WO2004006268A2 - Storage of hazardous materials - Google Patents

Storage of hazardous materials Download PDF

Info

Publication number
WO2004006268A2
WO2004006268A2 PCT/GB2003/002870 GB0302870W WO2004006268A2 WO 2004006268 A2 WO2004006268 A2 WO 2004006268A2 GB 0302870 W GB0302870 W GB 0302870W WO 2004006268 A2 WO2004006268 A2 WO 2004006268A2
Authority
WO
WIPO (PCT)
Prior art keywords
nuclear
cementitious material
fuel
cementitious
elements
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.)
Ceased
Application number
PCT/GB2003/002870
Other languages
French (fr)
Other versions
WO2004006268A3 (en
Inventor
Adele Charmaine Hollick
Nicholas Paul Hanigan
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.)
Sellafield Ltd
Original Assignee
British Nuclear Fuels PLC
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 British Nuclear Fuels PLC filed Critical British Nuclear Fuels PLC
Priority to AU2003251153A priority Critical patent/AU2003251153A1/en
Priority to US10/519,869 priority patent/US20060111603A1/en
Priority to EP20030762781 priority patent/EP1535287A2/en
Publication of WO2004006268A2 publication Critical patent/WO2004006268A2/en
Publication of WO2004006268A3 publication Critical patent/WO2004006268A3/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/28—Treating solids
    • G21F9/30—Processing
    • G21F9/301—Processing by fixation in stable solid media
    • G21F9/302—Processing by fixation in stable solid media in an inorganic matrix
    • G21F9/304—Cement or cement-like matrix
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/04—Portland cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00767—Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • This invention relates to a method for the treatment and storage of hazardous materials by encapsulation. More specifically, it is concerned with the encapsulation in cementitious media of materials encountered in the nuclear industry, and has specific application to uranium and so-called Magnox fuel elements.
  • EP-A-412913 teaches the use of a Portland Cement based grout in the consolidation of concrete structures affected by fine cracks, providing a cost-effective means of infilling both superficial and deeper fissures and cavities in such structures, including such as buildings, bridges and dams.
  • ZA-A-9209810 is concerned with a pumpable, spreadable grouting composition incorporating a cementitious and/or pozzolanic or equivalent material, and its application in sealing fissures and cracks, back-filling, providing mass fills in civil and mining works, or lining tunnels.
  • hydraulic setting compositions comprising particles of Portland Cement together with fine particles of silica fume containing amorphous silica, which are the subject of EP-A-534385 and are used in the production of concrete, mortar or grout having improved fluidity
  • GB-A-2187727 describes a rapid gelling, hydraulic cement composition which comprises an acrylic gelling agent, a fine filler and Portland Cement, this composition being thixotropic and finding particular application in the formation of bulk infills for underground mining, and in the filling of voids and cavities in construction or civil engineering.
  • a composition which also is useful in general building and construction work, and as an insulating material comprises a particulate filler, cellulose fibres and a cementitious binder, and is disclosed in GB-A-2117753.
  • EP-A-801124 Whilst the majority of these compositions of the prior art have a requirement for the addition of water, EP-A-801124 is concerned with a dry mixture, used for fine soil injection grout preparation, the mixture comprising fillers which do not react with water, cement and deflocculant; on addition of water, an agglomerate-free fine grout is formed, and this is easily injected into fine soil.
  • cured cementitious materials may advantageously be employed for the long term encapsulation of uranium and Magnox fuel elements, as well as fuel element debris, thereby providing a product which remains stable and monolithic for many hundreds of years.
  • a treatment method is provided which affords much greater efficiency, convenience and safety in handling, and has a consequent beneficial effect both in terms of environmental considerations and cost, thereby satisfying a long felt need in the nuclear industry wherein the waste management of materials is receiving ever greater attention in the global drive to ensure ever higher safety standards.
  • a method for the encapsulation of a nuclear material which comprises treating the material with an encapsulant which comprises a cementitious material and curing said cementitious material.
  • the nuclear material comprises a nuclear fuel material such as uranium metal or Magnox fuel elements or fuel element debris.
  • a nuclear fuel material such as uranium metal or Magnox fuel elements or fuel element debris.
  • it may comprise, for example, fast reactor fuel, metal oxide fuel or mixed oxide fuel.
  • the cementitious material may typically comprise, for example, Portland Cement or a similar commercially available product.
  • One or more additional inorganic fillers may optionally be added to the cementitious material; suitable fillers include blast furnace slag, pulverised fuel ash, hydrated lime, finely divided silica, limestone flour and organic and inorganic fluidising agents.
  • the invention also provides a method for the storage of a nuclear material which comprises encapsulation of the material in a cured cementitious material.
  • the method of the present invention is of particular value in the treatment of nuclear fuel materials. Such materials may be treated by this method in order to obtain a product which remains stable and monolithic for many hundreds of years, thereby offering a safe and convenient alternative means of handling other than nuclear fuel reprocessing.
  • a particular example of the application of the method involves placing the nuclear material in an appropriate container and adding a suitable cementitious material. Elements of the nuclear material may either be arrayed in the container or mixed haphazardly. The cementitious material is then added and allowed to at least partially cure, and the container may then be capped or, alternatively sent directly for storage or final disposal.
  • the capping process involves placing a cap of cement on top of the mixture of nuclear material and cementitious material in the container after this mixture has been allowed to partially cure; the procedure has proved to be especially valuable in ensuring the safe long term storage of the material, and it provides an additional benefit in the reduction of secondary waste.
  • the container may comprise any container of an appropriate form and size, for example a drum having a capacity in the region of 500 litres.
  • the amount of nuclear material which may safely be stored may be up to as many as 52 elements.
  • the number of elements would be of the order of 22.
  • the cementitious material is provided in the form of an aqueous composition with a water content preferably in the region of 40-50% (w/w).
  • the material may conveniently be pumped under pressure into the container.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention provides a method for the encapsulation of a nuclear material, which comprises treating the material with an encapsulant, which comprises a cementitious material, such as Portland Cement, and curing, said cementitious material. The method is particularly suitable for the treatment of nuclear fuel materials such as uranium metal, complete Magnox fuel elements, or fuel element debris, for which encapsulation treatments have never previously been known. Such materials may be treated by the method of the invention in order to obtain products which remains stable and monolithic for many hundreds of years, and the invention thereby offers a safe and convenient alternative means of handling other than nuclear fuel reprocessing.

Description

STORAGE OFHAZARDOUS MATERIALS
Field of the Invention
This invention relates to a method for the treatment and storage of hazardous materials by encapsulation. More specifically, it is concerned with the encapsulation in cementitious media of materials encountered in the nuclear industry, and has specific application to uranium and so-called Magnox fuel elements.
Background to the Invention Encapsulation has proved to be an especially favoured method for the disposal of certain hazardous materials; specifically it provides a suitable means for the conversion of these materials into a stable and safe form, which allows for long-term storage and/or ultimate disposal. The technique can find particular application in the nuclear industry, where the highly toxic and radioactive nature of the materials involved, and the extended timescales over which the toxicity is maintained, are the principal considerations when devising safe disposal methods.
In co-pending GB patent application No. 0130593.7, the present applicant has disclosed the use of cementitious grouting materials for the encapsulation of fine particulate sized wastes and provided details of a method for the encapsulation of fine particulate materials which comprises treating these materials with at least one microfine hydraulic inorganic filler.
The use of cement based injection grouting in the construction industry is well known from the prior art. Thus, EP-A-412913 teaches the use of a Portland Cement based grout in the consolidation of concrete structures affected by fine cracks, providing a cost-effective means of infilling both superficial and deeper fissures and cavities in such structures, including such as buildings, bridges and dams. Similarly, ZA-A-9209810 is concerned with a pumpable, spreadable grouting composition incorporating a cementitious and/or pozzolanic or equivalent material, and its application in sealing fissures and cracks, back-filling, providing mass fills in civil and mining works, or lining tunnels.
Also disclosed in the prior art are hydraulic setting compositions comprising particles of Portland Cement together with fine particles of silica fume containing amorphous silica, which are the subject of EP-A-534385 and are used in the production of concrete, mortar or grout having improved fluidity, whilst GB-A-2187727 describes a rapid gelling, hydraulic cement composition which comprises an acrylic gelling agent, a fine filler and Portland Cement, this composition being thixotropic and finding particular application in the formation of bulk infills for underground mining, and in the filling of voids and cavities in construction or civil engineering. A composition which also is useful in general building and construction work, and as an insulating material comprises a particulate filler, cellulose fibres and a cementitious binder, and is disclosed in GB-A-2117753.
Whilst the majority of these compositions of the prior art have a requirement for the addition of water, EP-A-801124 is concerned with a dry mixture, used for fine soil injection grout preparation, the mixture comprising fillers which do not react with water, cement and deflocculant; on addition of water, an agglomerate-free fine grout is formed, and this is easily injected into fine soil.
Thus, the use of such grouting materials in - primarily — civil engineering is well known, and its use in treating fine particulate sized wastes in the nuclear industry is t the subject of the above co-pending application. However, whilst attempts have previously been made to encapsulate broken Magnox fuel elements, the treatment of uranium metal and complete Magnox fuel elements involved in nuclear processing has always been reliant on reprocessing techniques, many of which are well known to those skilled in such technology. Nevertheless, there has long been a need for an alternative approach for dealing with such fuel materials, particularly for those cases where reprocessing is especially difficult or hazardous - or, on occasions, impossible. The present inventors have now found that cured cementitious materials may advantageously be employed for the long term encapsulation of uranium and Magnox fuel elements, as well as fuel element debris, thereby providing a product which remains stable and monolithic for many hundreds of years. Hence, a treatment method is provided which affords much greater efficiency, convenience and safety in handling, and has a consequent beneficial effect both in terms of environmental considerations and cost, thereby satisfying a long felt need in the nuclear industry wherein the waste management of materials is receiving ever greater attention in the global drive to ensure ever higher safety standards.
Statements of Invention
Thus, according to the present invention there is provided a method for the encapsulation of a nuclear material which comprises treating the material with an encapsulant which comprises a cementitious material and curing said cementitious material.
Generally, the nuclear material comprises a nuclear fuel material such as uranium metal or Magnox fuel elements or fuel element debris. Alternatively, it may comprise, for example, fast reactor fuel, metal oxide fuel or mixed oxide fuel.
The cementitious material may typically comprise, for example, Portland Cement or a similar commercially available product.
One or more additional inorganic fillers may optionally be added to the cementitious material; suitable fillers include blast furnace slag, pulverised fuel ash, hydrated lime, finely divided silica, limestone flour and organic and inorganic fluidising agents.
The invention also provides a method for the storage of a nuclear material which comprises encapsulation of the material in a cured cementitious material. Description of the Invention
The method of the present invention is of particular value in the treatment of nuclear fuel materials. Such materials may be treated by this method in order to obtain a product which remains stable and monolithic for many hundreds of years, thereby offering a safe and convenient alternative means of handling other than nuclear fuel reprocessing.
There exists a considerable worldwide stock of such nuclear fuel materials which, whilst safely stored for the medium term, requires a suitable route for long term disposal. This accumulation of this material provides powerful evidence of the absence of any suitable method of treatment. However, the present method now offers a safe and convenient technique for their disposal which should provide considerable environmental benefits.
A particular example of the application of the method involves placing the nuclear material in an appropriate container and adding a suitable cementitious material. Elements of the nuclear material may either be arrayed in the container or mixed haphazardly. The cementitious material is then added and allowed to at least partially cure, and the container may then be capped or, alternatively sent directly for storage or final disposal. The capping process involves placing a cap of cement on top of the mixture of nuclear material and cementitious material in the container after this mixture has been allowed to partially cure; the procedure has proved to be especially valuable in ensuring the safe long term storage of the material, and it provides an additional benefit in the reduction of secondary waste.
The container may comprise any container of an appropriate form and size, for example a drum having a capacity in the region of 500 litres. In such a case, the amount of nuclear material which may safely be stored may be up to as many as 52 elements. Preferably, however, the number of elements would be of the order of 22. Typically, the cementitious material is provided in the form of an aqueous composition with a water content preferably in the region of 40-50% (w/w). Thus, the material may conveniently be pumped under pressure into the container.

Claims

1. A method for the encapsulation of a nuclear material which comprises treating the material with an encapsulant which comprises a cementitious material and curing said cementitious material.
2. A method as claimed in claim 1 wherein the nuclear fuel material comprises uranium metal or Magnox fuel elements or fuel element debris.
3. A method as claimed in claim 1 or 2 wherein the cementitious material comprises Portland Cement.
4. A method as claimed in any one of claims 1, 2 or 3 wherein the cementitious material additionally comprises one or more inorganic fillers selected from blast furnace slag, pulverised fuel ash, hydrated lime, finely divided silica, limestone flour and organic and inorganic fluidising agents.
5. A method as claimed in any preceding claim wherein the cementitious material is provided in the form of an aqueous composition.
6. A method as claimed in claim 5 wherein the water content of the composition is in the region of 40-50% (w/w).
7. A method as claimed in any preceding claim wherein the nuclear material is placed in an appropriate container and a cementitious material is added and allowed to at least partially cure.
8. A method as claimed in claim 7 wherein elements of the nuclear material are either arrayed in the container or mixed haphazardly.
. A method as claimed in claim 7 or 8 wherein the container is subsequently capped.
10. A method as claimed in claim 7, 8 or 9 wherein the container comprises a drum having a capacity in the region of 500 litres.
11. A method as claimed in claim 10 wherein the amount of nuclear material stored is up to 52 elements.
12. A method as claimed in claim 11 wherein the number of elements is of the order of 22.
13. A method for the storage of a nuclear material which comprises encapsulation of the material in a cured cementitious material.
PCT/GB2003/002870 2002-07-03 2003-07-03 Storage of hazardous materials Ceased WO2004006268A2 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU2003251153A AU2003251153A1 (en) 2002-07-03 2003-07-03 Storage of hazardous materials
US10/519,869 US20060111603A1 (en) 2002-07-03 2003-07-03 Storage of hazardous materials
EP20030762781 EP1535287A2 (en) 2002-07-03 2003-07-03 Storage of hazardous materials

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0215341A GB0215341D0 (en) 2002-07-03 2002-07-03 Storage of hazardous materials
GB0215341.9 2002-07-03

Publications (2)

Publication Number Publication Date
WO2004006268A2 true WO2004006268A2 (en) 2004-01-15
WO2004006268A3 WO2004006268A3 (en) 2004-03-18

Family

ID=9939740

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2003/002870 Ceased WO2004006268A2 (en) 2002-07-03 2003-07-03 Storage of hazardous materials

Country Status (5)

Country Link
US (1) US20060111603A1 (en)
EP (1) EP1535287A2 (en)
AU (1) AU2003251153A1 (en)
GB (1) GB0215341D0 (en)
WO (1) WO2004006268A2 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005101426A1 (en) * 2004-04-13 2005-10-27 British Nuclear Fuels Plc Encapsulation of hazardous waste materials
GB2438889A (en) * 2006-06-07 2007-12-12 Costain Oil Gas & Process Ltd Process for the immobilisation of radioactive sludge

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10900842B2 (en) 2019-01-11 2021-01-26 MP High Tech Solutions Pty Ltd On-board radiation sensing apparatus

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4010108A (en) * 1972-01-24 1977-03-01 Nuclear Engineering Company, Inc. Radioactive waste disposal of water containing waste using urea-formaldehyde resin
US4582637A (en) * 1980-03-28 1986-04-15 British Nuclear Fuels Ltd. Reprocessing of irradiated nuclear fuel
US4416810A (en) * 1981-07-30 1983-11-22 Noakes John E Disposal of radioactive aromatic liquid wastes
FR2607957A1 (en) * 1986-12-05 1988-06-10 Commissariat Energie Atomique BLOCK CONTAINING WASTE FOR THEIR STORAGE AND METHOD OF MAKING SUCH A BLOCK
US4792385A (en) * 1987-11-03 1988-12-20 Westinghouse Electric Corp. Electrolytic decontamination apparatus and encapsulation process
US4931192A (en) * 1989-03-22 1990-06-05 The University Of Tennessee Research Corporation Method for the disposal of hazardous non-polar organic wastes
AU3126095A (en) * 1994-07-15 1996-02-16 Terra Environmental Cold processes for preparing glass through the use of a crystalline silicate matrix
US5946639A (en) * 1997-08-26 1999-08-31 The United States Of America As Represented By The Department Of Energy In-situ stabilization of radioactive zirconium swarf

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005101426A1 (en) * 2004-04-13 2005-10-27 British Nuclear Fuels Plc Encapsulation of hazardous waste materials
GB2438889A (en) * 2006-06-07 2007-12-12 Costain Oil Gas & Process Ltd Process for the immobilisation of radioactive sludge
GB2438889B (en) * 2006-06-07 2011-06-01 Costain Oil Gas & Process Ltd Process for the immobilisation of radioactive sludge

Also Published As

Publication number Publication date
EP1535287A2 (en) 2005-06-01
AU2003251153A8 (en) 2004-01-23
WO2004006268A3 (en) 2004-03-18
AU2003251153A1 (en) 2004-01-23
GB0215341D0 (en) 2002-08-14
US20060111603A1 (en) 2006-05-25

Similar Documents

Publication Publication Date Title
Saleh et al. Innovative cement-based materials for environmental protection and restoration
EP2024297B1 (en) Process for cementitious encapsulation of an aqueous solution containing boron and cementitious grout
EP1864299B1 (en) Waste disposal method
US20080134943A1 (en) Encapsulation Medium
CN106939165A (en) A kind of soil body curing agent and its preparation method and its gunnite method
RU2706019C1 (en) Method of processing liquid radioactive wastes containing, including tritium isotopes
US20060111603A1 (en) Storage of hazardous materials
EP1459326B1 (en) Treatment of waste products
KR102503145B1 (en) Expandable mortar composition and pile construction method
CN118724553A (en) A kind of all-solid waste grouting filling material, preparation method and application thereof
US20070219402A1 (en) Encapsulation Of Hazardous Waste Materials
KR101940033B1 (en) Disposal method for Radioactive waste
KR102335536B1 (en) Solidified material for radioactive waste using fine powder of waste concrete and treatment method of radioactive waste using the same
KR102113733B1 (en) Deep soil mixing method using solidifying composition
KR20180096441A (en) Composition for mine liner
KR102950168B1 (en) Eco-friendly solid material composition for preventing ground subsidence and reinforcing liquefaction and ground solidification method using the same
TWI893706B (en) Cementitious composition
KR102919761B1 (en) Solidification composition using composite reforming active binder and ground solidification method using the same
CN116283136B (en) Filling formula and method of bulk solid waste and medical plastic product waste
RU2315380C1 (en) Method for case-hardening radioactive waste in container
KR102933037B1 (en) Solidification composition of non-cement type for solar cell foundation using composite reforming active binder and reinforcement method of solar cell foundation pile using the same
CN110272226A (en) A kind of environment-friendly type melting and solidification body bituminous concrete and preparation method thereof
US11417438B2 (en) Method for producing solidifying material for radioactive waste disposal via recycling of radioactive concrete and method for disposing of radioactive waste using the same
JPH04359196A (en) Radioactive waste disposing method
Integrate et al. Cement materials for use as backfill, sealing and structural materials in geological disposal concepts. A review of current status

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

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 NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL 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: A2

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 HU IE IT LU MC NL 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
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: 2003762781

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 2003762781

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2006111603

Country of ref document: US

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 10519869

Country of ref document: US

WWP Wipo information: published in national office

Ref document number: 10519869

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP