EP0100280A1 - Abschreckbad und Verfahren zum Abschrecken von Metallen - Google Patents

Abschreckbad und Verfahren zum Abschrecken von Metallen Download PDF

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Publication number
EP0100280A1
EP0100280A1 EP83401521A EP83401521A EP0100280A1 EP 0100280 A1 EP0100280 A1 EP 0100280A1 EP 83401521 A EP83401521 A EP 83401521A EP 83401521 A EP83401521 A EP 83401521A EP 0100280 A1 EP0100280 A1 EP 0100280A1
Authority
EP
European Patent Office
Prior art keywords
quenching
hydrogenated starch
hah
bath
hydrolyzate
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
EP83401521A
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English (en)
French (fr)
Other versions
EP0100280B1 (de
Inventor
Serge Gosset
Michel Huchette
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.)
Roquette Freres SA
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Roquette Freres SA
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 Roquette Freres SA filed Critical Roquette Freres SA
Priority to AT83401521T priority Critical patent/ATE25110T1/de
Publication of EP0100280A1 publication Critical patent/EP0100280A1/de
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Publication of EP0100280B1 publication Critical patent/EP0100280B1/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 present invention relates to an aqueous bath for quenching ferrous and non-ferrous metals and their alloys. It also relates to the method of quenching metals using said bath as well as the application to quenching metals of the constituents of the bath.
  • the transformation law can be expressed as follows: for there to be quenching, it is essential that before the above-mentioned cooling the critical point corresponding to the end of the transformation due to heating is exceeded and that the temperature of the metal either such that it is completely in the stable state when hot.
  • the temperature zone corresponding to the desired structure that is to say at the point! equilibrium where the solubility of the various constituent elements is maximum, is sometimes between limits very little apart from each other.
  • the actual quenching is carried out, that is to say a more or less rapid cooling depending on the alloy and the kind of room ; the molecular distribution of the hot stable state is thus kept cold, which makes it possible to advantageously modify the mechanical characteristics of the alloy. It follows that, depending on the nature and composition of the metals or alloys to be treated, the quenching methods and the most suitable media for this operation are different.
  • the liquids used for quenching are therefore very varied: cold water, water containing sodium chloride or soda, lime water, acid water, hot water, petroleum, oils, tallow, and more recently water and polyvinyl alcohol , water and polyalkylene glycols.
  • quenching is a meticulous operation which requires a lot of precautions. It is in particular advisable to use suitable quenching baths capable of varying the cooling rate within the desired limits in order to to obtain the desired characteristics.
  • the quench bath according to the invention is characterized by a content of 0.2 to 80% by weight of the above hydrolyzate.
  • the quenching method according to the invention is characterized in that said metals are immersed, the temperature of which is brought beforehand inside the range corresponding to the desired structures, in an aqueous bath comprising of 0.2 to 80% by weight of the above hydrogenated starch hydrolyzate.
  • the starch can be hydrolyzed, by the acid route, by the enzymatic route or by the mixed acid-enzymatic route, to different degrees, the degree of hydrolysis being generally characterized by the Dextrose-Equivalent (DE) defined as being the reducing power of the hydrolyzate, expressed in D-glucose and related to the dry matter.
  • DE Dextrose-Equivalent
  • starch hydrolysates of different EDs and having a very varied distribution of products of different degrees of polymerization: glucose ( DP 1), maltose and isomaltose (DP 2), maltotriose (DP 3), oligosaccharides and polysaccharides.
  • the starch hydrolysates of varied composition thus obtained can then be hydrogenated, in a manner known per se, generally under hydrogen pressures and at high temperatures and in the presence of catalysts such as, for example, Raney nickel.
  • catalysts such as, for example, Raney nickel.
  • the various sugars constituting the starch hydrolyzate are thus transformed into corresponding polyols.
  • the hydrogenated starch hydrolyzate used for the constitution of the aqueous quenching baths according to the invention has a percentage of reducing sugars of less than 5% (percentage expressed on the dry matter of the hydrolyzate), preferably less than 2% and more preferably still less than 0.5%.
  • the hydrogenated starch hydrolyzate applied in accordance with the invention has a percentage of products of DP 1 and DP 2 of between 2 and 75%, and more preferably still of between 2 and 65%, the complement to 100 being consisting of products with a PD greater than or equal to 3.
  • the preferred hydrogenated starch hydrolysates are obtained by hydrogenation of starch hydrolysates having a DE of between 15 and 70.
  • HAH hydrogenated starch hydrolyzate
  • the quenching bath in accordance with the invention had performances significantly superior to those of aqueous quenching baths of the prior art comprising polyhydric alcohols selected from the group consisting of sorbitol, mannitol, maltitol and lactitol; these baths had previously been considered satisfactory.
  • the properties of the quench bath according to the invention vary according to the chosen concentration of HAH.
  • Baths with an accelerating effect contain from 0.2 to 40% and preferably from 0.5 to 35% by weight of HAH.
  • Baths which delay the cooling rate compared to water contain 40 to 80%, preferably 40 to 75% HAH.
  • the quenching bath according to the invention comprising from 0.2 to 80 3b of HAH, can be used at temperatures varying in particular from 4 to 60 ° C, preferably from 4 to 50 ° C and, more preferably still , from 10 to 45 ° C.
  • the HAH applied in accordance with the invention to the constitution of the quench bath according to the invention not only modifies, as indicated above, the cooling rate of the quenched metals, but also has other other advantages.
  • it does not exhibit aggressiveness with respect to metals and their alloys and can, on the contrary, even have a protective effect on surfaces. It avoids in particular the granular corrosion of aluminum alloys, corrosion which is formed in particular in quenching baths containing compounds of mineral origin such as sodium or potassium derivatives whose aggressiveness both with respect to ferrous alloys and light alloys is important.
  • the hardness imparted to the parts treated in accordance with the invention is greater than that of the parts treated conventionally, for example by water quenching.
  • Another advantage lies in the non-toxicity of the hydrogenated starch hydrolysates used in accordance with the invention, in their perfect biodegradability as well as in their non-flammability.
  • the hydrogenated starch hydrolyzate one or more oxyanion salts chosen in particular from the group of boron, tin , germanium, tellurium or arsenic, these salts being capable of forming water-soluble complexes with the hydrogenated starch hydrolyzate.
  • the preferred oxyanion consists of boron, and the salts preferably used are borates.
  • HAH (MS) / salt ratio is chosen between 100/1 and 1/2, and more preferably between 30/1 and 1/1.
  • these salts are dissolved in the hydrogenated starch hydrolyzate syrup and allowed to react with the latter before the formation of the baths.
  • the quench bath according to the invention can also contain various adjuvants such as antioxidants, anti-corrosion agents, bactericidal agents, and the like.
  • adjuvants such as antioxidants, anti-corrosion agents, bactericidal agents, and the like.
  • a control curve is produced with a bath consisting solely of distilled water, at a temperature of 30 ° C.
  • the quenching fluid now consisting of a 5% solution of dry matter of a hydrogenated starch hydrolyzate (HAH 1) in the distilled water.
  • This HAH 1 hydrolyzate was prepared from a starch hydrolyzate whose DE before hydrogenation was equal to 55 and which itself had previously been prepared by enzymatic double hydrolysis, with ⁇ -amylase then with ⁇ -amylase.
  • the percentage of reducing sugars in the hydrolyzate HAH 1 is less than 0.20 and its composition (in% on dry matter) as follows:
  • Curves 8 f (t) and (8) recorded with the quench bath based on the hydrolyzate HAH 1 are shown in Figure 1 in C 3 and C 4 respectively.
  • This example is a comparative example of the performances obtained with the hydrolyzate HAH 1 and two other hydrogenated hydrolysates HAH 2 and HAH 3, prepared by hydrogenation of starch hydrolysates of different composition having before hydrogenation EDs of 33 and 30 respectively.
  • composition of the HAH 2 and HAH 3 hydrolysates was as follows:
  • Example 2 The conditions of the tests were identical to those of Example 1, the quench baths tested containing respectively 5% of each of HAH 1, 2 and 3 and their temperature being 30 ° C.
  • This example was carried out to compare the performances recorded for the acceleration of the cooling rate, on the one hand, in the case of a quenching bath according to the invention and, on the other hand, in the case of two quenching baths according to the prior art.
  • the quench bath according to the invention consisted of a 5% solution of m.s. HAH 2 hydrolyzate in distilled water.
  • the temperature of the three baths was 30 ° C.
  • the performances obtained in the case of the hydrolyzate HAH 3 are compared with those obtained in the case of the same hydrolyzate in which borax had previously been dispersed in a proportion of 10% of borax decahydrate (percentage expressed as material as it is on the dry matter of the hydrolyzate).
  • the quench baths were at a concentration of 5% m. s. and at a temperature of 30 ° C.
  • borax slightly modifies the cooling rate obtained using the hydrolyzate alone.
  • the temperature of a quench bath can be maintained at around 30 ° C, but in reality the variations can range from a temperature of about 10 ° C, for a "fresh" quench bath, to 60 ° C approximately, for a very stressed quench bath if vigorous temperature control is not used.
  • the hydrogenated starch hydrolyzate used corresponds to that identified in Example 2 by HAH 3.
  • the parts treated by the so-called potting method are cast aluminum alloy parts of the AU 5 GT type.
  • the bath is at room temperature.
  • the duration of the immersion is 8 minutes.
  • the hardness generally required for quenched parts is at least 80 HB, a value which is just obtained by conventional quenching with water.
  • the purpose of this example is to illustrate the retarding effect exhibited by the baths according to the invention when their concentration is high.
  • the bath temperature was always 30 ° C.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Physics & Mathematics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Heat Treatment Of Strip Materials And Filament Materials (AREA)
  • Magnetic Heads (AREA)
  • Devices For Conveying Motion By Means Of Endless Flexible Members (AREA)
  • Compounds Of Iron (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Heat Treatment Of Articles (AREA)
EP83401521A 1982-07-23 1983-07-25 Abschreckbad und Verfahren zum Abschrecken von Metallen Expired EP0100280B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83401521T ATE25110T1 (de) 1982-07-23 1983-07-25 Abschreckbad und verfahren zum abschrecken von metallen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8212921 1982-07-23
FR8212921A FR2530668B1 (fr) 1982-07-23 1982-07-23 Application d'un hydrolysat d'amidon hydrogene a la trempe des metaux

Publications (2)

Publication Number Publication Date
EP0100280A1 true EP0100280A1 (de) 1984-02-08
EP0100280B1 EP0100280B1 (de) 1987-01-21

Family

ID=9276275

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83401521A Expired EP0100280B1 (de) 1982-07-23 1983-07-25 Abschreckbad und Verfahren zum Abschrecken von Metallen

Country Status (11)

Country Link
US (1) US4441937A (de)
EP (1) EP0100280B1 (de)
JP (1) JPS5935617A (de)
AT (1) ATE25110T1 (de)
AU (1) AU542742B2 (de)
BR (1) BR8303929A (de)
CA (1) CA1232828A (de)
DE (1) DE3369345D1 (de)
ES (1) ES8403973A1 (de)
FR (1) FR2530668B1 (de)
ZA (1) ZA835377B (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2671103A1 (fr) * 1990-12-27 1992-07-03 Roquette Freres Composition, bain et procede de trempe des metaux.

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0699242B1 (de) * 1993-05-18 2000-07-12 Aluminum Company Of America Verfahren zur wärmebehandlung von metall mit kühlung in einer flüssigkeit mit darin aufgelöstem gas
US6689227B2 (en) * 2001-01-23 2004-02-10 Tata Consultancy Services, Division Of Tata Sons Ltd Eco-friendly starch quenchants

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1167785A (fr) * 1956-11-13 1958-11-28 Procédé pour la trempe des métaux
FR1384244A (fr) * 1963-12-26 1965-01-04 Union Carbide Corp Milieu de trempe d'un métal
FR2438099A1 (fr) * 1978-03-14 1980-04-30 Centre Rech Metallurgique Procede d'augmentation de protection d'une bande d'acier contre la corrosion

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US710452A (en) * 1902-05-15 1902-10-07 Mary J R Greenman Process of hardening metals.
US2115828A (en) * 1935-04-13 1938-05-03 Bell Telephone Labor Inc Electron emitting cathode and method of preparation
US2770564A (en) * 1954-07-06 1956-11-13 Gordon Mack Method of quenching metals
US3022205A (en) * 1958-05-14 1962-02-20 Gen Motors Corp Method of quenching and quenching liquid
US3220893A (en) * 1963-11-29 1965-11-30 Union Carbide Corp Metal quenching medium
US3475232A (en) * 1966-11-23 1969-10-28 Houghton & Co E F Method of quenching
US3526551A (en) * 1968-01-17 1970-09-01 Herbert Sargent Process for heat treating metals
JPS5130695B2 (de) * 1972-08-25 1976-09-02
JPS5373406A (en) * 1973-12-17 1978-06-29 Kanto Yakin Kogyo Kk Quenching media for steel
US4192764A (en) * 1977-11-03 1980-03-11 Western Electric Company, Inc. Stabilizing composition for a metal deposition process

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1167785A (fr) * 1956-11-13 1958-11-28 Procédé pour la trempe des métaux
FR1384244A (fr) * 1963-12-26 1965-01-04 Union Carbide Corp Milieu de trempe d'un métal
FR2438099A1 (fr) * 1978-03-14 1980-04-30 Centre Rech Metallurgique Procede d'augmentation de protection d'une bande d'acier contre la corrosion

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DERWENT JAPANESE PATENTS REPORT, vol. 74, no. 45, 10 décembre 1974, section M, page 1, colonne de gauche, Londres, GB. & JP-A-49 040 324 (KANTO YAKIN KOGYO K.K.) 01-11-1974 *
PATENTS ABSTRACTS OF JAPAN, vol. 2, no. 110, 13 septembre 1978, page 2061 C 78 & JP-A-53 073 406 (NIKKEN KAGAKU K.K.) 29-06-1978 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2671103A1 (fr) * 1990-12-27 1992-07-03 Roquette Freres Composition, bain et procede de trempe des metaux.
WO1992012267A1 (fr) * 1990-12-27 1992-07-23 Roquette Freres Composition, bain et procede de trempe des metaux

Also Published As

Publication number Publication date
ZA835377B (en) 1985-02-27
EP0100280B1 (de) 1987-01-21
BR8303929A (pt) 1984-02-28
JPS5935617A (ja) 1984-02-27
AU542742B2 (en) 1985-03-07
US4441937A (en) 1984-04-10
CA1232828A (en) 1988-02-16
ES524360A0 (es) 1984-04-16
FR2530668B1 (fr) 1987-05-07
DE3369345D1 (en) 1987-02-26
FR2530668A1 (fr) 1984-01-27
AU1726283A (en) 1984-01-26
ES8403973A1 (es) 1984-04-16
ATE25110T1 (de) 1987-02-15

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