EP0931179A2 - Verfahren zur phosphatierung von stahlband - Google Patents
Verfahren zur phosphatierung von stahlbandInfo
- Publication number
- EP0931179A2 EP0931179A2 EP97942941A EP97942941A EP0931179A2 EP 0931179 A2 EP0931179 A2 EP 0931179A2 EP 97942941 A EP97942941 A EP 97942941A EP 97942941 A EP97942941 A EP 97942941A EP 0931179 A2 EP0931179 A2 EP 0931179A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- phosphating
- galvanized
- ions
- range
- free
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- C23C22/07—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
-
- 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
Definitions
- the invention relates to a method for phosphating steel strip or steel strip galvanized on one or both sides or galvanized with alloys by spraying or immersion treatment, which takes place for a period of time in the range from approximately 2 to approximately 15 seconds, depending on the belt speed.
- phosphating surfaces made of iron, steel, zinc and their alloys as well as aluminum and its alloys have long been state of the art.
- the phosphating of the surfaces mentioned serves to increase the adhesive strength of paint layers and to improve corrosion protection.
- the phosphating is carried out by immersing the metal surfaces in the phosphating solutions or by spraying the metal surfaces with the phosphating solutions. Combined methods are also known.
- Shaped metal parts such as automobile bodies can be phosphated, but also metal strips in high-speed conveyor systems.
- the present invention is concerned with such a band phosphating.
- Belt phosphating differs from partial phosphating in that, because of the high belt speeds, the phosphating, i.e. H. the growth of a closed metal phosphate layer must take place within a short period of time, for example from about 2 to about 15 seconds.
- phosphating metal strips in particular electrolytically galvanized or hot-dip galvanized steel strips
- WO 91/02829 describes a method for phosphating electrolytically and / or hot-dip galvanized steel strip due to short-term treatment with acid phosphating solutions, which contain manganese and nickel cations as well as anions of oxygen-containing acids with accelerating effect in addition to zinc and phosphate ions.
- acid phosphating solutions which contain manganese and nickel cations as well as anions of oxygen-containing acids with accelerating effect in addition to zinc and phosphate ions.
- the latter term is to be understood in particular as nitrate ions.
- DE-A-35 37 108 likewise describes a process for the phosphating of electrolytically galvanized steel strips by treatment with acidic phosphating solutions which, in addition to zinc, manganese and phosphate ions, contain further metal cations such as, for example, nickel ions and / or anions of oxygen-containing acids with accelerating action, in particular nitrate ions. contain.
- the contents of zinc cations are in the relatively low range of 0.1 to 0.8 g / 1.
- DE-A-42 28 470 teaches a method for phosphating one-sided electrolytically galvanized steel strip on the galvanized surface by treatment with acid phosphating solutions containing 1.0 to 6.0 g / 1 zinc cations, 0.5 to 5, Contain 0 g / 1 nickel cations and 14 to 25 g / 1 phosphate anions.
- acid phosphating solutions containing 1.0 to 6.0 g / 1 zinc cations, 0.5 to 5, Contain 0 g / 1 nickel cations and 14 to 25 g / 1 phosphate anions.
- water-soluble salts of the cations mentioned for example the nitrates
- the cations mentioned would be used in the form of their nitrates, the nitrate content having no effect on the phosphating result.
- phosphate layers with a mass per unit area of up to approximately 2.0 g / m 2 are formed on the galvanized surface of steel strips galvanized on one or both sides.
- galvanized steel surfaces could not be phosphated due to the short phosphating times in the range of about 2 to about 15 seconds.
- no phosphate layer was formed on the non-galvanized side. This could have been desirable. If these steel bands, galvanized and phosphated on one side, were later installed as parts of automobile bodies and phosphated again, The phosphating of the steel side often proved to be problematic because of the passivation caused by the pretreatment.
- the object of the invention is to provide a phosphating process for high-speed belt systems by means of which not only the galvanized side of galvanized or alloy-galvanized steel strip can be phosphated, but also non-galvanized steel strips or the non-galvanized side of single-sided galvanized steel strips.
- This provides a material that can advantageously be used for the construction of, for example, vehicle bodies or of household appliances, such as, for example, refrigerators and washing machines.
- This object is achieved by a method for phosphating steel strip or steel strip galvanized on one or both sides or alloy galvanized by spray or dip treatment for a period of time in the range from 2 to 15
- the steel strips can be galvanized or hot-dip galvanized or alloy-galvanized.
- “Galvanized alloy” is understood to mean that the steel surface has been coated with an alloy, the other besides zinc Contains metals such as iron, nickel or aluminum. Alloy galvanizing with a zinc-iron alloy can take place, for example, by tempering a galvanized steel strip, as a result of which iron atoms diffuse into the zinc layer and vice versa.
- the layer thicknesses of the galvanizing layers are usually in the range from approximately 5 to approximately 20 ⁇ m.
- free acid and total acid are generally known in the field of phosphating. They are determined by titrating the acid bath sample with 0.1 normal sodium hydroxide solution and measuring its consumption. The consumption in ml is given as a score.
- the number of free acids means the consumption in ml of 0.1 normal sodium hydroxide solution in order to titrate 10 ml of bath solution, which has been diluted to 50 ml with deionized water, up to a pH of 3.6 .
- the total acid score indicates consumption in ml up to a pH of 8.2.
- the inventive combination of very low nitrate contents or the complete absence of nitrate in the phosphating bath and the simultaneous presence of hydroxylamine or hydroxylamine-releasing compounds achieve the object of the invention to allow a closed metal phosphate layer to grow even on uncoated steel surfaces.
- Phosphating solutions with a nitrate content of no more than 0.1 g / 1 and in particular completely nitrate-free phosphating solutions are particularly preferred for the phosphating of galvanized steel strips, while low nitrate contents of up to 1 g / 1 are tolerable or even advantageous for the phosphating of non-galvanized steel strips can.
- hydroxylamine or its compounds in low-nitrate or nitrate-free phosphating solutions for high-speed conveyor systems makes it possible for the first time to also galvanize steel surfaces with spray or dipping processes.
- hydroxylamine as an accelerator has been known for some time for the part phosphating which works with longer treatment times. Examples of this are EP-A-315 059 and WO 93/03198.
- Hydroxylamine can be used as a free base, as a hydroxylamine-releasing compound such as hydroxylamine complexes and ketoximes or aldoximes or in the form of hydroxylammonium salts.
- free hydroxylamine is added to the phosphating bath or a phosphating bath concentrate, it will largely exist as a hydroxylammonium cation due to the acidic nature of these solutions.
- the sulfates and the phosphates are particularly suitable.
- the acid salts are preferred due to the better solubility.
- a combination of free hydroxyamine and hydroxylammonium sulfate can advantageously be used in order to take economic aspects into account on the one hand and on the other hand to not burden the phosphating baths with too much sulfate ions.
- Hydroxylamine or its compounds are added to the phosphating solution in amounts such that the calculated concentration of the free hydroxylamine is between about 0.1 to about 3 g / 1, preferably between about 0.15 and about 0.8 g / 1.
- the total phosphorus content of the phosphating bath is considered to be present in the form of phosphate ions? OA ⁇ ⁇ . Accordingly, the known fact that the pH values of the phosphating baths in the range from about 2.0 to about 3.6, which are in the acidic region, only a very small part of the phosphate is actually in the form is ignored in the concentration calculation or determination the triple negatively charged anions are present. At these pH values, it is rather to be expected that the phosphate is present primarily as a single negatively charged dihydrogen phosphate anion, together with undisociated phosphoric acid and with smaller amounts of double negatively charged hydrogen phosphate anions.
- the corrosion protection and paint adhesion properties of the phosphate layers can be improved if the phosphating solutions contain further cations that are incorporated into the phosphate layers.
- the presence of about 0.8 to about 3.5 g / l of nickel ions in the phosphating baths according to the invention has a favorable effect on the paint adhesion.
- nickel can be used with a similar effect.
- phosphating solutions are preferably used which contain about 0.002 to about 0.2 g / 1 copper ions, in particular about 0.003 to about 0.06 g / 1 copper ions.
- the phosphating solutions contain alkali metal and / or ammonium cations in order to adjust the value of the free acid to the desired range.
- a further preferred embodiment of the invention consists in using phosphating solutions which contain up to about 0.8 g / 1 fluoride in free or complex-bound form.
- the preferred fluoride contents are in the range from 0.0 to about 0.5 g / 1, in particular in the range from about 0.1 to about 0.2 g / 1.
- the phosphating solutions are generally prepared in the manner known to the person skilled in the art.
- phosphate is in the form of Phosphoric acid introduced into the phosphating solutions.
- the cations are added in the form of acid-soluble compounds such as, for example, the carbonates, the oxides or the hydroxides of phosphoric acid, so that this is partially neutralized.
- the further neutralization to the desired pH range is preferably carried out by adding sodium hydroxide or sodium carbonate.
- the copper ions to be used optionally can also be introduced into the phosphating solution preferably as sulfate or as acetate.
- Suitable sources of free fluoride anions are, for example, sodium or potassium fluoride.
- tetrafluoroborate or hexafluorosilicate can be used as complex fluorides.
- the invention relates to the use of the phosphating method described above for the production of phosphate layers on both sides with a mass per unit area in the range from approximately 0.4 to approximately 2.0 g / m 2 on steel strip or on steel strip galvanized or alloy-galvanized on one or both sides .
- Phosphate layers with a mass per unit area in the range from approximately 0.9 to approximately 1.8 g / m 2 are preferably produced.
- the mass per unit area (“layer weight”) can, as is known to the person skilled in the art, be determined by weighing a phosphated sample sheet, detaching the phosphate layer in 5% chromic acid solution and weighing the sample sheet back. This method is described, for example, in DIN 50942.
- phosphating solutions are preferably used, the free acid content of which is in the range from approximately 1.5 to approximately 2.5 points and the total acid content is in the range of approximately 20 to approximately 35 points Range from about 50 to about 70 ° C. and in particular in the range from about 55 to about 65 ° C. Preferred treatment times are in the range from about 5 to about 10 seconds.
- the metal surface must be completely water wettable before applying the phosphating solution. This is usually the case in continuously operating conveyor systems. However, if the belt surface is oiled, this oil must be removed by a suitable cleaner before phosphating. The procedures for this are common in the art. Before phosphating, activation is usually carried out using activation agents known in the art.
- Solutions or suspensions are usually used which contain titanium phosphates and sodium phosphates.
- the activation is followed by the use of the phosphating process according to the invention, which is advantageously followed by a passivating rinse.
- An intermediate rinse with water usually takes place between phosphating and passivating rinsing.
- Treatment baths containing chromic acid are widely used for passivating rinsing. For reasons of work and environmental protection and for disposal reasons, however, there is a tendency to replace these chromium-containing passivation baths with chromium-free treatment baths.
- Rinse solutions which contain 0.001 to 10 g / l of one or more of the following cations can also be used: lithium ions, copper ions, silver ions and / or bismuth ions.
- the metal strips phosphated according to the invention can be provided directly with an organic coating. However, they can also be assembled in the initially unpainted state after cutting, shaping and joining to form components such as automobile bodies or household appliances. The associated forming processes are facilitated by the phosphate layer. If the corrosive stress on the finished components is low, such as in household appliances, they can be assembled from the pre-phosphated metal Devices can be painted directly. For higher corrosion protection requirements, such as those made in automobile construction, it is advantageous to have a phosphating treatment again after assembling the bodies.
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)
- Laminated Bodies (AREA)
- Analysing Materials By The Use Of Radiation (AREA)
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19639596 | 1996-09-26 | ||
DE19639596A DE19639596A1 (de) | 1996-09-26 | 1996-09-26 | Verfahren zur Phosphatierung von Stahlband |
PCT/EP1997/005091 WO1998013534A2 (de) | 1996-09-26 | 1997-09-17 | Verfahren zur phosphatierung von stahlband |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0931179A2 true EP0931179A2 (de) | 1999-07-28 |
EP0931179B1 EP0931179B1 (de) | 2000-12-06 |
Family
ID=7806984
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97942941A Expired - Lifetime EP0931179B1 (de) | 1996-09-26 | 1997-09-17 | Verfahren zur phosphatierung von stahlband |
Country Status (11)
Country | Link |
---|---|
EP (1) | EP0931179B1 (de) |
JP (1) | JP2001508123A (de) |
KR (1) | KR20000048509A (de) |
CN (1) | CN1231706A (de) |
AT (1) | ATE197969T1 (de) |
AU (1) | AU4459397A (de) |
CA (1) | CA2266625A1 (de) |
DE (2) | DE19639596A1 (de) |
ES (1) | ES2153217T3 (de) |
ID (1) | ID21474A (de) |
WO (1) | WO1998013534A2 (de) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6179934B1 (en) | 1997-01-24 | 2001-01-30 | Henkel Corporation | Aqueous phosphating composition and process for metal surfaces |
JPH10204649A (ja) * | 1997-01-24 | 1998-08-04 | Nippon Parkerizing Co Ltd | 金属表面のりん酸塩処理水溶液及び処理方法 |
DE19740953A1 (de) * | 1997-09-17 | 1999-03-18 | Henkel Kgaa | Verfahren zur Phosphatierung von Stahlband |
DE19808755A1 (de) | 1998-03-02 | 1999-09-09 | Henkel Kgaa | Schichtgewichtsteuerung bei Bandphosphatierung |
DE19905479A1 (de) * | 1999-02-10 | 2000-08-17 | Metallgesellschaft Ag | Verfahren zur Phospatisierung von Zink- oder Aluminiumoberflächen |
DE10110834B4 (de) * | 2001-03-06 | 2005-03-10 | Chemetall Gmbh | Verfahren zur Beschichtung von metallischen Oberflächen und Verwendung der derart beschichteten Substrate |
DE10110833B4 (de) * | 2001-03-06 | 2005-03-24 | Chemetall Gmbh | Verfahren zum Aufbringen eines Phosphatüberzuges und Verwendung der derart phosphatierten Metallteile |
CN104313579B (zh) * | 2014-11-11 | 2017-01-18 | 武汉钢铁(集团)公司 | 一种电镀锌镁合金钢板的生产方法 |
CN105568274A (zh) * | 2015-12-31 | 2016-05-11 | 安徽红桥金属制造有限公司 | 一种环保的镀锌钝化剂及其制备方法 |
CN105925985B (zh) * | 2016-07-19 | 2018-04-20 | 东莞市凯盟表面处理技术开发有限公司 | 一种不锈铁常温化学抛光液及其制备方法和使用方法 |
CN111349867A (zh) * | 2020-04-10 | 2020-06-30 | 武汉钢铁有限公司 | 一种涂装友好的预磷化电镀锌汽车外板及其制备方法 |
CN112226755B (zh) * | 2020-09-23 | 2023-06-23 | 山东大业股份有限公司 | 一种金属线材表面处理用磷化方法及装置 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4228470A1 (de) * | 1992-08-27 | 1994-03-03 | Henkel Kgaa | Verfahren zur Phospatierung von einseitig verzinktem Stahlband |
DE4241134A1 (de) * | 1992-12-07 | 1994-06-09 | Henkel Kgaa | Verfahren zur Phosphatierung von Metalloberflächen |
ATE162233T1 (de) * | 1993-09-06 | 1998-01-15 | Henkel Kgaa | Nickelfreies phosphatierverfahren |
DE19606018A1 (de) * | 1996-02-19 | 1997-08-21 | Henkel Kgaa | Zinkphosphatierung mit geringen Gehalten an Nickel- und/oder Cobalt |
-
1996
- 1996-09-26 DE DE19639596A patent/DE19639596A1/de not_active Withdrawn
-
1997
- 1997-09-17 JP JP51522798A patent/JP2001508123A/ja active Pending
- 1997-09-17 AU AU44593/97A patent/AU4459397A/en not_active Abandoned
- 1997-09-17 WO PCT/EP1997/005091 patent/WO1998013534A2/de not_active Application Discontinuation
- 1997-09-17 ID IDW990112A patent/ID21474A/id unknown
- 1997-09-17 CN CN97198236A patent/CN1231706A/zh active Pending
- 1997-09-17 AT AT97942941T patent/ATE197969T1/de not_active IP Right Cessation
- 1997-09-17 DE DE59702741T patent/DE59702741D1/de not_active Expired - Fee Related
- 1997-09-17 KR KR1019990702409A patent/KR20000048509A/ko not_active Application Discontinuation
- 1997-09-17 CA CA002266625A patent/CA2266625A1/en not_active Abandoned
- 1997-09-17 ES ES97942941T patent/ES2153217T3/es not_active Expired - Lifetime
- 1997-09-17 EP EP97942941A patent/EP0931179B1/de not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
---|
See references of WO9813534A2 * |
Also Published As
Publication number | Publication date |
---|---|
JP2001508123A (ja) | 2001-06-19 |
ATE197969T1 (de) | 2000-12-15 |
CN1231706A (zh) | 1999-10-13 |
KR20000048509A (ko) | 2000-07-25 |
AU4459397A (en) | 1998-04-17 |
DE19639596A1 (de) | 1998-04-02 |
CA2266625A1 (en) | 1998-04-02 |
WO1998013534A3 (de) | 1998-08-27 |
ID21474A (id) | 1999-06-17 |
EP0931179B1 (de) | 2000-12-06 |
ES2153217T3 (es) | 2001-02-16 |
WO1998013534A2 (de) | 1998-04-02 |
DE59702741D1 (de) | 2001-01-11 |
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