EP0753083A1 - Bains et procede pour le polissage chimique de surfaces en acier inoxydable - Google Patents
Bains et procede pour le polissage chimique de surfaces en acier inoxydableInfo
- Publication number
- EP0753083A1 EP0753083A1 EP95913105A EP95913105A EP0753083A1 EP 0753083 A1 EP0753083 A1 EP 0753083A1 EP 95913105 A EP95913105 A EP 95913105A EP 95913105 A EP95913105 A EP 95913105A EP 0753083 A1 EP0753083 A1 EP 0753083A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- baths
- polishing
- aqueous solution
- baths according
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23F—NON-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
- C23F3/00—Brightening metals by chemical means
- C23F3/04—Heavy metals
- C23F3/06—Heavy metals with acidic solutions
Definitions
- the present invention relates to the composition of baths for the chemical polishing of stainless steel surfaces.
- Chemical polishing of metal surfaces is a well-known technique (electrolytic and chemical polishing of metals - W.J. Me G. TEGART - Dunod - 1960 - p. 122 et seq.); it consists in treating the metal surfaces to be polished with oxidizing baths.
- baths are generally used comprising a mixture, in aqueous solution, of hydrochloric, phosphoric and nitric acids.
- suitable additives such as surfactants, viscosity regulators and brighteners.
- composition of a bath for the chemical polishing of stainless steel surfaces comprising, in aqueous solution, a mixture of hydrochloric acid, nitric acid and acid. phosphoric, a surfactant and sulfosalicylic acid as a brightening agent.
- JP-A-52/72989 proposes to solve the pollution problem by using polishing baths free of phosphoric acid and comprising, in aqueous solution, hydrochloric acid, nitric acid, at least one derivative chosen from l sulfosalicylic acid, salicylic acid and thiourea, and a catio-surfactant. fuck.
- These phosphoric acid-free baths have the disadvantage of being effective only at a temperature above 80 ° C so that their polishing speed is very high; they do not allow slow and efficient polishing of stainless steel surfaces.
- the invention aims to provide polishing baths without phosphoric acid designed to carry out slow and efficient chemical polishing of stainless steel surfaces.
- the invention relates to baths for the chemical polishing of stainless steel surfaces, free of phosphoric acid and comprising, in aqueous solution, a mixture of hydrochloric acid and nitric acid, an optionally substituted hydroxybenzoic acid and a cationic surfactant, these baths being characterized in that they comprise, in the aqueous solution, ferricyanide complex ions.
- hydroxybenzoic acid acts as a brightening agent.
- Hydroxybenzoic acid can be unsubstituted such as salicylic acid or substituted such as 5-sulfosalicylic acid or aminosalicylic acid.
- Salicylic acid and 5-sulfosalicylic acid are preferred.
- the cationic surfactant advantageously comprises a quaternary ammonium salt.
- the quaternary ammonium salt is preferably selected from those which comprise at least one long-chain, linear or branched alkyl radical. Where appropriate, it is preferred to select the quaternary ammonium salt from those in which the long-chain alkyl group contains at least 8 carbon atoms, preferably at least 10 carbon atoms, such as the lauryl, cetyl and stearyl groups, for example.
- the long-chain alkyl radical defined above at least one other linear or branched alkyl radical or a substituted or unsubstituted benzyl radical may be present.
- Examples are the cetyldimethylbenzylammonium, distearyldimethylammomum, lauryldimethylbenzylammonium and lauryltrimethylammonium salts.
- Specially recommended quaternary ammonium salts belong to the class formed of water-soluble alkylpyridinium salts, especially cetylpyridinium and laurylpyridinium.
- Quaternary ammonium salts comprising a long-lasting alkyl radical chain as defined above, are preferably selected from halides, in particular from chlorides.
- Alkylpyridinium chlorides are particularly preferred, in particular laurylpyridinium chloride.
- Quaternary ammonium salts which can be used in the baths according to the invention are accessible among the products of the DEHYQUART® brand (HENKEL).
- the ferricyanide complex ions are complex cyanides of general formula [e ⁇ CN ⁇ ], also called hexa-cyanoferrates (ELI). They can be present in the aqueous solution in the form of all dissolved compounds such as, for example, hexacyanoferric acid (lu), ammonium ferricyanide and ferricyanides of alkali and alkaline earth metals. Preferred compounds are the alkali metal ferricyanides, potassium ferricyanide being especially preferred.
- the respective contents of hydrochloric, nitric and hydroxybenzoic acids, cationic surfactant and complex ferricyanide ions are chosen according to the grade of the stainless steel subjected to polishing as well as the conditions of the polishing, in particular the profile of the steel object subjected to polishing, its volume, the volume of the bath, its temperature and the agitation to which it is possibly subjected. They must therefore be determined in each particular case by routine laboratory tests.
- the hydrochloric acid content of the aqueous solution is advantageously at least equal to 1, preferably 2, moles per liter and it does not generally exceed 6, preferably 5, moles per liter.
- the nitric acid content is advantageously at least equal to 0.001, preferably 0.005, moles per liter of the aqueous solution and it does not generally exceed 0.3, preferably 0.03, moles per liter of the aqueous solution.
- the hydroxybenzoic acid content is advantageously at least equal to 0.1, preferably 1, mg per liter of the aqueous solution and it does not generally exceed 15000, preferably 7000, mg per liter of the aqueous solution.
- the content of cationic surfactant is advantageously at least equal to 0.1, preferably 1, mg per liter of aqueous solution and it does not generally exceed 1000, of preferably 100 mg per liter of aqueous solution.
- the content of ferricyanide complex ions is preferably at least equal to 1 ⁇ 10 mole per liter of aqueous solution and in a particularly preferred manner, the content of ferricyanide complex ions at least equal at 1 x 10 "5 mole per liter. Very particularly preferred is a content at least equal to 3 x 10 " 5 mole per liter.
- the content of ferricyanide complex ions preferably does not exceed 1 mole per liter and in a particularly preferred manner, the content of ferricyanide complex ions does not exceed 1 x 10 -3 mole per liter. Very particularly preferred is a content which does not exceed 3 x 10 "4 mole per liter.
- Baths according to the invention which are well suited for ensuring the chemical polishing of austenitic stainless steel surfaces, alloyed with chromium and nickel, in a time varying from 1 to 24 hours and at a temperature of between 20 and 80 ° C. are those in which the aqueous solution comprises, per liter,. from 2 to 5 moles of hydrochloric acid,. from 0.005 to 0.03 moles of nitric acid,. from 1 to 7000 mg of hydroxybenzoic acid,. from 1 to 100 mg of the cationic surfactant, and. from 1 x 10 ⁇ * to 1 x 10 " ⁇ mole of ferricyanide complex ions.
- these contain, in the aqueous solution, an additive capable of decomposing the nitrous acid.
- This additive has the function of decomposing at least part of the nitrous acid which is formed during the polishing of a steel surface, as a consequence of oxidation of ferrous ions released in the bath during
- the additive capable of decomposing nitrous acid is preferably selected from urea and its derivatives, such as thiourea and ureines.
- the optimum content of additive capable of decomposing nitrous acid is 0.01 5 g per liter of the aqueous solution
- the baths according to this embodiment of the invention are specially adapted for polishing treatments in which the ratio between the surface in contact with the bath and the volume thereof is greater at 10 m .
- the baths according to the invention may optionally contain additives usually present in the chemical polishing baths of metals, for example surfactants other than the cationic surfactant defined above, alcohols and viscosity regulators.
- the baths according to the invention can also contain other mineral acids commonly present in chemical polishing baths, for example sulfiiric acid. They are, however, essentially free of phosphoric acid and phosphate ions.
- the baths according to the invention are suitable for the chemical polishing of stainless steel surfaces. They are well suited for polishing austenitic steels containing between 16 and 26% by weight of chromium and between 6 and 22% by weight of nickel, such as steels of grades 18/8 and 18/10.
- the baths according to the invention are especially well suited for polishing austenitic steels containing molybdenum. Austenitic steels, with or without molybdenum, are typically AISI-304, 304L, 316, 316L, 904 and 904L steels.
- the baths according to the invention have the particularity of polishing such steels at low speed. They can be used at all temperatures below the boiling temperature of the bath.
- the baths according to the invention have the particularity of allowing slow polishing, which makes them suitable for polishing large industrial devices.
- the baths according to the invention have the additional advantage of performing good quality polishing of welded assemblies according to the rules of the art.
- the invention therefore also relates to a method for polishing a stainless steel surface, according to which the surface is brought into contact with a chemical polishing bath according to the invention.
- the contacting of the metal surface with the bath can be carried out in any suitable manner, by example by immersion.
- 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 the bath loses its polishing properties.
- the optimum contact time depends on many parameters such as the grade of steel, the initial configuration and roughness of the surface to be polished, the composition of the bath, the working temperature, the agitation of the bath in contact with the surface.
- the contact time of the surface to be polished with the bath is, in general, at least 1 hour, preferably at least 2 hours. In general, the contact time does not exceed 24 hours, preferably not 12 hours.
- the temperature at which the bath is used is, in general, lower than its boiling point.
- the processing temperature is less than 80 ° C.
- Good results are obtained at a temperature less than or equal to 70 ° C.
- the operating temperature of the bath is, in general, at least equal to room temperature.
- the temperature is at least 35 ° C.
- the bath is carried out, at normal atmospheric pressure, at a temperature of 35 to 70 ° C., and the surface to be polished is kept in contact with the bath for a time between 2 and 12 hours.
- Austenitic stainless steel plate of the AISI 316 type was immersed in a polishing bath in accordance with the invention, comprising, per liter:
- An AISI 904L type austenitic stainless steel plate was immersed in a polishing bath according to the invention, comprising, per liter:
- Example 3 (not in accordance with the invention) An austenitic stainless steel plate of the AISI 316 type was immersed in a polishing bath, comprising, per liter: 2.7 moles of hydrochloric acid, 0.01 mole of acid nitric, 10 mg salicylic acid,. 2 mg of the product DEHYQUART®C which contains as the main constituent laurylpyridinium chloride.
- the bath used is therefore different from the bath of Example 1 by the absence of potassium ferricyanide.
- Example 4 shows the progress made by the invention, with regard to roughness and the shine obtained after polishing.
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)
- Chemical Treatment Of Metals (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9403732A FR2717829B1 (fr) | 1994-03-28 | 1994-03-28 | Bains et procédé pour le polissage chimique de surfaces en acier inoxydable. |
FR9403732 | 1994-03-28 | ||
PCT/EP1995/000942 WO1995026428A1 (fr) | 1994-03-28 | 1995-03-13 | Bains et procede pour le polissage chimique de surfaces en acier inoxydable |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0753083A1 true EP0753083A1 (fr) | 1997-01-15 |
EP0753083B1 EP0753083B1 (fr) | 2001-11-21 |
Family
ID=9461575
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95913105A Expired - Lifetime EP0753083B1 (fr) | 1994-03-28 | 1995-03-13 | Bains et procede pour le polissage chimique de surfaces en acier inoxydable |
Country Status (26)
Country | Link |
---|---|
US (1) | US5762819A (fr) |
EP (1) | EP0753083B1 (fr) |
JP (1) | JPH10500732A (fr) |
CN (1) | CN1044264C (fr) |
AU (1) | AU2070295A (fr) |
BG (1) | BG62338B1 (fr) |
BR (1) | BR9507264A (fr) |
CA (1) | CA2186401A1 (fr) |
CZ (1) | CZ285932B6 (fr) |
DE (1) | DE69524072T2 (fr) |
ES (1) | ES2168360T3 (fr) |
FI (1) | FI963894A (fr) |
FR (1) | FR2717829B1 (fr) |
HR (1) | HRP950163B1 (fr) |
HU (1) | HU214367B (fr) |
IL (1) | IL112966A0 (fr) |
NO (1) | NO964114L (fr) |
PL (1) | PL316536A1 (fr) |
PT (1) | PT753083E (fr) |
RU (1) | RU2124577C1 (fr) |
SK (1) | SK281732B6 (fr) |
TW (1) | TW311942B (fr) |
UA (1) | UA48129C2 (fr) |
WO (1) | WO1995026428A1 (fr) |
YU (1) | YU48903B (fr) |
ZA (1) | ZA952067B (fr) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE1012670A3 (fr) * | 1999-05-07 | 2001-02-06 | Solvay | Bains et procede pour le polissage chimique de surfaces en acier inoxydable. |
US6489281B1 (en) | 2000-09-12 | 2002-12-03 | Ecolab Inc. | Cleaning composition comprising inorganic acids, an oxidant, and a cationic surfactant |
CN100424227C (zh) * | 2003-03-10 | 2008-10-08 | 长庚大学 | 一种金属表面处理水溶液组合物 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2662814A (en) * | 1949-08-27 | 1953-12-15 | Diversey Corp | Method and composition for chemically polishing metals |
US3709824A (en) * | 1971-01-07 | 1973-01-09 | Nippon Soda Co | Method and composition for chemical polishing of stainless steel surfaces |
JPS5642673B2 (fr) * | 1974-04-10 | 1981-10-06 | ||
JPS5272989A (en) * | 1975-12-15 | 1977-06-18 | Nippon Soda Co | Composites of chemical grinding agent for stainless steel |
FR2457315A1 (fr) * | 1979-05-25 | 1980-12-19 | Solvay | Bain pour le polissage chimique de surfaces en acier |
FR2476146A1 (fr) * | 1980-02-20 | 1981-08-21 | Solvay | Bain pour l'elimination d'une pellicule de magnetite d'une surface metallique |
FR2578271A1 (fr) * | 1985-03-04 | 1986-09-05 | Solvay | Bains et procede pour le polissage chimique de surfaces en acier. |
FR2582675B1 (fr) * | 1985-06-03 | 1992-10-02 | Solvay | Bains et procedes pour le polissage chimique de surfaces en acier inoxydable |
JPH05272289A (ja) * | 1992-03-25 | 1993-10-19 | Shimizu Corp | 立坑掘削装置及び立坑の掘削方法 |
-
1994
- 1994-03-28 FR FR9403732A patent/FR2717829B1/fr not_active Expired - Fee Related
-
1995
- 1995-03-11 TW TW084102328A patent/TW311942B/zh active
- 1995-03-13 HU HU9602669A patent/HU214367B/hu not_active IP Right Cessation
- 1995-03-13 BR BR9507264A patent/BR9507264A/pt not_active Application Discontinuation
- 1995-03-13 SK SK1282-96A patent/SK281732B6/sk unknown
- 1995-03-13 ES ES95913105T patent/ES2168360T3/es not_active Expired - Lifetime
- 1995-03-13 PT PT95913105T patent/PT753083E/pt unknown
- 1995-03-13 CA CA002186401A patent/CA2186401A1/fr not_active Abandoned
- 1995-03-13 WO PCT/EP1995/000942 patent/WO1995026428A1/fr active IP Right Grant
- 1995-03-13 IL IL11296695A patent/IL112966A0/xx not_active IP Right Cessation
- 1995-03-13 DE DE69524072T patent/DE69524072T2/de not_active Expired - Fee Related
- 1995-03-13 CN CN95193129A patent/CN1044264C/zh not_active Expired - Fee Related
- 1995-03-13 US US08/702,435 patent/US5762819A/en not_active Expired - Fee Related
- 1995-03-13 UA UA96093741A patent/UA48129C2/uk unknown
- 1995-03-13 AU AU20702/95A patent/AU2070295A/en not_active Abandoned
- 1995-03-13 ZA ZA952067A patent/ZA952067B/xx unknown
- 1995-03-13 PL PL95316536A patent/PL316536A1/xx unknown
- 1995-03-13 EP EP95913105A patent/EP0753083B1/fr not_active Expired - Lifetime
- 1995-03-13 CZ CZ962857A patent/CZ285932B6/cs not_active IP Right Cessation
- 1995-03-13 JP JP7524929A patent/JPH10500732A/ja active Pending
- 1995-03-27 YU YU19895A patent/YU48903B/sh unknown
- 1995-03-28 HR HR950163A patent/HRP950163B1/xx not_active IP Right Cessation
-
1996
- 1996-03-13 RU RU96119757A patent/RU2124577C1/ru active
- 1996-09-24 BG BG100865A patent/BG62338B1/bg unknown
- 1996-09-27 NO NO964114A patent/NO964114L/no not_active Application Discontinuation
- 1996-09-27 FI FI963894A patent/FI963894A/fi unknown
Non-Patent Citations (1)
Title |
---|
See references of WO9526428A1 * |
Also Published As
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