CN104988551B - Application of the lemon acid doping Cerium conversion film in AA2219 corrosive protection of aluminium alloy - Google Patents
Application of the lemon acid doping Cerium conversion film in AA2219 corrosive protection of aluminium alloy Download PDFInfo
- Publication number
- CN104988551B CN104988551B CN201510444063.0A CN201510444063A CN104988551B CN 104988551 B CN104988551 B CN 104988551B CN 201510444063 A CN201510444063 A CN 201510444063A CN 104988551 B CN104988551 B CN 104988551B
- Authority
- CN
- China
- Prior art keywords
- aluminum alloy
- citric acid
- application
- cerium conversion
- conversion film
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Fee Related
Links
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 42
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 42
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 title abstract description 26
- 244000248349 Citrus limon Species 0.000 title description 2
- 235000005979 Citrus limon Nutrition 0.000 title description 2
- 239000002253 acid Substances 0.000 title description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 49
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005260 corrosion Methods 0.000 claims abstract description 18
- 238000009713 electroplating Methods 0.000 claims abstract description 18
- 230000007797 corrosion Effects 0.000 claims abstract description 16
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000007739 conversion coating Methods 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000002585 base Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 230000008021 deposition Effects 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004327 boric acid Substances 0.000 abstract description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 abstract 2
- 239000000523 sample Substances 0.000 description 22
- 238000002360 preparation method Methods 0.000 description 14
- 238000004070 electrodeposition Methods 0.000 description 10
- 229910052761 rare earth metal Inorganic materials 0.000 description 10
- 150000002910 rare earth metals Chemical class 0.000 description 9
- 238000000151 deposition Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000002525 ultrasonication Methods 0.000 description 5
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- -1 carboxyl tricarboxylic acid Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Landscapes
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Chemical Treatment Of Metals (AREA)
- ing And Chemical Polishing (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
本发明公开了柠檬酸掺杂铈转化膜在AA2219铝合金防腐中的应用，选择硝酸铈、硼酸、柠檬酸和过氧化氢组成的电镀液，将预处理的铝合金、铂片置于电镀池内分别作为阴极、阳极并与直流稳压电源相连进行稳压直流沉积制备成柠檬酸掺杂铈转化膜。本发明提供一种粘着力以及耐蚀性好的防腐转化膜在防腐中的应用，该应用操作简便、费用低、耗时短、应用范围广，是一种集经济、高效、优质于一体的应用方法。
The invention discloses the application of citric acid-doped cerium conversion film in the anticorrosion of AA2219 aluminum alloy. The electroplating solution composed of cerium nitrate, boric acid, citric acid and hydrogen peroxide is selected, and the pretreated aluminum alloy and platinum sheet are placed in the electroplating pool. They are respectively used as cathode and anode and connected to a DC stabilized power supply for DC deposition to prepare citric acid-doped cerium conversion film. The invention provides an application of an anti-corrosion conversion film with good adhesion and corrosion resistance in anti-corrosion. The application is easy to operate, low in cost, short in time, and wide in application range. application method.
Description
本发明申请是母案申请“一种柠檬酸掺杂铈转化膜及其制备方法”的分案申请，母案申请号为201310396184.3，申请日为2013年9月3日。The application of the present invention is a divisional application of the parent application "a citric acid-doped cerium conversion film and its preparation method". The application number of the parent application is 201310396184.3, and the filing date is September 3, 2013.
技术领域technical field
本发明属于腐蚀防护技术领域，更加具体地说，涉及一种柠檬酸掺杂铈转化膜在AA2219铝合金防腐中的应用。The invention belongs to the technical field of corrosion protection, and more specifically relates to the application of a citric acid-doped cerium conversion film in AA2219 aluminum alloy anticorrosion.
背景技术Background technique
近年来，稀土铈转化膜以其无毒、无污染以及良好的自修复功能受到许多研究者的重视。但稀土铈转化膜由于膜层不均匀、工艺处理时间较长、盐溶液不稳定等问题，使其应用受到限制。一些研究者在稀土盐溶液中加入强氧化剂，如H2O2、KMnO4、(NH4)2S2O8等，以此来缩短转化膜的成膜时间、提高膜层的均匀性和致密性，但是，这种稀土铈转化膜层与基体的结合力差，易开裂，并不能有效的提高稀土铈转化膜的耐蚀性。In recent years, rare earth cerium conversion coatings have attracted the attention of many researchers for their non-toxic, non-polluting and good self-healing functions. However, the application of the rare earth cerium conversion coating is limited due to problems such as uneven coating, long processing time, and unstable salt solution. Some researchers add strong oxidants, such as H 2 O 2 , KMnO 4 , (NH 4 ) 2 S 2 O 8 , etc., to the rare earth salt solution to shorten the film-forming time of the conversion film, improve the uniformity and Density, however, this kind of rare earth cerium conversion coating layer has poor bonding force with the substrate, is easy to crack, and cannot effectively improve the corrosion resistance of the rare earth cerium conversion coating.
发明内容Contents of the invention
本发明的目的在于克服现有技术的不足，提供一种成本低、制备过程简单、耐蚀性好的柠檬酸掺杂铈转化膜的制备方法。The purpose of the present invention is to overcome the deficiencies of the prior art and provide a method for preparing a citric acid-doped cerium conversion coating with low cost, simple preparation process and good corrosion resistance.
本发明的技术目的通过下述技术方案予以实现：Technical purpose of the present invention is achieved through the following technical solutions:
一种柠檬酸掺杂铈转化膜的制备方法，按照下述步骤进行制备：A kind of preparation method of citric acid doped cerium conversion film, prepares according to following steps:
步骤1，在1L水溶液中，依次加入Ce(NO3)3·6H2O，H3BO3，30mL 30wt％的H2O2水溶液和柠檬酸，其中所述Ce(NO3)3·6H2O浓度为0.5g/L，所述H3BO3浓度为0.4g/L，所述柠檬酸浓度为0.1g/L—0.8g/L，优选0.2g/L—0.4g/L，并调节整个体系pH＝2.5。Step 1, in 1L aqueous solution, add Ce(NO 3 ) 3 ·6H 2 O, H 3 BO 3 , 30mL 30wt% H 2 O 2 aqueous solution and citric acid successively, wherein the Ce(NO 3 ) 3 ·6H 2 O concentration is 0.5g/L, the H 3 BO 3 concentration is 0.4g/L, the citric acid concentration is 0.1g/L-0.8g/L, preferably 0.2g/L-0.4g/L, and Adjust the pH of the whole system to 2.5.
在所述步骤1中，利用20wt％HNO3水溶液或者0.1M NaOH水溶液对整个体系进行调节，以使整个体系pH稳定在2.5。In the step 1, the whole system is adjusted with 20wt% HNO 3 aqueous solution or 0.1M NaOH aqueous solution, so that the pH of the whole system is stabilized at 2.5.
步骤2，利用直流稳压电源为电镀装置，阳极为铂片，阴极为待处理工件，外加电压为5—10V，电镀时间为5—15min。Step 2, using a DC stabilized power supply as the electroplating device, the anode is a platinum sheet, the cathode is a workpiece to be treated, the applied voltage is 5-10V, and the electroplating time is 5-15min.
在所述步骤2中，外加电压为5—8V，电镀时间为5—10min。In the step 2, the applied voltage is 5-8V, and the electroplating time is 5-10min.
在所述步骤2中，所述阳极铂片面积为1×1cm2。In the step 2, the area of the anode platinum sheet is 1×1 cm 2 .
在所述步骤2中，所述阴极为AA2219铝合金，并经过如下步骤处理，除去铝合金表面的氧化膜并且形成许多小的腐蚀坑：In the step 2, the cathode is AA2219 aluminum alloy, and processed through the following steps to remove the oxide film on the surface of the aluminum alloy and form many small corrosion pits:
(1)分别用800#，1000#，1500#，2500#砂纸逐级打磨至光滑，后用去离子水清洗干净，无水乙醇超声10min后干燥备用；(1) Use 800#, 1000#, 1500#, 2500# sandpaper to polish step by step until smooth, then clean it with deionized water, ultrasonically dry it for 10 minutes with absolute ethanol;
(2)将上述打磨之后的铝合金样品进行酸碱处理，碱处理液为1.25M NaOH水溶液，室温刻蚀5min，水冲洗；酸处理液为20wt％HNO3水溶液，室温出光5min，水冲洗后用吹风机吹干备用。(2) The aluminum alloy sample after the above grinding was subjected to acid-base treatment. The alkali treatment solution was 1.25M NaOH aqueous solution, etched at room temperature for 5 minutes, and rinsed with water; Blow dry and set aside.
在本发明的技术方案中，一些广泛应用于金属防护中的缓蚀剂，例如硼酸、柠檬酸、次磷酸钠等，这些缓蚀剂之间存在协同效应，在稀土盐溶液中添加这些缓蚀剂能够促使其形成完整、高耐蚀性并且与基体结合牢固的稀土铈转化膜。柠檬酸盐被发现对铝合金的腐蚀具有一定的缓蚀作用，而柠檬酸又是羧基三元羧酸，能够与稀土铈离子产生络合作用，不仅缩短了稀土成膜时间，而且形成了粘着力以及耐蚀性好的稀土铈转化膜，具有广泛的应用价值。本发明操作简便、费用低、耗时短、耐蚀性好、应用范围广，是一种集经济、高效、优质于一体的制备方法。In the technical scheme of the present invention, some corrosion inhibitors widely used in metal protection, such as boric acid, citric acid, sodium hypophosphite, etc., have a synergistic effect between these corrosion inhibitors, and these corrosion inhibitors are added in the rare earth salt solution Agents can promote the formation of complete, high corrosion resistance and strong combination with the substrate rare earth cerium conversion coating. Citrate was found to have a certain corrosion inhibitory effect on the corrosion of aluminum alloys, and citric acid is a carboxyl tricarboxylic acid, which can produce complexation with rare earth cerium ions, which not only shortens the film-forming time of rare earth, but also forms an adhesive The rare earth cerium conversion coating with good strength and corrosion resistance has a wide range of application values. The invention has the advantages of simple operation, low cost, short time consumption, good corrosion resistance and wide application range, and is a preparation method integrating economy, high efficiency and high quality.
附图说明Description of drawings
图1是本发明柠檬酸掺杂铈转化膜的形貌SEM照片。Figure 1 is a SEM photo of the morphology of the citric acid-doped cerium conversion coating of the present invention.
图2是本发明柠檬酸掺杂铈转化膜的线性极化曲线图，其中1为基体，2为铈转化膜，3为掺杂0.1g/L柠檬酸，4为掺杂0.2g/L柠檬酸，5为掺杂0.4g/L柠檬酸，6为掺杂0.8g/L柠檬酸。Fig. 2 is the linear polarization curve figure of citric acid doping cerium conversion film of the present invention, wherein 1 is matrix, 2 is cerium conversion film, 3 is doping 0.1g/L citric acid, 4 is doping 0.2g/L lemon acid, 5 is doped with 0.4g/L citric acid, and 6 is doped with 0.8g/L citric acid.
具体实施方式detailed description
下面结合具体实施例进一步说明本发明的技术方案。选择的AA2219铝合金成分如下表所示(wt％)：The technical solutions of the present invention will be further described below in conjunction with specific embodiments. The composition of the selected AA2219 aluminum alloy is shown in the following table (wt%):
实施例1：一种新型的铈转化膜，其特征在于：利用直流稳压电源在AA2219铝合金表面共沉积掺杂柠檬酸的铈转化膜。Embodiment 1: A new type of cerium conversion film, characterized in that: a citric acid-doped cerium conversion film was co-deposited on the surface of AA2219 aluminum alloy by using a DC stabilized voltage source.
电镀液的制备，在2×10-3M的Ce(NO3)3·6H2O水溶液中，依次加入0.4g/L H3BO3，0.1g/L的柠檬酸，30mL/L 30％的H2O2，用20％HNO3或者0.1M NaOH溶液调节电镀液，使其pH＝2.5。采用的电沉积装置是两电极系统，阳极为铂片，阴极为AA2219铝合金。上述所说的新型铈转化膜的制备方法其步骤如下：Preparation of electroplating solution : Add 0.4g / L H 3 BO 3 , 0.1g/L citric acid , 30mL/L 30% H 2 O 2 , use 20% HNO 3 or 0.1M NaOH solution to adjust the electroplating solution to pH=2.5. The electrodeposition device used is a two-electrode system, the anode is a platinum sheet, and the cathode is an AA2219 aluminum alloy. Its steps of the preparation method of above-mentioned novel cerium conversion film are as follows:
(1)将尺寸为15mm×10mm×1.5mm的AA2219铝合金试样表面分别用800#，1000#，1500#，2500#砂纸逐级打磨至光滑，后用去离子水清洗干净，无水乙醇超声10min后干燥备用。(1) The surface of the AA2219 aluminum alloy sample with a size of 15mm×10mm×1.5mm was polished step by step with 800#, 1000#, 1500#, 2500# sandpaper until smooth, and then cleaned with deionized water and absolute ethanol After ultrasonication for 10 min, it was dried for later use.
(2)将上述打磨之后的铝合金样品进行酸碱处理，碱处理液为1.25M NaOH溶液，室温刻蚀5min，水冲洗；酸处理液为20％HNO3溶液，室温出光5min，水冲洗后用吹风机吹干备用。(2) Acid-base treatment was carried out on the above-mentioned polished aluminum alloy sample. The alkali treatment solution was 1.25M NaOH solution, etched at room temperature for 5 minutes, and rinsed with water; Blow dry and set aside.
(3)将上述酸碱处理之后的样品放入电沉积装置中，采用沉积电压5V，时间10min。(3) Put the sample after the above acid-base treatment into the electrodeposition device, adopt a deposition voltage of 5V, and take 10 minutes.
(4)将样品取出，用水冲洗，在室温下自然干燥，即可以在铝合金表面沉积一层黄色的柠檬酸掺杂的铈转化膜。(4) The sample is taken out, rinsed with water, and dried naturally at room temperature, that is, a layer of yellow citric acid-doped cerium conversion coating can be deposited on the surface of the aluminum alloy.
实施例2：一种新型的铈转化膜，其特征在于：利用直流稳压电源在AA2219铝合金表面共沉积掺杂柠檬酸的铈转化膜。Embodiment 2: A new type of cerium conversion film, characterized in that: a citric acid-doped cerium conversion film is co-deposited on the surface of AA2219 aluminum alloy by using a DC stabilized voltage source.
电镀液的制备，在2×10-3M的Ce(NO3)3·6H2O水溶液中，依次加入0.4g/L H3BO3，0.2g/L的柠檬酸，30mL/L 30％的H2O2，用20％HNO3或者0.1M NaOH溶液调节电镀液，使其pH＝2.5。采用的电沉积装置是两电极系统，阳极为铂片，阴极为AA2219铝合金。上述所说的新型铈转化膜的制备方法其步骤如下：Preparation of electroplating solution : Add 0.4g / L H 3 BO 3 , 0.2g/L citric acid , 30mL/L 30% H 2 O 2 , use 20% HNO 3 or 0.1M NaOH solution to adjust the electroplating solution to pH=2.5. The electrodeposition device used is a two-electrode system, the anode is a platinum sheet, and the cathode is an AA2219 aluminum alloy. Its steps of the preparation method of above-mentioned novel cerium conversion film are as follows:
(1)将尺寸为15mm×10mm×1.5mm的AA2219铝合金试样表面分别用800#，1000#，1500#，2500#砂纸逐级打磨至光滑，后用去离子水清洗干净，无水乙醇超声10min后干燥备用。(1) The surface of the AA2219 aluminum alloy sample with a size of 15mm×10mm×1.5mm was polished step by step with 800#, 1000#, 1500#, 2500# sandpaper until smooth, and then cleaned with deionized water and absolute ethanol After ultrasonication for 10 min, it was dried for later use.
(2)将上述打磨之后的铝合金样品进行酸碱处理，碱处理液为1.25M NaOH溶液，室温刻蚀5min，水冲洗；酸处理液为20％HNO3溶液，室温出光5min，水冲洗后用吹风机吹干备用。(2) Acid-base treatment was carried out on the above-mentioned polished aluminum alloy sample. The alkali treatment solution was 1.25M NaOH solution, etched at room temperature for 5 minutes, and rinsed with water; Blow dry and set aside.
(3)将上述酸碱处理之后的样品放入电沉积装置中，采用沉积电压5V，时间10min。(3) Put the sample after the above acid-base treatment into the electrodeposition device, adopt a deposition voltage of 5V, and take 10 minutes.
(4)将样品取出，用水冲洗，在室温下自然干燥，即可以在铝合金表面沉积一层黄色的柠檬酸掺杂的铈转化膜。(4) The sample is taken out, rinsed with water, and dried naturally at room temperature, that is, a layer of yellow citric acid-doped cerium conversion coating can be deposited on the surface of the aluminum alloy.
实施例3：一种新型的铈转化膜，其特征在于：利用直流稳压电源在AA2219铝合金表面共沉积掺杂柠檬酸的铈转化膜。Embodiment 3: A new type of cerium conversion film, characterized in that: a citric acid-doped cerium conversion film is co-deposited on the surface of AA2219 aluminum alloy by using a DC stabilized voltage source.
电镀液的制备，在2×10-3M的Ce(NO3)3·6H2O水溶液中，依次加入0.4g/L H3BO3，0.4g/L的柠檬酸，30mL/L 30％的H2O2，用20％HNO3或者0.1M NaOH溶液调节电镀液，使其pH＝2.5。采用的电沉积装置是两电极系统，阳极为铂片，阴极为AA2219铝合金。上述所说的新型铈转化膜的制备方法其步骤如下：Preparation of electroplating solution : Add 0.4g /L H 3 BO 3 , 0.4g/L citric acid , 30mL/L 30% H 2 O 2 , use 20% HNO 3 or 0.1M NaOH solution to adjust the electroplating solution to pH=2.5. The electrodeposition device used is a two-electrode system, the anode is a platinum sheet, and the cathode is an AA2219 aluminum alloy. Its steps of the preparation method of above-mentioned novel cerium conversion film are as follows:
(1)将尺寸为15mm×10mm×1.5mm的AA2219铝合金试样表面分别用800#，1000#，1500#，2500#砂纸逐级打磨至光滑，后用去离子水清洗干净，无水乙醇超声10min后干燥备用。(1) The surface of the AA2219 aluminum alloy sample with a size of 15mm×10mm×1.5mm was polished step by step with 800#, 1000#, 1500#, 2500# sandpaper until smooth, and then cleaned with deionized water and absolute ethanol After ultrasonication for 10 min, it was dried for later use.
(2)将上述打磨之后的铝合金样品进行酸碱处理，碱处理液为1.25M NaOH溶液，室温刻蚀5min，水冲洗；酸处理液为20％HNO3溶液，室温出光5min，水冲洗后用吹风机吹干备用。(2) Acid-base treatment was carried out on the above-mentioned polished aluminum alloy sample. The alkali treatment solution was 1.25M NaOH solution, etched at room temperature for 5 minutes, and rinsed with water; Blow dry and set aside.
(3)将上述酸碱处理之后的样品放入电沉积装置中，采用沉积电压5V，时间10min。(3) Put the sample after the above acid-base treatment into the electrodeposition device, adopt a deposition voltage of 5V, and take 10 minutes.
(4)将样品取出，用水冲洗，在室温下自然干燥，即可以在铝合金表面沉积一层黄色的柠檬酸掺杂的铈转化膜。(4) The sample is taken out, rinsed with water, and dried naturally at room temperature, that is, a layer of yellow citric acid-doped cerium conversion coating can be deposited on the surface of the aluminum alloy.
实施例4：一种新型的铈转化膜，其特征在于：利用直流稳压电源在AA2219铝合金表面共沉积掺杂柠檬酸的铈转化膜。Embodiment 4: A new type of cerium conversion film, characterized in that: a citric acid-doped cerium conversion film is co-deposited on the surface of AA2219 aluminum alloy by using a DC stabilized voltage power supply.
电镀液的制备，在2×10-3M的Ce(NO3)3·6H2O水溶液中，依次加入0.4g/L H3BO3，0.8g/L的柠檬酸，30mL/L 30％的H2O2，用20％HNO3或者0.1M NaOH溶液调节电镀液，使其pH＝2.5。采用的电沉积装置是两电极系统，阳极为铂片，阴极为AA2219铝合金。上述所说的新型铈转化膜的制备方法其步骤如下：Preparation of electroplating solution : Add 0.4g /L H 3 BO 3 , 0.8g/L citric acid , 30mL/L 30% H 2 O 2 , use 20% HNO 3 or 0.1M NaOH solution to adjust the electroplating solution to pH=2.5. The electrodeposition device used is a two-electrode system, the anode is a platinum sheet, and the cathode is an AA2219 aluminum alloy. Its steps of the preparation method of above-mentioned novel cerium conversion film are as follows:
(1)将尺寸为15mm×10mm×1.5mm的AA2219铝合金试样表面分别用800#，1000#，1500#，2500#砂纸逐级打磨至光滑，后用去离子水清洗干净，无水乙醇超声10min后干燥备用。(1) The surface of the AA2219 aluminum alloy sample with a size of 15mm×10mm×1.5mm was polished step by step with 800#, 1000#, 1500#, 2500# sandpaper until smooth, and then cleaned with deionized water and absolute ethanol After ultrasonication for 10 min, it was dried for later use.
(2)将上述打磨之后的铝合金样品进行酸碱处理，碱处理液为1.25M NaOH溶液，室温刻蚀5min，水冲洗；酸处理液为20％HNO3溶液，室温出光5min，水冲洗后用吹风机吹干备用。(2) Acid-base treatment was carried out on the above-mentioned polished aluminum alloy sample. The alkali treatment solution was 1.25M NaOH solution, etched at room temperature for 5 minutes, and rinsed with water; Blow dry and set aside.
(3)将上述酸碱处理之后的样品放入电沉积装置中，采用沉积电压5V，时间10min。(3) Put the sample after the above acid-base treatment into the electrodeposition device, adopt a deposition voltage of 5V, and take 10 minutes.
(4)将样品取出，用水冲洗，在室温下自然干燥，即可以在铝合金表面沉积一层黄色的柠檬酸掺杂的铈转化膜。(4) The sample is taken out, rinsed with water, and dried naturally at room temperature, that is, a layer of yellow citric acid-doped cerium conversion coating can be deposited on the surface of the aluminum alloy.
实施例5：一种新型的铈转化膜，其特征在于：利用直流稳压电源在AA2219铝合金表面共沉积掺杂柠檬酸的铈转化膜。Embodiment 5: A new type of cerium conversion film, characterized in that: a citric acid-doped cerium conversion film is co-deposited on the surface of AA2219 aluminum alloy by using a DC stabilized voltage source.
电镀液的制备，在2×10-3M的Ce(NO3)3·6H2O水溶液中，依次加入0.4g/L H3BO3，30mL/L 30％的H2O2，用20％HNO3或者0.1M NaOH溶液调节电镀液，使其pH＝2.5。采用的电沉积装置是两电极系统，阳极为铂片，阴极为AA2219铝合金。For the preparation of electroplating solution, in 2×10 -3 M Ce(NO 3 ) 3 ·6H 2 O aqueous solution, add 0.4g/L H 3 BO 3 , 30mL/L 30% H 2 O 2 in sequence, and use 20% HNO 3 or 0.1M NaOH solution is used to adjust the electroplating solution so that its pH=2.5. The electrodeposition device used is a two-electrode system, the anode is a platinum sheet, and the cathode is an AA2219 aluminum alloy.
上述所说的新型铈转化膜的制备方法其步骤如下：Its steps of the preparation method of above-mentioned novel cerium conversion film are as follows:
(1)将尺寸为15mm×10mm×1.5mm的AA2219铝合金试样表面分别用800#，1000#，1500#，2500#砂纸逐级打磨至光滑，后用去离子水清洗干净，无水乙醇超声10min后干燥备用。(1) The surface of the AA2219 aluminum alloy sample with a size of 15mm×10mm×1.5mm was polished step by step with 800#, 1000#, 1500#, 2500# sandpaper until smooth, and then cleaned with deionized water and absolute ethanol After ultrasonication for 10 min, it was dried for later use.
(2)将上述打磨之后的铝合金样品进行酸碱处理，碱处理液为1.25M NaOH溶液，室温刻蚀5min，水冲洗；酸处理液为20％HNO3溶液，室温出光5min，水冲洗后用吹风机吹干备用。(2) Acid-base treatment was carried out on the above-mentioned polished aluminum alloy sample. The alkali treatment solution was 1.25M NaOH solution, etched at room temperature for 5 minutes, and rinsed with water; Blow dry and set aside.
(3)将上述酸碱处理之后的样品放入电沉积装置中，采用沉积电压5V，时间10min。(3) Put the sample after the above acid-base treatment into the electrodeposition device, adopt a deposition voltage of 5V, and take 10 minutes.
(4)将样品取出，用水冲洗，在室温下自然干燥，即可以在铝合金表面沉积一层黄色的铈转化膜。(4) The sample is taken out, rinsed with water, and dried naturally at room temperature, that is, a layer of yellow cerium conversion film can be deposited on the surface of the aluminum alloy.
通过扫描电子显微镜S4800，Hitachi，Japan，EDAX公司的能谱探头进行EDS测试，利用扫描电镜进行形貌分析(如附图1所示)和eds分析，材料薄膜表面元素分析Scanning electron microscope S4800, Hitachi, Japan, EDS test with energy spectrum probe of EDAX company, use scanning electron microscope for morphology analysis (as shown in Figure 1) and eds analysis, material film surface element analysis
利用的电化学工作站型号为Gamry Reference 600，测试介质为：3.5wt.％氯化钠水溶液，温度25±2℃。采用三电极系统测定极化曲线，工作电极为镀层，对电极为2×2cm2的铂网，参比电极为饱和甘汞电极，参数设置为：起始电位-0.9V，终止电位-0.35V，扫描速率1mV/s。极化曲线如附图2所示，随着柠檬酸的加入，曲线向左下角移动，即腐蚀速率降低，耐蚀性提高。The electrochemical workstation model used is Gamry Reference 600, the test medium is: 3.5wt.% sodium chloride aqueous solution, and the temperature is 25±2°C. A three-electrode system was used to measure the polarization curve, the working electrode was a coating, the counter electrode was a 2×2cm 2 platinum mesh, the reference electrode was a saturated calomel electrode, and the parameters were set as: initial potential -0.9V, end potential -0.35V , scan rate 1mV/s. The polarization curve is shown in Figure 2. With the addition of citric acid, the curve moves to the lower left corner, that is, the corrosion rate decreases and the corrosion resistance improves.
以上对本发明做了示例性的描述，应该说明的是，在不脱离本发明的核心的情况下，任何简单的变形、修改或者其他本领域技术人员能够不花费创造性劳动的等同替换均落入本发明的保护范围。The present invention has been described as an example above, and it should be noted that, without departing from the core of the present invention, any simple deformation, modification or other equivalent replacements that can be made by those skilled in the art without creative labor all fall within the scope of this invention. protection scope of the invention.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510444063.0A CN104988551B (en) | 2013-09-03 | 2013-09-03 | Application of the lemon acid doping Cerium conversion film in AA2219 corrosive protection of aluminium alloy |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510444063.0A CN104988551B (en) | 2013-09-03 | 2013-09-03 | Application of the lemon acid doping Cerium conversion film in AA2219 corrosive protection of aluminium alloy |
| CN201310396184.3A CN103436935B (en) | 2013-09-03 | 2013-09-03 | A kind of citric acid doped with cerium conversion film and preparation method thereof |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310396184.3A Division CN103436935B (en) | 2013-09-03 | 2013-09-03 | A kind of citric acid doped with cerium conversion film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104988551A CN104988551A (en) | 2015-10-21 |
| CN104988551B true CN104988551B (en) | 2017-07-07 |
Family
ID=49690647
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510444063.0A Expired - Fee Related CN104988551B (en) | 2013-09-03 | 2013-09-03 | Application of the lemon acid doping Cerium conversion film in AA2219 corrosive protection of aluminium alloy |
| CN201510443047.XA Expired - Fee Related CN105112973B (en) | 2013-09-03 | 2013-09-03 | A kind of preparation method of lemon acid doping Cerium conversion film |
| CN201310396184.3A Expired - Fee Related CN103436935B (en) | 2013-09-03 | 2013-09-03 | A kind of citric acid doped with cerium conversion film and preparation method thereof |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510443047.XA Expired - Fee Related CN105112973B (en) | 2013-09-03 | 2013-09-03 | A kind of preparation method of lemon acid doping Cerium conversion film |
| CN201310396184.3A Expired - Fee Related CN103436935B (en) | 2013-09-03 | 2013-09-03 | A kind of citric acid doped with cerium conversion film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (3) | CN104988551B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105506684A (en) * | 2016-02-19 | 2016-04-20 | 苏州市华婷特种电镀有限公司 | Electroplating solution for obtaining coating of gold |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1485466A (en) * | 2002-09-27 | 2004-03-31 | 长沙高新技术产业开发区英才科技有限 | Process of electricity sedimentation in aqueous solution for producing rare earth magnetic film alloy material |
| CN101469421A (en) * | 2007-12-29 | 2009-07-01 | 比亚迪股份有限公司 | Film forming solution for magnesium alloy chemical composition coating and preparation thereof |
| CN101525747A (en) * | 2009-04-17 | 2009-09-09 | 昆明理工大学 | Clean rare-earth salt passivation solution |
| CN102719864A (en) * | 2012-06-28 | 2012-10-10 | 上海大学 | Method for preparing cerium-containing zinc coating |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6818116B2 (en) * | 2002-08-08 | 2004-11-16 | The Curators Of The University Of Missouri | Additive-assisted cerium-based electrolytic coating process for corrosion protection of aluminum alloys |
| CN1858306A (en) * | 2005-05-08 | 2006-11-08 | 北京化工大学 | Process for cathode electrolytic deposition of rare-earth conversion film |
| CN101275265B (en) * | 2007-12-29 | 2010-08-04 | 大连海事大学 | A method for depositing cerium-containing compound in aluminum and its alloy anodized film |
| CN101328552B (en) * | 2008-07-11 | 2010-10-27 | 扬州嘉和散热器有限公司 | Aluminum Alloy Material for Cooling Flat Tubes of Radiator Used in Vehicles |
| CN101597758B (en) * | 2009-06-26 | 2011-03-30 | 袁兴 | Low chromium anticorrosive chemical conversion treating fluid on surface of constructive aluminium profile and use method thereof |
| CN101892477B (en) * | 2010-06-21 | 2012-06-20 | 华南理工大学 | Treatment solution for preparing aluminum alloy surface amorphous composite passivation film, preparation method and application |
| CN101949012B (en) * | 2010-09-21 | 2012-01-04 | 哈尔滨工业大学（威海） | Method for preparing nickel-rare earth composite film |
| CN102031548A (en) * | 2010-12-15 | 2011-04-27 | 北京化工大学 | Process for plating rare earth conversion coating onto aluminum alloy by using electric brush |
| CN103243371B (en) * | 2013-05-16 | 2015-06-17 | 中国船舶重工集团公司第七二五研究所 | Preparation method of zinc anode oxidation film layer |
-
2013
- 2013-09-03 CN CN201510444063.0A patent/CN104988551B/en not_active Expired - Fee Related
- 2013-09-03 CN CN201510443047.XA patent/CN105112973B/en not_active Expired - Fee Related
- 2013-09-03 CN CN201310396184.3A patent/CN103436935B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1485466A (en) * | 2002-09-27 | 2004-03-31 | 长沙高新技术产业开发区英才科技有限 | Process of electricity sedimentation in aqueous solution for producing rare earth magnetic film alloy material |
| CN101469421A (en) * | 2007-12-29 | 2009-07-01 | 比亚迪股份有限公司 | Film forming solution for magnesium alloy chemical composition coating and preparation thereof |
| CN101525747A (en) * | 2009-04-17 | 2009-09-09 | 昆明理工大学 | Clean rare-earth salt passivation solution |
| CN102719864A (en) * | 2012-06-28 | 2012-10-10 | 上海大学 | Method for preparing cerium-containing zinc coating |
Non-Patent Citations (4)
| Title |
|---|
| Corrosion protection of aliminium alloy by cerium conversion and conducting polymer duplex coatings;Herbert D.Johansen et al;《corrosion science》;20120623;第342-350页 * |
| Electrodeposited cerium film as chromate replacement for tinplate;Xingqiao Huang et al;《Thin Solid Films》;20070819;第1037-1043页 * |
| The corrosion resistance of hot dip galvanised steel and AA2024-T3 pre-treated with bis-[triethoxysilylpropyl]tetrasulfide solutions doped with Ce(NO3）3;A.M.Cabral et al;《Corrosion Science》;20060329;第3740-3758页 * |
| 热镀锌层柠檬酸改进型铈盐转化膜的生长机理;孔纲 等;《中国有色金属学报》;20120531;第22卷(第5期);第1390-1397页，第1390左栏第1段，右栏第1段，第1节，第1395页右栏第1段，1396页左栏第1段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105112973B (en) | 2017-07-07 |
| CN104988551A (en) | 2015-10-21 |
| CN103436935A (en) | 2013-12-11 |
| CN103436935B (en) | 2016-03-02 |
| CN105112973A (en) | 2015-12-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101880882B (en) | Stripping solution for sintered neodymium-iron-boron surface aluminum coating | |
| CN104505260A (en) | Method for preparing mid-high voltage corrosion foil by using pulse DC superposed current | |
| CN102242364A (en) | Preparation method of ceramic film through chemical conversion and micro-arc oxidation of aluminum and aluminum alloy | |
| CN105063721B (en) | The method that magnesium alloy anodic oxidation electrolyte and the electrolyte prepare anode oxide film | |
| CN104532321B (en) | Method for oxidizing anode of titanium-aluminum alloy in fluoride-added ethylene glycol solution | |
| CN102352501B (en) | Method for forming corrosion inhibiting film on steel and iron surface | |
| CN105040063A (en) | Preparation method of micro-arc oxidation electrolyte | |
| CN103924226B (en) | A kind of preparation method of hierarchy zinc phosphate chemical composition coating | |
| CN103710738B (en) | A kind of composite film preparation method improving Mg-based hydrogen storage surface corrosion resistance performance | |
| CN104047043A (en) | Preparation method of TiO2/SnO2 semiconductor double-layer composite film photoanode | |
| CN103243371A (en) | Preparation method of zinc anode oxidation film layer | |
| CN104911664B (en) | A kind of method for reducing silumin differential arc oxidation specific energy consumption | |
| CN110129858B (en) | A kind of ionic liquid-assisted magnesium-lithium alloy anodic oxidation film-forming method | |
| CN104988551B (en) | Application of the lemon acid doping Cerium conversion film in AA2219 corrosive protection of aluminium alloy | |
| CN105624664A (en) | Hole sealing method for magnesium alloy surface rare earth chemical conversion coating | |
| CN104805456A (en) | Burr removing solution and burr removing method | |
| CN105195161B (en) | A Ti/TiO2NT/Yb-Fe2O3-PbO2 electrode and its electrocatalytic degradation method for paraquat | |
| CN104022289A (en) | A RuNi/TiO2 nanotube electrode for direct methanol fuel cell and its preparation method | |
| CN101613868A (en) | A method of forming a self-assembled corrosion-inhibiting film on the surface of a copper electrode | |
| CN103911645A (en) | Magnesium alloy anode oxidation method | |
| CN109161951B (en) | A kind of magnesium alloy micro-arc oxidation electrolyte and its application | |
| CN101101817A (en) | Method for manufacturing electrolytic capacitor pure aluminum negative electrode foil by anodic oxidation | |
| CN110184636A (en) | The method that hydrotalcite film is prepared in situ in aluminium surface by more potential step methods | |
| CN102181851B (en) | Anhydrous pretreatment method for coating surfaces of magnesium alloys | |
| CN109772657A (en) | A kind of surface treatment method of stainless steel bipolar plate of proton exchange membrane fuel cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170707 Termination date: 20210903 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |