CN1303248C - Method of surface treatment for magnesium and/or magnesium alloy, and magnesium and/or magnesium alloy product - Google Patents
Method of surface treatment for magnesium and/or magnesium alloy, and magnesium and/or magnesium alloy product Download PDFInfo
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- CN1303248C CN1303248C CNB028229444A CN02822944A CN1303248C CN 1303248 C CN1303248 C CN 1303248C CN B028229444 A CNB028229444 A CN B028229444A CN 02822944 A CN02822944 A CN 02822944A CN 1303248 C CN1303248 C CN 1303248C
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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
- C23C22/06—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 aqueous acidic solutions with pH less than 6
- C23C22/48—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 aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/57—Treatment of magnesium or alloys based thereon
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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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Abstract
A method of surface treatment for magnesium and/or a magnesium alloy, which comprises treating magnesium and/or the magnesium alloy with an aqueous chemical treatment solution A containing 0.001 to 10 mass % of a carbonate salt compound. The method of surface treatment combines the use of a treating agent which is substantially free of a substance harmful to the environment or a human body and a low electric resistance of the resulting coating film.
Description
Technical field
The present invention relates to give the parts that form by MAGNESIUM METAL and/or magnesium alloy and goods with the high erosion resistance and the adhering surface treatment method of filming.More specifically, the present invention relates to be applicable to the surface treatment method of following magnesium alloy component: the automobile component that need have the erosion resistance after high film adhesivity and the application; The tame electrical article that also need have electroconductibility except that above-mentioned performance is as TV and stereo set etc.; And resemble electronicss such as PC and mobile telephone.In addition, the invention provides the process for treating surface that is expected to be used for the biomaterial made by MAGNESIUM METAL, the advantage of this technology is, is formed at not contain harmful elements such as chromium, manganese in the lip-deep film.
Background technology
Many officials patent gazette, academic paper and professional book disclose the chemical conversion processing technology of MAGNESIUM METAL and/or magnesium alloy.Wherein, the most frequently used is the chromate treating technology.The chromate treating technology has been used to a variety of goods, and it can make the magnesium goods have the excellent erosion resistance and the adhesivity of filming.Yet chemical conversion is handled in the chemical conversion film of bathing and making thus and is contained sexavalent chrome, and this can cause disadvantageous effect to human body and environment.Therefore, in order to develop chemical conversion processing method without chromium, promptly so-called " technology is handled in the Chrome-free chemical conversion ", people have carried out a lot of researchs, the result develops phosphorylation processing, the chemical conversion processing of zirconium class and manganese class chemical conversion processing technology, wherein the part technology has obtained application in practice, and for example the spy opens disclosed technology in flat 8-35073 communique and the flat 7-126858 communique of Te Kai.
The phosphorylation treatment technology makes the erosion resistance of magnesium alloy and the adhesivity of filming obtain raising to a certain degree, but the degree that improves in many cases is not enough, and therefore, its application has been subjected to certain limitation.This is owing to when the surface of magnesium alloy being carried out the phosphorylation processing, produced water miscible MgHPO in formed chemical conversion film
4, therefore be difficult to form film with enough erosion resistances.Its defective also has desired treatment temp harshness and treatment time long, and phosphoric acid also is considered to cause the reason of environmental pollutions such as soil eutrophication.
It is to form oxyhydroxide, oxide compound and the phosphoric acid salt of zirconium at Mg alloy surface that the chemical conversion of zirconium class is handled, thereby has given magnesium alloy with the erosion resistance and the adhesivity of filming.Yet, to compare with chromate treating, the erosion resistance generation deterioration to a certain degree in the time can making not application is in some cases handled in the chemical conversion of zirconium class, thereby makes it and can not be used fully.Zirconium is a kind of rare elements, and it is high because of the scarcity price of originating.In addition, in order to make its stable existence in solution, use the form of its fluorine complexing ion in the practice usually, but owing to be difficult to avoid the pollution of fluorine like this, therefore from the angle of environmental protection, this treatment process is undesirable.
The technology suitable with the chromate treating effect is manganese class chemical conversion processing technology.This technology is divided into the processing of phosphoric acid class substantially and non-phosphoric acid class is handled.It is the magnesium alloy case surface-treated mainstream technology of current notebook computer that the chemical conversion of manganese class is handled.Yet although do not resemble strict the sexavalent chrome for the control of manganese, it also belongs to the material of control discharging.If in the future more strict for the emission regulation of manganese, its use will be restricted.
If carry out not using the chemical conversion of heavy metal to handle, then be difficult to make magnesium alloy to obtain equilibrium at the required physical properties of the magnesium alloy product aspects such as adhesivity, erosion resistance and resistance characteristic of promptly filming for improving the problems referred to above.Particularly, when being used to resemble the occasions such as shell of data-processing equipment such as PC and mobile telephone when this class treatment process,, must make Mg alloy surface keep low resistance value from preventing the angle of charged grade.Must not form the high chemical conversion of resistance value in its surface and handle film.Therefore, wish that this film averages out between resistance as described below and erosion resistance: 24 hours corrosion rate of salt spray testing is not more than 5%, and the membrane resistance value is not more than about 0.2 Ω, and salt spray testing did not take place by peeling off of film in 120 hours.
In addition, in some forming method of magnesium alloy product, the releasing agent that the metallic surface can be difficult to remove pollutes, thereby is difficult to obtain enough erosion resistances and the adhesivity of filming, even yet in this case, also must make this metallic surface have enough erosion resistances and the adhesivity of filming.
Summary of the invention
Prior art has shortcoming as noted above, and promptly prior art is used the material to environment and human body harmful such as sexavalent chrome, high manganese ion, phosphate anion, and the film of gained can not satisfy the requirement of adhesivity and erosion resistance aspect simultaneously.Therefore, the purpose of this invention is to provide the surface treatment method of MAGNESIUM METAL and/or magnesium alloy and magnesium and/or the magnesium alloy product that adopts described surface treatment method to handle, described method is used and is not contained the treatment agent to environment and human body harmful's material such as chromium and manganese in fact, but can form the chemical conversion of satisfying performance requriements and handle film, the film that obtains has high erosion resistance, the adhesivity of filming and high membrane resistance.
The present invention relates to the surface treatment method of magnesium and/or magnesium alloy, it is characterized in that, use the chemical conversion of the carbonate cpds that contains 0.001 quality %～10 quality % to handle the aqueous solution (A) processing magnesium and/or magnesium alloy.
Described chemical conversion is handled in the aqueous solution (A) and is also preferably contained the adhesion promoter of filming, and the described adhesion promoter of filming is one or more compounds in the group of being made up of triazine thiol compound, silane coupling agent and polyallylamine of being selected from of 0.01 quality %～1 quality %.
The surface treatment method of described magnesium and/or magnesium alloy also preferably uses and contains magnesium and/or the magnesium alloy that the second chemical conversion processing aqueous solution (B) processing of filming adhesion promoter is handled through the described chemical conversion processing aqueous solution (A), wherein, described second adhesion promoter of filming preferably is selected from least a compound in the group of being made up of triazine thiol compound, silane coupling agent and polyallylamine.
Described triazine thiol compound preferably is selected from least a compound in the group of being made up of following material: 1,3,5-triazines-2,4,6-three mercaptan, 2-(dibutylamino)-4,6-dimercapto-1,3,5-triazines and 2-(phenylamino)-4,6-dimercapto-1,3,5-triazines.
Described silane coupling agent preferably is selected from least a compound in the group of being made up of following material: N-(6-ammonia hexyl) aminopropyl trimethoxysilane, N-(6-ammonia hexyl) aminopropyl triethoxysilane, N-(6-ammonia hexyl) aminopropyl trichlorosilane, N-(2-aminoethyl)-3-aminopropyl triethoxysilane, N-(2-aminoethyl)-3-aminopropyl trimethoxysilane, N-(2-aminoethyl)-3-aminopropyl trichlorosilane, 3-aminopropyl Ethoxysilane and 3-aminopropyl methoxy silane.
The described preferably triazine thiol compound of adhesion promoter of filming, the described second preferably polyallylamine of adhesion promoter of filming.
Before carrying out described surface treatment, preferably carry out degreasing, pickling and detergency and handle pollutent and the segregation thing that is present in the surface to remove.
The invention still further relates to magnesium and/or magnesium alloy product that the surface treatment method that uses described magnesium and/or magnesium alloy was handled.
Embodiment
Describe the present invention below in detail.
The surface treatment method of magnesium of the present invention and/or magnesium alloy is the surface treatment method that a kind of use does not contain the treatment agent of heavy metal in fact.Also promptly, this is that a kind of use does not contain the MAGNESIUM METAL of the treatment agent of heavy metal compounds such as chromium, manganese, zirconium, titanium, the surface treatment method of magnesium alloy in fact, and often uses above-mentioned heavy metal compound in the surface treatment method of traditional MAGNESIUM METAL, magnesium alloy.
About the surface treatment method of above-mentioned magnesium and/or magnesium alloy, the meaning that treatment agent does not contain heavy metal in fact is not have a mind to add any heavy metal ion, also is that the content deficiency of heavy metal in the treatment agent is so that heavy metal shows its effect.
MAGNESIUM METAL and the magnesium alloy handled with the surface treatment method of magnesium of the present invention and/or magnesium alloy are MAGNESIUM METAL and the magnesium alloy that is made by methods such as calendering, die casting or the thixotroping methods of forming.MAGNESIUM METAL is expected to as biomaterial, from the angle of economy, it is believed that and uses to such an extent that meeting often is the pure metal magnesium of AZ31 alloy and 99.9% in the future.The present invention can be used for multiple magnesium alloy.Particularly preferred alloy has AZ91, AZ31, AM60 and AM50 etc.Mark AZ herein and AM refer to the metallic element that adds.A represents aluminium, and M represents manganese, and Z represents zinc.Numeral behind these marks is added the interpolation concentration of element, and for example, AZ91 represents that aluminium accounts for 9%, and zinc accounts for 1%.M represented that Mn content was lower than 1% at 0 o'clock.Be particularly suitable for using more than or equal to 5% alloy as aluminium content such as AZ91 and AM60.
Machine oil and releasing agent in the processing of MAGNESIUM METAL or magnesium alloy, have been used.Particularly in die casting or thixotroping moulding, releasing agent not only can remain in the surface of metal or alloy, and can remain in the dark place of 20～30 μ m, metal or alloy inside, sometimes also can be darker.Therefore, traditional surface treatment method only provides the erosion resistance and the adhesivity of filming after the inadequate application, yet surface treatment method of the present invention but can be given this MAGNESIUM METAL or magnesium alloy fully effectively with the enough erosion resistances and the adhesivity of filming.
The surface treatment method of magnesium of the present invention and/or magnesium alloy (calling surface treatment method in the following text) is that the method that the aqueous solution (A) is handled magnesium and/or magnesium alloy is handled in the chemical conversion of a kind of use carbonate cpds of containing 0.001 quality %～10 quality %.
Described surface treatment method is characterised in that, uses and contains the aqueous solution of carbanion or contain carbanion and the aqueous solution of the adhesion promoter of filming processing MAGNESIUM METAL and/or magnesium alloy.For the surface treatment method that does not use the adhesion promoter of filming, it in main points chemically is, in MAGNESIUM METAL or magnesium alloy can the alkaline solutions of stable existence, for example at the K of 1 quality %
2CO
3In the solution, make the pH of solution be about 11.5 (definite), and make reaction solution keep high temperature by measuring, thus the formation of promotes oxidn thing film, hydroxide film or the blend films of the two; And the reaction by magnesium and carbanion forms magnesiumcarbonate.
The source of described carbanion comprises various carbonate cpdss, for example Quilonum Retard, yellow soda ash, salt of wormwood and lime carbonate etc.Consider solvability and cost, preferably use yellow soda ash or salt of wormwood.This moment, the concentration of described carbonate cpds was 0.001 quality %～10 quality %, the solubility limit that this concentration also can show up to used carbonate cpds.The preferred 0.01 quality % of described concentration～10 quality %, more preferably 0.1 quality %～3 quality %.If be lower than 0.001 quality %, then erosion resistance and membrane resistance deficiency can further not improved above-mentioned effect even described concentration surpasses 10 quality % yet, and this is uneconomic.
Have no particular limits for the method for handling the aqueous solution (A) processing magnesium and/or magnesium alloy with described chemical conversion, for example can using, spraying, impregnating known method make the chemical conversion processing aqueous solution (A) contact with the surface of object being treated.For the processing of the goods that are applicable to complicated shapes such as PC shell, mobile phone outer casing, automobile component, preferably adopt pickling process to handle.
In described surface treatment method, to handle the temperature of bathing for described chemical conversion and have no particular limits, this temperature is generally more than or equal to 50 ℃, preferably 60～90 ℃ scope, more preferably 80～90 ℃ scope.When described temperature was lower than 50 ℃, the formation of oxide film was insufficient, thereby can not demonstrate good performance, so be not preferred.When described temperature surpasses 90 ℃, can increase waste, but can not further improve performance, so be not preferred as aspects such as evaporating solns and assurance thermals source.
In described surface treatment, preferred 1～5 minute of its treatment time.Treatment time, the formation of oxide film was insufficient when being less than 1 minute, thereby can not demonstrate good performance, so be not preferred.Treatment time is when surpassing 5 minutes, can increase the waste of keeping etc. the aspect as solution evaporation and thermal source, but can not further improve performance, so be not preferred.More preferably 3～5 minutes treatment time.
Even though when only using described carbonate cpds to handle, described surface treatment method also can be given MAGNESIUM METAL and/or magnesium alloy with enough adhesivityes of filming, after further adhesion promoter is filmed in interpolation, the stronger adhesivity of filming will be obtained.Particularly, under the situation of having used the releasing agent that is difficult to remove, perhaps not good when forming vesicular structure etc. because of flowing in the mould, can cause the quality of magnesium foundry goods bad, described surface treatment method also can provide good anti-corrosion and the adhesivity of filming for the bad magnesium foundry goods of such quality.
The adhesion promoter of filming that uses in the preferred described surface treatment method is selected from terminal silane coupling agent, triazine thiol compound and polyallylamine as amino.
As described silane coupling agent for example amino silane compounds such as N-(6-ammonia hexyl) aminopropyl trimethoxysilane, N-(6-ammonia hexyl) aminopropyl triethoxysilane, N-(6-ammonia hexyl) aminopropyl trichlorosilane, N-(2-aminoethyl)-3-aminopropyl triethoxysilane, N-(2-aminoethyl)-3-aminopropyl trimethoxysilane, N-(2-aminoethyl)-3-aminopropyl trichlorosilane, 3-aminopropyl Ethoxysilane and 3-aminopropyl methoxy silane are arranged.
Described triazine thiol compound is the compound that has triazine ring and thiol group simultaneously.The 1,3,5-triazines that preferred especially mercaptan replaces.In addition, described triazine thiol compound can have the triazine ring that is partly replaced by alkylamino.The example of described triazine thiol compound has 1,3,5-triazines-2,4,6-three mercaptan, 2-(dibutylamino)-4,6-dimercapto-1,3,5-triazines and 2-(phenylamino)-4,6-dimercapto-1,3,5-triazines etc.
Described polyallylamine is the polymkeric substance by following general formula (1) expression:
In the above general formula (1), polymerization degree n is preferably 10～1200.When the polymerization degree is too low, the adhesivity of can not being filmed significantly; When the polymerization degree is too high, can bring the problem of the stability deterioration of reactive bath technique.Described polyallylamine can use day eastern PAA series product (PAA-01, PAA-03, PAA-05, PAA-15, PAA-15B, PAA-10C, PAA-H-10C) that spin society etc.
The adhesion promoter of filming that can be used for described surface treatment method is not limited to above-mentioned substance, it can be following organic molecule, this organic molecular species is stable under alkaline environment, and it has the functional group favourable to the adhesivity of filming, and can be handled film absorption by chemical conversion of the present invention.
The concentration of the described adhesion promoter of filming is preferably 0.01 quality %～1 quality %.When this concentration is lower than 0.01 quality %, can not reach desired effect.On the other hand, when this concentration is higher than 1 quality %, can not further increase effect, this is disadvantageous economically.When having used described filming during adhesion promoter, carbonate concentration during described processing is bathed can be identical with above-mentioned concentration when only using processes of carbonate treatment, this concentration can be 0.001 quality %～10 quality %, preferred 0.01 quality %～10 quality %, more preferably 0.1 quality %～3 quality %.In addition, when using described filming during adhesion promoter, described chemical conversion handle the temperature of bathing more than or equal to 40 ℃ better, be preferably 60～90 ℃, more preferably 60～80 ℃.
As mentioned above, the surface treatment method of preferred magnesium of the present invention and/or magnesium alloy is, at first, handle the aqueous solution (A) with the chemical conversion that contains 0.001 quality %～10 quality % carbonate cpdss and handle magnesium and/or magnesium alloy, then, handle the aqueous solution (B) above-mentioned magnesium of processing and/or magnesium alloy with containing second chemical conversion of filming adhesion promoter.
Handle the processing of the aqueous solution (A) by described chemical conversion, formed the blend films of magnesium compounds such as containing magnesiumcarbonate, magnesium hydroxide and magnesium oxide in the metallic surface, can produce erosion resistance thus, the processing again by the described chemical conversion processing aqueous solution (B) subsequently can further improve erosion resistance and the adhesivity of filming.Handle again by using described chemical conversion to handle the aqueous solution (B), on the blend films of described magnesium compound, formed the organic molecule adsorption layer, this organic molecule adsorption layer is made up of the described adhesion promoter and second of the filming adhesion promoter of filming, infer thus, the formation of described organic molecule adsorption layer has further improved erosion resistance, has increased the adhesivity of filming with MAGNESIUM METAL, Mg alloy surface simultaneously.In addition, because the blend films of described magnesium compound is a kind of film as thin as a wafer of molecular level, it gives MAGNESIUM METAL or magnesium alloy with the erosion resistance and the adhesivity of filming, but can significantly not damage its electroconductibility.
Handle the further processing of the aqueous solution (B) by described chemical conversion, even be difficult to carry out the object being treated that sufficient chemical conversion is handled for only using described chemical conversion to handle the aqueous solution (A), the bad magnesium foundry goods of quality that has for example adhered to releasing agent securely also can carry out sufficient chemical conversion and handle.
For using described chemical conversion to handle the situation that the aqueous solution (B) is for further processing, preferred described chemical conversion is handled the pH value of the aqueous solution (A) more than or equal to 10.The pH value is when this scope, and the chemical conversion of described employing carbonate cpds is handled and reacted and can effectively carry out, and can guarantee to realize high efficiency chemical conversion processing.Described pH value is more preferably greater than equaling 11.In addition, there is no particular limitation for the upper limit of pH value, but preferably smaller or equal to 13.
For using described chemical conversion to handle the situation that the aqueous solution (B) is for further processing, can handle the basic cpd that adds in the aqueous solution (A) as the pH regulator agent in described chemical conversion, so that the pH value is controlled in the above-mentioned scope.Have no particular limits for described basic cpd, it can be for example lithium hydroxide, sodium hydroxide, potassium hydroxide and ammonia.
Described second adhesion promoter of filming preferably is selected from least a compound in the group of being made up of triazine thiol compound, silane coupling agent and polyallylamine.Filming as second for these, there is no particular limitation for triazine thiol compound, silane coupling agent and the polyallylamine of adhesion promoter, and it can be for example above-mentioned compound that can be used as the described adhesion promoter of filming.
When using the triazine thiol compound to film adhesion promoter as described second, to handle in the aqueous solution (B) in described chemical conversion, the content of described triazine thiol compound is preferably in the scope of 10ppm～10000ppm.When being lower than 10ppm, can not obtain sufficient erosion resistance, when surpassing 10000ppm, can not further improve effect, this is disadvantageous economically.Above-mentioned lower limit more preferably is 100ppm, more preferably 500ppm.The above-mentioned upper limit more preferably is 5000ppm, more preferably 2000ppm.
When using amino silane compounds to film adhesion promoter as described second, to handle in the aqueous solution (B) in described chemical conversion, the content of described amino silane compounds is preferably in the scope of 10ppm～10000ppm.When the content of this compound is lower than 10ppm, can not obtain sufficient erosion resistance, when surpassing 10000ppm, can not further improve effect, this is disadvantageous economically.Above-mentioned lower limit more preferably is 100ppm, more preferably 500ppm.The above-mentioned upper limit more preferably is 5000ppm, more preferably 2000ppm.
When using polyallylamine to film adhesion promoter as described second, to handle in the aqueous solution (B) in described chemical conversion, the content of described polyallylamine is preferably in the scope of 50ppm～10000ppm.When being lower than 50ppm, can not obtain sufficient erosion resistance, when surpassing 10000ppm, can not further improve effect, this is disadvantageous economically.Above-mentioned lower limit more preferably is 100ppm, more preferably 500ppm.The above-mentioned upper limit more preferably is 5000ppm, more preferably 3000ppm.
Described second adhesion promoter of filming can be and the identical compound of the described adhesion promoter of filming, but in order to obtain the adhesion facilitation effect of better filming, preferably with the different compound of the described adhesion promoter of filming.
From increasing adhering angle, described film adhesion promoter and described second combination of filming adhesion promoter are preferably: the described adhesion promoter of filming is the triazine thiol compound, and described second adhesion promoter of filming is amino silane compounds or polyallylamine; Perhaps, the described adhesion promoter of filming is an amino silane compounds, and described second adhesion promoter of filming is a polyallylamine.Wherein, most preferred being combined as, the described adhesion promoter of filming is the triazine thiol compound, and described second adhesion promoter of filming is a polyallylamine.
Have no particular limits for the treatment process that adopts described chemical conversion to handle the aqueous solution (B), it can be for example to spray or impregnating makes chemical conversion handle the known method that the aqueous solution (B) contacts with the surface of object being treated.Effectively carry out in order to make described second chemical conversion handle reaction, described chemical conversion is handled the temperature of the aqueous solution (B) preferably in 40～80 ℃ scope.When this temperature was lower than 40 ℃, the formation of film was insufficient, thereby can not demonstrate good performance, so be not preferred.When temperature surpasses 80 ℃, can increase the waste of keeping etc. the aspect as solution evaporation and thermal source, but can not further improve performance, so be not preferred.More preferably 50 ℃ of above-mentioned lower limits, more preferably 60 ℃ of the above-mentioned upper limits.
In the surface treatment method of magnesium of the present invention and/or magnesium alloy,, preferably before carrying out described surface treatment, carry out degreasing, pickling and detergency and handle in order to handle effectively.For example, when the surface of object being treated with inside is all residual when releasing agent is arranged, must remove the releasing agent and the machine oil on object being treated surface.When preparing by the MAGNESIUM METAL of machine oil and releasing agent severe contamination, when magnesium alloy is handled, difference according to its pollution level, the step and the condition of removing described releasing agent and other pollutents are different, and the order of general step is degreasing → washing → acid etching → washing → detergency → washing.
In described defatting step, the general alkaline defatting agent aqueous solution that contains tensio-active agent that uses.The purpose of this step is to remove machine oil or the releasing agent that adheres on the object being treated surface.Have no particular limits for used grease-removing agent.Under the little situation of pollution level, it is just enough only to carry out this defatting step, but does so not enough in many cases, also need carry out acid etching usually.
The purpose of described acid etching step is to remove the machine oil of metal, the inhomogenous oxide skin of alloy surface, object being treated surface attachment and the releasing agent that infiltrates metal, alloy inside by dissolving.If the removal of these materials is insufficient, then can not obtain enough erosion resistances and the adhesivity of filming.In addition, although there is no need to remove fully releasing agent,, then can have a negative impact to the erosion resistance and the adhesivity of filming if the removal of releasing agent is too insufficient.Particularly, when by releasing agent when seriously polluted, this step is essential and important.
As the acid that is used for described acid etching step, can be mineral acids such as phosphoric acid, sulfuric acid, nitric acid, and organic acid such as oxalic acid, acetate.The concentration of acid is preferably 0.1～5g/l in the described acid etching solution, more preferably 0.3～1g/l.When this concentration is lower than 0.1g/l, rise because of the dissolving of magnesium makes the pH value, thereby increased the exchange frequency of solution, this is not preferred.When its concentration surpasses 5g/l, cause MAGNESIUM METAL, magnesium alloy significantly to dissolve, thereby hydrogen is acutely taken place.This can cause damage to metal, alloy surface, so be not preferred.In addition, when high density carboxylic acid that use to surpass 5g/l or phosphoric acid, oxalate or phosphoric acid salt can be separated out from the teeth outwards, thereby can not fully remove releasing agent.Even these acid also are effectively as oxalic acid and nitric acid when using separately, but the mixing acid of general preferred use acid more than 2 kinds or 2 kinds.For example can advantageously use the combination of sulfuric acid and nitric acid or the combination of phosphoric acid and silicofluoric acid etc.
In described detergency step, have no particular limits, can advantageously use with the aqueous solution of basic cpds such as KOH or NaOH as main component.The purpose of this step is to remove the surface deposits that is produced by acid etching, and removes the aluminium that goes out at the metal or alloy surface segregation, and removes the releasing agent around the aluminium that goes out attached to described segregation.
The MAGNESIUM METAL that the described surface treatment method of process is handled, the shell that magnesium alloy product can be suitable for use as mobile telephone and PC and cover plate etc.This magnesium alloy product has also constituted one aspect of the present invention.
The surface treatment method of magnesium of the present invention and/or magnesium alloy is handled the aqueous solution (A) with the chemical conversion that contains 0.001 quality %～10 quality % carbonate cpdss and is handled magnesium and/or magnesium alloy, thereby can on the surface of magnesium and/or magnesium alloy, form the film of the mixture of magnesium compound, so can obtain excellent erosion resistance, the adhesivity of filming and electroconductibility.In addition, handle the aqueous solution (A) when described chemical conversion and further contain when filming adhesion promoter, can further improve erosion resistance and the adhesivity of filming.
In addition, in described surface treatment method, when containing second chemical conversion of filming adhesion promoter, further use handles the aqueous solution (B) when handling, not only can form the blend films of described magnesium compound on the surface of object being treated, and can form the adsorption layer of water-soluble organic molecule.So the blend films of described magnesium compound provides higher erosion resistance, and described water-soluble organic molecule adsorption layer also provides the high adhesivity of filming when further providing good anti-corrosion.Whereby, even be difficult to carry out bad MAGNESIUM METAL, the magnesium alloy of quality that sufficient chemical conversion is handled, also can carry out sufficient chemical conversion by this method and handle for handle the aqueous solution (A) with described chemical conversion.In addition, because the blend films of formed magnesium compound is the film as thin as a wafer of molecular level, so the resistance value of treated MAGNESIUM METAL, Mg alloy surface does not significantly increase.Also promptly, handle the aqueous solution (B) by this further use chemical conversion and carry out the method that chemical conversion is handled, can obtain excellent more erosion resistance, the adhesivity of filming and electroconductibility.
Embodiment
Below by embodiment the present invention is described in further detail, but the present invention is not limited to these embodiment.In addition, if not explanation is arranged in addition, " part " in following examples all refers to " mass parts ".
Embodiment 1
The magnesium alloy AZ91D test plate (panel) that with thickness is the thixotroping moulding of 2mm carries out degreasing, washing, acid etching, washing, detergency, washing under the following conditions successively, chemical conversion is handled and washing, carries out powder coating after the drying.Water-washing step adopts the tap water spray, and other steps all adopt impregnation method to handle.With electric drying apparatus 100 ℃ of dryings 20 minutes.
(A) degreasing
Treatment solution: the Magdine SF100 sanitising agent (Nippon Paint Co., Ltd's system) of 1 quality %
Treatment temp: 50 ℃
Treatment time: 2 minutes
(B) acid etching
Treatment solution: the Magdine SF400 acid etching (Nippon Paint Co., Ltd's system) of 1 volume %
Treatment temp: 50 ℃
Treatment time: 10 minutes
(C) detergency
Treatment solution: the Magdine SF300 alkaline etching of 5 volume %
Treatment temp: 60 ℃
Treatment time: 5 minutes
(D) chemical conversion is handled
Treatment solution: the wet chemical of 1 quality %
PH value: 11.5
Treatment temp: 80 ℃
Treatment time: 5 minutes
The test plate (panel) that employing obtains, the resistance that the erosion resistance when estimating not application by the following method, chemical conversion are filmed, the erosion resistance after the application and the adhesivity of filming, the result is as shown in table 1.
The erosion resistance during application not
Salt spray testing: test plate (panel) is sprayed 48 hours shared ratios of post-etching part of visual assessment at 35 ℃ of salt solutions with 5%.
The resistance of chemical conversion film
Use surface resistivity determinator EP-T360 (Keyence corporate system), measure 9 points of chemical conversion film, remove maximum value and minimum value by two probe method, with the mean value of 7 points as described resistance value.
Erosion resistance after the application
With Magdine PD-E (epoxy resin powder coating, Nippon Paint Co., Ltd's system) application test plate (panel), making dry film thickness is 40 μ m, makes coated plate in 20 minutes 160 ℃ of bakings.With metal cutter cross cut, score reaches base metal deeply, carries out salt spray testing then, after 120 hours, sticks adhesive tape at the cross cut position and peels off then, according to the width evaluation of filming that is stripped from.
The adhesivity of filming
(1) test plate (panel) of described powder coating is carried out 120 hours salt spray testing, the cut-space with 1mm on the test plate (panel) that takes out goes out 100 grids, sticks adhesive tape and peels off then.Estimate by checking remaining number of squares.
(2) test plate (panel) with described powder coating soaked 120 hours in 50 ℃ warm water.Cut-space with 1mm on the test plate (panel) that takes out goes out 100 grids, sticks adhesive tape and peels off then.Estimate by measuring remaining number of squares.
Embodiment 2
Adopt method similarly to Example 1 to make test plate (panel), difference is, chemical conversion treatment solution used among the embodiment 1 is changed into the wet chemical of 0.1 quality %.In addition, adopt method similarly to Example 1 to make test plate (panel), difference is, adopts and thickness that the adhesivity of filming is relatively poor is that the die cast magnesium alloy AZ91D test plate (panel) of 1mm replaces that thickness is the thixotroping moulding magnesium alloy AZ91D test plate (panel) of 2mm among the embodiment 1.Then, estimate according to the method identical with embodiment 1, the result is as shown in table 1.
Embodiment 3
Adopt method similarly to Example 1 to make test plate (panel), difference is, the treatment temp among the embodiment 1 is become 60 ℃.Then, estimate according to the method identical with embodiment 1, the result is as shown in table 1.
Embodiment 4
Adopt method similarly to Example 1 to make test plate (panel), difference is, changes chemical conversion treatment solution used among the embodiment 1 into the unsaturated carbonate calcium aqueous solution (concentration 0.0014 quality %).Then, estimate according to the method identical with embodiment 1, the result is as shown in table 1.
Embodiment 5
Adopt method similarly to Example 1 to make test plate (panel), difference is, the chemical conversion treatment solution among the embodiment 1 is changed into the wet chemical of 5 quality %.Then, estimate according to the method identical with embodiment 1, the result is as shown in table 1.
Embodiment 6
With thickness is that the die cast magnesium alloy AZ91D test plate (panel) of 1mm immerses chemical conversion as follows and handles and bathe, thereby makes test plate (panel).Wherein, film adhesivity and the erosion resistance of die cast magnesium alloy AZ91D test plate (panel) are relatively poor.Then, estimate according to the method identical with embodiment 1, the result is as shown in table 1.Except that having carried out following chemical conversion processing, all the other steps are identical with embodiment 1 with condition.
(A) chemical conversion is handled: the K of 1 quality %
2CO
3With the 1,3,5-triazines-2,4 of 0.1 quality %, the aqueous solution of 6-three mercaptan.
pH：11.5
Treatment temp: 80 ℃
Treatment time: 2 minutes
Embodiment 7
Adopt method similarly to Example 6 to make test plate (panel), difference is, the triazine thiol concentration of bathing is handled in the chemical conversion among the embodiment 6 become 1 quality %.Then, estimate according to the method identical with embodiment 1, the result is as shown in table 1.
Embodiment 8
Adopt method similarly to Example 6 to make test plate (panel), difference is, the triazine thiol concentration of bathing is handled in the chemical conversion among the embodiment 6 become 0.01 quality %.Then, estimate according to the method identical with embodiment 1, the result is as shown in table 1.
Embodiment 9
Adopt method similarly to Example 6 to make test plate (panel), difference is, the temperature of bathing is handled in the chemical conversion among the embodiment 6 become 60 ℃.Then, estimate according to the method identical with embodiment 1, the result is as shown in table 1.
Embodiment 10
Adopt method similarly to Example 6 to make test plate (panel), difference is, the chemical conversion among the embodiment 6 is handled bathed the K that changes 1 quality % into
2CO
3The aqueous solution with N-(2-aminoethyl)-3-aminopropyl trimethoxysilane of 0.1 quality %.Then, estimate according to the method identical with embodiment 1, the result is as shown in table 1.
Comparative example 1
Adopt method similarly to Example 1 to make test plate (panel), difference is, the aqueous solution that uses 20% commodity manganous phosphate treatment agent Magdine SF572 (Nippon Paint Co., Ltd's system) replaces the chemical conversion among the embodiment 1 to handle 50 ℃ of dip treating 2 minutes with this.Then, estimate according to the method identical with embodiment 1, the result is as shown in table 1.
Comparative example 2
Adopt method similarly to Example 1 to make test plate (panel), difference is, the aqueous solution that uses 5% commodity zirconium phosphate treatment agent Alsurf 440 (Nippon Paint Co., Ltd's systems) replaces the chemical conversion among the embodiment 1 to handle 50 ℃ of dip treating 2 minutes with this.Then, estimate according to the method identical with embodiment 1, the result is as shown in table 1.
Comparative example 3
Adopt method similarly to Example 1 to make test plate (panel), difference is, uses deionized water 80 ℃ of dip treating 2 minutes, replaces the chemical conversion among the embodiment 1 to handle with this.Then, estimate according to the method identical with embodiment 1, the result is as shown in table 1.
Comparative example 4
Adopt method similarly to Example 1 to make test plate (panel), difference is, the chemical conversion treatment solution among the embodiment 1 is changed into the potassium hydroxide aqueous solution of 1 quality %.Then, estimate according to the method identical with embodiment 1, the result is as shown in table 1.
Comparative example 5
Adopt method similarly to Example 6 to make test plate (panel), difference is that the salt of wormwood that the chemical conversion of embodiment 6 is handled in bathing changes potassium hydroxide into.Then, estimate according to the method identical with embodiment 1, the result is as shown in table 1.
Table 1
| Object being treated (magnesium alloy) | The resistance value of filming (Ω) | The erosion resistance (%) during application not | Erosion resistance after the application (mm) | The adhesivity of filming | ||
| Brine spray | Warm water immersion | |||||
| Embodiment 1 | A | ≤0.1 | 0 | 0 | 100 | 100 |
| Embodiment 2 | A | ≤0.1 | 0 | 0 | 100 | 100 |
| B | ≤0.1 | 5 | 2 | 90 | 86 | |
| Embodiment 3 | A | ≤0.1 | 1 | 0 | 100 | 100 |
| Embodiment 4 | A | ≤0.1 | 1 | 0 | 100 | 100 |
| Embodiment 5 | A | ≤0.1 | 0 | 3 | 100 | 100 |
| Embodiment 6 | B | ≤0.1 | 1 | 0 | 100 | 100 |
| Embodiment 7 | B | ≤0.1 | 1 | 0 | 100 | 100 |
| Embodiment 8 | B | ≤0.1 | 3 | 0 | 100 | 100 |
| Embodiment 9 | B | ≤0.1 | 2 | 0 | 100 | 100 |
| Embodiment 10 | B | ≤0.2 | 3 | 1 | 100 | 100 |
| Comparative example 1 | A | ≤0.2 | 2 | 0 | 100 | 100 |
| Comparative example 2 | A | ≤0.1 | 2 | 0 | 100 | 100 |
| Comparative example 3 | A | ≤0.07 | 10 | 10 | 77 | 63 |
| Comparative example 4 | A | ≤0.07 | 10 | 10 | 100 | 100 |
| Comparative example 5 | A | ≤0.1 | 10 | 10 | 90 | 68 |
A: thickness is the magnesium alloy AZ91D test plate (panel) of the thixotroping moulding of 2mm
B: thickness is the magnesium alloy AZ91D test plate (panel) of the die casting of 1mm
Above result shows, by the surface treatment method of magnesium of the present invention and/or magnesium alloy, the magnesium alloy base material has had excellent erosion resistance, the adhesivity of filming and electroconductibility.When the wet chemical that uses 0.1 quality % during as chemical conversion treatment solution (embodiment 2), the treatment effect comparison thickness that to thickness is the die cast magnesium alloy AZ91D test plate (panel) of 1mm is that the treatment effect of thixotroping moulding magnesium alloy AZ91D test plate (panel) of 2mm is slightly poor, but when adding triazine thiol compound or amino silane compounds (embodiment 6～10) again in this treatment solution, treatment effect has obtained obvious improvement.
Embodiment 11
Will (this test plate (panel) pollutes more serious than embodiment 6 used test plate (panel)s by the magnesium alloy test plate (panel) of thixotroping moulding, thereby being difficult to carry out chemical conversion and handling) the Personal Computer shell made carries out successively under the following conditions that degreasing, washing, acid etching, washing, detergency, washing, first chemical conversion are handled, washing, second chemical conversion is handled and washing, carries out powder coating (operation example 1) after the drying.Wash by the tap water spray, other each steps are all carried out in the mode of dip treating.With electric drying apparatus 100 ℃ of dryings 20 minutes.The releasing agent severe contamination that is difficult to remove as the Personal Computer shell of object being treated is so be difficult to provide erosion resistance and the adhesivity of filming for it.
(A) degreasing
With embodiment 1.
(B) acid etching
With embodiment 1.
(C) detergency
With embodiment 1.
(D) first chemical conversion is handled
Treatment solution: the salt of wormwood of 1 quality % and the 1,3,5-triazines of 100ppm-2,4, the aqueous solution of 6-three mercaptan
pH：11.5
Treatment temp: 80 ℃
Treatment time: 2 minutes
(E) second chemical conversion is handled
The polyallylamine of treatment solution: 2000ppm (spin society and produce, PAA-5, aqueous solution n=87.7) by day east
Treatment temp: 60 ℃
Treatment time: 2 minutes
Estimate erosion resistance, the resistance of chemical conversion film, erosion resistance application after and the film adhesivity of gained test plate (panel) when the application not with following method, the result is as shown in table 2.
The erosion resistance during application not
Salt spray testing: at 35 ℃ of salt solutions test plate (panel) was sprayed 8 hours continuously, estimate erosion resistance with staging subsequently with 5%.
The resistance of chemical conversion film
Adopt method similarly to Example 1 to estimate.
Erosion resistance after the application
Adopt method similarly to Example 1 to estimate.
The adhesivity of filming
(1) adopt with above-mentioned application after the identical method of corrosion resistance test method, the test plate (panel) that passes through powder coating is carried out 72 hours salt spray testing, take out this test plate (panel), on this film, mark 100 grids that are spaced apart 1mm, peel off after sticking adhesive tape.Estimate by checking residual number of squares.
(2) adopt with above-mentioned application after the identical method of corrosion resistance test method, will in 50 ℃ deionized water, flood 72 hours through the test plate (panel) of powder coating.Take out this test plate (panel) subsequently, on this film, mark 100 grids that are spaced apart 1mm, stick adhesive tape and peel off then.Estimate by checking residual number of squares.
Embodiment 12～15
Adopt the chemical conversion of proportioning as shown in table 2 to handle the aqueous solution (A) and the chemical conversion processing aqueous solution (B), under condition shown in the table 2, adopt method similarly to Example 11 that magnesium alloy is carried out surface treatment.The result is as shown in table 2.In embodiment 12～14, the 1 described order of the operation example among the embodiment 11 changed into carry out that degreasing, washing, acid etching, washing, first chemical conversion are handled, washing, second chemical conversion is handled and washing, carries out powder coating step (operation example 2) after the drying.In addition, in embodiment 15, adopt the method identical to handle with embodiment 6.
Table 2
| Embodiment 11 | Embodiment 12 | Embodiment 13 | Embodiment 14 | Embodiment 15 | |||
| Object being treated (magnesium alloy) (1) | C | C | C | C | C | ||
| The aqueous solution is handled in first chemical conversion | Salt of wormwood (quality %) | 1 | 0.1 | 0.1 | 0.1 | 1 | |
| 1,3,5-triazines-2,4,6-three mercaptan (ppm) | 100 | 100 | - | 100 | 100 | ||
| Amino silane compounds (2)(ppm) | - | - | 100 | - | - | ||
| Potassium hydroxide (ppm) | - | 100 | 100 | 100 | - | ||
| Trimagnesium phosphate is a chemical conversion treatment solution (3)(quality %) | - | - | - | - | - | ||
| pH | 11.5 | 12.5 | 12.5 | 12.5 | 11.5 | ||
| Treatment temp (℃) | 80 | 80 | 80 | 80 | 80 | ||
| Treatment time (minute) | 2 | 5 | 5 | 5 | 2 | ||
| The aqueous solution is handled in second chemical conversion | Polyallylamine (ppm) | 2000 | 2000 | 2000 | - | - | |
| Amino silane compounds (1)(ppm) | - | - | - | 2000 | - | ||
| Treatment temp (℃) | 60 | 60 | 60 | 60 | - | ||
| Treatment time (minute) | 2 | 2 | 2 | 2 | - | ||
| The result | Membrane resistance value (Ω) | ≤0.1 | ≤0.1 | ≤0.1 | ≤0.1 | ≤0.1 | |
| The erosion resistance (%) during application not | 1 | 1 | 1 | 1 | 10 | ||
| Erosion resistance after the application (mm) | 0 | 0 | 0 | 0 | 2 | ||
| The adhesivity of filming | Brine spray | 100 | 100 | 100 | 100 | 97 | |
| Warm water immersion | 100 | 100 | 100 | 100 | 88 | ||
(1) C is the magnesium alloy test plate (panel) (this test plate (panel) pollutes more serious than embodiment 6 used test plate (panel)s, handle so be difficult to carry out chemical conversion) of thixotroping moulding
(2) N-(6-ammonia hexyl) aminopropyl trimethoxysilane
(3) the Magdine SF570 of Nippon Paint Co., Ltd's production
Result by table 2 is clear that, the surface treatment method that adopts magnesium of the present invention and/or magnesium alloy is when (comprising the method that further use second chemical conversion treatment solution is handled), and treated magnesium alloy has excellent erosion resistance, the adhesivity of filming and electroconductibility.As 1 of salt of wormwood that uses 1 quality % and 100ppm, 3,5-triazine-2,4, during the aqueous solution of 6-three mercaptan (embodiment 15), compare with the treatment effect that to thickness is the die cast magnesium alloy AZ91D test plate (panel) of 1mm, (pollute more serious to thixotroping moulding magnesium alloy test plate (panel) than embodiment 6 used test plate (panel)s, thereby the test plate (panel) that is difficult to carry out the chemical conversion processing) treatment effect is slightly poor, but when further using the chemical conversion that contains polyallylamine to handle the aqueous solution (B) (embodiment 11) when handling, treatment effect has obtained obvious improvement.
Industrial applicibility
The surface treatment method of magnesium of the present invention and/or magnesium alloy does not use the harmful substances such as chromium and manganese, compare with the effect of using manganese phosphate to process, method of the present invention can make magnesium metal and/or magnesium alloy have identical or better corrosion resistance and the adhesiveness of filming, and these performances and film resistance value are adapted, thereby decrease on the impact of environment and human body. In addition, because method of the present invention can be used existing chromate treatment facility or contain the chemical conversion treatment facility of manganese material, therefore need not to invest at equipment. In addition, when adopting infusion process to process, method of the present invention also is fit to process such as complex-shaped goods such as personal computer shell, mobile phone outer casing, auto parts and components.
Claims (6)
1. the surface treatment method of magnesium and/or magnesium alloy, this method comprises, use contains the carbonate cpds of 0.001 quality %～10 quality % and pH to be handled water solution A greater than 10 chemical conversion and handles under the condition that the temperature of bathing is higher than 50 ℃ in chemical conversion and handle magnesium and/or magnesium alloy, wherein, described carbonate cpds is a Quilonum Retard, yellow soda ash or salt of wormwood, and described chemical conversion is handled water solution A and is also contained the adhesion promoter of filming, and the described adhesion promoter of filming is being selected from by the triazine thiol compound of 0.01 quality %～1 quality %, end is amino silane coupling agent, at least a compound in the group of forming with polyallylamine.
2. the surface treatment method of magnesium as claimed in claim 1 and/or magnesium alloy, this method comprises, handle magnesium and/or the magnesium alloy that aqueous solution B handles the processing of the described chemical conversion processing of process water solution A with containing second chemical conversion of filming adhesion promoter, wherein said second films adhesion promoter for being selected from by handling aqueous solution B based on described chemical conversion separately, and the triazine thiol compound of 10-10000ppm, the end of 10-10000ppm be at least a compound in the group of polyallylamine composition of the silane coupling agent of amino and 50-10000ppm.
3. the surface treatment method of magnesium as claimed in claim 1 or 2 and/or magnesium alloy, wherein, described triazine thiol compound is at least a compound that is selected from the group of being made up of following material: 1,3,5-triazine-2,4,6-three mercaptan, 2-(dibutylamino)-4,6-dimercapto-1,3,5-triazine and 2-(phenylamino)-4,6-dimercapto-1,3, the 5-triazine.
4. the surface treatment method of magnesium as claimed in claim 1 or 2 and/or magnesium alloy, wherein, described end is at least a compound that is selected from the group of being made up of following material: N-(6-ammonia hexyl) aminopropyl trimethoxysilane for amino silane coupling agent, N-(6-ammonia hexyl) aminopropyl triethoxysilane, N-(6-ammonia hexyl) aminopropyl trichlorosilane, N-(2-aminoethyl)-3-aminopropyl triethoxysilane, N-(2-aminoethyl)-3-aminopropyl trimethoxysilane, N-(2-aminoethyl)-3-aminopropyl trichlorosilane, 3-aminopropyl Ethoxysilane and 3-aminopropyl methoxy silane.
5. the surface treatment method of magnesium as claimed in claim 2 and/or magnesium alloy, wherein, the described adhesion promoter of filming is the triazine thiol compound, described second adhesion promoter of filming is a polyallylamine.
6. the surface treatment method of magnesium as claimed in claim 1 or 2 and/or magnesium alloy is characterized in that, before carrying out described surface treatment, carries out degreasing, pickling and detergency and handles pollutent and the segregation thing that is present in the surface to remove.
Applications Claiming Priority (2)
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| JP356048/2001 | 2001-11-21 | ||
| JP2001356048 | 2001-11-21 |
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| KR (1) | KR20050044515A (en) |
| CN (1) | CN1303248C (en) |
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| CN101173353B (en) * | 2006-10-31 | 2010-05-12 | 佛山市顺德区汉达精密电子科技有限公司 | Magnesium alloy surface chemistry passivation technology |
| CN102154637A (en) * | 2011-05-18 | 2011-08-17 | 沈阳工业大学 | Surface treatment method for magnesium alloy |
| JP5727543B2 (en) * | 2013-04-23 | 2015-06-03 | 住友電気工業株式会社 | Magnesium-based metal member and method for producing magnesium-based metal member |
| CN103397325A (en) * | 2013-07-08 | 2013-11-20 | 光钰科技（临沂）有限公司 | Method for performing anticorrosive treatment on surface of magnesium alloy with recovered carbon dioxide |
| CN110129802A (en) * | 2019-06-18 | 2019-08-16 | 博敏电子股份有限公司 | A kind of printed board novel antioxidant and its application |
| CN113584470A (en) * | 2021-07-30 | 2021-11-02 | 重庆理工大学 | Magnesium-lithium alloy surface anticorrosion treatment method |
| CN114875396B (en) * | 2022-04-28 | 2023-03-14 | 厦门大学 | Surface treatment method of magnesium or magnesium alloy |
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| JPH06116740A (en) * | 1992-10-05 | 1994-04-26 | Mitsui Mining & Smelting Co Ltd | Surface treatment of magnesium alloy product |
| WO2000040777A1 (en) * | 1999-01-07 | 2000-07-13 | Otsuka Kagaku Kabushiki Kaisha | Surface-treating agent for magnesium-based part and method of surface treatment |
| CN1268582A (en) * | 1999-03-30 | 2000-10-04 | 米隆化学股份有限公司 | Chemical surface treatment liquid composition for magnesium contd. metallic material, surface treatment method and surface treatment matter thereof |
| JP2001049459A (en) * | 1999-08-02 | 2001-02-20 | Gunze Ltd | Pretreating method for magnesium molded body |
| CN1302341A (en) * | 1998-03-17 | 2001-07-04 | 松下电器产业株式会社 | Surface-treated article of magnesium or magnesium alloy, method of surface preparation and method of coating |
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|---|---|---|---|---|
| JPS55148766A (en) * | 1979-05-11 | 1980-11-19 | Hitachi Ltd | Surface treatment of magnesium or magnesium alloy |
| JP3286583B2 (en) * | 1997-10-31 | 2002-05-27 | ミリオン化学株式会社 | Chemical conversion treatment composition for magnesium-containing metal, surface treatment method and surface treatment product |
| WO2000050666A1 (en) * | 1999-02-25 | 2000-08-31 | Hosaka Inc. | Method for treating magnesium-based metal formed article and treating solution therefor |
-
2002
- 2002-11-21 WO PCT/JP2002/012146 patent/WO2003044243A1/en active Application Filing
- 2002-11-21 KR KR1020047007550A patent/KR20050044515A/en not_active Application Discontinuation
- 2002-11-21 CN CNB028229444A patent/CN1303248C/en not_active Expired - Fee Related
- 2002-11-21 TW TW091133907A patent/TW200300802A/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06116740A (en) * | 1992-10-05 | 1994-04-26 | Mitsui Mining & Smelting Co Ltd | Surface treatment of magnesium alloy product |
| CN1302341A (en) * | 1998-03-17 | 2001-07-04 | 松下电器产业株式会社 | Surface-treated article of magnesium or magnesium alloy, method of surface preparation and method of coating |
| WO2000040777A1 (en) * | 1999-01-07 | 2000-07-13 | Otsuka Kagaku Kabushiki Kaisha | Surface-treating agent for magnesium-based part and method of surface treatment |
| CN1268582A (en) * | 1999-03-30 | 2000-10-04 | 米隆化学股份有限公司 | Chemical surface treatment liquid composition for magnesium contd. metallic material, surface treatment method and surface treatment matter thereof |
| JP2001049459A (en) * | 1999-08-02 | 2001-02-20 | Gunze Ltd | Pretreating method for magnesium molded body |
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| CN1589337A (en) | 2005-03-02 |
| KR20050044515A (en) | 2005-05-12 |
| TW200300802A (en) | 2003-06-16 |
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