EP0589028B1 - Concentre pour fabriquer des mordants metalliques - Google Patents

Concentre pour fabriquer des mordants metalliques Download PDF

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Publication number
EP0589028B1
EP0589028B1 EP93908942A EP93908942A EP0589028B1 EP 0589028 B1 EP0589028 B1 EP 0589028B1 EP 93908942 A EP93908942 A EP 93908942A EP 93908942 A EP93908942 A EP 93908942A EP 0589028 B1 EP0589028 B1 EP 0589028B1
Authority
EP
European Patent Office
Prior art keywords
acid
water
compound
weight
amount
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 - Lifetime
Application number
EP93908942A
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German (de)
English (en)
Other versions
EP0589028A1 (fr
Inventor
Rolf Spiekermann
Norbert Scheer
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.)
METASCO Chemische-Technische Produkte GmbH
Original Assignee
METASCO Chemische-Technische Produkte GmbH
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Publication date
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Publication of EP0589028A1 publication Critical patent/EP0589028A1/fr
Application granted granted Critical
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Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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-promoting 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 their salts and a certain sulfonic acid (DE-AS 19 59 560).
  • 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.
  • 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 actual 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), b1) or b2) and optionally c) chosen above is intended to clarify that in addition to components a) and optionally c) either component b1) or component b2) is present. This does not rule out the fact that minor amounts of calcium and / or aluminum compound may be present in component b1 or minor amounts of magnesium compound may be present in the mordant when component b2 is used. 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, b1 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 b1.
  • 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.
  • 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.
  • 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.
  • a dimensioning which leads to a content of 1 to 10% by weight in the concentrate is particularly advantageous.
  • 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 peroxidisulfate 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 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 significantly increased if, according to a particular embodiment of the invention, the water-containing and water-free components are kept separately, 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 above-mentioned 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 mordant, in which the crystal water-containing component has a relatively large amount of crystal water, consists in preparing a pickling paste without the 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 be intended, for example, for the production of 1, 2, 5 or 10 liters of mordant. This applies equally to the case of the separation of water-containing and water-free concentrate components, in which case the contents of two packs 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 the 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.
  • 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 (NH4HF2), substance II from a mixture of magnesium nitrate (Mg (NO3) 2 ⁇ 6H2O) and potassium nitrate (KNO3) in a weight ratio of 2: 1.
  • NH4HF2 ammonium hydrogen fluoride
  • substance II from a mixture of magnesium nitrate (Mg (NO3) 2 ⁇ 6H2O) and potassium nitrate (KNO3) 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 (NH4HF2) and ammonium peroxydisulfate ((NH4) 2S2O8) in a weight ratio of 3.5:
  • substance II was a mixture of magnesium nitrate (Mg ( NO3) 2 ⁇ 6H2O) and potassium nitrate (KNO3) 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.

Claims (10)

  1. Concentré solide pour la préparation d'un mordant aqueux acide pour surfaces métalliques, caractérisé en ce qu'il contient, en tant que constituants :
    a) un composé de fluor et de nitrate;
    b1) un composé de magnésium ou;
    b2) un composé de calcium et/ou un composé d'aluminium, ainsi qu'éventuellement;
    c) un composé réagissant dans l'eau en tant qu'acide,
    chacun de ces constituants étant solide et soluble dans l'eau et/ou dans l'acide.
  2. Concentré suivant la revendication 1, caractérisé en ce qu'il contient en outre en tant que constituant
       d) un agent d'oxydation solide soluble dans l'eau et/ou dans l'acide.
  3. Concentré suivant la revendication 1 ou 2, caractérisé en ce qu'il contient le constituant (b1).
  4. Concentré suivant la revendication 1 ou 3, caractérisé en ce qu'il contient :
    a) un composé fluoré dans une proportion de 14 à 50% en poids (calculé vis-à-vis du fluor), un composé de nitrate dans une proportion de 10 à 50% en poids (calculé vis-à-vis de NO₃),
    b1) un composé de magnésium dans une proportion de 1 à 7% en poids (calculé vis-à-vis du magnésium);
    b2) un composé de calcium et/ou un composé d'aluminium dans une proportion de 1,5 à 5% en poids chacun (calculé vis-à-vis du Ca ou du Al), la somme des proportions étant 4 à 9% en poids en cas de présence d'un composé de Ca et d'un composé de Al;
    c) des composés réagissant en tant qu'acides dans une proportion telle qu'il résulte, dans le mordant auquel on a ajouté de l'eau, une teneur en acides libres correspondant à au moins 3,5% en poids de HF.
  5. Concentré suivant la revendication 2, caractérisé en ce qu'il contient les constituants d) dans une proportion de 1 à 10% en poids.
  6. Concentré suivant la revendication 2 ou 5, caractérisé en ce qu'il contient comme constituants d) du permanganate et/ou du peroxyde.
  7. Concentré suivant la revendication 2, 5 ou 6, caractérisé en ce qu'il contient comme constituants d) du peroxyde disulfate et/ou du peroxyde de carbamide.
  8. Concentré suivant la revendication 1, 3 ou 4, caractérisé en ce qu'il contient les constituants:
    a) sous forme de sels de métaux alcalins et/ou d'ammonium;
    b1) sous la forme de nitrates, sulfates et/ou citrates;
    b2) sous forme de nitrates et/ou de citrates;
    c) sous forme d'acide citrique, d'acide amidosulfurique et/ou de dihydrogénophosphates de métaux alcalins/d'ammonium.
  9. Concentré suivant une ou plusieurs des revendications 1 à 8, caractérisé en ce qu'il contient séparément des constituants contenant de l'eau de cristallisation et des constituants anhydres.
  10. Utilisation du concentrat suivant une ou plusieurs des revendications 1 à 9 sous la forme de portions emballées pour la préparation d'une quantité définie de mordant.
EP93908942A 1992-04-17 1993-04-15 Concentre pour fabriquer des mordants metalliques Expired - Lifetime EP0589028B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4212891 1992-04-17
DE4212891A DE4212891A1 (de) 1992-04-17 1992-04-17 Konzentrat zur Herstellung von Metallbeizmitteln
PCT/EP1993/000906 WO1993021362A2 (fr) 1992-04-17 1993-04-15 Concentre pour fabriquer des mordants metalliques

Publications (2)

Publication Number Publication Date
EP0589028A1 EP0589028A1 (fr) 1994-03-30
EP0589028B1 true EP0589028B1 (fr) 1996-02-14

Family

ID=6457030

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93908942A Expired - Lifetime EP0589028B1 (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)

Families Citing this family (2)

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

Family Cites Families (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
DE3105508A1 (de) * 1981-02-14 1982-09-02 Metallgesellschaft Ag, 6000 Frankfurt Beiz- und entrostungspaste fuer metalle
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

Also Published As

Publication number Publication date
EP0589028A1 (fr) 1994-03-30
WO1993021362A3 (fr) 1994-03-03
WO1993021362A2 (fr) 1993-10-28
DE4212891A1 (de) 1993-10-21
DE59301633D1 (de) 1996-03-28
AU3953293A (en) 1993-11-18

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