CN109777290A - A kind of process for treating surface of the ultralight corrosion-resistant aviation aluminum alloy material of high-performance - Google Patents
A kind of process for treating surface of the ultralight corrosion-resistant aviation aluminum alloy material of high-performance Download PDFInfo
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- CN109777290A CN109777290A CN201811582641.7A CN201811582641A CN109777290A CN 109777290 A CN109777290 A CN 109777290A CN 201811582641 A CN201811582641 A CN 201811582641A CN 109777290 A CN109777290 A CN 109777290A
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- 238000000034 method Methods 0.000 title claims abstract description 68
- 238000005260 corrosion Methods 0.000 title claims abstract description 62
- 230000007797 corrosion Effects 0.000 title claims abstract description 57
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 38
- 239000000956 alloy Substances 0.000 title claims abstract description 20
- 230000008569 process Effects 0.000 title claims description 42
- 239000003755 preservative agent Substances 0.000 claims abstract description 63
- 230000002335 preservative effect Effects 0.000 claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000002904 solvent Substances 0.000 claims abstract description 27
- 238000004381 surface treatment Methods 0.000 claims abstract description 23
- 239000003513 alkali Substances 0.000 claims abstract description 21
- 238000000576 coating method Methods 0.000 claims abstract description 20
- 238000005238 degreasing Methods 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 19
- 239000012224 working solution Substances 0.000 claims abstract description 14
- 238000012545 processing Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000012360 testing method Methods 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000005507 spraying Methods 0.000 claims abstract description 7
- -1 Rare-earth salts Chemical class 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 36
- 238000004140 cleaning Methods 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 125000005375 organosiloxane group Chemical group 0.000 claims description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 13
- 239000003518 caustics Substances 0.000 claims description 12
- 238000001514 detection method Methods 0.000 claims description 12
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- 238000002156 mixing Methods 0.000 claims description 11
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- 239000002585 base Substances 0.000 claims description 10
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- 238000003756 stirring Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000007605 air drying Methods 0.000 claims description 6
- 238000003556 assay Methods 0.000 claims description 6
- 229940117975 chromium trioxide Drugs 0.000 claims description 6
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 6
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 6
- 239000010931 gold Substances 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 230000035800 maturation Effects 0.000 claims description 6
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
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- 238000012797 qualification Methods 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- PKDCQJMRWCHQOH-UHFFFAOYSA-N triethoxysilicon Chemical compound CCO[Si](OCC)OCC PKDCQJMRWCHQOH-UHFFFAOYSA-N 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 230000036961 partial effect Effects 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 3
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
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- HHPPHUYKUOAWJV-UHFFFAOYSA-N triethoxy-[4-(oxiran-2-yl)butyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCCC1CO1 HHPPHUYKUOAWJV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
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- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 2
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- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 claims description 2
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
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Landscapes
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention discloses a kind of surface treatment method of the ultralight corrosion-resistant aviation aluminum alloy material of high-performance, including the following steps: it receives and testing stage, manual solvent wash phase, protects and shelve stage, ultrasonic degreasing alkali wash phase, water rinses, moisture film detection-phase, preservative treatment stage, deoxidation treatment stage, hot water drying stage and unload the frame removal protection stage.Wherein the step of preservative treatment stage are as follows: preservative is first made, then the metal conditioner of 23.4 mass parts and the deionized water of 96.5 mass parts are sufficiently mixed, preservative treatment working solution is made；It by the spraying of preservative treatment working solution, brushes or is immersed in aerolite surface, deposit and heat 0.5 ~ 2h in an oven, heating temperature is 50 ~ 60 DEG C, until aerolite surface forms coating, realizes surface anticorrosion processing.
Description
Technical field
The invention belongs to technical field of aluminum alloy surface treatment, in particular to a kind of ultralight corrosion-resistant aviation aluminium of high-performance closes
The process for treating surface of golden material.
Background technique
Between metal material and its product and locating natural atmosphere environment because of caused by the effect of meteorological and environmental factor metal
The atmospheric corrosion of the phenomenon that going bad, even destroying referred to as metal.Its corrode mechanism mainly by moisture, oxygen contained in atmosphere and
The combined effect of corrosive medium (including impurity, flue dust, the surface deposits etc. in rainwater).Chemical corruption can be divided by corrosion reaction
Erosion and two kinds of electrochemical corrosion, except tarnishing and change caused by surface oxidation, vulcanization occur in the atmospheric environment of dry no moisture
Color etc. belongs to outside chemical attack, in most cases belongs to electrochemical corrosion.Atmospheric corrosion is one kind of electrochemical corrosion
Special shape, is the corrosion process that metal surface is under thin electrolyte layer, and corrosion process had both submitted to the one of electrochemical corrosion
As rule, and have atmospheric corrosion itself the characteristics of.Electrolyte membrane be due to moisture in air in the adsorption-condensation of metal surface and
It is formed dissolved with air pollutant, cathodic process is the unpolarizing of oxygen, and anodic process is dissolution and the water of metal
Change, but is often blocked because anodic passivity and metal ion aquation process are difficult.Thickness of liquid film and dry and wet alternative frequency and
Oxygen diffuses into liquid film and the speed of metal interface determines corrosion of metal speed.
Aircraft positioned at coastal airport flies throughout the year, docks at high humility, in high temperature, highly-saline atmosphere, individual airports
Relative humidity is up to 40% in 80% or more time.The presence of water is plus difficult in the processing of aircaft configuration aluminium alloy, assembly and use
Accumulated with the gap of elimination, exposed metal surface, dust, surface scratching and the contact of inevitable dissimilar metal part are corrosion
Generation creates necessary condition.According to coastal area aircraft structure erosion situation investigation and corrosion, harmfulness.
Analysis finds that the Aircraft Corrosion that coastal area uses focuses primarily upon the high humidity position and ponding position of aircraft lower surface, such as big
Beam, stringer, in main gear wheels cabin, the positions such as Front wing spar web, covering lower wall panels edge and jointing.Wherein before wing
The corrosion of fine strain of millet web is the most serious, and the extent of corrosion of lower wall panels is also difficult to ignore at horizontal tail counterweight.Comparatively, the corruption of aircaft configuration
Erosion is mainly the atmospheric corrosion generated when the storage of ground, and seriously corroded degree is related with the calendar limit year that aircraft is on active service, and is on active service
Time is longer, and corrosion is more serious.It has been found that aircraft is in coastal area in use, fine strain of millet web and horizontal tail before 4 years wings are parked in airport
It begins to corrode at counterweight, with 9 years post-etching lesion developments to the degree for needing to return factory's overhaul.In addition, Boeing adopts
The aircraft structure corrosion data of collection show, the reporting rate more than each airline's second level corroded in the world, from 1993 to
1997 on a declining curve, and overall after 1998 is in rise trend.
For the service life for extending aircraft, guarantee safety, reliability and the durability of aircraft, each airline throws every year
Enter a considerable amount of human and material resources and financial resources, timely and necessary repairing is carried out to the corrosion location of aircaft configuration.Due to aluminium
Alloy corrosion is difficult to avoid that, wishes that the idea for thoroughly eliminating corrosion is difficult to realize by constantly repairing, best bet is only
It can be the corrosion damage of real-time monitoring aircraft structure under the premise of taking more perfect corrosion protection steps, in this, as
Corrode the Technical Reference repaired.And due in aircraft flight material gentlier facilitate its flight it is steady.Therefore, around winged
Machine structure erosion carries out " process for treating surface of ultralight corrosion-resistant aviation aluminum alloy material " research and has a very important significance.
Present, the main problems are as follows:
1, most common chromate chemical oxidizing process in current chemical oxidization method, although the corrosion resistance that can be enabled aluminum alloy to obtains significantly
It improves.But the shortcomings that technical method, is also very significant, as the hexavalent chromate occurred in its technical process be a kind of environment pole not
Friendly height carcinogen；And strong acid used in these technical process (including fluorine-containing strong acid), highly basic, Yi Jigong
A large amount of ejected wash water used in skill process all produces a large amount of process waste liquor and cleaning waste water in process of production, is working as
The preceding whole world is advocated under the overall background of environmentally friendly low-carbon, and the processing of these waste liquids and waste water is all that this technique brings great ring
Border problem and high environmental treatment cost.
2, in order to improve colloidal sol-gel coat antiseptic property, there is document description using double polysulfur silanes and add nanometer
Aluminium oxide or nanometer silicon dioxide particle, so that it may the sol- gel coating with preferable antiseptic property be made.But at chromate
Reason layer is compared, and the coating is without self-repair function, when encountering external force collision, scraping, exposed aluminum alloy surface at coating damage
Begin to fast erosion.It is described in Journal of Rare Earths, Vol 28, No.1, Feb.2010,117-122,
Double coatings that colloidal sol-gel coat and rare earth coating combine are prepared in aluminum alloy surface, to improve the property of corrosion-inhibiting coating
Energy.But this method need to coat twice, dry twice, increase operating procedure, increase technology difficulty and production cost.
3, traditional anti-corrosion spray process is low to sol solutions utilization rate, results in waste of resources, and for user not
It is economical.
4, the effect is unsatisfactory for the acquirement of traditional anti-corrosion anti-corrosion spray process.
Summary of the invention
Goal of the invention: in order to overcome the above deficiency, the object of the present invention is to provide a kind of ultralight corrosion-resistant aviations of high-performance
The surface treatment method of aluminum alloy materials prepares the material of preservative as chromate is replaced by using rare-earth salts, not only
So that preservative anti-corrosion deactivation function is more perfect, and its to compare chromate safer, environmentally friendly.And its system to preservative
Take the process rational and orderly of the surface treatment of process and aerolite and efficient and not high for equipment requirement, environment friend
Good, pollution-free, inexpensive, method is simple to operation, has extraordinary generalization.It is high to the utilization rate of sol solutions, except condensation
It is a kind of Eco-power production work of height almost without other losses except resulting small molecule product (such as water and ethyl alcohol etc.)
Skill.
Technical solution: to achieve the goals above, the present invention provides a kind of ultralight corrosion-resistant aerolites of high-performance
The surface treatment method of material, including the following steps:
1. reception and testing stage: receiving and examine to aerolite, enter next step after the assay was approved；
2. manual solvent wash phase: the manual solvent cleaning of aerolite progress to qualification is examined；
3. protecting and shelving the stage: shelving to the aerolite after manual solvent cleans is carried out to protect；
4. ultrasonic degreasing alkali wash phase: aerolite is carried out the cleaning of ultrasonic degreasing alkali；
5. water rinses: carrying out water cleaning to the aerolite after the cleaning of ultrasonic degreasing alkali；
6. moisture film detection-phase: aerolite contains moisture film and then returns to the 2. step cycle after detection, and aviation aluminium closes after detection
Moisture film does not enter next stage then to gold；
7. the deoxidation treatment stage: by aerolite 50 DEG C ~ 60 DEG C at a temperature of be placed in the sodium hydroxide solution of 40 ~ 60 g/L
Middle immersion, 0.5 ~ 1.5min of time, this process are known as caustic corrosion；Aerolite thoroughly cleans after caustic corrosion through water, then will
The concentrated nitric acid of 175ml65%, 50ml chromium trioxide, the hydrofluoric acid of 12.5ml47%, the thiocarbamide of 7.5ml, 0.5 ~ 1g Qula lead to X-
100 and suitable water be configured to the deoxidation liquid of 1L, the aerolite after water thoroughly cleans is immersed in deoxidation liquid at room temperature
Middle carry out deoxidation treatment, time are 2 ~ 3min；After deoxidation treatment, protective coating, the chemistry milling of use are coated within 24 h
Protective glue is AC850, and the sample after coating protective glue will carry out curing process, 24 h of natural air drying；
8. the preservative treatment stage: preservative is first made, then by the deionized water of the preservative of 23.4 mass parts and 96.5 mass parts
It is sufficiently mixed, preservative treatment working solution is made；By the spraying of preservative treatment working solution, brushes or be immersed in after deoxidation treatment
The surface of aerolite deposits in an oven and heats 0.5 ~ 2h, and heating temperature is 50 ~ 60 DEG C, until aerolite table
Face forms coating, realizes surface anticorrosion processing；
9. hot water dries up the stage: the aerolite after preservative treatment being carried out hot water cleaning and is dried up again with compressed air；
10. unloading the frame removal protection stage: terminating after the aerolite after drying is unloaded adduction removal protection.
Heretofore described reception and testing stage and moisture film detection-phase facilitates screening and meets further work
Aerolite, the setting examined in this way is so that whole surface treatment process is more rigorous fine.Manual solvent wash phase,
Ultrasonic degreasing alkali wash phase, water rinses, preservative treatment stage, deoxidation treatment stage and the setting science in hot water drying stage
Orderly, so that whole surface treatment process accurately and effectively carries out.Aerolite can not only be fixed by protecting and shelve the stage
Position so that it is subsequent cleaning efficiently carry out, aerolite can also be protected, it is allowed to be less subject to damage.
Heretofore described preservative is formed by following weight:
Organosiloxane: 1 ~ 12%；
Additive: 0.1 ~ 5%；
Rare-earth salts: 0.5 ~ 8%；
Catalyst: 0.1 ~ 5%；
Remaining as organic solvent.
Heretofore described organosiloxane is the hydridization by constituting along inorganic siloxane main chain suspending side organic group
Material, referred to as half inorganic polymer, surface tension is low, and characterization pressure is low, has liquid performance when high molecular weight, extremely low
Viscosity-temperature coefficient, hydrophobicity, pole be not easy with many materials gluing, so be that extraordinary preservative prepares raw material.Rare-earth salts is
As replace chromate come so that the preservative prepared have effects that be passivated product, compare chromate it is safer,
Environmental protection.Organic solvent is a major class widely applied organic compound in life and production, and molecular weight is little, it is present in painting
In material, adhesive, paint and detergent.Organic solvent can dissolve some (such as grease, wax, resin, rubber, dyestuffs not soluble in water
Deng) organic compound there is biggish volatility its main feature is that be in a liquid state at normal temperatures and pressures, in course of dissolution, solute
No changes have been made with the property of solvent.
The structural formula of organosiloxane of the present invention are as follows: [Si (R1) (R2) 3] n, in which: n=1 or 2, i.e., one
On a silicon atom containing one or two group R1 and 2 or 3 group R2 either on two adjacent silicon atoms and
Each silicon atom respectively contains one or two group R1 and 2 or 3 group R2.
Organosiloxane of the present invention is the hydridization material by constituting along inorganic siloxane main chain suspending side organic group
Material, referred to as half inorganic polymer, surface tension is low, and characterization pressure is low, and high molecular weight when has liquid performance, extremely low
Viscosity-temperature coefficient, hydrophobicity, pole be not easy with many materials gluing, so be that extraordinary preservative prepares raw material.
A kind of surface treatment method of the ultralight corrosion-resistant aviation aluminum alloy material of high-performance according to claim 3,
It is characterized by: the group R1 is inseparable and hydrolyzes, group R2 hydrolyzable simultaneously be can remove；The group R1 is first
Base, ethyl, propyl, n-butyl, isobutyl group, sec-butyl, tert-butyl, propyl disulfide group, vinyl, 1- acrylic, 2- propylene
Base, butenyl group, acetenyl, propynyl residue, phenyl, naphthyl group, methylacryloyl, methylacryloyl oxygen propyl group
One of group, glycidyl, glycidoxy groups, ammonia aryl or aminoalkyl group；The group R2 is first
Oxygroup, ethyoxyl, n-propoxy, iso- propoxyl group, n-butoxy, iso- butoxy, sec- butoxy, t-butoxy, n- penta
Oxygroup, n- hexyloxy group, cyclopropyl oxygroup, cyclohexyloxy, phenoxy group, acyloxy, acetoxyl group, propionyloxy or acetyl group
One of.
Organosiloxane of the present invention is the hydridization material by constituting along inorganic siloxane main chain suspending side organic group
Material, referred to as half inorganic polymer, surface tension is low, and characterization pressure is low, and high molecular weight when has liquid performance, extremely low
Viscosity-temperature coefficient, hydrophobicity, pole be not easy with many materials gluing, so be that extraordinary preservative prepares raw material.
Organosiloxane of the present invention is vinyltriethoxysilane, acrylic triethoxysilane, 3- amino
Propyl-triethoxysilicane, 3- (triethoxy silicon substrate) propylacrylate rouge, 3- glycidylpropyl triethoxysilane, 3- mercapto
Base propyl-triethoxysilicane, N- (2- amino-ethyl) -3-aminopropyltriethoxysilane, N- [N '-(2'- amino second
Base) -2- amino-ethyl] -3- aminopropyl-triethoxysilane, N- phenyl amino propyl triethoxysilane double-(3- (three
Ethyoxyl) silicon substrate propyl) one of tetrasulfide or double-(3- (triethoxy) silicon substrate propyl) ethane.
Organosiloxane of the present invention is the hydridization material by constituting along inorganic siloxane main chain suspending side organic group
Material, referred to as half inorganic polymer, surface tension is low, and characterization pressure is low, and high molecular weight when has liquid performance, extremely low
Viscosity-temperature coefficient, hydrophobicity, pole be not easy with many materials gluing, so be that extraordinary preservative prepares raw material.
Additive of the present invention is nano silica particle, and partial size is 50 ~ 100 nanometers.
SiO2 particle of the present invention is also known as silica, and chemical property is more stable, does not react with water, is acidic oxidation
Object, the acid reaction not with.Gaseous hydrogen fluoride generates Gaseous silicon tetrafluoride with silicon dioxde reaction.With heat dense strong base solution or
The alkali reaction of fusing generates silicate and water.It is reacted at high temperature with Multimetal oxide and generates silicate.For manufacturing stone
English glass, optical instrument, chemical ware, simple glass, refractory material, optical fiber, ceramics etc..The property of silica is not lived
It sprinkles, it does not act on (except hot concentrated phosphoric acid) with halogen, hydrogen halides and sulfuric acid, nitric acid, the perchloric acid other than fluorine removal, hydrogen fluoride.
It is as the product appearance for helping preservative to brush holding certain degree of hardness after solidification here.
Rare-earth salts of the present invention is the hydrate or hard of the hydrate of cerous nitrate, the hydrate of cerium oxide, cerous acetate
Resin acid cerium.
Rare-earth salts of the present invention is come as substitution chromate so that the preservative prepared has effects that passivation
Product, it is safer, environmentally friendly to compare chromate.
Catalyst of the present invention be aliphatic monocarboxylic acid such as acetic acid, dicarboxylic acids and tricarboxylic acid such as citric acid,
One of nitric acid, hydrochloric acid, ethanol amine, triethylamine or its mixing.
Heretofore described catalyst refers to that can change reactant chemical reaction rate in chemical reaction (improves or drop
It is low) without changing chemical balance, and the quality of itself and the chemical property substance that all no change has taken place before and after chemical reaction.
Its addition facilitates under the premise of not changing product quality, and preservative is highly efficient to be rapidly made.
Heretofore described organic solvent is the fatty alcohol of 1 to 10 carbon atoms.
Heretofore described organic solvent is a major class widely applied organic compound, molecule in life and production
Less, it is present in coating, adhesive, paint and detergent amount.Organic solvent can dissolve it is some it is not soluble in water (such as grease,
Wax, resin, rubber, dyestuff etc.) organic compound there is biggish volatility its main feature is that be in a liquid state at normal temperatures and pressures,
In course of dissolution, no changes have been made for the property of solute and solvent.
The preparation method of heretofore described preservative the following steps are included:
1. organosiloxane and rare-earth salts are added in organic solvent, 20 ~ 40 DEG C are warming up to, the solution A of stirring and dissolving；
2. additive and catalyst mixing are added in solution A, 60 ~ 80 DEG C are heated to, 30 ~ 50min is stirred, is cooled to room temperature,
Obtain solution B.
3. solution B is carried out maturation process, gained is preservative.
In the present invention to the producing process rational and orderly of preservative and efficiently, and not high for equipment requirement, environmental-friendly,
Pollution-free, inexpensive, method is simple to operation, has extraordinary generalization.First organosiloxane and rare-earth salts addition are had
It in solvent, is condensed between silanol, prevents gel agglomerates, be conducive to close in aluminum alloy surface Al-O-Si formation of chemical bond in aluminium
Gold surface forms fine and close highly cross-linked gel film layer, and the addition of diluted acid salt is conducive to graphene and divides in gel-sol system
It dissipates uniformly, forms a film in aluminum alloy surface, fill and lead up aluminum alloy surface defect, improve the anti-corrosive properties of aluminium alloy.It is added in the solution again
Additive and catalyst mixing, effectively control the reaction speed of organosiloxane, prevent organosiloxane from excessively hydrolyzing.And
And the additive of addition not only promotes the formation of collosol-gelatum system, promotes film forming, moreover, sol-gel is crosslinked cerium salt,
Keep gel layer finer and close, improves antiseptic property.
Compared with prior art, the present invention controls the addition sequence of the selection of raw material, dosage when in preparation process, makes to make
Standby gel mould is highly cross-linked, and compactness is good, can fill and lead up aluminum alloy surface defect, and then improve the corrosion resistance of aluminium alloy layer
Energy.
Above-mentioned technical proposal can be seen that the invention has the following beneficial effects:
1, rare-earth salts is used as chromate is replaced to prepare the material of preservative, not only makes preservative anti-corrosion deactivation function more
To be perfect, and its to compare chromate safer, environmentally friendly.
2, to the process rational and orderly of the surface treatment of the producing process of preservative and aerolite and efficiently, and right
Not high in equipment requirement, environmental-friendly, pollution-free, inexpensive, method is simple to operation, has extraordinary generalization.
3, high to the utilization rates of sol solutions, in addition to the resulting small molecule product (such as water and ethyl alcohol etc.) of condensation almost without
Other losses are a kind of Eco-power production technologies of height.
4, first organosiloxane and rare-earth salts are added in organic solvent, are condensed between silanol, prevent gel agglomerates, favorably
In in aluminum alloy surface Al-O-Si formation of chemical bond, fine and close highly cross-linked gel film layer, diluted acid salt are formed in aluminum alloy surface
Addition, be conducive to graphene and be uniformly dispersed in gel-sol system, aluminum alloy surface form a film, fill and lead up aluminum alloy surface
Defect improves the anti-corrosive properties of aluminium alloy.Additive and catalyst mixing is added in the solution again, effectively controls organosiloxane
Reaction speed, prevent organosiloxane from excessively hydrolyzing.The additive of addition not only promotes the formation of collosol-gelatum system,
Promote film forming, and sol-gel is crosslinked cerium salt, keeps gel layer finer and close, improves antiseptic property.
Specific embodiment
Combined with specific embodiments below, the present invention is furture elucidated.
Embodiment 1
A kind of surface treatment method of the ultralight corrosion-resistant aviation aluminum alloy material of the high-performance showed in the present embodiment, including with
Under several steps:
1. reception and testing stage: receiving and examine to aerolite, enter next step after the assay was approved；
2. manual solvent wash phase: the manual solvent cleaning of aerolite progress to qualification is examined；
3. protecting and shelving the stage: shelving to the aerolite after manual solvent cleans is carried out to protect；
4. ultrasonic degreasing alkali wash phase: aerolite is carried out the cleaning of ultrasonic degreasing alkali；
5. water rinses: carrying out water cleaning to the aerolite after the cleaning of ultrasonic degreasing alkali；
6. moisture film detection-phase: aerolite contains moisture film and then returns to the 2. step cycle after detection, and aviation aluminium closes after detection
Moisture film does not enter next stage then to gold；
7. the deoxidation treatment stage: by aerolite 50 DEG C ~ 60 DEG C at a temperature of be placed in the sodium hydroxide solution of 40 ~ 60 g/L
Middle immersion, 0.5 ~ 1.5min of time, this process are known as caustic corrosion；Aerolite thoroughly cleans after caustic corrosion through water, then will
The concentrated nitric acid of 175ml65%, 50ml chromium trioxide, the hydrofluoric acid of 12.5ml47%, the thiocarbamide of 7.5ml, 0.5 ~ 1g Qula lead to X-
100 and suitable water be configured to the deoxidation liquid of 1L, the aerolite after water thoroughly cleans is immersed in deoxidation liquid at room temperature
Middle carry out deoxidation treatment, time are 2 ~ 3min；After deoxidation treatment, protective coating, the chemistry milling of use are coated within 24 h
Protective glue is AC850, and the sample after coating protective glue will carry out curing process, 24 h of natural air drying；
8. the preservative treatment stage: 98.3wt% is added in the hydrate of 1wt% vinyltriethoxysilane and 0.5wt% cerous nitrate
1 carbon atom aliphatic alcohol solvent in, be warming up to 20 DEG C, the solution A of stirring and dissolving；The grain of 0.1wt% is added in solution A
SiO2 particle and 0.1wt% the acetic acid mixing that diameter is 70 nanometers, are heated to 60 DEG C, stir 30min, be cooled to room temperature, obtain solution
B；Solution B is subjected to maturation process, preservative is made.Again by the deionized water of the preservative of 23.4 mass parts and 96.5 mass parts
It is sufficiently mixed, preservative treatment working solution is made；By the spraying of preservative treatment working solution, aerolite surface is brushed or is immersed in,
0.5h is deposited and heated in an oven, and heating temperature is 50 DEG C, until aerolite surface forms coating, realizes that surface is anti-
Corruption processing；
9. hot water dries up the stage: the aerolite after preservative treatment being carried out hot water cleaning and is dried up again with compressed air；
10. unloading the frame removal protection stage, terminate after the aerolite after drying is unloaded adduction removal protection.
Embodiment 2
A kind of surface treatment method of the ultralight corrosion-resistant aviation aluminum alloy material of the high-performance showed in the present embodiment, including with
Under several steps:
1. reception and testing stage: receiving and examine to aerolite, enter next step after the assay was approved；
2. manual solvent wash phase: the manual solvent cleaning of aerolite progress to qualification is examined；
3. protecting and shelving the stage: protecting and shelve to the aerolite after manual solvent cleans is carried out；
4. ultrasonic degreasing alkali wash phase: aerolite is carried out the cleaning of ultrasonic degreasing alkali；
5. water rinses: carrying out water cleaning to the aerolite after the cleaning of ultrasonic degreasing alkali；
6. moisture film detection-phase: aerolite contains moisture film and then returns to the 2. step cycle after detection, and aviation aluminium closes after detection
Moisture film does not enter next stage then to gold；
7. the deoxidation treatment stage: by aerolite 50 DEG C ~ 60 DEG C at a temperature of be placed in the sodium hydroxide solution of 40 ~ 60 g/L
Middle immersion, 0.5 ~ 1.5min of time, this process are known as caustic corrosion；Aerolite thoroughly cleans after caustic corrosion through water, then will
The concentrated nitric acid of 175ml65%, 50ml chromium trioxide, the hydrofluoric acid of 12.5ml47%, the thiocarbamide of 7.5ml, 0.5 ~ 1g Qula lead to X-
100 and suitable water be configured to the deoxidation liquid of 1L, the aerolite after water thoroughly cleans is immersed in deoxidation liquid at room temperature
Middle carry out deoxidation treatment, time are 2 ~ 3min；After deoxidation treatment, protective coating, the chemistry milling of use are coated within 24 h
Protective glue is AC850, and the sample after coating protective glue will carry out curing process, 24 h of natural air drying；
8. the preservative treatment stage: by the hydrate of 3- (triethoxy silicon substrate) propylacrylate rouge and 8wt% cerium oxide of 12wt%
It is added in the aliphatic alcohol solvent of 2 carbon atoms of 70wt%, is warming up to 30 DEG C, the solution A of stirring and dissolving；It is added in solution A
The dicarboxylic acids mixing for the SiO2 particle and 5wt% that the partial size of 5wt% is 50 nanometers, is heated to 70 DEG C, stirs 40min, be cooled to
Room temperature obtains solution B；Solution B is subjected to maturation process, preservative is made.Again by the preservative of 23.4 mass parts and 96.5 matter
The deionized water of amount part is sufficiently mixed, and preservative treatment working solution is made；By the spraying of preservative treatment working solution, brush or be immersed in boat
Empty aluminum alloy surface deposits in an oven and heats 1h, and heating temperature is 55 DEG C, until aerolite surface forms coating,
Realize surface anticorrosion processing；
9. hot water dries up the stage: the aerolite after preservative treatment being carried out hot water cleaning and is dried up again with compressed air；
10. unloading the frame removal protection stage, terminate after the aerolite after drying is unloaded adduction removal protection.
Embodiment 3
A kind of surface treatment method of the ultralight corrosion-resistant aviation aluminum alloy material of the high-performance showed in the present embodiment, including with
Under several steps:
1. reception and testing stage: receiving and examine to aerolite, enter next step after the assay was approved；
2. manual solvent wash phase: the manual solvent cleaning of aerolite progress to qualification is examined；
3. protecting and shelving the stage: protecting and shelve to the aerolite after manual solvent cleans is carried out；
4. ultrasonic degreasing alkali wash phase: aerolite is carried out the cleaning of ultrasonic degreasing alkali；
5. water rinses: carrying out water cleaning to the aerolite after the cleaning of ultrasonic degreasing alkali；
6. moisture film detection-phase: aerolite contains moisture film and then returns to the 2. step cycle after detection, and aviation aluminium closes after detection
Moisture film does not enter next stage then to gold；
7. the deoxidation treatment stage: by aerolite 50 DEG C ~ 60 DEG C at a temperature of be placed in the sodium hydroxide solution of 40 ~ 60 g/L
Middle immersion, 0.5 ~ 1.5min of time, this process are known as caustic corrosion；Aerolite thoroughly cleans after caustic corrosion through water, then will
The concentrated nitric acid of 175ml65%, 50ml chromium trioxide, the hydrofluoric acid of 12.5ml47%, the thiocarbamide of 7.5ml, 0.5 ~ 1g Qula lead to X-
100 and suitable water be configured to the deoxidation liquid of 1L, the aerolite after water thoroughly cleans is immersed in deoxidation liquid at room temperature
Middle carry out deoxidation treatment, time are 2 ~ 3min；After deoxidation treatment, protective coating, the chemistry milling of use are coated within 24 h
Protective glue is AC850, and the sample after coating protective glue will carry out curing process, 24 h of natural air drying；
8. the preservative treatment stage: the hydrate of the 3- glycidylpropyl triethoxysilane of 6wt% and 4wt% cerous acetate is added
In the aliphatic alcohol solvent of 5 carbon atoms of 85wt%, 40 DEG C are warming up to, the solution A of stirring and dissolving；2wt% are added in solution A
SiO2 particle and 3wt% the citric acid mixing that diameter is 60 nanometers, are heated to 80 DEG C, stir 50min, be cooled to room temperature, obtain solution
B；Solution B is subjected to maturation process, preservative is made.Again by the deionized water of the preservative of 23.4 mass parts and 96.5 mass parts
It is sufficiently mixed, preservative treatment working solution is made；By the spraying of preservative treatment working solution, aerolite surface is brushed or is immersed in,
2h is deposited and heated in an oven, and heating temperature is 60 DEG C, until aerolite surface forms coating, realizes surface anticorrosion
Processing；
9. hot water dries up the stage: the aerolite after preservative treatment being carried out hot water cleaning and is dried up again with compressed air；
10. unloading the frame removal protection stage, terminate after the aerolite after drying is unloaded adduction removal protection.
Embodiment 4
A kind of surface treatment method of the ultralight corrosion-resistant aviation aluminum alloy material of the high-performance showed in the present embodiment, including with
Under several steps:
1. reception and testing stage: receiving and examine to aerolite, enter next step after the assay was approved；
2. manual solvent wash phase: the manual solvent cleaning of aerolite progress to qualification is examined；
3. protecting and shelving the stage: protecting and shelve to the aerolite after manual solvent cleans is carried out；
4. ultrasonic degreasing alkali wash phase: aerolite is carried out the cleaning of ultrasonic degreasing alkali；
5. water rinses: carrying out water cleaning to the aerolite after the cleaning of ultrasonic degreasing alkali；
6. moisture film detection-phase: aerolite contains moisture film and then returns to the 2. step cycle after detection, and aviation aluminium closes after detection
Moisture film does not enter next stage then to gold；
7. the deoxidation treatment stage: by aerolite 50 DEG C ~ 60 DEG C at a temperature of be placed in the sodium hydroxide solution of 40 ~ 60 g/L
Middle immersion, 0.5 ~ 1.5min of time, this process are known as caustic corrosion；Aerolite thoroughly cleans after caustic corrosion through water, then will
The concentrated nitric acid of 175ml65%, 50ml chromium trioxide, the hydrofluoric acid of 12.5ml47%, the thiocarbamide of 7.5ml, 0.5 ~ 1g Qula lead to X-
100 and suitable water be configured to the deoxidation liquid of 1L, the aerolite after water thoroughly cleans is immersed in deoxidation liquid at room temperature
Middle carry out deoxidation treatment, time are 2 ~ 3min；After deoxidation treatment, protective coating, the chemistry milling of use are coated within 24 h
Protective glue is AC850, and the sample after coating protective glue will carry out curing process, 24 h of natural air drying；
8. the preservative treatment stage: the 3- Mercaptopropyltriethoxysilane of 1wt% and 8wt% cerium stearate are added the 10 of 85wt%
In the aliphatic alcohol solvent of a carbon atom, 25 DEG C are warming up to, the solution A of stirring and dissolving；The partial size of addition 1wt% is in solution A
100 nanometers of SiO2 particle and 5wt% ethanol amine mixing, is heated to 75 DEG C, stirs 35min, be cooled to room temperature, obtain solution B；
Solution B is subjected to maturation process, preservative is made.The preservative of 23.4 mass parts and the deionized water of 96.5 mass parts are filled again
Divide mixing, preservative treatment working solution is made；By the spraying of preservative treatment working solution, aerolite surface is brushed or is immersed in,
1.5h is deposited and heated in baking oven, and heating temperature is 55 DEG C, until aerolite surface forms coating, realizes surface anticorrosion
Processing；
9. hot water dries up the stage: the aerolite after preservative treatment being carried out hot water cleaning and is dried up again with compressed air；
10. unloading the frame removal protection stage, terminate after the aerolite after drying is unloaded adduction removal protection.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the principle of the present invention, several improvement can also be made, these improvement also should be regarded as of the invention
Protection scope.
Claims (10)
1. a kind of surface treatment method of the ultralight corrosion-resistant aviation aluminum alloy material of high-performance, it is characterised in that: including following several
A step:
1. reception and testing stage: receiving and examine to aerolite, enter next step after the assay was approved；
2. manual solvent wash phase: the manual solvent cleaning of aerolite progress to qualification is examined；
3. protecting and shelving the stage: shelving to the aerolite after manual solvent cleans is carried out to protect；
4. ultrasonic degreasing alkali wash phase: aerolite is carried out the cleaning of ultrasonic degreasing alkali；
5. water rinses: carrying out water cleaning to the aerolite after the cleaning of ultrasonic degreasing alkali；
6. moisture film detection-phase: aerolite contains moisture film and then returns to the 2. step cycle after detection, and aviation aluminium closes after detection
Moisture film does not enter next stage then to gold；
7. the deoxidation treatment stage: by aerolite 50 DEG C ~ 60 DEG C at a temperature of be placed in 40 ~ 60 g/L sodium hydroxide it is molten
It is impregnated in liquid, 0.5 ~ 1.5min of time, this process is known as caustic corrosion；Aerolite thoroughly cleans after caustic corrosion through water, then
By the Qula of the concentrated nitric acid of 175ml65%, 50ml chromium trioxide, the hydrofluoric acid of 12.5ml47%, the thiocarbamide of 7.5ml, 0.5 ~ 1g
Logical X-100 and suitable water are configured to the deoxidation liquid of 1L, are at room temperature immersed in the aerolite after water thoroughly cleans de-
Deoxidation treatment is carried out in oxygen liquid, the time is 2 ~ 3min；After deoxidation treatment, protective coating, the chemistry of use are coated within 24 h
Milling protective glue is AC850, and the sample after coating protective glue will carry out curing process, 24 h of natural air drying；
8. the preservative treatment stage: preservative is first made, then by the deionized water of the preservative of 23.4 mass parts and 96.5 mass parts
It is sufficiently mixed, preservative treatment working solution is made；By the spraying of preservative treatment working solution, brushes or be immersed in after deoxidation treatment
The surface of aerolite deposits in an oven and heats 0.5 ~ 2h, and heating temperature is 50 ~ 60 DEG C, until aerolite table
Face forms coating, realizes surface anticorrosion processing；
9. hot water dries up the stage: the aerolite after preservative treatment being carried out hot water cleaning and is dried up again with compressed air；
10. unloading the frame removal protection stage, the aerolite after drying is unloaded frame and terminating after removing protection.
2. a kind of surface treatment method of the ultralight corrosion-resistant aviation aluminum alloy material of high-performance according to claim 1,
Be characterized in that: the preservative is formed by following weight:
Organosiloxane: 1 ~ 12%；
Additive: 0.1 ~ 5%；
Rare-earth salts: 0.5 ~ 8%；
Catalyst: 0.1 ~ 5%；
Remaining as organic solvent.
3. a kind of surface treatment method of the ultralight corrosion-resistant aviation aluminum alloy material of high-performance according to claim 2,
It is characterized in that: the structural formula of the organosiloxane are as follows: [Si (R1) (R2) 3] n, in which: n=1 or 2, i.e., in a silicon original
On son containing one or two group R1 and 2 or 3 group R2 either on two adjacent silicon atoms and each silicon
Atom respectively contains one or two group R1 and 2 or 3 group R2.
4. a kind of surface treatment method of the ultralight corrosion-resistant aviation aluminum alloy material of high-performance according to claim 3,
Be characterized in that: the group R1 is inseparable and hydrolyzes, and group R2 hydrolyzable simultaneously can remove；The group R1 be methyl,
Ethyl, propyl, n-butyl, isobutyl group, sec-butyl, tert-butyl, propyl disulfide group, vinyl, 1- acrylic, 2- acrylic,
Butenyl group, acetenyl, propynyl residue, phenyl, naphthyl group, methylacryloyl, methylacryloyl oxygen propyl group base
One of group, glycidyl, glycidoxy groups, ammonia aryl or aminoalkyl group；The group R2 is methoxy
Base, ethyoxyl, n-propoxy, iso- propoxyl group, n-butoxy, iso- butoxy, sec- butoxy, t-butoxy, n- penta oxygen
In base, n- hexyloxy group, cyclopropyl oxygroup, cyclohexyloxy, phenoxy group, acyloxy, acetoxyl group, propionyloxy or acetyl group
One kind.
5. a kind of surface treatment method of the ultralight corrosion-resistant aviation aluminum alloy material of high-performance according to claim 4,
Be characterized in that: the organosiloxane is vinyltriethoxysilane, acrylic triethoxysilane, 3- aminopropyl three
Ethoxysilane, 3- (triethoxy silicon substrate) propylacrylate rouge, 3- glycidylpropyl triethoxysilane, 3- mercaptopropyi
Triethoxysilane, N- (2- amino-ethyl) -3-aminopropyltriethoxysilane, N- [N '-(2'- amino-ethyl) -2- ammonia
Base ethyl] -3- aminopropyl-triethoxysilane, N- phenyl amino propyl triethoxysilane double-(3- (triethoxy) silicon
Base propyl) one of tetrasulfide or double-(3- (triethoxy) silicon substrate propyl) ethane.
6. a kind of surface treatment method of the ultralight corrosion-resistant aviation aluminum alloy material of high-performance according to claim 5,
Be characterized in that: the additive is nano silica particle, and partial size is 50 ~ 100 nanometers.
7. a kind of surface treatment method of the ultralight corrosion-resistant aviation aluminum alloy material of high-performance according to claim 6,
Be characterized in that: the rare-earth salts is the hydrate or stearic acid of the hydrate of cerous nitrate, the hydrate of cerium oxide, cerous acetate
Cerium.
8. a kind of surface treatment method of the ultralight corrosion-resistant aviation aluminum alloy material of high-performance according to claim 7,
Be characterized in that: the catalyst be aliphatic monocarboxylic acid such as acetic acid, dicarboxylic acids and tricarboxylic acid for example citric acid, nitric acid,
One of hydrochloric acid, ethanol amine, triethylamine or its mixing.
9. a kind of surface treatment method of the ultralight corrosion-resistant aviation aluminum alloy material of high-performance according to claim 8,
Be characterized in that: the organic solvent is the fatty alcohol of 1 to 10 carbon atoms.
10. a kind of surface treatment method of the ultralight corrosion-resistant aviation aluminum alloy material of high-performance according to claim 1,
Be characterized in that: the preparation method of the preservative the following steps are included:
1. organosiloxane and rare-earth salts are added in organic solvent, 20 ~ 40 DEG C are warming up to, the solution A of stirring and dissolving；
2. additive and catalyst mixing are added in solution A, 60 ~ 80 DEG C are heated to, 30 ~ 50min is stirred, is cooled to room temperature,
Obtain solution B；
3. solution B is carried out maturation process, gained is preservative.
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| CN114058230A (en) * | 2021-12-07 | 2022-02-18 | 深圳市美瑞金属材料有限公司 | Aluminum material with good corrosion resistance based on continuous surface treatment and preparation method thereof |
| CN114134500A (en) * | 2021-10-29 | 2022-03-04 | 北京卫星制造厂有限公司 | Surface bonding force improving treatment method for magnesium-lithium alloy skin |
| CN115382843A (en) * | 2022-09-02 | 2022-11-25 | 沈阳富创精密设备股份有限公司 | Ultra-clean cleaning process for aluminum-based multilayer porous parts in cavity of semiconductor equipment |
| WO2024055486A1 (en) * | 2022-09-13 | 2024-03-21 | 云南中宣液态金属科技有限公司 | Liquid metal substrate cleaning method and integrated apparatus for cleaning and coating |
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| CN114134500A (en) * | 2021-10-29 | 2022-03-04 | 北京卫星制造厂有限公司 | Surface bonding force improving treatment method for magnesium-lithium alloy skin |
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