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
  • C23C22/34—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
  • C23C22/07—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
  • C23C22/16—Orthophosphates containing zinc cations containing also peroxy-compounds
• • 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
  • C23C22/07—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
  • C23C22/184—Orthophosphates containing manganese cations containing also zinc cations containing also nickel 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
  • C23C22/365—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 containing also zinc and nickel 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
  • C23C22/73—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 characterised by the process
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
  • Y02T50/00—Aeronautics or air transport
  • Y02T50/60—Efficient propulsion technologies, e.g. for aircraft

Definitions

• the invention relates to a process for coating metallic surfaces with a phosphating solution which contains both hydrogen peroxide and also at least one guanidine compound, such as nitroguanidine, the corresponding phosphating solution and the use of the objects coated by the process according to the invention.
• phosphate layers on metallic objects has been used for decades with quite different compositions. These coatings primarily serve as protection from corrosion and to increase the adhesive strength of a subsequent layer, such as e.g. a lacquer layer.
• the phosphate layer here often has a layer thickness in the range from 1 to 30 ⁇ m.
• Phosphate coatings are widely used as corrosion protection layers, as an adhesive base for lacquers and other coatings and optionally as a shaping aid under a subsequently applied lubricant layer for cold shaping or also as a coating for adjusting the torque of special screws for automated screwing.
• the phosphate coatings are used as protection for a short time, in particular during storage, and are then e.g. lacquered, they are called a pretreatment layer before lacquering.
• pretreatment layer if no lacquer layer and no other type of organic coating follows the phosphate coating, treatment is referred to instead of pretreatment.
• These coatings are also called conversion layers if at least one cation is dissolved out of the metallic surface, that is to say the surface of the metallic object, and is co-used for building up the layer.
• Coating of metallic surfaces with phosphate layers can be carried out in diverse ways. Zinc-, manganese- or/and nickel-containing phosphating solutions are often employed here. Some of the metallic substrates to be coated on their surface in the baths or installations can also have a content of aluminium or aluminium alloys, which may possibly lead to problems.
• the phosphate layer(s) should usually have, together with at least one subsequently applied lacquer layer or lacquer-like coating, a good corrosion protection and a good lacquer adhesion. If more than one phosphate layer is applied, pre- and after-phosphating are usually referred to. Simultaneous phosphating of substrates with different metallic surfaces has increased in importance. In particular, the content of aluminium-containing surfaces in such systems is increasing, so that problems occur during phosphating in such systems more readily and more often than previously.
• nitrate and nitrite In zinc phosphating, acceleration by nitrate and nitrite is often chosen. In some cases only nitrate needs to be added here, since a low nitrite content is also formed from this independently via a redox reaction. Such phosphating systems are often good and inexpensive. The phosphating systems with nitrate or/and nitrite additions are particularly preferred for aluminium-rich surfaces in particular. However, such phosphating systems have the disadvantage that the high contents of nitrate used here are usually kept at a level of about 3 to 15 g/l of nitrate and thereby very severely pollute the waste water. Because of stricter environmental requirements, there is the need to decrease troublesome contents of the waste water as much as possible or to treat them by expensive chemical means.
• Such layers usually have layer thicknesses of up to about 0.5 ⁇ m or layer weights of up to about 1 g/m 2 .
• Such phosphate layers are of inadequate quality for many intended uses, in particular in respect of their corrosion resistance.
• the phosphate layers which have been prepared solely with the accelerator hydrogen peroxide show relatively large phosphate crystals, so that comparatively rough, non-uniform and uneven phosphate layers are formed. Tabular phosphate crystals often arise here.
• nitroguanidine can crystallize out on cooling to less than about 30° C. and then becomes concentrated unused in the sludge and possibly is also deposited on the metallic surfaces to be phosphated and can lead to lacquer defects, and that the consequently increased contents of this comparatively expensive accelerator lead to significantly higher raw material costs, since nitroguanidine is by far the most expensive component in phosphating.
• a phosphating temperature in the range from about 48 to 60° C. is conventionally necessary in these abovementioned phosphating systems.
• DE-C3 23 27 304 mentions, as an accelerator for application of zinc phosphate coatings to metallic surfaces, hydrogen peroxide, in particular with a content of 0.03 to 0.12 g/l in the phosphating solution.
• DE-C2 27 39 006 describes a process for the surface treatment of zinc or zinc alloys with an aqueous, acidic, nitrate- and ammonium-free phosphating solution which contains a high content of nickel or/and cobalt and 0.5 to 5 g/l of hydrogen peroxide and optionally also boron fluoride or free fluoride.
• EP-B1 0 922 123 protects aqueous phosphate-containing solutions for producing phosphate layers on metallic surfaces, which contain phosphate, 0.3 to 5 g/l of zinc and 0.1 to 3 g/l of nitroguanidine.
• the examples have a nitroguanidine content of 0.5 or 0.9 g/l.
• the doctrine of DE-A1 101 18 552 is a zinc phosphating process in which one or more accelerators chosen from chlorate, nitrite, nitrobenzenesulfonate, nitrobenzoate, nitrophenol and compounds based on hydrogen peroxide, hydroxylamine, reducing sugar, organic N oxide such as e.g. N-methylmorpholine, and organic nitro compound such as e.g. nitroguanidine, nitroarginine and nitro-furfurylidene diacetate, can be employed.
• the content of such organic nitro compounds in the phosphating solution only as long as no other accelerators are employed, can be in the range from 0.5 to 5 g/l.
• DE-C 977 633 describes, in the embodiment examples, zinc phosphate solutions which, starting from primary zinc phosphate, Zn(H 2 PO 4 ) 2 , simultaneously comprise on the one hand nitroguanidine or at least one other nitrogen-containing accelerator and on the other hand hydrogen peroxide.
• concentration of the organic accelerator or accelerators in the phosphating bath should be kept constantly above 1 g/l.
• the examples are evidently based on an initial composition of about 13.5 g/l of zinc, 38 g/l of PO 4 and in example 1 on 2 g/l of nitroguanidine and 2 g/l of hydrogen peroxide, in example 2 on 1 g/l of nitroguanidine and 2 g/l of H 2 O 2 , in example 3 on 3 g/l of nitroguanidine and 1 g/l of H 2 O 2 and in example 4 on 2.3 g/l of nitroguanidine and a high hydrogen peroxide content which is not stated in more detail. Unusually high temperatures, 85 and 95° C., are used here.
• the phosphate layer formed here should be closed, of fine-grained crystallinity (average edge length less than 20 ⁇ m) and, in at least some of the compositions, of sufficiently high corrosion resistance and sufficiently good lacquer adhesion. It should be possible to employ the process as easily and reliably as possible.
• the phosphate layer thicknesses are formed in a significantly thicker and more corrosion-resistant manner.
• Layer weights in particular in the range from 1.5 to 3 g/m 2 are formed by this means on surfaces of iron-based materials, layer weights in particular in the range from 1 to 6 g/m 2 on surfaces of aluminium-rich materials, and layer weights in particular in the range from 2 to 6 g/m 2 on surfaces of zinc-rich materials.
• 0.8 to 8 g/m 2 are usually achieved here.
• the object is achieved by a process for the treatment or pretreatment of surfaces of metallic objects—such as e.g. of components, profiles, strips or/and wires with metallic surfaces, in which optionally at least a portion of these surfaces can consist of aluminium or/and at least one aluminium alloy, and optionally the further metallic surfaces can consist predominantly of iron alloys, zinc or/and zinc alloys—with an acidic, aqueous solution containing zinc and phosphate, in which the phosphating solution contains
• the acidic, aqueous composition which is called here, inter alia, phosphating solution, and also the associated corresponding concentrate and the associated topping-up solution, can be a solution or a suspension, since the precipitation products from the solution which are necessarily formed form a suspension if a certain content of precipitation products are suspended.
• the phosphating solution preferably contains at least 0.2 g/l or 0.3 g/l of zinc, particularly preferably at least 0.4 g/l, very particularly preferably at least 0.5 g/l, in particular in some situations at least 0.8 g/l, in some cases at least 1.2 g/l, at least 1.7 g/l, at least 2.4 g/l or even at least 4 g/l. It preferably contains up to 8 g/l of zinc, particularly preferably up to 6.5 g/l, very particularly preferably up to 5 g/l, in particular in some situations up to 4 g/l, above all up to 3 g/l or up to 2 g/l.
• the phosphating solution preferably contains at least 5 g/l of phosphate, particularly preferably at least 7 g/l, very particularly preferably at least 10 g/l, in particular in some situations at least 14 g/l, at least 18 g/l, at least 24 g/l or even at least 30 g/l. It preferably contains up to 40 g/l of phosphate, particularly preferably up to 35 g/l, very particularly preferably up to 30 g/l, in particular in some situations up to 25 g/l, above all up to 20 g/l or up to 15 g/l.
• the ratio of zinc to phosphate can preferably be kept in the range from 1:40 to 1:4, particularly preferably in the range from 1:30 to 1:5, very particularly preferably in the range from 1:20 to 1:6.
• the contents of zinc and phosphate can greatly depend here on the desired concentration level, but in some cases also on the content of other cations, such as e.g. of Mn or/and Ni.
• the contents of zinc or zinc and manganese can be correlated with the contents of phosphate.
• Both the ratio of the total content of zinc and manganese to phosphate and the ratio of the total content of zinc, manganese and nickel to phosphate can preferably be kept in the range from 1:40 to 1:3, particularly preferably in the range from 1:30 to 1:3.5, very particularly preferably in the range from 1:20 to 1:4.
• the phosphating solution preferably contains at least 0.03 g/l of at least one guanidine compound containing at least one nitro group, such as e.g. nitroguanidine, or/and at least one alkylnitroguanidine, particularly preferably at least 0.05 g/l, very particularly preferably at least 0.07 g/l, in particular at least 0.09 g/l or even at least 0.12 g/l. It preferably contains up to 2.5 g/l, particularly preferably up to 2 g/l, very particularly preferably up to 1.5 g/l, in particular up to 1.2 g/l, above all up to 0.8 g/l or up to 0.5 g/l of at least one guanidine compound containing at least one nitro group.
• Alkylnitroguanidines which can be employed are e.g. methylnitroguanidine, ethylnitroguanidine, butylnitroguanidine or/and propylnitroguanidine.
• Aminoguanidine is preferably formed from nitroguanidine by this means.
• the at least one nitro group (NO 2 ) of guanidine compound(s) is converted into at least one amino group (NH 2 ) in the context of a redox reaction.
• the accelerator acts as an oxidizing agent by this means.
• the phosphating solution according to the invention should contain substantially no nitrite because of the potent oxidizing agent, and it should therefore also be possible for substantially no nitrous gases (NO x ) to be formed.
• the phosphating solution preferably contains at least 0.001 g/l of hydrogen peroxide, particularly preferably at least 0.003 g/l, very particularly preferably at least 0.005 g/l, in particular in some situations at least 0.01 g/l, at least 0.05 g/l, at least 0.1 g/l, at least 0.15 g/l or even at least 0.2 g/l. It preferably contains up to 0.9 g/l of hydrogen peroxide, particularly preferably up to 0.8 g/l, very particularly preferably up to 0.7 g/l, in particular in some situations up to 0.5 g/l, above all up to 0.3 g/l or up to 0.1 g/l.
• the contents in the phosphating solution of manganese can be 0.1 to 10 g/l or/and of nickel 0.01 to 1.8 g/l.
• the phosphating solution contains at least 0.2 g/l of manganese, particularly preferably at least 0.3 g/l, very particularly preferably at least 0.4 g/l, in particular in some situations at least 0.8 g/l, at least 1.5 g/l, at least 3 g/l or even at least 6 g/l. It preferably contains up to 8 g/l of manganese, particularly preferably up to 6 g/l, very particularly preferably up to 4 g/l, in particular in some situations up to 2.5 g/l, above all up to 1.5 g/l or up to 1 g/l. It is usually advantageous to add manganese.
• the ratio of zinc to manganese can be varied within wide ranges. It can preferably also be kept in the ratio of zinc to manganese in the range from 1:20 to 1:0.05, particularly preferably in the range from 1:10 to 1:0.1, very particularly preferably in the range from 1:4 to 1:0.2.
• a content of nickel in the phosphating bath may be advantageous in particular when bringing into contact with zinc-containing surfaces.
• a nickel content of the phosphating bath is usually not necessary for aluminium- or/and iron-rich surfaces.
• the phosphating solution it is particularly preferable for the phosphating solution to contain at least 0.02 g/l of nickel, particularly preferably at least 0.04 g/l, very particularly preferably at least 0.08 g/l or at least 0.15 g/l, in particular in some situations at least 0.2 g/l, at least 0.5 g/l, at least 1 g/l or even at least 1.5 g/l.
• It preferably contains up to 1.8 g/l of nickel, particularly preferably up to 1.6 g/l, very particularly preferably up to 1.3 g/l, in particular in some situations up to 1 g/l, above all up to 0.75 g/l or up to 0.5 g/l.
• the contents in the phosphating solution of Fe 2+ can be 0.005 to 1 g/l or/and of complexed Fe 3+ 0.005 to 0.5 g/l.
• the composition according to the invention will contain not more than 0.2 g/l of Fe 2 +, because of the content of hydrogen peroxide, and will therefore comprise e.g. 0.01, 0.03, 0.05, 0.08, 0.1, 0.14 or 0.18 g/l.
• the phosphating solution under certain circumstances can contain, in addition, at least 0.01 g/l of complexed Fe 3+ , particularly preferably at least 0.02 g/l, very particularly preferably at least 0.03 g/l or at least 0.05 g/l, in particular in some situations at least 0.08 g/l or even at least 0.1 g/l.
• It preferably contains up to 0.3 g/l of complexed Fe 3+ , particularly preferably up to 0.1 g/l, very particularly preferably up to 0.06 g/l, in particular in some situations up to 0.04 g/l.
• Noticeable contents of dissolved Fe are often only contained in the phosphating solution if this is or has been brought into contact with iron-based materials. Nevertheless, it may be advantageous to add dissolved Fe 3+ to the aqueous composition during the phosphating in particular of materials which are not iron-based, because a sludge of better consistency which is looser and easier to rinse off is then formed.
• Fe 2+ is a good pickling agent. The process according to the invention is normally not carried out on the iron side, because the Fe contents are not high enough for this.
• the contents in the phosphating solution of sodium can be 0.04 to 20 g/l, of potassium 0.025 to 35 g/l or/and of ammonium 0.01 to 50 g/l, the total of sodium, potassium and ammonium preferably being 0.025 to 70 g/l.
• the phosphating solution contains at least 0.05 g/l of sodium, particularly preferably at least 0.07 g/l, very particularly preferably at least 0.1 g/l or at least 0.15 g/l, in particular in some situations at least 0.3 g/l, at least 0.5 g/l, at least 1 g/l, at least 2 g/l or even at least 4 g/l. It preferably contains up to 15 g/l of sodium, particularly preferably up to 10 g/l, very particularly preferably up to 6 g/l, in particular in some situations up to 4 g/l, above all up to 3 g/l or up to 2 g/l.
• the phosphating solution contains at least 0.05 g/l of potassium, particularly preferably at least 0.07 g/l, very particularly preferably at least 0.1 g/l or at least 0.15 g/l, in particular in some situations at least 0.3 g/l, at least 0.5 g/l, at least 1 g/l, at least 2 g/l or even at least 4 g/l. It preferably contains up to 25 g/l of potassium, particularly preferably up to 15 g/l, very particularly preferably up to 8 g/l, in particular in some situations up to 5 g/l, above all up to 3 g/l or up to 2 g/l.
• the phosphating solution contains at least 0.03 g/l of ammonium, particularly preferably at least 0.06 g/l, very particularly preferably at least 0.1 g/l or at least 0.15 g/l, in particular in some situations at least 0.3 g/l, at least 0.5 g/l, at least 1 g/l, at least 2 g/l or even at least 4 g/l. It preferably contains up to 35 g/l of ammonium, particularly preferably up to 20 g/l, very particularly preferably up to 10 g/l, in particular in some situations up to 6 g/l, above all up to 3 g/l or up to 2 g/l.
• the phosphating solution prefferably contains a total content of sodium, potassium and ammonium of at least 0.05 g/l, particularly preferably of at least 0.1 g/l, very particularly preferably at least 0.2 g/l or at least 0.3 g/l, in particular in some situations at least 0.5 g/l, at least 1 g/l, at least 2 g/l, at least 4 g/l or even at least 8 g/l.
• Sodium, potassium or/and ammonium is advantageously added to the aqueous composition according to the invention if increased aluminium contents occur in the composition.
• An addition of sodium or/and potassium is preferable to ammonium for environment friendliness reasons.
• the contents in the phosphating solution of nitrate can be preferably 0.1 to 30 g/l, of chloride preferably 0.01 to 0.5 g/l or/and of sulfate preferably 0.005 to 5 g/l.
• the phosphating process according to the invention can be operated largely or completely free from nitrate.
• the phosphating solution may be particularly preferable for the phosphating solution to contain at least 0.3 g/l of nitrate, particularly preferably at least 0.6 g/l, very particularly preferably at least 1 g/l or at least 1.5 g/l, in particular in some situations at least 2 g/l, at least 3 g/l, at least 4 g/l, at least 6 g/l or even at least 8 g/l.
• It preferably contains up to 22 g/l of nitrate, particularly preferably up to 15 g/l, very particularly preferably up to 10 g/l, in particular in some situations up to 8 g/l, above all up to 6 g/l or up to 4 g/l.
• the phosphating solution may contain at least 0.03 g/l of chloride, particularly preferably at least 0.05 g/l, very particularly preferably at least 0.08 g/l or at least 0.12 g/l, in particular in some situations at least 0.15 g/l, at least 0.2 g/l or even at least 0.25 g/l. It preferably contains up to 0.35 g/l of chloride, particularly preferably up to 0.25 g/l, very particularly preferably up to 0.2 g/l, in particular in some situations up to 0.15 g/l, above all up to 0.1 g/l or up to 0.08 g/l.
• the phosphating solution contains at least 0.01 g/l of sulfate, particularly preferably at least 0.05 g/l, very particularly preferably at least 0.1 g/l or at least 0.15 g/l, in particular in some situations at least 0.3 g/l, at least 0.5 g/l, at least 0.7 g/l or even at least 1 g/l. It preferably contains up to 3.5 g/l of sulfate, particularly preferably up to 2 g/l, very particularly preferably up to 1.5 g/l, in particular in some situations up to 1 g/l or up to 0.5 g/l.
• nitrate may be advantageous here in order also to phosphate aluminium-rich surfaces by layer formation, that is to say with a phosphate layer which is not too thin.
• the addition e.g. of sodium, iron, manganese, nickel or/and zinc is also preferably effected at least partly via nitrates because of their good water-solubility.
• the contents in the phosphating solution of dissolved aluminium, including complexed aluminium can preferably be 0.002 to 1 g/l.
• a content of dissolved aluminium acts as a bath poison, in these situations it will be preferable for not more than 0.03 g/l of dissolved aluminium to be present in the phosphating solution, especially during dipping, although in some processes, such as e.g. in spraying, up to 0.1 g/l of aluminium can be dissolved, and in no-rinse processes, such as e.g. during rolling on, even up to about 1 g/l of aluminium can be dissolved.
• cryolite Na 3 AlF 6 and related aluminium-rich fluorine compounds such as e.g. elpasolite, K 2 NaAlF 6 , since they have a very low solubility in water.
• the phosphating solution preferably contains magnesium with a content of not more than 1 g/l or not more than 0.5 g/l, particularly preferably of not more than 0.15 g/l.
• magnesium with a content of not more than 1 g/l or not more than 0.5 g/l, particularly preferably of not more than 0.15 g/l.
• no calcium is added in the case of fluoride-containing phosphating systems.
• the contents in the phosphating solution of copper can be 0.002 to 0.05 g/l.
• the copper content of the phosphating solution is preferably not more than 0.03 g/l, particularly preferably not more than 0.015 g/l, in particular not more than 0.01 g/l.
• copper is only added if there are low or no contents of nickel in the phosphating solution.
• no copper is added intentionally. Copper contents may be advantageous in individual situations, in particular in the case of iron-based materials.
• Some of or the total content of cobalt and copper can also originate from impurities, entrained material or superficial pickling of the metallic surfaces of assemblies or pipelines.
• the contents of cobalt are also preferably below 0.05 g/l. Particularly preferably, no cobalt is to be added.
• the contents in the phosphating solution of free fluoride can be preferably 0.005 to 1 g/l or/and of total fluoride preferably 0.005 to 6 g/l.
• Free fluoride occurs in the bath solution as F ⁇ , while total fluoride can additionally also include contents of HF and all complex fluorides.
• the phosphating solution contains at least 0.01 g/l of free fluoride, particularly preferably at least 0.05 g/l, very particularly preferably at least 0.01 g/l or at least 0.03 g/l, in particular in some situations at least 0.05 g/l, at least 0.08 g/l, at least 0.1 g/l, at least 0.14 g/l or even at least 0.18 g/l. It preferably contains up to 0.8 g/l of free fluoride, particularly preferably up to 0.6 g/l, very particularly preferably up to 0.4 g/l, in particular in some situations up to 0.3 g/l or up to 0.25 g/l.
• the phosphating solution contains at least 0.01 g/l of total fluoride, particularly preferably at least 0.1 g/l, very particularly preferably at least 0.3 g/l or at least 0.6 g/l, in particular in some situations at least 0.9 g/l, at least 0.5 g/l, at least 0.8 g/l, at least 1 g/l or even at least 1.2 g/l. It preferably contains up to 5 g/l of total fluoride, particularly preferably up to 4 g/l, very particularly preferably up to 3 g/l, in particular in some situations up to 2.5 g/l or up to 2 g/l.
• Complex fluorides of Ti, Hf and Zr can act as bath poisons at higher contents since they can prematurely passivate the surface.
• the total of complex fluorides of Ti, Hf and Zr is not more than 0.8 g/l, particularly preferably not more than 0.5 g/l, very particularly preferably not more than 0.3 g/l, in particular not more than 0.15 g/l. It is therefore preferable if only complex fluorides of B or/and Si are present in the phosphating bath in a larger amount. In some cases only complex fluorides of B or Si are present in the phosphating bath in a larger amount, where it may be advantageous to use both side by side because they have slightly different properties.
• complex fluoride is particularly advantageous in the coating of zinc-containing surfaces, because the tendency to form specks (troublesome white spots) can be successfully suppressed by this means, in particular if at least 0.5 g/l of complex fluoride is added.
• An addition of silicofluoride is favourable in particular for preventing specks.
• Complex fluorides of boron and silicon moreover have the advantage that they display a buffer action in relation to free fluoride, so that with a suitable content of such complex fluorides it is possible to intercept a brief increase in the content of aluminium-containing objects, such as e.g. an aluminium-rich vehicle body, between galvanized vehicle bodies by an increased formation of free fluoride, without the bath having to be adapted to this changed consumption in the individual case.
• the contents in the phosphating solution of silicofluoride, calculated as SiF 6 can be 0.005 to 4.5 g/l or/and of boron fluoride, calculated as BF 4 , 0.005 to 4.5 g/l. It is preferable for the contents in the phosphating solution of complex fluoride of B and Si in total, where complex fluoride is added, to be in the range from 0.005 to 5 g/l, particularly preferably in the range from 0.1 to 4.5 g/l, very particularly preferably in the range from 0.2 to 4 g/l, in particular in the range from 0.3 to 3.5 g/l. A total content of such complex fluorides can then be, for example, 0.5, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.4, 2.8 or 3.2 g/l.
• the phosphating solution contains at least 0.01 g/l of silicofluoride, particularly preferably at least 0.1 g/l, very particularly preferably at least 0.2 g/l or at least 0.3 g/l, in particular in some situations at least 0.4 g/l, at least 0.6 g/l, at least 0.8 g/l, at least 1 g/l or even at least 1.2 g/l.
• It preferably contains up to 4 g/l of silicofluoride, particularly preferably up to 3 g/l, very particularly preferably up to 2.5 g/l, in particular in some situations up to 2.2 g/l or up to 2 g/l, where complex fluoride is added.
• the phosphating solution contains at least 0.01 g/l of boron fluoride, particularly preferably at least 0.1 g/l, very particularly preferably at least 0.2 g/l or at least 0.3 g/l, in particular in some situations at least 0.4 g/l, at least 0.6 g/l, at least 0.8 g/l, at least 1 g/l or even at least 1.2 g/l.
• It preferably contains up to 4 g/l of boron fluoride, particularly preferably up to 3 g/l, very particularly preferably up to 2.5 g/l, in particular in some situations up to 2.2 g/l or up to 2 g/l, where complex fluoride is added.
• the contents in the phosphating solution of titanium can be 0.01 to 2 g/l or/and of zirconium 0.01 to 2 g/l.
• the contents in the phosphating solution of titanium are particularly preferably not more than 1.5 g/l, very particularly preferably not more than 1 g/l, above all not more than 0.5 g/l, not more than 0.3 g/l or even not more than 0.1 g/l.
• the contents in the phosphating solution of zirconium are particularly preferably not more than 1.5 g/l, very particularly preferably not more than 1 g/l, above all not more than 0.5 g/l, not more than 0.3 g/l or even not more than 0.1 g/l.
• Contents of titanium or/and zirconium can be carried in via the liquids or attachments and other devices in particular if e.g. a titanium-containing activation or a zirconium-containing after-rinsing solution is employed.
• the phosphating solutions according to the invention here are preferably largely free or free from pickling inhibitors, such as e.g. di-n-butyl-thiourea, largely free or free from lubricants or/and have a total surfactant content of less than 1 g/l, since these substances can impair the formation of the phosphate layer or can generate foam. In many cases they are largely free or free from cations, such as e.g. antimony, arsenic, cadmium, chromium or/and tin.
• pickling inhibitors such as e.g. di-n-butyl-thiourea
• lubricants or/and have a total surfactant content of less than 1 g/l, since these substances can impair the formation of the phosphate layer or can generate foam.
• cations such as e.g. antimony, arsenic, cadmium, chromium or/and tin.
• the phosphating solutions according to the invention conventionally do not have a content of organic polymers of more than 0.8 g/l, including contents of surfactant(s) or/and oil(s) carried in.
• the phosphating solution can have a content of at least one water-soluble or/and water-dispersible organic polymeric compound, such as e.g. at least one polyelectrolyte or/and at least one polyether, such as, for example, at least one polysaccharide.
• these polymers can help to make the sludge even somewhat softer and easier to remove.
• Their content is preferably 0.001 to 0.5 g/l, in particular 0.003 to 0.2 g/l.
• the amount of sludge indeed is not usually reduced, but the sludge consistency and its ease of removal are significantly improved compared with phosphating systems with only one of the accelerators nitroguanidine or hydrogen peroxide. Furthermore, the phosphating in the process according to the invention proceeds faster than with only hydrogen peroxide acceleration.
• the consistency of the sludge precipitated in particular in the phosphating bath is more favourable than when solely the accelerator hydrogen peroxide is used in the phosphating solution.
• the accelerator combination of guanidine compound(s)—hydrogen peroxide smaller phosphate crystals are formed than with only hydrogen peroxide, so that the average edge length of the phosphate crystals is usually less than 10 ⁇ m.
• the crystals are in a looser accumulation of fine small crystals and can therefore easily be removed from the bath tank and the lines.
• a passivation effect of the guanidine compound(s) evidently moreover has a positive effect here.
• the sludge had about the same consistency as with the combination of guanidine compound(s)—hydrogen peroxide—nitrate/nitrite.
• the phosphating solution can contain
• the phosphating solution can contain
• KCl is added to saturation to 10 ml of the phosphating solution, without dilution, for the purpose of shifting the dissociation of the complex fluoride and titration is carried out with 0.1 M NaOH, using dimethyl yellow as the indicator, until the colour changes from red to yellow.
• the amount of 0.1 M NaOH consumed in ml gives the value of the free acid (FA-KCl) in points.
• the free acid is titrated in 100 ml of completely desalinated water with NaOH against dimethyl yellow as the indicator to the change from red to yellow.
• the amount of 0.1 M NaOH consumed in ml gives the value of the free acid (FA) in points.
• the so-called S value is obtained by dividing the value of the free acid KCl—or without the presence of complex fluoride in the phosphating solution—of the free acid by the value of the Fischer total acid.
• the total acid diluted (TA diluted ) is the sum of the divalent cations and free and bonded phosphoric acids (the later are phosphates) contained in the solution. It is determined by the consumption of 0.1 molar sodium hydroxide solution, using the indicator phenolphthalein, by 10 ml of phosphating solution diluted with 200 ml of completely desalinated water. This consumption of 0.1 M NaOH in ml corresponds to the total acid points number.
• the range of the free acid KCl is preferably 0.4 to 5.5 points, in particular 0.6 to 5 points.
• the range of the total acid diluted is preferably 12 to 50 points, in particular 18 to 44 points.
• the range of the Fischer total acid is preferably 7 to 42 points, in particular 10 to 30 points.
• the S value as the ratio of the number of points of free acid KCl—or free acid—to that of the Fischer total acid is preferably in the range from 0.01 to 0.40, in particular in the range from 0.03 to 0.35, above all in the range from 0.05 to 0.30.
• the pH of the phosphating solution can be in the range from 1 to 4, preferably in the range from 2.2 to 3.6, particularly preferably in the range from 2.8 to 3.3.
• the metallic surfaces can be phosphated at a temperature in the range from 30 to 75° C., in particular at 35 to 60° C., particularly preferably at up to 55° C. or at up to 50° C. or at up to 48° C.
• the metallic surfaces in particular during dipping or/and spraying—can be brought into contact with the phosphating solution over a period of time preferably in the range from 0.1 to 8 minutes, in particular over 0.2 to 5 minutes.
• the contact time can be reduced to fractions of a second.
• the phosphating solution according to the invention is suitable for the most diverse metallic surfaces, but in particular also for iron-based materials in the dipping process.
• the process according to the invention is also particularly suitable for phosphating for a mix of objects from various metallic materials, in particular chosen from aluminium, aluminium alloy(s), steel/steels, galvanized steel/galvanized steels and zinc alloy(s). This process is also particularly suitable for a high throughput of aluminium-rich surfaces.
• the metallic surfaces can be cleaned, pickled or/and activated before the phosphating, in each case optionally with at least one subsequent rinsing step.
• the last rinsing step of all after the phosphating and optionally after the after-rinsing is a rinsing operation with completely desalinated water.
• the phosphated metallic surfaces can then be rinsed, after-rinsed with an after-rinsing solution, dried or/and coated with in each case at least one lacquer, one lacquer-like coating, one adhesive or/and one foil.
• the after-rinsing solution can be of quite different composition, depending on the profile of requirements. The compositions are known in principle to the expert.
• the invention also relates to an acidic, aqueous solution which contains
• the acidic, aqueous solution according to the invention can additionally also contain
• the acidic, aqueous solution according to the invention can additionally also contain
• the nickel content is preferably not more than 1.5 g/l.
• the acidic, aqueous solution according to the invention can be on the one hand a phosphating solution which is employed as a phosphating bath, and on the other hand optionally also the corresponding concentrate or the corresponding topping-up solution in order to prepare a phosphating solution by dilution or to keep the phosphating solution in the desired concentration level in respect of essential constituents using the topping-up solution.
• the invention moreover also relates to a metallic object with a phosphate layer which has been prepared by the process according to the invention.
• the objects coated according to the invention can be used, for example, in vehicle construction, in particular in automobile series production, for the production of components or vehicle body components or pre-assembled elements in the vehicle or air travel industry, in the construction industry, in the furniture industry, for the production of equipment and installations, in particular domestic appliances, measuring instruments, control installations, test equipment, construction elements, linings and of hardware items.
• a layer weight of 2.5 to 3.5 g/m 2 is often determined with closed layers and a good layer formation, as a result of which a comparatively high consumption occurs.
• it has been possible to form phosphate layers which, at an average edge length of the phosphate crystals of the order of less than 10 ⁇ m, usually have a layer weight usually of the order of about 2 to 2.5 g/m 2 or, at an average edge length of the phosphate crystals of the order of about 6 ⁇ m, often have a layer weight of the order of about 1.5 to 2 g/m 2 , in particular also on steel.
• the phosphating can be carried out well or even very well here in the range from 30 to 65° C., in particular in the range from 35 to 55°.
• the lower the temperature, the lower the acidity of the bath can be kept, in particular the S value as the ratio of the free acid or the free acid KCl to the Fischer total acid.
• test metal sheets comprised a mix of metal sheets in each case in the ratio 1:1:1:1
• the substrate surfaces were cleaned in a 2% aqueous solution of a mildly alkaline cleaner for 5 minutes at 58 to 60° C. and thereby thoroughly degreased.
• the surfaces were then activated by dipping in an activating agent containing titanium phosphate for 0.5 minute at room temperature.
• the coated substrates were then dried in a drying oven at 80° C. for 10 minutes.
• the layer weight was also determined in this state.
• compositions of the particular phosphating solutions are listed in table 1.
• TABLE 1 Composition of the phosphating solutions in g/l and with the acidity data in points Examples Contents in g/l CE 1 CE 2 CE 3 CE 4 CE 5 E 6 E 7 E 8 E 9 E 10 E 11 E 12 E 13 E 14 E 15 E 16 Zn 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.0 1.0 1.0 1.0 1.3 1.3 1.3 1.3 1.3 1.3 Ni 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 — — 0.8 0.8 — Mn 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8
• Nitroguanidine was added to the phosphating solution as an accelerator with a content in the range from 0.1 to 0.5 g/l, hydrogen peroxide in the range from 0.005 to 0.05 g/l. Since hydrogen peroxide was consumed rapidly, hydrogen peroxide was topped up discontinuously. Fluorides and phosphates of Al, Fe, Zn and where appropriate other cations were found in the so-called “sludge”. However, practically nothing of these precipitation products was deposited on the metal sheet surfaces.
• the sludge was easy to remove from the wall of the tank and lines without pressure jets and without a mechanical action because of its finely crystalline loose consistency.
• the phosphating solutions according to the invention therefore offered a further possibility also to coat a metal mix which has low or also high contents of aluminium-containing surfaces in a simple, reliable, robust, good, inexpensive and fast manner.
• the phosphate layers of the examples according to the invention were finely crystalline and closed. Their corrosion resistance and adhesive strength corresponded to typical quality standards of similar zinc phosphate layers.
• the phosphate layers produced according to the invention look—in particular on steel surfaces—more uniform and more attractive than those of the comparison examples.
• Scanning electron microscope photographs demonstrated that the phosphate crystals have average edge lengths in the range below 15 ⁇ m, and in some cases even not more than 8 ⁇ m. Under 8 ⁇ m, the phosphate crystals were substantially isometric as substantially tabular. Scanning electron microscope photographs with perpendicular or angled observation of the phosphated steel surfaces were chosen here. Steel surfaces in particular normally rather present problems in the phosphating quality.

Landscapes

• Chemical & Material Sciences (AREA)
• General Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Chemical Treatment Of Metals (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Paints Or Removers (AREA)
• Application Of Or Painting With Fluid Materials (AREA)

Priority Applications (1)

Applications Claiming Priority (3)

Publications (1)

Family

ID=33441188

Family Applications (2)

Family Applications After (1)

Country Status (13)

Cited By (6)

Families Citing this family (12)

Citations (12)

Family Cites Families (9)

• 2003
  • 2003-05-23 DE DE10323305A patent/DE10323305B4/de not_active Expired - Fee Related
• 2004
  • 2004-05-17 DK DK04733319T patent/DK1633905T3/da active
  • 2004-05-17 US US10/555,929 patent/US20060278307A1/en not_active Abandoned
  • 2004-05-17 PT PT04733319T patent/PT1633905E/pt unknown
  • 2004-05-17 ES ES04733319T patent/ES2294498T3/es not_active Expired - Lifetime
  • 2004-05-17 CN CN2004800209863A patent/CN1826429B/zh not_active Expired - Lifetime
  • 2004-05-17 EP EP04733319A patent/EP1633905B1/de not_active Expired - Lifetime
  • 2004-05-17 AU AU2004241000A patent/AU2004241000B2/en not_active Ceased
  • 2004-05-17 DE DE502004004961T patent/DE502004004961D1/de not_active Expired - Lifetime
  • 2004-05-17 ZA ZA200509144A patent/ZA200509144B/en unknown
  • 2004-05-17 AT AT04733319T patent/ATE373117T1/de active
  • 2004-05-17 JP JP2006529846A patent/JP2006528280A/ja active Pending
  • 2004-05-17 BR BRPI0410585-0A patent/BRPI0410585B1/pt active IP Right Grant
  • 2004-05-17 WO PCT/EP2004/005282 patent/WO2004104266A1/de active IP Right Grant
• 2011
  • 2011-04-07 US US13/081,823 patent/US20110180186A1/en not_active Abandoned

Patent Citations (12)

Also Published As

Similar Documents

Legal Events