CN106048580A - Zirconium-manganese-vanadium passive film treating agent for die cast aluminium alloy and treatment method thereof - Google Patents
Zirconium-manganese-vanadium passive film treating agent for die cast aluminium alloy and treatment method thereof Download PDFInfo
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- CN106048580A CN106048580A CN201610522418.8A CN201610522418A CN106048580A CN 106048580 A CN106048580 A CN 106048580A CN 201610522418 A CN201610522418 A CN 201610522418A CN 106048580 A CN106048580 A CN 106048580A
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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
- C23C22/40—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 containing molybdates, tungstates or vanadates
- C23C22/44—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 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
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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
- C23C22/40—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 containing molybdates, tungstates or vanadates
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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
- C23C22/78—Pretreatment of the material to be coated
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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
- C23C22/82—After-treatment
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Abstract
The invention discloses a passive film treating agent for die cast aluminium alloy and a treatment method thereof. The passive film treating agent for die cast aluminium alloy comprises the following components in parts by mass: 1 to 20 parts of inorganic acid, 1 to 20 parts of zirconate, 1 to 20 parts of vanadate, 1 to 20 parts of manganate, 1 to 20 parts of calciate and 0.2 to 10 parts of an activating agent. Relative to a traditional phosphorus-containing chromium-free passive film treating agent for die cast aluminium alloy, which causes pollution to the environment, the passive film treating agent for die cast aluminium alloy can form a phosphorus-free chromium-free Zr-Mn-V passive film on the surface of die cast aluminium alloy, the passive film has the advantages that the adhesive force is good, the corrosion resistance is high, and the salt mist resistance and film forming uniformity are good, and besides, the obtained passive film can be guaranteed to have a silver white metal appearance the same as the die cast aluminium alloy.
Description
Technical field
The present invention relates to surface passivated membrane processing technology field, particularly relate to a kind of passivating film for pack alloy
Inorganic agent and processing method thereof.
Background technology
At present, pack alloy is one of widest non-ferrous metal structural material in commercial Application, owing to it can be pressed
The workpiece that type casting moulding is variously-shaped, reduces the high cost of CNC artistic carving, widely applies the most in the industry.Especially ADC12
The pack alloy of model, its performance is more excellent.Such as, the smart mobile phone shell that uses in daily life, smart mobile phone
In middle plate, panel computer shell, panel computer, plate, notebook computer casing, automobile audio power amplifier etc. all it is frequently necessary to make
With die-cast aluminum alloy material, e.g., use the die-cast aluminum alloy material of ADC12 model.
Further, the chemical passivation film of pack alloy processes is indispensable in die-cast aluminum alloy material pre-treating technology
Few important step, by forming passivating film on pack alloy surface, for strengthening the surface property of die-cast aluminum alloy material,
As, strengthen its corrosion-resistant, resistance to oxidation and salt spray resistance.Common, need to use pack alloy passivating film inorganic agent pair
After die-cast aluminum alloy material processes, pack alloy passivating film can be formed on die-cast aluminum alloy material surface.
But, traditional pack alloy passivating film inorganic agent usually contains Cr VI and/or trivalent chromium, in processing procedure
In, the waste water of discharge can contain harmful Cr VI and trivalent chromium.Owing to the compound of all chromium is the most toxic, its
In chromic toxicity maximum, Cr VI carcinogenecity is strong, and chromic toxicity is much smaller relative to for Cr VI, but, poison
Property less trivalent chromium and the violent Cr VI of toxicity in using and preserving can inversion of phases mutually, same serious harm human body is good for
Health and whole world biology are healthy.
Therefore, research and development pack alloy chemical passivation film inorganic agent and Chrome-free pack alloy passivating film processing method are one
The task that part is the most urgent, has profound significance to environmental conservation.
Summary of the invention
Based on this, it is necessary to provide a kind of enable to pack alloy Surface Creation chromium-free passivating film for die casting aluminium
The passivating film inorganic agent of alloy and processing method thereof.
A kind of passivating film inorganic agent for pack alloy, it is characterised in that include each component of following mass parts:
Wherein in an embodiment, described mineral acid includes at least in nitric acid, sulphuric acid, Fluohydric acid. and fluorine zirconic acid
Kind.
Wherein in an embodiment, described zirconates includes in potassium fluorozirconate, ammonium fluozirconate and sodium fluozirconate at least
A kind of.
Wherein in an embodiment, described vanadate includes in ammonium metavanadate, sodium metavanadate and potassium metavanadate at least
A kind of.
Wherein in an embodiment, described manganate includes at least one in manganese carbonate, manganese nitrate and manganese sulfate.
Wherein in an embodiment, described calciate includes at least one in calcium chloride, calcium carbonate and calcium nitrate.
Wherein in an embodiment, described activating agent includes sodium lauryl sulphate, dodecylbenzene sodium sulfonate and 2-
At least one in ethylhexyl sulfate.
A kind of passivating film processing method for pack alloy, comprises the steps:
Pack alloy is put into degreasing agent carries out degreasing degreasing process；
Described pack alloy after described degreasing degreasing processes is put into and etchant is etched process；
Put into whiten by the described pack alloy after described etch processes and agent is carried out whiten process；
By through described whiten process after described pack alloy put into bleach carry out bleaching；
Described pack alloy after described bleaching is put into the passivating film inorganic agent for pack alloy
In carry out chemical passivation film process, for described pack alloy surface formed passivating film, wherein, described for die casting aluminium close
The passivating film inorganic agent of gold includes each component of following mass parts: mineral acid 1 part～20 parts；Zirconates 1 part～20 parts；Vanadate
1 part～20 parts；Manganate 1 part～20 parts；Calciate 1 part～20 parts；Activating agent 0.2 part～10 parts；
Described pack alloy after described chemical passivation film processes is carried out drying and processing.
Wherein in an embodiment, after described degreasing degreasing processes, before described etch processes；After described etch processes,
Described whiten process before；Described whiten process after, before described bleaching；After described bleaching, at described chemical passivation film
Before reason；And after described chemical passivation film processes, before described drying and processing, the most also comprise the steps: described die casting aluminium is closed
Gold carries out adverse current water washing operations.
Wherein in an embodiment, described drying and processing is carried out at a temperature of 80 DEG C～90 DEG C.
Wherein in an embodiment, described drying and processing continues 10 minutes～25 minutes.
Relative to traditional phosphorous Chrome-free passivating film inorganic agent for pack alloy of environmental pollution can be caused, above-mentioned
For pack alloy passivating film inorganic agent by use mineral acid 1 part～20 parts；Zirconates 1 part～20 parts；Vanadate 1 part
～20 parts；Manganate 1 part～20 parts；Calciate 1 part～20 parts；Activating agent 0.2 part～10 parts.Can be on pack alloy surface
Form without phosphorus Chrome-free Zr-Mn-V passivating film, and passivating film has adhesive force degree good, corrosion-resistant height, salt spray resistance and one-tenth
The advantage that film uniformity is good.And it is able to ensure that the passivating film obtained keeps the silvery white metal identical with pack alloy self
Outward appearance.
Accompanying drawing explanation
Fig. 1 is the flow chart of steps of the passivating film processing method for pack alloy of an embodiment of the present invention.
Detailed description of the invention
Understandable, below in conjunction with the accompanying drawings to the present invention for enabling the above-mentioned purpose of the present invention, feature and advantage to become apparent from
Detailed description of the invention be described in detail.Elaborate a lot of detail in the following description so that fully understanding this
Bright.But the present invention can implement to be much different from alternate manner described here, and those skilled in the art can be not
Doing similar improvement in the case of running counter to intension of the present invention, therefore the present invention is not limited by following public specific embodiment.
The passivating film inorganic agent for pack alloy of one embodiment, including each component of following mass parts:
The passivating film inorganic agent for pack alloy of another embodiment, including each component of following mass parts:
The passivating film inorganic agent for pack alloy of another embodiment, including each component of following mass parts:
In order to preferably play the chemical passivation film process performance of the described passivating film inorganic agent for pack alloy, example
As, the described passivating film inorganic agent for pack alloy uses at a temperature of 25 DEG C～35 DEG C, as such, it is possible to preferably send out
Wave the chemical passivation film process performance of the described passivating film inorganic agent for pack alloy.
In order to improve the passivating film obtained after the described passivating film inorganic agent for pack alloy processes pack alloy
Adhesive force, corrosion-resistant degree, passivating film corrosion after produce metal ion carry out with pack alloy again metal bonding from
Repairing performance, salt spray resistance and one-tenth film uniformity, and guarantee that the described passivating film obtained keeps or close and die casting aluminium
The silvery white metal appearance that alloy self is identical, such as, described mineral acid includes in nitric acid, sulphuric acid, Fluohydric acid. and fluorine zirconic acid
At least one；And for example, described mineral acid includes nitric acid, sulphuric acid, Fluohydric acid. and fluorine zirconic acid；And for example, described nitric acid, sulphuric acid, hydrogen fluorine
Acid and the mass ratio (1～2.5) of fluorine zirconic acid: (1～1.5): (1～2.5): (1～2)；And for example, described mineral acid includes Fluohydric acid.
With fluorine zirconic acid, e.g., the mass ratio of Fluohydric acid. and fluorine zirconic acid is 1:(0.5～0.55), so, Fluohydric acid. and fluorine zirconic acid are playing erosion
Outside effect at quarter, it is also possible to provide zr element for zirconium-manganese-vanadium (Zr-Mn-V) passivating film, be conducive to improving the performance of passivating film；
In such manner, it is possible to improve the attached of the described passivating film obtained after the passivating film inorganic agent process pack alloy of pack alloy
Put forth effort, corrosion-resistant degree, passivating film corrosion after produce metal ion carry out the selfreparing of metal bonding with pack alloy again
Performance, salt spray resistance and one-tenth film uniformity, and guarantee that the described passivating film obtained keeps or close and pack alloy
The silvery white metal appearance that self is identical.
In order to improve the passivating film obtained after the described passivating film inorganic agent for pack alloy processes pack alloy
Adhesive force, corrosion-resistant degree, passivating film corrosion after produce metal ion carry out with pack alloy again metal bonding from
Repairing performance, salt spray resistance and one-tenth film uniformity, and guarantee that the described passivating film obtained keeps or close and die casting aluminium
The silvery white metal appearance that alloy self is identical, such as, described zirconates includes in potassium fluorozirconate, ammonium fluozirconate and sodium fluozirconate
At least one；And for example, described zirconates includes potassium fluorozirconate, ammonium fluozirconate and sodium fluozirconate；And for example, potassium fluorozirconate, fluorine zirconium
The mass ratio of acid ammonium and sodium fluozirconate is (1～1.5): (1～2.7): (1～3.4)；And for example, described zirconates is ammonium fluozirconate
With the mass ratio of sodium fluozirconate, ammonium fluozirconate and sodium fluozirconate is 1:(0.57～0.66), as such, it is possible to improve described use
Passivating film inorganic agent in pack alloy processes the adhesive force of passivating film obtained after pack alloy, corrosion-resistant degree, blunt
Change the metal ion produced after erosion carry out with pack alloy again the self-healing properties of metal bonding, salt spray resistance and
Become film uniformity, and guarantee that the described passivating film obtained keeps or close to the silvery white metal identical with pack alloy self
Outward appearance.
In order to improve the passivating film obtained after the described passivating film inorganic agent for pack alloy processes pack alloy
Adhesive force, corrosion-resistant degree, passivating film corrosion after produce metal ion carry out with pack alloy again metal bonding from
Repairing performance, salt spray resistance and one-tenth film uniformity, and guarantee that the described passivating film obtained keeps or close and die casting aluminium
The silvery white metal appearance that alloy self is identical, such as, described vanadate includes in ammonium metavanadate, sodium metavanadate and potassium metavanadate
At least one；And for example, described vanadate includes ammonium metavanadate, sodium metavanadate and potassium metavanadate；And for example, ammonium metavanadate, inclined vanadium
The mass ratio of acid sodium and potassium metavanadate is (1～2.3): (1～2.7): (1～3.6)；And for example, described vanadate is ammonium metavanadate
With the mass ratio of sodium metavanadate, ammonium metavanadate and sodium metavanadate is 1:(0.47～0.61), as such, it is possible to improve described use
Passivating film inorganic agent in pack alloy processes the adhesive force of passivating film obtained after pack alloy, corrosion-resistant degree, blunt
Change the metal ion produced after erosion carry out with pack alloy again the self-healing properties of metal bonding, salt spray resistance and
Become film uniformity, and guarantee that the described passivating film obtained keeps or close to the silvery white metal identical with pack alloy self
Outward appearance.
In order to improve the passivating film obtained after the described passivating film inorganic agent for pack alloy processes pack alloy
Adhesive force, corrosion-resistant degree, passivating film corrosion after produce metal ion carry out with pack alloy again metal bonding from
Repairing performance, salt spray resistance and one-tenth film uniformity, and guarantee that the described passivating film obtained keeps or close and die casting aluminium
The silvery white metal appearance that alloy self is identical, such as, described manganate includes in manganese carbonate, manganese nitrate and manganese sulfate at least
A kind of；And for example, described manganate includes manganese carbonate, manganese nitrate and manganese sulfate；And for example, the matter of manganese carbonate, manganese nitrate and manganese sulfate
Amount ratio is (1～3.5): (1～2.3): (2.1～2.5)；And for example, described manganate is manganese nitrate and manganese sulfate, manganese nitrate and sulfur
The mass ratio of acid manganese is 1:(0.44～0.75), process as such, it is possible to improve the described passivating film for pack alloy
The metal ion produced after the corrosion of the adhesive force of passivating film that agent obtains after processing pack alloy, corrosion-resistant degree, passivating film
Carry out the self-healing properties of metal bonding, salt spray resistance again with pack alloy and become film uniformity, and guaranteeing to obtain
Described passivating film keep or close to the silvery white metal appearance identical with pack alloy self.
In order to improve the passivating film obtained after the described passivating film inorganic agent for pack alloy processes pack alloy
Adhesive force, corrosion-resistant degree, passivating film corrosion after produce metal ion carry out with pack alloy again metal bonding from
Repairing performance, salt spray resistance and one-tenth film uniformity, and guarantee that the described passivating film obtained keeps or close and die casting aluminium
The silvery white metal appearance that alloy self is identical, such as, described calciate includes in calcium chloride, calcium carbonate and calcium nitrate at least
A kind of；And for example, described calciate includes calcium chloride, calcium carbonate and calcium nitrate；And for example, the matter of calcium chloride, calcium carbonate and calcium nitrate
Amount ratio is (1～3.5): (1～2.3): (2.1～2.5)；And for example, described calciate includes calcium carbonate and calcium nitrate, calcium carbonate and
The mass ratio of calcium nitrate is 1:(0.54～0.75), as such, it is possible to improve described at the passivating film of pack alloy
The metal that reason agent produces after processing the adhesive force of passivating film obtained after pack alloy, corrosion-resistant degree, passivating film corrosion from
Son carries out the self-healing properties of metal bonding, salt spray resistance again and becomes film uniformity with pack alloy, and guarantees
The described passivating film arrived keeps or close to the silvery white metal appearance identical with pack alloy self.It should be noted that it is logical
Cross and add described calciate the film forming of passivating film can be made more uniform, i.e. flatness is higher, and passivating film is to pack alloy table
The adhesive force in face is good.
In order to improve the passivating film obtained after the described passivating film inorganic agent for pack alloy processes pack alloy
Adhesive force, corrosion-resistant degree, passivating film corrosion after produce metal ion carry out with pack alloy again metal bonding from
Repairing performance, salt spray resistance and one-tenth film uniformity, and guarantee that the described passivating film obtained keeps or close and die casting aluminium
The silvery white metal appearance that alloy self is identical, such as, described activating agent includes sodium lauryl sulphate, DBSA
At least one at least one in sodium and sodium 2-ethylhexyl sulfate；And for example, described activating agent includes lauryl sulphate acid
Sodium, dodecylbenzene sodium sulfonate and sodium 2-ethylhexyl sulfate；And for example, sodium lauryl sulphate, dodecylbenzene sodium sulfonate and
The mass ratio of sodium 2-ethylhexyl sulfate is (1～1.5): (1～1.7): (2～3.5)；As such, it is possible to improve described use
Passivating film inorganic agent in pack alloy processes the adhesive force of passivating film obtained after pack alloy, corrosion-resistant degree, blunt
Change the metal ion produced after erosion carry out with pack alloy again the self-healing properties of metal bonding, salt spray resistance and
Become film uniformity, and guarantee that the described passivating film obtained keeps or close to the silvery white metal identical with pack alloy self
Outward appearance.
It should be noted that prior art is disclosed the inorganic agent for pack alloy zirconates chromium-free passivating film, this work
It is poor that skill does passivating film salt spray resistance for aluminum and aluminum alloy surface, is typically only capable to reach salt spray resistance 2 hours～8 hours, it is more difficult to
Reach industry requirement, as reached the salt spray resistance requirement in 24 hours～48 hours.Therefore, this inorganic agent or use this process
The process limitation of agent is bigger, it is more difficult to be applied to the big production of industry.Owing to, in some industrial circles, it requires pack alloy
The surface passivated membrane of material keeps or close to himself silvery white metal appearance, therefore, in the conventional technology, develops die casting
Aluminium alloy true qualities height salt spray resistance chromium-free passivating film difficulty bigger.The above-mentioned passivating film inorganic agent for pack alloy, i.e. uses
In pack alloy Chrome-free Zr-Mn-V height salt spray resistance passivating film inorganic agent, can thoroughly replace in the big production of industry at present (containing sexavalence
Chromium and trivalent chromium) aluminium alloy passivating film inorganic agent.
The above-mentioned passivating film inorganic agent for pack alloy can carry out surface process to pack alloy, is used for being formed
Chrome-free Zr-Mn-V passivating film, such as, passes sequentially through defat-wash-etch-wash-whiten (i.e. environmental protection is drawn white)-washing-bleaching
After (i.e. environmental protection bleaching)-passivating film processes the steps such as (chromium-free deactivation) washing drying, it is used for forming Chrome-free Zr-Mn-V passivation
Film, so, the Chrome-free Zr-Mn-V passivating film of formation has fully met aluminum or/and alloy product anticorrosion in the industrial production
Erosion performance and the appearance requirement of application.When the above-mentioned passivating film inorganic agent for pack alloy is applied to the big production of industry, complete
The discharge of wastewater trivalent chromium murder by poisoning to human body in tradition pack alloy trivalent chromium true qualities passivator all can be solved, because all chromium
Compound the most toxic, the most chromic toxicity is maximum.Chromic toxicity is much smaller relative to for Cr VI, but
Trivalent chromium that toxicity is less and the violent Cr VI of toxicity can inversion of phasess mutually in using and preserving.Therefore, above-mentioned for pressing
The passivating film inorganic agent of cast aluminium alloy is conducive to whole world environmental protection.Process through the above-mentioned passivating film inorganic agent for pack alloy
After die-cast aluminum alloy workpiece corrosion resistance of surface high, coating and matrix adhesive force are good.Can ban completely current industrial in a large number
Traditional pack alloy trivalent chromium true qualities passivator of application.
Be appreciated that the surface passivated membrane of pack alloy in the environment that there is corrosion factor, e.g., at acid or alkali environment
Under, the surface passivated membrane of pack alloy can be corroded, generation zirconium, manganese and/or vanadium metal ion, under external force, and these
Metal ion can leave passivating film body, say, that said process is the corrosion of the surface passivated membrane of pack alloy and damages
Consumption process, in order to improve the decay resistance of the surface passivated membrane of pack alloy, the gold especially produced after passivating film corrosion
Belong to ion and carry out the self-healing properties of metal bonding, the above-mentioned passivating film inorganic agent for pack alloy again with pack alloy
Use mineral acid 1 part～20 parts, zirconates 1 part～20 parts, vanadate 1 part～20 parts, manganate 1 part～20 parts, calciate 1 part
～20 parts, activating agent 0.2 part～10 parts, for forming without phosphorus Chrome-free Zr-Mn-V passivating film on pack alloy surface, in employing
State the passivating film with Zr-Mn-V (zirconium-manganese-vanadium) system that each component of each mass parts is formed, without the heavy metal such as chromium and nickel
Element, more friendly to environment, film layer compactness extent is higher, stronger with the adhesion on the surface of pack alloy.Especially needed finger
Going out, the passivating film with Zr-Mn-V (zirconium-manganese-vanadium) system using each component of above-mentioned each mass parts to be formed is placed in tool
Have in the environment of corrosion factor, although, the passivating film of above-mentioned Zr-Mn-V (zirconium-manganese-vanadium) system also can be the most rotten
Erosion, and produce zirconium, manganese and/or vanadium metal ion, but, above-mentioned passivating film zirconium, manganese and/or the vanadium metal of the generation that is corroded
Ion can be with parent metal, i.e. the aluminium element with pack alloy re-starts metal bonding, for repairing to a certain extent
The passivating film being corroded again, i.e. use that each component of above-mentioned each mass parts formed has Zr-Mn-V (zirconium-manganese-vanadium) system
Passivating film has self-healing properties.Additionally, above-mentioned passivating film is tested in 5% neutral salt spray test of 24～48 hours
After, and test result is qualified.
It is pointed out that the pack alloy of ADC12 model contains aluminum (Al) surplus, copper (Cu) 1.5～3.5, silicon
(Si) 9.6～12.0, magnesium (Mg)≤0.3, zinc (Zn)≤1.0, ferrum (Fe)≤1.3, manganese (Mn)≤0.5, nickel (Ni)≤0.5, stannum
(Sn)≤0.3, calcium (Ca)≤200ppm, lead (Pb)≤0.1, cadmium (Cd)≤0.005, it can be seen that the die casting aluminium of ADC12 model
Alloy contains larger amount of element silicon and copper, when the above-mentioned passivating film inorganic agent for pack alloy is to ADC12 model
Pack alloy be passivated film process after, and the pack alloy surface of ADC12 model formed Zr-Mn-V passivating film,
This Zr-Mn-V passivating film have more excellent adhesive force, corrosion-resistant degree, passivating film corrosion after produce metal ion again with pressure
Cast aluminium alloy carries out the self-healing properties of metal bonding, salt spray resistance and becomes film uniformity.
In order to preferably produce after pack alloy surface forms adhesive force degree good, corrosion-resistant height, passivating film corrosion
Metal ion carry out that the self-healing properties of metal bonding is good, salt spray resistance is good and becomes film uniformity again with pack alloy
Good Zr-Mn-V passivating film, such as, the passivating film inorganic agent for pack alloy of another embodiment, including following matter
Each component of amount part:
So, it is good, resistance to that each component using such as upper and lower mass parts can form well adhesive force on pack alloy surface
The metal ion that extent of corrosion is high, passivating film produces after corroding carries out the self-healing properties of metal bonding with pack alloy again
Zr-Mn-V passivating film good, that salt spray resistance is good and one-tenth film uniformity is good.
Further, the passivating film inorganic agent for pack alloy of another embodiment, each including following concentration
Component:
It is appreciated that when Fluohydric acid. and fluorine zirconic acid are respectively 1.5 grams per liters～10 grams per liters and 1.2 grams per liters～8.1 grams per liters
Time, pack alloy surface filming speed is moderate, and passivating film densification is smooth, and salt fog resistance is good；Dense when Fluohydric acid. and fluorine zirconic acid
When spending the most within the above range, pack alloy surface liberation of hydrogen excessive velocities or the slowest, film forming is coarse loose porous, salt fog resistance
Can be poor.
When ammonium fluozirconate and sodium fluozirconate are respectively 2.2 grams per liters～7.7 grams per liters and 0.5 grams per liter～10 grams per liter, blunt
The decay resistance changing film is preferable；When ammonium fluozirconate and sodium fluozirconate concentration the most within the above range time, film forming is uneven, resistance to
Erosion property is poor.
When ammonium metavanadate and sodium metavanadate are respectively 0.8 grams per liter～6.3 grams per liters and 4.1 grams per liters～10 grams per liter, blunt
The decay resistance changing film is preferable；When ammonium metavanadate and sodium metavanadate be not in above-mentioned concentration range, passivating film is in film forming mistake
, easily there is the uneven problem with corrosion-resistant of film layer in Cheng Zhong.
When manganese carbonate and manganese nitrate are respectively 1.2 grams per liters～8 grams per liters and 5.4 grams per liters～6.9 grams per liter, passivating film
Corrosion resistance is preferable；When manganese carbonate and manganese nitrate be not in above-mentioned concentration range, passivating film salt spray resistance is poor, has a strong impact on pressure
The passivating film surface on the cast aluminium alloy surface adhesive force to coating.
When calcium chloride and calcium carbonate are respectively 0.7 grams per liter～9.5 grams per liters and 1.3 grams per liters～8.5 grams per liter, passivating film
Fine and close smooth, uniform ground, salt fog resistance is good, enables in particular to strengthen the passivating film surface adhesive force to coating；When calcium chloride and
When calcium carbonate is not in above-mentioned concentration range, passivating film salt spray resistance is poor, and film layer loosens coarse, attached to coating of film surface
Put forth effort poor.
The passivating film inorganic agent for pack alloy described in any of the above-described embodiment is for pack alloy surface
After chemical passivation film processes, it is possible to the metal ion that formation adhesive force is good, passivating film produces after corroding enters with pack alloy again
The self-healing properties degree good, corrosion-resistant of row metal bonding is high, salt spray resistance and become the passivating film that film uniformity is good.
Relative to traditional phosphorous Chrome-free passivating film inorganic agent for pack alloy of environmental pollution can be caused, above-mentioned
For pack alloy passivating film inorganic agent by use mineral acid 1 part～20 parts；Zirconates 1 part～20 parts；Vanadate 1 part
～20 parts；Manganate 1 part～20 parts；Calciate 1 part～20 parts；Activating agent 0.2 part～10 parts.Can be on pack alloy surface
Form without phosphorus Chrome-free Zr-Mn-V passivating film, and passivating film has adhesive force degree good, corrosion-resistant height, salt spray resistance and one-tenth
The advantage that film uniformity is good.And it is able to ensure that the passivating film obtained keeps the silvery white metal identical with pack alloy self
Outward appearance.
Such as, in the passivating film inorganic agent for pack alloy described in any of the above-described embodiment, also include water, be used for
Other compositions in the passivating film inorganic agent for pack alloy described in dissolving；Such as, it is used for pressing described in use after dilution
The passivating film inorganic agent of cast aluminium alloy；And for example, the passivating film inorganic agent for pack alloy described in any of the above-described embodiment
In, also include 100 parts～200 parts of water；And for example, 200 parts～1000 parts of water is also included.Such as, described pack alloy Zr-Mn-V
Passivating film, refers to that described aluminum passivation film or aluminium alloy passivating film contain Zr, Mn and V element, i.e. contains zr element, manganese element and vanadium
Element, say, that pack alloy passivating film is the passivating film of Zr-Mn-V system.
In order to make the above-mentioned passivating film inorganic agent for pack alloy preferably form attachment on pack alloy surface
The without phosphorus Chrome-free Zr-Mn-V passivating film that power degree good, corrosion-resistant height, salt spray resistance and one-tenth film uniformity are good, and used
In optimizing passivation membrane treatment process, such as, also provide for the passivating film processing method for pack alloy, as follows:
Refer to Fig. 1, for the passivating film processing method of pack alloy in an embodiment, comprise the steps:
S110: described pack alloy is put in degreasing agent and carry out degreasing degreasing process.
It is appreciated that such as, pack alloy semi-finished product or die-cast aluminum alloy workpiece exist it is contemplated that pack alloy
During die cast, in order to the die-cast aluminum alloy workpiece after making molding is easily separated from mould, it is necessary to spray certain demoulding
Agent, i.e. mould release, e.g., oil-based release agent, it sticks on die-cast aluminum alloy workpiece surface, and traditional degreasing agent is difficult to clean
Falling, this is very big on follow-up etch effect impact, can make die-cast aluminum alloy workpiece appearance uneven color, also can make follow-up
In operation, passivating film color is the most inconsistent, is removed by releasing agent accordingly, it would be desirable to use degreasing degreasing to process.
However, it is contemplated that die-cast aluminum alloy workpiece all easy corrosive chameleon in acidity and alkaline environment solution, in die casting
Degreasing degreasing process, traditional acidity and alkaline degreasing powder all must be carried out to aluminum alloy surface before the passivation of Al alloy parts true qualities
The most all phenomenons of some corrosive chameleon, when using traditional true qualities passivator, the true qualities that are the most relatively hard to keep passivation effect,
In order to make die-cast aluminum alloy workpiece surface be not easy corrosive chameleon and preferably remove the releasing agent on pack alloy surface, example
As, the degreasing agent of an embodiment, including each component of following concentration:
Wherein, JFC penetrating agent is fatty alcohol-polyoxyethylene ether.
The degreasing system being appreciated that sodium citrate+sodium carbonate+sodium tetraborate+OP emulsifying agent is alkalescence neutral or on the weak side,
Even if die-cast aluminum alloy workpiece soaks in described degreasing agent for a long time, die-cast aluminum alloy workpiece surface also will not variable color, and not
There will be excessive erosion problem, it is ensured that follow-up true qualities or the passivating film treatment process close to true qualities can be smoothed out.Sodium citrate+
The alkalescence of sodium carbonate+sodium tetraborate is on the weak side, i.e. three's synergism, can slowly etch pack alloy table in skimming processes
Face, thus loosen the releasing agent on pack alloy surface, the beneficially surface uniform in road etching under die-cast aluminum alloy workpiece
Cause.Add sodium tetraborate and can preferably protect die-cast aluminum alloy workpiece, it is to avoid by excessive erosion, be particularly advantageous for protecting die casting aluminium
Alloy workpiece has the place of screwed hole, it is to avoid bigger than normal after being etched.
In order to preferably carry out degreasing degreasing process, such as, described degreasing degreasing processes 55 DEG C～the temperature strip of 70 DEG C
Carry out under part；And for example, described degreasing degreasing processes and continues 3 minutes～8 minutes, so, can preferably carry out at degreasing degreasing
Reason.
S120: the described pack alloy after described degreasing degreasing processes is put into and is etched place in etchant
Reason.
In order to play preferably etch effect, and in etching process, to guarantee the uniformity coefficient of etching and to avoid
Overetched problem, such as, the etchant of an embodiment occur, including each component of following concentration:
Sodium hydroxide 50 grams per liter～100 grams per liters；
Sodium carbonate 50 grams per liter～100 grams per liters；
Sodium gluconate 5 grams per liter～10 grams per liters.
In order to preferably be etched processing, such as, described etch processes is carried out under the temperature conditions of 40 DEG C～50 DEG C；
And for example, described etching continues 30 seconds～50 seconds, so, can preferably be etched processing.
S130: put into whiten by the described pack alloy after described etch processes and carry out in agent whitening process.
It is contemplated that die-cast aluminum alloy workpiece surface inherently has the region of oxidized corrosion before non-defat, in order to enter
One step disposes oxide skin, to guarantee that chromium-free passivating film processes being smoothed out of operation, for improving salt spray resistance effect further,
Therefore, after etching work procedure, in order to remove the oxide pushing down aluminum alloy surface further, need to increase after etching work procedure one
Road whitens operation, to remove the oxide on surface before Al alloy parts is not passivated.
Whiten effect to improve further, and remove the effect of pack alloy oxide on surface, an embodiment
Whiten agent, including each component of following mass parts:
Agent is whitened described in each component of as above mass parts, it is possible to increase whiten effect, and remove die casting by using
The effect of aluminum alloy surface oxide, and avoid the problem generation of excessive erosion.
It should be noted that whiten agent relative to tradition nitric acid+hydrofluoric acid system, wherein traditional pH value whitening agent is less than
1, use as above mass parts each component whiten agent, its pH value ≈ 2.5, it is possible to avoid during whitening, produce substantial amounts of
Yellow acid mist, and to more environment-friendly.But, whiten agent can solve the problem that yellow is harmful to the volatilization problems of acid mist although above-mentioned, but
It is inevitably can not to be dissolved in the above-mentioned residual dirt whitening agent at die-cast aluminum alloy workpiece remained on surface aluminium fluoride etc., because of
This, need above-mentioned whiten process operation after, be further added by one bleaching process for removing the residual dirts such as aluminium fluoride.
In order to preferably carry out whitening process, such as, whiten process described in carry out under the temperature conditions of 15 DEG C～30 DEG C；
And for example, described in whiten process continue 8 seconds～15 seconds, so, can preferably carry out whitening process.
S140: by through described whiten process after described pack alloy put into bleach carry out bleaching.
By the bleaching of S140, it is possible to by due to have employed without acid mist volatilization to whiten the aluminium fluoride etc. that agent produces residual
Dirt dissolves and removes.
In order to preferably remove the residual dirts such as aluminium fluoride, such as, the bleach of an embodiment, each including following mass parts
Component:
So, the bleach of as above each component of mass parts is used, it is possible to preferably remove the residual dirts such as aluminium fluoride, and can also
The problem enough avoiding excessive erosion.
S150: the described pack alloy after described bleaching is put at the passivating film of pack alloy
Reason agent carries out chemical passivation film process, for forming passivating film on described pack alloy surface, wherein, described for die casting
The passivating film inorganic agent of aluminium alloy includes each component of following mass parts: mineral acid 1 part～20 parts；Zirconates 1 part～20 parts；Vanadium
Hydrochlorate 1 part～20 parts；Manganate 1 part～20 parts；Calciate 1 part～20 parts；Activating agent 0.2 part～10 parts.
Relative to causing the tradition of the environmental pollution passivating film inorganic agent for pack alloy containing chromium, above-mentioned for
The passivating film inorganic agent of pack alloy is by using mineral acid 1 part～20 parts；Zirconates 1 part～20 parts；Vanadate 1 part～20
Part；Manganate 1 part～20 parts；Calciate 1 part～20 parts；Activating agent 0.2 part～10 parts, can be formed on pack alloy surface
Chrome-free true qualities Zr-Mn-V passivating film, and passivating film has that adhesive force degree good, corrosion-resistant is high, salt spray resistance and film forming equal
The advantage that even property is good.
In order to preferably form adhesive force degree good, corrosion-resistant height, salt spray resistance and one-tenth on pack alloy surface
The passivating film that film uniformity is good, and guarantee that the described passivating film obtained keeps the silvery white coloured gold identical with pack alloy self
Belonging to outward appearance, such as, the passivating film inorganic agent for pack alloy of another embodiment, including each group of following mass parts
Point: Fluohydric acid. 0.5 part～10 parts；Fluorine zirconic acid 0.5 part～10 parts；Ammonium fluozirconate 0.5 part～10 parts；Sodium fluozirconate 0.5 part～10
Part；Ammonium metavanadate 0.5 part～10 parts；Sodium metavanadate 0.5 part～10 parts；Manganese carbonate 0.5 part～10 parts；Manganese nitrate 0.5 part～10
Part；0.5 part～10 parts of calcium chloride；Calcium carbonate 0.5 part～10 parts；Sodium lauryl sulphate 0.1 part～0.5 part., so, permissible
Preferably form adhesive force degree good, corrosion-resistant height, salt spray resistance on pack alloy surface and become film uniformity good
Passivating film, and guarantee that the described passivating film obtained keeps the silvery white metal appearance identical with pack alloy self.
In order to preferably carry out chemical passivation film process, such as, described chemical passivation film processes 20 DEG C～the temperature of 30 DEG C
Carry out under the conditions of degree；And for example, described chemical passivation film processes and continues 2 minutes～3 minutes, so, can preferably carry out chemistry
Passivating film processes.
Such as, the described concentration for the passivating film inorganic agent of pack alloy is 100 grams per liters～200 grams per liters.
S160: the described pack alloy after described chemical passivation film processes is carried out drying and processing.
In order to preferably carry out drying and processing, such as, described drying and processing is carried out under the temperature conditions of 80 DEG C～90 DEG C；
And for example, described chemical passivation film processes and continues 10 minutes～25 minutes, so, can preferably carry out drying and processing.
The above-mentioned passivating film processing method for pack alloy can form Chrome-free Zr-Mn-V on pack alloy surface
Passivating film, the passivating film appearance uniform on die-cast aluminum alloy workpiece surface is consistent, and salt spray resistance is preferable.
Such as, after described degreasing degreasing processes, before described etch processes；After described etch processes, described in whiten process before；
Described whiten process after, before described bleaching；After described bleaching, before described chemical passivation film processes；And describedization
After learning passivating film process, before described drying and processing, the most also comprise the steps: that described pack alloy carries out adverse current washes behaviour
Make；And for example, described adverse current water washing operations uses air stirring to carry out；And for example, at normal temperatures, 3 times～5 times adverse current washings are carried out,
As such, it is possible to the impact that each operation reduced in pack alloy passivation membrane treatment process mutually produces, thus improve entirety
Pre-treatment effect.
Each technical characteristic of embodiment described above can combine arbitrarily, for making description succinct, not to above-mentioned reality
The each piece of all possible combination of technical characteristic executed in example is all described, but, as long as the combination of these technical characteristics is not deposited
In contradiction, all it is considered to be the scope that this specification is recorded.
The above embodiment only have expressed the several embodiments of the present invention, and it describes more concrete and detailed, but
Therefore the restriction to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that, for the ordinary skill people of this area
For Yuan, without departing from the inventive concept of the premise, it is also possible to make some deformation and improvement, these broadly fall into the present invention's
Protection domain.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. the passivating film inorganic agent for pack alloy, it is characterised in that include each component of following mass parts:
Passivating film inorganic agent for pack alloy the most according to claim 1, it is characterised in that described mineral acid bag
Include at least one in nitric acid, sulphuric acid, Fluohydric acid. and fluorine zirconic acid.
Passivating film inorganic agent for pack alloy the most according to claim 1, it is characterised in that described zirconates bag
Include at least one in potassium fluorozirconate, ammonium fluozirconate and sodium fluozirconate.
Passivating film inorganic agent for pack alloy the most according to claim 1, it is characterised in that described vanadate bag
Include at least one in ammonium metavanadate, sodium metavanadate and potassium metavanadate.
Passivating film inorganic agent for pack alloy the most according to claim 1, it is characterised in that described manganate bag
Include at least one in manganese carbonate, manganese nitrate and manganese sulfate.
Passivating film inorganic agent for pack alloy the most according to claim 1, it is characterised in that described calciate bag
Include at least one in calcium chloride, calcium carbonate and calcium nitrate.
Passivating film inorganic agent for pack alloy the most according to claim 1, it is characterised in that described activating agent bag
Include at least one in sodium lauryl sulphate, dodecylbenzene sodium sulfonate and sodium 2-ethylhexyl sulfate.
8. the passivating film processing method for pack alloy, it is characterised in that comprise the steps:
Pack alloy is put into degreasing agent carries out degreasing degreasing process；
Described pack alloy after described degreasing degreasing processes is put into and etchant is etched process；
Put into whiten by the described pack alloy after described etch processes and agent is carried out whiten process；
By through described whiten process after described pack alloy put into bleach carry out bleaching；
Put into enter in the passivating film inorganic agent of pack alloy by the described pack alloy after described bleaching
Row chemical passivation film processes, for forming passivating film on described pack alloy surface, wherein, described for pack alloy
Passivating film inorganic agent includes each component of following mass parts: mineral acid 1 part～20 parts；Zirconates 1 part～20 parts；Vanadate 1 part
～20 parts；Manganate 1 part～20 parts；Calciate 1 part～20 parts；Activating agent 0.2 part～10 parts；
Described pack alloy after described chemical passivation film processes is carried out drying and processing.
Passivating film processing method for pack alloy the most according to claim 8, it is characterised in that described defat removes
After oil processing, before described etch processes；After described etch processes, described in whiten process before；Described whiten process after, described bleaching
Before process；After described bleaching, before described chemical passivation film processes；And after described chemical passivation film processes, described drying
Before process, the most also comprise the steps: described pack alloy carries out adverse current water washing operations.
Passivating film processing method for pack alloy the most according to claim 8, it is characterised in that described drying
Process and carry out at a temperature of 80 DEG C～90 DEG C.
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