US3496017A - Method and composition for decontamination of stainless steel surfaces - Google Patents

Method and composition for decontamination of stainless steel surfaces Download PDF

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Publication number
US3496017A
US3496017A US546489A US3496017DA US3496017A US 3496017 A US3496017 A US 3496017A US 546489 A US546489 A US 546489A US 3496017D A US3496017D A US 3496017DA US 3496017 A US3496017 A US 3496017A
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US
United States
Prior art keywords
decontamination
stainless steel
solution
film
corrosion
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.)
Expired - Lifetime
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US546489A
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English (en)
Inventor
Ronald D Weed
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US Atomic Energy Commission (AEC)
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US Atomic Energy Commission (AEC)
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Publication of US3496017A publication Critical patent/US3496017A/en
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Classifications

    • GPHYSICS
    • G21NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21FPROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/001Decontamination of contaminated objects, apparatus, clothes, food; Preventing contamination thereof
    • G21F9/002Decontamination of the surface of objects with chemical or electrochemical processes
    • G21F9/004Decontamination of the surface of objects with chemical or electrochemical processes of metallic surfaces
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23GCLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00Cleaning or pickling metallic material with solutions or molten salts
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23GCLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02Cleaning or pickling metallic material with solutions or molten salts with acid solutions

Definitions

  • the tenacious magnetite film containing included radioactive contaminants which forms on stainless steel heat exchange surfaces of nuclear reactors is removed by a two step treatment.
  • the first step utilizes a hot, alkaline, aqueous solution of potassium permanganate.
  • the second utilizes a hot aqueous solution of oxalic acid, dibasic ammonium citrate, ferric sulfate or nitrate and diethyl thiourea.
  • the invention relates to a method of and a composition for the removal of radioactive contamination from metal surfaces. It is effective for removing the extremely tenacious radioactive film which forms on stainless steel surfaces on long exposure to hot Water containing radioisotopes. It is also effective for removing the less tenacious radioactive films formed on carbon steel, zircaloy, brass, bronze and other metals. At the same time there is no objectionable corrosion to any of these metals.
  • the principal object of the invention is the decontamination of nuclear reactor cooling systems composed primarily of stainless steel.
  • the radioactive corrosion films characteristic of recirculating water-cooled nuclear reactors must be periodically removed to permit contact maintenance and continuity of operation. Before these systems can be cleaned, procedures and processes must be developed which are suitable for use in the system. These processes must meet certain criteria which are discussed in the following paragraphs.
  • a decontamination reagent must dissolve the radioactive corrosion film and remove it from the system.
  • Large nuclear plants are no exception to other types of plants; they are built with inherent low velocity areas and other traps where particulate material will settle out. The particulates in these areas must be dissolved for successful removal. Therefore, a successful decontamination reagent must dissolve as well as remove the radioactive corrosion film because if it is only removed from the piping surfaces and not dissolved, it will settle out in the low velocity areas and traps.
  • a successful decontamination reagent must remove and dissolve radioactive films formed during extended periods of continuous operation (up to at least two or three years). From the limited data available in the AEC literature, it is probable that cleaning will not be required oftener unless under unusual circumstances or demands. It is desirous, in power reactor operation, to keep the down time at a minimum and possibly reach five years of continuous operation before cleaning. Therefore, the removal of these long term films is an essential requirement.
  • a successful decontamination reagent must not be excessively corrosive to the materials of construction in the primary system.
  • the reactor system will be constructed of primarily one or two materials, but there will be small quantities of many other types of materials in the system. These lesser materials will be found in such places as valves and sampling devices. All of these materials must be compatible with the reagent if they are in either direct or indirect contact with the solution, this is particularly true if the components are in a critical location, e.g., a drain valve plug, seat or stem.
  • the film which forms on stainless steel surfaces in the cooling systems in water cooled nuclear reactors appears to be primarily magnetite mixed with oxides of nickel and chromium. Radioactive ions present in the water are included in or adsorbed on this film so that they cannot be removed without removing the film itself. It is known in the art to decontaminate stainless steel nuclear reactor cooling systems by treatment with alkaline potassium permanganate followed by oxalic acid. However, previously known oxalic acid containing solutions have tended to deposit a secondary film on the surfaces. Sometimes the secondary film takes the form of a precipitate settling out in the low velocity regions and dead legs of the cooling system. This secondary film contains a considerable amount of radioactivity and its formation partially nullifies the decontamination.
  • composition at present is as follows:
  • the primary cooling system is composed principally of type 304 stainless steel.
  • Corrosion tests were then conducted on samples of various metals.
  • One corrosion test was conducted with the RDW-3 solution at 80 C. for 120 hours; the total corrosion incurred by the carbon steel samples exposed 3 was 0.22 mil and by the stainless steel samples was 0.01 mil.
  • a pale yellow film was deposited on the carbon steel samples when the test was terminated; the solution was a clear yellow color with no precipitates present.
  • a method of removing a tenacious magnetite film containing included radioactive contaminants from a nuclear reactor cooling system composed primarily of stainless steel, which system has been subject to extended circulation of hot water during recator operation which method comprises:

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Food Science & Technology (AREA)
  • Physics & Mathematics (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US546489A 1966-04-28 1966-04-28 Method and composition for decontamination of stainless steel surfaces Expired - Lifetime US3496017A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US54648966A 1966-04-28 1966-04-28

Publications (1)

Publication Number Publication Date
US3496017A true US3496017A (en) 1970-02-17

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Family Applications (1)

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US546489A Expired - Lifetime US3496017A (en) 1966-04-28 1966-04-28 Method and composition for decontamination of stainless steel surfaces

Country Status (9)

Country Link
US (1) US3496017A (2)
BE (1) BE696994A (2)
CH (1) CH468697A (2)
DE (1) DE1621670A1 (2)
ES (1) ES339132A1 (2)
GB (1) GB1130068A (2)
IL (1) IL27663A (2)
NO (1) NO122687B (2)
SE (1) SE321130B (2)

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3664870A (en) * 1969-10-29 1972-05-23 Nalco Chemical Co Removal and separation of metallic oxide scale
US3873362A (en) * 1973-05-29 1975-03-25 Halliburton Co Process for cleaning radioactively contaminated metal surfaces
US4063962A (en) * 1976-04-07 1977-12-20 General Atomic Company Method and apparatus for cleaning nuclear fuel elements
US4217192A (en) * 1979-06-11 1980-08-12 The United States Of America As Represented By The United States Department Of Energy Decontamination of metals using chemical etching
US4226640A (en) * 1978-10-26 1980-10-07 Kraftwerk Union Aktiengesellschaft Method for the chemical decontamination of nuclear reactor components
US4364900A (en) * 1977-06-09 1982-12-21 Atomic Energy Of Canada Limited Deposit suppression in the core of water-cooled nuclear reactors
US4452643A (en) * 1983-01-12 1984-06-05 Halliburton Company Method of removing copper and copper oxide from a ferrous metal surface
US4460479A (en) * 1978-09-14 1984-07-17 Mulder Gerard W Method for polishing, deburring and descaling stainless steel
US4470920A (en) * 1981-05-11 1984-09-11 Custom Research And Development Metal oxide remover for stainless steels
US4476047A (en) * 1982-03-22 1984-10-09 London Nuclear Limited Process for treatment of oxide films prior to chemical cleaning
US4481040A (en) * 1981-06-17 1984-11-06 Central Electricity Generating Board Of Sudbury House Process for the chemical dissolution of oxide deposits
US4587043A (en) * 1983-06-07 1986-05-06 Westinghouse Electric Corp. Decontamination of metal surfaces in nuclear power reactors
US4654170A (en) * 1984-06-05 1987-03-31 Westinghouse Electric Corp. Hypohalite oxidation in decontaminating nuclear reactors
US4668303A (en) * 1983-08-04 1987-05-26 Exxon Research And Engineering Company Method of preventing stress corrosion in a bellows expansion joint
US4690782A (en) * 1986-01-30 1987-09-01 Godfried Lemmens Process for decontaminating materials contaminated by radioactivity
EP0160831A3 (en) * 1984-04-12 1987-11-25 Siemens Aktiengesellschaft Process for chemically decontaminating metallic parts of nuclear reactor plants
US4839100A (en) * 1986-06-04 1989-06-13 British Nuclear Fuels Plc Decontamination of surfaces
US5205999A (en) * 1991-09-18 1993-04-27 British Nuclear Fuels Plc Actinide dissolution
US5257296A (en) * 1991-10-25 1993-10-26 Buford Iii Albert C Steam generator chemical solvent mixing system and method
US5468303A (en) * 1994-02-25 1995-11-21 Zt Corporation Rust, corrosion, and scale remover
US5591270A (en) * 1995-07-31 1997-01-07 Corpex Technologies, Inc. Lead oxide removal method
US5640703A (en) * 1994-04-18 1997-06-17 British Nuclear Fuels Plc Treatment of solid wastes
US5678232A (en) * 1995-07-31 1997-10-14 Corpex Technologies, Inc. Lead decontamination method
US5814204A (en) * 1996-10-11 1998-09-29 Corpex Technologies, Inc. Electrolytic decontamination processes
CN100577893C (zh) * 2005-12-23 2010-01-06 中国辐射防护研究院 一种去除金属表面放射性污染的电解去污方法
US20100072059A1 (en) * 2008-09-25 2010-03-25 Peters Michael J Electrolytic System and Method for Enhanced Radiological, Nuclear, and Industrial Decontamination
US20100278686A1 (en) * 2009-04-30 2010-11-04 Halpin Peter T Process for recovering metals and metal compounds from mined ore and other metal-bearing raw source materials

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2220005A (en) * 1988-06-28 1989-12-28 Borsodi Vegyi Komb Process for removing oxide layer and scale from metals and metal alloys
FR2699936B1 (fr) * 1992-12-24 1995-01-27 Electricite De France Procédé de dissolution d'oxydes déposés sur un substrat métallique.

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB763547A (en) * 1953-11-10 1956-12-12 Atomic Energy Authority Uk Improvements in or relating to detergent compositions effective in removing radioactive contamination
US2793190A (en) * 1954-04-15 1957-05-21 Du Pont Corrosion-inhibition of oxalic acid
US2959555A (en) * 1956-09-28 1960-11-08 Dow Chemical Co Copper and iron containing scale removal from ferrous metal
US3013909A (en) * 1960-03-31 1961-12-19 Guyon P Pancer Method of chemical decontamination of stainless steel nuclear facilities

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB763547A (en) * 1953-11-10 1956-12-12 Atomic Energy Authority Uk Improvements in or relating to detergent compositions effective in removing radioactive contamination
US2793190A (en) * 1954-04-15 1957-05-21 Du Pont Corrosion-inhibition of oxalic acid
US2959555A (en) * 1956-09-28 1960-11-08 Dow Chemical Co Copper and iron containing scale removal from ferrous metal
US3013909A (en) * 1960-03-31 1961-12-19 Guyon P Pancer Method of chemical decontamination of stainless steel nuclear facilities

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3664870A (en) * 1969-10-29 1972-05-23 Nalco Chemical Co Removal and separation of metallic oxide scale
US3873362A (en) * 1973-05-29 1975-03-25 Halliburton Co Process for cleaning radioactively contaminated metal surfaces
US4063962A (en) * 1976-04-07 1977-12-20 General Atomic Company Method and apparatus for cleaning nuclear fuel elements
US4364900A (en) * 1977-06-09 1982-12-21 Atomic Energy Of Canada Limited Deposit suppression in the core of water-cooled nuclear reactors
US4460479A (en) * 1978-09-14 1984-07-17 Mulder Gerard W Method for polishing, deburring and descaling stainless steel
US4226640A (en) * 1978-10-26 1980-10-07 Kraftwerk Union Aktiengesellschaft Method for the chemical decontamination of nuclear reactor components
US4217192A (en) * 1979-06-11 1980-08-12 The United States Of America As Represented By The United States Department Of Energy Decontamination of metals using chemical etching
US4470920A (en) * 1981-05-11 1984-09-11 Custom Research And Development Metal oxide remover for stainless steels
US4481040A (en) * 1981-06-17 1984-11-06 Central Electricity Generating Board Of Sudbury House Process for the chemical dissolution of oxide deposits
US4476047A (en) * 1982-03-22 1984-10-09 London Nuclear Limited Process for treatment of oxide films prior to chemical cleaning
US4452643A (en) * 1983-01-12 1984-06-05 Halliburton Company Method of removing copper and copper oxide from a ferrous metal surface
US4587043A (en) * 1983-06-07 1986-05-06 Westinghouse Electric Corp. Decontamination of metal surfaces in nuclear power reactors
US4668303A (en) * 1983-08-04 1987-05-26 Exxon Research And Engineering Company Method of preventing stress corrosion in a bellows expansion joint
EP0160831A3 (en) * 1984-04-12 1987-11-25 Siemens Aktiengesellschaft Process for chemically decontaminating metallic parts of nuclear reactor plants
US4654170A (en) * 1984-06-05 1987-03-31 Westinghouse Electric Corp. Hypohalite oxidation in decontaminating nuclear reactors
US4690782A (en) * 1986-01-30 1987-09-01 Godfried Lemmens Process for decontaminating materials contaminated by radioactivity
US4839100A (en) * 1986-06-04 1989-06-13 British Nuclear Fuels Plc Decontamination of surfaces
US5205999A (en) * 1991-09-18 1993-04-27 British Nuclear Fuels Plc Actinide dissolution
US5257296A (en) * 1991-10-25 1993-10-26 Buford Iii Albert C Steam generator chemical solvent mixing system and method
US5468303A (en) * 1994-02-25 1995-11-21 Zt Corporation Rust, corrosion, and scale remover
US5640703A (en) * 1994-04-18 1997-06-17 British Nuclear Fuels Plc Treatment of solid wastes
US5591270A (en) * 1995-07-31 1997-01-07 Corpex Technologies, Inc. Lead oxide removal method
US5678232A (en) * 1995-07-31 1997-10-14 Corpex Technologies, Inc. Lead decontamination method
US5814204A (en) * 1996-10-11 1998-09-29 Corpex Technologies, Inc. Electrolytic decontamination processes
CN100577893C (zh) * 2005-12-23 2010-01-06 中国辐射防护研究院 一种去除金属表面放射性污染的电解去污方法
US20100072059A1 (en) * 2008-09-25 2010-03-25 Peters Michael J Electrolytic System and Method for Enhanced Radiological, Nuclear, and Industrial Decontamination
US20100278686A1 (en) * 2009-04-30 2010-11-04 Halpin Peter T Process for recovering metals and metal compounds from mined ore and other metal-bearing raw source materials

Also Published As

Publication number Publication date
DE1621670A1 (de) 1971-06-24
NO122687B (2) 1971-07-26
BE696994A (2) 1967-09-18
ES339132A1 (es) 1968-12-01
SE321130B (2) 1970-02-23
CH468697A (de) 1969-02-15
GB1130068A (en) 1968-10-09
IL27663A (en) 1970-10-30

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