EP0898621A1 - Procede pour eliminer des couches de conversion alterees par des savons, subsistant sur des pieces metalliques - Google Patents

Procede pour eliminer des couches de conversion alterees par des savons, subsistant sur des pieces metalliques

Info

Publication number
EP0898621A1
EP0898621A1 EP97920718A EP97920718A EP0898621A1 EP 0898621 A1 EP0898621 A1 EP 0898621A1 EP 97920718 A EP97920718 A EP 97920718A EP 97920718 A EP97920718 A EP 97920718A EP 0898621 A1 EP0898621 A1 EP 0898621A1
Authority
EP
European Patent Office
Prior art keywords
cleaning
cleaner
workpieces
acid
aqueous phase
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
Application number
EP97920718A
Other languages
German (de)
English (en)
Other versions
EP0898621B1 (fr
Inventor
Joachim Geldner
Klaus Wittel
Georg Blümlhuber
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.)
GEA Group AG
Original Assignee
Metallgesellschaft AG
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 Metallgesellschaft AG filed Critical Metallgesellschaft AG
Publication of EP0898621A1 publication Critical patent/EP0898621A1/fr
Application granted granted Critical
Publication of EP0898621B1 publication Critical patent/EP0898621B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/36—Regeneration of waste pickling liquors
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/12—Light metals
    • C23G1/125—Light metals aluminium

Definitions

  • the invention relates to a process for the removal of conversion layers remaining after the cold forming on metallic workpieces, which are contaminated with soaps, with aqueous, acidic cleaners, and its application to the cleaning of soaped on the workpieces made of aluminum or aluminum alloys after the cold forming
  • the task is, among other things, to remove remaining phosphate, oxalate or aluminate layers, which are contaminated with lubricant, so-called drawn-in phosphate, oxalate and aluminate layers.
  • oils and soaps used with the previously used as lubricants React chemically applied phosphate, oxalate or aluminate layer and thereby form an intimate connection.
  • the preparation of cold forming by applying phosphate, oxalate and aluminate layers and the subsequent treatment with lubricants is particularly common in the field of tube drawing, wire drawing, cold extrusion or ironing.
  • the indented layers mentioned at the beginning must be removed especially if e.g. the intention is to anneal the workpiece softly, to carry out another chemical surface treatment or to paint it.
  • Acid cleaning of aluminum, in particular cold-formed aluminum is known and i.a. in US-A-3 969 135 using the example of the cleaning of lubricated aluminum cans which were produced by deep drawing and ironing from thin sheet blanks.
  • the basis of the acidic cleaner is sulfuric acid with a small amount of hydrofluoric acid.
  • EP-A 275 043 describes a further acidic cleaning for aluminum or aluminum alloys. A mineral acid from the group consisting of sulfuric acid, phosphoric acid and nitric acid is used as the basis. Both of the above-mentioned processes have in common that the aluminum or aluminum alloy surface to be cleaned has been reshaped without prior conversion treatment using only lubricant.
  • DE-A-3 843 148 describes a process for removing drawn-in conversion and soap layers with alkaline ones Cleaners and under the influence of ultrasound. After a correspondingly high load, the constituents of the detached conversion layers accumulate in the detergent bath and the bath must be disposed of, which is usually done by cleaving with acid.
  • a disadvantage of this process is that larger amounts of strongly alkaline solution not only have to be neutralized, but also have to be strongly acidified.
  • a further disadvantage of alkaline cleaning, especially of aluminum or aluminum alloys is that the material is dissolved when using strongly alkaline cleaners, or that the conversion layer containing lubricant is detached only very slowly and incompletely when using mild alkaline cleaners, even under the influence of ultrasound.
  • the object of the invention is to provide a method for removing conversion layers which have remained after the cold forming on metallic workpieces and which are contaminated with soaps, with aqueous cleaners, which avoids the known disadvantages, in particular those mentioned above, and enables the cleaner to have a long service life.
  • the object is achieved by designing the method of the type mentioned at the outset in such a way that cleaning is carried out with a cleaner containing nitric acid, phosphoric acid and / or amidosulfonic acid at a temperature above 60 ° C. and the cleaner is removed in the absence after a sufficiently high load cools the cleaned workpieces to a temperature below 55 ° C, separates the floating fatty acid layer and at least the predominant one Part of the aqueous phase is used to clean workpieces again.
  • the converted conversion layers which are contaminated with soap, are detached quickly and completely from the workpiece.
  • the fatty acid formed from the soap remains well dispersed in the cleaner at the cleaning temperatures of above 60 ° C, so that there is no further deposition of fatty acid on the workpieces.
  • the cleaner After the cleaner has been sufficiently loaded, it is cooled to a temperature below 55 ° C.
  • the fatty acid floats and can be removed in the simplest way. Cooling and removal of the fatty acid can be done in the cleaning bath itself, e.g. by stripping. The consequence of this measure is that the cleaning treatment must be temporarily interrupted. If this is not desired, part of the contaminated cleaner can be removed from the detergent bath, cooled in a separate device and freed from floating fatty acid Filtration or centrifugation is preferred.
  • An advantageous embodiment of the invention therefore provides for the aqueous phase to be used again for cleaning by adding to the target concentration of the cleaning effective components, especially the acid.
  • the amount of acid added can easily be determined by an acid-base titration.
  • Another preferred embodiment of the invention provides for cleaning to be carried out with a cleaner which contains a surfactant.
  • Surfactants based on alkylamine ethoxylates are particularly advantageous. Alkylamine ethoxylates react cationically in an acidic environment and non-ionically in a neutral environment. Examples of such surfactants are Genamin R C100 from Hoechst AG, described as ethoxylated coconut fatty amine with 10 moles of ethylene oxide per molecule, or Marlazin R L10 from Chemische Werke Hüls AG, described as fatty amine ethoxylate.
  • the method according to the invention offers the advantage that workpieces made of aluminum or aluminum alloys can be cleaned properly.
  • the advantages of the method according to the invention are particularly pronounced if, according to a further embodiment of the invention, the method is used to clean soaped calcium aluminate layers remaining on workpieces made of aluminum or aluminum alloys after cold forming.
  • Aluminate layers are preferably used as conversion layers in connection with soap on thick-walled aluminum workpieces, compare see G. Siemund "Combining lubrication and phosphating in cold forming", Drahtwelt, Issue 11, 1963.
  • Shock absorber tubes were made by cold extrusion from aluminum blanks, which had been provided with a conversion layer made of calcium aluminate before being formed and then treated with a reactive soap.
  • the amount of calcium aluminate and soap applied after the forming was about 10 g / m 2 .
  • the shock absorber tubes were cleaned in accordance with the invention at 70 ° C. for 10 minutes in immersion, then rinsed with water and dried. The following cleaners were used in the process according to the invention:
  • Comparative cleaner 1 80 g / 1 sodium hydroxide 20 g / 1 sodium gluconate
  • Comparative cleaner 2 20 g / 1 H, S0 4
  • Comparative cleaner 3 20 g / 1 HC1
  • Comparative cleaner 1 proved to be completely unusable.
  • the surfaces of the workpieces were rough, stained and matt after rinsing.
  • Comparative cleaner 2 initially led to clean, shiny surfaces. After the throughput of a few workpieces, a crystalline coating remained on the surface of the shock absorber tubes after cleaning, which was retained even after the cleaning-effective components had been supplemented and the acid concentration had increased. In addition, a greasy film formed on the surface of the cleaning bath, which consisted essentially of fatty acid and stubbornly stuck to the treated parts. Cleaning with comparative cleaner 3 also initially led to clean surfaces. However, pitting easily seen with the naked eye was observed. In contrast, the results achieved with cleaners A and B were satisfactory in every respect. Not only were clean, shiny surfaces achieved, the cleaning effect also remained flawless after prolonged throughput of the workpieces. Although the cleaners became milky during their use, the workpieces were still completely wettable with water after rinsing.
  • cleaners A and B In order to maintain the cleaning effect of the cleaners A and B, a bath sample of 5 ml was taken at certain intervals and titrated with bromocresol green as an indicator with 0.1N sodium hydroxide solution. The consumption of 1 ml 0.1 n sodium hydroxide solution corresponds to about 2 g / 1 free amidosulfonic acid or 1.3 g / 1 nitric acid. Depending on the titration result, cleaners A and B were supplemented with amidosulfonic acid or nitric acid and with the surfactant Genamin R C100 in the same ratio as when the cleaner was prepared.
  • the cleaner bath was lowered to a temperature of 45 ° C.
  • the phosphate and soap layers were completely removed by the above treatment.
  • the concentration of the detergent on cleaning-effective components was monitored by titration, used acid and other detergent components were supplemented in the manner mentioned above.
  • the contaminated cleaner was regenerated by cooling to 40 ° C, removing the floating, granular fatty acid and re-adjusting the cleaning components to the original concentration. The cleaner could be kept effective for several weeks.

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)

Abstract

L'invention concerne un procédé permettant d'éliminer des couches de conversion altérées par des savons, qui subsistent sur des pièces métalliques après formage à froid. Selon ce procédé, un nettoyage est effectué avec un nettoyant contenant de l'acide nitrique, de l'acide phosphorique et/ou de l'acide amidosulfonique, à une température supérieure à 60 °C. Le nettoyant est refroidi après sollicitation suffisamment marquée, sans les pièces nettoyées, pour parvenir à une température inférieure à 55 °C. La couche d'acide gras qui surnage alors est séparée et la majeure partie au moins de la phase aqueuse est réutilisée pour le nettoyage. Des variantes préférées du procédé se caractérisent en ce que la phase aqueuse à réutiliser pour le nettoyage est complétée pour être ajustée à la concentration théorique des constituants actifs en termes de nettoyage. Le nettoyage s'effectue au moyen d'un nettoyant contenant un tensioactif, notamment de l'éthoxylate d'alkylamine et le procédé s'utilise pour nettoyer des couches d'aluminate de calcium savonnées qui subsistent sur des pièces en aluminium ou en alliages d'aluminium après formage à froid.
EP97920718A 1996-05-10 1997-04-18 Procede pour eliminer des couches de conversion alterees par des savons, subsistant sur des pieces metalliques Expired - Lifetime EP0898621B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19618899A DE19618899A1 (de) 1996-05-10 1996-05-10 Verfahren zum Entfernen von mit Seifen behafteten Konversionsschichten von metallischen Werkstücken
DE19618899 1996-05-10
PCT/EP1997/001966 WO1997043462A1 (fr) 1996-05-10 1997-04-18 Procede pour eliminer des couches de conversion alterees par des savons, subsistant sur des pieces metalliques

Publications (2)

Publication Number Publication Date
EP0898621A1 true EP0898621A1 (fr) 1999-03-03
EP0898621B1 EP0898621B1 (fr) 1999-11-03

Family

ID=7793973

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97920718A Expired - Lifetime EP0898621B1 (fr) 1996-05-10 1997-04-18 Procede pour eliminer des couches de conversion alterees par des savons, subsistant sur des pieces metalliques

Country Status (6)

Country Link
US (1) US6153015A (fr)
EP (1) EP0898621B1 (fr)
AU (1) AU2699897A (fr)
CA (1) CA2254846A1 (fr)
DE (2) DE19618899A1 (fr)
WO (1) WO1997043462A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19618899A1 (de) 1996-05-10 1997-11-13 Metallgesellschaft Ag Verfahren zum Entfernen von mit Seifen behafteten Konversionsschichten von metallischen Werkstücken
US7737097B2 (en) 2003-06-27 2010-06-15 Lam Research Corporation Method for removing contamination from a substrate and for making a cleaning solution
DE102013226533A1 (de) 2013-12-18 2015-06-18 MAHLE Behr GmbH & Co. KG Reiniger für ein Aluminiumbauteil und ein Verfahren zur Reinigung von Aluminiumbauteilen
CN104313604A (zh) * 2014-09-26 2015-01-28 无锡市天力五金弹簧厂 一种弹簧清洗工艺
CN113182258B (zh) * 2021-04-29 2022-12-02 中国电子科技集团公司第九研究所 一种铁氧体球形谐振子清洗方法

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT293139B (de) * 1967-02-16 1971-09-27 Degussa Verfahren zum Entzundern von Metallen
AU466393B2 (en) * 1971-11-11 1975-10-30 Basf Wyandotte Corporation Acid cleaning bath for aluminum surfaces
BE788674A (fr) * 1972-02-19 1973-01-02 Parker Ste Continentale Solution de nettoyage et degraissage de pieces de fer et d'acier
US3969135A (en) * 1975-02-13 1976-07-13 Oxy Metal Industries Corporation Low temperature aluminum cleaning composition and process
JPS52104556A (en) * 1976-02-28 1977-09-02 Matsushita Electric Works Ltd Process for stripping inorganic coats
DE3105508A1 (de) * 1981-02-14 1982-09-02 Metallgesellschaft Ag, 6000 Frankfurt Beiz- und entrostungspaste fuer metalle
JPS6020463B2 (ja) * 1982-06-04 1985-05-22 日本パ−カライジング株式会社 鉄鋼材の冷間加工潤滑処理方法
US4415415A (en) * 1982-11-24 1983-11-15 Allegheny Ludlum Steel Corporation Method of controlling oxide scale formation and descaling thereof from metal articles
DE3247431A1 (de) * 1982-12-22 1984-06-28 Henkel KGaA, 4000 Düsseldorf Verfahren zur regenerierung bzw. zum recycling von waessrigen entfettungs- und reinigungsloesungen
JPS63172799A (ja) * 1987-01-12 1988-07-16 日本パ−カライジング株式会社 アルミニウムの表面洗浄剤
DE3843148A1 (de) * 1988-12-22 1990-06-28 Metallgesellschaft Ag Verfahren zum reinigen von werkstuecken
JPH02301579A (ja) * 1989-05-15 1990-12-13 Mazda Motor Corp 冷間プレス部品の表面処理方法
DE4244245A1 (de) * 1992-12-24 1994-06-30 Norsk Hydro Chemtech Gmbh Verwendung von leicht entfernbaren Inhibitoren in Beizsäuren
US5501741A (en) * 1994-01-11 1996-03-26 Uss-Posco Process for purifying aqueous rinse solutions used in metal forming operations
DE19618899A1 (de) * 1996-05-10 1997-11-13 Metallgesellschaft Ag Verfahren zum Entfernen von mit Seifen behafteten Konversionsschichten von metallischen Werkstücken

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9743462A1 *

Also Published As

Publication number Publication date
CA2254846A1 (fr) 1997-11-20
DE19618899A1 (de) 1997-11-13
DE59700669D1 (de) 1999-12-09
WO1997043462A1 (fr) 1997-11-20
EP0898621B1 (fr) 1999-11-03
AU2699897A (en) 1997-12-05
US6153015A (en) 2000-11-28

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