EP0194310A1 - Process for forming a surface layer on aluminum and aluminum alloy articles and so formed articles - Google Patents

Process for forming a surface layer on aluminum and aluminum alloy articles and so formed articles

Info

Publication number
EP0194310A1
EP0194310A1 EP19850905002 EP85905002A EP0194310A1 EP 0194310 A1 EP0194310 A1 EP 0194310A1 EP 19850905002 EP19850905002 EP 19850905002 EP 85905002 A EP85905002 A EP 85905002A EP 0194310 A1 EP0194310 A1 EP 0194310A1
Authority
EP
European Patent Office
Prior art keywords
manganese
nitrogen
oxygen
aluminum
sulphur
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.)
Withdrawn
Application number
EP19850905002
Other languages
German (de)
French (fr)
Inventor
Alfred Serbinski
Waldemar Serbinski
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from SE8404762A external-priority patent/SE445933B/en
Priority claimed from SE8404761A external-priority patent/SE445932B/en
Application filed by Individual filed Critical Individual
Publication of EP0194310A1 publication Critical patent/EP0194310A1/en
Withdrawn legal-status Critical Current

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
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
    • 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
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • 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

  • This invention is related to a process for producing a surface!
  • Said layer consists of manganese (Mn) comprising
  • Said layer exhibits a metallurgical bond (fusion bond) to the substrate, i.e. bonding to the substrate by diffusion caused by heating or optionally melting.
  • Galvanic (electrolytic) layers characteristically are inferior! to heat bonded layers as regards adherence.
  • galvanic (electrolytic) surface layers on j aluminum or aluminum alloy substrates with the same good
  • the invention uses a
  • the introduction of oxygen and nitrogen in the coating is preferably achieved by heat treating in an atmosphere which supplies nitrogen and oxygen to the manganese layer under the heat treating conditions, preferably an oxidizing treatment in an oxidizing atmosphere, preferably an atmosphere comprising water vapour, preferably for a period of at least 0.5 hours and preferably up to 1.5 hours, and a nitriding treatment, preferably in ammonia or cracked ammonia, preferably for a period of at least 0.5 hours and prefer-ably up to 6 hours.
  • oxidizing and nitriding treatments are preferably performed at a temperature of 753 to. 883°K and suitably simultaneously with the previously mentioned heat treatment for bonding the manganese .layer to the substrate.
  • the surface coating layer according to the invention comprises in addition to manganese also various compounds of manganese with nitrogen and oxygen, e.g. of the type Mn.N, Mn.,0., etc., as particulate precipitates in the manganese matrix, or various compounds of manganese with nitrogen, oxygen and sulphur, e.g. of the type Mn. (N, S, 0), in which the mutual quantity ratios of N, S and 0 may vary, i.e. from pure Mn,N, and, furthermore, compounds of the types Mn 2 (0,S),, Mn 3 (0,S) ., etc., as particulate precipitates in the manganese matrix.
  • the process according to the invention can basically be used for the treatment of all kinds of aluminum and aluminum alloy articles, e.g. parts for internal combustion engines, e.g. spark ignition and diesel engines, e.g. pistons and similar articles, engines with rotating piston, such as wankel engine ⁇ and in general for articles of aluminum and aluminum alloys which are subjected to wear and/or are intended to exhibit low friction.
  • the aluminum alloy should preferably have a compo ⁇ sition which permits coating, especially electrolytical coating with manganese (or optionally with manganese alloys consisting mainly or to at least 75% or 90% of manganese) and ; firm bonding of the manganese (or manganese alloy) coating to ; the aluminum substrate by heat bonding (metallurgical bonding) .
  • Electrolyte temperature 283-288°K, electrolyte pH 7.0
  • the electrolytic manganizing process was performed with anodes made from an alloy of, by weight:
  • the aluminum articles were subjected to an oxidizing treatment in water vapour for 0.5 hours and a nitriding treatment in ammonia for 2 hours, both at the temperature 813°K.
  • Example 2 The same substrates and pretreatment as in Example 1 were used but instead of the oxidizing-nitriding treatment of Example 1 the aluminum articles were subjected to a heat treatment for introducing oxygen (0), sulphur (S) and nitrogen (N). in an atmosphere comprising a nitrogen source (ammonia, NH.,), a sulphur source and an oxygen source (sulphur dioxide, S0 2 ) at a temperature of 883°K for 3 hours.
  • a nitrogen source ammonia, NH.,
  • S0 2 oxygen source
  • the articles were degreased in the same kind of solution and in the same way as according to Example 1.
  • the articles were ⁇ then rinsed in hot and cold water and thereafter immersed into ; a solution of:
  • Example 1 The composition of the electrolyte and the treatment conditions were the same as in Example 1.
  • the aluminum alloy articles were subjected to an oxidizing treatment in water vapour for 1.5 hours and a nitriding treatment in ammonia (cracked ammonia) for 6 hours, both at a temperature of 753°K.
  • the prepared coatings comprise Mn and hard Mn-,0 4 and Mn 4 particles.
  • Example 3 The same substrates and pretreatments as in Example 3 were used but instead of the oxidizing and nitriding treatments of Example 3 the aluminum alloy articles were subjected to a heat, treatment in an atmosphere comprising an oxygen source, a sulphur source and a nitrogen source for simultaneous intro ⁇ duction of said elements into the layer, said atmosphere comprising ammonia (NH-,) and sulphur dioxide (SO-) at a temperature of 753°K for 10 hours. Said treatment can be regarded as an oxygen, sulphur and nitrogen saturation treatment. _____,
  • the manganese coating according to this invention preferably comprises the compounds or reaction products of manganese with oxygen, nitrogen and optionally sulphur embedded as particles ' in a matrix of manganese metal or alloy, especially as a composite coating.
  • the amount of oxygen, nitrogen and optionally sulphur in the coating preferably is an amount corresponding at least to the amount introduced by heat treatment in water vapor or ammonia (or cracked ammoni ⁇ ) or a mixture of ammonia and sulphur dioxide for 0,5 hours at 753°K.
  • the manganese coating may optionally be applied also by e.g. electroless coating, flame spraying or plasma flame spraying deposition from a vapour phase, such as a manganese compound vapor phase , e.g. metallizing with manganese, e.t.c.
  • a vapour phase such as a manganese compound vapor phase
  • the reaction products with oxygen, nitrogen and optionally sulfur may be included into the manganese coating already in the coating step, e.g. as reaction products formed already prior to the coating step or in the coating step.
  • the coating may comprise also other constituents, such as conventional impurities normally present in the raw materials or deliberately added constituents which do not prevent or substantially reduce the desired inventive effect.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)

Abstract

Un procédé de formation d'une couche superficielle sur des produits en aluminium et en alliage d'aluminium se caractérise par la formation sur la surface du produit d'un revêtement comprenant du manganèse et des produits de réaction du manganèse avec de l'oxygène et de l'azote ou avec de l'oxygène, de l'azote et du soufre. Un produit comprenant au moins une partie de surface en alliage d'aluminium ou en aluminium se caractérise en ce que la surface d'aluminium ou d'alliage d'aluminium est pourvue d'un revêtement de surface comprenant du manganèse et des produits de réaction du manganèse avec de l'oxygène et de l'azote ou avec de l'oxygène, de l'azote et du soufre, de préférence sous la forme de particules dispersées dans une matrice d'une couche de surface de manganèse.A method of forming a surface layer on aluminum and aluminum alloy products is characterized by the formation on the product surface of a coating comprising manganese and products of reaction of manganese with oxygen and nitrogen or with oxygen, nitrogen and sulfur. A product comprising at least an aluminum alloy or aluminum surface part is characterized in that the aluminum or aluminum alloy surface is provided with a surface coating comprising manganese and reaction products manganese with oxygen and nitrogen or with oxygen, nitrogen and sulfur, preferably in the form of particles dispersed in a matrix of a surface layer of manganese.

Description

"Process for forming a surface layer on aluminum- ' and aluminum alloy articles and so formed articles".
This invention is related to a process for producing a surface!
! layer with high wear resistance and decreased coefficient of ] friction. Said layer consists of manganese (Mn) comprising | oxygen (O) and nitrogen (N) or oxygen (0), sulphur (S) and nitrogen (N) and is applied on surfaces of articles of aluminum (Al) and aluminum alloys. Said layer exhibits a metallurgical bond (fusion bond) to the substrate, i.e. bonding to the substrate by diffusion caused by heating or optionally melting.
Numerous efforts to improve the wear resistance of aluminum alloys by oxydizing, chromizing or iron coating said alloys by a galvanic treatment (anodic method) are previously known. ! Galvanic (electrolytic) layers characteristically are inferior! to heat bonded layers as regards adherence. Thus there is a \ need for forming galvanic (electrolytic) surface layers on j aluminum or aluminum alloy substrates with the same good | characteristics as heat bonded layers. !
Experiments performed with nitriding previously known galvanic layers of iron and chromium coated onto aluminum and aluminum alloy substrates have not given any useful results, e.g. because of peeling and chipping of the layer from the substrate.
According to this invention it is possible to form surface layers with good wear resistance and low friction and simultaneously good adherence to a substrate of aluminum and
■aluminum alloys. For this purpose the invention uses a
: coating based on manganese which is applied onto the surface of the substrate of aluminum or aluminum alloys, preferably by j galvanic or electrolytic coating. Methods for galvanic or i
;electrolytic coating of manganese onto aluminum and aluminum alloys are per se previously known. According to the inven¬ tion it is possible to obtain excellent adherence of such manganese coatings to the substrate of aluminum and aluminum alloys and simultaneously obtain the previously mentioned good characteristics as regards wear resistance and low friction. This is achieved according to the invention by heat treating the manganese coating and including oxygen and nitrogen or oxygen, sulphur and nitrogen in said coating. The heat treat¬ ment according to the invention is preferably performed at a temperature of from about 653 up to the melting point, prefer¬ ably up to 920°K, especially 753-883°K. Said heat treatment is preferably performed for a period of at least 0.5 hour and preferably up to 10 hours. The introduction of oxygen and nitrogen in the coating is preferably achieved by heat treating in an atmosphere which supplies nitrogen and oxygen to the manganese layer under the heat treating conditions, preferably an oxidizing treatment in an oxidizing atmosphere, preferably an atmosphere comprising water vapour, preferably for a period of at least 0.5 hours and preferably up to 1.5 hours, and a nitriding treatment, preferably in ammonia or cracked ammonia, preferably for a period of at least 0.5 hours and prefer-ably up to 6 hours. These oxidizing and nitriding treatments are preferably performed at a temperature of 753 to. 883°K and suitably simultaneously with the previously mentioned heat treatment for bonding the manganese .layer to the substrate. The introduction of oxygen, sulphur and ; nitrogen in the coating is preferably achieved by heat j treating in an atmosphere which supplies nitrogen, sulphur and' oxygen to the manganese layer under the heat treating conditions, preferably an atmosphere comprising ammonia (NH_) ! and sulphur dioxide (SO_). The introduction of oxygen, sulphur and nitrogen into the manganese layer is preferably performed simultaneously with the previously mentioned heat j treatment. Preferably ammonia and sulphur dioxide are supplied to the reaction in the gaseous state through separate conduits in order to facilitate and improve the control of the process. The quantity of SO„ added depends upon the size of the treated articles and is usually from 1.0 to a few per cent, e.g. up to 5% of the ammonia volume. With the process according to this invention it is possible to form on the surface of aluminum and aluminum alloy substrates a composite type coating layer which is characterized by high hardness and very good adherence to the substrate and a reduced coefficient of friction.
The surface coating layer according to the invention comprises in addition to manganese also various compounds of manganese with nitrogen and oxygen, e.g. of the type Mn.N, Mn.,0., etc., as particulate precipitates in the manganese matrix, or various compounds of manganese with nitrogen, oxygen and sulphur, e.g. of the type Mn. (N, S, 0), in which the mutual quantity ratios of N, S and 0 may vary, i.e. from pure Mn,N, and, furthermore, compounds of the types Mn2(0,S),, Mn3(0,S) ., etc., as particulate precipitates in the manganese matrix.
The maximum hardness in the layer is usually present at a certain distance from the surface, as is usual in nitriding processes, and may exceed HV 0.01 •= 900.
The process according to the invention can basically be used for the treatment of all kinds of aluminum and aluminum alloy articles, e.g. parts for internal combustion engines, e.g. spark ignition and diesel engines, e.g. pistons and similar articles, engines with rotating piston, such as wankel engine ■ and in general for articles of aluminum and aluminum alloys which are subjected to wear and/or are intended to exhibit low friction. The aluminum alloy should preferably have a compo¬ sition which permits coating, especially electrolytical coating with manganese (or optionally with manganese alloys consisting mainly or to at least 75% or 90% of manganese) and ; firm bonding of the manganese (or manganese alloy) coating to ; the aluminum substrate by heat bonding (metallurgical bonding) .
The invention is now illustrated with the following examples, j EXAMPLE 1
Substrate:aluminum articles which were degreased in a solution, of:
H2° 273 ml a3P04 13.5 g j
NaOH 2.1 g
Na2Si03 10.5 g
Temperature 323°K for 5 minutes. The articles were then rinsed in hot and cold water and then dipped into a solution of:
HCl 0.580 1
MnS04.5H20 7 g H20 1.76 1
Said treatment was performed at a temperature of 310°K and for 15-30 seconds. After careful rinsing in water the aluminum articles were directly subjected to an electrolytic manganizing treatment (electrolytic manganese precipitation) in an electrolyte of the following composition:
MnS04.5H-,0 200 g/1
(NH4)2S04 75 g/1 :
H20 to 1 litre
Electrolyte temperature 283-288°K, electrolyte pH = 7.0
2 Current density 10-15 x 10 A/m2.
The electrolytic manganizing process was performed with anodes made from an alloy of, by weight:
Sn 30%, Co 0.4%, balance Pb.
It is preferable to stir the electrolyte continuously and to use a diaphragm for dividing the anode from the cathode. Immediately after removal from said electrolyte the articles were immersed in a 5% aqueous solution of: Na2Cr207.2H20.
After said electrolytic manganizing the aluminum articles were subjected to an oxidizing treatment in water vapour for 0.5 hours and a nitriding treatment in ammonia for 2 hours, both at the temperature 813°K.
EXAMPLE 2
The same substrates and pretreatment as in Example 1 were used but instead of the oxidizing-nitriding treatment of Example 1 the aluminum articles were subjected to a heat treatment for introducing oxygen (0), sulphur (S) and nitrogen (N). in an atmosphere comprising a nitrogen source (ammonia, NH.,), a sulphur source and an oxygen source (sulphur dioxide, S02) at a temperature of 883°K for 3 hours.
EXAMPLE 3
Substrate:aluminum alloy articles with the following composition:
Si = 12.4%, Cu = 0.9%, Mg = 1.3%, Ni = 0.9%, Fe - 0.3%, balance Al.
The articles were degreased in the same kind of solution and in the same way as according to Example 1. The articles were ■ then rinsed in hot and cold water and thereafter immersed into; a solution of:
HN03 75% by volume ,
HF 25% by volume. !t (
I
Said treatment was performed at a temperature of 293°K and for; f
15-30 seconds. Immediately thereafter the articles were j carefully rinsed in water and subjected to electrolytic j manganizing. The composition of the electrolyte and the treatment conditions were the same as in Example 1.
After said electrolytic manganizing the aluminum alloy articles were subjected to an oxidizing treatment in water vapour for 1.5 hours and a nitriding treatment in ammonia (cracked ammonia) for 6 hours, both at a temperature of 753°K.
IThe prepared coatings comprise Mn and hard Mn-,04 and Mn4 particles. The surface hardness after said oxidizing and "nitriding treatments may exceed HV 0.01 = 1000.
EXAMPLE 4
The same substrates and pretreatments as in Example 3 were used but instead of the oxidizing and nitriding treatments of Example 3 the aluminum alloy articles were subjected to a heat, treatment in an atmosphere comprising an oxygen source, a sulphur source and a nitrogen source for simultaneous intro¬ duction of said elements into the layer, said atmosphere comprising ammonia (NH-,) and sulphur dioxide (SO-) at a temperature of 753°K for 10 hours. Said treatment can be regarded as an oxygen, sulphur and nitrogen saturation treatment. ____,
Among articles subjected to the treatments according to the examples were combustion engine pistons and cylinder blocks.
The manganese coating according to this invention preferably comprises the compounds or reaction products of manganese with oxygen, nitrogen and optionally sulphur embedded as particles 'in a matrix of manganese metal or alloy, especially as a composite coating. The amount of oxygen, nitrogen and optionally sulphur in the coating preferably is an amount corresponding at least to the amount introduced by heat treatment in water vapor or ammonia (or cracked ammoni^) or a mixture of ammonia and sulphur dioxide for 0,5 hours at 753°K.
The manganese coating thickness should be sufficient to give good bonding to the substrate and to form or comprise reaction products of manganese with oxygen and nitrogen or with oxygen, nitrogen and sulfur resp. A suitable thickness may be e.g. at least 0,1 micron, preferably at least 0,5 micron , at least 1 micron or at least 5 microns, optionally at least 10 microns, or at least 50 microns. A suitable upper thickness limit may be e.g. up to mm, up to 1 mm or up to 0,5 mm or optionally up to 0,1 mm. Also a coating thickness outside said ranges may be used
The manganese coating may optionally be applied also by e.g. electroless coating, flame spraying or plasma flame spraying deposition from a vapour phase, such as a manganese compound vapor phase , e.g. metallizing with manganese, e.t.c. Optionally the reaction products with oxygen, nitrogen and optionally sulfur may be included into the manganese coating already in the coating step, e.g. as reaction products formed already prior to the coating step or in the coating step.
The coating may comprise also other constituents, such as conventional impurities normally present in the raw materials or deliberately added constituents which do not prevent or substantially reduce the desired inventive effect.
Preferably the compsition of the substrate and of the coating are selected so that the coefficient of linear (thermal) expansion match, preferably with a difference in relation to the the aluminum or aluminum alloy substrate of at most 50$, optionally at most 25 % or at most 10.. or even at most 5% within the temperature range of intended use of the coated product.

Claims

1. A process for forming a surface layer on aluminum and aluminum alloy articles, characterized by forminng on the surface of the article a coating comprising manganese and reaction products of manganese with oxygen and nitrogen or with oxygen, nitrogen and sulphur.
2. A process according to claim 1 characterized by coating the surface of the article with a manganese layer and heating the coated article in a gas atmosphere or gas atmospheres which supplies-oxygen, nitrogen and optionally sulphur to the manganese layer.
3. A process according to claim 1 or 2, characterized in that said heating for supplying oxygen, nitrogen and optionally sulphur is performed for at least 0,5 hour at a teenmperature of at least 753 K and preferably up to 883°K.
-4. A process according to any of the preceding claims, characterized in that oxygen is supplied by an oxidizing treatment in a water vapour containing atmosphere, preferably for from 0,5 to 1,5 hours, and nitrogen is supplied by a nitriding treatment in an atmosphere comprising ammonia or cracked ammonia, preferably for from 0,5 to β hours; or oxygen, nitrogen and sulphur are supplied by a heat treatment in an atmosphere comprising ammonia and sulphur dioxide for from 0,5 to 10 hours.
5- A process according to any of the preceding claims, characterized in that the manganese coating is applied to the article with an electrolytic method.
o . A process according to any of the preceding claims, characterized in that said heat treatment is performed so that the manganese layer through said heat treatment is structur¬ ally or metallurgically bonded or united to the aluminum or aluminum alloy substrate.
7. An article comprising at least a surface part of aluminum or aluminum alloy, characterized in that the aluminum or aluminum alloy surface is provided with a surface coating comprising manganese and reaction products of manganese with oxygen and nitrogen, -or with oxygen,nitrogen and sulphur, preferably as particles dispersed in a manganese surface layer matrix.
8. An article according to claim η , characterized by consisting of an article which is intended to be subjected to or resistant to heating and/or wear, such as internal combustion engines, e.g. spark ignited and diesel engines.
9- ^An article according to claim 7 or 8 > characterized in that said manganese layer is by heat treatment diffusion or melt bonded and/or metallurgically bonded to the aluminum or aluminum alloy substrate and/or comprises compounds or reaction products of manganese with nitrogen and oxygen or with oxygen, nitrogen and sulphur
EP19850905002 1984-09-24 1985-09-24 Process for forming a surface layer on aluminum and aluminum alloy articles and so formed articles Withdrawn EP0194310A1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
SE8404762A SE445933B (en) 1984-09-24 1984-09-24 Procedure for applying a surface layer to objects of aluminium or aluminium alloy
SE8404762 1984-09-24
SE8404761A SE445932B (en) 1984-09-24 1984-09-24 Procedure for applying a surface layer to objects of aluminium or aluminium alloy
SE8404761 1984-09-24

Publications (1)

Publication Number Publication Date
EP0194310A1 true EP0194310A1 (en) 1986-09-17

Family

ID=26658789

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19850905002 Withdrawn EP0194310A1 (en) 1984-09-24 1985-09-24 Process for forming a surface layer on aluminum and aluminum alloy articles and so formed articles

Country Status (5)

Country Link
EP (1) EP0194310A1 (en)
AU (1) AU4964185A (en)
DK (1) DK245986D0 (en)
FI (1) FI862191A (en)
WO (1) WO1986001836A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4939308A (en) * 1988-04-29 1990-07-03 Allied-Signal Inc. Method of forming crystallite-oriented superconducting ceramics by electrodeposition and thin film superconducting ceramic made thereby
EP0411047A1 (en) * 1988-04-29 1991-02-06 AlliedSignal Inc. Superconducting ceramics by electrodeposition
WO2008124247A1 (en) * 2007-04-06 2008-10-16 Swagelok Company Activation qf aluminum

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3765847A (en) * 1972-04-17 1973-10-16 B Behl Process for plating aluminum alloys with manganese

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8601836A1 *

Also Published As

Publication number Publication date
WO1986001836A1 (en) 1986-03-27
FI862191A0 (en) 1986-05-26
FI862191A (en) 1986-05-26
AU4964185A (en) 1986-04-08
DK245986D0 (en) 1986-05-26

Similar Documents

Publication Publication Date Title
JP3001161B2 (en) Aluminum coating for super alloy
US3961098A (en) Coated article and method and material of coating
US4897315A (en) Yttrium enriched aluminide coating for superalloys
USRE31339E (en) Process for producing elevated temperature corrosion resistant metal articles
WO2001094664A2 (en) Coating system for high temperature stainless steel
EP0370838B1 (en) Process for the surface protection of metallic articles against high-temperature corrosion, and article treated by this process
JPH09509697A (en) Platinum enriched silicon modified corrosion resistant aluminum coating
CH661287A5 (en) PROCESS FOR THE PREPARATION BY DIFFUSION OF A PROTECTIVE LAYER ON ALLOYS BASED ON NICKEL, COBALT AND IRON.
US3846159A (en) Eutectic alloy coating
FR2571386A1 (en) PROTECTIVE METAL COATINGS
US3957454A (en) Coated article
JPH04214879A (en) Protective layer of metal substrate and its manufacture
US4913785A (en) Process for hot-dip metal-coating poorly wettable steel sheets
US4561892A (en) Silicon-rich alloy coatings
US6620518B2 (en) Vapor phase co-deposition coating for superalloy applications
CA2357407C (en) Coating system for high temperature stainless steels
EP0194310A1 (en) Process for forming a surface layer on aluminum and aluminum alloy articles and so formed articles
CN112962047A (en) Method for preparing Ti-Al system intermediate phase/Ti-Al-C system MAX phase composite coating on surface of titanium or titanium alloy
US3953193A (en) Coating powder mixture
CN113574208A (en) Object comprising a chromium-based coating on a substrate
US3184330A (en) Diffusion process
CN101163813A (en) Coating, substrate provided with a coating and method for the application of a corrosion-resistant coating
Marder Effects of surface treatments on materials performance
KR920009844B1 (en) Plated steel sheet having excellent coating performance
Bernabai et al. High-temperature oxidation of aluminum electroplated Fe-Mn alloys

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE FR GB IT LI LU NL SE

17P Request for examination filed

Effective date: 19860926

RBV Designated contracting states (corrected)

Designated state(s): DE FR GB IT

17Q First examination report despatched

Effective date: 19881018

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 19910331