CN101270494A - Galvano-chemistry preparation method for metallic face protection ceramic film - Google Patents
Galvano-chemistry preparation method for metallic face protection ceramic film Download PDFInfo
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- CN101270494A CN101270494A CNA2008100696455A CN200810069645A CN101270494A CN 101270494 A CN101270494 A CN 101270494A CN A2008100696455 A CNA2008100696455 A CN A2008100696455A CN 200810069645 A CN200810069645 A CN 200810069645A CN 101270494 A CN101270494 A CN 101270494A
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Abstract
The invention provides an electrochemistry preparation method for a protective ceramics film on the surface of a metal which overcomes the problems that preparing the protective ceramics film on the surface of a metal by using the existing sol-gel technology needs a plurality of coating, drying and sintering, has complex working procedures, wastes labor and time and a film layer has a weak bonding force and is easy to crack, etc. The technique flow of the method includes a preliminary treatment working procedure, an electrochemistry inducing sol-gel film forming treatment working procedure and a drying working procedure; the method is mainly characterized in that the electrochemistry inducing sol-gel film forming treatment working procedure integrates the advantages of the sol-gel technology and the electrochemistry technology, takes a compound sol mixed by any one or two of silicon sol, zirconium sol and cerium sol as an electrolyte, takes the metal to be treated as a cathode, takes a black lead piece as an anode and applies a DC current of 0.5 to 3V for 2 to 60 minutes under the normal temperature. The method can control the thickness of the film layer through adjusting the voltage and time; thereby being able to obtain a uniform compact effect protective ceramics film with regulated thickness for one time and the method has the advantages of simple working procedure as well as saving time and cost.
Description
Technical field
The present invention relates to field of metal surface treatment technology, specifically be meant the metallic surface ceramic membrane that utilizes electrochemistry to induce the sol-gel method preparation to have efficient barrier propterty.
Background technology
The metallic corrosion problem spreads all over the national economy every field, causes enormous economic loss and serious disaster accident to society.For bottom line is reduced in the loss that corrosion is caused, people create and have developed a lot of anticorrosion techniques, and process for treating surface is one of most widely used anticorrosion technique wherein.
Traditional metal surface treatment technology relates to the use that human body and environment is had the dichromate of very strong toxic action mostly, and along with the enhancing of people's environmental consciousness, chromic use just is being subjected to strict restriction.Therefore, development environment-friendly type metal surface treatment technology is very necessary and urgent.
The sol-gel technique of development in recent years is considered to tool for one of the environment-friendly type metal surface treatment technology of chromium potentiality (M.L.Zheludkevich, M.G.S.Ferreira, I.M.Miranda Salvado, J.Mater.Chem.Rev.15 (2005) 5099).Sol-gel technique has, and temperature of reaction is low, but preparation technology's environmental protection, film are formed and be easy to control big area advantage such as film, and using this technology can prepare ZrO in the metallic surface
2, Al
2O
3, CeO
2, SiO
2Etc. the single component or the polycomponent ceramic membrane of multiple oxide compound, this class film has higher chemical stability usually, and protective effect that can be stronger to multiple metal performance (Li Qing, Chen Yan. electroplate and covering with paint, 1999,18 (4): 19; Yang Yu, Li Yingjie is permitted more. material protection, 2005,38 (9): 35).
(as publication number is CN1900360A to utilize sol-gel technology preparing protecting metallic surface film to adopt pulling film forming usually, application number is 200610054441.5 " process for preparing magnesium alloy surface function gradient film ") or spin-coating (as publication number is CN 101050539A, application number be 200710099438.X's " the Mg alloy surface spin-coating method prepares even corrosion resistant hydrotalcite film and preparation method thereof "), and then dry, agglomerating mode.For obtaining the rete of even compact, generally need repeatedly coating, drying and sintering, thereby operation is various, the consumption worker is consuming time, and also be easy to cause membranous layer binding force weak, be easy to problems of crack.
Summary of the invention
At existing difficulty and the problem of utilizing sol-gel technology preparing protecting metallic surface ceramic membrane to exist, the objective of the invention is to utilize the electronic character of sol particles, provide a kind of and avoid repeatedly applying, drying and sintering and the membranous layer binding force that causes thus are weak, be easy to problems of crack, the electrochemical preparation method of the protecting metallic surface ceramic membrane that operation is simple, save time and cost.
The object of the present invention is achieved like this: a kind of electrochemical preparation method of protecting metallic surface ceramic membrane comprises that pretreatment procedure, electrochemistry induces sol-gel film forming treatment process and drying process; Wherein, 1. pretreatment procedure is washed operation, caustic wash process, Warm Wash operation, washing step, pure water by degreasing process, washing step, pure water and is washed operation, pickling process, washing step and pure water and wash operation, wherein degreasing process adopts ultrasonic cleaning in the acetone soln that contains 1～3% Sodium dodecylbenzene sulfonate under the normal temperature, and the treatment time was controlled at 1～10 minute; Alkaline wash consists of: sodium hydroxide 5～50g/L, and all the other are pure water; The alkali cleaning temperature is controlled at 40～60 ℃, and the alkali cleaning time was controlled at 3～20 minutes; Pickle solution consists of: nitric acid 1～50g/L, and all the other are pure water; Pickling temperature is controlled at 15～35 ℃, and the pickling time was controlled at 1～50 second;
Washing step is 1 road, and except that the Warm Wash process temperature after the alkali cleaning is 40～60 ℃, other washing step temperature all are controlled at 10～30 ℃;
2. to induce sol-gel film forming treatment process be that the complex sol that mixes with any one or wherein any two kinds of colloidal sols in silicon sol, zirconium colloidal sol, the cerium colloidal sol at normal temperatures is an electrolytic solution to electrochemistry, be negative electrode, be anode with the graphite flake with pending metal, require to determine dc voltage value and treatment time of applying according to thicknesses of layers: the volts DS scope is 0.5～3.0V, 2～60 minutes conduction time;
The preparation section of silicon sol, zirconium colloidal sol, cerium colloidal sol is: add solvent, presoma, stablizer or pure water or catalyzer, tensio-active agent, dry control agent and pH control agent at normal temperatures successively in container, stirred 1～4 hour; Solvent is ethanol or glycerol, and presoma is tetraethoxy or basic zirconium chloride or cerous nitrate, and stablizer is a methyl ethyl diketone, catalyzer is a citric acid, tensio-active agent is a sodium lauryl sulphate, and dry control agent is an ethylene glycol, and the pH control agent is rare nitric acid or ammoniacal liquor;
3. drying process adopts normal temperature vacuum-drying, and the time is 1～24 hour;
The beneficial effect that the present invention reached is: the present invention adopts electrochemistry to induce sol-gel film forming treatment process, combine the advantage of sol-gel technique and electrochemical techniques, the complex sol that mixes with any one or wherein any two kinds of colloidal sols in silicon sol, zirconium colloidal sol, the cerium colloidal sol is an electrolytic solution, be negative electrode, be anode with the graphite flake with pending metal, by regulating voltage and time controlling diaphragm layer thickness, thereby can disposablely obtain the efficient protective ceramic membrane of the specific thickness of even compact, and operation simple, save time and cost.
The present invention has overcome existing sol-gel technology preparing protecting metallic surface ceramic membrane needs repeatedly coating, drying and sintering, and operation is various, the consumption worker is consuming time and membranous layer binding force weak, be easy to problems of crack.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Fig. 2 is that the present invention carries out the synoptic diagram that electrochemistry induces the sol-gel film forming to handle.
Embodiment
Referring to illustrated in figures 1 and 2, a kind of electrochemical preparation method of protecting metallic surface ceramic membrane, technical process comprises that pretreatment procedure, electrochemistry induces sol-gel film forming treatment process and drying process; Its key feature is: it is that the complex sol that mixes with any one or wherein any two kinds of colloidal sols in silicon sol, zirconium colloidal sol, the cerium colloidal sol is an electrolytic solution that electrochemistry is induced sol-gel film forming treatment process, be negative electrode, be anode with the graphite flake with pending metal, require to determine dc voltage value and treatment time of applying according to thicknesses of layers: the volts DS scope is 0.5～3.0V, 2～60 minutes treatment times.
1. the preparation section of silicon sol, zirconium colloidal sol, cerium colloidal sol is: add solvent, presoma, stablizer or pure water or catalyzer, tensio-active agent, dry control agent and pH control agent at normal temperatures successively in container, stirred 1～4 hour.Wherein, solvent is alcoholic solutions such as ethanol, glycerol, presoma is ester class or inorganic salt such as basic zirconium chloride, cerous nitrate such as tetraethoxy, stablizer is materials such as methyl ethyl diketone, catalyzer is materials such as citric acid, tensio-active agent is materials such as sodium lauryl sulphate, and dry control agent is materials such as ethylene glycol, and the pH control agent is materials such as rare nitric acid or ammoniacal liquor.
2. pretreatment procedure is washed operation, caustic wash process, Warm Wash operation, washing step, pure water by degreasing process, washing step, pure water and is washed operation, pickling process, washing step and pure water and wash operation and constitute, wherein ultrasonic cleaning in the acetone soln that contains 1～3% Sodium dodecylbenzene sulfonate under the normal temperature is adopted in degreasing, and the treatment time was controlled at 1～10 minute; Alkaline wash consists of: sodium hydroxide 5～50g/L, and all the other are pure water; The alkali cleaning temperature is controlled at 40～60 ℃, and the alkali cleaning time was controlled at 3～20 minutes; Pickle solution consists of: nitric acid 1～50g/L, and all the other are pure water; Pickling temperature is controlled at 15～35 ℃, and the pickling time was controlled at 1～50 second;
Washing step is 1 road, and except that the Warm Wash process temperature after the alkali cleaning is 40～60 ℃, other washing step temperature all are controlled at 10～30 ℃.
3. drying process adopts normal temperature vacuum-drying, and the time is 1～24 hour.
Being used for surface-treated metal of the present invention is 6063 aluminum alloy plate materials, is fit to be applied to the metal or alloy of other model aluminium alloys and magnesium, copper, zinc and carbon steel, stainless steel equally.
Embodiment 1: a kind of electrochemical preparation method of protecting metallic surface ceramic membrane, and concrete steps are:
(1) will polish to 1000 step by step with waterproof abrasive paper
#6063 aluminum alloy sheets of 20mm * 10mm * 3.0mm, ultrasonic degreasing cleaned 5 minutes, carried out washing of 1 road and 1 road pure water then and washed; In alkaline wash, handled 10 minutes down again, carry out 1 road Warm Wash, the washing of 1 road and 1 road pure water then and wash in 50 ℃; In pickle solution, under room temperature, handled 40 seconds again, carry out washing of 1 road and 1 road pure water then and wash;
(2) carrying out electrochemistry induces the silicon sol-gel film forming to handle:
The film forming treatment condition: with the silicon sol is that electrolytic solution, 6063 aluminum alloy sheets are that negative electrode, graphite flake are anode, applies the 2.0V volts DS under the normal temperature 30 minutes.Wherein, the silicon sol preparation condition: normal temperature is down by 4: 1: 1: 0.2: 0.002 mol ratio adds solvent dehydrated alcohol, presoma tetraethoxy, stablizer methyl ethyl diketone, tensio-active agent sodium lauryl sulphate, dry control agent ethylene glycol successively in beaker, the pH value to 6.5 that the 2.0 rare nitric acid that with pH are are regulated described mixed solution, in said process, constantly stir and continue and stirred 1 hour, obtain stable silicon sol.
(3) 6063 aluminum alloy sheets of under the normal temperature step (2) being handled carry out vacuum-drying 24h;
(4) 6063 aluminum alloy sheets that step (3) is handled carry out the film quality check:
A. the thickness check is adopted Germany to produce the E110/E110B eddy current thickness meter and is measured thicknesses of layers.
B. brine soaking experiment check membranous layer corrosion resistance energy is adopted in the solidity to corrosion check, and salt solution is the NaCl solution of 50 ± 5g/L, and temperature is 35 ± 2 ℃, and the sample exposed area is 1cm with the brine volume ratio
2: 100L, 3 on parallel sample is made regular check on sample, record specimen surface corrosion generation time.
C. paint film bonding force check
Adopt cross-hatching to measure the bonding force of ceramic membrane and paint film.Promptly handling the specimen surface japanning and drying.Be divided into 100 little lattice with pocket knife at interval with 1mm, press sticking cellophane tape thereon, and then adhesive tape is uncovered, observe the little lattice of residue paint film on sample, represent with percentage ratio.Percentage ratio is big more to show that the bonding force of ceramic membrane and paint film is good more.
The film quality assay: thicknesses of layers is 5.1 μ m, and saline soak did not have corrosion in 257 hours paint film bonding force 100% takes place.
Following examples all adopt above-mentioned surface treatment procedure and quality test operation, and the just concrete electrochemistry that adopts is induced sol-gel film forming treatment process difference, and the quality test result of its embodiment and corresponding rete is as described below:
The electrochemistry of embodiment 2 is induced zirconium sol-gel film forming:
The film forming treatment condition: with zirconium colloidal sol is that electrolytic solution, 6063 aluminum alloy sheets are that negative electrode, graphite flake are anode, applies the 2.5V volts DS under the normal temperature 20 minutes.Wherein, zirconium colloidal sol preparation method: by 2.4: 0.05: 1.1: 0.2: 0.002 mol ratio adds solvent Virahol, presoma zirconium oxychloride, pure water, tensio-active agent sodium lauryl sulphate, dry control agent ethylene glycol successively in beaker, the pH value of regulating described mixed solution with ammoniacal liquor is 4.0 to get final product, in said process, constantly stir and continue and stirred 4 hours, obtain stable zirconium colloidal sol.
The film quality assay: thicknesses of layers is 4.6 μ m, and saline soak did not have corrosion in 248 hours paint film bonding force 100% takes place.
The electrochemistry of embodiment 3 is induced cerium sol-gel film forming:
The film forming treatment condition: with cerium colloidal sol is that electrolytic solution, 6063 aluminum alloy sheets are that negative electrode, graphite flake are anode, applies the 1.5V volts DS under the normal temperature 60 minutes.Wherein, cerium colloidal sol preparation method: by 86: 1: 1: 0.2: 0.002 mol ratio adds solvent dehydrated alcohol, presoma cerous nitrate, catalyzer citric acid, tensio-active agent sodium lauryl sulphate, dry control agent ethylene glycol successively in beaker, regulating the pH value with rare nitric acid (pH=2.0) is 4.5, in said process, constantly stir and continue and stirred 4 hours, obtain stable cerium colloidal sol.
The film quality assay: thicknesses of layers is 7.2 μ m, and saline soak did not have corrosion in 403 hours paint film bonding force 100% takes place.
The electrochemistry of embodiment 4 is induced silicon, zirconium complex sol-gel film forming:
The film forming treatment condition: with silicon, zirconium complex sol is that electrolytic solution, 6063 aluminum alloy sheets are that negative electrode, graphite flake are anode, applies the 2.0V volts DS under the normal temperature 30 minutes.Wherein, silicon, zirconium complex sol preparation method: freshly prepd single-component silicon colloidal sol and 10: 1 by volume ratio of zirconium colloidal sol are slowly mixed, in mixing process, constantly stir and continue and stirred 1 hour, obtain stable complex sol.
The film quality assay: thicknesses of layers is 5.3 μ m, and saline soak did not have corrosion in 286 hours paint film bonding force 100% takes place.
The electrochemistry of embodiment 5 is induced silicon, cerium complex sol-gel film forming:
The film forming treatment condition: with silicon, cerium complex sol is that electrolytic solution, 6063 aluminum alloy sheets are that negative electrode, graphite flake are anode, applies the 2.0V volts DS under the normal temperature 20 minutes.Wherein, silicon, cerium complex sol preparation method: freshly prepd single-component silicon colloidal sol and 10: 3 by volume ratio of cerium colloidal sol are slowly mixed, in mixing process, constantly stir and continue and stirred 1 hour, obtain stable complex sol.
The film quality assay: thicknesses of layers is 4.1 μ m, and saline soak did not have corrosion in 292 hours paint film bonding force 100% takes place.
By above embodiment mainly is in order to further specify the inventive method, the present invention is not subjected to the restriction of described embodiment, as the composition of complex sol and the kind of pending metal etc., pending metal can also be aluminium, magnesium, copper, zinc or alloy and carbon steel, stainless steel or the like.
Claims (5)
1, a kind of electrochemical preparation method of protecting metallic surface ceramic membrane comprises that pretreatment procedure, electrochemistry induces sol-gel film forming treatment process and drying process; It is characterized in that: it is that the complex sol that mixes with any one or wherein any two kinds of colloidal sols in silicon sol, zirconium colloidal sol, the cerium colloidal sol at normal temperatures is an electrolytic solution that electrochemistry is induced sol-gel film forming treatment process, be negative electrode, be anode with the graphite flake with pending metal, require to determine to apply voltage and treatment time according to thicknesses of layers: the volts DS scope is 0.5～3.0V, and be 2～60 minutes conduction time.
2, the electrochemical preparation method of protecting metallic surface ceramic membrane according to claim 1, it is characterized in that, described pretreatment procedure is washed operation, caustic wash process, Warm Wash operation, washing step, pure water by degreasing process, washing step, pure water and is washed operation, pickling process, washing step and pure water and wash operation, wherein degreasing process adopts ultrasonic cleaning in the acetone soln that contains 1～3% Sodium dodecylbenzene sulfonate under the normal temperature, and the treatment time was controlled at 1～10 minute; Alkaline wash consists of: sodium hydroxide 5～50g/L, and all the other are pure water; The alkali cleaning temperature is controlled at 40～60 ℃, and the alkali cleaning time was controlled at 3～20 minutes; Pickle solution consists of: nitric acid 1～50g/L, and all the other are pure water; Pickling temperature is controlled at 15～35 ℃, and the pickling time was controlled at 1～50 second;
Washing step is 1 road, and except that the Warm Wash process temperature after the alkali cleaning is 40～60 ℃, other washing step temperature all are controlled at 10～30 ℃.
3, the electrochemical preparation method of protecting metallic surface ceramic membrane according to claim 1 is characterized in that, described drying process adopts normal temperature vacuum-drying, and the time is 1～24 hour.
4, the electrochemical preparation method of protecting metallic surface ceramic membrane according to claim 1, it is characterized in that, the preparation section of described silicon sol, zirconium colloidal sol, cerium colloidal sol is: be respectively 4: 1: 1 at normal temperatures in molar ratio: 0.2: 0.002,2.4: 0.05: 1.1: 0.2: 0.002 or 86: 1: 1: successively to container in add solvent, presoma, stablizer or pure water or catalyzer, tensio-active agent and dry control agent at 0.2: 0.002, and to regulate the pH value with the pH control agent be 6.5,4.0 or 4.5, stirred 1～4 hour;
Described solvent is ethanol or glycerol, and presoma is tetraethoxy or basic zirconium chloride or cerous nitrate, and stablizer is a methyl ethyl diketone, catalyzer is a citric acid, tensio-active agent is a sodium lauryl sulphate, and dry control agent is an ethylene glycol, and the pH control agent is rare nitric acid or ammoniacal liquor.
5, the electrochemical preparation method of protecting metallic surface ceramic membrane according to claim 1 is characterized in that, described metal is the metal or alloy of aluminium, magnesium, copper, zinc and carbon steel, stainless steel.
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| CN102575370A (en) * | 2009-07-30 | 2012-07-11 | 斯奈克玛 | Method for manufacturing a thermal barrier |
| CN104195605A (en) * | 2014-08-04 | 2014-12-10 | 同济大学 | Method for repairing surface defects by virtue of local fine electroplating of gel media |
| CN104416307A (en) * | 2013-09-03 | 2015-03-18 | 宁波江丰电子材料股份有限公司 | Heating plate for welding bench, manufacturing method of welding bench and welding bench |
| CN104947168A (en) * | 2015-06-18 | 2015-09-30 | 哈尔滨工程大学 | Repair method of zirconium base film on surface of magnesium alloy |
| CN105603483A (en) * | 2015-12-31 | 2016-05-25 | 浙江大学 | Preparation method of titanium-based alloy high temperature oxidation resisting coating |
| CN106917087A (en) * | 2017-04-17 | 2017-07-04 | 东南大学 | One kind has steel bar anti-corrosion, the preparation method of hydrophobic double effects diaphragm |
| CN111674491A (en) * | 2020-05-12 | 2020-09-18 | 宁波吉胜铸业有限公司 | Aluminum shell for vehicle |
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2008
- 2008-05-08 CN CN2008100696455A patent/CN101270494B/en not_active Expired - Fee Related
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| CN102575370A (en) * | 2009-07-30 | 2012-07-11 | 斯奈克玛 | Method for manufacturing a thermal barrier |
| CN102575370B (en) * | 2009-07-30 | 2015-10-14 | 斯奈克玛 | A kind of method making thermal boundary |
| CN104416307A (en) * | 2013-09-03 | 2015-03-18 | 宁波江丰电子材料股份有限公司 | Heating plate for welding bench, manufacturing method of welding bench and welding bench |
| CN104416307B (en) * | 2013-09-03 | 2016-07-06 | 宁波江丰电子材料股份有限公司 | The hot plate of jig and the manufacture method of jig, jig |
| CN104195605A (en) * | 2014-08-04 | 2014-12-10 | 同济大学 | Method for repairing surface defects by virtue of local fine electroplating of gel media |
| CN104195605B (en) * | 2014-08-04 | 2016-08-17 | 同济大学 | The method of the fine plating repairing mould surface defect in gel media local |
| CN104947168A (en) * | 2015-06-18 | 2015-09-30 | 哈尔滨工程大学 | Repair method of zirconium base film on surface of magnesium alloy |
| CN104947168B (en) * | 2015-06-18 | 2017-08-08 | 哈尔滨工程大学 | The restorative procedure of zirconium base film on Mg alloy surface |
| CN105603483A (en) * | 2015-12-31 | 2016-05-25 | 浙江大学 | Preparation method of titanium-based alloy high temperature oxidation resisting coating |
| CN106917087A (en) * | 2017-04-17 | 2017-07-04 | 东南大学 | One kind has steel bar anti-corrosion, the preparation method of hydrophobic double effects diaphragm |
| CN111674491A (en) * | 2020-05-12 | 2020-09-18 | 宁波吉胜铸业有限公司 | Aluminum shell for vehicle |
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