, zirconates system solution is placed in ultrasonic dispersing machine under the conditions of frequency is 40KHZ, temperature is 20 DEG C
Ultrasonic disperse 30min is subsequently placed in micro-arc oxidation treatment slot as micro-arc oxidation electrolyte, 2A12 aluminium alloy plate is placed in micro-
It is used as anode in arc oxidation electrolyte, stainless steel plate is placed in micro-arc oxidation electrolyte as cathode, differential of the arc oxygen is then used
Change the pulse power, pulse frequency be 100Hz, duty ratio 5%, temperature be 30 DEG C under conditions of to aluminium alloy plate carry out the differential of the arc
Oxidation processes, and first differential arc oxidation 5min under conditions of voltage is 200V, continue the differential of the arc after voltage is then risen to 450V
30min is aoxidized, obtains polyvinylidene fluoride/aluminum oxide (Al on aluminium alloy plate surface2O3) composite membrane.
Embodiment 6
A kind of preparation method of aluminium and aluminum alloy surface polyvinylidene fluoride/aluminum oxide composite membrane, comprising the following steps:
Step 1, Kynoar is dissolved in dimethyl sulfoxide, obtaining concentration is 20g/L Kynoar solution.
Step 2, deionization is added in ammonium fluozirconate, Kynoar solution, sodium dihydrogen phosphate, calgon and borax
It in water, stirs evenly, sodium citrate is added and adjusts pH value to 6~7, obtains zirconates system solution；Wherein, fluorine in zirconates system solution
The concentration of zirconic acid ammonium is 25g/L, and the concentration of sodium dihydrogen phosphate is 20g/L, and the concentration of calgon is 14g/L, borax it is dense
Degree is 15g/L, and the concentration of Kynoar solution is 200mL/L.
Step 3, zirconates system solution is placed in ultrasonic dispersing machine under the conditions of frequency is 40KHZ, temperature is 25 DEG C
Ultrasonic disperse 30min is subsequently placed in micro-arc oxidation treatment slot as micro-arc oxidation electrolyte, 2A12 aluminium alloy plate is placed in micro-
It is used as anode in arc oxidation electrolyte, stainless steel plate is placed in micro-arc oxidation electrolyte as cathode, differential of the arc oxygen is then used
Change the pulse power, is 2000Hz in pulse frequency, duty ratio 50%, temperature carries out aluminium alloy plate under conditions of being 50 DEG C micro-
Arc oxidation processes, and first differential arc oxidation 5min under conditions of voltage is 50V, continue the differential of the arc after voltage is then risen to 400V
30min is aoxidized, obtains polyvinylidene fluoride/aluminum oxide (Al on aluminium alloy plate surface2O3) composite membrane.
Embodiment 7
A kind of preparation method of aluminium and aluminum alloy surface polyvinylidene fluoride/aluminum oxide composite membrane, comprising the following steps:
Step 1, Kynoar is dissolved in dimethyl sulfoxide, obtaining concentration is 40g/L Kynoar solution.
Step 2, deionization is added in ammonium fluozirconate, Kynoar solution, sodium dihydrogen phosphate, calgon and borax
It in water, stirs evenly, sodium citrate is added and adjusts pH value to 6~7, obtains zirconates system solution；Wherein, fluorine in zirconates system solution
The concentration of zirconic acid ammonium is 5g/L, and the concentration of sodium dihydrogen phosphate is 20g/L, and the concentration of calgon is 18g/L, the concentration of borax
For 25g/L, the concentration of Kynoar solution is 250mL/L.
Step 3, zirconates system solution is placed in ultrasonic dispersing machine under the conditions of frequency is 40KHZ, temperature is 25 DEG C
Ultrasonic disperse 30min is subsequently placed in micro-arc oxidation treatment slot as micro-arc oxidation electrolyte, 2A12 aluminium alloy plate is placed in micro-
It is used as anode in arc oxidation electrolyte, stainless steel plate is placed in micro-arc oxidation electrolyte as cathode, differential of the arc oxygen is then used
Change the pulse power, is 500Hz in pulse frequency, duty ratio 25%, temperature carries out aluminium alloy plate under conditions of being 50 DEG C micro-
Arc oxidation processes, and first voltage be 150V under conditions of differential arc oxidation 5min, then voltage is risen to after 300V continue it is micro-
Arc aoxidizes 10min, obtains polyvinylidene fluoride/aluminum oxide (Al on aluminium alloy plate surface2O3) composite membrane.
Embodiment 8
A kind of preparation method of aluminium and aluminum alloy surface polyvinylidene fluoride/aluminum oxide composite membrane, comprising the following steps:
Step 1, Kynoar is dissolved in dimethyl sulfoxide, obtaining concentration is 30g/L Kynoar solution.
Step 2, deionization is added in ammonium fluozirconate, Kynoar solution, sodium dihydrogen phosphate, calgon and borax
It in water, stirs evenly, sodium citrate is added and adjusts pH value to 6~7, obtains zirconates system solution；Wherein, fluorine in zirconates system solution
The concentration of zirconic acid ammonium is 50g/L, and the concentration of sodium dihydrogen phosphate is 25g/L, and the concentration of calgon is 20g/L, borax it is dense
Degree is 20g/L, and the concentration of Kynoar solution is 250mL/L.
Step 3, zirconates system solution is placed in ultrasonic dispersing machine under the conditions of frequency is 40KHZ, temperature is 25 DEG C
Ultrasonic disperse 30min is subsequently placed in micro-arc oxidation treatment slot as micro-arc oxidation electrolyte, 2A12 aluminium alloy plate is placed in micro-
It is used as anode in arc oxidation electrolyte, stainless steel plate is placed in micro-arc oxidation electrolyte as cathode, differential of the arc oxygen is then used
Change the pulse power, is 700Hz in pulse frequency, duty ratio 30%, temperature carries out aluminium alloy plate under conditions of being 10 DEG C micro-
Arc oxidation processes, and first voltage be 250V under conditions of differential arc oxidation 5min, then voltage is risen to after 450V continue it is micro-
Arc aoxidizes 60min, obtains polyvinylidene fluoride/aluminum oxide (Al on aluminium alloy plate surface2O3) composite membrane.
Table 1 is insulation resistance of the various sample under different voltages before and after the processing of embodiment 1.Measurement insulation resistance herein
When, piece test clamp of megameter (position for choosing No oxided film) another p-wire and sample on the riveting aluminium wire of sample
The oxidation film on surface is in close contact, and contact area is about 50mm2, test under dry environment of the air humidity less than 20% into
Row.Two voltage gears of 500V and 1000V are chosen, branch tests the insulation resistance of oxidation film, and test result is shown in Table 1.It can by table 1
Know, the pressure resistance of aluminium alloy and insulation resistance significantly improve after 1 micro-arc oxidation treatment of embodiment.
Insulation resistance/M Ω of 1 various sample of table under different voltages
Table 2 be embodiment 1 before and after the processing various sample alkali drip etching time.?DEG C, will about 10mg,
The NaOH solution of 100g/L drops to the surface of sample, visually observes at drop when generation corrosion bubble, the eating thrown of oxidation film
Between be oxidation film corrosion resistance, test result is shown in Table 2.As shown in Table 2, when treated the aluminium alloy alkali corrosion resistance of embodiment 1
Between significantly improve, thus illustrate Kynoar/Al that aluminum alloy surface generates after micro-arc oxidation treatment of the present invention2O3Composite ceramic
The alkali corrosion resistance of porcelain film is had excellent performance.
The alkali of 2 various sample of table drips etching time
Table 3 is the infiltration angle of embodiment 1 various sample and water before and after the processing.As shown in Table 3, at 3 differential arc oxidation of embodiment
The infiltration angle of aluminium alloy is greater than the aluminium alloy for being not added with Kynoar solution micro-arc oxidation treatment after reason, and poly- due to being not added with
The film layer of vinylidene solution micro-arc oxidation treatment is porous structure, thus illustrates aluminium alloy after micro-arc oxidation treatment of the present invention
Kynoar/Al of Surface Creation2O3The hole closing of composite ceramic film is preferable.
The infiltration angle of 3 various sample of table
Table 4 is the microhardness of the various sample before and after the processing of embodiment 1.Micro-hardness measurement is measured using microhardness testers
After 2A12 aluminium alloy and different condition differential arc oxidation gained film layer microhardness, added load be 100gf, protect the lotus time be
15s randomly selects 3 points in specimen surface and measures and be averaged, and the calculating of microhardness (HV) value is by measuring impression
Two cornerwise length, directly input, and equipment is directly calculated and exported according to the following formula (1).
F in formula --- the applied load of test, units Newtons (N)
D --- the arithmetic mean of instantaneous value of two impression catercorner lengths d1 and d2, unit millimeter (mm), test result is shown in Table 4.
As shown in Table 4, the microhardness of aluminium alloy significantly improves after 1 micro-arc oxidation treatment of embodiment.
Microhardness/HV of 4 various sample of table
In the above table 1-4, matrix is the sample before micro-arc oxidation treatment, and differential arc oxidation is to be not added with Kynoar solution
Sample after micro-arc oxidation treatment, differential arc oxidation compound film layer are polyvinylidene fluoride/aluminum oxide after 1 micro-arc oxidation treatment of embodiment
Composite membrane sample.
Fig. 1 be 1 micro-arc oxidation treatment of embodiment before, be not added with after Kynoar solution micro-arc oxidation treatment and this implementation
The outside drawing of aluminium alloy after example micro-arc oxidation treatment.As shown in Figure 1, any surface finish of aluminium alloy and have before micro-arc oxidation treatment
Metallic luster；Be not added with after Kynoar solution micro-arc oxidation treatment and the present embodiment micro-arc oxidation treatment after aluminum alloy surface
Gloss disappear, the uniform color of aluminum alloy surface composite membrane is consistent.
Fig. 2 be 1 micro-arc oxidation treatment of embodiment before, be not added with after Kynoar solution micro-arc oxidation treatment and this implementation
The infiltration angle figure of aluminium alloy after example micro-arc oxidation treatment.
Fig. 3 be 1 micro-arc oxidation treatment of embodiment before, be not added with after Kynoar solution micro-arc oxidation treatment and this implementation
Figure before the alkali drop corrosion of aluminium alloy after example micro-arc oxidation treatment.
Fig. 4 be 1 micro-arc oxidation treatment of embodiment before, be not added with after Kynoar solution micro-arc oxidation treatment and this implementation
Scheme after the alkali drop corrosion of aluminium alloy after example micro-arc oxidation treatment.
Fig. 5 be 1 aluminum alloy differential arc oxidation of embodiment processing generate polyvinylidene fluoride/aluminum oxide composite membrane section with not
The section SEM figure for the ceramic membrane that Kynoar solution micro-arc oxidation treatment generates is added, amplification factor is 1000 times.By Fig. 5
It is found that the surface of aluminium alloy and being not added with aluminium after Kynoar solution micro-arc oxidation treatment after the present embodiment micro-arc oxidation treatment
Kynoar/Al that Surface Creation a layer thickness of alloy is about 20um2O3Composite ceramic film.The composite ceramic film and aluminium close
The interface cohesion of auri body is close, no significant defect, interface shape be it is wavy, be firmly incorporated in one in indenting state
It rises, thus illustrates Kynoar/Al of aluminum alloy surface generation after micro-arc oxidation treatment of the invention2O3Composite membrane and aluminium close
The binding performance of auri body is excellent.
Fig. 6 is the section for the composite ceramic film that the processing of 1 aluminum alloy differential arc oxidation of embodiment generates and is not added with polyvinylidene fluoride
The surface SEM figure for the ceramic membrane that alkene solution micro-arc oxidation treatment generates, amplification factor are 500 times.It will be appreciated from fig. 6 that being not added with poly-
One layer of the Surface Creation of the aluminium alloy ceramic membrane with micropore after vinylidene solution micro-arc oxidation treatment, and micropore size compared with
Small, average pore size is less than 2 μm.And the ceramic membrane micropore of the Surface Creation of aluminium alloy quilt mostly after the present embodiment micro-arc oxidation treatment
Kynoar solution blocks.
Fig. 7 be 1 aluminum alloy differential arc oxidation of embodiment processing generate polyvinylidene fluoride/aluminum oxide composite membrane section with not
The surface SEM figure for the ceramic membrane that Kynoar solution micro-arc oxidation treatment generates is added, amplification factor is 1000 times and 1500
Times.As shown in Figure 7, one layer of Surface Creation of aluminium alloy after Kynoar solution micro-arc oxidation treatment is not added with micropore
Ceramic membrane, and micropore size is smaller, average pore size is less than 2 μm.And the surface of aluminium alloy is raw after the present embodiment micro-arc oxidation treatment
At ceramic membrane micropore blocked mostly by Kynoar solution.
Fig. 8 be 1 micro-arc oxidation treatment of embodiment after aluminum alloy surface polyvinylidene fluoride/aluminum oxide composite membrane be not added with it is poly-
The line in the section for the ceramic membrane that vinylidene solution micro-arc oxidation treatment generates scans EDS spectrogram.As shown in Figure 8, the present embodiment
Kynoar/Al that aluminum alloy surface generates after micro-arc oxidation treatment2O3Composite ceramic film is mainly by Zr, O, F, P and Al element
Composition, due to being free of Al element in micro-arc oxidation electrolyte, the Al element in the composite ceramic film should come from aluminium alloy
Matrix.Conversely, because alloy matrix aluminum is free of Zr element, therefore the Zr element in the composite ceramic film should come from zirconates system
Solution.It is indicated above in micro-arc oxidation electrolyte and adds zirconates, may be implemented to obtain in aluminium and aluminum alloy surface containing Zr member
The ceramic membrane of element.And it is not added with not tight F element in the ceramic membrane of Kynoar solution micro-arc oxidation treatment generation, therefore F element
It from Kynoar solution, is indicated above in differential arc oxidation and adds Kynoar solution, may be implemented in aluminium and aluminium
Alloy surface arrives the composite ceramic film containing Kynoar.
Fig. 9 is the XRD spectra of aluminum alloy surface polyvinylidene fluoride/aluminum oxide composite membrane after 1 micro-arc oxidation treatment of embodiment.
Although the present invention is described in detail with a general description of the specific embodiments in this specification,
But on the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.
Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed model
It encloses.
Claims (10)
1. a kind of aluminium and aluminum alloy surface polyvinylidene fluoride/aluminum oxide composite membrane, which is characterized in that including following raw material: poly- inclined
Vinyl fluoride solution, ammonium fluozirconate, sodium dihydrogen phosphate, calgon, borax and water.
2. aluminium according to claim 1 and aluminum alloy surface polyvinylidene fluoride/aluminum oxide composite membrane, which is characterized in that institute
The solvent for stating Kynoar solution is dimethyl sulfoxide.
3. aluminium according to claim 1 and aluminum alloy surface polyvinylidene fluoride/aluminum oxide composite membrane, which is characterized in that institute
State the dosage of raw material are as follows: 100-250 parts of Kynoar solution, 5-50 parts of ammonium fluozirconate, 20-30 parts of sodium dihydrogen phosphate, six are partially
14-20 parts and borax 15-25 parts of sodium phosphate.
4. aluminium according to claim 1 and aluminum alloy surface polyvinylidene fluoride/aluminum oxide composite membrane, which is characterized in that institute
The volume ratio for stating Kynoar solution and water is (0.1-0.25): 1.
5. aluminium according to claim 2 and aluminum alloy surface polyvinylidene fluoride/aluminum oxide composite membrane, which is characterized in that institute
The concentration for stating Kynoar in Kynoar solution is 10-50g/L.
6. the preparation method of a kind of aluminium and aluminum alloy surface polyvinylidene fluoride/aluminum oxide composite membrane, which is characterized in that including following
Step:
Step 1, Kynoar is dissolved in dimethyl sulfoxide, obtains Kynoar solution；
Step 2, ammonium fluozirconate, Kynoar solution, sodium dihydrogen phosphate, calgon and borax are added to the water, are stirred
Uniformly, pH value is adjusted to 6~7, obtains zirconates system solution；
Step 3, ultrasonic disperse carried out to the zirconates system solution, differential arc oxidation, obtain aluminium and aluminum alloy surface Kynoar/
Alumina composite film.
7. the preparation method of aluminium according to claim 6 and aluminum alloy surface polyvinylidene fluoride/aluminum oxide composite membrane, special
Sign is, in step 2, the adjusting pH value is adjusted using sodium citrate.
8. the preparation method of aluminium according to claim 6 and aluminum alloy surface polyvinylidene fluoride/aluminum oxide composite membrane, special
Sign is, in step 3, the method for the differential arc oxidation are as follows: zirconates system solution is placed in micro-arc oxidation treatment slot as micro-
Aluminum or aluminum alloy is placed in micro-arc oxidation electrolyte as anode, stainless steel plate is placed in differential arc oxidation by arc oxidation electrolyte
It is used as cathode in electrolyte, is 100~2000Hz in pulse frequency, duty ratio is 5~50% using the differential arc oxidation pulse power
Under conditions of carry out differential arc oxidation.
9. the preparation method of aluminium according to claim 8 and aluminum alloy surface polyvinylidene fluoride/aluminum oxide composite membrane, special
Sign is, in step 3, the temperature of the differential arc oxidation is 10~50 DEG C, and the time of differential arc oxidation is 15~65min.
10. the preparation method of aluminium according to claim 9 and aluminum alloy surface polyvinylidene fluoride/aluminum oxide composite membrane,
It is characterized in that, it, then will be electric by first differential arc oxidation 5min under conditions of voltage is 50~250V of aluminum or aluminum alloy in step 3
Pressure continues differential arc oxidation 10min~60min after rising to 300~450V.
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