CN108330472A - A method of the double hydroxy metal oxide coating corrosion resistances of enhancing Mg alloy surface - Google Patents
A method of the double hydroxy metal oxide coating corrosion resistances of enhancing Mg alloy surface Download PDFInfo
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- CN108330472A CN108330472A CN201810110469.9A CN201810110469A CN108330472A CN 108330472 A CN108330472 A CN 108330472A CN 201810110469 A CN201810110469 A CN 201810110469A CN 108330472 A CN108330472 A CN 108330472A
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- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
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- C23C18/1216—Metal oxides
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
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- C23C18/1295—Process of deposition of the inorganic material with after-treatment of the deposited inorganic material
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- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/12—Oxygen-containing compounds
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- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
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- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
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- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/16—Sulfur-containing compounds
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- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/16—Sulfur-containing compounds
- C23F11/165—Heterocyclic compounds containing sulfur as hetero atom
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- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/173—Macromolecular compounds
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- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
- C23F11/182—Sulfur, boron or silicon containing compounds
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- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
- C23F11/184—Phosphorous, arsenic, antimony or bismuth containing compounds
Abstract
The invention discloses a kind of methods of enhancing Mg alloy surface LDH coating corrosion resistances energy, including the polishing degreasing processing of magnesium-alloy material surface, the preparation of LDH solution, the growth of Mg alloy surface LDH, prepare corrosion inhibitor solution and deposition corrosion inhibiter, it is characterised in that follow these steps to carry out：（a）Pre-treatment is carried out to magnesium alloy,（b）The preparation of LDH solution,（c）The growth of Mg alloy surface LDH,（d）Corrosion inhibitor solution is prepared,（e）Corrosion inhibiter is deposited, has the magnesium alloy of LDH to immerse in corrosion inhibitor solution deposition, soak at room temperature after 12 72 hours, through water rinse well by taking-up, and dries up or air-dry.The present invention is detected through dynamic potential polarization curve, and corrosion electric current density drops to 1 Naan or less.
Description
Technical field
The present invention relates to field of metal surface treatment technology, the double hydroxy metal oxidations of especially a kind of enhancing Mg alloy surface
Object（LDH）The method of coating corrosion resistance energy.
Background technology
Energy crisis and environmental pollution are that the mankind are faced with and urgent problem to be solved 21 century.It reduces energy consumption and subtracts
A kind of important means of of low pollution object discharge is to realize product " lightweight ", i.e., uses light weight alloy component as far as possible.Aluminium closes
Gold and magnesium alloy are alloy in lightweight, the former density is about 2.7 g cm3, the density of the latter is about 1.7 g cm3.Although aluminium
The density higher of alloy, but relative to magnesium alloy, the former current application range is more extensive.One important reason is that aluminium closes
Gold itself can form one layer of oxidation film with protective effect on its surface, and the oxidation film that Mg alloy surface is formed is loose
Porous, the protective effect risen does not have practical value.Thus, although magnesium alloy also has specific strength high, mouldability can be good,
Damping performance is excellent, easily recycling many advantages, such as, but still fail scale moves towards market.In order to overcome magnesium alloy is perishable to lack
Point, current most important method is to be formed on its surface protective filmy layer.For example, traditional chromium conversion film, phosphating coat, plating or
Chemical deposit, anode or micro-arc oxidation films etc..But the above method and technique all more or less are unfavorable for advising in the presence of some
The shortcomings that modelling produces.For example, Cr VI environmental pollution is serious, high risks are constituted to human health, many fields
Through prohibiting；Differential arc oxidation needs to consume higher electric energy, and the effect of magnesium alloy differential arc oxidation is also not so good as in aluminium alloy
In it is so ideal；The processing of plating solution involved in plating and chemical plating method is a very stubborn problem, in recent years someone
Trial improves the resistance to corrosion of magnesium alloy with hydrotalcite film, is closed with magnesium as Chinese patent 201310368527.5 is disclosed
Rust inhibition anion intercalation hydrotalcite film prepared by gold surface hydrothermal deposition method come the method that reduces Corrosion Behaviors of Magnesium Alloys speed,
Specific practice includes the following steps：
（a）Pretreatment of deoiling of polishing is carried out to magnesium alloy sample；
（b）By soluble divalent metal salt AY2 and soluble trivalent metal salt BY3 according to the ratio between amount of substance 2: 1 be dissolved in from
In sub- water, it is configured to the mixed solution of 0.02~0.2 mol/L AY2 and 0.01~0.1 mol/L BY3, mixed solution is set
It stirred in three-necked flask, be heated to 60~80 DEG C；
（c）The NaOH and rust inhibition anion sodium salt for weighing the amount of certain substance are dissolved in step b）In the deionized water of equivalent,
N2It is slowly added under protection in three-necked flask described in step b, it is 9~10 to adjust pH, and temperature is maintained at 60~80 DEG C, adds
72 h of thermal agitation is aged 12 h, and LDHs colloidal sols are made；
（d）Magnesium alloy sample and LDHs colloidal sols that pretreatment obtains are placed in hydrothermal reaction kettle, wherein LDHs colloidal sol compactednesses
It is 70%, hydrothermal reaction kettle is put into drying box carries out hydrothermal deposition later, temperature is 120~160 DEG C, the time 12
~72 h are to get rust inhibition anion intercalation hydrotalcite film.The film shows good application prospect, 3.5%
12 hours surfaces are impregnated in NaCl solution without pitting.But because its technique not enough optimizes, operational reaction conditions etc. still need into one
Step is improved, the single LDH coatings that such as above-mentioned Mg alloy surface is formed impregnated in 3.5% NaCl solution a couple of days just occur it is bright
Aobvious point corrosion pit.To greatly test for the application of LDH coatings if in more rugged environment.Therefore it develops a kind of
Optimize the preparation process of LDH coatings, improves the corrosion resistance of LDH coatings, highly corrosion resistant coating of the development suitable for magnesium alloy
It is very necessary.
Invention content
That it is an object of the invention to overcome the deficiencies of the prior art and provide a kind of techniques is more simplified, further enhances magnesium conjunction
The method of gold surface LDH coating corrosion resistances.The purpose of the present invention is realized by following technical proposals：A kind of enhancing magnesium conjunction
Gold surface LDH coating corrosion resistances can method, including the polishing degreasing processing of magnesium-alloy material surface, the preparation of LDH solution,
Corrosion inhibitor solution and deposition corrosion inhibiter are prepared in the growth of Mg alloy surface LDH, it is characterised in that follow these steps to carry out：
（a）Pre-treatment is carried out to magnesium alloy, including mechanical grinding, oil removing, mechanical grinding are being thrown using the sand paper of 200-2000 mesh
It is completed on ray machine；Oil removing is cleaned 10-15 minutes with ultrasonic cleaner or in acetone with alkaline solution oil removing, and alkaline solution is
It is compounded with one or more in sodium hydroxide, phosphate and carbonate, a concentration of 15-60 g/L, is 55-65 in temperature
Cleaned under conditions of degree Celsius 10-15 minutes it is spare；
（b）The preparation of LDH solution takes soluble metal ion divalent salts, trivalent salt and carbonate or molybdate and deionized water
It is 6 to be configured to molar ratio：2：1 solution is used in combination sodium hydroxide or potassium hydroxide basic solution to adjust pH value to 12 spare；
（c）The above-mentioned magnesium alloy through pre-treatment is put into hydrothermal reaction kettle and pours into LDH solution by the growth of Mg alloy surface LDH,
It is subsequently placed in drying box, reacts 12-72 h under being 110-160 degrees Celsius in temperature, rinsed through water after taking-up, and in drying
Be dried overnight in case has the magnesium alloy of LDH spare up to deposition；
（d）Corrosion inhibitor solution is prepared, corrosion inhibiter and deionized water are configured to solution for standby by mass concentration for 0.5%-2.5%；
（e）Corrosion inhibiter is deposited, has the magnesium alloy of LDH to immerse in corrosion inhibitor solution deposition, soak at room temperature takes after 12-72 hours
Go out and rinsed well through water, and dries up or air-dry to get finished product.
The soluble metal ion divalent salts are Mg (NO3)2、Co(NO3)2、Mn(NO3)2Or Cu (NO3)2。
The soluble trivalent metal salt is Al (NO3)3、Cr(NO3)3、AlCl3Or CrCl3。
The carbonate is sodium carbonate, potassium carbonate.
The molybdate is sodium molybdate, potassium molybdate.
The corrosion inhibiter is lignosulfonates, dodecyl（Benzene）Sulfonate, diethyldithiocar bamic acid, vinegar
Hydrochlorate, phosphoric acid（Hydrogen, dihydro）Salt, oilstone acid potassium salt, alginate, silicate, 8-hydroxyquinoline and its derivative, 2- mercaptos
Benzothiazole and its derivative, benzotriazole and its derivative any type.
Currently, there is no mentioned by the present invention by the simple corrosion inhibiter that directly impregnates to enhance LDH coating corrosion resistance energy
Method report.The advantages of the present invention are embodied in（1）Relative to the method for preparing LDH coatings at present, this hair
The bright technique for preparing LDH coatings is simpler, and molybdate or carbonate can be mixed directly with nitrate, and LDH solution is in process for preparation
In be not necessarily to nitrogen protection, before pouring into reaction kettle without prolonged stirring and aging, thus prepare LDH solution
More convenient operation；（2）After LDH coatings impregnate in corrosion inhibiter, corrosion inhibiter can be adsorbed in coating surface, to keep coating corrosion-resistant
Performance is significantly increased.It is detected through dynamic potential polarization curve, does not impregnate the corrosion electric current density of LDH coatings of corrosion inhibiter relative to magnesium
Alloy substrates are remarkably decreased, and value is about hundreds of microamperes, but after impregnating corrosion inhibiter, corrosion electric current density then drops to 1 Naan
Hereinafter, referring to Fig. 1.
Description of the drawings
Fig. 1 is magnesium alloy substrate, LDH coatings and the potentiodynamic polarization of the present invention for impregnating the sample after corrosion inhibiter
Curve.A is magnesium alloy substrate, and B is LDH coatings, and C is that the embodiment of the present invention 2 deposits the LDH coatings after corrosion inhibiter.
Specific implementation mode
With reference to embodiment, the invention will be further described.
Embodiment 1：A method of enhancing Mg alloy surface LDH coating corrosion resistance energy, including magnesium-alloy material surface
Polishing degreasing processing, the growth of Mg alloy surface LDH, prepares corrosion inhibitor solution and deposition corrosion inhibiter at the preparation of LDH solution,
It is characterized in that, following these steps to carry out：
（a）Pre-treatment, including mechanical grinding, oil removing are carried out to magnesium alloy.Mechanical grinding is using the sand paper of 200 mesh on polishing machine
Mg alloy surface is carried out to be polishing to the smooth and bright like a mirror face in surface, oil removing cleans oil removing in 10 minutes with ultrasonic cleaner in acetone
It is spare；
（b）The preparation of LDH solution takes soluble metal ion divalent salts, trivalent salt and carbonate or molybdate and deionized water
It is 6 to be configured to molar ratio：2：1 solution.The present embodiment selects Co (NO3)2·6H217.5 grams of O, Cr (NO3)3·9H2O 8.0
Gram, 1.1 grams of sodium carbonate and 1000 ml mixed dissolutions of deionized water are configured to 0.06 mol/L Co (NO3)2, 0.02 mol/L
Cr(NO3)3, the LDH solution of 0.01 mol/L sodium carbonate is used in combination sodium hydroxide solution to adjust pH value to 12 spare；
（c）The above-mentioned magnesium alloy through pre-treatment is put into hydrothermal reaction kettle and pours into LDH solution by the growth of Mg alloy surface LDH,
Solution packing density is 70%, is subsequently placed in drying box, is reacted 72 hours under being 110 degrees Celsius in temperature, through water after taking-up
It rinses, and be dried overnight in drying box has the magnesium alloy of LDH spare up to deposition；
（d）Corrosion inhibitor solution is prepared, corrosion inhibiter and deionized water are configured to solution for standby by weight 0.5% ~ 2.5%.
The present embodiment selects 25.0 grams of neopelex to be configured to 2.5% slow corrosion inhibitor solution with 1000 mL of deionized water.
（e）Corrosion inhibiter is deposited, has the magnesium alloy of LDH to immerse in corrosion inhibitor solution deposition, soak at room temperature takes after 12 hours
Go out and rinsed well through water, and dries up or air-dry to get finished product.
Embodiment 2：A method of enhancing Mg alloy surface LDH coating corrosion resistance energy, including magnesium-alloy material surface
Polishing degreasing processing, the growth of Mg alloy surface LDH, prepares corrosion inhibitor solution and deposition corrosion inhibiter at the preparation of LDH solution,
It is characterized in that, following these steps to carry out：
（a）Pre-treatment, including mechanical grinding are carried out to magnesium alloy, oil removing, mechanical grinding is using the sand paper of 1000 mesh in polishing machine
On be polishing to the smooth and bright like a mirror face in surface, oil removing alkaline solution oil removing to Mg alloy surface, alkaline solution is to use hydroxide
One or more in sodium, phosphate and carbonate are compounded, and the present embodiment selects sodium hydroxide solution, a concentration of 40 g/
L, temperature be 65 degrees Celsius under conditions of cleaning 10 minutes it is spare；
（b）The preparation of LDH solution takes soluble metal ion divalent salts, trivalent salt and carbonate or molybdate and deionized water
It is 6 to be configured to molar ratio：2：1 solution.The present embodiment selects Mg (NO3)2·6H215.4 grams of O, Al (NO3)3·9H2O 7.5
Gram, 1.1 grams of sodium carbonate and 1000 mL mixed dissolutions of deionized water are configured to 0.06 mol/L Mg (NO3)2, 0.02 mol/L
Al(NO3)3, the LDH solution of 0.01 mol/L sodium carbonate is used in combination potassium hydroxide solution to adjust pH value to 12 spare；
（c）The above-mentioned magnesium alloy through pre-treatment is put into hydrothermal reaction kettle and to pour into LDH molten by the growth of Mg alloy surface LDH
Liquid, solution packing density are 70%, are subsequently placed in drying box, react 24 hours under being 140 degrees Celsius in temperature, are passed through after taking-up
Water rinses, and be dried overnight in drying box has the magnesium alloy of LDH spare up to deposition；
（d）Corrosion inhibitor solution is prepared, it is spare that corrosion inhibiter is configured to deionized water to 0.5%-2.5% by weight.This implementation
It is spare that example selects 8.0 grams of 8-hydroxyquinoline with 1000 mL of deionized water to be configured to 0.8% corrosion inhibitor solution；
（e）Corrosion inhibiter is deposited, has the magnesium alloy of LDH to immerse in corrosion inhibitor solution deposition, soak at room temperature takes out warp after 36 hours
Water is rinsed well, and is dried up or air-dried to get finished product.
Embodiment 3：A method of enhancing Mg alloy surface LDH coating corrosion resistance energy, including magnesium-alloy material surface
Polishing degreasing processing, the growth of Mg alloy surface LDH, prepares corrosion inhibitor solution and deposition corrosion inhibiter at the preparation of LDH solution,
It is characterized in that, following these steps to carry out：
（a）Pre-treatment, including mechanical grinding are carried out to magnesium alloy, oil removing, mechanical grinding is using the sand paper of 2000 mesh in polishing machine
On Mg alloy surface is carried out to be polishing to the smooth and bright like a mirror face in surface, oil removing is cleaned 15 minutes with ultrasonic cleaner remove in acetone
Oil is spare；
（b）The preparation of LDH solution takes soluble metal ion divalent salts, trivalent salt and carbonate or molybdate and deionized water
It is 6 to be configured to molar ratio：2：1 solution.The present embodiment selects Mn (NO3)2·6H2O17.2 grams, AlCl3·6H2O4.8 grams, molybdenum
2.1 grams of sour sodium and 1000 ml mixed dissolutions of deionized water, are configured to 0.06 mol/L Mn (NO3)2, 0.02 mol/L AlCl3,
The LDH solution of 0.01 mol/L sodium molybdates is used in combination sodium hydroxide solution to adjust pH value to 12 spare；
（c）The above-mentioned magnesium alloy through pre-treatment is put into hydrothermal reaction kettle and to pour into LDH molten by the growth of Mg alloy surface LDH
Liquid, solution packing density are 70%, are subsequently placed in drying box, are reacted 72 hours under being 110 degrees Celsius in temperature, through water after taking-up
It rinses, and be dried overnight in drying box has the magnesium alloy of LDH spare up to deposition；
（d）Corrosion inhibitor solution is prepared, buffer and deionized water are configured to 0.5%-2.5% solution for standby by weight, this
Embodiment is selected；5.0 grams of sodium potassium tartrate tetrahydrate is configured to 0.5% slow corrosion inhibitor solution with 1000 mL of deionized water.
（e）Corrosion inhibiter is deposited, has the magnesium alloy of LDH to immerse in corrosion inhibitor solution deposition, room temperature soaked real bubble after 72 hours,
Taking-up is rinsed well through water, and is dried up or air-dried to get finished product.
Apply example 4：A method of enhancing Mg alloy surface LDH coating corrosion resistance energy, including magnesium-alloy material surface are beaten
It grinds off oily waste treatment, the preparation of LDH solution, the growth of Mg alloy surface LDH, prepare corrosion inhibitor solution and deposition corrosion inhibiter,
It is characterized in that, follows these steps to carry out：
（a）Pre-treatment, including mechanical grinding, oil removing are carried out to magnesium alloy.Mechanical grinding is using the sand paper of 200 mesh on polishing machine
Mg alloy surface is carried out to be polishing to the smooth and bright like a mirror face in surface, oil removing cleans oil removing in 10 minutes with ultrasonic cleaner in acetone
It is spare；
（b）The preparation of LDH solution takes soluble metal ion divalent salts, trivalent salt and carbonate or molybdate and deionized water
It is 6 to be configured to molar ratio：2：1 solution.The present embodiment selects Mg (NO3)2·6H215.4 grams of O, AlCl3·6H2O4.8 grams, carbon
1.4 grams of sour potassium and 1000 ml mixed dissolutions of deionized water, are configured to 0.06 mol/L Mg (NO3)2, 0.02 mol/L AlCl3,
The LDH solution of 0.01 mol/L potassium carbonate is used in combination sodium hydroxide solution to adjust pH value to 12 spare；
（c）The above-mentioned magnesium alloy through pre-treatment is put into hydrothermal reaction kettle and to pour into LDH molten by the growth of Mg alloy surface LDH
Liquid, solution packing density are 70%, are subsequently placed in drying box, react 72 hours under being 110 degrees Celsius in temperature, are passed through after taking-up
Water rinses, and be dried overnight in drying box has the magnesium alloy of LDH spare up to deposition；
（d）Corrosion inhibitor solution is prepared, corrosion inhibiter and deionized water are configured to solution for standby by weight 0.5%- 2.5%.This
Embodiment selects 25.0 grams of neopelex to be configured to 2.5% slow corrosion inhibitor solution with 1000 mL of deionized water.
（e）Corrosion inhibiter is deposited, has the magnesium alloy of LDH to immerse in corrosion inhibitor solution deposition, soak at room temperature takes after 15 hours
Go out and rinsed well through water, and dries up or air-dry to get finished product.
Embodiment 5：A method of enhancing Mg alloy surface LDH coating corrosion resistance energy, including magnesium-alloy material surface
Polishing degreasing processing, the growth of Mg alloy surface LDH, prepares corrosion inhibitor solution and deposition corrosion inhibiter at the preparation of LDH solution,
It is characterized in that, following these steps to carry out：
（a）Pre-treatment, including mechanical grinding are carried out to magnesium alloy, oil removing, mechanical grinding is using the sand paper of 1000 mesh in polishing machine
On be polishing to the smooth and bright like a mirror face in surface, oil removing alkaline solution oil removing to Mg alloy surface, alkaline solution is to use hydroxide
One or more in sodium, phosphate and carbonate are compounded, and the present embodiment selects sodium hydroxide solution, a concentration of 40 g/
L, temperature be 65 degrees Celsius under conditions of cleaning 10 minutes it is spare；
（b）The preparation of LDH solution takes soluble metal ion divalent salts, trivalent salt and carbonate or molybdate and deionized water
It is 6 to be configured to molar ratio：2：1 solution.The present embodiment selects Cu (NO3)2·3H214.5 grams of O, CrCl3·6H25.3 grams of O,
2.1 grams of sodium molybdate and 1000 mL mixed dissolutions of deionized water, are configured to 0.06 mol/L Cu (NO3)2, 0.02 mol/L
CrCl3, the LDH solution of 0.01 mol/L sodium molybdates is used in combination potassium hydroxide solution to adjust pH value to 12 spare；
（c）The above-mentioned magnesium alloy through pre-treatment is put into hydrothermal reaction kettle and pours into LDH solution by the growth of Mg alloy surface LDH,
Solution packing density is 70%, is subsequently placed in drying box, reacts 24 hours under being 140 degrees Celsius in temperature, is rushed through water after taking-up
It washes, and be dried overnight in drying box has the magnesium alloy of LDH spare up to deposition；
（d）Corrosion inhibitor solution is prepared, it is spare that corrosion inhibiter is configured to deionized water to 0.5%-2.5% by weight.This implementation
It is spare that example selects 8.0 grams of 8-hydroxyquinoline with 1000 mL of deionized water to be configured to 0.8% corrosion inhibitor solution；
（e）Corrosion inhibiter is deposited, has the magnesium alloy of LDH to immerse in corrosion inhibitor solution deposition, soak at room temperature takes out warp after 36 hours
Water is rinsed well, and is dried up or air-dried to get finished product.
Claims (6)
1. a kind of method of enhancing Mg alloy surface LDH coating corrosion resistances energy, including the polishing degreasing of magnesium-alloy material surface
Processing, the growth of Mg alloy surface LDH, prepares corrosion inhibitor solution and deposition corrosion inhibiter at the preparation of LDH solution, it is characterised in that
It follows these steps to carry out：
（a）Pre-treatment is carried out to magnesium alloy, including mechanical grinding, oil removing, mechanical grinding are being thrown using the sand paper of 200-2000 mesh
It is completed on ray machine；Oil removing is cleaned 10-15 minutes with ultrasonic cleaner or in acetone with alkaline solution oil removing, and alkaline solution is
It is compounded with one or more in sodium hydroxide, phosphate and carbonate, 60 g/L of a concentration of 15-, is 55- in temperature
Cleaned under conditions of 65 degrees Celsius 10-15 minutes it is spare；
（b）The preparation of LDH solution takes soluble metal ion divalent salts, trivalent salt and carbonate or molybdate and deionized water
It is 6 to be configured to molar ratio：2：1 solution is used in combination sodium hydroxide or potassium hydroxide basic solution to adjust pH value to 12 spare；
（c）The above-mentioned magnesium alloy through pre-treatment is put into hydrothermal reaction kettle and pours into LDH solution by the growth of Mg alloy surface LDH,
It is subsequently placed in drying box, reacts 12-72 h under being 110-160 degrees Celsius in temperature, rinsed through water after taking-up, and in drying
Be dried overnight in case has the magnesium alloy of LDH spare up to deposition；
（d）Corrosion inhibitor solution is prepared, corrosion inhibiter and deionized water are configured to solution for standby by mass concentration for 0.5%-2.5%；
（e）Corrosion inhibiter is deposited, has the magnesium alloy of LDH to immerse in corrosion inhibitor solution deposition, soak at room temperature takes after 12-72 hours
Go out and rinsed well through water, and dries up or air-dry.
2. a kind of method of enhancing Mg alloy surface LDH coating corrosion resistances energy according to claim 1, feature exist
In：The soluble metal ion divalent salts are Mg (NO3)2、Co(NO3)2、Mn(NO3)2Or Cu (NO3)2In any one.
3. a kind of method of enhancing Mg alloy surface LDH coating corrosion resistances energy according to claim 1, feature exist
In：The soluble trivalent metal salt is Al (NO3)3、Cr(NO3)3、AlCl3Or CrCl3Wang meanings are a kind of.
4. a kind of method of enhancing Mg alloy surface LDH coating corrosion resistances energy according to claim 1, feature exist
In：The carbonate is sodium carbonate or potassium carbonate.
5. a kind of method of enhancing Mg alloy surface LDH coating corrosion resistances energy according to claim 1, feature exist
In：The molybdate is sodium molybdate or potassium molybdate.
6. a kind of method of enhancing Mg alloy surface LDH coating corrosion resistances energy according to claim 1, feature exist
In：The corrosion inhibiter is lignosulfonates, dodecyl（Benzene）Sulfonate, diethyldithiocar bamic acid, acetate,
Phosphoric acid（Hydrogen, dihydro）Salt, oilstone acid potassium salt, alginate, silicate, 8-hydroxyquinoline and its derivative, 2- mercaptos benzene a pair of horses going side by side
Thiazole and its derivative, benzotriazole and its derivative any one.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110627097A (en) * | 2019-09-20 | 2019-12-31 | 海洋化工研究院有限公司 | Preparation of intercalation material and application thereof in polar water-based anticorrosive paint |
| CN111607796A (en) * | 2019-02-25 | 2020-09-01 | 天津大学 | Controlled-release magnetic zinc-aluminum-cerium hydrotalcite-loaded 2-mercaptobenzothiazole corrosion inhibitor and preparation method thereof |
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| CN114875396A (en) * | 2022-04-28 | 2022-08-09 | 厦门大学 | Surface treatment method of magnesium or magnesium alloy |
| CN115094418A (en) * | 2022-06-22 | 2022-09-23 | 西华师范大学 | Method for sealing micropores of layered double metal hydroxide coating on surface of magnesium alloy |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101050539A (en) * | 2007-05-21 | 2007-10-10 | 北京化工大学 | Preparing even corrosion resistant hydrotalcite film through surface spin coating method for magnesium alloy, and preparation method |
| CN102140642A (en) * | 2011-02-18 | 2011-08-03 | 中国科学院海洋研究所 | Sustained-release type benzoic acid radical anion intercalation layered double hydroxides (LDHs) anti-corrosion material for carbon steel as well as preparation and application thereof |
| CN102677038A (en) * | 2011-03-10 | 2012-09-19 | 中国科学院金属研究所 | Film forming solution for growing Mg-Al hydrotalcite film in situ on surface of magnesium alloy and application thereof |
| CN103184447A (en) * | 2013-03-26 | 2013-07-03 | 大连理工大学 | Aluminum and aluminum alloy surface self-repairing and corrosion-resisting conversion coating and preparation method thereof |
| CN105274506A (en) * | 2015-10-27 | 2016-01-27 | 天津彩意科技有限公司 | Preparation method of LDHs functional thin-film material |
| CN106283017A (en) * | 2016-09-07 | 2017-01-04 | 南京工程学院 | Magnesium and Mg alloy surface have the Mg (OH) of intercalation configuration2/ Mg Sn houghite composite membrane and preparation method thereof |
| CN107059005A (en) * | 2016-12-22 | 2017-08-18 | 山东科技大学 | A kind of preparation method of the silane oxidation cerium hydrotalcite composite coating of magnesium/magnesium alloy matrix surface |
-
2018
- 2018-02-05 CN CN201810110469.9A patent/CN108330472A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101050539A (en) * | 2007-05-21 | 2007-10-10 | 北京化工大学 | Preparing even corrosion resistant hydrotalcite film through surface spin coating method for magnesium alloy, and preparation method |
| CN102140642A (en) * | 2011-02-18 | 2011-08-03 | 中国科学院海洋研究所 | Sustained-release type benzoic acid radical anion intercalation layered double hydroxides (LDHs) anti-corrosion material for carbon steel as well as preparation and application thereof |
| CN102677038A (en) * | 2011-03-10 | 2012-09-19 | 中国科学院金属研究所 | Film forming solution for growing Mg-Al hydrotalcite film in situ on surface of magnesium alloy and application thereof |
| CN103184447A (en) * | 2013-03-26 | 2013-07-03 | 大连理工大学 | Aluminum and aluminum alloy surface self-repairing and corrosion-resisting conversion coating and preparation method thereof |
| CN105274506A (en) * | 2015-10-27 | 2016-01-27 | 天津彩意科技有限公司 | Preparation method of LDHs functional thin-film material |
| CN106283017A (en) * | 2016-09-07 | 2017-01-04 | 南京工程学院 | Magnesium and Mg alloy surface have the Mg (OH) of intercalation configuration2/ Mg Sn houghite composite membrane and preparation method thereof |
| CN107059005A (en) * | 2016-12-22 | 2017-08-18 | 山东科技大学 | A kind of preparation method of the silane oxidation cerium hydrotalcite composite coating of magnesium/magnesium alloy matrix surface |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111607796A (en) * | 2019-02-25 | 2020-09-01 | 天津大学 | Controlled-release magnetic zinc-aluminum-cerium hydrotalcite-loaded 2-mercaptobenzothiazole corrosion inhibitor and preparation method thereof |
| CN110627097A (en) * | 2019-09-20 | 2019-12-31 | 海洋化工研究院有限公司 | Preparation of intercalation material and application thereof in polar water-based anticorrosive paint |
| CN114150301A (en) * | 2021-10-29 | 2022-03-08 | 北京卫星制造厂有限公司 | Magnesium-lithium alloy skin surface anticorrosion treatment method |
| CN114150301B (en) * | 2021-10-29 | 2023-12-12 | 北京卫星制造厂有限公司 | Magnesium-lithium alloy skin surface anti-corrosion treatment method |
| EP4063540A2 (en) | 2021-12-30 | 2022-09-28 | Politechnika Slaska | Method of producing porous oxide layers on aluminum containing polymeric corrosion inhibitors |
| CN114875396A (en) * | 2022-04-28 | 2022-08-09 | 厦门大学 | Surface treatment method of magnesium or magnesium alloy |
| CN114875396B (en) * | 2022-04-28 | 2023-03-14 | 厦门大学 | Surface treatment method of magnesium or magnesium alloy |
| CN115110068A (en) * | 2022-06-21 | 2022-09-27 | 江汉大学 | Corrosion-resistant hydrotalcite-like compound/metal composite coating and preparation method and application thereof |
| CN115094418A (en) * | 2022-06-22 | 2022-09-23 | 西华师范大学 | Method for sealing micropores of layered double metal hydroxide coating on surface of magnesium alloy |
| CN115094418B (en) * | 2022-06-22 | 2023-11-14 | 西华师范大学 | Method for sealing micropores of layered double hydroxide coating on magnesium alloy surface |
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