CN108149232B - Environment-friendly passivation solution for aluminum or seven-series aluminum alloy and preparation method and treatment process thereof - Google Patents
Environment-friendly passivation solution for aluminum or seven-series aluminum alloy and preparation method and treatment process thereof Download PDFInfo
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- CN108149232B CN108149232B CN201711413641.XA CN201711413641A CN108149232B CN 108149232 B CN108149232 B CN 108149232B CN 201711413641 A CN201711413641 A CN 201711413641A CN 108149232 B CN108149232 B CN 108149232B
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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
- C23C22/34—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 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
- C23C22/78—Pretreatment of the material to be coated
Abstract
The invention provides an environment-friendly passivation solution for aluminum or a seven-series aluminum alloy, and a preparation method and a treatment process thereof, wherein the passivation solution comprises a main film-forming agent, a secondary film-forming agent, a strong-oxidizing pore filling agent, a film-forming promoter, a complexing agent, a low-foaming surfactant and a thickening agent; and adjusting the pH value of the passivation solution to 5.2-5.8 by using sodium hydroxide or an ammonia water regulator, and the balance being deionized water. The passivation solution has high stability, uniform and compact passivation film, high corrosion resistance, short and simple preparation process and treatment process operation and low energy consumption.
Description
Technical Field
The invention relates to the technical field of aluminum or aluminum alloy surface treatment, in particular to an aluminum or seven-series aluminum alloy environment-friendly chromium-free passivation solution and a preparation method and a treatment process thereof.
Background
The aluminum alloy is obtained by adding elements such as magnesium, zinc, copper and the like into pure aluminum, and has a series of advantages of small specific gravity, high mechanical strength, excellent electrical conductivity, thermal conductivity, corrosion resistance and the like, so that the aluminum alloy has wide application prospects and irreplaceable positions in the aviation, aerospace, ship, nuclear industry and weapon industry, and the aluminum or aluminum alloy technology is listed as a key technology and a basic technology for key development of national defense science and technology. The seven series aluminum alloy is aluminum-zinc-magnesium-copper alloy, the strength and the hardness of the seven series aluminum alloy are close to those of steel, the welding performance is good, 7055 and 7075 are the seven series aluminum alloys with the highest strength, and the seven series aluminum alloy can be strengthened by heat treatment. The application range is aviation (bearing component and landing gear of airplane), rocket, propeller, wall plate of aviation airship, landing gear, skin and the like.
However, an oxide film with a thickness of only 2-10nm is very easily formed on the surface of aluminum and its alloys in the atmosphere, and has a certain protection function on the substrate, but the natural protective film is very thin, so that the natural protective film is very easily corroded in humid atmosphere, especially in the case of containing Cl-, the aluminum and its alloys are very easily corroded, and the use of aluminum or aluminum alloys is lost. The currently common methods for protecting aluminum or aluminum alloys are: anodic oxidation, electroplating of other corrosion resistant metal films, electroless plating, and passivation with a passivating solution.
For the passivation solution passivation method, it is also called metal conversion film method: the method is characterized in that atoms on the surface layer of metal (including plating metal) and anions in a medium react with each other to generate an isolating layer with good adhesive force on the surface of the metal, and the reaction formula is as follows: mM + nAz-→MmAn+ nze-Historically, chromate conversion films have been the most widely used, and this technology has been pioneered for one hundred years. Adding corresponding chemical substances on the basis of chromate, and passing through a film-forming solution under specific process conditionsAnd the chromium is chemically reacted with the surface of aluminum and aluminum alloy to form a layer of passive film on the surface of the matrix, and the chromium exists in the film in the form of hexavalent and trivalent compounds. However, hexavalent chromium ions have extremely high toxicity, and no matter how the hexavalent chromium ions in the waste liquid are treated or whether a product containing the hexavalent chromium ions after film forming can be safely used becomes a hidden danger of the technology, the relative service life of the aluminum product is short, and the hexavalent chromium ions contained in the waste product can cause secondary pollution to the environment. In 2003, two prohibitions issued by the european union prohibit the industrial use of hexavalent chromium conversion technology, and people focus on finding a new green aluminum alloy surface treatment technology to replace hexavalent chromium conversion technology. The current system for replacing chromium as passivation solution mainly uses molybdate system, permanganate system, rare earth system and titanium zirconium system, and there is similarity in chemical properties between molybdate and chromate, and the toxicity and environmental pollution of the molybdate and chromate are much less than those of chromate. The permanganate system mainly adopts potassium permanganate as a basic additive of the solution, and various inorganic and organic additives are added in an auxiliary manner on the basis, so that a colored conversion film is formed on the surfaces of aluminum and aluminum alloy. Similar to the molybdate system, the permanganate system has also been proposed because manganese is chemically similar to chromium. Permanganate mainly shows strong oxidizing property in a film forming system, and reaction speed of aluminum alloy surface dissolution and new film layer deposition in a film forming process is improved, but the corrosion resistance of a molybdate passivation film is lower than that of a chromate passivation film. The cerium salt passive film contains cerium oxide and hydroxide, has good corrosion resistance, and is close to the low chromate passive film. But has the defects of long treatment time, high treatment temperature, complexity and the like, and has a certain distance from the actual production. The prior chromium-free passivation solution has the problems of low efficiency, inferior corrosion resistance to chromate and the like, and needs to be improved in all aspects.
Disclosure of Invention
The invention aims to provide a high-efficiency and environment-friendly passivation solution, a preparation method thereof and a process for treating aluminum or aluminum alloy aiming at the problems of poor stability of the passivation solution, poor corrosion resistance of a passivation film, uneven thickness, low compactness and the like of the passivation film, and the passivation solution has the advantages of high stability, uniform and compact passivation film, high corrosion resistance, short and simple preparation process and treatment process, and low energy consumption.
The invention provides an environment-friendly passivation solution for aluminum or a seven-series aluminum alloy, which comprises the following components in percentage by weight:
a main film-forming agent: 2-3g/L of fluotitanic acid and 0.5-1.5 g/L of fluozirconic acid;
secondary film-forming agent: cerium salt 0.2-0.5 g/L;
strong oxidizing pore-filling agent: 0.2-0.4 g/L of potassium permanganate;
film formation accelerator: 0.1-0.3 g/L of sodium fluoride or sodium fluoroborate;
complexing agent: 1-1.5 g/L of nitrilotrimethylene phosphate or 1-hydroxyethylene-1, 1-diphosphonic acid;
low-foaming surfactant: 0.1-0.3 g/L of acetylene glycol nonionic surfactant;
thickening agent: methyl cellulose or ethyl cellulose, 0.1-0.3 g/L;
adjusting the pH value of the passivation solution to 5.2-5.8 by using sodium hydroxide or an ammonia water regulator, wherein the error range is +/-0.2;
the remainder was deionized water.
Preferably, the passivation solution comprises the following components:
a main film-forming agent: 2.5g/L of fluotitanic acid and 1g/L of fluozirconic acid;
secondary film-forming agent: cerium salt 0.45 g/L;
strong oxidizing pore-filling agent: potassium permanganate of 0.35 g/L;
film formation accelerator: 0.3g/L of sodium fluoride or sodium fluoroborate;
complexing agent: nitrilotrimethylene phosphate or 1-hydroxyethylene-1, 1-diphosphonic acid, 1.5 g/L;
low-foaming surfactant: acetylene glycol nonionic surfactant, 0.2 g/L;
thickening agent: methyl cellulose or ethyl cellulose, 0.3 g/L;
and adjusting the pH value of the passivation solution to 5.2-5.8 by using a sodium hydroxide regulator.
The invention also provides aluminum or sevenThe preparation method of the environment-friendly passivation solution for the aluminum alloy comprises the following steps: firstly, adding a proper amount of deionized water into a reaction kettle, adding a low-foaming surfactant, and heating to 40-50 DEGoAnd C, stirring to completely dissolve, cooling to room temperature, adding the main film-forming agent and the secondary film-forming agent under a stirring state, stirring at 100-200 r/min to completely dissolve, sequentially adding the strong-oxidizing pore-filling agent, the film-forming promoter and the complexing agent under a stirring state, stirring at 100-200 r/min to completely dissolve to obtain solution A, adding a proper amount of deionized water into another reaction kettle, slightly heating to 35-40 ℃, slowly adding the thickening agent, stirring at 200-300 r/min to completely dissolve, cooling to obtain solution B, adding the solution B into the solution A, stirring for 10-20 min, adding deionized water, adjusting the pH value of the passivation solution to 5.2-5.8 by using sodium hydroxide or ammonia water to obtain passivation solution, and standing for later use.
In addition, the invention also provides a process for treating aluminum or a seven-series aluminum alloy by using the passivation solution, which comprises the following steps:
(1) mechanical polishing: removing natural oxide film with thickness of 3-10 nm on the surface of aluminum or aluminum alloy, and using 100#-500#-800#Sequentially polishing by using abrasive paper;
(2) acid washing and degreasing: organic pollutants on the surface of aluminum or aluminum alloy are removed, and the hydrogen embrittlement phenomenon cannot occur, and the degreasing fluid comprises the following components: sulfuric acid, d =1.84, 230-260 ml/L, OP-10 emulsifier 9-10 g/L, and acid washing temperature 25-35oC, the time is 5-10 min;
(3) washing with water: washing with deionized water for 2-3 min;
(4) acid washing and activating: etching the redundant oxide film on the surface, activating the surface, and pickling and activating the solution to form: 10-15 wt.% of nitric acid, 2-2.5 wt.% of sulfuric acid and 1-2 wt.% of phosphoric acid, wherein the temperature is room temperature, the time is about 3-5 min, and the surface is bright;
(5) washing with water: washing with deionized water for 20-30 s;
(6) chemical passivation: the passivation method is soaking or spraying for 10-30 min;
(7) washing with water: washing the residual passivation solution with deionized water or tap water for 30-60 s;
(8) and (3) hot air drying:placing the passivated aluminum or aluminum alloy in a blast drying oven at the temperature of 70-90 DEG CoC，5~10min。
In the passivation process, the pH value of the passivation solution is checked regularly, the pH value is kept within 5.2-5.8, the error range is +/-0.2, and sodium hydroxide or ammonia water is used for adjusting the pH value of the passivation solution.
The passivation process can be explained by the following process: first, Al → Al of anode3++3e-(ii) a Cathode is O2+2H2O+4e-→4OH-The progress of the cathodic reaction causes a local increase in pH, which in turn causes Zr in fluotitanic acid and fluozirconic acid4++4OH-→ZrO2↓+2H2O；Ti4++4OH-→ZrO2↓+2H2O, since titanium in the fluorotitanic acid and zirconium in the fluorozirconic acid are precipitated almost simultaneously, thereby producing (ZrTi) O4The porous oxide of (1), wherein Al3+→Al2O3Therefore, the invention takes fluotitanic acid and fluozirconic acid as main film forming agents and (ZrTi) O4Is more porous, so a rare earth element secondary film-forming agent and a potassium permanganate pore-filling agent are introduced, wherein the potassium permanganate generates MnO at a cathode due to strong oxidizing property4 -+4H++3e-→MnO2(stabilizing MnO)x)+2H2O, the directly reduced manganese oxide can directly enter porous (ZrTi) O4In the method, the compactness of the passivation film is obviously improved; and Ce3+Or Ce4+Formation of Ce (OH) x and, finally, formation of Ce during subsequent drying2O3、CeO2Finally, the primary film-forming agent and the secondary film-forming agent play a role of dual protection, thereby improving the corrosion resistance of the passive film, namely the state of the passive film at the moment is (ZrTiCe) O4-a MnOx dense passivation film. And the film-forming accelerator is mainly F-And BF4-The effect of film formation can be accelerated, so that a thicker passivation film can be obtained at normal temperature. The complexing agent is nitrilotrimethylene phosphoric acid or 1-hydroxyethylidene-1, 1-diphosphonic acid, which not only can well complex metal ions, but also has phosphate group-PO (OH)2Can react with (Ti-Zr-Ce) OxReaction to form phosphoric acid better covering the surface of the substrateAnd (4) a salt layer. The surfactant is selected from acetylene glycol nonionic surfactant, and can be selected from common surfactants such as sodium dodecyl sulfate, sodium dodecyl sulfate or betaine, and is mainly used for reducing surface tension of passivation solution and increasing wetting effect, because there is H in passivation process2If the hydrogen is retained on the surface of the aluminum alloy and is difficult to separate, a passivation film pinhole phenomenon is caused, the corrosion resistance is not facilitated, and in addition, the use of the surfactant should not cause a large amount of foam as much as possible, so that the uneven passivation layer is avoided. The thickening agent can reduce the film forming time in the spraying and brushing processes and has a certain slow release effect. Secondly, as for the passivation solution, the influence of pH value on the formation of the passivation film and the corrosion resistance of the passivation film is very large, in detail, the passivation film is generated in the process of dissolution and generation, when the pH value is too low, the dissolution speed of the passivation film is greater than the generation speed, and the film formation is difficult; when the pH value is too high, the precipitation is too fast, such as flocculent precipitation, and the film layer is too thick, so that the film layer is loose and not compact.
Advantageous effects
The passivation solution consisting of the main film-forming agent, the secondary film-forming agent, the strong-oxidizing pore-filling agent, the film-forming promoter, the complexing agent, the low-foaming surfactant and the thickening agent has the following excellent effects:
(1) the passive film generated on the surface of the aluminum alloy is compact, the thickness is suitable, and the surface has no uneven and pinhole phenomena;
(2) the corrosion resistance of the passive film is high;
(3) the stability of the passivation solution is good, and the binding force of the passivation film and the base material is high;
(4) the preparation process and the treatment process are simple and convenient to operate, low in energy consumption, safe and pollution-free.
Detailed Description
Example 1
An environment-friendly passivation solution for aluminum or a seven-series aluminum alloy, comprising:
a main film-forming agent: 2g/L of fluotitanic acid and 0.5g/L of fluozirconic acid;
secondary film-forming agent: cerium salt 0.2 g/L;
strong oxidizing pore-filling agent: potassium permanganate of 0.2 g/L;
film formation accelerator: 0.1g/L of sodium fluoride or sodium fluoroborate;
complexing agent: 1g/L of nitrilotrimethylene phosphate;
low-foaming surfactant: acetylene glycol nonionic surfactant, 0.1 g/L;
thickening agent: methyl cellulose, 0.1 g/L;
adjusting the pH value of the passivation solution to 5.2-5.8 by using an ammonia water regulator, wherein the error range is +/-0.2;
the remainder was deionized water.
The preparation method of the passivation solution comprises the following steps: firstly, adding a proper amount of deionized water into a reaction kettle, adding a low-foaming surfactant, and heating to 40-50 DEGoAnd C, stirring to completely dissolve, cooling to room temperature, adding the main film-forming agent and the secondary film-forming agent under a stirring state, stirring at a speed of 100-200 r/min to completely dissolve, sequentially adding the strong-oxidizing pore-filling agent, the film-forming promoter and the complexing agent under a stirring state, stirring at a speed of 100-200 r/min to completely dissolve to obtain solution A, adding a proper amount of deionized water into another reaction kettle, slightly heating to 35-40 ℃, slowly adding the thickening agent, stirring at a speed of 200-300 r/min to completely dissolve, cooling to obtain solution B, adding the solution B into the solution A, stirring for 10-20 min, adding deionized water, adjusting the pH value of the passivation solution to 5.2-5.8 by using ammonia water to obtain passivation solution, and standing for later use.
The process for treating aluminum or aluminum alloy by using the passivation solution comprises the following steps:
(1) mechanically polishing to remove 3-10 nm natural oxide film on the surface of aluminum or aluminum alloy, and using 100 nm natural oxide film#-500#-800#Sequentially polishing by using abrasive paper;
(2) acid washing and degreasing: organic pollutants on the surface of aluminum or aluminum alloy are removed, and the hydrogen embrittlement phenomenon cannot occur, and the degreasing fluid comprises the following components: sulfuric acid, d =1.84, 230-260 ml/L, OP-10 emulsifier 9-10 g/L, temperature 25-35oC, the time is 5-10 min;
(3) washing with water: washing with deionized water for 2-3 min;
(4) acid washing and activating: etching the redundant oxide film on the surface, activating the surface, and pickling and activating the solution to form: 10-15 wt.% of nitric acid, 2-2.5 wt.% of sulfuric acid and 1-2 wt.% of phosphoric acid, wherein the temperature is room temperature, the time is about 3-5 min, and the surface is bright;
(5) washing with water: washing with deionized water for 20-30 s;
(6) chemical passivation: the passivation method is soaking or spraying for 10-30 min;
(7) washing with water: washing the residual passivation solution with deionized water or tap water for 30-60 s;
(8) and (3) hot air drying: placing the passivated aluminum or aluminum alloy in a blast drying oven at the temperature of 70-90 DEG CoC，5~10min。
In addition, in the passivation process, the pH value of the passivation solution needs to be checked regularly, the pH value is kept within 5.2-5.8, the error range is +/-0.2, and sodium hydroxide or ammonia water is used for adjusting the pH value of the passivation solution.
Example 2
An environment-friendly passivation solution for aluminum or a seven-series aluminum alloy, comprising:
a main film-forming agent: 2.5g/L of fluotitanic acid and 1g/L of fluozirconic acid;
secondary film-forming agent: cerium salt 0.45 g/L;
strong oxidizing pore-filling agent: potassium permanganate of 0.35 g/L;
film formation accelerator: sodium fluoride or sodium fluoroborate, 0.3g/L
Complexing agent: nitrilotrimethylene phosphate 1.5g/L
Low-foaming surfactant: acetylene glycol nonionic surfactant, 0.2g/L
Thickening agent: methyl cellulose, 0.3 g/L;
and adjusting the pH value of the passivation solution to 5.2-5.8 by using a sodium hydroxide regulator.
The process for treating aluminum or aluminum alloy by using the passivation solution comprises the following steps:
(1) mechanically polishing to remove 3-10 nm natural oxide film on the surface of aluminum or aluminum alloy, and using 100 nm natural oxide film#-500#-800#Sequentially polishing by using abrasive paper;
(2) acid washing and degreasing: removing surfaces of aluminium or aluminium alloysOrganic pollutants, and hydrogen embrittlement phenomenon can not occur, and the degreasing fluid comprises the following components: sulfuric acid, d =1.84, 250ml/L, OP-10 emulsifier 10g/L, temperature 35oC, the time is 7 min;
(3) washing with water: washing with deionized water for 2.5 min;
(4) acid washing and activating: etching the redundant oxide film on the surface, activating the surface, and pickling and activating the solution to form: 12wt.% of nitric acid, 2.3wt.% of sulfuric acid and 1wt.% of phosphoric acid, wherein the temperature is room temperature, the time is about 3min, and the surface is bright;
(5) washing with water: washing with deionized water for 25 s;
(6) chemical passivation: the passivation method is soaking for 20 min;
(7) washing with water: washing residual passivation solution with deionized water or tap water for 40 s;
(8) and (3) hot air drying: placing the passivated aluminum or aluminum alloy in a blast drying oven at the temperature of 80 DEG CoC，8min。
In addition, in the passivation process, the pH value of the passivation solution needs to be checked regularly, the pH value is kept within 5.2-5.8, the error range is +/-0.2, and sodium hydroxide or ammonia water is used for adjusting the pH value of the passivation solution.
Example 3
An environment-friendly passivation solution for aluminum or a seven-series aluminum alloy, comprising:
a main film-forming agent: 3g/L of fluotitanic acid and 1.5g/L of fluozirconic acid;
secondary film-forming agent: cerium salt 0.5 g/L;
strong oxidizing pore-filling agent: potassium permanganate of 0.4 g/L;
film formation accelerator: 0.3g/L of sodium fluoride or sodium fluoroborate;
complexing agent: 1-hydroxyethyl-1, 1-diphosphonic acid, 1.5 g/L;
low-foaming surfactant: acetylene glycol nonionic surfactant, 0.3 g/L;
thickening agent: ethyl cellulose, 0.3 g/L;
adjusting the pH value of the passivation solution to 5.2-5.8 by using a sodium hydroxide regulator, wherein the error range is +/-0.2;
the remainder was deionized water.
And (3) corrosion resistance testing:
7075 aluminum alloy was cut into 3cm by 1mm samples. Blank test: sequentially polishing the test sample by sand paper, ultrasonically cleaning the test sample by using deionized water, absolute ethyl alcohol and acetone, drying the test sample by using cold air, weighing the test sample by using W0. Soaking the treated aluminum alloy in 2.5% NaCl corrosive solution for 36h, taking out, washing with deionized water to remove excessive corrosion products on the surface, drying with cold air, weighing, and drying1。
The aluminum alloy weighed after pretreatment is prepared by the method in example 2 to obtain the aluminum alloy with the passivation film on the surface, the aluminum alloy is placed into 2.5% NaCl corrosion solution to be soaked for 36 hours and then taken out, then the aluminum alloy is washed by deionized water to remove redundant corrosion products on the surface, and the aluminum alloy is dried by cold air and weighed. Five groups of parallel experiments are respectively carried out under the same conditions, and the average value is taken. The corrosion rate was calculated using the following formula: v = (W)0-W1) V is the corrosion rate in g/cm2.h；W0And W1The mass of the sample before and after the corrosion was expressed in g, s is the total surface area of the sample, and m2(ii) a t is the sample soaking time in units of h.
Table 1 shows the corrosion rate measurements and the hardness changes before and after passivation of 7075 aluminum alloy after treatment in example 2 by soaking in sodium chloride solution for 36 hours.
TABLE 1
| Sample (I) | W0-W1 | v(g/cm2.h) | Hardness of |
| Blank test | 0.0437 | 1.348 | 83Hv |
| Example 2 | 0.0092 | 0.284 | 157Hv (passivation 20min) |
| Lack of secondary film-forming agent | 0.0191 | 0.859 | 132 Hv (passivation 20min) |
| Lack of pore-filling agent | 0.0137 | 0.423 | 127 Hv (passivation 20min) |
From the above table, it can be known that the main film-forming agent, the secondary film-forming agent and the strong-oxidizing pore-filling agent have important effects on improving the corrosion resistance and hardness of the passivation layer, are vital and have no defects, and after other additives are added, the passivation film generated on the surface of the aluminum alloy is compact, the thickness is applicable, and the surface has no uneven and pinhole phenomena; and the preparation process and the treatment process are simple and convenient to operate, low in energy consumption, safe and pollution-free.
The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.
Claims (4)
1. A preparation method of an environment-friendly passivation solution for aluminum or a seven-series aluminum alloy is characterized by firstly adding a proper amount of deionized water into a reaction kettle, adding a low-foaming surfactant, heating to 40-50 ℃, stirring to be completely dissolved, cooling to room temperature, then adding a main film-forming agent and a secondary film-forming agent under a stirring state, stirring to be completely dissolved at 100-200 r/min, then sequentially adding a strong-oxidative pore-filling agent, a film-forming promoter and a complexing agent under a stirring state, stirring to be completely dissolved at 100-200 r/min to obtain a solution A, then adding a proper amount of deionized water into the other reaction kettle, slightly heating to 35-40 ℃, then slowly adding a thickening agent, stirring at 200-300 r/min to be completely dissolved, cooling to obtain a solution B, then adding the solution B into the solution A, stirring for 10-20 min, adding deionized water, then adjusting the pH value of the passivation solution to 5.2-5.8 by using sodium hydroxide or ammonia water, obtaining passivation solution, standing for later use, and finally obtaining a passivation film on the surface of the aluminum or aluminum alloy in a (ZrTiCe) O state4-a dense passivation film of MnOx,
the passivation solution comprises:
a main film-forming agent: 2-3g/L of fluotitanic acid and 0.5-1.5 g/L of fluozirconic acid;
secondary film-forming agent: cerium salt 0.2-0.5 g/L;
strong oxidizing pore-filling agent: 0.2-0.4 g/L of potassium permanganate;
film formation accelerator: 0.1-0.3 g/L of sodium fluoride or sodium fluoroborate;
complexing agent: 1-1.5 g/L of nitrilotrimethylene phosphate or 1-hydroxyethylene-1, 1-diphosphonic acid;
low-foaming surfactant: 0.1-0.3 g/L of acetylene glycol nonionic surfactant;
thickening agent: methyl cellulose or ethyl cellulose, 0.1-0.3 g/L;
the remainder was deionized water.
2. The method for preparing the environment-friendly passivation solution for aluminum or the seven-series aluminum alloy according to claim 1, wherein the passivation solution comprises:
a main film-forming agent: 2.5g/L of fluotitanic acid and 1g/L of fluozirconic acid;
secondary film-forming agent: cerium salt 0.45 g/L;
strong oxidizing pore-filling agent: potassium permanganate of 0.35 g/L;
film formation accelerator: 0.3g/L of sodium fluoride or sodium fluoroborate;
complexing agent: nitrilotrimethylene phosphate or 1-hydroxyethylene-1, 1-diphosphonic acid, 1.5 g/L;
low-foaming surfactant: acetylene glycol nonionic surfactant, 0.2 g/L;
thickening agent: methyl cellulose or ethyl cellulose, 0.3 g/L;
and adjusting the pH value of the passivation solution to 5.2-5.8 by using a sodium hydroxide regulator.
3. The process for treating aluminum or a seven-series aluminum alloy by using the passivation solution prepared by the preparation method according to claim 1, which comprises the following steps:
(1) mechanical polishing: removing a natural oxide film with the thickness of 3-10 nm on the surface of the aluminum or the aluminum alloy, and sequentially polishing by using 100# -500# -800# abrasive paper;
(2) acid washing and degreasing: organic pollutants on the surface of aluminum or aluminum alloy are removed, and the hydrogen embrittlement phenomenon cannot occur, and the degreasing fluid comprises the following components: sulfuric acid, d =1.84, 230-260 ml/L, OP-10 emulsifier 9-10 g/L, and acid washing temperature 25-35oC, the time is 5-10 min; (3) washing with water: washing with deionized water for 2-3 min;
(4) acid washing and activating: etching the redundant oxide film on the surface, activating the surface, and pickling and activating the solution to form: 10-15 wt.% of nitric acid, 2-2.5 wt.% of sulfuric acid and 1-2 wt.% of phosphoric acid, wherein the pickling temperature is room temperature, the pickling time is 3-5 min, and the surface is bright;
(5) washing with water: washing with deionized water for 20-30 s;
(6) passivating by using a passivating solution: the passivation method is soaking or spraying for 10-30 min;
(7) washing with water: washing the residual passivation solution with deionized water or tap water for 30-60 s;
(8) and (3) hot air drying: placing the passivated aluminum or aluminum alloy in a blast drying oven at the temperature of 70-90 DEG CoC，5~10min。
4. The process for treating aluminum or a hepta-aluminum alloy by using the passivation solution prepared by the preparation method according to claim 3, wherein the pH value of the passivation solution is checked regularly during passivation, the pH value is kept within 5.2-5.8, and sodium hydroxide or ammonia water is used for adjusting the pH value of the passivation solution.
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