US3409551A - Lubricant-coolant emulsion - Google Patents

Lubricant-coolant emulsion Download PDF

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Publication number
US3409551A
US3409551A US589520A US58952066A US3409551A US 3409551 A US3409551 A US 3409551A US 589520 A US589520 A US 589520A US 58952066 A US58952066 A US 58952066A US 3409551 A US3409551 A US 3409551A
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United States
Prior art keywords
emulsion
oil
metal
filter
hardness
Prior art date
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Expired - Lifetime
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US589520A
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English (en)
Inventor
Treat Lyle
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.)
Dow Chemical Co
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Dow Chemical Co
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Filing date
Publication date
Priority to DE19661594398 priority Critical patent/DE1594398A1/de
Priority to GB13905/66A priority patent/GB1118224A/en
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Priority to US589520A priority patent/US3409551A/en
Priority to US589730A priority patent/US3408843A/en
Priority to GR670133300A priority patent/GR33300B/el
Priority to DE1594412A priority patent/DE1594412C3/de
Priority to ES335836A priority patent/ES335836A1/es
Priority to GB3061/67A priority patent/GB1154303A/en
Priority to NL6701434A priority patent/NL6701434A/xx
Priority to FR95076A priority patent/FR1514458A/fr
Priority to SE3197/67A priority patent/SE342471B/xx
Priority to NO167488A priority patent/NO122493B/no
Priority to BE705624D priority patent/BE705624A/xx
Application granted granted Critical
Publication of US3409551A publication Critical patent/US3409551A/en
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00—Lubricating compositions containing more than 10% water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B45/00—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
    • B21B45/02—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills for lubricating, cooling, or cleaning
    • B21B45/0239—Lubricating
    • B21B45/0242—Lubricants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C9/00—Cooling, heating or lubricating drawing material
    • B21C9/02—Selection of compositions therefor
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/042—Sulfate esters
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • 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
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/09—Complexes with metals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/06—Groups 3 or 13
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/241—Manufacturing joint-less pipes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/242—Hot working
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/243—Cold working
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
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    • C10N2040/244—Metal working of specific metals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
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    • C10N2040/245—Soft metals, e.g. aluminum
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/244—Metal working of specific metals
    • C10N2040/246—Iron or steel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/244—Metal working of specific metals
    • C10N2040/247—Stainless steel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/01—Emulsions, colloids, or micelles
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/015—Dispersions of solid lubricants
    • C10N2050/02—Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Semi-solids; greasy
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/26—Oils; Viscous liquids; Paints; Inks
    • G01N33/28—Oils, i.e. hydrocarbon liquids
    • G01N33/2894—Oils, i.e. hydrocarbon liquids for metal working or machining

Definitions

  • of unchelated hardness (expressed as CaC and exhibits a pH of about to 11, has an oil phase in the form of globules with an average diameter in the range of about 1 to 25 microns, is substantially free of continuous free oil phase, is stable, and filterable whereby solid particulate material having maximum dimensions in the range of about 0.5 to microns or larger is readily removed therefrom.
  • the amount of unchelated hardness is about 25 to 400 ppm.
  • the invention relates to the hot or cold working, cutting or other shaping of metal in any operation wherein there is used a flowing lubricant-coolant oil-in-water emulsion which is recycled and reused.
  • the invention also relates to the composition of such emulsions as well as a method for improving such emulsions.
  • aluminum and its alloys containing at least 70 percent by weight of aluminum are hereinafter referred to as aluminum;
  • magnesium and its alloys containing at least 70 percent by weight of magnesium are hereinafter referred to as magnesium;
  • copper and its alloys containing at least 50 percent by weight of copper are hereinafter referred to as copper;
  • iron and its alloys containing at least 75 percent by weight of iron are hereinafter referred to as ferrous metal;
  • the operations of rolling, working, drawing, cutting, milling, scalping, drilling, or grinding and the like of metals are hereinafter referred to variously, as method of shaping a metal, metal shaping, and the like;
  • the phrase flowing lubricant-coolant oil-in-water emulsion is intended to encompass such emulsions which are sprayed on the workpiece or tool.
  • the emulsion serves: (1) to control the frictional forces existing between the work piece and the work tool; (2) to promote the development of desired tool coatings during the shaping process, e.g., roll-coating during rolling; and (3) to prevent excessive transfer of metal from the work piece to the tool or from the tool to the work piece, e.g., between the rolls and the work piece as in rolling operations.
  • Typical lubricant-coolant oil-in-water emulsions that have been used for metal shaping operations such as rolling or cutting have consisted essentially of from about 0.5 to 20 percent by weight of an oil in water, the oil being a mixture referred to in the trade as neat soluble oil or soluble oil.
  • Such neat soluble oil is widely sold as a concentrate containing, generally, about 70-90 percent by weight of a base oil, such as a light mineral oil, from about 1 to 20 percent by weight, based on said neat soluble oil, of one or more anionic and/or nonionic oil-iu-water emulsifying agents and the balance substantially water.
  • the neat soluble oil must also contain from about 0.5 to 15 percent by weight of lubricity additives such as long chain fatty acids and salts or esters thereof, e.g., alkanolamine soaps, or, esters such as butyl stearates which serve as extreme pressure agents.
  • lubricity additives such as long chain fatty acids and salts or esters thereof, e.g., alkanolamine soaps, or, esters such as butyl stearates which serve as extreme pressure agents.
  • emulsions are made up conventionally by admixing one of the commercially available substantially water-free concentrations with water.
  • the commercial concentrates usually contain up to 0.5 percent by weight of a bactericide and from about 0.5 to 5 percent by weight of a coupling agent, i.e., a substance which stabilizes the concentrate during storage prior to use.
  • composition of the neat soluble oil itself forms no part of the present invention.
  • the method and composition of the invention are usable with substantially all of the commonly known and used commercially available neat soluble oils, without modification of the soluble oil per se.
  • Suitable commercial compound-ed oils include, for example, Solvac 1535G, Prosol 44 and Prosol 66 supplied by Socony Mobil Oil Company, Rollex A supplied by the Shell Chemical Company, Majestic 101 supplied by Fiske Brothers Refining Company, Rol- Kleen 53 supplied by the D. A. Stuart Oil Company, Ltd., A-lOO supplied by Far Best, W.S. 51821 supplied by the Humble Oil Company and Tandemol C86 and Tandemol K87 by E. F. Hougton and Company.
  • a typical neat soluble oil that is commercially available has the following general composition, by weight:
  • the base oil used in making up a neat soluble oil generally is selected from a light hydrocarbon or light hydrocarbon mixture having a viscosity of about 40 to 200 Saybolt Universal Seconds (SUS) at F.
  • SUS Saybolt Universal Seconds
  • other lubricious materials such as fatty oils, e.g., palm oil, or synthetic materials, e.g., palm oil substitutes, are also used as a base oil in making up soluble oil.
  • Such other lubricious materials may have viscosities as high as about 850 SUS.
  • base oil is understood to encompass the light hydrocarbon or hydrocarbon mixtures recognized as light mineral oils, in addition to lubricious materials including vegetable oils, such as palm oil, animal fats, such as lard oil, and palm oil substitutes and the equivalents thereof, e.g., polyglycols and ethers and esters thereof, selected from those which are n0n-stain in g of the metal being shaped.
  • fatty alkyl sulfates such as CH (CH OSO Na
  • sulfonated fatty amines such as '(4) the alkali metal salts of sulfonated fatty acids; and the like.
  • the other alkali metal salts of these compounds and the triethanolamine salts are equivalents of the sodium salts described above.
  • the alkanolamine soaps of long chain fatty acids are particularly suitable e.g., the diisopropanolamine, diethanolamine or monoethanolamine salts of oleic acid, palmetic acid or stearic acid, the salts being useful singly or as mixtures.
  • Suitable nonionic oil-in-Water emulsifiers include the nonionic ethers such as those derived from alkylphenols and ethylene oxide, e.g., C8H17C6H4OC2H4(0C2H4)X0H wherein x has a value of 9 to 14 or more, the primary alcohol-ethylene oxide adducts, and the secondary alcohol-ethylene oxide adducts.
  • the emulsion begins to break and the droplets of the oil phase agglomerate into larger droplets some of which coalesce sufficiently to provide a substantialy quantity of continuous free oil phase.
  • an emulsion which contains no more than about 0.2 percent by weight of continuous free oil phase is considered to be free of such free oil phase.
  • Typical industrial emulsion systems vary in size from perhaps 5,000 to 10,000 gallons or less for smaller cutting or grinding operations to systems as large as 100,000 to 500,000 gallons for large rolling mills, some of which require the circulation of 1,000 to 10,000 gallons of emulsion per minute to one or more mill stands.
  • Another object of the invention is to provide a method of stabilizing and reusing a lubricant-coolant oil-in-water emulsion in metal shaping operations. 7
  • Another object of the invention is to provide a method of removing particulate matter and eliminating or reducing continuous free oil phase from lubricant-coolant oilin-water emulsion, apart from a normal level of about 0.2 percent by weight of such oil phase, which is not detrimental in effect.
  • a further object of the invention is to provide a method of increasing the service life of lubricant-coolant oil-inwater emulsions used in the shaping of metal.
  • Yet another object of the invention isto provide an improved lubricant-coolant oil-in-water emulsion for use in metal shaping operations.
  • a conventional rolling or cutting oil emulsion is improved by the addition thereto of an alkaline alkali metal or ammonium or amine salt of a polycarboxylic acid chelating agent in an amount sufficient to chelate calcium, magnesium, aluminum, heavy metal or other polyvalent metal ions present or accumulating in such an emulsion whereby the hardness content, expressed as CaCO is reduced below about 400 p.p.m., and the emulsion pH is brought into the range of about 5 to 11. Where foaming is a problem it is much preferred to bring the hardness content to about 25 to 400 p.p.m.
  • the maintenance of a controlled level of hardness content below about 400 p.p.m., expressed as CaCO and a pH in the range of about 5 to about 11 is essential.
  • Such management of the emulsion substantially prevents oil separation therefrom and has the following further important effects: (a) the emulsion is stabilized so that it can be filtered through a mechanical filter capable of removing solid particulate matter larger than 10 to 20 microns size, and preferably larger than 1 micron, such as a filter provided with a siliceous precoating; (b) solid particulate contamination such as dirt, metal fines, and metal oxide particles are readily removed on the filter without premature filter blank off problems; (c) light viscosity tramp oils leaking into the system are substantially emulsified thus minimizing the quantity of free oil phase; and (d) oxidized oils and reaction products thereof are removed on filtration.
  • a mechanical filter capable of removing solid particulate matter larger than 10 to 20 microns size, and preferably larger than 1 micron, such
  • An important aspect of the present invention is the discovery that the particle diameter of the globules of emulsified oil is at least partly a function both of pH and hard ness content of the emulsion, the nature and concentration of'the emulsifying materials present being also controlling factors.
  • This role of hardness had not been appreciated heretofore.
  • Both calcium and magnesium hardness are generally derived in part from the water used to make up the emulsion. Large quantities of water are frequently and periodically added in many metal shaping operations to replace losses due to evaporation bringing about the addition of substantial amounts of calcium and magnesiurn hardness. Calcium, and to some extend magnesium ions, also enter the emulsion from concrete mill pits or sumps and storage tanks in which the emulsion is received or stored.
  • the workpiece employed is a substantial source of magnesium and/or calcium and/or aluminum ions. These appear to be the main sources which provide for a build-up of hardness content in the emulsion, particularly calcium and magnesium, as the emulsion is recycled and reused.
  • foaming of the emulsionduring'pumping and spraying operations tends'to be a problem in most operations when the hardness level falls too low.
  • foaming tends to be excessive and undesired, a hardness level in the range of 100 to 200 p.p.m. expressed as CaCO is preferred; where foaming is less of a problem, a hardness level in the range of 25 to 100 p.p.m. is preferred.
  • the metals which may be rolled or shaped according to the present invention include aluminum, copper, ferrous metal, such as steel, and magnesium. These metals may be shaped cold, or at temepratures as high as about 1050 F., using the emulsion of the invention.
  • the chelating agents used in the method of this invention are the alkali metal or ammonium or amine salts of polycarboxylic acids, including citric acid, tartaric acid, the alkylene polyamine polyacetic acids, and mixtures of any of the said salts of such polycarboxylic acids.
  • the alkylene polyamine polyacetic acids include ethylenediaminetetraacetic acid and its well-known homologs and analogs such as N-hydoxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, N-2-hydroxyethyliminodiacetic acid, cyclohexanediaminetetraacetic acid and their obvious equivalents.
  • the amine salts or soaps referred to include particularly the salts made from one of these polycarboxylic acids and any one of ethanolamine, diethanolamine, and triethanolamine.
  • the reused lubricant-coolant oil-in-water e-mulsion'ordinarily employed according to the invention in the shaping of a metal wherein the work piece is contacted with a flowing stream of said emulsion comprises:
  • the emulsion may also contain 1) an anti-foaming agent and/or (2) a corrosion inhibitor and/or (3) an additional lubricity agent, such additions not exceeding a total of about 5 percent by weight.
  • the reused emulsion is further characterized by having a pH in the range of about 5 to about 11, but preferably 7 to 10, by the dispersed oil being in the form of globules having an average globule diameter in the range of about 1 to 25 microns and substantially no globules having a diameter exceeding about 50 microns, by a preselected globule diameter being readily maintainable, by the emulsion being readily filterable through a mechanical filter capable of removing solid particles larger than 10 to 20 microns size but preferably particles larger than 0.5 to 1 micron, and by the emulsion being (1) substantially free of solid particles larger than about 10 to 20 microns but preferably no larger than 0.5 to 1 micron and (2) free of more than about 0.2 percent of a free oil phase.
  • the reused emulsion is a tight emulsion designed for reversing mill work and cutting operation, for example, the reused emulsion is also further characterized by the dispersed base oil being in the form of globules having an average globule diameter in the range of about 1 to 2 microns and substantially no globules having a diameter exceeding'about 5 microns.
  • the dispersed oil phase is in the form of globules having a'n'average globule diameter in the range of about 2 to 5 microns with substanstantially no globules larger than about 15 microns.
  • the dispersed oil phase is often in the form of globules having an average globule diameter in the range of about 5 to 20 microns with substantially no globules larger than about 50 microns diameter.
  • Each of tight, loose and coarse emulsions are readily filterable when treated and maintained according to the invention.
  • An important aspect of the invention is the provision for maintenance and control of globule diameters while avoiding emulsion breakage. Even the normally metastable emulsions are maintainable.
  • Tight emulsions are obtained and maintained upon pumping, mixing or otherwise thoroughly agitating the emulsion and further filtering the emulsion under conditions in which the concentration of unchelated hardness is below about p.p.m.
  • Coarse emulsions tend to arise and be maintained under conditions wherein the amount of unchelated hardness is substanstially above 200 parts per million,
  • the basic tendency of the emulsion to exhibit fine or coarse globules is dependent upon the materials used to make up the compounded soluble oil concentrate. It is to be understood that making up and maintaining an emulsion according to the present invention provides an effect that is superimposed upon the basic nature of the preselected emulsion. The net result is that the emulsion size moves to a dynamically stable size and is controllably maintainable at such dynamically stable size using the composition and 'method of the invention.
  • an emulsion is made up generally from water and a commercial neat soluble oil of the type described hereinabove. If desired, the emulsion may be made up from the individual components.
  • the alkali metal or ammonium or amine salt of polycarboxylic acid chelating agent used according to the invention is added to the water employed in making up the emulsion or the chelating agent may be added to the diluted emulsion in any convenient form, i.e., as a solution, slurry, or dry particulate solid.
  • the chelating agent usually in the form of a 20 to 40 percent by weight aqueous alkaline solution, is added in the requisite amount to bring the hardness level and the pH into the ranges indicated hereinabove.
  • the water employed or the finished emulsion is analyzed in order to determine the needed quantity of chelating agent solution.
  • the completed emulsion is then placed in service in metal shaping operations.
  • clean emulsion is circulated from clean storage to the work piece where it is used.
  • the emulsion flowing off the work piece and off the tool or mill is collected as a in a sump where some of the particulate matter present settles out.
  • the emulsion may be allowed to settle further in a system with a large inventory of emulsion, but in general, the emulsion is more or less in constant circulation.
  • a brief quiet period in a dirty tank is advantageous in the collection and removal of tramp oils before subsequent filtration.
  • the emulsion is sampled for analysis, and hardness level and pH are adjusted by the addition of the indicated requirements of alkaline solution of chelating agent
  • the emulsion is then pumped to clean storage; if desired, the addition of chelating agent solution may be made to the emulsion in the clean storage vessel.
  • the emulsion after settling in dirty storage is filtered before sampling, adjusting the hardness and pH levels, and pumping to clean storage.
  • Filtering is conveniently and effectively carried out with most any mechanical filter, such as one employing a filter paper or membrane, and especially a filter using a precoat of a siliceous material such as diatomaceous earth.
  • the filter must be capable of removing fine particulate matter, preferably all matter coarser than one micron size.
  • a very effective form of filter for handling large volumes of emulsion rapidly is a tube-type filter using an array of cylindrical tubes formed of wire mesh made of Monel metal having mesh openings in the range of 0.004 inch to 0.008 inch and coated with a filter aid such as Celite 545 diatomaceous earth of which about 80 percent of the particles are finer than about 40 microns.
  • the filter aid forms a filter cake on each tube that retains solids greater than about 1 micron in shortest dimension.
  • the filter tube extends into the emulsion to be filtered providing a very extensive filtering surface within a compact zone.
  • the clean emulsion remains in clean storage until use when the cycle commences again with the pumping of the lubricant-coolant emulsion to the metal shaping operation. Normally, the retention in clean storage is brief, being of the order of 5 to 30 minutes unless a very large inventory of emulsion is used. Lubricant-coolant emulsion so-handled and maintained remains stable and usable throughout many many cycles completed during the space of from several months to several years and usually during at least 6 months or more of steady use.
  • Example 1 This example will best be understood with reference to the accompanying drawing on which there is depicted a schematic flow diagram for an 18,000 gallon emulsion system.
  • the reference numeral 1 refers generally to an 84 inch wide 4-high reversing hot mill.
  • 5,000-pound slabs of aluminum ingot (not shown) were rolled from an initial thickness of approximately 14 inches to various gauges down to a final gauge less than about A inch thick, the metal at the final pass having the form of either sheet or plate.
  • Product from this mill must be suitable either as a final product, or as re-roll stock to be further processed before use.
  • a flood lubricant-coolant emulsion as described above, was applied to the workrolls through a system of spray-nobbles, (not shown).
  • the relative distribution of coolant across the width of the rolls was regulated by adjusting the flow through the various nozzles provided.
  • the emulsion temperature was in the preferred 120-130 F. range as it is initially on the mill rolls.
  • the coolant then passed by gravity into a mill pit 2, a 5,0000 gallon reservoir beneath the mill, and thence to a 4,000 gallon sump 3.
  • These two reservoirs serve primarily as collection points for coolant, but a valuable secondary function is that of foam storage. Foam that is generated at the mill, particularly in spray-quench operations, needs time to break down, and these reservoirs provide a storage capacity to afford this time. Foam breakdown may be assisted by the addition of appropriate antifoaming agents to the mill pit contents.
  • Sump pumps 4 then carried the lubricant-coolant emulsion to a 12,000 gallon storage tank 5 which is divided into a 4,000 gallon clean compartment 6, and an 8,000 gallon dirty compartment 7. From the sump, the emulsion was directed first to dirty compartment 7. From there it was pumped through a mechanical filter 8 precoated with Celite 545 diatomaceous earth, and returned to the clean compartment 6.
  • the filter has a capacity of 1,500 gallons per minute, a rate that is faster than the normal mill-demand rate. Therefore, while the clean and dirty compartments of the storage tank communicate with each other, normally the fiow not needed in the metal shaping operations was directed from the clean compartment 6 to the dirty compartment 7.
  • a secondary coarse strainer filter 9 was provided in the system to remove particles large enough to clog the spray nozzles used at the mill. From the clean compartment 6 the coolant ordinarily flowed through such secondary filter 9 on its way to the mill.
  • the mechanical filter was a tube-type filters, containing about 750 tubes of woven Monel-wire mesh. Each tube was l-inch in diameter and 3 feet long. The wire diameter was 0.011 inch. The mesh openings have maximum dimensions of 0.006 inch to 0.008 inch while the average openings are 0.004 inch x 0.006 inch.
  • the filter tubes were precoated with Celite 545 diatomaceous earth, a filter aid of which about percent of the particles are finer than about 40 microns.
  • the precoat or filter cake formed on each tube retained solids greater than one micron in diameter.
  • the precoat was introduced into the suction side of the filter pump 10 from a 150 gallon tank 11 in the form of a suspension containing pounds of filter aid and the balance water. One-half of the contents of this tank was used to precoat the filter; thus 50 pounds of filter aid formed the initial cake.
  • the porosity of the filter was controlled during the useful life of the filter cake by periodic controlled additions of filter aid, as well understood in the art.
  • body feed which consisted of about 50 pounds of filter aid and the balance being 300 gallons of water. Normally, body feed was metered in during approximately three seconds out of each minute at a rate suflicient to provide about 50 pounds of filter aid during each 24-hour period. In addition to the original 50 pounds precoat, the filter can handle an additional 200 pounds of body feed. Thus, under normal operating conditions, about five days of filter operation were attainable between back-washes. When an unusual condition occurred, such as excessive leakage of tramp oils into the system, or greater dirt load from rolling certain alloys, a faster rate of body feed was employed to avoid excessive pressuredrop build-up across the filter. In this case, the cycle between back-washes was shortened.
  • the back-wash operation requires about 35 minutes.
  • coolant from the filter vessel was discharged into the 1,500 gallon recovery storage tank 13.
  • the entire recovery filter cycle takes about 7 hours. Filtration of the back-wash to retain used filter aid solids for waste disposal was accomplished advantageously by.
  • Samples for analytical control were removed after the final filtering just before the lubricant-coolant emulsion was pumped to the mill.
  • the composition of the lubricant-coolant emulsion was maintained in the following manner.
  • the oil phase of the emulsion consisted of 4.5 to 6.0 weight percent of a light oil, having a viscosity, at 100 F., of 100-200 SUS, emulsified in water with one or more anionic and/or nonionic emulsifiers as described above.
  • the emulsion was made up with water.
  • an aqueous solution of an alkaline chelant was added to the resulting emulsion.
  • the quantity of such alkaline chelating agent used was such as to bring the hardness of the aqueous phase of the emulsion within a range of 100-200 p.p.m., expressed as CaCO and the pH within a range of 9 to 10, to give the emulsion the desired properties of stability and lubricity.
  • more chelatin agent was added.
  • Percent soluble oil This test gives the concentration of oil in the emulsion. The concentration is determined by breaking a sample of the emulsion with acid, centrifuging the broken emulsion, and measuring the oil layer. Adjustment of the oil concentration to the desired range is accomplished by the addition of neat soluble oil or de-ionized water.
  • Percent free oil This is determined by centrifuging a sample of the emulsion for a predetermined time and measuring the oil layer. Generally one expects only a trace to be visible. Preferably, when the free oil level reaches from 0.2 to 0.4 percent, chelant salt is added to correct the problem. When the free oil level reaches a level of 0.6 percent by weight, mill entry problems are encountered because of excess lubricity.
  • Example 2 The procedure of Example 1 was followed for a number of successive mill passes. Both aluminum plate and coil were rolled over a period of 7 days. The hardness of the lubricant emulsion gradually increased to about 250 p.p.m., calculated as CaCO At this time 15 gallons of aqueous 38 percent tetrasodium ethylenediaminetetraacetic acid (Na EDTA) was added to bring the hardness level down to 170 p.p.m., calculated as 02100;,. In six more 8-hour shifts of operation, the hardness built up to 200 p.p.m. of (CaCO At this time, 5 gallons of 38 percent Na EDTA were added and the hardness dropped to 180 p.p.m. (as CaCO when sampled and analyzed 24 hours later. This procedure was repeated again after four more 8-hour shifts of operation in which the hardness was adjusted below 200 p.p.m.
  • CaCO tetrasodium ethylenediaminet
  • Example 3 The procedure of Example 1 was followed for a large number of successive mill passes. Some of each of aluminum plate and coil and magnesium plate and coil were rolled interchangeably on the same mill over a period of 15 months.
  • the hardness of the lubricant emulsion gradually increased periodically to about 250 p.p.m., calculated as CaCO Each time the hardness reached such a level of concentration, about 15 gallons of aqueous 38 percent tetrasodium salt of ethylenediaminetetraacetic acid was added to the emulsion to bring the hardness level down to about to 100 p.p.m., expressed as CaCO In each instance the hardness level was reduced so as to maintain hardness within the range of about 100-200 p.p.m., expressed as CaCO Occasionally a SS-gallon drum of soluble oil concentrate containing emulsifying agent was added to the emulsion to make up for base oil taken out by the filter and especially for accidental spillage or sewerage of the emulsion. Water losses
  • the emulsion was filtered using the filter and precoat described in Example 1. During periods of active use, the emulsion was filtered steadily during transfer from the dirty compartment 7 to the clean compartment 6. During such times the filter was back-washed and recoated about every 48 hours.
  • the emulsion remained stable and clean and readily filterable.
  • Theoil globules of thetemulsion remained in stablev form with an average globule diameter in the range of 1 to 2 microns with no globules. larger than about microns.
  • no coalesced or continuous phase of free oil in excess of about 0.2 percent by weight appeared except during accidental leakage into the system of unusually large quantities of hydraulic oil.
  • the lubricating properties of the emulsion were completely satisfactory during this period and the surface quality of the rolled metal was good to excellent throughout the entire period.
  • Example 4 Cold rolling of steel is carried out on a 5-stand tandem mill in which steel sheet is reduced in thickness from about 0.10 to 0.15 inch to about 0.015 to 0.05 inch. During rolling, the steel sheet and the rolls are lubricated by 1000 gallons per minute of an oil-in-water emulsion from a recirculating system containing 15,000 gallons of emulsion. About one gallon of neat oil is applied per 8,000 pounds of metal rolled.
  • the base oil used in making up the emulsion is palm oil.
  • the palm oil is emulsified with standard emulsifiers and constitutes about 3 percent by weight of the emulsion.
  • the emulsion pH is adjusted to about 8.5 and the hardness present in the emulsion is adjusted to about 100 p.p.m., expressed as CaCO by the addition of the requisite amount of the trisoium salt of nitrilotriacetic acid.
  • the emulsion flooding the rolls and cascading over the sheet metal is collected in an underlying sump, pumped to dirty storage, then filtered through a precoated mechanical filter employing a siliceous material for precoating and capable of removing solid particulate matter larger than 1 micron size.
  • the filtered emulsion is collected in clean storage and is again promptly reused in the mill.
  • the emulsion being pumped to the filter is sampled, analyzed, and the requisite additions of the sodium salt of nitriliotriacetic acid are made to maintain the pH of the emulsion in the range of 8.5 to 9.5 and the hardness content of the emulsion in the range of 100 to 200 p.p.m., expressed as CaCO Peri odically, additions of water and of neat soluble oil are made to compensate for losses by evaporation and dragout. Periodic tests show that the oil globule sizes in the emulsion remain stable at an average size of about 15 microns diameter with substantially no globules larger than 40 microns diameter.
  • the emulsion remains stable and substantially free of continuous free oil phase, the oil globule sizes remain stable at about 15 microns diameter, the sheet steel is satisfactorily reduced in thickness in the rolls and the surface of the rolled metal is smooth and bright and substantially free of surface imperfections.
  • Example 5 Cold rolling of brass is carried out on each of a Z-high reversing breakdown mill, a 2-high rundown mill, and a 1'2 W 4-stand tandem finish mill.
  • continuous cast 26 inch wide fiat brass bars each weighing about 3,000 pounds are cold rolled from 3.25 inch thickness to 0.540 inch gauge fiat plate on the breakdown mill.
  • Nine passes and two intermediate anneals are required to accomplish'the reduction in thickness/Throlls and workpieces are lubricated by a'fiow and spray application of 800 gallons per minute of a recirculating, filtered, lubricant-coolant,oil-in-water emulsion from a system containing 16,000 gallons of emulsion.
  • the emulsion has a neat soluble oil concentration of about 12 percent by weight, average oil globule diameters of about 1 to 2 microns, 'a hardness content of 100 to 200 p.p.m., expressed as CaCO and a pH of about 7.8 to 8.5. Hardness and pH are maintained by periodic additions of the trisodium salt of nitrilotriacetic' acid to the e'mul'sion. Overhauling (scalping) removes any' stain that develops on the rolled plate.
  • brass strip is rolled from 0.500 to 0.102 inch thick without annealing.
  • strip is rolled from- 0.102 inch thickness to 0.012 inch gauge with intermediate anneals as necessary.
  • the workpieces and the rolls of each mill are cooled and lubricated with 650 gallons per minute of a recirculating, filtered lubricant-coolant oil-in-Water emulsion from a common system holding 20,000 gallons of emulsion.
  • the emulsion has a neat soluble oil concentration of about 7 percent, an average oil globule diameter in the range of about 5 microns, a hardness content maintained in the range of 25 to p.p.m., expressed as CaCO and a pH of about 7.3 to 7.8.
  • the emulsion is madeup from the soluble oil Prosol 66, supplied by Socony Mobil Vacuum Company, Prosol 66 soluble oil is low in sulfur compounds and is non-staining of copper and copper alloys. Hardness and pH are maintained by periodic additions to the system of the tetramonium salt of ethylenediaminetetraacetic acid. Routine losses of emulsion are made up adding new emulsion to the system.
  • an oil-in-water emulsion containing 1 percent by weight of a soluble oil is supplied to each of 15 grinders at a rate of 20 gallons per minute and lubricates and cools the work pieces and the grinding wheels.
  • the used emulsion flows onto a collecting plate having a central depressioncovered by a coarse screen (0.2 inch screen openings) and piping means draining the collecting plate to a common sump.
  • Emulsion collected in the sump is pumped to a filter employing a microcel membrane which passes particulate no larger than 1 to 2 microns size.
  • Filtered emulsion collects in a clean storage com partment until recirculated to the grindersp
  • the emulsion has an average oil globule diameter in the range of about 1 to 2 microns, a hardness content maintained-in the range of to 200 p.p.m., expressed as CaCO and a pH of about 8.5 to 9.5. Hardness and pH are maintained by periodic additions of the disodium salt of N-2-hydroxyethyliminodiacetic acid. Emulsion losses are made up by the addition of fresh soluble oil and tap water and enough disodium salt of N-Z-hydroxyethyliminodiacetic acid to maintain the said hardness level. After 13 months of operation the emulsion system is clean and stable, the emulsion globule sizes have not substantially changed, and the emulsion remains readily filterable and reusable in the grinding operations.
  • the sodium, potassium, ammonium, and amine salts of each of ethylenediaminetetraacetic acid N-hydroxyethylethylenediaminetriacetic acid, N-2-hydroxyethyliminodiacetic acid, diethylenetriaminepentaacetic acid, nitroltriacetic acid and cyclohexanediaminetetraacetic acid are useful in controlling and maintaining oil-in-water lubricant-coolant emulsions employed in metal shaping operations including rolling, working, drawing, cutting, milling, scalping, drilling, machining and grinding of magnesium, aluminum, copper and ferrous metal.
  • the emulsions managed and reused according to the invention, including fine filtering are further characterized by surprisingly low ion concentrations of metals such as aluminum, iron and silicon, the ion concentrations, respectively, remaining generally below about 1 to 30 p.p.m.
  • metal surfaces in continuous or repeated contact with the present treated emulsions seem to become passivated toward the emulsions so that there is little metal ion uptake.
  • the chelating agents employed tie up substantial proporitons of metal ions in the emulsions which would otherwise react with metal surfaces to provide molecular hydrogen.
  • Molecular hydrogen which has a powerful catalytic effect on the growth of anaerobic bacteria, is largely avoided.
  • initial bacterial growth is largely filtered out so that colonies are not readily established. Removal of metal fines by filtration also removes metal fines which would otherwise contribute to the electrochemical action which provides the undesired molecular hydrogen.
  • Another advantage of the stable emulsions and the method of the invention is the avoidance of the problems associated with (1) cleaning up a system after an emulsion breaks, and (2) starting up a system with a completely new emulsion or after a major addition to a used emulsion.
  • New emulsions need to be used up to 2 weeks before they exhibit really good filterability.
  • a reused lubricant-coolant oil-in-water emulsion that has been employed steadily during a period of at least several months in the shaping of a metal wherein the workpiece and the tool used are contacted with a flowing stream of said emulsion, said emulsion comprising: from about 0.5 to 20 percent by weight of a neat soluble oil, polycarboxylic acid chelant spent with polyvalent metal ions, up to 400 p.p.m. of unchelated hardness, expressed as CaCO and the balance substantially water;
  • said reused emulsion being further characterized by having a pH in the range of about 5 to 11, by the oil phase being in the form of globules having an average diameter in the range of about 1 to 25 microns and substantially no globules having a diameter exceeding about 50' microns, by the emulsion being readily filterable through a mechanical filter, by the emulsion being substantially free of solid particles larger than a predetermined size in the range of 0.5 to 10 microns and by the emulsion being substantially free of continuous free oil phase.
  • the emulsion as in claim 1 substantially free of solid particulate matter above a predetermined size in the range of about 0.5 to 1 micron.
  • polycarboxylic acid chelant is an alkali metal salt, ammonium salt or amine salt of an alkyleneaminopolyacetic acid.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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US589520A 1965-03-29 1966-10-26 Lubricant-coolant emulsion Expired - Lifetime US3409551A (en)

Priority Applications (13)

Application Number Priority Date Filing Date Title
DE19661594398 DE1594398A1 (de) 1965-03-29 1966-01-26 Gleitmittelstabilisierung zur Rueckgewinnung beim Walzen von Aluminium und dessen Legierungen
GB13905/66A GB1118224A (en) 1965-03-29 1966-03-29 Lubricant stabilization of recovery in the rolling of aluminum and its alloys
US589520A US3409551A (en) 1965-03-29 1966-10-26 Lubricant-coolant emulsion
US589730A US3408843A (en) 1965-03-29 1966-10-26 Lubricant-coolant emulsion stabilization and reuse
GR670133300A GR33300B (el) 1966-10-26 1967-01-13 Γαλακτωμα λιπανσεως - ψυξεως.
ES335836A ES335836A1 (es) 1965-03-29 1967-01-19 Un metodo para preparar una emulsion lubricante y refrige- rante de aceite en agua.
DE1594412A DE1594412C3 (de) 1965-03-29 1967-01-19 Öl-in-Wasser-Emulsion
GB3061/67A GB1154303A (en) 1965-03-29 1967-01-20 Lubricant-Coolant Emulsion
NL6701434A NL6701434A (de) 1965-03-29 1967-01-30
FR95076A FR1514458A (fr) 1965-03-29 1967-02-15 Emulsions lubrifiant-réfrigérant utilisées dans le laminage ou d'autres procédés de mise en forme des métaux
SE3197/67A SE342471B (de) 1965-03-29 1967-03-08
NO167488A NO122493B (de) 1965-03-29 1967-03-29
BE705624D BE705624A (de) 1965-03-29 1967-10-25

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US44352865A 1965-03-29 1965-03-29
US589730A US3408843A (en) 1965-03-29 1966-10-26 Lubricant-coolant emulsion stabilization and reuse
US589520A US3409551A (en) 1965-03-29 1966-10-26 Lubricant-coolant emulsion

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DE (2) DE1594398A1 (de)
ES (1) ES335836A1 (de)
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GB (2) GB1118224A (de)
NL (1) NL6701434A (de)
NO (1) NO122493B (de)
SE (1) SE342471B (de)

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US3783664A (en) * 1971-01-13 1974-01-08 Alcan Res & Dev Process for control of lubricants in an aluminium rolling mill
US4027512A (en) * 1976-05-04 1977-06-07 The Dow Chemical Company Lubricant-coolant emulsion additive for metal working operations
DE2732142A1 (de) * 1977-07-15 1979-01-18 Dow Chemical Co Zusatzstoff fuer eine schmiermittel- kuehlmittel-emulsion
US4202193A (en) * 1978-10-03 1980-05-13 National Steel Corporation Apparatus for controlling the concentration and stability of an emulsion
US5611636A (en) * 1993-07-13 1997-03-18 Flory; John F. Tension member termination with segmented potting socket and central passage
US6435198B2 (en) * 1994-05-16 2002-08-20 Masco Corporation Of Indiana System for cooling and washing a part formed in a metal forming machine
US7074338B2 (en) * 2004-10-01 2006-07-11 Kabushiki Kaisha Nikuni Filtering method and filtering device
US20150027187A1 (en) * 2011-12-29 2015-01-29 Sms Siemag Aktiengesellschaft Method and device for rolling stock and use of a cooling lubricant

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BE758537A (fr) * 1969-11-05 1971-05-05 Dow Chemical Co Procede de filtration d'agents de nettoyage a base de metaux alcalins
US3756052A (en) * 1971-12-27 1973-09-04 Dow Corning Metal working lubricant
US3750847A (en) * 1972-05-03 1973-08-07 Master Chemical Corp Method of supplying an aqueous cutting fluid to machine tools
ZA741228B (en) * 1973-03-02 1975-01-29 Ici Ltd Filtration
US3846319A (en) * 1973-03-27 1974-11-05 Chevron Res Dioxan-containing aluminum lubricant
CH625829A5 (en) * 1976-09-01 1981-10-15 Nat Res Lab Stabilised fluid composition usable for metal machining
DE2736874C2 (de) * 1977-08-16 1987-03-26 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur Erleichterung der Kaltumformung von Metallen
JPS5841083B2 (ja) * 1978-10-05 1983-09-09 日産自動車株式会社 水溶性切削剤の再生方法
US4377487A (en) * 1978-10-31 1983-03-22 Occidental Chemical Corporation Metal coating process and compositions
EP0019670B1 (de) * 1979-05-23 1983-06-22 Glyco Chemicals, Inc. Antimikrobielle Zusammensetzungen, Verfahren zum Hemmen des Wachstums von Mikroorganismen und diese antimikrobiellen Zusammensetzungen enthaltende fliessfähige Metallbearbeitungs-Zusammensetzungen
DE3247426A1 (de) * 1982-12-22 1984-06-28 Merck Patent Gmbh, 6100 Darmstadt Schneidoel fuer die spangebende bearbeitung von buntmetallen
DE3447346A1 (de) * 1984-12-24 1986-06-26 Dow Corning GmbH, 8000 München Schmierstoff fuer wasserarmaturen, wie wasserhaehne und dergleichen
EP0332788B1 (de) * 1988-03-17 1992-07-22 Societe Des Ceramiques Techniques Verfahren zur Behandlung verunreinigter Öl-in-Wasser-Emulsionen oder-Mikroemulsionen
FR2628749B1 (fr) * 1988-03-17 1993-10-22 Cgee Alsthom Procede de traitement des emulsions ou des microemulsions d'huile dans l'eau polluees
US6275512B1 (en) 1998-11-25 2001-08-14 Imra America, Inc. Mode-locked multimode fiber laser pulse source
US7569526B2 (en) * 2003-04-08 2009-08-04 Crompton Corporation Anti-oxidants in soluble oil base for metal working fluids
US20070048343A1 (en) * 2005-08-26 2007-03-01 Honeywell International Inc. Biocidal premixtures
WO2011117892A2 (en) 2010-03-25 2011-09-29 Indian Oil Corporation Ltd. Composition of oil for high speed thin and thick gauge steel sheet rolling in tandem mills
CN109201757A (zh) * 2018-09-30 2019-01-15 泰安市国士环保科技有限公司 一种轧钢废油的处理方法
CN110257154B (zh) * 2019-05-30 2022-08-02 山西太钢不锈钢股份有限公司 轧制润滑液基础油的制备方法
CN118616695B (zh) * 2024-08-12 2024-10-11 贵州贵铝新材料股份有限公司 一种铝合金加工用循环冷却水自动控制系统

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3783664A (en) * 1971-01-13 1974-01-08 Alcan Res & Dev Process for control of lubricants in an aluminium rolling mill
US4027512A (en) * 1976-05-04 1977-06-07 The Dow Chemical Company Lubricant-coolant emulsion additive for metal working operations
DE2732142A1 (de) * 1977-07-15 1979-01-18 Dow Chemical Co Zusatzstoff fuer eine schmiermittel- kuehlmittel-emulsion
US4202193A (en) * 1978-10-03 1980-05-13 National Steel Corporation Apparatus for controlling the concentration and stability of an emulsion
US5611636A (en) * 1993-07-13 1997-03-18 Flory; John F. Tension member termination with segmented potting socket and central passage
US6435198B2 (en) * 1994-05-16 2002-08-20 Masco Corporation Of Indiana System for cooling and washing a part formed in a metal forming machine
US7074338B2 (en) * 2004-10-01 2006-07-11 Kabushiki Kaisha Nikuni Filtering method and filtering device
US20150027187A1 (en) * 2011-12-29 2015-01-29 Sms Siemag Aktiengesellschaft Method and device for rolling stock and use of a cooling lubricant
US9700924B2 (en) * 2011-12-29 2017-07-11 Sms Group Gmbh Method and device for rolling stock and use of a cooling lubricant

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DE1594412C3 (de) 1979-05-10
SE342471B (de) 1972-02-07
DE1594398A1 (de) 1970-08-06
GB1118224A (en) 1968-06-26
NO122493B (de) 1971-07-05
DE1594412B2 (de) 1973-06-20
ES335836A1 (es) 1968-03-16
GB1154303A (en) 1969-06-04
US3408843A (en) 1968-11-05
DE1594412A1 (de) 1970-11-05
NL6701434A (de) 1968-04-29
FR1514458A (fr) 1968-02-23
BE705624A (de) 1968-04-25

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