EP0196836B1 - Abschreckmittel für Metalle - Google Patents

Abschreckmittel für Metalle Download PDF

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Publication number
EP0196836B1
EP0196836B1 EP86302092A EP86302092A EP0196836B1 EP 0196836 B1 EP0196836 B1 EP 0196836B1 EP 86302092 A EP86302092 A EP 86302092A EP 86302092 A EP86302092 A EP 86302092A EP 0196836 B1 EP0196836 B1 EP 0196836B1
Authority
EP
European Patent Office
Prior art keywords
quenchant
metal
quenchants
oxazoline polymer
polyoxyalkylene glycol
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
Application number
EP86302092A
Other languages
English (en)
French (fr)
Other versions
EP0196836A1 (de
Inventor
John James Lakin
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.)
BASF UK Ltd
Original Assignee
BP Chemicals Ltd
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 BP Chemicals Ltd filed Critical BP Chemicals Ltd
Priority to AT86302092T priority Critical patent/ATE42768T1/de
Publication of EP0196836A1 publication Critical patent/EP0196836A1/de
Application granted granted Critical
Publication of EP0196836B1 publication Critical patent/EP0196836B1/de
Expired legal-status Critical Current

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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 present invention relates to metal quenchants which are used in the heat treatment of metals.
  • the present invention relates to novel metal quenchants containing oxazoline polymers and to heat treatment processes which employ such metal quenchants.
  • Transformation stresses in steels arise because during quenching, the steel transforms from a high temperature stable Austenite phase having one structure to a low temperature stable Martensite phase having a different physical structure. Since the Austenite phase is denser than the Martensite phase the overall effect of the transformation is to cause the metal to expand. If however the steel is quenched to rapidly, transformation of Austenite to Martensite occurs initially at the metal surface only, resulting in a steel having regimes of the Martensite phase surrounding the Austenite phase. Subsequent transformation of the residual Austenite phase then generates surface tensile stresses in the cold steel thereby increasing the likelihood that the steel will crack or deform.
  • oil can be used as an alternative to water.
  • oil quenches metal at a slower rate than water does, it suffers from the disadvantages of (1) being flammable and (2) of being prone to faul the metal surface. It is desirable, therefore, to produce a quenchant having quenchant properties similar to those of oil without the associated drawbacks.
  • US 4,486,246 discloses an aqueous based metal quenchant fluid which has properties more comparable with oil than water while avoiding flammability and fouling problems.
  • the quenchant comprises an aqueous solution of a nonionic water-soluble or water-dispersable sub-' stituted oxazoline polymer having recurring units of the formula -[N(COR)CH 2 CH 2] - where R is an organic radical.
  • the quenchants are claimed to be of lower viscosity than, for example, aqueous polyoxyalkylene quenchants such as are described in US 3,220,893.
  • the present invention provides a quenchant for use in the heat treatment of metals or alloys characterised in that the quenchant comprises an aqueous solution of a polyoxyalkylene glycol and an oxazoline polymer.
  • poly(oxyethylene)(oxypropylene) glycol this is suitably a poly(oxyethylene)(oxypropylene) glycol, known in the art as a PAG, made by polymerising ethylene oxide and propylene oxide on an alcohol or polyfunctional alcohol starter.
  • the poly(oxyethylene)oxypropylene)glycol can be either a random or block copolymer.
  • the polyoxyalkylene glycol should preferably have a viscosity in the range 15-30,000 centi- stokes at 40°C (corresponding to a molecular weight in the range 10,000-20,000).
  • the polyoxyalkylene glycol suitably constitutes between 2 and 25% by weight of the quenchant preferably between 5 and 20%.
  • oxazoline polymers which can be used in the quenchants of the present invention have been disclosed in US 4,486,246. These oxazoline polymers are water soluble or water dispersable and are suitably constructed of units having the formula -[N(COR)CH 2 CH 2] - where R is an organic group selected from the group consisting of substituted or unsaturated phenyl groups and C l -C 7 alkyl groups. It is preferable that the oxazoline polymer has a molecular weight in the range 5000-1,000,000 most preferably 50,000-750,000 and that at least 50% of the R groups are a C 1 -C 3 alkyl groups.
  • R groups include methyl, ethyl, propyl, butyl, isobutyl, phenyl and substituted, e.g. halogenated and alkoxylated, derivatives thereof.
  • the oxazoline polymer may be either a homopolymer or a copolymer made from one or more types of the units mentioned.
  • Oxazoline polymers can be prepared by polymerising unsaturated oxazoline monomers under an inert atmosphere in the presence of a catalyst. A method which may be used to carry out a polymerisation is described in US 3,483,141. Certain oxazoline polymers, e.g. polyethyloxazoline, are commercially available.
  • the oxazoline polymer should be present in the quenchant in amounts corresponding to between 0.1 and 5% by weight of the quenchant. Preferably between 0.5 and 2% by weight oxazoline polymer should be used.
  • the rate of quenching decreases as the concentration of the oxazoline polymer in the quenchant increases.
  • rate of quenching decreases as the concentration of polyoxyalkylene glycol in the quenchant increases.
  • the presence of large quantities of polyoxyalkylene glycol should be avoided if possible, however, in order to avoid the quenchant becoming too viscous.
  • components described above may optionally be added to improve the performance of the quenchant.
  • Such components include corrosion inhibitors, for example sodium nitrite and alkanolamines, defoamers, biocides and metal deactivators.
  • the quenchants of the present invention are particularly suitable for the quenching of steels and especially so far those which have been heated above their Austenite-Martensite transition temperature. The exact temperature of this transition will depend upon the exact composition of the steel.
  • the quenching is carried out by immersing an ingot or casting of the hot steel in a large bath or vat of the quenchant. Once the steel is cool, it is removed and washed to remove any quenchant adhering to it.
  • the quenchants of the present invention may be supplied to those who use it as an aqueous solution. However it may also be supplied in the form of a concentrate comprising the polyoxyalkylene glycol and the oxazoline polymer which is suitable for dilution with water immediately prior to use. Suitably, such concentrates have polyoxyalkylene glycol to oxazoline polymer weight ratios in the range 1:2.5-250:1 preferably 2.5:1-40:1.
  • a probe manufactured of lnconel 600 (Inconel is a registered trade mark), which was 60 mm long and 12.5 mm in diameter was heated to 850°C and soaked at temperature for 5 minutes. The temperature of the probe was measured by means of an NiCr/NiAI thermocouple mounted at the geometric centre of the probe.
  • Example 1 The method used in Example 1 was followed except that water was used in place of the polyoxyalkylene glycol in the quenchant. Time-temperature and temperature-temperature differential plots are also shown in Figure 1.
  • Example 1 The method of Example 1 was repeated except that 2% by weight PEOX was used.
  • the time-temperature and temperature-temperature differential plots are shown in Figures 3 and 4 respectively.
  • Example was repeated except that the PEOX was omitted from the quenchant.
  • the time-temperature and temperature-temperature differential plots are shown in Figures 3 and 4 respectively.
  • Example 1 was repeated except that a sample of a cold quenching oil after a period of industrial service was used as quenchant.
  • the time-temperature and temperature-temperature differential plots are shown in Figures 3 and 4 respectively.
  • Figures 3 and 4 show that the quenchants of the present invention are more oil-like in their behaviour than the polyoxyalkylene glycol/water or the oil quenchants of the prior art. Hence the quenchants of the better invention will be better for cooling steels and the like.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (10)

1. Abschreckmittel zur Verwendung bei der Wärmebehandlung von Metallen oder Legierungen, dadurch gekennzeichnet, daß das Abschreckmittel eine wässerige Lösung eines Polyoxyalkylenglykols und eines Oxazolinpolymeren umfaßt.
2. Abschreckmittel nach Anspruch 1, worin das Oxazolinpolymer ein Molekulargewicht im Bereich von 50 000 bis 750 000 hat.
3. Abschreckmittel nach Anspruch 1 oder Anspruch 2, worin das Oxazolinpolymer Einheiten der Formel -[N(COR)CH2CH2]- umfaßt, worin wenigstens 50% der R-Gruppen C1- bis C3-Alkylgruppen sind.
4. Abschreckmittel nach Anspruch 3, worin das Oxazolinpolymer Polyethyloxazolin ist.
5. Abschreckmittel nach einem der vorhergehenden Ansprüche, welches eine wässerige Lösung von zwischen 5 und 20 Gew.-% Polyalkylenglykol und zwischen 0,5 und 2 Gew.-% Oxazolinpolymer umfaßt.
6. Verfahren zum Abschrecken eines Metalles oder einer Legierung, welches Verfahren das Eintauchen eines Blocks oder Gußteiles des heißen Metalles oder der heißen Legierung in ein Bad des Abschreckmittels nach Anspruch 1 umfaßt.
7. Verfahren nach Anspruch 6, wobei das eingesetzte Metall oder die eingesetzte Legierung Stahl ist.
8. Verfahren nach Anspruch 6 oder Anspruch 7, wobei das Abschreckmittel eine wässerige Lösung eines Polyoxyalkylenglykols und von Polyethyloxazolin umfaßt.
9. Metallabschreckmittelkonzentrat, welches, wenn es mit Wasser verdünnt wird, ein Abschreckmittel gemäß Anspruch 1 bildet, wobei das Metallabschreckmittelkonzentrat ein Gemisch eines Polyoxyalkylenglykols und eines Oxazolinpolymers umfaßt.
10. Metallabschreckmittelkonzentrat nach Anspruch 9, worin das Gewichtsverhältnis von Polyoxyalkylenglykol zu Oxazolinpolymer in den Bereich von 2,5:1 bis 40:1 fällt.
EP86302092A 1985-03-29 1986-03-21 Abschreckmittel für Metalle Expired EP0196836B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86302092T ATE42768T1 (de) 1985-03-29 1986-03-21 Abschreckmittel fuer metalle.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8508317 1985-03-29
GB858508317A GB8508317D0 (en) 1985-03-29 1985-03-29 Metal quenchants

Publications (2)

Publication Number Publication Date
EP0196836A1 EP0196836A1 (de) 1986-10-08
EP0196836B1 true EP0196836B1 (de) 1989-05-03

Family

ID=10576920

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86302092A Expired EP0196836B1 (de) 1985-03-29 1986-03-21 Abschreckmittel für Metalle

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EP (1) EP0196836B1 (de)
AT (1) ATE42768T1 (de)
DE (1) DE3663149D1 (de)
GB (1) GB8508317D0 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102643963B (zh) * 2012-05-09 2014-05-07 上海福岛化工科技发展有限公司 环保水溶性淬火液

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3220893A (en) * 1963-11-29 1965-11-30 Union Carbide Corp Metal quenching medium
US3483141A (en) * 1964-07-13 1969-12-09 Allied Chem Carbon-nitrogen backbone chain polymers
US4486246A (en) * 1983-05-18 1984-12-04 E. F. Houghton & Co. Polyoxazolines in aqueous quenchants

Also Published As

Publication number Publication date
DE3663149D1 (en) 1989-06-08
GB8508317D0 (en) 1985-05-09
EP0196836A1 (de) 1986-10-08
ATE42768T1 (de) 1989-05-15

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