CN116607154A - Photochemical treatment liquid for pretreatment of metal surface and chemical cleaning method - Google Patents
Photochemical treatment liquid for pretreatment of metal surface and chemical cleaning method Download PDFInfo
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- CN116607154A CN116607154A CN202310481051.XA CN202310481051A CN116607154A CN 116607154 A CN116607154 A CN 116607154A CN 202310481051 A CN202310481051 A CN 202310481051A CN 116607154 A CN116607154 A CN 116607154A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 76
- 239000002184 metal Substances 0.000 title claims abstract description 76
- 239000007788 liquid Substances 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000004140 cleaning Methods 0.000 title claims abstract description 29
- 239000000126 substance Substances 0.000 title claims abstract description 27
- 239000002738 chelating agent Substances 0.000 claims abstract description 47
- 238000005260 corrosion Methods 0.000 claims abstract description 45
- 230000007797 corrosion Effects 0.000 claims abstract description 43
- 239000000758 substrate Substances 0.000 claims abstract description 41
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 38
- 239000003112 inhibitor Substances 0.000 claims abstract description 21
- 108010007859 Lisinopril Proteins 0.000 claims abstract description 19
- RLAWWYSOJDYHDC-BZSNNMDCSA-N lisinopril Chemical compound C([C@H](N[C@@H](CCCCN)C(=O)N1[C@@H](CCC1)C(O)=O)C(O)=O)CC1=CC=CC=C1 RLAWWYSOJDYHDC-BZSNNMDCSA-N 0.000 claims abstract description 19
- 229960002394 lisinopril Drugs 0.000 claims abstract description 19
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000007524 organic acids Chemical class 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract 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 abstract description 9
- 229940029614 triethanolamine stearate Drugs 0.000 claims abstract description 9
- -1 triethanolamine stearate quaternary ammonium salt Chemical class 0.000 claims abstract description 9
- 239000013543 active substance Substances 0.000 claims abstract description 7
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 5
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000013556 antirust agent Substances 0.000 claims abstract description 5
- 239000000467 phytic acid Substances 0.000 claims abstract description 5
- 229940068041 phytic acid Drugs 0.000 claims abstract description 5
- 235000002949 phytic acid Nutrition 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 150000002191 fatty alcohols Chemical class 0.000 claims description 5
- 238000009713 electroplating Methods 0.000 claims description 4
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims 1
- 238000007747 plating Methods 0.000 abstract description 24
- 238000005238 degreasing Methods 0.000 abstract description 12
- 239000000243 solution Substances 0.000 description 33
- 238000012360 testing method Methods 0.000 description 20
- 239000010410 layer Substances 0.000 description 17
- 230000000694 effects Effects 0.000 description 16
- 229910000838 Al alloy Inorganic materials 0.000 description 10
- OHSHFZJLPYLRIP-BMZHGHOISA-M Riboflavin sodium phosphate Chemical compound [Na+].OP(=O)([O-])OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O OHSHFZJLPYLRIP-BMZHGHOISA-M 0.000 description 9
- 238000000576 coating method Methods 0.000 description 8
- 229950001574 riboflavin phosphate Drugs 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- HJVAFZMYQQSPHF-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;boric acid Chemical compound OB(O)O.OCCN(CCO)CCO HJVAFZMYQQSPHF-UHFFFAOYSA-N 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 229910001431 copper ion Inorganic materials 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 description 1
- 239000010963 304 stainless steel Substances 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 229910000737 Duralumin Inorganic materials 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- 239000004166 Lanolin Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229940039717 lanolin Drugs 0.000 description 1
- 235000019388 lanolin Nutrition 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 1
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229940087562 sodium acetate trihydrate Drugs 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- SRLLRIILXLQLHZ-UHFFFAOYSA-N sodium;hydrofluoride Chemical compound F.[Na] SRLLRIILXLQLHZ-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant 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
- 238000010998 test method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/22—Light metals
Abstract
The invention discloses an photochemical treatment liquid for metal surface pretreatment and a chemical cleaning method, and relates to the technical field of metal surface pretreatment. The photochemical treatment liquid comprises: liquid A and liquid B; the solution A comprises organic acid, corrosion inhibitor, EDTA tetrasodium and triethanolamine stearate quaternary ammonium salt; the organic acid comprises one of citric acid and phytic acid; the solution B comprises a chelating agent, a surfactant, an antirust agent, a corrosion inhibitor and an active agent; the chelating agent includes a novel chelating agent which is a modified compound obtained by chemically modifying polyacrylamide with lisinopril. The photochemical treatment liquid prepared by the invention has more excellent degreasing and deoiling capabilities, remarkably improves the corrosion resistance of the substrate after the metal substrate is treated, and has lower corrosion phenomenon on the metal substrate; and simultaneously, the bonding capability between the metal substrate and the plating layer is effectively improved.
Description
Technical Field
The invention belongs to the technical field of metal surface pretreatment, and particularly relates to an photochemical treatment liquid for metal surface pretreatment and a chemical cleaning method.
Background
In a practical marine environment, surface coating methods are generally used to prevent atmospheric corrosion, such as coatings, zinc plating, and the like. The atmospheric corrosion protection mechanism of these surface coverings is to reduce the likelihood of corrosion by isolating the droplets from the substrate. The prepared coating layer has lower bonding firmness degree with the metal substrate body, gaps and air holes are formed, and the defects can cause the plating metal to fall off from the surface of the substrate or generate larger gaps in the middle of the aluminum profile, so that the service life of the plating layer is further influenced. In order to avoid the problems described above, the metal surface is effectively cleaned prior to plating, including cleaning to remove oil, rust, etc.
Aluminum is an active metal, and the surfaces of aluminum and aluminum alloy are easy to react with oxygen and water vapor in the air to form a layer of thinner oxide film, and the oxide film can cause the adhesion between a metal coating and an aluminum substrate to be weak, so that the process requirement cannot be met. Therefore, aluminum and aluminum alloys must be subjected to an activation treatment to eliminate oxide films before plating to ensure good adhesion during the aluminum and aluminum alloy plating treatment. The chemical cleaning is to make use of the erosion of the dissolving liquid to the surface of the workpiece under the proper dissolving liquid and process conditions to level the surface of the workpiece, thus obtaining a relatively bright surface. The chemical polishing solutions for aluminum and its alloys are two types, phosphoric acid-based solutions and non-phosphoric acid-based solutions. For the present time, multiple acids are mixed, single HNO 3 Free of HNO 3 Is the three main light-emitting processes in China. If the aluminum alloy contains less impurities and has qualified quality, the aluminum alloy can be subjected to photochemical treatment by general conventional nitric acid, so that a satisfactory effect can be obtained; because of the relatively complex chemical composition of duralumin alloys, if not subjected to photochemical treatment with a powerful chemical cleaning solution, the lack of a desired effect of the photochemical treatment results in a significant amount of residues remaining on the surface of the metal, which residues can form tiny galvanic cells under the coating, undergo self-reaction, which can seriously affect the corrosion resistance of the metal. For example: the surface of the aluminum alloy contains a large amount of copper element compounds, when a conversion film forming reaction is carried out, the copper elements are changed into copper ions when encountering a strong oxidant, but the copper ions are not removed from the surface of the aluminum alloy, but enter the surface of the aluminum alloy in other forms, and the entering copper ions can generate great interference on the conversion reaction, so that the corrosion resistance of the aluminum alloy conversion film is greatly reduced, and therefore, the surface treatment technology plays an important role in improving the corrosion resistance of metals.
Disclosure of Invention
The invention aims to provide an photochemical treatment liquid for metal surface pretreatment and a chemical cleaning method, wherein the photochemical treatment liquid has more excellent degreasing and deoiling capabilities, remarkably improves the corrosion resistance of a substrate after being treated on the metal substrate, and has lower corrosion phenomenon on the metal substrate; and simultaneously, the bonding capability between the metal substrate and the plating layer is effectively improved.
The technical scheme adopted by the invention for achieving the purpose is as follows:
an actinic treatment liquid for pretreatment of a metal surface, comprising: liquid A and liquid B;
the solution A comprises organic acid, corrosion inhibitor, EDTA tetrasodium and triethanolamine stearate quaternary ammonium salt; the organic acid comprises one of citric acid and phytic acid;
the solution B comprises a chelating agent, a surfactant, an antirust agent, a corrosion inhibitor and an active agent; the chelating agent comprises a novel chelating agent and an organic acid; the novel chelating agent is modified polyacrylamide; the modified polyacrylamide comprises a modified compound obtained by chemically modifying polyacrylamide with lisinopril. The photochemical treatment liquid provided by the invention is in a form of separating A liquid from B liquid, firstly, the A liquid is adopted to treat the substrate, and the oxide on the surface of the metal substrate is damaged; and then treating by using the solution B to achieve photochemical treatment on the surface of the substrate. The modified polyacrylamide is added into the raw material component of the solution B, and comprises a novel chelating agent obtained by chemically modifying polyacrylamide with lisinopril, so that the adsorption chelating capacity of the novel chelating agent to metal ions such as copper ions is remarkably enhanced, and the novel chelating agent can effectively react with residues such as metal ions remained on a metal substrate, so that tiny primary cells are prevented from generating under a plating layer formed by electroplating, and self-reaction is carried out, thereby effectively enhancing the corrosion resistance of metal; meanwhile, the problem that a layer of loose material is formed on the metal surface due to the fact that metal ions such as copper are remained on the metal surface, and therefore poor bonding capability between a metal substrate and a plating layer is caused can be effectively avoided, and the bonding capability between the substrate and the plating layer can be effectively improved. Meanwhile, the modified polyacrylamide prepared by the invention can also generate a certain synergistic effect with other components through molecular assembly forces such as hydrogen bonds, so that the number of the components in the high-performance cleaning agent is reduced to a certain extent, the compatibility among the components is enhanced, a good corrosion inhibition effect is achieved, corrosion damage to a metal substrate in the cleaning process is avoided, and the corrosion effect of an photochemical treatment liquid on the metal substrate is effectively reduced; and the oil removing and degreasing capabilities of the photochemical treatment liquid are obviously enhanced by the synergistic effect of the photochemical treatment liquid and other components.
The preparation method of the novel chelating agent comprises the following steps: the novel chelating agent is prepared by amidation reaction of lisinopril and polyacrylamide.
Specifically, the preparation method of the novel chelating agent comprises the following steps:
and heating a polyacrylamide solution with the concentration of 0.8-2wt% to 25-40 ℃, then adding a lisinopril aqueous solution with the concentration of 45-60wt%, regulating the pH of the system to 3-4 for reaction for 2-4 hours, and after the reaction, performing rotary evaporation concentration and dialysis to remove small molecular substances, and performing vacuum drying to obtain the novel chelating agent.
Specifically, the molar ratio of the polyacrylamide structural units to lisinopril is 1: 2-3.
Specifically, the molecular weight of the polyacrylamide is 15-30 ten thousand.
Specifically, the rust inhibitor includes triethanolamine borate.
Specifically, the surfactant comprises at least one of alkylphenol ethoxylates and fatty alcohol ethoxylates.
Specifically, the active agent includes sodium fluorohydride.
Specifically, the raw material component of the solution A in the photochemical treatment solution for metal surface pretreatment comprises: 4-6 g/L of organic acid, 4-7 g/L of corrosion inhibitor, 0.5-2 g/L of EDTA tetrasodium and 0.5-1.5 g/L of triethanolamine stearate quaternary ammonium salt.
Specifically, the raw material component of the liquid B in the photochemical treatment liquid for metal surface pretreatment comprises: 0.5-2 g/L of chelating agent, 4-8 g/L of surfactant, 30-60 g/L of antirust agent, 2-5 g/L of active agent and 1-3 g/L of corrosion inhibitor.
More preferably, the raw material component of the B liquid of the photochemical treatment liquid for metal surface pretreatment further comprises 0.5-2 g/L riboflavin sodium phosphate. According to the invention, the riboflavin sodium phosphate is added into the raw material of the photochemical treatment liquid B, so that the riboflavin sodium phosphate can be used in combination with other components, the uniformity and smoothness of the surface structure of the metal substrate after the photochemical treatment liquid are effectively improved, and the bonding capability between a substrate and a plating layer is obviously improved; meanwhile, the addition of the riboflavin sodium phosphate obviously reduces the corrosion performance of the photochemical pretreatment liquid to the base material, and has excellent anti-corrosion effect; and under the condition that modified polyacrylamide exists, the modified polyacrylamide and the photochemical pretreatment solution are compounded in a synergistic way, so that the corrosion capability of the photochemical pretreatment solution on the metal substrate is further reduced.
A method of chemically cleaning a metal surface comprising: the surface of the metal substrate is treated by the solution A and washed by water, then treated by the solution B, and then washed by water.
Specifically, the metal surface chemical cleaning method comprises the following steps:
washing the surface of the metal substrate with a solution A at 40-60 ℃ for 10-20 min, and then washing with water at the same temperature for 2-5 times, wherein each time lasts for 5-10 min; then adopting the solution B to process; and then washing with water at 40-60 ℃ for 2-5 times, wherein each time lasts for 5-10 min, and then the chemical cleaning is completed.
Specifically, the metal substrate includes aluminum and its alloys, stainless steel, copper.
Specifically, the liquid B treatment conditions include: the temperature is controlled at 25-40 ℃, the treatment time is 25-40 min, and the soaking mode is adopted.
Still another object of the present invention is to provide the use of the above-mentioned metal surface chemical cleaning method in a marine engineering electroplating process.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the lisinopril Li Gaixing polyacrylamide is added into the raw material component of the B solution of the photochemical treatment solution, so that the adsorption chelating capacity of the lisinopril Li Gaixing polyacrylamide to metal ions such as copper ions is obviously enhanced, and the corrosion resistance of metal is effectively enhanced; the bonding capability between the substrate and the plating layer is remarkably improved. Meanwhile, the metal substrate is effectively prevented from being corroded and damaged in the cleaning process by cooperation with other components; the oil removing and degreasing capability of the photochemical treatment liquid is obviously enhanced. In addition, the riboflavin sodium phosphate is added into the raw material of the photochemical treatment liquid B, so that the bonding capability between a metal matrix and a plating layer can be effectively improved; the corrosion performance of the photochemical pretreatment liquid on the base material is obviously reduced, the excellent anti-corrosion effect is achieved, and the effect is better in the presence of modified polyacrylamide.
Therefore, the invention provides the photochemical treatment liquid for metal surface pretreatment and the chemical cleaning method, the photochemical treatment liquid has more excellent degreasing and deoiling capabilities, the corrosion resistance of the substrate is obviously improved after the metal substrate is treated, and the corrosion phenomenon generated on the metal substrate is lower; and simultaneously, the bonding capability between the metal substrate and the plating layer is effectively improved.
Drawings
FIG. 1 is an infrared spectrum of the polyacrylamide of the present invention and the novel chelating agent prepared in example 1.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to the specific embodiments and the attached drawings:
the polyacrylamide used in the embodiment of the invention is ultra-low molecular weight polyacrylamide, and ordered from Shandong polymer Co., ltd, and the molecular weight is 25 ten thousand. The corrosion inhibitor used is CLEANS-1003 corrosion inhibitor.
Example 1:
preparation of novel chelators:
heating a polyacrylamide solution with the concentration of 1.5wt% to 32 ℃, then adding a lisinopril aqueous solution with the concentration of 52wt%, regulating the pH of the system to 3.5 for reaction for 3 hours, and performing rotary evaporation concentration and dialysis to remove small molecular substances after the reaction is finished, thus obtaining the novel chelating agent; wherein, the mol ratio of the polyacrylamide structural unit to the lisinopril is 1:2.6.
an photochemical treatment liquid for pretreatment of metal surfaces comprises the following raw material components:
and (3) solution A: 5g/L of citric acid, 5.5g/L of corrosion inhibitor, 1.2g/L of EDTA tetrasodium salt and 0.9g/L of triethanolamine stearate quaternary ammonium salt.
And (2) liquid B: 1.2g/L of novel chelating agent, 6g/L of fatty alcohol polyoxyethylene ether, 48g/L of triethanolamine borate, 3.6g/L of sodium bifluoride and 2g/L of corrosion inhibitor.
The chemical cleaning method comprises the following steps:
washing the surface of the metal substrate with 50 ℃ solution A for 15min, and then washing with water with the same temperature for 4 times, wherein each time lasts for 8min; then adopting solution B to process, controlling the temperature at 30 ℃ and the processing time at 30min, and adopting a soaking mode; then washing with water of 50deg.C for 5 times for 10min each time to finish chemical cleaning.
Example 2:
the preparation of the novel chelating agent differs from example 1: the molar ratio of the polyacrylamide structural units to lisinopril is 1:2.1.
an photochemical treatment liquid for pretreatment of metal surfaces comprises the following raw material components:
and (3) solution A: 4.4g/L of phytic acid, 4g/L of corrosion inhibitor, 0.7g/L of EDTA tetrasodium and 0.6g/L of triethanolamine stearate quaternary ammonium salt.
And (2) liquid B: 0.8g/L of novel chelating agent, 5g/L of alkylphenol ethoxylate, 34g/L of triethanolamine borate, 2.8g/L of sodium fluohydride and 1.4g/L of corrosion inhibitor.
The metal surface chemical cleaning method is the same as in example 1.
Example 3:
the preparation of the novel chelating agent differs from example 1: the molar ratio of the polyacrylamide structural units to lisinopril is 1:2.8.
an photochemical treatment liquid for pretreatment of metal surfaces comprises the following raw material components:
and (3) solution A: 5.4g/L of citric acid, 6.2g/L of corrosion inhibitor, 1.6g/L of EDTA tetrasodium and 1.1g/L of triethanolamine stearate quaternary ammonium salt.
And (2) liquid B: 1.7g/L of novel chelating agent, 6.6g/L of alkylphenol ethoxylate, 53g/L of triethanolamine borate, 4.5g/L of sodium fluohydride and 2g/L of corrosion inhibitor.
The metal surface chemical cleaning method is the same as in example 1.
Example 4:
the preparation of the novel chelating agent differs from example 1: the molar ratio of the polyacrylamide structural units to lisinopril is 1:3.
an photochemical treatment liquid for pretreatment of metal surfaces comprises the following raw material components:
and (3) solution A: 6g/L of phytic acid, 7g/L of corrosion inhibitor, 2g/L of EDTA tetrasodium and 1.5g/L of triethanolamine stearate quaternary ammonium salt.
And (2) liquid B: 2g/L of novel chelating agent, 8g/L of surfactant, 60g/L of triethanolamine borate, 5g/L of sodium bifluoride and 1.5g/L of corrosion inhibitor. Wherein the surfactant comprises alkylphenol ethoxylates and fatty alcohol ethoxylates, and the mass ratio of the alkylphenol ethoxylates to the fatty alcohol ethoxylates is 1:1.
the metal surface chemical cleaning method is the same as in example 1.
Example 5:
the novel chelating agent was prepared as in example 1.
The raw material composition of the photochemical treatment liquid for metal surface pretreatment was different from that of example 1: the solution B also comprises 1.4g/L riboflavin sodium phosphate.
The metal surface chemical cleaning method is the same as in example 1.
Example 6:
the raw material composition of the photochemical treatment liquid for metal surface pretreatment was different from that of example 5: and polyacrylamide is adopted to replace a novel chelating agent.
The metal surface chemical cleaning method is the same as in example 5.
Example 7:
the raw material composition of the photochemical treatment liquid for metal surface pretreatment was different from that of example 1: and polyacrylamide is adopted to replace a novel chelating agent.
The metal surface chemical cleaning method is the same as in example 1.
Test example 1:
infrared sign
Test instrument: fourier infrared spectrometer; the testing method comprises the following steps: potassium bromide tabletting method, wave number range of 4000-500 cm -1 Resolution of 4cm -1 。
The above test was performed on polyacrylamide with the novel chelator prepared in example 1, and the results are shown in figure 1. As shown by analysis in the figure, compared with the infrared spectrum of polyacrylamide, the infrared spectrum of the novel chelating agent is 1600-1400 cm -1 The absorption peak of the vibration characteristic of the benzene ring framework appears in the range, which shows that the novel chelating agent in the example 1 is successfully prepared.
Test example 2:
chelating agent adsorption of Cu 2+ Capacity determination
Preparing a solution: adding copper chloride into tap water to prepare Cu-containing water of 25mg/L 2+ Aqueous solution, and pH was adjusted to 6.8 with hydrochloric acid solution.
Test method detailsThe method comprises the following steps: 400mL of Cu-containing alloy is taken 2+ Adding 130mg/L novel chelating agent sample into the aqueous solution, stirring for 2min at 125r/min, stirring for 8min at 50r/min, standing for 15min, sucking supernatant at a position 2cm away from the liquid surface with a pipette, and measuring Cu with flame atomic absorption spectrophotometer 2+ Residual concentration and Cu was calculated according to the following formula 2+ The removal rate.
Cu 2+ Percent removal = (C 0 －C 1 ）/C 0 ×100%
Wherein C is 0 Indicating Cu before sample addition 2+ Concentration; c (C) 1 Indicating Cu after sample addition 2+ Residual concentration.
The above test was performed on the novel chelating agents prepared in examples 1 to 4 and example 7, and the results are shown in table 1:
table 1 Cu 2+ Removal ability test results
From the analysis in Table 1, it is understood that Cu of the novel chelating agent prepared in example 1 2+ The removal rate is obviously higher than that of example 7, and the effects of examples 2-4 are equivalent to those of example 1, which shows that the chelating agent prepared by chemically modifying polyacrylamide by lisinopril can effectively enhance the adsorption chelating ability of the chelating agent to metal ions and promote Cu 2+ Removing effect.
Test example 3:
measurement of degreasing Effect
The formula of the artificial oil stain comprises the following components: 10% lithium grease, 6% lanolin, 30% vaseline, 46% crude oil, 8% dichloro trioxide, and then uniformly smearing the prepared artificial oil stain on a test piece (aluminum sheet or 304 stainless steel, original mass is m) 0 ) Surface, weigh and record as m 1 The method comprises the steps of carrying out a first treatment on the surface of the Then at 30 ℃, the test piece is chemically cleaned by adopting an photochemical treatment liquid sample, and is dried and weighed and marked as m after finishing 2 . The degreasing rate (expressed as the weight loss rate) was calculated according to the following formula:
degreasing% 1 －m 2 ）/（m 1 －m 0 ）×100%
The above test was performed on the photochemical treatment liquids prepared in examples 1 to 7, and the results are shown in table 2:
TABLE 2 degreasing Performance test results
As can be seen from the analysis in Table 2, after the surface of the aluminum alloy and the stainless steel is treated by the photochemical treatment liquid prepared in the example 1, the degreasing rate is obviously higher than that of the example 7, which shows that the chelating agent prepared by chemically modifying polyacrylamide by lisinopril is added into the treatment liquid, and the degreasing capability of the photochemical treatment liquid is obviously enhanced by the synergistic effect of the chelating agent and other components. The effect of example 5 is equivalent to example 1 and the effect of example 6 is equivalent to example 7, indicating that the addition of riboflavin sodium phosphate to the photochemical treatment fluid does not negatively affect its degreasing properties.
Corrosion determination
Polishing and cleaning a test piece (made of aluminum), weighing and marking as M 0 Then the sample of photochemical treatment liquid is used for chemical cleaning, and is weighed again and marked as M after blow-drying 1 Comparing with the cleaned test piece to check the appearance, and the quality change DeltaM= |M of the test piece 0 －M 1 | a. The invention relates to a method for producing a fibre-reinforced plastic composite. According to the specification of the standard requirement JB/T4323.1, the mass change is less than or equal to 2mg.
The above test was performed on the photochemical treatment liquids prepared in examples 1 to 7, and the results are shown in table 3:
TABLE 3 corrosive test results
As can be seen from the analysis in Table 3, the quality change of the photochemical treatment liquid prepared in example 1 is obviously lower than that of example 7, and the fact that the chelating agent prepared by chemically modifying polyacrylamide by lisinopril is added into the treatment liquid has a synergistic effect with other components, so that the corrosion performance of the photochemical treatment liquid on the substrate can be obviously reduced when the surface of the substrate is cleaned, and the corrosion prevention effect is excellent. The effect of example 5 is obviously better than that of examples 1 and 6, and the effect of example 6 is better than that of example 7, which shows that the combination of the sodium riboflavin phosphate and other components in the photochemical treatment liquid further improves the bonding capability between the matrix and the plating layer; and the corrosion resistance effect is better in the presence of lisinopril Li Gaixing polyacrylamide.
Test example 4:
determination of the binding force of the coating to the substrate
Preparation of electroplating samples: and taking the aluminum piece subjected to chemical cleaning, and performing chemical nickel plating treatment at 80 ℃ for 120min. The formula of the nickel plating solution is as follows: 30g/L of nickel sulfate hexahydrate, 33g/L of sodium hypophosphite, 36g/L of sodium acetate trihydrate and 20g/L of citric acid.
The determination process of the binding force: the plating sample was clamped in the bench clamp and the test site was at the cross section. Wherein, the file forms 45 degrees with the plating layer surface, the edge of the plating layer is filed from the base metal to the plating layer direction, and whether the plating layer near the file opening is lifted or falls off is observed.
The above test was performed on the photochemical treatment liquids prepared in examples 1 to 7, and the results are shown in table 4:
TABLE 4 results of binding force test
From the analysis in table 4, it is known that the adhesion of the coating formed by electrodeposition after the aluminum part is treated by the photochemical treatment solution prepared in example 1 is significantly better than that of the coating formed in example 7, and the chelating agent prepared by chemically modifying polyacrylamide with lisinopril is added into the treatment solution, and the chelating agent and other components are compounded to cooperate to effectively improve the bonding capability between the substrate and the coating after the substrate surface is cleaned. Example 6 is better than example 7, showing that the combination of riboflavin sodium phosphate with other components in the photochemical treatment solution further improves the bonding capability between the substrate and the plating layer.
The conventional technology in the above embodiments is known to those skilled in the art, and thus is not described in detail herein.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. An actinic treatment liquid for pretreatment of a metal surface, comprising: liquid A and liquid B;
the solution A comprises organic acid, a corrosion inhibitor, EDTA tetrasodium and triethanolamine stearate quaternary ammonium salt; the organic acid comprises one of citric acid and phytic acid;
the solution B comprises a chelating agent, a surfactant, an antirust agent, a corrosion inhibitor and an active agent; the chelating agent includes novel chelating agents; the novel chelating agent is modified polyacrylamide; the modified polyacrylamide comprises a modified compound obtained by chemically modifying polyacrylamide with lisinopril.
2. An photochemical treatment liquid for pretreatment of a metal surface according to claim 1, wherein: the molecular weight of the polyacrylamide is 15-30 ten thousand.
3. An photochemical treatment liquid for pretreatment of a metal surface according to claim 1, wherein: the modified polyacrylamide is prepared by adopting an amide reaction.
4. An photochemical treatment liquid for pretreatment of a metal surface according to claim 1, wherein: the surfactant comprises at least one of alkylphenol ethoxylates and fatty alcohol ethoxylates.
5. An photochemical treatment liquid for pretreatment of a metal surface according to claim 1, wherein: the active agent comprises sodium bifluoride.
6. An photochemical treatment liquid for pretreatment of a metal surface according to claim 1, wherein: the photochemical treatment liquid for metal surface pretreatment comprises a liquid A raw material component, and comprises the following components: 4-6 g/L of organic acid, 4-7 g/L of corrosion inhibitor, 0.5-2 g/L of EDTA tetrasodium and 0.5-1.5 g/L of triethanolamine stearate quaternary ammonium salt.
7. An photochemical treatment liquid for pretreatment of a metal surface according to claim 1, wherein: the photochemical treatment liquid for metal surface pretreatment comprises a liquid B raw material component, and comprises the following components: 0.2-1.5 g/L of chelating agent, 4-8 g/L of surfactant, 30-60 g/L of antirust agent, 2-5 g/L of active agent and 1-3 g/L of corrosion inhibitor.
8. A method of chemically cleaning a metal surface comprising: the surface of the metal substrate is treated by the solution A in claim 1, washed by water, then treated by the solution B in claim 1, and then washed by water.
9. A method of chemically cleaning a metal surface according to claim 8, wherein: the metal substrate comprises aluminum and alloys thereof, stainless steel and copper.
10. Use of the metal surface chemical cleaning method of claim 8 in a marine engineering electroplating process.
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