WO2015174095A1 - 管用ねじ継手用めっき液及び管用ねじ継手の製造方法 - Google Patents
管用ねじ継手用めっき液及び管用ねじ継手の製造方法 Download PDFInfo
- Publication number
- WO2015174095A1 WO2015174095A1 PCT/JP2015/002456 JP2015002456W WO2015174095A1 WO 2015174095 A1 WO2015174095 A1 WO 2015174095A1 JP 2015002456 W JP2015002456 W JP 2015002456W WO 2015174095 A1 WO2015174095 A1 WO 2015174095A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- plating solution
- plating
- pyrophosphate
- plating film
- pipes
- Prior art date
Links
- 238000007747 plating Methods 0.000 title claims abstract description 186
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 230000008878 coupling Effects 0.000 title abstract description 15
- 238000010168 coupling process Methods 0.000 title abstract description 15
- 238000005859 coupling reaction Methods 0.000 title abstract description 14
- -1 mercapto compound Chemical class 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 20
- 239000011593 sulfur Substances 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008139 complexing agent Substances 0.000 claims abstract description 10
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims abstract description 10
- 235000011180 diphosphates Nutrition 0.000 claims abstract description 10
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 10
- OMSYGYSPFZQFFP-UHFFFAOYSA-J zinc pyrophosphate Chemical compound [Zn+2].[Zn+2].[O-]P([O-])(=O)OP([O-])([O-])=O OMSYGYSPFZQFFP-UHFFFAOYSA-J 0.000 claims abstract description 10
- GEZAUFNYMZVOFV-UHFFFAOYSA-J 2-[(2-oxo-1,3,2$l^{5},4$l^{2}-dioxaphosphastannetan-2-yl)oxy]-1,3,2$l^{5},4$l^{2}-dioxaphosphastannetane 2-oxide Chemical compound [Sn+2].[Sn+2].[O-]P([O-])(=O)OP([O-])([O-])=O GEZAUFNYMZVOFV-UHFFFAOYSA-J 0.000 claims abstract description 9
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 239000000539 dimer Substances 0.000 claims abstract description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 45
- 239000000956 alloy Substances 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 41
- 229910020994 Sn-Zn Inorganic materials 0.000 claims description 37
- 229910009069 Sn—Zn Inorganic materials 0.000 claims description 37
- 238000009713 electroplating Methods 0.000 claims description 36
- 239000000126 substance Substances 0.000 claims description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- 230000007797 corrosion Effects 0.000 abstract description 40
- 238000005260 corrosion Methods 0.000 abstract description 40
- 229910006069 SO3H Inorganic materials 0.000 abstract 1
- MDFFNEOEWAXZRQ-UHFFFAOYSA-N aminyl Chemical compound [NH2] MDFFNEOEWAXZRQ-UHFFFAOYSA-N 0.000 abstract 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract 1
- 230000006334 disulfide bridging Effects 0.000 abstract 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 86
- 239000010949 copper Substances 0.000 description 25
- 229910000831 Steel Inorganic materials 0.000 description 24
- 239000010959 steel Substances 0.000 description 24
- 230000001050 lubricating effect Effects 0.000 description 14
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 13
- 239000011701 zinc Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 10
- 239000011135 tin Substances 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 229910017755 Cu-Sn Inorganic materials 0.000 description 8
- 229910017927 Cu—Sn Inorganic materials 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000002775 capsule Substances 0.000 description 8
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229940048084 pyrophosphate Drugs 0.000 description 8
- 229910052718 tin Inorganic materials 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 6
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003129 oil well Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- MQHUHNALGOSWPX-QIFMNYRTSA-N (2r)-2-amino-3-[[(2r)-2-amino-2-carboxyethyl]disulfanyl]propanoic acid;(2r)-2-amino-3-sulfanylpropanoic acid Chemical compound SC[C@H](N)C(O)=O.OC(=O)[C@@H](N)CSSC[C@H](N)C(O)=O MQHUHNALGOSWPX-QIFMNYRTSA-N 0.000 description 1
- CSJDJKUYRKSIDY-UHFFFAOYSA-N 1-sulfanylpropane-1-sulfonic acid Chemical compound CCC(S)S(O)(=O)=O CSJDJKUYRKSIDY-UHFFFAOYSA-N 0.000 description 1
- LMPMFQXUJXPWSL-UHFFFAOYSA-N 3-(3-sulfopropyldisulfanyl)propane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCSSCCCS(O)(=O)=O LMPMFQXUJXPWSL-UHFFFAOYSA-N 0.000 description 1
- NJEWPZKUUKXAAA-UHFFFAOYSA-H CS(=O)(=O)[O-].[Cu+2].[Sn+4].CS(=O)(=O)[O-].CS(=O)(=O)[O-].CS(=O)(=O)[O-].CS(=O)(=O)[O-].CS(=O)(=O)[O-] Chemical compound CS(=O)(=O)[O-].[Cu+2].[Sn+4].CS(=O)(=O)[O-].CS(=O)(=O)[O-].CS(=O)(=O)[O-].CS(=O)(=O)[O-].CS(=O)(=O)[O-] NJEWPZKUUKXAAA-UHFFFAOYSA-H 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- BNKRJYKXAKKTCW-UHFFFAOYSA-J [Sn+4].[Cu+2].[O-]P([O-])(=O)OP(=O)([O-])[O-] Chemical compound [Sn+4].[Cu+2].[O-]P([O-])(=O)OP(=O)([O-])[O-] BNKRJYKXAKKTCW-UHFFFAOYSA-J 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- MRUAUOIMASANKQ-UHFFFAOYSA-N cocamidopropyl betaine Chemical compound CCCCCCCCCCCC(=O)NCCC[N+](C)(C)CC([O-])=O MRUAUOIMASANKQ-UHFFFAOYSA-N 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- VKFFEYLSKIYTSJ-UHFFFAOYSA-N tetraazanium;phosphonato phosphate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])(=O)OP([O-])([O-])=O VKFFEYLSKIYTSJ-UHFFFAOYSA-N 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
-
- 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
- C25D7/003—Threaded pieces, e.g. bolts or nuts
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L15/00—Screw-threaded joints; Forms of screw-threads for such joints
- F16L15/04—Screw-threaded joints; Forms of screw-threads for such joints with additional sealings
Definitions
- the present invention relates to a plating solution, and more particularly to a plating solution for a threaded joint for pipes and a method for manufacturing a threaded joint for a pipe using the plating solution.
- Steel pipes used in oil fields and natural gas fields have a unit length of more than a dozen meters. Steel pipes are connected by threaded joints, and the total length of an oil well pipe is several thousand meters.
- Threaded joints for pipes are classified into T & C (Threaded and Coupled) types and integral types.
- the T & C type threaded joint for pipes includes two pins formed at ends of two steel pipes and two boxes formed at both ends of a coupling of a short pipe having a larger outer diameter than the steel pipe.
- Each pin has an outer surface on which external threads are formed.
- Each box has an inner surface formed with an internal thread.
- Each pin is inserted into each box and screwed. That is, in the T & C type threaded joint for pipes, two steel pipes are connected via the coupling.
- the integral type threaded joint for pipe includes a box formed at the end of the first steel pipe and a pin formed at the end of the second steel pipe.
- the pin of the second steel pipe is inserted into the box of the first steel pipe and screwed, and the first and second steel pipes are connected to each other.
- the first steel pipe is directly connected to the second steel pipe. Coupling is unnecessary if an integral threaded joint for pipes is used. Therefore, there is no protrusion to the outside of the wall thickness of the coupling, and it does not interfere with the inner surface of the steel pipe on the outside. Therefore, integral type threaded joints for pipes are used for special purposes such as horizontal excavation.
- a threaded joint for a pipe is required to withstand the tensile force in the axial direction due to the weight of the connected steel pipe and to withstand the pressure of the fluid inside and outside.
- seizure resistance is required for threaded joints for pipes. Specifically, good seizure resistance is required even after repeated use for the casing (large diameter size) 4 times or more and for the tubing (small diameter size) 10 times or more.
- a copper plating film is formed on a contact surface of a pin or box of a threaded joint for pipes, or surface treatment such as phosphate treatment is performed.
- the contact surface is a surface portion where the pin and the box are in contact with each other, and includes a screw portion where a screw is formed and a screwless metal contact portion where the screw is not formed.
- the seal portion corresponds to a screwless metal contact portion.
- Dope is a compound grease containing a heavy metal such as Pb.
- the use of dopes containing heavy metals is being limited. Therefore, recently, a dope not containing heavy metals such as Pb, Zn and Cu (referred to as green dope) has been developed. However, the green dope has lower seizure resistance than the conventional dope.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2003-74763 (Patent Document 1) and Japanese Patent Application Laid-Open No. 2008-215473 (Patent Document 2) propose a threaded joint for pipes excellent in seizure resistance (galling resistance).
- a Cu-Sn alloy layer is formed in a thread part and an unthreaded metal contact part among threaded joints for pipes.
- Patent Document 2 a Cu—Zn—M1 alloy layer (M1 is one or more elements selected from Sn, Bi, and In) is formed on the screw portion and the unthreaded metal contact portion.
- M1 is one or more elements selected from Sn, Bi, and In
- An object of the present invention is to provide a plating solution for a threaded joint for pipes for forming a plating film excellent in seizure resistance, crevice corrosion resistance and exposure corrosion resistance, and a method for producing a threaded joint for pipes using the plating solution. Is to provide.
- the plating solution of this embodiment is a plating solution for pipe threaded joints.
- the plating solution contains no cyanide, copper pyrophosphate, tin pyrophosphate, zinc pyrophosphate, pyrophosphate as a metal complexing agent, and sulfur content of 40 g / L or less (excluding 0).
- the sulfur-containing compound is one or more of mercapto compounds, sulfide compounds, dimers formed by disulfide bonds of mercapto compounds, and salts thereof as defined by chemical formula (1).
- m and n are integers of 1 or 0.
- X 1 , X 2 , X 3 and X 4 are any of hydrogen, OH, NH 2 , SO 3 H and CO 2 H. However, none of X 1 , X 2 , X 3 and X 4 is hydrogen.
- R is any one of hydrogen, a methyl group and an ethyl group.
- the method of manufacturing a threaded joint for pipes includes a step of preparing the plating solution, and an electroplating process for the pin or box of the threaded joint for pipes using the plating solution. And a step of forming a Cu—Sn—Zn alloy plating film.
- Threaded joints for pipes manufactured using the plating solution of this embodiment are excellent in seizure resistance, crevice corrosion resistance and exposure corrosion resistance.
- the present inventors investigated the mechanism of seizure and corrosion at the threaded joint for pipes, and examined the countermeasures. As a result, the present inventors obtained the following knowledge.
- the contact surfaces of the pin and box When repeatedly tightening (make-up) and unscrewing (breakout) with a threaded joint for pipes, the contact surfaces of the pin and box come into contact with each other and slide. In this case, the contact surface generates heat due to deformation resistance. At this time, the temperature of a part of the contact surface may locally rise above the melting point. At the surface portion where the temperature has risen above the melting point, the metals are fused together and seizure occurs.
- crevice corrosion is considered to occur for the following reason. Electrochemically, Fe is a base metal than Cu. Therefore, when the Cu—Sn alloy plating film is formed on the surface of the threaded joint for pipes, a microgalvanic cell is formed between Cu in the plating film and base steel (Fe) in contact with Cu. Therefore, corrosion (crevice corrosion) occurs in the non-plated portion (Fe) that comes into contact with the plating film.
- the Cu-Sn alloy contains a base metal rather than Fe. Specifically, the Cu—Sn alloy contains Zn to form a Cu—Sn—Zn alloy plating film. In this case, the occurrence of crevice corrosion is suppressed.
- Patent Document 2 also discloses a Cu—Sn—Zn alloy plating film.
- a plating solution made of an aqueous solution containing a cyanide compound hereinafter referred to as a cyanide plating solution
- Cu is complexed with a cyanide to form a metal complex.
- the deposition potential of Cu can be shifted to the base. Therefore, in the electroplating process, only an appropriate amount of Cu is precipitated (eutectoid) together with Zn having a low deposition potential without excessive precipitation of Cu alone. As a result, a Cu—Sn—Zn alloy plating film is formed.
- spot rust may occur on the Cu—Sn—Zn alloy plating film depending on the storage environment, storage period, and the like. That is, the Cu—Sn—Zn alloy plating film cannot be said to have high exposure corrosion resistance.
- the mechanism by which spot rust occurs is considered as follows.
- a cyanide is used, the current efficiency in the electroplating process is reduced.
- hydrogen is generated together with the metal precipitation reaction.
- a large amount of electricity is used to generate hydrogen. Therefore, fine void defects (porosity) are formed in the plating film due to the generated hydrogen.
- the porosity is connected, oxygen enters the plating film from the outer surface of the plating film through the porosity, and reaches the steel material (Fe) under the plating film. In this case, spot rust occurs.
- a cyanide plating solution generates toxic cyanide gas when mixed with an acidic solution.
- a very thin plating film Ni plating film or the like
- This process is called a strike process. If a thin plating film is formed by performing the strike treatment, the adhesion of the plating film formed by the subsequent electroplating treatment to the steel material is enhanced.
- the plating solution (strike solution) used for the strike treatment is an acidic liquid.
- a strike tank in which the strike liquid is accumulated In the case of T & C type threaded joints for pipes, a strike tank in which the strike liquid is accumulated, a water tank for washing, and a plating tank in which the plating liquid is accumulated are prepared.
- the coupling in which the box is formed is immersed in a strike tank to perform a strike treatment.
- the box after the strike treatment is immersed in a water tank and washed with water. By washing with water, the acidic strike liquid is almost completely removed from the coupling. Therefore, even if a cyanide is contained in the plating tank used in the electroplating process in the next step, hydrocyanic acid gas is not generated.
- the coupling of the T & C type thread joint for pipes is a short pipe, it can be immersed in a tank.
- it is difficult to immerse the pin or box in the bathtub. This is because the integral type threaded joint for pipes usually reaches several tens of meters. Therefore, when the plating film is formed on the pin or box of the integral type threaded joint for pipes, the electroplating process is performed by another method different from the above-described method.
- the electroplating treatment of the integral type threaded joint for pipes is performed by the following method.
- a sealable capsule is attached to a pin or box of an integral type threaded joint for pipes.
- a strike liquid is supplied into the capsule to perform a strike process.
- the strike liquid in the capsule is discharged.
- the plating solution is supplied to the capsule and electroplating is performed.
- the strike solution remaining in the capsule and the plating solution may be mixed.
- hydrocyanic acid gas may be generated. Therefore, it is not preferable to use a plating solution containing a cyanide compound.
- the present inventors examined a plating solution that can form a Cu—Sn—Zn alloy plating film that does not contain a cyanide compound and has excellent exposure corrosion resistance. As a result, the present inventors obtained the following knowledge.
- Cu-Sn-Zn alloy plating film can be formed without using a cyanide compound by using a plating solution containing an alkaline aqueous solution mainly composed of pyrophosphate and a highly reducing sulfur-containing compound. is there.
- the current efficiency is about 30%. In this case, about 70% of the plating current is used for hydrogen generation.
- the current efficiency is about 80%. Therefore, the porosity in the Cu—Sn—Zn alloy plating film formed with this plating solution is small. Therefore, the occurrence of spot rust is suppressed, and excellent exposure corrosion resistance is obtained. Further, since the porosity in the Cu—Sn—Zn alloy plating film is small, it has high hardness. Therefore, the seizure resistance is also increased.
- the plating solution for pipe threaded joints completed based on the above knowledge does not contain a cyanide compound, copper pyrophosphate, tin pyrophosphate, zinc pyrophosphate, pyrophosphate as a metal complexing agent, 40 g / L or less (not including 0) of a sulfur-containing compound.
- the sulfur-containing compound is one or more of mercapto compounds, sulfide compounds, dimers formed by disulfide bonds of mercapto compounds, and salts thereof as defined by chemical formula (1).
- m and n are integers of 1 or 0.
- X 1 , X 2 , X 3 and X 4 are any of hydrogen, OH, NH 2 , SO 3 H and CO 2 H. However, none of X 1 , X 2 , X 3 and X 4 is hydrogen.
- R is any one of hydrogen, a methyl group and an ethyl group.
- the electroplating process is performed using the plating solution of this embodiment, the generation of hydrogen is suppressed. Therefore, the amount of porosity in the Cu—Sn—Zn alloy plating film formed by the electroplating process can be suppressed. As a result, the occurrence of spot rust is suppressed and the exposure corrosion resistance is excellent.
- the Cu—Sn—Zn alloy plating film is further excellent in crevice corrosion resistance. Furthermore, since the amount of porosity in the Cu—Sn—Zn alloy plating film is small, the hardness of the Cu—Sn—Zn alloy plating film is high and the seizure resistance is excellent. Further, the plating solution of this embodiment can form a Cu—Sn—Zn alloy plating film without containing a cyanide compound. Therefore, there is no possibility that hydrocyanic acid gas is generated in the plating process.
- the method for manufacturing a threaded joint for pipes includes the steps of preparing the plating solution and performing electroplating on the pin or box of the threaded joint for pipes using the plating solution. And a step of forming a Cu—Sn—Zn alloy plating film.
- the plating solution of this embodiment is used for the electroplating process with respect to the pin or box of the threaded joint for pipes.
- the plating solution does not contain a cyanide compound, and contains copper pyrophosphate, tin pyrophosphate and zinc pyrophosphate, a metal complexing agent, an additive, and a solvent.
- the solvent is water.
- Copper pyrophosphate, tin pyrophosphate, and zinc pyrophosphate are essential compounds for forming a Cu—Sn—Zn alloy plating film.
- the minimum with preferable copper pyrophosphate content in a plating solution is 1 g / L in copper conversion, More preferably, it is 3 g / L.
- the upper limit with preferable copper pyrophosphate content is 50 g / L in copper conversion, More preferably, it is 15 g / L.
- the minimum with preferable tin pyrophosphate content in a plating solution is 0.5 g / L in conversion of tin, More preferably, it is 2 g / L.
- the upper limit with preferable tin pyrophosphate content in a plating bath is 50 g / L in tin conversion, More preferably, it is 14 g / L.
- the minimum with preferable zinc pyrophosphate content in a plating solution is 0.5 g / L in conversion of zinc, More preferably, it is 1 g / L.
- the upper limit with preferable zinc pyrophosphate content in a plating solution is 50 g / L in conversion of zinc, More preferably, it is 20 g / L.
- the plating solution further contains a pyrophosphate as a metal complexing agent.
- the pyrophosphate as the metal complexing agent is, for example, sodium pyrophosphate, potassium pyrophosphate, ammonium pyrophosphate, or a mixture thereof.
- a preferable content of pyrophosphate as a metal complexing agent in the plating solution is 6 to 15 in terms of P ratio.
- a more preferable upper limit of the P ratio is 10, and a more preferable upper limit is 9.
- the P ratio is defined by the following equation (A).
- P ratio mass of metal complexing agent in plating solution and mass of P 2 O 7 in pyrophosphate as copper, tin, zinc metal salt / mass of copper, tin and zinc metal in plating solution (A)
- the plating solution further contains a highly reducing sulfur-containing compound as an additive.
- a sulfur containing compound contains the 1 type (s) or 2 or more types of the mercapto compound and sulfide compound defined by Chemical formula (1), the dimer by the disulfide bond of a mercapto compound, and these salts.
- m and n are integers of 1 or 0.
- X 1 , X 2 , X 3 and X 4 are any of hydrogen, OH, NH 2 , SO 3 H and CO 2 H. However, none of X 1 , X 2 , X 3 and X 4 is hydrogen.
- R is any one of hydrogen, a methyl group and an ethyl group.
- sulfur-containing compound examples include mercaptoacetic acid, 2-mercaptopropionic acid, 2-aminoethanethiol, 2-mercaptoethanol, 1-thioglycerol, mercaptopropanesulfonic acid, bis (3-sulfopropyl) disulfide, mercaptosuccinic acid, cysteine Cystine, methionine and the like.
- the sulfur-containing compound may be a combination of these compounds.
- the highly reducible sulfur-containing compound enables eutectoid of Zn, which is a base metal, suppresses the generation of hydrogen during electroplating, and reduces the amount of porosity in the plating film. If the content of the highly reducing sulfur-containing compound in the plating solution is too high, the Cu—Sn—Zn alloy plating film is difficult to be formed, and an unplated portion may occur. Therefore, the preferable upper limit of the sulfur-containing compound in the plating solution is 40 g / L. A preferable lower limit of the sulfur-containing compound in the plating bath is 0.01 g / L.
- the plating solution may further contain a surfactant.
- the surfactant facilitates the discharge of hydrogen gas generated during the electroplating process from the steel surface and the plating film to the outside.
- a preferable content of the surfactant in the plating bath is 0.0001 g / L to 10 g / L.
- the plating solution of this embodiment does not contain a cyanide compound. Although the plating solution does not contain a cyanide compound, a Cu—Sn—Zn alloy plating film can be formed by electroplating.
- the manufacturing method of the pipe threaded joint using the above-mentioned plating solution is as follows. First, the above plating solution is prepared. Next, the electroplating process using the said plating solution is implemented with respect to the contact surface of the pin or box of a threaded joint for pipes.
- the electroplating method is not particularly limited. When the threaded joint for pipes is a T & C type, the electroplating process may be performed using the above-described plating tank. Further, in the case of an integral type threaded joint for pipes, electroplating may be performed using the above-described capsule, or electroplating may be performed by other methods. A strike treatment may be performed before the electroplating treatment.
- the threaded joint for pipes is manufactured by the above manufacturing process.
- the conditions for the electroplating treatment bath temperature, plating solution pH, current density, etc.
- pretreatment such as degreasing or pickling may be performed.
- the threaded joint for pipes manufactured by the manufacturing method described above includes a Cu—Sn—Zn alloy plating film formed on a pin or a box.
- the Cu—Sn—Zn alloy plating film contains Cu, Sn, and Zn, and the balance consists of impurities.
- the preferable Cu content in the Cu—Sn—Zn plating film is 40 to 70 mass%, the preferable Sn content is 20 to 50 mass%, and the preferable Zn content is 2 to 20 mass%.
- the preferred thickness of the Cu—Sn—Zn alloy plating film is 30 to 40 ⁇ m.
- a Ni plating film may be formed under the Cu—Sn—Zn alloy plating film, or a Cu plating film may be formed instead of the Ni plating film.
- the Cu—Sn—Zn alloy plating film produced by the above production method has a lower porosity content than the Cu—Sn—Zn alloy plating film produced with a conventional plating solution containing a cyanide compound. For this reason, the threaded joint for pipes having the Cu—Sn—Zn alloy plating film produced by the above production method is less likely to cause spot rust and has excellent exposure corrosion resistance. Furthermore, since the porosity content is low, the Cu—Sn—Zn alloy plating film is high in hardness and excellent in seizure resistance. Further, the Cu—Sn—Zn alloy plating film is excellent in crevice corrosion resistance as compared with the Cu—Sn alloy plating film.
- the lubricating film may be a viscous liquid or semi-solid lubricating film, or may be a solid lubricating film. Further, it may be a lower layer solid lubricating film and an upper viscous liquid or semi-solid two-layered lubricating film, or may be a lubricating film containing a solid powder.
- the solid powder is not particularly limited as long as it is a known substance that exhibits a lubricating effect.
- solid powder examples include graphite, MoS 2 (molybdenum disulfide), WS 2 (tungsten disulfide), BN (boron nitride), PTFE (polytetrafluoroethylene), CF (fluorinated carbon), and CaCO 3 (calcium carbonate).
- the threaded joint for pipes manufactured by the manufacturing method of the present embodiment exhibits excellent seizure resistance even when the above lubricating film is used instead of using a dope containing a conventional heavy metal.
- a plating film was formed on the threaded joint for pipes.
- the obtained plating film was investigated for uniformity, seizure resistance, crevice corrosion resistance and exposure corrosion resistance.
- each seamless steel pipe contained 13% by mass of Cr.
- the outer diameter of each seamless steel pipe was 244.5 mm, the wall thickness was 13.84 mm, and the length was 1200 mm.
- internal threading is performed on the inner surface of one end of each steel pipe to form a box, and external threading is performed on the outer surface of the other pipe end to form a pin.
- An integral type threaded joint for pipes was manufactured.
- test number 8 a T & C type threaded joint for pipes was prepared.
- the inner surface of both ends of the coupling was subjected to female threading to form a box.
- the outer diameter of the coupling was 267.2 mm, the wall thickness was 24.0 mm, and the length was 335 mm.
- the solution was within the composition range of the plating solution of the present embodiment.
- the solutions (C-1) and (E-1) were sulfuric acid baths mainly composed of sulfuric acid.
- the solution (F-1) was a cyan bath containing a cyanide compound.
- Test Nos. 1 and 2 and Test Nos. 4 to 5 the product name Amhitor 24B manufactured by Kao Corporation was used as an amphoteric surfactant.
- Test No. 3 used the product name Softazoline LPB manufactured by Kawaken Fine Chemical Co., Ltd. as an amphoteric surfactant.
- Test No. 6 used polyoxyethylene nonyl ether as a nonionic surfactant.
- Test Nos. 1 to 5 (solution (A-1)) were further adjusted to pH 8 to obtain a plating solution. For adjustment of pH, polyphosphoric acid was used for Test No. 1 and Test Nos. 3 to 5, and orthophosphoric acid was used for Test No. 2.
- Electroplating was performed on the integral type screw joint box for pipes using the plating solution shown in Table 1. Specifically, a capsule capable of being sealed was put on the box of the threaded joint for pipes. The capsule was filled with a plating solution and electroplated. The bath temperature for Test Nos. 1-7 was 35 ° C. The plating time was as shown in Table 1.
- Test No. 8 performed an electroplating process on the coupling of a T & C type threaded joint for pipes using the plating solution shown in Table 1. Specifically, the electroplating process was performed by immersing the coupling in a plating bath. The bath temperature was 45 ° C. The plating time was as shown in Table 1.
- the chemical composition of the obtained plating film was measured using EDX (energy dispersive X-ray analysis).
- the chemical compositions in the Cu—Sn—Zn alloy plating films of Test Nos. 1 to 5 and Test No. 8 are Cu content: 55 mass%, Sn content: 35 mass%, Zn content: 10 mass%. there were.
- the chemical composition of the Cu—Sn alloy plating film of test number 6 was Cu content: 55 mass% and Sn content: 45 mass%.
- the chemical composition of the Cu plating film of test number 7 was Cu content: 100% by mass.
- Non-plated area judgment test In the plating film formed under the conditions of each test number, it is visually judged whether or not an unplated part (a part where the plating film is not locally formed and the surface of the steel material is exposed) has occurred. did. Specifically, the plating film of each test number was visually observed to check for “burn”. Table 1 shows the determination results. “E” (Excellent) means that no burn was confirmed and the plating film was formed uniformly. “NA” (Not Acceptable) means that “burn” was confirmed in the plating film.
- a lubricant film was formed by the following method on the contact surface of the box on which the plated film was formed under the conditions of each test number.
- a green dope was used as the lubricant, and specifically, a product name: Bestlife “3010” NM SPECIAL manufactured by Bestlife Corporation was used.
- the thickness of the lubricating coating was 100 ⁇ m.
- Screw tightening and unscrewing is repeated up to 10 times, and the number of times when seizure is first observed is subtracted from 1 (ie, N-1 times, hereinafter this number is referred to as M & B number). It was. When the number of M & B is “10”, it means that seizure was not observed even after screw tightening and screw unscrewing were repeated 10 times.
- the test results are shown in Table 1.
- test pieces collected from the plate material the test pieces that are not electroplated (hereinafter referred to as non-plated test pieces) and the plating test pieces of each test number are kept in contact with each other with bolts, A fixed test piece was prepared.
- the contact surface between the fixed plating test piece and the non-plating test piece was 50 mm ⁇ 50 mm.
- the crevice corrosion test was carried out using fixed test pieces.
- the fixed test piece was immersed in boiling water containing 20% by mass of NaCl for one month (31 days). One month later, the fixed test piece was taken out, and the maximum corrosion depth on the surface of the non-plated test piece that was in contact with the plated test piece was measured.
- Table 1 shows the measurement results. “E” (Excellent) in the table means that the maximum corrosion depth was less than 1 ⁇ m. “G” (Good) means that the maximum corrosion depth was less than 1-5 ⁇ m. “A” (Acceptable) means that the maximum corrosion depth was less than 5-10 ⁇ m. “NA” (Not Acceptable) means that the maximum corrosion depth was 10 ⁇ m or more.
- the plating solution of Test No. 4 contained no sulfur-containing compound as an additive although the basic composition of the plating solution was appropriate. Therefore, the number of M & Bs was less than 4 and the seizure resistance of the plating film was low. Furthermore, scorching was observed in the plating film. This is considered to indicate the occurrence of non-plated portions.
- the basic composition of the plating solution of Test No. 5 was appropriate, the content of the sulfur-containing compound as an additive was too high. Therefore, the number of M & Bs was also as low as less than 4, and the seizure resistance was low. Furthermore, scorching was observed in the plating film. This is considered to indicate the occurrence of non-plated portions.
- the film formed with the plating solution of test number 6 was a Cu—Sn alloy plating film. Therefore, crevice corrosion resistance and exposure corrosion resistance were low.
- the film formed with the plating solution of test number 7 was a Cu plating film. Therefore, the number of M & Bs was also as low as less than 4, and the seizure resistance was low.
- a plating solution containing a cyanide compound was used in the plating solution of test number 8.
- a Cu—Sn—Zn alloy plating film was uniformly formed.
- the Cu—Sn—Zn alloy plating film formed with this plating solution had low resistance to exposure corrosion. It is considered that since the plating solution contained a cyanide compound, a lot of hydrogen was generated during the electroplating process, and as a result, a lot of porosity was formed in the plating film.
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Abstract
Description
RS-(CHX1)m-(CHX2)n-CHX3X4 (1)
ここで、m、nは、1又は0の整数である。X1、X2、X3及びX4は、水素、OH、NH2、SO3H及びCO2Hのいずれかである。ただし、X1、X2、X3及びX4のいずれもが水素であることはない。Rは水素、メチル基及びエチル基のいずれかである。
RS-(CHX1)m-(CHX2)n-CHX3X4 (1)
ここで、m、nは、1又は0の整数である。X1、X2、X3及びX4は、水素、OH、NH2、SO3H及びCO2Hのいずれかである。ただし、X1、X2、X3及びX4のいずれもが水素であることはない。Rは水素、メチル基及びエチル基のいずれかである。
本実施形態のめっき液は、管用ねじ継手のピン又はボックスに対する電気めっき処理に利用される。めっき液は、シアン化合物を含有せず、ピロリン酸銅、ピロリン酸スズ及びピロリン酸亜鉛と、金属錯化剤と、添加剤と、溶媒とを含有する。本実施形態において、溶媒は水である。
ピロリン酸銅、ピロリン酸スズ、及びピロリン酸亜鉛は、Cu-Sn-Zn合金めっき皮膜を形成するために必須の化合物である。めっき液中のピロリン酸銅含有量の好ましい下限は銅換算で1g/Lであり、さらに好ましくは3g/Lである。ピロリン酸銅含有量の好ましい上限は銅換算で50g/Lであり、さらに好ましくは15g/Lである。
添加剤の作用効果を高めるために、めっき液はさらに、金属錯化剤としてのピロリン酸塩を含有する。金属錯化剤としてのピロリン酸塩はたとえば、ピロリン酸ナトリウム、ピロリン酸カリウム、ピロリン酸アンモニウム、又は、これらの混合物である。
P比=めっき液中の金属錯化剤及び銅、スズ、亜鉛金属塩としてのピロリン酸塩中のP2O7の質量/めっき液中の銅、スズ及び亜鉛金属の質量 (A)
めっき液はさらに、添加剤として高還元性の硫黄含有化合物を含有する。硫黄含有化合物は、化学式(1)で定義されるメルカプト化合物及びスルフィド化合物、メルカプト化合物のジスルフィド結合による二量体、及びこれらの塩類の1種又は2種以上を含有する。
RS-(CHX1)m-(CHX2)n-CHX3X4 (1)
ここで、m、nは、1又は0の整数である。X1、X2、X3及びX4は、水素、OH、NH2、SO3H及びCO2Hのいずれかである。ただし、X1、X2、X3及びX4のいずれもが水素であることはない。Rは水素、メチル基及びエチル基のいずれかである。
めっき液はさらに、界面活性剤を含有してもよい。界面活性剤は、電気めっき処理中に発生した水素ガスを鋼材表面及びめっき皮膜から外部に排出しやすくする。めっき浴中の界面活性剤の好ましい含有量は0.0001g/L~10g/Lである。
上述のめっき液を用いた管用ねじ継手の製造方法は次のとおりである。初めに、上述のめっき液を準備する。次に、管用ねじ継手のピン又はボックスの接触表面に対して、上記めっき液を用いた電気めっき処理を実施する。電気めっき処理方法は特に限定されない。管用ねじ継手がT&C型である場合、上述のめっき槽を用いて電気めっき処理を実施すればよい。また、インテグラル型の管用ねじ継手である場合、上述のカプセルを用いて電気めっき処理を実施してもよいし、他の方法で電気めっき処理を実施してもよい。電気めっき処理前にストライク処理を実施してもよい。以上の製造工程により、管用ねじ継手が製造される。電気めっき処理の条件(浴温、めっき液のpH、電流密度等)は周知の方法で適宜設定されれば、特に限定されない。電気めっき処理前に、脱脂又は酸洗等の前処理が実施されてもよい。
上述の製造方法により製造された管用ねじ継手は、ピン又はボックスに形成されたCu-Sn-Zn合金めっき皮膜を含む。Cu-Sn-Zn合金めっき皮膜は、Cuと、Snと、Znとを含有し、残部は不純物からなる。Cu-Sn-Znめっき皮膜中の好ましいCu含有量は40~70質量%であり、好ましいSn含有量は20~50質量%であり、好ましいZn含有量は2~20質量%である。
めっき液は、次の4種類を準備した。
(A-1)溶液:
・ピロリン酸スズ:スズ換算で10g/L
・ピロリン酸銅:銅換算で10g/L
・ピロリン酸亜鉛:亜鉛換算で10g/L
・ピロリン酸ナトリウム:300g/L
・P比=7.7
(C-1)溶液:
・メタンスルホン酸スズ:スズ換算で15g/L
・メタンスルホン酸銅:銅換算で15g/L
・硫酸:180g/L、
(E-1)溶液:
・硫酸銅:250g/L
・硫酸:110g/L
(F-1)溶液(日本化学産業株式会社製):
・Sn:8.5g/L
・Cu:23.0g/L
・Zn:0.7g/L
・シアン化ナトリウム:19.0g/L
・苛性ソーダ:13.0g/L
試験番号1~7は、表1に示すめっき液を用いて、インテグラル型の管用ねじ継手のボックスに対して電気めっき処理を実施した。具体的には、管用ねじ継手のボックスに対して、密閉可能なカプセルを被せた。カプセル内にめっき液を充填して、電気めっき処理を実施した。試験番号1~7の浴温は35℃とした。めっき時間は表1に示すとおりであった。
各試験番号の条件で形成されためっき皮膜において、不めっき部(局所的にめっき皮膜が形成されておらず、鋼材の表面が露出している部分)が発生したか否かを、目視により判定した。具体的には、各試験番号のめっき皮膜を目視で観察し、「焦げ」の有無を確認した。表1に判定結果を示す。「E」(Excellent)は、焦げが確認されず、めっき皮膜が均一に形成されたことを意味する。「NA」(Not Acceptable)は、めっき皮膜中に「焦げ」が確認されたことを意味する。
各試験番号の条件でめっき皮膜を形成されたボックスの接触表面に対して、次の方法により潤滑被膜を形成した。潤滑剤にはグリーンドープを使用し、具体的には、Bestolife Corporation社製の商品名:Bestolife “3010”NM SPECIALを使用した。潤滑被膜の厚さは100μmであった。
炭素鋼からなる(JIS G3141(2011)に定義されたSPCCに相当)板材を準備した。板材から、複数の試験片を採取した。試験片に対して、各試験番号のめっき液を利用して上述の条件で電気めっきを実施して、表1に示すめっき皮膜を表面に有するめっき試験片を準備した。
上記隙間腐食試験で使用したものと同じめっき試験片を準備した。試験片の表面のうち、めっき皮膜が形成された表面(観察面という)は50mm×50mmであった。各めっき試験片に対して、JIS Z2371(2000)に準拠した塩水噴霧試験を、24時間実施した。試験後の観察面において、錆(点錆)が発生した部分の面積を求めた。試験結果を表1に示す。表1中の「E」は、観察面全面に錆が発生しなかったことを意味する。「G」は、観察面における錆の発生した面積率が5%未満であったことを意味する。「A」は、観察面における錆の発生した面積率が5%~20%未満であったことを意味する。「NA」は、観察面における錆の発生した面積率が20%以上であったことを意味する。
表1を参照して、試験番号1~3は、めっき液の基本組成及び添加剤の両方が本願の範囲内であった。そのため、形成されたCu-Sn-Zn合金めっき皮膜は均一に形成され、焦げは発生しなかった。さらに、M&B回数はいずれも10回であり、優れた耐焼付き性を示した。さらに、これらの試験番号のめっき皮膜では優れた耐隙間腐食性及び耐暴露腐食性が得られた。
Claims (2)
- 管用ねじ継手用めっき液であって、シアン化合物を含有せず、
ピロリン酸銅と、
ピロリン酸スズと、
ピロリン酸亜鉛と、
金属錯化剤としてのピロリン酸塩と、
化学式(1)で定義されるメルカプト化合物及びスルフィド化合物、前記メルカプト化合物のジスルフィド結合による二量体、及びこれらの塩類の1種又は2種以上であって、40g/L以下(0を含まない)の硫黄含有化合物とを含有する、管用ねじ継手用めっき液。
RS-(CHX1)m-(CHX2)n-CHX3X4 (1)
ここで、m、nは、1又は0の整数である。X1、X2、X3及びX4は、水素、OH、NH2、SO3H及びCO2Hのいずれかである。ただし、X1、X2、X3及びX4のいずれもが水素であることはない。Rは水素、メチル基及びエチル基のいずれかである。 - 請求項1に記載の前記めっき液を準備する工程と、
前記めっき液を用いて、管用ねじ継手のピン又はボックスに対して電気めっき処理を実施して、前記ピン又は前記ボックスに、Cu-Sn-Zn合金めっき皮膜を形成する工程とを備える、管用ねじ継手の製造方法。
Priority Applications (7)
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JP2016519122A JP6250150B2 (ja) | 2014-05-15 | 2015-05-15 | 管用ねじ継手用めっき液及び管用ねじ継手の製造方法 |
CA2947534A CA2947534C (en) | 2014-05-15 | 2015-05-15 | Plating solution for threaded connection for pipe or tube and producing method of threaded connection for pipe or tube |
EP15792205.5A EP3144415B1 (en) | 2014-05-15 | 2015-05-15 | Plating solution for threaded connection for pipe or tube and producing method of threaded connection for pipe or tube |
CN201580024905.5A CN106460215B (zh) | 2014-05-15 | 2015-05-15 | 管用螺纹接头用镀液及管用螺纹接头的制造方法 |
US15/308,104 US10370770B2 (en) | 2014-05-15 | 2015-05-15 | Plating solution for threaded connection for pipe or tube and producing method of threaded connection for pipe or tube |
MX2016014930A MX2016014930A (es) | 2014-05-15 | 2015-05-15 | Solucion de recubrimiento para conexion roscada para tubo o tuberia de conduccion y metodo de produccion de la conexion roscada para tubo o tuberia de conduccion. |
RU2016148650A RU2658521C2 (ru) | 2014-05-15 | 2015-05-15 | Раствор для металлизации резьбового соединения трубопроводов или труб и способ производства резьбового соединения для трубопроводов или труб |
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CA3028938C (en) * | 2016-06-30 | 2020-06-09 | Nippon Steel & Sumitomo Metal Corporation | Threaded connection for pipe and method for producing threaded connection for pipe |
JP6645609B2 (ja) | 2018-07-27 | 2020-02-14 | 三菱マテリアル株式会社 | 錫合金めっき液 |
CN112236548B (zh) * | 2018-07-27 | 2022-03-04 | 三菱综合材料株式会社 | 锡合金镀液 |
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CA2947534A1 (en) | 2015-11-19 |
CN106460215A (zh) | 2017-02-22 |
RU2016148650A (ru) | 2018-06-19 |
CA2947534C (en) | 2019-02-12 |
US10370770B2 (en) | 2019-08-06 |
RU2016148650A3 (ja) | 2018-06-19 |
EP3144415B1 (en) | 2019-08-14 |
CN106460215B (zh) | 2019-07-16 |
EP3144415A1 (en) | 2017-03-22 |
JPWO2015174095A1 (ja) | 2017-04-20 |
AR100422A1 (es) | 2016-10-05 |
US20170051421A1 (en) | 2017-02-23 |
JP6250150B2 (ja) | 2017-12-20 |
EP3144415A4 (en) | 2018-01-10 |
MX2016014930A (es) | 2017-04-11 |
RU2658521C2 (ru) | 2018-06-21 |
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