EP1381711A2 - Method for improving metal surfaces to prevent thermal tarnishing - Google Patents
Method for improving metal surfaces to prevent thermal tarnishingInfo
- Publication number
- EP1381711A2 EP1381711A2 EP01991656A EP01991656A EP1381711A2 EP 1381711 A2 EP1381711 A2 EP 1381711A2 EP 01991656 A EP01991656 A EP 01991656A EP 01991656 A EP01991656 A EP 01991656A EP 1381711 A2 EP1381711 A2 EP 1381711A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- iii
- coating
- layer
- sol
- compounds
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1229—Composition of the substrate
- C23C18/1241—Metallic substrates
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1254—Sol or sol-gel processing
Definitions
- the present invention relates to a ner driving to prevent or at least reduce the yellowing or discoloration of metallic surfaces (e.g. stainless steel, copper, brass and bronze) that are exposed to elevated temperatures.
- metallic surfaces e.g. stainless steel, copper, brass and bronze
- Such processes include annealing treatments in an inert atmosphere coupled with pickling processes, as are described in the Japanese patent application (applicant. JP 06079990, published on April 19, 1994). Furthermore, the corrosion resistance can be increased by electrolytic polishing.
- Such layers act as a diffusion barrier for oxygen.
- they are applied in thicknesses of more than 1 ⁇ m baked thickness (DE-A 197 14 949). Thinner layers, for example based on sol-gel, lead to optically disturbing interferences.
- Sol-gel processes are used in particular to apply glass-like layers.
- the technique of the sol-gel process is well known to the person skilled in the art and is described in detail, for example, in Brinker-Scherer, The Physics and Chemistry of Sol-Gel Processing, Sol-Gel Science, Academic Press (1990).
- Sol-gel processes are hydrolysis-condensation reactions (for example of silanes such as R n SiX ⁇ n or a mixture of such melanes, where R is for example hydrogen or an aliphatic or aromatic radical and X is a hydrolyzable radical such as alkoxy or can be phenoxy), in which structures with, for example, Si-O bonds are formed with simultaneous branching and crosslinking of this product after complete removal of water from the reaction product (chemical in the sense of condensation; water from the solvent, if present).
- the particle size (particle diameter) in the structures is 100 nm or less.
- Si-O layers By removing the solvent, a gel (with increased viscosity and increased degree of crosslinking) is formed, which is then dried to form an airgel and finally, by further heating (at about 500 ° C.), becomes a (in the case of using silanes: glass-like) layer which contains both silicon and oxygen (in a stoichiometric ratio of about 1: 2).
- silanes: glass-like glass-like layers which contains both silicon and oxygen (in a stoichiometric ratio of about 1: 2).
- Such a sol-gel process is for silanes of the general formula R n SiX 4 . n described in DE-A 197 14 949.
- the glass-like layers described there improve not only the corrosion / tarnish protection, but also the possibility of cleaning and, depending on the thickness, the scratch resistance of the substrate.
- they are susceptible to cracks, presumably due to shrinkage processes and differences in the expansion coefficients, with layer thicknesses of 2 ⁇ m and above.
- This sensitivity to cracks is due to the fact that the layers treated in this way at temperatures above approx. 350 ° C. due to outgassing the organic components lose their flexibility.
- more complex geometries cannot be coated with these thickness tolerances in terms of production technology. If the layers are applied with a smaller thickness (less than 1000 nm), they are not sensitive to the formation of cracks and can also be applied in a manageable manner using thinners, but they show interference colors that the user regularly sees as undesirable.
- thicker sol-gel layers are on surfaces of stainless steel, but also on other metals such as copper, brass and bronze, especially if they are used in the household (ovens, stoves , etc.), but technically and practically uninteresting, since the cracking leads to loss of function.
- the glass-like Si-O layers require temperatures which are above the starting temperature of the respective metal, e.g. usual stainless steels (stainless steel), (the starting temperatures for steel are usually around 200 ⁇ 20 ° C).
- structure of the slot effect means on the one hand densification processes of the layer, the densified layer then acting as a diffusion barrier for oxygen, but on the other hand also chemical reactions at the interface with the steel or metal / alloy, which prevent the formation of visually disturbing oxide layers ,
- These network converters are built into the Si-O network and interrupt it, so that the modified Si-O network approaches the water glass to a greater or lesser extent depending on the concentration of the alkali (s) used.
- the effect of the network converters is, among other things, to lower the compression temperatures of the layers. In other words: the structure of the protective effect and thus the protection against oxygen can be generated at lower temperatures compared to sol-gel processes without the use of network converters. This in turn means that the temporal or temperature-reversed sequence is reversed: the tarnish protection layer can form at times or at temperatures before or below which visible tarnish colors appear.
- network converters has one major disadvantage: it generally reduces the chemical resistance of the layers. If chemically particularly resistant (glass-like) layers are to be obtained, they must be baked in an oxygen-free atmosphere (e.g. under nitrogen or possibly also argon as protective gas) without using network converters. However, this in turn requires a relatively high level of effort, which makes a sol-gel process under an inert gas atmosphere economically unattractive.
- an oxygen-free atmosphere e.g. under nitrogen or possibly also argon as protective gas
- sol-gel processes based on suitable Ti, Zr, Al and / or B compounds are not used. This is partly because the protective effect is not built up at temperatures below the start-up temperature, so the stainless steel / metal / alloy already yellowed / tarnished during the protective treatment.
- An object which the inventors have therefore set themselves in view of the prior art has been to provide a process which makes it possible to produce surfaces of stainless steel, but also of other metals or alloys such as copper, brass and bronze, without using To coat network converters and still prevent the tarnish protection layer from forming at times or at temperatures after or above which visible tarnish colors have already appeared. After such a process has been carried out, the metallic original impression of the surface should be retained, even if the sol-gel process is carried out on the basis of suitable Ti, Zr, Al and / or B compounds.
- a second object of the inventors was to provide a method which provides good corrosion / tarnishing protection for the stainless steel or the other metals and alloys even at continuous use temperatures up to 450 ° C., preferably up to 500 ° C. and even up to 550 ° C, while maintaining the metallic original impression and the possibility of simple or improved cleaning of the substrate, ie metal or alloy, is guaranteed and at the same time the occurrence of interference colors with low Layer thicknesses preferably prevented, but at least significantly reduced. Because of the small layer thicknesses, the problem of keeping the coating susceptible to cracking is also solved.
- step (i) which provides for treatment of the metallic surface in order to achieve it
- Step (ii) which involves mechanical and / or chemical roughening of the metallic surface to be coated, in order to achieve the second of the above-mentioned objects.
- Step (iii) which involves coating the roughened surface using e.g. of a sol gel
- Process comprises, wherein the layer is applied in a thickness of less than 1000 nm, preferably 800 nm or less, 600 nm or less, 500 nm or less, or 400 nm or less, and which solves the third task when it step (ii) succeeds.
- a variant of this method also comprises the optional step (i) and then to carry out step (ii) simultaneously with the coating step (iii), step (ii) representing the introduction of a second phase and the layer having a thickness of less than 1000 nm , preferably 800 nm or less, 600 nm or less, 500 nm or less, or 400 nm or less.
- one aspect of the present invention relates to the methods outlined above.
- Another aspect of the present invention relates to a component, e.g. a metal sheet made of chrome-nickel steel that has been subjected to such a process.
- step (i) can be dispensed with without endangering the tasks defined above. This can be done by using a special steel is selected that starts relatively late (even in an oxygen-containing atmosphere). Examples of such special steels are Cro ifer 45 and Cronifer 2 from Krupp VDM.
- step (i) is also not necessary if the stoving is carried out in an inert or non-oxidizing atmosphere (then, according to the prior art, no network converter is necessary either).
- step (i) is indispensable in the other cases if the task (s) to be solved is to provide surfaces free from tarnish colors and if the aforementioned preconditions are not met ( no use of special steel as defined in the penultimate paragraph; no network converters; no work in a non-oxidizing atmosphere).
- the metallic surfaces to be treated are preferably those of stainless steels, in particular surfaces of the steel types 1.4301 and 1.4016 (chromium-nickel or chromium steel), which otherwise, that is to say untreated, at working temperatures of 200 ° C. and oxidize higher in the air atmosphere and consequently turn yellow during substep (iii) (in the absence of network converters).
- a first step (i) of the method according to the invention consists in treating the metallic surface in order to raise its starting temperature and thus to solve the first of the three above-mentioned tasks.
- Step (i) of the preferred embodiment ( ⁇ ) can be carried out by any method in which the metal can form a tarnish protection before there is a discolouring oxide layer.
- This step is preferably the method described in EP-A 1 022 357.
- Step (i) preferably comprises the steps of heating the metallic surface up to 550 ° C. and then pickling the heated surface with mineral acid (as described in EP-A 1 022 357). It is particularly preferred to increase the start-up temperature of the metallic surface to about 300 ° C.
- step (iii) can be carried out in an oxygen atmosphere without the need for network converters.
- step to increase the starting temperature or “step to increase the starting temperature”.
- step (ii) by means of which the metallic surface is roughened
- step (iii) a conventional coating process, e.g. a sol-gel process, one after the other or at the same time, with the result that the tarnish protection of the metal / alloy treated in this way, such as steel, copper, brass or bronze, is not lost even at temperatures up to 550 ° C.
- the organic constituents for example methyl, ethyl, 1-propyl, isopropyl residues; for chemistry in general and the organic residues in particular see below, page 9) of the layers are not completely burned out , Then you get a easy to clean, resistant to tarnishing surface low • surface energy.
- the temperature at which the burnout must take place it only requires little effort to test the temperature at which the burnout must take place in accordance with this preferred embodiment. A precise temperature range or even value cannot be determined, since this depends on numerous parameters familiar to the person skilled in the art (for example chemical, qualitative and quantitative composition). Burning out takes place regularly at a temperature which is above the (later) application temperatures.
- the burnout should be carried out at temperatures of 450 ° C. or above 450 ° C., preferably at about 470. at about 480, at about 490 or at about 500 ° C.
- the interference colors of the layers which occur with small layer thicknesses can be suppressed by mechanical and / or chemical and / or physical roughening of the (stainless) steel surface.
- physical roughening is defined as the (physical) introduction of second phases (such as light-scattering particles or pores). Examples of the different types of roughening are Grinding or blasting, in particular sandblasting or shot peening (mechanical), etching, e.g.
- step (i) is a pure cleaning process for removing the oxide layer without forming a microstructure in the (substrate) surface to be treated, but also the incorporation of light-scattering particles and / or pores (physically).
- Suitable light-scattering particles are, in particular, TiO 2 and ZrO 2, in general all those particles whose refractive index is greater than that of the respective layer, in any case the geometries of the mechanical, chemical or physical roughening which interfere with the interference according to the invention are of the order of magnitude from 2 to 1000 nm, preferably in a range from 15 to 500 nm, in a range from 40 to 300 nm, in a range from 50 to 250 nm or in a range from 100 to 200 nm (range specifications in each case based on the diameter ).
- Preferred ranges for the chemical and mechanical roughness are 50-1000 nm, in particular 200-500 nm.
- Preferred ranges for the (light-scattering) particles are 2-30 nm, in particular 5-25 or 10 - 20 nm (depends mainly on the type of particle and its refractive index).
- Preferred areas for the pores are 2-100 nm, in particular 5-50 nm.
- step (ii) When using the light-scattering particles or pores in step (ii) to prevent the interference, attention must be paid to a certain ratio between Me (e.g. Si) of the matrix on the one hand and particles or pores on the other. It is essential that the volume fraction of particles / pores in the fired layer is 0.05-20%, preferably 0.1-15%, but particularly preferably 1-5%.
- Me e.g. Si
- Particles can be incorporated by adding light-scattering particles during the sol-gel process finally, due to their refractive index (which differs from that of the matrix, that is to say the layer) and small size of approximately 2 to 30 nm (for example 20 nm; specified as particle diameter), they can prevent the interference colors from occurring or at least significantly reduce their intensity .
- Suitable particles are, for example, Al 2 O 3 , TiO 2 , ZrO 2 and SiO 2 .
- a blowing agent is added during the sol-gel process, which leaks at the latest during the stoving process, i.e. during the conversion of the airgel into the coating, leaving pores behind.
- the layers applied according to the present invention are transparent, so they do not change the appearance of the metallic surface.
- starting compounds for the hydrolysis and subsequent condensation are compounds of the general formula R n MeX 4 . n , where X and R are defined as in DE-A 197 14 949 (column 2, lines 18-34; column 3, lines 1-9), where n is 0, 1, 2 or 3, and where Me is selected is made of Si, AI, Zr, B and Ti.
- Me AI or B, it is understood by the person skilled in the art that the above-mentioned formula because of the trivalent nature of the central atoms AI and BR n MeX 3 . n must be.
- the organic radicals R and X generally have 1 to 16 carbon atoms, with 1 to 12, in particular 1 to 8, carbon atoms being preferred (for the aryl radicals, of course, only that 6 or 10 carbon atoms are preferred).
- Residues with 1 to 4 (alkyl, alkenyl, akinyl) or 6 (aryl) or 7 to 10 (aralkyl, alkaryl) carbon atoms are particularly preferred.
- the ratio R: Me (corresponding to n) on a molar basis preferably being on average from 0.2 to 1.5.
- the hydrolysis and condensation reactions are preferably carried out in a solvent mixture of water and an organic solvent such as methanol, ethanol, acetone, ethyl acetate, DMSO or dimethyl sulfone.
- the organic solvent can also be a mixture of two or more solvents.
- the solvents mentioned and which can be used according to the invention are all miscible with water, so that the hydrolysis can take place without phase separation.
- the coating can be applied to the metallic surfaces in various known ways: by dipping, spinning, spraying, flooding or rubbing in; the metallic surface in the bath of e.g. Immersing silanes is a preferred method.
- the thickness with which the layers are applied according to the invention are in a range from 100 to less than 1000 nm, preferably in a range from 200 to 850 nm, particularly preferably in a range from 300 to 750 nm, very particularly preferably 350 to 600 nm.
- layer thicknesses of 100 to 300 nm, more preferably 100 to 200 nm, are also preferred for the purposes of the present invention. example
- Chromium steel 1.4016 (without tarnish colors) pickled (step (i)) and then shot peened (step (ii)) according to the process described in EP-A 1 022 357 was treated with a 5% solution of Dynasil GH 02 (According to the manufacturer, Degussa Hüls, the Dynasil solution is based on hydrolyzed and partially condensed silanes) dip-coated in 1-butanol, dried and baked at 550 ° C. The steel did not tarnish after the treatment even at a temperature of 500 ° C (10 h holding time). No interference colors were observed.
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10064134 | 2000-12-19 | ||
DE10064134A DE10064134A1 (en) | 2000-12-19 | 2000-12-19 | Process for finishing metallic surfaces to avoid thermal tarnishing |
PCT/DE2001/004824 WO2002050330A2 (en) | 2000-12-19 | 2001-12-19 | Method for improving metal surfaces to prevent thermal tarnishing |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1381711A2 true EP1381711A2 (en) | 2004-01-21 |
EP1381711B1 EP1381711B1 (en) | 2007-06-06 |
Family
ID=7668357
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01991656A Expired - Lifetime EP1381711B1 (en) | 2000-12-19 | 2001-12-19 | Method for improving metal surfaces to prevent thermal tarnishing |
Country Status (5)
Country | Link |
---|---|
US (2) | US20030232206A1 (en) |
EP (1) | EP1381711B1 (en) |
DE (2) | DE10064134A1 (en) |
ES (1) | ES2287183T3 (en) |
WO (1) | WO2002050330A2 (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8569665B2 (en) * | 2006-10-17 | 2013-10-29 | Meyer Intellectual Properties Limited | Cookware with tarnish protected copper exterior |
DE102008013166A1 (en) * | 2008-03-07 | 2009-09-10 | Iplas Innovative Plasma Systems Gmbh | Method for producing an interference color-free protective layer |
JP5899615B2 (en) * | 2010-03-18 | 2016-04-06 | 株式会社リコー | Insulating film manufacturing method and semiconductor device manufacturing method |
FR2988404B1 (en) * | 2012-03-21 | 2015-02-13 | Centre Techn Ind Mecanique | METHOD FOR DEPOSITING ANTI-CORROSION COATING |
CN105849312A (en) * | 2013-12-18 | 2016-08-10 | 波里格拉特股份有限公司 | Method for the production of colored stainless steel surfaces |
DE102014210671A1 (en) | 2014-06-05 | 2015-12-17 | BSH Hausgeräte GmbH | METHOD FOR PREVENTING INTERFERENCE COLORS ON THIN-COATED METAL SURFACES |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55127561A (en) * | 1979-03-26 | 1980-10-02 | Canon Inc | Image forming member for electrophotography |
US5192410A (en) * | 1988-07-28 | 1993-03-09 | Nippon Steel Corporation | Process for manufacturing multi ceramic layer-coated metal plate |
JPH03130356A (en) * | 1989-10-13 | 1991-06-04 | Masuzo Hamamura | Rust-and corrosion-preventive working method effective over a long term |
US5272295A (en) * | 1991-01-23 | 1993-12-21 | Sumitomo Electric Industries, Ltd. | Electric contact and method for producing the same |
US5420400A (en) * | 1991-10-15 | 1995-05-30 | The Boeing Company | Combined inductive heating cycle for sequential forming the brazing |
EP0690517B1 (en) * | 1994-05-30 | 2003-10-01 | Canon Kabushiki Kaisha | Rechargeable lithium battery |
EP0798130B1 (en) * | 1996-03-29 | 2000-06-07 | Agfa-Gevaert N.V. | Lithographic plates with coating |
JP4104026B2 (en) * | 1996-06-20 | 2008-06-18 | 財団法人国際科学振興財団 | Method for forming oxidation passivated film, fluid contact parts and fluid supply / exhaust system |
EP0831538A3 (en) * | 1996-09-19 | 1999-07-14 | Canon Kabushiki Kaisha | Photovoltaic element having a specific doped layer |
TW338729B (en) * | 1996-09-30 | 1998-08-21 | Kawasaki Steel Co | Hot roll stainless steel tape and the manufacturing method |
DE19645043A1 (en) * | 1996-10-31 | 1998-05-07 | Inst Neue Mat Gemein Gmbh | Process for the production of substrates with high-temperature and UV-stable, transparent, colored coatings |
US5869141A (en) * | 1996-11-04 | 1999-02-09 | The Boeing Company | Surface pretreatment for sol coating of metals |
DE19708808B4 (en) * | 1997-03-04 | 2010-10-21 | Biedermann, Bianca | Method and device for applying transparent protective layers to objects |
US5881972A (en) * | 1997-03-05 | 1999-03-16 | United Technologies Corporation | Electroformed sheath and airfoiled component construction |
DE19714949A1 (en) * | 1997-04-10 | 1998-10-15 | Inst Neue Mat Gemein Gmbh | Process for providing a metallic surface with a glass-like layer |
DE19719948A1 (en) * | 1997-05-13 | 1998-11-19 | Inst Neue Mat Gemein Gmbh | Production of nano-structured mouldings and coatings |
JP3404286B2 (en) * | 1998-04-16 | 2003-05-06 | 日本パーカライジング株式会社 | Metal surface treatment method, and metal member having a surface obtained by the surface treatment method |
ES2162546B1 (en) * | 1999-01-22 | 2003-05-01 | Bsh Fabricacion Sa | METHOD AND INSTALLATION FOR THE SURFACE TREATMENT OF STAINLESS STEEL. |
-
2000
- 2000-12-19 DE DE10064134A patent/DE10064134A1/en not_active Ceased
-
2001
- 2001-12-19 ES ES01991656T patent/ES2287183T3/en not_active Expired - Lifetime
- 2001-12-19 EP EP01991656A patent/EP1381711B1/en not_active Expired - Lifetime
- 2001-12-19 WO PCT/DE2001/004824 patent/WO2002050330A2/en active IP Right Grant
- 2001-12-19 DE DE50112610T patent/DE50112610D1/en not_active Expired - Lifetime
-
2003
- 2003-06-19 US US10/465,243 patent/US20030232206A1/en not_active Abandoned
-
2005
- 2005-11-04 US US11/267,680 patent/US20060057284A1/en not_active Abandoned
Non-Patent Citations (1)
Title |
---|
See references of WO0250330A2 * |
Also Published As
Publication number | Publication date |
---|---|
US20030232206A1 (en) | 2003-12-18 |
ES2287183T3 (en) | 2007-12-16 |
WO2002050330A3 (en) | 2003-11-20 |
EP1381711B1 (en) | 2007-06-06 |
DE10064134A1 (en) | 2002-06-27 |
US20060057284A1 (en) | 2006-03-16 |
WO2002050330A2 (en) | 2002-06-27 |
DE50112610D1 (en) | 2007-07-19 |
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