CN1780937A - Enhancing silver tarnish-resistance - Google Patents
Enhancing silver tarnish-resistance Download PDFInfo
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- CN1780937A CN1780937A CNA2004800113752A CN200480011375A CN1780937A CN 1780937 A CN1780937 A CN 1780937A CN A2004800113752 A CNA2004800113752 A CN A2004800113752A CN 200480011375 A CN200480011375 A CN 200480011375A CN 1780937 A CN1780937 A CN 1780937A
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- 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
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- 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
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
An alkanethiol, alkyl thioglycollate, dialkyl sulfide or dialkyl disulfide may be used to surface treat of an alloy of silver containing an amount of germanium that is effective to reduce firestain and/or tarnishing. The treatment has been found to further reduce tarnishing of the alloy such that a sample can be supported close above a 20% solution of ammonium polysulphide for at least 30 minutes while retaining a generally untarnished appearance. The treatment may be carried out at the end of manufacturing a shaped article to give rise to an article that will preserve its untarnished appearance both during transit to a point of sale but during subsequent display for an extended period. The invention therefore also includes a method for manufacturing a tarnish-resistant silver article, which comprises the steps of forming a shaped article of an alloy of silver containing an amount of germanium that is effective to reduce firestain and/or tarnishing, surface treating the article with an alkanethiol, alkyl thioglycollate, dialkyl sulphide or dialkyl disulphide; and introducing the article into packaging. Also disclosed for use in treating an alloy of silver as aforesaid is a water-based composition comprising a treatment agent selected from an alkanethiol, alkyl thioglycollate, dialkyl sulfide or dialkyl disulfide and a mixture of an anionic surfactant and an amphoteric or nonionic surfactant in a concentration that is effective to solubilise the treatment agent.
Description
Technical field
The present invention relates to the application of sulfur-containing organic compound in improving the silver alloys rust resistance, relate to the silverware of the high rust resistance of having handled with described sulfur-containing organic compound on the surface, and the method that relates to the preservation and the displaying of treated goods.The invention still further relates to the aqueous composition that can be used for handling metal, described metal can be silver alloys, but it also can be other metal that needs surface treatment that rust resistance is provided, for example copper, brass or nickel.
Background technology
Silver alloys and rust resistance thereof
Standard Stirling silver (Sterling silver) provides a kind of general and material reliably for manufacturers and silversmith, but inevitably, finished product need further to clean and polishing, so that temporarily remove undesirable corrosion product.As you know, owing to be exposed under the atmospheric condition every day, silver and silver alloys produce the dark film that tarnishes that is called the corrosion thing.
Since ancient times, have recognized that ' refining ' silver of alloying is not too soft, so that can not normally use, add a certain proportion of base metal in the practice, so that improve hardness and intensity.In Britain, the minimum silver content of the goods that the rules and regulations that just existed since trecento are sold is 92.5% (Stirling silver label standard), but does not stipulate base metal.Early experience makes the silversmith be sure of that copper is their the most suitable available metal.Modern times, silver plate manufacturers observed this composition usually, though replace a certain proportion of copper with cadmium sometimes, so that obtain bigger ductility.The Stirling silver of 2.5% cadmium content is the standard material that is used for spinning (spinning) and punching press.Many areas are usually used in producing holloware and tableware (cutlery) to the silver alloys of lower grade in Europe.800 grade alloys (per thousand parts silver-colored umbers) are mainly used in southern Europe and Central Europe, and in the Scandinavia based on 830 standards.
In the manufacturing company of nearly all maximum, thermal treatment that finished product or crude product assembling are required and soldering are carried out with the flame of air gas spray gun.The unique skill by the silversmith of the oxidation of flame or reducing property and temperature of articles is controlled.Oxygen is easy to by fine silver, particularly when silver is heated to red heat.Silver not oxidation in air, but the copper in silver/copper alloy is oxidized to Red copper oxide or cupric oxide.The oxidized surface of pickling goods is removed the most surperficial but is not cupric oxide than deep layer in the dilute sulphuric acid of heat, thus the fine silver that covers by silver/copper oxide mixture layer of surface or not the silver of alloying form.In further heat-processed, fine silver is easy to be infiltrated, and makes to be in the darker copper oxidation of lower face.Thermal treatment successively, cold working and acid pickling step show the surface of pure lustre of silver when producing slight the polishing, but heavier polishing shows stain dark color and that diminish outward appearance that is called " fiery spot (firestain or fire) ".Owing to relate to higher temperature, brazing operation produces much more dark fiery spot.When the degree of depth of fiery spot surpassed about 0.025 millimeter (0.010 inch), alloy was easier to cracking and is difficult to soldering, because oxide surface not by wetting, does not consequently generate suitable metallurgical binding.
Patent GB-B-2255348 (Rateau, Albert and Johns; MetalcuropRecherche) disclose a kind of novel silver alloy that can keep inherent hardness and gloss character in the Ag-Cu alloy, alleviated simultaneously because copper content is easy to the variety of issue that oxidation produces.Described alloy is a ternary Ag-Cu-Ge alloy, contains at least 92.5 weight %Ag, 0.5-3 weight %Ge, and all the other are copper except impurity.It is said that described alloy is rustless in traditional production, deformation and finishing operations process in ambient air, easily deformable when cold conditions, be easy to hard brazing filler metal and when casting, can not cause serious contraction.It is said that but they also demonstrate good ductility and tensile strength and thermal treatment and reach required hardness.It is believed that germanium provides defencive function, it is the reason of the advantageous property combination that shows of novel alloy, germanium be solid-solubilized in silver mutually with copper mutually in.The microstructure that it is believed that alloy is made of two-phase, and the sosoloid of germanium and copper is surrounded by the thread sosoloid of germanium, silver and copper in the silver.It is believed that the germanium in the copper-rich phase passes through to form GeO or GeO
2The protectiveness film suppresses the surface oxidation of described phase, and the protectiveness film stops the appearance of fiery spot in hard brazing filler metal and flame heat treatment process, and at high temperature fiery spot is produced by the oxidation of copper.In addition, the expansion of corrosion is obviously delayed by the adding of germanium, surface become little Huang rather than black, and corrosion product is easy to remove with ordinary tap water.It is said that described alloy is specially adapted to adorn articles for use.But disclosed alloy is subjected to various restrictions in above-mentioned patent, because it has big grain-size, thereby the low-melting-point eutectic of deformation performance difference and local melt surface generation when alloy heats with the air gas spray gun forms big molten bath.
US-A-6168071 and EP-B-0729398 (Johns) disclose a kind of silver/germanium alloy, described alloy contains at least 77 weight % silver and 0.4-7 weight % germanium, all the other are mainly copper outside the removal of impurity, described alloy contains element boron as grain-refining agent, and its concentration is greater than 0ppm with less than 20ppm.The boron content of alloy can provide by the copper/boron mother alloy that contains 2 weight % element borons.According to reports, compare with the silver/germanium alloy that does not have boron, the boron of lower concentration provides fabulous grain refine surprisingly in silver/germanium alloy like this, provides bigger intensity and ductility to alloy.Boron in the alloy even in the ornaments industry, be used for also suppressing under the temperature of soldering the growth of crystal grain, the sample of alloy has pitting resistance according to reports, even under the occasion that is heated to copper in the conventional alloys/germanium eutectic melt temperature repeatedly.Joint strong and aesthetic satisfaction between the discrete component of described alloy can form between the free surface at two elements under the condition of not using packing material, can be by the joint of diffusion process or resistance welding or Laser Welding technology formation butt joint or overlap joint.Compare with the welding joint in the Stirling silver, the welding joint in the above-mentioned alloy has much smaller average grain size, and it is improved the formability of welding joint and ductility, and 830 alloys are with the welding of plasma body welding process, and polished and do not need to grind.
Ternary and quad alloy for example Ag-Cu-Ge alloy and Ag-Cu-Zn-Ge alloy comprise two kinds of lowpriced metal alloy element Cu and Ge in the precious metals ag mother metal.When being exposed in the oxidizing atmosphere, need to consider two kinds of oxidation reaction.At first, the copper oxidation generates Red copper oxide:
Secondly, the germanium oxidation generates germanium dioxide:
Aforesaid equation is represented germanium oxide (IV) GeO
2Generation, but also can generate germanium oxide (II) GeO or intermediate materials Ge
xO
y, wherein x be 1 and y greater than 1 but less than 2.Under standard conditions, just pure Cu reacts under 1 normal atmosphere with purity oxygen with pure Ge and generates pure-oxide mutually, and two kinds of reactions all are feasible, and the chemical driving force of reaction (2) is bigger 1.65 times than reaction (1).
According to WO 02/095082 (Johns), the rust resistance of the ternary alloy of silver, copper and germanium or the quad alloy of silver, copper, zinc and germanium can improve by following steps: molten mixture is cast as alloy, then alloy is annealed to reduce its thickness, and make crystal grain recrystallize in the alloy, at selective oxidation atmosphere H for example
2/ H
2O or CO/CO
2In anneal, promote GeO
2Generate, and stop Cu
2O generates.
Be used to remove or prevent the treatment compositions of silver-colored corrosion
To cleaning or protecting Stirling silver and other known rank silver to propose various suggestions so that remove corrosion and/or the generation of inhibition corrosion.
US-A-2841501 discloses a kind of based on lapping powder and C
12-C
20The silver-colored rumbling compound of normal chain alkyl mercaptan, it is believed that it is nontoxic, gentle smell is arranged, and make not corrosion of silver by generating unimolecular layer R-S-Ag, wherein R represents the alkane chain of mercaptan, forms the physical barriers layer between the activeconstituents of described layer in silver and atmosphere.
GB-A-1130540 relates to the protection of finished surface of Stirling silver or britannia metal as the step in the production process, and discloses a kind of method that may further comprise the steps:
With the volatile organic solvent that contains 99 weight parts trieline or 1 for example, 1,1-trichloroethane and 0.1-1.8 weight part contain-SH group and can on silver surface, generate for example silver surface of the cleaning of the solution-wet goods of Stearyl mercaptan and hexadecyl mercaptan or thioglycollate of water white protective layer organic solute;
Solution and surface reaction form such one deck, allow solvent evaporation then; And
Use the detergent solution washing surface, allow its drying then with the hot water clean surface.Before goods are delivered in user's hand, it is said that aforesaid method provides the shelf-life of hope to think " long-term finish " of need.
It is believed that the solvent that halohydrocarbon is best suited for, but they have a question also now to the suitability of environment.It is believed that ethers is combustible and deleterious, and it is believed that low-carbon alcohol is a poor solvent.Do not mention water as solvent.The applicant has seen a report from ATOFINAChemicals Inc on the Internet, the solvability of mercaptan in water progressively drops to 0.00115 grams per liter of nonyl mercaptan from 23.30 grams per liters of methyl mercaptan, and the data of hexadecyl mercaptan and Stearyl mercaptan (CAS 2885-00-9) point out that they are water-insoluble.
US-A-6183815 (Enick) is also open, and the processing of the above-mentioned type generates the self-assembly coating by mercaptan compound, and the sulphur atom binding is to the metallic surface in the described mercaptan compound, and the alkyl afterbody is away from the metallic surface.In the embodiment of described specification sheets, with the alcohol solution CF for example of the fluoro-alkyl acid amides in the isopropanol water solution for example
3(CF
2)
5CONH (CH
2)
2SH is sprayed on the silver surface, and clean surface is dried with soft cloth more subsequently.The fluoro-alkyl acid amides does not have the smell that can measure, and dissolves in low-carbon alcohol and the alcohol/water mixture, though very clear from specification sheets and embodiment, not every alcoholic solvent all obtains good film.
The absorption of report mercaptan on silver such as Yousong Kim are undertaken by anodic oxidation reactions, and anodic oxidation reactions produces the skew of open circuit potential on the negative pole direction of substrate metal, if or electromotive force be fixed, it produces peak-anode current:
http://www.electrochem.org/meetings/past/200/abstracts/
symposia/h1/1026.pdf
Kwan Kim, Adsorption and Reaction of Thiols and Sulfideson Noble Metals, Raman SRS-2000,14-17 August 2000, Xaimen, Fujian, China,
Http:// pcoss.org/icorsxm/paper/kuankim.pdf, also disclose the formation of self-assembled monolayer, and point out the self-assembly of the dithoiolates that alkyl sulfhydryl, dialkyl sulfide and dialkyl group disulfide form by two Ag-S keys of formation and aliphatic two mercaptan on silver surface.
By contrast, the document of relevant alkyl sulfhydryl germanium generation seldom.H
2S generates the disassociation absorption of the absorption-SH base and the hydride of absorption by reports such as Nelen on Ge 100 surfaces, Applied SurfaceScience, and 150,65-72 (1999), referring to
Http:// www.chem.missouri.edu/ Greenlief/pubs/00005797.pdf, also referring to Professor Michael Greenlief ofthe University of Missouri-Columbia
Http:// www.chem.missouri.edu/ Greenlief/Research.htmlReport, H
2S at room temperature is exposed to Ge (100) and produces disassociation absorption, and it is easy to follow the tracks of with ultraviolet photoelectron spectrum.What alkyl sulfhydryl and Ge generated high quality monolayer is reflected at Han etc., and J.Am.Chem.Soc. reports in 123,2422 (2001) the semi-conductor and the paper of nanotechnology.In described experiment, Ge (111) wafer acoustic treatment in acetone makes the organic impurity dissolving, is immersed in then among the dense HF, so that remove residual oxide compound, generate the end capped surface of hydrogen, after this wafer is immersed in the aqueous isopropanol of alkyl sulfhydryl, acoustic treatment is dry then in propyl alcohol.
Summary of the invention
Though claiming, GB-A1130540 provides long-term finish, but one of contriver's (he is a silversmith) experience is, this class is handled to solve fully and is being made and offering the various difficult problems that for some time corrosion produces between ultimate purchaser or the user, and many shortcomings are arranged.Though silverware can be delivered to retailer place under unattacked state, it mainly is because the result of the packing that manufacturers provides, and described packing makes goods avoid the air influence.In case removing this packing and goods for example shows in retail environment and shows in the showcase at hotel, it is subjected to the influence of ambient air and artificial illumination heat there, the goods of tradition Stirling silver needed to polish after a week again, and after two weeks, be subjected to corrosion like this usually, so that can not sell.When showing, the displaying time limit of goods before obvious corrosion may be as short as 3-4 days.Polishing can produce wearing and tearing and trickle scratch again, unless goods can be sold rapidly, otherwise it all loses original outward appearance.The demand of frequent polish display silver increases the labour cost of ornaments manufacturers or other retail sectors, and managerial personnel think that its staff should spend time on the merchandising rather than on the cleaning oddment.So selling or showing that the corrosion of point is a serious problem, it makes with the stock and shows that the wish of the personnel in the relevant distribution chain of silverware descends, and these do not solve so far fully.
When goods were sent to the ultimate purchaser, it was the least possible and do not need as far as possible certainly to wish to remove the work of corrosion.
According to the silver alloys of the disclosure of GB-B-2255348 and EP-B-0729398, can buy in the Europe and the U.S. by trade mark Argentium now, term used herein " Argentium " refers to those alloys.Though for example compare them high rust resistance is arranged, and any corrosion that generates can remove all by simple washing, but still have the space of improving rust resistance with Stirling silver.Even resembling in WO 02/095082 disclosedly when annealing is carried out in the oxidizing atmosphere of selecting, this remains like this.
Have now found that, alkyl sulfhydryl, mercaptoacetic acid alkyl ester, dialkyl sulfide or dialkyl group disulfide can be used for containing the surface treatment of the silver alloys of some amount germanium, described germanium effectively reduces fiery spot and/or corrosion, so that reduce or further reduce the corrosion of alloy, so that the hydrogen sulfide on sample at room temperature can withstand at least 30 minutes (usually 45-60 minute) 20% ammonium polysulfide solution, and keep general unattacked outward appearance.
So, the invention still further relates to contain-SH or-organic compound of S-S-key is in the application of the rust oxidation that is used for preparing silver/germanium alloy goods, so that reduce the corrosion of described alloy, so that sample can 30 minutes (45-60 minute usually) closely be positioned on 20% ammonium polysulfide solution at least, and keeping general unattacked outward appearance, described organic compound for example is C
2-C
40(preferred C
12-C
24) alkyl sulfhydryl, mercaptoacetic acid alkyl ester, dialkyl sulfide or dialkyl group disulfide, the silver content of described silver/germanium alloy is 0.1-7 weight % at least 77 weight % and ge content.
The moulded products that the present invention also provides a kind of silver alloys or made by described alloy, described alloy contains the germanium of some amount, and it effectively reduces fiery spot and/or corrosion, and uses C
12-C
24Alkyl sulfhydryl, mercaptoacetic acid alkyl ester, dialkyl sulfide or dialkyl group disulfide are handled.
The present invention also provides a kind of method that is used to prepare the rust resistance silverware, and described method may further comprise the steps:
Make the silver alloys moulded products that contains some amount germanium, the germanium of described amount effectively reduces fiery spot and/or corrosion;
With alkyl sulfhydryl, mercaptoacetic acid alkyl ester, dialkyl sulfide or dialkyl group disulfide surface treatment goods; And
Goods are packed.
Goods stand the hydrogen sulfide effect from ammonium polysulfide solution in the above-mentioned accelerated corrosion test, goods are suspended on for example 30 millimeters height of the described solution of distance, described accelerated test is corresponding to 1 year or longer time in the retail environment, goods are demonstrated and are exposed in the ambient atmosphere in this retail environment, can stand to heat up.It is the combining of further provide protection of defencive function and sulfur-containing organic compound of the ge content of alloy, it is believed that this is the reason that observed rust resistance improves.Goods still keep three times of corresponding time of goods that can be during this period of time not of its not corrosion outward appearance handled with sulfur-containing organic compound or longer under these exacting terms; this is beyond thought, does not demonstrate that the unattacked life-span is significantly increased between the state that untreated state and organosulfur are handled because tradition is not contained identical accelerated corrosion test that the Stirling silverware of protectiveness germanium carries out at the same terms.Show with being immersed in the accelerated corrosion test that Argentium in Stearyl mercaptan and the hexadecyl mercaptan solution and standard Stirling silver sample carries out; in that (EnSolv 765 with being immersed in solvent; a kind of positive propyl bromo of discussing below is the solvent cleaner on basis) fabric when cleaning, protectiveness mercaptan is removed from standard Stirling silver sample rather than from Argentium silver.In accelerated test, the zone of solvent scouring standard Stirling silver is than rapider the fading in zone of not cleaning, and in Argentium silver, do not see perceptible difference in appearance between the zone of cleaning and do not clean, thereby show that the mercaptan bonding is stronger or more effective.
U.S. silversmith association (Society of American Silversmiths) has reported with the accelerated corrosion test of ammonium polysulfide to Argentium Stirling silver, referring to
Http:// www.silversmithing.com/largentium4.htmAnd in simultaneous test, Argentium Stirling silver is still unattacked after 1 hour, and traditional Stirling silver less than 15 minutes by corrosion.But, in this test, 0.5 milliliter of 20% ammonium polysulfide solution mixed with 200 ml distilled waters, so that testing severity, to be exposed to 20% solution itself than sample much lower.In WO 02/095082, sample is suspended on 20% ammonium polysulfide solution, but exposure duration is shorter relatively, expose 3-5 minute later Ag-Cu-Ge alloy and begin jaundice.Other test of reporting in its specification sheets relates to sample and is placed in the moisture eliminator that flowers of sulfur and nitrocalcite are housed, and its harshness is lower than the ammonium polysulfide test.
Part as the improvement prescription plan of developing above-mentioned treatment agent, the applicant unexpectedly finds, treatment agent directly can be dissolved or be dispersed in the water phase surfactant mixture, and do not need to be dissolved in treatment agent in the organic solvent in advance and subsequently the solution that generates to be mixed with liquid, aqueous.At ambient temperature, the embodiment of above-mentioned composition is optically transparent and shelf-stable in several weeks or several months.So treatment compositions can be water base, and contain the mixture of alkyl sulfhydryl, mercaptoacetic acid alkyl ester, dialkyl sulfide or dialkyl group disulfide and anion surfactant and neutrality or amphoterics and water.
Detailed Description Of The Invention
Silver-copper-germanium alloy
Can comprise the silver alloys that contains some amount germanium by the alloy that the present invention handles, described germanium effectively reduces fiery spot and/or corrosion.It may be effective that US-A-6406664 (Diamond) discloses the germanium amount that is low to moderate 0.1 weight %, condition is to have the tin of significant quantity to exist, but,, do not provide goods or the corrosion of the goods that sheet material is made or the data of fiery spot of relevant casting manufacturing though provided formulation Example.The inventor thinks that 0.5 weight %Ge provides preferred and more real lower limit, is undesirable and use less than 1 weight %Ge in practice.A kind of not copper bearing alloy of two components can contain 99%Ag and 1%Ge, has reported a kind of non-corroding casting alloy that is used for ornaments, and it contains 2.5%Pt, 1%Ge, and all the other are Ag, optional Zr, Si or the Sn of containing.
Be fit to the ternary Ag-Cu-Ge alloy handled with the inventive method and quaternary Ag-Cu-Zn-Ge alloy for by weight alloy silver content at least 30%, preferred at least 60%, more preferably at least 80% and most preferably at least 92.5% until maximum level is not more than 98%, preferably be not more than those alloys of 97%.By the weight of alloy, the ge content of Ag-Cu-(Zn)-Ge alloy should at least 0.1%, preferably at least 0.5%, more preferably at least 1.1% and most preferably at least 1.5% until maximum level preferably is not more than 6.5%, more preferably no more than 4%.
If desired, germanium can partly substitute with one or more elements with oxidation potential that are selected from Al, Ba, Be, Cd, Co, Cr, Er, Ga, In, Mg, Mn, Ni, Pb, Pd, Pt, Si, Sn, Ti, V, Y, Yb and Zr, and condition is that the fire-resistant spot that can not provide germanium and the effect of rust resistance produce undue disadvantageous effect.The weight ratio of germanium and alternative element can be 100: 0 to 60: 40, preferred 100: 0 to 80: 20.Preferably, ge content is made up of germanium fully, and just described weight ratio is 100: 0.
Except impurity and any grain-refining agent, the rest part of ternary Ag-Cu-Ge alloy is made up of copper, and by the weight of alloy, copper quantity is at least 0.5%, preferably at least 1%, more preferably at least 2% and most preferably at least 4%.For ' 800 grades ' ternary alloy, for example copper content is 18.5% to be fit to.Except impurity and any grain-refining agent, the rest part of quaternary Ag-Cu-Zn-Ge alloy will be made up of copper, by the weight of alloy, copper quantity is at least 0.5%, preferably at least 1%, more preferably at least 2% and most preferably at least 4%, and the weight ratio of zinc and copper should be not more than 1: 1.So zinc is optional to be present in silver-copper alloy, quantity is the 0-100 weight % of copper content.For ' 800 grades ' quad alloy, for example copper content be 10.5% and zinc content be 8% to be fit to.
Except silver, copper and germanium and optional zinc, alloy preferably contains grain-refining agent, so that suppress particle growth in the alloy course of processing.The grain-refining agent that is fit to comprises boron, iridium, iron and nickel, and boron is particularly preferred.By the weight of alloy, the quantity of grain-refining agent (being preferably boron) in Ag-Cu-(Zn)-Ge alloy can be 1-100ppm, preferred 2-50ppm, more preferably 4-20ppm.
In a preferred embodiment, alloy is a ternary alloy, and by the weight of alloy, except impurity and any grain-refining agent, described ternary alloy is made up of 80-96% silver, 0.1-5% germanium and 1-19.9% copper.In a preferred embodiment, alloy is a ternary alloy, by the weight of alloy, except impurity and grain-refining agent, described ternary alloy is made up of 92.5-98% silver, 0.3-3% germanium and 1-7.2% copper, also has 1-40ppm boron as grain-refining agent.In a preferred embodiment, alloy is a ternary alloy, and by the weight of alloy, except impurity and grain-refining agent, described ternary alloy is made up of 92.5-96% silver, 0.5-2% germanium and 1-7% copper, also has 1-40ppm boron as grain-refining agent.
Protective material
Can use contain chain alkyl and-SH or-compound of S-S base is as protective material, for example alkyl sulfhydryl, dialkyl sulfide or dialkyl group disulfide, its medium chain is preferably the long-chain of at least 10 carbon atoms, can be C
12-C
24Spendable containing-SH or-compound of S-S comprises C
16-C
24The straight chain saturated aliphatic compound, for example hexadecyl mercaptan and Stearyl mercaptan and mercaptoacetic acid cetyl ester and mercaptoacetic acid stearyl, its molecular formula is as follows.
Stearyl mercaptan is an extremely faint yellow waxy solid of white, and water insoluble, its fusing point is 15-16 ℃.Hexadecyl mercaptan also is white or faint yellow waxy solid, and its fusing point is 30 ℃.
Prescription based on organic solvent
Protective material is used in such solution; solvent for example is a non-polar organic solvent; alcohol (for example methyl alcohol or ethanol), ketone (for example acetone or methylethylketone), ether (for example ether), ester (for example n-butyl acetate), hydro carbons, halocarbon (methylene dichloride, 1 for example for example; 1,1-trichloroethane, trieline, tetrachloroethylene or HCFC 141b).Protective material can account for the 0.1-1 weight % of solvent.Can use based on the halid solvent of alkyl or aryl positive propyl bromo for example, it is preferred at present, because the atmospheric lifetime of described compound is short, comparing with other halocarbon has relative low toxicity, and favourable chemistry and physical properties and boiling point, specific heat and vaporization heat.
US-A-5616549 discloses a kind of solvent mixture, and it contains 90 to about 96.5% positive propyl bromo; 0 to about 6.5% terpene blend and 3.5 mixtures to about 5% low boiling point solvent, and described terpene blend contains 35 to about 50% suitable-pinanes and 35 to about 50% anti--pinanes; Described low boiling point solvent mixture contains 1 of 0.5-1% Nitromethane 99Min., 0.5-1%, 1 of 2-butylene oxide ring and 2.5-3%, 3-dioxolane.Described solvent mixture has following advantage:
(i) it to any produce by the oxidation of mixture in the presence of the air, produce by the hydrolysis of mixture in the presence of the water and under temperatures involved by the suitable stabilization of free acid of the pyrolysis generation of mixture;
(ii) it is non-flammable and incorrosive;
(iii) the various components of solvent mixture are not subjected to the restriction of U.S. Clean Air Act (the U.S.Clean Air Act); And
It is (iv) known that not have a kind of component of solvent mixture be carcinogen (just these components are not by N.T.I., and I.A.R.C. and California Proposition 65 list, and they are not limited by OSHA yet).
And described solvent mixture has high dissolving power, and kauri butanol value is greater than 120, more preferably greater than 125.In addition, the vaporator rate of described solvent mixture is at least 0.96, wherein 1=1.When evaporation, solvent mixture stays the non-volatile residue (NVR) less than 2.5 milligrams, does not more preferably have residue.Solvent by above-mentioned patent preparation can be from Enviro-Tech International, Inc of Melrose Park, and Illinois, USA buys with trade name EnSolv.
Prescription based on organic solvent and water
Under many occasions, for example various light industry are used, and to carry out the corrosion resistant processing be preferred with being mainly aqueous solvent system.For this reason; can be with in the water-soluble immiscible organic solvent of protective material; for example based on the solvent of positive propyl bromo; can be with the solution that generates and relative dense water base soap or detergent composition mixing as " carrier "; after this water is added in the mixture of generation, obtains aqueous dipping solution or compound degreasing and treatment soln.Therefore, aqueous dipping solution has some advantages like this: unnecessary solvent degreasing system, easily flood, but cold conditions is used, the All Ranges of submergence goods all can contact with Stearyl mercaptan or other treatment agent, and Argentium silver only needs 2 minutes to 1 hour dippings, and the cleaning of goods and drying are easy to carry out, because water droplet is subjected to polishing the exclusion of silver, goods can be easy to use steeping fluid in manufacturing environment before delivering to the retailer.
Preferred aqueous detergent can be based on tensio-active agent or its mixture of anionic, oxyalkylated non-ionic type or water-soluble cationic, and preferred pH value is 7 or near 7.Cationic surfactant can be based on alkyl sodium sulfate ester and Phenylsulfonic acid alkyl ester, and the roughness that its long-term epidermis exposes can or use oxyethyl group alkyl sodium sulfate ester to reduce (US-A-3793233, people such as Rose by coexistence; 4024078 Gilbert; 4316824 Pancherni).Other known tensio-active agent for example trimethyl-glycine also can exist, for example referring to US-A-4555360 (Bissett).In Britain, the suitable prescription that contains 5-15 weight % nonionic surface active agent and 15-30 weight % aniorfic surfactant can trade name FairyLiquid (Proctor ﹠amp; Gamble) be commercially available.
Liquid, aqueously also can prepare by following steps: treatment agent is dissolved in the non-organic solvent, the liquid, aqueous adding of washing composition that will be dense relatively then, for example undiluted Fairy Liquid adds.So just obtain a kind of detergent liquid that many advantages are arranged: be easy to make soap lye, described liquid is easy to be coated on the Argentium silverware with wet sponge/cotton, wool/cloth etc., liquid and foam make Stearyl mercaptan or other treatment agent enter those unmanageable goods zones that cloth may not reach, the cleaning of goods and drying are easily carried out, because water droplet is subjected to polishing the exclusion of silver, goods can be easy to use this process in manufacturing environment before delivering to the retailer, also can be easy to be used for retail or home environment.In addition, with mercaptan of the present invention be hydrophobic nature that the processing carried out of treatment agent on basis offers silver/silver alloys can alleviate or overcome make or domestic environment in problems such as the washmarking that produces by cleaning process or water spots.
Based on liquid, aqueous prescription
Find surprisingly, the prescription that contains effective quantity treatment agent can such prepare in liquid, aqueous by they directly are dissolved in, described liquid, aqueous aniorfic surfactant and neutral surface active agent or the amphoterics of containing, do not contain not and water-soluble mixed organic solvent, preferably do not contain other all solvents.Treatment agent can be dissolved in dense relatively containing in tensio-active agent liquid, aqueous, they can use same as before or dilute with water after use the concrete content that provides referring to upper section.
Before the dilution, treatment agent can exist in described composition, and its quantity is at least 0.1 weight %, preferred at least 1 weight %, and the solid content of composition is at least 5 weight %, is generally 10-40 weight %, may be 50 weight % or higher.Also do not describe at present the dissolving of aqueous surfactant liquid or disperseed the high-carbon alkyl sulfhydryl of so relative high density to be reported as the ability of highly water-insoluble treatment agent with other.The enriched material dilutable water that generates; obtain aqueous treatment and embathe liquid or combination skim soln; and the liquid that embathes that is used as above-mentioned explanation; found that treatment agent can stay in such dilution later solution or suspension; may be still to silver-copper or silver-copper-germanium alloy and may other metal for example the surface treatment of copper, yellow copper and mickel be that effectively its surface protection film can stop corrosion.Particularly, from the stability and the viewpoint of validity, can directly be mixed into by hexadecyl mercaptan (liquid state) and also in statu quo use the available good result of use behind solution or the dilute with water in the tensio-active agent " carrier ".
Particularly, treatment agent of the present invention can successfully be dispersed in the mixture that contains neutral surface active agent and aniorfic surfactant liquid, aqueous, and the neutral surface active agent for example accounts for about 33 weight % of total surfactant.The treatment agent that can be dispersed in such reagent comprises n-hexadecyl mercaptan and Octadecane base mercaptan.Also they successfully can be dispersed in the liquid, aqueous of the mixture that contains amphoterics or zwitterionics and aniorfic surfactant, such mixture can obtain the optically transparent solution of high relatively shelf-stable, and treatment agent does not almost have or do not have sedimentary tendency again.Under described situation, the weight ratio of amphoterics or zwitterionics and aniorfic surfactant can be 1: 10 to 10: 1, usually near 1: 3.
That can use separately or mix mutually and/or mix the amphoterics of use or the derivative of derivative, heterocyclic secondary and heterocycle tertiary amine that zwitterionics can be secondary amine or tertiary amine mutually with nonionic surface active agent and/or with aniorfic surfactant, or the derivative of quaternary ammonium, quaternary phosphine or uncle's sulfonium compound.Cation atom in the quaternary compound can be a heterocyclic part.In all these compounds, exist the aliphatic group of straight or branched of at least one 3 to 18 carbon atom of having an appointment and at least one to contain the aliphatic substituting group of anionic water-soluble group (for example carboxyl, sulfonate radical, sulfate radical, phosphate radical or phosphonate radical).
The example of spendable zwitterionics comprises that beet alkali surface activator (it is preferred), tetrahydroglyoxaline are basic tensio-active agent, amino-alkane acid ester surface active agent and iminodiacetic chain alkyl ester tensio-active agent.This class tensio-active agent that is fit to comprises the amido carboxybetaine, for example cocounut oil amido dimethyl carboxymethyl betaine, lauryl amido dimethyl carboxymethyl betaine, hexadecyl amido dimethyl carboxymethyl betaine and cocounut oil amido-two-(2-hydroxyethyl) carboxymethyl-trimethyl-glycine.Particularly preferably be the amido carboxybetaine of following molecular formula, wherein R is C
8-C
18Alkyl, for example cocoamidopropyl (cocamidopropyl betaine).It is safe that described compound is considered to usually: in the Salmonella reversion test that BASF carries out, do not prove Salmonellas indication organism is caused change, and human body repeat patch irritant test (human repeated patch insult test) (HRIPT) in, do not show to have contact allergy reaction or photoallergy (the MAFO CAB cocounut oil amido third amido betaine data plot of publishing referring to BASF):
The thetine tensio-active agent also is suitable for, amido thetine for example, for example the amino sulfo-CAB of the lauroyl of following molecular formula,
Cocounut oil amido-2-hydroxypropyl sultaine, cocounut oil amido dimethyl sulfo group dipropyl trimethyl-glycine, octadecyl amido dimethyl sulfopropyl betaine and lauryl amido-two-(2-hydroxyethyl)-sulfopropyl betaine.Tetrahydroglyoxaline also is suitable for for the tensio-active agent on basis, comprise glycinate and both sexes acetate compound (for example cocounut oil both sexes carboxyl propionic ester, cocounut oil both sexes carboxyl propionic acid, cocounut oil both sexes carboxyl glycinate and cocounut oil both sexes acetic ester), amino-alkane acid ester surface active agent (for example positive alkyl aminopropionic acid ester) and positive alkyl imino-diacetic propionic ester, for example N-lauryl-beta-amino dipropionic acid and salt thereof and N-lauryl-β-imino-propionic acid and salt thereof.
The nonionic surface active agent that can use or mix use separately comprises by alkylene oxide and the compound that can be hydrophobic organic compound condensation generation aliphatic series or alkyl aromatic.Can regulate and the hydrophilic segment of any specific hydrophobic compound condensation or the length of poly (oxyalkylene) base section, between hydrophilic segment and hydrophobic part, be hopeful the equilibrated water-soluble cpds so that obtain.Also semi-polar nonionic surface active agent be can use, amine oxide, phosphine oxide and sulfone comprised.The compound that is fit to classification comprises:
The polyethylene oxide condensation product of alkylphenol.These compounds comprise the C that has an appointment
6-C
12The alkylphenol of straight or branched alkyl and the condensation product of oxyethane, the quantity of described oxyethane are that every mole of alkylphenol has the 5-25 moles of ethylene oxide.Alkyl substituent in the compound for example can be obtained by polymeric propylene, diisobutylene, octene or nonene like this.
Fatty alcohol with at the condensation product of oxyethane.That the alkyl chain of fatty alcohol can be straight chain or side chain, contain usually and have an appointment 8 to about 22 carbon atoms.
The condensation product of oxyethane and the product that reaction obtains between propylene oxide and quadrol.
Amine oxide surfactant, oxidation diethyl lauryl amine for example, cacodyl oxide base tetradecylamine, ethyl oxide methyl tetradecylamine, oxidation hexadecyldimethyl benzyl ammonium amine, cacodyl oxide base octadecylamine, oxidation hexadecyl ethyl propyl amine, oxidation diethyl lauryl amine, oxidation diethyl tetradecylamine, oxidation dipropyl lauryl amine, bis oxide-(2-hydroxyethyl) lauryl amine, bis oxide-(2-hydroxyethyl)-3-dodecyloxy-2-hydroxypropyl amine, oxidation (2-hydroxypropyl) methyl tetradecylamine, cacodyl oxide base oil base amine, cacodyl oxide base-(2-hydroxyl dodecyl) amine, and the corresponding decyl of above-claimed cpd, hexadecyl and octadecyl homologue.
The phosphine oxide tensio-active agent, cacodyl oxide base dodecyl phosphine for example, cacodyl oxide base tetradecyl phosphine, ethyl oxide methyl tetradecyl phosphine, oxidation hexadecyldimethyl benzyl ammonium phosphine, cacodyl oxide base octadecyl phosphine, oxidation hexadecyl ethyl propyl phosphine, oxidation diethyl dodecyl phosphine, oxidation diethyl tetradecyl phosphine, oxidation dipropyl dodecyl phosphine, oxidation dipropyl dodecyl phosphine, bis oxide-(methylol) dodecyl phosphine, bis oxide-(2-hydroxyethyl) dodecyl phosphine, oxidation (2-hydroxypropyl) methyl tetradecyl phosphine, cacodyl oxide base oil base phosphine and cacodyl oxide base-(2-hydroxyl dodecyl) phosphine, and the corresponding decyl of above-claimed cpd, hexadecyl and octadecyl homologue.
Sulfone tensio-active agent, for example octadecyl methyl sulfone, dodecyl methyl sulfoxide, tetradecyl methyl sulfone, 3-hydroxyl tridecyl methyl sulfone, 3-methoxytridecylmethysulfoxide methyl sulfone, 3-hydroxyl-4-dodecyloxy butyl methyl sulfone, octadecyl 2-hydroxyethyl sulfone and dodecyl ethyl sulfone.
Glycollic amide is the tensio-active agent on basis, for example coconut fatty acid single ethanol amide or diglycollic amide.
Wherein R is C
10-C
40Alkyl, particularly C
12-C
18Alkyl, for example oil base or cocoyl.Other tensio-active agent can be the quaternary compound on basis, for example diamidoamine ethoxylate and tetrahydroglyoxaline and esterquats based on diethylenetriamine (DETA).As a class, esterquats can be based on comprising methyldiethanolamine (MDEA), trolamine (TEA) and N, N-dimethyl-3-aminopropane-1, and 2-glycol (DMAPD) is at interior compound.
Various alkyl sodium sulfate esters can be used as aniorfic surfactant, comprise fatty alcohol sulfate, fatty alcohol ether sulfate, alkyl phenol ether sulfuric ester, alkyl aryl sulphonic acid and salt, isopropyl benzene, toluene and xylene monosulfonic acid and salt thereof and sulfosuccinic acid alkyl ester (salt), for example Sodium Lauryl Sulphate BP/USP or Texapon Special.But a preferred anionoid type tensio-active agent is molecular formula RO-(CH
2CH
2)
nSO
3The poly-hydroxy monoalky lether vitriol of M, R is C in the formula
10-C
18Alkyl, n are 2-6 (preferred about 2 to 3), and M is a univalent cation.Such compound is the C of sulfonated ethoxylation
10-C
18Alkanol, the latter can be made by Oleum Cocois or butter, maybe can synthesize.The Zetesol NL (Sodium laureth sulfate) that success is here used on average has two moles of ethylene oxide and Sulfated Zetesol NL as ethoxylation to each mole lauric acid, and following molecular formula CH is arranged
3(CH
2)
10CH
2(OCH
2CH
2)
2OSO
3Na.
Except the simple process agent, also above-mentioned composition can be mixed with metal polish, for example be used for silver or brass.Such product can be formulated as liquid product, object for example ornaments or cutlery can flood wherein.After the dip-coating, object is cleaned in water, dry with soft cloth.Alternative prescription is paste or paste form, and it applies with soft cloth and removes then.
In order to be mixed with dip-coating composition, activeconstituents is generally pKa and is not more than 5 acid, for example phosphoric acid, citric acid, oxalic acid and tartrate, with the thiocarbamide or derivatives thereof for example alkyl derivative (for example methylthiourea or ethyl thiourea) use.In order to be mixed with paste or mashed prod, can contain the soft abrasive material of for example about 25 weight %, for example deposit chalk, diatomite, silicon oxide or gama-alumina (for example 0.05 micron order).It is believed that these components and tensio-active agent and treatment agent are compatible, available simple mixing adds easily.
Treatment step
After finishing, the manufacturing step of the molded article that alloy is made to carry out surface treatment.Described goods can be flatware (flatware), holloware (hollowware) or ornaments (Jewellery).Preparation process can comprise spinning, compacting, forging, casting, chasing, sheet material forging, finish rolling, the connection by soldering, brazing or welding, annealing and with polishing wheel/burnisher and aluminum oxide or the polishing of ferric oxide polishing powder.
The goods to be processed degreasing that can in all sorts of ways:
With ultrasonic wave or need not hyperacoustic water vapor degreasing
With ultrasonic wave or need not hyperacoustic water-based degreasing
With ultrasonic wave or need not hyperacoustic organic solvent degreasing (for example before thiol treatment with ethanol or acetone degreasing, thiol treatment can obtain good accelerated corrosion test result).
Degreasing simultaneously and thiol treatment, mercaptan is contained in organic degreasing medium or the moisture degreasing medium.
For example, goods can ultrasonic degreasing in treatment trough, is immersed in treatment agent is housed for example has in the groove of 1 weight % Stearyl mercaptan in solvent (for example EnSolv), cleans in one or more solvent troughs, then evaporation drying.Preferred use the identical excessive mercaptan of solvent flush away of thiol treatment so that remove not the mercaptan with the metallic surface reaction, and not with any other substance reaction.Solvent should not stay or not stay basically residue, so that unnecessary water subsequently or water-containing solvent washing, can make product dried then.Then can be with described goods packing, so that be sent to sales section.This can comprise goods are encapsulated in one or more protecting sheets, it is placed in the gift box and gift box is packaged in the protectiveness big envelope for example in the heat-shrunk plastics film.With above-mentioned containing-SH or-organic compound of S-S-group was that handled not only should deliver to its point of sale with goods that pack under good condition, but also should for example show long-time on shelf or in the showroom, estimated at least 6 months even possible 12 months or longer, still do not produce tangible corrosion.
On the other hand, goods can with contain 1-5 weight % sulfur-containing organic compound for example Stearyl mercaptan rumbling compound with tensio-active agent and sanitising agent for example the diatomite in the solvent polish simply.As another selection scheme, their available dipping sulfur-containing organic compounds are the cloth polishing of hexadecyl mercaptan or Stearyl mercaptan for example, for example is used in for example treatment agent dipping in the positive propyl bromo of organic solvent, subsequent drying.The advantage of cleaning cloth is that it is easy to preparation, can be easy to be used for retail environment or commercial environment, is applicable to the general maintenance (if necessary) of Argentium silver.
Treatment process of the present invention is being particularly advantageous in the protection of the corrosion resistant of punching press coin blank before the punching operation, because found that the embodiment of film of the present invention can be most of or all stand punching operation, and can provide corrosion protection to newly making coin.Will be appreciated that the packaged collection of coin in the coinage condition, seldom handle, and for example all there is the danger that damages coin in each with the soft cloth polishing when handling.Such damage danger can prolong rust resistance by the present invention and handle and reduce.
With reference now to following examples, further describe the present invention, these embodiment only as an illustration.In all embodiments, the term " high rust resistance " of the sample of handling with Stearyl mercaptan refers to compare with the sample without the Argentium silver of any processing except that polishing and degreasing.
Embodiment 1
Solvent dip (sample of solvent degreasing)
Preparation contains a plurality of solution of Stearyl mercaptan (0.1,0.5 and 1.0 gram) in EnSolv 765 (100 milliliters).Will through polishing and in EnSolv 765 2 minutes Argentium Sterling sample of ultrasonic degreasing in one of Stearyl mercaptan solution, distinguish submergence 2 minutes, 5 minutes and 15 minutes respectively.Then with the raw cotton wiping of cleaning.
For evaluate tarnish resistance, alloy sample is supported on the slide glass in the stink cupboard, about 25 millimeters in 20% ammonium polysulfide solution surface, so that be exposed in the hydrogen sulfide that solution produces.In 1 hour process of the test, all samples all has good rust resistance, and being exposed in the hydrogen sulfide 45 minutes has very light yellow later on.Light film on sample is easy to remove with the cleaning cloth that is impregnated with Stearyl mercaptan.
As a comparison, in a single day the Stirling of standard silver sample carries out above-mentioned test and just begins variable color, generates serious black tarnish later in 1 hour, and it can not be removed with the cleaning cloth that is impregnated with Stearyl mercaptan.The result who obtains through the silver-colored sample of second Stirling of cleaning cloth wiping is similarly, just begins variable color in the test in case sample is in.Corrosion appearred later in the Argentium Sterling alloy of producing according to EP-B-0729398 at 3 minutes.Corrosion appearred later in another Argentium Sterling alloy sample (as disclosed in WO 02/09502) annealed in selective oxidation atmosphere at 6 minutes.Do not occur improving under the situation that delays corrosion at standard Stirling silverware, the obvious delay that the above-mentioned corrosion time occurs is unexpected.
Embodiment 2
The influence of the solvent cleaning of aftertreatment
The Argentium sample is repeated embodiment 1, and different is in thiol treatment is not later on to use the raw cotton wiping, but sample ultrasonic degreasing 2 minutes in EnSolv 765.Then, with the disclosed corrosion test that carries out among sample such as the embodiment 1, all discoveries have high rust resistance.Stearyl mercaptan is handled the protective effect that withstands the ultrasonic cleaning among the EnSolv is shown, the surface reaction by comprising germanium possible among Stearyl mercaptan and the Argentium Silver rather than by forming fat or oil reservoir reaches rust resistance on the Argentium surface.
Embodiment 3
Aqueous dip (sample of solvent degreasing)
Prepare corrosion protection treatment soln with following component:
Stearyl mercaptan 1 gram
765 5 milliliters of EnSolv
40 milliliters in washing composition (Fairy Liquid)
100 milliliters of deionized waters
Stearyl mercaptan is dissolved among the EnSolv 765, subsequently the solution that generates is mixed with washing composition (Fairy Liquid) and dilute with water, obtain moisture steeping fluid.Polishing ArgentiumSilver sample, ultrasonic degreasing 2 minutes in EnSolv 765 then, submergence 2 minutes in above-mentioned moisture steeping fluid is at normal temperatures cleaned in the tap water that flows then.Notice that described water repels from polished surface immediately, makes sample drying.As disclosed in embodiment 1, sample is carried out corrosion test, all showing has high rust resistance.
Embodiment 4
Aqueous dip 2 (sample of washing composition degreasing)
With the degreasing in 2% water-detergent solution (Fairy Liquid) of Argentium Sterling sample, be immersed in then in the treatment soln of embodiment 3.Notice that treated sample is hydrophobic, as disclosed among the embodiment 3.Sample is by the disclosed corrosion test that carries out among the embodiment 1, and all showing has high rust resistance.Repeat above-mentioned test, the Fairy Liquid that different is in the treatment soln hand-washes soap (40 milliliters) with liquid and replaces.In the time of in being exposed to ammonium polysulfide solution, do not show that sample has high rust resistance.This may be because the hand washing soap is rarer.
Embodiment 5
Degreasing simultaneously and resistant to tarnishing are handled
Prepare following solution:
-1 gram Stearyl mercaptan
-5 milliliters of EnSolv 765
-20 milliliters of washing composition (Fairy Liquid)
-100 ml deionized water
-1 gram Stearyl mercaptan
-5 milliliters of EnSolv 765
-30 milliliters of washing composition (Fairy Liquid)
-100 ml deionized water
-1 gram Stearyl mercaptan (preferred amounts)
-5 milliliters of EnSolv 765
-40 milliliters of washing composition (Fairy Liquid)
-100 ml deionized water
-1 gram Stearyl mercaptan
-5 milliliters of EnSolv 765
-40 milliliters of washing composition (Fairy Liquid)
-500 ml deionized water
-1 gram Stearyl mercaptan
-5 milliliters of EnSolv 765
-40 milliliters of washing composition (Fairy Liquid)
-1000 ml deionized water
Solution in the ultrasonic cleaning jar is heated to 50 ℃.Through ArgentiumSilver sample ultrasonic degreasing 2 minutes in solution of polishing, in the mobile tap water, clean then.For above-mentioned first three treatment soln, observe water and repel from the surface, make sample drying.Sample with above-mentioned first three solution-treated carries out the 1 disclosed corrosion test as embodiment, and all have a high rust resistance.But under the situation with the sample of latter two solution-treated, water can not be opened from exclusion in wash phase.Streak variable color in the corrosion test process appears on their surface when sample drying.The sample of handling with 500 ml solns has less variable color than the sample of handling with 1000 ml solns.Above-mentioned experiment shows that Argentium Silver can use the thiol treatment agent to carry out degreasing and rust protection protection simultaneously, and Stearyl mercaptan/EnSolv/ washing composition/aqueous solution is dense more in Aquo System, the rust resistance of generation is good more.
Embodiment 6
Direct coating-pure detergent solution (sample of solvent degreasing/moisture degreasing)
Prepare following solution:
-1 gram Stearyl mercaptan
-5 milliliters of EnSolv 765
-40 milliliters of washing composition (Fairy Liquid) (preferred quantity)
-1 gram Stearyl mercaptan
-5 milliliters of EnSolv 765
-40 milliliters of soaps (liquid hand washing soap)
At first Stearyl mercaptan is dissolved in EnSolv.Then washing composition is mixed in the solution.With Argentium Silver sample polishing, ultrasonic degreasing 2 minutes in EnSolv 765 then.Use the moor cotton that Stearyl mercaptan/EnSolv/ detergent solution directly is coated on the surface of Argentium Silver sample then, and massage out foam.In the mobile tap water, clean sample then.Under each situation, water all repels from polished surface, and sample is kept dry.As in embodiment 1, made sample carry out corrosion test in 1 hour by sample being exposed to pure ammonium polysulfide solution.All all showing has high rust resistance.The method of above-mentioned direct coating Stearyl mercaptan is tested the sample of degreasing in the 2%Fairy Liquid aqueous solution.Obtain high rust resistance once more.
Embodiment 7
Cloth applies (sample of solvent degreasing)
The cotton of cleaning is immersed in and makes the cotton drying prepare described cloth in the following solution then
-be dissolved in 0.1 of 100 milliliters of EnSolv to restrain Stearyl mercaptan
-be dissolved in 0.5 of 100 milliliters of EnSolv to restrain Stearyl mercaptan
-be dissolved in 1.0 of 100 milliliters of EnSolv to restrain Stearyl mercaptans (preferably)
With described cloth wiping Argentium Silver sample (polished and in EnSolv 765 ultrasonic degreasing 2 minutes), dry with the raw cotton of cleaning then.As in embodiment 1,, make sample carry out corrosion test by sample being exposed to ammonium polysulfide solution 1 hour.All all showing has high rust resistance.
Embodiment 8
Hexadecyl mercaptan in Fairy Liquid and Stearyl mercaptan
Mix with the hexadecyl mercaptan of liquid state (1 gram) and Fairy Liquid (tensio-active agent that contains aniorfic surfactant and nonionic surface active agent) and with water by following quantity:
| Reference number | Fairy Liquid (milliliter) | Deionized water (milliliter) |
| 8.1 8.2 8.3 8.4 8.5 | 40 100 200 40 40 | Do not have 100 200 |
Each component of solution 8.2 it seems and mix thoroughly that hexadecyl mercaptan does not need to be dissolved in advance organic solvent.With the submergence 10 minutes in the solution that generates of Argentium Silver sample, clean then.The surface of Argentium Silver sample becomes hydrophobic, shows to form the hexadecyl mercaptan layer that is attached to Argentium Silver surface.It is easy to clean in water, cleans the back and stays on the surface without any tangible settling.Be used in a zone of the raw cotton wipe samples of dipping among the EnSolv 765, carry out 45 minutes corrosion tests with pure ammonium polysulfide then.Obtain fabulous rust resistance, do not have significant difference between the regional and untreated zone with EnSolv 765 processing.Prepared similar solution by Stearyl mercaptan and Fairy Liquid.At first they are transparent, but less stable, isolate the upper layer of Stearyl mercaptan after the several months.
Embodiment 9
Hexadecyl mercaptan in Simple shower gel
The hexadecyl mercaptan and the Simple shower gel of liquid state is (a kind of from Accentia Health and Beauty Ltd, Birmingham, the transparent showergel that UK obtains it is believed that and contains Zetesol NL and cocoamidopropyl and deposit component as major surfaces promoting agent and coconut oleoyl amine DEA and idol) and mix with water by following quantity:
| Reference number | HDM (gram) | Sample (milliliter) | Deionized water (milliliter) |
| 9.1 9.2 9.3 9.4 | 1 1 5 1 | 100 100 100 200 | Do not have 100 100 100 |
Soon, solution 9.1 and 9.4 is complete transparent viscous gel, does not have the separation of perceptible hexadecyl mercaptan after mixing.Sample 9.2 also is fully transparent, but the same denseness of water is arranged, and does not also have hexadecyl mercaptan to separate.Sample 9.3 also is the denseness that has water the same, is rendered as the lactous emulsion when shaking, but the surface exists hexadecyl mercaptan to separate when static.
In preliminary experiment,, clean then the submergence 10 minutes in solution 9.1 of Argentium Silver sample.The surface of Argentium Silver sample becomes hydrophobic, shows to form the hexadecyl mercaptan layer that is attached on the Argentium Silver sample surfaces.It thoroughly cleans in water, cleans the back and stays on the surface without any tangible settling.When testing, obtain fabulous rust resistance with pure ammonium polysulfide.
Argentium Silver sample and the specimen preparation of traditional Stirling silver are as follows.With the Steelbright rumbling compound with the polishing of each sample, then with the polishing of ferric oxide polishing powder, then in the 2 weight %Fairy Liquid aqueous solution 54 ℃ of following ultrasonic degreasings 2 minutes.Further degreasing 5 minutes in ethanol then is immersed in the testing liquid at normal temperatures.After the taking-up,, carry out 45 minutes corrosion tests with pure ammonium polysulfide then with a part that is immersed in the every kind of sample of fabric wiping among the EnSolv 765.Argentium Silver sample shows fabulous rust resistance and mercaptan binding, compares with 9.3 with the solution 9.2 of high water content, and solution 9.1 and 9.4 gives especially good results.Solution 9.1 and 9.4 be it seems also provides some rust protection to standard Stirling silver, but the mercaptan layer can be easy to remove, as the obvious visible of difference between the zone of handling from untreated zone and EnSolv 765.
Embodiment 10
The mixture of cocoamidopropyl (CPB) and Zetesol NL (SLS)
Above-mentioned materials as dumpable liquid, aqueous of heavy-gravity and as the highly spissated gelationus liquid (70% active ingredient) that slightly is by Sunfachem Ltd of Leeds, United Kindgom provides.Liquid hexadecyl mercaptan (1 milliliter) is mixed by following quantity with these materials:
| Reference number | SLS (milliliter) | CPB (milliliter) | Water (milliliter) |
| 10.1 10.2 10.3 10.4 10.5 | 40 40 30 10 30 | 40 20 10 30 10 | 100 100 100 50 160 |
For solution 10.1, hexadecyl mercaptan is added in the viscous mixture of Zetesol NL and cocoamidopropyl, add entry subsequently, then solution is mixed cooling.The mixture that generates has heavy-gravity white foam structure at first, becomes clear gel when leaving standstill.Some is similar for solution 10.2.Solution 10.3 is as water, and is sub-translucent at first, on solution top numerous air-bubble arranged, and becomes transparent during standing over night.Solution 10.4 is mixed, and mitigation is heated to about 35 ℃.It seems that heating has nation to help to mixing step.After the mixed number minute, mixture seriously bubbles.Allow the mixture standing over night, generate viscous solution.Solution 10.5 is heated to about 35 ℃, stirs simultaneously.The last component of water for adding.Heating is favourable to mixing.It seems that solution be easy to bubble, but leave standstill a few hours (in 12 hours), generates than water heavy-gravity clear solution slightly.
Prepare Argentium Silver sample with following step: polish with the ferric oxide polishing powder then with Steelbright, ultrasonic degreasing degreasing in acetone then in the 2 weight %Fairy Liquid aqueous solution, at room temperature in testing liquid, flooded 10 minutes, and in refrigerative flows tap water, wash.With the bottom of each sample of fabric wiping that floods among the EnSolv, so that remove all mercaptan, sample is left standstill 45 minutes subsequently, be exposed to pure ammonium polysulfide accelerated corrosion test 45 minutes then.
In cleaning process, all samples all have fabulous hydrophobicity performance, show the existence of mercaptan.Water droplet is excluded, and does not need dry each sample.Sample shows in corrosion test well, and the difference that has between rust resistance and the zone of drying and the zone of not drying is very little.Draw in each test sample hexadecyl mercaptan all forms rust resistance on Argentium Silver surface mercaptan binding layer.
Claims (23)
1. chain alkyl thioalcohol, mercaptoacetic acid alkyl ester, dialkyl sulfide or dialkyl group disulfide are used to contain the silver alloys surface-treated application of some amount germanium, described some amount germanium can effectively reduce fiery spot and/or corrosion, this processing is in order to reduce or further reduce the corrosion of alloy, so that sample can closely be supported on 20% ammonium polysulfide solution 30 minutes at least, kept unattacked outward appearance usually simultaneously.
2. according to the application of claim 1, wherein chain alkyl thioalcohol, mercaptoacetic acid alkyl ester, dialkyl sulfide or dialkyl group disulfide have C
12-C
24Alkyl.
3. according to the application of claim 1 or 2, wherein chain alkyl thioalcohol, mercaptoacetic acid alkyl ester, dialkyl sulfide or dialkyl group disulfide are in organic solvent.
4. according to the application of claim 3, wherein chain alkyl thioalcohol, mercaptoacetic acid alkyl ester, dialkyl sulfide or dialkyl group disulfide are generally neutral.
5. according to the application of claim 3 or 4, wherein chain alkyl thioalcohol, mercaptoacetic acid alkyl ester, dialkyl sulfide or dialkyl group disulfide are in containing the solvent of positive propyl bromo.
6. according to the application of claim 3 or 4, chain alkyl thioalcohol wherein, the mercaptoacetic acid alkyl ester, dialkyl sulfide or dialkyl group disulfide pass through described chain alkyl thioalcohol at (a), the mercaptoacetic acid alkyl ester, dialkyl sulfide or dialkyl group disulfide are dissolved in organic solvent and then dense relatively hydrated soap or washing composition are added in the composition that can make in the described solution, or (b) by with described chain alkyl thioalcohol, the mercaptoacetic acid alkyl ester, dialkyl sulfide or dialkyl group disulfide are dissolved in organic solvent and then dense relatively hydrated soap or washing composition are added in the aqueous dispersion that the mixture of dilute with water generation can make again in the described solution, or (c) pass through described chain alkyl thioalcohol, the mercaptoacetic acid alkyl ester, dialkyl sulfide or dialkyl group disulfide directly are dissolved in the composition that can make in aniorfic surfactant and neutral surface active agent's aqueous mixture or the aniorfic surfactant.
7. according to the application of claim 6, wherein composition contains the treatment agent that is selected from chain alkyl thioalcohol, mercaptoacetic acid alkyl ester, dialkyl sulfide or dialkyl group disulfide, aniorfic surfactant and the amphoterics that its concentration makes the effective solubilising of treatment agent.
8. according to the application of claim 6, wherein composition contains the treatment agent that is selected from chain alkyl thioalcohol, mercaptoacetic acid alkyl ester, dialkyl sulfide or dialkyl group disulfide, aniorfic surfactant and the neutral surface active agent that its concentration makes the effective solubilising of treatment agent.
9. according to the application of claim 1 or 2, wherein chain alkyl thioalcohol, mercaptoacetic acid alkyl ester, dialkyl sulfide or dialkyl group disulfide are contained in the rumbling compound, or are immersed in the polish cloth.
10. according to the application of above-mentioned any claim, wherein chain alkyl thioalcohol or mercaptoacetic acid alkyl ester are selected from Stearyl mercaptan, hexadecyl mercaptan, mercaptoacetic acid stearyl and mercaptoacetic acid cetyl ester.
11. according to the application of above-mentioned any claim, the alloy surface that also contains grain-refining agent that is used for is handled.
12., be used for the surface treatment of the ternary alloy of silver, copper and germanium according to the application of above-mentioned any claim.
13. according to the application of claim 12, wherein by the weight of alloy, except impurity and any grain-refining agent, ternary alloy is made up of 80-96% silver, 0.1-5% germanium and 1-19.9% copper.
14. according to the application of claim 12, wherein by the weight of alloy, except impurity and grain-refining agent, ternary alloy is made up of 92.5-98% silver, 0.3-3% germanium and 1-7.2% copper, also has 1-40ppp boron as grain-refining agent.
15. according to the application of claim 12, wherein by the weight of alloy, except impurity and grain-refining agent, ternary alloy is made up of 92.5-96% silver, 0.5-2% germanium and 1-7% copper, also has 1-40ppp boron as grain-refining agent.
16. each is used for the application of the quad alloy of Processing Ag, copper, zinc and germanium among the claim 1-11.
17. according to the application of claim 16, wherein by weight, the ratio of zinc and copper is not more than 1: 1.
18. each application in requiring according to aforesaid right, its interalloy is finished product or crude product.
19.C
12-C
24The application in the rust oxidation of preparation silver/germanium alloy goods of chain alkyl thioalcohol, mercaptoacetic acid alkyl ester, dialkyl sulfide or dialkyl group disulfide, the silver content of described alloy is at least 77 weight %, ge content is 0.4-7 weight %, all the other are mainly copper, so that the corrosion of alloy is reduced, so that sample can closely be bearing on 20% ammonium polysulfide solution 30 minutes at least, kept unattacked outward appearance usually simultaneously.
20. one kind contains the silver alloys of a certain amount of germanium or the moulded products that is made by described alloy, described a certain amount of germanium is effectively for reducing fiery spot and/or corrosion, and has used C
12-C
24Chain alkyl thioalcohol, mercaptoacetic acid alkyl ester, dialkyl sulfide or dialkyl group disulfide are handled.
21. a method for preparing the rust resistance silverware, described method may further comprise the steps:
Make the silver alloys moulded products that contains a certain amount of germanium, described a certain amount of germanium is effective for reducing fiery spot and/or corrosion;
With chain alkyl thioalcohol, mercaptoacetic acid alkyl ester, dialkyl sulfide or dialkyl group disulfide surface treatment goods; And
Goods are packed.
22. according to the method for claim 21, wherein said packing comprises gift box.
23. according to the method for claim 22, wherein said packing comprises the outside envelope that is used for gift box.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0307290.7 | 2003-03-31 | ||
| GBGB0307290.7A GB0307290D0 (en) | 2003-03-31 | 2003-03-31 | Enhancing silver tarnish-resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1780937A true CN1780937A (en) | 2006-05-31 |
Family
ID=9955796
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2004800113752A Pending CN1780937A (en) | 2003-03-31 | 2004-03-30 | Enhancing silver tarnish-resistance |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US20070039665A1 (en) |
| EP (1) | EP1611267A1 (en) |
| JP (1) | JP2006523266A (en) |
| CN (1) | CN1780937A (en) |
| AU (1) | AU2004225693A1 (en) |
| CA (1) | CA2520807A1 (en) |
| EA (1) | EA008833B1 (en) |
| GB (1) | GB0307290D0 (en) |
| MX (1) | MXPA05010452A (en) |
| WO (1) | WO2004087996A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109477226A (en) * | 2016-06-23 | 2019-03-15 | 德国艾托特克公司 | Aqueous composition for metal surface post-processing |
| CN113957498A (en) * | 2020-07-21 | 2022-01-21 | 江苏汉宜新材料有限公司 | Modification liquid for reducing surface energy of silver-plated layer of cavity |
| CN114959715A (en) * | 2022-05-17 | 2022-08-30 | 中北大学 | Preparation and corrosion inhibition application of thioether copper-based self-assembled film |
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| GB2412666B (en) * | 2004-03-30 | 2008-10-08 | Paul Gilbert Cole | Water-based metal treatment composition |
| GB0517166D0 (en) * | 2005-08-23 | 2005-09-28 | Middlesex Silver Co Ltd | Silver wire |
| DE102005047843A1 (en) * | 2005-10-05 | 2007-04-12 | OTB Oberflächentechnik in Berlin GmbH & Co. | Passivating and lubricating agents for gold, silver and copper surfaces and methods of use |
| US7972655B2 (en) * | 2007-11-21 | 2011-07-05 | Enthone Inc. | Anti-tarnish coatings |
| ES2736731T3 (en) | 2008-07-18 | 2020-01-07 | Suneeta Neogi | Method to produce nanocrystalline diamond coatings on precious stones |
| MX2011011843A (en) | 2009-05-12 | 2011-12-08 | Jostens Inc | Gold alloys. |
| IT1398698B1 (en) | 2010-02-24 | 2013-03-08 | Mesa S A S Di Malimpensa Simona E Davide E C | METHOD FOR THE PROTECTION OF SILVER SURFACES AND ITS UNDERSTANDING ALLOYS. |
| US8802202B2 (en) * | 2010-03-05 | 2014-08-12 | Suneeta S. Neogi | Method for imparting tarnish protection or tarnish protection with color appearance to silver, silver alloys, silver films, silver products and other non precious metals |
| ITMI20121412A1 (en) * | 2012-08-08 | 2014-02-09 | San Lorenzo S R L | PROCEDURE FOR THE CONSTRUCTION OF A KITCHEN MANUFACTURED WITH AN INSIDE OF SILVER OR ITS ELECTROFORMED ALLOYS. |
| US9005522B2 (en) | 2012-08-30 | 2015-04-14 | Jostens, Inc. | Silver alloy |
| CN103525313A (en) * | 2012-11-03 | 2014-01-22 | 连新兰 | Silverware brightening method |
| GB2561376A (en) * | 2017-04-12 | 2018-10-17 | Argentium International Ltd | Silver alloys, investment casting using the alloys and casting grain |
| CN111996081A (en) * | 2020-08-31 | 2020-11-27 | 河北银瓷天成文化传播有限公司 | Silver ornament silver wiping cloth and preparation method thereof |
| CN115852354A (en) * | 2022-11-28 | 2023-03-28 | 北京市三强钢筋预应力设备有限公司 | Processing technology of extrusion anchor |
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| US2841501A (en) * | 1957-04-17 | 1958-07-01 | James G Murphy | Silver polish |
| GB1070383A (en) * | 1963-06-25 | 1967-06-01 | Goddard & Sons Ltd J | Improvements in or relating to metal protecting preparations |
| US3330672A (en) * | 1964-06-29 | 1967-07-11 | Hunt Chem Corp Philip A | Silver antitarnish compositions |
| GB1070384A (en) * | 1964-08-19 | 1967-06-01 | Goddard & Sons Ltd J | Improvements in or relating to metal protecting preparations |
| US3398003A (en) * | 1965-04-26 | 1968-08-20 | Verle C. Smith | Silver polish-tarnish retarder containing a dialkyl disulfide having from 8 to 20 carbon atoms in each alkyl radical |
| GB1130540A (en) * | 1966-02-18 | 1968-10-16 | Goddard & Sons Ltd J | Protecting silver against tarnish |
| BE759280A (en) * | 1969-11-24 | 1971-05-24 | Procter & Gamble | LIQUID DETERGENT COMPOSITIONS |
| US4024078A (en) * | 1975-03-31 | 1977-05-17 | The Procter & Gamble Company | Liquid detergent composition |
| US4316824A (en) * | 1980-06-26 | 1982-02-23 | The Procter & Gamble Company | Liquid detergent composition containing alkyl sulfate and alkyl ethoxylated sulfate |
| US4555360A (en) * | 1984-06-22 | 1985-11-26 | The Procter & Gamble Company | Mild detergent compositions |
| DE4041596A1 (en) * | 1990-12-22 | 1992-07-02 | Duerrwaechter E Dr Doduco | Compsn. for protecting silver@ surfaces against tarnishing |
| FR2675817B1 (en) * | 1991-04-29 | 1993-08-20 | Metaleurop Rech | NEW TERNARY ALLOY BASED ON SILVER. |
| GB2283933B (en) * | 1993-11-18 | 1996-04-24 | Univ Middlesex Serv Ltd | A method of joining materials together by a diffusion process using silver/germanium alloys |
| US6183815B1 (en) * | 1994-04-01 | 2001-02-06 | University Of Pittsburgh | Method and composition for surface treatment of metals |
| US6168071B1 (en) * | 1994-11-17 | 2001-01-02 | Peter Gamon Johns | Method for joining materials together by a diffusion process using silver/germanium alloys and a silver/germanium alloy for use in the method |
| US5616549A (en) * | 1995-12-29 | 1997-04-01 | Clark; Lawrence A. | Molecular level cleaning of contaminates from parts utilizing an envronmentally safe solvent |
| 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 |
| JP3025245B1 (en) * | 1998-11-04 | 2000-03-27 | 株式会社日本ゲルマニウム研究所 | Silver alloy for accessories and accessories |
| US6406664B1 (en) * | 1999-08-16 | 2002-06-18 | Lawrence H. Diamond | Silver germanium alloy |
| GB0112623D0 (en) * | 2001-05-23 | 2001-07-18 | Johns Peter G | Method of producing silver-copper alloys |
-
2003
- 2003-03-31 GB GBGB0307290.7A patent/GB0307290D0/en not_active Ceased
-
2004
- 2004-03-30 US US10/551,476 patent/US20070039665A1/en not_active Abandoned
- 2004-03-30 EP EP04724313A patent/EP1611267A1/en not_active Ceased
- 2004-03-30 JP JP2006506057A patent/JP2006523266A/en active Pending
- 2004-03-30 MX MXPA05010452A patent/MXPA05010452A/en unknown
- 2004-03-30 WO PCT/GB2004/001373 patent/WO2004087996A1/en active Application Filing
- 2004-03-30 CA CA002520807A patent/CA2520807A1/en not_active Abandoned
- 2004-03-30 CN CNA2004800113752A patent/CN1780937A/en active Pending
- 2004-03-30 AU AU2004225693A patent/AU2004225693A1/en not_active Abandoned
- 2004-03-30 EA EA200501542A patent/EA008833B1/en not_active IP Right Cessation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109477226A (en) * | 2016-06-23 | 2019-03-15 | 德国艾托特克公司 | Aqueous composition for metal surface post-processing |
| CN113957498A (en) * | 2020-07-21 | 2022-01-21 | 江苏汉宜新材料有限公司 | Modification liquid for reducing surface energy of silver-plated layer of cavity |
| CN114959715A (en) * | 2022-05-17 | 2022-08-30 | 中北大学 | Preparation and corrosion inhibition application of thioether copper-based self-assembled film |
| CN114959715B (en) * | 2022-05-17 | 2024-02-06 | 中北大学 | Preparation and corrosion inhibition application of thioether copper-based self-assembled film |
Also Published As
| Publication number | Publication date |
|---|---|
| US20070039665A1 (en) | 2007-02-22 |
| EA200501542A1 (en) | 2006-04-28 |
| MXPA05010452A (en) | 2006-05-10 |
| EA008833B1 (en) | 2007-08-31 |
| GB0307290D0 (en) | 2003-05-07 |
| JP2006523266A (en) | 2006-10-12 |
| EP1611267A1 (en) | 2006-01-04 |
| CA2520807A1 (en) | 2004-10-14 |
| AU2004225693A1 (en) | 2004-10-14 |
| WO2004087996A1 (en) | 2004-10-14 |
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