CN115572965A - Chromium-free passivation solution and method for passivating copper-tin alloy coating of petroleum casing by applying same - Google Patents
Chromium-free passivation solution and method for passivating copper-tin alloy coating of petroleum casing by applying same Download PDFInfo
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- CN115572965A CN115572965A CN202211279088.6A CN202211279088A CN115572965A CN 115572965 A CN115572965 A CN 115572965A CN 202211279088 A CN202211279088 A CN 202211279088A CN 115572965 A CN115572965 A CN 115572965A
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- copper
- tin alloy
- passivation
- solution
- chromium
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- 238000002161 passivation Methods 0.000 title claims abstract description 151
- 238000000576 coating method Methods 0.000 title claims abstract description 79
- 239000011248 coating agent Substances 0.000 title claims abstract description 78
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical class [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000003208 petroleum Substances 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 29
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims abstract description 52
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 39
- 235000010288 sodium nitrite Nutrition 0.000 claims abstract description 26
- LJRGBERXYNQPJI-UHFFFAOYSA-M sodium;3-nitrobenzenesulfonate Chemical compound [Na+].[O-][N+](=O)C1=CC=CC(S([O-])(=O)=O)=C1 LJRGBERXYNQPJI-UHFFFAOYSA-M 0.000 claims abstract description 20
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims description 113
- 238000005406 washing Methods 0.000 claims description 101
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 53
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 33
- 238000002156 mixing Methods 0.000 claims description 31
- 238000002791 soaking Methods 0.000 claims description 31
- 239000003513 alkali Substances 0.000 claims description 29
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 26
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 23
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 20
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 claims description 17
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 14
- 239000012964 benzotriazole Substances 0.000 claims description 14
- 239000004202 carbamide Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 238000007747 plating Methods 0.000 claims description 8
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 7
- 239000001263 FEMA 3042 Substances 0.000 claims description 7
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 7
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 7
- 229940033123 tannic acid Drugs 0.000 claims description 7
- 235000015523 tannic acid Nutrition 0.000 claims description 7
- 229920002258 tannic acid Polymers 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 17
- 239000002184 metal Substances 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 9
- 230000001681 protective effect Effects 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 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 abstract description 2
- 229910052708 sodium Inorganic materials 0.000 abstract description 2
- 239000011734 sodium Substances 0.000 abstract description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 abstract description 2
- 238000005253 cladding Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- 230000007935 neutral effect Effects 0.000 description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 24
- 239000008367 deionised water Substances 0.000 description 24
- 229910021641 deionized water Inorganic materials 0.000 description 24
- 230000007797 corrosion Effects 0.000 description 21
- 238000005260 corrosion Methods 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 21
- 230000000694 effects Effects 0.000 description 14
- 239000010410 layer Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 8
- 238000005554 pickling Methods 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 6
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 230000001050 lubricating effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 238000005411 Van der Waals force Methods 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000005903 acid hydrolysis reaction Methods 0.000 description 3
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 3
- -1 molybdate ions Chemical class 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- 229920001864 tannin Polymers 0.000 description 3
- 235000018553 tannin Nutrition 0.000 description 3
- 239000001648 tannin Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 231100000167 toxic agent Toxicity 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000012360 testing method Methods 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
- 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
- C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/04—Tubes; Rings; Hollow bodies
Abstract
The application relates to the field of passivation solution, in particular to chromium-free passivation solution and a method for passivating a copper-tin alloy coating of a petroleum casing by applying the same. The chromium-free passivation solution for the copper-tin alloy coating of the petroleum casing pipe is characterized by comprising the following components in parts by weight: 15-27 parts of sodium nitrite; 3-8 parts of sodium m-nitrobenzenesulfonate; 65-90 parts of an auxiliary film-forming agent; 5-15 parts of sodium dodecyl sulfate. This application is through selecting for use sodium nitrite as the main material of passivation solution, through the characteristic that sodium nitrite can form the protective passive film on metal surface in the alkalescence environment, cooperation sodium metanitrobenzene sulfonate is oxidation in coordination to form more compact rete on the cladding material surface, improved the protective effect.
Description
Technical Field
The application relates to the field of passivation solution, in particular to chromium-free passivation solution and a method for passivating a copper-tin alloy coating of a petroleum casing by applying the same.
Background
The copper-tin alloy plated petroleum casing is widely applied to the oil and gas exploitation industry, and the main production processes of electroplating copper-tin alloy on the petroleum casing sequentially comprise alkali washing, cleaning, acid washing, cleaning, electroplating, cleaning, passivation, cleaning and drying. Passivation is one of indispensable processes in the electroplating production process, and is a means for improving the apparent state, corrosion resistance and other performances of the copper-tin alloy plating layer.
The conventional method in the current production is hexavalent chromium treatment, a passive film after chromate passivation treatment is very thin, the corrosion resistance is excellent, the process is simple, and the method is the most common passivation treatment method in copper-tin alloy electroplating production for a long time.
In view of the above-mentioned related technologies, the inventors found that, because the existing passivation agent uses dichromate or chromic anhydride as the main salt in the passivation process, hexavalent chromium contained in dichromate is a strong toxic substance, which causes great harm to human body and environment.
Disclosure of Invention
In order to overcome the defect that the existing passivation solution contains a strong toxic substance hexavalent chromium, the application provides a chromium-free passivation solution and a method for passivating a copper-tin alloy coating of a petroleum casing by using the same.
In a first aspect, the application provides a chromium-free passivation solution, which adopts the following technical scheme:
a chromium-free passivation solution comprises the following substances in parts by weight:
15-27 parts of sodium nitrite;
3-8 parts of sodium m-nitrobenzenesulfonate;
65-90 parts of an auxiliary film-forming agent;
5-15 parts of sodium dodecyl sulfate.
By adopting the technical scheme, the sodium nitrite is selected as the main material of the passivation solution, the characteristic that the sodium nitrite can form a protective passivation film on the metal surface in a slightly alkaline environment is adopted, and the sodium metanitrobenzene sulfonate is cooperated for oxidation. The introduction of sodium nitrite, sodium m-nitrobenzenesulfonate and an auxiliary film-forming agent improves the passivation protection effect and overcomes the defects of high passivation temperature and long reaction time of a single passivation solution.
Preferably, the chromium-free passivation solution also comprises 20-40 parts of a film forming agent, wherein the film forming agent comprises the following substances in parts by weight: 45-50 parts of molybdic acid-tungstate entangled particles;
3-5 parts of tannic acid;
0.5 to 1.5 portions of ammonium persulfate.
By adopting the technical scheme, the components of the chromium-free passivation solution are further optimized, and molybdic acid-tungstate entangled particles are selected as the main passivation material, so that on one hand, the adsorption of chloride ions can be weakened due to the fact that molybdate ions and chloride ions can compete for adsorption at metal surface defects, and the pitting corrosion resistance of the passivation film is improved. On the other hand, when single molybdate is passivated, the corrosion resistance can not meet the requirement due to the insufficient compactness of the formed film, the using amount is large, and the cost is high, so that the passivation effect is effectively improved by compounding tungstate with the tungstate. On this basis, this application forms compact passive film on metal surface through selecting for use the active group that tannin acid hydrolysis generated to react with metal, improves metal corrosion resistance, further adopts ammonium persulfate again, oxidizes copper to the ionic state, promotes going on of passivation to the passivation effect of passivation solution has further been improved.
Preferably, the molybdic acid-tungstate entangled particles are two-dimensional tungsten disulfide and two-dimensional molybdenum disulfide mixed ball-milled particles.
Preferably, the two-dimensional tungsten disulfide is prepared by adopting the following scheme:
and (3) stirring and mixing tungsten hexachloride and thiourea, adding a surfactant, heating, carrying out hydrothermal reaction, collecting reaction liquid, and filtering to obtain the two-dimensional tungsten disulfide.
Preferably, the two-dimensional molybdenum disulfide is prepared by adopting the following scheme:
and (2) mixing DMF (dimethyl formamide) and dodecyl mercaptan, adding molybdenum disulfide into the mixed solution, stirring, mixing, ultrasonically dispersing, centrifuging to remove precipitates, vacuum-filtering supernatant, washing and drying to obtain the two-dimensional molybdenum disulfide.
By adopting the technical scheme, the structure of molybdic acid-tungstate entanglement particles is further optimized, on one hand, the two-dimensional molybdenum disulfide surface contains dodecyl functional groups, and the two-dimensional tungsten disulfide covalent bonds are combined to form a hexagonal arrangementThe layers are superposed together through weak van der Waals force interaction, interlayer sliding is easy to occur when the layers are subjected to smaller shearing force, and the special layered structure enables the two-dimensional nano WS to be in contact with the inner wall of the shell 2 The lubricating structure can form a good lubricating structure, so that the molybdenum disulfide forms a compact coating structure on the surface of the coating in the passivation process, and the problem of poor coating density of single molybdenum disulfide is solved.
On the other hand, the wrapped structure intertwined in the technical scheme of the application fills the pores to increase the density of the passivation film, and simultaneously increases the difficulty of the corrosion factor contacting the plating layer, increases the complexity of the penetration path of the corrosion factor, and reduces the contact of the corrosion factor and the zinc coating, thereby further improving the passivation effect of the passivation solution.
Preferably, the auxiliary film-forming agent comprises one or both of urea or iminohydroxypolyether.
By adopting the technical scheme, the urea or the imino hydroxyl polyether is selected as the auxiliary film forming agent, and the two auxiliary film forming agents have certain corrosion inhibition effect and can perform composite action with the film forming agent to improve the passivation effect.
In a second aspect, the application provides a method for passivating a copper-tin alloy coating of a petroleum casing by using a chromium-free passivating solution, which comprises the following steps:
s1, washing treatment: carrying out alkali washing treatment on the surface of the copper-tin alloy plating layer of the petroleum casing pipe, after the alkali washing is finished, washing with clear water, then carrying out acid washing treatment, and washing with clear water again;
s2, passivating: and (3) taking the passivation solution to be matched with benzotriazole, collecting the treatment solution, placing the copper-tin alloy coating of the petroleum casing into the treatment solution, and soaking and passivating to complete passivation treatment.
Preferably, the temperature of the soaking passivation is 20-30 ℃, and the soaking passivation time is 30-300 s.
By adopting the technical scheme, the structure of the coating after passivation is further improved by optimizing the temperature and time of soaking passivation, so that the coating has a compact passivation layer.
In summary, the present application has the following beneficial effects:
firstly, sodium nitrite is selected as a main material of the passivation solution, and a protective passivation film can be formed on the surface of a metal by the aid of the characteristic that the sodium nitrite can form a protective passivation film on the surface of the metal in a slightly alkaline environment in cooperation with synergistic oxidation of sodium m-nitrobenzenesulfonate. The introduction of sodium nitrite, sodium m-nitrobenzenesulfonate and an auxiliary film-forming agent improves the passivation protection effect and overcomes the defects of high passivation temperature and long reaction time of a single passivation solution.
Secondly, the component of the chromium-free passivation solution is further optimized, molybdic acid-tungstate entangled particles are selected as a main passivation material, and on one hand, molybdate ions and chloride ions can compete for adsorption at metal surface defects, so that adsorption of the chloride ions can be weakened, and the pitting corrosion resistance of the passivation film is improved. On the other hand, when single molybdate is passivated, the corrosion resistance can not meet the requirement due to the insufficient compactness of the formed film, the using amount is large, and the cost is high, so that the passivation effect is effectively improved by compounding tungstate with the tungstate. On this basis, this application forms compact passive film on metal surface through selecting for use the active group that tannin acid hydrolysis generated to react with metal, improves metal corrosion resistance, further adopts ammonium persulfate again, oxidizes copper to the ionic state, promotes going on of passivation to the passivation effect of passivation solution has further been improved.
Thirdly, the structure of molybdic acid-tungstate entanglement particles is further optimized, on one hand, the two-dimensional molybdenum disulfide surface contains dodecyl functional groups, the two-dimensional tungsten disulfide covalent bonds are combined into hexagonal arrangement, the layers are overlapped together through weak van der waals force interaction, interlayer sliding is easy to occur when small shearing force is applied, the special layered structure enables the two-dimensional nanometer WS2 to form a good lubricating structure, the molybdenum disulfide forms a compact coating structure on the surface of a coating layer in the passivation process, and the problem of poor coating density of single molybdenum disulfide is solved.
On the other hand, the wrapped structure intertwined in the technical scheme of the application fills the pores to increase the density of the passivation film, and simultaneously increases the difficulty of the corrosion factor contacting the plating layer, increases the complexity of the penetration path of the corrosion factor, and reduces the contact of the corrosion factor and the zinc coating, thereby further improving the passivation effect of the passivation solution.
Detailed Description
The present application will be described in further detail with reference to examples.
Preparation example 1: molybdic-tungstate entangled particles:
taking 50g of tungsten hexachloride and 450g of thiourea, stirring and mixing, adding 0.5g of surfactant sodium dodecyl benzene sulfonate, heating to 250 ℃, carrying out hydrothermal reaction, collecting reaction liquid, and filtering to obtain two-dimensional tungsten disulfide;
and mixing 100mL of DMF and 3mL of dodecyl mercaptan, adding 1g of molybdenum disulfide into the mixed solution, stirring, mixing, placing under 300W, ultrasonically dispersing for 12h, centrifuging at 1000rpm for 60min, removing precipitates, carrying out vacuum suction filtration on the supernatant, washing, and drying at 90 ℃ for 24h to obtain the two-dimensional molybdenum disulfide.
Stirring and mixing 1g of two-dimensional molybdenum disulfide and 0.5g of two-dimensional tungsten disulfide, then carrying out ball milling treatment in a ball milling device, and sieving with a 2000-mesh sieve to prepare molybdic acid-tungstate entangled particles 1.
Preparation example 2: molybdic-tungstate entangled particles:
taking 55g of tungsten hexachloride and 475g of thiourea, stirring and mixing, adding 0.65g of surfactant sodium dodecyl benzene sulfonate, heating to 275 ℃, carrying out hydrothermal reaction, collecting reaction liquid, and filtering to obtain two-dimensional tungsten disulfide;
and mixing 125mL of DMF and 4mL of dodecyl mercaptan, adding 3g of molybdenum disulfide into the mixed solution, stirring, mixing, placing at 400W, ultrasonically dispersing for 12h, centrifuging at 1000rpm for 60min, removing the precipitate, vacuum-filtering the supernatant, washing, and drying at 90 ℃ for 24h to obtain the two-dimensional molybdenum disulfide.
Stirring and mixing 2g of two-dimensional molybdenum disulfide and 1.7g of two-dimensional tungsten disulfide, then carrying out ball milling treatment in a ball milling device, and sieving with a 2000-mesh sieve to prepare molybdic acid-tungstate entangled particles 2.
Preparation example 3: molybdic-tungstate entangled particles:
taking 60g of tungsten hexachloride and 600g of thiourea, stirring and mixing, adding 0.8g of surfactant sodium dodecyl benzene sulfonate, heating to 290 ℃, carrying out hydrothermal reaction, collecting reaction liquid, and filtering to obtain two-dimensional tungsten disulfide;
and mixing 150mL of DMF and 5mL of dodecanethiol, adding 5g of molybdenum disulfide into the mixed solution, stirring, mixing, ultrasonically dispersing at 500W for 12h, centrifuging at 1000rpm for 60min, removing the precipitate, vacuum-filtering the supernatant, washing, and drying at 90 ℃ for 24h to obtain the two-dimensional molybdenum disulfide.
Stirring and mixing 3g of two-dimensional molybdenum disulfide and 2.5g of two-dimensional tungsten disulfide, then carrying out ball milling treatment in a ball milling device, and sieving with a 2000-mesh sieve to prepare molybdic acid-tungstate entangled particles 3.
Preparation example 4
Auxiliary film-forming agent 1: and (2) stirring and mixing 500g of urea and 300g of imino hydroxyl polyether to prepare the auxiliary film-forming agent 1.
Preparation example 5
Film-forming agent: 450g of molybdic acid-tungstate entangled particles 1, 30g of tannic acid and 5g of ammonium persulfate are taken, stirred and mixed to prepare the film-forming agent 1.
Preparation example 6
Film-forming agent: 475g of molybdic acid-tungstate entangled particles 1, 40g of tannic acid and 10g of ammonium persulfate are taken, stirred and mixed to prepare the film-forming agent 2.
Preparation example 7
Film-forming agent: 500g of molybdic acid-tungstate entangled particles 1, 50g of tannic acid and 15g of ammonium persulfate are taken, stirred and mixed to prepare the film-forming agent 3.
Preparation example 8
Film forming agent: 475g of molybdic acid-tungstate entangled particles 2, 40g of tannic acid and 10g of ammonium persulfate are taken, stirred and mixed to prepare the film-forming agent 4.
Preparation example 9
Film-forming agent: 475g of molybdic acid-tungstate entangled particles 3, 40g of tannic acid and 10g of ammonium persulfate are taken, stirred and mixed to prepare the film-forming agent 5.
Examples
Example 1
A chromium-free passivation solution for a copper-tin alloy coating of a petroleum casing comprises 15g of sodium nitrite, 3g of sodium m-nitrobenzenesulfonate, 65g of urea, 5g of sodium dodecyl sulfate and 1L of deionized water.
A method for passivating a copper-tin alloy coating of a petroleum casing by using a chromium-free passivation solution comprises the following preparation steps:
s1, washing treatment: performing alkali washing treatment on the surface of the copper-tin alloy coating of the petroleum casing by using 0.1mol/L sodium hydroxide solution, and washing the surface to be neutral by using clear water after the alkali washing is finished; then, after the washing is finished by carrying out 0.1mol/L hydrochloric acid pickling treatment, washing with clean water again until the washing liquid is neutral;
s2, passivating: and (3) mixing 40mL of passivation solution with 2g of benzotriazole, placing the mixture into 1L of deionized water, collecting treatment solution, placing the copper-tin alloy coating of the petroleum casing into the treatment solution, and soaking and passivating at the soaking and passivating temperature of 20 ℃ for 30s to complete passivation treatment.
Example 2
A chromium-free passivation solution for a copper-tin alloy coating of a petroleum casing comprises 20g of sodium nitrite, 5g of sodium m-nitrobenzenesulfonate, 80g of urea, 10g of sodium dodecyl sulfate and 1L of deionized water.
A method for passivating a copper-tin alloy coating of a petroleum casing by using a chromium-free passivation solution comprises the following preparation steps:
s1, washing treatment: performing alkali washing treatment on the surface of the copper-tin alloy coating of the petroleum casing by using 0.1mol/L sodium hydroxide solution, and washing the surface to be neutral by using clear water after the alkali washing is finished; then, after the washing is finished by carrying out 0.1mol/L hydrochloric acid pickling treatment, washing with clean water again until the washing liquid is neutral;
s2, passivating: and (3) mixing 60mL of passivation solution with 4g of benzotriazole, placing the mixture into 1L of deionized water, collecting treatment solution, placing the copper-tin alloy coating of the petroleum casing into the treatment solution, and soaking and passivating at the soaking and passivating temperature of 25 ℃ for 60s to complete passivation.
Example 3
A chromium-free passivation solution for a copper-tin alloy coating of a petroleum casing comprises 27g of sodium nitrite, 8g of sodium m-nitrobenzenesulfonate, 90g of urea, 15g of sodium dodecyl sulfate and 1L of deionized water.
A method for passivating a copper-tin alloy coating of a petroleum casing by using a chromium-free passivation solution comprises the following preparation steps:
s1, washing treatment: the surface of the copper-tin alloy plating layer of the petroleum casing is subjected to alkali washing treatment by adopting 0.1mol/L sodium hydroxide solution, and after the alkali washing is finished, the surface is washed to be neutral by clear water; washing with 0.1mol/L hydrochloric acid, and washing with clear water until the washing solution is neutral;
s2, passivation treatment: and (3) mixing 80mL of passivation solution with 6g of benzotriazole, placing the mixture into 1L of deionized water, collecting treatment solution, placing the copper-tin alloy coating of the petroleum casing into the treatment solution, and soaking and passivating at the soaking and passivating temperature of 30 ℃ for 300s for passivation to complete passivation treatment.
Example 4
A chromium-free passivation solution for a copper-tin alloy coating of a petroleum casing comprises 27g of sodium nitrite, 8g of sodium m-nitrobenzenesulfonate, 90g of urea, 20g of a film-forming agent 1, 15g of sodium dodecyl sulfate and 1L of deionized water.
A method for passivating a copper-tin alloy coating of a petroleum casing by using a chromium-free passivation solution comprises the following preparation steps:
s1, washing treatment: performing alkali washing treatment on the surface of the copper-tin alloy coating of the petroleum casing by using 0.1mol/L sodium hydroxide solution, and washing the surface to be neutral by using clear water after the alkali washing is finished; then, after the washing is finished by carrying out 0.1mol/L hydrochloric acid pickling treatment, washing with clean water again until the washing liquid is neutral;
s2, passivation treatment: and (3) mixing 80mL of passivation solution with 6g of benzotriazole, placing the mixture into 1L of deionized water, collecting treatment solution, placing the copper-tin alloy coating of the petroleum casing into the treatment solution, and soaking and passivating at the soaking and passivating temperature of 30 ℃ for 300s for passivation to complete passivation treatment.
Example 5
A chromium-free passivation solution for a copper-tin alloy coating of a petroleum casing comprises 27g of sodium nitrite, 8g of sodium m-nitrobenzenesulfonate, 90g of urea, 30g of a film-forming agent 1, 15g of sodium dodecyl sulfate and 1L of deionized water.
A method for passivating a copper-tin alloy coating of a petroleum casing by using a chromium-free passivation solution comprises the following preparation steps:
s1, washing treatment: performing alkali washing treatment on the surface of the copper-tin alloy coating of the petroleum casing by using 0.1mol/L sodium hydroxide solution, and washing the surface to be neutral by using clear water after the alkali washing is finished; washing with 0.1mol/L hydrochloric acid, and washing with clear water until the washing solution is neutral;
s2, passivating: and (3) mixing 80mL of passivation solution with 6g of benzotriazole, placing the mixture into 1L of deionized water, collecting treatment solution, placing the copper-tin alloy coating of the petroleum casing into the treatment solution, and soaking and passivating at the soaking and passivating temperature of 30 ℃ for 300s for passivation to complete passivation treatment.
Example 6
A chromium-free passivation solution for a copper-tin alloy coating of a petroleum casing comprises 27g of sodium nitrite, 8g of sodium m-nitrobenzenesulfonate, 90g of urea, 40g of a film-forming agent 1, 15g of sodium dodecyl sulfate and 1L of deionized water.
A method for passivating a copper-tin alloy coating of a petroleum casing by using a chromium-free passivation solution comprises the following preparation steps:
s1, washing treatment: performing alkali washing treatment on the surface of the copper-tin alloy coating of the petroleum casing by using 0.1mol/L sodium hydroxide solution, and washing the surface to be neutral by using clear water after the alkali washing is finished; washing with 0.1mol/L hydrochloric acid, and washing with clear water until the washing solution is neutral;
s2, passivation treatment: and (3) mixing 80mL of passivation solution with 6g of benzotriazole, placing the mixture into 1L of deionized water, collecting treatment solution, placing the copper-tin alloy coating of the petroleum casing into the treatment solution, and soaking and passivating at the soaking and passivating temperature of 30 ℃ for 300s for passivation to complete passivation treatment.
Example 7
A chromium-free passivation solution for a copper-tin alloy coating of a petroleum casing comprises 27g of sodium nitrite, 8g of sodium m-nitrobenzenesulfonate, 90g of urea, 40g of a film-forming agent 2, 15g of sodium dodecyl sulfate and 1L of deionized water.
A method for passivating a copper-tin alloy coating of a petroleum casing by using a chromium-free passivation solution comprises the following preparation steps:
s1, washing treatment: performing alkali washing treatment on the surface of the copper-tin alloy coating of the petroleum casing by using 0.1mol/L sodium hydroxide solution, and washing the surface to be neutral by using clear water after the alkali washing is finished; then, after the washing is finished by carrying out 0.1mol/L hydrochloric acid pickling treatment, washing with clean water again until the washing liquid is neutral;
s2, passivation treatment: and (3) mixing 80mL of passivation solution with 6g of benzotriazole, placing the mixture into 1L of deionized water, collecting treatment solution, placing the copper-tin alloy coating of the petroleum casing into the treatment solution, and soaking and passivating at the soaking and passivating temperature of 30 ℃ for 300s for passivation to complete passivation treatment.
Example 8
A chromium-free passivation solution for a copper-tin alloy coating of a petroleum casing comprises 27g of sodium nitrite, 8g of sodium m-nitrobenzenesulfonate, 90g of urea, 40g of a film-forming agent 3, 15g of sodium dodecyl sulfate and 1L of deionized water.
A method for passivating a copper-tin alloy coating of a petroleum casing by using a chromium-free passivation solution comprises the following preparation steps:
s1, washing treatment: performing alkali washing treatment on the surface of the copper-tin alloy coating of the petroleum casing by using 0.1mol/L sodium hydroxide solution, and washing the surface to be neutral by using clear water after the alkali washing is finished; then, after the washing is finished by carrying out 0.1mol/L hydrochloric acid pickling treatment, washing with clean water again until the washing liquid is neutral;
s2, passivation treatment: and (3) mixing 80mL of passivation solution with 6g of benzotriazole, placing the mixture into 1L of deionized water, collecting treatment solution, placing the copper-tin alloy coating of the petroleum casing into the treatment solution, and soaking and passivating at the soaking and passivating temperature of 30 ℃ for 300s for passivation to complete passivation treatment.
Example 9
A chromium-free passivation solution for a copper-tin alloy coating of a petroleum casing comprises 27g of sodium nitrite, 8g of sodium m-nitrobenzenesulfonate, 90g of urea, 40g of a film-forming agent 4, 15g of sodium dodecyl sulfate and 1L of deionized water.
A method for passivating a copper-tin alloy coating of a petroleum casing by using a chromium-free passivation solution comprises the following preparation steps:
s1, washing treatment: performing alkali washing treatment on the surface of the copper-tin alloy coating of the petroleum casing by using 0.1mol/L sodium hydroxide solution, and washing the surface to be neutral by using clear water after the alkali washing is finished; washing with 0.1mol/L hydrochloric acid, and washing with clear water until the washing solution is neutral;
s2, passivation treatment: and (3) mixing 80mL of passivation solution with 6g of benzotriazole, placing the mixture into 1L of deionized water, collecting treatment solution, placing the copper-tin alloy coating of the petroleum casing into the treatment solution, and soaking and passivating at the soaking and passivating temperature of 30 ℃ for 300s for passivation to complete passivation treatment.
Example 10
A chromium-free passivation solution for a copper-tin alloy coating of a petroleum casing comprises 27g of sodium nitrite, 8g of sodium m-nitrobenzenesulfonate, 90g of urea, 40g of a film forming agent 5, 15g of sodium dodecyl sulfate and 1L of deionized water.
A method for passivating a copper-tin alloy coating of a petroleum casing by using a chromium-free passivation solution comprises the following preparation steps:
s1, washing treatment: the surface of the copper-tin alloy plating layer of the petroleum casing is subjected to alkali washing treatment by adopting 0.1mol/L sodium hydroxide solution, and after the alkali washing is finished, the surface is washed to be neutral by clear water; then, after the washing is finished by carrying out 0.1mol/L hydrochloric acid pickling treatment, washing with clean water again until the washing liquid is neutral;
s2, passivation treatment: and (3) mixing 80mL of passivation solution with 6g of benzotriazole, placing the mixture into 1L of deionized water, collecting treatment solution, placing the copper-tin alloy coating of the petroleum casing into the treatment solution, and soaking and passivating at the soaking and passivating temperature of 30 ℃ for 300s for passivation to complete passivation treatment.
Example 11
A chromium-free passivation solution for a copper-tin alloy coating of a petroleum casing comprises 27g of sodium nitrite, 8g of sodium m-nitrobenzenesulfonate, 90g of iminohydroxy polyether, 40g of a film forming agent 5, 15g of sodium dodecyl sulfate and 1L of deionized water.
A method for passivating a copper-tin alloy coating of a petroleum casing by using a chromium-free passivation solution comprises the following preparation steps:
s1, washing treatment: performing alkali washing treatment on the surface of the copper-tin alloy coating of the petroleum casing by using 0.1mol/L sodium hydroxide solution, and washing the surface to be neutral by using clear water after the alkali washing is finished; then, after the washing is finished by carrying out 0.1mol/L hydrochloric acid pickling treatment, washing with clean water again until the washing liquid is neutral;
s2, passivation treatment: and (3) mixing 80mL of passivation solution with 6g of benzotriazole, placing the mixture into 1L of deionized water, collecting treatment solution, placing the copper-tin alloy coating of the petroleum casing into the treatment solution, and soaking and passivating at the soaking and passivating temperature of 30 ℃ for 300s to complete passivation treatment.
Example 12
A chromium-free passivation solution for a copper-tin alloy coating of a petroleum casing comprises 27g of sodium nitrite, 8g of sodium m-nitrobenzenesulfonate, 90g of an auxiliary film forming agent 1, 40g of a film forming agent 5, 15g of sodium dodecyl sulfate and 1L of deionized water.
A method for passivating a copper-tin alloy coating of a petroleum casing by using a chromium-free passivation solution comprises the following preparation steps:
s1, washing treatment: performing alkali washing treatment on the surface of the copper-tin alloy coating of the petroleum casing by using 0.1mol/L sodium hydroxide solution, and washing the surface to be neutral by using clear water after the alkali washing is finished; then, after the washing is finished by carrying out 0.1mol/L hydrochloric acid pickling treatment, washing with clean water again until the washing liquid is neutral;
s2, passivation treatment: and (3) mixing 80mL of passivation solution with 6g of benzotriazole, placing the mixture into 1L of deionized water, collecting treatment solution, placing the copper-tin alloy coating of the petroleum casing into the treatment solution, and soaking and passivating at the soaking and passivating temperature of 30 ℃ for 300s for passivation to complete passivation treatment.
Comparative example
Comparative example 1
Compared with the example 1, the silicon-aluminum adsorption material is prepared by using 80g of traditional chromic anhydride, 20g of 0.5mol/L sulfuric acid and 1L of water as a passivating agent, and is passivated for 60s at 25 ℃, and the rest passivating steps are the same.
Performance test
The passivated coatings of examples 1 to 12 and the passivated coating of comparative example 1 were examined by the methods described in GB-6458-86. The test results are shown in table 1 below:
TABLE 1 Performance test Table
By combining the data of examples 1-12 and comparative example 1, it can be found that, in the present application, sodium nitrite is used as a main material of the passivation solution, and the sodium nitrite can form a protective passivation film on the metal surface in a slightly alkaline environment, and is matched with the synergistic oxidation of sodium m-nitrobenzenesulfonate, because the sodium nitrite and the sodium m-nitrobenzenesulfonate have relatively stable performance in neutral and weakly alkaline media and have relatively weak oxidizability, a coating film is formed by oxidizing the surface of a coating layer and then forming an auxiliary film-forming agent, so that a more compact film layer is formed on the surface of the coating layer, and the protection effect is improved.
On the basis, the data of the examples 4 to 10 and 11 to 12 show that the components of the chromium-free passivation solution are further optimized, molybdic acid-tungstate entangled particles are selected as the main passivation material, and on one hand, the adsorption of chloride ions can be weakened due to the fact that molybdate ions and chloride ions can compete for adsorption at metal surface defects, and the pitting corrosion resistance of the passivation film is improved. On the other hand, when single molybdate is passivated, the corrosion resistance can not meet the requirement due to the insufficient compactness of the formed film, the using amount is large, and the cost is high, so that the passivation effect is effectively improved by compounding tungstate with the tungstate. On this basis, this application forms compact passive film on metal surface through selecting for use the active group that tannin acid hydrolysis generated to react with metal, improves metal corrosion resistance, further adopts ammonium persulfate again, oxidizes copper to the ionic state, promotes going on of passivation to the passivation effect of passivation solution has further been improved.
Further, the structure of molybdic acid-tungstate entangled particles is optimized, on one hand, the surface of two-dimensional molybdenum disulfide contains dodecyl functional groups, two-dimensional tungsten disulfide covalent bonds are combined to form a hexagonal arrangement, the two layers are overlapped together through weak van der waals force interaction, interlayer sliding is easy to occur when small shearing force is applied, the special layered structure enables the two-dimensional nano WS2 to form a good lubricating structure, and the molybdenum disulfide forms a compact coating structure on the surface of a coating layer in a passivation process, so that the problem of poor coating density of single molybdenum disulfide is solved.
On the other hand, the tangled coating structure in the technical scheme of the application fills the pores to increase the density of the passivation film, increases the difficulty of contacting the coating with corrosion factors, increases the complexity of a penetration path of the corrosion factors, and reduces the contact between the corrosion factors and a zinc coating, thereby further improving the passivation effect of the passivation solution.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (8)
1. The chromium-free passivation solution for the copper-tin alloy coating of the petroleum casing pipe is characterized by comprising the following components in parts by weight:
15-27 parts of sodium nitrite;
3-8 parts of sodium m-nitrobenzenesulfonate;
65-90 parts of an auxiliary film-forming agent;
5-15 parts of sodium dodecyl sulfate.
2. The chromium-free passivation solution for the copper-tin alloy coating of the petroleum casing according to claim 1, further comprising 20-40 parts of a film forming agent, wherein the film forming agent comprises the following substances in parts by weight: 45-50 parts of molybdic acid-tungstate entangled particles;
3-5 parts of tannic acid;
0.5 to 1.5 portions of ammonium persulfate.
3. The chromium-free passivation solution for the copper-tin alloy coating of the petroleum casing pipe as claimed in claim 2, wherein the molybdic acid-tungstate entangled particles are two-dimensional tungsten disulfide and two-dimensional molybdenum disulfide mixed ball-milled particles.
4. The chromium-free passivation solution for the copper-tin alloy coating of the petroleum casing pipe as claimed in claim 3, wherein the two-dimensional tungsten disulfide is prepared by adopting the following scheme:
and (3) stirring and mixing tungsten hexachloride and thiourea, adding a surfactant, heating, carrying out hydrothermal reaction, collecting reaction liquid, and filtering to obtain the two-dimensional tungsten disulfide.
5. The chromium-free passivation solution for the copper-tin alloy coating of the petroleum casing pipe as claimed in claim 3, wherein the two-dimensional molybdenum disulfide is prepared by adopting the following scheme:
and (2) mixing DMF (dimethyl formamide) and dodecyl mercaptan, adding molybdenum disulfide into the mixed solution, stirring, mixing, ultrasonically dispersing, centrifuging to remove precipitates, vacuum-filtering supernatant, washing and drying to obtain the two-dimensional molybdenum disulfide.
6. The chromium-free passivation solution for the copper-tin alloy coating of the oil casing according to claim 1, wherein the auxiliary film forming agent comprises one or both of urea or imino hydroxyl polyether.
7. A method for passivating a copper-tin alloy coating of a petroleum casing by using the chromium-free passivating solution as defined in any one of claims 1 to 6, which is characterized by comprising the following steps of:
s1, washing treatment: carrying out alkali washing treatment on the surface of the copper-tin alloy plating layer of the petroleum casing pipe, after the alkali washing is finished, washing with clear water, then carrying out acid washing treatment, and washing with clear water again;
s2, passivation treatment: and (3) taking the passivation solution to be matched with benzotriazole, collecting the treatment solution, placing the copper-tin alloy coating of the petroleum casing into the treatment solution, and soaking and passivating to complete passivation treatment.
8. The method for passivating the copper-tin alloy plating layer of the petroleum casing pipe by using the chromium-free passivation solution as claimed in claim 7, wherein the soaking passivation temperature is 20-30 ℃ and the soaking passivation time is 30-300 s.
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| CN101445923A (en) * | 2008-12-30 | 2009-06-03 | 罗冲 | Passivation method for brass antitarnish |
| CN109735850A (en) * | 2018-12-28 | 2019-05-10 | 南京馥安投资管理有限公司 | A kind of method of pickling iron and steel and water circulation use |
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