US3297580A - Neutral metal cleaning compositions containing hydrazine and a polycarboxylamino acid - Google Patents

Neutral metal cleaning compositions containing hydrazine and a polycarboxylamino acid Download PDF

Info

Publication number
US3297580A
US3297580A US375985A US37598564A US3297580A US 3297580 A US3297580 A US 3297580A US 375985 A US375985 A US 375985A US 37598564 A US37598564 A US 37598564A US 3297580 A US3297580 A US 3297580A
Authority
US
United States
Prior art keywords
hydrazine
acid
solution
polycarboxylamino
molar
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
Application number
US375985A
Inventor
Edgar C Pitzer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to US375985A priority Critical patent/US3297580A/en
Application granted granted Critical
Publication of US3297580A publication Critical patent/US3297580A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • C23G1/24Cleaning or pickling metallic material with solutions or molten salts with neutral solutions

Definitions

  • Removalof oxide corrosion products from metal surfaces may be accomplished by several physical or chemicalmeans; Scraping, sandblasting, pickling, and reduction are exemplary of a few of the well known cleaning methods which may be used. All of these methods may be easily employed with no particular problem when the metal surfaces are exposed and accessible. However, when corrosion or crud removal from inaccessible metal interiors is necessary, application of phyical removal means isimpossible and resort to chemical compositions must be-taken.:
  • Certain: of the metal cleaning chemical compositions inthe prior art contained sulfur compounds. These compositions, while acceptable for certain applications, were objectionable for apparatus constructed from expensive alloys which were subject to abnormal stresses. Sulfite embrit-tlement or crevice. corrosion resulting from attack on 31116 metal surfaces by the sulfur compounds produced equipment having unsatisfactory strength and reliability. Often, as a result of the use of these sulfur containing compositions, the cleaned product was structurally more unsatisfactory than the corroded metal.
  • the primary object. of this invention is to provide t substantially neutral metal cleaning compositions; which Ilwill remove all objectionable metallic oxide filmsvwithout etching the surface.
  • a furtherobject of this invention is to provide a safe, substantially neutral metal cleaning composition having a pH range of between 6.5 and 9.5.
  • An additional object of this invention is to provide neutral metal cleaning compositions which will effectively clean .-a wide variety of structural metals and alloys.
  • Chelating agents whichjcontain 3 to 5 carboxyl groups appear tohe roughly equivalent in this solution.
  • Exemplarypolycarboxylamine acids which are equivalent constitutents of: these novel cleaning compositions are nitrolotriacetic acid, N- hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, and 1,2-diaminocyclohexanetetraacetic acid; however, ethylenediaminetetraacetic. acid is preferred.
  • No sulfur compounds or More particularly, this invention relates' to 3,297,580 Patented Jan. 10, 1967 other constituents leading to sulfite embrittlement, crevice corrosion, or other mishap are present in the ingredients.
  • the metal cleaning composition according to this invention is non-corrosive to all ferrous metals and alloys.
  • Hydrazine alone, or the metal salts of the polycarboxylamino acids in the absence of hydrazine have no appreciable effect upon certain mixed metal oxides, that is, oxides of iron, cobalt, nickel, and manganese.
  • a synergistic action evidenced by the unexpected improved solubility of the metal axides, occurs when the two compounds are mixed in the proper proportions. This synergistic action dissolves metal oxides which were substantially immune to the separate ingredients- Ethylenediaminetetraacetic acid (EDTA) is mixed '7 with hydrazine in proportions which will result in a pH of from 6.5 to 9.5 and preferably in a range of 7 to 9.
  • EDTA Ethylenediaminetetraacetic acid
  • Ammonia may be substituted as a buffering agent for a portion of the hydrazine when it is necessary to adjust the pH of the resulting solution to bring it within the desired range.
  • the proportions of hydrazine and ethylenediaminetetraacetic acid are not critical provided at least 0.1 molar concentration of hydrazine is used and the pH remains within the prescribed range. Generally, a ratio of 2 to 6 moles of hydrazine per mole of ethylenediaminetetraacetic acid will keep the cleaning solution within the prescribed pH range. However, if the proportions of the ingredients render the pH of the solution below the 6.5 to 9.5 range, ammonia may be added to make the necessary adjustments in the pH.
  • the minimum concentration of ethylenediamineteteraaceti acid which is effectively used must be at least 0.08 molar; however, a concentration of 0.25 molar is preferred.
  • the concentration of hydrazine used with the ethylenediaminetetraacetic acid has li tle consequence on the effectiveness of the solution, provided the solution is at least 0.1 molar in hydrazine.
  • Dissolution of metal corrosion products is better effected the cleaning solution is employed at elevated temperatures.
  • Dissolution of magnetic iron oxide (E2 0 may normally be achieved in approximately two hours with the solution at 95 to 100 C.; however, significant dissolution may be effected after a one hour application at temperatures between and 100 C. Although dissolution has been detected at temperatures as low as 65 C., in order to maintain a rapid reaction, temperatures in the range of to 100 C. are preferred.
  • EXAMPLE I Several samples were prepared in which the hydrazine concentration in the cleaning solution was varied from 0.1 to 0.5 molar. Ammonia was added to the solution in amounts sufl'icient to bring the pH within the 6.5 to 9.5 range. A blue or greenish blue coloration upon the addition of bromthymol indicator denoted the proper pH of the solution.
  • Example II Additional samples were prepared to determine the effect of the hydrazine-EDTA solution on oxides of mixed metals, particularly, oxides of iron, nickel, cobalt, and manganese. Separate samples of these mixed metal oxides were heated to 400 C. and to 600 C. The composition of the metals oxides was determined by X-ray fluorescent analysis to contain 76% Fe, 7.2% Ni, 8.4% Co, and
  • test conditions under which this solution was tested were more severe than normally encountered. Normally, the corrosion products of metal alloys are not exposed to temperatures as high at 400 C. to 600 C. These conditions are far more severe than those in which the solution is normally applied.
  • Example 111 Several more samples were prepared using a hydrazine- EDTA solution of the same formulation as in Example II. Radioactive oxide corrosion products scraped from a nuclear reactor fuel element were placed in the solution and heated at 95 for 4 hours. The results obtained from the test are summarized in the following table:
  • Iron, nickel, and cobalt oxides showed satisfactory solubility while chromium remained unaffected by the solution.
  • Example IV Other samples were prepared for the purpose of determining the solubility of magnetic iron oxide in a solution containing hydrazine and a different chelating agent. A solution containing hydrazine and nitrilotriacetic acid (NTA) was prepared. Weighted samples of magnetic iron oxide were placed in portions of the neutral solution and heated to 95 C. for 2 hours. The following table summarizes the results obtained for the test.
  • Example V The hyd-razine-EDTA solution, according to this invention, was employed in the decontamination of a primary loop pressurizer in a pressurized water reactor cooling system.
  • the initial dose rate in the pressurizer averaged approximately 1,0 00 to 1,200 mirlliroentgens per hour.
  • One application of the hydrazine-EDTA solution produced a decontamination factor of from 2 to 5.
  • the decontamination factor is defined as the initial dose rate divided by the final dose rate.
  • Outstanding decontamination was achieved by an additional treatment with potassium permanganate followed by a second hydrazine- EDTA application. This three-step process reduced the initial average dose to an average of approximately 5 milliroentgens per hour, giving a decontamination factor range from 400 to 900.
  • comparisons were made between prior art compositions and the hydrazine-EDTA solution.
  • Example VI Magnetic iron oxide (Fe O pellets were placed in test solutions and all of the samples were heated for one hour at C. Oxalic and citric acids and their salts were compared with hydrazine-EDTA, as shown in the following table.
  • the neutral hydrazine-EDTA solution according to this invention offers numerous advantages over the prior art cleaning compositions.
  • the solution is, of course, attractive not only from the standpoint of being effective in the removal of corrosion products which are only partially dissolved or removed by prior art compositions, but also from the sandpoint of being completely safe with respect to the personnel handling the solution, due to its neutral or nearly neutral pH.
  • a substantially neutral metal cleaning composition consisting essentially of an aqueous solution of hydrazine and a polycarboxylarnino acid having 3 to 5 carboxyl groups in proportions yielding a solution having a pH between 6.5 to 9.5 and wherein the concentration of hydrazine is from 0.1 molar to 0.5 molar.
  • a substantially neutral metal cleaning composition a/ccorging to claim 1 wherein the pH of the solution is 3.
  • a substantially neutral metal cleaning composition according to claim 1 wherein the polycarboxylamino acid is N-hydroxyethylethylenediaminetriacetic acid
  • a substantially neutral metal cleaning composition according to claim, 1 wherein the polycarboxylarnino acid iss:1,2 diarninocyclohexanetetraacetic acid.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Description

United. 31 States Patent T Edgar Ct Pitzer, Scotia,.N.Y., assignor to the United States of Americans represented by the United States Atomic Energy Commission No Drawing. Filed June 17, 19.64, Ser. No. 375,985
10. Claims. (Cl. 252-142) This invention relates to chemical compositions and a process for the removal of corrosion products from metal surfaces? substantially neutral chemical compositions and the process: of employing them for the removal of oxide films fromiron and ferrous alloys in inaccessible places.
Removalof oxide corrosion products from metal surfaces:;may be accomplished by several physical or chemicalmeans; Scraping, sandblasting, pickling, and reduction are exemplary of a few of the well known cleaning methods which may be used. All of these methods may be easily employed with no particular problem when the metal surfaces are exposed and accessible. However, when corrosion or crud removal from inaccessible metal interiors is necessary, application of phyical removal means isimpossible and resort to chemical compositions must be-taken.:
In. the past, the chemical compositions which were employed for crud and corrosion removal were either strongly acidic. or strongly basic and required special precautionary -measures for handling and application. Moreover; application of solutions in the extreme pH ranges etched highly finished metal surfaces so that previously close .fitting tolerances were ruined, and even then, dissolution of all the objectionable oxides forming the crud was not always effected. Particularly resistant to dissolution .was magnetic iron oxide.
Certain: of the metal cleaning chemical compositions inthe prior art contained sulfur compounds. These compositions, while acceptable for certain applications, were objectionable for apparatus constructed from expensive alloys which were subject to abnormal stresses. Sulfite embrit-tlement or crevice. corrosion resulting from attack on 31116 metal surfaces by the sulfur compounds produced equipment having unsatisfactory strength and reliability. Often, as a result of the use of these sulfur containing compositions, the cleaned product was structurally more unsatisfactory than the corroded metal.
The primary object. of this invention, therefore, is to provide t substantially neutral metal cleaning compositions; which Ilwill remove all objectionable metallic oxide filmsvwithout etching the surface.
A furtherobject of this invention is to provide a safe, substantially neutral metal cleaning composition having a pH range of between 6.5 and 9.5.
An additional object of this invention is to provide neutral metal cleaning compositions which will effectively clean .-a wide variety of structural metals and alloys.
Further; objects will become apparent to those skilled in the art from the following explanation and examples.
The foregoing objects are achieved according to this invention wby formulating buffered aqueous solutions of hydrazine: and a polycarboxylamine acid chelating agent.
. Chelating agentswhichjcontain 3 to 5 carboxyl groups appear tohe roughly equivalent in this solution. Exemplarypolycarboxylamine acids which are equivalent constitutents of: these novel cleaning compositions are nitrolotriacetic acid, N- hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, and 1,2-diaminocyclohexanetetraacetic acid; however, ethylenediaminetetraacetic. acid is preferred. No sulfur compounds or More particularly, this invention relates' to 3,297,580 Patented Jan. 10, 1967 other constituents leading to sulfite embrittlement, crevice corrosion, or other mishap are present in the ingredients. The metal cleaning composition according to this invention is non-corrosive to all ferrous metals and alloys.
Hydrazine, alone, or the metal salts of the polycarboxylamino acids in the absence of hydrazine have no appreciable effect upon certain mixed metal oxides, that is, oxides of iron, cobalt, nickel, and manganese. A synergistic action, evidenced by the unexpected improved solubility of the metal axides, occurs when the two compounds are mixed in the proper proportions. This synergistic action dissolves metal oxides which were substantially immune to the separate ingredients- Ethylenediaminetetraacetic acid (EDTA) is mixed '7 with hydrazine in proportions which will result in a pH of from 6.5 to 9.5 and preferably in a range of 7 to 9. Ammonia may be substituted as a buffering agent for a portion of the hydrazine when it is necessary to adjust the pH of the resulting solution to bring it within the desired range. The proportions of hydrazine and ethylenediaminetetraacetic acid are not critical provided at least 0.1 molar concentration of hydrazine is used and the pH remains within the prescribed range. Generally, a ratio of 2 to 6 moles of hydrazine per mole of ethylenediaminetetraacetic acid will keep the cleaning solution within the prescribed pH range. However, if the proportions of the ingredients render the pH of the solution below the 6.5 to 9.5 range, ammonia may be added to make the necessary adjustments in the pH.
The minimum concentration of ethylenediamineteteraaceti acid which is effectively used must be at least 0.08 molar; however, a concentration of 0.25 molar is preferred. The concentration of hydrazine used with the ethylenediaminetetraacetic acid has li tle consequence on the effectiveness of the solution, provided the solution is at least 0.1 molar in hydrazine.
Dissolution of metal corrosion products is better effected the cleaning solution is employed at elevated temperatures. Dissolution of magnetic iron oxide (E2 0 may normally be achieved in approximately two hours with the solution at 95 to 100 C.; however, significant dissolution may be effected after a one hour application at temperatures between and 100 C. Although dissolution has been detected at temperatures as low as 65 C., in order to maintain a rapid reaction, temperatures in the range of to 100 C. are preferred.
EXAMPLE I Several samples were prepared in which the hydrazine concentration in the cleaning solution was varied from 0.1 to 0.5 molar. Ammonia was added to the solution in amounts sufl'icient to bring the pH within the 6.5 to 9.5 range. A blue or greenish blue coloration upon the addition of bromthymol indicator denoted the proper pH of the solution.
Approximately 0.2 gram of magnetic iron oxide (Fe O was added to each of the various concentrations and heated for two hours at C. An examination of the various samples after completion of the treatment showed that the solutions 0.2 to 0.5 molar in hydrazine dissolved 99.9% of the magnetic iron oxide. The solution 0.1 molar in hydrazine dissolved 99.7% of the magnetic iron oxide.
Example II Additional samples were prepared to determine the effect of the hydrazine-EDTA solution on oxides of mixed metals, particularly, oxides of iron, nickel, cobalt, and manganese. Separate samples of these mixed metal oxides were heated to 400 C. and to 600 C. The composition of the metals oxides was determined by X-ray fluorescent analysis to contain 76% Fe, 7.2% Ni, 8.4% Co, and
8.4% Mn. Samples of these mixed oxides were heated for two hours at 95 C. in a solution 0.1 molar in ethylenediaminetetraacetic acid and 0.5 molar in hydrazine. Approximately 91.8% of the mixed oxides which were heated to 400 C. were dissolved in the solution. The mixed metal oxides which were heated to 600 C. were slightly more resistant to dissolution in the same composition than the ones heated to 400 C. About 76.5% of the mixed metal oxides which were heated to 600 C. were dissolved in the solution. An analysis of the mixed metal oxide residue showed that approximately 95.0% of the iron oxide, 87% f the nickel oxide, 89% of the cobalt oxide, and 57% of the manganese oxide in the original sample were dissolved.
The test conditions under which this solution was tested were more severe than normally encountered. Normally, the corrosion products of metal alloys are not exposed to temperatures as high at 400 C. to 600 C. These conditions are far more severe than those in which the solution is normally applied.
Example 111 Several more samples were prepared using a hydrazine- EDTA solution of the same formulation as in Example II. Radioactive oxide corrosion products scraped from a nuclear reactor fuel element were placed in the solution and heated at 95 for 4 hours. The results obtained from the test are summarized in the following table:
Iron, nickel, and cobalt oxides showed satisfactory solubility while chromium remained unaffected by the solution.
Example IV Other samples were prepared for the purpose of determining the solubility of magnetic iron oxide in a solution containing hydrazine and a different chelating agent. A solution containing hydrazine and nitrilotriacetic acid (NTA) was prepared. Weighted samples of magnetic iron oxide were placed in portions of the neutral solution and heated to 95 C. for 2 hours. The following table summarizes the results obtained for the test.
TABLE II Undis- N TA Hydrazine pH pH solved (molar) (molar) Initially Finally Residue,
Percent Similar results were obtained with solutions containing ammonia as partial replacement for hydrazine. Solutions in which the pH was adjusted by an ammonia bufier, meantime taking care to maintain at least an 0.3 molar concentration of hydrazine in the solution, had substantially no detrimental effect on the dissolving power of the solution, and residues comparable to those shown in Table II were produced.
Example V The hyd-razine-EDTA solution, according to this invention, was employed in the decontamination of a primary loop pressurizer in a pressurized water reactor cooling system. The initial dose rate in the pressurizer averaged approximately 1,0 00 to 1,200 mirlliroentgens per hour. One application of the hydrazine-EDTA solution produced a decontamination factor of from 2 to 5. The decontamination factor is defined as the initial dose rate divided by the final dose rate. Outstanding decontamination was achieved by an additional treatment with potassium permanganate followed by a second hydrazine- EDTA application. This three-step process reduced the initial average dose to an average of approximately 5 milliroentgens per hour, giving a decontamination factor range from 400 to 900. In order to appreciate the benefits and advantages 0 fthis neutral hydrazine-chelate solution, and the improvements which it makes over the prior art, comparisons were made between prior art compositions and the hydrazine-EDTA solution.
Example VI Magnetic iron oxide (Fe O pellets were placed in test solutions and all of the samples were heated for one hour at C. Oxalic and citric acids and their salts were compared with hydrazine-EDTA, as shown in the following table.
TABLE III Undissolved Compounds Molar pH Residue,
Percent 0. 25 0. 99 48. 4 0. 25 1. 61 91. 6 0. 20 4. 75 81. 3 0. 20 0. 50 Ammonia 0. 60 8. 55 0. 92
It is evident from an observation of the amount of the residues that salts of these carboxylic acids commonly used in descaling solutions were not nearly as effective as the hydrazine-EDTA solution.
From the afore-disclosed examples, it can be seen that the neutral hydrazine-EDTA solution according to this invention offers numerous advantages over the prior art cleaning compositions. The solution is, of course, attractive not only from the standpoint of being effective in the removal of corrosion products which are only partially dissolved or removed by prior art compositions, but also from the sandpoint of being completely safe with respect to the personnel handling the solution, due to its neutral or nearly neutral pH.
It is to be understood that certain changes and modifications can be performed on the composition disclosed herein without departing from the spirit and scope of the invention. Having thus described my invention, I claim:
1. A substantially neutral metal cleaning composition consisting essentially of an aqueous solution of hydrazine and a polycarboxylarnino acid having 3 to 5 carboxyl groups in proportions yielding a solution having a pH between 6.5 to 9.5 and wherein the concentration of hydrazine is from 0.1 molar to 0.5 molar.
2. A substantially neutral metal cleaning composition a/ccorging to claim 1 wherein the pH of the solution is 3. A substantially neutral metal cleaning composition according to claim 1 wherein the polycarboxylamino acid is ethylenediaminetetraacetic acid.
4. A substantially neutral metal cleaning composition according to claim 1 wherein the polycarboxylamino acid is nitrilotriacetic acid.
5. A substantially neutral metal cleaning composition according to claim 1 wherein the polycarboxylamino acid is N-hydroxyethylethylenediaminetriacetic acid,
7. A substantially neutral metal cleaning composition according to claim, 1 wherein the polycarboxylarnino acid iss:1,2 diarninocyclohexanetetraacetic acid.
8. .A substantially neutral metal cleaning composition according to claim 1 wherein the proportions are 2 to 6 molesiof hydrazine per mole of polycarboxylamino acid.
9. A substantially neutral metal cleaning composition according to claim 1 wherein the concentration of the polycarboxylamino acid is from 0.08 molar to 0.25 molar.
10. 11A substantially neutral metal cleaning composition 1 according to claim 1 wherein a portion of the hydrazine isreplaced by ammonia.
6.i=A"su'bstantial1y neutral metal cleaning composition according to claim 1 wherein the polycarboxylamino acid is diethylenetriaminepentaacetic acid.
References Cited by the Examiner UNITED STATES PATENTS 2,908,547 10/1959 Nicholls et a1. 23-339 3,054,746 9/1962 Gaden et a']. 25230l.1 3,054,747 9/1962 Gaden et a1. 25230l.l 3,154,500 10/1964 Jansen et a1. 252-6011 CARL D. QUARFORTH, Primary Examiner.
S. I. LECHERT, JR., Assistant Examiner.

Claims (1)

1. A SUBSTANTIALLY NEUTRAL METAL CLEANING COMPOSITION CONSISTING ESSENTIALLY OF AN AQUEOUS SOLUTION OF HYDRAZINE AND A POLYCARBOXYLAMINO ACID HAVING 3 TO 5 CARBOXYL GROUPS IN PROPORTIONS YIELDING A SOLUTION HAVING A PH BETWEEN 6.5 TO 9.5 AND WHEREIN THE CONCENTRATION OF HYDRAZINE IS FROM 0.1 MOLAR TO 0.5 MOLAR.
US375985A 1964-06-17 1964-06-17 Neutral metal cleaning compositions containing hydrazine and a polycarboxylamino acid Expired - Lifetime US3297580A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US375985A US3297580A (en) 1964-06-17 1964-06-17 Neutral metal cleaning compositions containing hydrazine and a polycarboxylamino acid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US375985A US3297580A (en) 1964-06-17 1964-06-17 Neutral metal cleaning compositions containing hydrazine and a polycarboxylamino acid

Publications (1)

Publication Number Publication Date
US3297580A true US3297580A (en) 1967-01-10

Family

ID=23483207

Family Applications (1)

Application Number Title Priority Date Filing Date
US375985A Expired - Lifetime US3297580A (en) 1964-06-17 1964-06-17 Neutral metal cleaning compositions containing hydrazine and a polycarboxylamino acid

Country Status (1)

Country Link
US (1) US3297580A (en)

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3506488A (en) * 1967-07-24 1970-04-14 Ethyl Corp Method of removing manganese containing deposits
US3507892A (en) * 1967-08-17 1970-04-21 Weston Chemical Corp Heavy metal chelates of amino hydrazide chelating agents
US3543389A (en) * 1969-07-07 1970-12-01 Bell Telephone Labor Inc Method for cleaning metal surfaces
EP0052509A2 (en) * 1980-11-17 1982-05-26 Hitachi, Ltd. Method of removing oxide on a metal surface
US4659512A (en) * 1983-12-21 1987-04-21 Pedro B. Macedo Fixation of dissolved metal species with a complexing agent
US4708805A (en) * 1986-11-24 1987-11-24 Muhala Thomas F D Barium sulfate removal and anti-deposition compositions and process of use therefor
US4726907A (en) * 1983-08-10 1988-02-23 Nuclear Technology Corp Hydrazides of amino-polyacetic acids as chelants
US4729855A (en) * 1985-11-29 1988-03-08 Westinghouse Electric Corp. Method of decontaminating radioactive metal surfaces
US4731124A (en) * 1980-08-11 1988-03-15 Central Electricity Generating Board Application technique for the descaling of surfaces
US4775491A (en) * 1983-08-10 1988-10-04 Nuclear Technology Corp. Hydrazides of amino-polyacetic acids as chelants
US4789406A (en) * 1986-08-20 1988-12-06 Betz Laboratories, Inc. Method and compositions for penetrating and removing accumulated corrosion products and deposits from metal surfaces
EP0299166A1 (en) * 1987-07-17 1989-01-18 Mitsubishi Jukogyo Kabushiki Kaisha Method for removing scale on inner surfaces of boiler tube members
US5205999A (en) * 1991-09-18 1993-04-27 British Nuclear Fuels Plc Actinide dissolution
US5292456A (en) * 1992-03-20 1994-03-08 Associated Universities, Inc. Waste site reclamation with recovery of radionuclides and metals
US5342450A (en) * 1989-01-26 1994-08-30 Kay Chemical Company Use of noncorrosive chemical composition for the removal of soils originating from an animal or vegetable source from a stainless steel surface
US5401311A (en) * 1992-12-17 1995-03-28 Betz Laboratories, Inc. Method for removing deposits from cooling water systems
US5401323A (en) * 1993-09-08 1995-03-28 Betz Laboratories, Inc. Method for removing clay deposits from cooling water systems
US5640703A (en) * 1994-04-18 1997-06-17 British Nuclear Fuels Plc Treatment of solid wastes
WO2006053626A1 (en) * 2004-11-11 2006-05-26 Areva Np Gmbh Cleaning method for removing deposits containing magnetite out of a pressure vessel of a power plant
EP2090676A1 (en) * 2008-02-01 2009-08-19 Ateco Services AG Method for removing coatings and deposits
US20100078040A1 (en) * 2008-02-01 2010-04-01 Marc Philippe Vernier Use of an Aqueous Neutral Cleaning Solution and Method for Removing Rouging from Stainless Steel Surfaces

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2908547A (en) * 1949-09-19 1959-10-13 Nicholls Cyril Minchin Separation of uranium, plutonium, and fission products
US3054747A (en) * 1960-07-22 1962-09-18 Radiation Applic Inc Method of separating non-surface active ionic materials from solution
US3054746A (en) * 1959-05-06 1962-09-18 Radiation Applic Inc Separation of dissimilar metal ions
US3154500A (en) * 1962-06-13 1964-10-27 Jr George Jansen Strontium recovery process

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2908547A (en) * 1949-09-19 1959-10-13 Nicholls Cyril Minchin Separation of uranium, plutonium, and fission products
US3054746A (en) * 1959-05-06 1962-09-18 Radiation Applic Inc Separation of dissimilar metal ions
US3054747A (en) * 1960-07-22 1962-09-18 Radiation Applic Inc Method of separating non-surface active ionic materials from solution
US3154500A (en) * 1962-06-13 1964-10-27 Jr George Jansen Strontium recovery process

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3506488A (en) * 1967-07-24 1970-04-14 Ethyl Corp Method of removing manganese containing deposits
US3507892A (en) * 1967-08-17 1970-04-21 Weston Chemical Corp Heavy metal chelates of amino hydrazide chelating agents
US3543389A (en) * 1969-07-07 1970-12-01 Bell Telephone Labor Inc Method for cleaning metal surfaces
US4731124A (en) * 1980-08-11 1988-03-15 Central Electricity Generating Board Application technique for the descaling of surfaces
EP0052509A2 (en) * 1980-11-17 1982-05-26 Hitachi, Ltd. Method of removing oxide on a metal surface
EP0052509A3 (en) * 1980-11-17 1982-06-02 Hitachi, Ltd. Method of removing oxide on a metal surface
US4726907A (en) * 1983-08-10 1988-02-23 Nuclear Technology Corp Hydrazides of amino-polyacetic acids as chelants
US4775491A (en) * 1983-08-10 1988-10-04 Nuclear Technology Corp. Hydrazides of amino-polyacetic acids as chelants
US4659512A (en) * 1983-12-21 1987-04-21 Pedro B. Macedo Fixation of dissolved metal species with a complexing agent
US4729855A (en) * 1985-11-29 1988-03-08 Westinghouse Electric Corp. Method of decontaminating radioactive metal surfaces
US4789406A (en) * 1986-08-20 1988-12-06 Betz Laboratories, Inc. Method and compositions for penetrating and removing accumulated corrosion products and deposits from metal surfaces
US4708805A (en) * 1986-11-24 1987-11-24 Muhala Thomas F D Barium sulfate removal and anti-deposition compositions and process of use therefor
EP0299166A1 (en) * 1987-07-17 1989-01-18 Mitsubishi Jukogyo Kabushiki Kaisha Method for removing scale on inner surfaces of boiler tube members
US5342450A (en) * 1989-01-26 1994-08-30 Kay Chemical Company Use of noncorrosive chemical composition for the removal of soils originating from an animal or vegetable source from a stainless steel surface
US5205999A (en) * 1991-09-18 1993-04-27 British Nuclear Fuels Plc Actinide dissolution
US5292456A (en) * 1992-03-20 1994-03-08 Associated Universities, Inc. Waste site reclamation with recovery of radionuclides and metals
US5401311A (en) * 1992-12-17 1995-03-28 Betz Laboratories, Inc. Method for removing deposits from cooling water systems
US5401323A (en) * 1993-09-08 1995-03-28 Betz Laboratories, Inc. Method for removing clay deposits from cooling water systems
US5640703A (en) * 1994-04-18 1997-06-17 British Nuclear Fuels Plc Treatment of solid wastes
WO2006053626A1 (en) * 2004-11-11 2006-05-26 Areva Np Gmbh Cleaning method for removing deposits containing magnetite out of a pressure vessel of a power plant
US20070267046A1 (en) * 2004-11-11 2007-11-22 Areva Np Gmbh Cleaning Process For Removing Magnetite-Containing Deposits From A Pressure Vessel Of A Power Station
EP2090676A1 (en) * 2008-02-01 2009-08-19 Ateco Services AG Method for removing coatings and deposits
US20100078040A1 (en) * 2008-02-01 2010-04-01 Marc Philippe Vernier Use of an Aqueous Neutral Cleaning Solution and Method for Removing Rouging from Stainless Steel Surfaces
US8192550B2 (en) 2008-02-01 2012-06-05 Ateco Services Ag Use of an aqueous neutral cleaning solution and method for removing rouging from stainless steel surfaces

Similar Documents

Publication Publication Date Title
US3297580A (en) Neutral metal cleaning compositions containing hydrazine and a polycarboxylamino acid
US3013909A (en) Method of chemical decontamination of stainless steel nuclear facilities
US4587043A (en) Decontamination of metal surfaces in nuclear power reactors
US4886616A (en) Aluminum surface cleaning agent
US3409522A (en) Electrochemical machining of titanium and alloys thereof
US4705573A (en) Descaling process
KR970011260B1 (en) Process for the decontamination of surfaces
US4111830A (en) Method of inhibiting corrosion
US4610728A (en) Method and composition for dissolving deposits of magnetite
JP6558573B2 (en) Stainless steel scale remover
US3951681A (en) Method for descaling ferrous metals
US3080323A (en) Composition for radioactive decontamination and descaling of cobalt alloys
US2836566A (en) Cleaning composition and method
EP0164988B1 (en) Method of decontaminating metal surfaces
US5093072A (en) Process for the radioactive decontamination of metal surfaces, particularly portions of primary circuits of water-cooled nuclear reactors
US5278743A (en) Alkaline-permanganate process
US5858947A (en) Metal cleaning and de-icing compositions
US2981643A (en) Process for descaling and decontaminating metals
US3280038A (en) Method for cleaning stainless steel
US3138485A (en) Composition and process for treating aluminum
US2977204A (en) Method of improving corrosion resistance of zirconium
US3440095A (en) Process for treating metal
US2913360A (en) Method of descaling nickel alloys
US2853364A (en) Method of inhibiting the corrosiveness of aqueous solutions of sodium bisulfate towards stainless steels
Bloom et al. Some Effects of Alkalis on Corrosion Of Mild Steel in Steam Generating Systems