US3902929A - Water-based quenching composition comprising polyvinylpyrrolidone and method of quenching - Google Patents

Water-based quenching composition comprising polyvinylpyrrolidone and method of quenching Download PDF

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US3902929A
US3902929A US438937A US43893774A US3902929A US 3902929 A US3902929 A US 3902929A US 438937 A US438937 A US 438937A US 43893774 A US43893774 A US 43893774A US 3902929 A US3902929 A US 3902929A
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percent
polymer
quenching
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component
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Anthony George Meszaros
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PARK METALLURGICAL Corp A DE CORP
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Park Chemical Co
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Priority to JP1329175A priority patent/JPS5333284B2/ja
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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 object of this invention is to provide a new method of quenching metals utilizing special water base quenching composition.
  • Another object of this invention is to provide a new method of quenching metals wherein a special water soluble quenching additive is utilized.
  • Another object of this invention is to provide a new water base quenching medium which will stay in the form of a liquid yet will not form more than a very thin solid film on the parts being quenched after the water has evaporated.
  • Another object of the invention is to provide a method of quenching wherein smooth cooling curves (time versus temperature) are obtained at the various levels of quenchant concentration, whereas this has not been possible with prior polyvinyl alcohol quenching mediums.
  • Another object of the present invention is to provide a new quenching method wherein highly satisfactory quenching characteristics such as hardening, low drag out, and the avoidance of undersirable film formation are provided.
  • the present invention concerns a method of quenching metals or metal like materials wherein the metal is immersed in a water base quenching composition
  • component (a) Of unique importance in the above quenching medium is the special additive polymer referred to as component (a) above.
  • component (a) Of unique importance in the above quenching medium is the special additive polymer referred to as component (a) above.
  • the polymer used herein as referred to in sub paragraph (a) above should be a water soluble polymer of a C -C olefin with an unsaturated cyclic carbon, nitrogen and oxygen containing side group.
  • the polymer should have a molecular weight within the range of about 5,000 to about 400,000. Preferably this average molecular weight should be within the range of about 50,000 to about 360,000 and best results are obtained with an average molecular weight between about 100,000 and 200,000. Particularly suitable results are obtained in accordance with the invention using a polymer of polyvinylpyrrolidone.
  • the polymer should be present in an amount from about 1 to about 13 percent by weight of the quenching composition. Preferably this polymer should be present from about 2 to about 8 percent by weight of the composition.
  • the rust inhibiting agent used herein may be selected from a number of rust inhibiting materials such as Borax or sodium nitrite. Other rust inhibiting agents may be used.
  • the rust inhibiting agent should be present in the compostion up to a level of about 5 percent by weight thereof. Preferably it should be present within the range of about 0.005 up to about 5 percent.
  • the bacteriocidal agent used in the invention should be present in an amount up to about 3 percent by weight of the composition. Preferably this bacteriocidal material should be present within the range of about 0.001 up to about 3 percent.
  • the preferred bacteriocidal material used herein is paraformaldehyde. Other bacteriocidal materials may also be used.
  • the quenching medium herein may also optionally include a minor amount of at least one water soluble material selected from the group consisting of polyvinyl alcohol, a polyoxyalkylene polymer, or a cellulosic polymer. Generally this minor amount should be less than percent by weight of the composition.
  • said polymer has an average molecular weight of about 50,000 to about 360,000.
  • said polymer has an average molecular weight of about 100,000 to about 200,000.
  • component (b) is present in an amount of at least about 0.005 percent.
  • component (c) is present in an amount of at least about 0.001 percent.
  • component (a) is present from about 2 percent to about 8 percent.
  • composition also includes a minor amount of at least one water soluble material selected from the group consisting of polyvinyl alcohol, a polyoxyalkylene polymer, or a cellulosic polymer.
  • said minor amount is less than 5 percent.
  • a method of quenching metals or metal like materials comprising immersing said metals in a water based quenching composition consisting essentially of in weight percent,
  • said component (a) is a polyvinylpyrrolidone polymer.
  • a water based quenching composition consisting essentially of a. a special quenching additive therein of about 1 percent to about 13 percent by weight of a water soluble polymer of a C C olefin with an unsaturated cyclic earbon, nitrogen and oxygen containing side group, wherein said polymer has an average molecular weight between about 5,000 and about 400,000,
  • said (a) component is a pyrrolidone type polymer.
  • said component (a) is a polyvinylpyrrolidone polymer.

Abstract

A method of quenching metals utilizing a special water base quenching composition which includes a unique quenching additive polymer.

Description

United States Patent Meszaros Sept. 2, 1975 WATER-BASED QUENCHING [56] References Cited COMPOSITION COMPRISING UNITED S S P T POLYVINYLPYRROLIDONE AND METHOD 2,600,290 6/1952 Comeil 148/18 0F QUENCHIN 2,770,564 11 1956 Gordon 148/18 3,224,910 12/1965 McEwen 148/143 [75 1 Inventor z George Meszams wmdsor 3,269,946 8/1966 Wiese 252/74 a 3,378,494 4/1968 Berger 252 77 [73] Assignee; Park Chemical Company, Detroit, 3,553,285 l/1971 Vemaleken et al. 260/80.73 Mich 3,666,404 5 1972 Hwa et al 252 75 [22] Filed: 1974 Primary Examiner-Walter R. Satterfield [2]] Appl. No.: 438,937 Attorney, Agent, or Firm--Harness, Dickey & Pierce 52 us. c1. 148/28; 148/29; 252/74; [57] ABSTRACT 2 77 A method of quenching metals utilizing a special [51] Int. Cl. B23K 35/24 water base quenching composition which includes a [58] Field Of Search 148/27, 28, 29, 18, 20.6, unique quenching additive polymer,
13 Claims, No Drawings WATER-BASED QUENCIIING COMPOSITION COMPRISING POLYVINYLPYRROLIDONE AND METHOD OF QUENCHING BACKGROUND OF THE INVENTION This invention broadly relates to a new method of quenching metals or metal like materials.
The state of the art is indicated by Chase et al, U.S. Pat. No. 3,022,205; Blackwood et al, U.S. Pat No. 3,220,893; Lewis et al, U.S. Pat. No. 3,475,232; Corneil, U.S. Pat. No. 2,600,290; and, Gordon, U.S. Pat. No. 2,770,564. The disclosures of each of said patents is hereby incorporated herein by reference.
The object of this invention is to provide a new method of quenching metals utilizing special water base quenching composition.
Another object of this invention is to provide a new method of quenching metals wherein a special water soluble quenching additive is utilized.
Another object of this invention is to provide a new water base quenching medium which will stay in the form of a liquid yet will not form more than a very thin solid film on the parts being quenched after the water has evaporated.
Also another object of the invention is to provide a method of quenching wherein smooth cooling curves (time versus temperature) are obtained at the various levels of quenchant concentration, whereas this has not been possible with prior polyvinyl alcohol quenching mediums.
Another object of the present invention is to provide a new quenching method wherein highly satisfactory quenching characteristics such as hardening, low drag out, and the avoidance of undersirable film formation are provided.
Other objects, features and advantages of the present invention will become apparent from the subsequent description and the appended claims.
SUMMARY OF THE INVENTION Briefly stated the present invention concerns a method of quenching metals or metal like materials wherein the metal is immersed in a water base quenching composition comprising in weight percent, (a) about 1 percent to about 13 percent of the polymer CH /C=O N l CH- CH n wherein said polymer has an average molecular weight between about 5,000 and about 400,000, (b) zero to about 5 percent of rust inhibitor material for preventing rust on said metals, (c) zero to about 3 percent of bacteriocidal material for preventing bacteria development in the composition, ((1) and the balance water.
Of unique importance in the above quenching medium is the special additive polymer referred to as component (a) above. The quenching mechanism in accordance with the invention discovered and disclosed herein appears to offer unique advantages over other prior water base quenching techniques. In accordance with the invention herein there is a significant advantage of maximizing quenching rates in the upper (vapor) stage in various quenchings while achieving a slower quenching rate in the lower stage.
DESCRIPTION OF PREFERRED EMBODIMENTS A preferred formulation for use as the quenching composition herein is as follows:
by weight l water 83.95
(2) paraformaldehyde (bacteriocidal agent and preservative) 0.05
(3) Borax (rust inhibiting agent) 0.80
(4) sodium nitrite (rust inhibiting agent) 0.20
(5) polymer having an average molecular weight 160,000 at 45% solution in water, GAF Corp. product K-60 In order to prepare the quenching bath, approximately a 1/3 quantity of item (1) above is transferred into an oil heated mixer apparatus and the temperature is then brought to about F. Items, (2), (3), and (4) are then added and mixed until all the solids are dissolved and a clear solution is obtained and then heating is discontinued. Then the remainder of item (1) is added and then item (5) is added and mixed until the makeup is clear and uniform in solution. This product is then placed in a rust proof container by drawing it through a 40 mesh screen.
The polymer used herein as referred to in sub paragraph (a) above should be a water soluble polymer of a C -C olefin with an unsaturated cyclic carbon, nitrogen and oxygen containing side group. The polymer should have a molecular weight within the range of about 5,000 to about 400,000. Preferably this average molecular weight should be within the range of about 50,000 to about 360,000 and best results are obtained with an average molecular weight between about 100,000 and 200,000. Particularly suitable results are obtained in accordance with the invention using a polymer of polyvinylpyrrolidone. The polymer should be present in an amount from about 1 to about 13 percent by weight of the quenching composition. Preferably this polymer should be present from about 2 to about 8 percent by weight of the composition.
The rust inhibiting agent used herein may be selected from a number of rust inhibiting materials such as Borax or sodium nitrite. Other rust inhibiting agents may be used. The rust inhibiting agent should be present in the compostion up to a level of about 5 percent by weight thereof. Preferably it should be present within the range of about 0.005 up to about 5 percent.
The bacteriocidal agent used in the invention should be present in an amount up to about 3 percent by weight of the composition. Preferably this bacteriocidal material should be present within the range of about 0.001 up to about 3 percent. The preferred bacteriocidal material used herein is paraformaldehyde. Other bacteriocidal materials may also be used.
The quenching medium herein may also optionally include a minor amount of at least one water soluble material selected from the group consisting of polyvinyl alcohol, a polyoxyalkylene polymer, or a cellulosic polymer. Generally this minor amount should be less than percent by weight of the composition.
In order to further illustrate the invention the following examples are provided. It is to be understood, however, that the examples are included for illustrative purposes and are not intended to be limiting the scope of the invention as set forth in the subjoined claims.
% by weight Ex. paraformsodium No. Water aldehyde Borax nitrile polymer* 1 balance GAF K-30 to 100% 0.1% 2.0% 2% 2 1.2% 0.1% GAF K-l5 4% 3 1.5% 0.009% 0.006% GAF K-60 4 GAF K-90 slated us '71 of polymer solids mer CIH CH CH C=O CH CH n wherein said polymer has an average molecular weight between about 5,000 and about 400,000,
b. zero to about 5 percent of rust inhibitor material different than said (a) component for preventing rust on said metals,
c. zero to about 3 percent of bacteriacidal material for preventing bacteria development in the composition,
d. and the balance water.
2. The method of claim 1 wherein,
said polymer has an average molecular weight of about 50,000 to about 360,000.
3. The method of claim 1 wherein,
said polymer has an average molecular weight of about 100,000 to about 200,000.
4. The method of claim 1 wherein,
component (b) is present in an amount of at least about 0.005 percent.
5. The method of claim 4 wherein,
component (c) is present in an amount of at least about 0.001 percent.
6. The method of claim 1 wherein,
component (a) is present from about 2 percent to about 8 percent.
7. The method of claim 1 wherein,
said composition also includes a minor amount of at least one water soluble material selected from the group consisting of polyvinyl alcohol, a polyoxyalkylene polymer, or a cellulosic polymer.
8. The method of claim 7 wherein,
said minor amount is less than 5 percent.
9. A method of quenching metals or metal like materials, comprising immersing said metals in a water based quenching composition consisting essentially of in weight percent,
a. about 1 percent to about 13 percent of a water soluble polymer of a C C olefin with an unsaturated cyclic carbon, nitrogen and oxygen containing side group, wherein said polymer has an average molecular weight between about 5,000 and about 400,000,
b. zero to about 5 percent of rust inhibitor material different than said (a) component for preventing rust on said metals,
0. zero to about 3 percent bacteriacidal material for preventing bacteria development in the composition,
cl. and the balance water.
10. The method of claim 9 wherein,
said component (a) is a polyvinylpyrrolidone polymer.
1 l. A water based quenching composition, consisting essentially of a. a special quenching additive therein of about 1 percent to about 13 percent by weight of a water soluble polymer of a C C olefin with an unsaturated cyclic earbon, nitrogen and oxygen containing side group, wherein said polymer has an average molecular weight between about 5,000 and about 400,000,
b. about 0.005 percent to about 5 percent of rust inhibitor material different than said (a) component for preventing rust on said metals c. about 0.001 percent to about 3 percent of bacteriacidal material for preventing bacteria development in the composition,
d. and the balance water.
12. The composition of claim 1 1 wherein,
said (a) component is a pyrrolidone type polymer.
13. The composition of claim 11 wherein,
said component (a) is a polyvinylpyrrolidone polymer.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3, 902,929
DATED September 2, 1975 INVENTOR(S): thony G. Meszaros it is certified that error appears in the above-identified patent and that said Letters Patent 0 are hereby corrected as shown beiow:
Claim 4, line 5, "Claim 1" should read Claim 6 Signed and Scaled this twenty-fifth Day Of November 1975 ISEAL] I Attest:
RUTH CJIASON c. MARSHALL DANN Arresting Officer Commissioner ufParents and Trademarks

Claims (13)

1. A METHOD OF QUENCHING METALS OR METAL LIKE MATERIALS, COMPRISING IMMERSING SAID METALS IN A WATER BASED QUENCHING COMPOSITION ESSENTIALLY OF IN WEIGHT PERCENT. A. ABOUT 1 PERCENT TO ABOUT 13 PERCENT OF THE POLYMER
2. The method of claim 1 wherein, said polymer has an average molecular weight of about 50,000 to about 360,000.
3. The method of claim 1 wherein, said polymer has an average molecular weight of about 100,000 to about 200,000.
4. The method of claim 1 wherein, component (b) is present in an amount of at least about 0.005 percent.
5. The method of claim 4 wherein, component (c) is present in an amount of at least about 0.001 percent.
6. The method of claim 1 wherein, component (a) is present from about 2 percent to about 8 percent.
7. The method of claim 1 wherein, said composition also includes a minor amount of at least one water soluble material selected from the group consisting of polyvinyl alcohol, a polyoxyalkylene polymer, or a cellulosic polymer.
8. The method of claim 7 wherein, said minor amount is less than 5 percent.
9. A method of quenching metals or metal like materials, comprising immersing said metals in a water based quenching composition consisting essentially of in weight percent, a. about 1 percent to about 13 percent of a water soluble polymer of a C2 - C4 olefin with an unsaturated cyclic carbon, nitrogen and oxygen containing side group, wherein said polymer has an average molecular weight between about 5,000 and about 400,000, b. zero to about 5 percent of rust inhibitor material different than said (a) component for preventing rust on said metals, c. zero to about 3 percent bacteriacidal material for preventing bacteria development in the composition, d. and the balance water.
10. The method of claim 9 wherein, said component (a) is a polyvinylpyrrolidone polymer.
11. A water based quenching composition, consisting essentially of a. a special quenching additive therein of about 1 percent to about 13 percent by weight of a water soluble polymer of a C2 -C4 olefin with an unsaturated cyclic carbon, nitrogen and oxygen containing side group, wherein said polymer has an average molecular weight between about 5,000 and about 400,000, b. about 0.005 percent to about 5 percent of rust inhibitor material different than said (a) component for preventing rust on said metals c. about 0.001 percent to about 3 percent of bacteriacidal material for preventing bacteria development in the composition, d. and the balance water.
12. The composition of claim 11 wherein, said (a) component is a pyrrolidone type polymer.
13. The composition of claim 11 wherein, said component (a) is a polyvinylpyrrolidone polymer.
US438937A 1974-02-01 1974-02-01 Water-based quenching composition comprising polyvinylpyrrolidone and method of quenching Expired - Lifetime US3902929A (en)

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Cited By (22)

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Publication number Priority date Publication date Assignee Title
US4297398A (en) * 1979-03-02 1981-10-27 Centre De Recherches Metallurgiques-Centrum Voor Research In De Metallurgie Manufacturing coated steel strip
US4381205A (en) * 1982-04-05 1983-04-26 E. F. Houghton & Company Metal quenching process
US4447348A (en) * 1981-02-25 1984-05-08 The Lubrizol Corporation Carboxylic solubilizer/surfactant combinations and aqueous compositions containing same
US4448703A (en) * 1981-02-25 1984-05-15 The Lubrizol Corporation Carboxylic solubilizer/surfactant combinations and aqueous compositions containing same
FR2537998A1 (en) * 1982-12-16 1984-06-22 Ugine Kuhlmann ADDITIVE FOR AQUEOUS DIPPING BY IMMERSION OF ALUMINUM ALLOYS
FR2537997A1 (en) * 1982-12-16 1984-06-22 Ugine Kuhlmann PROCESS FOR TEMPERING FERROUS ALLOYS IN AQUEOUS ENVIRONMENT
EP0143133A1 (en) * 1983-11-25 1985-06-05 Fire Out Enterprises Company, Inc. Cooling heated metal surfaces
US4528044A (en) * 1983-12-16 1985-07-09 E. F. Houghton & Co. Aqueous quenchants containing polyoxazolines and n-vinyl heterocyclic polymers and their use in quenching steel
US4666620A (en) * 1978-09-27 1987-05-19 The Lubrizol Corporation Carboxylic solubilizer/surfactant combinations and aqueous compositions containing same
US4738731A (en) * 1986-01-15 1988-04-19 Park Chemical Company Method of heat treating metal using a washable synthetic quenchant
US4770803A (en) * 1986-07-03 1988-09-13 The Lubrizol Corporation Aqueous compositions containing carboxylic salts
US4826545A (en) * 1987-06-02 1989-05-02 Foreman Robert W Method of heat treating metal parts using a washable synthetic quenchant
USRE34119E (en) * 1985-08-19 1992-11-03 Park Chemical Company Method of heat treating metal using a washable synthetic quenchant
US5298178A (en) * 1990-06-13 1994-03-29 Ciba-Geigy Corporation Triazole compounds useful as metal deactivators
USRE36479E (en) * 1986-07-03 2000-01-04 The Lubrizol Corporation Aqueous compositions containing nitrogen-containing salts
US20070197721A1 (en) * 2005-04-14 2007-08-23 Basf Aktiengesellschaft Method for Producing Aqueous Polyvinyllactam Dispersions
US20090095384A1 (en) * 2007-10-11 2009-04-16 Houghton Technical Corp. Aqueous quenching media and use thereof in quenching metal substrates
DE102008048596A1 (en) 2008-09-23 2010-04-08 Henkel Ag & Co. Kgaa Quench passivation of aluminum die-cast parts
WO2012065928A1 (en) 2010-11-17 2012-05-24 Basf Se Aqueous metal quenching medium
WO2013060679A1 (en) 2011-10-27 2013-05-02 Basf Se Use of a composition containing vinyl-lactam-containing polymer, solvent and at least one halogen-free biocide as a metal-quenching medium
US9023234B2 (en) 2010-02-22 2015-05-05 Idemitsu Kosan Co., Ltd. Aqueous heat treatment liquid composition
US10526447B2 (en) 2015-04-15 2020-01-07 Houghton Technical Corp. Materials that provide bioresistance and/or defoaming and slower cooling properties for aqueous quenchants

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Cited By (31)

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US4666620A (en) * 1978-09-27 1987-05-19 The Lubrizol Corporation Carboxylic solubilizer/surfactant combinations and aqueous compositions containing same
US4297398A (en) * 1979-03-02 1981-10-27 Centre De Recherches Metallurgiques-Centrum Voor Research In De Metallurgie Manufacturing coated steel strip
US4447348A (en) * 1981-02-25 1984-05-08 The Lubrizol Corporation Carboxylic solubilizer/surfactant combinations and aqueous compositions containing same
US4448703A (en) * 1981-02-25 1984-05-15 The Lubrizol Corporation Carboxylic solubilizer/surfactant combinations and aqueous compositions containing same
US4381205A (en) * 1982-04-05 1983-04-26 E. F. Houghton & Company Metal quenching process
WO1983003566A1 (en) * 1982-04-05 1983-10-27 Houghton & Co E F Metal quenching process
FR2537997A1 (en) * 1982-12-16 1984-06-22 Ugine Kuhlmann PROCESS FOR TEMPERING FERROUS ALLOYS IN AQUEOUS ENVIRONMENT
DE3345253A1 (en) * 1982-12-16 1984-07-12 PCUK Produits Chimiques Ugine Kuhlmann, Paris METHOD FOR QUARKING IRON ALLOYS IN AQUEOUS MEDIUM
GB2133047A (en) * 1982-12-16 1984-07-18 Ugine Kuhlmann Additive for aqueous quenching by immersion of aluminium-base alloys
GB2133048A (en) * 1982-12-16 1984-07-18 Ugine Kuhlmann Method of quenching ferrous alloys in an aqueous medium
FR2537998A1 (en) * 1982-12-16 1984-06-22 Ugine Kuhlmann ADDITIVE FOR AQUEOUS DIPPING BY IMMERSION OF ALUMINUM ALLOYS
EP0143133A1 (en) * 1983-11-25 1985-06-05 Fire Out Enterprises Company, Inc. Cooling heated metal surfaces
US4528044A (en) * 1983-12-16 1985-07-09 E. F. Houghton & Co. Aqueous quenchants containing polyoxazolines and n-vinyl heterocyclic polymers and their use in quenching steel
EP0179545A1 (en) * 1984-10-12 1986-04-30 E.F. HOUGHTON & Co. Aqueous quenchants containing polyoxazolines and N-vinyl heterocyclic polymers
USRE34119E (en) * 1985-08-19 1992-11-03 Park Chemical Company Method of heat treating metal using a washable synthetic quenchant
US4738731A (en) * 1986-01-15 1988-04-19 Park Chemical Company Method of heat treating metal using a washable synthetic quenchant
US4770803A (en) * 1986-07-03 1988-09-13 The Lubrizol Corporation Aqueous compositions containing carboxylic salts
USRE36479E (en) * 1986-07-03 2000-01-04 The Lubrizol Corporation Aqueous compositions containing nitrogen-containing salts
US4826545A (en) * 1987-06-02 1989-05-02 Foreman Robert W Method of heat treating metal parts using a washable synthetic quenchant
US5298178A (en) * 1990-06-13 1994-03-29 Ciba-Geigy Corporation Triazole compounds useful as metal deactivators
US20070197721A1 (en) * 2005-04-14 2007-08-23 Basf Aktiengesellschaft Method for Producing Aqueous Polyvinyllactam Dispersions
WO2009048648A1 (en) 2007-10-11 2009-04-16 Houghton Technical Corp. Aqueous quenching media and use therof in quenching metal substrates
US20090095384A1 (en) * 2007-10-11 2009-04-16 Houghton Technical Corp. Aqueous quenching media and use thereof in quenching metal substrates
US20110094638A1 (en) * 2007-10-11 2011-04-28 Houghton Technical Corp. Aqueous Quenching Media and Use Thereof in Quenching Metal Substrates
US8764914B2 (en) 2007-10-11 2014-07-01 Houghton Technical Corp. Aqueous quenching media and use thereof in quenching metal substrates
US9803255B2 (en) 2007-10-11 2017-10-31 Houghton Technical Corporation Aqueous quenching media and use thereof in quenching metal substrates
DE102008048596A1 (en) 2008-09-23 2010-04-08 Henkel Ag & Co. Kgaa Quench passivation of aluminum die-cast parts
US9023234B2 (en) 2010-02-22 2015-05-05 Idemitsu Kosan Co., Ltd. Aqueous heat treatment liquid composition
WO2012065928A1 (en) 2010-11-17 2012-05-24 Basf Se Aqueous metal quenching medium
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JPS5333284B2 (en) 1978-09-13
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