US3900348A - Method for protecting copper surfaces against corrosion - Google Patents
Method for protecting copper surfaces against corrosion Download PDFInfo
- Publication number
- US3900348A US3900348A US423684A US42368473A US3900348A US 3900348 A US3900348 A US 3900348A US 423684 A US423684 A US 423684A US 42368473 A US42368473 A US 42368473A US 3900348 A US3900348 A US 3900348A
- Authority
- US
- United States
- Prior art keywords
- copper
- sulfur
- amines
- layer
- sulfide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000010949 copper Substances 0.000 title claims abstract description 47
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 45
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 230000007797 corrosion Effects 0.000 title claims abstract description 18
- 238000005260 corrosion Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 26
- 239000011593 sulfur Substances 0.000 claims abstract description 26
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001412 amines Chemical class 0.000 claims abstract description 5
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 5
- 229940102253 isopropanolamine Drugs 0.000 claims description 5
- 239000010410 layer Substances 0.000 abstract description 19
- 239000002344 surface layer Substances 0.000 abstract description 13
- -1 hydroxyalkyl amines Chemical class 0.000 abstract description 9
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 abstract description 7
- 150000003973 alkyl amines Chemical class 0.000 abstract description 4
- 150000004982 aromatic amines Chemical class 0.000 abstract description 4
- 230000001464 adherent effect Effects 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 21
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 14
- 238000012360 testing method Methods 0.000 description 10
- 238000010790 dilution Methods 0.000 description 9
- 239000012895 dilution Substances 0.000 description 9
- 239000012530 fluid Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000008399 tap water Substances 0.000 description 6
- 235000020679 tap water Nutrition 0.000 description 6
- MNJSYRKQHUMXNB-UHFFFAOYSA-N C(O)CN.[S] Chemical compound C(O)CN.[S] MNJSYRKQHUMXNB-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910000906 Bronze Inorganic materials 0.000 description 3
- 239000010974 bronze Substances 0.000 description 3
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical class [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 2
- 229960004887 ferric hydroxide Drugs 0.000 description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 241001572615 Amorphus Species 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910052946 acanthite Inorganic materials 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007705 chemical test Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 description 1
- OJKANDGLELGDHV-UHFFFAOYSA-N disilver;dioxido(dioxo)chromium Chemical compound [Ag+].[Ag+].[O-][Cr]([O-])(=O)=O OJKANDGLELGDHV-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229950004394 ditiocarb Drugs 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
- 229940056910 silver sulfide Drugs 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 238000005494 tarnishing Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 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
- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
- C23C22/63—Treatment of copper or alloys based thereon
Definitions
- Such transformation is accomplished according to the invention in that the surfaces'are treated with solutions of elementary sulfur in organic amines, namely, in alkyl amines, aryl amines, hydroxyalkyl amines or hydroxyaryl amines, which solutions are preferably diluted with water for use.
- This treatment results in the formation of a relatively loosely deposited copper sultide layer and a layer, which has been formed by chemical interdiffusion and can be detected by a microscopic examination revealing an exchange of copper by sulfur in the crystal lattice of the copper.
- the first-mentioned layer has only a small resistance to mechanical and thermal stresses.
- the layer formed by chemical interdiffusion is the, result of the incorporation of a foreign substance and resists all stresses which may occur.
- the quantities of copper dissolved in the testing fluid were colorimetrically determined in an AF 201 Lovibond Comparator by the sodium-diethyldithiocarbamate method.
- the quantities of dissolved copper were higher' by about one power of ten for the untreated tubes than for the treated tubes, as follows:
- testing specimens 5 and 6 freshly precipitated ferric hydroxide was flushed into the testing fluid and the specimens were also left in the testing fluid for 4-40 weeks. The specimens were then removed from the testing fluid and the ferric hydroxide still contained in the fluid was flushed out with distilled water. Distinct bulges due to corrosion were observed on the uncoated tube where it had been supported. Only rough areas were observed on the coated tube.
- Tap water C1 in amounts of 0.3, 0.1, and 5.0
- Tap water N0 (as Ca(NO or Mg(.NO in amounts of 20 and 100 milligrams per liter;
- the specimens treated with aqueous solutions of monoethanolamine containing 20% sulfur and with isopropanolamine containing 15% sulfur in a dilution of 1:500 at room temperature (20 C.) for a time of 5 minutes or 10 minutes showed in uncovered surface portions as a result of an insufficient degreasing. Besides, the covering was very thin so that the copper still shines through. After a treatment under the above mentioned conditions for a time of 30 or 60 minutes, the covering formed by the treatment with monoethanolamine-sulfur was satisfactory and had a mat finish and the covering formed by the treatment with isopropanolamine-sulfur was uniform (surface without defects) but thinner.
- Specimens treated for 30 or 60 minutes with an aqueous solution of monoethanolamine-sulfur in a dilution of 1:500 at 50 C. were not improved in surface finish over the specimens treated at 20 C.
- the previously degreased copper tubes were additionally degreased with carbon tetrachloride and acetone.
- the treatment with an aqueous solution of monoethanolamine-sulfur at 20 C. for 30 or 60 minutes resulted in a much thicker copper-sulfur layer.
- Copper tubes 40 centimeters long and 14 millimeters in diameter were provided. Part of these tubes were in the as-drawn condition and another part had been blown through with superheated steam. When these copper tubes were treated with a monoethanolaminesulfur solution at a dilution of 1:500 at C. for about minutes, a glossy sulfide surface layer was formed in both cases on the inside surface of the tube. No bare copper areas were found in the tubes that had been blown through with superheated steam.
- a plurality of copper tubes having a length of 40 centimeters and 14 millimeters in diameter were treated once as described hereinbefore for 30 minutes with a solution of monoethanolamine-sulfur in a dilution of 1:500 at 20 C. for 30 minutes and once for 60 minutes with a similar solution but in a dilution of 1:1000 at 20 C.
- the resulting specimens were investigated.
- a method for protecting copper surfaces against corrosion comprising treating the surfaces to be protected with a solution of elementary sulfur in the proportion of 15 to 20% by weight in a hydroxyalkyl amine, said solution being diluted with H O in the ratio of 1:100 to 1:1000 before application.
- a method for protecting copper surfaces against corrosion comprising treating the copper surfaces with a 20% by weight solution of elementary sulfur in monoethanolamine which is diluted with water in the ratio of 1:500.
- a method for protecting copper surfaces against corrosion comprising treating the copper surfaces with a 15% by weight solution of elementary sulfur in isopropanolamine which is diluted with water in the ratio of 1:500.
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Chemical Treatment Of Metals (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT1060172A AT322318B (de) | 1972-12-13 | 1972-12-13 | Verfahren zum schutz von kupferoberflaechen gegen korrosion |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3900348A true US3900348A (en) | 1975-08-19 |
Family
ID=3623456
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US423684A Expired - Lifetime US3900348A (en) | 1972-12-13 | 1973-12-11 | Method for protecting copper surfaces against corrosion |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US3900348A (de) |
| AT (1) | AT322318B (de) |
| CH (1) | CH590937A5 (de) |
| DE (1) | DE2361529A1 (de) |
| GB (1) | GB1403157A (de) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5244739A (en) * | 1975-10-07 | 1977-04-08 | Nissan Motor | Steel pipe |
| WO1987002856A1 (en) * | 1985-10-24 | 1987-05-07 | Enthone, Incorporated | Copper oxide treatment in printed circuit board |
| US20100126698A1 (en) * | 2008-11-21 | 2010-05-27 | Caterpillar Inc. | Heat exchanger including selectively activated cathodic protection useful in sulfide contaminated environments |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102006054761A1 (de) * | 2006-11-14 | 2008-05-15 | Hansgrohe Ag | Bereitstellung von wasserführenden Bauteilen aus Messinglegierungen mit verringerter Metallionenfreisetzung |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2266378A (en) * | 1938-10-19 | 1941-12-16 | Standard Oil Co California | Treatment of metallic frictional surfaces |
| US2876148A (en) * | 1954-10-05 | 1959-03-03 | Singer Fritz | Cold working metals coated with colloidal sulfur |
| US3062612A (en) * | 1959-04-25 | 1962-11-06 | Inst Francais Du Petrole | Method of protecting metals against electrochemical corrosion of the acidic type |
-
1972
- 1972-12-13 AT AT1060172A patent/AT322318B/de not_active IP Right Cessation
-
1973
- 1973-12-07 CH CH1717873A patent/CH590937A5/xx not_active IP Right Cessation
- 1973-12-11 US US423684A patent/US3900348A/en not_active Expired - Lifetime
- 1973-12-11 DE DE2361529A patent/DE2361529A1/de active Pending
- 1973-12-12 GB GB5753073A patent/GB1403157A/en not_active Expired
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2266378A (en) * | 1938-10-19 | 1941-12-16 | Standard Oil Co California | Treatment of metallic frictional surfaces |
| US2876148A (en) * | 1954-10-05 | 1959-03-03 | Singer Fritz | Cold working metals coated with colloidal sulfur |
| US3062612A (en) * | 1959-04-25 | 1962-11-06 | Inst Francais Du Petrole | Method of protecting metals against electrochemical corrosion of the acidic type |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5244739A (en) * | 1975-10-07 | 1977-04-08 | Nissan Motor | Steel pipe |
| WO1987002856A1 (en) * | 1985-10-24 | 1987-05-07 | Enthone, Incorporated | Copper oxide treatment in printed circuit board |
| US4717439A (en) * | 1985-10-24 | 1988-01-05 | Enthone, Incorporated | Process for the treatment of copper oxide in the preparation of printed circuit boards |
| US20100126698A1 (en) * | 2008-11-21 | 2010-05-27 | Caterpillar Inc. | Heat exchanger including selectively activated cathodic protection useful in sulfide contaminated environments |
| US8511370B2 (en) | 2008-11-21 | 2013-08-20 | Caterpillar Inc. | Heat exchanger including selectively activated cathodic protection useful in sulfide contaminated environments |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2361529A1 (de) | 1974-06-27 |
| AT322318B (de) | 1975-05-12 |
| GB1403157A (en) | 1975-08-13 |
| CH590937A5 (de) | 1977-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1172525A (en) | Copper-containing articles with a corrosion inhibitor coating and method of producing the coating | |
| KR100358654B1 (ko) | 납함유구리계합금제저함량의납방출용배관부품및이의제조방법 | |
| JPH09503823A (ja) | 金属表面用の化成被覆剤 | |
| US3686123A (en) | Cleaning composition | |
| US3900348A (en) | Method for protecting copper surfaces against corrosion | |
| WO2004022817A1 (ja) | バルブ・管継手等の銅合金製配管器材の鉛・ニッケル溶出防止法及びその銅合金製配管器材並びにその配管器材洗浄処理用処理液 | |
| US4610798A (en) | Method and composition of matter for conditioning and passivating certain metals | |
| CN106011807B (zh) | 一种钛合金油管螺纹表面处理方法 | |
| US3398010A (en) | Masking composition for galvanized metal | |
| US20030209521A1 (en) | Non-chromate metal surface etching solutions | |
| WO1999015832A1 (en) | Method for reducing lead leaching in fixtures | |
| US4070193A (en) | Corrosion resistant metal sealing formulation | |
| JPS63169391A (ja) | 半導体製造装置用金属部材 | |
| JP5180644B2 (ja) | 銅合金製接液器材のニッケル溶出防止方法 | |
| US3096220A (en) | Corrosion protection of aluminum | |
| JP3829189B2 (ja) | 旧オーステナイト粒界を組織に持つ鋼の結晶粒界測定法 | |
| JPH02305973A (ja) | 燐酸塩皮膜処理用の組成物及び処理方法 | |
| HUP0201234A2 (en) | Method for nuclear power plant decontamination | |
| KR102622751B1 (ko) | 마스크 세정용 조성물 및 이를 이용한 마스크 세정 방법 | |
| KR100477172B1 (ko) | 음용수용 배관연결구의 납용출 방지방법 | |
| JPS61272392A (ja) | 緑青除去方法 | |
| Hammadi | estimating pitting corrosion depth and density on carbon steel (C-4130) using artificial neural networks | |
| Ray | An Investigation into a Potential Source of Corrosion in Transistor Packages | |
| JPS602389B2 (ja) | 鉄鋼製部材の化学洗浄方法 | |
| Laouali et al. | Evaluation of inhibitor efficiency on corrosion of the aluminium heart exchangers and radiators in central heating |