JP5651855B2 - 変色から銀と銀合金の表面を保護するための方法 - Google Patents
変色から銀と銀合金の表面を保護するための方法 Download PDFInfo
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- JP5651855B2 JP5651855B2 JP2012554436A JP2012554436A JP5651855B2 JP 5651855 B2 JP5651855 B2 JP 5651855B2 JP 2012554436 A JP2012554436 A JP 2012554436A JP 2012554436 A JP2012554436 A JP 2012554436A JP 5651855 B2 JP5651855 B2 JP 5651855B2
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- 238000000034 method Methods 0.000 title claims description 42
- 229910052709 silver Inorganic materials 0.000 title claims description 40
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims description 38
- 239000004332 silver Substances 0.000 title claims description 38
- 238000002845 discoloration Methods 0.000 title claims description 31
- 229910001316 Ag alloy Inorganic materials 0.000 title claims description 5
- 150000003573 thiols Chemical class 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 17
- 238000013019 agitation Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- ORTRWBYBJVGVQC-UHFFFAOYSA-N hexadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCS ORTRWBYBJVGVQC-UHFFFAOYSA-N 0.000 claims description 2
- IGMQODZGDORXEN-UHFFFAOYSA-N pentadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCS IGMQODZGDORXEN-UHFFFAOYSA-N 0.000 claims description 2
- CCIDWXHLGNEQSL-UHFFFAOYSA-N undecane-1-thiol Chemical compound CCCCCCCCCCCS CCIDWXHLGNEQSL-UHFFFAOYSA-N 0.000 claims description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims 2
- 239000003929 acidic solution Substances 0.000 claims 1
- 229910001923 silver oxide Inorganic materials 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 17
- 239000010410 layer Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 230000008859 change Effects 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000010953 base metal Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 235000017281 sodium acetate Nutrition 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 229910001092 metal group alloy Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 3
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000012154 double-distilled water Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 229940087562 sodium acetate trihydrate Drugs 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229910017935 Ag-OH Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GWGDGGFEVZKALA-UHFFFAOYSA-N O=S.[Ag] Chemical compound O=S.[Ag] GWGDGGFEVZKALA-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 229910000923 precious metal alloy Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003378 silver Chemical group 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/16—Sulfur-containing compounds
- C23F11/161—Mercaptans
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
- B05D1/185—Processes for applying liquids or other fluent materials performed by dipping applying monomolecular layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C23C22/02—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 non-aqueous solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2202/00—Metallic substrate
- B05D2202/40—Metallic substrate based on other transition elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2350/00—Pretreatment of the substrate
- B05D2350/60—Adding a layer before coating
- B05D2350/63—Adding a layer before coating ceramic layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
- B05D3/0486—Operating the coating or treatment in a controlled atmosphere
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Composite Materials (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Chemically Coating (AREA)
- Chemical Treatment Of Metals (AREA)
- Laminated Bodies (AREA)
- Cleaning By Liquid Or Steam (AREA)
Description
―特許文献1に記載の組み立て手順は、表面の銀の原子とチオールの硫黄原子との間の所定の共有結合の構成が、反応:
非酸化表面上のAg+RSH→Ag−SR+1/2H2(Rは一般的なアルキル)で、すなわち、
酸化表面上のAg−O1/2+RSH→Ag−SR+1/2H2Oで、すなわち
ヒドロキシル化した表面上のAg−OH+RSH→Ag−SR+H2O
によって自然に生じると仮定している。しかしながら、これらの反応は周囲温度では完成せず、その結果、物理吸着チオールから薄くコーティングされる表面の一部がコーティングされず、起こり得る局所的な酸化プロセス(点食)の引き金を引くこともある。さらに、表面に存在するチオールの小片は、物理吸着されることができるが化学吸着されることができないため、軽い処理条件下でも機械的または化学的手段によって表面から容易に除去可能である。
―固体の銀で、または、銀層でコーティングされた卑金属または金属合金で作られた品物の表面に、マイクロメーター幅の引っかき傷(scoring)存在していることは、金属の表面がチオール溶液に全体的に浸潤していること、つまり、チオールとは完全には反応しないことを意味している。このことにより、保護されていない表面領域で起こり得る酸化プロセスの引き金が引かれ、結果として、表面変色(均一でないのが一般的)の外観の説明がつく。
−70°Cでトリクロロエチレン中で(または、65°でシクロヘキサン中で)10分
−60°Cで超音波撹拌下で、トリクロロエチレン(または、シクロヘキサン)中でさらに10分
−60°Cでアセトン中で10分
−60°Cで超音波撹拌下で、アセトン中でさらに10分
−70°Cでエタノール中で10分、
−60°Cで超音波撹拌下で、エタノール中でさらに10分
Claims (9)
- 変色から銀と銀合金の表面を保護するための方法であって、
前記方法は、
−処理される表面を有機溶媒中で洗浄による事前処理にまず晒す工程と、
−酸化銀の薄層の形成を保証することができる酸性溶液に、洗浄した表面を浸す工程と、
−nが10と16の間である、式 CH3(CH2)nSHの少なくとも1つのチオールの溶液に、酸化させた表面を浸す工程と、
−少なくとも10分間、少なくとも50℃の温度で水蒸気を含む環境下で、あらかじめ酸化させた銀表面に、前記チオールの分子を化学反応させる工程を含むことを特徴とする方法。 - 処理される表面を、少なくとも1つの有機溶媒中に浸すことによって洗浄する工程を含むことを特徴とする請求項1に記載の方法。
- 有機溶媒中に浸された表面を加熱する工程を含むことを特徴とする請求項1または2のいずれかに記載の方法。
- 前記加熱工程において、表面を熱攪拌にさらす工程を含むことを特徴とする請求項3に記載の方法。
- 硫酸溶液中に、あらかじめ洗浄された表面を浸す工程を含むことを特徴とする請求項1乃至4のいずれかに記載の方法。
- ペンタデカンチオール溶液中に、酸化させた表面を浸す工程を含むことを特徴とする請求項1乃至5のいずれかに記載の方法。
- ヘキサデカンチオール溶液中に、酸化させた表面を浸す工程を含むことを特徴とする請求項1乃至6のいずれかに記載の方法。
- ウンデカンチオール溶液中に、酸化させた表面を浸す工程を含むことを特徴とする請求項1乃至7のいずれかに記載の方法。
- 少なくとも2時間、約30℃の温度で、少なくとも1つのチオールの溶液中に、酸化させた表面を浸す工程を含むことを特徴とする請求項1乃至8のいずれかに記載の方法。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ITVE2010A000008 | 2010-02-24 | ||
ITVE2010A000008A IT1398698B1 (it) | 2010-02-24 | 2010-02-24 | Metodo per la protezione di superfici di argento e sue leghe dall'imbrunimento. |
PCT/IB2011/000369 WO2011104614A1 (en) | 2010-02-24 | 2011-02-23 | Method for protecting silver and silver alloy surfaces against tarnishing |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2013520570A JP2013520570A (ja) | 2013-06-06 |
JP5651855B2 true JP5651855B2 (ja) | 2015-01-14 |
Family
ID=42752925
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2012554436A Active JP5651855B2 (ja) | 2010-02-24 | 2011-02-23 | 変色から銀と銀合金の表面を保護するための方法 |
Country Status (10)
Country | Link |
---|---|
US (1) | US9057135B2 (ja) |
EP (1) | EP2539487B1 (ja) |
JP (1) | JP5651855B2 (ja) |
CN (1) | CN102906307B (ja) |
BR (1) | BR112012021150B1 (ja) |
CA (1) | CA2789532A1 (ja) |
DK (1) | DK2539487T3 (ja) |
IT (1) | IT1398698B1 (ja) |
RU (1) | RU2556162C2 (ja) |
WO (1) | WO2011104614A1 (ja) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013147698A1 (en) * | 2012-03-26 | 2013-10-03 | Innomart Pte Ltd | An aqueous solution for forming an alkylthiol self-assembled monolayer and a method for forming the same using the solution |
CN102747350B (zh) * | 2012-07-18 | 2016-05-25 | 深圳市成功科技有限公司 | 金、银镀层表面保护剂 |
CN103525313A (zh) * | 2012-11-03 | 2014-01-22 | 连新兰 | 一种银器亮光的方法 |
TR201909369T4 (tr) | 2014-12-16 | 2019-07-22 | Agere S R L | Soy metallerin ve/veya alaşımlarının yüzeylerinin kararmaya karşı korunması için geliştirilmiş işlem. |
WO2017220790A1 (en) * | 2016-06-23 | 2017-12-28 | Atotech Deutschland Gmbh | A water-based composition for post-treatment of metal surfaces |
JP2019214126A (ja) * | 2016-10-17 | 2019-12-19 | アルプスアルパイン株式会社 | 複合成形部材および複合成形部材の製造方法、ならびに電子・電気部品および電子・電気部品の製造方法 |
JP6969869B2 (ja) * | 2016-12-19 | 2021-11-24 | 株式会社大和化成研究所 | 気化性変色防止剤 |
CN109776366B (zh) * | 2017-11-13 | 2020-12-25 | 深圳市华星光电技术有限公司 | 一种铜保护剂 |
IT201800006484A1 (it) | 2018-06-20 | 2019-12-20 | Enrico Rossi | Protezione dall'ossidazione di oggetti d'argento (ag) leghe di argento, oro (au) ed altri metalli in lega ottenuti anche come deposito galvanico |
CN112501603B (zh) * | 2020-12-02 | 2021-08-17 | 深圳技术大学 | 一种黑色银饰及其制备方法 |
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JPS5327693B2 (ja) * | 1973-02-09 | 1978-08-10 | ||
JPS52111430A (en) * | 1976-03-15 | 1977-09-19 | Alps Electric Co Ltd | Method of preventing tarnish of silver and silver alloy |
JPS5871479A (ja) * | 1981-10-23 | 1983-04-28 | Citizen Watch Co Ltd | 時計用文字板 |
DE3905850A1 (de) | 1989-02-24 | 1990-08-30 | Blasberg Oberflaechentech | Verfahren zum schuetzen von blanken silberoberflaechen |
JPH04110474A (ja) * | 1990-08-30 | 1992-04-10 | Meidensha Corp | 銀めっきの後処理方法 |
EP0492487B1 (de) * | 1990-12-22 | 1996-03-20 | DODUCO GMBH + Co Dr. Eugen DÀ¼rrwächter | Mittel zum zeitweiligen Schutz von blanken Silber- und Kupferoberflächen gegen Anlaufen und Verfahren zu seiner Anwendung |
WO1999048682A1 (en) * | 1998-03-27 | 1999-09-30 | University Of Pittsburgh | Tarnish resistant article, preparation, manufacture and methods of use of same |
US6165284A (en) * | 1998-06-25 | 2000-12-26 | Albemarle Corporation | Method for inhibiting tarnish formation during the cleaning of silver surfaces with ether stabilized, N-propyl bromide-based solvent systems |
US7261839B2 (en) * | 2002-01-22 | 2007-08-28 | Northern Technologies International Corp. | Tarnish inhibiting composition and article containing it |
GB0307290D0 (en) * | 2003-03-31 | 2003-05-07 | Cole Paul G | Enhancing silver tarnish-resistance |
GB2402399B (en) * | 2003-06-03 | 2005-10-12 | Cole Paul Gilbert | Silver ternary alloy |
GB2412666B (en) * | 2004-03-30 | 2008-10-08 | Paul Gilbert Cole | Water-based metal treatment composition |
WO2008047375A1 (en) | 2006-10-19 | 2008-04-24 | Ramot At Tel-Aviv University Ltd | Method for electrochemical deposition of monolayers on metallic surfaces and objects coated with an organic monolayer |
CN100531934C (zh) * | 2006-10-26 | 2009-08-26 | 大连海事大学 | 利用有机超薄膜的金属抗变色方法 |
US7972655B2 (en) | 2007-11-21 | 2011-07-05 | Enthone Inc. | Anti-tarnish coatings |
KR101973460B1 (ko) | 2015-02-09 | 2019-05-02 | 한국전자통신연구원 | 다중 입력 영상 보정 장치 및 방법 |
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2010
- 2010-02-24 IT ITVE2010A000008A patent/IT1398698B1/it active
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2011
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- 2011-02-23 EP EP11713353.8A patent/EP2539487B1/en active Active
- 2011-02-23 CN CN201180011268.XA patent/CN102906307B/zh active Active
- 2011-02-23 JP JP2012554436A patent/JP5651855B2/ja active Active
- 2011-02-23 DK DK11713353.8T patent/DK2539487T3/da active
- 2011-02-23 RU RU2012140455/02A patent/RU2556162C2/ru not_active IP Right Cessation
- 2011-02-23 CA CA2789532A patent/CA2789532A1/en not_active Abandoned
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DK2539487T3 (da) | 2015-01-05 |
BR112012021150B1 (pt) | 2021-01-05 |
BR112012021150A2 (pt) | 2017-07-18 |
CA2789532A1 (en) | 2011-09-01 |
CN102906307B (zh) | 2015-04-15 |
RU2012140455A (ru) | 2014-03-27 |
US20120305141A1 (en) | 2012-12-06 |
IT1398698B1 (it) | 2013-03-08 |
ITVE20100008A1 (it) | 2011-08-25 |
CN102906307A (zh) | 2013-01-30 |
RU2556162C2 (ru) | 2015-07-10 |
US9057135B2 (en) | 2015-06-16 |
WO2011104614A1 (en) | 2011-09-01 |
EP2539487A1 (en) | 2013-01-02 |
EP2539487B1 (en) | 2014-09-17 |
JP2013520570A (ja) | 2013-06-06 |
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