CN108642502A - The corrosion-resistant pre-treating method of aluminium alloy - Google Patents
The corrosion-resistant pre-treating method of aluminium alloy Download PDFInfo
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- CN108642502A CN108642502A CN201810415004.4A CN201810415004A CN108642502A CN 108642502 A CN108642502 A CN 108642502A CN 201810415004 A CN201810415004 A CN 201810415004A CN 108642502 A CN108642502 A CN 108642502A
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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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/12—Light metals
- C23G1/125—Light metals aluminium
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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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/48—Coating with alloys
- C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel
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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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
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Abstract
The invention discloses a kind of corrosion-resistant pre-treating methods of aluminium alloy, include the following steps：(1) aluminium alloy is put into impregnation in cleaning solution；(2) aluminium alloy is put into impregnation in corrosion-resistance treatment liquid, obtains anticorrosion aluminium.After the processing of the pre-treating method of the present invention, the corrosion resistance of aluminium alloy is strong, can meet the corrosion condition in modern environment, and material is easy to make, and cost is smaller, easy to spread；Treated, and aluminum alloy surface hardness is big, and wear-resisting property protrudes, and is hardly damaged, service life is long, using effect is good.
Description
Technical field
The present invention relates to the corrosion-resistant pre-treatment sides of a kind of pre-treating method of aluminium alloy more particularly to a kind of aluminium alloy
Method.
Background technology
Aluminum alloy materials due to it has the characteristics that density is small, intensity is high and large storage capacity Aeronautics and Astronautics, naval vessel, building materials,
The industrial aspects extensive use such as household electrical appliances, telecommunications and power cable has consequence and effect.High-strength aluminum alloy exists at present
Industrial circle operation strategies are more and more extensive, but that there are corrosion resistances is low for alloy aluminum in the prior art, under field conditions (factors),
Aluminum alloy surface is easy to form the natural oxide film of a thickness about 4nm, but this tunic is porous, uneven and corrosion stability is poor, difficult
To resist the corrosion of adverse circumstances, service life is short, this make use of the high-strength aluminum alloy material in industrial circle by
Limitation.To solve the above-mentioned problems, it usually needs protection processing carried out to aluminum alloy surface, including chemical conversion, anodic oxidation,
Coating, plasma spray technology and nano coating technology etc..
Chemical oxidization method refers to the process of by chemically reacting in one layer of thin oxidation film of Surface Creation.What this method obtained
For oxide thickness about at 0.5~4 μm, film layer is porous, has good adsorptivity, may generally serve as the bottom of organic coating.Often
The method for oxidation seen has chromate oxidations method, alkaline chromate oxidizing process, phosphate-chromate oxidations method.Chromate oxidations method
The film layer of acquisition has the features such as film layer is thin, electric conductivity and corrosion resistance are good, good with organic coating binding force, in electrical, mechanical, boat
It is widely used in empty and daily necessities manufacture field.But the treatment fluid containing chromium can cause environment greatly to pollute and break
It is bad, develop novel, Chrome-free, efficient corrosion-resistance treatment liquid becomes urgent problem to be solved.
Anodized refers in electrolyte solution, and the test specimen with conductive surface is placed in anode, in extrinsic current
Under effect, the process of oxidation film is formed in surface of test piece, the film generated is anode oxide film or electrochemical conversion film.Anodic oxygen
The oxidation film that change is handled is thicker, therefore corrosion resistance is preferable, but due to coating poor adhesive force, it is of high cost and
The reasons such as coating impact resistance is undesirable use less in the industrial production.
Since aluminium is very active metal, surface easily forms oxidation film in the solution, interferes the formation of metallic bond, therefore
Its surface carry out plating or chemical plating it is relatively difficult, generally all can first in aluminum alloy surface nickel preplating, then again on the basis of
Plate other metals.Most widely used in nickel chemical plating technology is chemical Ni-P plating, mainly there is leaching zinc-pre-plating layer method and directly chemistry
Two kinds of nickel plating.The major defect of leaching zinc method is in moist corrosive environment, and zinc is anode relative to nickel coating, will be by transverse direction
Corrosion eventually leads to nickel layer peeling.
Heat spraying method is a kind of ripe, effective surface treatment method.The technique is flexible, applied widely, production effect
Rate is high, and matrix and sprayed on material are extensive, in addition to flame spray welding and plasma arc powder built-up welding, with the workpiece of hot-spraying technique processing
It is heated less, the stress deformation very little that workpiece generates.Although thermal spray metal is improved to the corrosion resistance of aluminium alloy, but
Be thermal spraying the obtained coating of mode it is relatively low in the binding force of matrix in layered distribution, coating porosity is higher, these are all needed
Further to improve.
Above-mentioned processing method, which all exists, limits the shortcomings that it is widely applied, and in order to develop, one kind is novel, efficient, environment is friendly
Good treatment technology, the present invention provides a kind of corrosion-resistant pre-treating method of aluminium alloy, by sol gel process, surface alloying
Technique is combined, and improves the corrosion resistance and wear-resisting property of aluminium alloy.
Invention content
The present invention provides a kind of corrosion-resistant pre-treating methods of aluminium alloy.To solve the above problems, the present invention is using such as
Lower technical solution：
A kind of corrosion-resistant pre-treating method of aluminium alloy, includes the following steps：
(1) aluminium alloy is put into impregnation in cleaning solution；
(2) aluminium alloy is put into impregnation in corrosion-resistance treatment liquid, obtains anticorrosion aluminium.
A kind of corrosion-resistant pre-treating method of aluminium alloy, includes the following steps：
(1) aluminium alloy is put into cleaning solution and is impregnated 10-50 minutes, dipping temperature is 25-50 DEG C, aluminium alloy and cleaning solution
Mass ratio be 1:(10-50), after the aluminium alloy after dipping is rinsed with the water that quality is 20-60 times of aluminium alloy quality, in 30-
80 DEG C 1-5 hours dry；
(2) aluminium alloy after step (1) is dry, which is put into corrosion-resistance treatment liquid, to be impregnated, and dipping temperature is 25-50 DEG C, and aluminium closes
Gold and the mass ratio of corrosion-resistance treatment liquid are 1:(10-50), dip time are 20-60 minutes, aluminium alloy are taken out, at 50-90 DEG C
It is 2-6 hours dry, obtain anticorrosion aluminium.
The preparation method of the cleaning solution is as follows：By 5-15g sulfosalicylic acids, 10-40g EDETATE SODIUMs, 10-40g 12
Sodium alkyl benzene sulfonate, 10-40g potassium pyrophosphates are added in 80-150g water, are stirred at 25-50 DEG C, with 100-800 revs/min of rotating speed
It mixes 20-60 minutes, obtains cleaning solution.
The corrosion-resistance treatment liquid is formulated using following methods：20-60g ethyl alcohol, 100-300g water are uniformly mixed,
With salt acid for adjusting pH to 2-5,3-8g ethyl orthosilicates, 10-30g vinyl three (2- methoxy ethoxies) silane, 0.05- is added
0.5g modified mineral powder is stirred 4-12 hours at 30-50 DEG C, with 100-300 revs/min of rotating speed, 0.5-5g ionic liquids is added
Body stirs 1-5 hours at 30-50 DEG C, with 100-300 revs/min of rotating speed, and it is high that 0.5-5g metal salts, 0.5-5g oxalic acid is added
Iron ammonium is stirred 2-6 hours at 30-50 DEG C, with 100-300 revs/min of rotating speed, obtains corrosion-resistance treatment liquid, the ionic liquid
Body is the ionic liquid with pyridyl group, and the metal salt is that nickel nitrate, cerous nitrate, cobalt acetate are (1-2) in mass ratio：(1-2)：
The mixture of (1-2).A concentration of 2-8mol/L of the hydrochloric acid, preferably 5mol/L.
Metal salt described in corrosion-resistance treatment liquid is preferably that nickel nitrate, cerous nitrate, cobalt acetate are 2 in mass ratio：1：1 it is mixed
Close object.
Metal salt can form alloy-layer under the action of ammonium ferric oxalate in aluminum alloy surface, by adjusting three kinds of metal salts
Ratio, improve the hardness and consistency of alloy-layer, and then improve wear-resisting property and corrosion resistance.
Modified mineral powder described in corrosion-resistance treatment liquid is the talcum powder and/or tri-tert boric acid that butyl titanate is modified
Ester modified attapulgite.The modified mineral powder is more preferably the talcum powder and tri-tert boron that butyl titanate is modified
The mixture for the attapulgite that acid esters is modified, ester modified recessed of talcum powder and tri-tert boric acid that the butyl titanate is modified
The mass ratio of convex stick soil is (1-3)：(1-3).
The preparation method for the talcum powder that the butyl titanate is modified is as follows：70-140g ethyl alcohol and 5-25g water are mixed equal
After even, 0.5-5g butyl titanates are added, is stirred 0.5-5 hours, is added with 100-300 revs/min of rotating speed at 30-50 DEG C
30-80g talcum powder is stirred 4-12 hours at 30-50 DEG C with 100-500 revs/min of rotating speed, crosses 2000-3000 mesh sieve,
60-90 DEG C 12-48 hours dry, obtains the talcum powder of butyl titanate modification.
The preparation method of the ester modified attapulgite of tri-tert boric acid is as follows：By 70-140g ethyl alcohol and 5-25g water
After mixing, 0.5-5g tri-tert borates are added, 0.5-3 is stirred with 100-300 revs/min of rotating speed at 30-50 DEG C
Hour, 50-100g attapulgites are added, is stirred 4-12 hours with 100-300 revs/min of rotating speed at 30-50 DEG C, crosses 200-
800 mesh sieve, 12-48 hours dry at 60-95 DEG C, obtain the ester modified attapulgite of tri-tert boric acid.
Addition modified mineral powder can enhance compactness, the hardness of the anticorrosion film of aluminum alloy surface formation, to improve
Its corrosion resistance and wearability.Talcum powder and attapulgite are done into capable of the improving in itself and corrosion-resistance treatment liquid of modification respectively
The compatibility and dispersibility of other components, to form film layer uniformly, fine and close after aluminum alloy surface drying.
Ionic liquid with pyridyl group described in corrosion-resistance treatment liquid is preferably N- hexyl -4- picoline tetrafluoro boric acids
One kind in salt, N- butyl-pyridiniums fluoroform sulphonate, N- butyl-pyridinium tetrafluoroborates is further preferably N- butyl pyrroles
Pyridine fluoroform sulphonate.Ionic liquid can be adsorbed on aluminum alloy surface and delay corrosive effect to improve.
The corrosion-resistant pre-treating method of the aluminium alloy of the present invention closes sol gel process, surface by largely testing
Aurification technique is combined, and by ionic liquid of the addition with slow release effect and modified minerals powder, improves aluminum alloy surface
Compactness, the hardness of the film layer of formation, to improve corrosion resistance and abrasion resistance properties.
The beneficial effects of the invention are as follows：
1, after the processing of the pre-treating method of the present invention, the corrosion resistance of aluminium alloy is strong, can meet in modern environment
Corrosion condition, material is easy to make, and cost is smaller, easy to spread.2, treated, and aluminum alloy surface hardness is big, and wear-resisting property is prominent
Go out, is hardly damaged, service life is long, using effect is good.
On the basis of common knowledge of the art, above-mentioned each optimum condition, can be each preferably to get the present invention in any combination
Embodiment.
Specific implementation mode
It is further illustrated the present invention below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
Product specification selects.
In following embodiments, primary raw material and instrument used are as follows：
Aluminium alloy, 5052 aluminium alloys, component mass percent are：Si：≤ 0.25%, Fe：≤ 0.40%, Cu：≦
0.10%, Mn：≤ 0.10%, Mg：2.20%-2.80%, Cr：0.15%-0.35%, Zn：≤ 0.10%, Al：Surplus.Purchase
From Lan Xiang Aluminums (Shanghai) Co., Ltd..
Sulfosalicylic acid, No. CAS：5965-83-3.
EDETATE SODIUM, No. CAS：6381-92-6.
Neopelex, No. CAS：25155-30-0.
Potassium pyrophosphate, K4O7P2, No. CAS：7320-34-5.
Ethyl alcohol, No. CAS：64-17-5.
Ethyl orthosilicate, No. CAS：78-10-4.
Vinyl three (2- methoxy ethoxies) silane, No. CAS：1067-53-4.
N- hexyl -4- picoline tetrafluoroborates, No. CAS：95242-73-1.
N- butyl-pyridinium tetrafluoroborates, No. CAS：203389-28-0.
N- butyl-pyridinium fluoroform sulphonates, No. CAS：390423-43-5.
Nickel nitrate, Ni (NO3)2, No. CAS：14216-75-2.
Cerous nitrate, Ce (NO3)3·6H2O, No. CAS：10294-41-4.
Cobalt acetate, C4H6CoO4, No. CAS：71-48-7.
Ammonium ferric oxalate, C4H3FeNO8, No. CAS：14221-47-7.
Butyl titanate, No. CAS：5593-70-4.
Talcum powder, 1000 mesh of grain size, model MJ-TCHS, the production of Suzhou Ming Jiang Fine Chemical Co., Ltd.
Tri-tert borate, No. CAS：7397-43-5.
Attapulgite, main ingredient and its content：SiO2：49.76%, TiO2：0.72%, Al2O3：15.54%, Fe2O3：
6.76%, MgO：5.89%, CaO：2.01%, K2O：3.75%, P2O5：14.64%.120 mesh of grain size.Purchase converges prosperous from Jiangsu
Ao Tu Co., Ltds.
In following embodiments, used test method and key instrument are as follows：
Copper sulphate drop is tested：It is tested according to GB 6807-1986, the group of copper sulphate point dropping liquid becomes 41g/L sulfuric acid
Copper, 35g/L sodium chloride and 13mL/L hydrochloric acid (mass fraction of hydrochloric acid is 36.5%), under the conditions of 25 DEG C, with rubber head dropper resistance to
Corrode aluminum alloy surface and drip 0.05ml copper sulphate point dropping liquids, while starting stopwatch, record copper sulphate point dropping liquid from blue blackening when
Between, it randomly chooses 8 different positions in each specimen surface and is tested, as a result take the average value of 8 results.
Neutral salt spray test is tested：According to GB/T10125-2012's《Artificial atmosphere corrosion experiment-salt spray test》It carries out
Test.It observes and records specimen surface and starts the hickie time occur, the corrosion resistance of sample is evaluated with this.
Wear-resisting property is tested：It is ground using high temperature friction and wear testing machine (CSEM companies of Switzerland produce, model THT07-135)
The wearability for studying carefully anticorrosion aluminium surface is tested at 25 DEG C, the ZrO that friction bead is diameter 6mm2Ceramic Balls, friction
Speed is 4cm/s, load 5N, friction length 8mm, before and after 350 turns of anticorrosion aluminium mantle friction, record friction test
Anticorrosion aluminium quality m1And m2, calculate mass loss rate, mass loss rate=(m1-m2)/m1× 100%.
It is further illustrated the present invention below by the mode of embodiment, unless otherwise specified, used number is attached most importance to
Measure number.
Embodiment 1
A kind of corrosion-resistant pre-treating method of aluminium alloy, includes the following steps：
(1) aluminium alloy is put into cleaning solution and is impregnated 25 minutes, dipping temperature is 35 DEG C, the quality of aluminium alloy and cleaning solution
Than being 1:30, it is 3 hours dry at 35 DEG C after the aluminium alloy after dipping is rinsed with the water that quality is 30 times of aluminium alloy quality；
(2) aluminium alloy after step (1) is dry, which is put into corrosion-resistance treatment liquid, to be impregnated, and dipping temperature is 35 DEG C, aluminium alloy
Mass ratio with corrosion-resistance treatment liquid is 1:35, dip time is 40 minutes, takes out aluminium alloy, 3 hours dry at 70 DEG C, is obtained
Anticorrosion aluminium.
The preparation method of the cleaning solution is as follows：By 8g sulfosalicylic acids, 15g EDETATE SODIUMs, 20g detergent alkylate sulphurs
Sour sodium, 15g potassium pyrophosphates are added in 100g water, are stirred 40 minutes at 30 DEG C, with 500 revs/min of rotating speed, obtain cleaning solution.
The preparation method of the corrosion-resistance treatment liquid is as follows：40g ethyl alcohol, 160g water are uniformly mixed, with 5mol/L hydrochloric acid
PH to 3 is adjusted, 5g ethyl orthosilicates, 15g vinyl three (2- methoxy ethoxies) silane, 0.2g modified mineral powder is added,
35 DEG C, stirred 6 hours with 200 revs/min of rotating speed, 2g ionic liquids are added, are stirred at 35 DEG C, with 200 revs/min of rotating speed
2 hours, 4g metal salts, 3g ammonium ferric oxalates is added, stirs 3 hours, obtains corrosion-resistant at 35 DEG C, with 200 revs/min of rotating speed
Treatment fluid.
Wherein, the ionic liquid is N- butyl-pyridinium fluoroform sulphonates；The metal salt be nickel nitrate, cerous nitrate,
Cobalt acetate is 2 in mass ratio：1：1 mixture；The modified mineral powder is the talcum powder and three tertiary fourths that butyl titanate is modified
The mixture of the ester modified attapulgite of ylboronic acid, the talcum powder and tri-tert boric acid that the butyl titanate is modified are ester modified
Attapulgite mass ratio be 3:1.
The preparation method for the talcum powder that the butyl titanate is modified is as follows：After mixing by 92g ethyl alcohol and 8g water, add
Enter 1.5g butyl titanates, is stirred 1 hour with 200 revs/min of rotating speed at 35 DEG C, 65g talcum powder is added, at 35 DEG C with 200
Rev/min rotating speed stir 6 hours, cross 2000 mesh sieve, dry 36 hours at 85 DEG C, obtain the talcum of butyl titanate modification
Powder；
The preparation method of the ester modified attapulgite of tri-tert boric acid is as follows：92g ethyl alcohol and 8g water are mixed equal
After even, 1.5g tri-tert borates are added, is stirred 1 hour with 200 revs/min of rotating speed at 35 DEG C, 65g concave convex rods is added
Soil is stirred 6 hours at 35 DEG C with 200 revs/min of rotating speed, crosses 500 mesh sieve, 36 hours dry at 85 DEG C, obtains tri-tert
The ester modified attapulgite of boric acid.
Embodiment 2
It is substantially the same manner as Example 1, it differs only in, in the present embodiment 2：The preparation method of the corrosion-resistance treatment liquid
It is as follows：40g ethyl alcohol, 160g water are uniformly mixed, with 5mol/L salt acid for adjusting pH to 3,5g ethyl orthosilicates, 15g ethylene is added
Base three (2- methoxy ethoxies) silane, 0.2g modified mineral powder are stirred 6 hours at 35 DEG C, with 200 revs/min of rotating speed, are added
Enter 2g ionic liquids, is stirred 2 hours at 35 DEG C, with 200 revs/min of rotating speed, 4g metal salts, 3g ammonium ferric oxalates is added,
35 DEG C, stirred 3 hours with 200 revs/min of rotating speed, obtain corrosion-resistance treatment liquid.The ionic liquid is N- hexyl -4- methyl
Pyridinium tetrafluoroborate salt；The metal salt is that nickel nitrate, cerous nitrate, cobalt acetate are 2 in mass ratio：1：1 mixture；It is described to change
Property mineral powder be butyl titanate be modified talcum powder and the ester modified attapulgite of tri-tert boric acid mixture, the titanium
The mass ratio for the talcum powder and the ester modified attapulgite of tri-tert boric acid that sour four butyl esters are modified is 3:1.Butyl titanate changes
The preparation method is the same as that of Example 1 for the ester modified attapulgite of the talcum powder and tri-tert boric acid of property.
Embodiment 3
It is substantially the same manner as Example 1, it differs only in, in the present embodiment 3：The preparation method of the corrosion-resistance treatment liquid
It is as follows：40g ethyl alcohol, 160g water are uniformly mixed, with 5mol/L salt acid for adjusting pH to 3,5g ethyl orthosilicates, 15g ethylene is added
Base three (2- methoxy ethoxies) silane, 0.2g modified mineral powder are stirred 6 hours at 35 DEG C, with 200 revs/min of rotating speed, are added
Enter 2g ionic liquids, is stirred 2 hours at 35 DEG C, with 200 revs/min of rotating speed, 4g metal salts, 3g ammonium ferric oxalates is added,
35 DEG C, stirred 3 hours with 200 revs/min of rotating speed, obtain corrosion-resistance treatment liquid.The ionic liquid is N- butyl-pyridiniums four
Borofluoride；The metal salt is that nickel nitrate, cerous nitrate, cobalt acetate are 2 in mass ratio：1：1 mixture；The modified mineral
Powder is the mixture of talcum powder and the ester modified attapulgite of tri-tert boric acid that butyl titanate is modified, four fourth of the metatitanic acid
The mass ratio of ester modified talcum powder and the ester modified attapulgite of tri-tert boric acid is 3:1.The cunning that butyl titanate is modified
The preparation method is the same as that of Example 1 for mountain flour and the ester modified attapulgite of tri-tert boric acid.
Embodiment 4
It is substantially the same manner as Example 1, it differs only in：In the present embodiment 4：The preparation method of the corrosion-resistance treatment liquid is such as
Under：40g ethyl alcohol, 160g water are uniformly mixed, with 5mol/L salt acid for adjusting pH to 3,5g ethyl orthosilicates, 15g vinyl is added
Three (2- methoxy ethoxies) silane, 0.2g modified mineral powder are stirred 6 hours at 35 DEG C, with 200 revs/min of rotating speed, are added
2g ionic liquids are stirred 2 hours at 35 DEG C, with 200 revs/min of rotating speed, 4g metal salts, 3g ammonium ferric oxalates are added, 35
DEG C, stirred 3 hours with 200 revs/min of rotating speed, obtain corrosion-resistance treatment liquid.The ionic liquid is N- butyl-pyridinium trifluoros
Mesylate；The metal salt is that nickel nitrate, cerous nitrate, cobalt acetate are 1 in mass ratio：2：1 mixture；The modified mineral
Powder is the mixture of talcum powder and the ester modified attapulgite of tri-tert boric acid that butyl titanate is modified, four fourth of the metatitanic acid
The mass ratio of ester modified talcum powder and the ester modified attapulgite of tri-tert boric acid is 3:1.The butyl titanate is modified
Talcum powder and the ester modified attapulgite of tri-tert boric acid the preparation method is the same as that of Example 1.
Embodiment 5
It is substantially the same manner as Example 1, it differs only in：In the present embodiment 5：The preparation method of the corrosion-resistance treatment liquid
It is as follows：40g ethyl alcohol, 160g water are uniformly mixed, with 5mol/L salt acid for adjusting pH to 3,5g ethyl orthosilicates, 15g ethylene is added
Base three (2- methoxy ethoxies) silane, 0.2g modified mineral powder are stirred 6 hours at 35 DEG C, with 200 revs/min of rotating speed, are added
Enter 2g ionic liquids, is stirred 2 hours at 35 DEG C, with 200 revs/min of rotating speed, 4g metal salts, 3g ammonium ferric oxalates is added,
35 DEG C, stirred 3 hours with 200 revs/min of rotating speed, obtain corrosion-resistance treatment liquid.The ionic liquid is N- butyl-pyridiniums three
Fluorine mesylate；The metal salt is that nickel nitrate, cerous nitrate, cobalt acetate are 1 in mass ratio：1：2 mixture；The modified mine
Object powder is the mixture of talcum powder and the ester modified attapulgite of tri-tert boric acid that butyl titanate is modified, the metatitanic acid four
The mass ratio of talcum powder and the ester modified attapulgite of tri-tert boric acid that butyl ester is modified is 3:1.The butyl titanate changes
The preparation method is the same as that of Example 1 for the ester modified attapulgite of the talcum powder and tri-tert boric acid of property.
Embodiment 6
It is substantially the same manner as Example 1, it differs only in, in the present embodiment 6：The preparation method of the corrosion-resistance treatment liquid
It is as follows：40g ethyl alcohol, 160g water are uniformly mixed, with 5mol/L salt acid for adjusting pH to 3,5g ethyl orthosilicates, 15g ethylene is added
Base three (2- methoxy ethoxies) silane, 0.2g modified mineral powder are stirred 6 hours at 35 DEG C, with 200 revs/min of rotating speed, are added
Enter 2g ionic liquids, is stirred 2 hours at 35 DEG C, with 200 revs/min of rotating speed, 4g metal salts, 3g ammonium ferric oxalates is added,
35 DEG C, stirred 3 hours with 200 revs/min of rotating speed, obtain corrosion-resistance treatment liquid.The ionic liquid is N- butyl-pyridiniums three
Fluorine mesylate；The metal salt is that nickel nitrate, cerous nitrate, cobalt acetate are 2 in mass ratio：1：1 mixture；The modified mine
Object powder is the talcum powder that butyl titanate is modified.The preparation method is the same as that of Example 1 for the talcum powder that the butyl titanate is modified.
Embodiment 7
It is substantially the same manner as Example 1, it differs only in, in the present embodiment 7：The preparation method of the corrosion-resistance treatment liquid
It is as follows：40g ethyl alcohol, 160g water are uniformly mixed, with 5mol/L salt acid for adjusting pH to 3,5g ethyl orthosilicates, 15g ethylene is added
Base three (2- methoxy ethoxies) silane, 0.2g modified mineral powder are stirred 6 hours at 35 DEG C, with 200 revs/min of rotating speed, are added
Enter 2g ionic liquids, is stirred 2 hours at 35 DEG C, with 200 revs/min of rotating speed, 4g metal salts, 3g ammonium ferric oxalates is added,
35 DEG C, stirred 3 hours with 200 revs/min of rotating speed, obtain corrosion-resistance treatment liquid.The ionic liquid is N- butyl-pyridiniums three
Fluorine mesylate；The metal salt is that nickel nitrate, cerous nitrate, cobalt acetate are 2 in mass ratio：1：1 mixture；The modified mine
Object powder is the ester modified attapulgite of tri-tert boric acid.The preparation method of the ester modified attapulgite of tri-tert boric acid
With embodiment 1.
Comparative example 1
It is substantially the same manner as Example 1, it differs only in, in this comparative example 1：The preparation method of the corrosion-resistance treatment liquid
It is as follows：40g ethyl alcohol, 160g water are uniformly mixed, with 5mol/L salt acid for adjusting pH to 3,5g ethyl orthosilicates, 15g ethylene is added
Base three (2- methoxy ethoxies) silane, 0.2g modified mineral powder are stirred 6 hours at 35 DEG C, with 200 revs/min of rotating speed, are added
Enter 4g metal salts, 3g ammonium ferric oxalates, is stirred 3 hours at 35 DEG C, with 200 revs/min of rotating speed, obtain corrosion-resistance treatment liquid.
The metal salt is that nickel nitrate, cerous nitrate, cobalt acetate are 2 in mass ratio：1：1 mixture；The modified mineral powder is metatitanic acid
The mixture for the talcum powder and the ester modified attapulgite of tri-tert boric acid that four butyl esters are modified, what the butyl titanate was modified
The mass ratio of talcum powder and the ester modified attapulgite of tri-tert boric acid is 3:1.The talcum powder that the butyl titanate is modified
The preparation method is the same as that of Example 1 for ester modified attapulgite with tri-tert boric acid.
Measure of merit
The experiment of copper sulphate drop, neutral salt spray test and wearability test are carried out to anticorrosion aluminium, are shown in Table 1.
Table 1：The experiment of aluminium alloy drop, neutral salt spray test and wearability test table
| Drop time, s | Resistance to neutral salt spray time, h | Mass loss rate, % | |
| Embodiment 1 | 62.5 | 196 | 2.2 |
| Embodiment 2 | 57.2 | 188 | 2.3 |
| Embodiment 3 | 53.4 | 183 | 2.5 |
| Embodiment 4 | 56.2 | 185 | 4.2 |
| Embodiment 5 | 52.1 | 175 | 4.3 |
| Embodiment 6 | 52.8 | 178 | 4.9 |
| Embodiment 7 | 53.6 | 182 | 4.5 |
| Comparative example 1 | 50.2 | 176 | 2.6 |
The corrosion-resistant pre-treating method of the aluminium alloy of the present invention handles passivating technique instead of phosphatization and chromic acid, pollution-free,
It is easy to operate.By forming silane and alloy combined anti-corrosion layer in aluminum alloy surface, reaches and improve aluminum alloy corrosion resistant and resistance to
The effect of mill property.Ionic liquid containing pyridyl group in the corrosion-resistance treatment liquid used, corrosion-resistance treatment liquid is in aluminum alloy surface
Film layer is formed after drying, ionic liquid loads wherein and can be adsorbed on aluminum alloy surface, reaches slow corrosive effect.Corrosion-resistance treatment
The talcum powder and the ester modified attapulgite of tri-tert boric acid being modified containing butyl titanate in liquid, improve the densification of film layer
Property and hardness, make film layer have good corrosion-resistant and wearability.
The preferred embodiment of the present invention has been described in detail above.It should be appreciated that those skilled in the art without
It needs creative work according to the present invention can conceive and makes many modifications and variations.Therefore, all technologies in the art
Personnel are available by logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea
Technical solution, all should be in the protection domain being defined in the patent claims.
Claims (8)
1. a kind of corrosion-resistant pre-treating method of aluminium alloy, which is characterized in that include the following steps：
(1) aluminium alloy is put into impregnation in cleaning solution；
(2) aluminium alloy is put into impregnation in corrosion-resistance treatment liquid, obtains anticorrosion aluminium.
2. a kind of corrosion-resistant pre-treating method of aluminium alloy, which is characterized in that include the following steps：
(1) aluminium alloy is put into cleaning solution and is impregnated 10-50 minutes, dipping temperature is 25-50 DEG C, the matter of aluminium alloy and cleaning solution
Amount is than being 1:(10-50), after the aluminium alloy after dipping is rinsed with the water that quality is 20-60 times of aluminium alloy quality, at 30-80 DEG C
It is 1-5 hours dry；
(2) aluminium alloy after step (1) is dry, which is put into corrosion-resistance treatment liquid, to be impregnated, and dipping temperature is 25-50 DEG C, aluminium alloy with
The mass ratio of corrosion-resistance treatment liquid is 1:(10-50), dip time are 20-60 minutes, aluminium alloy are taken out, in 50-90 DEG C of drying
2-6 hours, obtain anticorrosion aluminium.
3. the corrosion-resistant pre-treating method of aluminium alloy according to claim 1 or 2, which is characterized in that the cleaning solution
Preparation method is as follows：By 5-15g sulfosalicylic acids, 10-40g EDETATE SODIUMs, 10-40g neopelexes, 10-40g
Potassium pyrophosphate is added in 80-150g water, is stirred 20-60 minutes at 25-50 DEG C, with 100-800 revs/min of rotating speed, obtains institute
State cleaning solution.
4. the corrosion-resistant pre-treating method of aluminium alloy according to claim 1 or 2, which is characterized in that the corrosion-resistant place
The preparation method for managing liquid is as follows：20-60g ethyl alcohol, 100-300g water are uniformly mixed, with salt acid for adjusting pH to 2-5,3-8g is added
Ethyl orthosilicate, 10-30g vinyl three (2- methoxy ethoxies) silane, 0.05-0.5g modified mineral powder, 30-50 DEG C,
Stirred 4-12 hour with 100-300 revs/min of rotating speed, 0.5-5g ionic liquids be added, 30-50 DEG C, with 100-300 turns/
The rotating speed of minute stirs 1-5 hours, 0.5-5g metal salts, 0.5-5g ammonium ferric oxalates is added, at 30-50 DEG C, with 100-300
Rev/min rotating speed stir 2-6 hour, obtain the corrosion-resistance treatment liquid, the ionic liquid is the ionic liquid with pyridyl group
Body, the metal salt are that nickel nitrate, cerous nitrate, cobalt acetate are (1-2) in mass ratio：(1-2)：The mixture of (1-2), it is described to change
Property mineral powder be talcum powder and/or the ester modified attapulgite of tri-tert boric acid that butyl titanate is modified.
5. the corrosion-resistant pre-treating method of aluminium alloy according to claim 4, which is characterized in that the butyl titanate changes
The preparation method of the talcum powder of property is as follows：After mixing by 70-140g ethyl alcohol and 5-25g water, four fourth of 0.5-5g metatitanic acids is added
Ester is stirred 0.5-5 hour at 30-50 DEG C with 100-300 revs/min of rotating speed, addition 30-80g talcum powder, 30-50 DEG C with
100-500 revs/min of rotating speed stirs 4-12 hours, crosses 2000-3000 mesh sieve, 12-48 hours dry at 60-90 DEG C, obtains
The talcum powder that butyl titanate is modified；The preparation method of the ester modified attapulgite of tri-tert boric acid is as follows：By 70-
After mixing, 0.5-5g tri-tert borates are added, at 30-50 DEG C with 100-300 revs/min in 140g ethyl alcohol and 5-25g water
The rotating speed of clock stirs 0.5-3 hours, and 50-100g attapulgites are added, and is stirred with 100-300 revs/min of rotating speed at 30-50 DEG C
4-12 hours, 200-800 mesh sieve is crossed, it is 12-48 hours dry at 60-95 DEG C, obtain the ester modified concave convex rod of tri-tert boric acid
Soil.
6. the corrosion-resistant pre-treating method of aluminium alloy according to claim 4, which is characterized in that it is described with pyridyl group from
Sub- liquid is N- hexyl -4- picolines tetrafluoroborate, N- butyl-pyridiniums fluoroform sulphonate, N- butyl-pyridinium tetrafluoro boric acids
One kind in salt.
7. the corrosion-resistant pre-treating method of aluminium alloy according to claim 6, which is characterized in that it is described with pyridyl group from
Sub- Liquids Ionic liquids are N- butyl-pyridinium fluoroform sulphonates.
8. the corrosion-resistant pre-treating method of aluminium alloy according to claim 4, which is characterized in that the modified mineral powder is
The mixture for the talcum powder and the ester modified attapulgite of tri-tert boric acid that butyl titanate is modified, the butyl titanate change
Property talcum powder and the ester modified attapulgite of tri-tert boric acid mass ratio be (1-3)：(1-3).
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| CN111621791A (en) * | 2020-05-06 | 2020-09-04 | 中国石油天然气集团有限公司 | Oil refining distillation tower top corrosion inhibitor capable of resisting corrosion of dilute hydrochloric acid and hydrogen sulfide |
| CN111621791B (en) * | 2020-05-06 | 2022-05-10 | 中国石油天然气集团有限公司 | Oil refining distillation tower top corrosion inhibitor capable of resisting corrosion of dilute hydrochloric acid and hydrogen sulfide |
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