WO2005118185A1 - Wear resistant alloy powders and coatings - Google Patents

Wear resistant alloy powders and coatings Download PDF

Info

Publication number
WO2005118185A1
WO2005118185A1 PCT/US2005/018423 US2005018423W WO2005118185A1 WO 2005118185 A1 WO2005118185 A1 WO 2005118185A1 US 2005018423 W US2005018423 W US 2005018423W WO 2005118185 A1 WO2005118185 A1 WO 2005118185A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight percent
alloy
wear resistant
chromium
molybdenum
Prior art date
Application number
PCT/US2005/018423
Other languages
English (en)
French (fr)
Inventor
William J. C. Jarosinski
Lewis B. Temples
Original Assignee
Praxair S. T. Technology, Inc.
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 Praxair S. T. Technology, Inc. filed Critical Praxair S. T. Technology, Inc.
Priority to US11/596,624 priority Critical patent/US20080274010A1/en
Priority to JP2007515312A priority patent/JP5222553B2/ja
Priority to CA2567089A priority patent/CA2567089C/en
Priority to MXPA06013558A priority patent/MXPA06013558A/es
Priority to BRPI0511582-5A priority patent/BRPI0511582A/pt
Priority to EP05753987A priority patent/EP1768802A4/en
Publication of WO2005118185A1 publication Critical patent/WO2005118185A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • C22C1/045Alloys based on refractory metals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/03Alloys based on nickel or cobalt based on nickel
    • C22C19/05Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/053Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 30% but less than 40%
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C27/00Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/04Alloys based on tungsten or molybdenum
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C27/00Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/06Alloys based on chromium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • This invention relates to chromium-molybdenum alloys and wear resistant alloy powders useful for deposition through thermal spray devices.
  • the wear resistant alloy powders are useful for forming coatings having the same composition.
  • Hard surface coating metals and alloys are known in the art.
  • chromium metal has been used as an electroplated coating for many years to restore worn or damaged parts to their original dimensions, to increase wear and corrosion resistance, and to reduce friction.
  • Hard chromium electroplate has a number of limitations. When the configuration of the part becomes complex, obtaining a uniform coating thickness by electro-deposition is difficult. A non- uniform coating thickness necessitates grinding to a finished surface configuration, which is both difficult and expensive with electroplated chromium because of its inherent brittleness and hardness. The rate of deposition by electroplating is relatively low, and thus a substantial capital investment in plating equipment is required.
  • 3,846,084 discloses coatings made by the plasma or detonation gun process that are superior to hard chromium electroplate in compatibility, frictional characteristics and wear resistance by incorporating a dispersion of chromium carbide particles in a chromium matrix. Coatings of this type can be made from mechanical mixtures of powders. However, there are certain limitations to the quality of coatings made from them. Plasma, HVOF and detonation-gun coatings result in a multilayer structure of overlapping lamellae or "splats." Each splat is derived from a single particle of the powder used to produce the coating. There appears to be little, if any, combining or alloying of two or more powder particles during the coating deposition process. U.S. Patent No.
  • 6,562,480 Bl discloses a wear resistant coating for protecting a surface undergoing sliding contact with another surface such as piston rings and cylinder liners of internal combustion engines.
  • the wear resistant coating is applied by HVOF deposition of a powder which comprises a blend of about 13 weight percent to about 43 weight percent of a nickel -chromium alloy, about 25 weight percent to about 64 weight percent chromium carbide, and about 15 weight percent to about 50 weight percent molybdenum.
  • U.S. Patent No. 6,503,290 Bl discloses a corrosion resistant powder useful for deposition through thermal spray devices.
  • the powder comprises about 30 to 60 weight percent tungsten, about 27 to 60 weight percent chromium, about 1.5 to 6 weight percent carbon, a total of about 10 to 40 weight percent cobalt plus nickel and incidental impurities plus melting point suppressants.
  • the corrosion resistant powder is useful for forming coatings having the same composition.
  • a need continues to exist for powders and coatings that can be deposited by thermal spray devices and that exhibit excellent wear and/or corrosion resistance. Therefore, a need continues to exist for developing new powders and for exploring their potential for thermal spray deposition of wear and corrosion resistant coatings. It would therefore be desirable in the art to provide powders and coatings that can be deposited by thermal spray devices and that exhibit excellent wear and corrosion resistance .
  • the alloys include precipitated carbides (and optionally nitrides) of chromium and molybdenum interspersed throughout.
  • This invention also relates to wear resistant alloy powders useful for deposition through thermal spray devices.
  • the powders comprise an alloy of about 20 to 65 weight percent chromium, about 20 to 65 weight percent molybdenum, about 0.5 to 3 weight percent carbon, and about 10 to 45 weight percent nickel.
  • the wear resistant alloy powders are useful for forming coatings having the same composition.
  • this invention relates to wear resistant alloy powders useful for deposition through thermal spray devices such as plasma, HVOF or detonation gun.
  • the powders are made from alloys comprising about 20 to 65 weight percent chromium, about 20 to 65 weight percent molybdenum, about 0.5 to 3 weight percent carbon, and about 10 to 45 weight percent nickel .
  • the alloys include precipitated carbides and optionally nitrides of chromium and molybdenum interspersed throughout.
  • the alloys are useful for forming wear resistant powders and coatings having the same composition.
  • the alloys herein rely upon a large concentration of chromium and molybdenum for excellent wear resistance.
  • the alloys contain at least about 20 weight percent chromium, preferably at least about 30 weight percent chromium, and more preferably at least about 35 weight percent chromium. Powders containing less than about 20 weight percent chromium may exhibit inadequate wear resistance for many applications. Chromium levels in excess of about 65 weight percent may tend to detract from the wear resistance of the coating because the coating may become too brittle. Similarly, the alloys contain at least about 20 weight percent molybdenum, preferably at least about 25 weight percent molybdenum, and more preferably about 30 or 35 weight percent molybdenum. Powders containing less than about 20 weight percent molybdenum may exhibit inadequate wear resistance for many applications.
  • the alloys comprise about 20 to 65, preferably about 30 to 60, and more preferably about 35 to 55, weight percent chromium; about 20 to 65, preferably about 25 to 60, and more preferably about 30 to 55, weight percent molybdenum; about 0.5 to 3, preferably about 1 to 2.5, and more preferably about 1.5 to 2, weight percent carbon; and about 10 to 45, preferably about 15 to 35, and more preferably about 20 to 35, weight percent nickel.
  • These alloys are useful for forming wear resistant powders and coatings having the same composition.
  • the alloys comprise about 50 to 90, preferably about 60 to 80, and more preferably about 65 to 75, weight percent chromium and molybdenum; about 0.5 to 3, preferably about 1 to 2.5, and more preferably about 1.5 to 2, weight percent carbon; and about 10 to 45, preferably about 15 to 35, and more preferably about 20 to 35, weight percent nickel.
  • These alloys are useful for forming wear resistant powders and coatings having the same composition.
  • the carbon concentration controls the hardness and wear properties of coatings formed with the powders. A minimum of about 0.5 weight percent carbon may be necessary to impart adequate hardness into the coatings. If the carbon exceeds about 3 weight percent, the melting temperature of the powder may become too high and it may become too difficult to atomize the powder.
  • cobalt may be included in the alloys, powders and coatings.
  • the powders may contain about 10 to 45, preferably about 15 to 35, and more preferably about 20 to 35, weight percent nickel plus cobalt. This may facilitate the melting of the chromium/molybdenum/carbon combination that, if left alone, would form carbides having too high of melting temperatures for atomization.
  • Increasing the concentration of cobalt and nickel may also tend to increase the deposition efficiency for thermal spraying the powder. Because total nickel plus cobalt levels above about 45 weight percent may tend to soften the coating and limit the wear resistance of the coating, the total concentration of nickel plus cobalt may best be maintained below about 45 weight percent.
  • the alloys may contain only nickel or cobalt since coatings with only nickel (e.g., about 10 to 45 weight percent nickel) or only cobalt (e.g., about 10 to 45 weight percent cobalt) may form powders with wear resistance tailored for specific applications. But for most applications, cobalt and nickel appear to be interchangeable.
  • boron, silicon and/or manganese may be included in the alloys, powders and coatings.
  • the alloys may contain about 0.5 to 3, preferably about 1 to 2.5, and more preferably about 1.5 to 2, weight percent carbon plus boron, silicon and/or manganese.
  • the alloys may optionally contain melting point suppressants such as boron, silicon and manganese.
  • the alloys include precipitated carbides (and optionally nitrides) of chromium and molybdenum interspersed throughout .
  • the alloys may contain a volume fraction of the precipitated carbides and optionally nitrides in excess of 0.25.
  • the volume fraction of the precipitated carbides and optionally nitrides dispersed in the alloys may be 0.25 or greater and more preferably between 0.35 and 0.80.
  • the precipitated carbide and optionally nitride grains may be of micrometer and submicrometer size, for example, between 0.5 or less and 20 micrometers, more preferably between 1 and 10 micrometers in its largest dimensions.
  • the size and volume fraction of the precipitated carbides and optionally nitrides can be adjusted by varying the chromium, molybdenum and carbon content.
  • the alloys of this invention may be blended with molybdenum to form powders with wear resistance tailored for specific applications.
  • the amount of molybdenum that may be blended with the alloys of this invention is not narrowly critical and may range from about 10 to 50, preferably about 15 to 45, and more preferably about 20 to 40, weight percent of the total alloy/molybdenum blend composition.
  • the amount of blended molybdenum is in addition to the amount of alloy molybdenum.
  • the amount of blended molybdenum will depend upon the desired application.
  • the powders of this invention may be produced by means of inert gas atomization of a mixture of elements in the proportions stated herein.
  • Preferred atomization methods that may be employed in making the powders of this invention are described in U.S. Patent 5,863,618, the disclosure of which is incorporated herein by reference.
  • the alloys of these powders are typically melted at a temperature of about 1600°C and then atomized in a protective atmosphere (e.g., argon, helium or nitrogen). Most advantageously the atmosphere is argon.
  • a nitrogen atmosphere may be employed which may result in the formation of additional hard phases interspersed throughout the alloys, e.g., nitrides.
  • the alloy may optionally contain melting point suppressants like boron, silicon and manganese.
  • melting point suppressants like boron, silicon and manganese.
  • gas atomization however represents the most effective method for manufacturing the powder. Gas atomization techniques typically produce a powder having a size distribution of about 1 to 500 microns. For thermal spray applications, the powder is classified to a size of about 1 to 100 microns. Coatings may be produced using the alloys of this invention by a variety of methods well known in the art.
  • Thermal spray is a preferred method for deposition of powders to form the coatings of this invention.
  • the wear resistant alloy powders of this invention are useful for forming coatings having the same composition.
  • the alloy powders of this invention are useful for forming coatings or objects having excellent wear properties, for example, wear resistant coatings for protecting surfaces undergoing sliding contact with other surfaces such as piston rings and cylinder liners of internal combustion engines.
  • the examples that follow are intended as an illustration of certain preferred embodiments of the invention, and no limitation of the invention is implied.
  • Example 1 The alloy powders listed in Table I were made by processes alike to those described in U.S. Patent 5,863,618.
PCT/US2005/018423 2004-05-28 2005-05-26 Wear resistant alloy powders and coatings WO2005118185A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US11/596,624 US20080274010A1 (en) 2004-05-28 2005-05-26 Wear Resistant Alloy Powders and Coatings
JP2007515312A JP5222553B2 (ja) 2004-05-28 2005-05-26 耐摩耗性合金粉末および被覆
CA2567089A CA2567089C (en) 2004-05-28 2005-05-26 Wear resistant alloy powders and coatings
MXPA06013558A MXPA06013558A (es) 2004-05-28 2005-05-26 Polvos y recubrimientos de aleacion resistentes al desgaste.
BRPI0511582-5A BRPI0511582A (pt) 2004-05-28 2005-05-26 liga, e, pó resistente ao desgaste
EP05753987A EP1768802A4 (en) 2004-05-28 2005-05-26 POWDERS AND COATINGS OF WEAR-RESISTANT ALLOYS

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US57492904P 2004-05-28 2004-05-28
US60/574,929 2004-05-28

Publications (1)

Publication Number Publication Date
WO2005118185A1 true WO2005118185A1 (en) 2005-12-15

Family

ID=35462777

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2005/018423 WO2005118185A1 (en) 2004-05-28 2005-05-26 Wear resistant alloy powders and coatings

Country Status (8)

Country Link
US (1) US20080274010A1 (es)
EP (1) EP1768802A4 (es)
JP (1) JP5222553B2 (es)
CN (1) CN1997474A (es)
BR (1) BRPI0511582A (es)
CA (1) CA2567089C (es)
MX (1) MXPA06013558A (es)
WO (1) WO2005118185A1 (es)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103981398A (zh) * 2014-05-27 2014-08-13 湘潭大学 一种高性能金属陶瓷覆层材料及其制备方法

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006042549C5 (de) * 2006-09-11 2017-08-17 Federal-Mogul Burscheid Gmbh Nasse Zylinderlaufbuchse mit kavitationsresistenter Oberfläche
JP5626947B2 (ja) * 2008-09-22 2014-11-19 独立行政法人物質・材料研究機構 大気中プラズマ溶射及び溶線式アーク溶射に使用される合金粒子及び線材
DE102009035210B3 (de) * 2009-07-29 2010-11-25 Federal-Mogul Burscheid Gmbh Gleitelement mit thermisch gespritzter Beschichtung und Herstellungsverfahren dafür
US8906130B2 (en) 2010-04-19 2014-12-09 Praxair S.T. Technology, Inc. Coatings and powders, methods of making same, and uses thereof
FI124135B (fi) * 2010-06-08 2014-03-31 Wärtsilä Finland Oy Mäntämoottorin sylinteriholkki
BRPI1101402A2 (pt) * 2011-03-29 2013-06-04 Mahle Metal Leve Sa elemento deslizante
KR20140083020A (ko) 2011-10-25 2014-07-03 가부시키가이샤 아이에이치아이 피스톤 링
US9611532B2 (en) * 2013-07-03 2017-04-04 Mahle International Gmbh Coating additive
CN108085550A (zh) * 2017-12-21 2018-05-29 厦门佰事兴新材料科技有限公司 一种超音速火焰喷涂用喷管

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3030206A (en) * 1959-02-17 1962-04-17 Gen Motors Corp High temperature chromiummolybdenum alloy
US4556607A (en) * 1984-03-28 1985-12-03 Sastri Suri A Surface coatings and subcoats
US4692305A (en) * 1985-11-05 1987-09-08 Perkin-Elmer Corporation Corrosion and wear resistant alloy
US4822415A (en) * 1985-11-22 1989-04-18 Perkin-Elmer Corporation Thermal spray iron alloy powder containing molybdenum, copper and boron
JPH08325698A (ja) * 1995-05-26 1996-12-10 Nittetsu Hard Kk 連続溶融金属めっき浴中ロール軸部材用被覆材料
US6248292B1 (en) * 1998-02-25 2001-06-19 Toyota Jidosha Kabushiki Kaisha Overlay welding alloy and engine valve overlayed therewith
US6887585B2 (en) * 2000-09-21 2005-05-03 Federal-Mogul Burscheid Gmbh Thermally applied coating of mechanically alloyed powders for piston rings

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2868639A (en) * 1955-10-06 1959-01-13 Wall Colmonoy Corp Metallic composition
US3846084A (en) * 1973-08-15 1974-11-05 Union Carbide Corp Chromium-chromium carbide powder and article made therefrom
JPS59100263A (ja) * 1982-11-29 1984-06-09 Teikoku Piston Ring Co Ltd 溶射ピストンリング
JPS59211546A (ja) * 1983-05-17 1984-11-30 Sumitomo Metal Ind Ltd コバルト基溶射合金
EP0223135A1 (en) * 1985-11-05 1987-05-27 The Perkin-Elmer Corporation Corrosion resistant self-fluxing alloys for thermal spraying
DE3802920C1 (es) * 1988-02-02 1989-05-03 Goetze Ag, 5093 Burscheid, De
US5141571A (en) * 1991-05-07 1992-08-25 Wall Colmonoy Corporation Hard surfacing alloy with precipitated bi-metallic tungsten chromium metal carbides and process
JPH07300642A (ja) * 1994-04-27 1995-11-14 Nittetsu Hard Kk 被覆用材料及びこの材料が被覆された金属浴浸漬用部材
JPH07316696A (ja) * 1994-05-27 1995-12-05 Mitsubishi Materials Corp 鋳造用Ni基合金
FI100388B (fi) * 1996-01-22 1997-11-28 Rauma Materials Tech Oy Kulutusta kestävä, sitkeä teräs
JPH09209095A (ja) * 1996-01-30 1997-08-12 Mitsubishi Materials Corp 耐摩耗性に優れた鉄基焼結合金
DE10061751C1 (de) * 2000-12-12 2002-07-25 Federal Mogul Burscheid Gmbh Verschleißschutzschicht für Kolbenringe
US6503290B1 (en) * 2002-03-01 2003-01-07 Praxair S.T. Technology, Inc. Corrosion resistant powder and coating
US6863990B2 (en) * 2003-05-02 2005-03-08 Deloro Stellite Holdings Corporation Wear-resistant, corrosion-resistant Ni-Cr-Mo thermal spray powder and method

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3030206A (en) * 1959-02-17 1962-04-17 Gen Motors Corp High temperature chromiummolybdenum alloy
US4556607A (en) * 1984-03-28 1985-12-03 Sastri Suri A Surface coatings and subcoats
US4692305A (en) * 1985-11-05 1987-09-08 Perkin-Elmer Corporation Corrosion and wear resistant alloy
US4822415A (en) * 1985-11-22 1989-04-18 Perkin-Elmer Corporation Thermal spray iron alloy powder containing molybdenum, copper and boron
JPH08325698A (ja) * 1995-05-26 1996-12-10 Nittetsu Hard Kk 連続溶融金属めっき浴中ロール軸部材用被覆材料
US6248292B1 (en) * 1998-02-25 2001-06-19 Toyota Jidosha Kabushiki Kaisha Overlay welding alloy and engine valve overlayed therewith
US6887585B2 (en) * 2000-09-21 2005-05-03 Federal-Mogul Burscheid Gmbh Thermally applied coating of mechanically alloyed powders for piston rings

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1768802A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103981398A (zh) * 2014-05-27 2014-08-13 湘潭大学 一种高性能金属陶瓷覆层材料及其制备方法

Also Published As

Publication number Publication date
CA2567089C (en) 2010-04-20
US20080274010A1 (en) 2008-11-06
MXPA06013558A (es) 2007-02-08
JP5222553B2 (ja) 2013-06-26
CA2567089A1 (en) 2005-12-15
CN1997474A (zh) 2007-07-11
EP1768802A4 (en) 2009-07-22
JP2008501073A (ja) 2008-01-17
EP1768802A1 (en) 2007-04-04
BRPI0511582A (pt) 2008-01-02

Similar Documents

Publication Publication Date Title
CA2567089C (en) Wear resistant alloy powders and coatings
EP1485220B1 (en) Corrosion resistant powder and coating
US9291264B2 (en) Coatings and powders, methods of making same, and uses thereof
EP0223202B1 (en) Iron alloy containing molybdenum, copper and boron
US3313633A (en) High temperature flame spray powder
EP0138228B1 (en) Abrasion resistant coating and method for producing the same
EP0224724B1 (en) Amorphous alloy
US9919358B2 (en) Sintered molybdenum carbide-based spray powder
US3378392A (en) High temperature flame spray powder and process
US5966585A (en) Titanium carbide/tungsten boride coatings
US3779720A (en) Plasma sprayed titanium carbide tool steel coating
EP1077272A1 (en) Titanium carbide/tungsten boride coatings
US5837327A (en) Method for producing a TiB2 -based coating
JP6985961B2 (ja) ピストンリング及びその製造方法
JP6411875B2 (ja) ピストンリング及びその製造方法
JPH0564706B2 (es)
US4588606A (en) Abrasion resistant coating and method for producing the same
JPH0258345B2 (es)
BRPI0511582B1 (pt) Leather, and, wear resistant powder

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 BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KM KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NG NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA 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 HU IE IS IT LT LU MC NL PL PT RO SE SI 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
WWE Wipo information: entry into national phase

Ref document number: 2567089

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: PA/a/2006/013558

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 200580017117.X

Country of ref document: CN

Ref document number: 2007515312

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

WWW Wipo information: withdrawn in national office

Ref document number: DE

REEP Request for entry into the european phase

Ref document number: 2005753987

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2005753987

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 2005753987

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 11596624

Country of ref document: US

ENP Entry into the national phase

Ref document number: PI0511582

Country of ref document: BR