CN109280912A - A kind of aluminum alloy surface processing phosphating solution and method for bonderizing - Google Patents
A kind of aluminum alloy surface processing phosphating solution and method for bonderizing Download PDFInfo
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- CN109280912A CN109280912A CN201811243064.9A CN201811243064A CN109280912A CN 109280912 A CN109280912 A CN 109280912A CN 201811243064 A CN201811243064 A CN 201811243064A CN 109280912 A CN109280912 A CN 109280912A
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- aluminum alloy
- phosphating solution
- phosphatization
- phosphating
- bonderizing
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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
- C23C22/36—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 containing also phosphates
- C23C22/362—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 containing also phosphates containing also zinc cations
-
- 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
- C23C22/73—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 characterised by the process
-
- 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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- 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
The present invention relates to technical field of aluminum alloy surface treatment, it is related to a kind of aluminum alloy surface processing phosphating solution and method for bonderizing.The phosphating solution each component concentration are as follows: 17~23g/L of zinc dihydrogen phosphate, 45~60g/L of zinc nitrate, 85% 2.5~3.5g/L of phosphoric acid, 6~10g/L of nickel nitrate, 2.0~2.5g/L of sodium fluoride, 1.5~2.1g/L of sodium chlorate, 2.0~4.0g/L of sodium nitrite, 1.0~1.5g/L of guanidine nitrate, 2.5~3.5g/L of hydroxyl sulfate, 1.0~1.5g/L of phytic acid, surplus are deionized water.Method for bonderizing includes: the pretreatment of (1) aluminum alloy sheet；(2) pretreated aluminum alloy sheet is put into above-mentioned phosphating solution the phosphatization at 40~50 DEG C, 10~20min of phosphating time；(3) the aluminum alloy sheet deionized water after phosphatization rinses and uses hot blast drying.Present invention process is simple, easy to operate, and processing cost is low；Phosphatization at low temperature saves the energy；Chromium is not used in phosphating solution, avoids chromium to the murder by poisoning problem of environment and human body；Sediment when work is few；The cementability of the film even compact that phosphatization is formed, film layer and alloy matrix aluminum is strong, has good corrosion resistance.
Description
Technical field
The present invention relates to aluminum alloy surface process field, specific field is that Zinc phosphating solution is used in a kind of processing of aluminum alloy surface
And method for bonderizing.
Background technique
Aluminium alloy is widely used in mechanical industry, household electrical appliances and transportation.Since its activity is higher, easy shape in air
At one layer of thin porous oxidation film, make the reduction of its mechanical strength, corrosion resisting property is deteriorated.To improve its corrosion resisting property, frequently with
Electrochemistry or chemical method make its surface form one layer of conversion film with protective effect, enhance matrix corrosion resistance, extend
Service life.Chemical method is more advantageous in cost and efficiency, is therefore widely used in aluminum alloy surface processing.Chemistry
The conversion film that method generates has chromate film, phosphate layer, phosphate-chromate film etc., due to Cr VI in conversion film containing chromium
Toxicity it is high and easily it is carcinogenic, therefore its application be restricted.The corrosion resisting property of phosphating coat is good, can enable aluminum alloy to be led by excellent
Body is changed into non-conductor, to inhibit the formation of aluminum alloy surface micro cell, significantly improves the binding force of matrix and coating.Cause
This finds a kind of aluminium alloy non-chromium phosphating process and has important practical significance.Aluminium phosphating solution used at present, film is loose, film
Weight is larger, causes phosphating coat poor with paint film adhesion, poor corrosion resistance；Phosphatization crystal size is larger, in needle-shaped or blocky, does not have
There is crystalline particulate.
The method for bonderizing of aluminium alloy articles is disclosed in Chinese invention patent application CN103451639A, which is only referred to
Phosphating solution principal component and concentration are 5~10g/L of ZnO, H3PO410~20g/L does not disclose the type and content of promotor, system
Standby phosphorization film layer covering is uneven, and corrosion resistance is poor.Chinese patent CN101307440A discloses a kind of aluminium alloy and black
Non-ferrous metal phosphating solution, formula is: phosphatase 11 55-165g/L, 163~167g/L of zinc nitrate, 0.1~0.2g/L of potassium permanganate, alkane
Base 2.2~2.4g/L of benzene sulfonic acid sodium salt, 42~48g/L of zinc oxide, 5~6g/L of hydrofluoric acid contain potassium permanganate in the formula, cause
The stability of phosphating solution is not high, and the patent does not disclose the technological parameter of phosphating solution, and inconvenience uses.Chinese invention patent application
A kind of aluminum products surface treatment phosphating solution is disclosed in CN104357824A, it includes 60~65% phosphoric acid, oxalic acid, propylene
Acid, hydrofluoric acid, zinc dihydrogen phosphate, ammonium molybdate, chromium sulfate, nickel nitrate, cobalt naphthenate, zinc tetroxy chromate, defoaming agent, dispersion
Agent, distilled water, constituent is complicated, higher using temperature, also contains chromium, is unsuitable for industrialization promotion.
Summary of the invention
The purpose of the present invention is to provide a kind of aluminium alloy phosphating solution and method for bonderizing, which is free of toxic chromium,
Also chromium is free of in phosphating coat, avoids murder by poisoning of the chromium to environment and human body in aluminium and aluminium alloy coating process.The phosphating solution work simultaneously
Sediment when making is few；Phosphating coat film forming speed is fast；The film even compact formed after phosphorating treatment has good corrosion-resistant
Property, and have the effects that antifriction, lubrication, increase the bond strength of coating and alloy matrix aluminum.
To achieve the above object, the invention provides the following technical scheme:
A kind of aluminum alloy surface processing phosphating solution, constituent content are 17~23g/L of zinc dihydrogen phosphate, zinc nitrate 45~
60g/L, 85% 2.5~3.5g/L of phosphoric acid, 6~10g/L of nickel nitrate, 2.0~2.5g/L of sodium fluoride, 1.5~2.1g/L of sodium chlorate,
2.0~4.0g/L of sodium nitrite, 1.0~1.5g/L of guanidine nitrate, 2.5~3.5g/L of hydroxyl sulfate, phytic acid 1.0~1.5g/L are remaining
Amount is deionized water.
Preferably, constituent content be the phosphoric acid of 18~22g/L of zinc dihydrogen phosphate, zinc nitrate 50~55g/L, 85% 2.8~
3.2g/L, 8~10g/L of nickel nitrate, 2.0~2.2g/L of sodium fluoride, 1.8~2.0g/L of sodium chlorate, 2.5~3.6g/ of sodium nitrite
L, 1.2~1.4g/L of guanidine nitrate, 2.8~3.0g/L of hydroxyl sulfate, 1.2~1.5g/L of phytic acid, surplus are deionized water.
Wherein, the pH value of phosphating solution is transferred to 3.5~3.7 with the sodium hydroxide solution of 1mol/L.
The method that phosphatization is carried out to aluminium alloy using any of the above-described phosphating solution, comprising the following steps:
A. aluminium alloy pre-processes, and aluminum alloy sheet is successively used to No. 240, No. 360, No. 600, No. 1200 silicon carbide paper polishing throwings
Light, with acetone oil removing, deionized water cleaning；
B. by treated in step a, aluminium alloy test piece is immersed in concentration as 1.0mol/L, the hydrogen-oxygen that temperature is 60~70 DEG C
Change in sodium solution alkali cleaning 30~60 seconds, to remove Natural Oxide Film, is immersed in 1.0mol/L nitric acid solution and neutralizes at once after taking-up
It 15~30 seconds, is rinsed, is dried up with deionized water；
C. aluminium alloy test piece in step b is put into phosphating solution and carries out phosphatization, controlled at 40~50 DEG C, when phosphating reaction
Between be 10~20 minutes.
D. phosphatization test piece is taken out, is first rinsed 2 minutes with flowing running water, then is rinsed 1 minute with deionized water；Then with 65
~75 DEG C of hot blast drying obtains phosphatization aluminium alloy.
Compared with prior art, the beneficial effects of the present invention are:
(1) simple process, easy to operate, processing cost is low；
(2) phosphatization at low temperature saves the energy；
(3) chromium is not used in phosphating solution, avoids chromium to the murder by poisoning problem of environment and human body；Sediment when work is few；
(4) cementability of the film even compact that phosphatization is formed, film layer and alloy matrix aluminum is strong, has good corrosion-resistant
Property.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1
The formula of phosphating solution is used in the present embodiment are as follows: zinc dihydrogen phosphate 18g, zinc nitrate 55g, 85% phosphoric acid 3.2g, nitre
Sour nickel 9g, sodium fluoride 2.0g, sodium chlorate 2.0g, sodium nitrite 2.5g, guanidine nitrate 1.4g, hydroxyl sulfate 2.8g, phytic acid 1.2g.It will
Above compound is dissolved in deionized water, is configured to 1 liter of phosphating solution, and be transferred to pH value 3.5 with the sodium hydroxide solution of 1mol/L
~3.7.
Aluminum alloy sheet: successively being used No. 240, No. 360, No. 600, No. 1200 silicon carbide paper sanding and polishings by method for bonderizing, is used
Acetone oil removing, deionized water cleaning；Then aluminium alloy test piece is immersed in concentration is 1.0mol/L, the sodium hydroxide that temperature is 65 DEG C
It is immersed in 1.0mol/L nitric acid solution within alkali cleaning 50 seconds in solution and neutralizes 20 seconds at once to remove Natural Oxide Film, after taking-up, spend
Ionized water rinses, drying；Then aluminium alloy test piece is put into phosphating solution and carries out phosphatization, controlled at 40 DEG C, when phosphating reaction
Between be 20 minutes.Phosphatization test piece is taken out, first rinses 2min with flowing running water, then rinse 1min with deionized water.Then with 65
~75 DEG C of hot blast drying obtains phosphatization aluminium alloy.
The phosphating coat of aluminum phosphate alloy surface is detected, appearance is in grey black, and even compact, film is thin, and film weight is
4.5g/m2；The copper sulphate drop time is 103s；Phosphorization membrane adhesive force reaches 1 grade.
Embodiment 2
The formula of phosphating solution is used in the present embodiment are as follows: zinc dihydrogen phosphate 20g, zinc nitrate 50g, 85% phosphoric acid 3.0g, nitre
Sour nickel 8g, sodium fluoride 2.2g, sodium chlorate 1.8g, sodium nitrite 3.0g, guanidine nitrate 1.2g, hydroxyl sulfate 3.0g, phytic acid 1.5g.It will
Above compound is dissolved in deionized water, is configured to 1 liter of phosphating solution, and be transferred to pH value 3.5 with the sodium hydroxide solution of 1mol/L
~3.7.
Method for bonderizing: the pre-treatment of aluminium alloy and last handling process are identical with above-described embodiment 1.Unlike: phosphorus
Changing process control reaction temperature is 50 DEG C, and the control of phosphating reaction time is 10 minutes.
The phosphating coat of aluminum phosphate alloy surface is detected, appearance is in grey black, and even compact, film is thin, and film weight is
3.5g/m2；The copper sulphate drop time is 98s；Phosphorization membrane adhesive force reaches 1 grade.
Embodiment 3
The formula of phosphating solution is used in the present embodiment are as follows: zinc dihydrogen phosphate 23g, zinc nitrate 60g, 85% phosphoric acid 3.0g, nitre
Sour nickel 6g, sodium fluoride 2.5g, sodium chlorate 1.5g, sodium nitrite 2.8g, guanidine nitrate 1.5g, hydroxyl sulfate 3.2g, phytic acid 1.0g.It will
Above compound is dissolved in deionized water, is configured to 1 liter of phosphating solution, and be transferred to pH value 3.5 with the sodium hydroxide solution of 1mol/L
~3.7.
Method for bonderizing: the pre-treatment of aluminium alloy and last handling process are identical with above-described embodiment 1.The difference is that phosphatization
Process control reaction temperature is 45 DEG C, and the control of phosphating reaction time is 15 minutes.
The phosphating coat of aluminum phosphate alloy surface is detected, appearance is in grey black, and even compact, film is thin, and film weight is
3.7g/m2；The copper sulphate drop time is 93s；Phosphorization membrane adhesive force reaches 1 grade.
Embodiment 4
The film forming corrosion resistance comparative experiments of phosphating solution of the present invention and aluminium alloy phosphating solution in the prior art.
For the film forming corrosion resistance of phosphating solution more of the invention and existing phosphating solution, two kinds of phosphorus being listed in table in selection
Change liquid and carries out parallel laboratory test, the drop time for the phosphating coat that measurement is generated using two kinds of phosphating solutions.It can from the data result in table
Know, the higher phosphating coat of corrosion resistance, phosphatization film spot made from phosphating solution of the invention can be obtained using phosphating solution of the invention
Drip drop time of the time much larger than phosphating coat obtained by aluminium alloy phosphating solution in the prior art.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (9)
1. a kind of aluminum alloy surface processing phosphating solution, it is characterised in that: its constituent content is 17~23g/L of zinc dihydrogen phosphate,
Zinc nitrate 45~60g/L, 85% 2.5~3.5g/L of phosphoric acid, 6~10g/L of nickel nitrate, 2.0~2.5g/L of sodium fluoride, sodium chlorate
1.5~2.1g/L, 2.0~4.0g/L of sodium nitrite, 1.0~1.5g/L of guanidine nitrate, 2.5~3.5g/L of hydroxyl sulfate, phytic acid 1.0
~1.5g/L, surplus are deionized water.
2. aluminum alloy surface processing phosphating solution according to claim 1, it is characterised in that: its constituent content is di(2-ethylhexyl)phosphate
Hydrogen 18~22g/L of zinc, zinc nitrate 50~55g/L, 85% 2.8~3.2g/L of phosphoric acid, 8~10g/L of nickel nitrate, sodium fluoride 2.0~
2.2g/L, 1.8~2.0g/L of sodium chlorate, 2.5~3.6g/L of sodium nitrite, 1.2~1.4g/L of guanidine nitrate, hydroxyl sulfate 2.8~
3.0g/L, 1.2~1.5g/L of phytic acid, surplus are deionized water.
3. aluminum alloy surface processing phosphating solution according to claim 1, it is characterised in that: the pH value of phosphating solution is used
The sodium hydroxide solution of 1mol/L is transferred to 3.5~3.7.
4. the method for carrying out phosphatization to aluminium alloy using any phosphating solution of claim 1-3, which is characterized in that including following
Step:
A. aluminium alloy pre-processes；
B. by treated in step (a), aluminium alloy test piece is immersed in alkali cleaning 30~60 seconds in sodium hydroxide solution, natural to remove
Oxidation film is immersed in nitric acid solution at once after taking-up and neutralizes 15~30 seconds, rinsed with deionized water, drying；
C. aluminium alloy test piece in step (b) is put into phosphating solution and carries out phosphatization；
D. phosphatization test piece is taken out, drying is rinsed, obtains phosphatization aluminium alloy.
5. method for bonderizing according to claim 4, it is characterised in that: the step a is specifically, aluminum alloy sheet is successively used
No. 240, No. 360, No. 600, No. 1200 silicon carbide paper sanding and polishings, with acetone oil removing, deionized water cleaning.
6. method for bonderizing according to claim 4, it is characterised in that: the concentration of sodium hydroxide solution is in the step b
1.0mol/L, soaking temperature are 60~70 DEG C.
7. method for bonderizing according to claim 4, it is characterised in that: nitric acid solution concentration is 1.0mol/ in the step b
L。
8. method for bonderizing according to claim 4, it is characterised in that: in the step c, controlled at 40~50 DEG C,
The phosphating reaction time is 10~20 minutes.
9. method for bonderizing according to claim 4, it is characterised in that: in the step d, first rinse 2 with flowing running water
Minute, then rinsed 1 minute with deionized water, then with 65~75 DEG C of hot blast drying.
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| CN201811243064.9A CN109280912A (en) | 2018-10-24 | 2018-10-24 | A kind of aluminum alloy surface processing phosphating solution and method for bonderizing |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112442699A (en) * | 2019-08-29 | 2021-03-05 | 晟通科技集团有限公司 | Surface cleaning agent |
| CN112898859A (en) * | 2019-11-19 | 2021-06-04 | 湖南崀山家俱有限公司 | Environment-friendly paint baking finish process |
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| CN101812682A (en) * | 2009-02-24 | 2010-08-25 | 中化化工科学技术研究总院 | Zinc phosphating solution of aluminium and aluminium alloy |
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| CN106498380A (en) * | 2016-11-30 | 2017-03-15 | 江苏经纬技术创新咨询有限公司 | Corrosion-resistant Phosphating Solution of a kind of room temperature and preparation method thereof |
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| CN101348906A (en) * | 2008-08-13 | 2009-01-21 | 瑞阳汽车零部件（仙桃）有限公司 | Microcrystalline phosphating solution for brake block hardware |
| CN101812682A (en) * | 2009-02-24 | 2010-08-25 | 中化化工科学技术研究总院 | Zinc phosphating solution of aluminium and aluminium alloy |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112442699A (en) * | 2019-08-29 | 2021-03-05 | 晟通科技集团有限公司 | Surface cleaning agent |
| CN112898859A (en) * | 2019-11-19 | 2021-06-04 | 湖南崀山家俱有限公司 | Environment-friendly paint baking finish process |
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Application publication date: 20190129 |