EP1900854B1 - Procédé pour durcissement de couches de chrome plaqué - Google Patents
Procédé pour durcissement de couches de chrome plaqué Download PDFInfo
- Publication number
- EP1900854B1 EP1900854B1 EP06120448A EP06120448A EP1900854B1 EP 1900854 B1 EP1900854 B1 EP 1900854B1 EP 06120448 A EP06120448 A EP 06120448A EP 06120448 A EP06120448 A EP 06120448A EP 1900854 B1 EP1900854 B1 EP 1900854B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- substrate
- process according
- metal
- chromium
- 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.)
- Not-in-force
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
Definitions
- the invention relates to a method for coating a substrate, preferably metallic substrates or metallized substrates, with a diffusion layer formed from an outer galvanic chromium layer and at least one metallic intermediate layer, substrates comprising this diffusion layer and the use of the diffusion layer.
- the diffusion layer forms a hard, tough, oxidation resistant and aggressive media resistant overlay on the substrate.
- the diffusion-coated substrates obtained according to the invention can be used as workpieces and components in general mechanical engineering, building and construction
- the DE-A-4035790 relates to a method for inner and outer coating of hollow components with an aluminum-based coating by a powder-pack coating method with heat treatment.
- the EP-A-0906967 discloses the use of an alloy of aluminum and titanium as a temperature-resistant and corrosion-resistant coating material for heat-resistant steel.
- Aluminum and titanium react by reacting with the process environment to form extremely stable oxides which form an oxidic protective layer.
- the DE-A-10116762 describes the production of diffusion layers with high contents of aluminum and titanium and their use as corrosion protection for metallic materials (eg Stahl Wst. Nr. 1.4841) in reducing, sulfiding environments with high carbon activities at temperatures up to at least 700 ° C, the layer in the codiffusion process using the diffusion elements Al and Ti as pure metal powders in the weight ratio 1: (0.1-5) is produced.
- the process provides for concurrent indiffusion of Al and Ti in a powder packing process.
- the deposition takes place without prior deposition of intermediate layers.
- no TiAl alloy is produced, but it formed depending on the composition of the substrate mixed phases of Al, Cr, Fe, Ni and Ti.
- a problem underlying the invention was the provision of a method which allows the hard functional layers, which have a ductile Cr-alloyed "Superalloy" substructure, which in addition to wet corrosion protection, the degradation of stresses in the structure and thus ensure the stability of the structure have to apply separately from the coatings.
- the desired structural state should be adjustable by targeted temperature control during the process.
- the present invention was thus further based on the object of providing a process for the production of metallic workpieces provided with a hard, crack-free, oxidation-resistant and delamination-free chromium functional layer with ductile anti-corrosive "superalloy" substructure.
- substrates preferably metallic substrates or metallized substrates, which have such a functional layer, and of workpieces and components comprising these coated substrates.
- the objects were achieved by a method for coating a substrate with a diffusion layer, wherein the diffusion layer is formed by electrodeposition of a chromium layer on at least one metallic intermediate layer arranged on the substrate and subsequent thermal treatment.
- the invention further relates to a diffusion-coated substrate, preferably metal substrate or metallized substrate, which can be obtained by the method according to the invention.
- the invention also relates to a workpiece or component comprising the diffusion-coated substrate according to the invention, preferably metal substrate or metallized substrate.
- the invention relates to a diffusion layer obtainable by the method according to the invention from at least one intermediate layer and a galvanic chromium layer arranged thereon.
- the invention further relates to the use of the diffusion layer according to the invention for placement on a substrate, preferably a metallic substrate or metallized substrate, preferably for modifying and / or protecting the substrate.
- the metallic chromium which is incorporated as an alloying component in the workpiece surface, comes from the electrodeposition and not from a packing or CVD process. Packing and CVD processes are usually carried out at temperatures above 800 ° C. Thus, in the packing and CVD process of the alloy and
- Diffusion step which leads to the final formation of the chromium alloy or functional layer, already largely or completely integrated into the deposition process of the chromium.
- the galvanic deposition takes place in a temperature range in which diffusion processes do not yet take place at a measurable speed. This leads to the fact that the interdiffusion, ie the diffusion of the elements of the individual layers between the layers, is omitted and the diffusion step is adjusted as an independent, heat treatment in a separate process step. According to the method of the invention, it is thus possible to separate the deposition of the metal layers from the alloy.
- this offers the possibility of targeted formation of cover or functional layers and, on the other hand, accelerated workpiece cooling can be brought about by an increased flushing rate, which enables hardening or adjustment of the desired structural state of the workpiece or component. This is in contrast to the packing or CVD process, where this is not possible during the heat treatment.
- the subsequent thermal treatment according to the method of the invention may typically be at a temperature of 120 ° C or 500 ° C to 1600 ° C, preferably at a temperature of 800 ° C to 1300 ° C, more preferably at a temperature of 900 ° C up to 1200 ° C performed.
- the thermal treatment can be carried out for a period of 0.1 h to 250 h or 125 h, preferably from 2 h to 16 h, particularly preferably from 3 h to 12 h.
- the subsequent thermal treatment is carried out in vacuo (for example in the induction furnace) or in the presence of process gases.
- process gases referred to in the context of the invention are selected from the group consisting of argon, hydrogen, nitrogen, nitrogen-containing gases, carbonaceous gases, boron-containing gases and mixtures thereof.
- the carbonaceous gases are selected from the group consisting of methane, ethane, propane, butane, acetylene, carbon monoxide and mixtures thereof. Preference is given to mixtures of methane with carbon monoxide and
- the diffusion layer obtained by the method according to the invention is characterized in that it contains carbides and / or nitrides and / or carbonitrides and / or borides.
- the substrate is electrically conductive and preferably selected from the group consisting of metallic substrates, metallized substrates, conductively rendered conductive by conductivity, intrinsically non-conductive materials, electrically conductive organic polymers and made conductive by metal or graphite deposits organic polymers.
- substrate is mentioned below, it means the above-mentioned electrically conductive substrate.
- Suitable substrates can thus for example be provided with metal layers, including conductive paints, body of a per se electrically non-conductive material, such as organic polymers or inorganic compounds (salts, etc.) or mixtures thereof, or even substrates entirely of a metal and by a Metal or graphite content (eg metal particles, metal particles, graphite powder) made electrically conductive, not conductive per se substrates, such as substrates of organic polymers or inorganic compounds.
- metal layers including conductive paints, body of a per se electrically non-conductive material, such as organic polymers or inorganic compounds (salts, etc.) or mixtures thereof, or even substrates entirely of a metal and by a Metal or graphite content (eg metal particles, metal particles, graphite powder) made electrically conductive, not conductive per se substrates, such as substrates of organic polymers or inorganic compounds.
- the metallic substrate (metal substrate) or the metallization of the substrate may consist of unalloyed, low-alloyed or high-alloy steel, cast iron, pure Cu, a Cu-based alloy, pure Ni, a Ni or Co base alloy, pure Ti, a Ti alloy or ⁇ -TiAl, the metals W, Mo, Ta, Nb, Zr, V, Hf, Ru, Rh, Os, Ir, Pd, Pt, Re or alloys, which are used as a main component of one of the elements W, Mo , Ta, Nb, Zr, V, Hf, Ru, Rh, Os, Ir, Pd, Pt, Re.
- the at least one intermediate layer may be composed of pure Ni, Co, Mn, Cr, W, Mo, Pt, Pd, Ir, Rh, Re, Au, Ag, Cu or an alloy which is a main constituent of one of Ni, Co, Mn , Cr, W, Mo, Pt, Pd, Ir, Rh, Re, Au, Ag, Cu and optionally additionally P, B, N, C.
- the intermediate layer may comprise a plurality of layers of different ones of the above-mentioned metals or metal alloys in a sandwich construction.
- the layer thickness of the at least one intermediate layer may be from 0.1 ⁇ m to 500 ⁇ m, preferably from 1 ⁇ m to 100 ⁇ m, particularly preferably from 2 ⁇ m to 30 ⁇ m, the thickness specification being based on the layer thickness of all intermediate layers as a whole.
- the element (s) contained in the respective adjacent intermediate layers is / are different from one another.
- the middle of the intermediate layers in their metals is different from the adjacent intermediate layers, wherein the outer intermediate layers may be composed of identical metals.
- the intermediate layer may be deposited by a continuous or discontinuous chemical or galvanic process, a PVD process or decomposition reactions of volatile metal compounds.
- Volatile metal compounds are understood to mean those which have a sublimation or boiling point of 300 ° C. or less at normal pressure (101.325 kPa).
- metal compounds are metal alkyls (C 1 -C 10 alkyl), metal carbonyls, metal ⁇ complexes and
- the intermediate layers serve, inter alia, to control the diffusion or alloying process and can be used for targeted modification of the layer structure, the layer composition and thus the layer properties and the properties of the interdiffusion zone between substrate and alloyed functional layer.
- the interlayers may further prevent the formation of Kirkendall pores and may complicate, prevent or even improve interdiffusion between the substrate and the outer layer.
- this essentially means that alloys are formed from the elements which have been applied via the electrodeposited Cr deposition and from the elements involved in the construction of the intermediate layer, and components of the substrate are incorporated only to a limited extent or not at all into the diffusion layer and the layer composition can be set largely or completely independent of substrate, on the other hand it prevents that too rapid depletion of the chromium of the cover layer takes place by strong diffusion towards the substrate and the protective layer collapses prematurely therewith.
- the at least one intermediate layer arranged on the substrate can in a particular embodiment of the invention be thermally treated before application of the electroplated chromium layer, preferably at 120 ° C. to 1600 ° C.
- the duration of the treatment of the intermediate layer before application of the chromium layer can be from 0.1 h to 250 h, preferably from 2 h to 16 h, particularly preferably from 3 h to 12 h.
- the electroplated chromium layer can be deposited by a continuous process.
- the chromium plating layer may be deposited via a batch process, e.g. a rack or drum process or via a continuous process (continuous process) are deposited.
- the layer thickness of the chromium plating layer may generally be 0.1 ⁇ m to 500 ⁇ m, preferably from 1 ⁇ m to 100 ⁇ m, particularly preferably from 2 ⁇ m to 30 ⁇ m.
- the process according to the invention may be characterized by a further step which comprises a controlled, preferably accelerated cooling of the coated substrate in the presence of process gases and / or other media, eg liquid media such as oil, water, liquid gases, or molten lead.
- process gases and / or other media eg liquid media such as oil, water, liquid gases, or molten lead.
- process gases and / or other media eg liquid media such as oil, water, liquid gases, or molten lead.
- the chromium layer formed by the process according to the invention and contained in the diffusion layer structure is characterized in that it is formed by interdiffusion of metals of the intermediate layer (s) in the outer chromium layer and optionally of the substrate. In carbonaceous substrates, carbon may also migrate to the forming diffusion layer to form metal carbides.
- the diffusion layer is defined by the state which, due to the method according to the invention, is established by the interdiffusion between the individual layers and the substrate-related layers and the substrate associated with the method. This results in an alloying of the elements of the outer layer, the / the intermediate layer (s) and the metallic substrate.
- the diffusion layer is one or more mixed crystal layers and / or one or more intermetallic phases. If the diffusion layer is composed of mixed crystal layers and / or intermetallic phases with phase width, it may be a multilayer gradient layer structure in which the composition of an axis perpendicular to the layer plane changes continuously.
- the diffusion layer formed on the metallic substrate by the method according to the invention comprising the original outer layer and the original intermediate layer (s), has a layer thickness of from 0.2 ⁇ m to 2 mm, preferably from 2 ⁇ m to 400 ⁇ m, particularly preferred from 4 ⁇ m to 120 ⁇ m.
- coated substrates such as workpieces, moldings and components can be produced, which are characterized by the absence of cracking and / or Kirkendall pores.
- the workpieces are preferably used in general mechanical engineering, the construction and automotive industry, aviation, the chemical and petrochemical industry and general industry. Concrete examples of workpieces and components are bearings, as well as tools for cold and hot work, in particular casting tools, Casting tool dies, forming tools, wires, sheets, screws, nuts, machine components, engines, engines or parts thereof eg turbine blades or pistons.
- a 20 ⁇ m thick Cr layer was applied by means of galvanic, continuous process (strip).
- a subsequent heat treatment at 900 ° to 1150 ° C under nitrogen and oxygen-free inert gas, such as argon, H 2 or a mixture thereof, which additionally allows hardening of the substrate by targeted austenitization and subsequent rapid cooling by blowing Ar forms a Cr-carbide alloy layer on the surface, which in particular has the composition Cr 23 C 6 .
- the carbon passes from the steel by diffusion through the intermediate layer into the outer chromium layer, where it forms chromium carbide.
- This structure has next to the with about 2000HV 0.01 (Vickers hardness) very hard edge zone a with about 200HV relatively soft surface, which in addition to a strong corrosion protection effect allows the reduction of tension.
- 2000HV 0.01 Very hardness
- very hard edge zone a with about 200HV relatively soft surface, which in addition to a strong corrosion protection effect allows the reduction of tension.
- the result is therefore a crack-free structure of the very hard outer Cr carbide layer in contrast to the previously known Inchromier Anlagenen without Ni intermediate layer, which show clearly normal cracks to the surface.
- a 20 ⁇ m thick chromium layer was applied by means of a galvanic continuous process (strip).
- a subsequent heat treatment at 900 ° C to 1150 ° C under inert gas argon, H 2 or a mixture thereof and N 2 here additionally hardening of the substrate by targeted austenitization and subsequent rapid cooling by blowing Ar and / or N 2 allows, forms a very hard carbonitride layer on the surface, which has in particular the composition Cr2C and Cr2N.
- this construction In addition to the hard edge zone, which is very hard with about 2000HV, this construction has a substrate which is relatively soft with about 200HV and, in addition to a strong corrosion protection effect, enables the reduction of stresses. The result is therefore a crack-free structure of the very hard, outer carbonitride layer in contrast to the previously known Inchromier Anlagenen without nickel intermediate layer, which show clearly normal cracks to the surface. In addition, this coating has demonstrated a very high resistance to aggressive Fe-free Al melts.
- nickel plated 100Cr6 substrate was applied by means of galvanic continuous process (tape) 20 .mu.m Cr layer.
- a subsequent heat treatment at 900 ° C to 1150 ° C under inert gas argon, H 2 or a mixture thereof which additionally allows hardening of the substrate by targeted austenitizing and subsequent rapid cooling by blowing Ar, forms a Cr-carbide alloy layer on the surface, which in particular has the composition Cr 23 C 6 .
- this construction has a substrate which is relatively soft with about 200HV and, in addition to a strong corrosion protection effect, enables the reduction of stresses. This results in the outside a crack-free structure of the very hard Cr-carbide layer in contrast to the previously known Inchromier Anlagenen without nickel intermediate layer, which show clearly normal cracks to the surface.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Electroplating Methods And Accessories (AREA)
- Physical Vapour Deposition (AREA)
- Polymerisation Methods In General (AREA)
Claims (15)
- Procédé pour revêtir un substrat avec une couche de diffusion, ladite couche de diffusion étant formée par électrodéposition d'une couche de chrome sur au moins une couche intermédiaire procurée sur le substrat et traitement thermique consécutif, dans lequel le traitement thermique est effectué en présence de gaz de procédé choisis dans le groupe consistant en argon, hydrogène, azote, gaz azotés, gaz carbonés, gaz borés et de mélanges de ceux-ci, le procédé comprenant comme étape supplémentaire un refroidissement accéléré en présence de gaz de procédé et/ou d'autres milieux, caractérisé en ce que la couche de diffusion contient en outre des carbures et/ou des nitrures et/ou des carbonitrures et/ou des borures.
- Procédé selon la revendication 1, caractérisé en ce que le substrat est électroconducteur, de préférence choisi dans le groupe consistant en des substrats métalliques, des substrats métallisés, des matériaux intrinsèquement non conducteurs redus conducteurs à la surface par des laques conductrices, des polymères organiques électroconducteurs, et des polymères organiques redus conducteurs par des inclusions de métal ou de graphite.
- Procédé selon la revendication 1 ou 2, caractérisé en ce que la couche intermédiaire métallique est traitée à une température de 120 °C à 1600 °C avant l'électrodéposition de la couche de chrome.
- Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que le traitement thermique consécutif est effectué à une température de 120 °C à 1600 °C, de préférence à une température de 800 °C à 1300 °C, de préférence encore à une température de 900 °C à 1200 °C.
- Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que le traitement thermique est effectué pendant une durée comprise entre 0,1 h et 250 h, de préférence entre 2 h et 16 h, de préférence encore entre 3 h et 12 h.
- Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le gaz carboné est choisi dans le groupe consistant en méthane, éthane, propane, butane, acétylène, monoxyde de carbone et des mélanges de ceux-ci.
- Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que le substrat, notamment le substrat métallique ou la couche de métallisation du substrat, consiste en acier non allié, faiblement allié ou fortement allié, fer de fonte, Cu pur, un alliage à base de Cu, Ni pur, un alliage à base de Ni ou Co, Ti pur, un alliage de Ti ou γ-TiAl, les métaux W, Mo, Ta, Nb, Zr, V, Hf, Ru, Rh, Os, Ir, Pd, Pt, Re ou des alliages contenant comme composant principal un des éléments W, Mo, Ta, Nb, Zr, V, Hf, Ru, Rh, Os, Ir, Pd, Pt, Re.
- Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que ladite au moins une couche intermédiaire consiste en Ni, Co, Mn, Cr, W, Mo, Pt, Pd, Ir, Rh, Re, Au, Ag, Cu purs ou un alliage monophasique ou polyphasique contenant comme composant principal un des éléments Ni, Co, Mn, Cr, W, Mo, Pt, Pd, Ir, Rh, Re, Au, Ag, Cu ainsi qu'éventuellement en outre P et/ou B et/ou N et/ou C.
- Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que l'épaisseur de couche de ladite au moins une couche intermédiaire est de 0,1 µm à 500 µm, de préférence de 1 µm à 100 µm, de préférence encore de 2 µm à 30 µm.
- Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que l'épaisseur de couche de ladite couche de chrome électrodéposée est de 0,1 µm à 500 µm, de préférence de 1 µm à 100 µm, de préférence encore de 2 µm à 30 µm.
- Procédé selon l'une quelconque des revendications 1 à 10, caractérisé en ce que ladite couche intermédiaire est déposée par un procédé chimique ou d'électrodéposition, continu ou discontinu, par un procédé PVD ou par des réactions de décomposition de composés métalliques hautement volatils.
- Procédé selon l'une quelconque des revendications 1 à 11, caractérisé en ce que lesdits composés métalliques hautement volatils sont choisis dans le groupe consistant en alkyles métalliques, carbonyles métalliques, complexes π métalliques et composés métalliques comprenant plusieurs de ces structures en mélange.
- Procédé selon l'une quelconque des revendications 1 à 12, caractérisé en ce que ladite couche de chrome électrodéposée est déposée par un procédé continu ou discontinu.
- Procédé selon l'une quelconque des revendications 1 à 13, caractérisé en ce que ladite couche de diffusion contient, à part le chrome, un ou plusieurs éléments de ladite au moins une couche intermédiaire et éventuellement du métal du substrat comme composants d'alliage.
- Procédé selon l'une quelconque des revendications 1 à 14, caractérisé en ce que ladite couche de diffusion a une épaisseur de couche comprise entre 0,2 µm et 2 mm, de préférence entre 2 µm et 400 µm, de préférence encore entre 4 µm et 120 µm.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP06120448A EP1900854B1 (fr) | 2006-09-11 | 2006-09-11 | Procédé pour durcissement de couches de chrome plaqué |
AT06120448T ATE487813T1 (de) | 2006-09-11 | 2006-09-11 | Verfahren zum härten von galvanischen chromschichten |
DE502006008289T DE502006008289D1 (de) | 2006-09-11 | 2006-09-11 | Verfahren zum Härten von galvanischen Chromschichten |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP06120448A EP1900854B1 (fr) | 2006-09-11 | 2006-09-11 | Procédé pour durcissement de couches de chrome plaqué |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1900854A1 EP1900854A1 (fr) | 2008-03-19 |
EP1900854B1 true EP1900854B1 (fr) | 2010-11-10 |
Family
ID=38169208
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP06120448A Not-in-force EP1900854B1 (fr) | 2006-09-11 | 2006-09-11 | Procédé pour durcissement de couches de chrome plaqué |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP1900854B1 (fr) |
AT (1) | ATE487813T1 (fr) |
DE (1) | DE502006008289D1 (fr) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI441961B (zh) * | 2012-10-11 | 2014-06-21 | Chang Yi Chen | 披覆碳化鉻基金屬陶瓷電鍍層之疏水性導電工具及其製作方法 |
EP2955249B1 (fr) * | 2014-06-12 | 2018-06-27 | thyssenkrupp AG | Procédé de fabrication d'une tôle d'acier revêtue d'un système anticorrosion |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB287194A (en) * | 1926-11-08 | 1928-03-08 | Thomas Edward Murray | Protection of ferrous metals against corrosion |
GB303034A (en) * | 1927-06-25 | 1928-12-27 | Ig Farbenindustrie Ag | Improvements in the production of metallic coatings on iron or steel, or alloys thereof |
GB343982A (en) * | 1929-11-27 | 1931-02-27 | Standard Telephones Cables Ltd | Improvements in continuously loaded signalling conductors |
US2195499A (en) * | 1937-05-25 | 1940-04-02 | Joseph K Schofield | Process of metal coating |
US2463039A (en) * | 1942-02-21 | 1949-03-01 | Gen Motors Corp | Electroplating copper containing coating |
US2900715A (en) * | 1956-05-28 | 1959-08-25 | Steel Improvement & Forge Co | Protection of titanium |
US3205153A (en) * | 1962-05-21 | 1965-09-07 | Chandler Evans Inc | Process and product of chrome plating nitrided steel |
US3771972A (en) * | 1971-12-16 | 1973-11-13 | Battelle Development Corp | Coated article |
JPS5278719A (en) * | 1975-12-26 | 1977-07-02 | Nippon Kagaku Sangyo Kk | Plating method of aluminum and aluminum alloy |
GB2188942B (en) * | 1986-04-11 | 1990-04-04 | Rolls Royce Plc | Protective coating |
-
2006
- 2006-09-11 AT AT06120448T patent/ATE487813T1/de active
- 2006-09-11 DE DE502006008289T patent/DE502006008289D1/de active Active
- 2006-09-11 EP EP06120448A patent/EP1900854B1/fr not_active Not-in-force
Also Published As
Publication number | Publication date |
---|---|
EP1900854A1 (fr) | 2008-03-19 |
ATE487813T1 (de) | 2010-11-15 |
DE502006008289D1 (de) | 2010-12-23 |
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