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WO2012065928A1 - Milieu de trempe aqueux pour métaux - Google Patents

Milieu de trempe aqueux pour métaux Download PDF

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Publication number
WO2012065928A1
WO2012065928A1 PCT/EP2011/069994 EP2011069994W WO2012065928A1 WO 2012065928 A1 WO2012065928 A1 WO 2012065928A1 EP 2011069994 W EP2011069994 W EP 2011069994W WO 2012065928 A1 WO2012065928 A1 WO 2012065928A1
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WO
WIPO (PCT)
Prior art keywords
monomers
copolymer
aqueous metal
quenching medium
metal quenching
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.)
Ceased
Application number
PCT/EP2011/069994
Other languages
German (de)
English (en)
Inventor
Frank Fischer
Stephan Bauer
Erik Bohrer
Ludger Wegmann
Antonietta Mauri
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 SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of WO2012065928A1 publication Critical patent/WO2012065928A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C08F226/10—N-Vinyl-pyrrolidone
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide

Definitions

  • Aqueous metal quenching medium Aqueous metal quenching medium
  • the present invention relates to an aqueous metal quenching medium comprising a copolymer CP which is composed of
  • R 1 to R 5 independently of one another are hydrogen or a linear or branched, optionally substituted C 1 -C 10 -alkyl radical, and
  • x an integer from 2 to 8 means.
  • the present invention relates to the use of a copolymer CP as a component in an aqueous metal quenching medium, in particular a metal quench bath.
  • the hardening of steels is a widely used method for selectively influencing the quality of a steel, such as, for example, hardness and toughness.
  • the steel is first heated to a temperature of about 850 ° C and then rapidly cooled by means of a metal quenching medium to room temperature.
  • a temperature of approx. 400 ° C the steel transforms from the cubic face-centered austenite to the desired metastable tetragonal distorted body-centered martensite crystal structure, resulting in a significant increase in the hardness of the steel.
  • Austenite into the martensite structure occurs when the cooling is too rapid, for example
  • Use of water as a quenching medium in a temperature range below about 400 ° C at the same time to a volume contraction, which in particular in the interior of a steel workpiece tensions.
  • These different voltages lead to cracks and unwanted dimensional and shape changes in large components, such as gear wreaths for wind turbines. For this reason, water alone can not be used as a quenching medium for these steel components.
  • An alternative here are hardening oils. They allow rapid cooling down to a temperature of approx. 400 ° C. Due to the reduced thermal conductivity of the oil but then sets in a much slower cooling.
  • aqueous metal quenching media which, in addition to water, also contain about 1 to 25% by weight of a water-soluble polymer such as, for example, polyvinyl alcohol, polyethylene glycol, polyacrylic acid sodium salt and, in particular, polyvinylpyrrolidone as the active component.
  • US Pat. No. 3,902,929 discloses metal quench baths which contain from 1 to 13% by weight of polyvinylpyrrolidone having an average molecular weight between 5000 and 400 000 g / mol as water-soluble polymers.
  • US-A 2009/65107 discloses metal quench baths, which as essential components inorganic nanoparticles having an average diameter of 0.2 to 10 ⁇ , in particular phyllosilicates, such as talc, mica, montmorillonite, hectorite or saponite and a water-soluble polymer such as polyalkylene glycol , Polyvinylpyrrolidone, polyacrylamide or polyvinyl alcohol.
  • phyllosilicates such as talc, mica, montmorillonite, hectorite or saponite
  • a water-soluble polymer such as polyalkylene glycol , Polyvinylpyrrolidone, polyacrylamide or polyvinyl alcohol.
  • the object of the present invention was therefore to provide copolymers as a component for aqueous metal quenching media, which in the case of a metal article having a temperature of about 850 ° C. lead to a significantly slower cooling behavior compared to polyvinylpyrrolidone at the same concentration.
  • the object was achieved by the use of a copolymer CP as a component in an aqueous metal quenching medium or by an aqueous metal quenching medium which contains a copolymer CP as a component.
  • the copolymers CP used according to the invention are composed of
  • R 1 to R 5 independently of one another represent hydrogen or a linear or branched, optionally substituted C 1 -C 10 -alkyl radical, such as methyl, ethyl,
  • n-propyl isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl and their isomeric compounds, optionally substituted by an or more functional group (s), such as hydroxy, amino, alkoxy, such as methoxy or ethoxy, alkoxycarbonyl, such as methoxycarbonyl or ethoxycarbonyl, halogen, such as fluorine, chlorine or bromine groups , and
  • radicals R 1 to R 5 are hydrogen or an unsubstituted linear or branched Ci-Cio-alkyl radical.
  • R 1 is advantageously hydrogen and / or methyl, where R 1 is, in particular, hydrogen.
  • R 2 and R 3 are not simultaneously hydrogen.
  • R 2 and / or R 3 represent an unsubstituted C 1 -C 4, in particular a C 2 -C 4, Alkyl radical such as ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl, with isopropyl and tert-butyl are particularly preferred.
  • Particularly advantageously, only one of the radicals R 2 or R 3 is a C 2 -C 4 -alkyl radical.
  • As monomers A it is particularly preferred to use N-isopropylacrylamide and / or N-tert-butylacrylamide.
  • a copolymer CP may also contain mixtures of different monomers A in copolymerized form.
  • the total amount of monomers A in the copolymers CP used according to the invention is> 0.1 and ⁇ 70% by weight, preferably> 5 and ⁇ 40% by weight and more preferably> 10 and ⁇ 35% by weight in copolymerized form Shape.
  • N-vinyllactams of the general formula (II) are used.
  • R 4 and R 5 can independently of one another be hydrogen and / or C 1 -C 10 -alkyl.
  • R 4 and R 5 are preferred hydrogen and methyl. Especially preferred is hydrogen.
  • the monomer B contains no or only a total of one methyl group.
  • x stands for an integer from 2 to 8, frequently for 3, 4, 5, 6 and 7.
  • x stands for an integer from 3 to 5, but particularly advantageously for the numbers 3 and 5.
  • monomers B are the N-vinyl derivatives of the following lactams: 2-pyrrolidone, 2-piperidone, ⁇ -caprolactam and their alkyl derivatives, for example 3-methyl-2-pyrrolidone, 4-methyl-2-pyrrolidone, 5 Methyl 2-pyrrolidone, 3-ethyl-2-pyrrolidone,
  • the copolymer CP also several different monomers B can be present in copolymerized form.
  • N-vinylpyrrolidone and / or N-vinylcaprolactam use with N-vinylpyrrolidone is particularly preferred as the monomer B.
  • the total amount of monomers B in the novel copolymers CP used is> 30 and ⁇ 99.9 wt .-%, preferably> 60 and ⁇ 95 wt .-% and particularly preferably> 65 and ⁇ 90 wt .-% in copolymerized form.
  • Suitable monomers C are all those ethylenically unsaturated compounds which differ from the monomers A and B and are readily copolymerizable with them in a simple manner, for example vinylaromatic monomers, such as styrene, ⁇ -methylstyrene, o-chlorostyrene or vinyltoluenes, vinyl halides such as vinyl chloride or vinylidene Chloride, esters of vinyl alcohol and monocarboxylic acids having 1 to 18 C atoms, such as vinyl acetate, vinyl propionate, vinyl-n-butyl-rat, vinyl neodecanoate, vinyl laurate and vinyl stearate, esters of preferably 3 to 6 carbon atoms having ⁇ , ⁇ -monoethylenically unsaturated Mono- and dicarboxylic acids, such as, in particular, acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, with alkanols generally having 1 to 12,
  • these monomers have only a moderate to low solubility in water under standard conditions [20 ° C., 1 atm (absolute)].
  • the abovementioned monomers C are used only as modifying monomers C in amounts of ⁇ 10% by weight, preferably ⁇ 5% by weight and particularly preferably ⁇ 3% by weight, based in each case on the total amount of monomers C.
  • no such monomers C are advantageously used.
  • Monomers C which have an increased water solubility under the abovementioned conditions, are those which contain either at least one carboxylic acid or sulfonic acid group or its corresponding anion and / or at least one amino, ureido or N-heterocyclic group and / or their contain nitrogen-protonated or alkylated ammonium derivatives.
  • the abovementioned monomers C are used as main monomers C in amounts of> 50% by weight, preferably> 80% by weight and particularly preferably> 90% by weight, based in each case on the total amount of monomers C.
  • no such monomers C are advantageously used.
  • Monomers C which usually increase the internal strength of the films of a polymer matrix, normally have at least one hydroxyl, at least one epoxy, or at least one carbonyl group or at least two non-conjugated ethylenically unsaturated double bonds.
  • monomers having two vinyl radicals monomers having two vinylidene radicals and monomers containing two alkenyl radicals.
  • Particularly advantageous are the diesters of dihydric alcohols with ⁇ , ⁇ -monoethylenically unsaturated monocarboxylic acids, among which acrylic and methacrylic acid are preferred.
  • alkylene glycol diacrylates and dimethacrylates such as ethylene glycol diacrylate, 1, 2-propylene glycol diacrylate, 1, 3-propylene glycol diacrylate, 1, 3-butylene glycol diacrylate, 1, 4-butylene glycol glycol diacrylates and ethylene glycol dimethacrylate, 1,2-propylene glycol dimethacrylate, 1,3-propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate and divinylbenzene, ⁇ , ⁇ '-divinylethyleneurea, vinyl methacrylate, vinyl acrylate, allyl methacrylate, allyl acrylate , Diallyl maleate, diallyl fumarate, methylenebisacrylamide, cyclopentadienyl acrylate, triallylcyanurate or triallyl iso
  • hydroxy-functionalized acrylic or methacrylic acid alkyl esters for example 2-hydroxyethyl, 2-hydroxypropyl or 4-hydroxybutyl acrylate or methacrylate.
  • the abovementioned crosslinking monomers C are used in amounts of ⁇ 10% by weight, but preferably in amounts of ⁇ 3% by weight, in each case based on the total amount of monomers C. However, in particular, preferably no such monomers C are used.
  • the total amount of monomers C in the novel copolymers CP used is> 0 and ⁇ 50 wt .-%, preferably> 0 and ⁇ 20 wt .-% and particularly preferably> 0 and ⁇ 10 wt .-% in copolymerized form.
  • the copolymers CP do not contain any monomers C in copolymerized form.
  • copolymers CP are therefore preferably R 1, R 4 and R 5 is hydrogen, x is an integer from 3 to 5 and R 2 and R 3 are not simultaneously hydrogen.
  • R 2 and / or R 3 is an unsubstituted C 2 -C 4 -alkyl radical, in particular a tert-butyl radical or isopropyl radical.
  • the aqueous quenching media according to the invention therefore advantageously comprise copolymers CP which contain N-tert-butylacrylamide and / or isopropylacrylamide as monomers A in copolymerized form.
  • the preparation of the copolymers CP used according to the invention is not critical and is carried out by polymerization, preferably by free-radical polymerization of the monomers A and B and optionally C.
  • the radical polymerization of the monomers A and B and optionally C in the form of a bulk or in the form of a solution See, for example, S. Dincer, Z. Rzaev, E. Piskin, J. Poly. Research 2006, 13, pages 121 to 131; F. Eeckman, A. Moes, K. Amighi, Eur. Polym , 40, pages 873 to 881 and I. Nam, J. Bae, K. Jee, J. Lee, K. Park, Macromol.Res., 2002, 10, pages 1 to 121).
  • copolymers CP In the preparation of the copolymers CP according to the invention, it is possible, if appropriate, to submit in each case a partial or total amount of monomers A and B and, if appropriate, C in the polymerization vessel. However, it is also possible in each case to meter in the total amount or any remaining amount of monomers A and B and if appropriate C during the polymerization reaction. The respective total amount or any remaining amount of monomers A and B and, if appropriate, C can be metered into the polymerization vessel batchwise in one or more portions or continuously with constant or varying flow rates.
  • copolymers CP are also included which are obtained by the so-called stepwise or gradient procedure.
  • the copolymers CP used according to the invention have a K value in the range> 30 and ⁇ 150 (determined at 25 ° C. in a 1% strength by weight aqueous solution).
  • the copolymers have a K value in the range> 60 and ⁇ 120.
  • the adjustment of the K values in the preparation of the copolymers CP is familiar to the person skilled in the art and is advantageously carried out by free-radically initiated solution polymerization in the presence of radical-chain-transferring compounds, the so-called free-radical chain regulators.
  • the mood of the K value is also familiar to the person skilled in the art (see, for example, H.
  • the copolymers CP used according to the invention generally have weight-average molecular weights> 30,000 and ⁇ 3,000,000 g / mol and advantageously> 50,000 and ⁇ 2,500,000 g / mol
  • the weight-average molecular weights are determined by gel permeation chromatography using defined polyvinylpyrrolidone standards (general method see, for example, MJR Cantow et al., Journal of Polymer Science: Part A-1, Vol. 5, 1967, pages 1391 to 1394).
  • copolymers CP used according to the invention additionally exhibit
  • copolymers CP are used which give a solution in any ratio with deionized water under the abovementioned conditions.
  • copolymers CP used according to the invention are advantageously used in the form of aqueous solutions and / or powders.
  • the aqueous metal quenching media according to the invention comprise as essential component at least one of the abovementioned copolymers CP.
  • the novel aqueous metal quenching media comprise copolymers CP which are synthesized in copolymerized form
  • the novel aqueous metal quenching media comprise at least one of the abovementioned copolymers CP in a total amount of> 0.1 and ⁇ 10% by weight, advantageously> 0.1 and ⁇ 5% by weight and particularly advantageously> 0.5 and ⁇ 3% by weight. -%.
  • the aqueous Metallabschreckmedien can contain conventional, known to the expert additives, such as especially active against microorganisms, such as, biocides, bactericides or fungicides, for example, polyaminopropyl biguanide (available from the Fa.
  • aqueous metal-quenching media according to the invention are used is also familiar to the person skilled in the art.
  • a metal object to be cooled to be quenched
  • an aqueous metal quenching medium according to the invention can be sprayed or sprinkled with an aqueous metal quenching medium according to the invention. It is also possible to pass a quenching metal article through a downflowing liquid film of aqueous metal quenching medium.
  • a metal object to be quenched is submerged (quenched) in an aqueous metal quenching medium according to the invention, whereby the thermal energy is dissipated particularly efficiently, which is why the use of copolymers CP in such metal quench baths is particularly preferred.
  • aqueous metal quenching media in particular aqueous metal quench baths
  • aqueous metal quench baths based on polyvinylpyrrolidone - metallic objects, for example of iron-, aluminum- and / or titanium-containing alloys , but especially from steels, let cool much slower
  • the cooling curves are in the range between the cooling curves of the polyvinylpyrrolidone and the mineral oil-based hardening oil. It is also important that the costly addition of inorganic nanoparticles or other copolymers can be dispensed with. Furthermore, residual amounts of copolymers CP still adhering to the metal objects after the cooling process can be simply rinsed off with water in a simple manner.
  • the polymerization mixture was heated to 85 ° C and stirred for a further 90 minutes at this temperature.
  • the polymerization mixture with formic acid to a pH value ⁇ 4 was set (pH measurement of a sample at room temperature) and further stirred at 85 ° C for 3 hours.
  • the polymerization batch was then cooled to room temperature and adjusted to a pH of 7 by addition of triethanolamine. This gave a polymer solution having a solids content of 17 wt .-%.
  • the K value of the copolymer CP1 was 95.
  • the solids content was generally determined by drying a defined amount of the aqueous polymer solution (about 1 g) in an aluminum crucible with an inner diameter of about 5 cm at 120 ° C. in a drying oven to constant weight (about 2 hours). Two separate measurements were carried out in each case. The values given in the examples represent the mean value of the respective two measurement results.
  • the K value determination according to Fikentscher was generally carried out at 25 ° C. using a device from Schott, Mainz (capillary: micro-Ostwald, type: MO-1c).
  • the resulting aqueous copolymer solutions were diluted with deionized water in such a way that the resulting homogeneous solutions had a polymer content of 1.0% by weight.
  • the preparation of the copolymer CP2 was carried out analogously to the preparation of the copolymer CP1, with the difference that 45.0 g of N-isopropylacrylamide, 105 g of N-vinylpyrrolidone and 570 g of deionized water were used.
  • the mixture was metered into the original mixture of 121.5 g of N-vinylpyrrolidone and 13.5 g of N-tert-butylacrylamide within 3 hours with a constant flow rate with stirring. Thereafter, the polymerization mixture was heated to 85 ° C and stirred for a further 90 minutes at this temperature. Subsequently, a solution consisting of 0.5 g Wako V59 ® and 2.0 g of isopropanol was added to the polymerization mixture at one time and polymerization was continued for 2 hours under stirring at 85 ° C.
  • the polymerization mixture with formic acid to a pH value ⁇ 4 was set (pH measurement of a sample at room temperature) and further stirred at 85 ° C for 3 hours.
  • the polymerization batch was then cooled to room temperature and adjusted to a pH of 7 by addition of triethanolamine.
  • a copolymer solution having a solids content of 20% by weight was obtained.
  • the K value of the copolymer CP3 was 75. 1 .4 Copolymer CP4
  • copolymer CP4 was carried out analogously to the preparation of the copolymer CP3 with the difference that 3.0 g of N-tert-butylacrylamide, 12.0 g of N-vinylpyrrolidone and 570 g of deionized water and a mixture of 108 g of N-Vinylpyrroli -don and 27.0 g of N-tert-butylacrylamide was added.
  • the comparative VCP 20 wt .-% was aqueous solution of polyvinylpyrrolidone having a K value of 97 (Luvitec K 90 ®; BASF SE commercial product) was used. 1 .6 hardening oil
  • Cooling rate determinations were made using the Smart Quench test system from Swerea IVF, Sweden.
  • the cylindrical standard rüfanalysis be of rigid Inconel ® 600 with a diameter of 12.5 mm and a length of 60 mm, equipped with a thermocouple in the center of the body, which is heated to 860 ° C and subsequently, into the associated circulation, containing 1 5 liters of the appropriate quenching medium ACP1 to ACP4 and AVCP or hardness oil, with a temperature of 23 ° C, was immersed.
  • the stirring speed of the circulation device was set to 1000 rpm during the measurements.
  • the cooling measurements were automatically started at 850 ° C.
  • the total measurement time was 20 seconds each.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Metallurgy (AREA)
  • Thermal Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne des milieux de trempe aqueux pour métaux, contenant des copolymères vinyllactame/acrylamide.
PCT/EP2011/069994 2010-11-17 2011-11-14 Milieu de trempe aqueux pour métaux Ceased WO2012065928A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP10191477 2010-11-17
EP10191477.8 2010-11-17

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WO2012065928A1 true WO2012065928A1 (fr) 2012-05-24

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105200200A (zh) * 2015-09-10 2015-12-30 安徽日飞轴承有限公司 一种轴承套圈的热处理方法

Citations (8)

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US3006900A (en) * 1953-08-22 1961-10-31 Basf Ag Production of water-soluble copolymers of methacrylamide and n-vinylpyrrolidone
US3902929A (en) 1974-02-01 1975-09-02 Park Chem Co Water-based quenching composition comprising polyvinylpyrrolidone and method of quenching
US4167439A (en) * 1976-12-14 1979-09-11 Rohm And Haas Company Non-ionic, water-soluble polymers for improving the dry-strength of paper
EP0256797A1 (fr) * 1986-08-08 1988-02-24 Exxon Research And Engineering Company Terpolymères
USRE34119E (en) 1985-08-19 1992-11-03 Park Chemical Company Method of heat treating metal using a washable synthetic quenchant
US20030120028A1 (en) * 2001-12-19 2003-06-26 Industrial Technology Research Institute Thermal responsive, water-soluble polymers
US20090065107A1 (en) 2007-09-07 2009-03-12 Industrial Technology Research Institute Polymeric quenchant, manufacture thereof, and method for quenching steel
US20090095384A1 (en) 2007-10-11 2009-04-16 Houghton Technical Corp. Aqueous quenching media and use thereof in quenching metal substrates

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3006900A (en) * 1953-08-22 1961-10-31 Basf Ag Production of water-soluble copolymers of methacrylamide and n-vinylpyrrolidone
US3902929A (en) 1974-02-01 1975-09-02 Park Chem Co Water-based quenching composition comprising polyvinylpyrrolidone and method of quenching
US4167439A (en) * 1976-12-14 1979-09-11 Rohm And Haas Company Non-ionic, water-soluble polymers for improving the dry-strength of paper
USRE34119E (en) 1985-08-19 1992-11-03 Park Chemical Company Method of heat treating metal using a washable synthetic quenchant
EP0256797A1 (fr) * 1986-08-08 1988-02-24 Exxon Research And Engineering Company Terpolymères
US20030120028A1 (en) * 2001-12-19 2003-06-26 Industrial Technology Research Institute Thermal responsive, water-soluble polymers
US20090065107A1 (en) 2007-09-07 2009-03-12 Industrial Technology Research Institute Polymeric quenchant, manufacture thereof, and method for quenching steel
US20090095384A1 (en) 2007-10-11 2009-04-16 Houghton Technical Corp. Aqueous quenching media and use thereof in quenching metal substrates

Non-Patent Citations (7)

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Title
"Encyclopedia of Chemical Technology, 2. Ausgabe", vol. 21, 1970, pages: 427 - 428
CELLULOSE - CHEMIE, pages 71 - 74
F. EECKMAN, A. MOES, K. AMIGHI, EUR. POLYM. J., vol. 40, 2004, pages 878 - 881
H. FIKENTSCHER: "Sys- tematik der Cellulosen aufgrund ihrer Viskosität in Lösung", CELLULOSE-CHEMIE, vol. 13, 1932, pages 58 - 64
I. NAM, J. BAE, K. JEE, J. LEE, K. PARK, MACROMOL. RES., vol. 10, 2002, pages 115 - 121
M.J.R. CANTOW ET AL., JOURNAL OF POLYMER SCIENCE: PART A, vol. 5, 1967, pages 1391 - 1394
S. DINCER, Z. RZAEV, E. PISKIN, J. POLY, RESEARCH, vol. 13, 2006, pages 121 - 131

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105200200A (zh) * 2015-09-10 2015-12-30 安徽日飞轴承有限公司 一种轴承套圈的热处理方法

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