EP0321370B1 - Verfahren zur Veränderung des Kühlvermögens von wässrigen Flüssigkeiten zur Härtung von Metall-Legierungen - Google Patents

Verfahren zur Veränderung des Kühlvermögens von wässrigen Flüssigkeiten zur Härtung von Metall-Legierungen Download PDF

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Publication number
EP0321370B1
EP0321370B1 EP88420422A EP88420422A EP0321370B1 EP 0321370 B1 EP0321370 B1 EP 0321370B1 EP 88420422 A EP88420422 A EP 88420422A EP 88420422 A EP88420422 A EP 88420422A EP 0321370 B1 EP0321370 B1 EP 0321370B1
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EP
European Patent Office
Prior art keywords
lcst
chosen
water
process according
soluble
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EP88420422A
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English (en)
French (fr)
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EP0321370A1 (de
Inventor
François Moreaux
Gérard Beck
Abderrahim Louai
Jeanne Francois
Gilbert Pollet
Jean-Paul Betend
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Servimetal SA
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Servimetal SA
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Priority to AT88420422T priority Critical patent/ATE76104T1/de
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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/56—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering characterised by the quenching agents
    • C21D1/60—Aqueous agents

Definitions

  • the invention relates to a method for modifying the cooling power of aqueous media intended for the quenching of metal alloys, these media being made up of so-called reverse-soluble water-soluble organic polymers, which precipitate by increasing the temperature. It also relates to aqueous quenching fluids, the cooling power of which can be modified by adding water-soluble additives.
  • each quenching medium and at equal initial temperature of the quenched parts, to draw temperature curves as a function of time and of the cooling rate as a function of time or of temperature (derivative curves) which are called often: "drasticity curves".
  • the quenching medium is selected so as to slow or accelerate the cooling in the zones of high temperature or in the zone below approximately 300 ° C. (critical zone of the martensitic transformation) in which deformation or even "quenching nipples" may occur.
  • this requires a whole range of quenching fluids, each corresponding to a type of alloy.
  • US-A-3475232 describes a method for quenching metals, in which a liquid quenching medium formed of water is used in a water-soluble oxyalkylene polymer, normally liquid, having higher oxyethylene and oxyalkylene groups as well as a water-soluble alcohol chosen from glycerol, glycols which contain from 2 to 7 carbon atoms and monoalkyl ethers of short carbon chain of the said glycols, in which the alkyl group contains from 1 to 4 carbon atoms.
  • a water-soluble oxyalkylene polymer normally liquid, having higher oxyethylene and oxyalkylene groups as well as a water-soluble alcohol chosen from glycerol, glycols which contain from 2 to 7 carbon atoms and monoalkyl ethers of short carbon chain of the said glycols, in which the alkyl group contains from 1 to 4 carbon atoms.
  • the subject of the present invention is a process for modifying the cooling power of at least one organic polymer with reverse solubility, having a lower critical solubility temperature (usually abbreviated as LCST, Low critical solution temperature) this process being as defined in claim 1
  • Another object of the invention is an aqueous medium for the quenching of metal alloys, comprising at least one water-soluble polymer with reverse solubility, with an LCST point and at least one additive intended to increase or decrease the LCST, characterized in that that it simultaneously comprises at least one compound acting on its LCST in the opposite direction.
  • additives will be preferred whose efficiency is greatest so as to limit the salt concentration of the quenching medium to the strict minimum for obvious reasons.
  • Figure 1 embodies all that has just been exposed on the effect of the two groups of additives; we note, moreover, that the cloud point is lowered in a substantially linear manner, by the addition of increasing amounts of mineral salts: it appears that the disodium carbonate Na2CO3 has, at equal concentration, a higher efficiency than that of sodium metaborate ( Borax).
  • Borax sodium metaborate
  • Propylene glycol and acetamide raise the cloud point more effectively than their respective lower counterparts, ethylene glycol and formamide, while the effect of potassium iodide is insignificant as previously reported. .
  • Table I gives the characteristics of the solutions used for the drasticity measurements. In all cases, the basic solution is EMKAROX FC31-165000 at 4% by weight.
  • the present invention provides a solution to the problem of the multiplicity of aqueous quenching fluids required by the treatment of parts made of different alloys or requiring different quenching speeds in particular temperature ranges. It is possible to model the cooling curve at the option of the users, from a single solution of water-soluble polymer, to which a cloud point of a predetermined value can be given. It also allows, on a secondary basis, to correct the effect, on the point of cloudiness of auxiliary additives, such as biocides, defoamers, anticorrosives, etc. Finally, it can temporarily restore the LCST point on solutions which begin to be affected by aging due to prolonged use, for example to complete a series of quenches before the complete renewal of the solution.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Heat Treatments In General, Especially Conveying And Cooling (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Heat Treatment Of Strip Materials And Filament Materials (AREA)
  • Lubricants (AREA)
  • Eyeglasses (AREA)

Claims (13)

1. Verfahren zur Änderung der Abkühlungsfähigkeit einer wäßrigen Lösung aus mindestens einem wasserlöslichen organischen Polymeren mit einer unteren kritischen Lösungstemperatur ("LCST" genannt), zwecks Verwendung zur Abschreckung von metallischen Legierungen, bei dem man in jene Lösung eine vorbestimmte Menge eines wasserlöslichen Zusatzstoffes einbringt, der jene kritische Temperatur in kontrollierter weise im Sinne einer Verringerung oder Erhöhung ändert, dadurch gekennzeichnet, daß man die durch die Anwesenheit mindestens einer Verbindung, die zur Änderung dieser LCST in einem bestimmten Sinne führt, verursachte Änderung der LCST durch Zugabe mindestens einer Verbindung, die auf die LCST im umgekehrten Sinne einwirkt, kompensiert.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man zur Verringerung der LCST der Lösung als Zusatzstoff ein Mineralsalz einer Mineralsäure oder organischen Säure mit einer Konzentration zwischen 0,1 und 200 Gramm pro Liter verwendet.
3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß das Mineralsalz unter Salzen von Alkali- und Erdalkalimetallen, einschließlich Magnesium und Zink, ausgewählt ist.
4. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß das Anion des Mineralsalzes unter den Anionen B₄O₇⁻⁻, PO₄⁻⁻, CO₃⁻⁻, SO₄⁻⁻, SiO₃⁻⁻, F⁻, Cl⁻, CH₃COO⁻, Br⁻, ClO₃⁻, J⁻ ausgewählt ist.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das Mineralsalz unter Natriumcarbonat, Trinatriumphosphat, Borax, Natriumsilicat und Natriumsulfat ausgewählt ist.
6. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man zur Erhöhung oder gegebenenfalls Erniedrigung der LCST der Lösung ein wasserlösliches organisches Derivat in einer Konzentration zwischen 0,1 und 200 Gramm pro Liter zugibt.
7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß das organische Derivat unter aliphatischen Verbindungen mit mindestens einer aus Alkoholen, Säuren, Aldehyden, Amiden und Aminen ausgewählten Funktion ausgewählt ist.
8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß das organische Derivat zur Erhöhung der LCST unter 1,3-Butandiol, Acetamid, Propylenglykol, Ethanol, Methanol, Formamid und Ethylenglykol ausgewählt ist.
9. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß es sich bei dem organischen Derivat zur Verringerung der LCST um Propanol oder Butanol handelt.
10. Verfahren nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß das wasserlösliche Polymere mit Trübungspunkt unter Oxyethylenpolymeren, Copolymeren aus Ethylenoxid und Propylenoxid mit einem Propylenoxid/Ethylenoxid-Verhältnis zwischen 0 und 1, Polyvinylmethylethern und Polydimethoxyethylenen ausgewählt ist.
11. Wäßriges Medium zur Abschreckung metallischer Legierungen, das mindestens ein wasserlösliches organisches Polymeres mit Trübungspunkt und mindestens einen Zusatzstoff zur Änderung (Erhöhung oder Verringerung) der LCST enthält, dadurch gekennzeichnet, daß es gleichzeitig mindestens eine Verbindung enthält, die auf dessen LCST im umgekehrten Sinne einwirkt.
12. Wäßriges Medium nach Anspruch 11, dadurch gekennzeichnet, daß der Zusatzstoff, mit dem sich die LCST verringern läßt, unter wasserlöslichen Alkali- und Erdalkali- (einschließlich Magnesium) und Zinksalzen von Mineralsäuren oder organischen Säuren in einer Konzentration zwischen 0,1 und 200 Gramm pro Liter ausgewählt ist.
13. wäßriges Medium nach Anspruch 11, dadurch gekennzeichnet, daß der Zusatzstoff, mit dem sich die LCST erhöhen läßt, unter wasserlöslichen, aliphatischen organischen Derivaten mit mindestens einer aus Alkoholen, Säuren, Aldehyden, Amiden und Aminen ausgewählten Funktion in einer Konzentration zwischen 0,1 und 200 Gramm pro Liter ausgewählt ist.
EP88420422A 1987-12-17 1988-12-15 Verfahren zur Veränderung des Kühlvermögens von wässrigen Flüssigkeiten zur Härtung von Metall-Legierungen Expired - Lifetime EP0321370B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88420422T ATE76104T1 (de) 1987-12-17 1988-12-15 Verfahren zur veraenderung des kuehlvermoegens von waessrigen fluessigkeiten zur haertung von metalllegierungen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8718109A FR2624875B1 (fr) 1987-12-17 1987-12-17 Procede de modification du pouvoir refroidissant de milieux aqueux destines a la trempe d'alliages metalliques
FR8718109 1987-12-17

Publications (2)

Publication Number Publication Date
EP0321370A1 EP0321370A1 (de) 1989-06-21
EP0321370B1 true EP0321370B1 (de) 1992-05-13

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EP88420422A Expired - Lifetime EP0321370B1 (de) 1987-12-17 1988-12-15 Verfahren zur Veränderung des Kühlvermögens von wässrigen Flüssigkeiten zur Härtung von Metall-Legierungen

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EP (1) EP0321370B1 (de)
JP (1) JPH0637665B2 (de)
AT (1) ATE76104T1 (de)
DE (1) DE3871106D1 (de)
ES (1) ES2037267T3 (de)
FR (1) FR2624875B1 (de)
GR (1) GR3005214T3 (de)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3621101B2 (ja) * 1993-05-18 2005-02-16 アルミナム カンパニー オブ アメリカ 溶解ガスを含む冷却液による金属の熱処理方法
JPH1150212A (ja) 1997-07-31 1999-02-23 Mazda Motor Corp 軽合金鋳物の熱処理方法
FR2780508B1 (fr) * 1998-06-24 2000-08-18 Durferrit Sarl Procede et dispositif pour le controle du pouvoir refroidissant d'un fluide
DE10035849A1 (de) * 2000-07-24 2002-02-21 Henkel Kgaa Teilchenförmiges Kompositmaterial zur gesteuerten Freisetzung eines Wirkstoffs
EP2821510A4 (de) * 2012-03-02 2015-11-11 Idemitsu Kosan Co Wässriges kühlmittel
JP6227248B2 (ja) * 2012-12-27 2017-11-08 出光興産株式会社 水系冷却剤
JP6405301B2 (ja) * 2013-03-26 2018-10-17 住友精化株式会社 水溶性金属加工油剤
DE102019202835A1 (de) * 2019-03-01 2020-09-03 Thyssenkrupp Ag Verfahren zur beschleunigten Abkühlung von Stahlflachprodukten
JP7357535B2 (ja) * 2019-12-17 2023-10-06 三井化学株式会社 アルキレンオキシド重合体の製造方法
JP7422530B2 (ja) * 2019-12-17 2024-01-26 三井化学株式会社 アルキレンオキシド重合体の曇点測定用溶媒

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3022205A (en) * 1958-05-14 1962-02-20 Gen Motors Corp Method of quenching and quenching liquid
US3475232A (en) * 1966-11-23 1969-10-28 Houghton & Co E F Method of quenching
FR2537997B1 (fr) * 1982-12-16 1988-05-20 Ugine Kuhlmann Procede de trempe d'alliages ferreux en milieu aqueux
US4584033A (en) * 1985-06-28 1986-04-22 Union Carbide Corporation Method of quenching

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Publication number Publication date
JPH0637665B2 (ja) 1994-05-18
FR2624875B1 (fr) 1992-06-26
ATE76104T1 (de) 1992-05-15
FR2624875A1 (fr) 1989-06-23
ES2037267T3 (es) 1993-06-16
DE3871106D1 (de) 1992-06-17
JPH01259119A (ja) 1989-10-16
GR3005214T3 (de) 1993-05-24
EP0321370A1 (de) 1989-06-21

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