CN104831327B - Method for coating aluminum alloy by using micro-arc oxidation green film layer - Google Patents
Method for coating aluminum alloy by using micro-arc oxidation green film layer Download PDFInfo
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Abstract
The invention relates to a method for coating aluminum alloy by using a micro-arc oxidation green film layer. The method comprises the following steps of using the 6063 aluminum alloy as a matrix; adding glycerinum and potassium fluoride (KF) in a system in which Na2SiO3-KOH serves as main electrolyte; preparing coloring electrolyte by using NH4VO3 as coloring agents; and preparing a green micro-arc oxidation ceramic film layer. Influences of electrolyte parameters and electric parameters on an organization structure and the performance of the micro-arc oxidation film layer are researched. Phase composition, microstructure and element contents of the film layer are respectively represented through an X-ray diffractometer (XRD), a scanning electron microscope (SEM) and an energy dispersive spectrometer (EDS), the thickness of the micro-arc oxidation ceramic layer and the strength of bonding between the micro-arc oxidation ceramic layer and the matrix are detected by an eddy coating thickness gage and a scratch spectrometer, the electrochemistry corrosion resisting property of the ceramic layer is analyzed by using an electrochemical corrosion method, technological parameters are optimized, and a green micro-arc oxidation film with high performance is prepared.
Description
Technical field
The invention belongs to field of new, the method that more particularly to a kind of aluminum alloy differential arc oxidation green film layer.
Background technology
Aluminium is active metal, and its surface can at once form one layer of loose, porous aluminum oxide film in dry air,
Although the further oxidation of aluminium can be prevented, protective and ornamental effect can not be effectively played.Meanwhile, the electrode of aluminium
Current potential is relatively low, causes it to be easily corroded in malaria, bronsted lowry acids and bases bronsted lowry liquid.So, prepare in aluminium and its aluminum alloy surface
There is color and the film layer of certain barrier propterty to have highly important actual application value to go out one layer.
Aluminium and its new dye technology of alloy surface include：Chemically transformed film technique, electrophoretic techniques, electrostatic powder spraying skill
Art and differential arc oxidization technique etc..Wherein, differential arc oxidation is increasingly deep into daily life as a kind of emerging technology
In, although, the technology is not also very perfect, and is not in high volume put in the middle of production, but has been obtained in some fields
To being widely applied.
But with the increasingly mature and extensive application of micro-arc oxidation of aluminum alloy surface ceramic film technology, to aluminum alloy surface
Micro-Arc Oxidized Ceramic Coating technology proposes ornamental new demand, due to the color of Micro-Arc Oxidized Ceramic Coating it is more single,
And great majority are white and grey, so, the ceramic film for producing different colours is particularly significant.Compared with other dye technologies,
The ceramic film that differential arc oxidation dye technology is generated has color uniform, it is not easy to fade, and quality of colour is good with good delustring
The features such as performance.At present, mainly by studying technological parameter and addition colouring agent, to prepare performance excellent for differential arc oxidation dye technology
Ceramic films different and with different colours, and solve to develop life-span length, can be better than big, the industry such as recycling of electrolyte
A difficult problem.In decoration, the aspect such as material protection and optical instrument has great application prospect and actual differential arc oxidation dye technology
Meaning.
Chinese patent CN1554807A discloses the electrolytic solution that a kind of aluminium alloy castings differential arc oxidation is processed, and the electrolysis is molten
Liquid by weight with cumulative volume ratio, including sodium phosphate 10g/L-20g/L, sodium metasilicate 5g/L-10g/L, potassium hydroxide 1g/L-4g/L,
Sodium molybdate 10g/L-15g/L, and the pH value of electrolytic solution is 8-12.Aluminium alloy castings surface is carried out using the electrolytic solution micro-
Arc oxidation processes, improve the wearability on aluminium alloy castings surface.But the electrolytic solution provided using the invention is entered to aluminium alloy
After row differential arc oxidation, the resistance to soiling of resulting micro-arc oxidation films, scratch resistance and compactness are poor.Chinese patent
CN102797024B discloses a kind of method that aluminum alloy differential arc oxidation blue film layer, and the composition concentration of electrolyte is：Silicic acid
Sodium 5-11g/L, potassium hydroxide 0.5-2.0g/L；Sodium fluoride 0.3-0.6g/L, cobaltous sulfate 0.4-1.1g/L, using the method process
Aluminium alloy afterwards, surface is presented blue, and even compact, but corrosion resistance has much room for improvement.
The content of the invention
It is of the invention based on 6063 aluminium alloys to solve the above problems, in sodium metasilicate-potassium hydroxide (Na2SiO3-KOH)
As glycerine and potassium fluoride (KF) is added in main electrolyte system, with ammonium metavanadate (NH4VO3) it is colouring agent, prepare coloring electrolysis
Liquid, prepares green Micro-Arc Oxidized Ceramic Coating, and the film layer has hardness height, good toughness, porosity low, even film layer, wear-resisting, resistance to
The characteristics of corrosion energy and good insulation preformance.
For achieving the above object, the present invention is adopted the following technical scheme that：
A kind of method that aluminum alloy differential arc oxidation green film layer, including step is as follows：
(1) select aluminium alloy as matrix, prepare electrolyte system, the composition concentration of electrolyte is：Ammonium metavanadate 3-9g/
L, sodium metasilicate 4-12g/L, potassium hydroxide 2-6g/L；Potassium fluoride 0.3-0.6g/L, glycerine 3-6mL/L, pH8-10.
(2) aluminum alloy surface after the cleaning carries out differential arc oxidation process with electrolyte, and electrical quantity is：Forward voltage 400-
450V, negative voltage is 30-80V；Frequency is 300-500Hz；Positive and negative dutycycle is respectively 20-40%, 15-25%；Control temperature
Less than 60 degrees Celsius of degree, process time is 15 minutes.
Preferably, aluminium alloy described in step (1) is 6063 aluminium alloys.
Preferably, the composition concentration of electrolyte is in step (1)：Sodium metasilicate 6-10g/L, potassium hydroxide 2-6g/L；Fluorine
Change potassium 0.5g/L, ammonium metavanadate 5-8/L.
Preferably, the composition concentration of electrolyte is in step (1)：Sodium metasilicate 8g/L, potassium hydroxide 4g/L；Potassium fluoride
0.5g/L, ammonium metavanadate 6g/L.
Preferably, electrical quantity is in step (2)：Positive, negative voltage is respectively 440V, 40V, and frequency is 400Hz；
Positive and negative dutycycle is respectively 30%, 20%.
According to Al-alloy parts prepared by above-mentioned method.
Coloring treatment is carried out to aluminum alloy surface using said method.
The design principle of the present invention：
This test adopts NH4VO3As additive, it is because, on the one hand, according to the difference of its price, it is aoxidized V element
Thing can present different colors；On the other hand, NH4VO3Water is relatively insoluble in, it can be seen from physical chemistry knowledge, the dissolving of solute
Degree is less, and its adsorption capacity is stronger, due to NH4VO3It is relatively weak with the interaction force of electrolyte, in the work of highfield
With under, NH4VO3Easily adsorb on the surface of film layer, be conducive to the carrying out reacted.By analysis contrast different electrolytes composition
(NH4VO3、Na2SiO3And KF) and electrical quantity (positive and negative voltage and positive dutycycle) to the color of green film layer, thickness, phase composition,
Microstructure, with reference to the impact of force intensity and corrosion resisting property etc..
The invention has the beneficial effects as follows：
1. technological process is simple, and early stage process is simple.Using differential arc oxidation dye technology in 6063 alloy matrix aluminum samples
Surface prepares that color is uniform, film quality preferably green film layer, and the certain ornamental requirement of satisfaction is reached.The film layer tool
There are hardness height, good toughness, porosity low, the characteristics of even film layer, wear-resisting, corrosion resisting property and good insulation preformance.
2. in micro-arc oxidation process, the difference of bath composition has different effects to coloring.With NH4VO3Concentration
Raise, the color of film layer is gradually deepened, and the aperture of micropore becomes larger in film layer, and the thickness of film layer linearly increases within the specific limits
Greatly, film layer becomes larger with the adhesion of matrix, and the corrosion resisting property of film layer reduces again after first increasing.With Na2SiO3The liter of concentration
Height, the color of film layer shoals again from light to dark, works as Na2SiO3When concentration is higher, just face is relatively rough for film layer, and the thickness of film layer exists
Linearly increase in certain limit, the adhesion first increases and then decreases of film layer and matrix, the corrosion resisting property of film layer subtracts again after first increasing
It is little.With the rising of KF concentration, the color of film layer shoals again from light to dark, and the thickness of film layer gradually increases within the specific limits,
Film layer is constant after first increasing within the specific limits with the adhesion of matrix, and the corrosion resisting property of film layer reduces again after first increasing.Pass through
Analysis contrast draws：Work as NH4VO3、Na2SiO3When being respectively 6g/L, 8g/L and 0.5g/L with the concentration of KF, film quality is most
It is good.
3. during differential arc oxidation coloring, positive and negative voltage, time of positive and negative dutycycle and film forming etc. can be considered shadow
Ring the external factor of MAO layer tissue structure and performance.Forward voltage is conducive to the growth speed of film layer
Degree, also, when coating growth is to certain thickness, is only improved forward voltage and can be only achieved its energy for puncturing again, film layer
Ability continued growth, so, forward voltage is the main factor for affecting thicknesses of layers.With the rising of forward voltage, film layer
Roughness become big, the thickness of film layer becomes big, and the adhesion between matrix and film layer becomes big, the corrosion resisting property of film layer first increase after again
Reduce.With the rising of negative voltage, film layer can become more and more coarse, the thickness increase of film layer, the knot between matrix and film layer
Make a concerted effort to be gradually reduced, the corrosion resisting property of film layer is gradually reduced.With the increase of positive dutycycle, the roughness of film layer has increased,
The thickness of film layer gradually increases within the specific limits, rationally gradually increasing between matrix and film layer, the corrosion resisting property elder generation of film layer
Reduce after increase.Drawn by analyzing contrast：When forward voltage, negative voltage and positive dutycycle be respectively 440V, -40V and
When 30%, film quality is best.
4. in micro-arc oxidation process, the formation of green film layer can substantially be divided into three phases.Mainly contain in film layer Al,
Tetra- kinds of elements of Si, V and O.O, Si and V element almost through whole film layer, V element be distributed where hole is more it is more,
Si is more evenly distributed in surface, Al and O elements are mainly distributed on the melt substance region of projection, and Al is concentrated mainly on film
In layer compacted zone.
5.NH4VO3Decompose during the course of the reaction and generate V2O5, V2O5A part is piled up in film surface, is partly into
In discharge channel.Under the scattering process of light, film surface and in electric discharge micropore V2O5So that ceramic film present it is green
Color.
6. detect containing Al in film layer3V, this intermetallic compound can improve the hardness of aluminum alloy surface.
Description of the drawings
The NH of Fig. 1 variable concentrations4VO3The color of the green film layer of generation
(a) 5g/L, (b) 6g/L, (c) 7g/L
The NH of Fig. 2 variable concentrations4VO3The XRD spectrum of the green film layer of generation
The NH of Fig. 3 variable concentrations4VO3The surface microscopic topographic of the green film layer of generation
(a1,a2)5g/L；(b1,b2)6g/L；(c1,c2)7g/L
The NH of Fig. 4 variable concentrations4VO3Sound emission-the curve of load of the green film layer of generation
The NH of Fig. 5 variable concentrations4VO3The moving electrode potential curve of the green film layer of generation
The Na of Fig. 6 variable concentrations2SiO3The Film color of generation
(a)6g/L；(b)10g/L
The Na of Fig. 7 variable concentrations2SiO3The XRD spectrum of the green film layer of generation
The Na of Fig. 8 variable concentrations2SiO3The surface microscopic topographic of the green film layer of generation
(a1,a2)6g/L；(b1,b2)10g/L
The Na of Fig. 9 variable concentrations2SiO3Sound emission-the curve of load of the green film layer of generation
Figure 10 variable concentrations Na2SiO3The moving electrode potential curve of the green film layer of generation
The green film layer exterior appearance that the KF of Figure 11 variable concentrations is generated
(a)0.4g/L；(b)0.6g/L
The XRD spectrum of the green film layer that the KF of Figure 12 variable concentrations is generated
The surface microscopic topographic of the green film layer that the KF of Figure 13 variable concentrations is generated
(a1,a2)0.4g/L；(b1,b2)0.6g/L
Sound emission-the curve of load of the green film layer that the KF of Figure 14 variable concentrations is generated
The moving electrode potential curve of the green film layer that Figure 15 variable concentrations KF is generated
Specific embodiment
Embodiment 1
The present invention selects 6063 aluminium alloys as matrix material, and its chemical composition as shown in table 1, tests chemical reagent used
As shown in table 2.
The al alloy component of table 1 6063 (wt%)
Table 2 tests chemical reagent used
In the present invention, 6063 aluminium sheets are cut into into the rectangular piece of 7mm × 7mm × 12mm on WEDM,
Drilled on one side (Ф 2.5mm) with drilling machine, tapping is carried out with the corresponding screw tap in hole, in order to anti-in differential arc oxidation
Aluminum conductor during answering and after tapping is completely embedded, it is ensured that sample will not fall off in course of reaction.By sample in different thicknesses
SiC sand paper on polished, from the beginning of 400# coarse sandpapers, the polishing of Jing 5 times, until thin 1000#.Sample is placed in alcohol and is soaked
Bubble, so as to the grease on its surface of going out, is finally dried up with hair-dryer, is wrapped with preservative film, is placed on stand-by in sample strip.
The 6063 aluminium alloy styles anticipated are immersed in the electrolyte for preparing, the electrical quantity of test are set,
Differential arc oxidation process is carried out to style, process time is 15 minutes.Electrolyte parameter is:Sodium metasilicate 8g/L, potassium hydroxide 4g/L；
Potassium fluoride 0.5g/L, ammonium metavanadate 6g/L.Electrical quantity is：Positive, negative voltage is respectively 440V, 40V, and frequency is 400HZ；
Positive and negative dutycycle is respectively 30%, 20%, and the film layer for obtaining is grass green, and surface is smooth and uniformity, i.e. A2.
Embodiment 2
It is 5g/L to change ammonium metavanadate concentration in embodiment 1, and other parameters are constant, and the film layer A1 color for obtaining is very uneven
It is even, and many places local is presented black.
Embodiment 3
The concentration for changing ammonium metavanadate in embodiment 1 is 7g/L, and other parameters are constant, and the film layer A3 Film color for obtaining is
Blackish green, surface is more smooth.
Embodiment 4
The concentration for changing sodium metasilicate in embodiment 1 is 6g/L, and other parameters are constant, film layer A4 for obtaining.Embodiment 5
The concentration for changing sodium metasilicate in embodiment 1 is 10g/L, and other parameters are constant, film layer A2 for obtaining.Embodiment 6
The concentration for changing potassium fluoride in embodiment 1 is 0.4g/L, and other parameters are constant, film layer A5 for obtaining.Embodiment 7
The concentration for changing potassium fluoride in embodiment 1 is 0.6g/L, and other parameters are constant, film layer A6 for obtaining.Embodiment 10
1.1NH4VO3Impact to green Film color
Variable concentrations NH4VO3The color of the green film layer of generation is as shown in figure 1, work as NH4VO3When concentration is 5g/L, sample
A1 Film colors are very uneven, and many places local is presented black；Work as NH4VO3When concentration is 6g/L, the Film color of Sample A 2 is grass
Green, surface is smooth and uniformity；Work as NH4VO3When concentration is 5g/L, the Film color of Sample A 3 is blackish green, surface relatively light
It is sliding.It can be seen that with NH4VO3The increase of concentration, the color of film layer is gradually deepened, this is because, with NH4VO3
The increase of concentration, improves the electric conductivity of electrolyte so that the aperture of the micropore in film layer diminishes so that the surface energy drop of film layer
It is low, more V2O5Into conductive channel, thus be conducive to the formation of green ceramic film layer.
1.2NH4VO3The impact thick to green film tunic
Variable concentrations NH4VO3The thickness of the green film layer of generation is as shown in table 3, as the NH of addition4VO3Concentration is respectively
When 5g/L, 6g/L and 7g/L, the thicknesses of layers of Sample A 1, A2, A3 is respectively 10 μm, 15 μm and 20 μm.Can from table 3
Go out, the thickness of film layer is with NH4VO3The increase of concentration and become big, and within the specific limits, the thickness and NH of ceramic film4VO3
Concentration be directly proportional.But when additive concentration is excessive, the electric conductivity of electrolyte can rapidly become big so that film surface local electricity
Press through greatly, produce and there is destructive electric current, cause slowing for film forming, the film layer speed of dissolving is more than the film layer thickness for generating
Degree, film layer is thinning, and the phenomenons such as loose, hole occurs.
Table 3 adds variable concentrations NH4VO3The thickness of the green film layer of Shi Shengcheng
1.3NH4VO3Impact to green film layer phase composition
The NH of variable concentrations4VO3The XRD spectrum of the green film layer of generation is as shown in Fig. 2 it can be seen that film layer master
There is V2O5、Al3V、α-Al2O3、γ-Al2O3And Al9Several phases such as Si are constituted.V2O5And Al3The peak value of V phases first increases and subtracts afterwards
It is little, illustrate V2O5And Al3The relative amount of V is also first to increase to diminish afterwards.γ-Al2O3Content almost do not change, and α-Al2O3
Amount it is few, this be likely due to current density when differential arc oxidation reacts it is less caused by.
1.4NH4VO3Impact to green film layer microscopic appearance
The NH of variable concentrations4VO3The surface microscopic topographic of the green film layer of generation is as shown in figure 3, work as NH4VO3Concentration be
During 5g/L, the micropore of film surface is less, and maximum diameter of hole is at 2 μm or so, and the Aperture deviation between micropore is less, and there is local model
Interior indivedual little projection is enclosed, overall upper surface is still more smooth.Work as NH4VO3Concentration be 6g/L when, the micropore of film surface
It is more, 5 μm or so of maximum diameter of hole, Aperture deviation is less, and distribution is fine and close.Work as NH4VO3Concentration be 7g/L when, film surface it is micro-
7 μm or so of the more maximum diameter of hole in hole, Aperture deviation is big, and there are indivedual larger projections.This is because, work as NH4VO3Concentration
When higher, excessive V2O5Film surface can be deposited in, it is impossible to enter in discharge channel, be may proceed under high voltages and Al elements
Reaction, generates the Al of melting3V.The NH of addition variable concentrations4VO3The characteristics of film layer of generation is respectively provided with differential arc oxidation film layer, this
The aluminum oxide for being because the melting gushed out in discharge channel is quickly cooled down by the electrolyte of surrounding.
The NH of variable concentrations4VO3The content of V element is as shown in table 4 in the green film layer of generation.Can from table 4 and Fig. 1
Go out, NH4VO3Concentration it is higher, Film color is deeper, and in film layer V element content it is also higher.Relevant research shows, certain
In the range of, the concentration of the colouring agent of addition is higher, and the color of corresponding film layer is also deeper.
The NH of the variable concentrations of table 44VO3The content of V element in the green film layer of generation
1.5NH4VO3Impact to green film layer and basal body binding force intensity
The NH of variable concentrations4VO3The combination force intensity of the ceramic film of generation is as shown in figure 4, as the NH of addition4VO3Concentration
Respectively 5g/L, 6g/L and 7g/L when, the adhesion of the film layer of Sample A 1, A2, A3 is respectively 40N, 30N and 26N.From Fig. 4
As can be seen that during differential arc oxidation, the resistance R of sample ceramic filmelectrolyte(RElectrolyte) and Rcoating(RCeramic film) electricity
The resistance of solution liquid constitutes the series circuit of a closure, and the two resistance have shared the provided gross energy of reaction, resistance
RelectrolyteThe energy for being consumed can enter puncturing for film layer, grow and sinter conversion.Its power is：
Wherein U works as voltage, U and RcoatingWhen constant, WcoatingDepend primarily on Relectrolyte.Its numerical value is bigger
WcoatingIt is less, then puncture for film layer, the energy for growing and sintering conversion is less, the metallurgical binding of matrix and ceramic film
Area it is less, cause to combine force intensity and and then reduce.
1.6NH4VO3On the corrosion proof impact of green film layer
The corrosion resisting property of differential arc oxidation film layer is generally characterized using the method for potentiodynamic polarization.The NH of variable concentrations4VO3
The moving electrode potential curve of the green film layer of generation is as shown in Figure 5.Corrosion potential Ecorr, corrosion current density Icorr, sun
Pole/negative electrode Tafel slope (ba,bc) and polarization impedance RpNumerical value is listed in table 5, polarization impedance RpNumerical value is by Stern-Geary formula
It is calculated：
As can be seen that the E of film layer from Fig. 5 and Biao 5corrWith NH4VO3The increase of concentration, IcorrFirst reduce and increase afterwards,
The R of film layerp, there is this phenomenon and is possibly due to film layer in the side such as porosity, thickness and micro-crack quantity in first increases and then decreases
Face has differences.NH is worked as in this explanation4VO3Concentration be 6g/L when, its corrosion resisting property is best.In electrochemical corrosion test,
Because the corrosion current of 6063 matrixes exceedes protective current 2mA, test is forced to terminate, thus could not obtain the moving electrode electricity of matrix
Position curve.Differential arc oxidation film layer porous surface, film layer is mainly by outside porous layer, intermediate layer and interior solid layer three-layered node
Structure is constituted, and surface micropore does not extend through whole film layer, the Cl in electrochemical corrosion course, in corrosive medium-Ion can be worn
Cross porous layer and transition zone, but the final barrier effect due to by compacted zone and cannot fast erosion matrix, therefore corrode
Impedance is improved.So, the corrosion resisting property of film layer is better than matrix.
The NH of the variable concentrations of table 54VO3The moving electrode potential test result of the green film layer of generation
2.1Na2SiO3Impact to green Film color
The Na of variable concentrations2SiO3The color of the green film layer of generation is as shown in fig. 6, work as Na2SiO3Concentration be 6g/L
When, the color of the film layer of Sample A 4 is light green color, surface smoother, densification, and distribution of color is than more uniform；Work as Na2SiO3Concentration
When being 10g/L, the color of the film layer of Sample A 5 is also light green color, but surface is more rough, and distribution of color is uneven, there is local model
Enclose interior spot.This is possibly due to, Na2SiO3Addition, not only increase the conductance of electrolyte, and improve absorption
The quantity of particle discharge centers, so as to reduce critical discharge voltage.I.e. under constant voltage mode, ultra-voltage will increase (apply with
Critical discharge voltage numerical value is only poor) so that the breakdown strength of plasma is improved, be conducive to the quick formation of film layer.
Work as Na2SiO3Concentration it is relatively low when, there is provided granule for absorbing discharge centers it is less, so color is shallower：Work as Na2SiO3Concentration
When higher, granule for absorbing discharge centers are excessive, cause ultra-voltage excessive, and temperature is too high, cause multiple local area portions that film layer occurs
Melt phenomenon again, cause film layer loose, rough surface, and distribution of color is uneven.
2.2Na2SiO3The impact thick to green film tunic
The Na of variable concentrations2SiO3The thickness of the green film layer of generation is as shown in table 6, as the Na of addition2SiO3Concentration is distinguished
For 6g/L, 8g/L and 10g/L when, the thicknesses of layers of Sample A 4, A2 and A5 is respectively 7 μm, 15 μm and 23 μm. can be with from chart
Find out, the thickness of film layer is with Na2SiO3The increase of concentration and become big, and within the specific limits, the thickness of ceramic film with
Na2SiO3Concentration is proportional.This is because, Na2SiO3The conductance of electrolyte can be improved, while also increasing accordingly
The electric-field intensity of film layer, so as to increase micro-arc oxidation process in driving force, be conducive to the formation and growth of film layer.Due to
The process of differential arc oxidation can be modeled as a closed loop procedure, and in course of reaction, resistance and the electrical conductivity of electrolyte are in inverse relation,
The electrical conductivity of electrolyte is bigger, then the V above sampleps(transient voltage and amp product) is bigger, the formation and life of ceramic film
Long speed is faster, thus, in the range of finite concentration, the thickness and Na of film layer2SiO3Concentration it is linear.
The Na of the variable concentrations of table 62SiO3The thickness of the green film layer of generation
2.3Na2SiO3Impact to green film layer phase composition
The Na of variable concentrations2SiO3The XRD spectrum of the green film layer of generation is as shown in Figure 7, it can be seen that with what is added
Na2SiO3Amount increase, V2O5And Al3The intensity at the peak of V is significantly increased, V2O5And Al3Relative amount showed increased (other of V
Peak coincides with Al, and Al is primarily present in matrix), wherein Al3V can significantly improve the hardness of film layer.But with addition
Na2SiO3The increase of amount, the color of film layer shoals again from light to dark, and thicknesses of layers is linearly increased.This is because, when
Na2SiO3Concentration it is relatively low when, Na2SiO3The negligible amounts of the absorption discharge centers of offer, promote NH4VO3Move to matrix table
The driving force in face is less, and reaction temperature is low, the metalwork compound Al of generation3V is also less；Work as Na2SiO3Concentration it is higher when,
Produce more V2O5And Al3V, and many V2O5Just face is introduced into reaction channel to stay in film layer, so thicknesses of layers increase is thin
Loose layer.α-Al2O3With γ-Al2O3Content almost without what change.
2.4Na2SiO3Impact to green film layer microscopic appearance
The Na of variable concentrations2SiO3The surface microscopic topographic of the green film layer of generation is as shown in Figure 8.Work as Na2SiO3Concentration
For 6g/L when, the micropore of film surface is more, aperture very little, be distributed it is dense, the aperture difference between aperture is also smaller,
Film layer smoother is shown on macro morphology.The micropore major part of these diameter very littles is by melt substance cooled and solidified
When, what surrounding escaping gas was produced.Because working as Na2SiO3Concentration it is relatively low when, the discharge centers in electrolyte are less, film layer
The voltage on surface is less, and the energy of single pulse is little, and the melt substance produced in discharge channel is little to the scope around sprayed.When
Na2SiO3Concentration when being 10g/L, micropore also compares many, is distributed than more uniform, but the aperture difference between aperture is very big, some
There are some kicks in side, this causes to there are some flecks on macro morphology.This is because working as Na2SiO3Concentration compared with
Gao Shi, the discharge centers in electrolyte are more, and the electrical conductivity of electrolyte is high, and the energy of single pulse is big, molten in discharge channel
Melt material moment to around spraying, so as to form larger micropore.
The Na of variable concentrations2SiO3The content of V element is as shown in table 7 in the green film layer of generation.Can from table 7 and Fig. 6
Go out, work as Na2SiO3Concentration it is relatively low when, film surface is more smooth and content of V element is relatively low.Work as Na2SiO3Concentration it is relatively low
Height, film surface is rougher and content of V element is also higher.
The Na of the variable concentrations of table 72SiO3The content of V element in the green film layer of generation
2.5Na2SiO3Impact to green film layer and basal body binding force intensity
The Na of variable concentrations2SiO3The adhesion of the ceramic film of generation is as shown in figure 9, as the Na of addition2SiO3Concentration point
Not Wei 6g/L, 8g/L and 10g/L when, the adhesion of the film layer of Sample A 4, A2, A5 is respectively 24N, 30N and 27N, it can be seen that
With Na2SiO3Concentration increase, the combination force intensity first increases and then decreases of matrix and film layer, because working as Na2SiO3It is dense
When spending relatively low, adsorb the negligible amounts of discharge centers, electric-field intensity is relatively low, is adsorbed onto the Al (OH) of film layer4 -Jelly and
NH4VO3Less, the region that melting occurs is less, so adhesion strength ratio is relatively low；Work as Na2SiO3Concentration when being 8g/L, by
Na2SiO3The quantity of the absorption discharge centers of offer is more, and electric-field intensity is high, and the disruptive critical voltage of reaction is reduced, melt region
It is larger, with reference to force intensity also than larger：Work as Na2SiO3Concentration it is higher when, on the one hand, excessive V2O5In film surface, and nothing
Method enters into anti-passage；On the other hand, electric-field intensity is too high, causes temperatures at localized regions too high, occurs anti-in subrange
Multiple melting phenomenon, so, have with reference to force intensity and reduced.
2.6Na2SiO3On the corrosion proof impact of green film layer
From Figure 10 and Biao 8 as can be seen that working as Na2SiO3Concentration be 6g/L when, Ecorr、IcorrAnd RpRespectively -1.29V,
1.85×10-7A/cm2With 0.03 × 107Ω/cm2.Work as Na2SiO3Concentration be 10g/L when, Ecorr、IcorrAnd RpRespectively-
0.72V、1.42×10-9A/cm2With 0.006 × 107Ω/cm2.The E of film layercorrWith Na2SiO3The increase of concentration, IcorrFirst subtract
Increase, the R of film layer after littlepFirst increases and then decreases.Na is worked as in this explanation2SiO3Concentration be 8g/L when, its corrosion resisting property is best
's.Because the corrosion resistance of film layer is relevant with the porosity of film layer, thickness and micro-crack quantity etc., work as Na2SiO3Concentration it is relatively low
When, the film layer of generation is relatively thin, and its compacted zone is also relatively thin, so its corrosion resisting property is poor.Work as Na2SiO3Concentration it is higher when generate
Film layer it is thicker, but the aperture of the micropore in film layer is very big, Cl-Ion is easy to by these larger apertures, so its is resistance to
Corrosion can be reduced also.
The variable concentrations Na of table 82SiO3The moving electrode potential test result of the green film layer of generation
Impacts of the 3.1KF to green Film color
The exterior appearance of the green film layer that the KF of variable concentrations is generated is as shown in figure 11, when the concentration of KF is 0.4g/L,
The color of the film layer of Sample A 6 is celadon, surface smoother, densification, but marginal portion distribution of color is not very uniform；Work as KF
Concentration when being 0.6g/L, the color of the film layer of Sample A 7 is light green color, and marginal portion is relatively rough, and distribution of color is less uniform,
And there is a small amount of blackspot.This is because, according to the discharge principle of Albella impurity centers, the increase of KF concentration, improve
The electrical conductivity of electrolyte, O atom and NH4VO3Absorption forms the discharge centers of impurity, so as to produce plasma in specimen surface
Electric discharge, micro-arc breakdown formed heat energy make matrix surface produce melting, sintering, this is easy to the combination of matrix and O atom, has
Beneficial to the formation and growth of film layer, when the concentration of KF is relatively low, adsorb the NH on surface4VO3Few, the Film color of generation is shallower,
When the concentration of KF is higher, excessive NH4VO3Surface is deposited in, the diffusion and the further reaction with matrix of O is hindered so that
Sintering is insufficient, so as to cause film surface than more loose, and there is the spot in subrange.
Impacts of the 3.2KF to green oxidation film layer thickness
The thickness of the green film layer that variable concentrations KF is generated as shown in table 9, when the KF concentration of addition be respectively 0.4g/L,
During 0.5g/L and 0.6g/L, the thicknesses of layers of Sample A 6, A2 and A7 is respectively 11 μm, 15 μm and 22 μm.As can be seen from Table 9,
F-As smallest size of anion, the electrical conductivity of electrolyte can be significantly improved, so as to increased the electric-field intensity of electrolyte,
It is beneficial to the formation of film layer.Meanwhile, the reaction speed of the aluminium of oxygen and melting is accelerated, aluminum oxide can be allowed preferably to be aoxidized, plus
The fast speed of growth of film layer.F-Be conducive to the formation and growth of compacted zone, and the thickness of film layer increases with the increase of KF concentration
Greatly, therefore, it is possible to judge that the thickness for going out film layer compacted zone is increase.
The thickness of the green film layer that the KF of the variable concentrations of table 9 is generated
Impacts of the 3.3KF to green film layer phase composition
The XRD spectrum of the green film layer that the KF of variable concentrations is generated is as shown in figure 12.It can be seen that with KF it is dense
The rising of degree, the relative intensity at No. 4 peaks first reduces and increases afterwards, the relative intensity first increases and then decreases at No. 6 peaks, the change of other peak values
Change trend is not apparent.Therefore, it is possible to judge that going out Al3The content of V is first to reduce to increase afterwards, and is difficult to judge V2O5Contain
The change of amount.Due to Al3V is present in film surface, is conducive to improving the elastic strength and hardness of film layer.
Impacts of the 3.4KF to green film layer microscopic appearance
The surface microscopic topographic of the green film layer that the KF of variable concentrations is generated is as shown in figure 13.When the concentration of KF is 0.4g/L
When, the micropore of film surface is more, and away from larger, maximum gauge reaches 6um or so to the aperture difference between micropore, minimum less than 1um,
But their cross-distributions and be distributed than more uniform, densification, film surface smoother is shown as on macro morphology.It is dense as KF
Spend for 0.6g/L when, the micropore of film surface is more, the universal larger and very irregular in aperture, and film layer is shown as on macro morphology
Surface distribution of color in subrange is uneven and relatively rough.This is possibly due to F-Electrolyte can be significantly improved
Electrical conductivity, when KF concentration is higher, because the electric-field intensity of specimen surface is too high, cause temperature also higher, individual pulse energy
Amount is excessive, and the sputtering of the melt substance of generation is acutely and scope is wider, so, the micro-pore diameter of formation is larger and irregular.
The content of V element is as shown in table 10 in the green film layer that the KF of variable concentrations is generated.Can from table 10 and Figure 11
Go out, the content of V element diminishes afterwards as the increase of KF concentration first increases in green film layer.
The content of V element in the green film layer that the KF of the variable concentrations of table 10 is generated
Impacts of the 3.5KF to green film layer and basal body binding force intensity
The combination force intensity of the green film layer that the KF of variable concentrations is generated as shown in figure 14, can be seen that from Fig. 4 and Figure 14
When the KF concentration of addition is respectively 0.4g/L, 0.5g/L and 0.6g/L, the combination force intensity of Sample A 6, A2 and A7 is respectively
24N, 30N and 30N.When KF concentration is 0.4g/L, because concentration is less, the electrical conductivity of the electrolyte that is not significantly increased, base
The electric-field intensity in body surface face is also less, and film layer is also relatively thin, so adhesion is little.When KF concentration be 0.6g/L when because concentration compared with
Greatly, the electrical conductivity of electrolyte is significantly improved, the fine and close Zeng Bianhou of film layer, and, the local area of melting zone also increases, therefore,
Adhesion increases.
Impacts of the 3.6KF to differential arc oxidation film layer corrosion resisting property
The moving electrode potential curve of the green film layer that the KF of variable concentrations is generated is as shown in figure 15.Can be with by Figure 15 and Biao 11
Find out, when the concentration of KF is 0.4g/L, Ecorr、IcorrAnd RpRespectively -0.89V, 1.11 × 10-7A/cm2With 0.08 × 107
Ω/cm2.When the concentration of KF is 0.6g/L, Ecorr、IcorrAnd RpRespectively -0.72V, 2.82 × 10-7A/cm2With 0.01 × 107
Ω/cm2.The E of film layercorrWith the increase of KF concentration, IcorrFirst reduce and increase afterwards, the R of film layerpFirst increases and then decreases.This explanation
When the concentration of KF is 0.5g/L, its corrosion resisting property is best.With the increase of KF concentration, the thickness of the compacted zone of film layer
Increase therewith, its corrosion resisting property is also accordingly mentioned[93].But when KF concentration is larger, the aperture of micropore is larger in film layer, leads
Film layer is caused than more loose, so as to reduce the corrosion resistance of film layer.
The moving electrode potential test result of the green film layer that the variable concentrations KF of table 11 is generated
4 brief summaries
(1) with NH4VO3The rising of concentration, the color of film layer is gradually deepened, and the aperture of micropore becomes larger in film layer, film
The thickness of layer linearly increases within the specific limits, and film layer becomes larger with the adhesion of matrix, and the corrosion resisting property of film layer first increases
Reduce again afterwards.Drawn by analyzing contrast：Work as NH4VO3Concentration be 6g/L when, film quality is best.
(2) with Na2SiO3The rising of concentration, the color of film layer shoals again from light to dark, works as Na2SiO3When concentration is higher,
Just face is relatively rough for film layer, and the thickness of film layer linearly increases within the specific limits, and film layer first increases with the adhesion of matrix and subtracts afterwards
Little, the corrosion resisting property of film layer reduces again after first increasing.Drawn by analyzing contrast：Work as Na2SiO3Concentration be 8g/L when, film layer
It is best in quality.
(3) with the rising of KF concentration, the color of film layer shoals again from light to dark, the thickness of film layer within the specific limits by
Cumulative big, film layer is constant after first increasing within the specific limits with the adhesion of matrix, and the corrosion resisting property of film layer subtracts again after first increasing
It is little.Drawn by analyzing contrast：When the concentration of KF is 0.5g/L, film quality is best.
Although the above-mentioned accompanying drawing that combines is described to the specific embodiment of the present invention, not to present invention protection model
The restriction enclosed, one of ordinary skill in the art should be understood that on the basis of technical scheme those skilled in the art are not
Need the various modifications made by paying creative work or deformation still within protection scope of the present invention.
Claims (7)
1. a kind of method that aluminum alloy differential arc oxidation green film layer, is characterized in that, including step is as follows：
(1) select aluminium alloy as matrix, prepare electrolyte system, the composition concentration of electrolyte is：Ammonium metavanadate 3-9g/L, silicon
Sour sodium 4-12g/L, potassium hydroxide 2.0-6.0g/L；Potassium fluoride 0.3-0.6g/L, glycerine 3-6mL/L, pH8-10；
(2) aluminum alloy surface after the cleaning carries out differential arc oxidation process with electrolyte, and electrical quantity is：Forward voltage 400-
450V, negative voltage is 30-80V；Frequency is 300-500Hz；Positive and negative dutycycle is respectively 20-40%, 15-25%；Control temperature
Less than 60 degrees Celsius of degree, process time is 15 minutes.
2. the method that aluminum alloy differential arc oxidation according to claim 1 green film layer, is characterized in that, institute in step (1)
Aluminium alloy is stated for 6063 aluminium alloys.
3. the method that aluminum alloy differential arc oxidation according to claim 1 green film layer, is characterized in that, electricity in step (1)
Solution liquid composition concentration be：Sodium metasilicate 6-10g/L, potassium hydroxide 2.0-6.0g/L；Potassium fluoride 0.5g/L, ammonium metavanadate 5-8/L.
4. the method that aluminum alloy differential arc oxidation according to claim 3 green film layer, is characterized in that, electricity in step (1)
Solution liquid composition concentration be：Sodium metasilicate 8g/L, potassium hydroxide 4g/L；Potassium fluoride 0.5g/L, ammonium metavanadate 6g/L.
5. the method that aluminum alloy differential arc oxidation according to claim 1 green film layer, is characterized in that, electricity in step (2)
Parameter is：Positive, negative voltage is respectively 440V, 40V, and frequency is 400Hz；Positive and negative dutycycle is respectively 30%, 20%.
6. the Al-alloy parts that prepared by method according to claim 1.
7. application of the arbitrary methods described of claim 1-5 in aluminum alloy surface coloring.
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| CN107201538B (en) * | 2017-05-22 | 2019-06-18 | 北京科技大学 | A kind of inner wall of metal tube chrominaalumina preparation method of composite coating |
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| CN109023473B (en) * | 2018-11-02 | 2020-07-03 | 中国科学院兰州化学物理研究所 | Micro-arc oxidation method in non-aqueous electrolyte system |
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