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WO2021027748A1 - 一种铝合金氧化成膜所用的电解氧化液以及铝合金氧化成膜方法 - Google Patents

一种铝合金氧化成膜所用的电解氧化液以及铝合金氧化成膜方法 Download PDF

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WO2021027748A1
WO2021027748A1 PCT/CN2020/108026 CN2020108026W WO2021027748A1 WO 2021027748 A1 WO2021027748 A1 WO 2021027748A1 CN 2020108026 W CN2020108026 W CN 2020108026W WO 2021027748 A1 WO2021027748 A1 WO 2021027748A1
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Prior art keywords
film formation
aluminum alloy
electrolytic
electrolysis
film
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PCT/CN2020/108026
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English (en)
French (fr)
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西华昆
马康慷
张祥华
庄乾浩
毕小雪
杨维玉
高瑞安
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临朐县检验检测中心
高瑞安
潍坊国一铝材有限公司
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Priority to AU2020327479A priority Critical patent/AU2020327479B2/en
Publication of WO2021027748A1 publication Critical patent/WO2021027748A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/10—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing organic acids

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  • the invention relates to the technical field of surface treatment of aluminum alloy profiles, in particular to a treatment technology using electrochemical oxidation to form a film.
  • the surface oxidation treatment of aluminum alloy is mainly to generate a protective film on the surface of the aluminum profile.
  • This layer of film has protective, decorative and some other functional characteristics to meet the needs of aluminum anodizing for construction, aluminum anodizing for decoration, aluminum anodizing for corrosion protection, and aluminum anodizing for engineering. According to different purposes of use and different performance requirements, make full use of the characteristics of the film to meet different purposes.
  • barrier type anodic oxide film electrolytes are roughly divided into: boric acid, neutral borate, neutral phosphate, neutral tartrate, neutral citrate, and neutral oxalic acid Salt; porous anodic oxide film electrolyte: sulfuric acid, oxalic acid, chromic acid, phosphoric acid, sulfuric acid plus organic acid, etc.
  • the porous oxidizing electrolyte in the prior art has the problem that the aluminum ions in the solution continue to rise as the electrolysis time is extended.
  • the electrolyte In order to control the concentration of aluminum ions in the electrolyte, the electrolyte must be continuously discharged to supplement the electrolyte without aluminum ions. Maintain the aluminum ion concentration range.
  • the oxidation film formation process in the existing technology is as follows:
  • the anion SO 4 2- participates in the anodic reaction process of aluminum, and finally produces an anodic oxide film containing sulfate:
  • the aluminum ion concentration in the electrolyte will continue to increase. Generally speaking, it will have a beneficial effect if it is below 10g/L, and it will have an adverse effect if it exceeds 10g/L.
  • the method of discharging part of the old bath is generally used to reduce the aluminum content.
  • the discharge of the electrolyte takes away a large amount of H 2 SO 4 , and AI 3+ causes pollution to the environment. Most of them are neutralized by lime, so a large amount of Of solid waste, causing tremendous pressure on the environment.
  • the existing technology is not conducive to environmental protection, is also a key process point for the current aluminum profile enterprises to generate a large amount of solid waste, and increases production costs.
  • the first technical problem to be solved by the present invention is to provide an electrolytic oxidizing solution for aluminum alloy oxidation film formation in view of the shortcomings of the prior art.
  • the aluminum ion concentration generally reaches about 0.1g/L to produce ionization balance.
  • the oxidizing solution does not need to be replaced and can be recycled.
  • the generated oxide film is an organic and inorganic fluorine-containing oxide film, which has a honeycomb-like uniform oxide film with corrosion resistance, impact resistance, high hardness and high wear resistance.
  • the second technical problem to be solved by the present invention is: in view of the shortcomings of the prior art, an aluminum alloy oxidation film forming method is provided, the process method is simple, the electrolyte waste does not need to be replaced, and the environmental protection problem is solved.
  • the technical solution of the present invention is:
  • electrolytic oxidizing solution for aluminum alloy oxidation and film formation
  • the electrolytic oxidizing solution contains the following components: hydrogen fluoride ammonia 0.1-1g/L, oxalic acid 5-60g/L; Al 3+ equilibrium solubility in the oxidizing solution It is 0.01 ⁇ 1g/L.
  • the electrolytic oxidation solution contains the following components: 0.1 ⁇ 0.6g/L of hydrogen fluoride ammonia, 10 ⁇ 40g/L of oxalic acid; the equilibrium solubility of Al 3+ in the oxidation solution is 0.01 ⁇ 1g /L.
  • the presence of F ions in the electrolytic oxidation solution of the present invention reduces the chemical energy of AI and makes it easier to generate AI 3+.
  • concentration of oxalic acid is about 50 times that of ammonium hydrogen fluoride, and it also ensures that AI 3+ can generate aluminum oxalate and participate in film formation.
  • F ions also act as catalysts during the reaction.
  • the strong complexation of F ions on Al 3+ accelerates the dissolution of the oxide film and the continuous formation of porous oxide film layers.
  • Oxalic acid participates in the joint process of anodic oxide film formation-anodic oxidation-chemical dissolution-chemical film formation. However, if the concentration of NH 3 HF reaches about 1.5 g/l, it will become a film dissolving effect.
  • the film-forming solution reaches equilibrium, and the film will no longer increase; when it is increased to about 5.0g/l, the film-forming film will be larger than the film-forming in the oxidation process, and the oxide film cannot be formed and lead to the concentration of AI 3+ in the solution Keep rising.
  • the dissolution of the aluminum matrix mainly depends on the concentration of fluoride ion, and the film formation depends on oxalic acid. By coordinating the ratio of the two, the balance of dissolution and film formation can be achieved, and the Al 3+ concentration of the system pretreatment system can be maintained basically unchanged.
  • the electrolytic oxidation solution also contains one or more of soluble fluoride salt, oxalate and sulfate.
  • the added amount of the fluoride salt, oxalate salt and sulfate salt is 0.1-60 g/L.
  • the electrolytic oxidation solution also contains one or more of sodium fluoride, sodium oxalate and sodium sulfate.
  • the addition of sodium fluoride and sodium oxalate can effectively increase the content of organic components in the oxide film and aluminum hexafluoride salt, aluminum trifluoride, and sulfate can also participate in film formation, and the addition of salt can also reduce electrical resistance and reduce electrolysis energy consumption.
  • the technical solution of the present invention is:
  • An aluminum alloy oxidation film formation method uses the above-mentioned electrolytic oxidation solution and an electrolysis method to form an organic-inorganic fluorine-containing oxide film on the surface of the aluminum alloy through chemical film formation and electrochemical film formation.
  • the constant-voltage method is used for electrolysis during the electrolysis, and the voltage during the electrolysis by the constant-voltage method is 20-60v.
  • the constant current method is used for electrolysis during the electrolysis, and the current during the constant current electrolysis is 1 to 5 A/dm 2 .
  • the electrolysis time during the electrolysis is 1 min-6h.
  • the organic-inorganic fluorine-containing oxide film has a thickness of 0.5-60 ⁇ m.
  • the electrolytic oxidizing solution used for the oxidation of aluminum alloy film of the present invention contains the following components: hydrogen fluoride ammonia 0.1 to 1 g/L, oxalic acid 5 to 60 g/L; Al 3+ equilibrium dissolved in the oxidizing solution The degree is 0.01 ⁇ 1g/L.
  • the electrolytic oxidizing solution of the present invention is used for electrolytic oxidation to form a film, chemical film forming and electrochemical film forming work together, and the film forming process is fast; the aluminum ion concentration in the oxidizing solution is generally about 0.1g/L, that is, ionization balance occurs, and the aluminum ion concentration is not It is increased again, so the oxidizing liquid does not need to be replaced and can be recycled.
  • the oxide film produced by the electrolysis of the present invention is an organic-inorganic fluorine-containing oxide film.
  • the oxide film After SEM+EDS detection and analysis, the oxide film has a uniform honeycomb shape, and the film porosity is above 60%.
  • the fluorine content is 1-15%
  • the C content is 3-20%
  • the O content is about 46%
  • the formed film has the advantages of high corrosion resistance, high impact resistance, toughness, high hardness and high wear resistance, and the film hardness Around 400HV.
  • the present invention adopts the electrolytic oxidation solution oxidation film forming method, which is simple, easy to control, and fast in film forming speed.
  • Constant voltage electrolysis or constant current electrolysis can be used, both of which can quickly obtain a uniformly formed honeycomb oxide film .
  • the electrolysis time is 1-20 minutes to get an oxide film with a thickness of 5-20 ⁇ m.
  • the electrolyte Al ion in the electrolyte is about 0.1g/L, which produces an electrolytic balance.
  • the aluminum ion concentration will not increase over 12 months, and the low electrolyte concentration is used, and the fluoride ion is used as the electrolytic film to dissolve the film.
  • Agent interferes with the phenomenon of local interference (such as pitting) caused by other ions on the surface of the anodic anodized film.
  • the qualitative change of the chemical film formation and the electrochemical film formation can reduce the influence of the concentration on the film formation. Large current can be used to quickly form a film to reduce oxidation costs.
  • the electrolysis method of the present invention can obtain a colorless transparent to golden yellow composite film by controlling the voltage and current density, controlling the film forming speed, and changing the film forming composition.
  • Figure 1 is a surface topography of an oxide film with a thickness of 15 ⁇ m detected by SEM of the present invention
  • Fig. 2 is a surface topography of an oxide film with a thickness of 20 ⁇ m detected by SEM of the present invention
  • Figure 3 is an EDS analysis energy spectrum of a certain point in Figure 1;
  • Figure 4 is an EDS analysis energy spectrum diagram of another point in Figure 1;
  • Figure 5 is an EDS analysis energy spectrum of a certain point in Figure 2;
  • Figure 6 is an EDS analysis energy spectrum diagram of another point in Figure 2;
  • Figure 7 is an XPS spectrum of a certain point in Figure 1.
  • the oxide film prepared by the present invention has higher hardness and stronger corrosion resistance.
  • electrolytic oxidizing solution used for aluminum alloy oxidation film formation contains the following components: hydrogen fluoride ammonia 0.2g/L, oxalic acid 10g/L; the equilibrium solubility of Al 3+ in the oxidizing solution is 0.1g /L.
  • electrolytic oxidizing solution used for aluminum alloy oxidation film formation contains the following components: hydrogen fluoride ammonia 0.4g/L, oxalic acid 20g/L; the equilibrium solubility of Al 3+ in the oxidizing solution is 0.2g /L.
  • electrolytic oxidizing solution for aluminum alloy oxidation and film formation
  • the electrolytic oxidizing solution contains the following components: hydrogen fluoride ammonia 0.6g/L, oxalic acid 30g/L; the equilibrium solubility of Al 3+ in the oxidizing solution is 0.22g /L.
  • An electrolytic oxidation solution containing the following components is used: 0.5 g/L of hydrogen fluoride ammonia, 35 g/L of oxalic acid, and 2 g/L of sodium fluoride; the equilibrium solubility of Al 3+ in the oxidation solution is 0.2 g/L. Under normal temperature, electrolysis is carried out with a direct current density of 2.5A/dm 2 (constant current method), and the electrolysis time is 10 minutes.
  • An electrolytic oxidation solution containing the following components is used: 0.6 g/L of hydrogen fluoride ammonia and 40 g/L of oxalic acid; the equilibrium solubility of Al 3+ in the oxidation solution is 0.18 g/L. Under normal temperature, the electrolysis is carried out with a DC current density of 3.0A/dm 2 (constant current method), and the electrolysis time is 15 minutes.
  • An electrolytic oxidation solution containing the following components is used: 0.45 g/L of hydrogen fluoride ammonia, 30 g/L of oxalic acid, and 5 g/L of sodium oxalate; the equilibrium solubility of Al 3+ in the oxidation solution is 0.2 g/L. Under normal temperature, the electrolysis is carried out with a DC voltage of 40v (constant voltage method), and the electrolysis time is 15 minutes.
  • An electrolytic oxidation solution containing the following components is used: 0.55 g/L of hydrogen fluoride ammonia and 35 g/L of oxalic acid; the equilibrium solubility of Al 3+ in the oxidation solution is 0.2 g/L. Under normal temperature, the electrolysis is carried out with a DC voltage of 30v (constant voltage method), and the electrolysis time is 20 minutes.
  • An electrolytic oxidation solution containing the following components is used: 0.35 g/L of hydrogen fluoride ammonia and 38 g/L of oxalic acid; the equilibrium solubility of Al 3+ in the oxidation solution is 0.21 g/L. Under normal temperature, the electrolysis is carried out with a DC voltage of 60v (constant voltage method), and the electrolysis time is 30min.
  • Electrolytically oxidizing the prior art solution using sulfuric acid a sulfuric acid concentration of electrolyte 18g / L, a temperature of 18 °C ⁇ 1, current density of 1.5A / dm 2, the electrolysis time was 30min.
  • the oxide films prepared by the present invention are all uniform honeycomb, with a porosity of more than 65%, and are organic-inorganic combined fluorine-containing oxide films with high hardness. And within a certain range, as the electrolysis time increases, the film thickness increases.
  • the comparative example obtained an inorganic film without honeycomb and fluorine.
  • the film porosity is only 18% and the hardness is low.
  • the electrolytic oxidizing solution used for the oxidation and film formation of aluminum alloy of the present invention contains the following components: hydrogen fluoride ammonia 0.1-1g/L, oxalic acid 5-60g/L; Al 3+ in the oxidizing solution The equilibrium solubility is 0.01 ⁇ 1g/L.
  • the electrolytic oxidizing solution of the present invention is used for electrolytic oxidation to form a film, chemical film forming and electrochemical film forming work together, and the film forming process is fast; the aluminum ion concentration in the oxidizing solution is generally about 0.1g/L, that is, ionization balance occurs, and the aluminum ion concentration is not It is increased again, so the oxidizing liquid does not need to be replaced and can be recycled.
  • the solid waste is reduced.
  • about 50 tons of Al 3+ are discharged, which reduces wastewater discharge by more than 80% and reduces wastewater consumption
  • the oxygen content is more than 90%, so it has good industrial applicability.
  • the oxide film produced by the electrolysis of the present invention is an organic-inorganic fluorine-containing oxide film. After SEM+EDS detection and analysis, the oxide film has a uniform honeycomb shape, and the film porosity is above 60%. Among them, the fluorine content is 1-15%, the C content is 3-20%; the O content is about 46%, and the formed film has the advantages of high corrosion resistance, high impact resistance, toughness, high hardness and high wear resistance, and the film hardness Around 400HV, it has good industrial applicability.
  • the present invention uses the electrolytic oxidation solution to oxidize and form a film.
  • the method is simple, easy to control, and the film formation speed is fast. Constant voltage electrolysis or constant current electrolysis can be used, and uniformly formed honeycombs can be quickly obtained.
  • Oxide film, the electrolysis time is 1-20 minutes to get an oxide film with a thickness of 5-20 ⁇ m.
  • the colorless transparent to golden yellow composite film can be obtained by controlling the voltage and current density, controlling the film forming speed, and changing the film composition.
  • the process method is simple and controllable, so it has good industrial applicability.
  • the electrolyte Al ion in the electrolyte will produce electrolytic equilibrium at about 0.1g/L, and the aluminum ion concentration will not increase over 12 months, and the low electrolyte concentration is used, and the fluoride ion is used as the electrolytic oxide film.
  • Membrane agent porolytic agent

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Abstract

本发明公开了一种铝合金氧化成膜所用的电解氧化液以及铝合金氧化成膜方法，所述电解氧化液中含有以下组分：氟化氢氨0.1～1g/L，草酸5～60g/L；所述氧化液中Al 3+平衡浓度为0.01～1g/L。一种铝合金氧化成膜方法，使用上述的电解氧化液，采用电解法，在铝合金表面通过化学成膜和电化学成膜共同作用形成一层有机无机含氟氧化膜。使用本发明的电解氧化液电解氧化成膜，化学成膜电化学成膜共同作用，成膜过程快；氧化液中铝离子浓度一般在0.1g/L左右即产生电离平衡，铝离子浓度不再增加，因此氧化液不需更换，可循环使用，因此相比现有技术固废减少。

Description

一种铝合金氧化成膜所用的电解氧化液以及铝合金氧化成膜方法 技术领域
本发明涉及铝合金型材表面处理技术领域，具体涉及一种使用电化学氧化成膜处理技术。
背景技术
铝合金的表面氧化处理，主要是在铝型材表面生成一种保护膜。这层膜具有防护性、装饰性以及一些其它的功能特征，以获得满足建筑用铝阳极氧化、装饰用铝阳极氧化、腐蚀保护用铝阳极氧化、工程用铝阳极氧化的需求。根据不同的使用目的和不同的性能要求，充分利用膜的特性满足不同的用途。
现有技术中根据电解液的不同大致分为，壁垒型阳极氧化膜电解液：硼酸、中性硼酸盐、中性磷酸盐、中性酒石酸盐、中性柠檬酸盐、中性乙二酸盐；多孔型阳极氧化膜电解液：硫酸、草酸、铬酸、磷酸、硫酸加有机酸等。
现有技术中多孔型氧化电解液，均存在随着电解时间延长溶液中铝离子不断升高问题，为了控制电解液中的铝离子浓度必须不断排放电解液，补充不含铝离子的电解液以维持铝离子浓度范围。
现有的技术中氧化成膜过程如下：
成膜过程2Al+3H 2O→Al 2O 3+6H ++6e -
膜溶解过程Al 2O 3+6H +→2Al 3++3H 2O
阴极上发生水的分解析出气体：
6H 2O+6e -→3H 2↑+6OH -
以硫酸为例，阴离子SO 4 2-参与了铝的阳极反应过程，最终生成含硫酸根的阳极氧化膜：
2Al+6H +→2Al 3++3H 2↑
2Al 3++3H 2O+3SO 4 2-→【Al 2O 3】+3H 2SO 4
Al 3++XH 2O+YSO 4 2-→【Al(OH) Y(SO 4) X】+XH +
这是一个成膜与溶膜不断发生的过程。
以上氧化过程中，溶液中如果F -、Cl -超过50μg/g浓度，型材就会出现腐蚀斑点，因此必须严格控制。
以上不管是用哪种多孔氧化膜生产工艺，电解液中铝离子浓度都会不断升高，一般来说10g/L以下产生有利影响，超过10g/L造成不利影响。为了控制铝离子浓度，一般采用排放部分旧槽液的方法来降低铝含量，电解液的排放带走大量H 2SO 4，AI 3+对环境造成污染，大部分采用石灰中和，因此产生大量的固体废物，对环境造成巨大压力。现有技术既不利于环境保护，也是当前铝型材企业产生大量固废的关键工艺点，而且增加生产成本。
发明内容
本发明所要解决的第一个技术问题是：针对现有技术存在的不足，提供一种铝合金氧化成膜所用的电解氧化液，铝离子浓度一般达在0.1g/L左右即产生电离平衡，氧化液不需更换，可循环使用，且生成的氧化膜是有机无机含氟氧化膜，具有耐腐蚀性、耐冲击、高硬度、高耐磨的蜜蜂窝状均匀的氧化膜。
本发明所要解决的第二个技术问题是：针对现有技术存在的不足，提供一种铝合金氧化成膜方法，工艺方法简单，电解废液不需要更换，解决了环保问题。
为解决上述第一个技术问题，本发明的技术方案是：
一种铝合金氧化成膜所用的电解氧化液，所述电解氧化液中含有以下组分：氟化氢氨0.1～1g/L，草酸5～60g/L；所述氧化液中Al 3+平衡溶度为0.01～1g/L。
作为一种优选的技术方案，所述电解氧化液中含有以下组分：氟化氢氨0.1～0.6g/L，草酸10～40g/L；所述氧化液中Al 3+平衡溶度为0.01～1g/L。
本发明的电解氧化液中F离子的存在降低了AI的化学能，更易生成AI 3+，，草酸的浓度是氟化氢氨的50倍左右，又保证AI 3+能生成草酸铝而参与成膜。F离子在反应过程中也起了催化剂的作用，F离子对Al 3+的强络合作用加速了氧化膜的溶解、多孔氧化膜层不断生成。草酸参与阳极氧化膜的生成-阳极氧化-化学溶解-化学成膜共同作用过程。但如果NH 3HF浓度达到1.5g/l左右反而成为溶膜作用。膜厚度达到10μm左右，成膜溶膜达到平衡，膜将不再增加；在提高 到5.0g/l左右，在氧化过程中溶膜大于成膜，无法形成氧化膜并导致溶液中AI 3+浓度不断升高。铝基体溶解主要取决于氟离子浓度，成膜取决于草酸，通过协调二者比例，达到溶解-成膜平衡，可以维持体系预处理体系Al 3+浓度基本不变。
作为改进的一种技术方案，所述电解氧化液中还含有可溶性的氟化盐、草酸盐和硫酸盐中的一种或几种。所述氟化盐、草酸盐和硫酸盐的加入量为0.1～60g/L。
作为优选的一种技术方案，所述电解氧化液中还含有氟化钠、草酸钠和硫酸钠中的一种或几种。加入氟化钠和草酸钠可以有效增加氧化膜中有机成分含量以及六氟化铝盐，三氟化铝，硫酸根也参与成膜，并且加入盐还可以降低电阻，降低电解能耗。
为解决上述第二个技术问题，本发明的技术方案是：
一种铝合金氧化成膜方法，使用上述的电解氧化液，采用电解法，在铝合金表面通过化学成膜和电化学成膜共同作用形成一层有机无机含氟氧化膜。
作为改进的一种技术方案，所述电解时采用恒压法进行电解，所述恒压法进行电解时的电压为20～60v。
作为改进的另一种技术方案，所述电解时采用恒流法进行电解，所述恒流进行电解时的电流为1～5A/dm 2。
作为优选的一种技术方案，所述电解时的电解时间为1min～6h。
作为优选的一种技术方案，所述有机无机含氟氧化膜的厚度为0.5～60μm。
由于采用了上述技术方案，本发明的有益效果是：
本发明的铝合金氧化成膜所用的电解氧化液，所述电解氧化液中含有以下组分：氟化氢氨0.1～1g/L，草酸5～60g/L；所述氧化液中Al 3+平衡溶度为0.01～1g/L。使用本发明的电解氧化液去电解氧化成膜，化学成膜电化学成膜共同作用，成膜过程快；氧化液中铝离子浓度一般在0.1g/L左右即产生电离平衡，铝离子浓度不再增加，因此氧化液不需更换，可循环使用，因此相比现有技术固废减少，每生产5000吨型材少排放Al 3+50吨左右，减少废水排放量80％以上，且减少废水耗氧量90％以上。而且本发明电解生成的氧化膜是有机无机含氟氧化 膜，经SEM+EDS检测和分析，氧化膜为均匀的蜂窝状，膜孔率在60％以上。其中氟成分含量1-15％，C含量3-20％；O含量46％左右，且形成的膜具有高耐蚀性、高耐冲击性、韧性、高硬度和高耐磨的优点，膜硬度在400HV左右。
本发明采用所述电解氧化液氧化成膜方法，方法简单，容易控制，成膜速度快，可采用恒压法电解，也可以采用恒流法电解，均可以快速得到成型均匀的蜂窝状氧化膜，电解时间为1-20分即可得到厚度为5-20μm的氧化膜。而且经长期试验，电解液中该电解液Al离子在0.1g/L左右即产生电解平衡，超过12个月铝离子浓度不会增加，且采用低电解质浓度,利用氟离子为电氧化膜溶膜剂(溶孔剂)，干扰了其他离子对阳极阳化膜表面产生局部干扰的现象(如点蚀)，化学成膜电化学成膜共同发生质变，减少了浓度对成膜的影响，而且还可以采用大电流快速成膜，降低氧化成本。
本发明电解方法可以通过控制电压和电流密度，控制成膜速度，改变成膜成份，即可获得无色透明到金黄色复合膜。
附图说明
下面结合附图和实施例对本发明进一步说明。
图1是本发明SEM检测到的氧化膜厚度为15μm的表面形貌图；
图2是本发明SEM检测到的氧化膜厚度为20μm的表面形貌图；
图3是对图1中某一点的EDS分析能谱图；
图4是对图1中另一点的EDS分析能谱图；
图5是对图2中某一点的EDS分析能谱图；
图6是对图2中另一点的EDS分析能谱图；
图7是对图1中某一点的的XPS谱图。
具体实施方式
下面结合附图和实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
如附图1-2所示，本发明电解生成的氧化膜的膜孔直径在100nm以下呈均匀蜂窝状；分别对厚度为15μm和20μm的图1和图2中任选两点做EDS分析；分别对应图3、图4、图5和图6的能谱图，分析结果如下表1、表2、表3和表4所示。从图中可以看出，本发明的氧化膜表面的C主要以C-C、C-O、C＝O等官能团的形式存在，F以AlF3/Na3AlF6形式存在；因而证明，本发明氧化膜存在着化学成膜过程。
表1
Figure PCTCN2020108026-appb-000001
表2
Figure PCTCN2020108026-appb-000002
表3
Figure PCTCN2020108026-appb-000003
表4
Figure PCTCN2020108026-appb-000004
按照GB/T 9790-1988、GB/T12967.3-2008对现有技术的传统硫酸法的氧化膜和本发明的铝合金氧化膜耐腐蚀性及显微硬度检测，结果如下表5。
Figure PCTCN2020108026-appb-000005
可见在厚度更小的前提下，本发明制备的氧化膜硬度更高，耐腐蚀性更强。
实施例1
一种铝合金氧化成膜所用的电解氧化液，所述电解氧化液中含有以下组分：氟化氢氨0.2g/L，草酸10g/L；所述氧化液中Al 3+平衡溶度为0.1g/L。
实施例2
一种铝合金氧化成膜所用的电解氧化液，所述电解氧化液中含有以下组分：氟化氢氨0.4g/L，草酸20g/L；所述氧化液中Al 3+平衡溶度为0.2g/L。
实施例3
一种铝合金氧化成膜所用的电解氧化液，所述电解氧化液中含有以下组分：氟化氢氨0.6g/L，草酸30g/L；所述氧化液中Al 3+平衡溶度为0.22g/L。
实施例4
采用含有以下组分的电解氧化液：氟化氢氨0.5g/L，草酸35g/L，氟化钠 2g/L；所述氧化液中Al 3+平衡溶度为0.2g/L。常温下，利用直流电流密度2.5A/dm 2(恒流法)进行电解，电解时间为10min。
实施例5
采用含有以下组分的电解氧化液：氟化氢氨0.6g/L，草酸40g/L；所述氧化液中Al 3+平衡溶度为0.18g/L。常温下，利用直流电流密度3.0A/dm 2(恒流法)进行电解，电解时间为15min。
实施例6
采用含有以下组分的电解氧化液：氟化氢氨0.45g/L，草酸30g/L，草酸钠5g/L；所述氧化液中Al 3+平衡溶度为0.2g/L。常温下，利用直流电压40v(恒压法)进行电解，电解时间为15min。
实施例7
采用含有以下组分的电解氧化液：氟化氢氨0.55g/L，草酸35g/L；所述氧化液中Al 3+平衡溶度为0.2g/L。常温下，利用直流电压30v(恒压法)进行电解，电解时间为20min。
实施例8
采用含有以下组分的电解氧化液：氟化氢氨0.35g/L，草酸38g/L；所述氧化液中Al 3+平衡溶度为0.21g/L。常温下，利用直流电压60v(恒压法)进行电解，电解时间为30min。
对比例1
电解氧化液采用现有技术的硫酸法，电解液中硫酸浓度为18g/L，温度为18℃±1，电流密度1.5A/dm 2，电解时间为30min。
上述实施例4-8以及对比例1制备得到的氧化膜的厚度和硬度，以及经SEM+EDS检测和分析的膜表面形貌和成分情况见表5。
表5
Figure PCTCN2020108026-appb-000006
Figure PCTCN2020108026-appb-000007
从表5可以看出，本发明制备得到的氧化膜均为均匀的蜂窝状，膜孔率超过65％，且为有机无机结合含氟的氧化膜，硬度高。且在一定范围内随电解时间增加，膜厚度增加。而对比例得到的是没有蜂窝状且不含氟的无机膜。膜孔率仅为18％，硬度低。
工业实用性
1、本发明的铝合金氧化成膜所用的电解氧化液，所述电解氧化液中含有以下组分：氟化氢氨0.1～1g/L，草酸5～60g/L；所述氧化液中Al 3+平衡溶度为0.01～1g/L。使用本发明的电解氧化液去电解氧化成膜，化学成膜电化学成膜共同作用，成膜过程快；氧化液中铝离子浓度一般在0.1g/L左右即产生电离平衡，铝离子浓度不再增加，因此氧化液不需更换，可循环使用，因此相比现有技术固废减少，每生产5000吨型材少排放Al 3+50吨左右，减少废水排放量80％以上，且减少废水耗氧量90％以上，因而具有很好的工业实用性。
2、本发明电解生成的氧化膜是有机无机含氟氧化膜，经SEM+EDS检测和分析，氧化膜为均匀的蜂窝状，膜孔率在60％以上。其中氟成分含量1-15％，C含量3-20％；O含量46％左右，且形成的膜具有高耐蚀性、高耐冲击性、韧性、高硬度和高耐磨的优点，膜硬度在400HV左右，因而具有很好的工业实用性。
3、本发明采用所述电解氧化液氧化成膜方法，方法简单，容易控制，成膜速度快，可采用恒压法电解，也可以采用恒流法电解，均可以快速得到成型均匀的蜂窝状氧化膜，电解时间为1-20分即可得到厚度为5-20μm的氧化膜。可以通过控制电压和电流密度，控制成膜速度，改变成膜成份，即可获得无色透明到金黄色复合膜，工艺方法简单，可控，因而具有很好的工业实用性。
4、经长期试验，电解液中该电解液Al离子在0.1g/L左右即产生电解平衡，超过12个月铝离子浓度不会增加，且采用低电解质浓度,利用氟离子为电氧化膜溶膜剂(溶孔剂)，干扰了其他离子对阳极阳化膜表面产生局部干扰的现象(如点蚀)，化学成膜电化学成膜共同发生质变，减少了浓度对成膜的影响，而且还可以采用大电流快速成膜，降低氧化成本，因而具有很好的工业实用性。

Claims (9)

  1. 一种铝合金氧化成膜所用的电解氧化液，其特征在于所述电解氧化液中含有以下组分：氟化氢氨0.1～1g/L，草酸5～60g/L；所述氧化液中Al 3+平衡浓度为0.01～1g/L。
  2. 如权利要求1所述的铝合金氧化成膜所用的电解氧化液，其特征在于：所述电解氧化液中含有以下组分：氟化氢氨0.1～0.6g/L，草酸10～40g/L；所述氧化液中Al 3+平衡溶度为0.1～1g/L。
  3. 如权利要求1所述的铝合金氧化成膜所用的电解氧化液，其特征在于：所述电解氧化液中还含有可溶性的氟化盐、草酸盐和硫酸盐中的一种或几种。
  4. 如权利要求3所述的铝合金氧化成膜所用的电解氧化液，其特征在于：所述电解氧化液中还含有氟化钠、草酸钠和硫酸钠中的一种或几种。
  5. 一种铝合金氧化成膜方法，其特征在于：使用权利要求1至4任一项所述的电解氧化液，采用电解法，在铝合金表面通过化学成膜和电化学成膜共同作用形成一层有机无机含氟氧化膜。
  6. 如权利要求5所述的铝合金氧化成膜方法，其特征在于：所述电解时采用恒压法进行电解，所述恒压法进行电解时的电压为20～60v。
  7. 如权利要求5所述的铝合金氧化成膜方法，其特征在于：所述电解时采用恒流法进行电解，所述恒流进行电解时的电流为1～5A/dm 2。
  8. 如权利要求5所述的铝合金氧化成膜方法，其特征在于：所述电解时的电解时间为1min～6h。
  9. 如权利要求5所述的铝合金氧化成膜方法，其特征在于：所述有机无机含氟氧化膜的厚度为0.5～60μm。
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108950549A (zh) * 2018-07-05 2018-12-07 哈尔滨工业大学 一种铝合金表面低太阳吸收率高发射率导电热控涂层的制备方法
CN109852978A (zh) * 2019-03-26 2019-06-07 高瑞安 一种铝合金除油抛光二合一处理液及对铝合金进行除油抛光处理的方法
CN110284174A (zh) * 2019-08-12 2019-09-27 潍坊国一铝材有限公司 一种铝合金氧化成膜所用的电解氧化液以及铝合金氧化成膜方法
CN111349958A (zh) * 2020-04-10 2020-06-30 高瑞安 一种电泳铝型材及其表面处理方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4502925A (en) * 1984-06-11 1985-03-05 American Hoechst Corporation Process for aluminum surface preparation
JP4814073B2 (ja) * 2006-12-14 2011-11-09 株式会社神戸製鋼所 半導体又は液晶製造装置用アルミニウム合金およびその製造方法
RU2529328C1 (ru) * 2013-08-27 2014-09-27 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Нижегородский государственный технический университет им. Р.Е. Алексеева", НГТУ Электролит для анодирования алюминия и его сплавов перед нанесением медных гальванопокрытий
CN106757266A (zh) * 2016-12-14 2017-05-31 玉林师范学院 一种铝合金表面阳极氧化膜的彩色封孔方法
CN106400082A (zh) * 2016-12-14 2017-02-15 玉林师范学院 一种表面具有高硬度阳极氧化膜的铝合金的制备工艺
CN107541764B (zh) * 2017-09-07 2019-05-31 上海脉诺金属表面处理技术有限公司 一种高硅高铜压铸铝阳极氧化工艺及高硅高铜压铸铝合金
CN109023473B (zh) * 2018-11-02 2020-07-03 中国科学院兰州化学物理研究所 一种非水电解液体系中的微弧氧化方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108950549A (zh) * 2018-07-05 2018-12-07 哈尔滨工业大学 一种铝合金表面低太阳吸收率高发射率导电热控涂层的制备方法
CN109852978A (zh) * 2019-03-26 2019-06-07 高瑞安 一种铝合金除油抛光二合一处理液及对铝合金进行除油抛光处理的方法
CN110284174A (zh) * 2019-08-12 2019-09-27 潍坊国一铝材有限公司 一种铝合金氧化成膜所用的电解氧化液以及铝合金氧化成膜方法
CN111349958A (zh) * 2020-04-10 2020-06-30 高瑞安 一种电泳铝型材及其表面处理方法

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DHAHRI S.; FAZIO E.; BARRECA F.; NERI F.; EZZAOUIA H.: "Porous aluminum room temperature anodizing process in a fluorinated-oxalic acid solution", APPLIED PHYSICS A MATERIALS SCIENCE & PROCESSING, SPRINGER BERLIN HEIDELBERG, BERLIN/HEIDELBERG, vol. 122, no. 8, 19 July 2016 (2016-07-19), Berlin/Heidelberg, pages 1 - 7, XP036027583, ISSN: 0947-8396, DOI: 10.1007/s00339-016-0280-8 *
JAGMINAS, A. VRUBLEVSKY, I. KUZMARSKYTE, J. JASULAITIENE, V.: "Composition, structure and electrical properties of alumina barrier layers grown in fluoride-containing oxalic acid solutions", ACTA MATERIALIA., ELSEVIER, OXFORD, GB, vol. 56, no. 6, 15 January 2008 (2008-01-15), GB, pages 1390 - 1398, XP022514472, ISSN: 1359-6454, DOI: 10.1016/j.actamat.2007.11.029 *
MANDAL PROSUN, SUBHAS CHANDRA MONDAL: "Investigation of Electro-Thermal Property for Cu-MWCNT Composite Coating on Anodized 6061 Aluminium Alloy", APPLIED SURFACE SCIENCE, pages 138 - 147, XP055779659 *
XIONG, JINSONG: "Analysis of Aluminum Ion in Oxalic Acid Anodizing Bath Solution", AEROSPACE MANUFACTURING TECHNOLOGY, no. 4, 28 August 2003 (2003-08-28), ISSN: 1674-5108 *

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