EP0193239B1 - Bains et procédé pour le polissage chimique de surfaces en acier - Google Patents

Bains et procédé pour le polissage chimique de surfaces en acier Download PDF

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Publication number
EP0193239B1
EP0193239B1 EP86200262A EP86200262A EP0193239B1 EP 0193239 B1 EP0193239 B1 EP 0193239B1 EP 86200262 A EP86200262 A EP 86200262A EP 86200262 A EP86200262 A EP 86200262A EP 0193239 B1 EP0193239 B1 EP 0193239B1
Authority
EP
European Patent Office
Prior art keywords
baths
mol
aqueous solution
ferricyanide
bath
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
Application number
EP86200262A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0193239A1 (fr
Inventor
Daniel Tytgat
Pierre Lefevre
Michel Marechal
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.)
Solvay SA
Original Assignee
Solvay SA
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 Solvay SA filed Critical Solvay SA
Priority to AT86200262T priority Critical patent/ATE44553T1/de
Publication of EP0193239A1 publication Critical patent/EP0193239A1/fr
Application granted granted Critical
Publication of EP0193239B1 publication Critical patent/EP0193239B1/fr
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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
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F3/00Brightening metals by chemical means
    • C23F3/04Heavy metals
    • C23F3/06Heavy metals with acidic solutions

Definitions

  • the present invention relates to the composition of baths for the chemical polishing of steel surfaces, in particular stainless steel.
  • a composition of a bath for the chemical polishing of stainless steel surfaces comprising, in aqueous solution, a mixture of phosphoric acid, nitric acid and d hydrochloric acid, a viscosity regulator chosen from water-soluble polymers, a surfactant and sulfosalicylic acid as a brightening agent.
  • This known polishing bath has proven to be very effective. However, it has the disadvantage of containing several organic additives, which add to the cost, complicate its implementation and constitute a source of pollution during the rejection of the spent bath.
  • a bath of simpler composition for the chemical polishing of steels, this bath comprising, in aqueous solution, a mixture of hydrochloric acid, phosphoric acid and nitric acid, potassium ferrocyanide and the surfactant OP- 7 which is a nonionic surfactant from the family of alkylphenols (Central Patents Index, Basic Abstracts Journal, section E, Derwent Publications Ltd, London, abbreviated 13581 U-EM: Soviet author's certificate SU-344 035).
  • this known bath has however proved powerless to achieve uniform polishing, of good quality.
  • the known polishing baths which have just been described have the common characteristic of attacking the metal at very high speed.
  • a polishing treatment of a steel surface with such baths can generally not exceed a few minutes, at the risk of causing local corrosion.
  • This high speed of action of known polishing baths is a drawback, because it makes them unusable for certain applications, in particular for polishing the internal face of the walls of large tanks, such as boilers, autoclaves or crystallizers .
  • the time required for filling and emptying such tanks being generally much greater than the duration of the optimum chemical polishing treatment, it indeed becomes impossible to obtain a uniform polish of the wall, certain areas of the latter being insufficiently others are deeply corroded.
  • the high speed of action of known chemical polishing baths also makes polishing control difficult. These known baths are also ineffective for polishing surfaces in contact with which the renewal of the bath is difficult, since this results in abrupt modifications to the local compositions of the bath.
  • the object of the present invention is to remedy the aforementioned drawbacks of known polishing baths, by providing bath compositions for the chemical polishing of austenitic stainless steel surfaces, in particular steel alloyed with chromium and nickel, which make it possible to avoid the use of multiple additives, which are effective in all types of application including the polishing of large surfaces or surfaces that are difficult to access and which make it possible to produce polishes of excellent quality.
  • the invention therefore relates to baths for the chemical polishing of steel surfaces, comprising, in aqueous solution, a mixture of hydrochloric acid, phosphoric acid and nitric acid; according to the invention, the baths comprise, in the aqueous solution, ferricyanide complex ions.
  • the ferricyanide complex ions are complex cyanides of general formula [Fe lil (CN) 6] 3- , also called hexacyanoferrates (III) (Encyclopedia of Chemical Technology - Kirk-Othmer - John Wiley & Sons , Inc. - 1967 - Vol. 12 - pages 25, 26, 31, 32). They can be present in the aqueous solution in the form of any dissolved compounds such as, for example, hexacyanoferric acid (III), ammonium ferricyanide and ferricyanides of alkali and alkaline earth metals. Preferred compounds are the alkali metal ferricyanides, potassium ferricyanide being especially recommended.
  • Preferred baths are those which are essentially free of such additives.
  • these contain anions selected from the bromide, iodide and thiocyanate ions.
  • These anions can generally be used in the state of alkali metal bromide, iodide or thiocyanate, the latter advantageously being sodium.
  • the baths according to this embodiment of the invention have proved to be particularly advantageous for the polishing of welded assemblies, at the level of the weld beads. The best results are obtained for contents of bromide anion, iodide or thiocyanate comprised between 10-5 and 1 gram-ion per liter, the contents of between 10- 4 and 10- 2 gram-ion per liter being preferred.
  • the baths according to the invention are suitable for polishing all austenitic stainless steel surfaces. They find a particularly advantageous application in the polishing of austenitic stainless steels alloyed with chromium and nickel, in particular those containing between 12 and 26% of chromium and between 6 and 22% of nickel, such as steels 18/8 and 18/10 , for example.
  • the invention therefore also relates to a method for polishing a steel surface, according to which the surface is brought into contact with a chemical polishing bath according to the invention.
  • a prefabricated bath can be used, in contact with which the metal surface to be polished is then placed.
  • the metal surface is first brought into contact with an aqueous solution of hydrochloric acid, phosphoric acid and nitric acid, then added complex ferricyanide ions to the solution, while it is in contact with the metal surface.
  • the contact time of the surface to be polished with the bath must be sufficient to achieve effective polishing of the surface; however, it cannot exceed a critical value beyond which local corrosions may appear on the surface.
  • the optimum contact time depends on many parameters such as the metal or alloy constituting the surface to be polished, the configuration and initial roughness thereof, the composition of the bath, the working temperature, the possible turbulence of the bath in contact with the surface, the ratio between the area of the metal surface to be polished and the volume of the bath used; it must be determined in each particular case by routine laboratory work.
  • the surface to be polished is brought into contact with the aqueous acid solution at a temperature between 15 and 70 ° C. preferably 20 and 55 ° C., the ferricyanide complex ions are added to said solution after having maintained the surface in contact for at least 15 minutes, and then the maintenance of the surface in contact with the resulting bath is continued for a time at least equal 1 hour.
  • the addition of the ferricyanide complex ions to the acid solution can for example be carried out after the surface to be polished has been kept in contact with said solution for a time between 30 and 60 minutes and the resulting bath can then be kept in contact with the surface for a time between 6 and 24 hours.
  • a chemical polishing bath in accordance with the invention was used to polish the internal face of a spherical stainless steel tank with a capacity of 6 m 3 and a diameter of 2.4 m, made of stainless steel of grade ASTM-316L , which is a steel alloyed with chromium (16.0 to 18.0% nickel (10.0 to 14.0% and molybdenum (2.0 to 3.0% (Engineering techniques - Metallurgy -M 323A-8 (Table G) - July 1983).
  • the bath used had the following composition: Mixture of acids:
  • the bath was introduced into the tank, at a rate of 3.9 per dm 2 of surface to be polished, and it was subjected to a stirring movement therein by means of a three-blade agitator, while maintaining its temperature between 45 and 50 ° C.
  • the tank was drained and rinsed with demineralized water.
  • a chemical polishing bath in accordance with the invention was used to polish the external surface of the tubes of a tubular heat exchanger made of stainless steel 1.9 m in diameter and 6 m in length.
  • This exchanger was equipped with 455 tubes of 50 mm in diameter and 9 baffles made, like the ferrule, in stainless steel grade ASTM-304L, which is a steel alloyed with chromium (18.0 to 20.0%) and Nickel (8.0 to 12.0%) (Techniques de l'In distributedur Métallurgie-M.323A - 8 (Table G) July 1983).
  • the bath used had the following composition: Mixture of acids in aqueous solution
  • This bath was introduced into a shuttle circuit at the rate of 1.3 per dm 2 of surface to be polished and it was subjected to a linear passage movement over the surfaces to be treated by means of a circulation pump, while maintaining its temperature between 45 and 50 C by injecting steam inside the tubes.
  • This bath made it possible to chemically polish, almost perfectly, the outside surface of the tube bundle.

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)
  • ing And Chemical Polishing (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Polyethers (AREA)
  • Artificial Filaments (AREA)
EP86200262A 1985-03-04 1986-02-20 Bains et procédé pour le polissage chimique de surfaces en acier Expired EP0193239B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86200262T ATE44553T1 (de) 1985-03-04 1986-02-20 Zusammensetzungen und verfahren zum chemischen polieren von stahloberflaechen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8503263 1985-03-04
FR8503263A FR2578271A1 (fr) 1985-03-04 1985-03-04 Bains et procede pour le polissage chimique de surfaces en acier.

Publications (2)

Publication Number Publication Date
EP0193239A1 EP0193239A1 (fr) 1986-09-03
EP0193239B1 true EP0193239B1 (fr) 1989-07-12

Family

ID=9316903

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86200262A Expired EP0193239B1 (fr) 1985-03-04 1986-02-20 Bains et procédé pour le polissage chimique de surfaces en acier

Country Status (8)

Country Link
US (1) US4652340A (es)
EP (1) EP0193239B1 (es)
JP (1) JPS61217600A (es)
AT (1) ATE44553T1 (es)
DE (1) DE3664339D1 (es)
ES (1) ES8705930A1 (es)
FR (1) FR2578271A1 (es)
PT (1) PT82125B (es)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE1003579A3 (fr) * 1989-10-26 1992-04-28 Solvay Bains et procede pour le polissage chimique de surfaces en acier inxoydable.
US5279707A (en) * 1992-10-23 1994-01-18 Time Savers Die discoloration remover solution and method
US5338375A (en) * 1993-10-18 1994-08-16 Rohm And Haas Company Use of iron salts as corrosion inhibitors in titanium vessels
FR2717829B1 (fr) * 1994-03-28 1996-05-24 Solvay Bains et procédé pour le polissage chimique de surfaces en acier inoxydable.
CN108570699A (zh) * 2018-05-16 2018-09-25 扬州虹扬科技发展有限公司 一种电镀前处理药剂及处理工艺
CN110724999B (zh) * 2019-10-23 2021-09-28 沈阳航空航天大学 一种用于高Cr含量的CoCrNi多主元合金的电解液及腐蚀工艺
CN111876783A (zh) * 2020-07-10 2020-11-03 山东电力工业锅炉压力容器检验中心有限公司 一种金相化学抛光液及在奥氏体不锈钢金相检测领域的应用

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1809041A (en) * 1930-02-03 1931-06-09 Swann Res Inc Inhibitor
US2502621A (en) * 1945-10-08 1950-04-04 Menasco Mfg Company Method of determining oxygen concentration in steel
US2662814A (en) * 1949-08-27 1953-12-15 Diversey Corp Method and composition for chemically polishing metals
LU30914A1 (es) * 1950-10-27
LU38281A1 (es) * 1959-03-09
US3457107A (en) * 1965-07-20 1969-07-22 Diversey Corp Method and composition for chemically polishing metals
FR2457315A1 (fr) * 1979-05-25 1980-12-19 Solvay Bain pour le polissage chimique de surfaces en acier
FR2465010A1 (fr) * 1979-09-17 1981-03-20 Solvay Procede pour inhiber la corrosion d'une installation metallique au contact d'un bain acide
FR2476146A1 (fr) * 1980-02-20 1981-08-21 Solvay Bain pour l'elimination d'une pellicule de magnetite d'une surface metallique
US4289576A (en) * 1980-05-27 1981-09-15 Halliburton Company Method for removing cobalt-containing deposits from surfaces

Also Published As

Publication number Publication date
ES552595A0 (es) 1987-05-16
EP0193239A1 (fr) 1986-09-03
FR2578271A1 (fr) 1986-09-05
ES8705930A1 (es) 1987-05-16
PT82125B (pt) 1988-04-21
JPS61217600A (ja) 1986-09-27
PT82125A (fr) 1986-04-01
DE3664339D1 (en) 1989-08-17
US4652340A (en) 1987-03-24
ATE44553T1 (de) 1989-07-15
JPH0577751B2 (es) 1993-10-27

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