WO2001066830A2 - Verfahren zum aufbringen einer metallschicht auf leichtmetalloberflächen - Google Patents
Verfahren zum aufbringen einer metallschicht auf leichtmetalloberflächen Download PDFInfo
- Publication number
- WO2001066830A2 WO2001066830A2 PCT/DE2001/000944 DE0100944W WO0166830A2 WO 2001066830 A2 WO2001066830 A2 WO 2001066830A2 DE 0100944 W DE0100944 W DE 0100944W WO 0166830 A2 WO0166830 A2 WO 0166830A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- compounds
- iron
- deposition
- layers
- bath
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/20—Electroplating: Baths therefor from solutions of iron
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
Definitions
- the invention relates to a method for applying a metal layer on surfaces of light metals, in particular on surfaces of aluminum, magnesium and their alloys, applications of the method for coating cylinder running surfaces of internal combustion engines and of rotationally symmetrical parts with layers with very high wear resistance, in particular valves , Nozzles and other parts of high-pressure injection systems for motor vehicle engines and a nanocrystalline iron / phosphor layer.
- aluminum materials include nickel / phosphorus layers and nickel layers applied by electroplating, in which hard materials are embedded in the layer as a dispersion, for example with silicon carbide as a dispersed substance, can be compensated in a suitable manner, so that the surface properties of the light metal meet the requirements for cylinder surfaces in internal combustion engines. These layers give the surfaces good corrosion resistance and wear protection. Alternatively, good wear properties can also be achieved with hard chrome layers on the light metal surfaces, optionally aftertreated by a plasma nitrate. Alternatively, thermal spray processes can also be used, for example the powder or wire spray process.
- tungsten carbide particles can be applied to the surfaces in a metal matrix, for example in a cobalt or cobalt / chrome layer, so that a very adherent and in particular particularly corrosion-resistant layer is formed.
- Plasma spraying can also be used to produce tungsten carbide layers that have very good tribological behavior.
- the layers mentioned have different disadvantages depending on the production process: in some cases, the production of these layers is extremely complex and therefore expensive, so that they are not suitable for mass use as in automobile construction (for example detonation spraying and HVOF technology).
- the described electroplated nickel / phosphor layers do not have sufficiently good tribological properties.
- An alternative coating system is specified in DE 196 53 210 A1. These are corrosion-resistant layers of iron that contain 0.02 to 0.5% by weight of nitrogen. It is stated that these layers can be electroplated onto aluminum and its alloys. As an application of such layers, the coating of the inside of aluminum cylinders of internal combustion engines is given as an example.
- a deposition bath containing iron (II) ions is used for the deposition of the layers and the layer is deposited electrolytically using an anode consisting of iron or preferably using an insoluble anode which consists of a film of an oxide of ruthenium, iridium, tantalum, Titanium plate containing tungsten, rhodium, cobalt or manganese.
- US-A-4,746,412 discloses a bath for the deposition of iron / phosphor alloy layers.
- Such baths contain iron (II) ions, hypophosphorous acid, a hypophosphite, phosphorous acid or an orthophosphite and optionally boric acid or aluminum chloride.
- the layers obtained have a phosphorus content of 0.1 to 9.9% by weight.
- Layers are applied, for example, to the inner walls of pistons from combustion applied motors. According to the information in this document, the layers have good tribological properties.
- the present invention is therefore based on the problem of avoiding the disadvantages of the known coating processes and, in particular, of finding a process with which functional layers are formed on the light metal surfaces, on the one hand with regard to the wear properties required for certain applications, the corrosion resistance and the adhesive strength of the Layers on the surfaces met the desired specifications.
- the process should be able to be used in industrial mass production. For this purpose, it should be easy to monitor, so that there is no need for ongoing analyzes and constant replenishment of chemicals for the bath composition.
- the The properties of the layers that can be deposited using the method fluctuate only within a narrow tolerance range, without the need for complex monitoring and control technology. Rather, the method should have the greatest possible automation potential.
- the method should also be able to reproducibly deposit such functional layers on cylinder running surfaces of internal combustion engines in a uniform thickness.
- the process according to the invention fulfills the very important process capability for use on an industrial scale, the properties of the functional layers which can be deposited by the process being easily maintained within narrow tolerance limits.
- iron is electrolytically deposited from an aqueous deposition bath containing Fe (II) compounds using dimensionally stable, inert (insoluble) anodes in the deposition bath on the surfaces of workpieces.
- Fe (II) salts for example FeSO 4 or FeCl 2 , are preferably used as Fe (II) compounds.
- Fe (III) compounds can also be used.
- an insoluble, inert anode is used in the process according to the invention, for example an activated titanium anode, an activated stainless steel anode, a graphite anode or a lead anode.
- the titanium and stainless steel anodes are activated, for example, by platinizing these electrodes. As a result, the overvoltage of the electrochemical reactions taking place at these electrodes is reduced.
- the geometry of the anodes does not change during the coating process, so that the geometric relationships once provided between the anodes and the surfaces to be coated remain constant and layers with an extremely uniform and constant layer thickness distribution are formed.
- measures must be taken to separate the anode sludge formed. When using inert anodes, however, no anode sludge is formed.
- rod-shaped dimensionless anodes can be used to coat the cylinder surfaces of internal combustion engines, which are sunk concentrically into the cylinders for coating in the axial direction. Due to the rotational symmetry of the rod anode / cylinder pair, a constant electric field density is generated in the cylinder space during electrolytic deposition, so that the cathodic current density on the cylinder walls is identical at all points. A very uniform thickness of the deposited functional layer can thereby be achieved. Since the geometry of the anode does not change, these conditions remain constant over a long period of time. Likewise, a very uniform layer thickness is also achieved on other rotationally symmetrical parts that are used, for example, in automobile construction. For example, valve parts and nozzles of high-pressure injection systems for motor vehicles with very wear-resistant layers can be coated uniformly on the outside if a suitable geometry of the pair of workpiece to be coated and the anode is selected.
- the method can also be easily automated by, for example, using an appropriate device to sink the anodes into the cylinder to a precisely defined depth and to fill the deposition bath into the cylinder.
- the electroplating device can be can be automated and reproducibly moved to the next cylinder or engine block.
- the deposition solution is removed from the coated cylinder. Subsequently, further solutions are filled into the cavity to rinse and treat the cylinder walls.
- the cylinder walls can be pretreated beforehand by filling pretreatment solutions and rinsing liquids into the cylinders.
- the deposited iron layers adhere extremely well to the light metal surfaces. It is noteworthy that this can also be achieved without extensive pretreatment, for example by zincate treatment, which usually has to be used, for example, to nickel-plate aluminum surfaces. The coating process is therefore easy to carry out.
- the concentration of the iron compounds (Fe (II) compounds and Fe (III) compounds) in the deposition bath can only be kept constant with considerable effort.
- the Fe (II) compounds become poor in the iron deposition in the solution and the necessity to set a constant concentration of these compounds without complex
- the deposition bath be filled into the cylinders and remain there during the deposition.
- the deposition bath only relatively small volumes of the deposition bath are kept in a bath tank, so that a certain volume conversion of the Fe (II) compounds becomes even more noticeable as a change in concentration.
- insoluble (inert) anodes are used in electrolytic metal deposition processes, it is basically possible to add the Fe (II) compounds used in the deposition to the bath in the form of solutions of these compounds or of solid salts. This leads to the problems described above.
- the addition of solid iron salts to the deposition baths is not a solution here, since such a method of addition is known to be always difficult and technically complex, so that it is also out of the question.
- Fe (III) compounds formed on the insoluble anode can be regarded as parasitic in the current state of the art, because the Fe (III) compounds first have to be reduced cathodically to Fe (II) compounds. As a result, the current efficiency of the iron separation from the separation bath drops.
- a step according to the invention of the claimed process therefore essentially starts from the problem that the Fe (II) compounds are consumed by the iron deposition and that fluctuating concentrations the bath components, especially the Fe (II) compounds, are intolerable.
- the solution to this problem is to form the Fe (II) compounds by bringing the Fe (III) compounds formed on the anodes during their oxidation into contact with iron parts and reacting them chemically, whereby dissolve the iron parts.
- the claimed process is extremely elegant and simple to carry out compared to processes in which the Fe (II) compounds are added to the deposition bath in the form of dissolved salts when insoluble anodes are used, since Fe (II) compounds are essentially only ever form to an extent how Fe (III) compounds are formed at the anode by the electrochemical oxidation reaction.
- the content of the Fe (II) compounds is thus automatically adjusted to the desired value. Exceeding this value is practically impossible, as well as falling below this value if suitable process parameters are set beforehand. This eliminates error-prone monitoring and management of the bath through ongoing analyzes and replenishment with regard to the Fe (II) concentration, as when supplementing with solutions of the Fe (II) compounds or their solid salts.
- the iron parts are preferably housed in a separate container.
- the deposition bath is circulated between the treatment compartment, in which the surfaces to be coated and the anode are located, and this separate container.
- the bath solution is preferably passed into the separate container, for example pumped, immediately after contact with the anode, on which Fe (III) compounds are formed by electrochemical reaction, in order to bring the Fe (III) compounds into contact to avoid with the cathode surface. Otherwise, the Fe (III) compounds would be parasitically reduced to Fe (II) compounds at this point, so that the cathodic current yield would be reduced even further.
- Fe 3+ ions are consumed in the separate container according to the following reaction equation, again forming Fe 2+ ions:
- Fe (II) compounds It is therefore necessary to supplement Fe (II) compounds. In the manner according to the invention, it is entirely sufficient to bring the bath solution into contact with a sufficiently large iron surface.
- Iron granules, iron chips or iron pellets are preferably used in the separate container.
- the size and shape of the separate container and the choice of the amount, type and size of the iron parts can be optimized according to the known principles of chemical process engineering.
- the composition of the deposition solution nevertheless changes with prolonged operation. This was found in particular when the method was carried out at a relatively high cathodic current density.
- a high anodic current density for example in the range from 10 A / dm 2 to 100 A / dm 2 , is required for industrial use of the method, in particular in mass production, for economic reasons.
- the change in the composition of the bath (increase in the iron concentration ) could be attributed to the low cathodic current efficiency of the iron deposition under these conditions, while the anodic current yield is not affected in principle.
- the anodic current yield corresponds to the cathodic current yield for iron deposition over time.
- the anodic current density is increased at least temporarily to such an extent that the anodic current yield for the oxidation of the Fe (II) compounds to Fe (III) compounds is at least as great as the cathodic current yield for iron deposition from the deposition bath.
- hydrogen is also developed in the deposition bath on the workpieces to be coated.
- the anodic current density is set to the desired value by selecting the anode surface. This can be achieved in a simple manner by suitable dimensioning of the anode.
- the geometry of the anode is selected for a specific cathodic current density. If components to be machined with workpiece surfaces of different sizes are used or if the current density is changed, the cathodic see current density also changes, so that an anode with likewise adapted dimensions must be used to adapt to these changed conditions. However, this is complex and cannot easily be carried out in an industrial manufacturing process requiring flexibility.
- part of the anode surface is switched on and off intermittently, the ratio of the switch-off to the switch-on time being set on a value which is so great that the anodic current yield for the oxidation of the Fe ( II) compounds to Fe (III) compounds time-averaged is as great as the cathodic current yield for iron deposition from the deposition bath.
- the anodic current density is temporarily increased in order to lower the anodic current yield and in this way to keep the formation balance of the Fe (II) compounds in the overall system constant over time.
- the production rate of Fe (III) compounds to Fe (II) compounds is adapted to the respective conditions, so that on the one hand in stationary equilibrium, Fe (II) compounds cathodic reaction are consumed on the workpiece surface, on the other hand the Fe (II) compounds are formed by the dissolution of the iron parts by their reaction with the Fe (III) compounds and finally by the anode reaction Fe (II) compounds, respectively adapted to the changing conditions, are consumed:
- the concentrations of the Fe (II) and Fe (III) compounds can be adjusted very easily at any time by controlling the anodic current yield according to the invention.
- a preferred procedure for controlling (lowering) the anodic current yield for the oxidation of the Fe (II) to the Fe (III) compounds is also to surround the anode with a diaphragm.
- a liquid-permeable fabric can be used as the diaphragm. This at least prevents or at least severely hinders the convective transport of Fe (II) compounds to the anode.
- the deposition solution additionally contains at least one compound from the group consisting of hypophosphite, orthophosphite, molybdenum compounds and tungsten compounds. contains.
- the salts for example alkali metal salts (NaHP0 2 , KHP0 2 , Na 2 HP0 3 , K 2 HP0 3 etc.), and their acids (H 2 P0 2 , H 3 P0 3 ) can be used as hypophosphite and orthophosphite compounds.
- Alkaline molybdate in particular can be used as the molybdenum compound and alkali tungstate in particular, but also other molybdate and tungsten can be used as tungsten compounds.
- iron alloys are formed with phosphorus, molybdenum and / or tungsten.
- very hard functional layers are formed which additionally have a high wear resistance.
- the layers which can be produced in the deposition bath using molybdenum and / or tungsten compounds also have a high hardness and very good corrosion resistance.
- the tribological properties of the layers obtained with the aforementioned bath additives are also very good: in tribological tests, no tears were found from the layers applied to the light metal surfaces.
- the layers that can be produced with these additives are particularly suitable for coating cylinder running surfaces of internal combustion engines.
- the hypophosphite and orthophosphite compounds which are sometimes labile against oxidation, are not oxidized at the inert, dimensionally stable anode. Therefore, their usability under the conditions chosen here with an inert anode was not predictable.
- iron / phosphor layers are deposited which contain phosphorus in an amount of 0.5 to 3% by weight, preferably about 1% by weight. These layers were examined using physical methods (scanning electron microscopy, X-ray diffraction studies). It was found that the iron / phosphorus alloys produced are nanocrystalline, ie consist of crystallites with a size of at most about 500 nm, preferably at most 200 nm. This was determined with scanning electron microscope examinations using the backscattering method.
- the aqueous separating bath preferably contains the bath components in dissolved form.
- the bath can also contain acids, for example inorganic acids, preferably hydrochloric acid, sulfuric acid, fluoroboric acid and / or perchloric acid.
- Particularly suitable organic acids are sulfonic acids, such as methanesulfonic acid, amidosulfonic acid, formic acid and acetic acid.
- the bath can form complexing agents for iron to influence the separation potential as well as other additives such as wetting agents to influence the surface tension of the bath. see inhibitors for influencing the deposition properties, other additives influencing the deposition or other additives.
- Such additives are generally known from the electroplating of metals.
- the light metal surfaces are pretreated before being coated with the deposition bath.
- they can be cleaned, for example, with a solution containing a wetting agent and optionally acid or base.
- the surfaces are then preferably pickled in order to increase the adhesive strength of the functional layer on the surfaces.
- an alkaline stain consisting of an aqueous solution of NaOH can be used for this purpose.
- the surfaces are then preferably treated with a solution with which iron can be cemented onto the light metal surfaces.
- an aqueous hydrochloric acid solution of FeCI 3 is used.
- the functional layer is then deposited from the deposition bath.
- a direct current method is generally used for this.
- a pulse current method can also be used, in which the workpiece surface is briefly subjected to a cathodic current pulse and then either to a plating break or to an anodic current pulse. Galvanizing breaks can also be provided between the cathodic and anodic current pulses. With these methods, the uniformity of the metal deposition can be increased if necessary.
- the temperature of the deposition bath is optimized depending on the bath composition. A temperature above room temperature, for example 60 ° C., has proven advantageous. For economic reasons, the temperature of the bath solution in the separate container containing the iron parts should be the same as the temperature in the separation container.
- the light metal surfaces are rinsed between the individual process steps and after the metal deposition has been completed.
- the individual treatment fluids can each be filled into the cylinder cavities for coating cylinder running surfaces of internal combustion engines.
- the cavities are connected via suitable pump systems to the separate container containing the iron parts and further storage containers in which the individual treatment liquids are located.
- the treatment liquids and the rinsing water are pumped into the cavities one after the other according to a precisely predetermined time schedule, left there for a certain period of time and removed again after the end of the respective treatment.
- the other required process conditions in the cavities are set, for example a suitable forced convection in the treatment liquids, flushing the liquids with oxygen or air and setting the desired treatment temperatures. With this procedure, the treads can easily be automatically covered with the functional layer.
- Example 1 With the degradation rates for Fe 3+ determined in Example 1, the necessary effective surface of the iron parts (chips or granules) for Fe 3+ reduction and thus for the regeneration of the Fe 2+ concentration in the bath solution could be determined depending on the current density:
- the regeneration process could also be carried out under technically practicable conditions.
- a light metal sheet made of AISi10 was treated as follows for the following coating:
- Steps 2 to 5 were repeated once.
- the deposition was carried out under the following conditions:
- the hardness of the layer measured according to Vickers, was 700 ⁇ 20 HV 01
- the stresses in the layer were determined using a spiral contractometer.
- the layers had tensile stress (deflection about 290 °).
- the values obtained corresponded to those with electrodeposited nickel and electrolessly deposited nickel / phosphor layers.
- the wear coefficient was determined in [mm 3 / Nm], ie the volume removal on the piston ring and the cylinder surface.
- the coefficient of friction f a was also determined as a coefficient from the torque and the normal force F N applied.
- the comparison values in the right column indicate the values for gray cast iron instead of the iron coating.
- the comparison values in the right column indicate the values for gray cast iron instead of the iron coating.
- FIG. 1 shows a schematic illustration of a preferred electrochemical arrangement for iron deposition on the wall surfaces of cylinders of internal combustion engines.
- the interior 2 of a cylinder 1 consisting of an aluminum alloy is filled with electrolyte liquid up to level 3.
- An anode 4 made of titanium, which is coated with ruthenium oxide, is sunk concentrically into the interior 2.
- the anode 4 is surrounded by a diaphragm 5 which is resistant to the electrolyte liquid and is made of polypropylene, for example.
- the interior 2 is closed with a cover (not shown).
- the cylinder is 1 further connected via a supply line 6 to the negative pole and the anode 4 via a supply line 7 to the positive pole of a current source (not shown).
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- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Cylinder Crankcases Of Internal Combustion Engines (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE50104686T DE50104686D1 (de) | 2000-03-09 | 2001-03-07 | Verfahren zum aufbringen einer metallschicht auf leichtmetalloberflächen |
US10/220,939 US7138043B2 (en) | 2000-03-09 | 2001-03-07 | Method for applying a metal layer to a light metal surface |
EP01929243A EP1264009B1 (de) | 2000-03-09 | 2001-03-07 | Verfahren zum aufbringen einer metallschicht auf leichtmetalloberflächen |
AU56113/01A AU5611301A (en) | 2000-03-09 | 2001-03-07 | Method for applying a metal layer to a light metal surface |
JP2001565431A JP4431297B2 (ja) | 2000-03-09 | 2001-03-07 | 軽金属表面に金属層を施与するための方法 |
AT01929243T ATE283935T1 (de) | 2000-03-09 | 2001-03-07 | Verfahren zum aufbringen einer metallschicht auf leichtmetalloberflächen |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10013298.7 | 2000-03-09 | ||
DE10013298A DE10013298C2 (de) | 2000-03-09 | 2000-03-09 | Verfahren zum Aufbringen einer Metallschicht auf Leichtmetalloberflächen und Anwendung des Verfahrens |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2001066830A2 true WO2001066830A2 (de) | 2001-09-13 |
WO2001066830A3 WO2001066830A3 (de) | 2002-03-21 |
Family
ID=7635296
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/DE2001/000944 WO2001066830A2 (de) | 2000-03-09 | 2001-03-07 | Verfahren zum aufbringen einer metallschicht auf leichtmetalloberflächen |
Country Status (9)
Country | Link |
---|---|
US (1) | US7138043B2 (de) |
EP (1) | EP1264009B1 (de) |
JP (1) | JP4431297B2 (de) |
AT (1) | ATE283935T1 (de) |
AU (1) | AU5611301A (de) |
DE (2) | DE10013298C2 (de) |
ES (1) | ES2232618T3 (de) |
PT (1) | PT1264009E (de) |
WO (1) | WO2001066830A2 (de) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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EP1522610A2 (de) | 2003-10-10 | 2005-04-13 | Audi Ag | Verfahren zur Herstellung einer Verschleissschutzschicht |
US7494578B2 (en) | 2004-03-01 | 2009-02-24 | Atotech Deutschland Gmbh | Iron-phosphorus electroplating bath and method |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
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DE10159890B4 (de) * | 2001-12-06 | 2006-02-16 | Federal-Mogul Burscheid Gmbh | Verfahren für das Beschichten von Aluminiumwerkstoffen mit Funktionsschichten aus Eisen |
JP4054813B2 (ja) * | 2005-04-08 | 2008-03-05 | 株式会社共立 | アルミニウム合金製素材のめっき方法 |
DE102006029835A1 (de) | 2006-06-27 | 2008-01-03 | Bombardier Transportation Gmbh | Fahrwerksrahmen eines Schienenfahrzeugs |
US20090242081A1 (en) * | 2008-03-26 | 2009-10-01 | Richard Bauer | Aluminum Treatment Composition |
JP5223449B2 (ja) * | 2008-05-12 | 2013-06-26 | スズキ株式会社 | めっき処理ライン |
CN102787933A (zh) * | 2012-08-29 | 2012-11-21 | 芜湖鼎恒材料技术有限公司 | 具有纳米合金涂层的气缸 |
CN103966634B (zh) * | 2014-04-09 | 2017-01-04 | 上海大学 | 直接电镀得到纳米铁镀层的方法 |
US10941766B2 (en) * | 2019-06-10 | 2021-03-09 | Halliburton Energy Sendees, Inc. | Multi-layer coating for plunger and/or packing sleeve |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3086927A (en) * | 1960-08-29 | 1963-04-23 | Horst Corp Of America V D | Iron-phosphorus electroplating |
US4101389A (en) * | 1976-05-20 | 1978-07-18 | Sony Corporation | Method of manufacturing amorphous alloy |
US4533441A (en) * | 1984-03-30 | 1985-08-06 | Burlington Industries, Inc. | Practical amorphous iron electroform and method for achieving same |
US4629659A (en) * | 1983-05-14 | 1986-12-16 | Kawasaki Steel Corporation | Corrosion resistant surface-treated steel strip and process for making |
US4746412A (en) * | 1986-07-03 | 1988-05-24 | C. Uyemura & Co., Ltd. | Iron-phosphorus electroplating bath and electroplating method using same |
EP0624662A1 (de) * | 1993-05-12 | 1994-11-17 | Hughes Aircraft Company | Verfahren zum direkten Plattieren von Eisen auf Aluminium |
DE19653210A1 (de) * | 1995-12-21 | 1997-06-26 | Toyota Motor Co Ltd | Korrosionsbeständiger Eisenplattierungsfilm und Verfahren zu seiner Herstellung |
EP0861699A1 (de) * | 1997-02-19 | 1998-09-02 | Basf Aktiengesellschaft | Feinteiliges phosphorhaltiges Eisen |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1945107A (en) * | 1931-05-27 | 1934-01-30 | Frederic A Eustis | Method of making ductile electrolytic iron |
EP0265887B1 (de) * | 1986-10-31 | 1994-01-05 | Asahi Glass Company Ltd. | Verfahren zur Behandlung einer Plattierungslösung |
JPH0248635B2 (ja) * | 1989-05-12 | 1990-10-25 | Uemura Kogyo Kk | Tetsu*rindenkimetsukyoku |
JPH04372907A (ja) | 1991-06-21 | 1992-12-25 | Canon Inc | 導波型分岐、結合素子 |
GB2308387B (en) | 1995-12-21 | 1998-01-14 | Toyota Motor Co Ltd | Corrosion resistant iron plating film and method of forming the same |
-
2000
- 2000-03-09 DE DE10013298A patent/DE10013298C2/de not_active Expired - Fee Related
-
2001
- 2001-03-07 AT AT01929243T patent/ATE283935T1/de active
- 2001-03-07 PT PT01929243T patent/PT1264009E/pt unknown
- 2001-03-07 US US10/220,939 patent/US7138043B2/en not_active Expired - Fee Related
- 2001-03-07 JP JP2001565431A patent/JP4431297B2/ja not_active Expired - Fee Related
- 2001-03-07 DE DE50104686T patent/DE50104686D1/de not_active Expired - Lifetime
- 2001-03-07 WO PCT/DE2001/000944 patent/WO2001066830A2/de active IP Right Grant
- 2001-03-07 AU AU56113/01A patent/AU5611301A/en not_active Abandoned
- 2001-03-07 EP EP01929243A patent/EP1264009B1/de not_active Expired - Lifetime
- 2001-03-07 ES ES01929243T patent/ES2232618T3/es not_active Expired - Lifetime
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3086927A (en) * | 1960-08-29 | 1963-04-23 | Horst Corp Of America V D | Iron-phosphorus electroplating |
US4101389A (en) * | 1976-05-20 | 1978-07-18 | Sony Corporation | Method of manufacturing amorphous alloy |
US4629659A (en) * | 1983-05-14 | 1986-12-16 | Kawasaki Steel Corporation | Corrosion resistant surface-treated steel strip and process for making |
US4533441A (en) * | 1984-03-30 | 1985-08-06 | Burlington Industries, Inc. | Practical amorphous iron electroform and method for achieving same |
US4746412A (en) * | 1986-07-03 | 1988-05-24 | C. Uyemura & Co., Ltd. | Iron-phosphorus electroplating bath and electroplating method using same |
EP0624662A1 (de) * | 1993-05-12 | 1994-11-17 | Hughes Aircraft Company | Verfahren zum direkten Plattieren von Eisen auf Aluminium |
DE19653210A1 (de) * | 1995-12-21 | 1997-06-26 | Toyota Motor Co Ltd | Korrosionsbeständiger Eisenplattierungsfilm und Verfahren zu seiner Herstellung |
EP0861699A1 (de) * | 1997-02-19 | 1998-09-02 | Basf Aktiengesellschaft | Feinteiliges phosphorhaltiges Eisen |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1522610A2 (de) | 2003-10-10 | 2005-04-13 | Audi Ag | Verfahren zur Herstellung einer Verschleissschutzschicht |
DE10347145A1 (de) * | 2003-10-10 | 2005-05-12 | Audi Ag | Verfahren zur Herstellung einer Verschleißschutzschicht |
DE10347145B4 (de) * | 2003-10-10 | 2006-01-12 | Audi Ag | Verfahren zur Herstellung einer Verschleißschutzschicht |
US7494578B2 (en) | 2004-03-01 | 2009-02-24 | Atotech Deutschland Gmbh | Iron-phosphorus electroplating bath and method |
US7588675B2 (en) | 2004-03-01 | 2009-09-15 | Atotech Deutschland Gmbh | Iron-phosphorus electroplating bath and method |
Also Published As
Publication number | Publication date |
---|---|
US20030116442A1 (en) | 2003-06-26 |
JP2003526015A (ja) | 2003-09-02 |
AU5611301A (en) | 2001-09-17 |
JP4431297B2 (ja) | 2010-03-10 |
US7138043B2 (en) | 2006-11-21 |
PT1264009E (pt) | 2005-04-29 |
ATE283935T1 (de) | 2004-12-15 |
DE50104686D1 (de) | 2005-01-05 |
EP1264009A2 (de) | 2002-12-11 |
EP1264009B1 (de) | 2004-12-01 |
ES2232618T3 (es) | 2005-06-01 |
DE10013298C2 (de) | 2003-10-30 |
WO2001066830A3 (de) | 2002-03-21 |
DE10013298A1 (de) | 2001-09-20 |
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