CN105714354A - Electrolyte used for preparing N-doped micro-arc oxidation ceramic layer - Google Patents
Electrolyte used for preparing N-doped micro-arc oxidation ceramic layer Download PDFInfo
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- CN105714354A CN105714354A CN201610159875.5A CN201610159875A CN105714354A CN 105714354 A CN105714354 A CN 105714354A CN 201610159875 A CN201610159875 A CN 201610159875A CN 105714354 A CN105714354 A CN 105714354A
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- electrolyte
- triethylamine
- ceramic layer
- distilled water
- arc oxidation
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
Abstract
The invention relates to aluminum alloy surface treatment, in particular to a treatment method for an abrasion-resisting and corrosion-resisting surface of an aluminum alloy part, and particularly relates to an electrolyte used for preparing an N-doped micro-arc oxidation ceramic layer. For the part made of an aluminum alloy, the micro-arc oxidation technology is adopted, and the abrasion-resisting and corrosion-resisting ceramic layer is prepared on the surface of the aluminum alloy. After triethylamine is added in the electrolyte, the self-corrosion current of the corrosion-resisting performance of the micro-arc oxidation ceramic layer is reduced by 2 orders of magnitudes compared with the self-corrosion current obtained when the triethylamine is not added and is lower than that of a base alloy by 4 orders of magnitudes.
Description
Technical field
The present invention relates to the surface treatment of aluminium alloy, refer in particular to a kind of wear-resisting, Corrosion resistant surface treatment method for aluminum alloy part, specifically, for a kind of electrolyte for preparing N doping arc differential oxide ceramic layer.
Background technology
Aluminum and alloy thereof become the main material of lightweight manufacture because of light weight, the advantage such as specific strength is high, conduction (heat) property is good.Due to the deficiency of the performances such as aluminum and the wearability of alloy itself, rotproofness, limit its wider application.
Differential arc oxidation (MicroarcOxidation) is also known as plasma micro-arc oxidation (MicroplasmaOxidation), it is a kind of environmental protection, respond well process for treating surface, it is exactly that Al or its alloy are placed in electrolyte aqueous solution, makes the surface of material produce the method that spark discharge speckle generates ceramic film under the combineds effect such as High Temperature High Pressure, heat chemistry, plasma chemistry and electrochemistry.It makes the oxide-film being electrochemically generated occur mutually and the change of structure through the High Temperature High Pressure effect of microplasma, so that the oxide-film of disordered structure becomes the α-Al containing certain crystalline state2O3Phase (also referred to as corundum) and γ-Al2O3The dense ceramic membrane of phase, the ceramic membrane that differential arc oxidation produces has high hardness, wearability and corrosion resistance.
Aluminium alloy is carried out differential arc oxidation and processes the range of application that can significantly widen aluminium alloy, and the quality of differential arc oxidation film layer directly influences its application performance.At present, electrolyte composition and the optimum organization of electrical quantity technique (such as: the parameters such as the voltage of differential arc oxidation applying, oxidization time, electric current density, dutycycle, frequency) are generally adopted, it is thus achieved that there is certain thickness ceramic layer.
Ceramic layer structure is made up of weaker zone, compacted zone, and anti-corrosion, the wearability of rete is to be determined by the thickness of compacted zone, rather than determined by the thickness of micro-arc oxidation films.The thickness of ceramic layer is limited mainly by the control of voltage, electric current density and time.Increasing the voltage applied, differential arc oxidation film thickness is advanced the speed soon；Oxidization time extends, and also can increase the thickness of ceramic film to a certain extent, but with time not direct proportionality.Improve and apply voltage, be subject to the restriction of microarc oxidation equipment provided performance on the one hand, on the other hand, too high applying voltage, can reduce the performance of oxidation film layer；Meanwhile, differential arc oxidation is crossed long-time more long, increases the roughness of oxidation film layer.Ceramic layer thickness is excessive, spare part outside measurement is changed relatively big, affects such as follow-up assembling, and surface roughness is high, affects presentation quality, and these deficiencies above-mentioned all have impact on the further application of arc differential oxide ceramic layer.
Summary of the invention
For solving differential arc oxidization technique above shortcomings, the invention provides a kind of electrolyte for preparing N doping arc differential oxide ceramic layer, and utilize this electrolyte to carry out, in aluminum alloy surface, the arc differential oxide ceramic layer that surface treatment acquisition is nitrogenous, improve the surface property of aluminium alloy.
The technical scheme is that a kind of electrolyte for preparing N doping arc differential oxide ceramic layer, described electrolyte contains the organic base of 10-25ml/L.
Described organic base is triethylamine.
The present invention adds a certain amount of triethylamine in the electrolyte of differential arc oxidation, electrolyte is stirred with blowing air by preparation process, for reducing the volatilization of triethylamine, lid need to be added on differential arc oxidation electrolysis bath, it is ensured that what in electrolyte, triethylamine was stable maintains finite concentration.
Described electrolyte can be conventionally used in this area in the electrolyte of arc differential oxide ceramic layer add triethylamine obtain, preferential, electrolyte of the present invention is composed as follows:
NaOH1.0~1.5g/L
Na2SiO312.0~16.0g/L
NaF0.5~1.0g/L
Triethylamine 10-25ml/L
Solvent is distilled water.
More preferential, described electrolyte is composed as follows:
NaOH1.2g/L
Na2SiO315g/L
NaF0.7g/L
Triethylamine 15ml/L
Solvent is distilled water.
Or, described electrolyte is composed as follows:
KOH2.0~3.5g/L
Na2SiO39.0~15g/L
Triethylamine 10-25ml/L
Solvent is distilled water.
More preferential, described electrolyte is composed as follows:
KOH3.0g/L
Na2SiO312g/L
Triethylamine 18ml/L
Solvent is distilled water.
Or, described electrolyte is composed as follows:
KOH2.5-4.0g/L
Na3PO430-40g/L
Triethylamine 10-25ml/L
NaF0.5~1.0g/L
Solvent is distilled water.
More preferential, described electrolyte is composed as follows:
KOH3.0g/L
Na3PO435g/L
Triethylamine 15ml/L
NaF0.8g/L
Solvent is distilled water.
The electrolyte preparing N doping arc differential oxide ceramic layer for differential arc oxidation of the present invention, described nitrogenous arc differential oxide ceramic layer is often referred to the ceramic layer that aluminum alloy surface is implemented.Aluminium alloy of the present invention typically refers to the Aluminium Alloys in Common Uses such as 2A12,6061,6063.
The invention still further relates to the method utilizing aforementioned electrolyte that aluminum alloy surface is processed, described method includes: adopt dipulse microarc oxidation equipment provided, it is immersed in described electrolyte with aluminium alloy for anode, with rustless steel container for negative electrode, controlling to apply positive voltage is 400-500V, and negative voltage is 60-120V, when differential arc oxidation, the pattern of constant voltage after the first constant current of employing, the electric current density of constant-current phase is 20-25A/dm2, the time is 1 ~ 2min.The differential arc oxidation time is 40-60min, obtains surface and covers the aluminium alloy of nitrogenous ceramic layer.
Beneficial effects of the present invention: 1) ceramic layer prepared has the decay resistance of excellence；2) surface ceramii layer prepared is more smooth, and roughness is little.
Accompanying drawing explanation
Fig. 1 is the embodiment of the present invention 1 differential arc oxidation film layer surface topography, and wherein, figure a is not added with triethylamine in electrolyte, and figure b is interpolation triethylamine in electrolyte；
When Fig. 2 is add triethylamine in the embodiment of the present invention 1 electrolyte, the X ray diffracting spectrum on differential arc oxidation film layer surface；
Fig. 3 is the polarization curve comparison diagram of the embodiment of the present invention 1 differential arc oxidation film layer.
Detailed description of the invention
For disclosing technical scheme further, describe embodiments of the present invention in detail below in conjunction with accompanying drawing:
Embodiment 1
Adopting 2A12 aluminium alloy is matrix material, and electrolyte consists of: NaOH1.2g, Na2SiO315g, NaF0.7g, triethylamine 15ml, distilled water 1L.Adopt that 30kW dipulse is microarc oxidation equipment provided tests, test positive voltage 400V, negative voltage 60V, positive voltage frequency 300Hz；Negative voltage frequency 100Hz；Positive voltage dutycycle is 50%；Negative voltage dutycycle is 30%；The differential arc oxidation time is 40min.In experimentation, keep solution temperature at about 5 DEG C.When differential arc oxidation, the pattern of constant voltage after the first constant current of employing, the electric current density of constant-current phase is 20A/dm, and the time is 2min.
Laboratory observation by contrast, when electrolyte is not added with triethylamine, Surfaces rough surface, porosity high (as shown in Figure 1a), and the differential arc oxidation film layer surfacing obtained after the PROCESS FOR TREATMENT of the present invention, smooth and low porosity (as shown in Figure 1 b).
Adopting X-ray diffractometer (BrukerD8Advance) that ceramic layer structure is characterized, Fig. 2 is shown in the phase composition of ceramic layer；Adopting electrochemical workstation (PARSTAT2273) to carry out decay resistance test, polarization curve is as shown in Figure 3.
Embodiment 2
Adopting 2A12 aluminium alloy is matrix material, and electrolyte consists of: NaOH1g, Na2SiO312g, NaF0.5g, triethylamine 10ml, distilled water 1L.Adopt the method identical with embodiment 1, utilize described electrolyte that 2A12 aluminum alloy surface is processed, obtain surface and cover the aluminium alloy of nitrogenous ceramic layer.
Embodiment 3
Adopting 2A12 aluminium alloy is matrix material, and electrolyte consists of: NaOH1.5g, Na2SiO316g, NaF1g, triethylamine 25ml, distilled water 1L.Adopt the method identical with embodiment 1, utilize described electrolyte that 2A12 aluminum alloy surface is processed, obtain surface and cover the aluminium alloy of nitrogenous ceramic layer.
Embodiment 4
Adopting 6061 aluminium alloys is matrix material, and electrolyte consists of: KOH3.0g, Na2SiO312g, triethylamine 18ml, distilled water 1L.Adopt that 30kW dipulse is microarc oxidation equipment provided tests, test positive voltage 500V, negative voltage 120V, positive voltage frequency 500Hz；Negative voltage frequency 300Hz；Positive voltage dutycycle is 55%；Negative voltage dutycycle is 45%；The differential arc oxidation time is 60min.In experimentation, keep solution temperature at about 5 DEG C.When differential arc oxidation, the pattern of constant voltage after the first constant current of employing, the electric current density of constant-current phase is 25A/dm, and the time is 1min.
Embodiment 5
Adopting 6061 aluminium alloys is matrix material, and electrolyte consists of: KOH2.0g, Na2SiO39g, triethylamine 10ml, distilled water 1L.Adopt the method identical with embodiment 4, utilize described electrolyte that 6061 aluminum alloy surface are processed, obtain surface and cover the aluminium alloy of nitrogenous ceramic layer.
Embodiment 6
Adopting 6061 aluminium alloys is matrix material, and electrolyte consists of: KOH3.5g, Na2SiO315g, triethylamine 25ml, distilled water 1L.Adopt the method identical with embodiment 4, utilize described electrolyte that 6061 aluminum alloy surface are processed, obtain surface and cover the aluminium alloy of nitrogenous ceramic layer.
Embodiment 7
Adopting 6063 aluminium alloys is matrix material, and electrolyte consists of: KOH3.0g, Na3PO435g, triethylamine 15ml, NaF0.8g, distilled water 1L.Adopt that 30kW dipulse is microarc oxidation equipment provided tests, test positive voltage 450V, negative voltage 100V, positive voltage frequency 400Hz；Negative voltage frequency 200Hz；Positive voltage dutycycle is 50%；Negative voltage dutycycle is 40%；The differential arc oxidation time is 50min.In experimentation, keep solution temperature at about 5 DEG C.When differential arc oxidation, the pattern of constant voltage after the first constant current of employing, the electric current density of constant-current phase is 20A/dm, and the time is 2min.
Embodiment 8
Adopting 6063 aluminium alloys is matrix material, and electrolyte consists of: KOH2.5g, Na3PO430g, triethylamine 10ml, NaF0.5g, distilled water 1L.Adopt the method identical with embodiment 7, utilize described electrolyte that 6063 aluminum alloy surface are processed, obtain surface and cover the aluminium alloy of nitrogenous ceramic layer.
Embodiment 9
Adopting 6063 aluminium alloys is matrix material, and electrolyte consists of: KOH4g, Na3PO440g, triethylamine 25ml, NaF1g, distilled water 1L.Adopt the method identical with embodiment 7, utilize described electrolyte that 6063 aluminum alloy surface are processed, obtain surface and cover the aluminium alloy of nitrogenous ceramic layer.
Claims (7)
1. the electrolyte being used for preparing N doping arc differential oxide ceramic layer, it is characterised in that described electrolyte is composed as follows:
NaOH1.0~1.5g/L
Na2SiO312.0~16.0g/L
NaF0.5~1.0g/L
Triethylamine 10-25ml/L
Solvent is distilled water.
2. electrolyte according to claim 1, it is characterised in that described electrolyte is composed as follows:
NaOH1.2g/L
Na2SiO315g/L
NaF0.7g/L
Triethylamine 15ml/L
Solvent is distilled water.
3. the electrolyte being used for preparing N doping arc differential oxide ceramic layer, it is characterised in that described electrolyte is composed as follows:
KOH2.0~3.5g/L
Na2SiO39.0~15g/L
Triethylamine 10-25ml/L
Solvent is distilled water.
4. electrolyte according to claim 3, it is characterised in that described electrolyte is composed as follows:
KOH3.0g/L
Na2SiO312g/L
Triethylamine 18ml/L
Solvent is distilled water.
5. the electrolyte being used for preparing N doping arc differential oxide ceramic layer, it is characterised in that described electrolyte is composed as follows:
KOH2.5-4.0g/L
Na3PO430-40g/L
Triethylamine 10-25ml/L
NaF0.5~1.0g/L
Solvent is distilled water.
6. electrolyte according to claim 5, it is characterised in that described electrolyte is composed as follows:
KOH3.0g/L
Na3PO435g/L
Triethylamine 15ml/L
NaF0.8g/L
Solvent is distilled water.
7. utilize the technique that aluminum alloy surface is carried out differential arc oxidation process by the electrolyte as described in any one of claim 1-6, described technique includes: adopt dipulse microarc oxidation equipment provided, it is immersed in described electrolyte with aluminium alloy for anode, with rustless steel container for negative electrode, controlling to apply positive voltage is 400-500V, and negative voltage is 60-120V, when differential arc oxidation, the pattern of constant voltage after the first constant current of employing, the electric current density of constant-current phase is 20-25A/dm2, the time is 1 ~ 2min；The differential arc oxidation time is 40-60min, obtains surface and covers the aluminium alloy of nitrogenous ceramic layer.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111058077A (en) * | 2020-01-19 | 2020-04-24 | 常州大学 | Electrolyte for micro-arc oxidation of black ceramic membrane, preparation method of electrolyte and micro-arc oxidation method |
| WO2022186706A1 (en) * | 2021-03-02 | 2022-09-09 | Cirrus Materials Science Limited | A process to protect light metal substrates |
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| WO1998042892A1 (en) * | 1997-03-24 | 1998-10-01 | Magnesium Technology Limited | Anodising magnesium and magnesium alloys |
| CN1793438A (en) * | 2005-11-25 | 2006-06-28 | 湖南大学 | Anode oxidating electrolysing liquid under inhibiting arc state of magnesium alloy and process for anode oxidating |
| CN102230205A (en) * | 2011-06-20 | 2011-11-02 | 华南理工大学 | Aluminum alloy micro-arc oxidation black ceramic membrane and preparation method thereof |
| CN102321903A (en) * | 2011-06-23 | 2012-01-18 | 兰州理工大学 | Preparation method of composite film on surface of metallic material and solution composition for preparation method |
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2016
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Patent Citations (5)
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| WO1998042892A1 (en) * | 1997-03-24 | 1998-10-01 | Magnesium Technology Limited | Anodising magnesium and magnesium alloys |
| CN1793438A (en) * | 2005-11-25 | 2006-06-28 | 湖南大学 | Anode oxidating electrolysing liquid under inhibiting arc state of magnesium alloy and process for anode oxidating |
| CN102230205A (en) * | 2011-06-20 | 2011-11-02 | 华南理工大学 | Aluminum alloy micro-arc oxidation black ceramic membrane and preparation method thereof |
| CN102321903A (en) * | 2011-06-23 | 2012-01-18 | 兰州理工大学 | Preparation method of composite film on surface of metallic material and solution composition for preparation method |
| CN102828218A (en) * | 2012-09-14 | 2012-12-19 | 戚威臣 | Electrolyte used for magnesium alloy anode oxidation treatment and treatment method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111058077A (en) * | 2020-01-19 | 2020-04-24 | 常州大学 | Electrolyte for micro-arc oxidation of black ceramic membrane, preparation method of electrolyte and micro-arc oxidation method |
| WO2022186706A1 (en) * | 2021-03-02 | 2022-09-09 | Cirrus Materials Science Limited | A process to protect light metal substrates |
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Application publication date: 20160629 |