EP3508561A1 - Für metallbearbeitungsanwendungen nützliche, mizellare emulsionen - Google Patents

Für metallbearbeitungsanwendungen nützliche, mizellare emulsionen Download PDF

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Publication number
EP3508561A1
EP3508561A1 EP18150506.6A EP18150506A EP3508561A1 EP 3508561 A1 EP3508561 A1 EP 3508561A1 EP 18150506 A EP18150506 A EP 18150506A EP 3508561 A1 EP3508561 A1 EP 3508561A1
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EP
European Patent Office
Prior art keywords
emulsion
sulfurized
fluid
disclosure
surfactants
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.)
Withdrawn
Application number
EP18150506.6A
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English (en)
French (fr)
Inventor
Andre Antonius Maria HENDRIKSEN
Hendrik Percy PESCHEL
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Castrol Ltd
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Castrol Ltd
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Publication date
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Priority to EP18150506.6A priority Critical patent/EP3508561A1/de
Priority to PCT/EP2019/050256 priority patent/WO2019134999A1/en
Publication of EP3508561A1 publication Critical patent/EP3508561A1/de
Withdrawn legal-status Critical Current

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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
    • C10M173/00—Lubricating compositions containing more than 10% water
    • C—CHEMISTRY; METALLURGY
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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
    • C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/022—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least two hydroxy groups
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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
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/128—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof
    • C—CHEMISTRY; METALLURGY
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/288—Partial esters containing free carboxyl groups
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/108—Polyethers, i.e. containing di- or higher polyoxyalkylene groups etherified
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08—Amides
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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
    • C10M2219/022—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
    • 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
    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/024—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of esters, e.g. fats
    • 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
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/055—Particles related characteristics
    • C10N2020/06—Particles of special shape or size
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/18—Anti-foaming property
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/24—Emulsion properties
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/76—Reduction of noise, shudder, or vibrations
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    • 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
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    • 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
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    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/01—Emulsions, colloids, or micelles
    • C10N2050/011—Oil-in-water
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    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/01—Emulsions, colloids, or micelles
    • C10N2050/013—Water-in-oil
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    • C10N2070/00—Specific manufacturing methods for lubricant compositions

Definitions

  • micellar emulsions This disclosure relates generally to micellar emulsions. This disclosure relates more particularly to micellar emulsions useful as metalworking fluids and as concentrates therefor, methods for preparing such emulsions, and methods of using such emulsions.
  • Metalworking fluids find many applications within the metalworking industry. They are typically used in destructive metalworking (i.e., applications in which material is substantially removed from the workpiece, such as in the form of chips or other particles, such as milling or grinding) and in deformation metalworking (i.e., applications in which material is not substantially removed from the workpiece, such as rolling).
  • a metalworking fluid is often used in a metalworking process, for example, at a surface between a tool and a workpiece.
  • Known metalworking fluids are generally emulsions comprising common constituents: an aqueous component, and an oleaginous component and a surfactant dispersed in the aqueous component.
  • Such oleaginous components are typically derived from hydrocarbon sources, for example, the hydrocarbons resulting from refining of crude oil or shale oil, or the hydrocarbons resulting from esterification.
  • aqueous components and oleaginous components used in metalworking fluids are naturally immiscible. Therefore, stable incorporation of aqueous components into an oleaginous base or oleaginous components into an aqueous base generally involves the use of emulsifiers such as surfactants to create an emulsion.
  • emulsifiers such as surfactants
  • defoamers or anti-foam compounds are often used in such fluids.
  • a popular class of defoamers / anti-foam compounds for use with metalworking fluids are those having a silicon component. These compounds-typically water insoluble-are also insoluble in the metalworking fluid precursors or in the final, diluted metalworking fluid. Therefore, although they are useful in reducing the foaming of the metalworking fluid in use, these components create solubility and stability issues in the final emulsion.
  • emulsions suitable for use as metalworking fluids as complete, stable emulsions without the use of defoamers, anti-foaming compounds, and/or excess or additional surfactants.
  • emulsions with no residual immiscible components.
  • Such emulsions should be stable with no separation of the individual components during storage or use.
  • the user Prior to using the conventional metalworking fluids in metalworking applications, the user generally dilutes them prior to use. Thus, it would also be advantageous to provide the metalworking fluid emulsions that can be used in lower concentrations, without losing lubrication performance. Such emulsions would be more cost effective and sustainable than the conventional metalworking fluids.
  • the present inventors have noted that, while surfactants have to be provided in an amount that is sufficient ensure the complete emulsification of the components, using too much surfactant can result in foaming of the emulsified mixture, either immediately on mixing or during use.
  • the present inventors have found simple, cost-efficient, and sustainable emulsions that do not require the use of excess surfactants and/or defoamers and anti-foaming compounds.
  • the emulsions of the disclosure can, for example, also provide improved lubrication performance, for example on aluminum alloys, even at lower concentrations as compared to commercially available metalworking fluids.
  • an emulsion including:
  • the one or more oleaginous materials are present in the emulsion (e.g., in the micelles).
  • the emulsions can be provided in relatively concentrated form, suitable, for example, for use as a top-treat additive, or a concentrate suitable for dilution to provide a metalworking fluid.
  • the emulsions can be provided in relatively dilute form, suitable, for example, for use as a metalworking fluid.
  • the one or more oleaginous materials are not substantially present in the emulsion.
  • the emulsions can be provided in relatively concentrated form, suitable, for example, as use as a top-treat additive.
  • the one or more oleaginous materials may be present in the emulsion, but are not substantially present in micelles together with the sulfurized additive.
  • Such emulsions can be provided in a relatively dilute form, for example, having the sulfurized additive-containing micelles present together with micelles containing one or more oleaginous materials.
  • Such materials can be formed by top-treating an existing metalworking fluid (i.e., which contains micelles containing one or more oleaginous materials).
  • the one or more surfactants is substantially bound into the micelles.
  • the emulsion is substantially free of defoamers and anti-foam compounds.
  • a method for providing a top-treated metalworking fluid includes providing an existing metalworking fluid (e.g., containing a plurality of micelles including one or more oleaginous materials) and combining it with an emulsion of the disclosure.
  • an existing metalworking fluid e.g., containing a plurality of micelles including one or more oleaginous materials
  • Another aspect of the disclosure provides a method for preparing a metalworking fluid, including combining an emulsion of the disclosure with an aqueous fluid.
  • the aqueous fluid can be, for example, water or some aqueous solution, or alternatively can be an existing metalworking fluid (e.g., a metalworking fluid that is partially spent, thus top-treating the other metalworking fluid).
  • Another aspect of the disclosure provided a method of working a metal, the method including contacting a surface of a metal article with a metalworking fluid of the disclosure; and forming the surface of the metal article to a desired shape while in contact with the metalworking fluid.
  • Another aspect of the disclosure provides a method of preparing an emulsion (e.g., an emulsion as described herein), the method comprising:
  • Another aspect of the disclosure provides a method of preparing an emulsion (e.g., an emulsion as described herein), the method comprising:
  • Another aspect of the disclosure provides a method of preparing an emulsion (e.g., an emulsion as described herein), the method comprising:
  • each embodiment disclosed herein can comprise, consist essentially of or consist of its particular stated element, step, ingredient or component.
  • the transition term “comprise” or “comprises” means includes, but is not limited to, and allows for the inclusion of unspecified elements, steps, ingredients, or components, even in major amounts.
  • the transitional phrase “consisting of” excludes any element, step, ingredient or component not specified.
  • the transition phrase “consisting essentially of” limits the scope of the embodiment to the specified elements, steps, ingredients or components and to those that do not materially affect the embodiment.
  • the term "about” has the meaning reasonably ascribed to it by a person skilled in the art when used in conjunction with a stated numerical value or range, i.e., denoting somewhat more or somewhat less than the stated value or range, to within a range of ⁇ 20% of the stated value; ⁇ 19% of the stated value; ⁇ 18% of the stated value; ⁇ 17% of the stated value; ⁇ 16% of the stated value; ⁇ 15% of the stated value; ⁇ 14% of the stated value; ⁇ 13% of the stated value; ⁇ 12% of the stated value; ⁇ 11% of the stated value; ⁇ 10% of the stated value; ⁇ 9% of the stated value; ⁇ 8% of the stated value; ⁇ 7% of the stated value; ⁇ 6% of the stated value; ⁇ 5% of the stated value; ⁇ 4% of the stated value; ⁇ 3% of the stated value; ⁇ 2% of the stated value; or ⁇ 1% of the stated value.
  • the disclosed materials and methods, and apparatus provide improvements in emulsions (for example, suitable for use as metalworking fluid) that can, in various embodiments, be cost-efficient and sustainable, and provide good lubrication properties.
  • the emulsions of the disclosure do not include excess surfactant not bound up in micelles.
  • the emulsions of the disclosure need not include defoamers and anti-foaming compounds.
  • the emulsions of the disclosure can also, in certain embodiments, provide improved lubrication performance, for example on aluminum alloys, even at lower concentrations as compared to commercially available metalworking fluids.
  • an emulsion including:
  • the disclosure also provides an emulsion including:
  • the emulsion is substantially free of non-sulfurized oleaginous materials.
  • This emulsion can be formed, e.g., at relatively low water concentration suitable for use as a top-treat additive to be added to an existing metalworking fluid.
  • the emulsion may be referred to as a "top-treat" emulsion.
  • the one or more oleaginous materials may be present in the emulsion, but are not substantially present in micelles together with the sulfurized additive.
  • Such emulsions can be provided in a relatively dilute form, for example, having the sulfurized additive-containing micelles present together with micelles containing one or more oleaginous materials.
  • Such materials can be formed by top-treating an existing metalworking fluid (i.e., which contains micelles containing one or more oleaginous materials).
  • the emulsion is substantially free of defoamers and anti-foam compounds.
  • the present inventors have determined that the emulsification techniques described herein can provide emulsions that are not highly susceptible to foaming, despite not including substantial amounts of defoamers/anti-foam compounds.
  • the emulsion of the disclosure comprises no more than 2 wt % of the one or more one or more defoamers and anti-foam compounds based on the total weight of the emulsion, e.g., no more than 1 wt %, or no more than 0.5 wt %, or no more than 0.1 wt %, or no more than 0.01 wt %, or no more than 0.005 wt %, or even no more than 0.001 wt %.
  • Typical anti-foam/defoamer compositions used commonly used in metalworking fluids include organo-modified siloxane antifoams, PDMS (polydimethylsiloxane) antifoams, and wax defoamers. Both organo-modified siloxane antifoams and PDMS antifoams are based on a poly-siloxane backbone. In a PDMS antifoam, only methyl groups and oxygen are bonded at the silicon atom. In organo-modified siloxane antifoams, organic side chains (such as copolymers of ethylene-/propylene-oxide are chemically bonded to the polysiloxane backbone.
  • Typical wax defoamers include, but are not limited to, ethylene bis stearamide (EBS), paraffin waxes, ester waxes, and fatty alcohol wax.
  • EBS ethylene bis stearamide
  • paraffin waxes paraffin waxes
  • ester waxes ester waxes
  • fatty alcohol wax ethylene bis stearamide
  • the emulsion of the disclosure comprises no more than 1 wt % total of organo-modified siloxane antifoams, PDMS (polydimethylsiloxane) antifoams, and wax defoamers, or no more than 2 wt % of the one or more one or more defoamers and anti-foam compounds based on the total weight of the emulsion, e.g., no more than 1 wt %, or no more than 0.5 wt %, or no more than 0.1 wt %, or no more than 0.01 wt %, or no more than 0.005 wt %, or even no more than 0.001 wt %.
  • a metalworking fluid of the disclosure there can be defoamers and anti-foam compounds present, for example, arising from a metalworking fluid to which a top-treat emulsion as described herein is added.
  • the present inventors have determined that in certain embodiments the emulsions described herein can have substantially low foaming properties, even in the absence of defoamers and anti-foam additives.
  • the foaming performance of a material can be quantified using a comparative laboratory test. In the test to quantify foam performance, a graduated cylinder is filled halfway with an emulsion as described herein. Once the emulsion has settled in the cylinder it is inspected to determine whether there is any separation between the components of the emulsion and whether any foam is generated.
  • FIG. 3 The results of using such a test method are illustrated in FIG. 3 .
  • a graduated cylinder was partially filled with (A) a dilution of an emulsion according to one embodiment of the disclosure prepared by the methods disclosed herein, or (B) a dilution of a composition prepared by single vessel batch blending.
  • Both (A) and (B) are 5 wt% aqueous dilutions of materials containing an identical combination of oleaginous materials, surfactants, and sulfurized additives, differing only in the way they were made.
  • the emulsion of the disclosure (A) prepared by the methods disclosed herein shows no foaming.
  • the non-emulsified composition (B) obtained by single vessel batch blending shows significant foaming and emulsion instability.
  • an emulsion in accordance with certain embodiments of the disclosure can result in there being virtually no foam (i.e., such emulsion is substantially free of foam), even in cases where there is substantially no defoamer or anti-foam compound present, as the generation of micelles in such an emulsion is highly efficient.
  • the emulsions according to certain embodiments of the disclosure can provide for substantially no foam formation. Accordingly, in certain embodiments of the metalworking methods as described herein, no foam is visible on the surface of the workpiece.
  • the emulsions of the disclosure include water.
  • the water is desirably present in a substantial amount, for example, at least about 8 wt%, or at least about 10 wt%, or at least about 15 wt%, at least about 20 wt%, at least about 30 wt%, or even at least about 40 wt%, of the emulsion.
  • water is present in an amount of at least about 50 wt%, at least about 60 wt%, or even at least about 70 wt% of the emulsion.
  • water is present in an amount of at least about 80 wt%, at least about 90 wt%, or even at least about 95 wt% of the emulsion.
  • the amount of water used will depend on whether the emulsion is itself a metalworking fluid, in which case relatively high amounts of water may be used, or rather whether the emulsion is to be used as a concentrate or top-treat additive for a metalworking fluid, in which case, relatively low amounts of water may be used; based on the disclosure herein, the person of ordinary skill in the art will provide an appropriate water concentration for a desired use. Moreover, the person of ordinary skill in the art will appreciate that a variety of additives can be present; certain such additives can be dissolved in the water phase.
  • the amount of water can be, e.g., in the range of 8 wt% to 60 wt%.
  • the amount of water is in the range of about 8 wt% to about 50 wt%, or about 8 wt% to about 40 wt%, or about 8 wt% to about 30 wt%, or about 8 wt% to about 20 wt%, or about 8 wt% to about 15 wt%, or about 10 wt% to about 50 wt%, or about 10 wt% to about 40 wt%, or about 10 wt% to about 30 wt%, or about 10 wt% to about 20 wt%, or about 10 wt% to about 15 wt%, or about 15 wt% to about 50 wt%, or about 15 wt% to about 40 wt%, or about
  • the amount of water can be, e.g., at least about 60 wt%, at least about 70 wt%, at least about 80 wt%, at least about 90 wt%, at least about 95 wt%, or even at least about 97 wt%.
  • the amount of water is in the range of about 60 wt% to about 99%, or about 70 wt% to about 99 wt%, or about 80 wt% to about 99 wt%, or about 90 wt% to about 99 wt%, or about 95 wt% to about 99 wt%, or about 97 wt% to about 99 wt%, or about 60 wt% to about 98%, or about 70 wt% to about 98 wt%, or about 80 wt% to about 98 wt%, or about 90 wt% to about 98 wt%, or about 95 wt% to about 98 wt%.
  • certain emulsions of the disclosure comprise one or more oleaginous materials.
  • the oleaginous material is oily, oil-based, or oil-containing material.
  • the oleaginous material may be a lubricating composition.
  • Lubricating composition may be a fully formulated lubricant or may be a blend of components, wherein at least one component has lubricating properties.
  • a fully formulated lubricant is typically based on a lubricating base oil stock.
  • Many different lubricating base oils are known, including, but not limited to, synthetic oils, natural oils, or mixtures thereof. Base oils may also be used in refined or in unrefined state (i.e., with or without at least one purification step).
  • Natural oil includes, but is not limited to, vegetable oil, paraffinic oil, naphthenic oils, paraffinic-naphthenic oil, petroleum oil, treated (e.g., solvent, acid, or distillates derived) paraffinic, naphthenic, or asphaltic oil, and oils derived from coal or shale.
  • Synthetic oil includes, but is not limited to, hydrocarbon oil and halo-substituted hydrocarbon oil (such as polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(I-hexenes), poly(I-octenes), poly(I-decenes), dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl) benzenes, biphenyls, terphenyls, alkylated polyphenyls, alkylated diphenyl ethers, alkylated diphenyl sulfides, etc.), polyalphaolefins (PAOs), the linear or branched C 10 -C 18 alkanes, the linear or branched haloalkanes, polyhaloalkanes, perhaloalkanes, cycl
  • Base oil stock categories have been defined by the American Petroleum Institute (API Publication 1509) providing a set of guidelines for all lubricant base oils. These are shown in Table 1.
  • the lubricating composition is a Group I, II, II, IV, or V base oil as defined by the American Petroleum Institute (API Publication 1509).
  • Table 1 Base Oil Stocks API Guidelines Saturates Sulphur content Viscosity Index (VI) Group I ⁇ 90 and/or >0.03% and ⁇ 80 and ⁇ 120 Group II ⁇ 90 and ⁇ 0.03% and ⁇ 80 and ⁇ 120 Group III ⁇ 90 and ⁇ 0.03% and ⁇ 120 Group IV Includes polyalphaolefins (PAO) and GTL (gas-to-liquid) products Group V All other base oils not included in Groups I, II, III or IV
  • Group II and/or Group III base oils are wells known base oils.
  • Group III oil base stock tend to be highly paraffinic with saturates higher than 90%, a viscosity index over 125, low aromatic content (less than 3%), and an aniline point of at least 118.
  • PAOs are typically derived from C 6 , C 8 , C 10 , C 12 , C 14 , and C 16 olefins or mixtures thereof and have a viscosity index greater than 135.
  • PAOs can be manufactured by catalytic oligomerisation (polymerisation to low molecular weight products) of linear ⁇ -olefin (otherwise known as LAO) monomers. This leads to the presence of two classes of materials, PAOs and HVI-PAOs (high viscosity index PAOs), with PAOs being formed in the presence of a catalyst such as AlCl 3 or BF 3 , and HVI-PAOs being formed using a Friedel-Crafts catalyst or a reduced chromium catalyst.
  • a catalyst such as AlCl 3 or BF 3
  • HVI-PAOs high viscosity index PAOs
  • Esters also form a useful base oil stock, including synthetic esters, as do GTL (gas-to-liquid) materials, particularly those derived from a hydrocarbon source.
  • GTL gas-to-liquid
  • the esters of dibasic acids with monoalcohols, or the polyol esters of monocarboxylic acid may be useful in the emulsions of the disclosure.
  • Such esters should typically have a viscosity of less than 10,000 cP at -35°C, in accordance with ASTM D5293.
  • the base oil will comprise one or more of esters and one or more of natural oils (such as paraffin oil).
  • the one or more oleaginous materials is a naphthenic oil.
  • the one or more oleaginous materials is an ester base oil stock.
  • the emulsion includes the one or more oleaginous materials in an amount up to about 70 wt% based on the total weight of the emulsion.
  • the one or more oleaginous materials is present in an amount up to about 50 wt%, or up to about 30 wt%, or up to about 15 wt%, or up to about 10 wt%, or up to about 5 wt%, or up to about 3 wt%, or up to about 2 wt%.
  • the one or more oleaginous materials is present in an amount of 15 wt% to 70 wt%, for example, 20 wt% to 70 wt%, or 25 wt% to 70 wt%, or 30 wt% to 70 wt%, or 40 wt% to 70 wt%, or 15 wt% to 50 wt%, or 20 wt% to 50 wt%, or 25 wt% to 50 wt%, or 30 wt% to 50 wt%.
  • the oleaginous materials can be, for example, present in the micelles with the sulfurized additive, present in micelles different from those in which the sulfurized additive is disposed, or a combination thereof.
  • the one or more oleaginous materials is present in an amount in the range of 0.5 wt% to 15 wt%, e.g., 0.5 wt% to 10 wt%, or 0.5 wt% to 5 wt%, or 0.5 wt% to 3 wt%, or 0.5 wt% to 2 wt%, or 0.5 wt% to 1.5 wt%, or 1 wt% to 15 wt%, or 1 wt% to 10 wt%, or 1 wt% to 5 wt%, or 1 wt% to 3wt%.
  • compositions and methods of the present disclosure can allow for the use of relatively low amounts of oleaginous materials in a metalworking fluid.
  • the oleaginous materials can be, for example, present in the micelles with the sulfurized additive, present in micelles different from those in which the sulfurized additive is disposed, or a combination thereof.
  • the emulsion when the emulsion is to be used as a top-treat additive, there is substantially no non-sulfurized oleaginous material in the emulsion.
  • the one or more oleaginous materials are present in the micellar emulsion (e.g., in the micelles with the sulfurized additive).
  • the one or more oleaginous materials may be a heavy mineral oil basestock.
  • the oleaginous materials of the disclosure may have various viscosities depending on the end application of the emulsion of the disclosure.
  • one or more oleaginous materials has a kinematic viscosity at 40 °C of up to 12000 cSt, e.g., 8000 to about 12000 cSt, or about 8000 to about10000 cSt, or about 8000 to about 9000 cSt, or about 1 to about 8000 cSt, or about 1 to about 7000 cSt, or about 1 to about 6000 cSt, or about 1 to 5000 cSt or about 1 to about 4000 cSt, or about 1 to about 3000 cSt, or about 1 to about 2000 cSt, or about 1 to about 1000 cSt, as measured in accordance with ASTM D455.
  • the oleaginous materials of the disclosure may have high or very high viscosity index (VI), depending on the end application of the emulsion of the disclosure.
  • VI is a measure for the change of viscosity if the oil with variations in temperature. The lower the VI, the greater the change of viscosity of the oil with temperature.
  • one or more oleaginous materials has viscosity index of up to 120. In certain embodiments of the emulsions as otherwise described herein, one or more oleaginous materials has viscosity index of between 80 and 120.
  • the emulsions of the disclosure include one or more surfactants.
  • the one or more surfactants is substantially bound into the micelle.
  • no more than 1 wt % of the one or more surfactants is present in the emulsion in an unbound state (i.e., not part of a micelle), based on the total weight of the emulsion.
  • no more than 0.5 wt %, or no more than 0.1 wt %, or no more than 0.05 wt %, or even no more than 0.01 wt % is present in the emulsion in an unbound state, based on the total weight of the emulsion.
  • the point at which an emulsion becomes substantially free of excess surfactant can be determined by measuring the surface tension of the emulsion. Once the critical micelle concentration has been reached, and no more surfactant molecules are included in the surface layer(s), the surface tension of the emulsion exhibits a discontinuity. This may be detected by surface tension measurement techniques known to those skilled in the art. Other techniques for determining this point include nuclear magnetic resonance (NMR) techniques and optical scattering techniques. These include those taught in James-Smith et al, Journal of Colloid and Interface Science, 310: 590-598 (2007 ).
  • NMR nuclear magnetic resonance
  • Surfactants suitable for use in the embodiments of the disclosure include ionic surfactants, non-ionic surfactants, or combinations thereof.
  • the main surfactant component may be a non-ionic surfactant and the minor surfactant component may be an ionic surfactant.
  • ionic surfactants include, but are not limited to, potassium oleate, sodium laurate, potassium stearate, potassium caprolate, sodium palmitate, tetracosenyl benzene sulfonate, sodium nonylbenzene sulfonate and potassium dodecylbenzene sulfonate, sodium dodecyl sulfate, sodium dihexyl sulfosuccinate and sodium dioctyl sulfosuccinate, dodecyl ammonium hydrochloride, dodecyl trimethyl quaternary ammonium chloride, ethoxylated fatty amines, etc.
  • non-ionic surfactant examples include, but are not limited to, saturated and unsaturated C 16 - C 18 fatty esters, C 16 - C 18 fatty alcohol ethoxylates - with an ethoxylation range of 0-9 moles (fatty alcohol polyglycol ethers), C 16 -C 18 fatty alcohol ethoxylate and propoxylate, C 16 -C 18 fatty acid ethoxylates and propoxylates, C 6 /C 8 /C 16-18 alkyl polyoxyethylene ether carboxylic acids with a 2 to 9 mole ethoxylation range, alkyl ether ethoxylate mono phosphate esters - alkyl chain C 16 -C 18 , with a 2 to 5 mole ethoxylation range, ethoxylated oleine with a 6/9 mole ethoxylation range, ethoxylated castor oils, and polyethylene glycol esters of C 16 -C 18 fatty acids).
  • the emulsions of the disclosure include one surfactant. In certain embodiments, the emulsions of the disclosure include at least two different surfactants.
  • the choice of suitable surfactant will depend on the desired hydrophilic-lipophilic balance (HLB) value.
  • HLB hydrophilic-lipophilic balance
  • the one or more surfactants has an average HLB value of about 8 to about 16, e.g., from about 8 to about 14, or from about 9 to about 12, or from about 10 to about 16, or from about 12 to about 16.
  • the emulsions of the disclosure include one or more surfactants selected from saturated and unsaturated C 16 - C 18 fatty esters, C 16 - C 18 fatty alcohol ethoxylates, alkyl ether ethoxylate mono phosphate esters, C 16 -C 18 fatty acid ethoxylates and propoxylates, and ethoxylated castor oils.
  • the emulsions of the disclosure include one or more surfactants in an amount within the range of about 0.1 wt% to about 10 wt% based on the total weight of the emulsion.
  • the one or more surfactants is present in an amount of about 0.01 wt% to about 8 wt%, or about 0.01 wt% to about 5 wt%, or about 0.01 wt% to about 2 wt%, or about 0.01 wt% to about 1 wt%, or about 0.1 wt% to about 10 wt%, or about 0.1 wt% to about 8 wt%, or about 0.1 wt% to about 5 wt%, or about 0.1 wt% to about 2 wt%, or about 0.1 wt% to about 1 wt%, or about 0.2 wt% to about 10 wt%, or about 0.2
  • the emulsions of the disclosure include one or more additives selected from sulfurized fatty acid esters, sulfurized fatty oil, sulfurized and polymerized fatty esters, and sulfurized polyolefins
  • the emulsion comprises one or more sulfurized additives in a total amount within the range of about 0.1 wt% to about 80 wt% based on the total weight of the emulsion.
  • the one or more sulfurized additives are present in an amount in the range of about 10 wt% to about 80 wt%, e.g., about 10 wt% to 70 wt%, or about 10 wt% to 60 wt%, or about 10 wt% to 50 wt%, or about 10 wt% to about 40 wt%, or about 10 wt% to about 30 wt%, or about 20 wt% to about 80 wt%, or about 20 wt% to about 70 wt%, or about 20 wt% to about 60 wt%, or about 20 wt% to about 50 wt%, or about 20 wt%
  • the one or more sulfurized additives are present in an amount in the range of about 0.1 wt% to about 10 wt%, e.g., about 0.2 wt% to about 10 wt%, or about 0.5 wt% to about 10 wt%, or about 1 wt% to about 10 wt%, or about 2 wt% to about 10 wt%, or about 0.1 wt% to about 5 wt%, or about 0.2 wt% to about 5 wt%, or about 0.5 wt% to about 5 wt%, or about 1 wt% to about 5 wt%, or about 2 wt% to about 5 wt%, or about 0.1 wt% to about 2 wt%, or about 0.2 wt% to about 2 wt%, or about 0.5 wt% to about 2 wt%, based on the total weight of the e
  • the one or more sulfurized additives is selected from sulfurized fatty acid esters.
  • the person of ordinary skill in the art will identify a suitable sulfurized fatty acid ester for use in a particular composition.
  • the sulfurized fatty acid esters may be sulfurized saturated or unsaturated C 8 - C 22 fatty esters.
  • Examples of sulfurized fatty acid esters include those sold under the names Roscan 278 and 389 (available from PCAS, Longjumeau, France), those sold under names RC2811 and RC 5250 (available from RheinChemie, Mannheim, Germany), and those sold under names DeoAdd LR11H, VP 332-1, VP 332-2, and VP-288 (available from DOG-Chemie, Hamburg, Germany).
  • the sulfurized fatty acid ester of the disclosure may have, for example, a total sulfur content of between about 1 wt% and about 40 wt%, e.g., about 1 wt% to about 30 wt%, or about 1 wt% to about 25 wt%, or about 1 wt% to about 20 wt%, or about 1 wt% to about 15 wt%, or about 1 wt% to about 10 wt%, or about 10 wt% to about 40 wt%, or about 10 wt% to about 30 wt%, or about 10 wt% to about 25 wt%, or about 10 wt% to about 20 wt%, or about 10 wt% to about 15 wt%.
  • the total sulfur content is measured using the ASTM D 1552 (LECO) test method.
  • One particular sulfurized ester has the following characteristics: Sulfur content approx. 14.5 wt% (ASTM D 1552 (LECO)), density @ 15 °C 1.00 - 1.05 g/mL (DIN EN ISO 12185), viscosity (kinematic) @ 40 °C approx.. 5000 (DIN 51562 Part 1).
  • the emulsion includes one or more sulfurized fatty acid esters in a total amount within the range of about 0.1 wt% to about 80 wt% based on the total weight of the emulsion.
  • the one or more sulfurized additives are present in an amount in the range of about 10 wt% to about 80 wt%, e.g., about 10 wt% to 70 wt%, or about 10 wt% to 60 wt%, or about 10 wt% to 50 wt%, or about 10 wt% to about 40 wt%, or about 10 wt% to about 30 wt%, or about 20 wt% to about 80 wt%, or about 20 wt% to about 70 wt%, or about 20 wt% to about 60 wt%, or about 20 wt% to about 50 wt%, or about 20 wt%
  • the one or more sulfurized additives are present in an amount in the range of about 0.1 wt% to about 10 wt%, e.g., about 0.2 wt% to about 10 wt%, or about 0.5 wt% to about 10 wt%, or about 1 wt% to about 10 wt%, or about 2 wt% to about 10 wt%, or about 0.1 wt% to about 5 wt%, or about 0.2 wt% to about 5 wt%, or about 0.5 wt% to 5 wt%, or about 1 wt% to about 5 wt%, or about 2 wt% to about 5 wt%, or about 0.1 wt% to about 2 wt%, or about 0.2 wt% to about 2 wt%, or about 0.5 wt% to about 2 wt%, based on the total weight of the emulsion
  • one or more of (e.g., each of) the one or more sulfurized additives has a kinematic viscosity at 40 °C of at least 1000 cSt.
  • one or more of (e.g., each of) the one or more sulfurized additives has a kinematic viscosity at 40 °C of at least 2000 cSt, or at least 4000 cSt, or about 4000 to about 50000 cSt, or about 4000 to about 25000 cSt, or about 4000 to about 20000 cSt, or about 4000 to about 10000 cSt, or about 5000 to about 50000 cSt, or about 5000 to about 25000 cSt, or about 5000 to about 20000 cSt, or about 5000 to about 10000 cSt.
  • kinematic viscosities are measured in accordance with ASTM D455.
  • the ratio of the amount of oleaginous material and the one or more sulfurized additives selected from sulfurized fatty acid esters, sulfurized fatty oil, sulfurized and polymerized fatty esters, and sulfurized polyolefins to the amount of surfactant will be a factor that determines the micelle size.
  • the weight ratio of the sum of the amounts of oleaginous materials and sulfurized additives to the amount of surfactant is in the range of 1 to 100.
  • the ratio of the total amount of the one or more sulfurized additives to the amount of surfactant will be a factor that determines the micelle size of the top-treat emulsion.
  • the weight ratio of the amount of the one or more sulfurized additives to the amount of surfactant is in the range of 1 to 100.
  • the emulsions can also include a variety of other components, such as those conventional in compositions for metalworking fluid applications. Examples include, but are not limited to, corrosion inhibitors, rust inhibitors, lubricity enhancers, friction modifiers, chelating agents, coupling agents, yellow metals, esters, and biocides.
  • Suitable corrosion inhibitors include, but are not limited to, amine/alkali salts of short chain carboxylic mono acids, di- and tri-acids, short chain acidic phosphate esters, including alkoxylated esters, semi-succinate half esters, amide-carboxylic acid salts, fatty amides, and amine and alkali sulphonates, or their derivatives.
  • Suitable yellow metals include, but are not limited to, benzotriazole or its derivatives and tolutriazole or its derivatives.
  • Suitable esters include, but are not limited to, trimethylol propane (TMP), mono-, di- and tri- esters of C 8 - C1 8 fatty acids, glycol esters of predominantly olely fatty acids, methyl or isopropyl esters of predominantly oleyl fatty acids or triglycerides, natural triglycerides (such as rapeseed), and modified natural oils (such as blown rapeseed).
  • TMP trimethylol propane
  • mono-, di- and tri- esters of C 8 - C1 8 fatty acids glycol esters of predominantly olely fatty acids, methyl or isopropyl esters of predominantly oleyl fatty acids or triglycerides, natural triglycerides (such as rapeseed), and modified natural oils (such as blown rapeseed).
  • TMP trimethylol propane
  • mono-, di- and tri- esters of C 8 - C1 8 fatty acids glycol est
  • Suitable biocides include, but are not limited to, formaldehyde releasing agents including ortho-formal, hexahydratriazine and derivatives, methylene bis morpholene, oxazoladine and derivatives, isothiazolinones and derivatives and iodo propyl butyl carbamate-fungicide.
  • the emulsion may further comprise one or more of corrosion inhibitors, rust inhibitors, lubricity enhancers, friction modifiers, chelating agents, coupling agent, yellow metals, esters, biocides, and combinations thereof, for example, present in an amount up to 15 wt%, for example, up to 10 wt%, up to 8 wt% or up to 5 wt%, based on the total weight of the emulsion.
  • one or more of corrosion inhibitors, rust inhibitors, lubricity enhancers, friction modifiers, chelating agents, coupling agent, yellow metals, esters, biocides, and combinations thereof are present in an amount in the range of about 0.01 wt% to about 15 wt%, or about 0.01 wt% to about 10 wt%, or about 0.01 wt% to about 8 wt%, or about 0.01 wt% to about 5 wt%, or about 0.01 wt% to about 1 wt%, or about 1 wt% to about 15 wt%, or about 1 wt% to about 10 wt%, or about 1 wt% to about 8 wt%, or about 1 wt% to about 5 wt%, or about 2 wt% to about 15 wt%, or about 2 wt% to about 10 wt%, or about 2 wt% to about 8 wt%, or about 2 wt% to about 2 wt
  • an emulsion of the disclosure includes: about 10 to about 50 wt% of the one or more oleaginous materials; about 3 to about 8 wt% of the one or more surfactants; about 1 wt% to about 30 wt% of the one or more sulfurized additives selected from sulfurized fatty acid esters, sulfurized fatty oil, sulfurized and polymerized fatty esters, and sulfurized polyolefins; and at least 25 wt% water.
  • the emulsion further includes about 5.0 to about 10 wt% of a corrosion inhibitor.
  • Such an emulsion can be, for example, used as a concentrate for a metalworking fluid.
  • an emulsion of the disclosure includes: about 0.5 to about 5 wt% (e.g., about 0.5 to about 3 wt%) of the one or more oleaginous materials; about 0.01 to about 1 wt% of the one or more surfactants; about 0.1 wt% to about 5 wt% of the one or more sulfurized additives selected from sulfurized fatty acid esters, sulfurized fatty oil, sulfurized and polymerized fatty esters, and sulfurized polyolefins; and at least 90 wt% water.
  • the emulsion further includes about 2 to about 5 wt% of a corrosion inhibitor.
  • Such an emulsion can be, for example, used as a metalworking fluid.
  • an emulsion of the disclosure includes: about 1 to about 20 wt% of the one or more oleaginous materials; about 0.01 to about 5 wt% of the one or more surfactants; about 0.25 wt% to about 20 wt% of the one or more sulfurized additives selected from sulfurized fatty acid esters, sulfurized fatty oil, sulfurized and polymerized fatty esters, and sulfurized polyolefins; and at least 50 wt% water.
  • the emulsion further includes about 0.5 to about 2 wt% of a corrosion inhibitor.
  • an emulsion of the disclosure includes: about 3 to about 8 wt% of the one or more surfactants; about 1 wt% to about 50 wt% of the one or more sulfurized additives selected from sulfurized fatty acid esters, sulfurized fatty oil, sulfurized and polymerized fatty esters, and sulfurized polyolefins; and at least 25 wt% water.
  • the emulsion is substantially free of a non-sulfurized oleaginous material.
  • Such an emulsion can be, for example, used as a top-treatment for a metalworking fluid.
  • an emulsion of the disclosure includes: about 3 to about 15 wt% of the one or more surfactants; about 50 wt% to about 80 wt% of the one or more sulfurized additives selected from sulfurized fatty acid esters, sulfurized fatty oil, sulfurized and polymerized fatty esters, and sulfurized polyolefins; and at least 8 wt% water.
  • the emulsion is substantially free of a non-sulfurized oleaginous material.
  • Such emulsions can be, for example, used as a top-treatment for a metalworking fluid.
  • the chief constituents are water, one or more surfactants, and one or more sulfurized additives selected from sulfurized fatty acid esters, sulfurized fatty oil, sulfurized and polymerized fatty esters, and sulfurized polyolefins, and, optionally, one or more oleaginous materials.
  • the total amount of water, one or more oleaginous materials, one or more surfactants, and one or more sulfurized additives selected from sulfurized fatty acid esters, sulfurized fatty oil, sulfurized and polymerized fatty esters, and sulfurized polyolefins in the emulsion is at least 70%, at least 80%, or at least 85 wt%, or at least 90 wt%, or at least 95 wt%, or at least 98 wt%, or even at least 99 wt%.
  • the chief constituents are water, one or more surfactants, and one or more sulfurized additives selected from sulfurized fatty acid esters, sulfurized fatty oil, sulfurized and polymerized fatty esters, and sulfurized polyolefins.
  • the total amount of water, one or more surfactants, and one or more sulfurized additives selected from sulfurized fatty acid esters, sulfurized fatty oil, sulfurized and polymerized fatty esters, and sulfurized polyolefins in the top-treat emulsion is at least 80%, or at least 85 wt%, or at least 90 wt%, or at least 95 wt%, or at least 98 wt%, or even at least 99 wt%.
  • a micelle is an aggregate of surfactant molecules dispersed in a colloid, where particles of a first material are suspended in a second material, creating a two-phase system. Unlike in a solution, the first material is insoluble or immiscible in the second material (i.e., it becomes an emulsion). In an aqueous solution, a micelle forms an aggregate with the hydrophobic tails of the surfactant molecules facing inwards and the hydrophilic heads of the surfactant molecules facing outwards. This forms a normal-phase micelle, leading to an oil-in-water phase mixture.
  • An inverse-phase micelle has the inverse structure, where the hydrophilic heads of the surfactant molecules face inwards and the hydrophobic tails face outwards. This leads to a water-in-oil phase mixture.
  • the packing behaviour of the surfactant molecules may lead to a single layer of surfactant molecules around the core of the micelle, which, following surface energy considerations, may typically form a sphere.
  • the micelles of the disclosure are generally spherical in structure.
  • Further layers of surfactant may also be packed around the outside of the micelle. This will be the case when further surfactant is added to the mixture.
  • the molecules of the oleaginous material stretch. This stretching causes the molecules to flatten out and form a laminar structure, thus increasing the surface area any surfactant has available to be attracted to.
  • the packing fraction of the surfactant increases from ⁇ 1/3 to > 1/2.
  • the shear force is removed from the molecule, it forms a spherical micelle due to surface energy considerations, unless, of course, the structure of the surfactant causes the minimum surface energy configuration of a micelle to be laminar or cylindrical.
  • Gemini surfactants sometimes known as dimeric surfactants, have two hydrophobic tails that distort the core of the micelle into an elongated ovoid shape.
  • the surfactant packing fraction then reduces back to ⁇ 1/3 for spherical micelles, so any surfactant that had been attracted to the temporary laminar configuration of the molecule forms additional layers of surfactant around the micelle.
  • the surfactant molecules are disposed around a hydrophobic core in a single molecular layer. In certain other embodiments, the surfactant molecules are disposed around a hydrophobic core in three or more molecular layers. In certain embodiments, different molecular layers may comprise two or more surfactants. For example, a non-ionic surfactant may be present within the surface layers, and ionic surfactants may be present within the layer.
  • One further advantage of the emulsions and methods of certain embodiments of the disclosure is a relatively uniform size of the micelles in the emulsion.
  • the present inventors have determined that use of the methods described herein can provide a micellar emulsion with a relatively uniform micellar size.
  • the distribution of the average diameters of the micelles typically follows a Gaussian profile.
  • the distribution of the average diameters of the micelles has a mean ⁇ and a standard deviation ⁇ , determined using conventional statistical analysis.
  • the standard deviation ⁇ is no more than 0.5 ⁇ , no more than 0.2 ⁇ , or even no more than 0.1 ⁇ .
  • the standard deviation of the average micelle diameter is 0.06 ⁇ m or less.
  • the average micelle diameter is an average of various diameter measurements taken for a particular micelle, which in the case of spherical micelles is approximately equal to the micelle diameter (since there is little or no variation of the diameter regardless of where the measurement is taken).
  • the advantage of having a narrow range of average micelle diameters lies in the ability of the emulsion, for example when used as a metalworking fluid, to fully cover a surface.
  • the coverage of the fluid across a surface is variable. This is due to regions of equal surface area having different volumes of fluid on them. If the average micelle diameter is in a small range, however, the surface coverage is far more efficient and extensive as the regions of equal surface area will have approximately equal volumes of fluid on them. This leads to more even wear and improved surface/interface protection.
  • the micelles have a mean average diameter of no more than about 1.5 ⁇ m, for example, no more than about 1 ⁇ m, no more than about 0.5 ⁇ m, or even no more than about 0.4 ⁇ m. In certain embodiments, the micelles have a mean average diameter in the range of about 0.1 ⁇ m to about 1.5 ⁇ m, or about 0.1 ⁇ m to about 1 ⁇ m, or about 0.1 ⁇ m to about 0.75 ⁇ m, or about 0.1 ⁇ m to about 0.5 ⁇ m, or about 0.1 ⁇ m to about 0.4 ⁇ m, or about 0.05 ⁇ m to about 0.4 ⁇ m, or about 0.2 ⁇ m to about 0.5 ⁇ m, or about 0.3 ⁇ m to about 0.4 ⁇ m.
  • Suitable measurement techniques to determine both the average micelle diameter and the distribution of average micelle diameters include, for use in quantification of values in the present disclosure, sizes are measured using laser particle size analysis using a Beckman Coulter Laser Diffraction PS Analyzer (LS 13 320), which uses Polarization Intensity Differential Scattering (PIDS) technology to determine particle size and size distribution.
  • PIDS Polarization Intensity Differential Scattering
  • micellar size distribution can be characterized by d50, d10 and d90 values, where d50 is the median particle size, d10 is the particle size at the 10 th percentile of particles ranked by size, and d90 is the particle size at the 90 th percentile of particles ranked by size.
  • the micelles of a particular emulsion as otherwise described herein have a d50 value in the range of 0.1 ⁇ m to 1.5 ⁇ m; e.g., or about 0.1 ⁇ m to about 1 ⁇ m, or about 0.1 ⁇ m to about 0.75 ⁇ m, or about 0.1 ⁇ m to about 0.5 ⁇ m, or about 0.1 ⁇ m to about 0.4 ⁇ m, or about 0.05 ⁇ m to about 0.4 ⁇ m, or about 0.2 ⁇ m to about 0.5 ⁇ m, or about 0.3 ⁇ m to about 0.4 ⁇ m.
  • d10 is no less than 50% of d50 and d90 is no more than 150% of d50.
  • d10 is no less than 60% of d50 and d90 is no more than 140% of d50. In certain embodiments, d10 is no less than 70% of d50 and d90 is no more than 130% of d50. In certain embodiments, d10 is no less than 75% of d50 and d90 is no more than 125% of d50. In certain embodiments, d10 is no less than 80% of d50 and d90 is no more than 120% of d50.
  • micellar particle size analysis using a Beckman Coulter Laser Diffraction PS Analyzer (LS 13 320) is used. This method employs Fraunhoffer diffraction and Polarization Intensity Differential Scanning (PIDS) to determine the particle size.
  • PIDS Polarization Intensity Differential Scanning
  • the micelle size and size distribution described herein apply to the micelles containing a sulfurized additive (e.g., arising from a top-treat emulsion or a concentrate containing a sulfurized additive), and not to all micelles in a metalworking fluid.
  • a sulfurized additive e.g., arising from a top-treat emulsion or a concentrate containing a sulfurized additive
  • the emulsions of the disclosure can be provided in a variety of concentrations.
  • an emulsion of the disclosure is provided at a concentration that is itself suitable for use as a metalworking fluid, i.e. such an emulsion can be used undiluted in metalworking applications.
  • an emulsion of the disclosure is provided at a concentration suitable for use as a metalworking fluid concentrate, i.e., at a concentration that can be diluted with aqueous media to provide a metalworking fluid.
  • a top-treat emulsion of the disclosure is used as a top-treat fluid to form a metalworking fluid from an existing metalworking fluid.
  • an emulsion of the disclosure may also be provided by diluting a more concentrated emulsion (e.g., a more concentrated emulsion of the disclosure).
  • one aspect of the disclosure provides a metalworking fluid prepared by combining an emulsion of the disclosure with an aqueous fluid.
  • An emulsion of the disclosure may be diluted, for example, with a desired quantity of water or other aqueous fluid, to convert a metalworking concentrate to a metalworking fluid.
  • the emulsion is used in an amount of about 0.25 wt% to about 20 wt% based on the total weight of the metalworking fluid; e.g., about 0.25 wt% to about 5 wt%, or about 1 wt% to about 10 wt%, or about 5 wt% to about 10 wt%, or about 5 wt% to about 6 wt%, or about 6 wt% to about 10%.
  • An emulsion of the disclosure may also be used as a top-treat fluid, e.g., to provide the sulfurized additive-containing micelles to a spent metalworking fluid or an existing metalworking fluid.
  • the top-treat emulsion is used in an amount of about 0.5 wt% to about 20 wt% based on the total weight of the metalworking fluid; e.g., about 0.5 wt% to about 10 wt%, or about 0.5 wt% to about 5 wt%, or about 0.5 wt% to about 2%, or about 1 wt% to about 20 wt%, or about 1 wt% to about 10 wt%, or about 1 wt% to about 5 wt%.
  • the dilution may be carried out more than once; for example, the process may effectively form a series of metalworking fluids with each subsequent fluid having a lower concentration of the emulsion of the disclosure.
  • One of skill in the art may dilute the metalworking fluid until the desired viscosity and/or lubrication performance is achieved.
  • a method of working a metal comprises contacting a surface of a metal article with the emulsion of the disclosure or the metalworking fluid of the disclosure, and forming the surface of the metal article to a desired shape.
  • Working a metal may be destructive metalworking process, i.e., the process where chips are produced, such as drilling, grinding, milling, and turning, or a deforming metalworking process, i.e., the process where a material is deformed or shaped such that no chips are produced, for example such as steel rolling, tapping, and shearing.
  • the metal is steel.
  • the metal is aluminium.
  • one aspect of the disclosure provides a method of preparing the emulsion of the disclosure, the method comprising obtaining a first fluid comprising one or more surfactants dissolved in water (e.g., in the form of an aqueous solution); obtaining a second fluid comprising one or more oleaginous materials and one or more sulfurized additives; contacting the first fluid with the second fluids under a shear force to produce an intermediate fluid.
  • This intermediate fluid may be in the form of a colloidal emulsion, and may be free-flowing or gel-like.
  • the intermediate fluid may also have a greater viscosity than either the first fluid or the second fluid, e.g., at least 5 % higher, or at least 10% higher, or at least 50% higher.
  • This intermediate fluid may comprise micelles of the oleaginous material in the aqueous emulsion.
  • Both the first fluid and the second fluid may be added to a chamber in which stirrers are used to mix the two fluids together under shear force by rotating at a rotational speed of about 1200 to about 1600 rpm.
  • the shape of the chamber and size of the stirrers may be chosen to ensure that a region around the walls of the chamber is devoid of turbulent flow.
  • an aqueous suspension of a surfactant can flow around the chamber in this region thereby producing a laminar flow.
  • a third fluid may be added to the intermediate fluid under laminar flow (for example, increasing the water content of the aqueous fluid to decrease the viscosity of the resulting metalworking fluid).
  • Another aspect of the disclosure provides a method of preparing the top-treat emulsion of the disclosure, the method comprising obtaining a first fluid comprising one or more surfactants dissolved in water (e.g., in the form of an aqueous solution); obtaining a second fluid comprising one or more sulfurized additives; contacting the first fluid with the second fluids under a shear force to produce an intermediate fluid.
  • This intermediate fluid may be in the form of a colloidal emulsion, and may be free-flowing or gel-like.
  • the intermediate fluid may also have a greater viscosity than either the first fluid or the second fluid, e.g., at least 5 % higher, or at least 10% higher, or at least 50% higher.
  • Both the first fluid and the second fluid may be mixed as noted above.
  • a third fluid may be added to the intermediate fluid under laminar flow (for example, increasing the water content of the aqueous fluid to decrease the viscosity of the resulting emulsion).
  • the methods of the disclosure allow for materials with high viscosities to be emulsified into a stable emulsion. It is currently difficult to emulsify fluids having a viscosity of greater than approximately 100 to 150 cSt at 40 °C using the current techniques.
  • the method of the disclosure can be used to emulsify fluids having a viscosity of 8,000 to 12,000 cSt at 40°C.
  • the actual limit is dependent upon the temperature of the various components during emulsification. For example, it may be necessary to heat components up to around 90°C to achieve emulsification.
  • substantially all of the surfactant becomes bound within the micelle structure as described above as a result of the shear mixing. That is, substantially all of the surfactant molecules form at least one layer over the surface of the core of the micelle. There is substantially no unbound surfactant present in such emulsions, where unbound surfactant is characterised as free surfactant molecules within the emulsion detectable alone without being part of a micelle.
  • substantially all of the surfactant being bound within the micelle structure can result in the emulsion of the disclosure being substantially free of excess surfactant.
  • the emulsion according to certain embodiments of the disclosure can be substantially foam-free, and does not foam when in use.
  • the emulsions of the disclosure can, in certain embodiments, also substantially free of defoamers and/or anti-foam compounds (i.e., in such embodiments, these are no longer required to compensate for any foaming of an oleaginous/aqueous emulsion).
  • each emulsion comprised 10 wt% of oleaginous material, and 0.25 wt%, 0.5 wt%, or 1 wt% of a sulfurized additive, which was sulfurized fatty acid ester.
  • MB10 (available from Castrol, Lewiston, NY under label HYSOL MB 10) is a semi-synthetic metalworking fluid with a 10% mineral oil content
  • MB20 (available from Castrol, Lewiston, NY under label HYSOL MB 20) is a semi-synthetic metalworking fluid with a 20% mineral oil content
  • MB50 (available from Castrol, Lewiston, NY under label HYSOL MB 20) is a semi-synthetic metalworking fluid with a 50% mineral oil content.
  • AU68 (available from Castrol, Lewiston, NY under label ALUSOL AU 68) is a semi-synthetic metalworking fluid with a 20-40% mineral oil content.
  • the emulsions of the disclosure or commercially available metalworking fluids were diluted to a concentration of between 5 and 10 wt% and tested for power required to thread the pre-drilled hole using Mori Seiki NH4000 milling machine. The lower power indicates the improved lubrication performance.
  • FIG. 1 provides the tapping power test on wrought automotive grade aluminum alloy 6061-T6 (available, for example, from Alcoa, Chicago, IL).
  • Softer cast aluminum such as cast automotive grade aluminum alloy 356 (available, for example, from Alcoa, Chicago, IL), is more difficult to tap because the metal tends to be softer and stickier when cut than wrought alloys.
  • MB10 does not lubricate sufficiently to prevent machinery damage.
  • metalworking fluids with higher mineral oil content need to be used, such as MB20 and MB50.
  • the emulsions of the disclosure were diluted to a concentration of 5 wt%, where MB20, MB50, and AU68 were diluted to a concentration of 8 wt%. As shown in FIG. 2 , the emulsions of the disclosure comprising between 0.25 and 1 wt% of the sulfurized additive all outperformed MB20 and MB50.
  • top-treat emulsion of the disclosure was prepared using the general procedure noted above. The specific amounts and materials are noted in Table 2.
  • Table 2 Component Supplier Name Weight % sulfurized fatty acid ester DeoAdd VP 288, D.O.G Deutsche Oelfabrik, Germany 69.9 glycerin (86%) (emulsifier) Brenntag, Germany 8.8 sodium hydroxide (50% solution) Natronlauge, Brenntag, Germany 0.15 12-hydroxystearic acid Oleo-Chemie, Germany 1.14
  • Example 3A was an emulsion of caprylic / capric triglyceride, NanoGel CCT (available from Clariant AG, Muttenz, Switzerland) with 4 wt% of an ethoxylated phosphoric ester.
  • Example 3B is an emulsion of NanoGel CCT with 3 wt% of an ethoxylated phosphoric ester, and 3 wt% of sulfurized fatty acid ester, DeoAdd VP332-1 (available from D.O.G.Deutsche Oelfabrik, Hamburg, Germany).
  • Example 3C is an emulsion of NanoGel CCT and 4 wt% of DeoAdd VP332-1. Top Treat 1 was the DeoAdd VP332-1.
  • LD0094 and CFX are both metalworking products available from Castrol (Lewiston, New York), and Avantin 3309 is a coolant product for metalworking available from Carl Bechem GmbH (Hagen, Germany).
  • the CFX product contains a sulfurized fatty acid ester (sold as VPP 228 by D. O. G. Deutshce Oelfabrik) and had been emulsified to create micelles of the ester in water.
  • VPP 228 sulfurized fatty acid ester
  • D. O. G. Deutshce Oelfabrik the use of a small amount of the sulfurized fatty acid ester with a relatively weak concentration of the base metalworking fluid gives a performance increase.
  • a machining test to determine the effect of adding sulfurized esters to metalworking fluids for use on different materials was carried out.
  • the test comprised machining 24 holes using an M8 bit in firstly, a block of steel (42CrMo 4 ) 250 x 110 x 50 mm in size using a Sandvik M8 E308 threadformer.
  • the tool was driven at a rotational speed of 1800rpm and a lateral speed of 45m/min.
  • FIG. 4 illustrates the results for the power required to turn the tool and drill the holes at this rate.
  • the test was then replicated on a block of aluminum of the same size.
  • FIG. 5 illustrates the results for the power required to turn the tool and drill the holes at this rate.
  • FIG. 4 illustrates a base fluid comprising an 8% concentration of Hysol CGX 100 metalworking fluid available from Castrol Limited, a conventional high-phosphorous and high sulfur metalworking fluid.
  • the top treat used was that shown in Example 5 above.
  • the base fluid plus top treat required a lower power to machine the holes, indicating an improvement in the efficiency of the machining process due to the addition of a sulfurized ester component in the top treat.
  • FIG. 5 illustrates a base fluid comprising an 8% concentration of a base fluid comprising a micellular emulsion of a mineral oil, and a top treat comprising a micellular emulsion of a sulfurized ester and undecenylic acid. Again, the power required to machin the holes was lower when the top treat was employed in the metalworking fluid.

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EP18150506.6A 2018-01-05 2018-01-05 Für metallbearbeitungsanwendungen nützliche, mizellare emulsionen Withdrawn EP3508561A1 (de)

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PCT/EP2019/050256 WO2019134999A1 (en) 2018-01-05 2019-01-07 Micellar emulsions useful for metalworking applications

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1599715A (en) * 1977-05-17 1981-10-07 Standard Oil Co High production rate metal-working fluid
US5391310A (en) * 1993-11-23 1995-02-21 Cincinnati Milacron Inc. Sulfurized aqueous machining fluid composition
EP1063280A1 (de) * 1999-06-21 2000-12-27 Quaker Chemical Corporation Metallbearbeitungflüssigkeiten (Kühlschmierstoffe)
US6245723B1 (en) * 1997-01-29 2001-06-12 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Cooling lubricant emulsion
EP2161327A1 (de) * 2008-09-05 2010-03-10 Cognis IP Management GmbH Emulgatoren für Metallbearbeitungsflüssigkeiten
WO2010129951A1 (en) * 2009-05-08 2010-11-11 Quaker Chemical Corporation Small particle size oil in water lubricant fluid
US20130201785A1 (en) 2010-05-07 2013-08-08 Otc Gmbh Emulsification device for continuously producing emulsions and/or dispersions

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1599715A (en) * 1977-05-17 1981-10-07 Standard Oil Co High production rate metal-working fluid
US5391310A (en) * 1993-11-23 1995-02-21 Cincinnati Milacron Inc. Sulfurized aqueous machining fluid composition
US6245723B1 (en) * 1997-01-29 2001-06-12 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Cooling lubricant emulsion
EP1063280A1 (de) * 1999-06-21 2000-12-27 Quaker Chemical Corporation Metallbearbeitungflüssigkeiten (Kühlschmierstoffe)
EP2161327A1 (de) * 2008-09-05 2010-03-10 Cognis IP Management GmbH Emulgatoren für Metallbearbeitungsflüssigkeiten
WO2010129951A1 (en) * 2009-05-08 2010-11-11 Quaker Chemical Corporation Small particle size oil in water lubricant fluid
US20130201785A1 (en) 2010-05-07 2013-08-08 Otc Gmbh Emulsification device for continuously producing emulsions and/or dispersions

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Title
JAMES-SMITH ET AL., JOURNAL OF COLLOID AND INTERFACE SCIENCE, vol. 310, 2007, pages 590 - 598

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