CN107012457A - A kind of silane cerium salt magnesium hydroxide composite coating of magnesium alloy substrates and preparation method thereof - Google Patents
A kind of silane cerium salt magnesium hydroxide composite coating of magnesium alloy substrates and preparation method thereof Download PDFInfo
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- CN107012457A CN107012457A CN201710171793.7A CN201710171793A CN107012457A CN 107012457 A CN107012457 A CN 107012457A CN 201710171793 A CN201710171793 A CN 201710171793A CN 107012457 A CN107012457 A CN 107012457A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C18/16—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 reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1637—Composition of the substrate metallic substrate
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
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Abstract
The invention discloses a kind of preparation method of the silane oxidation cerium magnesium hydroxide composite coating of magnesium/magnesium alloy matrix surface, it first deposits one layer of magnesium hydroxide coating using hydro-thermal method in magnesium/magnesium alloy substrate surface, afterwards in one layer of silane oxidation cerium composite coating of magnesium hydroxide coating over-assemble, using the low-surface-energy of silane, excellent adhesive property, by CeO2The hole of the faults of construction such as the point corrosion pit/hole or micro-crack that exist to magnesium hydroxide coating carries out closure processing, so as to obtain, compact structure, hydrophobicity be good, corrosion resisting property is excellent, there's almost no any point corrosion pit/hole or micro-crack defect and magnesium hydroxide coating organically combines integral composite coating with silane oxidation cerium composite coating.Simple, the obtained composite coating structure of present invention process is fine and close, hydrophobicity is good, corrosion resisting property is excellent, and the corrosion resistance and service life of magnesium alloy coating can be substantially improved.
Description
Technical field
The present invention relates to a kind of magnesium alloy corrosion-resistant finishes and preparation method thereof, more particularly to a kind of silicon of magnesium alloy substrates
Alkane-cerium salt-magnesium hydroxide composite coating and preparation method thereof.
Background technology
The chemical property of magnesium is very active, not anti-corrosion, the meeting in corrosive medium in acid, neutral and weakly alkaline solution
Loose porous oxide-film is generated, also, magnesia film layer can not be provided for matrix as aluminum oxide film layer and is effectively protected.
It is well known that magnesium and its alloy are in the higher corrosive medium of chloride ion content, corrode rapider.
At present, if in magnesium or magnesium alloy substrates surface deposition or attachment last layer or dried layer corrosion-resistant finishes, into
One of effective means to improve magnesium and its alloy corrosion resistance energy.
Wherein, chemical composition coating is most common, most easy in surface treatment method of Mg alloy.Prepare chemical composition coating
Method mainly has chemical precipitation method and hydro-thermal method.
Chemical conversion film process is carried out to magnesium alloy, it is anti-to occur chemistry after mainly being contacted by magnesium alloy with conversion solution
Should, the good corrosion resistance of Mg alloy surface and specific feature can be assigned by generating corresponding film layer, to meet different purposes
The need for.
However, the decay resistance of the film layer of single component is still undesirable, service life is also partially short, it is impossible to meet numerous works
The demand of industry application field.
In recent years, the corrosion-resistant composite coating of Mg alloy surface has become a study hotspot.Wherein, silane treatment technology
It is a kind of environment-friendly type metal surface guard technology, the features such as with being simple to operate and friendly to environment.
The chemical composition formula of silane is R'(CH2)nSi(OR)3, wherein R' is organo-functional group, and R is hydrolyzable groups.
Silane easily generates Si-OH groups in hydrolytic process, and Si-O-Me (Me generations are generated with-OH groups the dehydrating condensation of metal surface
Table metal), in addition, silane can also self shrinking combinate form into the three-dimensional netted silane films of Si-O-Si.Condition is simple needed for reaction, Ke Yi
The more uniform organic film of matrix surface formation, improves the anti-corrosion effect of metal.
But, the single or composite coating obtained by various magnesium alloy coating preparation methods of the prior art, or it is many or
Less, there is the defects such as many point corrosion pit/hole or micro-crack in equal generally existing layer, have become restriction magnesium alloy coating resistance to
The main restricting factor given full play to of corrosive nature.
Point corrosion pit/the hole or micro-crack of composite film are how effectively solved or eliminate, either, to the point of composite film
Pit/hole or micro-crack carry out sealing pores, or prepare that structure is finer and close and point corrosion pit/hole or micro- of film layer
Crack defect it is less even without magnesium alloy corrosion-resistant finishes, have become those skilled in the art's technology urgently to be resolved hurrily and ask
Topic.
The content of the invention
It is an object of the present invention to provide a kind of preparation side of the silane of magnesium alloy substrates-cerium salt-magnesium hydroxide composite coating
Method, simple, the obtained composite coating of its technique has that compact structure, hydrophobicity are good, there's almost no any point corrosion pit/hole
The features such as hole or micro-crack defect, fine corrosion resistance.
The present invention to achieve the above object the technical scheme adopted is that a kind of silane of magnesium/magnesium alloy base material-cerium salt-
The preparation method of magnesium hydroxide composite coating, it is characterised in that comprise the following steps：
The first step, magnesium/magnesium alloy base material pre-treatment step
Magnesium/magnesium alloy blank is taken, polishing removes the oxide layer on surface, after being cleaned up with deionized water, 20-60 DEG C of warm wind
Drying, it is standby；
Second step, the preparation of magnesium hydroxide coating
The above-mentioned magnesium/magnesium alloy base material by pretreatment is placed in hydrothermal reaction kettle, implantation quality percent concentration is
5% sodium hydroxide solution, until magnesium/magnesium alloy base material is submerged under liquid level completely；
Then, closure hydrothermal reaction kettle be placed in drying box, at 100~170 DEG C be incubated 2~8h, take out, spend from
Sub- water, which is rinsed, to be cleaned, and obtaining surface deposition has the magnesium/magnesium alloy of magnesium hydroxide coating；
3rd step, the preparation of composite coating
400-800 in mass ratio:100-300:1200-1700:1-3 ratio, takes absolute ethyl alcohol, silane coupled respectively
Agent, deionized water and soluble cerium salt, it is standby；
Taken absolute ethyl alcohol is poured into container, silane coupler, deionized water is sequentially added, stirs 0.5-3 hours, matches somebody with somebody
Into mixed solution A；
Then, soluble cerium salt is added into mixed solution A, continues to stir 0.5-3 hours, obtains mixed solution B；
The magnesium/magnesium alloy that above-mentioned surface, which is deposited, magnesium hydroxide coating is placed in mixed solution B container, is immersed in liquid
Under face, it is placed in drying box, 2~3h is assembled at 50~70 DEG C；Take out, rinsed well with absolute ethyl alcohol, then be placed in baking oven
In, dry, produce at 100~150 DEG C.
The technical effect directly brought by the technical proposal is that, technique is simple, and obtained composite coating has structure cause
Close, composite coating there's almost no any point corrosion pit/hole or micro-crack defect.
For more fully understand the composite coating obtained by above-mentioned technical proposal there's almost no any point corrosion pit/hole or
The reason for micro-crack defect, now it is briefly described as follows：
The core technology thought of above-mentioned technical proposal is：Applied using hydro-thermal method in Mg alloy surface synthesis magnesium hydroxide
Layer, and then utilize low-surface-energy, excellent adhesive property and the CeO with nano structure of silane2, in magnesium hydroxide
One layer of silane/cerium salt composite coating is coated on coating, and relies on CeO2To the hydroxide on (having been deposited on) Mg alloy surface
Point corrosion pit/the hole or micro-cracked structure defect of magnesium coating carry out closure processing, so that it is good, resistance to obtain compact structure, hydrophobicity
Lose function admirable, point corrosion pit/hole or micro-crack defect less even without silane-cerium salt-magnesium hydroxide composite coating.
It is believed that reason is, the CeO of nano structure2In " hole " of inciting somebody to action preferential " entrance " magnesium hydroxide, from
And the structure for turning into a kind of similar " skeleton " in hole (detects and found, be Si-O- between silane coating and magnesium hydroxide coating
Mg chemical bonds, it was demonstrated that the science and correctness of the conclusion)；And, organosilicon even compact " coating " in hydroxide
The top layer of magnesium.Nano Ce O2Generation play obvious filling effect, coating network structure can be effectively filled to, painting is reduced
The defect level of layer, improves screening ability of the coating to chlorion；Meanwhile, nano Ce O2Presence can suppress magnesium alloy electricity
Pole anode reaction, so as to slow down its corrosion rate.
That is, magnesium hydroxide-silane-cerium salt composite coating of Mg alloy surface is although be that the first film layer is hydrogen in preparation process
Magnesium oxide coating, on the basis of magnesium hydroxide coating, is coated with the composite membrane of one layer of silane/cerium salt.But, because silane rises
To be coating agent effect, what cerium salt played a part of is the filler of point corrosion pit/hole or micro-crack defect, and is formed
Si-O-Mg chemical bonds.Therefore, what is finally obtained is silane-cerium salt-magnesium hydroxide composite coating by matrix of magnesium alloy
(it is " composite bed ", rather than " the two layers " of stacking).
Obviously, integral structure shape is organically combined between this magnesium hydroxide coating and silane-cerium salt composite coating
The composite coating of formula, structure will be finer and close, the fault of construction such as point corrosion pit/hole or micro-crack of coating is few, even without.
Therefore, magnesium alloy painting can be substantially improved in the silane obtained by above-mentioned technical proposal-cerium salt-magnesium hydroxide composite coating
The corrosion resistance and service life of layer.
In above-mentioned technical proposal, using hydro-thermal method, at a lower temperature, prepare that purity is high, knot in Mg alloy surface
Strong protectiveness film layer with joint efforts, thicknesses of layers is easily controllable.Also, relative to other method, hydro-thermal method has technique simply easy
Control, the features such as the reaction time is short, production efficiency is high.
In addition, above-mentioned technical proposal, the chemical reagent used is nontoxic, and it is environmentally safe, it is environmental friendly.
Preferably, the preparation method of the silane of above-mentioned magnesium/magnesium alloy base material-cerium salt-magnesium hydroxide composite coating, made
Silane-cerium salt-magnesium hydroxide composite coating thickness be 12-14 μm, the contact angle on surface be 151 °, corrosion potential
It is 2.46 × 10 for -1.67V, corrosion current density-8A/cm2。
What the optimal technical scheme was directly brought has the technical effect that, obtained composite coating hydrophobicity is good, corrosion resisting property
It is excellent.
Obtained silane-cerium salt-magnesium hydroxide composite coating, the contact angle on its surface can reach 151 °, with super thin
Water effect (explanation：The single magnesium hydroxide coating of prior art or single organic silicon coating, the contact angle on its surface are respectively less than
150 °, without super-hydrophobic effect).Further preferably, above-mentioned silane is silane coupler, including N- octyl group triethoxysilicanes
Alkane, γ propyltrimethoxy silane, MTES, chloropropyl triethoxysilane, Y- glycidyl ether oxygen propyls
Trimethoxy silane, vinyltrimethoxy silane, 3- aminopropyl trimethoxysilanes, dimethoxydiphenylsilane or methyl
Trimethoxy silane；
The soluble cerium salt is cerous nitrate, cerous sulfate, cerous acetate or ammonium ceric nitrate.
What the optimal technical scheme was directly brought has the technical effect that, alternative silane coupler species is more, and only
If soluble cerium salt can be selected arbitrarily, the facility in production is brought.Also, due to cerous nitrate, cerous sulfate, cerous acetate or nitre
Sour cerium ammonium is respectively provided with good water solubility, is easy to it dispersed in organosilicon (solvent), and then ensures organic silicon coating
Uniform quality with stably.
Further preferably, above-mentioned magnesium alloy includes the following trade mark：AZ31、AZ91、AM50、Mg-0.5Ca、Mg-1Ca、Mg-
1.5Ca, Mg-1Li-1Ca, Mg-1Li-1Ca-1Y, Mg-4Li-1Ca, Mg-4Li-1Ca-1Y, Mg-8Li-1Ca or Mg-8Li-
1Ca-Y。
What the optimal technical scheme was directly brought has the technical effect that, obtained composite coating can be firmly attached to various boards
Number magnesium alloy substrates surface on, with universality.
In summary, the present invention is simple with technology controlling and process relative to prior art, and prepared composite coating structure is caused
It is close, with the adhesion of base material is strong, hydrophobic performance is excellent, composite coating there's almost no any point corrosion pit/hole or micro-crack
Defect, the beneficial effect such as corrosion resistance and service life so as to which magnesium alloy coating is substantially improved.
Brief description of the drawings
Fig. 1 is the Fourier infrared spectrum figure (FT-IR) of the product obtained by embodiment 1；
Fig. 2-1 is ESEM (SEM) photo (multiplication factor is 2000 times) and the contact of the product obtained by embodiment 1
Angle photo；
Fig. 2-2 is the EDS figures of the product obtained by embodiment 1；
Fig. 3 (according to needed for detection, is coated with for the longitudinal section SEM figures of the product obtained by embodiment 1 on the surface of product
One layer of epoxy resin)；
Fig. 4-1 is the full spectrograms of XPS of the product obtained by embodiment 1；
Fig. 4-2 is the XPS spectrum figure of the Ce elements of the product obtained by embodiment 1；
Fig. 5 is the dynamic potential polarization curve figure of the product obtained by embodiment 1；
Fig. 6 is the electrochemistry bode figures of the product obtained by embodiment 1；
Fig. 7 is the electrochemistry nyquist figures of the product obtained by embodiment 1；
The silane that Fig. 8 is obtained by embodiment 1/cerium salt is modified the liberation of hydrogen figure of composite coating and AZ31 magnesium alloy substrates；
Fig. 9 be stereoscan photograph (multiplication factor is 2000 times) after the failure 7 days of the product obtained by embodiment 1 and
EDS schemes.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in detail.
Embodiment 1
Basic material is pure magnesium, and preparation method is as follows：
The first step, magnesium substrates pre-treatment step
Pure magnesium base substrate is polished, successively with 150#、400#、800#、1500#Silicon carbide paper polishing specimen surface, use
Organic solvent or deionized water are cleaned up, and are dried up with hair-dryer at 25~60 DEG C, standby.
Second step, the preparation of magnesium hydroxide coating
The sodium hydroxide solution that mass fraction is 5% is prepared, the pure magnesium matrix and sodium hydroxide solution that have pre-processed are put
In hydrothermal reaction kettle, and it is put into drying box, taking-up after 2~8h is incubated at 100~170 DEG C, drying is cleaned.
3rd step, the preparation of composite coating
In mass ratio 400:100:1200:1 ratio, takes absolute ethyl alcohol, silane coupler, deionized water and nitric acid respectively
Cerium, it is standby；
Taken absolute ethyl alcohol is poured into container, silane coupler, deionized water is sequentially added, stirs 0.5-3 hours, matches somebody with somebody
Into mixed solution A；
Then, cerous nitrate is added into mixed solution A, continues to stir 0.5 hour, obtains mixed solution B；
The magnesium/magnesium alloy that above-mentioned surface, which is deposited, magnesium hydroxide coating is placed in mixed solution B container, is immersed in liquid
Under face, and
It is placed in drying box, 2h is assembled at 50 DEG C；Take out, rinsed well with absolute ethyl alcohol, then be placed in baking oven,
Dry, produce at 100~150 DEG C.
Embodiment 2
Basic material is Mg alloy AZ91, and preparation method is as follows：
The first step, magnesium alloy substrates pre-treatment step
Magnesium alloy base substrate is polished, successively with 150#、400#、800#、1500#Silicon carbide paper polishing specimen surface,
Cleaned up, dried up with hair-dryer at 25~60 DEG C with organic solvent or deionized water, it is standby.
Second step, the preparation of magnesium hydroxide coating
The sodium hydroxide solution that mass fraction is 5% is prepared, by the magnesium alloy substrate pre-processed and sodium hydroxide solution
It is placed in hydrothermal reaction kettle, and is put into drying box, taking-up after 2~8h is incubated at 100~170 DEG C, drying is cleaned.
3rd step, the preparation of composite coating
In mass ratio 600:180:1500:3 ratio, takes absolute ethyl alcohol, silane coupler, deionized water and sulfuric acid respectively
Cerium, it is standby；
Taken absolute ethyl alcohol is poured into container, silane coupler, deionized water is sequentially added, stirs 2 hours, is made into mixed
Close solution A；
Then, cerous sulfate is added into mixed solution A, continues to stir 2 hours, obtains mixed solution B；
The magnesium/magnesium alloy that above-mentioned surface, which is deposited, magnesium hydroxide coating is placed in mixed solution B container, is immersed in liquid
Under face, and
It is placed in drying box, 2h is assembled at 70 DEG C；Take out, rinsed well with absolute ethyl alcohol, then be placed in baking oven,
Dry, produce at 100~150 DEG C.
Embodiment 3
Basic material is magnesium alloy AM50, and preparation method is as follows：
The first step, magnesium alloy substrates pre-treatment step
Magnesium alloy base substrate is polished, successively with 150#、400#、800#、1500#Silicon carbide paper polishing specimen surface,
Cleaned up, dried up with hair-dryer at 25~60 DEG C with organic solvent or deionized water, it is standby.
Second step, the preparation of magnesium hydroxide coating
The sodium hydroxide solution that mass fraction is 5% is prepared, by the magnesium alloy substrate pre-processed and sodium hydroxide solution
It is placed in hydrothermal reaction kettle, and is put into drying box, taking-up after 8h is incubated at 120 DEG C, drying is cleaned.
3rd step, the preparation of composite coating
In mass ratio 800:300:1600:2 ratio, takes absolute ethyl alcohol, silane coupler, deionized water and acetic acid respectively
Cerium, it is standby；
Taken absolute ethyl alcohol is poured into container, silane coupler, deionized water is sequentially added, stirs 3 hours, is made into mixed
Close solution A；
Then, cerous acetate is added into mixed solution A, continues to stir 3 hours, obtains mixed solution B；
The magnesium/magnesium alloy that above-mentioned surface, which is deposited, magnesium hydroxide coating is placed in mixed solution B container, is immersed in liquid
Under face, and
It is placed in drying box, 3h is assembled at 60 DEG C；Take out, rinsed well with absolute ethyl alcohol, then be placed in baking oven,
Dry, produce at 100~150 DEG C.
Embodiment 4
Basic material is magnesium alloy Mg-8Li-1Ca-Y, and preparation method is as follows：
The first step：Magnesium alloy substrates pre-treatment step
Magnesium alloy base substrate is polished, successively with 150#、400#、800#、1500#Silicon carbide paper polishing specimen surface,
Cleaned up, dried up with hair-dryer at 25~60 DEG C with organic solvent or deionized water, it is standby.
Second step, the preparation of magnesium hydroxide coating
The sodium hydroxide solution that mass fraction is 5% is prepared, by the magnesium alloy substrate pre-processed and sodium hydroxide solution
It is placed in hydrothermal reaction kettle, and is put into drying box, taking-up after 4h is incubated at 170 DEG C, drying is cleaned.
3rd step, the preparation of composite coating
In mass ratio 800:220:1700:2 ratio, takes absolute ethyl alcohol, silane coupler, deionized water and nitric acid respectively
Cerium ammonium, it is standby；
Taken absolute ethyl alcohol is poured into container, silane coupler, deionized water is sequentially added, stirs 2.5 hours, is made into
Mixed solution A；
Then, ammonium ceric nitrate is added into mixed solution A, continues to stir 3 hours, obtains mixed solution B；
The magnesium/magnesium alloy that above-mentioned surface, which is deposited, magnesium hydroxide coating is placed in mixed solution B container, is immersed in liquid
Under face, and
It is placed in drying box, 3h is assembled at 70 DEG C；Take out, rinsed well with absolute ethyl alcohol, then be placed in baking oven,
Dry, produce at 100~150 DEG C.
Embodiment 5
Basic material is magnesium alloy Mg-4Li-1Ca, and preparation method is as follows：
The first step, magnesium alloy substrates pre-treatment step
Magnesium alloy base substrate is polished, successively with 150#、400#、800#、1500#Silicon carbide paper polishing specimen surface,
Cleaned up, dried up with hair-dryer at 25~60 DEG C with organic solvent or deionized water, it is standby.
Second step, the preparation of magnesium hydroxide coating
The sodium hydroxide solution that mass fraction is 5% is prepared, by the magnesium alloy substrate pre-processed and sodium hydroxide solution
It is placed in hydrothermal reaction kettle, and is put into drying box, taking-up after 4h is incubated at 150 DEG C, drying is cleaned.
3rd step, the preparation of composite coating
In mass ratio 480:180:1450:2 ratio, takes absolute ethyl alcohol, silane coupler, deionized water and nitric acid respectively
Cerium, it is standby；
Taken absolute ethyl alcohol is poured into container, silane coupler, deionized water is sequentially added, stirs 0.5 hour, is made into
Mixed solution A；
Then, cerous nitrate is added into mixed solution A, continues to stir 0.5 hour, obtains mixed solution B；
The magnesium/magnesium alloy that above-mentioned surface, which is deposited, magnesium hydroxide coating is placed in mixed solution B container, is immersed in liquid
Under face, and
It is placed in drying box, 2h is assembled at 55 DEG C；Take out, rinsed well with absolute ethyl alcohol, then be placed in baking oven,
Dry, produce at 100~150 DEG C.
Embodiment 6
Basic material is magnesium alloy Mg-1Li-1Ca, and preparation method is as follows：
The first step, magnesium alloy substrates pre-treatment step
Magnesium alloy base substrate is polished, successively with 150#、400#、800#、1500#Silicon carbide paper polishing specimen surface,
Cleaned up, dried up with hair-dryer at 25~60 DEG C with organic solvent or deionized water, it is standby.
Second step, the preparation of magnesium hydroxide coating
The sodium hydroxide solution that mass fraction is 5% is prepared, by the magnesium alloy substrate pre-processed and sodium hydroxide solution
It is placed in hydrothermal reaction kettle, and is put into drying box, taking-up after 4h is incubated at 120 DEG C, drying is cleaned.
3rd step, the preparation of composite coating
In mass ratio 700:180:1500:3 ratio, takes absolute ethyl alcohol, silane coupler, deionized water and solvable respectively
Property cerium salt, it is standby；
Taken absolute ethyl alcohol is poured into container, silane coupler, deionized water is sequentially added, stirs 0.5 hour, is made into
Mixed solution A；
Then, soluble cerium salt is added into mixed solution A, continues to stir 1 hour, obtains mixed solution B；
The magnesium/magnesium alloy that above-mentioned surface, which is deposited, magnesium hydroxide coating is placed in mixed solution B container, is immersed in liquid
Under face, and
It is placed in drying box, 3h is assembled at 70 DEG C；Take out, rinsed well with absolute ethyl alcohol, then be placed in baking oven,
Dry, produce at 100~150 DEG C.
Embodiment 7
Basic material is magnesium alloy Mg-1.5Ca, and preparation method is as follows：
The first step, magnesium alloy substrates pre-treatment step
Magnesium alloy Mg-1.5Ca base substrates are polished, successively with 150#、400#、800#、1500#Silicon carbide paper polishing
Specimen surface, is cleaned up with organic solvent or deionized water, is dried up with hair-dryer at 25~60 DEG C, standby.
Second step, the preparation of magnesium hydroxide coating
The sodium hydroxide solution that mass fraction is 5% is prepared, by the magnesium alloy substrate pre-processed and sodium hydroxide solution
It is placed in hydrothermal reaction kettle, and is put into drying box, taking-up after 2h is incubated at 120 DEG C, drying is cleaned.
3rd step, the preparation of composite coating
In mass ratio 800:300:1700:1.8 ratio, takes absolute ethyl alcohol, silane coupler, deionized water and second respectively
Sour cerium ammonium, it is standby；
Taken absolute ethyl alcohol is poured into container, silane coupler, deionized water is sequentially added, stirs 3 hours, is made into mixed
Close solution A；
Then, cerous acetate ammonium is added into mixed solution A, continues to stir 3 hours, obtains mixed solution B；
The magnesium/magnesium alloy that above-mentioned surface, which is deposited, magnesium hydroxide coating is placed in mixed solution B container, is immersed in liquid
Under face, and
It is placed in drying box, 3h is assembled at 70 DEG C；Take out, rinsed well with absolute ethyl alcohol, then be placed in baking oven,
Dry, produce at 100~150 DEG C.
The detection and inspection of product：
Selection example 1 is seen as embodiment is represented to the ESEM that magnesium alloy substrate and coating carry out different multiples
Examine, energy spectrum analysis, FT-IR, XPS, electro-chemical test analysis, and in 3.5wt.%NaCl solution soak 7d after fail experiment
Analysis and impedance analysis, as a result as shown in Figures 1 to 9.
Fig. 1 is the Fourier infrared spectrum figure of the magnesium alloy substrate of embodiment 1 and coating.
As shown in figure 1,3696cm-1The absworption peak at place is typical Mg-OH peaks, 3460cm-1Locate the vibration peak for-OH.
In 2974cm-1And 2925cm-1C-H vibration absorption peak can be nearby detected, in 1135cm-1And 1029cm-1It is attached
Closely there is Si-O-C and Si-O-Si vibration absorption peak, in 1275cm-1And 772cm-1Nearby there is Si-C characteristic absorption peak,
This explanation silane successful application is on magnesium hydroxide coating.
Fig. 2 is stereoscan photograph (multiplication factor is 2000 times), the contact angle of the magnesium alloy substrate of embodiment 1 and coating
Picture and EDS figures.
As shown in Fig. 2-1, it can be seen that silane uniform fold is on magnesium hydroxide coating, magnesium hydroxide " foliaceous " typical case
Pattern disappears substantially, and be polycondensed into polysiloxanes is covered in Mg alloy surface to part silane certainly, adds surface roughness, makes contact
Angle reaches 151 °, with super-hydrophobic effect, illustrates that the presence of silane film significantly improves the hydrophobic performance of magnesium alloy materials.From figure
As can be seen that sample surfaces Mg constituent content highests, O elements take second place, followed by Si elements in 2-2.
Explanation：Silane and magnesium hydroxide laminated film are covered in matrix surface, wherein, the presence of Ce elements illustrates cerium salt
Modified success.
Fig. 3 is the longitudinal section of embodiment 1AZ31 magnesium alloy substrates and coating.
As shown in figure 3, it can be found that sample surfaces are covered by two membranes, and obvious line of demarcation is had no between two membranes.Say
Bright two membranes are with chemical bonds, and adhesion is strong, and silane film is penetrated into magnesium hydroxide coating, are effectively filled with sky between film layer
Gap.In figure, magnesium hydroxide coating layer thickness is about 2.98 μm, and silane/cerium oxide modified coating is about 9.41 μm.
Fig. 4 is the XPS collection of illustrative plates of the magnesium alloy substrate of embodiment 1 and coating.
As shown in Fig. 4-1, C, O, Mg, Si, Ce element are detected in the total spectrograms of XPS, it is corresponding with Fig. 1, it was demonstrated that hydrogen
The successful preparation of magnesia and silane film layer, meanwhile, the presence of Ce elements illustrates the success that cerium salt is modified.And Fig. 4-2 is proved
Ce elements can be acted synergistically, and be filled with the point corrosion pit and fine fisssure of silane with being present in the form of cerium oxide in film layer with silane
Line, improves membranous layer stability.
Fig. 5 is the dynamic potential polarization curve figure of the magnesium alloy substrate of embodiment 1 and coating.
As shown in figure 5, comparing result it can be found that the modified magnesium alloy sample of silane/cerium salt compare magnesium alloy substrate,
Corrosion current density is substantially reduced, by 1.51 × 10-5A/cm2It is reduced to 2.46 × 10-8A/cm2, have dropped about 3 quantity
Level；
With reference to the XPS data in Fig. 4, it may infer that cerium salt with CeO2Form be present in composite coating, be used as inhibition
Agent acts synergistically with silane coating, significantly improves the corrosion resisting property of magnesium alloy.
Fig. 6 is the electrochemistry bode figures of the magnesium alloy substrate of embodiment 1 and coating.
As shown in Figure 6, it can be seen that compared with magnesium alloy substrate, the impedance of silane/cerium salt Modified Membrane is significantly increased, this
It is consistent with the tafel Dependence Results in Fig. 5.
Fig. 7 schemes for the electrochemistry nyquist of the magnesium alloy coating of embodiment 1, and illustration is schemed for the nyquist of magnesium alloy substrate.
It can be seen from figure 7 that compared with magnesium alloy substrate, the capacitive reactance arc of silane/cerium salt Modified Membrane significantly becomes big, this with
Tafel Dependence Results in Fig. 5 are consistent.
Fig. 8 is the liberation of hydrogen figure of the magnesium alloy substrate of embodiment 1 and coating.
As shown in figure 8, with the extension of soak time, the liberation of hydrogen speed of magnesium alloy substrate first increases to be reduced afterwards, with leaching
The extension of bubble time, the generation and dissolving of corrosion product reach balance, and liberation of hydrogen speed tends to be steady.
Compared with the liberation of hydrogen speed of magnesium alloy substrate, the liberation of hydrogen speed of composite coating levels off to zero, in the time investigated
In the range of liberation of hydrogen data have no significant change, explanation：Composite coating provides long-effective protection for magnesium alloy substrate.
Fig. 9 be stereoscan photograph (multiplication factor is 2000 times) after the failure 7 days of the magnesium alloy coating of embodiment 1 and
EDS schemes.
As shown in Figure 9, it can be seen that the Mg alloy surface after soaking 7 days has no significant change, and EDS collection of illustrative plates also illustrate that
Silane and Mg (OH)2Coating still exists in magnesium alloy matrix surface, prevents the intrusion of corrosive ion, illustrates silane/cerium
Salt Modified Membrane can be with digital preservation magnesium alloy materials from corrosion, and this is consistent with Fig. 8 result.
Supplementary notes：Technical scheme for magnesium alloy substrates without particular/special requirement, except being enumerated in above-described embodiment
Outside, our experiences show that, in technical scheme, the trade mark of magnesium alloy can also be：Mg-0.5Ca、Mg-
The common commercially available prod such as 1Ca, Mg-1Li-1Ca-1Y, Mg-4Li-1Ca, Mg-4Li-1Ca-1Y or Mg-8Li-1Ca.
Claims (4)
1. a kind of preparation method of silane of magnesium/magnesium alloy base material-cerium salt-magnesium hydroxide composite coating, it is characterised in that including
Following steps：
The first step, magnesium/magnesium alloy base material pre-treatment step
Magnesium/magnesium alloy blank is taken, polishing removes the oxide layer on surface, and after being cleaned up with deionized water, 20-60 DEG C of warm wind blows
It is dry, it is standby；
Second step, the preparation of magnesium hydroxide coating
The above-mentioned magnesium/magnesium alloy base material by pretreatment is placed in hydrothermal reaction kettle, implantation quality percent concentration is 5%
Sodium hydroxide solution, until magnesium/magnesium alloy base material is submerged under liquid level completely；
Then, closure hydrothermal reaction kettle is placed in drying box, and 2~8h is incubated at 100~170 DEG C, is taken out, is used deionized water
Rinse and clean, obtaining surface deposition has the magnesium/magnesium alloy of magnesium hydroxide coating；
3rd step, the preparation of composite coating
400-800 in mass ratio:100-300:1200-1700:1-3 ratio, takes absolute ethyl alcohol, silane coupler, goes respectively
Ionized water and soluble cerium salt, it is standby；
Taken absolute ethyl alcohol is poured into container, silane coupler, deionized water is sequentially added, stirs 0.5-3 hours, is made into mixed
Close solution A；
Then, soluble cerium salt is added into mixed solution A, continues to stir 0.5-3 hours, obtains mixed solution B；
The magnesium/magnesium alloy that above-mentioned surface, which is deposited, magnesium hydroxide coating is placed in mixed solution B container, is immersed in liquid level
Under, it is placed in drying box, 2~3h is assembled at 50~70 DEG C；Take out, rinsed well with absolute ethyl alcohol, then be placed in baking oven,
Dry, produce at 100~150 DEG C.
2. the preparation method of the silane of magnesium/magnesium alloy base material according to claim 1-cerium salt-magnesium hydroxide composite coating,
Characterized in that, the thickness of obtained silane-cerium salt-magnesium hydroxide composite coating is 12-14 μm, the contact angle on surface is
151 °, corrosion potential be that -1.67V, corrosion current density are 2.46 × 10-8A/cm2。
3. the preparation method of the silane of magnesium/magnesium alloy base material according to claim 1-cerium salt-magnesium hydroxide composite coating,
Characterized in that, the silane is silane coupler, including N- octyltri-ethoxysilanes, γ propyltrimethoxy silane, first
Ethyl triethoxy silicane alkane, chloropropyl triethoxysilane, Y- glycidyl ether oxygen propyl trimethoxy silicanes, vinyl trimethoxy
Base silane, 3- aminopropyl trimethoxysilanes, dimethoxydiphenylsilane or MTMS；
The soluble cerium salt is cerous nitrate, cerous sulfate, cerous acetate or ammonium ceric nitrate.
4. the preparation method of the silane of magnesium/magnesium alloy base material according to claim 1-cerium salt-magnesium hydroxide composite coating,
Characterized in that, the magnesium alloy includes the following trade mark：AZ31、AZ91、AM50、Mg-0.5Ca、Mg-1Ca、Mg-1.5Ca、Mg-
1Li-1Ca, Mg-1Li-1Ca-1Y, Mg-4Li-1Ca, Mg-4Li-1Ca-1Y, Mg-8Li-1Ca or Mg-8Li-1Ca-Y.
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| CN107699885A (en) * | 2017-08-22 | 2018-02-16 | 山东科技大学 | A kind of preparation method of the magnesium hydroxide calcium phosphate composite coating of magnesium/magnesium alloy |
| CN112813468A (en) * | 2020-12-29 | 2021-05-18 | 葛卫江 | Preparation method of super-hydrophobic double-layer anti-corrosion coating |
| CN112877697A (en) * | 2020-12-21 | 2021-06-01 | 重庆大学 | Surface porous magnesium alloy and preparation method thereof |
| CN113073365A (en) * | 2021-03-25 | 2021-07-06 | 北京冬曦既驾科技咨询有限公司 | High-corrosion-resistance magnesium alloy electroplated layer and preparation method thereof |
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| CN107699885A (en) * | 2017-08-22 | 2018-02-16 | 山东科技大学 | A kind of preparation method of the magnesium hydroxide calcium phosphate composite coating of magnesium/magnesium alloy |
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| CN112813468A (en) * | 2020-12-29 | 2021-05-18 | 葛卫江 | Preparation method of super-hydrophobic double-layer anti-corrosion coating |
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| CN115522243A (en) * | 2022-11-03 | 2022-12-27 | 青岛理工大学 | Two-in-one adhesive epoxy coating and preparation method and application thereof |
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