WO1993021362A2 - Concentre pour fabriquer des mordants metalliques - Google Patents

Concentre pour fabriquer des mordants metalliques Download PDF

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Publication number
WO1993021362A2
WO1993021362A2 PCT/EP1993/000906 EP9300906W WO9321362A2 WO 1993021362 A2 WO1993021362 A2 WO 1993021362A2 EP 9300906 W EP9300906 W EP 9300906W WO 9321362 A2 WO9321362 A2 WO 9321362A2
Authority
WO
WIPO (PCT)
Prior art keywords
water
acid
concentrate
compound
nitrate
Prior art date
Application number
PCT/EP1993/000906
Other languages
German (de)
English (en)
Other versions
WO1993021362A3 (fr
Inventor
Rolf Spiekermann
Norbert Scheer
Original Assignee
Metasco Chemisch-Technische Produkte Gmbh
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 Metasco Chemisch-Technische Produkte Gmbh filed Critical Metasco Chemisch-Technische Produkte Gmbh
Priority to EP93908942A priority Critical patent/EP0589028B1/fr
Priority to DE59301633T priority patent/DE59301633D1/de
Publication of WO1993021362A2 publication Critical patent/WO1993021362A2/fr
Publication of WO1993021362A3 publication Critical patent/WO1993021362A3/fr

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
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • C23G1/086—Iron or steel solutions containing HF
    • 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

Definitions

  • the invention relates to a solid concentrate for the production of an acidic aqueous pickling agent for metal surfaces and its use in the form of portion packs for the production of a defined amount of pickling agent.
  • metal surfaces e.g. made of steel and / or aluminum and their alloy
  • unsightly and corrosion-demanding oxide layers such as those e.g. in the heat treatment of metals (welding) or caused by the influence of the environment.
  • acid solutions for example based on hydrochloric acid, sulfuric acid, phosphoric acid or hydrofluoric acid.
  • Acidic pastes can also be applied to the areas to be cleaned, especially for large parts or local oxide formation. This dissolves part of the oxides and the base metal attached to them, so that the oxides lose their adhesion to the metal surface. After an appropriate time, they are rinsed off with water or removed by brushing.
  • Such a pickling or rust removal paste based on phosphoric acid contains e.g. as a thickener, saponifiable oil or a fatty acid that can be converted into soap (DE-AS 10 82 475).
  • Another known cleaning and etching agent consists of hydrofluoric acid, a magnesium compound, at least one acid from the group of nitric acid, phosphoric acid and sulfuric acid in the form of free acid or in the form -2-
  • pickling and rust removal pastes have been proposed which, in addition to fluoride ions, contain a mixture of compounds of calcium and trivalent iron and / or aluminum and have an acidity corresponding to at least 10% by weight of free acid (calculated as 100% HF) ( DE-OS 31 05 508).
  • Such pickling pastes are primarily intended for the treatment of alloyed steels.
  • the object of the invention is to take suitable measures for formulating pickling agents with which the known, in particular the aforementioned disadvantages are eliminated and which in particular solve the transport problem.
  • the object is achieved by formulating the mordant as a solid concentrate, the components of which are solid, water- and / or acid-soluble
  • magnesium compound or b2) calcium and / or aluminum compound and possibly
  • solid agents suitable for the production of pickling baths for stainless steel and the like consist of soluble inorganic fluoride, soluble phosphate and optionally organic base and are added in such quantities of dilute nitric acid that pickling baths of a certain fluoride concentration are formed (DE- B-1546138).
  • these are not solid pickling agent concentrates in the strict sense, i.e. concentrates that only need water as a solvent or dispersant. Because of the need to dissolve the solid agent in nitric acid, the problem of transporting aggressive liquids ultimately remains unsolved.
  • the solid concentrate according to the invention does not contain any ineffective sorbents, and at most water is required as an auxiliary to prepare the mordant.
  • the formulation of the concentrate components with a), bl) or b2) and optionally c) chosen above is intended to clarify that in addition to components a) and optionally c) either component bl) or component b2) is present. This does not rule out the fact that minor amounts of calcium and / or aluminum compound, or minor amounts of magnesium compound when component b2 is used, may be present in the mordant. If component b2 is present, calcium and aluminum compounds can of course be used together.
  • the fluoride is introduced as an acid salt with component a), it simultaneously represents a compound in component c) which is acidic in water, so that a separate addition of a compound which is acidic in water may be unnecessary.
  • the concentrate contains, in addition to a f bl or b2 and optionally c, as an additional component d) solid, water- and / or acid-soluble oxidizing agent.
  • oxidizing agent content causes a higher aggressiveness of the pickling agent and thus an accelerated dissolution or detachment of rust and scale and possibly increases the metal removal.
  • Another advantageous embodiment of the invention provides for the concentrate to be formulated with component bl.
  • the use of magnesium compound leads to a better thickening in the preparation of the mordant than the use of component b2, ie than the use of calcium and / or aluminum compound.
  • a concentrate is particularly advantageous
  • the free acid content to be set depends essentially on the aim pursued by the pickling process. If removal or dissolution of thin layers of scale is required, contents of 3.5% by weight (calculated as HF) or slightly more are sufficient. However, if thick layers of scale are to be removed or a certain metal removal is intended, the free acid content should be at least 10% by weight HF. If the concentrate according to the invention contains solid, water- and / or acid-soluble oxidizing agent (component d) according to the aforementioned preferred embodiment, a dimensioning which leads to a content of 1 to 10% by weight in the concentrate is particularly advantageous. As a rule, when using weak oxidizing agents, the content is in the upper range, when using strong oxidizing agents in the lower range mentioned above.
  • Further preferred embodiments of the invention consist of using permanganate and / or peroxide, in particular peroxydisulfate and / or carbamide peroxide, as component d). These substances are characterized by a particularly high effectiveness and also have the advantage of considerable resistance - even when mixed with the other components of the concentrate.
  • the concentrate should be the component
  • the individual components of the concentrate are mixed thoroughly. In order to prevent segregation of the individual components - especially during transport - it is advisable to use them with the same and expediently small particle size.
  • the shelf life of the concentrate according to the invention depends essentially on the crystal water content of the components used. When using largely water-free components, it is at least one month.
  • the shelf life can be increased considerably if, in accordance with a particular embodiment of the invention, the components containing water of crystallization and those free of water of crystallization are kept separate, i.e. only crystal water-containing and crystal water-free components are mixed with each other (if several substances of one type or another are used at all).
  • a certain disadvantage of the aforementioned separation is, however, that two doses have to be carried out to produce the mordant.
  • a special case of the present invention with separate keeping of only crystal water-free and only crystal water-containing components of the pickling agent, in which the crystal water-containing component has a relatively large amount of crystal water, consists in applying a pickling paste without additional use of water.
  • one of the two components brings the amount of water required to form the pickling paste in a chemically bound form.
  • a particularly advantageous, user-oriented embodiment of the invention which also eliminates the aforementioned disadvantage of the need for double dosing, consists in using the concentrate in the form of portion packs for the production of defined amounts of mordant.
  • the packaged portions can be graduated to different sizes and can be used, for example, to produce 1, 2, 5 or 10 1 pickling agents. This applies equally to the case of the separation of concentrate components containing water of crystallization and water free of water of crystallization, in which case the contents of two packs in each case must be dissolved and / or dispersed in water.
  • the concentrate is mixed with water, the amount of water depending in particular on the desired viscosity of the mordant and this in turn on the form of application, for example by spraying or brushing.
  • the amount of water required to produce the mordant can be up to 60% by weight (based on the finished mordant).
  • the pickling agent is expediently produced using a stirrer until homogeneous distribution. Depending on the amount of mordant to be produced and the mixing intensity of the stirrer, the required stirring times are between about 1 and 5 minutes.
  • the pickling agent was produced from two separate solid substances I and II.
  • Substance I consisted of ammonium hydrogen fluoride (NH.HF,)
  • substance II consisted of a mixture of magnesium nitrate (Mg (N0 3 ) 2 «6H 2 0) and potassium nitrate (KN0 3 ) in a weight ratio of 2: 1.
  • the pickling agent was again produced from two separate substances I and II.
  • Substance I was a mixture of ammonium hydrogen fluoride (NH.HF «) and ammonium peroxydisulfate ((NH 4 ) -S_0 8 ) in a weight ratio of 3.5: 1, substance II one Mixture of magnesium nitrate (Mg (N0 _) _ «6H_0) and potassium nitrate (KN0_) in a weight ratio of 2: 1.

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)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un concentré solide utilisé pour fabriquer un mordant aqueux acide pour les surfaces métalliques. Ce mordant contient les différents composés suivants qui sont chacun solides, solubles dans l'eau et/ou dans l'acide: a) composé de fluor et de nitrate, de préférence sous forme de sel alcalin et/ou de sel d'ammonium; b1) composé de magnésium, de préférence sous forme de nitrate, de sulfate et/ou de citrate; b2) composé de calcium et/ou d'aluminium, de préférence sous forme de nitrate et/ou de citrate ainsi qu'éventuellement c) un composé à réaction acide dans l'eau, de préférence sous forme d'acide citrique, d'acide amidosulfurique et/ou d'alcali/ammonium. Sous une forme préférentielle, le concentré peut contenir en outre un agent d'oxydation solide, soluble dans l'eau et/ou dans l'acide. Il est particulièrement avantageux de maintenir à part les constituants qui contiennent de l'eau de cristallisation et ceux qui en sont exempts. Le concentrat peut être utilisé sous forme de doses conditionnées permettant de fabriquer une quantité déterminée de modant.
PCT/EP1993/000906 1992-04-17 1993-04-15 Concentre pour fabriquer des mordants metalliques WO1993021362A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP93908942A EP0589028B1 (fr) 1992-04-17 1993-04-15 Concentre pour fabriquer des mordants metalliques
DE59301633T DE59301633D1 (de) 1992-04-17 1993-04-15 Konzentrat zur herstellung von metallbeizmitteln

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4212891.9 1992-04-17
DE4212891A DE4212891A1 (de) 1992-04-17 1992-04-17 Konzentrat zur Herstellung von Metallbeizmitteln

Publications (2)

Publication Number Publication Date
WO1993021362A2 true WO1993021362A2 (fr) 1993-10-28
WO1993021362A3 WO1993021362A3 (fr) 1994-03-03

Family

ID=6457030

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1993/000906 WO1993021362A2 (fr) 1992-04-17 1993-04-15 Concentre pour fabriquer des mordants metalliques

Country Status (4)

Country Link
EP (1) EP0589028B1 (fr)
AU (1) AU3953293A (fr)
DE (2) DE4212891A1 (fr)
WO (1) WO1993021362A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997041278A1 (fr) * 1996-04-29 1997-11-06 Ki Won Lee Procede de decapage d'une surface metallique, solutions de decapage utilisees selon ce procede et procede de regeneration de solutions de decapage epuisees

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AUPP762398A0 (en) * 1998-12-09 1999-01-14 Cairnscorp Technology Pty. Limited Cleaning solutions containing citric acid and uses thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5794578A (en) * 1980-12-04 1982-06-12 Taimu Chem:Kk Acidic cleaner having viscosity
EP0058257A1 (fr) * 1981-02-14 1982-08-25 Metallgesellschaft Ag Pâte à décaper et à dérouiller pour métaux
DE3530132A1 (de) * 1985-08-23 1987-02-26 August Wittig Oberflaechen beiz- und entrostungspaste zum reinigen von metalloberflaechen insbesondere aus edelstahl und/oder aluminium u. aluminiumlegierungen
DD248379A1 (de) * 1986-04-22 1987-08-05 Bitterfeld Chemie Mittel zum sauren beizen von austenitischen edelstahloberflaechen

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5794578A (en) * 1980-12-04 1982-06-12 Taimu Chem:Kk Acidic cleaner having viscosity
EP0058257A1 (fr) * 1981-02-14 1982-08-25 Metallgesellschaft Ag Pâte à décaper et à dérouiller pour métaux
DE3530132A1 (de) * 1985-08-23 1987-02-26 August Wittig Oberflaechen beiz- und entrostungspaste zum reinigen von metalloberflaechen insbesondere aus edelstahl und/oder aluminium u. aluminiumlegierungen
DD248379A1 (de) * 1986-04-22 1987-08-05 Bitterfeld Chemie Mittel zum sauren beizen von austenitischen edelstahloberflaechen

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 108, no. 16, 18. April 1988, Columbus, Ohio, US; abstract no. 135900n, WIEDNER WOLGANG ET AL. 'acid pastes for pickling austenitic stainless steels.' Seite 260 ;Spalte 2 ; & DD,A,248 379 (VEB CHEMIEKOMBINAT BITTERFELD) 5. August 1987 *
PATENT ABSTRACTS OF JAPAN vol. 6, no. 180 (C-125)(1058) 14. September 1982 & JP,A,57 094 578 (TAIMU CHEMICAL K.K.) 12. Juni 1982 *
See also references of EP0589028A1 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997041278A1 (fr) * 1996-04-29 1997-11-06 Ki Won Lee Procede de decapage d'une surface metallique, solutions de decapage utilisees selon ce procede et procede de regeneration de solutions de decapage epuisees
US6361613B2 (en) * 1996-04-29 2002-03-26 Ki Won Lee Method for pickling mettalic surface, pickling solutions therefor, and process for regenerating spent pickling solutions

Also Published As

Publication number Publication date
EP0589028A1 (fr) 1994-03-30
WO1993021362A3 (fr) 1994-03-03
EP0589028B1 (fr) 1996-02-14
DE4212891A1 (de) 1993-10-21
DE59301633D1 (de) 1996-03-28
AU3953293A (en) 1993-11-18

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