CN115261841A - Treatment process of steel-aluminum mixed base material - Google Patents
Treatment process of steel-aluminum mixed base material Download PDFInfo
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- CN115261841A CN115261841A CN202210771340.9A CN202210771340A CN115261841A CN 115261841 A CN115261841 A CN 115261841A CN 202210771340 A CN202210771340 A CN 202210771340A CN 115261841 A CN115261841 A CN 115261841A
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 50
- 230000008569 process Effects 0.000 title claims abstract description 47
- 239000000463 material Substances 0.000 title claims abstract description 45
- 239000013527 degreasing agent Substances 0.000 claims abstract description 56
- 238000005237 degreasing agent Methods 0.000 claims abstract description 54
- 238000005260 corrosion Methods 0.000 claims abstract description 48
- 230000007797 corrosion Effects 0.000 claims abstract description 47
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000005238 degreasing Methods 0.000 claims abstract description 35
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 28
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims abstract description 28
- -1 fluorine ions Chemical class 0.000 claims abstract description 27
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 18
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 18
- 239000011737 fluorine Substances 0.000 claims abstract description 18
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 16
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 claims abstract description 15
- MFXMOUUKFMDYLM-UHFFFAOYSA-L zinc;dihydrogen phosphate Chemical compound [Zn+2].OP(O)([O-])=O.OP(O)([O-])=O MFXMOUUKFMDYLM-UHFFFAOYSA-L 0.000 claims abstract description 15
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 14
- NAAXGLXYRDSIRS-UHFFFAOYSA-L dihydrogen phosphate;manganese(2+) Chemical compound [Mn+2].OP(O)([O-])=O.OP(O)([O-])=O NAAXGLXYRDSIRS-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000011656 manganese carbonate Substances 0.000 claims abstract description 14
- 235000006748 manganese carbonate Nutrition 0.000 claims abstract description 14
- 229940093474 manganese carbonate Drugs 0.000 claims abstract description 14
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims abstract description 14
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims abstract description 14
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 14
- 239000011591 potassium Substances 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 27
- 230000003750 conditioning effect Effects 0.000 claims description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 13
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 13
- 239000003112 inhibitor Substances 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims description 9
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 9
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 9
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 9
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 9
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 9
- 239000000176 sodium gluconate Substances 0.000 claims description 9
- 235000012207 sodium gluconate Nutrition 0.000 claims description 9
- 229940005574 sodium gluconate Drugs 0.000 claims description 9
- PHIQPXBZDGYJOG-UHFFFAOYSA-N sodium silicate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-][Si]([O-])=O PHIQPXBZDGYJOG-UHFFFAOYSA-N 0.000 claims description 9
- 239000001433 sodium tartrate Substances 0.000 claims description 9
- 229960002167 sodium tartrate Drugs 0.000 claims description 9
- 235000011004 sodium tartrates Nutrition 0.000 claims description 9
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 239000002351 wastewater Substances 0.000 claims description 6
- 229910001385 heavy metal Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000013522 chelant Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000004065 wastewater treatment Methods 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims 1
- 229910000838 Al alloy Inorganic materials 0.000 abstract description 67
- 239000010960 cold rolled steel Substances 0.000 abstract description 24
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 16
- 230000001360 synchronised effect Effects 0.000 abstract description 2
- 238000004886 process control Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 21
- 238000001878 scanning electron micrograph Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 9
- 239000007921 spray Substances 0.000 description 9
- 230000009286 beneficial effect Effects 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000003973 paint Substances 0.000 description 7
- 239000004411 aluminium Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229910001094 6061 aluminium alloy Inorganic materials 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001962 electrophoresis Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910020826 NaAlF6 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001610 cryolite Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
- C23C22/62—Treatment of iron or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The application relates to a treatment process of a steel-aluminum mixed base material, which comprises the following steps: degreasing: treating with a degreasing agent with a pH value of 10.5-11.3; washing with water: washing with water to remove residual degreasing agent on the surface; and (4) table adjustment: treating by adopting a surface conditioner; phosphorization: treating by adopting phosphating solution, wherein the phosphating solution comprises the following components in parts by weight: 25 to 35 parts of zinc dihydrogen phosphate, 1 to 3 parts of nickel nitrate, 4 to 8 parts of manganese dihydrogen phosphate, 1 to 2 parts of manganese carbonate, 2 to 4 parts of phosphoric acid, 0.5 to 1.5 parts of magnesium nitrate, 1 to 2 parts of potassium fluoborate, 2 to 3 parts of ferric nitrate and 1.5 to 3.5 parts of sodium hydrogen fluoride, wherein the concentration of fluorine ions in the phosphating solution is 80 to 260mg/L. The treatment process controls the PH of the degreasing agent, and solves the problem that the aluminum alloy is blackened due to excessive corrosion in the high-alkalinity degreasing agent; the phosphating solution with the fluoride ion content of 80-260mg/L is suitable for phosphating cold-rolled steel sheets and 5 series and 6 series aluminum alloys, so that the cold-rolled steel sheets and the aluminum alloys can realize synchronous phosphating in the same tank.
Description
Technical Field
The application relates to the technical field of metal surface treatment, in particular to a treatment process of a steel-aluminum mixed base material.
Background
With the requirements of energy conservation and emission reduction and light weight of automobiles, the aluminum alloy is used as one of main materials for light weight of automobile bodies and is gradually applied to the automobile bodies of commercial vehicles, wherein 5-series aluminum alloy and 6-series aluminum alloy are more and more widely applied to the automobile bodies of the commercial vehicles due to the excellent performance of the aluminum alloy. There is a trend toward the blending of automotive body materials from all cold rolled steel sheets to cold rolled steel sheets and aluminum alloy sheets.
In order to increase the corrosion resistance and the paint film binding force of the base material, a treatment process is usually required before the paint film coating of the vehicle body, and the coating of the current mixed vehicle body with different metal base materials mainly comprises three technical routes: film pretreatment, two-step phosphating and improved phosphating. Although the film pretreatment is environment-friendly and energy-saving, the cold-rolled steel plate after the film treatment is matched with the electrophoresis, so that the requirement of high corrosion resistance of the automobile body is difficult to stably meet, and the film pretreatment is mainly applied to the automobile body made of all-aluminum or a mixture of a galvanized plate, an aluminum alloy and a small amount of steel plates. The two-step phosphating method is characterized in that a passivation process is added after a phosphating process, the conventional phosphating production line needs to be modified, and the investment is huge. The improved phosphating technology is improved on the basis of the traditional phosphating technology, and realizes the collinear coating of the cold-rolled steel plate and the aluminum alloy on the basis of not modifying a production line in a large amount.
The body of the all-iron commercial vehicle adopts a phosphating pretreatment technology, and the basic process route is as follows: degreasing → water washing → surface conditioning → phosphating, and then water washing and electrophoretic coating are carried out, wherein degreasing, surface conditioning and phosphating are three main processes of the vehicle body paint coating pretreatment. The degreasing process mainly has the function of removing oil stains on the surface of a substrate, and an alkaline degreasing agent is usually adopted. The surface regulation is mainly to regulate the active adsorption of the metal surface of particles to provide nucleation points for the growth of phosphorized grains, and the conventional surface regulation is usually carried out by powder or liquid. The phosphating treatment is mainly to form a phosphating film on the surface of the metal, and can improve the adhesive force and the corrosion resistance of a paint film.
Because the phosphating and film-forming performances of the aluminum alloy and the cold-rolled steel plate are different, the pretreatment of the steel-aluminum mixed material automobile body by adopting the existing all-steel automobile body treatment process or the all-aluminum alloy automobile body treatment process cannot give consideration to the performances of the aluminum alloy and the steel at the same time, and the anti-corrosion performance of paint coatings of various substrates after electrophoresis cannot meet the requirement. Therefore, only the modification of the production line or the new construction of the production line can be performed to treat two kinds of base materials respectively, which undoubtedly increases the production cost of enterprises.
Disclosure of Invention
The embodiment of the application provides a treatment process of a steel-aluminum mixed base material, and aims to solve the problems that the steel-aluminum mixed base material cannot be subjected to collinear pre-painting treatment and the treatment effect is not ideal in the related art.
The treatment process of the steel-aluminum mixed base material comprises the following steps:
degreasing: treating with a degreasing agent with a pH value of 10.5-11.3;
washing with water: washing with water to remove residual degreasing agent on the surface;
and (4) table adjustment: treating by adopting a surface conditioner;
phosphorization: adopting a phosphating solution for treatment, wherein the phosphating solution comprises the following components in parts by weight:
25-35 parts of zinc dihydrogen phosphate, 1-3 parts of nickel nitrate, 4-8 parts of manganese dihydrogen phosphate, 1-2 parts of manganese carbonate, 2-4 parts of phosphoric acid, 0.5-1.5 parts of magnesium nitrate, 1-2 parts of potassium fluoborate, 2-3 parts of ferric nitrate and 1.5-3.5 parts of sodium hydrogen fluoride, wherein the concentration of fluoride ions in the phosphating solution is 80-260 mg/L.
In some embodiments, further comprising wastewater treatment: and (3) adjusting the pH value of the phosphating solution wastewater after phosphating treatment by using sodium hydroxide, and trapping heavy metal nickel by using a treating agent to form insoluble chelate for precipitation and separation.
In some embodiments, the degreasing agent comprises the following components by weight:
20 to 30 portions of sodium carbonate or sodium bicarbonate, 10 to 25 portions of sodium silicate nonahydrate, 1 to 5 portions of potassium hydroxide, 1 to 2 portions of sodium tartrate, 1 to 4 portions of ethylene diamine tetraacetic acid tetrasodium salt, 2 to 3 portions of sodium gluconate, 2 to 3 portions of ethoxylated alkyl alcohol, 1 to 2 portions of nonylphenol polyoxyethylene ether and 0.5 to 3 portions of aluminum corrosion inhibitor.
In some embodiments, the free alkalinity of the degreaser is 6.5 to 8.5pt;
the temperature of the degreasing agent is 40-50 ℃.
In some embodiments, "tone: the treatment with the surface conditioner "includes:
immersing the substrate into a surface conditioning tank dissolved with a surface conditioning agent for treatment, wherein the concentration of the surface conditioning agent in the surface conditioning tank is 3.5-5.0 pt, and the pH value of the surface conditioning agent is 9.5-11.0.
In some embodiments, the formulation comprises the following components by weight:
15-18 parts of zinc phosphate and 2-5 parts of dispersant; the particle size of the zinc phosphate particles in the zinc phosphate is 0.6 to 0.8 mu m.
In some embodiments, the phosphating solution has a free acidity of 0.5 to 0.8pt;
the total acidity of the phosphating solution is 21-24 pt.
In some embodiments, the concentration of the fluoride ions in the phosphating solution is 80-150 mg/L.
In some embodiments, the concentration of the fluoride ions in the phosphating solution is 200-260 mg/L.
In some embodiments, the concentration of the fluoride ions in the phosphating solution is 150-200 mg/L.
The technical scheme who provides this application brings beneficial effect includes: the treatment process of the steel-aluminum mixed base material provided by the embodiment of the application solves the problem that the aluminum alloy blackens due to excessive corrosion in the high-alkalinity degreasing agent by controlling the PH of the degreasing agent within the range of 10.5-11.3, and effectively enables the degreasing corrosion amount of the 5-series aluminum alloy to be 60mg/m2The degreasing corrosion amount of the 6-series aluminum alloy was controlled to 100mg/m2The following;
the phosphating solution with the fluoride ion content of 80-260mg/L is suitable for phosphating cold-rolled steel plates and 5-series and 6-series aluminum alloys, so that the cold-rolled steel plates and the aluminum alloys can realize synchronous phosphating treatment in the same tank, a production line does not need to be additionally built, the enterprise cost is reduced, meanwhile, a steel-aluminum mixed base material treated by the phosphating solution can form an even phosphating film with the coverage rate of more than 95%, and the salt spray resistance after being matched with cathode electrophoretic paint can meet the high-corrosivity requirement.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is an SEM photograph of the surface of a 5052 sample of example 2 after a degreasing step;
FIG. 2 is an SEM image of the surface of a 5052 sample of comparative example 1 after a degreasing step;
FIG. 3 is an SEM image of the surface of a sample of 5052 of example 1 after a phosphating step;
FIG. 4 is an SEM image of the surface of a sample of DC04 of example 1 after a phosphating step;
FIG. 5 is an SEM image of the surface of a sample of 5052 of example 6 after a phosphating step;
FIG. 6 is an SEM photograph of the surface of a sample DC04 of example 6 after a phosphating step;
FIG. 7 is an SEM image of the surface of a sample of 5052 of example 7 after a phosphating step;
FIG. 8 is an SEM image of the surface of the sample DC04 of example 7 after the phosphating step;
FIG. 9 is an SEM image of the surface of the 6061 template of example 9 after the phosphating step;
FIG. 10 is an SEM photograph of the surface of the sample DC0 of example 9 after being subjected to a phosphating step;
FIG. 11 is an SEM image of the surface of the 6061 template of example 10 after the phosphating step;
FIG. 12 is an SEM image of the surface of a sample of DC04 from example 10 after a phosphating step;
FIG. 13 is an SEM image of the surface of the 6061 template subjected to a phosphating step in example 11;
FIG. 14 is an SEM photograph of the surface of a sample DC04 of example 11 after being subjected to a phosphating step;
FIG. 15 is an SEM image of the surface of a 6061 template from comparative example 6 after a phosphating step;
FIG. 16 is an SEM image of the surface of a DC04 sample plate of comparative example 6 after a phosphating step.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application without making creative efforts shall fall within the protection scope of the present application.
The embodiment of the application provides a treatment process of a steel-aluminum mixed base material, which comprises the following steps:
degreasing: treating with a degreasing agent with the pH value of 10.5-11.3;
washing with water: washing with water to remove residual degreasing agent on the surface;
and (4) table adjustment: treating by adopting a surface conditioner;
phosphorization: treating by adopting phosphating solution, wherein the phosphating solution comprises the following components in parts by weight:
25-35 parts of zinc dihydrogen phosphate, 1-3 parts of nickel nitrate, 4-8 parts of manganese dihydrogen phosphate, 1-2 parts of manganese carbonate, 2-4 parts of phosphoric acid, 0.5-1.5 parts of magnesium nitrate, 1-2 parts of potassium fluoborate, 2-3 parts of ferric nitrate and 1.5-3.5 parts of sodium hydrogen fluoride, wherein the concentration of fluoride ions in the phosphating solution is 80-260 mg/L.
The steel-aluminum hybrid substrate described herein refers to a substrate composed of two substrates, i.e., a cold-rolled steel sheet and an aluminum alloy, wherein the aluminum alloy is present in an amount of 30% or less by area in the hybrid substrate. The aluminum alloy refers to a 5-series aluminum alloy and/or a 6-series aluminum alloy, the 5-series aluminum alloy can adopt 5-series aluminum alloy commonly used in the field, including but not limited to 5052, 5005, 5083 and 5A05 series, and the 6-series aluminum alloy can adopt 6-series aluminum alloy commonly used in the field, including but not limited to 6005, 6060, 6061, 6063, 6082, 6201, 6262, 6463 and 6A02 series.
The degreasing aims to remove impurities and oil stains on the surface of a base material, in addition, a layer of compact oxidation film is formed on the surface of the aluminum alloy, and the oxidation film is unfavorable for formation of a phosphating film in a subsequent phosphating process, so that the phosphating crystal growth is nonuniform, local thick and the like are generated, and therefore, the oxidation film on the surface of the aluminum alloy needs to be synchronously removed in the degreasing process, and the inventor finds that through a large number of experiments, the pH of the degreasing agent is controlled within the range of 10.5-11.3, the degreasing agent is enough in alkalinity, so that the oil stains on the surface of the base material and the oxidation film on the surface of the aluminum alloy can be completely removed, the phenomenon of excessive corrosion of the aluminum alloy caused by the excessively strong alkalinity of the degreasing agent is avoided, and the problem of incomplete coverage of the phosphating film after phosphating is avoided;
the embodiment of the invention can ensure that the degreasing corrosion amount of the 5-series aluminum alloy is 60mg/m2The degreasing corrosion amount of the 6-series aluminum alloy was controlled to 100mg/m2The following is advantageous for the formation of a subsequent phosphate film.
In addition, through researches and a large number of experiments on the phosphating film forming mechanism of cold-rolled steel sheets and aluminum alloys, the inventor finds that sodium bifluoride added into the phosphating solution is used as a corrosive agent of the aluminum alloys on one hand and used as a complexing agent of free aluminum ions on the other hand. In the phosphating solution without free fluorine, almost no phosphating film is generated on the surface of the aluminum alloy, the corrosion of the aluminum alloy matrix is accelerated along with the increase of the concentration of fluorine ions, hydrogen ions are consumed by corrosion, dihydric phosphate and monohydrogen phosphate are further hydrolyzed, the crystallization deposition of zinc phosphate on the surface of the matrix metal is promoted, and the corrosion of the aluminum alloy is realized to promote the formation of the phosphating film. However, al dissolved in the phosphating solution3+More easily form precipitates with phosphate radicals and inhibit the formation of zinc phosphate crystals, by adding fluoride and Na to the phosphating solution+、K+Allowing Al to react3+And F-、Na+、K+And (3) reacting and discharging from the phosphating solution in a precipitate form, wherein the reaction is as follows:
Al3++3Na++6F-→Na3AlF6↓
Al3++2K++Na++6F-→K2NaAlF6↓
the inventor finds that the fluorine ion concentration is too high, so that the coordination precipitation of fluorine and aluminum and zinc phosphate are co-deposited on the aluminum surface to influence the formation of a phosphating film, and therefore, the problem that a cold-rolled steel plate and an aluminum alloy cannot be subjected to collinear phosphating treatment is solved by controlling the fluorine ion content to be within the range of 80-260mg/L, and the phosphating film of the cold-rolled steel plate treated by the embodiment of the invention has uniform crystallization, the size of phosphating crystal grains is about 3-6 mu m, and the film weight is 1.9-2.5g/m2The coverage rate is more than 98 percent; the phosphating film of the 5 series aluminum alloy has uniform crystallization, the size of phosphating crystal grains is about 6 to 10 mu m, and the weight of the film is 0.8 to 1.5g/m2The coverage rate is more than 95 percent; the phosphating film of the 6 series aluminum alloy has uniform crystallization, the size of phosphating crystal grains is about 3 to 8 mu m, and the weight of the film is 1.5 to 2.0g/m2The coverage rate is more than 98%.
Specifically, the inventor balances the mixture ratio of each component in the phosphating solution to achieve a better film forming effect. For example, when the content of phosphoric acid is low, the film formation is too slow and too thin, and even the film formation cannot be performed, whereas the film formation is too fast due to too fast reaction, and the freshly formed film is dissolved, so that the film is not strong enough, so that the weight part of phosphoric acid is preferably 2 to 4 parts in this embodiment. The zinc dihydrogen phosphate and the phosphoric acid have the effects of providing main components of the phosphating film, the nickel nitrate is used as an accelerator for accelerating phosphating, refining crystallization and improving the corrosion resistance of the phosphating film, and the nickel nitrate is too low in content, so that the phosphating film is too thin.
In some embodiments, the process for treating a steel-aluminum hybrid substrate further comprises wastewater treatment: and (3) adjusting the pH value of the phosphating solution wastewater after phosphating treatment by using sodium hydroxide, and trapping heavy metal nickel by using a treating agent to form insoluble chelate for precipitation and separation.
Because heavy metal nickel is contained in the phosphating solution, in order to avoid the pollution to the environment caused by direct discharge of the phosphating solution, the phosphating solution wastewater is treated before being discharged, and is used for forming a precipitate for removing the heavy metal nickel in the phosphating solution, so that the subsequent centralized treatment is facilitated, and the national discharge standard is reached.
In a preferred embodiment, the treatment agent comprises 2% concentration of dithiocarbamate or polydithiocarbamate (e.g., ammonium polydithiocarbamate), the pH of the phosphating solution wastewater is adjusted to be 5.0-7.0, and the wastewater is treated for 15-30min.
In some embodiments, the degreasing agent comprises the following components by weight:
20 to 30 portions of sodium carbonate or sodium bicarbonate, 10 to 25 portions of sodium silicate nonahydrate, 1 to 5 portions of potassium hydroxide, 1 to 2 portions of sodium tartrate, 1 to 4 portions of ethylene diamine tetraacetic acid tetrasodium salt, 2 to 3 portions of sodium gluconate, 2 to 3 portions of ethoxylated alkyl alcohol, 1 to 2 portions of nonylphenol polyoxyethylene ether and 0.5 to 3 portions of aluminum corrosion inhibitor.
In the degreasing agent system, the pH value of the degreasing agent is controlled within the range of 10.5-11.3 by controlling the weight components of sodium carbonate or sodium bicarbonate, and the degreasing agent has a corrosion inhibition effect on aluminum alloy corrosion by matching with an aluminum corrosion inhibitor and silicate, so that subsequent surface conditioning and phosphating operation are facilitated.
The aluminum corrosion inhibitor includes, but is not limited to, styrene-maleic acid copolymer, acrylic acid copolymer, and the like.
In some embodiments, the free alkalinity of the degreaser is 6.5 to 8.5pt;
the temperature of the degreasing agent is 40-50 ℃.
The degreasing agent has excessively low free alkalinity, grease on the surface of a base material and an oxide film on the surface of the aluminum alloy cannot be completely removed, the degreasing agent has excessively high free alkalinity, so that the aluminum alloy is excessively corroded to generate blackened or gray corrosion products, the formation of a subsequent phosphating film is influenced, and the degreasing agent within the temperature range can accelerate the degreasing process and increase the degreasing effect.
In a preferred embodiment, "degreasing: the treatment by using the degreasing agent with the pH value of 10.5-11.3 comprises the following steps:
pre-degreasing: treating in a spraying mode for 50-90 s;
primary degreasing: the immersion treatment is carried out for 180 to 240 seconds.
The two procedures of pre-degreasing and main degreasing are adopted, so that an oxide film is removed, degreasing is more sufficient, and cleaning is more thorough.
In a preferred embodiment, the "pre-degreasing: and treating in a spraying mode for 50-90 s, wherein the treatment time is 60s, and the spraying system is adopted, the spraying pressure of the circulating pump is controlled to be 0.08-0.2 MPa, and the degreasing agent is sprayed to the surface of the base material.
In a preferred embodiment, the "main degreasing: the treatment is carried out by adopting an immersion method, the treatment time is 180-240 s', and the treatment time is 180s.
In some embodiments, the "key: the treatment with the surface conditioner "includes:
immersing the substrate into a surface conditioning tank dissolved with a surface conditioning agent for treatment, wherein the concentration of the surface conditioning agent in the surface conditioning tank is 3.5-5.0 pt, and the pH value of the surface conditioning agent is 9.5-11.0.
The table call is used for adjusting the active adsorption of the metal surface of the particle, providing nucleation points for the growth of the phosphating crystal grains, accelerating the phosphating speed, refining the crystal grains of the phosphating film, being beneficial to improving the appearance of the phosphating film, enhancing the bonding strength of the phosphating film and the metal surface and improving the corrosion resistance of the phosphating film.
In some embodiments, the formulation comprises the following components by weight:
15-18 parts of zinc phosphate and 2-5 parts of a dispersing agent; the particle size of the zinc phosphate particles in the zinc phosphate is 0.6 to 0.8 mu m.
In some embodiments, the phosphating solution has free acidity of 0.5 to 0.8pt, total acidity of 21 to 24pt, and a promoter concentration of 3.0 to 5.0pt.
The free acidity of the phosphating solution refers to the content of free phosphoric acid in the phosphating solution, the too low free acidity is not beneficial to the dissolution of a base material and difficult to form a film, the too high free acidity can increase the dissolution speed of a phosphating film and is not beneficial to the film formation, even difficult to form the film, and therefore, the free acidity is preferably 0.5-0.8 pt;
the total acidity of the phosphating solution refers to the sum of phosphate, nitrate and free acid, the total acidity is in reaction with the size of internal power of phosphating, the total acidity is high, which indicates that the internal power of phosphating is high, the speed is high, the crystallization is fine, however, the total acidity is too high, the generated sediments and powder attachments are more, the total acidity is too low, the phosphating is slow, the crystallization is coarse, and therefore, the total acidity is preferably 21-24 pt.
In some embodiments, the concentration of the fluoride ions in the phosphating solution is 80-150 mg/L.
The inventor combines the film forming mechanism of 5 series aluminum alloy and a large number of experiments to find that the phosphating solution with the fluorine ion concentration of 80-150 mg/L is only suitable for cold-rolled steel plates and 5 series aluminum alloy mixed base materials, the phosphating film formed in the range has excellent property, and the salt spray resistance meets the requirement of high corrosion resistance.
In some embodiments, the concentration of the fluoride ions in the phosphating solution is 200-260 mg/L.
The inventor combines the 6 series aluminum alloy film forming mechanism and a large number of experiments to find that the phosphating solution with the fluoride ion concentration of 200-260 mg/L is only suitable for cold-rolled steel plates and 6 series aluminum alloy mixed base materials, the phosphating film formed in the range has better property, and the salt spray resistance meets the requirement of high corrosion resistance.
In some embodiments, the concentration of fluoride ions in the phosphating solution is 150-200 mg/L.
The inventor combines film forming mechanisms of 5 series aluminum alloy and 6 series aluminum alloy and a large number of experiments to find that the phosphating solution with the fluorine ion concentration of 150-200 mg/L is simultaneously suitable for 5 series and 6 series aluminum alloy mixed base materials, the formed phosphating film has excellent property, and the salt spray resistance meets the requirement of high corrosion resistance.
That is, the phosphating solutions provided by the embodiments of the present application are suitable for 5-series aluminum alloys in which the phosphating solution with the fluorine ion concentration in the range of 80-200mg/L is suitable for 6-series aluminum alloys in which the phosphating solution with the fluorine ion concentration in the range of 150-260mg/L is suitable for both 5-series aluminum alloys and 6-series aluminum alloys.
The present invention will be further illustrated by the following examples.
Example 1
This example is used to illustrate the treatment process of the steel-aluminum mixed base material disclosed in the present invention, and includes the following steps:
degreasing: treating a cold-rolled steel plate DC04 and 5052 aluminum alloy sample plate for 4min at 45 ℃ by adopting a degreasing agent with the pH of 10.5, wherein the degreasing agent comprises the following components in parts by weight:
20 parts of sodium carbonate, 5 parts of sodium bicarbonate, 10 parts of sodium silicate nonahydrate, 1 part of potassium hydroxide, 2 parts of sodium tartrate, 4 parts of EDTA tetrasodium, 3 parts of sodium gluconate, 3 parts of ethoxylated alkyl alcohol, 2 parts of nonylphenol polyoxyethylene ether and 0.5 part of aluminum corrosion inhibitor styrene-maleic acid copolymer.
Washing with water: washing the degreased sample plate with water at normal temperature for 30s;
and (4) table adjustment: immersing the washed vehicle body into surface conditioning bath solution, wherein the total concentration of the surface conditioning bath solution is 3.5pt, the pH value is 9.5, the surface conditioning treatment time is 60s,
the surface conditioner consists of 16 percent of zinc phosphate, 5 percent of high molecular dispersant and the balance of water;
phosphorization: immersing the car body in a phosphating solution with the temperature of 35 ℃, the free acidity of 0.6pt, the total acidity of 22.0pt, the concentration of an accelerant of 4.2pt and the concentration of fluorine ions of 80mg/L for treatment for 3min,
the phosphating solution comprises the following components in parts by weight:
30 parts of zinc dihydrogen phosphate, 2 parts of nickel nitrate, 6 parts of manganese dihydrogen phosphate, 1 part of manganese carbonate, 3 parts of phosphoric acid, 0.5 part of magnesium nitrate, 1 part of potassium fluoborate, 2 parts of ferric nitrate and 1.5 parts of sodium hydrogen fluoride.
Example 2
This example is for explaining the treatment process of the steel-aluminum mixed base material disclosed by the present invention, including most of the operation steps of example 1, except that:
degreasing: treating a cold-rolled steel plate DC04 and 5052 aluminum alloy sample plate for 4min at 45 ℃ by using a degreasing agent with the pH of 11.0, wherein the degreasing agent comprises the following components in parts by weight:
22 parts of sodium carbonate, 3 parts of sodium bicarbonate, 20 parts of sodium silicate nonahydrate, 3 parts of potassium hydroxide, 1 part of sodium tartrate, 1 part of EDTA tetrasodium, 2 parts of sodium gluconate, 2 parts of ethoxylated alkyl alcohol, 1 part of nonylphenol polyoxyethylene ether and 2 parts of aluminum corrosion inhibitor styrene-maleic acid copolymer.
Example 3
This example is used to illustrate the treatment process of the steel-aluminum mixed base material disclosed by the present invention, which includes most of the operation steps of example 1, except that:
degreasing: treating cold-rolled steel plate DC04 and 6061 aluminum alloy sample plates for 4min at 45 ℃ by using a degreasing agent with the pH of 10.5, wherein the degreasing agent comprises the following components in parts by weight:
20 parts of sodium carbonate, 5 parts of sodium bicarbonate, 10 parts of sodium silicate nonahydrate, 1 part of potassium hydroxide, 2 parts of sodium tartrate, 4 parts of EDTA tetrasodium, 3 parts of sodium gluconate, 3 parts of ethoxylated alkyl alcohol, 2 parts of nonylphenol polyoxyethylene ether and 0.5 part of aluminum corrosion inhibitor styrene-maleic acid copolymer.
Example 4
This example is used to illustrate the treatment process of the steel-aluminum mixed base material disclosed by the present invention, which includes most of the operation steps of example 1, except that:
degreasing: treating cold-rolled steel plate DC04 and 6061 aluminum alloy sample plates for 4min at 45 ℃ by using a degreasing agent with the pH of 11.3, wherein the degreasing agent comprises the following components in parts by weight:
25 parts of sodium carbonate, 3 parts of sodium bicarbonate, 23 parts of sodium silicate nonahydrate, 5 parts of potassium hydroxide, 1 part of sodium tartrate, 1 part of EDTA tetrasodium, 2 parts of sodium gluconate, 2 parts of ethoxylated alkyl alcohol, 1 part of nonylphenol polyoxyethylene ether and 3 parts of aluminum corrosion inhibitor styrene-maleic acid copolymer.
Example 5
This example is used to illustrate the treatment process of the steel-aluminum mixed base material disclosed by the present invention, which includes most of the operation steps of example 1, except that:
phosphorization: immersing the car body in a phosphating solution with the temperature of 35 ℃, the free acidity of 0.6pt, the total acidity of 22.0pt, the concentration of an accelerant of 4.2pt and the concentration of fluorine ions of 150mg/L for treatment for 3min,
the phosphating solution comprises the following components in parts by weight:
30 parts of zinc dihydrogen phosphate, 2 parts of nickel nitrate, 6 parts of manganese dihydrogen phosphate, 1 part of manganese carbonate, 3 parts of phosphoric acid, 0.5 part of magnesium nitrate, 1 part of potassium fluoborate, 2 parts of ferric nitrate and 2 parts of sodium hydrogen fluoride.
Example 6
This example is used to illustrate the treatment process of the steel-aluminum mixed base material disclosed by the present invention, which includes most of the operation steps of example 1, except that:
phosphorization: immersing the car body in a phosphating solution with the temperature of 35 ℃, the free acidity of 0.6pt, the total acidity of 22.0pt, the concentration of an accelerant of 4.2pt and the concentration of fluorine ions of 200mg/L for treatment for 3min,
the phosphating solution comprises the following components in parts by weight:
30 parts of zinc dihydrogen phosphate, 2 parts of nickel nitrate, 6 parts of manganese dihydrogen phosphate, 1 part of manganese carbonate, 3 parts of phosphoric acid, 0.5 part of magnesium nitrate, 1 part of potassium fluoborate, 2 parts of ferric nitrate and 2.5 parts of sodium hydrogen fluoride.
Example 7
This example is for explaining the treatment process of the steel-aluminum mixed base material disclosed by the present invention, including most of the operation steps of example 1, except that:
phosphorization: immersing the car body in a phosphating solution with the temperature of 35 ℃, the free acidity of 0.6pt, the total acidity of 22.0pt, the concentration of an accelerant of 4.2pt and the concentration of fluorine ions of 250mg/L for treatment for 3min,
the phosphating solution comprises the following components in parts by weight:
30 parts of zinc dihydrogen phosphate, 2 parts of nickel nitrate, 6 parts of manganese dihydrogen phosphate, 1 part of manganese carbonate, 3 parts of phosphoric acid, 0.5 part of magnesium nitrate, 1 part of potassium fluoborate, 2 parts of ferric nitrate and 3 parts of sodium hydrogen fluoride.
Example 8
This example is for explaining the treatment process of the steel-aluminum mixed base material disclosed by the present invention, including most of the operation steps of example 3, except that:
phosphorization: immersing the vehicle body into phosphating solution with the temperature of 35 ℃, the free acidity of 0.6pt, the total acidity of 22.0pt, the concentration of an accelerant of 4.2pt and the concentration of fluorine ions of 100mg/L for treatment for 3min,
the phosphating solution comprises the following components in parts by weight:
30 parts of zinc dihydrogen phosphate, 2 parts of nickel nitrate, 6 parts of manganese dihydrogen phosphate, 1 part of manganese carbonate, 3 parts of phosphoric acid, 0.5 part of magnesium nitrate, 1 part of potassium fluoborate, 2 parts of ferric nitrate and 1.7 parts of sodium hydrogen fluoride.
Example 9
This example is for explaining the treatment process of the steel-aluminum mixed base material disclosed by the present invention, including most of the operation steps of example 3, except that:
phosphorization: immersing the car body in a phosphating solution with the temperature of 35 ℃, the free acidity of 0.6pt, the total acidity of 22.0pt, the concentration of an accelerant of 4.2pt and the concentration of fluorine ions of 150mg/L for treatment for 3min,
the phosphating solution comprises the following components in parts by weight:
30 parts of zinc dihydrogen phosphate, 2 parts of nickel nitrate, 6 parts of manganese dihydrogen phosphate, 1 part of manganese carbonate, 3 parts of phosphoric acid, 0.5 part of magnesium nitrate, 1 part of potassium fluoborate, 2 parts of ferric nitrate and 2 parts of sodium hydrogen fluoride.
Example 10
This example is used to illustrate the treatment process of the steel-aluminum mixed base material disclosed by the present invention, which includes most of the operation steps of example 3, except that:
phosphorization: immersing the vehicle body into a phosphating solution with the temperature of 35 ℃, the free acidity of 0.6pt, the total acidity of 22.0pt, the concentration of an accelerant of 4.2pt and the concentration of fluorine ions of 200mg/L for treatment for 3min,
the phosphating solution comprises the following components in parts by weight:
30 parts of zinc dihydrogen phosphate, 2 parts of nickel nitrate, 6 parts of manganese dihydrogen phosphate, 1 part of manganese carbonate, 3 parts of phosphoric acid, 0.5 part of magnesium nitrate, 1 part of potassium fluoborate, 2 parts of ferric nitrate and 2.5 parts of sodium hydrogen fluoride.
Example 11
This example is used to illustrate the treatment process of the steel-aluminum mixed base material disclosed by the present invention, which includes most of the operation steps of example 3, except that:
phosphorization: immersing the vehicle body into phosphating solution with the temperature of 35 ℃, the free acidity of 0.6pt, the total acidity of 22.0pt, the concentration of an accelerant of 4.2pt and the concentration of fluorine ions of 260mg/L for treatment for 3min,
the phosphating solution comprises the following components in parts by weight:
30 parts of zinc dihydrogen phosphate, 2 parts of nickel nitrate, 6 parts of manganese dihydrogen phosphate, 1 part of manganese carbonate, 3 parts of phosphoric acid, 0.5 part of magnesium nitrate, 1 part of potassium fluoborate, 2 parts of ferric nitrate and 3.5 parts of sodium hydrogen fluoride.
Comparative example 1
This comparative example is used for comparative illustration of the treatment process of a steel-aluminium hybrid substrate disclosed in the present invention, comprising most of the operating steps of example 1, with the following differences:
degreasing: treating a cold-rolled steel plate DC04 and 5052 aluminum alloy sample plate for 4min at 45 ℃ by using a degreasing agent with the pH of 11.5, wherein the degreasing agent comprises the following components in parts by weight:
25 parts of sodium carbonate, 10 parts of sodium bicarbonate, 25 parts of sodium silicate nonahydrate, 10 parts of potassium hydroxide, 1 part of sodium tartrate, 1 part of EDTA tetrasodium, 2 parts of sodium gluconate, 2 parts of ethoxylated alkyl alcohol, 1 part of nonylphenol polyoxyethylene ether and 3 parts of aluminum corrosion inhibitor styrene-maleic acid copolymer.
Comparative example 2
This comparative example is used to illustrate by comparison the treatment process of a steel-aluminium hybrid substrate disclosed in the present invention, comprising most of the operating steps of example 1, with the following differences:
degreasing: treating cold-rolled steel plate DC04 and 6061 aluminum alloy sample plates for 4min at 45 ℃ by adopting a degreasing agent with the pH of 11.5, wherein the degreasing agent comprises the following components in parts by weight:
25 parts of sodium carbonate, 10 parts of sodium bicarbonate, 25 parts of sodium silicate nonahydrate, 10 parts of potassium hydroxide, 1 part of sodium tartrate, 1 part of EDTA tetrasodium, 2 parts of sodium gluconate, 2 parts of ethoxylated alkyl alcohol, 1 part of nonylphenol polyoxyethylene ether and 3 parts of aluminum corrosion inhibitor styrene-maleic acid copolymer.
Comparative example 3
This comparative example is used to illustrate by comparison the treatment process of a steel-aluminium hybrid substrate disclosed in the present invention, comprising most of the operating steps of example 1, with the following differences:
degreasing: the cold-rolled steel sheet DC04 and 5052 aluminum alloy sample plate is treated with a degreasing agent with the pH of 12.33 at 45 ℃ for 4min, wherein the degreasing agent is an FC-E2011 alkaline degreasing agent of tradegard, ghan-Bar.
Comparative example 4
This comparative example is used for comparative illustration of the treatment process of a steel-aluminium hybrid substrate disclosed in the present invention, comprising most of the operating steps of example 1, with the following differences:
degreasing: the cold-rolled steel plate DC04 and 6061 aluminum alloy sample plate is treated for 4min at 45 ℃ by using a degreasing agent with the pH of 12.33, wherein the degreasing agent is an FC-E2011 alkaline degreasing agent of tradegard warper GmbH.
Comparative example 5
This comparative example is used to illustrate by comparison the treatment process of a steel-aluminium hybrid substrate disclosed in the present invention, comprising most of the operating steps of example 1, with the following differences:
phosphorization: immersing the car body in a phosphating solution with the temperature of 35 ℃, the free acidity of 0.6pt, the total acidity of 22.0pt, the concentration of an accelerant of 4.2pt and the concentration of fluorine ions of 50mg/L for treatment for 3min,
the phosphating solution comprises the following components in parts by weight:
30 parts of zinc dihydrogen phosphate, 2 parts of nickel nitrate, 6 parts of manganese dihydrogen phosphate, 1 part of manganese carbonate, 3 parts of phosphoric acid, 0.5 part of magnesium nitrate, 1 part of potassium fluoborate, 2 parts of ferric nitrate and 0.8 part of sodium hydrogen fluoride.
Comparative example 6
This comparative example is used to illustrate by comparison the treatment process of a steel-aluminium hybrid substrate disclosed in the present invention, comprising most of the operating steps of example 3, with the following differences:
phosphorization: immersing the vehicle body into a phosphating solution with the temperature of 35 ℃, the free acidity of 0.6pt, the total acidity of 22.0pt, the concentration of an accelerant of 4.2pt and the concentration of fluorine ions of 290mg/L for treatment for 3min,
the phosphating solution comprises the following components in parts by weight:
30 parts of zinc dihydrogen phosphate, 2 parts of nickel nitrate, 6 parts of manganese dihydrogen phosphate, 1 part of manganese carbonate, 3 parts of phosphoric acid, 0.5 part of magnesium nitrate, 1 part of potassium fluoborate, 2 parts of ferric nitrate and 3.8 parts of sodium hydrogen fluoride.
Performance testing
The following performance tests were performed on the samples of examples 1-4 and comparative examples 1-4 after the degreasing step:
1) And (3) corrosion amount testing:
the test board is cleaned by acetone, so that the surface of the board is free from oil stains. And washing the test board with water, putting the test board into an oven, drying the test board for 10min at 80 ℃, and putting the dried test board into a dryer to cool the test board to normal temperature. The test panel was weighed using an analytical balance and the weight W1 of the test panel before corrosion was recorded.
And (3) putting the weighed plate into degreasing solution of each condition for processing for corresponding time, taking out the plate, washing and drying the plate by using tap water, putting the plate into an oven for drying at 80 ℃ for 10min, putting the dried test plate into a dryer for cooling to normal temperature, weighing the test plate by using an analytical balance, and recording the weight W2 of the degreased and corroded test plate. The corrosion amount of the test panel = (W1-W2)/S, wherein S is the area of the test panel.
2) Appearance: the appearance of the aluminum alloy specimens was visually observed.
The test results obtained are filled in Table 1.
The following performance tests were performed on the plaques of examples 1, 5-11 and comparative example 5 after the phosphating step:
salt spray resistance: after subjecting the samples of examples 1, 5 to 11 and comparative examples 5 to 6 to the phosphating step to cathodic electrophoresis, the surfaces of the samples were crossed and subjected to a neutral salt spray test in accordance with GB 1771.
The test results are filled in table 2.
TABLE 1
As can be seen from the test results shown in Table 1, the corrosion amounts of the 5-series and 6-series aluminum alloys of examples 1 to 4 were controlled to 100mg/m after treatment with the degreasing agent having a pH value in the range of 10.5 to 11.32Hereinafter, the appearance is bright, and it is described that black or gray corroded materials are not excessively generated by corrosion. The PH value of the degreasing agent adopted in the comparative examples 1-4 is too high, so that the degreasing agent is not suitable for 5-series and 6-series aluminum alloys, the sample plate is blackened after treatment, and excessive corrosion is not beneficial to the formation of a subsequent phosphating film, which indicates that the PH value of the degreasing agent is controlled to be 10.5-11.3, so that the condition that the existing degreasing agent is not suitable for 5-series and 6-series aluminum alloys can be effectively improved.
TABLE 2
According to the test results in the table 2, the concentration of the fluorine ions in the phosphating solution is controlled within the range of 80-260mg/L, so that the cold-rolled steel plate and the 5-series aluminum alloy or the 6-series aluminum alloy can be subjected to collinear phosphating, a treated phosphating film is well matched with the electrophoretic paint, and the 1000-hour salt spray test can meet the requirement of high corrosion resistance;
wherein, according to the test results of the embodiment 1 and the embodiments 5 to 7, the fluorine ion concentration in the embodiment 7 is as high as 250mg/L, which is not beneficial to forming a phosphating film, the 1000h salt spray test shows that the expanding corrosion width along the fork single side reaches 10mm, which is not more than or equal to 2mm meeting the requirement of high corrosion resistance, while the fluorine ion concentration in the embodiments 1 and 5 to 6 is 80 to 200mg/L, and the expanding corrosion width of the sample plate along the fork single side is less than 2mm, which shows that the fluorine ion concentration of the 5 series aluminum alloy base material is preferably 80 to 200mg/L, so as to meet the requirement of high corrosion resistance;
according to the test results of the examples 8 to 11, the lower fluorine ion concentration in the example 8 is only 100mg/L, which is not beneficial to forming a phosphating film, the salt spray test is carried out for 1000h, the expanding corrosion width along the single side of the fork reaches 3mm, which is not more than 2mm meeting the requirement of high corrosion resistance, the fluorine ion concentration in the examples 9 to 11 is 150 to 260mg/L, the expanding corrosion width of the processed sample plate along the single side of the fork is less than 2mm, which shows that the fluorine ion concentration of the 6 series aluminum alloy substrate is preferably 150 to 260mg/L, and the high corrosion resistance requirement can be met.
The above description is merely exemplary of the present application and is presented to enable those skilled in the art to understand and practice the present application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The treatment process of the steel-aluminum mixed base material is characterized by comprising the following steps of:
degreasing: treating with a degreasing agent with the pH value of 10.5-11.3;
washing with water: washing with water to remove residual degreasing agent on the surface;
and (4) table adjustment: treating by adopting a surface conditioner;
phosphorization: treating by adopting phosphating solution, wherein the phosphating solution comprises the following components in parts by weight:
25-35 parts of zinc dihydrogen phosphate, 1-3 parts of nickel nitrate, 4-8 parts of manganese dihydrogen phosphate, 1-2 parts of manganese carbonate, 2-4 parts of phosphoric acid, 0.5-1.5 parts of magnesium nitrate, 1-2 parts of potassium fluoborate, 2-3 parts of ferric nitrate and 1.5-3.5 parts of sodium hydrogen fluoride, wherein the concentration of fluoride ions in the phosphating solution is 80-260 mg/L.
2. The process for treating a steel-aluminum mixed base material according to claim 1, further comprising wastewater treatment: and (3) adjusting the pH value of the phosphating solution wastewater after phosphating treatment by using sodium hydroxide, and trapping heavy metal nickel by using a treating agent to form insoluble chelate for precipitation and separation.
3. The process for treating a steel-aluminum mixed base material according to claim 1, wherein the degreasing agent comprises the following components by weight:
20-30 parts of sodium carbonate and/or sodium bicarbonate, 10-25 parts of sodium silicate nonahydrate, 1-5 parts of potassium hydroxide, 1-2 parts of sodium tartrate, 1-4 parts of ethylene diamine tetraacetic acid tetrasodium salt, 2-3 parts of sodium gluconate, 2-3 parts of ethoxylated alkyl alcohol, 1-2 parts of nonylphenol polyoxyethylene ether and 0.5-3 parts of aluminum corrosion inhibitor.
4. The process for treating a steel-aluminum mixed base material according to claim 3, wherein the degreasing agent has a free basicity of 6.5 to 8.5pt;
the temperature of the degreasing agent is 40-50 ℃.
5. The process for treating a steel-aluminum hybrid substrate according to claim 1, wherein the "surface conditioning: the treatment with the surfactant "includes:
immersing the substrate into a surface conditioning tank dissolved with a surface conditioning agent for treatment, wherein the concentration of the surface conditioning agent in the surface conditioning tank is 3.5-5.0 pt, and the pH value of the surface conditioning agent is 9.5-11.0.
6. The treatment process of the steel-aluminum hybrid substrate according to claim 1, wherein the surface conditioner comprises the following components in parts by weight:
15-18 parts of zinc phosphate and 2-5 parts of a dispersing agent; the particle size of the zinc phosphate particles in the zinc phosphate is 0.6 to 0.8 mu m.
7. The treatment process of the steel-aluminum mixed base material according to claim 1, wherein the free acidity of the phosphating solution is 0.5 to 0.8pt;
the total acidity of the phosphating solution is 21-24 pt.
8. The treatment process of the steel-aluminum mixed base material as recited in claim 1, wherein the concentration of the fluorine ions in the phosphating solution is 80 to 150mg/L.
9. The treatment process of the steel-aluminum mixed base material as recited in claim 1, wherein the concentration of the fluorine ions in the phosphating solution is 200 to 260mg/L.
10. The treatment process of the steel-aluminum mixed base material as recited in claim 1, wherein the concentration of the fluorine ions in the phosphating solution is 150 to 200mg/L.
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