CN107429404A - The coloured chromium-free passivation liquid of titanium zirconium system for aluminum alloy surface processing, the method and its application using its processing aluminum alloy surface - Google Patents
The coloured chromium-free passivation liquid of titanium zirconium system for aluminum alloy surface processing, the method and its application using its processing aluminum alloy surface Download PDFInfo
- Publication number
- CN107429404A CN107429404A CN201580000402.4A CN201580000402A CN107429404A CN 107429404 A CN107429404 A CN 107429404A CN 201580000402 A CN201580000402 A CN 201580000402A CN 107429404 A CN107429404 A CN 107429404A
- Authority
- CN
- China
- Prior art keywords
- aluminum alloy
- passivation liquid
- free passivation
- acid
- chromium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
A kind of coloured chromium-free passivation liquid of titanium zirconium system for aluminum alloy surface processing, include the component of following mass-volume concentration：Main 0.01~80g/L of film forming agent, 0.01~80g/L of oxidant, 0.01~50g/L of film forming accelerating; inorganic 0.01~50g/L of coalescents; organic 0.01~50g/L of film-forming protecting agents, the pH value of solution is adjusted to the pH adjusting agent of 26 amount, and the water as solvent.A kind of method for handling aluminum alloy surface comprises the following steps：Coloured chromium-free passivation liquid is diluted 1 to 80 times first；Then sprayed by the aluminium alloy dipping by degreasing pretreatment in the passivating solution or by the passivating solution on the surface of aluminium alloy, operating temperature is 0 DEG C 40 DEG C；Question response is 10 500s, then takes out Al alloy parts and washes and dry.Also disclose a kind of coloured chromium-free passivation liquid application of titanium zirconium system.
Description
The present invention relates to the technical field of aluminum alloy surface processing more particularly to a kind of method and its application that aluminum alloy surface is handled for the coloured chromium-free passivation liquid of titanium zirconium of aluminum alloy surface processing, using it.
Aluminium alloy is that metal alloy obtained from the elements such as magnesium, titanium, copper is added in fine aluminium, since its specific gravity is small, high mechanical strength, and there is excellent conductive, thermally conductive and corrosion stability, it is widely applied in recent years in fields such as aerospace, automobile, house ornamentation and mobile electronic devices.Aluminium, because the electrode potential of each metal is different and the formation of the second phase, is easy to produce galvanic effect, causes the corrosion of aluminium alloy after other metallic elements are added and form alloy.In order to enable aluminum alloy to from dielectric corrosion, and the binding force between external coating film and alloy matrix aluminum is improved, major measure is to be formed on its surface the high conversion film layer of corrosion resistance.The main technique for currently forming conversion film has: anodic oxidation, chromating and the passivation of non-chromium system.The advantages of anodic oxidation conversion film be it is wear-resisting, can be used for decorating protection, but anodic oxidation exist big investment, Gao Chengben, highly energy-consuming and it is seriously polluted the disadvantages of；Chromating technics comparing maturation and perfect and low in cost is presently the most mature passivation technology, but Cr VI is one of the strongest heavy metal of toxicity having determined at present, has strong carcinogenicity to organism.Chromate waste water is emitted into environment, the serious polluted source of meeting and soil, and can accumulated in vivo, long-term hazards human health leads to serious hematologic disease, treating bone diseases.Therefore, American-European countries has just carried out the research of Chrome-free substitution since the seventies, and more and more industry is inhibited in pre-treatment step using there is chromium process.Chinese new environmental law is formally implemented on January 1st, 2015, and with the method protection scope and the increasing for implementing dynamics, traditional chromating treatment process will be limited greatly.Aluminium spraying has been trend of the times using chromium-free deactivation pretreatment technology.
Currently, commercially available chromium-free deactivation product is based on zirconium titanium system product.Although avoiding the pollution of chromium of heavy metal, but its performance of the conversion film of these product formations is difficult to compare favourably with conversion film containing chromium, and mostly colourless conversion film, it is difficult to make promptly and accurately intuitive judgement to film forming situation from the appearance, brings inconvenience to field worker construction.Such as, Chinese patent CN 103254782A discloses a kind of corrosion resistant chromium-free metal surface silane finish, forms (grams of each component in every liter of mixed liquor) are as follows: N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane 60-65, methylbenzotriazole 1-2, ethylene glycol 6-8, diisooctyl succinate sodium sulfonate 3-4, ammonium chloride 2-3, ammonium fluozirconate 1-2, coalescing agent 2-4, it is remaining be water.The corrosion resistant Metal surface silane treatment agent treatment process of patent production does not generate sediment, and safety and environmental protection has excellent corrosion resistance with the silane coating that metal surface is formed.Its disadvantage is high expensive, and the acceptable degree in market is lower, and forms a film and colourless be unfavorable for constructing operation.For another example, Chinese patent CN201410167681.0 discloses a kind of Chrome-free film agent and preparation method thereof, it is characterised in that by percentage to the quality, it is prepared from the following raw materials: fluorine zirconic acid 2-6%, built up silane couple 1.7-6.7%, basic zirconium chloride 0.8-1.5%, citric acid 0.5-1%, surplus are water.The Chrome-free film agent of the invention has the characteristics that short processing time, sediment are few, compact crystallization, tank liquor are stable, film forming corrosion resistance when handling workpiece, but is similarly colourless conversion film, it is difficult to recognize.Chinese patent CN201410673939.4 discloses a kind of manganese zirconium chromium-free passivation liquid and its processing method for aluminum alloy surface processing, the chromium-free passivation liquid includes the component of following mass-volume concentration: 0.01~10g/L of permanganate, 0.01~10g/L of fluozirconate or fluorine zirconic acid, 0.01~4g/L of promotor, acid-base modifier, remaining is water, pH value 3.0-6.8.The patent is conducive to constructing operation and improves productivity most distinct feature is that its film forming is the golden yellow conversion film that easily recognizes.But the shortcoming of the film is to be easy powder of detached after film forming places a period of time, and coating performance is poor.Therefore, the task of top priority that high-performance, environment-friendly type and the coloured no Cr-Al alloy passivating solution convenient for constructing operation are still the field is developed.
Summary of the invention
It is a kind of not comprising chromium it is an object of the invention to provide in view of the above problems, and enable aluminum alloy to that obvious color change can be generated after passivation, the processing method and its application of the coloured chromium-free passivation liquid of titanium zirconium, aluminum alloy surface that handle for aluminum alloy surface.
In order to achieve the goal above, in one aspect, the technical solution adopted by the present invention is that:
A kind of coloured chromium-free passivation liquid of titanium zirconium for aluminum alloy surface processing; the passivating solution includes the component of following mass-volume concentration: main 0.01~80g/L of film forming agent; 0.01~80g/L of oxidant; 0.01~50g/L of film forming accelerating; inorganic 0.01~50g/L of coalescing agent; film forming 0.01~50g/L of organic protective agent, the pH value of solution is adjusted to 2-6 amount pH adjusting agent, and the water as solvent.
Further, which is selected from least one of the group being made of fluotitanic acid, potassium fluotitanate, titanium sodium fluoride, ammonium titanium fluoride, fluotitanic acid lithium, fluorine zirconic acid, potassium fluorozirconate, sodium fluozirconate, ammonium fluozirconate and fluorine zirconic acid lithium.
Further, which is selected from least one of the group being made of hydrogen peroxide, potassium hyperchlorate, sodium perchlorate, Potassiumiodate, potassium metaperiodate, sodium metaperiodate, potassium peroxydisulfate, ammonium persulfate, sodium peroxydisulfate and cerous sulfate.
Further, which is selected from least one of the group being made of sodium fluoride, potassium fluoride, ammonium fluoride, magnesium fluoride, lithium fluoride and its hydrate.
Further, which is selected from least one of the group being made of nickel sulfate, nickel nitrate, nickel chloride, cobaltous sulfate, cobalt nitrate, cobalt chloride, manganese sulfate, manganese nitrate, manganese chloride, sodium tungstate, potassium tungstate, ammonium tungstate, ammonium metatungstate, ammonium molybdate, sodium molybdate, potassium molybdate and its hydrate.
Further, which is selected from least one of the group being made of acrylic acid, polyacrylic acid, acrylamide, polyacrylamide, N hydroxymethyl acrylamide, pyrrolidones, polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, ethylenediamine tetra-acetic acid, carboxymethyl cellulose, chitosan, polysorbate, polyethylene oxide and polypropylene oxide.
Further, which is selected from least one of the group being made of hydrofluoric acid, sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid and citric acid.
Further, the dosage of the pH adjusting agent makes the pH value of coloured chromium-free passivation liquid be adjusted to 2-6.
On the other hand, the present invention provides a kind of methods that the surface for aluminium alloy is handled, method includes the following steps: above-mentioned coloured chromium-free passivation liquid 1) is diluted with water to 1 to 80 times；2) it will be sprayed on the surface of aluminium alloy by the pretreated aluminium alloy dipping of degreasing in the passivating solution or by the passivating solution；And 3) aluminium alloy is washed and dried after reacting a period of time.
Further, the operating temperature used in the processing method is 0 DEG C -40 DEG C, and the reaction time of passivating solution and aluminium alloy is 10-500s.
In yet another aspect, the present invention provides a kind of using the above-mentioned coloured chromium-free passivation liquid of titanium zirconium is processed or application by the above-mentioned processed aluminium alloy extrusions of processing method in mobile phone, laptop, building materials, automobile, furniture house ornamentation, sports equipment, product packaging and spacecraft field.
In a further aspect, the application the present invention provides a kind of above-mentioned coloured chromium-free passivation liquid of titanium zirconium in the surface of processing aluminium alloy.
Do not contain heavy metal chromium in coloured chromium-free passivation liquid of the invention, thus can harm and environmental pollution to avoid heavy metal chromium to human body, reduce the processing cost of aluminium alloy coating enterprise chromate waste water.The passivating solution is in the yellow of homogeneous transparent, and storage stability is good at room temperature, places generate without precipitating for a long time, convenient for the storage and transport of product.Through the passivating solution, treated that aluminum alloy surface will form one layer of fine and close lurid conversion film, the quality of film layer is intuitively judged by the depth and the uniformity of observation conversion film color convenient for technical staff, it is made adjustment in time with the operation to next step, is simplified production technology.The conversion film formed through the passivating solution processing has excellent Corrosion Protection, and the time for occurring 50% hot spot in neutral salt spray test (35 ± 1 DEG C) reaches 200h or more (salt mist experiment executes chinese national standard GB/T10125-2012/ISO9227:2006)；With the sodium chloride solution 20mL+0.1mol/L of the copper-bath 40mL+10wt.% of 10wt./%
Hydrochloric acid 1mL carries out resistance to drop experiment, and the corrosion-resistant time was up to 150 seconds.This conversion film can significantly increase the binding force in aluminum alloy surface coating.The coated film formed through spraying-heat curing process remains to keep good binding force with alloy matrix aluminum after the experiment such as paint film lattice drawing, mechanical shock, high temperature and pressure water erosion.In addition, the operating temperature of coloured chromium-free passivation liquid of the invention is 0 DEG C -40 DEG C, the range of effective pH value is 2-6, there was only 10-500s with the reaction time of aluminium alloy, thus under conditions of without heating, being not necessarily to regular adjusting pH value, continuous, efficient production can be kept, improves production efficiency.In addition, can be applied in mobile phone, laptop, building materials, automobile, furniture house ornamentation, sports equipment, product packaging and spacecraft field using the processed aluminium alloy extrusions of the coloured chromium-free passivation liquid of titanium zirconium of the invention.
Fig. 1 is to be passivated color contrast before and after the processing to Al alloy parts using the passivating solution in the embodiment of the present invention 1: the left side of Al alloy parts is processed, and the right side of Al alloy parts is untreated.
Fig. 2 is the effect picture that coating is carried out using the Al alloy parts surface that the coloured chromium-free passivation liquid in the embodiment of the present invention 1 is handled.
Fig. 3 is to draw the test results of lattice using the processed aluminum alloy surface coated film of passivating solution in the embodiment of the present invention 1 (to execute the cross cut test of national standard GB-T9286-1998 paint and varnish paint film, draw compartment away from for 1mm).
Fig. 4 is the paint film impact test method test result using the processed aluminum alloy surface coated film of passivating solution in the embodiment of the present invention 1: left side is forward impact, and right side is that reverse impact (executes national standard GB/T1732-93 paint film impact test method, weight quality is 1000g, free-falling height 50cm).
Fig. 5 is processed using the passivating solution in the embodiment of the present invention 1 and the comparison diagram of the test result of the aluminum alloy surface coated film pressure cooker boiling of passivating solution processing is not used: top is untreated aluminum alloy surface coated film, lower section is the aluminum alloy surface coated film handled by passivating solution of the invention (sample submerges, and digestion time is 90 minutes).
In order to keep objects and advantages of the present invention clearer, claimed technical solution of the invention is described in further detail now in conjunction with embodiment.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention and is not intended to limit the present invention.
In an embodiment of the invention; the present invention provides a kind of coloured chromium-free passivation liquids of titanium zirconium for aluminum alloy surface processing; component including following mass-volume concentration: main 0.01~80g/L of film forming agent, 0.01~80g/L of oxidant, 0.01~50g/L of film forming accelerating, inorganic 0.01~50g/L of coalescing agent, organic 0.01~50g/L of film-forming protecting agents, the pH value of solution is adjusted to 2-6 amount pH adjusting agent, and the water as solvent.
Preferably, in the coloured chromium-free passivation liquid of titanium zirconium, which is selected from least one of the group being made of fluotitanic acid, potassium fluotitanate, titanium sodium fluoride, ammonium titanium fluoride, fluotitanic acid lithium, fluorine zirconic acid, potassium fluorozirconate, sodium fluozirconate, ammonium fluozirconate and fluorine zirconic acid lithium.
Preferably, in the coloured chromium-free passivation liquid of titanium zirconium, which is selected from least one of the group being made of hydrogen peroxide, potassium hyperchlorate, sodium perchlorate, Potassiumiodate, potassium metaperiodate, sodium metaperiodate, potassium peroxydisulfate, ammonium persulfate, sodium peroxydisulfate and cerous sulfate.
Preferably, in the coloured chromium-free passivation liquid of titanium zirconium, which is selected from least one of the group being made of sodium fluoride, potassium fluoride, ammonium fluoride, magnesium fluoride, lithium fluoride and its hydrate.
Preferably, in the coloured chromium-free passivation liquid of titanium zirconium, which is selected from least one of the group being made of nickel sulfate, nickel nitrate, nickel chloride, cobaltous sulfate, cobalt nitrate, cobalt chloride, manganese sulfate, manganese nitrate, manganese chloride, sodium tungstate, potassium tungstate, ammonium tungstate, ammonium metatungstate, ammonium molybdate, sodium molybdate, potassium molybdate and its hydrate.
Preferably, in the coloured chromium-free passivation liquid of titanium zirconium, which is selected from by acrylic acid, polyacrylic acid, acrylamide, polyacrylamide, N hydroxymethyl acrylamide, pyrrolidones, polyvinyl pyrrole
At least one of alkanone, polyvinyl alcohol, polyethylene glycol, ethylenediamine tetra-acetic acid, carboxymethyl cellulose, chitosan, polysorbate, polyethylene oxide and group of polypropylene oxide composition.
Preferably, in the coloured chromium-free passivation liquid of titanium zirconium, which is selected from least one of the group being made of hydrofluoric acid, sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid and citric acid.
In another embodiment, the present invention provides a kind of methods that the surface for aluminium alloy is handled, method includes the following steps:
1) above-mentioned coloured chromium-free passivation liquid is diluted with water to 1 to 80 times；
2) it will be sprayed on the surface of aluminium alloy by the pretreated aluminium alloy dipping of degreasing in above-mentioned passivating solution or by above-mentioned passivating solution；And
3) aluminium alloy is washed and is dried after reacting a period of time.
Preferably, operating temperature is 0 DEG C -40 DEG C used in the method, and the reaction time of the passivating solution and aluminium alloy is 10-500s.
In yet another embodiment, the present invention provides a kind of using the above-mentioned coloured chromium-free passivation liquid of titanium zirconium is processed or application by the processed aluminium alloy extrusions of the above method in mobile phone, laptop, building materials, automobile, furniture house ornamentation, sports equipment, product packaging and spacecraft field.
In yet another embodiment, the application the present invention provides a kind of above-mentioned coloured chromium-free passivation liquid of titanium zirconium in the surface of processing aluminium alloy.
Embodiment 1
In the present embodiment, when preparing the coloured chromium-free passivation liquid of determined volume, required component: potassium fluotitanate 10g/L, sodium peroxydisulfate 2g/L, sodium fluoride 5g/L are weighed according to following mass-volume concentration；Then the above component is added in the deionized water of about eighty per cant determined volume and uniformly mixes by manganese sulfate 3g/L, polyacrylamide 3g/L.Next, the pH value of the passivating solution is adjusted to 4.0 with hydrofluoric acid, specific dosage is depending on actual conditions.
The volume of the passivating solution is set to reach determined volume finally, adding deionized water.Prepared appearance is transferred in PVC plastic material container in the coloured chromium-free passivation liquid of homogeneous transparent shape, stores spare (without being protected from light) at room temperature.
When handling the surface of aluminium alloy using the passivating solution, the passivating solution is diluted 20 times first, then ungrease treatment is carried out by surface of the degreaser to aluminium alloy, then at room temperature, the Al alloy parts to Passivation Treatment are immersed in the passivating solution or by passivating solution spray on the surface of Al alloy parts.After surface and the chromium-free passivation liquid haptoreaction 100s of Al-alloy parts, one layer of fine and close light yellow conversion film is formed on the surface of workpiece, Fig. 1 is Al alloy parts in the color contrast using the passivating solution before and after the processing.Technical staff can intuitively judge the quality of film layer by observing the depth, uniformity of conversion film color etc., and adjust concentration or the reaction time of working solution (passivating solution) in time as needed.After taking out workpiece, washing process and drying and processing should be carried out to Al alloy parts in time, be contacted with workpiece long-time to avoid the passivating solution of Al alloy parts surface residual and cause the uneven of conversion film.Studies have shown that the Al alloy parts surface handled through the passivating solution has excellent anti-corrosion capability, test its durability up to 220h through neutral salt spray test (salt mist experiment executes chinese national standard GB/T10125-2012/ISO9227:2006).The Al alloy parts and external coating film of passivated processing have good binding force.Fig. 2 is the effect picture that coating is carried out by using the Al alloy parts surface of the passivating solution processing in embodiment 1.Fig. 3 is that the result for carrying out cross cut test to the coated film of the processed aluminum alloy surface of the passivating solution used in embodiment 1 (executes the cross cut test of national standard GB-T9286-1998 paint and varnish paint film, compartment is drawn away from 1mm), the phenomenon that compartment is without peeling, shedding.Fig. 4 is the test result that impact test is carried out to the processed coated film of the passivating solution used in the embodiment of the present invention 1: left side is forward impact, right side is that reverse impact (executes national standard GB/T1732-93 paint film impact test method, weight quality is 1000g, free-falling height 50cm).As can be seen that either forward impact or reverse impact, coated film all maintains good binding force with substrate, without peeling, shedding phenomenon around shock surface.Fig. 5 is processed using the passivating solution in the embodiment of the present invention 1 and the coated film of passivating solution processing is not used by the test result of pressure cooker gluten substitute: top is untreated aluminum alloy surface coated film, and lower section is the aluminium alloy table handled by passivating solution of the invention
Face coated film (sample submerges, and digestion time is 90 minutes).The result shows that phenomena such as serious blistering, decortication occurs in untreated aluminum alloy surface coated film, and the aluminum alloy surface coated film handled through passivating solution of the invention still maintains and the good binding force of substrate.
Embodiment 2
In the present embodiment, when preparing the coloured chromium-free passivation liquid of determined volume, required component: sodium fluozirconate 10g/L, ammonium persulfate 2g/L, the total 5g/L of potassium fluoride are weighed according to following mass-volume concentration；Then the above component is added in the deionized water of about eighty per cant determined volume and uniformly mixes by manganese nitrate 4g/L, potassium molybdate 6g/L, N hydroxymethyl acrylamide 5g/L.Next, the pH value of the passivating solution is adjusted to 5 at least one of hydrofluoric acid, sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, specific dosage is depending on actual conditions.Finally, water supplement makes the volume of the passivating solution reach determined volume.Prepared appearance is transferred in PVC plastic material container in the coloured chromium-free passivation liquid of homogeneous transparent shape, stores spare (without being protected from light) at room temperature.
When using passivating solution processing aluminum alloy surface, above-mentioned coloured chromium-free passivation liquid is diluted in 5 times of volume merging passivating solution washing troughs first.Then, ungrease treatment is carried out by surface of the degreaser to aluminium alloy, then at room temperature, the Al alloy parts to Passivation Treatment is immersed in passivating solution leaching or by passivating solution spray on the surface of the Al alloy parts.Behind the surface and chromium-free passivation liquid haptoreaction 120s for enabling aluminum alloy to workpiece, one layer of fine and close light yellow conversion film is formed on the surface of workpiece.After taking out workpiece, washing process and drying and processing should be carried out to Al-alloy parts in time, be contacted with workpiece long-time to avoid the passivating solution of Al alloy parts surface residual and cause the uneven of conversion film.Experiment shows that the Al alloy parts surface handled through the passivating solution has excellent anti-corrosion capability, tests its durability up to 230h through neutral salt spray test.The Al alloy parts and external coating film of passivated processing have good binding force.
Embodiment 3
In the present embodiment, when preparing the coloured chromium-free passivation liquid of determined volume, required component: the total 10g/L of potassium fluotitanate, sodium fluozirconate, potassium peroxydisulfate, sodium peroxydisulfate, over cure is first weighed according to following mass-volume concentration
The sour total 5g/L of ammonium, the total 5g/L of sodium fluoride, potassium fluoride, ammonium fluoride；Then the above component is added in the deionized water of about eighty per cant determined volume and uniformly mixes by the total 6g/L of manganese nitrate, manganese sulfate, sodium tungstate, the total 5g/L of polyacrylamide, N hydroxymethyl acrylamide, polyacrylic acid.Next, the pH value of the passivating solution is adjusted to 4 at least one of hydrofluoric acid, sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, specific dosage is depending on actual conditions.Finally, water supplement makes the volume of the passivating solution reach determined volume.Prepared appearance is transferred in PVC plastic material container in the coloured chromium-free passivation liquid of yellow green homogeneous transparent shape, stores spare (without being protected from light) at room temperature.
When using the surface of passivating solution processing aluminium alloy, above-mentioned coloured chromium-free passivation liquid is diluted in 15 times of volume merging passivating solution washing troughs first.Then, ungrease treatment is carried out by surface of the degreaser to aluminium alloy, then at room temperature, the Al-alloy parts to Passivation Treatment is immersed in passivating solution leaching or by passivating solution spray on the surface of the Al alloy parts.Behind the surface and chromium-free passivation liquid haptoreaction 180s for enabling aluminum alloy to workpiece, one layer of fine and close light yellow conversion film is formed on the surface of workpiece.After workpiece taking-up, washing process and drying and processing should be carried out to Al alloy parts in time, be contacted with workpiece long-time to avoid the passivating solution of Al alloy parts surface residual and cause the uneven of conversion film.Experiment shows that the Al alloy parts surface handled through the passivating solution has excellent anti-corrosion capability, tests its durability up to 250h through neutral salt spray test.The Al alloy parts and external coating film of passivated processing have good binding force.
The main film forming agent potassium fluotitanate in potassium fluotitanate, sodium fluozirconate corresponding embodiment 1 in the present embodiment, potassium peroxydisulfate, sodium peroxydisulfate, the oxidant sodium peroxydisulfate in ammonium persulfate corresponding embodiment 1；Sodium fluoride, potassium fluoride, the film forming accelerating sodium fluoride in ammonium fluoride corresponding embodiment 1；Cobalt nitrate, manganese sulfate, the inorganic coalescing agent manganese sulfate in sodium tungstate corresponding embodiment 1；Polyacrylamide, N hydroxymethyl acrylamide, the film forming organic protective agent polyacrylamide in polyacrylic acid corresponding embodiment 1；Hydrofluoric acid, sulfuric acid, phosphoric acid, nitric acid, the pH adjusting agent in hydrochloric acid corresponding embodiment 1.Rise phase same-action substance can there are many, their mechanism of action during forming conversion film are similar, it is main difference is that its molecular weight difference or the degree of dissociation difference in aqueous solvent, difference on effect can be adjusted by adjusting the specific mass-volume concentration in passivating solution in using effect.
Other embodiments of the invention will be provided with following form, and the preparation method of passivating solution and the processing method of aluminum alloy surface are similar with above three embodiments.It the difference is that only, the type and content of each component substance used in each embodiment in table are different, and different using prepared passivating solution processing aluminum alloy surface the reaction time.In following embodiment, passivating solution prepares the surface treatment for completing that aluminium alloy is used for after diluting.Neutral salt spray test all executes chinese national standard GB/T10125-2012/ISO9227:2006.
Furthermore, cross cut test, which is carried out, with coated film of the mode similar with embodiment 1 to the processed aluminum alloy surface of each embodiment used in table above (executes the cross cut test of national standard GB-T9286-1998 paint and varnish paint film, compartment is drawn away from 1mm), test result shows the phenomenon that compartment is without peeling, shedding.
Above embodiments are only some preferred embodiments of the invention, but protection scope of the present invention is not limited to that.It should be appreciated by those skilled in the art that all be divided into the mode of several Section combinations all within protection scope of the present invention without departing from any modification of spirit and scope of the invention, replacement or by the present invention.
Claims (11)
- A kind of coloured chromium-free passivation liquid of titanium zirconium for aluminum alloy surface processing; component including following mass-volume concentration: main 0.01~80g/L of film forming agent, 0.01~80g/L of oxidant, 0.01~50g/L of film forming accelerating, inorganic 0.01~50g/L of coalescing agent, organic 0.01~50g/L of film-forming protecting agents, the pH value of solution is adjusted to 2-6 amount pH adjusting agent, and the water as solvent.
- Titanium zirconium coloured chromium-free passivation liquid according to claim 1 for aluminum alloy surface processing, it is characterized in that, the main film forming agent is selected from least one of the group being made of fluotitanic acid, potassium fluotitanate, titanium sodium fluoride, ammonium titanium fluoride, fluotitanic acid lithium, fluorine zirconic acid, potassium fluorozirconate, sodium fluozirconate, ammonium fluozirconate and fluorine zirconic acid lithium.
- Titanium zirconium coloured chromium-free passivation liquid according to claim 1 for aluminum alloy surface processing, wherein, the oxidant is selected from least one of the group being made of hydrogen peroxide, potassium hyperchlorate, sodium perchlorate, Potassiumiodate, potassium metaperiodate, sodium metaperiodate, potassium peroxydisulfate, ammonium persulfate, sodium peroxydisulfate and cerous sulfate.
- Titanium zirconium coloured chromium-free passivation liquid according to claim 1 for aluminum alloy surface processing, which is characterized in that the film forming accelerating is selected from least one of the group being made of sodium fluoride, potassium fluoride, ammonium fluoride, magnesium fluoride, lithium fluoride and its hydrate.
- Titanium zirconium coloured chromium-free passivation liquid according to claim 1 for aluminum alloy surface processing, wherein, the inorganic coalescing agent is selected from least one of the group being made of nickel sulfate, nickel nitrate, nickel chloride, cobaltous sulfate, cobalt nitrate, cobalt chloride, manganese sulfate, manganese nitrate, manganese chloride, sodium tungstate, potassium tungstate, ammonium tungstate, ammonium metatungstate, ammonium molybdate, sodium molybdate, potassium molybdate and its hydrate.
- Titanium zirconium coloured chromium-free passivation liquid according to claim 1 for aluminum alloy surface processing; it is characterized in that, organic film-forming protecting agents are selected from by acrylic acid, polyacrylic acid, acrylamide, polyacrylamide, N hydroxymethyl acrylamide, pyrrolidones, polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, second At least one of ethylenediamine tetraacetic acid (EDTA), carboxymethyl cellulose, chitosan, polysorbate, polyethylene oxide and group of polypropylene oxide composition.
- Titanium zirconium coloured chromium-free passivation liquid according to claim 1 for aluminum alloy surface processing, which is characterized in that the pH adjusting agent is selected from least one of the group being made of hydrofluoric acid, sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid and citric acid.
- A method of it is handled for the surface to aluminium alloy, which is characterized in that the described method comprises the following steps:1) coloured chromium-free passivation liquid according to any one of claim 1 to 7 is diluted with water to 1 to 80 times；2) it will be sprayed on the surface of aluminium alloy by the pretreated aluminium alloy dipping of degreasing in the passivating solution or by the passivating solution；And3) aluminium alloy is washed and is dried after reacting a period of time.
- According to the method described in claim 8, the reaction time of the passivating solution and aluminium alloy is 10-500s it is characterized in that, the operating temperature used in the method is 0 DEG C -40 DEG C.
- It is a kind of using the coloured chromium-free passivation liquid of titanium zirconium described in any one of -7 is processed according to claim 1 or passes through application of the processed aluminium alloy extrusions of method in mobile phone, laptop, building materials, automobile, furniture house ornamentation, sports equipment, product packaging and spacecraft field according to any one of claim 8-9.
- Application of the coloured chromium-free passivation liquid of titanium zirconium described in any one of -7 in the surface of processing aluminium alloy according to claim 1.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2015/083230 WO2017000315A1 (en) | 2015-07-02 | 2015-07-02 | Titanium-zirconium coloured chromium-free passivation solution for surface treatment of aluminium alloy, method for treating aluminium alloy surface using same, and use thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107429404A true CN107429404A (en) | 2017-12-01 |
Family
ID=57607548
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580000402.4A Pending CN107429404A (en) | 2015-07-02 | 2015-07-02 | The coloured chromium-free passivation liquid of titanium zirconium system for aluminum alloy surface processing, the method and its application using its processing aluminum alloy surface |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN107429404A (en) |
| WO (1) | WO2017000315A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111074255A (en) * | 2019-12-05 | 2020-04-28 | 刘广付 | Metal surface pretreatment agent and preparation method and application thereof |
| CN113151815A (en) * | 2020-12-22 | 2021-07-23 | 苏州帝航防护设施有限公司 | Corrosion-resistant metal surface treating agent |
| CN114045478A (en) * | 2021-10-13 | 2022-02-15 | 东莞理工学院 | Preparation method of aluminum alloy conductive conversion film |
| CN114774904A (en) * | 2022-04-24 | 2022-07-22 | 安徽光铧帝业化学有限公司 | Aluminum alloy chromium-free passivation agent containing fluorescent agent and preparation method and use method thereof |
| CN115404473A (en) * | 2022-08-30 | 2022-11-29 | 江苏中天科技股份有限公司 | Passivation solution for aluminum surface treatment, aluminum surface passivation method and corrosion-resistant aluminum material with nano conversion coating |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109183016B (en) * | 2018-07-27 | 2020-11-27 | 博罗县东明化工有限公司 | ADC12 die casting aluminum alloy black chromium-free conversion film treating agent and ADC12 die casting aluminum alloy surface treatment method |
| CN109675779A (en) * | 2018-12-28 | 2019-04-26 | 广东兴发铝业（河南）有限公司 | A kind of processing method of fluorine carbon dust Spray-painted aluminum profile |
| CN111441044B (en) * | 2020-04-26 | 2022-11-25 | 深圳市钝化技术有限公司 | Phosphorus-free, nitrogen-free and chromium-free stainless steel passivation solution |
| CN111944335A (en) * | 2020-07-24 | 2020-11-17 | 苏州波菲特新材料科技有限公司 | Vitrification agent, preparation method thereof and stirring device |
| CN112713339A (en) * | 2020-12-07 | 2021-04-27 | 乐凯胶片股份有限公司 | Aluminum-plastic flexible packaging film, preparation method and flexible packaging battery |
| CN113088951A (en) * | 2021-04-08 | 2021-07-09 | 上海兴赛尔表面材料有限公司 | Multifunctional chromium-free passivation solution for galvanized sheet and preparation method and application thereof |
| CN113430509B (en) * | 2021-06-24 | 2022-09-16 | 浙江固的管业有限公司 | Anticorrosive treatment process for stainless steel pipe fitting |
| CN113846332A (en) * | 2021-09-10 | 2021-12-28 | 大富科技(安徽)股份有限公司 | Method for processing etched surface of aluminum antenna |
| CN114921780B (en) * | 2022-04-19 | 2024-01-23 | 南京艾布纳新材料股份有限公司 | Environment-friendly passivation solution for aluminum alloy and preparation method and treatment process thereof |
| CN114875281A (en) * | 2022-05-11 | 2022-08-09 | 山东骏程金属科技有限公司 | Anti-fatigue and corrosion-resistant forged Al-Mg-Si-Zr aluminum alloy wheel and preparation method thereof |
| CN115369393B (en) * | 2022-08-11 | 2024-05-10 | 江苏特昊新材料有限公司 | Metal surface pretreatment film forming liquid and preparation method and application thereof |
| CN115449791A (en) * | 2022-08-24 | 2022-12-09 | 江苏和兴汽车科技有限公司 | Method for improving corrosion resistance of die-cast aluminum |
| CN115726016B (en) * | 2022-12-05 | 2023-08-11 | 仙桃市伟方新材料科技有限公司 | Nickel-free fluoride-free medium-temperature sealing agent containing rare earth component and preparation method thereof |
| CN116043207A (en) * | 2023-02-23 | 2023-05-02 | 浙江乔老爷铝业有限公司 | Chromium-free passivation room temperature treatment process for aluminum profile surface |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101161861A (en) * | 2007-11-22 | 2008-04-16 | 东北大学 | Non-chromium deactivation liquid for processing aluminium alloy and method of use thereof |
| CN101967633A (en) * | 2010-09-16 | 2011-02-09 | 华南理工大学 | Treatment liquid and method or preparing Ti/Zr-containing yellow passive film on surface of aluminum alloy |
| CN102634785A (en) * | 2012-05-07 | 2012-08-15 | 东莞市闻誉实业有限公司 | Method for passivation of zinc and zinc alloy and chromium-free passivation solution |
| CN102782186A (en) * | 2010-02-24 | 2012-11-14 | 埃托特克德国有限公司 | Chromium -free passivation process of vapor deposited aluminum surfaces |
| CN104294249A (en) * | 2013-07-19 | 2015-01-21 | 无锡永发电镀有限公司 | Environmentally-friendly wrought aluminum alloy passivating solution |
| CN104388915A (en) * | 2014-11-24 | 2015-03-04 | 毛山红 | Manganese-zirconium chromate-free passivating solution for surface treatment of aluminum alloy and method for manganese-zirconium chromate-free passivating treatment of surface of aluminum alloy |
-
2015
- 2015-07-02 CN CN201580000402.4A patent/CN107429404A/en active Pending
- 2015-07-02 WO PCT/CN2015/083230 patent/WO2017000315A1/en active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101161861A (en) * | 2007-11-22 | 2008-04-16 | 东北大学 | Non-chromium deactivation liquid for processing aluminium alloy and method of use thereof |
| CN102782186A (en) * | 2010-02-24 | 2012-11-14 | 埃托特克德国有限公司 | Chromium -free passivation process of vapor deposited aluminum surfaces |
| CN101967633A (en) * | 2010-09-16 | 2011-02-09 | 华南理工大学 | Treatment liquid and method or preparing Ti/Zr-containing yellow passive film on surface of aluminum alloy |
| CN102634785A (en) * | 2012-05-07 | 2012-08-15 | 东莞市闻誉实业有限公司 | Method for passivation of zinc and zinc alloy and chromium-free passivation solution |
| CN104294249A (en) * | 2013-07-19 | 2015-01-21 | 无锡永发电镀有限公司 | Environmentally-friendly wrought aluminum alloy passivating solution |
| CN104388915A (en) * | 2014-11-24 | 2015-03-04 | 毛山红 | Manganese-zirconium chromate-free passivating solution for surface treatment of aluminum alloy and method for manganese-zirconium chromate-free passivating treatment of surface of aluminum alloy |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111074255A (en) * | 2019-12-05 | 2020-04-28 | 刘广付 | Metal surface pretreatment agent and preparation method and application thereof |
| CN113151815A (en) * | 2020-12-22 | 2021-07-23 | 苏州帝航防护设施有限公司 | Corrosion-resistant metal surface treating agent |
| CN114045478A (en) * | 2021-10-13 | 2022-02-15 | 东莞理工学院 | Preparation method of aluminum alloy conductive conversion film |
| CN114774904A (en) * | 2022-04-24 | 2022-07-22 | 安徽光铧帝业化学有限公司 | Aluminum alloy chromium-free passivation agent containing fluorescent agent and preparation method and use method thereof |
| CN115404473A (en) * | 2022-08-30 | 2022-11-29 | 江苏中天科技股份有限公司 | Passivation solution for aluminum surface treatment, aluminum surface passivation method and corrosion-resistant aluminum material with nano conversion coating |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2017000315A1 (en) | 2017-01-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107429404A (en) | The coloured chromium-free passivation liquid of titanium zirconium system for aluminum alloy surface processing, the method and its application using its processing aluminum alloy surface | |
| CN1327031C (en) | Post-treatment for metal coated substrates | |
| CN102337532B (en) | Chromium-free passivation liquid applied to surface of zinc-coated layer | |
| CN101146929B (en) | Process for sealing phosphoric acid anodized aluminums | |
| CN102443794B (en) | Aluminum alloy scratch resistant and fingerprint resistant chromium-free chemical conversion solution for ship and preparation method of conversion film | |
| CN106756942B (en) | A kind of stainless steel chromium-free passivation liquid | |
| AU2016363456A1 (en) | Chromium-free surface-treated tinplate, production method and surface treating agent therefor | |
| CN102766862A (en) | Treating fluid and method for preparing vanadium-zirconium composite conversion coatings with self-repairing performance on aluminum alloy surfaces through same | |
| CN109943836A (en) | A kind of aluminum alloy surface chrome-free tanning agent and its application | |
| CN103695889A (en) | Chromium-free passivation solution for surface treatment of galvanized plate, aluminum and copper alloy | |
| CN108220940B (en) | A kind of normal temperature environment friendly aluminium alloy passivating solution, preparation method and application method | |
| CN104073796A (en) | Metal plating passivation solution and preparation method thereof | |
| CN102268664A (en) | Chromium-free passivating solution used for black passivation treatment of zinc plating and preparation method thereof | |
| CN103451645B (en) | A kind of adopt magnesium alloy film agent that magnesium alloy is carried out the method for surface treatment | |
| CN109338347A (en) | A kind of chromium-free deactivation composition, chromium-free passivation liquid and preparation method thereof | |
| CN110016659A (en) | It is used to prepare the preparation method of the treatment fluid of the compound conversion film of fluorine zirconic acid, preparation method and conversion film | |
| CN109023331A (en) | A kind of chrome-free tanning agent and its application method | |
| CN106700880A (en) | Paint for aircraft stealth and preparation method thereof | |
| CN101166848A (en) | Process for preparing chromium conversion coatings for magnesium alloys | |
| CN104342683A (en) | Magnesium alloy work-piece surface anti-corrosion conversion film treatment process | |
| CN106756939A (en) | aluminum passivation liquid and preparation method thereof | |
| CN104451636A (en) | Chromium-free passivation solution for tin-plated steel plate and preparation method of chromium-free passivation solution | |
| CN102363881B (en) | General bonderite used before spray coating of steel and aluminum combined shell body, and preparation method of general bonderite | |
| CN102808172B (en) | Universal environment-friendly non-phosphorus phosphating solution | |
| CN103088329B (en) | Aluminum alloy treating agent before application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20171201 |