CN102296339A - Method for in situ growing blue ceramic membrane layer on surface of aluminium alloy and aluminium-based composite material - Google Patents
Method for in situ growing blue ceramic membrane layer on surface of aluminium alloy and aluminium-based composite material Download PDFInfo
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Abstract
A method for in situ growing a blue ceramic membrane layer on the surface of an aluminium alloy and an aluminium-based composite material disclosed in the invention relates to a method for preparing a blue ceramic membrane layer on the surface of the aluminium alloy and aluminium-based composite material, solving the problems that the blue ceramic membrane layer with uniform color can not be prepared on the surface of the aluminium alloy and aluminium-based composite material, and the electrolyte used for the preparation of the blue ceramic membrane loses efficacy fast and cannot be reused multiple times in the present microarc oxidation method. The method comprises the following steps: 1, preparing the electrolyte which comprises at least the following ingredients: primary film-forming agent and color additives, wherein, the primary film-forming agent comprises one of phosphoric acid, sulfuric acid and citric acid or a mixture of several of phosphoric acid, sulfuric acid and citric acid; and 2, fixing the washed aluminium-based material in the electrolyte, turning on the power supply and carrying out oxidation. The obtained blue ceramic membrane layer on the surface of the aluminium-based material has uniform blue CoAl2O4, and the blue is uniform and beautiful. The ceramic membrane layer has high bonding strength with the aluminium-based material, has excellent wear resistance, corrosion resistance, and heat resistance, and realizes the integrated preparation of a decorative coating and a constructional coating.
Description
Technical field
The present invention relates to a kind of method for preparing the blue ceramic rete at aluminium alloy and aluminum matrix composite.
Background technology
Alumina is the class important meals material that consumption is only second to iron and steel, is widely used in fields such as aerospace, communications and transportation, printing, buildings.But alumina exists, and outward appearance is single, the soft corrosive shortcoming that is easy in moist atmosphere of quality, is difficult to satisfy the requirement of space industry, navigation industry, automotive industry and building industry and strong weather resisteant ornamental to alumina.For the decorative effect that improves alumina, strengthen erosion resistance and increase the service life, one all will carry out surface treatment alumina.One adopts anodic oxidation/chemical dyeing technology the blue alumina of decorating in surface, this kind preparation technology at first carries out anodic oxidation to alumina, make the surface of material generate the porous oxide film, then blue dyes is flooded the into inside of porous oxide film, thereby obtain the blue alumina of decorating.Though this technology has realized the blue effect of decorating of alumina, the material wear ability that adopts this technology to obtain is relatively poor; It is poor that dyestuff combines with substrate, and at rain drop erosion and sun exposure, dyestuff can be flushed away and take place oxidation, makes the alumina forfeiture blue, or cause blueness to be the mottled alumina surface that is non-uniformly distributed in, and decoration function is lost greatly.It is significant to develop a kind of method of modifying that can make the alumina surface generate the strong weather resisteant of one deck, wear-resistant, anticorrosive blue ceramic rete.
The liquid phase plasma oxidation is a new technology at metallic surface growth in situ ceramic membrane.The discharge that produces in the micro-plasma oxidation process is the effect to the local microcell in metallic surface, the discharge channel temperature is (but electrolyte temperature is a room temperature) up to 4000～8000 ℃, pressure can reach more than the 100MPa, electrolyte solution and anode material all participate in reaction in the plasma oxidation process, ceramic membrane is a growth in situ on matrix, the ceramic membrane good uniformity, with the substrate combinating strength height, ceramic film has excellent wear-resisting, corrosion-resistant, resistance toheat.Utilize the micro-plasma oxidation technology to carry out omnibearing processing to a large amount of complex-shaped parts simultaneously, be not subjected to the restriction of matrix size shape, this is that other process for modifying surface institute is unapproachable.
Though for preparation bibliographical information is arranged, but the rete of having reported is at the preparation of alkaline electrolysis liquid system, Co in alloy matrix aluminum blue Micro-Arc Oxidized Ceramic Coating
2+Ion is extremely unstable in alkaline system, and very fast formation precipitation settles down, and this just causes the very fast inefficacy of electrolytic solution, can not repeated multiple times use, and owing to Co in the reaction process
2+The content of ion in solution is unsettled, and the blue rete irregular colour of preparation is even, the aesthetic property extreme difference.Therefore, a kind of to prepare the uniform blue rete technology of color distribution significant in development.
Summary of the invention
The objective of the invention is in order to solve the blue ceramic rete that existing differential arc oxidation method can not obtain color even in aluminium alloy and aluminum matrix composite surface preparation, and the electrolytic solution that is used to prepare the blue ceramic film problem fast, that can not repeated multiple times use that lost efficacy, the invention provides the method for a kind of aluminium alloy and aluminum matrix composite surface in situ growth blue ceramic rete.
The method of aluminium alloy of the present invention and aluminum matrix composite surface in situ growth blue ceramic rete realizes by following steps: one, clean the aluminium base surface, remove surface and oil contaminant and impurity, described aluminium base is aluminium alloy or aluminum matrix composite; Two, preparation electrolytic solution: by main membrane-forming agent concentration is that 1g/L～50g/L, color additive concentration are that 1g/L～50g/L, secondary film formers concentration are that 0g/L～40g/L and complexing agent concentration are that 0g/L～20g/L takes by weighing main membrane-forming agent, color additive, secondary film formers, complexing agent and water respectively, prepare electrolytic solution, wherein, main membrane-forming agent is a kind of or wherein several composition in phosphoric acid, sulfuric acid and the citric acid, and color additive is inorganic salt or the organic salt that contains cobalt element; Three, the aluminium base after step 1 is handled fixedly being placed the electrolytic solution that is contained in stainless steel trough body, is anode then with the aluminium base, and stainless steel trough body is a negative electrode, adopts direct supply or unidirectional pulse power supply, is 0.01A/cm in current density
2～0.20A/cm
2Oxidation 10～180min under the condition; Four, the aluminium base after step 3 is handled is taken out, flushing back seasoning or oven dry under 80～100 ℃ obtain the blue ceramic rete on the aluminium base surface, finish the method for aluminium alloy and aluminum matrix composite surface in situ growth blue ceramic rete.
Can also adopt following steps to replace in the step 3 of the present invention: the aluminium base after step 1 is handled is fixedly placed the electrolytic solution that is contained in stainless steel trough body, be anode then with the aluminium base, stainless steel trough body is a negative electrode, adopt the diphasic pulse AC power, adjust peak voltage ranges between-200～600V, positive and negative phase current density value is 0.01A/cm
2～0.16A/cm
2, frequency is 10～2000Hz, positive and negative phase dutycycle is 0.1～0.45, oxidation 10～180min under the constant current conditions.
Secondary film formers in the step 2 of the present invention is a kind of or several combinations by any ratio wherein in boric acid, borax and the sodium phosphate.Complexing agent in the step 2 is one or both the combination by any ratio in ethylenediamine tetraacetic acid (EDTA) and the tartrate.Color additive in the step 2 is specially rose vitriol, Cobaltous diacetate, cobalt chloride or Xiao Suangu.
The present invention adopts the acidic electrolysis liquid system, and the color additive that contains the inorganic salt of cobalt element or organic salt is stable with Co in the acidic electrolysis liquid system
2+Ionic species exists, and can not form precipitation, and therefore, in oxidising process, electrolytic solution is stable, can use repeatedly more than ten times.Co is arranged in electrolytic solution
2+Ion stabilized existence in the plasma oxidation process, can generate CoAl on the surface of aluminium base
2O
4Component, CoAl
2O
4Present blueness, this component is evenly distributed on the surface of ceramic film, is dark blue or light blue at rete in the color that how much has determined rete of content according to it.Realize CoAl by the mode of regulating current density and color additive concentration
2O
4The variation of content in rete.
Utilize the method for aluminium alloy of the present invention and aluminum matrix composite surface in situ growth blue ceramic rete, the blueness of the blue ceramic rete that obtains on aluminium base (aluminium alloy and aluminum matrix composite) surface evenly, and is attractive in appearance.And the blue ceramic rete of growth in situ and aluminium base (aluminium alloy and aluminum matrix composite) bonding strength height, have excellent wear-resisting, corrosion-resistant, resistance toheat.Realized the incorporate preparation of ornamental and structural coating.
The blue ceramic rete that the present invention obtains in the growth of aluminium alloy and aluminum matrix composite surface in situ adopts the GCr15 bearing steel ball to carry out the friction and wear behavior test, the wear resistance height, the rotating speed of 180N high-load 150rev./min is wearing and tearing down, and the rate of weight loss optimum only is 8mg/min.
The present invention utilizes the Tafel curve of blue ceramic rete in 3.5% NaCl solution to estimate the corrosion resistance nature of ceramic membrane, test, polarization resistance is by 0.08 * 10 of the LY12 aluminium alloy
7Ω/cm
2Optimally bring up to 1.90 * 10
7Ω/cm
2, corrosion resistance nature increases substantially.
The blue ceramic rete that obtains in the growth of aluminium alloy and aluminum matrix composite surface in situ of the present invention must be through 120 circulations through the thermal shock experiment test, and rete color no change, no rete come off or the skin effect phenomenon generation.
Description of drawings
Fig. 1 is embodiment 26 obtains the blue ceramic rete in the LY12 aluminum alloy surface an X-ray diffraction spectrogram.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: present embodiment is the method for aluminium alloy and aluminum matrix composite surface in situ growth blue ceramic rete, it is realized by following steps: one, clean the aluminium base surface, remove surface and oil contaminant and impurity, described aluminium base is aluminium alloy or aluminum matrix composite; Two, preparation electrolytic solution: by main membrane-forming agent concentration is that 1g/L～50g/L, color additive concentration are that 1g/L～50g/L, secondary film formers concentration are that 0g/L～40g/L and complexing agent concentration are that 0g/L～20g/L takes by weighing main membrane-forming agent, color additive, secondary film formers, complexing agent and water respectively, prepare electrolytic solution, wherein, main membrane-forming agent is a kind of or wherein several composition in phosphoric acid, sulfuric acid and the citric acid, and color additive is inorganic salt or the organic salt that contains cobalt element; Three, the aluminium base after step 1 is handled fixedly being placed the electrolytic solution that is contained in stainless steel trough body, is anode then with the aluminium base, and stainless steel trough body is a negative electrode, adopts direct supply or unidirectional pulse power supply, is 0.01A/cm in current density
2～0.20A/cm
2Oxidation 10～180min under the condition; Four, the aluminium base after step 3 is handled is taken out, flushing back seasoning or oven dry under 80～100 ℃ obtain the blue ceramic rete on the aluminium base surface, finish the method for aluminium alloy and aluminum matrix composite surface in situ growth blue ceramic rete.
When main membrane-forming agent is a several composition in phosphoric acid, sulfuric acid and the citric acid in the present embodiment, with any than combination.
Present embodiment adopts the acidic electrolysis liquid system, and the color additive that contains the inorganic salt of cobalt element or organic salt is stable with Co in the acidic electrolysis liquid system
2+Ionic species exists, and can not form precipitation, and therefore, in oxidising process, electrolytic solution is stable, can use repeatedly more than ten times.Co is arranged in electrolytic solution
2+Ion stabilized existence in the plasma oxidation process, can generate CoAl on the surface of aluminium base
2O
4Component, CoAl
2O
4Present blueness, this component is evenly distributed on the surface of ceramic film, is dark blue or light blue at rete in the color that how much has determined rete of content according to it.Present embodiment realizes CoAl by the mode of regulating current density and color additive concentration
2O
4Content in rete reaches 1%～77%.
Utilize the method for the aluminium alloy and the aluminum matrix composite surface in situ growth blue ceramic rete of present embodiment, the blueness of the blue ceramic rete that obtains on aluminium base (aluminium alloy and aluminum matrix composite) surface evenly, and is attractive in appearance.And the blue ceramic rete of growth in situ and aluminium base (aluminium alloy and aluminum matrix composite) bonding strength height, have excellent wear-resisting, corrosion-resistant, resistance toheat.Realized the incorporate preparation of ornamental and structural coating.
Embodiment two: what present embodiment and embodiment one were different is that the concrete grammar that cleans the aluminium base surface in the step 1 is: aluminium base is placed ethanol or acetone, aluminium base surface and oil contaminant and impurity cleaned remove, polishing is removed oxide film and is got final product again.Other step and parameter are identical with embodiment one.
Embodiment three: what present embodiment was different with embodiment one or two is that aluminium base is that the trade mark is the aluminium alloy of LY12, LF3, LD11, LC4, Zl101 or L3 in the step 1, perhaps for silicon carbide, aluminum borate, magnesium borate or aluminum oxide serving as enhancing body enhanced aluminum matrix composite.Other step and parameter are identical with embodiment one or two.
Embodiment four: present embodiment and embodiment one, two or three are different is to be that 1g/L～50g/L, color additive concentration are that 1g/L～50g/L, secondary film formers concentration are that 0.1g/L～40g/L and complexing agent concentration are that 0.1g/L～20g/L takes by weighing main membrane-forming agent, color additive, secondary film formers, complexing agent and water respectively by main membrane-forming agent concentration in the step 2.Other step and parameter are identical with embodiment one, two or three.
Embodiment five: present embodiment and embodiment one, two or three are different is to be that 2g/L～40g/L, color additive concentration are that 1.5g/L～40g/L, secondary film formers concentration are that 0.2g/L～30g/L and complexing agent concentration are that 0.2g/L～10g/L takes by weighing main membrane-forming agent, color additive, secondary film formers, complexing agent and water respectively by main membrane-forming agent concentration in the step 2.Other step and parameter are identical with embodiment one, two or three.
Embodiment six: present embodiment and embodiment one, two or three are different is to be that 4g/L～30g/L, color additive concentration are that 3g/L～30g/L, secondary film formers concentration are that 0.5g/L～20g/L and complexing agent concentration are that 0.5g/L～5g/L takes by weighing main membrane-forming agent, color additive, secondary film formers, complexing agent and water respectively by main membrane-forming agent concentration in the step 2.Other step and parameter are identical with embodiment one, two or three.
Embodiment seven: present embodiment and embodiment one, two or three are different is to be that 8g/L～20g/L, color additive concentration are that 8g/L～20g/L, secondary film formers concentration are that 1g/L～10g/L and complexing agent concentration are that 0.8g/L～2g/L takes by weighing main membrane-forming agent, color additive, secondary film formers, complexing agent and water respectively by main membrane-forming agent concentration in the step 2.Other step and parameter are identical with embodiment one, two or three.
Embodiment eight: present embodiment and embodiment one, two or three are different is to be that 16g/L, color additive concentration are that 14g/L, secondary film formers concentration are that 2g/L and complexing agent concentration are that 1g/L takes by weighing main membrane-forming agent, color additive, secondary film formers, complexing agent and water respectively by main membrane-forming agent concentration in the step 2.Other step and parameter are identical with embodiment one, two or three.
Embodiment nine: present embodiment is different with one of embodiment one to eight is to be that 1g/L～50g/L and color additive concentration are that 1g/L～50g/L takes by weighing main membrane-forming agent, color additive and water respectively by main membrane-forming agent concentration in the step 2.Other step and parameter are identical with one of embodiment one to eight.
Embodiment ten: present embodiment is different with one of embodiment one to eight is to be that 2g/L～40g/L, color additive concentration are that 1.5g/L～40g/L takes by weighing main membrane-forming agent, color additive and water respectively by main membrane-forming agent concentration in the step 2.Other step and parameter are identical with one of embodiment one to eight.
Embodiment 11: present embodiment is different with one of embodiment one to eight is to be that 4g/L～30g/L, color additive concentration are that 3g/L～30g/L takes by weighing main membrane-forming agent, color additive and water respectively by main membrane-forming agent concentration in the step 2.Other step and parameter are identical with one of embodiment one to eight.
Embodiment 12: present embodiment is different with one of embodiment one to eight is to be that 8g/L～20g/L, color additive concentration are that 8g/L～20g/L takes by weighing main membrane-forming agent, color additive and water respectively by main membrane-forming agent concentration in the step 2.Other step and parameter are identical with one of embodiment one to eight.
Embodiment 13: present embodiment is different with one of embodiment one to eight is to be that 14g/L, color additive concentration are that 16g/L takes by weighing main membrane-forming agent, color additive and water respectively by main membrane-forming agent concentration in the step 2.Other step and parameter are identical with one of embodiment one to eight.
Embodiment 14: what present embodiment was different with one of embodiment one to 13 is that color additive is rose vitriol, Cobaltous diacetate, cobalt chloride or Xiao Suangu in the step 2.Other step and parameter are identical with one of embodiment one to 13.
Embodiment 15: present embodiment is different with one of embodiment one to 14 is that secondary film formers in the step 2 is a kind of or several combinations by any ratio wherein in boric acid, borax and the sodium phosphate.Other step and parameter are identical with one of embodiment one to 14.
Embodiment 16: present embodiment is different with one of embodiment one to 15 is that complexing agent in the step 2 is one or both the combination by any ratio in ethylenediamine tetraacetic acid (EDTA) and the tartrate.Other step and parameter are identical with one of embodiment one to 15.
Embodiment 17: present embodiment is different with one of embodiment one to 16 is to be 0.02A/cm in current density in the step 3
2～0.15A/cm
2Oxidation 60～160min under the condition.Other step and parameter are identical with one of embodiment one to 16.
Embodiment 18: present embodiment is different with one of embodiment one to 16 is to be 0.04A/cm in current density in the step 3
2～0.12A/cm
2Oxidation 90～150min under the condition.Other step and parameter are identical with one of embodiment one to 16.
Embodiment 19: present embodiment is different with one of embodiment one to 16 is to be 0.05A/cm in current density in the step 3
2～0.08A/cm
2Oxidation 100～140min under the condition.Other step and parameter are identical with one of embodiment one to 16.
Embodiment 20: present embodiment is different with one of embodiment one to 16 is to be 0.06A/cm in current density in the step 3
2Oxidation 120min under the condition.Other step and parameter are identical with one of embodiment one to 16.
Embodiment 21: what present embodiment was different with one of embodiment one to 20 is to adopt following steps to replace in the step 3: the aluminium base after step 1 is handled is fixedly placed the electrolytic solution that is contained in stainless steel trough body, be anode then with the aluminium base, stainless steel trough body is a negative electrode, adopt the diphasic pulse AC power, adjust peak voltage ranges between-200～600V, positive and negative phase current density value is 0.01A/cm
2～0.16A/cm
2, frequency is 10～2000Hz, positive and negative phase dutycycle is 0.1～0.45, oxidation 10～180min under the constant current conditions.Other step and parameter are identical with one of embodiment one to 20.
The ratio of positive current density and negative current density is 1: 1 in the present embodiment.
Embodiment 22: what present embodiment and embodiment 21 were different is that positive and negative phase current density value is 0.02A/cm
2～0.15A/cm
2, frequency is 50～1500Hz, positive and negative phase dutycycle is 0.15～0.45, oxidation 20～150min under the constant current conditions.Other step and parameter are identical with embodiment 21.
Embodiment 23: what present embodiment and embodiment 21 were different is that positive and negative phase current density value is 0.04A/cm
2～0.12A/cm
2, frequency is 100～1000Hz, positive and negative phase dutycycle is 0.2～0.45, oxidation 50～120min under the constant current conditions.Other step and parameter are identical with embodiment 21.
Embodiment 24: what present embodiment and embodiment 21 were different is that positive and negative phase current density value is 0.05A/cm
2～0.09A/cm
2, frequency is 200～500Hz, positive and negative phase dutycycle is 0.3～0.45, oxidation 80～100min under the constant current conditions.Other step and parameter are identical with embodiment 21.
Embodiment 25: what present embodiment and embodiment 21 were different is that positive and negative phase current density value is 0.06A/cm
2, frequency is 300Hz, positive and negative phase dutycycle is 0.45, oxidation 90min under the constant current conditions.Other step and parameter are identical with embodiment 21.
Embodiment 26: present embodiment is the method for aluminium alloy and aluminum matrix composite surface in situ growth blue ceramic rete, it is realized by following steps: one, clean the aluminium base surface with ethanol, remove surface and oil contaminant and impurity, described aluminium base is that the trade mark is the aluminium alloy of LY12; Two, preparation electrolytic solution: by main membrane-forming agent phosphoric acid (H
3PO
4) concentration is that 16g/L, color additive Cobaltous diacetate concentration are that 14g/L, secondary film formers boric acid concentration are that 2g/L and complexing agent ethylenediamine tetraacetic acid (EDTA) concentration are that 1g/L takes by weighing phosphoric acid, Cobaltous diacetate, boric acid, ethylenediamine tetraacetic acid (EDTA) and water respectively, prepare electrolytic solution; Three, the LY12 aluminium alloy after step 1 is handled fixedly being placed the electrolytic solution (the step 2 preparation) that is contained in stainless steel trough body, is anode with the LY12 aluminium alloy then, and stainless steel trough body is a negative electrode, adopts the unidirectional pulse power supply, is 0.06A/cm in current density
2Oxidation 120min under the condition; Four, the LY12 aluminium alloy after step 3 is handled is taken out, flushing back seasoning obtains the blue ceramic rete in the LY12 aluminum alloy surface, finishes the method for LY12 aluminum alloy surface growth in situ blue ceramic rete.
Present embodiment obtains blue ceramic rete Smalt in the LY12 aluminum alloy surface and is evenly distributed, and rete is attractive in appearance.Its X-ray diffraction spectrogram as shown in Figure 1, " ▼ " is CoAl among the figure
2O
4, " ● " is γ-Al
2O
3, " ■ " is α-Al
2O
3, " " is Al.As seen, contain CoAl in the blue ceramic rete of present embodiment
2O
4Component, CoAl
2O
4Present blueness, and CoAl
2O
4Component is evenly distributed on ceramic film.
The blue ceramic rete that present embodiment obtains at LY12 aluminum alloy surface growth in situ adopts the GCr15 bearing steel ball to carry out the friction and wear behavior test, test to such an extent that under the rotating speed of 180N high-load 150rev./min, wear and tear, rate of weight loss only is 8mg/min, the wear resistance height.
Present embodiment utilizes the Tafel curve of blue ceramic rete in 3.5% NaCl solution to estimate the corrosion resistance nature of ceramic membrane, and testing software is CHI1140, and reference electrode is a saturated calomel electrode, and supporting electrode is a platinum electrode, and test area is 1cm
2, test, polarization resistance is by 0.08 * 10 of the LY12 aluminium alloy
7Ω/cm
2Bring up to 1.90 * 10
7Ω/cm
2, corrosion resistance nature increases substantially.
Present embodiment is carried out the thermal shock experiment to the blue ceramic rete that obtains at LY12 aluminum alloy surface growth in situ, thermal shock experiment concrete operations are as follows: use the silicon controlled rectifier high-temperature electric resistance furnace as heating unit, earlier electric furnace is heated to 300 ℃, sample is put in the electric furnace, take out rapidly and put in the cold water behind the insulation 8min, observe the specimen surface form, rete is non-foaming, do not occur scaling off etc. and the isolating phenomenon of matrix, illustrate that the film base is in conjunction with good, if sample is no any variation after a thermal shocking, should proceed thermal shocking as stated above till ceramic membrane is destroyed, record heat shock cycling number of times.After carrying out the thermal shock experiment as stated above, the blue ceramic rete that obtains at LY12 aluminum alloy surface growth in situ of present embodiment circulates through 120 times, and rete color no change, no rete come off or skin effect phenomenon takes place.
As seen, the blue ceramic rete of the method growth in situ of present embodiment combines the intensity height with the LY12 aluminium alloy, has excellent wear-resisting, corrosion-resistant, resistance toheat.Realized the incorporate preparation of ornamental and structural coating.
Embodiment 27: present embodiment is the method for aluminium alloy and aluminum matrix composite surface in situ growth blue ceramic rete, it is realized by following steps: one, clean the aluminium base surface with ethanol, remove surface and oil contaminant and impurity, described aluminium base is that the trade mark is the aluminium alloy of LY12; Two, the LY12 aluminium alloy after step 1 is handled is fixedly placed the electrolytic solution (this electrolytic solution is embodiment 27 used electrolytic solution) that is contained in stainless steel trough body, be anode with the LY12 aluminium alloy then, stainless steel trough body is a negative electrode, adopting the unidirectional pulse power supply, is 0.06A/cm in current density
2Oxidation 120min under the condition; Four, the LY12 aluminium alloy after step 3 is handled is taken out, flushing back seasoning obtains the blue ceramic rete in the LY12 aluminum alloy surface, finishes the method for LY12 aluminum alloy surface growth in situ blue ceramic rete.
After present embodiment is taken out the LY12 aluminium alloy through step 4, get the aluminum alloy base material of new LY12 again, recycling electrolytic solution carries out at the primary growth blue ceramic of LY12 aluminum alloy surface rete, so the old electrolytic solution of recycling obtains 12 blue ceramic retes that obtain in the LY12 aluminum alloy surface.
Observe above-mentioned 12 blue ceramic retes that obtain in the LY12 aluminum alloy surface, evenly blue, rete is attractive in appearance.Have and identical wear-resisting, corrosion-resistant, the resistance toheat of blue ceramic rete in the embodiment 26.Realized the incorporate preparation of ornamental and structural coating.
Embodiment 28: present embodiment is the method for aluminium alloy and aluminum matrix composite surface in situ growth blue ceramic rete, it is realized by following steps: one, clean the aluminium base surface with ethanol, remove surface and oil contaminant and impurity, described aluminium base is that the trade mark is the aluminium alloy of LY12; Two, preparation electrolytic solution: by main membrane-forming agent phosphoric acid (H
3PO
4) concentration is that 16g/L, color additive Cobaltous diacetate concentration are that 14g/L, secondary film formers boric acid concentration are that 2g/L and complexing agent ethylenediamine tetraacetic acid (EDTA) concentration are that 1g/L takes by weighing phosphoric acid, Cobaltous diacetate, boric acid, ethylenediamine tetraacetic acid (EDTA) and water respectively, prepare electrolytic solution; Three, the LY12 aluminium alloy after step 1 is handled is fixedly placed the electrolytic solution (the step 2 preparation) that is contained in stainless steel trough body, be anode with the LY12 aluminium alloy then, stainless steel trough body is a negative electrode, adopt the diphasic pulse AC power, adjust peak voltage ranges between-200～600V, positive and negative phase current density value is 0.06A/cm
2, frequency is 300Hz, positive and negative phase dutycycle is 0.45, oxidation 90min under the constant current conditions; Four, the LY12 aluminium alloy after step 3 is handled is taken out, the flushing back obtains the blue ceramic rete 80～100 ℃ of oven dry down in the LY12 aluminum alloy surface, finishes the method for LY12 aluminum alloy surface growth in situ blue ceramic rete.
The positive current density equates with the negative current density in the present embodiment step 3.
The blue ceramic rete that present embodiment obtains in the LY12 aluminum alloy surface, evenly blue, rete is attractive in appearance.
Testing method according to record in the embodiment 26, the blue ceramic rete of present embodiment is carried out wear-resisting, corrosion-resistant, resistance toheat test, and wear-resisting, corrosion-resistant, the resistance toheat of the blue ceramic rete that test obtains is close with the performance of embodiment 26 described ceramic films.
Embodiment 29: present embodiment is the method for aluminium alloy and aluminum matrix composite surface in situ growth blue ceramic rete, it is realized by following steps: one, clean the aluminium base surface with acetone, remove surface and oil contaminant and impurity, polishing and removing surface layer oxide film, described aluminium base is that the trade mark is the aluminium alloy of LY12; Two, preparation electrolytic solution: by main membrane-forming agent phosphoric acid (H
3PO
4) concentration is that 14g/L and color additive Cobaltous diacetate concentration are that 16g/L takes by weighing phosphoric acid, Cobaltous diacetate and water respectively, prepare electrolytic solution; Three, the LY12 aluminium alloy after step 1 is handled fixedly being placed the electrolytic solution (the step 2 preparation) that is contained in stainless steel trough body, is anode with the LY12 aluminium alloy then, and stainless steel trough body is a negative electrode, adopts the unidirectional pulse power supply, is 0.06A/cm in current density
2Oxidation 120min under the condition; Four, the LY12 aluminium alloy after step 3 is handled is taken out, flushing back seasoning obtains the blue ceramic rete in the LY12 aluminum alloy surface, finishes the method for LY12 aluminum alloy surface growth in situ blue ceramic rete.
The blue ceramic rete that present embodiment obtains in the LY12 aluminum alloy surface, evenly blue, rete is attractive in appearance.
Testing method according to record in the embodiment 26, the blue ceramic rete of present embodiment is carried out wear-resisting, corrosion-resistant, resistance toheat test, and wear-resisting, corrosion-resistant, the resistance toheat of the blue ceramic rete that test obtains is close with the performance of embodiment 26 described ceramic films.
Claims (10)
1. the method for aluminium alloy and aluminum matrix composite surface in situ growth blue ceramic rete, the method that it is characterized in that aluminium alloy and aluminum matrix composite surface in situ growth blue ceramic rete, it is realized by following steps: one, clean the aluminium base surface, remove surface and oil contaminant and impurity, described aluminium base is aluminium alloy or aluminum matrix composite; Two, preparation electrolytic solution: by main membrane-forming agent concentration is that 1g/L～50g/L, color additive concentration are that 1g/L～50g/L, secondary film formers concentration are that 0g/L～40g/L and complexing agent concentration are that 0g/L～20g/L takes by weighing main membrane-forming agent, color additive, secondary film formers, complexing agent and water respectively, prepare electrolytic solution, wherein, main membrane-forming agent is a kind of or wherein several composition in phosphoric acid, sulfuric acid and the citric acid, and color additive is inorganic salt or the organic salt that contains cobalt element; Three, the aluminium base after step 1 is handled fixedly being placed the electrolytic solution that is contained in stainless steel trough body, is anode then with the aluminium base, and stainless steel trough body is a negative electrode, adopts direct supply or unidirectional pulse power supply, is 0.01A/cm in current density
2～0.20A/cm
2Oxidation 10～180min under the condition; Four, the aluminium base after step 3 is handled is taken out, flushing back seasoning or oven dry under 80～100 ℃ obtain the blue ceramic rete on the aluminium base surface, finish the method for aluminium alloy and aluminum matrix composite surface in situ growth blue ceramic rete.
2. the method for aluminium alloy according to claim 1 and aluminum matrix composite surface in situ growth blue ceramic rete, it is characterized in that aluminium base is that the trade mark is the aluminium alloy of LY12, LF3, LD11, LC4, Zl101 or L3 in the step 1, perhaps for silicon carbide, aluminum borate, magnesium borate or aluminum oxide serving as enhancing body enhanced aluminum matrix composite.
3. the method for aluminium alloy according to claim 1 and 2 and aluminum matrix composite surface in situ growth blue ceramic rete is characterized in that in the step 2 by main membrane-forming agent concentration being that 4g/L～30g/L, color additive concentration are that 3g/L～30g/L, secondary film formers concentration are that 0.5g/L～20g/L and complexing agent concentration are that 0.5g/L～5g/L takes by weighing main membrane-forming agent, color additive, secondary film formers, complexing agent and water respectively.
4. the method for aluminium alloy according to claim 1 and 2 and aluminum matrix composite surface in situ growth blue ceramic rete is characterized in that in the step 2 by main membrane-forming agent concentration being that 8g/L～20g/L, color additive concentration are that 8g/L～20g/L, secondary film formers concentration are that 1g/L～10g/L and complexing agent concentration are that 0.8g/L～2g/L takes by weighing main membrane-forming agent, color additive, secondary film formers, complexing agent and water respectively.
5. the method for aluminium alloy according to claim 1 and 2 and aluminum matrix composite surface in situ growth blue ceramic rete is characterized in that in the step 2 by main membrane-forming agent concentration being that 8g/L～20g/L, color additive concentration are that 8g/L～20g/L takes by weighing main membrane-forming agent, color additive and water respectively.
6. the method for aluminium alloy according to claim 1 and 2 and aluminum matrix composite surface in situ growth blue ceramic rete is characterized in that color additive is rose vitriol, Cobaltous diacetate, cobalt chloride or Xiao Suangu in the step 2.
7. the method for aluminium alloy according to claim 1 and 2 and aluminum matrix composite surface in situ growth blue ceramic rete is characterized in that in the step 3 in current density being 0.04A/cm
2～0.12A/cm
2Oxidation 90～150min under the condition.
8. the method for aluminium alloy according to claim 1 and 2 and aluminum matrix composite surface in situ growth blue ceramic rete is characterized in that in the step 3 in current density being 0.05A/cm
2～0.08A/cm
2Oxidation 100～140min under the condition.
9. the method for aluminium alloy according to claim 1 and 2 and aluminum matrix composite surface in situ growth blue ceramic rete, it is characterized in that step 3 adopts following steps to replace: the aluminium base after step 1 is handled is fixedly placed the electrolytic solution that is contained in stainless steel trough body, be anode then with the aluminium base, stainless steel trough body is a negative electrode, adopt the diphasic pulse AC power, adjust peak voltage ranges between-200～600V, positive and negative phase current density value is 0.01A/cm
2～0.16A/cm
2, frequency is 10～2000Hz, positive and negative phase dutycycle is 0.1～0.45, oxidation 10～180min under the constant current conditions.
10. the method for aluminium alloy according to claim 9 and aluminum matrix composite surface in situ growth blue ceramic rete is characterized in that positive and negative phase current density value is 0.05A/cm
2～0.09A/cm
2, frequency is 200～500Hz, positive and negative phase dutycycle is 0.3～0.45, oxidation 80～100min under the constant current conditions.
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| CN107338466A (en) * | 2017-05-09 | 2017-11-10 | 逢甲大学 | The differential of the arc handles the colouring method of metal works |
| CN107338466B (en) * | 2017-05-09 | 2019-03-01 | 逢甲大学 | The colouring method of differential of the arc processing metal works |
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