WO2003012168A1 - Tube, method of coating and use of same - Google Patents

Tube, method of coating and use of same Download PDF

Info

Publication number
WO2003012168A1
WO2003012168A1 PCT/SE2002/001418 SE0201418W WO03012168A1 WO 2003012168 A1 WO2003012168 A1 WO 2003012168A1 SE 0201418 W SE0201418 W SE 0201418W WO 03012168 A1 WO03012168 A1 WO 03012168A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating
tubes
tube
aluminium
aluminium oxide
Prior art date
Application number
PCT/SE2002/001418
Other languages
French (fr)
Other versions
WO2003012168B1 (en
Inventor
Jan Olof Olsson
Original Assignee
Thermalloys Ab
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
Application filed by Thermalloys Ab filed Critical Thermalloys Ab
Priority to EP02751943A priority Critical patent/EP1423554A1/en
Publication of WO2003012168A1 publication Critical patent/WO2003012168A1/en
Publication of WO2003012168B1 publication Critical patent/WO2003012168B1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/14—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying for coating elongate material
    • C23C4/16—Wires; Tubes
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/18—After-treatment
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L58/00—Protection of pipes or pipe fittings against corrosion or incrustation
    • F16L58/02—Protection of pipes or pipe fittings against corrosion or incrustation by means of internal or external coatings
    • F16L58/04—Coatings characterised by the materials used
    • F16L58/08—Coatings characterised by the materials used by metal
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L58/00—Protection of pipes or pipe fittings against corrosion or incrustation
    • F16L58/02—Protection of pipes or pipe fittings against corrosion or incrustation by means of internal or external coatings
    • F16L58/04—Coatings characterised by the materials used
    • F16L58/10—Coatings characterised by the materials used by rubber or plastics
    • F16L58/1054—Coatings characterised by the materials used by rubber or plastics the coating being placed outside the pipe
    • F16L58/1072—Coatings characterised by the materials used by rubber or plastics the coating being placed outside the pipe the coating being a sprayed layer

Definitions

  • This invention concerns tubes for environments, where the tubes are exposed to high temperatures and aggressive environments.
  • the invention also concerns ways of manufacturing such tubes and the use of such tubes.
  • tubes according to this invention are radiant tubes for the treatment, melting and heating of metallic and ceramic materials, tubes for heat exchangers and recuperators as well as thermocouple protection tubes for the measurements of high temperatures using thermocouples.
  • Radiant tubes are used in industrial furnaces, which are used for many different purposes and with varying atmospheres in the furnaces. Radiant tubes in furnaces are constantly exposed to corrosive atmospheres of different kinds. Oxidizing environments are common as well as strongly carburizing and sulphur containing environments. The temperature conditions can be unsuitable for the service life o the tubes. Both a very high temperature as well as specific temperature intervals below the highest temperature of application, can cause corrosion damages as well as other damages to quickly appear on the tubes. Both temperature conditions as well as other conditions can vary in a furnace, in continous furnaces are, for example, often the temperature lower in the inlet part ofthe furnace.
  • NiCr- and NiCrFe-alloys have limited service lives.
  • NiCr- and FeNiCr-alloys are alloyed with Si (silicon) to receive a surface layer of Si ⁇ 2 as protection to attacks from a corrosive atmosphere.
  • FeCrAl-alloys have been used for radiant tubes, among other things due to the advantageous properties of these alloys in strongly carburizing and sulphur containing atmospheres.
  • the FeCrAl-alloys contain aluminium, which forms a layer of a thin aluminium oxide, which has a good resistance in most ofthe furnace atmospheres that are common today.
  • the protecting aluminium oxide layer which forms on the surface do efficiently protect the base material from most corrosive environments.
  • the FeCrAl-alloys spontanously form aluminium oxide if the temperature is high enough and if the atmosphere contains oxygen.
  • the protecting aluminium oxide layer there are applications where this is not enough and as a result not even FeCrAl-tubes display enough good properties.
  • the formation and the preservation ofthe protecting layer also require that the radiant tubes are surrounded by an atmosphere containing a high enough oxygen content.
  • NiCr-, FeNiCr- and FeCrAl-alloys can be used in many applications and in different atmospheres, but in certain applications, a satisfactorily service life of tubes in these alloys are not achieved.
  • the present invention makes it possible to avoid quick failures in furnaces and other applications with, for other tubes, an unsuitable atmosphere and/or temperature. This is also of increasing interest in continous heat treatment processes, where a production stop is of great disadvantage in planning and costs. This invention makes it possible to work with longer periods between production stops for maintenance works.
  • the purpose ofthe present invention is that during certain special conditions concerning for example atmospheres or temperature ranges, to achieve a prolonged service life for tubes.
  • This purpose is achieved by the present invention, which concerns tubes with a coating which reinforces the protective oxide layers with, primarily, aluminium oxide.
  • the invention concerns also ways of manufacturing such tubes as well as the use of such tubes.
  • a surface layer of aluminium and/or aluminium oxide is brought onto the tube, whereafter the tube is heat treated at about 1050 C at enough long time, whereby the aluminium oxide layer on the FeCrAl-alloys are improved and the NiCr- and FeNiCr-alloys are given an aluminium oxide layer as protection in corrosive environments.
  • the purpose ofthe coating is to significantly increase the service life for critical applications and at increased service temperatures for tubes in these alloys. The good properties ofthe aluminium oxide are in this way utilized in most atmospheres where these alloys earlier could not be used.
  • Tubes according to this invention give advantages in many different areas of applications, among which the following examples can be given:
  • thermoelements used to measure the temperature of metal melts of aluminium and zinc.
  • the tubes are lowered into the melt for a shorter or a longer period of time.
  • the coatmg is performed with a thick aluminium oxide layer followed by a preoxidation.
  • the tubes both NiCr-, FeNiCr- and FeCrAl-tubes, with a thick aluminium oxide layer and perform a preoxidation afterwards, the protection and therefore also the service life, are significantly improved.
  • the purpose of this invention is to improve the aluminium oxide layer of the FeCrAl-alloys and to give the NiCr- and FeNiCr-alloys an aluminium oxide layer, as protection in a corrosive environment.
  • the purpose ofthe coating is to significantly increase the service life in critical applications as well as increased service temperatures for the NiCr- and FeNiCr-alloys.
  • tubes for the use at high temperatures or any other aggressive environment are coated with a coating of a layer of aluminium and aluminium oxide with a thickness of at least 0,3 mm, on the outside ofthe tube.
  • a coating of a layer of aluminium and aluminium oxide with a thickness of at least 0,3 mm on the outside ofthe tube.
  • it is suitable to coat the tube with many layers and perform an oxidation of every coated layer before next layer is put on usually the coating is made with 2 or 3 layers to a layer thickness of 0,3-0,7 mm, preferable ca 0,5 mm.
  • Suitable methods for coating are flame spraying, high velocity spraying, plasma spraying or other ways of thermal spraying or a combination of these methods.
  • the material which is put on is aluminium or possibly a mixture of aluminium and aluminium oxide.
  • aluminium also means alloys of aluminium with small amounts of alloy additions, preferably less than 5 weight percent.
  • a substantial amount ofthe coating material oxidizes, and the coating often contains a large amount of aluminium oxide.
  • a heat treatment is performed, which causes the coatmg material to completely transform into aluminium oxide. This treatment means heating to ca 1050 C during at least four hours. This procedure gives an aluminium oxide layer, which is not sensitive to mechanical damage and which stays on also at low temperatures, where one cannot expect spontanous aluminium oxide formation to occur.
  • FIG. 1-2 One example of the use of a tube according the mvention is shown in figures 1-2, which showns a dosing furnace for melted aluminium.
  • Figure 1 is a side view ofthe cross section ofthe furnace.
  • FIG. 1 shows the furnace from above with the cover removed.
  • the tube consists, according to the invention, by a high temperature alloy, on which a 0,5 mm thick surface layer has been put on, distributed on two separate layers, according to the desription above.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)
  • Laminated Bodies (AREA)
  • Coating By Spraying Or Casting (AREA)

Abstract

This invention concerns tubes for the use at high temperatures or any other aggressive environment. Tubes according to the invention have a coating consisting of a layer of aluminium and aluminium oxide with a thickness of at leat 0,3 mm on the outside of the tubes. The coating can consist of many layers and preferably be put on using flame spraying, high velocity spraying, plasma spraying or any other thermal spraying technique or a combination fo these methods. After the coating has been put on, it is oxidized by heating to ca 1050 C during at least four hours.

Description

TUBE, METHOD OF COATING AND USE OF SAME
This invention concerns tubes for environments, where the tubes are exposed to high temperatures and aggressive environments. The invention also concerns ways of manufacturing such tubes and the use of such tubes.
Examples of applications for tubes according to this invention are radiant tubes for the treatment, melting and heating of metallic and ceramic materials, tubes for heat exchangers and recuperators as well as thermocouple protection tubes for the measurements of high temperatures using thermocouples.
Radiant tubes are used in industrial furnaces, which are used for many different purposes and with varying atmospheres in the furnaces. Radiant tubes in furnaces are constantly exposed to corrosive atmospheres of different kinds. Oxidizing environments are common as well as strongly carburizing and sulphur containing environments. The temperature conditions can be unsuitable for the service life o the tubes. Both a very high temperature as well as specific temperature intervals below the highest temperature of application, can cause corrosion damages as well as other damages to quickly appear on the tubes. Both temperature conditions as well as other conditions can vary in a furnace, in continous furnaces are, for example, often the temperature lower in the inlet part ofthe furnace.
It is common to use radiant tubes in NiCr- and NiCrFe-alloys, however, these have limited service lives. NiCr- and FeNiCr-alloys are alloyed with Si (silicon) to receive a surface layer of Siθ2 as protection to attacks from a corrosive atmosphere.
Recently, also FeCrAl-alloys have been used for radiant tubes, among other things due to the advantageous properties of these alloys in strongly carburizing and sulphur containing atmospheres. The FeCrAl-alloys contain aluminium, which forms a layer of a thin aluminium oxide, which has a good resistance in most ofthe furnace atmospheres that are common today. The protecting aluminium oxide layer which forms on the surface do efficiently protect the base material from most corrosive environments. The FeCrAl-alloys spontanously form aluminium oxide if the temperature is high enough and if the atmosphere contains oxygen. Despite the protecting aluminium oxide layer, there are applications where this is not enough and as a result not even FeCrAl-tubes display enough good properties. The formation and the preservation ofthe protecting layer also require that the radiant tubes are surrounded by an atmosphere containing a high enough oxygen content.
NiCr-, FeNiCr- and FeCrAl-alloys can be used in many applications and in different atmospheres, but in certain applications, a satisfactorily service life of tubes in these alloys are not achieved.
The present invention makes it possible to avoid quick failures in furnaces and other applications with, for other tubes, an unsuitable atmosphere and/or temperature. This is also of increasing interest in continous heat treatment processes, where a production stop is of great disadvantage in planning and costs. This invention makes it possible to work with longer periods between production stops for maintenance works.
The purpose ofthe present invention is that during certain special conditions concerning for example atmospheres or temperature ranges, to achieve a prolonged service life for tubes. This purpose is achieved by the present invention, which concerns tubes with a coating which reinforces the protective oxide layers with, primarily, aluminium oxide. The invention concerns also ways of manufacturing such tubes as well as the use of such tubes.
According to the present invention, a surface layer of aluminium and/or aluminium oxide is brought onto the tube, whereafter the tube is heat treated at about 1050 C at enough long time, whereby the aluminium oxide layer on the FeCrAl-alloys are improved and the NiCr- and FeNiCr-alloys are given an aluminium oxide layer as protection in corrosive environments. The purpose ofthe coating is to significantly increase the service life for critical applications and at increased service temperatures for tubes in these alloys. The good properties ofthe aluminium oxide are in this way utilized in most atmospheres where these alloys earlier could not be used.
Tubes according to this invention give advantages in many different areas of applications, among which the following examples can be given:
- In continous furnaces, where one wants to prolong the service life ofthe radiant tubes, and avoid unexpected stops in production.
- In contious hardening furnaces, where a low temperature in combination with a corrosive environment, especially in the inlet part, make both FeNiCr-alloys and FeCrAl-alloys to fail after a very short time.
- In continous furnaces with high temperatures, 1000-1050 C, in carburizing atmospheres with high carbon potentials, where the presence of oxygen is low, why no spontanous aluminium oxide formation occurs.
- In dosing furnaces for aluminium -zink melts, an exteme furnace environment, in which degassing and raffination take place, and where splashes and mechanical damage strongly reduse the service life of the radiant tubes.
- In holding furnaces for aluminium -zink melts with aggressive slag covers and additions of alloying materials.
- Protection tubes for thermoelements used to measure the temperature of metal melts of aluminium and zinc. The tubes are lowered into the melt for a shorter or a longer period of time.
- Recuperators within the glass industry, which work in corrosive environments, for example crystal glass, where large additions of lead into the furnaces are made.
The coatmg is performed with a thick aluminium oxide layer followed by a preoxidation. By coating the tubes , both NiCr-, FeNiCr- and FeCrAl-tubes, with a thick aluminium oxide layer and perform a preoxidation afterwards, the protection and therefore also the service life, are significantly improved.
The purpose of this invention is to improve the aluminium oxide layer of the FeCrAl-alloys and to give the NiCr- and FeNiCr-alloys an aluminium oxide layer, as protection in a corrosive environment. The purpose ofthe coating is to significantly increase the service life in critical applications as well as increased service temperatures for the NiCr- and FeNiCr-alloys.
In the coating procedure according to this invention, tubes for the use at high temperatures or any other aggressive environment, are coated with a coating of a layer of aluminium and aluminium oxide with a thickness of at least 0,3 mm, on the outside ofthe tube. In many applications it is suitable to coat the tube with many layers and perform an oxidation of every coated layer before next layer is put on, usually the coating is made with 2 or 3 layers to a layer thickness of 0,3-0,7 mm, preferable ca 0,5 mm. Suitable methods for coating are flame spraying, high velocity spraying, plasma spraying or other ways of thermal spraying or a combination of these methods. The material which is put on is aluminium or possibly a mixture of aluminium and aluminium oxide. With aluminium also means alloys of aluminium with small amounts of alloy additions, preferably less than 5 weight percent. At the high temperatures which are prevailing during the coatmg process, a substantial amount ofthe coating material oxidizes, and the coating often contains a large amount of aluminium oxide. After the layer or the layers and possible also between the coating of two layers, a heat treatment is performed, which causes the coatmg material to completely transform into aluminium oxide. This treatment means heating to ca 1050 C during at least four hours. This procedure gives an aluminium oxide layer, which is not sensitive to mechanical damage and which stays on also at low temperatures, where one cannot expect spontanous aluminium oxide formation to occur.
One example of the use of a tube according the mvention is shown in figures 1-2, which showns a dosing furnace for melted aluminium.
Figure 1 is a side view ofthe cross section ofthe furnace.
Figure 2 shows the furnace from above with the cover removed.
In the furnace there is melted aluminium, 1, which is hold at temperature using three elements, placed horisontally above the surface of aluminium. Every element includes an electric resistance element, 3, which is surrounded by the tube, 2. The tube consists, according to the invention, by a high temperature alloy, on which a 0,5 mm thick surface layer has been put on, distributed on two separate layers, according to the desription above.

Claims

Claims
1.) Tube for use at high temperature or any other aggressive environment, characterized therein, that a coating of a layer of aluminium and aluminium oxide with a thickness of at least 0,3 mm has been applied onto the outside ofthe tubes.
2.) Tube according to claim 1, characterized therein, that the coating consists of many layers.
3.) Tube according to claims 1 or 2, characterized therein, that the tube consists of an alloy of NiCr, FeNiCr or FeCrAl.
4.) Procedure of manufacturing of a tube for use at high temperature or any other aggressive environment characterized therein, that the tube is coated by aluminium and aluminium oxide on the outside ofthe tube and with a thickness of at least 0,3 mm.
5.) Procedure according to claim 4, characterized therein, that the coating is applied using flame spraying, high velocity spraying, plasma spraying or any other thermal spraying or a combination of these methods.
6.) Procedure according to claim 4, characterized therein, that the coating applied, is oxidized by heat treating at ca 1050 C during at least four hours.
7.) Procedure according to any ofthe claims 4-6, characterized therein, that the coating is applied in many layers, till the required layer thickness has been arrived at.
8.) Procedure according to claim 7, characterized therein, that at least one oxidation by heat treating at ca 1050 C is performed after coating of with separate layers 9.) Use of tubes according to any of the claims 1-8, in an aggressive environment.
PCT/SE2002/001418 2001-07-27 2002-07-26 Tube, method of coating and use of same WO2003012168A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP02751943A EP1423554A1 (en) 2001-07-27 2002-07-26 Tube, method of coating and use of same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE0102626-9 2001-07-27
SE0102626A SE522102C2 (en) 2001-07-27 2001-07-27 Pipes for use in an aggressive environment, as well as methods for coating such pipes

Publications (2)

Publication Number Publication Date
WO2003012168A1 true WO2003012168A1 (en) 2003-02-13
WO2003012168B1 WO2003012168B1 (en) 2004-04-08

Family

ID=20284951

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/SE2002/001418 WO2003012168A1 (en) 2001-07-27 2002-07-26 Tube, method of coating and use of same

Country Status (3)

Country Link
EP (1) EP1423554A1 (en)
SE (1) SE522102C2 (en)
WO (1) WO2003012168A1 (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1149163A (en) * 1966-03-22 1969-04-16 Ici Ltd Protection against carburisation
EP0366289A1 (en) * 1988-10-11 1990-05-02 Midwest Research Technologies, Inc. Multi-layer wear resistant coatings
EP0564665A2 (en) * 1990-05-14 1993-10-13 Kanthal AB Cracking Furnace

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1149163A (en) * 1966-03-22 1969-04-16 Ici Ltd Protection against carburisation
EP0366289A1 (en) * 1988-10-11 1990-05-02 Midwest Research Technologies, Inc. Multi-layer wear resistant coatings
EP0564665A2 (en) * 1990-05-14 1993-10-13 Kanthal AB Cracking Furnace

Also Published As

Publication number Publication date
SE522102C2 (en) 2004-01-13
SE0102626D0 (en) 2001-07-27
SE0102626L (en) 2003-01-28
EP1423554A1 (en) 2004-06-02
WO2003012168B1 (en) 2004-04-08

Similar Documents

Publication Publication Date Title
JP2010502550A (en) Method and apparatus for minimizing oxidation pitting corrosion in refractory metal baths
JPH05339082A (en) Coated ceramic article
US4668262A (en) Protective coating for refractory metal substrates
NO984240L (en) Corrosion resistance of high-temperature alloys
EP0524851B1 (en) Process for deposing metal or metal alloys on a metal strip and guide pieces for implementing this process
EP0570219B1 (en) Use of a molten zinc resistant alloy
JPH0124223B2 (en)
EP1423554A1 (en) Tube, method of coating and use of same
JPH0745703B2 (en) High temperature resistant thermal spray coating
JPH05473B2 (en)
JPS6326183B2 (en)
JP4042367B2 (en) Thermocouple, protective tube material and method of using the material
EP0022272B1 (en) Method of anti-corrosion protection of silicon carbide elements and apparatus for carrying out the method
JPH06104888B2 (en) Conveyor roll for high temperature steel
JPS6028903B2 (en) Surface treatment method for metal materials
JP3641759B2 (en) Manufacturing method of temperature sensor with integrated thermocouple and protective tube
JP3014093U (en) Temperature sensor with thermocouple and protective tube integrated
JPS62103314A (en) Manufacture of transfer roll for heat treating furnace
US4019926A (en) Prevention of corrosion of metals
CA1188078A (en) Method of anti-corrosive protection of silicon carbide products
JPS60131786A (en) Sheathed motor
JPS62188724A (en) Roll for heat treating furnace
JPS58213864A (en) Coating method of shell of hot stove
JPH03226517A (en) In-furnace roll for heat treatment
JPH07215782A (en) Corrosion resistant insulating coating method for silicon carbide heating element

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PH PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BY BZ CA CH CN CO CR CU CZ DE DM DZ EC EE ES FI GB GD GE GH HR HU ID IL IN IS JP KE KG KP KR LC LK LR LS LT LU LV MA MD MG MN MW MX MZ NO NZ PH PL PT RO SD SE SG SI SK SL TJ TM TR TT TZ UG US UZ VN YU ZA

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ UG ZM ZW AM AZ BY KG KZ RU TJ TM AT BE BG CH CY CZ DK EE ES FI FR GB GR IE IT LU MC PT SE SK TR BF BJ CF CG CI GA GN GQ GW ML MR NE SN TD TG

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LU MC NL PT SE SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 2002751943

Country of ref document: EP

B Later publication of amended claims

Effective date: 20030224

WWP Wipo information: published in national office

Ref document number: 2002751943

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP