WO2019154142A1 - 一种氧化膜的制备方法和终端设备 - Google Patents

一种氧化膜的制备方法和终端设备 Download PDF

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WO2019154142A1
WO2019154142A1 PCT/CN2019/073322 CN2019073322W WO2019154142A1 WO 2019154142 A1 WO2019154142 A1 WO 2019154142A1 CN 2019073322 W CN2019073322 W CN 2019073322W WO 2019154142 A1 WO2019154142 A1 WO 2019154142A1
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Prior art keywords
oxide film
terminal device
anodizing
sulfuric acid
aluminum alloy
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PCT/CN2019/073322
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English (en)
French (fr)
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朱旭
龚建国
姜文杰
计超
邓前勇
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华为技术有限公司
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Publication of WO2019154142A1 publication Critical patent/WO2019154142A1/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
    • C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
    • 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
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04M—TELEPHONIC COMMUNICATION
    • H04M1/00—Substation equipment, e.g. for use by subscribers
    • H04M1/02—Constructional features of telephone sets
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04M—TELEPHONIC COMMUNICATION
    • H04M1/00—Substation equipment, e.g. for use by subscribers
    • H04M1/02—Constructional features of telephone sets
    • H04M1/0202—Portable telephone sets, e.g. cordless phones, mobile phones or bar type handsets
    • H04M1/0279—Improving the user comfort or ergonomics
    • H04M1/0283—Improving the user comfort or ergonomics for providing a decorative aspect, e.g. customization of casings, exchangeable faceplate

Definitions

  • the present invention relates to the field of terminals, and in particular, to a method and a terminal for preparing an oxide film.
  • the oxide film prepared by the ordinary aluminum alloy anodizing process is widely used in electronic consumer appearance parts, such as mobile phones, because of its advantages of beautiful color, excellent texture, good decoration, good corrosion resistance, good insulation performance and good insulation. Since the iPhone 5's champagne was first introduced to the process, the consumer electronics industry has set off a wave of anodizing. What followed, however, was the problem of marketed products eroding and scratching, especially for dark-colored versions (eg black, deep ochre and blue).
  • the problem of product falling off and scratching is that the hardness, anti-wear and scratch resistance of the oxide film prepared by the common anodizing process are relatively poor, and the density of the anode layer is relatively low, resulting in poor toughness.
  • the electrolyte used in the anodizing process is sulfuric acid.
  • the oxidation temperature is 5-20 ° C
  • the electrolysis voltage is 11-16 V
  • the electrolysis current is 1-1.5 A/dm 2
  • the film obtained has an oxide film thickness of 8-12 ⁇ m and a hardness of 150 HV 0.3 .
  • the porosity is relatively high, the surface state is relatively smooth, and the film layer is transparent in color.
  • the industrial design (ID) of the oxide film obtained by this anodizing process has a good appearance.
  • the invention provides a preparation method and a terminal device for an oxide film.
  • an anodizing process of an anodizing process is realized by changing a ratio of an electrolyte component, and the obtained oxide film is obtained by an ordinary anodizing process.
  • the oxide film increases the hardness and toughness of the oxide film and improves the resistance to abrasion and scratching.
  • a method for preparing an oxide film comprising:
  • a mixed solution of oxalic acid and sulfuric acid in a concentration ratio of (1.5-3):1 is used as an electrolytic solution to oxidize the aluminum alloy workpiece to be oxidized, and an oxide film is formed on the surface of the aluminum alloy workpiece to be oxidized.
  • the mass concentration of oxalic acid is 15-90 g/L, and the mass concentration of sulfuric acid is 10-30 g/L.
  • the anodization process uses a temperature of 20-30 ° C; the anodization uses an oxidation voltage of 15-22 V.
  • the anodization process has an oxidation time of 60-150 min.
  • the hardness of the oxide film is 200-380HV 0.3, wherein, HV 0.3 represents measured at 0.3 kg force load obtained Vickers hardness values.
  • the oxide film has a thickness of 16-30 ⁇ m.
  • the mass concentration of oxalic acid is 40 g/L and the concentration of sulfuric acid is 20 g/L.
  • the mass concentration of oxalic acid is 45 g/L and the mass concentration of sulfuric acid is 20 g/L.
  • a terminal device comprising a component, the component comprising an oxide film prepared by the preparation method of the first aspect or any of the possible aspects of the first aspect.
  • the terminal device is a mobile phone, a tablet computer, or a wearable device; the components include a back cover, a middle frame, a metal card tray, a side button, or an appearance member of the terminal device.
  • the concentration ratio of oxalic acid and sulfuric acid is (1.5-3):1, and the electrolysis voltage is 15-22V.
  • the electrolysis voltage is 15-22V.
  • an oxide film is obtained, which increases the hardness and toughness of the oxide film and improves the wear resistance and scratch resistance.
  • FIG. 1 is a schematic flow chart of a general anodizing process
  • FIG. 2 is a schematic diagram of an anodizing principle according to an embodiment of the present invention.
  • FIG. 3 is a schematic flow chart of an anodizing process according to an embodiment of the present invention.
  • the embodiment of the invention provides a preparation method and a terminal for an oxide film.
  • a preparation method and a terminal for an oxide film By changing the electrolyte used in the anodizing treatment process, an oxide film with high hardness, good scratch resistance, good wear resistance and good decorative property is obtained.
  • the product or the product component obtained by using the oxide film prepared by the preparation method improves the scratch resistance and wear resistance of the product, improves the appearance effect of the product, and fundamentally solves the problem that the dark wear-resistant paint is removed. The problem is to improve the user experience.
  • the product may be a tangible item that can be supplied to the market, used and consumed by people, and meets people's needs, such as a terminal device, where the terminal device may include: a smart phone, a tablet computer, a wearable device (for example, Bracelet) and so on.
  • the oxide film prepared by the method for preparing an oxide film provided by the embodiment of the invention can be used as a component of the terminal device for decorating the terminal device.
  • it can be used as a unibody mobile phone metal back cover, a mobile phone metal middle frame, a mobile phone metal card holder and a side button; it can be used as a middle frame, a back cover, a card holder of a tablet computer, and an appearance part of a wearable device, etc. .
  • the common anodizing process is shown in Figure 1, and includes three stages of pretreatment, anodization, and post treatment.
  • Pretreatment includes degreasing, polishing, alkaline etching, and blackening of the film; post treatment includes activation, dyeing, sealing, and drying.
  • Degreasing refers to the removal of grease remaining on the surface of a workpiece (such as an aluminum workpiece) that has been subjected to forging, die casting, or polishing.
  • the degreasing process consists of two reactions: saponification and emulsification; saponification is the reaction of the alkali in the degreasing solution with the oil on the surface of the workpiece to form a water-soluble substance; the emulsification is to remove the oil and other residues which cannot be removed by saponification on the surface of the workpiece.
  • Polishing is done by some means to make the surface of the workpiece smoother.
  • the polishing may include mechanical polishing and chemical polishing; the mechanical polishing is to polish the workpiece by a polishing machine, and the relative grinding and rolling generated between the fine polishing powder and the grinding surface removes the blade left by the processing of the workpiece surface. Or scratches to improve the flatness of the surface of the workpiece.
  • Chemical polishing is the use of a polishing agent to make the surface of the workpiece brighter.
  • the anodizing process uses the anodizing principle to achieve anodization of the workpiece.
  • the anodizing principle is actually the principle of water electrolysis: when current flows through the workpiece, hydrogen is released at the cathode end of the workpiece; The anode end releases oxygen (including molecular oxygen, atomic oxygen, and ionic oxygen), oxidizing the aluminum at the anode end to form anhydrous alumina.
  • the electrolyte used for the anodization is usually a sulfuric acid solution.
  • Aluminum is anodized in a sulfuric acid solution to form an aluminum oxide (Al 2 O 3 ) film, which is accompanied by dissolution of the oxide film in the process of forming an oxide film. among them,
  • the oxide film formation process is: 2Al+3H 2 O ⁇ Al 2 O 3 +6H + +6e;
  • the process of dissolving the oxide film is: Al 2 O 3 + 6H + ⁇ 2Al 3+ + 3H 2 O.
  • the obtained oxide film has a two-layer structure, the inner layer is dense and non-porous, and is composed of less water Al 2 O 3 , and the outer layer is a porous layer composed of pores and pore walls, and the oxide film is a high porosity and adsorbable dye. Oxide film.
  • Activation is the process of chemically dissolving alumina using an organic acid, a mineral acid or an acid salt as an activator. During the dissolution process, the pore walls of the oxide film are dissolved from the outside to the inside. By controlling the length of the activation time, an oxide film having a different pore size can be obtained to achieve pore reaming, increase the porosity, and thereby improve the ability of the oxide film pore to adsorb the dye.
  • Dyeing is the use of the adsorption of the pores of the oxide film to deposit a dye in the pores of the oxide film to color the metal aluminum workpiece.
  • the sealing is treated in boiling water, and after hydration reaction, the dyed film formed by the dye is ensured to firmly dye the dye, and the surface of the dyed film exhibits the desired color of the dye. It also gives the surface the ability to prevent fingerprints, stains and grease.
  • Drying is to remove moisture from the workpiece.
  • the oxide film obtained by the ordinary anodizing process has a relatively low hardness, a poor abrasion resistance, and the film layer is easily peeled off, causing a problem of paint falling.
  • FIG. 3 The process of anodizing provided by the embodiment of the present invention is shown in FIG. 3 .
  • a mixed liquid of oxalic acid and sulfuric acid is used as the electrolyte, and the concentration ratio of oxalic acid and sulfuric acid is (1.5-3):1, and the aluminum alloy workpiece to be oxidized is anodized.
  • An oxide film is formed on the surface of the aluminum alloy.
  • oxalic acid having a mass concentration of 15-90 g/L, sulfuric acid having a mass concentration of 10-30 g/L, an oxidation temperature of 20-30 ° C, and an oxidation voltage of 15 may be used.
  • the aluminum alloy was anodized under an -22 V condition to obtain an oxide film.
  • Oxidation of 60-150min can obtain an oxide film with a film thickness of 16-30 ⁇ m and a hardness of 200-380HV 0.3 , which is harder than the oxide film obtained by the conventional anodizing process, and has improved scratch resistance and wear resistance.
  • the film thickness is moderate (compared to the film thickness of the oxide film shown in Table 1), which is transparent, improves the decorative performance, and further improves the user experience.
  • the hardness values of the oxide films mentioned are the Vickers hardness values measured under a load of 0.3 kg.
  • Table 1 shows the treatment process of the conventional hard anodization, the conditions for preparing the oxide film, and the performance parameters of the obtained oxide film.
  • the electrolyte used is a mixture of oxalic acid and sulfuric acid, anodized at a temperature of -5 ° C to 10 ° C, an oxidation voltage of more than 30 V, and an oxide film having a thickness of more than 25 ⁇ m is obtained after 60 minutes.
  • the hardness is approximately 400 HV 0.3 .
  • the oxide film having a relatively high hardness (about 400 HV 0.3 ) and excellent scratch resistance and wear resistance can be prepared by this conventional hard anodizing treatment process, the oxide film is thick (more than 25 ⁇ m) due to the prepared film thickness.
  • the color is dark and opaque, and the pore size (porosity) of the oxide film is relatively large, the surface roughness is relatively high, and the surface is usually "orange", and the decorative effect is relatively poor, resulting in a poor appearance of the ID.
  • the temperature used for the anodization must be maintained in a lower range: -5 ° C to 10 ° C, and the energy consumption for preparing the oxide film is large and the cost is high. Therefore, the treatment process using the conventional hard anodization is not suitable for application to a product having high decorative requirements, such as the terminal device mentioned in the embodiment of the present invention.
  • the production of a highlight version of a component which is a component on a terminal device, such as a back cover of a mobile phone, can be processed by mechanical polishing, mirror polishing, degreasing, anodizing, dyeing, sealing, oxygen tossing and drying.
  • the mirror polishing is to enhance the appearance of the gloss, so that the appearance of the surface to achieve a mirror effect.
  • Mirror polishing can be divided into mechanical mirror polishing and chemical solution mirror polishing.
  • Mechanical mirror polishing is a polishing process (including rough grinding, fine grinding) and a polishing process on an aluminum alloy to make the surface of the aluminum alloy flat and bright like a mirror surface; chemical solution mirror polishing is to soak the aluminum alloy with a chemical solution to remove The oxide film on the surface of the aluminum alloy achieves a bright effect.
  • the processing processes that can be employed are: mechanical polishing, surface treatment, degreasing, chemical polishing, light extraction, anodizing, dyeing, sealing and drying.
  • the surface treatment includes sandblasting, wire drawing, drilling and the like of the aluminum alloy workpiece subjected to mechanical polishing.
  • a unibody back cover structure is fabricated using 6063 aluminum alloy.
  • the 6063 aluminum alloy is mechanically polished, mirror-polished, and degreased.
  • anodizing is performed at 6063.
  • An oxide film is formed on the surface of the aluminum alloy.
  • the anodizing process uses a mixed solution of oxalic acid having a mass concentration of 40 g/L and a sulfuric acid concentration of 20 g/L as an electrolyte, and anodizing the 6063 aluminum alloy at a temperature of 26 ° C and an oxidation voltage of 18 V. Oxidation for 75 min gave an oxide film having a film thickness of 17.33 ⁇ m.
  • the integrated back cover obtained by the conventional anodizing process is The Vickers hardness of the oxide film obtained by the anodizing treatment provided by the embodiment of the present invention reaches 277 HV 0.3 , which is increased by 60%.
  • the conditions for anodizing and the specific properties of the examples of the present invention are shown in Tables 1 and 2.
  • the thickness (17.33 ⁇ m) of the oxide film obtained by the embodiment of the present invention was thicker than that of the oxide film obtained by the conventional technique (16.33 ⁇ m), and the Vickers hardness was high.
  • the oxide film obtained by the conventional technology and the oxide film of the embodiment of the invention are respectively tested by steel wool, vibration friction and sand micro-drop.
  • the oxide film obtained by the conventional technology can withstand less than 500 times of steel.
  • the velvet brush has a vibration friction of less than 60 min, and the sand particles of 20 times are slightly dropped.
  • the oxide film obtained by the embodiment of the invention can reach a steel wool brush of more than 1000, the vibration friction of more than 180 min, and the sand of the sand is slightly decreased 60 times.
  • the steel wool test performance of the embodiment of the invention is improved by 50%
  • the vibration friction test performance is improved by 200%
  • the sand micro-drop test performance is improved by 200%. It is apparent that the oxide film obtained by the method for preparing an oxide film provided by the embodiment of the present invention improves the hardness, toughness, wear resistance and scratch resistance of the oxide film.
  • the middle frame + double-glazed structure of the terminal device is manufactured by using 6013 aluminum alloy, and the 6013 aluminum alloy is first subjected to mechanical polishing, mirror polishing and degreasing, and after the cleaning treatment, anodizing treatment is performed.
  • An oxide film is formed on the surface of the 6013 aluminum alloy.
  • the anodizing process uses an aqueous solution of oxalic acid having a mass concentration of 45 g/L and a sulfuric acid concentration of 20 g/L as an electrolyte to anodize the 6013 aluminum alloy at a temperature of 30 ° C and an oxidation voltage of 20 V. Oxidation for 90 min gave an oxide film having a film thickness of 19.1 ⁇ m.
  • the thickness (19.1 ⁇ m) of the oxide film obtained by the embodiment of the present invention was thicker than that of the oxide film obtained by the conventional technique (16 ⁇ m), and the Vickers hardness was much higher.
  • the oxide film obtained by the conventional technology and the oxide film of the embodiment of the invention are respectively tested by steel wool, vibration friction and sand micro-drop.
  • the oxide film obtained by the conventional technology can withstand 1000 times of steel wool. Brushing, vibration friction of less than 60 min, 20 times of sand particles slightly falling, and the oxide film obtained by the embodiment of the present invention can reach a steel wool sanding brush of more than 1000, vibration friction greater than 180 min, and 150 sand grains slightly falling.
  • the vibration friction test performance of the embodiment of the invention is improved by 200%, and the sand micro-drop test performance is improved by 650%. It is apparent that the oxide film obtained by the method for preparing an oxide film provided by the embodiment of the present invention improves the hardness, toughness, wear resistance and scratch resistance of the oxide film.
  • the method for preparing an oxide film provided by the embodiment of the invention solves the problem that the dark-type electronic consumer product is easy to scratch and wear off the paint. At the same time, the user's demand for the decorative appearance of the ID appearance film layer is satisfied.
  • Embodiments of the present invention also provide a terminal including a component including an oxide film prepared by the method of preparing an oxide film of an embodiment of the present invention.

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Abstract

本发明实施例提供了一种氧化膜的制备方法，该制备方法包括：在阳极氧化过程中，采用草酸和硫酸的浓度比例为(1.5-3)：1的混合溶液作为电解液对待氧化的铝合金工件进行阳极氧化，在所述待氧化的铝合金工件表面生成氧化膜，提升了氧化膜硬度、韧性、耐磨性和抗刮伤性能。

Description

一种氧化膜的制备方法和终端设备
本申请要求于2018年02月08日提交中国专利局、申请号为201810130472.7、申请名称为“一种氧化膜的制备方法和终端设备”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及终端领域，尤其涉及一种氧化膜的制备方法和终端。
背景技术
普通铝合金阳极氧化工艺制备的氧化膜，由于具有色彩绚丽、质感优异、装饰性好，耐腐蚀性好、绝缘性能好和绝缘性好等优点，被广泛应用于电子消费品外观件，例如手机。自iPhone5的香槟色首次采用该工艺以来，消费电子行业掀起了采用阳极氧化工艺的浪潮。然而随之而来的就是市场产品磨损掉漆和易刮伤的问题，尤其是深色系(例如：黑色、深锖色和蓝色)高亮版本的产品。
而出现产品掉漆和易刮伤的问题是由于普通阳极氧化工艺制备的氧化膜的硬度、抗磨损和抗划伤性能比较差，且由于阳极层致密度比较低，韧性差造成的。普通阳极氧化工艺中阳极氧化通常采用的电解液是硫酸，在电解温度为5-20℃，电解电压为11-16V，电解电流为1-1.5A/dm 2的条件下，阳极氧化30min得到氧化膜，得到的氧化膜膜厚为8-12μm，硬度为150HV 0.3，孔隙率比较高，表面状态比较光滑，膜层颜色透明。通过这种阳极氧化工艺得到的氧化膜工业设计(Industrial Design，ID)外观效果较好。
发明内容
本发明提供了一种氧化膜的制备方法和终端设备，在阳极氧化工艺的阳极氧化过程中，通过改变电解液组分的比例实现阳极氧化的过程，得到的氧化膜相比普通阳极氧化工艺得到的氧化膜，增大了氧化膜的硬度、韧性、提高了抗耐磨和抗刮伤的性能。
第一方面，提供了一种氧化膜的制备方法，该制备方法包括：
在阳极氧化过程中，采用草酸和硫酸的浓度比例为(1.5-3)：1的混合溶液作为电解液对待氧化的铝合金工件进行阳极氧化，在待氧化的铝合金工件表面生成氧化膜。
在一个可能实现的方式中，草酸的质量浓度为15-90g/L，硫酸的质量浓度为10-30g/L。
在一个可能实现的方式中，阳极氧化过程采用的温度为20-30℃；阳极氧化采用的氧化电压为15-22V。
在一个可能实现的方式中，阳极氧化过程的氧化时长为60-150min。
在一个可能实现的方式中，氧化膜的硬度为200-380HV 0.3，其中，HV 0.3表示在0.3千克力载荷下测得的维氏硬度值。
在一个可能实现的方式中，氧化膜的厚度为16-30μm。
在另一个可能实现的方式中，草酸的质量浓度为40g/L，硫酸的浓度为20g/L。
在另一个可能实现的方式中，草酸的质量浓度为45g/L，硫酸的质量浓度为20g/L。
第二方面，提供了一种终端设备，该终端设备包括部件，该部件可以包括采用第一方面或第一方面的任意一种可能实现的方式中的制备方法制备的氧化膜。
在一个可能的实现中，终端设备为手机、平板电脑或穿戴设备；部件包括终端设备的后盖、中框、金属卡托、侧键或外观件。
基于提供的一种氧化膜的制备方法和终端设备，在阳极氧化工艺的阳极氧化过程中，采用草酸和硫酸的浓度比例为(1.5-3):1的电解液，电解电压15-22V的条件下，阳极氧化60-150min得到氧化膜，增大了氧化膜的硬度、韧性、提高了抗耐磨和抗刮伤的性能。
附图说明
图1为普通阳极氧化处理工艺的流程示意图；
图2为本发明实施例提供的一种阳极氧化原理示意图；
图3为本本发明实施例提供的一种阳极氧化处理工艺的流程示意图。
具体实施方式
本发明实施例提供了一种氧化膜的制备方法和终端，通过改变阳极氧化处理工艺中采用的电解液，得到硬度高，抗划伤、耐磨损性能好和装饰性好的氧化膜。进一步通过使用该制备方法制备的氧化膜得到的产品或产品部件，提高了产品的抗划伤性和耐磨损性，提高了产品的外观效果，从根本上解决了深色系磨损掉漆的问题，提高了用户体验。
在本发明实施例中，产品可以为能够供给市场，被人们使用和消费，并满足人们需求的有形物品，例如终端设备，这里的终端设备可以包括：智能手机、平板电脑、可穿戴设备(例如手环)等。本发明实施例提供的氧化膜制备方法制备的氧化膜，可用作终端设备的一个部件，用于装饰终端设备。例如，可以作为一体成型(unibody)的手机金属后盖、手机金属中框、手机金属卡托和侧键；可以作为平板电脑的中框、后盖、卡托；以及可穿戴设备的外观件等。
普通的阳极氧化处理工艺如图1所示，包括前处理、阳极氧化和后处理三个处理阶段。前处理包括脱脂、抛光、碱性腐蚀和剥黑膜；后处理包括活化、染色、封孔和烘干。
脱脂是指除去经过锻压、压铸或抛光等处理的工件(如铝工件)表面残留的油脂。脱脂过程包括两个反应:皂化和乳化；皂化是将脱脂液中的碱与工件表面的油脂进行反应，生成水溶性物质；乳化是除去工件表面上皂化无法取出的油脂和其他残留物。
抛光是通过一些手段使工件表面更光滑。该抛光可以包括机械抛光和化学抛光；机械抛光是通过抛光机对工件进行抛光，靠极细的抛光粉和磨面间产生的相对磨削和滚压，除去工件外观面加工留下的刀纹或划痕，以提高工件表面的平整度。化学抛光是通过抛光剂使工件表面更光亮。
碱性腐蚀和剥黑膜，除去工件表面原有的氧化膜。
阳极氧化的过程，如图2所示，是采用阳极氧化原理实现工件的阳极氧化，阳极 氧化原理实际上就是水电解原理：当电流通过工件时，在工件的阴极端释放出氢气；在工件的阳极端释放氧(包括分子态氧、原子态氧和离子态氧)，氧化阳极端的铝，形成无水的氧化铝。
通常阳极氧化采用的电解液为硫酸溶液。铝在硫酸液中阳极氧化生成氧化铝(Al 2O 3)膜，在生成氧化膜的过程中也伴随着氧化膜的溶解。其中，
氧化膜形成过程为：2Al+3H 2O→Al 2O 3+6H ++6e；
氧化膜溶解的过程为：Al 2O 3+6H +→2Al 3++3H 2O。
得到的氧化膜为双层结构，内层为致密无孔隙，且少水的Al 2O 3构成，外层是由孔隙和孔壁组成的多孔层，该氧化膜为高孔隙率、可吸附染料的氧化膜。
活化是采用有机酸、无机酸或酸性盐作为活化剂，对氧化铝进行化学溶解的过程。溶解过程中，氧化膜的孔壁从外向内溶解，通过控制活化时间的长短，可以得到孔径大小不同的氧化膜，达到扩孔，增加孔隙率，进而提高氧化膜孔吸附染料的能力。
染色是利用氧化膜孔的吸附性，在氧化膜孔内沉积染料，给金属铝工件上色。
封孔是在沸水中处理，经过水合反应，保证染料形成的染色膜牢固染料，并使染色膜表面表现出染料应有的色泽。还可以使表面具有防指印、色斑及油脂的能力。
烘干就是去除工件的水分。
采用普通阳极氧化的工艺得到的氧化膜的硬度比较低，耐磨损性能差，膜层容易脱落，造成掉漆问题。
而本发明实施例提供的阳极氧化的处理工艺如图3所示。本发明实施例，在保证ID外观效果的情况下，采用草酸和硫酸的混合液体作为电解液，草酸和硫酸的浓度比例为(1.5-3):1，对待氧化的铝合金工件进行阳极氧化，在铝合金表面生成氧化膜。
可选地，在本发明的一个实施例中，可以采用质量浓度为15-90g/L的草酸，质量浓度为10-30g/L的硫酸，在氧化温度为20-30℃，氧化电压为15-22V的条件下对铝合金进行阳极氧化得到氧化膜。氧化60-150min可以得到膜厚为16-30μm，硬度为200-380HV 0.3的氧化膜，比普通阳极氧化处理工艺得到的氧化膜的硬度大，增加了抗划伤和耐磨的性能。同时膜厚适中(相比表1所示氧化膜的膜厚)，透明，提高了装饰性能，进一步提高了用户体验。需要说明的是，在本发明实施例中，提到的氧化膜的硬度值均是在0.3千克力负载下测得的维氏硬度值。
表1
Figure PCTCN2019073322-appb-000001
表1所示的是传统硬质阳极氧化的处理工艺，制备氧化膜的条件以及得到氧化膜的性能参数。表1中，采用的电解液为草酸和硫酸的混合液，在温度为-5℃至10℃，氧化电压大于30V的条件下进行阳极氧化，经过60min得到厚度大于25μm的氧化膜， 氧化膜的硬度大约在400HV 0.3。虽然通过这种传统硬质阳极氧化处理工艺可以制备硬度比较大(大约400HV 0.3)和抗划伤、耐磨性能较好的氧化膜，但由于制备的膜厚较厚(大于25μm)，氧化膜色泽灰暗不透明，且氧化膜的孔径(孔隙率)比较大，表面粗糙度比较高，表面通常呈“橘纹”状，装饰效果比较差，造成ID外观效果比较差。且为了保证氧化膜性能，避免局部温度升高造成烧灼的问题，阳极氧化时所采用的温度必须维持在较低的范围：-5℃至10℃，制备氧化膜的能耗较大，成本高，因此，采用传统硬质阳极氧化的处理工艺并不适合应用于对装饰性要求较高的产品上，例如本发明实施例所提到的终端设备上。
在本发明实施例中，除采用本发明实施例所提供的氧化膜制备条件外，还可以根据用户需求，进行不同的处理工艺流程。
例如生产高亮版本部件，该部件为终端设备上的部件，例如手机后盖，可以采用的处理工艺流程为：机械抛光、镜面抛光、脱脂、阳极氧化、染色、封孔、氧抛和烘干。其中，镜面抛光是提升外观光泽度，使外观面达到镜面效果。镜面抛光可以分为机械镜面抛光和化学溶液镜面抛光。机械镜面抛光是在铝合金上经过磨光工序(包括粗磨、细磨)和抛光工序从而使铝合金的表面达到平整、光亮似镜面；化学溶液镜面抛光是使用化学溶液进行浸泡铝合金，去除铝合金表面的氧化膜从而达到光亮的效果。
又例如，生产非高亮版本部件，可以采用的处理工艺流程为：机械抛光、表面处理、脱脂、化学抛光、出光、阳极氧化、染色、封孔和烘干。其中，表面处理包括对进行过机械抛光的铝合金工件的喷砂、拉丝、钻雕等处理。
在本发明的一个实施例中，采用6063铝合金制造一体成型(unibody)的后盖架构，首先对6063铝合金进行机械抛光、镜面抛光和脱脂，经过清洗处理后，进行阳极氧化处理，在6063铝合金的表面生成氧化膜。阳极氧化处理的过程采用草酸的质量浓度为40g/L，硫酸的质量浓度为20g/L的混合溶液作为电解液，对6063铝合金进行阳极氧化，在温度26℃，氧化电压为18V的条件下，氧化75min，得到膜厚为17.33μm的氧化膜。阳极氧化处理完成后，进行染色、封孔、氧抛和烘干，得到一体成型的后盖。在保证ID外观效果和全套涂层可靠性测试性能一致的情况下，即在确保膜层装饰性和百格附着力一致的情况下，与采用传统阳极氧化处理工艺得到的一体成型的后盖相比，采用本发明实施例提供的阳极氧化处理工艺得到的氧化膜的维氏硬度达到了277HV 0.3，提升了60％。本发明实施例阳极氧化的条件以及具体性能的比较如表1和表2所示。
表1
Figure PCTCN2019073322-appb-000002
表2
Figure PCTCN2019073322-appb-000003
如表1所示，采用本发明实施例得到的氧化膜的厚度(17.33μm)比传统技术得到的氧化膜的膜厚(16.33μm)要厚，维氏硬度要高。且分别对传统技术得到的氧化膜和本发明实施例的氧化膜采用钢丝绒、振动摩擦和沙粒微跌进行性能测试，如表2所示，传统技术得到的氧化膜可以承受小于500次的钢丝绒磨刷，小于60min的振动摩擦，20次的沙粒微跌，而本发明实施例得到的氧化膜可达到大于1000的钢丝绒磨刷，大于180min的振动摩擦，60次的沙粒微跌。与传统技术相比，本发明实施例钢丝绒测试表现提升50％，振动摩擦测试表现提升200％，沙粒微跌测试表现提升200％。很显然，采用本发明实施例提供的氧化膜制备方法得到的氧化膜，提升了氧化膜硬度、韧性、耐磨性和抗刮伤性能。
在本发明的另一实施例中，采用6013铝合金制造终端设备的中框+双层玻璃架构，首先对6013铝合金进行机械抛光、镜面抛光和脱脂，经过清洗处理后，进行阳极氧化处理，在6013铝合金的表面生成氧化膜。阳极氧化处理的过程采用草酸的质量浓度为45g/L，硫酸的质量浓度为20g/L的混合溶液作为电解液，对6013铝合金进行阳极氧化，在温度30℃，氧化电压为20V的条件下，氧化90min，得到膜厚为19.1μm的氧化膜。阳极氧化处理完成后，进行染色、封孔和烘干，得到一体成型的中框。在确保膜层装饰性和百格附着力一致的情况下，与采用传统阳极氧化处理工艺得到的一体成型的后盖相比，采用本发明实施例提供的阳极氧化处理工艺得到的氧化膜的维氏硬度达到了310HV 0.3，提升了72％。本发明实施例阳极氧化的条件以及具体性能的比较如表3和表4所示。
表3
Figure PCTCN2019073322-appb-000004
表4
Figure PCTCN2019073322-appb-000005
如表3所示，采用本发明实施例得到的氧化膜的厚度(19.1μm)比传统技术得到的氧化膜的膜厚(16μm)要厚，维氏硬度要高很多。且分别对传统技术得到的氧化膜和本发明实施例的氧化膜采用钢丝绒、振动摩擦和沙粒微跌进行性能测试，如表4所示，传统技术得到的氧化膜可以承受1000次的钢丝绒磨刷，小于60min的振动摩擦，20次的沙粒微跌，而本发明实施例得到的氧化膜可达到大于1000的钢丝绒磨刷，大于180min的振动摩擦，150次的沙粒微跌。与传统技术相比，本发明实施例振动摩擦测试表现提升200％，沙粒微跌测试表现提升650％。很显然，采用本发明实施例提供的氧化膜制备方法得到的氧化膜，提升了氧化膜硬度、韧性、耐磨性和抗刮伤性能。
采用本发明实施例提供的氧化膜制备方法解决了深色系电子消费品易刮伤和磨损掉漆的问题。同时满足了用户对ID外观膜层装饰性的需求。
本发明实施例还提供了一种终端，该终端包括部件，该部件包括采用本发明实施例氧化膜制备的方法制备的氧化膜。
以上所述，仅为本申请较佳的具体实施方式，但本申请的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本申请揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本申请的保护范围之内。因此，本申请的保护范围应该以权利要求的保护范围为准。

Claims (10)

  1. 一种氧化膜的制备方法，其特征在于，所述制备方法包括：
    在阳极氧化过程中，采用草酸和硫酸的浓度比例为(1.5-3)：1的混合溶液作为电解液对待氧化的铝合金工件进行阳极氧化，在所述待氧化的铝合金工件表面生成氧化膜。
  2. 根据权利要求1所述的制备方法，其特征在于，所述草酸的质量浓度为15-90g/L，硫酸的质量浓度为10-30g/L。
  3. 根据权利要求1至2所述的制备方法，其特征在于，阳极氧化过程采用的温度为20-30℃；所述阳极氧化采用的氧化电压为15-22V。
  4. 根据权利要求1至3任一项所述的制备方法，其特征在于，所述阳极氧化过程的氧化时长为60-150min。
  5. 根据权利要求1至4任一项所述的制备方法，其特征在于，所述氧化膜的硬度为200-380HV 0.3，其中，HV 0.3表示在0.3千克力载荷下测得的维氏硬度值。
  6. 根据权利要求1至5所述的制备方法，其特征在于，所述氧化膜的厚度为16-30μm。
  7. 根据权利要求1至6任一项所述的制备方法，其特征在于，所述草酸的质量浓度为40g/L，所述硫酸的浓度为20g/L。
  8. 根据权利要求1至6任一项所述的制备方法，其特征在于，所述草酸的质量浓度为45g/L，所述硫酸的质量浓度为20g/L。
  9. 一种终端设备，其特征在于，所述终端设备包括部件，所述部件包括采用权利要求1至8任一项所述的制备方法制备的氧化膜。
  10. 根据权利要求9所述的终端设备，其特征在于，所述终端设备为手机、平板电脑或穿戴设备；所述部件包括终端设备的后盖、中框、金属卡托、侧键或外观件。
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