CN100447305C - Method for preparing magnesium oxide anti-corrosion protective film by sol-gel technology - Google Patents
Method for preparing magnesium oxide anti-corrosion protective film by sol-gel technology Download PDFInfo
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- CN100447305C CN100447305C CNB2006100544434A CN200610054443A CN100447305C CN 100447305 C CN100447305 C CN 100447305C CN B2006100544434 A CNB2006100544434 A CN B2006100544434A CN 200610054443 A CN200610054443 A CN 200610054443A CN 100447305 C CN100447305 C CN 100447305C
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Abstract
A sol-gel technology preparing magnesia anticorrosion protective film method overcomes shortages of expensive experimental equipment in current dry process and poor sol stability and repetitiveness in wet process. Said anticorrosion method uses inorganic magnesium salts as raw material under normal temperature and pressure, to prepare sol film suitable for different easy corrosion metal base material, said thin layer having good corrosion preventive properties to easy corrosion metal.
Description
Technical field
The present invention relates to chemical industry, metallic substance, surface modification field, is exactly a kind of method that adopts the sol-gel technology preparing magnesia anticorrosion protective film specifically.
Background technology
Coating technology is one of important channel of realizing alloy surface modifying.When sol-gel method prepares metal oxide film, elder generation is with the organic alkoxide of metal or inorganic salt are hydrolyzed, polymerization, form metal salt solution or colloidal sol, use crystal pulling method, spin-coating method or spraying method etc. evenly to be coated on colloidal sol (solution) on the body material then, form porous, loose xerogel film, carry out drying, curing and thermal treatment at last again and can form fine and close film.
Sol-Gel (sol-gel) coating technology is compared with CVD, PVD, sputter, spraying thermolysis and plasma spray coating technology, owing to have the following advantages: (1) directly obtains oxide compound, glass, pottery, inorganic-coatings such as organic double compound from liquid phase, low temperature; (2) can obtain the high and uniform matrix material of molecular level of purity; (3) do not need expensive plant and instrument; (4) simple, the good reproducibility of technology; (5) big area coating and low cost etc. be can implement, thereby people's very big interest and great attention caused.In the world the eighties just the someone begin to explore the surface property that the Sol-Gel technology is improved metal or alloy, or give the new functional performance of material surface etc., and than system with to carry out this technical study be in the early 1990s comprehensively, carried out SiO so far
2, SiO
2-TiO
2, SiO
2-Al
2O
3, SiO
2-B
2O
3, TiO
2, Al
2O
3, ZrO
2, ZrO
2-Y
2O
3, ZrO
2-CeO
2And CeO
2Deng coated material and correlation technique, and they are as the The Characteristic Study such as anti-oxidant, corrosion-resistant and wear-resisting of metal or alloy material surface coating.Though these researchs and exploration be at common metal and alloy material surface modification and also be in the development in laboratory stage, use and development prospect very good.Discussion realizes common material to substitute by surface modification means cheaply the approach of expensive material.As the CN200310117750.9 patent application, adopt sol-gel method (Sol-Gel Process is called for short the S-G method) on substrates such as slide glass, monocrystalline silicon piece, aluminium flake or stainless steel, to prepare ZrO
2Ceramic membrane utilizes dip-coating (Dip-coating) technology at ZrO then
2Prepared individual layer PFPE ultrathin lubrication membrane on the ceramic membrane, the preparation of inorganic hard coat and the preparation of organic polymer ultrathin lubrication membrane have been combined,, provide effective means for solving the protection and the lubrication problem of material in micromachine and the magnetic recording system.As the CN200510085466.7 patent application, employing is used to prepare powder with this routine of sol-gel method, the technology of film coating material is incorporated on the surperficial anodic oxidation treatment of magnesium alloy, selected a kind of anodic oxidation of magnetism alloy base soln that has the performance that well mixes with silicon sol, utilize the adsorption of sol particle at magnesium alloy matrix surface, and a large amount of heats that distinctive spark phenomenon produces in the anodic oxidation of magnetism alloy process solidify sol particle, and the final and product one of the anodic oxidation Mg alloy surface that coexists own has formed one deck anodic oxidation composite film.
Nano-MgO is the novel high function fine inorganic material of a kind of particle diameter between 1～100nm, has the specific functions such as heat, light, electricity, mechanics and chemistry that are different from bulk material owing to its particle granular.Adopt nano-MgO, do not use sintering aid just can realize low-temperature sintering, make high fine and close thin brilliant pottery and be expected to be developed as tip materials under the severe condition such as high temperature, high corrosive environment; It also can be used as the sintering aid and the stablizer of other nanoparticles such as zirconium white, aluminum oxide, ferric oxide, and obtains high-quality nanophase pottery; In addition, nano magnesia also can be used as the filler of paint, paper and makeup, the subsidiary material of the weighting agent of plastics and rubber and strengthening agent and various electronic materials; And nano-MgO can be used as adsorbing agent carrier, is adsorbed with poisonous gas, shown good load effect in many reactions.
MgO film (coating) is to be prepared into powder body material to be used in the photoelectric material aspect, as the JP2004022288A2 patent, at the front rete of plasma display surface deposition MgO thin layer as plasma display mostly at present; Matsushita company, deposition and form monocrystalline MgO thin layer on the Si matrix, with this thin layer as piezoelectric film etc.; Magnesia film can be used as the special functions such as stable blocking layer of preparation high-temperature superconductor and ferroelectric membranc, as grow the high-temperature superconducting thin film YBaCu of c axle orientation on the MgO film of (111) orientation
3O
7, the MgO thin film epitaxial growth of (111) orientation goes out the ferroelectric membranc of excellent property, and a lot of scholars work that goes in for the study is in this respect arranged in recent years.
The method for preparing magnesia film is a lot, such as pulsed laser deposition, electron beam evaporation, even coprecipitation method, chemical vapour deposition, electrochemical dissolution magnesium anode etc., pass high people as Zhu and adopt electrochemistry " sacrifice " magnesium anode dissolution method, in appropriate organic solvent, the electrolysis magnesium sheet obtains the alkoxide of MAGNESIUM METAL, control certain pH direct hydrolysis contains the electrolytic solution of presoma, makes the nano-MgO powder after high-temperature calcination.In the research of MgO film preparation and application facet thereof, the research work of Japan is more outstanding, as far back as eighties of last century nineties, has just prepared the MgO film, and has used.Prepare the MgO rete as people PVD such as nineteen ninety Yamamoto and have superconductivity, and applied for patent; At Imai in 1993, people such as Nobuhiko adopted CVD to prepare MgO transparent plastics screened film, and this rete has the better protecting effect to oxygen and damp atmosphere; MIT, rare earth doped oxide compound in the MgO powder as the two electrodes layer of plasma display, plays the certain protection effect behind sintering.
The experimental installation costliness that present magnesian dried preparation is required, the condition harshness; And wet method uses the alkoxide of MAGNESIUM METAL as setting out raw material in preparing mostly, metal alkoxide not only costs an arm and a leg, and is easy to hydrolysis in air, difficult control hydrolysis and polyreaction in preparation colloidal sol, collosol stability is relatively poor simultaneously, can make repeated variation because of air humidity varies.And the research of adopting sol-gel method to prepare magnesia film is reported also seldom.On the other hand magnesia film be yet there are no report as the research of corrosion-resistant protective layer; utilize mostly magnesia film and semiconductor substrate materials Si, electrode materials Pt and the ferroelectric and superconducting material of research at present utilize the key property such as lattice parameter of its supraconductivity very approaching, as a kind of very good substrate material.
Summary of the invention
The objective of the invention is to; at present magnesia film preparation method; such as pulsed laser deposition; electron beam evaporation; even coprecipitation method; chemical vapour deposition; the limitation of electrochemical dissolution magnesium anode etc.; and sol-gel method prepares among the existing preparation method of magnesia film and to use the magnesium alkoxide as setting out raw material; metal alkoxide not only costs an arm and a leg; and in air, be easy to hydrolysis; difficult control hydrolysis and polyreaction in preparation colloidal sol; colloidal sol can make problems such as repeated variation because of air humidity varies simultaneously; a kind of method with the sol-gel technology preparing magnesia anticorrosion protective film is provided; solve magnesia film (coating) preparation method's industrial feasibleization, and it is applied.This method can be at normal temperatures and pressures, use lower-cost raw material, simple and feasible processing condition, and preparation is applicable to the sol pellicle (coating) of different easy corrosion metal base material.It is precursor that the present invention adopts inorganic magnesium salt, adds appropriate solvent and additive, adopts sol-gel method to prepare magnesia film, and this thin film layer commute corroding metal has good corrosion protection.
The present invention realizes through the following steps:
With inorganic magnesium salt is precursor, it is dissolved in the ethanolic soln, with the collodion that is dissolved in the ethanolic soln is annex solution, the mass ratio that makes inorganic magnesium salt and collodion is 0.04: 1～0.32: 1, the volume ratio of controlling alcohol solvent and annex solution simultaneously is 6: 4～8: 2, be heated to 70～80 ℃ of stirring and refluxing 30min, promptly get the magnesium oxide colloidal sol of stable transparent; With perishable metal is substrate, after carrying out pretreatment of base material, adopts and to soak damp crystal pulling method and film, and pull rate is controlled at 2 * 10
-4Ms
-1～2 * 10
-3Ms
-1Between, low-temperature heat treatment after the film forming progressively is warmed up to 180 ℃, constant temperature 30～60min obtains the magnesium oxide single thin film, treats that alcohol solvent volatilization back is in 350～800 ℃ of sintering, obtain mono-layer oxidized magnesium nanoparticulate thin films, repeat aforesaid operations process 4～6 times, obtain the multilayered particles film.
Inorganic magnesium salt is meant magnesium nitrate, magnesium acetate etc. in the aforesaid method, and easy corrosion metal base material is meant magnesium alloy, aluminium alloy, magnetic neodymium iron boron etc.
Advantage of the present invention is, this method is the raw material that sets out with inorganic magnesium salt, the present magnesia film preparation method apparatus expensive or the problems such as raw material costliness and instability of setting out have been overcome, at normal temperatures and pressures, use lower-cost raw material, simple and feasible processing condition, preparation is applicable to the sol pellicle of different easy corrosion metal base material, and this thin film layer commute corroding metal has good corrosion protection.
Embodiment
Embodiment 1:
With magnesium nitrate (Mg (NO
3)
26H
2O) be precursor, it is dissolved in the ethanolic soln (is called A liquid), with the collodion is annex solution, be dissolved in the ethanolic soln and (be called B liquid), the mass ratio that makes inorganic magnesium salt and collodion is 0.04: 1, and the volume ratio of control alcohol solvent and annex solution is 6: 4, be heated to 70～80 ℃ and stir A liquid, during backflow B liquid is dropwise joined in the A liquid, continue heated and stirred backflow 30min, promptly get the magnesium oxide colloidal sol of stable transparent; With the magnesium alloy is substrate, after carrying out pretreatment of base material, adopts and to soak damp crystal pulling method and film, and pull rate is controlled at 2 * 10
-4Ms
-1～2 * 10
-3Ms
-1, low-temperature heat treatment after the film forming progressively is warmed up to 180 ℃, and constant temperature 30min obtains the magnesium oxide single thin film, treats that alcohol solvent volatilization back in 350 ℃ of sintering, obtains mono-layer oxidized magnesium nanoparticulate thin films, repeats aforesaid operations process 4 times, obtains the multilayered particles film.
Embodiment 2:
With magnesium acetate (Mg (CH
3COO)
24H
2℃) be precursor, it is dissolved in the ethanolic soln (is called A liquid), with the collodion is annex solution, be dissolved in the ethanolic soln and (be called B liquid), the mass ratio that makes inorganic magnesium salt and collodion is 0.32: 1, and the volume ratio of control alcohol solvent and annex solution is 8: 2, be heated to 70～80 ℃ and stir A liquid, during backflow B liquid is dropwise joined in the A liquid, continue heated and stirred backflow 30min, promptly get the magnesium oxide colloidal sol of stable transparent; With the aluminium alloy is substrate, after carrying out pretreatment of base material, adopts and to soak damp crystal pulling method and film, and pull rate is controlled at 2 * 10
-4Ms
-1～2 * 10
-3Ms
-1, low-temperature heat treatment after the film forming progressively is warmed up to 180 ℃, and constant temperature 60min obtains the magnesium oxide single thin film, treats that alcohol solvent volatilization back in 800 ℃ of sintering, obtains mono-layer oxidized magnesium nanoparticulate thin films, repeats aforesaid operations process 6 times, obtains the multilayered particles film.
Embodiment 3:
With magnesium acetate (Mg (CH
3COO)
24H
2O) be precursor, it is dissolved in the ethanolic soln (is called A liquid), with the collodion is annex solution, be dissolved in the ethanolic soln and (be called B liquid), the mass ratio that makes inorganic magnesium salt and collodion is 0.16: 1, and the volume ratio of control alcohol solvent and annex solution is 7: 3, be heated to 70～80 ℃ and stir A liquid, during backflow B liquid is dropwise joined in the A liquid, continue heated and stirred backflow 30min, promptly get the magnesium oxide colloidal sol of stable transparent; With the magnetic neodymium iron boron is substrate, after carrying out pretreatment of base material, adopts and to soak damp crystal pulling method and film, and pull rate is controlled at 2 * 10
-4Ms
-1～2 * 10
-3Ms
-1, low-temperature heat treatment after the film forming progressively is warmed up to 180 ℃, and constant temperature 45min obtains the magnesium oxide single thin film, treats that alcohol solvent volatilization back in 600 ℃ of sintering, obtains mono-layer oxidized magnesium nanoparticulate thin films, repeats aforesaid operations process 5 times, obtains the multilayered particles film.
Claims (2)
1, a kind of method with the sol-gel technology preparing magnesia anticorrosion protective film is characterized in that realizing through the following steps:
With inorganic magnesium salt is precursor, it is dissolved in the ethanolic soln, making A liquid, is annex solution with the collodion, is dissolved in and makes B liquid in the ethanolic soln, the mass ratio that makes inorganic magnesium salt and collodion is 0.04: 1～0.32: 1, the volume ratio of controlling alcohol solvent and annex solution simultaneously is 6: 4～8: 2, is heated to 70～80 ℃ and stirs A liquid, during backflow B liquid is dropwise joined in the A liquid, continue heated and stirred backflow 30min, promptly get the magnesium oxide colloidal sol of stable transparent; With perishable metal is substrate, after carrying out pretreatment of base material, adopts and to soak damp crystal pulling method and film, and pull rate is controlled at 2 * 10
-4Ms
-1～2 * 10
-3Ms
-1Between, low-temperature heat treatment after the film forming progressively is warmed up to 180 ℃, constant temperature 30～60min obtains the magnesium oxide single thin film, treats that alcohol solvent volatilization back is in 350～800 ℃ of sintering, obtain mono-layer oxidized magnesium nanoparticulate thin films, repeat aforesaid operations process 4～6 times, obtain the multilayered particles film.
2, method according to claim 1 is characterized in that, inorganic magnesium salt is meant magnesium nitrate or magnesium acetate, and easy corrosion metal base material is meant magnesium alloy, aluminium alloy or magnetic neodymium iron boron.
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| CNB2006100544434A CN100447305C (en) | 2006-07-14 | 2006-07-14 | Method for preparing magnesium oxide anti-corrosion protective film by sol-gel technology |
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| CN100447305C true CN100447305C (en) | 2008-12-31 |
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| CN102776477A (en) * | 2012-07-16 | 2012-11-14 | 福州阿石创光电子材料有限公司 | Waterproof film and preparation method thereof |
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| CN105032162A (en) * | 2015-06-15 | 2015-11-11 | 浙江爱科乐环保有限公司 | Filter material for processing harmful gas and preparation method thereof |
| CN106252224A (en) * | 2016-09-14 | 2016-12-21 | 齐鲁工业大学 | A kind of low temperature liquid phase preparation method of magnesium oxide dielectric film |
| CN108623827A (en) * | 2018-05-07 | 2018-10-09 | 亨特瑞（昆山）新材料科技有限公司 | A kind of silver chlorate antibacterial colloidal sol PET film |
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| CN111875263B (en) * | 2020-07-23 | 2022-09-06 | 安徽晶驰光电科技有限公司 | Anti-glare film coating method for anti-reflection glass |
| CN115993420A (en) * | 2023-02-17 | 2023-04-21 | 杭州臻盛科技有限公司 | Efficient heat conduction trap and manufacturing method thereof |
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