EP0068061A1 - Méthode pour empêcher la lixiviation de cobalt et de nickel de surfaces métalliques et concentré utilisé pour cette méthode - Google Patents

Méthode pour empêcher la lixiviation de cobalt et de nickel de surfaces métalliques et concentré utilisé pour cette méthode Download PDF

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Publication number
EP0068061A1
EP0068061A1 EP81730057A EP81730057A EP0068061A1 EP 0068061 A1 EP0068061 A1 EP 0068061A1 EP 81730057 A EP81730057 A EP 81730057A EP 81730057 A EP81730057 A EP 81730057A EP 0068061 A1 EP0068061 A1 EP 0068061A1
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EP
European Patent Office
Prior art keywords
parts
water
concentrate
thiadiazole
hydrogen
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
EP81730057A
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German (de)
English (en)
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EP0068061B1 (fr
Inventor
John M. Mcchesney
Perry E. Landers
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Ashland LLC
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Ashland Oil Inc
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Publication date
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Priority to DE8181730057T priority Critical patent/DE3171913D1/de
Priority to AT81730057T priority patent/ATE15066T1/de
Priority to EP81730057A priority patent/EP0068061B1/fr
Publication of EP0068061A1 publication Critical patent/EP0068061A1/fr
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Publication of EP0068061B1 publication Critical patent/EP0068061B1/fr
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/16—Sulfur-containing compounds
    • C23F11/165—Heterocyclic compounds containing sulfur as hetero atom
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    • C10M2207/10—Carboxylix acids; Neutral salts thereof
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    • C10M2207/10—Carboxylix acids; Neutral salts thereof
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/141—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings monocarboxylic
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/142—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings polycarboxylic
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/22—Acids obtained from polymerised unsaturated acids
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    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/08—Halogenated waxes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/08—Amides [having hydrocarbon substituents containing less than thirty carbon atoms]
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    • C10M2215/08—Amides [having hydrocarbon substituents containing less than thirty carbon atoms]
    • C10M2215/082—Amides [having hydrocarbon substituents containing less than thirty carbon atoms] containing hydroxyl groups; Alkoxylated derivatives
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/221—Six-membered rings containing nitrogen and carbon only
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
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    • C10M2215/226—Morpholines
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • C10M2215/28—Amides; Imides
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    • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • C10M2215/30—Heterocyclic compounds
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
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    • C10M2219/106—Thiadiazoles

Definitions

  • This invention relates to corrosion inhibitors for cobalt and nickel in the metallic form. More specifically this invention relates to water-base, oil-base, and oil-in-water emulsion lubricant and coolant compositions, used in the drilling, cutting and milling and other metal working operations.
  • a large percentage of industrial cutting tools used to drill, cut, grind and mill metals are made of tungsten carbide ⁇ particles held together by a cobalt bonding agent.
  • the bonding agent may be nickel or platinum.
  • the drilling, cutting, milling, or other metal working step requires the application of a liquid coolant or lubricant at the area of contact between the metal surface being machined and the drilling, cutting or milling tool.
  • water or mineral oil can be used alone as a coolant or lubricant the practice has been to add compounds which increase the lubricity and cooling ability of the liquid and which delay its deterioration. These added compounds often, however, contain sequestering (chelating) agents and moities such as sulfur, chlorine, carboxyl groups and hydroxyl ions.
  • An object of this invention is to reduce the corrosion of cobalt and nickel surfaces. Another object of this invention is to prevent or reduce the rate of leaching of cobalt and nickel binder from machining tools made up of abrasive particles such as tungsten carbide and a binder material such as cobalt or nickel.
  • Another object of this invention is to prevent or reduce the corrosion or oxidation of aluminum alloys during the said machining action when water-base coolants and lubricants are used.
  • this invention comprises contacting with a solution of a triazole or thiadiazole compound a cobalt or nickel surface exposed to leaching action by a liquid agent. Ordinarily the triazole or thiadiazole compound will be contained in the liquid leaching agent.
  • this invention comprises a concentrate for preparing an aqueous base, oil base or oil-in-water emulsion lubricant and coolant composition containing therein a triazole or thiadiazole or mixtures thereof.
  • this invention comprises the coolant and lubricant composition made by diluting the concentrate with oil or water.
  • this invention comprises the method of drilling, grinding, cutting or otherwise working a metal utilizing the coolant and lubricant composition described above.
  • the utility of the water-base concentrate and water-base coolant composition is further enhanced by the addition of 1 to 4 parts of sodium gluconate. Specifically when aluminum is being machined the sodium gluconate prevents corrosion.
  • the triazole compounds utilized in this invention have the generic formula: where R is hydrogen or a methyl substituent. If R is hydrogen the compound is benzene triazole and if R is a methyl radical then the compound is tolyl triazole.
  • the thiadiazole compounds utilized in this invention can have the generic formula: where R' is a hydrogen or a methyl substituent. When R' is hydrogen then the compound is 2,1,3,-benzothiadiazole.
  • Other thiadiazole compounds which can be utilized are 2,5-dimercapto-1,3,4-thiadiazole having the structural formula the disodium salt thereof, disodium 2,5-dimercaptothiadiazole having the formula and di-(triethanolammonium) dimercaptothiadiazole. In the following description all compositions are described in parts by weight unless specified otherwise.
  • the oil-base working-composition comprises between 80 and 95 parts of mineral oil; and between 1 and 5 parts of one . of the triazole or dithiazole compounds shown ab ove or mixtures thereof.
  • additives can be added such as between 1 and 10 parts of an extreme pressure lubricant, between 1 and 5 parts of rust preventive and between 1 and 5 parts of mist suppressant. These additives are known to those skilled in the art and are readily available in commerce.
  • the preferred triazole compound is benzyltriazole and the preferred thiadiazole compound is 2,1,3-benzothiadiazole.
  • a suitable extreme pressure lubricant is Klora 6001 manufactured by Kiel Chemical.
  • a suitable rust preventive is Tectyl 477 manufactured by Valvoline International and a suitable mist suppressant is manufactured by Exxon Corporation.
  • the triazole and thiadiazole compounds are most effective since the introduction of these materials also bring into the lubricant composition those agents thought to be responsible for the leaching of cobalt and nickel from cutting and grinding tools.
  • the concentrate which is to be subsequently diluted with water to form an oil-in-water emulsion coolant and lubricant comprises between 60 and 80 parts of mineral oil; between 1 and 5 parts of one of the triazole or thiadiazole compounds above or mixtures thereof; and between 15 and 25 parts of an emulsifier.
  • an emulsifier optionally there may also be added between 1 and 2 parts of a bactericide, between 3 and 10 parts of an extreme pressure lubricant and between 1 and 3 parts of an antifoaming agent.
  • the lubricant and coolant composition is prepared by diluting the above-described composition with water until the concentration of triazole or thiadiazole is between about 250 and about 2000 parts per million.
  • the preferred triazole is benzyltriazole and the preferred thiadiazole is 2,5-dimercapto-1,3,4-thiadiazole.
  • a suitable emulsifier is sodium sulfate, a suitable bactericide is Bioban P 1487; a suitable extreme pressure lubricant is Kloro 6001 and a suitable antifoaming agent is Nopco NDW available from Diamond Shamrock Corporation.
  • the concentrate which is to be subsequently diluted with water to form a water-base coolant and lubricant comprises between 60 and 80 parts of water; between 3 and 10 parts of a triazole or thiadiazole or mixtures thereof; between 2 and 8 parts of an aromatic or paraffinic carboxylic acid; between 2 and 10 parts of boric acid; and between 5 and 20 parts of an amine or mixture of amines that will react with the carboxylic acid component of the composition.
  • a wetting agent between 1 and 2 parts of a bactericide and fungicide; and between 1 and 2 parts of an antifoaming agent.
  • the triazole and thiadiazole compounds are particularly effectiv against the leaching of cobalt and nickel when these optiona additives are included since they bring into the system those moities which contribute to leaching.
  • the preferred triazole compound is the sodium salt of 2,5-dimercaptothiadiazole.
  • the aromatic or paraffinic carboxylic acid can be any of the following:
  • the amine component can be any secondary or tertiary amine of.sufficient reactivity to react with the boric acid and organic carboxylic acid components. Suitable amines include di- or tri-ethanolamine or triisopropanol amine; and 2-dimethylamino, 2-methyl, 1-propanol amine.
  • the carboxylic acid can be arylsulfonamidocarboxylic acid.
  • the wetting agent can be any wetting agent compatible with the remainder of the system. It should be low foaming and totally water soluble. Suitable wetting agents are Pluronic L-43 available from the BASF Wyandotte Corporation, and Niaproof 08 from Niacet Chemical Company.
  • compatible germicides fungicides and bactericides
  • fungicides and bactericides optionally can also be included in amounts up to 6 parts per 100 parts of additive.
  • a suitable fungicide and a bactericide are Grotan and Bioban, available from the Lehn and Fink Co., Inc.,and IMC Chemicals Group, Inc. respectively.
  • the antifoaming agent is added in an amount up to 1 part per 100 parts by weight of additive.
  • a suitable antifoaming agent is SAG 30 available from Union Carbide Corporation.
  • the remainder of the additive (concentrate) is made up with water added to bring the total weight of the additive up to 100 parts by weight.
  • aqueous grinding or cutting fluid composition To formulate an aqueous grinding or cutting fluid composition, the above-described additive (concentrate) is diluted with additional water in an amount of between 2 and 15 parts of additive per 100 parts of water.
  • the resulting cutting fluid composition is applied to the metal surface being worked such as by machining, milling or cutting in the conventional manner.
  • An oil-base coolant and lubricant was prepared by mixing the following components:
  • Oil-in-water-emulsion concentrate and coolant and lubricant composition Oil-in-water-emulsion concentrate and coolant and lubricant composition
  • a concentrate was prepared by mixing the following components:
  • This concentrate was then used to prepare a metal-working coolant and lubricant by diluting it in a ratio of 3 parts by weight of concentrate to 97 parts of water.
  • This concentrate was diluted in a ratio of 3 parts of concentrate to 97 parts of water to form a water-base metal working coolant and lubricant.
  • Tests of metal-working coolant and lubricant compositions in each of the preceding examples were conducted.
  • the resistance of specimens of tungsten carbide particles bonded together with cobalt to leaching by the liquid coolants and lubricants was observed to be substantially reduced.
  • the metal working coolants and lubricants are compatible with ferrous and non-ferrous metals including the yellow metal alloys such as brass and copper.
  • the water-base compositions are markedly effective in minimizing the corrosion of aluminum.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Lubricants (AREA)
  • Manufacture And Refinement Of Metals (AREA)
EP81730057A 1981-06-25 1981-06-25 Méthode pour empêcher la lixiviation de cobalt et de nickel de surfaces métalliques et concentré utilisé pour cette méthode Expired EP0068061B1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE8181730057T DE3171913D1 (en) 1981-06-25 1981-06-25 Method for preventing the leaching of cobalt and nickel metal surfaces and a concentrate used in such method
AT81730057T ATE15066T1 (de) 1981-06-25 1981-06-25 Verfahren zum verhindern des auslaugens von kobalt und nickel aus metalloberflaechen und ein in diesem verfahren verwendetes konzentrat.
EP81730057A EP0068061B1 (fr) 1981-06-25 1981-06-25 Méthode pour empêcher la lixiviation de cobalt et de nickel de surfaces métalliques et concentré utilisé pour cette méthode

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP81730057A EP0068061B1 (fr) 1981-06-25 1981-06-25 Méthode pour empêcher la lixiviation de cobalt et de nickel de surfaces métalliques et concentré utilisé pour cette méthode

Publications (2)

Publication Number Publication Date
EP0068061A1 true EP0068061A1 (fr) 1983-01-05
EP0068061B1 EP0068061B1 (fr) 1985-08-21

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EP (1) EP0068061B1 (fr)
AT (1) ATE15066T1 (fr)
DE (1) DE3171913D1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0180561A1 (fr) * 1984-10-30 1986-05-07 Berol Kemi Ab Procédé de travail mécanique de métal contenant du cobalt et solution concentrée qui, après dilution à l'eau convient à l'utilisation du procédé
EP0173427A3 (fr) * 1984-06-26 1986-09-17 Betz Europe, Inc. Inhibition de la corrosion
US5874390A (en) * 1997-12-22 1999-02-23 Cincinnati Milacron Inc. Aqueous machining fluid and method

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3186946A (en) * 1961-06-09 1965-06-01 Master Chemical Corp Aqueous cutting fluid
US3265620A (en) * 1963-08-29 1966-08-09 Donald K Heiman Cutting fluid
GB1130663A (en) * 1966-06-29 1968-10-16 Nalco Chemical Co Metal rolling process
FR2002205A1 (fr) * 1968-02-19 1969-10-17 Armour Ind Chem Co Procede pour conferer des proprietes lubrifiantes a des milieux aqueux a l'aide de composes amines amphoteres
US3681247A (en) * 1969-02-17 1972-08-01 Procter & Gamble Lubricant composition
FR2237957A1 (fr) * 1973-07-19 1975-02-14 Lubrizol Corp
US4218329A (en) * 1978-08-28 1980-08-19 Koh Kook Wha Cooling and lubricating fluid for metal working

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3186946A (en) * 1961-06-09 1965-06-01 Master Chemical Corp Aqueous cutting fluid
US3265620A (en) * 1963-08-29 1966-08-09 Donald K Heiman Cutting fluid
GB1130663A (en) * 1966-06-29 1968-10-16 Nalco Chemical Co Metal rolling process
FR2002205A1 (fr) * 1968-02-19 1969-10-17 Armour Ind Chem Co Procede pour conferer des proprietes lubrifiantes a des milieux aqueux a l'aide de composes amines amphoteres
US3681247A (en) * 1969-02-17 1972-08-01 Procter & Gamble Lubricant composition
FR2237957A1 (fr) * 1973-07-19 1975-02-14 Lubrizol Corp
US4218329A (en) * 1978-08-28 1980-08-19 Koh Kook Wha Cooling and lubricating fluid for metal working

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0173427A3 (fr) * 1984-06-26 1986-09-17 Betz Europe, Inc. Inhibition de la corrosion
EP0180561A1 (fr) * 1984-10-30 1986-05-07 Berol Kemi Ab Procédé de travail mécanique de métal contenant du cobalt et solution concentrée qui, après dilution à l'eau convient à l'utilisation du procédé
US4976919A (en) * 1984-10-30 1990-12-11 Berol Kemi Ab Method for mechanically working cobalt-containing metal
US5874390A (en) * 1997-12-22 1999-02-23 Cincinnati Milacron Inc. Aqueous machining fluid and method

Also Published As

Publication number Publication date
DE3171913D1 (en) 1985-09-26
EP0068061B1 (fr) 1985-08-21
ATE15066T1 (de) 1985-09-15

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