Patent Number: 048287903
Section: claims

1. A process for inhibiting deposition of radioactive substances on nuclear power plant components which comprises forming a positively charged oxide film on surface of components contacting with nuclear reactor cooling water containing radioactive substances by treating the surface of components with a solution containing anions and polyvalent metal cations, the anions having a lower valence number than the cations at a time of forming an oxide film or after the formation of the oxide film, wherein the polyvalent metal cations are at least one member selected from the group consisting of Al.sup.3+, Fe.sup.3+, Ba.sup.2+, Ca.sup.2+, Co.sup.2+, Mg.sup.2+, Ni.sup.2+, Pb.sup.2+, Zn.sup.2+ and Cu.sup.2+, and the anions are at least one member selected from the group consisting of HCO.sub.3.sup.-, H.sub.2 PO.sub.4.sup.-, MnO.sub.4.sup.-, NO.sub.2.sup.-, NO.sub.3.sup.-, OH.sup.-, HCOO.sup.-, CH.sub.3 COO.sup.-, MnO.sub.4.sup.2-, HPO.sub.4.sup.2-, SO.sub.4.sup.2- and WO.sub.4.sup.2-. 2. A process according to claim 1, wherein the solution containing the polyvalent metal cations and the anions has a temperature of 150.degree. to 300.degree. C. 3. A process according to claim 1, wherein the polyvalent metal cations are used in a concentration of 3 ppb to 1000 ppm. 4. A process according to claim 1, wherein said polyvalent metal cations are selected from the group consisting of Al.sup.3+, Fe.sup.3+, Ba.sup.2+, Ca.sup.2+, Co.sup.2+, Mg.sup.2+, Ni.sup.2+, Pb.sup.2+, Zn.sup.2+ and Cu.sup.2+, and wherein the anions are selected from the group consisting of HCO.sub.3.sup.-, H.sub.2 PO.sub.4.sup.-, MnO.sub.4.sup.-, NO.sub.2.sup.-, NO.sub.3.sup.-, OH.sup.-, HCOO.sup.- and CH.sub.3 COO.sup.-. 5. A process according to claim 1, wherein said polyvalent metal cations are selected from the group consisting of Al.sup.3+ and Fe.sup.3+, and wherein the anions are selected from the group consisting of MoO.sub.4.sup.2-, HPO.sub.4.sup.2-, SO.sub.4.sup.2- and WO.sub.4.sup.2-. 6. A process according to claim 3, wherein the positively charged iron oxide film is formed to have a thickness of at least 300 .ANG.. 7. A process according to claim 1, wherein the components are formed of materials selected from the group consisting of stainless steel; carbon steel; cobalt-chromium-tungsten alloy; and nickel-chromium-iron alloy. 8. A process according to claim 7, wherein the components are formed of carbon steel. 9. A process according to claim 7, wherein the components are formed of materials selected from the group consisting of cobalt-chromium-tungsten alloy and nickel-chromium-iron alloy. 10. A process according to claim 1, wherein said treating is performed by pouring said solution into said cooling water, whereby solution-containing cooling water treats the surfaces of the components. 11. A process according to claim 10, wherein said surfaces of components are made of stainless steel. 12. A process for inhibiting deposition of radioactive substances on nuclear power plant components which comprises forming a positively charged iron oxide film containing metallic elements giving polyvalent metal cations and chromium on surfaces of components contacting with nuclear reactor cooling water containing radioactive substances, the positively charged iron oxide film being formed by contacting said surfaces of components with a solution containing said polyvalent metal cations and anions having a lower valence number than the cations, wherein the polyvalent metal cations are at least one member selected from the group consisting of Al.sup.3+, Fe.sup.3+, Ba.sup.2+, Ca.sup.2+, Co.sup.2+, Mg.sup.2+, Ni.sup.2+, Pb.sup.2+, Zn.sup.2+ and Cu.sup.2+, and the anions are at least one member selected from the group consisting of HCO.sub.3.sup.-, H.sub.2 PO.sub.4.sup.-, MnO.sub.4.sup.-, NO.sub.2.sup.-, NO.sub.3.sup.-, OH.sup.-, HCOO.sup.-, CH.sub.3 COO.sup.-, MnO.sub.4.sup.2-, HPO.sub.4.sup.2- , SO.sub.4.sup.2- and WO.sub.4.sup.2-. 13. A process according to claim 12, wherein the chromium content in the iron oxide film is 12% by weight or more. 14. A process according to claim 12, wherein the polyvalent metal cations are used in a concentration of 3 ppb to 1000 ppm. 15. A process according to claim 14, wherein the components are made of stainless steel. 16. A process according to claim 15, wherein the solution has a temperature of 150.degree. to 300.degree. C. 17. A process for inhibiting deposition of radioactive substances on nuclear power plant components made of an iron series material and contacting with reactor cooling water containing radioactive substances, which comprises treating surfaces of components made of a chromium-containing iron series material with heated water or heated steam to form an oxide film containing chromium in an amount of 12% by weight or more. formed thereon, prior to operation of the plant to provide nuclear heating, the oxide film having a chromium content of at least 12% by weight, wherein said oxide film is a positively charged oxide film, formed by contacting said surfaces with a solution containing polyvalent metal cations and anions having a lower valence number than the cations. 18. A process according to claim 17, further comprising the step of treating said surfaces of components with a solution containing polyvalent metal cations and anions having a lower valence number than the cations so as to form a positively charged iron oxide film on said surfaces of components, whereby said surfaces have a positively charged iron oxide film and an oxide film containing chromium in an amount of 12% by weight or more. 19. A process according to claim 18, wherein the polyvalent metal cations are at least one member selected from the group consisting of Al.sup.3+, Fe.sup.3+, Ba.sup.2+, Ca.sup.2+, Mg.sup.2+, Ni.sup.2+, Pb.sup.2+, Zn.sup.2+ and Cu.sup.2+, and the anions are at least one member selected from the group consisting of HCO.sub.3.sup.-, H.sub.2 PO.sub.4.sup.-, MnO.sub.4.sup.-, NO.sub.2.sup.-, NO.sub.3.sup.-, OH.sup.-, HCOO.sup.-, CH.sub.3 COO.sup.-, MnO.sub.4.sup.2-, HPo.sub.4.sup.2-, SO.sub.4.sup.2- and WO.sub.4.sup.2-. 20. A process according to claim 19, wherein the polyvalent metal cations are used in a concentration of 3 ppb to 1000 ppm. 21. A process according to claim 20, wherein the heated water or the heated steam contains a reducing agent. 22. A process according to claim 17, wherein the heated water has a temperature of 150.degree. to 300.degree. C. 23. A process according to claim 17, wherein the heated steam has a temperature of 150.degree. to 1000.degree. C. 24. A process according to claim 17, wherein said surfaces are a coating of chromium or chromium-containing iron series material, said coating being a chromium plated film, chromizing treated film or chromium vapor deposited film. 25. A process according to claim 17, wherein the components are formed of materials selected from the group consisting of stainless steel; carbon steel; and cobalt-chromium-tungsten alloy; and nickel-chromium-iron alloy. 26. A process according to claim 25, wherein the components are formed of carbon steel. 27. A process according to claim 25, wherein the components are formed of materials selected from the group consisting of cobalt-chromium-tungsten alloy and nickel-chromium-iron alloy. 28. A process according to claim 21, wherein the reducing agent is also a chelating agent. 29. A process according to claim 21, wherein the reducing agent is a Ni salt of ethylenediamine-tetraacetic acid or a nickel salt of nitrilotriacetic acid. 30. In a nuclear power plant comprising a reactor, a turbine, a condenser, a condensed water demineralizer, a supplying water heater, a demineralizer for a reactor cleaning system, and a reactor re-circulation piping system, the improvement wherein a positively charged iron oxide film is formed on surfaces which contact with nuclear reactor cooling water in said plant, the positively charged iron oxide film being formed by contacting said surfaces with a solution containing polyvalent metal cations and anions having a lower valence number than the cations. 31. A nuclear power plant according to claim 30, wherein the polyvalent metal cations are at least one member selected from the group consisting of Al.sup.3+, Fe.sup.3+, Ba.sup.2+, Co.sup.2+, Mg.sup.2+, Ni.sup.2+, Pb.sup.2+, Zn.sup.2+ and Cu.sup.2+, and the anions are at least one member selected from the group consisting of HCO.sub.3.sup.-, H.sub.2 PO.sub.4.sup.-, MnO.sub.4.sup.-, NO.sub.2.sup.-, NO.sub.3.sup.-, OH.sup.-, HCOO.sup.-, CH.sub.3 COO.sup.-, MnO.sub.4.sup.2-, HPO.sub.4.sup.2-, SO.sub.4.sup.2- and WO.sub.4.sup.2-. 32. In a nuclear power plant comprising a reactor, a turbine, a condenser, a condensed water demineralizer, a supplying water heater, a demineralizer for a reactor cleaning system, and a reactor re-circulation piping system, the improvement wherein a positively charged iron oxide film is formed on surfaces which contact with nuclear reactor cooling water in said plant, the positively charged iron oxide film being formed by contacting said surfaces with a solution containing polyvalent metal cations and anions having a lower valence number than the cations, after the construction of said plant and prior to the operation thereof to provide nuclear heating. 33. A nuclear power plant according to claim 32, wherein the polyvalent metal cations are at least one member selected from the group consisting of Al.sup.3+, Fe.sup.3+, Ba.sup.2+, Ca.sup.2+, Co.sup.2+, Mg.sup.2+, Ni.sup.2+, Pb.sup.2+, Zn.sup.2+ and Cu.sup.2+, and the anions are at least one member selected from the group consisting of HCO.sub.3.sup.-, H.sub.2 PO.sub.4.sup.-, MnO.sub.4.sup.-, NO.sub.2.sup.-, NO.sub.3.sup.-, OH.sup.-, HCOO.sup.-, CH.sub.3 COO.sup.-, MnO.sub.4.sup.2-, HPO.sub.4.sup.2-, SO.sub.4.sup.2- and WO.sub.4.sup.2-. 34. In a nuclear power plant comprising a reactor, a turbine, a condenser, a condensed water demineralizer, a supplying water heater, a demineralizer for a reactor cleaning system, and a reactor re-circulation piping system, the improvement wherein a positively charged iron oxide film is formed on surfaces which contact with nuclear reactor cooling water contaminated with radioactive substances after the operation of said plant, the positively charged iron oxide film being formed by contacting said surfaces with a solution containing polyvalent metal cations and anions having a lower valence number than the cations. 35. A nuclear power plant according to claim 34, wherein the polyvalent metal cations are at least one member selected from the group consisting of Al.sup.3+, Fe.sup.3+, Ba.sup.2+, Ca.sup.2+, Co.sup.2+, Mg.sup.2+, Ni.sup.2+, Pb.sup.2+, Zn.sup.2+ and Cu.sup.2+, and the anions are at least one member selected from the group consisting of HCO.sub.3.sup.-, H.sub.2 PO.sub.4.sup.-, MnO.sub.4.sup.-, NO.sub.2.sup.-, NO.sub.3.sup.-, OH.sup.-, HCOO.sup.-, CH.sub.3 COO.sup.-, MnO.sub.4.sup.2-, HPO.sub.4.sup.2-, SO.sub.4.sup.2- and WO.sub.4.sup.2-. 36. In a nuclear power plant comprising a reactor, a turbine, a condenser, a condensed water demineralizer, a supplying water heater, a demineralizer for a reactor cleaning system, and a reactor re-circulation piping system, the improvement wherein surfaces of the plant which contact with nuclear reactor cooling water have an oxide film formed thereon, prior to operation of the plant to provide nuclear heating, the oxide film having a chromium content of at least 12% by weight, wherein said oxide film is a positively charged oxide film, formed by contacting said surfaces with a solution containing polyvalent metal cations and anions having a lower valence number than the cations.