Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
  • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
  • C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
  • C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
  • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
  • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
  • C23C22/08—Orthophosphates
  • C23C22/12—Orthophosphates containing zinc cations
  • C23C22/13—Orthophosphates containing zinc cations containing also nitrate or nitrite anions
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
  • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
  • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
  • C23C22/08—Orthophosphates
  • C23C22/18—Orthophosphates containing manganese cations
  • C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
  • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
  • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
  • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
  • C23C22/364—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
  • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
  • C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
  • C23C22/42—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also phosphates

Definitions

• the invention relates to methods for phosphating metal surfaces with aqueous, acid phosphating solutions, the zinc, manganese and phosphate ions and hydroxylamine in free or bound form and / or m-nitrobenzenesulfonic acid or contain their water-soluble salts, and their Application as pretreatment of the metal surfaces for a subsequent Painting, especially an electro dip painting.
• the procedure is applicable for the treatment of surfaces made of steel, galvanized or galvanized alloy Steel, aluminum, aluminized or alloy aluminized Steel, in particular for the treatment of galvanized on one or both sides, preferably electrolytically galvanized steel.
• the phosphating of metals pursues the goal on the metal surface to produce firmly grown metal phosphate layers that are in themselves improve the corrosion resistance and in connection with paints and other organic coatings to significantly increase the Paint adhesion and resistance to infiltration when exposed to corrosion contribute.
• Such phosphating processes have long been known.
• For pretreatment before painting is particularly suitable for low-zinc phosphating processes, where the phosphating solutions are comparatively low levels of zinc ions of e.g. B. 0.5 to 2 g / l.
• An essential parameter in these low-zinc phosphating baths is the weight ratio of phosphate ions to zinc ions, which is usually is in the range> 8 and can take values up to 30.
• the high content of nickel ions in the phosphating solutions of the trication processes and of nickel and nickel compounds in the phosphate layers formed however, has disadvantages in that nickel and nickel compounds from the point of view of environmental protection and workplace hygiene as be critically classified.
• low-zinc phosphating processes have been becoming increasingly common described without sharing from nickel to high-quality phosphate layers similar to that lead nickel-containing processes.
• nitrite and Nitrates are increasingly raised concerns about possible formation of nitrous gases.
• DE-A-39 20 296 describes a phosphating process which dispenses with nickel and uses magnesium ions in addition to zinc and manganese ions.
• the phosphating baths described here contain from 0.2 to 10 g / l nitrate ions other oxidizing agents acting as accelerators, selected from nitrite, chlorate or an organic oxidizing agent.
• EP-A-60 716 discloses low zinc phosphating baths which are considered essential Cations contain zinc and manganese and that as an optional ingredient May contain nickel.
• the necessary accelerator is preferred selected from nitrite, m-nitrobenzenesulfonate or hydrogen peroxide.
• EP-A-228 151 also describes phosphating baths which are essential Cations contain zinc and manganese.
• the phosphating accelerator is selected from nitrite, nitrate, hydrogen peroxide, m-nitrobenzenesulfonate, m-nitrobenzoate or p-nitrophenol.
• the nitrate content to 5 to about 15 g / l and an optional nickel content specified between 0.4 and 4 g / l.
• the exemplary embodiments contain this all nickel and nitrate.
• the main focus of this application is due to the fact that chlorate-free phosphating processes are provided will.
• EP-A-544 650 teaches something similar.
• the phosphating process disclosed in WO-A-86/04931 works without nitrates.
• the accelerator system is based on a combination of 0.5 - 1 g / l Bromate and 0.2-0.5 g / l m-nitrobenzenesulfonate.
• the phosphating solutions preferably contain in addition to zinc, at least 2 of these optional metals.
• EP-A-36689 teaches the use of preferably 0.03-0.2% by weight of nitrobenzenesulfonate in Combination with preferably 0.1-0.5% by weight chlorate in phosphating baths, whose manganese content is 5-33% by weight of the zinc content.
• DE-A-40 13 483 discloses phosphating processes with which similarly good ones Corrosion protection properties as achieved with the trication process can. These processes do without nickel and use instead Copper in low concentrations, 0.001 to 0.03 g / l.
• Oxygen and / or other equivalent functions serve in the trivalent stage Oxidizing agent. As such are nitrite, chlorate, bromate, peroxy compounds and organic nitro compounds, such as nitrobenzenesulfonate, specified.
• German patent application with the file number P 42 10 513.7 modifies this process in that as a modifying agent for the Morphology of the phosphate crystals formed hydroxylamine, its salts or complexes are added in an amount of 0.5 to 5 g / l hydroxylamine.
• EP-A-321 059 teaches zinc phosphating baths which contain 0.1 to 2.0 g / l zinc and an accelerator also 0.01 to 20 g / l tungsten in the form of a soluble tungsten compound, preferably alkali metal or ammonium tungstate or silicotungstate, alkaline earth metal silicotungstate or boro- or silicotungstic acid.
• the accelerator is selected from nitrite, m-nitrobenzenesulfonate or hydrogen peroxide.
• nickel in quantities of 0.1 - 4 g / l and nitrate in quantities 0.1 - 15 g / l.
• DE-C-27 39 006 describes a phosphating process for surfaces Zinc or zinc alloys that are free of nitrate and ammonium ions.
• an essential content of zinc in amounts between 0.1 and 5 g / l are 1 to 10 parts by weight of nickel and / or cobalt per part by weight of zinc required.
• Hydrogen peroxide is used as an accelerator. From the From the point of view of workplace hygiene and environmental protection, cobalt is not one Alternative to nickel.
• the object of the invention is to provide phosphating baths positions that are free from environmental and workplace hygiene Reasonably questionable nickel or the similarly questionable cobalt, no Contain nitrite and at the same time a greatly reduced nitrate content have and are preferably free of nitrate. Furthermore, the Phosphating baths should be free of copper, the dosage of which according to DE-A-40 13 483 effective concentration range of 1 - 30 ppm is problematic.
• phosphating baths are free of nickel, copper, nitrite and oxo anions Halogens mean that these elements or ions not deliberately added to the phosphating baths. However, it is in the Practice does not rule out that such components are beyond what is to be treated Material, the preparation water or the ambient air in traces in the Phosphating baths are entered. In particular, it cannot be ruled out that in the phosphating of coated with zinc-nickel alloys Steel nickel ions are introduced into the phosphating solution. However, the expectation is placed on the phosphating baths according to the invention that that under technical conditions the nickel concentration in the Baths is below 0.01 g / l, in particular below 0.0001 g / l.
• baths Preferably no nitrate is added to the baths.
• the baths contain the nitrate content of the locally available drinking water (according to Drinking water regulation in Germany maximum 50 mg / l) or by evaporation have higher nitrate levels due to The invention
• baths should have a maximum nitrate content of 0.5 g / l and preferably contain less than 0.1 g / l nitrate.
• Hydroxylamine can be used as a free base, as a hydroxylamine complex or in the form of Hydroxylammonium salts are used. If you add free hydroxylamine Phosphating bath or a phosphating bath concentrate too, it is due of the acidic character of these solutions largely as a hydroxylammonium cation available.
• Sulfates and the phosphates are particularly suitable. In the case of the phosphates the acidic salts are preferred because of their better solubility.
• Hydroxylamine or its compounds in the phosphating bath in such Amounts added that the calculated concentration of free hydroxylamine is between 0.1 and 5 g / l, in particular between 0.4 and 2 g / l. It has proven to be beneficial to choose the hydroxylamine concentration so that the ratio of the sum of the concentrations of zinc and manganese for the concentration of the hydroxylamine, in each case in g / l, 1.0 to 6.0, preferably Is 2.0 to 4.0.
• the inventive Phosphating baths containing hydroxylamine or hydroxylamine compounds the presence of soluble compounds of hexavalent tungsten Advantages in terms of corrosion resistance and paint adhesion, although with the Phosphating method according to the invention, in contrast to the teaching of EP-A-321 059, without the accelerators nitrite or hydrogen peroxide can be.
• Phosphating solutions are used that additionally 20 to 800 mg / l, preferably 50 to 600 mg / l tungsten in the form of water-soluble tungstates, Silicotungstates and / or borotungstates contain.
• the mentioned anions in the form of their acids and / or their ammonium, Alkali metal and / or alkaline earth metal salts are used.
• m-Nitrobenzenesulfonate can be used as a free acid or in the form of water-soluble Salts are used.
• Such salts become "water-soluble” referred to, which dissolve in the phosphating baths so far that the required concentrations of 0.2 to 2 g / l m-nitrobenzenesulfonate can be achieved.
• the alkali metal salts are particularly suitable for this the sodium salts.
• the phosphating baths preferably contain 0.4 to 1 g / l m-nitrobenzenesulfonate.
• a ratio of 1:10 to 10: 1 between the more reductive Hydroxylamine and the more oxidative m-nitrobenzenesulfonate can lead to special advantages with regard to layer formation, in particular regarding the shape of the crystals formed.
• the phosphating baths contain either hydroxylamine or m-nitrobenzenesulfonic acid.
• the weight ratio of phosphate ions to zinc ions in the phosphating baths can fluctuate within wide limits, provided it is in the range between 3.7 and 30 lies. A weight ratio between 10 and 20 is particularly preferred.
• Those skilled in the art are further parameters for controlling phosphating baths the free acid and total acid contents are known. The one in this Font used determination method of this parameter is in the example part specified. Free acid values between 0.3 and 1.5 points for partial phosphating, with band phosphating up to 2.5 points and the total acidity between about 15 and about 25 points are in the usual technical range Range and are suitable in the context of this invention.
• the manganese content of the phosphating bath should be between 0.3 and 4 g / l, since the lower the manganese content, the positive influence on the corrosion behavior the phosphate layers no longer exist and at higher ones Manganese content no further positive effect occurs. Keep between 0.3 and 2 g / l and in particular between 0.5 and 1.5 g / l are preferred.
• the zinc content is set in phosphating baths, which only act as accelerators Contain hydroxylamine, according to EP-A-315 059 preferably to values between 0.45 and 1.1 g / l, for phosphating baths, which only accelerate m-nitrobenzenesulfonate contain, preferably to values between 0.6 and 1.4 g / l a.
• the current zinc content of the worker Bath increases up to 2 g / l. It is important to ensure that the manganese content is at least 50% of the zinc content, otherwise it is insufficient Corrosion protection properties result.
• the Zinc and manganese ions are introduced into the phosphating baths basically irrelevant. In order to meet the conditions according to the invention, however, are the nitrites, nitrates, and salts with oxo anions of halogens these cations cannot be used. It is particularly useful as Zinc and / or manganese source to use the oxides and / or carbonates. In addition to the divalent cations mentioned, they contain phosphating baths usually sodium, potassium and / or ammonium ions to adjust the parameters free acid and total acid are used. Ammonium ions can also be formed by degradation of the hydroxylamine.
• iron goes in the form of iron (II) ions in solution. Since the phosphating baths according to the invention do not contain substances that are strong compared to iron (II) have an oxidizing effect, the divalent iron mainly goes off in succession Air oxidation into the trivalent state, so that it is called ferric phosphate can fail. Therefore, in the phosphating baths according to the invention Build up iron (II) levels that are well above the levels which contain baths containing oxidizing agents. With that in mind Iron (II) concentrations up to 50 ppm normal, with short-term in the production process Values up to 500 ppm can also occur. For the invention Phosphating processes are such iron (II) concentrations not harmful.
• the phosphating baths can be used in hard water also the hardness cations Mg (II) and Ca (II) in a total concentration up to 7 mmol / l.
• the method according to the invention is suitable for phosphating surfaces made of steel, galvanized or alloy galvanized steel, aluminum, aluminized or alloy aluminized steel.
• Baths containing hydroxylamine are especially designed for the treatment of galvanized on one or both sides, preferably electrolytically galvanized steel.
• the materials mentioned can - as is increasingly common in automotive engineering will also exist side by side.
• the procedure is for the application suitable in immersion, spray or spray / immersion processes. It can be used in particular in the automotive industry, where treatment times between 1 and 8 minutes are common. Use in tape phosphating in the steel mill, with treatment times between 5 and 12 seconds, is also possible.
• Suitable bath temperatures are also common in the prior art between 30 and 70 ° C, the temperature range between 40 and 60 ° C is preferred.
• the phosphating process according to the invention is used to produce a sliding layer for forming and in particular for treating the metal surfaces mentioned before painting, for example before a cathodic one Electro-dip coating thought as it is common in automotive engineering.
• the phosphating process is part of the technically usual pretreatment chain to see. In this chain, phosphating is common the steps cleaning / degreasing, rinsing and activating upstream, the activation usually with titanium phosphate-containing Activating agents are carried out.
• the phosphating according to the invention can if necessary after an intermediate rinse, a passivating after-treatment consequences. Chromic acid-containing ones are used for such a passivating aftertreatment Treatment baths widely used.
• the mass per unit area (“layer weight”) was determined by dissolving in 5% chromic acid solution in accordance with DIN 50942, Table 6. Corrosion tests were carried out according to the VDA alternating climate test 621-415 with KTL primer (KTL-light gray from BASF, FT 85- 7042); partly also with a complete paint structure (top coat: alpine white, VW).
• KTL primer KTL-light gray from BASF, FT 85- 7042
• top coat alpine white, VW.
• Layer weights were determined by dissolving in 5% chromic acid solution. Corrosion tests were carried out according to the VDA alternating climate test 621-415 both with KTL primer (ED 12 MB from PPG) and with a complete paint system (KTL as above, filler: 1-component high-solid PU filler gray, top coat: DB 744 metallic basecoat and clearcoat). The paint infiltration (mm) was evaluated after every 10 week test cycles. In addition, a shot put test was carried out according to the Mercedes-Benz standard analogous to DIN 53 230 (6 bar corresponding to 250 km / h), evaluation at substrate temperature -20 ° C. The damage area was assessed in mm 2 (Mercedes-Benz standard: max.

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• Chemical & Material Sciences (AREA)
• General Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Chemical Treatment Of Metals (AREA)
• Catalysts (AREA)
• Electroplating Methods And Accessories (AREA)

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• 1994
  • 1994-08-29 JP JP50842695A patent/JP3348856B2/ja not_active Expired - Fee Related
  • 1994-08-29 BR BR9407485A patent/BR9407485A/pt not_active IP Right Cessation
  • 1994-08-29 DE DE59405046T patent/DE59405046D1/de not_active Expired - Lifetime
  • 1994-08-29 WO PCT/EP1994/002848 patent/WO1995007370A1/de active IP Right Grant
  • 1994-08-29 AU AU75373/94A patent/AU678284B2/en not_active Ceased
  • 1994-08-29 CA CA002171180A patent/CA2171180A1/en not_active Abandoned
  • 1994-08-29 US US08/612,925 patent/US5792283A/en not_active Expired - Lifetime
  • 1994-08-29 KR KR1019960701115A patent/KR100327287B1/ko not_active Expired - Fee Related
  • 1994-08-29 CN CN94193230A patent/CN1041001C/zh not_active Expired - Fee Related
  • 1994-08-29 EP EP94925483A patent/EP0717787B1/de not_active Expired - Lifetime
  • 1994-08-29 AT AT94925483T patent/ATE162233T1/de not_active IP Right Cessation
  • 1994-08-29 CZ CZ1996673A patent/CZ286514B6/cs not_active IP Right Cessation
  • 1994-08-29 ES ES94925483T patent/ES2111949T3/es not_active Expired - Lifetime

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