WO2017000315A1 - 用于铝合金表面处理的钛锆系有色无铬钝化液、使用其处理铝合金表面的方法及其应用 - Google Patents

用于铝合金表面处理的钛锆系有色无铬钝化液、使用其处理铝合金表面的方法及其应用 Download PDF

Info

Publication number
WO2017000315A1
WO2017000315A1 PCT/CN2015/083230 CN2015083230W WO2017000315A1 WO 2017000315 A1 WO2017000315 A1 WO 2017000315A1 CN 2015083230 W CN2015083230 W CN 2015083230W WO 2017000315 A1 WO2017000315 A1 WO 2017000315A1
Authority
WO
WIPO (PCT)
Prior art keywords
aluminum alloy
passivation solution
zirconium
titanium
chromium
Prior art date
Application number
PCT/CN2015/083230
Other languages
English (en)
French (fr)
Inventor
付华峰
姚川
李�浩
魏宁卡
Original Assignee
许昌学院
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 许昌学院 filed Critical 许昌学院
Priority to PCT/CN2015/083230 priority Critical patent/WO2017000315A1/zh
Priority to CN201580000402.4A priority patent/CN107429404A/zh
Publication of WO2017000315A1 publication Critical patent/WO2017000315A1/zh

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides

Definitions

  • the invention relates to the technical field of aluminum alloy surface treatment, in particular to a titanium zirconium-based colored chromium-free passivation solution for surface treatment of aluminum alloy, a method for treating the surface of the aluminum alloy, and an application thereof.
  • Aluminum alloy is a metal alloy obtained by adding elements such as magnesium, titanium and copper to pure aluminum. Due to its small specific gravity, high mechanical strength, and excellent electrical conductivity, thermal conductivity and corrosion resistance, it has been used in aerospace and automotive in recent years. Widely used in fields such as home improvement and mobile electronic devices.
  • the electrode potential of each metal is different and the second phase is formed, which tends to cause a galvanic effect and cause corrosion of the aluminum alloy.
  • the main measure is to form a conversion film layer having high corrosion resistance on the surface thereof.
  • the main processes for forming conversion coatings are: anodizing, chromate passivation and non-chromium system passivation.
  • the advantage of the anodized conversion coating is wear resistance, which can be used for decorative protection, but the anodizing has the disadvantages of large investment, high cost, high energy consumption and serious pollution; the chromate passivation process is relatively mature and perfect, and the cost is low.
  • the most mature passivation process but hexavalent chromium is one of the most toxic heavy metals that have been identified, and it is highly carcinogenic to organisms.
  • the commercially available chromium-free passivation products are mainly zirconium-titanium products.
  • the conversion film formed by these products is difficult to match the performance of the chromium-containing conversion coating, and most of them are colorless conversion coatings. It is difficult to make the film formation condition timely and accurate. Judging, it brings a lot of inconvenience to the construction of on-site workers.
  • Chinese patent CN 103254782A discloses a corrosion-resistant chromium-free metal surface silane treating agent whose composition (grams of each component in a mixture of liters) is: N-( ⁇ -aminoethyl)- ⁇ - Aminopropyltrimethoxysilane 60-65, methyl benzotriazole 1-2, ethylene glycol 6-8, sodium diisooctyl succinate 3-4, ammonium chloride 2-3, Ammonium fluorozirconate 1-2, film forming aid 2-4, and the rest is water.
  • the patented corrosion-resistant metal surface silane treatment agent does not produce sediment, is safe and environmentally friendly, and has excellent corrosion resistance with the silane coating formed on the metal surface.
  • the Chinese patent CN201410167681.0 discloses a chromium-free coating agent and a preparation method thereof, which are characterized in that, by mass percentage, it is made of the following raw materials: 2-6% fluorozirconate, silane coupling agent 1.7 -6.7%, zirconium oxychloride 0.8-1.5%, citric acid 0.5-1%, the balance being water.
  • the chrome-free coating agent of the invention has the characteristics of short processing time, minimal sedimentation, dense crystal, stable bath, and film-forming corrosion resistance when the workpiece is processed, but is also a colorless conversion film and is difficult to recognize.
  • Chinese patent CN201410673939.4 discloses a manganese zirconium-free chromium-free passivation solution for surface treatment of aluminum alloy and a treatment method thereof, the chromium-free passivation liquid comprising the following components of mass and volume concentration: permanganate 0.01 ⁇ 10g / L, fluorozirconate or fluorozirconic acid 0.01 ⁇ 10g / L, accelerator 0.01 ⁇ 4g / L, acid-base regulator, the rest is water, pH 3.0-6.8.
  • permanganate 0.01 ⁇ 10g / L fluorozirconate or fluorozirconic acid 0.01 ⁇ 10g / L
  • accelerator 0.01 ⁇ 4g / L accelerator 0.01 ⁇ 4g / L
  • acid-base regulator the rest is water, pH 3.0-6.8.
  • the most obvious feature of this patent is that it is formed into an easily recognizable golden-yellow conversion film, which is beneficial to construction operations and improves productivity.
  • the insufficiency of the film is that the film is easily pulverized and peeled off after being left for a while, and the coating performance is poor. Therefore, the development of high-performance, environmentally friendly and easy to construct operation of colored chromium-free aluminum alloy passivation solution is still a top priority in this field.
  • the object of the present invention is to provide a titanium-zirconium-colored non-chromium passivation solution and an aluminum alloy which do not contain chromium and which can produce a more obvious color change after passivation, and are used for surface treatment of aluminum alloy. Surface treatment methods and their applications.
  • the technical solution adopted by the present invention is:
  • a titanium-zirconium-based colored chromium-free passivation solution for surface treatment of aluminum alloy comprising the following components of mass and volume concentration: a main film-forming agent of 0.01-80 g/L, and an oxidizing agent of 0.01-80 g/L. a film accelerator of 0.01 to 50 g/L, an inorganic film-forming aid of 0.01 to 50 g/L, a film-forming organic protective agent of 0.01 to 50 g/L, a pH adjuster for adjusting the pH of the solution to a value of 2 to 6, and Solvent water.
  • the main film-forming agent is selected from the group consisting of fluorotitanic acid, potassium fluorotitanate, sodium fluorotitanate, ammonium fluorotitanate, lithium fluorotitanate, fluorozirconic acid, potassium fluorozirconate, sodium fluorozirconate, and fluorozirconium. At least one of the group consisting of ammonium acid and lithium fluorozirconate.
  • the oxidizing agent is selected from the group consisting of hydrogen peroxide, potassium perchlorate, sodium perchlorate, potassium iodate, potassium periodate, sodium periodate, potassium persulfate, ammonium persulfate, sodium persulfate, and barium sulfate. At least one of them.
  • the film formation promoter is at least one selected from the group consisting of sodium fluoride, potassium fluoride, ammonium fluoride, magnesium fluoride, lithium fluoride, and hydrates thereof.
  • the inorganic film-forming auxiliary agent is selected from the group consisting of nickel sulfate, nickel nitrate, nickel chloride, cobalt sulfate, cobalt nitrate, cobalt chloride, manganese sulfate, manganese nitrate, manganese chloride, sodium tungstate, potassium tungstate, tungsten. At least one of the group consisting of ammonium acid, ammonium metatungstate, ammonium molybdate, sodium molybdate, potassium molybdate, and hydrates thereof.
  • the organic film-forming protective agent is selected from the group consisting of acrylic acid, polyacrylic acid, acrylamide, polyacrylamide, N-methylol acrylamide, pyrrolidone, polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, ethylenediamine four At least one of the group consisting of acetic acid, carboxymethyl cellulose, chitosan, polysorbate, polyethylene oxide, and polypropylene oxide.
  • the pH adjusting agent is at least one selected from the group consisting of hydrofluoric acid, sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, and citric acid.
  • the pH adjusting agent is used in an amount such that the pH of the colored chromium-free passivation solution is adjusted to 2-6.
  • the present invention provides a method for treating a surface of an aluminum alloy, the method comprising the steps of: 1) diluting the above colored chromium-free passivation solution to 1 to 80 times with water; 2) The degreased pretreated aluminum alloy is immersed in the passivation solution or sprayed on the surface of the aluminum alloy; and 3) the aluminum alloy is washed with water and dried after a period of reaction.
  • the working temperature used in the treatment method is from 0 ° C to 40 ° C
  • the reaction time of the passivation solution and the aluminum alloy is from 10 to 500 s.
  • the present invention provides an aluminum alloy profile treated with the above-described titanium-zirconium-based colored chromium-free passivation solution or treated by the above-mentioned treatment method in mobile phones, notebook computers, building materials, automobiles, furniture and home furnishings. , sports equipment, product packaging, and applications in the spacecraft field.
  • the present invention provides the use of the above-described titanium-zirconium-based colored chromium-free passivation solution for treating the surface of an aluminum alloy.
  • the colored chromium-free passivation liquid of the invention does not contain heavy metal chromium, so that the harm of heavy metal chromium to the human body and environmental pollution can be avoided, and the treatment cost of the chromium-containing wastewater of the aluminum alloy coating enterprise can be reduced.
  • the passivation solution is uniformly transparent yellow, and has good storage stability under room temperature conditions, and no precipitation occurs for a long time, which is convenient for storage and transportation of products.
  • the surface of the aluminum alloy treated by the passivation solution will form a dense pale yellow conversion film, which is convenient for the technician to visually judge the quality of the film layer by observing the color depth and uniformity of the conversion film, so as to proceed to the next operation. Timely adjustments are made to simplify the production process.
  • the conversion film formed by the passivation treatment has excellent anti-corrosion performance, and the time of occurrence of 50% corrosion point in the neutral salt spray experiment (35 ⁇ 1 °C) reaches 200 h or more (the salt spray experiment implements the Chinese national standard GB/ T10125-2012/ISO9227:2006); using 10wt./% copper sulfate solution 40mL+10wt.% sodium chloride solution 20mL+0.1mol/L 1mL of hydrochloric acid was subjected to a drip-resistant test, and the corrosion resistance time was up to 150 seconds.
  • This conversion film can significantly enhance the bonding force on the surface of the aluminum alloy.
  • the coating film formed by the spray-heat curing process can still maintain a good bonding force with the aluminum alloy substrate after the paint film is cut, mechanically impacted, and subjected to high temperature and high pressure water etching.
  • the colored chromium-free passivation solution of the invention has an operating temperature of 0 ° C to 40 ° C, an effective pH range of 2-6, and a reaction time of only 10 to 500 s with the aluminum alloy, so that no heating is required, and no recurrence is required. Under the condition of adjusting the pH value, continuous and efficient production can be maintained and the production efficiency can be improved.
  • the aluminum alloy profile treated with the titanium-zirconium-based colored chromium-free passivation solution of the present invention can be applied to mobile phones, notebook computers, building materials, automobiles, furniture and home furnishings, sports equipment, product packaging, and spacecraft.
  • Example 1 is a color comparison before and after passivation treatment of an aluminum alloy workpiece using the passivation liquid in Example 1 of the present invention: the left side of the aluminum alloy workpiece is treated, and the right side of the aluminum alloy workpiece is untreated.
  • Fig. 2 is a view showing the effect of coating the surface of an aluminum alloy workpiece treated with the colored chromium-free passivation solution of Example 1 of the present invention.
  • Example 3 is a test result of cross-cutting of a surface coating film of an aluminum alloy treated with a passivation solution in Example 1 of the present invention (executing a cross-cut test of a national standard GB-T9286-1998 paint and varnish film, The grid spacing is 1mm).
  • Example 4 is a test result of a paint film impact test method of a surface coating film of an aluminum alloy treated with a passivation solution in Example 1 of the present invention: a positive impact on the left side and a reverse impact on the right side (execution country) Standard GB/T1732-93 paint film impact test method, weight mass 1000g, free fall height 50cm).
  • Figure 5 is a comparison of test results of autoclave cooking of an aluminum alloy surface coated film treated with the passivation solution of Example 1 of the present invention and not treated with the passivation solution: the upper surface of the untreated aluminum alloy surface
  • the coating film below, is an aluminum alloy surface coating film treated with the passivation solution of the present invention (all samples are immersed in water for a cooking time of 90 minutes).
  • the present invention provides a titanium-zirconium-based colored chromium-free passivation solution for surface treatment of aluminum alloys, comprising the following components of mass and volume concentration: main film-forming agent 0.01-80 g/L , oxidizing agent 0.01 ⁇ 80g / L, filming accelerator 0.01 ⁇ 50g / L, inorganic filming aid 0.01 ⁇ 50g / L, organic film forming agent 0.01 ⁇ 50g / L, the pH of the solution is adjusted to 2-6 The amount of pH adjuster, as well as water as a solvent.
  • the main film-forming agent is selected from the group consisting of fluorotitanic acid, potassium fluorotitanate, sodium fluorotitanate, ammonium fluorotitanate, lithium fluorotitanate, and fluorozirconic acid. At least one of the group consisting of potassium fluorozirconate, sodium fluorozirconate, ammonium fluorozirconate, and lithium fluorozirconate.
  • the oxidizing agent is selected from the group consisting of hydrogen peroxide, potassium perchlorate, sodium perchlorate, potassium iodate, potassium periodate, sodium periodate, potassium persulfate, and persulfuric acid. At least one of the group consisting of ammonium, sodium persulfate, and barium sulfate.
  • the film-forming accelerator is selected from the group consisting of sodium fluoride, potassium fluoride, ammonium fluoride, magnesium fluoride, lithium fluoride and hydrate thereof. At least one of them.
  • the inorganic film-forming auxiliary agent is selected from the group consisting of nickel sulfate, nickel nitrate, nickel chloride, cobalt sulfate, cobalt nitrate, cobalt chloride, manganese sulfate, manganese nitrate, At least one of the group consisting of manganese chloride, sodium tungstate, potassium tungstate, ammonium tungstate, ammonium metatungstate, ammonium molybdate, sodium molybdate, potassium molybdate, and hydrate thereof.
  • the organic film-forming protective agent is selected from the group consisting of acrylic acid, polyacrylic acid, acrylamide, polyacrylamide, N-methylol acrylamide, pyrrolidone, polyvinylpyrrole At least one of the group consisting of alkanone, polyvinyl alcohol, polyethylene glycol, ethylenediaminetetraacetic acid, carboxymethylcellulose, chitosan, polysorbate, polyethylene oxide, and polypropylene oxidekind.
  • the pH adjuster is at least one selected from the group consisting of hydrofluoric acid, sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, and citric acid.
  • the present invention provides a method for treating a surface of an aluminum alloy, the method comprising the steps of:
  • the operating temperature used in the method is from 0 ° C to 40 ° C, and the reaction time of the passivation solution with the aluminum alloy is from 10 to 500 s.
  • the present invention provides an aluminum alloy profile treated with the above-described titanium-zirconium-colored non-chromium passivation solution or treated by the above method in mobile phones, notebook computers, building materials, automobiles, furniture and home furnishings. , sports equipment, product packaging, and applications in the spacecraft field.
  • the present invention provides the use of the above-described titanium-zirconium-based colored chromium-free passivation solution for treating the surface of an aluminum alloy.
  • the desired components are weighed according to the following mass and volume concentrations: potassium fluorotitanate 10 g/L, sodium persulfate 2 g/L, sodium fluoride 5 g/L; manganese sulfate 3 g/L, polyacrylamide 3 g/L, and then the above components were added to about 80% of the quantitative volume of deionized water to be uniformly mixed.
  • the pH of the passivation solution was adjusted to 4.0 with hydrofluoric acid, and the specific amount was determined depending on the actual situation.
  • deionized water is added to bring the volume of the passivation solution to a quantitative volume. Transfer the prepared transparent chromium-free passivation solution into a PVC plastic container and store it at room temperature (no need to avoid light).
  • FIG. 1 is a color comparison of the aluminum alloy workpiece before and after treatment with the passivation solution.
  • the technician can visually judge the quality of the film layer by observing the depth and uniformity of the color of the conversion film, and adjust the concentration or reaction time of the working fluid (passivation solution) as needed.
  • the aluminum alloy workpiece should be washed and dried in time to avoid the uneven contact of the passivation liquid on the surface of the aluminum alloy workpiece and the workpiece for a long time.
  • the research shows that the surface of the aluminum alloy workpiece treated by the passivation solution has excellent corrosion resistance, and its durability can reach 220h after being tested by neutral salt spray test (the salt spray experiment carries out the Chinese national standard GB/T10125-2012/ISO9227: 2006).
  • the passivated aluminum alloy workpiece has a good bonding force with the surface coating film.
  • FIG. 2 is a view showing the effect of coating the surface of an aluminum alloy workpiece treated by using the passivation liquid in Example 1.
  • Figure 3 is a cross-sectional test of the coating film of the surface of the aluminum alloy treated with the passivation solution of Example 1 (executing the cross-cut test of the national standard GB-T9286-1998 paint and varnish film, The grid spacing is 1mm), there is no peeling and powder removal between the grids.
  • 4 is a test result of an impact test on a coating film treated with a passivation solution in Example 1 of the present invention: a forward impact on the left side and a reverse impact on the right side (executing the national standard GB/T1732- 93 paint film impact test method, the weight of the weight is 1000g, the free fall height is 50cm).
  • FIG. 5 is a test result of a coating film treated with the passivation solution of Example 1 of the present invention and treated without using the passivation solution, subjected to a autoclave cooking test: the upper surface is an untreated aluminum alloy surface coating film, Below is the aluminum alloy watch treated by the passivation solution of the present invention Topcoat film (all samples are immersed in water for a cooking time of 90 minutes). The results show that the untreated aluminum alloy surface coating film has severe foaming, peeling and the like, and the aluminum alloy surface coating film treated by the passivation solution of the invention still maintains a good bonding force with the substrate.
  • the desired components when preparing a quantitative volume of the colored chromium-free passivation solution, the desired components are weighed according to the following mass and volume concentrations: sodium fluorozirconate 10 g/L, ammonium persulfate 2 g/L, potassium fluoride. A total of 5g / L; manganese nitrate 4g / L, potassium molybdate 6g / L, N-methylol acrylamide 5g / L, and then the above components were added to about 80% of the quantitative volume of deionized water to mix evenly.
  • the pH of the passivation solution is adjusted to 5 with at least one of hydrofluoric acid, sulfuric acid, phosphoric acid, nitric acid, and hydrochloric acid, and the specific amount thereof is determined depending on the actual situation. Finally, water is added to bring the volume of the passivation solution to a quantitative volume. Transfer the prepared transparent chromium-free passivation solution into a PVC plastic container and store it at room temperature (no need to avoid light).
  • the above colored chromium-free passivation solution is first diluted to a volume of 5 times and placed in a passivation bath. Then, the surface of the aluminum alloy is degreased by a degreaser, and then the aluminum alloy workpiece to be passivated is immersed in the passivation liquid immersion or the passivation liquid is sprayed on the aluminum alloy workpiece at room temperature. on the surface. After the surface of the aluminum alloy workpiece was brought into contact with the chromium-free passivation solution for 120 s, a dense pale yellow conversion film was formed on the surface of the workpiece.
  • the aluminum alloy parts should be washed and dried in time to avoid the uneven contact of the passivation liquid on the surface of the aluminum alloy workpiece and the workpiece for a long time.
  • the surface of the aluminum alloy workpiece treated by the passivation solution has excellent corrosion resistance, and its durability can reach 230h through neutral salt spray test.
  • the passivated aluminum alloy workpiece has a good bonding force with the surface coating film.
  • the desired components are first weighed according to the following mass and volume concentrations: potassium fluorotitanate, sodium fluorozirconate, 10 g/L, potassium persulfate.
  • sodium persulfate, sulfur peroxide 5 g/L of ammonium acid, 5 g/L of sodium fluoride, potassium fluoride and ammonium fluoride; 6 g/L of manganese nitrate, manganese sulfate and sodium tungstate, polyacrylamide, N-methylol acrylamide, poly A total of 5 g/L of acrylic acid was added to the above components and uniformly mixed into about 80% of the volume of deionized water.
  • the pH of the passivation solution is adjusted to 4 with at least one of hydrofluoric acid, sulfuric acid, phosphoric acid, nitric acid, and hydrochloric acid, and the specific amount thereof is determined depending on the actual situation.
  • the prepared colored chromium-free passivation liquid with a yellow-green uniform transparency is transferred into a PVC plastic container and stored at room temperature for use (no need to be protected from light).
  • the above colored chromium-free passivation solution is first diluted to a volume of 15 times and placed in a passivation bath. Then, the surface of the aluminum alloy is degreased by a degreaser, and then the aluminum alloy piece to be passivated is immersed in the passivation liquid immersion or the passivation liquid is sprayed on the aluminum alloy at room temperature. On the surface of the workpiece. When the surface of the aluminum alloy workpiece was brought into contact with the chromium-free passivation solution for 180 s, a dense pale yellow conversion film was formed on the surface of the workpiece.
  • the aluminum alloy workpiece should be washed and dried in time to avoid the uneven contact of the passivation liquid on the surface of the aluminum alloy workpiece and the workpiece for a long time.
  • the surface of the aluminum alloy workpiece treated by the passivation solution has excellent corrosion resistance, and its durability can reach 250 h after neutral salt spray test.
  • the passivated aluminum alloy workpiece has a good bonding force with the surface coating film.
  • the potassium fluorotitanate and sodium fluorozirconate in this example correspond to the main film-forming agent potassium fluorotitanate in the first embodiment, potassium persulfate, sodium persulfate and ammonium persulfate corresponding to the oxidizing agent sodium persulfate in the first embodiment.
  • the coating film of the surface of the aluminum alloy treated using the respective examples in the above table was subjected to a cross-cut test in a manner similar to that in Example 1 (the implementation of the national standard GB-T9286-1998 paint and varnish film)
  • the cross-cut test, the spacing of the cross-cuts is 1mm), and the test results show that there is no peeling or powder removal between the cells.

Abstract

一种用于铝合金表面处理的钛锆系有色无铬钝化液,包括以下质量体积浓度的组分：主成膜剂0.01～80g/L，氧化剂0.01～80g/L，成膜促进剂0.01～50g/L，无机成膜助剂0.01～50g/L，有机成膜保护剂0.01～50g/L，将溶液的pH值调节至2-6的量的pH调节剂，以及作为溶剂的水。一种处理铝合金表面的方法包括以下步骤：首先将有色无铬钝化液稀释1到80倍；然后将经过脱脂预处理的铝合金浸渍在该钝化液中或将该钝化液喷淋在铝合金的表面上，工作温度为0℃-40℃；待反应为10-500s，然后将铝合金工件取出水洗并烘干。还公开了一种钛锆系有色无铬钝化液应用。

Description

用于铝合金表面处理的钛锆系有色无铬钝化液、使用其处理铝合金表面的方法及其应用 技术领域
本发明涉及铝合金表面处理的技术领域，尤其涉及一种用于铝合金表面处理的钛锆系有色无铬钝化液、使用其处理铝合金表面的方法及其应用。
背景技术
铝合金是在纯铝中加入镁、钛、铜等元素而得到的金属合金，由于它的比重小，机械强度高，且具有优良的导电、导热和抗蚀性，近年来在航空航天、汽车、家装及移动电子设备等领域广泛应用。铝在加入其它的金属元素形成合金后，因各金属的电极电位不同及第二相的形成，容易产生原电池效应，引起铝合金的腐蚀。为了使铝合金免受介质腐蚀，并提高表面涂装膜与铝合金基体间的结合力，主要措施是在其表面形成耐蚀性高的转化膜层。目前形成转化膜的主要工艺有：阳极氧化、铬酸盐钝化和非铬体系钝化。阳极氧化转化膜的优点是耐磨，可用于装饰防护，但阳极氧化存在投资大、高成本、高耗能以及污染严重等缺点；铬酸盐钝化工艺比较成熟和完善，且成本低廉，是目前最为成熟的钝化工艺，但六价铬是目前已经确定的毒性最强的重金属之一，对生物体具有强致癌性。将含铬废水排放至环境中，会严重污染水源和土壤，并会在生物体内累积，长期危害人类健康，导致严重的血液疾病、骨质疾病。因此，欧美国家从70年代开始就进行了无铬替代的研究，并且越来越多的行业被禁止在前处理步骤中使用有铬工艺。中国新环保法已于2015年1月1日正式实施，随着该法保护范围和实施力度的加大，传统的铬酸盐钝化处理工艺必将受到极大地限制。铝材喷涂采用无铬钝化前处理技术已是大势所趋。
目前，市售的无铬钝化产品以锆钛系产品为主。虽然避免了重金属的铬污染，但这些产品形成的转化膜其性能难以与含铬转化膜相媲美，而且多为无色的转化膜，很难从外观上对成膜状况做出及时准确直观的判断，给现场工人施工带来诸多不便。例如，中国专利CN 103254782A公开了一种耐腐蚀的无铬金属表面硅烷处理剂，其组成(每升混合液中各组分的克数)为：N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷60-65、甲基苯骈三氮唑1-2、乙二醇6-8、丁二酸二异辛酯磺酸钠3-4、氯化铵2-3、氟锆酸铵1-2、成膜助剂2-4、剩余的为水。该专利生产的耐腐蚀的金属表面硅烷处理剂处理过程不产生沉渣，安全环保，与金属表面形成的硅烷涂层具有优异的耐腐蚀性能。其缺点为成本偏高，市场可接受度较低，且成膜无色不利于施工操作。又如，中国专利CN201410167681.0公开了一种无铬皮膜剂及其制备方法，其特征在于以质量百分比计，由以下原料制成：氟锆酸2-6％，复配硅烷偶联剂1.7-6.7％，氯氧化锆0.8-1.5％，柠檬酸0.5-1％，余量为水。该发明的无铬皮膜剂在处理工件时，具有处理时间短、沉渣极少、结晶致密、槽液稳定、成膜耐蚀性等特点，但同样为无色转化膜，难以辨识。中国专利CN201410673939.4公开了一种用于铝合金表面处理的锰锆系无铬钝化液及其处理方法，该无铬钝化液包括以下质量体积浓度的组分：高锰酸盐0.01～10g/L，氟锆酸盐或氟锆酸0.01～10g/L，促进剂0.01～4g/L，酸碱调节剂，其余为水，pH值为3.0-6.8。该专利最明显的特征是其成膜为易辨识的金黄色转化膜，有利于施工操作而提高生产率。但该膜的不足之处是成膜放置一段时间后容易粉化脱落，涂装性能较差。因此，开发高性能、环保型且便于施工操作的有色无铬铝合金钝化液仍是该领域的当务之急。
发明内容
本发明的目的在于针对以上问题提供一种不包含铬，并且使铝合金在钝化后能产生较明显的颜色变化，用于铝合金表面处理的钛锆系有色无铬钝化液、铝合金表面的处理方法及其应用。
为了实现以上目的，在一个方面，本发明采用的技术方案是：
一种用于铝合金表面处理的钛锆系有色无铬钝化液，该钝化液包括以下质量体积浓度的组分：主成膜剂0.01～80g/L，氧化剂0.01～80g/L，成膜促进剂0.01～50g/L，无机成膜助剂0.01～50g/L，成膜有机保护剂0.01～50g/L、将溶液的pH值调节至2-6的量的pH调节剂，以及作为溶剂的水。
进一步地，该主成膜剂选自由氟钛酸、氟钛酸钾、氟钛酸钠、氟钛酸铵、氟钛酸锂、氟锆酸、氟锆酸钾、氟锆酸钠、氟锆酸铵、和氟锆酸锂组成的组中的至少一种。
进一步地，该氧化剂选自由双氧水、高氯酸钾、高氯酸钠、碘酸钾、高碘酸钾、高碘酸钠、过硫酸钾、过硫酸铵、过硫酸钠、和硫酸铈组成的组中的至少一种。
进一步地，该成膜促进剂选自由氟化钠、氟化钾、氟化铵、氟化镁、氟化锂及其水合物组成的组中的至少一种。
进一步地，该无机成膜助剂选自由硫酸镍、硝酸镍、氯化镍、硫酸钴、硝酸钴、氯化钴、硫酸锰、硝酸锰、氯化锰、钨酸钠、钨酸钾、钨酸铵、偏钨酸铵、钼酸铵、钼酸钠、钼酸钾及其水合物组成的组中的至少一种。
进一步地，该有机成膜保护剂选自由丙烯酸、聚丙烯酸、丙烯酰胺、聚丙烯酰胺、N-羟甲基丙烯酰胺、吡咯烷酮、聚乙烯吡咯烷酮、聚乙烯醇、聚乙二醇、乙二胺四乙酸、羧甲基纤维素、壳聚糖、聚山梨酯、聚环氧乙烷、和聚环氧丙烷组成的组中的至少一种。
进一步地，该pH调节剂选自由氢氟酸、硫酸、磷酸、硝酸、盐酸、和柠檬酸组成的组中的至少一种。
进一步地，该pH调节剂的用量使有色无铬钝化液的pH值调节至2-6。
在另一个方面，本发明提供了一种用于对铝合金的表面进行处理的方法，该方法包括以下步骤：1)将上述的有色无铬钝化液用水稀释至1到80倍；2)将经过脱脂预处理的铝合金浸渍在该钝化液中或将该钝化液喷淋在铝合金的表面上；以及3)待反应一段时间后对铝合金进行水洗并烘干。
进一步地，在所述处理方法中使用的工作温度为0℃-40℃，钝化液与铝合金的反应时间为10-500s。
在又一个方面，本发明提供了一种使用上述的钛锆系有色无铬钝化液处理过的或者通过上述的处理方法处理过的铝合金型材在手机、笔记本电脑、建材、汽车、家具家装、运动器材、产品包装以及航天器领域中的应用。
在又一个方面中，本发明提供了一种上述的钛锆系有色无铬钝化液在处理铝合金的表面中的应用。
本发明的有色无铬钝化液中不含有重金属铬，因此可以避免重金属铬对人体的危害和环境污染，降低铝合金涂装企业含铬废水的处理成本。该钝化液呈均匀透明的黄色，在室温条件下储存稳定性良好，长时间放置无沉淀产生，便于产品的存放与运输。经该钝化液处理后的铝合金表面会形成一层致密的浅黄色的转化膜，便于技术人员通过观察转化膜颜色的深浅和均匀度直观地判断膜层的质量，以对下一步的操作及时地作出调整，使生产工艺得以简化。经该钝化液处理形成的转化膜具有优良的防腐蚀性能，在中性盐雾实验(35±1℃)中出现50％腐蚀点的时间达到200h以上(盐雾实验执行中国国家标准GB/T10125-2012/ISO9227：2006)；用10wt./％的硫酸铜溶液40mL+10wt.％的氯化钠溶液20mL+0.1mol/L 盐酸1mL进行耐点滴实验，耐腐蚀时间可达150秒。此转化膜能够显著增强在铝合金表面涂装的结合力。经喷涂-热固化工艺形成的涂装膜，经漆膜划格、机械冲击、高温高压水蚀等实验后仍能与铝合金基体保持良好的结合力。此外，本发明的有色无铬钝化液的工作温度为0℃-40℃，有效pH值的范围为2-6，与铝合金的反应时间只有10-500s，因而在无需加热、无需经常性调节pH值的条件下，即可保持连续、高效生产，提高生产效率。此外，使用本发明的钛锆系有色无铬钝化液处理过的铝合金型材可以应用在手机、笔记本电脑、建材、汽车、家具家装、运动器材、产品包装以及航天器领域中。
附图说明
图1为使用本发明的实施例1中的钝化液对铝合金工件进行钝化处理前后的颜色对比：铝合金工件的左侧为已处理，而铝合金工件的右侧为未处理。
图2为使用本发明的实施例1中的有色无铬钝化液处理的铝合金工件表面进行涂装的效果图。
图3为使用本发明的实施例1中的钝化液处理过的铝合金表面涂装膜划格的测试结果(执行国家标准GB-T9286-1998色漆和清漆漆膜的划格试验，划格间距为1mm)。
图4为使用本发明的实施例1中的钝化液处理过的铝合金表面涂装膜的漆膜冲击试验法测试结果：左侧为正向冲击，而右侧为反向冲击(执行国家标准GB/T1732-93漆膜冲击试验法，重锤质量为1000g，自由下落高度50cm)。
图5为使用本发明的实施例1中的钝化液处理过的和未使用该钝化液处理的铝合金表面涂装膜高压锅蒸煮的测试结果的对比图：上方为未处理的铝合金表面涂装膜，下方为经过本发明的钝化液处理的铝合金表面涂装膜(样品全部浸入水中，蒸煮时间为90分钟)。
具体实施方式
为了使本发明的目的及优点更加清楚，现结合实施例对本发明所要求保护的技术方案作进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明而并不用于限定本发明。
在本发明的一个实施方式中，本发明提供了一种用于铝合金表面处理的钛锆系有色无铬钝化液，包括以下质量体积浓度的组分：主成膜剂0.01～80g/L、氧化剂0.01～80g/L、成膜促进剂0.01～50g/L、无机成膜助剂0.01～50g/L、有机成膜保护剂0.01～50g/L、将溶液的pH值调节至2-6的量的pH调节剂，以及作为溶剂的水。
优选地，在该钛锆系有色无铬钝化液中，该主成膜剂选自由氟钛酸、氟钛酸钾、氟钛酸钠、氟钛酸铵、氟钛酸锂、氟锆酸、氟锆酸钾、氟锆酸钠、氟锆酸铵、和氟锆酸锂组成的组中的至少一种。
优选地，在该钛锆系有色无铬钝化液中，该氧化剂选自由双氧水、高氯酸钾、高氯酸钠、碘酸钾、高碘酸钾、高碘酸钠、过硫酸钾、过硫酸铵、过硫酸钠和硫酸铈组成的组中的至少一种。
优选地，在该钛锆系有色无铬钝化液中，该成膜促进剂选自由氟化钠、氟化钾、氟化铵、氟化镁、氟化锂及其水合物组成的组中的至少一种。
优选地，在该钛锆系有色无铬钝化液中，该无机成膜助剂选自由硫酸镍、硝酸镍、氯化镍、硫酸钴、硝酸钴、氯化钴、硫酸锰、硝酸锰、氯化锰、钨酸钠、钨酸钾、钨酸铵、偏钨酸铵、钼酸铵、钼酸钠、钼酸钾及其水合物组成的组中的至少一种。
优选地，在该钛锆系有色无铬钝化液中，该有机成膜保护剂选自由丙烯酸、聚丙烯酸、丙烯酰胺、聚丙烯酰胺、N-羟甲基丙烯酰胺、吡咯烷酮、聚乙烯吡咯 烷酮、聚乙烯醇、聚乙二醇、乙二胺四乙酸、羧甲基纤维素、壳聚糖、聚山梨酯、聚环氧乙烷、和聚环氧丙烷组成的组中的至少一种。
优选地，在该钛锆系有色无铬钝化液中，该pH调节剂选自由氢氟酸、硫酸、磷酸、硝酸、盐酸、和柠檬酸组成的组中的至少一种。
在另一个实施方式中，本发明提供了一种用于对铝合金的表面进行处理的方法，该方法包括以下步骤：
1)将上述的有色无铬钝化液用水稀释至1到80倍；
2)将经过脱脂预处理的铝合金浸渍在上述钝化液中或将上述钝化液喷淋在铝合金的表面上；以及
3)待反应一段时间后对铝合金进行水洗并烘干。
优选地，在该方法中使用的工作温度为0℃-40℃，该钝化液与铝合金的反应时间为10-500s。
在又一个实施方式中，本发明提供了一种使用上述的钛锆系有色无铬钝化液处理过的或者通过上述方法处理过的铝合金型材在手机、笔记本电脑、建材、汽车、家具家装、运动器材、产品包装以及航天器领域中的应用。
在又一个实施方式中，本发明提供了一种上述的钛锆系有色无铬钝化液在处理铝合金的表面中的应用。
实施例1
在本实施例中，在配制定量体积的有色无铬钝化液时，根据以下质量体积浓度称取所需的组分：氟钛酸钾10g/L，过硫酸钠2g/L，氟化钠5g/L；硫酸锰3g/L，聚丙烯酰胺3g/L，然后将以上组分加入到约八成定量体积的去离子水中均匀混合。接下来，用氢氟酸将该钝化液的pH值调节至4.0，其具体的用量视实际情况而定。 最后，补加去离子水使该钝化液的体积达到定量体积。将配制好的外观呈均匀透明状的有色无铬钝化液转入到PVC塑料容器中，在室温下贮存备用(无需避光)。
使用该钝化液处理铝合金的表面时，首先将该钝化液稀释20倍，接着通过除油剂对铝合金的表面进行脱脂处理，然后在室温条件下，将待钝化处理的铝合金工件浸渍在该钝化液中或将钝化液喷淋在铝合金工件的表面上。当铝合金件的表面与无铬钝化液接触反应100s后，在工件的表面上形成一层致密的浅黄色转化膜，图1为铝合金工件在使用该钝化液处理前后的颜色对比。技术人员可通过观察转化膜颜色的深浅、均匀度等来直观地判断膜层的质量，并根据需要及时地调整工作液(钝化液)的浓度或反应时间。在将工件取出后，应及时对铝合金工件进行水洗处理和烘干处理，以避免铝合金工件表面残余的钝化液与工件长时间接触造成转化膜的不均匀。研究表明，经该钝化液处理的铝合金工件表面具有优良的防腐蚀能力，经中性盐雾实验测试其耐久性可达220h(盐雾实验执行中国国家标准GB/T10125-2012/ISO9227：2006)。经钝化处理的铝合金工件与表面涂装膜具有良好的结合力。图2为通过使用实施例1中的钝化液处理的铝合金工件表面进行涂装的效果图。图3是对使用实施例1中的钝化液处理过的铝合金表面的涂装膜进行划格测试的结果(执行国家标准GB-T9286-1998色漆和清漆漆膜的划格试验，划格间距1mm)，格间无起皮、脱粉的现象。图4是对使用本发明的实施例1中的钝化液处理过的涂装膜进行冲击试验的测试结果：左侧为正向冲击，右侧为反向冲击(执行国家标准GB/T1732-93漆膜冲击试验法，重锤质量为1000g，自由下落高度50cm)。可以看出，无论是正向冲击还是反向冲击，涂装膜都与基底保持了良好的结合力，在冲击面周围无起皮、脱粉现象。图5为使用本发明的实施例1中的钝化液处理过的和未使用该钝化液处理的涂装膜经过高压锅蒸煮实验的测试结果：上方为未处理的铝合金表面涂装膜，下方为经过本发明的钝化液处理的铝合金表 面涂装膜(样品全部浸入水中，蒸煮时间为90分钟)。结果表明，未经处理的铝合金表面涂装膜出现严重的起泡、脱皮等现象，而经本发明的钝化液处理的铝合金表面涂装膜依然保持了与基材良好的结合力。
实施例2
在本实施例中，在配制定量体积的有色无铬钝化液时，根据以下质量体积浓度称取所需的组分：氟锆酸钠10g/L，过硫酸铵2g/L，氟化钾共5g/L；硝酸锰4g/L，钼酸钾6g/L，N-羟甲基丙烯酰胺5g/L，然后将以上组分加入到约八成定量体积的去离子水中均匀混合。接下来，用氢氟酸、硫酸、磷酸、硝酸、盐酸中的至少一种将该钝化液的pH值调节至5，其具体的用量视实际情况而定。最后，补加水使该钝化液的体积达到定量体积。将配制好的外观呈均匀透明状的有色无铬钝化液转入到PVC塑料容器中，在室温下贮存备用(无需避光)。
在使用该钝化液处理铝合金表面时，首先将上述有色无铬钝化液稀释至5倍体积置入钝化液洗槽中。然后，通过除油剂对铝合金的表面进行脱脂处理，然后在室温条件下，将待钝化处理的铝合金工件浸渍在该钝化液浸中或将钝化液喷淋在该铝合金工件的表面上。在使铝合金工件的表面与无铬钝化液接触反应120s后，在工件的表面上形成一层致密的浅黄色转化膜。在将工件取出后，应及时对铝合金件进行水洗处理和烘干处理，以避免铝合金工件表面残余的钝化液与工件长时间接触造成转化膜的不均匀。实验表明，经该钝化液处理的铝合金工件表面具有优良的防腐蚀能力，经中性盐雾实验测试其耐久性可达230h。经钝化处理的铝合金工件与表面涂装膜具有良好的结合力。
实施例3
在本实施例中，在配制定量体积的有色无铬钝化液时，先根据以下质量体积浓度称取所需的组分：氟钛酸钾、氟锆酸钠共10g/L，过硫酸钾、过硫酸钠、过硫 酸铵共5g/L，氟化钠、氟化钾、氟化铵共5g/L；硝酸锰、硫酸锰、钨酸钠共6g/L，聚丙烯酰胺、N-羟甲基丙烯酰胺、聚丙烯酸共5g/L，然后将以上组分加入到约八成定量体积的去离子水中均匀混合。接下来，用氢氟酸、硫酸、磷酸、硝酸、盐酸中的至少一种将该钝化液的pH值调节至4，其具体的用量视实际情况而定。最后，补加水使该钝化液的体积达到定量体积。将配制好的外观呈黄绿色均匀透明状的有色无铬钝化液转入PVC塑料容器中，在室温下贮存备用(无需避光)。
在使用该钝化液处理铝合金的表面时，首先将上述有色无铬钝化液稀释至15倍体积置入钝化液洗槽中。然后，通过除油剂对铝合金的表面进行脱脂处理，然后在室温条件下，将待钝化处理的铝合金件浸渍在该钝化液浸中或将该钝化液喷淋在该铝合金工件的表面上。当使铝合金工件的表面与无铬钝化液接触反应180s后，在工件的表面上形成一层致密的浅黄色转化膜。在工件取出后，应及时对铝合金工件进行水洗处理和烘干处理，以避免铝合金工件表面残余的钝化液与工件长时间接触造成转化膜的不均匀。实验表明，经该钝化液处理的铝合金工件表面具有优良的防腐蚀能力，经中性盐雾实验测试其耐久性可达250h。经钝化处理的铝合金工件与表面涂装膜具有良好的结合力。
本实施例中的氟钛酸钾、氟锆酸钠对应实施例1中的主成膜剂氟钛酸钾，过硫酸钾、过硫酸钠、过硫酸铵对应实施例1中的氧化剂过硫酸钠；氟化钠、氟化钾、氟化铵对应实施例1中的成膜促进剂氟化钠；硝酸钴、硫酸锰、钨酸钠对应实施例1中的无机成膜助剂硫酸锰；聚丙烯酰胺、N-羟甲基丙烯酰胺、聚丙烯酸对应实施例1中的成膜有机保护剂聚丙烯酰胺；氢氟酸、硫酸、磷酸、硝酸、盐酸对应实施例1中的pH调节剂。起相同作用的物质可有多种，它们在形成转化膜过程中的作用机制相似，在使用效果上其主要差别在于其分子量不同或在水溶剂中的解离度不同，其效果差异可通过调节钝化液中的具体质量体积浓度进行调整。
本发明的其它实施例将以如下表格形式给出，其钝化液的配制方法及铝合金表面的处理方法与上述三个实施例类似。不同之处仅在于，表中的各实施例所使用的各组分物质的种类和含量不同，以及在使用所配制的钝化液处理铝合金表面时反应时间不同。在以下各实施例中，钝化液配制完成经稀释后用于铝合金的表面处理。中性盐雾实验全部执行中国国家标准GB/T10125-2012/ISO9227：2006。
Figure PCTCN2015083230-appb-000001
Figure PCTCN2015083230-appb-000002
Figure PCTCN2015083230-appb-000003
Figure PCTCN2015083230-appb-000004
Figure PCTCN2015083230-appb-000005
Figure PCTCN2015083230-appb-000006
Figure PCTCN2015083230-appb-000007
此外，以与实施例1中类似的方式对使用上面表中的各实施例处理过的铝合金表面的涂装膜进行划格测试(执行国家标准GB-T9286-1998色漆和清漆漆膜的划格试验，划格间距1mm)，试验结果表明，格间无起皮、脱粉的现象。
以上实施例仅是本发明的一些优选实施方式，但本发明的保护范围并不仅限于此。本领域技术人员应该理解，所有未背离本发明精神和范围的任何修改、替换或将本发明分成若干部分再行组合的方式都在本发明的保护范围之内。

Claims (11)

  1. 一种用于铝合金表面处理的钛锆系有色无铬钝化液，包括以下质量体积浓度的组分：主成膜剂0.01～80g/L、氧化剂0.01～80g/L、成膜促进剂0.01～50g/L、无机成膜助剂0.01～50g/L、有机成膜保护剂0.01～50g/L、将溶液的pH值调节至2-6的量的pH调节剂，以及作为溶剂的水。
  2. 根据权利要求1所述的用于铝合金表面处理的钛锆系有色无铬钝化液，其特征在于，所述主成膜剂选自由氟钛酸、氟钛酸钾、氟钛酸钠、氟钛酸铵、氟钛酸锂、氟锆酸、氟锆酸钾、氟锆酸钠、氟锆酸铵和氟锆酸锂组成的组中的至少一种。
  3. 根据权利要求1所述的用于铝合金表面处理的钛锆系有色无铬钝化液，其中，所述氧化剂选自由双氧水、高氯酸钾、高氯酸钠、碘酸钾、高碘酸钾、高碘酸钠、过硫酸钾、过硫酸铵、过硫酸钠和硫酸铈组成的组中的至少一种。
  4. 根据权利要求1所述的用于铝合金表面处理的钛锆系有色无铬钝化液，其特征在于，所述成膜促进剂选自由氟化钠、氟化钾、氟化铵、氟化镁、氟化锂及其水合物组成的组中的至少一种。
  5. 根据权利要求1所述的用于铝合金表面处理的钛锆系有色无铬钝化液，其中，所述无机成膜助剂选自由硫酸镍、硝酸镍、氯化镍、硫酸钴、硝酸钴、氯化钴、硫酸锰、硝酸锰、氯化锰、钨酸钠、钨酸钾、钨酸铵、偏钨酸铵、钼酸铵、钼酸钠、钼酸钾及其水合物组成的组中的至少一种。
  6. 根据权利要求1所述的用于铝合金表面处理的钛锆系有色无铬钝化液，其特征在于，所述有机成膜保护剂选自由丙烯酸、聚丙烯酸、丙烯酰胺、聚丙烯酰胺、N-羟甲基丙烯酰胺、吡咯烷酮、聚乙烯吡咯烷酮、聚乙烯醇、聚乙二醇、乙 二胺四乙酸、羧甲基纤维素、壳聚糖、聚山梨酯、聚环氧乙烷、和聚环氧丙烷组成的组中的至少一种。
  7. 根据权利要求1所述的用于铝合金表面处理的钛锆系有色无铬钝化液，其特征在于，所述pH调节剂选自由氢氟酸、硫酸、磷酸、硝酸、盐酸、和柠檬酸组成的组中的至少一种。
  8. 一种用于对铝合金的表面进行处理的方法，其特征在于，所述方法包括以下步骤：
    1)将根据权利要求1至7中任一项所述的有色无铬钝化液用水稀释至1到80倍；
    2)将经过脱脂预处理的铝合金浸渍在所述钝化液中或将所述钝化液喷淋在铝合金的表面上；以及
    3)待反应一段时间后对铝合金进行水洗并烘干。
  9. 根据权利要求8所述的方法，其特征在于，在所述方法中使用的工作温度为0℃-40℃，所述钝化液与铝合金的反应时间为10-500s。
  10. 一种使用根据权利要求1-7中任一项所述的钛锆系有色无铬钝化液处理过的或者通过根据权利要求8-9中任一项所述的方法处理过的铝合金型材在手机、笔记本电脑、建材、汽车、家具家装、运动器材、产品包装以及航天器领域中的应用。
  11. 根据权利要求1-7中任一项所述的钛锆系有色无铬钝化液在处理铝合金的表面中的应用。
PCT/CN2015/083230 2015-07-02 2015-07-02 用于铝合金表面处理的钛锆系有色无铬钝化液、使用其处理铝合金表面的方法及其应用 WO2017000315A1 (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/CN2015/083230 WO2017000315A1 (zh) 2015-07-02 2015-07-02 用于铝合金表面处理的钛锆系有色无铬钝化液、使用其处理铝合金表面的方法及其应用
CN201580000402.4A CN107429404A (zh) 2015-07-02 2015-07-02 用于铝合金表面处理的钛锆系有色无铬钝化液、使用其处理铝合金表面的方法及其应用

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2015/083230 WO2017000315A1 (zh) 2015-07-02 2015-07-02 用于铝合金表面处理的钛锆系有色无铬钝化液、使用其处理铝合金表面的方法及其应用

Publications (1)

Publication Number Publication Date
WO2017000315A1 true WO2017000315A1 (zh) 2017-01-05

Family

ID=57607548

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2015/083230 WO2017000315A1 (zh) 2015-07-02 2015-07-02 用于铝合金表面处理的钛锆系有色无铬钝化液、使用其处理铝合金表面的方法及其应用

Country Status (2)

Country Link
CN (1) CN107429404A (zh)
WO (1) WO2017000315A1 (zh)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109183016A (zh) * 2018-07-27 2019-01-11 博罗县东明化工有限公司 Adc12压铸铝合金黑色无铬转化膜处理剂及adc12压铸铝合金的表面处理方法
CN109675779A (zh) * 2018-12-28 2019-04-26 广东兴发铝业（河南）有限公司 一种氟碳粉末喷涂铝型材的加工方法
CN111441044A (zh) * 2020-04-26 2020-07-24 深圳市钝化技术有限公司 无磷无氮无铬不锈钢钝化液
CN111944335A (zh) * 2020-07-24 2020-11-17 苏州波菲特新材料科技有限公司 一种陶化剂、其制备方法及搅拌装置
CN112713339A (zh) * 2020-12-07 2021-04-27 乐凯胶片股份有限公司 铝塑软包装膜、制备方法以及软包电池
CN113088951A (zh) * 2021-04-08 2021-07-09 上海兴赛尔表面材料有限公司 一种镀锌板用的多功能无铬钝化液及其制备方法和用途
CN113430509A (zh) * 2021-06-24 2021-09-24 浙江固的管业有限公司 一种不锈钢管件的防腐处理工艺
CN113846332A (zh) * 2021-09-10 2021-12-28 大富科技(安徽)股份有限公司 铝制天线蚀刻面的处理方法
CN114774904A (zh) * 2022-04-24 2022-07-22 安徽光铧帝业化学有限公司 一种含有荧光剂的铝合金无铬钝化药剂及其制备方法和使用方法
CN114875281A (zh) * 2022-05-11 2022-08-09 山东骏程金属科技有限公司 一种抗疲劳及耐腐蚀的锻造Al-Mg-Si-Zr铝合金车轮及其制备方法
CN114921780A (zh) * 2022-04-19 2022-08-19 南京艾布纳密封技术股份有限公司 一种铝合金用环保钝化液及其制备方法和处理工艺
CN115369393A (zh) * 2022-08-11 2022-11-22 江苏特昊新材料有限公司 一种金属表面前处理成膜液及其制备方法与应用
CN115449791A (zh) * 2022-08-24 2022-12-09 江苏和兴汽车科技有限公司 一种提升压铸铝抗腐蚀性能的方法
CN115726016A (zh) * 2022-12-05 2023-03-03 仙桃市伟方新材料科技有限公司 一种含有稀土成分的无镍无氟中温封闭剂及其制备方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111074255A (zh) * 2019-12-05 2020-04-28 刘广付 一种金属表面前处理剂及其制备方法和应用
CN113151815A (zh) * 2020-12-22 2021-07-23 苏州帝航防护设施有限公司 一种抗腐蚀的金属表面处理剂
CN114045478A (zh) * 2021-10-13 2022-02-15 东莞理工学院 一种铝合金导电转化膜的制备方法
CN115404473A (zh) * 2022-08-30 2022-11-29 江苏中天科技股份有限公司 用于铝材表面处理的钝化液及铝材表面钝化方法和具有纳米转化膜的防腐蚀型铝材

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101161861A (zh) * 2007-11-22 2008-04-16 东北大学 一种用于处理铝合金的无铬钝化液及其使用方法
CN101967633A (zh) * 2010-09-16 2011-02-09 华南理工大学 制备铝合金表面含Ti/Zr黄色钝化膜的处理液及方法
CN102634785A (zh) * 2012-05-07 2012-08-15 东莞市闻誉实业有限公司 一种锌和锌合金钝化方法及无铬钝化液
CN102782186A (zh) * 2010-02-24 2012-11-14 埃托特克德国有限公司 气相沉积的铝表面的不含铬的钝化方法
CN104294249A (zh) * 2013-07-19 2015-01-21 无锡永发电镀有限公司 一种变形铝合金环保钝化液
CN104388915A (zh) * 2014-11-24 2015-03-04 毛山红 用于铝合金表面处理的锰锆系无铬钝化液及其处理方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101161861A (zh) * 2007-11-22 2008-04-16 东北大学 一种用于处理铝合金的无铬钝化液及其使用方法
CN102782186A (zh) * 2010-02-24 2012-11-14 埃托特克德国有限公司 气相沉积的铝表面的不含铬的钝化方法
CN101967633A (zh) * 2010-09-16 2011-02-09 华南理工大学 制备铝合金表面含Ti/Zr黄色钝化膜的处理液及方法
CN102634785A (zh) * 2012-05-07 2012-08-15 东莞市闻誉实业有限公司 一种锌和锌合金钝化方法及无铬钝化液
CN104294249A (zh) * 2013-07-19 2015-01-21 无锡永发电镀有限公司 一种变形铝合金环保钝化液
CN104388915A (zh) * 2014-11-24 2015-03-04 毛山红 用于铝合金表面处理的锰锆系无铬钝化液及其处理方法

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109183016B (zh) * 2018-07-27 2020-11-27 博罗县东明化工有限公司 Adc12压铸铝合金黑色无铬转化膜处理剂及adc12压铸铝合金的表面处理方法
CN109183016A (zh) * 2018-07-27 2019-01-11 博罗县东明化工有限公司 Adc12压铸铝合金黑色无铬转化膜处理剂及adc12压铸铝合金的表面处理方法
CN109675779A (zh) * 2018-12-28 2019-04-26 广东兴发铝业（河南）有限公司 一种氟碳粉末喷涂铝型材的加工方法
CN111441044B (zh) * 2020-04-26 2022-11-25 深圳市钝化技术有限公司 无磷无氮无铬不锈钢钝化液
CN111441044A (zh) * 2020-04-26 2020-07-24 深圳市钝化技术有限公司 无磷无氮无铬不锈钢钝化液
CN111944335A (zh) * 2020-07-24 2020-11-17 苏州波菲特新材料科技有限公司 一种陶化剂、其制备方法及搅拌装置
CN112713339A (zh) * 2020-12-07 2021-04-27 乐凯胶片股份有限公司 铝塑软包装膜、制备方法以及软包电池
CN113088951A (zh) * 2021-04-08 2021-07-09 上海兴赛尔表面材料有限公司 一种镀锌板用的多功能无铬钝化液及其制备方法和用途
CN113430509A (zh) * 2021-06-24 2021-09-24 浙江固的管业有限公司 一种不锈钢管件的防腐处理工艺
CN113846332A (zh) * 2021-09-10 2021-12-28 大富科技(安徽)股份有限公司 铝制天线蚀刻面的处理方法
CN114921780A (zh) * 2022-04-19 2022-08-19 南京艾布纳密封技术股份有限公司 一种铝合金用环保钝化液及其制备方法和处理工艺
CN114921780B (zh) * 2022-04-19 2024-01-23 南京艾布纳新材料股份有限公司 一种铝合金用环保钝化液及其制备方法和处理工艺
CN114774904A (zh) * 2022-04-24 2022-07-22 安徽光铧帝业化学有限公司 一种含有荧光剂的铝合金无铬钝化药剂及其制备方法和使用方法
CN114875281A (zh) * 2022-05-11 2022-08-09 山东骏程金属科技有限公司 一种抗疲劳及耐腐蚀的锻造Al-Mg-Si-Zr铝合金车轮及其制备方法
CN115369393A (zh) * 2022-08-11 2022-11-22 江苏特昊新材料有限公司 一种金属表面前处理成膜液及其制备方法与应用
CN115449791A (zh) * 2022-08-24 2022-12-09 江苏和兴汽车科技有限公司 一种提升压铸铝抗腐蚀性能的方法
CN115726016A (zh) * 2022-12-05 2023-03-03 仙桃市伟方新材料科技有限公司 一种含有稀土成分的无镍无氟中温封闭剂及其制备方法
CN115726016B (zh) * 2022-12-05 2023-08-11 仙桃市伟方新材料科技有限公司 一种含有稀土成分的无镍无氟中温封闭剂及其制备方法

Also Published As

Publication number Publication date
CN107429404A (zh) 2017-12-01

Similar Documents

Publication Publication Date Title
WO2017000315A1 (zh) 用于铝合金表面处理的钛锆系有色无铬钝化液、使用其处理铝合金表面的方法及其应用
Zhong et al. Self-repairing vanadium–zirconium composite conversion coating for aluminum alloys
CN103866311B (zh) 一种基于钼酸盐在铝合金表面制备化学转化膜方法
CN105132900B (zh) 铝合金表面环保型钛锆转化处理/静电喷涂的防腐处理工艺
CN101851755B (zh) 一种镁合金无铬无氟磷化溶液及磷化方法
EP1853750A2 (en) Process for sealing phosphoric acid anodized aluminums
CN102776501A (zh) 一种铝和铝合金无铬钝化方法及无铬钝化液
CN109112519A (zh) 含有氧化石墨烯的铝合金型材无铬钝化剂及其制备方法
CN111593335A (zh) 一种用于金属表面处理的改良锆基转化膜及其制备方法与应用
CN103710688A (zh) 一种弱酸性无磷转化剂
CN106894012B (zh) 一种锰酸盐作为主盐的铝和铝合金表面处理用钝化液及其应用
CN104357825A (zh) 一种镀锡钢板表面处理液及其制备方法
CN104294258A (zh) 金属环保型硅烷陶化皮膜处理剂及制备方法
CN104342683A (zh) 一种镁合金工件表面耐蚀转化膜处理工艺
CN104451636A (zh) 一种用于镀锡钢板的无铬钝化液及其制备方法
CN105063596A (zh) 一种铝型材涂装前无铬钝化处理液及其制备方法
CN103397320A (zh) 一种用于汽车热镀锌板表面阴极电泳前处理液
CN103088329B (zh) 一种铝合金涂装前处理剂
CN105441927A (zh) 冷轧钢板·镀锌钢板辊涂涂装前无铬钝化剂及制备方法
CN109338347A (zh) 一种无铬钝化组合物、无铬钝化液及其制备方法
CN106232872B (zh) 用于铝的非铬酸盐有色转化涂料
CN104611689A (zh) 一种镁合金化学氧化液
CN109023331B (zh) 一种无铬钝化剂及其使用方法
WO2018006270A1 (zh) 无铬铝皮膜剂、铝材及其表面皮膜化处理方法
CN109183015B (zh) 一种无镍皮膜剂及其制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15896846

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15896846

Country of ref document: EP

Kind code of ref document: A1