WO2001027226A1 - Lubricant for metal machining with ferromagnetic or ferrimagnetic nanoparticles - Google Patents

Lubricant for metal machining with ferromagnetic or ferrimagnetic nanoparticles Download PDF

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Publication number
WO2001027226A1
WO2001027226A1 PCT/EP2000/009686 EP0009686W WO0127226A1 WO 2001027226 A1 WO2001027226 A1 WO 2001027226A1 EP 0009686 W EP0009686 W EP 0009686W WO 0127226 A1 WO0127226 A1 WO 0127226A1
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WO
WIPO (PCT)
Prior art keywords
lubricant
oil
ferromagnetic
water
ferrimagnetic
Prior art date
Application number
PCT/EP2000/009686
Other languages
German (de)
French (fr)
Inventor
Ilona Lange
Marcel Roth
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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Filing date
Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to EP00972675A priority Critical patent/EP1232235A1/en
Publication of WO2001027226A1 publication Critical patent/WO2001027226A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/44—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of magnetic liquids, e.g. ferrofluids
    • H01F1/445—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of magnetic liquids, e.g. ferrofluids the magnetic component being a compound, e.g. Fe3O4
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23Q—DETAILS, COMPONENTS, OR ACCESSORIES FOR MACHINE TOOLS, e.g. ARRANGEMENTS FOR COPYING OR CONTROLLING; MACHINE TOOLS IN GENERAL CHARACTERISED BY THE CONSTRUCTION OF PARTICULAR DETAILS OR COMPONENTS; COMBINATIONS OR ASSOCIATIONS OF METAL-WORKING MACHINES, NOT DIRECTED TO A PARTICULAR RESULT
    • B23Q11/00—Accessories fitted to machine tools for keeping tools or parts of the machine in good working condition or for cooling work; Safety devices specially combined with or arranged in, or specially adapted for use in connection with, machine tools
    • B23Q11/10—Arrangements for cooling or lubricating tools or work
    • B23Q11/1038—Arrangements for cooling or lubricating tools or work using cutting liquids with special characteristics, e.g. flow rate, quality
    • B23Q11/1061—Arrangements for cooling or lubricating tools or work using cutting liquids with special characteristics, e.g. flow rate, quality using cutting liquids with specially selected composition or state of aggregation
    • 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
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/04—Metals; Alloys
    • 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
    • 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
    • C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/44—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of magnetic liquids, e.g. ferrofluids
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C—CHEMISTRY; METALLURGY
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    • C10M2201/02—Water
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    • C10M2201/04—Elements
    • C10M2201/05—Metals; Alloys
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    • C10M2201/06—Metal compounds
    • C10M2201/061—Carbides; Hydrides; Nitrides
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    • C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
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    • C10M2201/087—Boron oxides, acids or salts
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    • C10M2201/14—Inorganic compounds or elements as ingredients in lubricant compositions inorganic compounds surface treated with organic compounds
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    • C10M2201/18—Ammonia
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    • C10M2207/02—Hydroxy compounds
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    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C10M2207/046—Hydroxy ethers
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    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
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    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

Definitions

  • the invention relates to oil-based lubricants for the shaping or machining of metals. These lubricants are used as cooling lubricants. An improvement in the lubricating effect compared to conventional cooling lubricants is achieved in that the lubricants contain ferromagnetic or ferrimagnetic nanoparticles. Furthermore, the invention relates to methods for forming or for machining metals, oil-based lubricants containing ferromagnetic or ferrimagnetic nanoparticles being used as the cooling lubricant.
  • Lubricants hereinafter also referred to as cooling lubricants, are preparations / mixtures that are used in grinding or cutting / sawing, in metal cutting and in metal forming to cool and lubricate the tools.
  • the most important machining processes differ in the type of movements that the machined part and tool perform, the geometry of the parts to be manufactured and the machining parameters. A distinction is made, for example, between milling, turning, drilling and grinding as machining operations, as well as rolling, deep drawing and cold extrusion as non-cutting forming.
  • the common principle of metal-cutting processes is that the cutting edge engages the material and lifts a chip off the surface, creating a new surface. Very high pressures are required to break up the material. The deformation of the chip and the friction that occurs under pressure create heat that heats up the workpiece, the tool and, above all, the chips.
  • cooling lubricants The desired effect of using cooling lubricants is therefore the lowering of the temperature that would otherwise occur in the chips.
  • B. can rise to 1000 ° C, and ⁇ ie oei ⁇ en nergesteluen parts influence the dimensional accuracy Has.
  • Another main task of cooling lubricants is to improve the service life of tools that wear out quickly under the influence of high temperatures.
  • the use of a cooling lubricant reduces the roughness of the surfaces, since the lubricant prevents welding of the tool and the workpiece surface and prevents particles from sticking.
  • the cooling lubricant takes on the task of removing the chips that have formed.
  • Water-mixed cooling lubricants are produced by the user by mixing a concentrate of the water-miscible cooling lubricant with process water. As a rule, approximately 5% aqueous emulsions are produced.
  • the advantage of this type of cooling lubricant is the good cooling effect, which is based on the thermal properties of the water. Due to the good cooling effect, it is possible to achieve very high working speeds and thus increase the productivity of machines.
  • the lubricating effect of the water-mixed cooling lubricants is sufficient for most machining processes in machining. Another advantage is the low cost that can be achieved by mixing the concentrate with water.
  • water-mixed cooling lubricants are sensitive to external influences, in particular to attack by microorganisms, and therefore require more control and maintenance than non-water-miscible cooling lubricants such as cutting oils, grinding oils and forming oils.
  • Ulimann 's Encyclopaedia of Industrial Cnemisiry provides an overview of the shaping processes and the tools that are usually used for this purpose. 5th Ec. vol. AI 5 479-486. The spectrum The forms of supply of the auxiliaries in question range from oils to oil-in-water emulsions to aqueous solutions.
  • Non-water-miscible and water-miscible cooling lubricants are often based on mineral oil.
  • the mineral oil qualities used are predominantly combinations of paraffinic, naphthenic and aromatic hydrocarbon compounds.
  • so-called synthetic lubricants such as polyalphaolefins, polyalkylene glycols and glycol ethers, dialkyl ethers, acetals, natural ester oils and synthetic esters and their derivatives are also important.
  • cooling lubricants In order to meet practical requirements, cooling lubricants must contain various components in addition to the base oil.
  • the most important substance groups are the emulsifiers, anti-corrosion additives, biocides, EP additives, polar additives, anti-fog additives, anti-aging agents, solid lubricant additives and defoamers.
  • Emulsifiers e.g. surfactants, petroleum sulfonates, alkali soaps, alkanolamine soaps
  • Emulsifiers stabilize the fine distribution of oil droplets in the aqueous working fluid, which is an oil-in-water emulsion.
  • the emulsifiers represent an important group of additives for water-miscible cooling lubricants.
  • Usual corrosion protection additives e.g. alkanolamines and their salts, sulfonates, organic boron compounds, fatty acid amides, aminodicarboxylic acids, phosphoric acid esters, thiophosphonic acid esters, dialkyldithiophosphates, mono- and dialkylarylsulfonates, benzothazoles, polyisobutene succinic acid derivatives
  • Some corrosion protection additives also have emulsifying properties and are therefore also used as emulsifiers.
  • Biocides e.g. phenol derivatives, formaldehyde derivatives, Kathon MW
  • EP additives e.g. sulfurized fats and oils, compounds containing phosphorus, organochlorine compounds
  • Polar additives e.g. natural fats and oils, synthetic esters
  • Anti-aging agents e.g. organic sulfides, zinc dithiophosphates, aromatic amines
  • the second important function of the cooling lubricants is the lubricating effect.
  • the effect of the lubricating components is based on the formation of surface layers that have a lower shear strength than the base material and thus reduce friction and wear.
  • the spectrum of the surface states ranges from adsorptively bound layers through chemisorption to chemical reaction layers that create a firm bond to the metal surface.
  • lubricant coating on a surface is adsorptive lubricant layers. They are produced, for example, by mineral oils without special additives.
  • the formation of the adsorption layers can be increased by adding polar active ingredients such as fatty alcohols or fatty esters.
  • polar active ingredients such as fatty alcohols or fatty esters.
  • chemisorptive lubricant film formers are fatty acids.
  • the hydrophilic carboxyl group is chemically bound to the metal surface by reaction with the metal atoms and the hydrophobic hydrocarbon residue is aligned perpendicular to the surface.
  • the increased adhesive strength of the chemisorptive layer improves the pressure absorption capacity compared to purely adsorptive lubricant layers, but is still not sufficient for many cases of metal forming to reduce friction and wear. It is only when EP or AW additives (extreme pressure or anti wear additives) are added that there is a sufficient improvement in lubrication performance so that even difficult forming processes are possible.
  • EP or AW additives extreme pressure or anti wear additives
  • Water-mixed cooling lubricants are a widely used type of cooling lubricant. In practice, however, different water-mixed cooling lubricants are used in order to meet the different requirements with regard to corrosion protection for the different processed materials, lubricating effect at high working speeds, service life and, last but not least, occupational safety and environmental behavior.
  • the lubrication properties of conventional lubricants can be specifically improved by using nanoparticles.
  • An article by ZS Hu, JX Dong, G. X Chen (Tribology Intern. Vol. 31, No 7, pp 355-360) describes the use of amorphous iron oxide with a particle size of 20-50 nm to improve the abrasion resistance and Friction coefficient described. This material is obtained from ethanol by drying under supercritical conditions.
  • Fe 3 0 4 is used in a mixture with other oxides in a particle size smaller than 2 ⁇ m.
  • WO 9114757 describes iron oxide in a concentration of 1-30% and a particle size of 10 ⁇ m.
  • JP 01083309 / US 5468402 describes the use of FeO and Fe 3 ⁇ 4 (> 10 ⁇ m) for hot rolling processes.
  • F ⁇ 3 ⁇ 4 with particle sizes of 1-5 ⁇ m is described by SU 765344 in concentrations of 8-15% as a solid lubricant for magnetizable surfaces.
  • Quaternary ammonium salts are used as stabilizers in the production of the particles, which can also be carried out by a continuous process Aqueous colloidal suspensions are obtained which are stable for months. If the magnetic particles are separated and dried, the powders obtained can be resuspended under the action of ultrasound el polymerized.
  • German utility model DE-U-93 21 479 discloses an aqueous-based magnetic liquid, magnetic iron oxide particles, which preferably have a size of 5 to 20 nm, by a first monomolecular adsorption layer made of saturated or unsaturated fatty acids and a second adsorption layer made of surface-active alkoxylated Fatty alcohols are stabilized.
  • DE 199 23 625 describes a process for the preparation of redispersible metal oxides or metal hydroxides with a volume-weighted average crystallite size between 1 and 20 nm, where metal hydroxide or metal oxide is precipitated from aqueous solutions of metal salts by raising the pH with a base in the presence of polymeric carboxylic acids separates at least part of the aqueous phase from the metal oxide or metal hydroxide obtained.
  • the aim of the present invention is to provide lubricants and lubricating methods using them, in which an improved lubricating effect is achieved.
  • the invention relates to oil-based lubricants for metalworking which contain 0.1 to 5% by weight, based on the ready-to-use lubricant, of ferromagnetic or ferrimagnetic particles with a volume-weighted average crystallite size in the range from 2 to 80 nm.
  • the volume-weighted average crystallite size is preferably in the range from 8 to 20 nm.
  • the ready-to-use lubricant can be an essentially anhydrous oil or an oil-in-water emulsion.
  • ⁇ is the wavelength of the X-rays used
  • ß is the full width at half the height of the reflection at the diffraction position 2 ⁇ .
  • K is a constant of the order of 1, the exact value of which depends on the crystal shape. This indeterminacy of K can be avoided by determining the line broadening as an integral width ß, where ß is defined as the area under the X-ray diffraction reflex divided by its maximum intensity l 0 :
  • the sizes 2 ⁇ and 2 ⁇ 2 are the minimum and maximum angle position of the Bragg reflex on the 2 ⁇ lens.
  • I (2 ⁇ ) is the measured intensity of the reflection as a function of 29. Using this relationship results in the equation for determining the volume-weighted average crystallite size D.
  • D ⁇ / ßicos ⁇
  • ferromagnetic or ferrimagnetic particles which have a hydrophobic organic coating.
  • a hydrophobic organic coating can be achieved, for example, by coating the particles with organic sulfonic or phosphonic acids or with alcohols, each carrying an alkyl radical with a chain length such that the surfaces of the particles are rendered hydrophobic and the dispersibility of the particles in the oil phase is improved , This is the case, for example, with alkyl radicals with chain lengths in the range from 8 to 22 carbon atoms.
  • ferromagnetic or ferrimagnetic particles whose hydrophobizing organic coating consists at least in part of carboxylic acids or whose anions have 8 to 44, preferably 12 to 22, carbon atoms. These are chain lengths that are usually found in fatty acids or so-called dimer fatty acids.
  • the ferromagnetic or ferrimagnetic particles can be selected from doped or undoped cobalt ferrite, manganese ferrite, zinc ferrite, nickel ferrite and ⁇ -Fe 2 O 3 . The latter is particularly preferred.
  • the lubricants in which the ferromagnetic or ferrimagnetic nanoparticles are dispersed can be an essentially anhydrous oil.
  • oils are known in the technical field concerned as cutting or forming oils. They can contain other additives, as exemplified in the introduction. Since the ferromagnetic or ferrimagnetic nanoparticles contribute significantly to the lubricating effect, the oil used as a lubricant can contain considerably fewer EP additives than usual or even be free of such additives.
  • the lubricants are an oil-in-water emulsion, the ferromagnetic or ferrimagnetic particles being dispersed in the oil phase.
  • Such emulsions are usually prepared by using low or anhydrous emulsion concentrates Mixed water, usually 10 to 50 parts by weight of water are used per part by weight of concentrate.
  • emulsion concentrates can be used to produce the oil-in-water emulsions which differ from the concentrates known and commercially available only in that they contain ferromagnetic or ferrimagnetic nanoparticles.
  • the emulsion concentrates and the oil-in-water emulsions which can be prepared therefrom may contain the components which are customary in the technical field concerned and which have been listed above by way of example.
  • the addition of conventional EP additives can at least largely be dispensed with.
  • the oil used as a lubricant or the oil phase of the oil-in-water emulsions can consist of any oil, as is customary in the area of application concerned.
  • oils such as, for example, polyolefins, acetals or dialkyl ethers or biologically based oils, for example ester oils which are triglycerides or modification products thereof occurring in plants or animals, wax esters and fatty acid esters of monoalkanols having 4 to 12 carbon atoms , for example tallow fatty acid ethylhexyl ester or transesterified rapeseed oil, and also fatty acid esters of polyols, it being possible in particular to use trimethyloipropane as the polyol component. Mixtures of such oils can of course also be used.
  • the invention further relates to the use of a dispersion of ferromagnetic or ferrimagnetic particles with a volume-weighted average crystallite size in the range from 2 to 80 nm, preferably from 8 to 20 nm in oil for the production of a lubricant as described above.
  • a dispersion of ferromaonetic or ferrimaonetic particles in oil to produce the lubricants which is about 10 to 35 Wt .-% of the ferromagnetic or ferrimagnetic particles based on the total weight of the dispersion contains.
  • Another aspect of the invention resides in a process for forming or machining metals using a tool and an oil-based lubricant, using an oil-based lubricant as described above which contains ferromagnetic or ferrimagnetic nanoparticles. Examples of the above-mentioned working methods "forming” and “machining” were mentioned at the beginning.
  • a particular advantage of the invention shows itself when the tool is magnetized during the forming or machining of metals or when, for. B. in non-magnetic metals, the place of chip production is exposed to a permanent magnetic field.
  • This can be done electromagnetically, for example.
  • the magnetized tool attracts the ferromagnetic or ferrimagnetic oil phase due to the presence of the ferromagnetic or ferrimagnetic nanoparticles and thus holds them in place at the machining site, i.e. in the tribo zone. This makes it more difficult to shear off the oil phase.
  • This process aspect is particularly advantageous if an oil-in-water emulsion is used as the cooling lubricant, the oil phase of which contains ferromagnetic or ferrimagnetic nanoparticles.
  • the ferromagnetic or ferrimagnetic oil phase binds to the tool.
  • a desired particularly high oil concentration is thus present in the tribozone, while sufficient water phase is available for cooling in the periphery of the tribozone.
  • the swarf can be easily removed with the cooling lubricant.
  • ferromagnetic or ferrimagnetic nanoparticles for producing oil-based lubricants is that these nanoparticles can have a biocidal, in particular bactericidal, effect.
  • the service life and the service life of the lubricants are improved without the addition of conventional preservatives, for example based on Formaldehyde releasing, is required.
  • a further aspect of the invention resides in a method for forming or machining metals using an oil-based lubricant, the oil-based lubricant not being mixed with a conventional biocide. This is particularly advantageous in terms of occupational and environmental protection.
  • the ferromagnetic or ferrimagnetic nanoparticles can be produced by known processes and provided with a hydrophobic coating.
  • the method described in DE 199 23 625 may be mentioned.
  • the manufacturing process can also be operated continuously, which means increased efficiency of the process.
  • the procedure is such that metal hydroxide or metal oxide is continuously precipitated from aqueous solutions of metal salts by raising the pH with a base in the presence of polymeric carboxylic acids by a) a first container with the aqueous solution of the metal salts and a second container with provides an aqueous alkaline solution of a base and a polymeric carboxylic acid, b) continuously removes solution from both containers and mixes the two solutions in a mixing section and, if desired c) closes the precipitation reaction in a tube behind the mixing section.
  • FeCI 3 are dissolved in 40g water.
  • 3.97 g of FeCI 2 * 4H 2 0 are dissolved in a mixture of 8 ml of deionized water and 2 ml of 37% hydrochloric acid. Shortly before the solutions are used in the precipitation process, they are combined to form a mixture.
  • the residue is taken up with 70g soybean oil.
  • the coated magnetic particles are transferred into the oil phase by shaking and adding water.
  • a friction wear test according to Reichert was carried out as a suitability test. This procedure is used to determine the pressure absorption capacity (EP behavior) and to determine the adhesive strength of liquid lubricants.
  • a test roller is adapted to a rotating slip ring by means of a lever system, the lower third of which is immersed in the lubricant to be tested.
  • the test roll which has been cleaned in white spirit, is installed in the swiveling holder.
  • the holder is swung in and clamped.
  • the slip ring remains clamped in the device for several test runs, where it is also cleaned with white spirit after each test run.
  • the test roller is placed on the slip ring by slowly applying the load weight (1.5 kg).
  • the counter on the Reichertwaage is set to 0.
  • the rotating slip ring immersed in the lubricant continuously supplies the contact point with lubricant.
  • the test roller is removed from the slip ring.
  • the test roller is removed and the cut mark is measured using a magnifying glass.
  • the ellipse area is calculated as 0.785 * length * width, or is read off using a number table. So many test runs are carried out until the ellipse surfaces of the last 3 test runs do not differ from one another by more than 10%. The smaller the determined elliptical surface, the greater the pressure absorption capacity.
  • Cooling lubricant emulsions in the form of an oil-in-water emulsion were used as the lubricant.
  • a concentrate of the following composition was mixed with water in the amounts specified below: emulsion concentrate
  • the samples are set up as follows:
  • the emulsion concentrate is 5% based on the finished emulsion, here 3 g.
  • the ferrofluid is added in concentrations of ferromagnetic or ferrimagnetic nanoparticles of 0.63% - 5%, also based on the finished emulsion. It is made up with water so that a total of 60 g of emulsion is formed.
  • the lubrication performance improves significantly when a magnet is placed on the test specimen.
  • the lubricant ( ⁇ -Fe 2 O 3 ) is thus fixed at the place of action (in this case, test cylinder).

Abstract

An oil-based lubricant for metal machining which comprises 0.1 to 5 wt % ferromagnetic or ferrimagnetic particles based on the ready-to-use product, with a volume weighted average crystallite size ranging from 2 to 80 nm.

Description

"Schmiermittel zur Metallbearbeitung mit ferromagnetischen oder ferrimagnetischen Nanopartikeln""Lubricants for metal processing with ferromagnetic or ferrimagnetic nanoparticles"
Die Erfindung betrifft olbasierte Schmiermitttel für die Umformung oder die spanabhebende Bearbeitung von Metallen. Diese Schmiermittel werden als Kühlschmierstoff eingesetzt. Eine Verbesserung der Schmierwirkung gegenüber herkömmlichen Kühlschmierstoffen wird dadurch erreicht, daß die Schmierstoffe ferromagnetische oder ferrimagnetische Nanopartikel enthalten. Weiterhin betrifft die Erfindung Verfahren zum Umformen oder zur spanabhebenden Bearbeitung von Metallen, wobei als Kühlschmierstoff olbasierte Schmiermittel eingesetzt werden, die ferromagnetische oder ferrimagnetische Nanopartikel enthalten.The invention relates to oil-based lubricants for the shaping or machining of metals. These lubricants are used as cooling lubricants. An improvement in the lubricating effect compared to conventional cooling lubricants is achieved in that the lubricants contain ferromagnetic or ferrimagnetic nanoparticles. Furthermore, the invention relates to methods for forming or for machining metals, oil-based lubricants containing ferromagnetic or ferrimagnetic nanoparticles being used as the cooling lubricant.
Schmiermittel, im weiteren auch als Kühlschmierstoffe bezeichnet, sind Zubereitungen/Gemische, die beim Schleifen oder Schneiden/Sägen, bei der Metallzerspanung und bei der Metallumformung zum Kühlen und Schmieren der Werkzeuge verwendet werden. Die wichtigsten Bearbeitungsverfahren unterscheiden sich durch die Art der Bewegungen, die das bearbeitete Teil und Werkzeug ausführen, durch die Geometrie der herzustellenden Teile und die Bearbeitungsparameter. Man unterscheidet beispielsweise Fräsen, Drehen, Bohren und Schleifen als spanabhebende Bearbeitungen sowie Walzen, Tiefziehen und Kaltfließpressen als spanlose Umformungen.Lubricants, hereinafter also referred to as cooling lubricants, are preparations / mixtures that are used in grinding or cutting / sawing, in metal cutting and in metal forming to cool and lubricate the tools. The most important machining processes differ in the type of movements that the machined part and tool perform, the geometry of the parts to be manufactured and the machining parameters. A distinction is made, for example, between milling, turning, drilling and grinding as machining operations, as well as rolling, deep drawing and cold extrusion as non-cutting forming.
Das gemeinsame Prinzip der spanabhebenden Metallbearbeitungsverfahren ist, daß die Werkzeugschneide in das Material eingreift und dabei einen Span von der Oberfläche abhebt, so daß eine neue Oberfläche entsteht. Für die Zerteilung des Materials sind sehr hohe Drücke erforderlich. Durch die Verformung des Spans und durch die auftretende Reibung unter dem Druck entsteht Wärme, die das Werkstück, das Werkzeug und vor aliem die Späne aufheizt.The common principle of metal-cutting processes is that the cutting edge engages the material and lifts a chip off the surface, creating a new surface. Very high pressures are required to break up the material. The deformation of the chip and the friction that occurs under pressure create heat that heats up the workpiece, the tool and, above all, the chips.
Die erwünschte Wirkung des Einsatzes von Kühlschmierstoffen ist daher die Senkung der Temperatur, die ansonsten in den Spänen z. B. bis auf 1000° C steigen kann, und αie oei αen nergesteluen Teilen Einfluß auf die Maßhaltigkeit hat. Eine weitere Hauptaufgabe der Kühlschmierstoffe ist, die Standzeit der Werkzeuge zu verbessern, die unter dem Einfluß hoher Temperatur schnell verschleißen. Durch Verwendung eines Kühlschmierstoffes wird die Rauhigkeit der Oberflächen vermindert, da der Schmierstoff Verschweißungen von Werkzeug und Werkstückoberfläche verhindert und das Anhaften von Partikeln vermeidet. Darüber hinaus übernimmt der Kühlschmierstoff die Aufgabe, die gebildeten Späne abzutransportieren.The desired effect of using cooling lubricants is therefore the lowering of the temperature that would otherwise occur in the chips. B. can rise to 1000 ° C, and αie oei αen nergesteluen parts influence the dimensional accuracy Has. Another main task of cooling lubricants is to improve the service life of tools that wear out quickly under the influence of high temperatures. The use of a cooling lubricant reduces the roughness of the surfaces, since the lubricant prevents welding of the tool and the workpiece surface and prevents particles from sticking. In addition, the cooling lubricant takes on the task of removing the chips that have formed.
Mit der Neufassung der DIN 51385 Nr. 1 wurde eine eindeutige Benennung der Kühlschmierstoffe geschaffen, wobei von nichtwassermischbaren, wassermischbaren und von wassergemischten Kühlschmierstoffen die Rede ist. Nach DIN 51385 wird unter den Begriffen "wassergemischt" der Endzustand des fertigen Mediums (meistens ÖI-in-Wasser-Emulsionen), unter "wassermischbar" jedoch der Zustand des Konzentrates verstanden.With the new version of DIN 51385 No. 1, a clear designation of the cooling lubricants was created, whereby we speak of non-water-miscible, water-miscible and water-mixed cooling lubricants. According to DIN 51385, the terms "water-mixed" mean the final state of the finished medium (mostly oil-in-water emulsions), but "water-miscible" means the state of the concentrate.
Wassergemischte Kühlschmierstoffe werden beim Verwender hergestellt durch Mischen eines Konzentrates des wassermischbaren Kühlschmierstoffs mit Betriebswasser. In der Regel werden ca. 5 %ige wäßrige Emulsionen hergestellt. Vorteil dieses Kühlschmierstofftyps ist die gute Kühlwirkung, die auf den thermischen Eigenschaften des Wassers beruht. Durch die gute Kühlwirkung ist es möglich, sehr hohe Arbeitsgeschwindigkeiten zu erreichen und damit die Produktivität von Maschinen zu steigern. Die Schmierwirkung der wassergemischten Kühlschmierstoffe reicht für die meisten Bearbeitungsverfahren in der spanabhebenden Fertigung aus. Ein weiterer Vorteil sind die niedrigen Kosten, die durch die mögliche Mischung des Konzentrates mit Wasser erreicht werden. Nachteil von wassergemischten Kühlschmierstoffen ist, daß sie gegen Fremdeinflüsse, insbesondere gegen den Befall durch Mikroorganismen empfindlich sind und daher mehr Kontrolle und Pflege erfordern als nicht wassermischbare Kühlsschmierstoffe wie beispielsweise Schneidöle, Schleiföle und Umformöie.Water-mixed cooling lubricants are produced by the user by mixing a concentrate of the water-miscible cooling lubricant with process water. As a rule, approximately 5% aqueous emulsions are produced. The advantage of this type of cooling lubricant is the good cooling effect, which is based on the thermal properties of the water. Due to the good cooling effect, it is possible to achieve very high working speeds and thus increase the productivity of machines. The lubricating effect of the water-mixed cooling lubricants is sufficient for most machining processes in machining. Another advantage is the low cost that can be achieved by mixing the concentrate with water. The disadvantage of water-mixed cooling lubricants is that they are sensitive to external influences, in particular to attack by microorganisms, and therefore require more control and maintenance than non-water-miscible cooling lubricants such as cutting oils, grinding oils and forming oils.
Ein Überblick über die formgebenden Metailbearbeitungsprozesse und die hierfür üblicherweise verwendeien Hilfsmittel ist beispielsweise Ulimann's Encyclopaedia of Industrial Cnemisiry. 5th Ec. vol. AI 5 479-486 zu entnenmer,. Das Spektrum der Anbietungsformen der in Betracht kommenden Hilfsmittel reicht dabei von Ölen über ÖI-in-Wasser-Emulsionen bis hin zu wäßrigen Lösungen.Ulimann 's Encyclopaedia of Industrial Cnemisiry, for example, provides an overview of the shaping processes and the tools that are usually used for this purpose. 5th Ec. vol. AI 5 479-486. The spectrum The forms of supply of the auxiliaries in question range from oils to oil-in-water emulsions to aqueous solutions.
Nichtwassermischbare und wassermischbare Kühlschmierstoffe sind häufig auf Mineralöl aufgebaut. Die verwendeten Mineralölqualitäten sind überwiegend Kombinationen von paraffinischen, naphthenischen und aromatischen Kohlenwasserstoffverbindungen. Neben den Mineralölen haben auch sog. synthetische Schmiermittel ("synthetische Öle") wie Polyalphaolefine, Polyalkylenglykole und -glykolether, Dialkylether, Acetale, natürliche Esteröle sowie synthetische Ester und ihre Derivate Bedeutung.Non-water-miscible and water-miscible cooling lubricants are often based on mineral oil. The mineral oil qualities used are predominantly combinations of paraffinic, naphthenic and aromatic hydrocarbon compounds. In addition to mineral oils, so-called synthetic lubricants ("synthetic oils") such as polyalphaolefins, polyalkylene glycols and glycol ethers, dialkyl ethers, acetals, natural ester oils and synthetic esters and their derivatives are also important.
Um die Anforderungen der Praxis erfüllen zu können, müssen Kühlschmierstoffe neben dem Grundöl verschiedene Komponenten enthalten. Die wichtigsten Substanzgruppen sind die Emulgatoren, Korrosionschutzzusätze, Biozide, EP- Zusätze, polare Zusätze, Antinebelzusätze, Alterungsschutzstoffe, Festschmierzusätze und Entschäumer.In order to meet practical requirements, cooling lubricants must contain various components in addition to the base oil. The most important substance groups are the emulsifiers, anti-corrosion additives, biocides, EP additives, polar additives, anti-fog additives, anti-aging agents, solid lubricant additives and defoamers.
Emulgatoren (z. B. Tenside, Petroleumsulfonate, Alkaliseifen, Alkanolaminseifen) stabilisieren die feine Verteilung von Öltröpfchen in der wäßrigen Arbeitsflüssigkeit, die eine ÖI-in-Wasser-Emulsion darstellt. Die Emulgatoren stellen mengenmäßig eine wichtige Gruppe an Zusatzstoffen bei den wassermischbaren Kühlschmierstoffen dar.Emulsifiers (e.g. surfactants, petroleum sulfonates, alkali soaps, alkanolamine soaps) stabilize the fine distribution of oil droplets in the aqueous working fluid, which is an oil-in-water emulsion. In terms of quantity, the emulsifiers represent an important group of additives for water-miscible cooling lubricants.
Übliche Korosionsschutzzusätze (z. B. Alkanolamine und ihre Salze, Sulfonate, organische Borverbindungen, Fettsäureamide, Aminodicarbonsäuren, Phosphorsäureester, Thiophosphonsäureester, Dialkyldithiophosphate, Mono- und Dialkylarylsulfonate, Benzothazole, Polyisobutenbernsteinsäurederivate) sollen das Rosten von Metalloberflächen verhindern. Einige Korrosionsschutzzusätze haben gleichzeitig emulgierende Eigenschaften und finden deshalb auch als Emulgator ihre Anwendung. Biozide (z. B. Phenol-Derivate, Formaldehydabkömmlinge, Kathon MW) sollen das Wachstum von Bakterien und Pilzen verhindern. EP-Zusätze (z. B. geschwefelte Fette und Öle, phosphorhaltige Verbindungen, chlororganische Verbindungen) sollen Mikroverschweißungen zwischen Metalloberflächen bei hohen Drücken und Temperaturen verhindern. Polare Zusätze (z. B. natürliche Fette und Öle, synthetische Ester) erhöhen die Schmierungseigenschaften. Alterungsschutzstoffe (z. B. organische Sulfide, Zinkdithiophosphate, aromatische Amine) gewährleisten eine lange Gebrauchsdauer der Kühlschmierstoffe.Usual corrosion protection additives (e.g. alkanolamines and their salts, sulfonates, organic boron compounds, fatty acid amides, aminodicarboxylic acids, phosphoric acid esters, thiophosphonic acid esters, dialkyldithiophosphates, mono- and dialkylarylsulfonates, benzothazoles, polyisobutene succinic acid derivatives) are intended to prevent rusting of metal surfaces. Some corrosion protection additives also have emulsifying properties and are therefore also used as emulsifiers. Biocides (e.g. phenol derivatives, formaldehyde derivatives, Kathon MW) are intended to prevent the growth of bacteria and fungi. EP additives (e.g. sulfurized fats and oils, compounds containing phosphorus, organochlorine compounds) are intended to prevent micro-welding between metal surfaces at high pressures and temperatures. Polar additives (e.g. natural fats and oils, synthetic esters) increase the lubrication properties. Anti-aging agents (e.g. organic sulfides, zinc dithiophosphates, aromatic amines) ensure a long service life of the cooling lubricants.
Neben der Kühlwirkung liegt die zweite wichtige Funktion der Kühlschmierstoffe in der Schmierwirkung. Dabei beruht die Wirkung der schmierenden Komponenten auf der Bildung von Oberflächenschichten, die gegenüber dem Grundwerkstoff eine niedrigere Scherfestigkeit besitzen und damit Reibung und Verschleiß herabsetzen. Das Spektrum der Oberfiächenzustände reicht dabei von adsorptiv gebundenen Schichten über Chemiesorption bis zu chemischen Reaktionsschichten, die einen festen Verbund zur Metalloberfläche erzeugen.In addition to the cooling effect, the second important function of the cooling lubricants is the lubricating effect. The effect of the lubricating components is based on the formation of surface layers that have a lower shear strength than the base material and thus reduce friction and wear. The spectrum of the surface states ranges from adsorptively bound layers through chemisorption to chemical reaction layers that create a firm bond to the metal surface.
Die einfachste Form der Schmierstoffbelegung einer Oberfläche sind adsorptive Schmierstoffschichten. Sie werden beispielsweise durch Mineralöle ohne besondere Additive erzeugt. Die Bildung der Adsorptionsschichten kann durch Zusätze polarer Wirkstoffe wie Fettalkohole oder Fettester verstärkt werden. Dabei tritt über die rein physikalische Adsorption hinaus eine Wechselwirkung zwischen der Metalloberfläche und den Schmierstoffmolekülen ein, die zu einer partiellen chemiesorptiven Bindung der Fettalkohole oder der Fettester führt.The simplest form of lubricant coating on a surface is adsorptive lubricant layers. They are produced, for example, by mineral oils without special additives. The formation of the adsorption layers can be increased by adding polar active ingredients such as fatty alcohols or fatty esters. In addition to the purely physical adsorption, there is an interaction between the metal surface and the lubricant molecules, which leads to a partial chemisorptive binding of the fatty alcohols or fatty esters.
Typische Vertreter chemiesorptiver Schmierstoff-Schichtbildner sind Fettsäuren. Die hydrophile Carboxylgruppe wird durch Reaktion mit den Metallatomen chemisch an die Metalloberfläche gebunden und der hydrophobe Kohlenwasserstoffrest richtet sich senkrecht zur Oberfläche aus. Die erhöhte Haftfestigkeit der chemiesorptiven Schicht verbessert zwar das Druckaufnahmevermögen gegenüber rein adsorptiven Schmierstoff schichten, reicht jedoch für viele Fälle der Metailumformung zur Reib- und Verschleißminderung noch nicht aus. Hier bringen erst Beimengungen von EP- bzw. AW-Zusäizen (extreme pressure bzw. anti wear-Zusäize) eine hinreichende Verbesserung der Schmierieistung, so daß auch schwierige Umformprozesse ermöglich: werden. Hierbei nandelt es sich in der Regel um Chlor-, Phosphoroder Schwefel-haiiige Wirkstoffe. Deren WirKung beruht auf der Ausbildung von chemiscnen Reakuonsscnicnien in Form vcn IVietallchioπαen. Metal nosDnaten oder Metallsulfiden. Aus Entsorgungsgründen besteht heute das Bestreben, auf Chlor-haltige EP-Zusätze nach Möglichkeit zu verzichten. Die an der Metalloberfläche gebildeten Reaktionsschichten wirken einerseits als Festschmierstoffschichten, die während des Umformvorganges ständig abgetragen und erneuert werden. Andererseits bilden Sie monomolekulare Oberflächenfilme, die weitere Schmierstoffkomponenten anlagern können.Typical representatives of chemisorptive lubricant film formers are fatty acids. The hydrophilic carboxyl group is chemically bound to the metal surface by reaction with the metal atoms and the hydrophobic hydrocarbon residue is aligned perpendicular to the surface. The increased adhesive strength of the chemisorptive layer improves the pressure absorption capacity compared to purely adsorptive lubricant layers, but is still not sufficient for many cases of metal forming to reduce friction and wear. It is only when EP or AW additives (extreme pressure or anti wear additives) are added that there is a sufficient improvement in lubrication performance so that even difficult forming processes are possible. These are usually chlorine, phosphorus or sulfur-free agents. Their effect is based on the formation of chemical reactivity in the form of IVietallchioπαen. Metal nosDnaten or metal sulfides. For reasons of disposal, there is an attempt today to avoid using chlorine-containing EP additives wherever possible. The reaction layers formed on the metal surface act on the one hand as solid lubricant layers that are constantly removed and renewed during the forming process. On the other hand, they form monomolecular surface films that can attach additional lubricant components.
Wassergemischte Kühlschmierstoffe stellen einen weit verbreiteten Kühlschmierstofftyp da. In der Praxis sind jedoch unterschiedliche wassergemischte Kühlschmierstoffe im Einsatz, um die unterschiedlichen Anforderungen hinsichtlich Korrosionsschutz für die verschiedenen bearbeiteten Materialien, Schmierwirkung bei hoher Arbeitsgeschwindigkeit, Standzeit und nicht zuletzt Arbeitsschutz und Umweltverhalten zu erfüllen.Water-mixed cooling lubricants are a widely used type of cooling lubricant. In practice, however, different water-mixed cooling lubricants are used in order to meet the different requirements with regard to corrosion protection for the different processed materials, lubricating effect at high working speeds, service life and, last but not least, occupational safety and environmental behavior.
Durch den Einsatz von Nanopartikeln lassen sich die Schmiereigenschaften von herkömmlichen Schmiermitteln gezielt verbessern. In einem Artikel von Z. S. Hu, J. X. Dong, G. X Chen (Tribology Intern. Vol. 31 , No 7, pp 355-360) wird der Einsatz von amorphem Eisenoxid mit einer Teilchengröße von 20-50 nm zur Verbesserung der Abriebbeständigkeit und des Reibwertes beschrieben. Dieses Material wird über Trocknung unter superkritischen Bedingungen aus Ethanol erhalten.The lubrication properties of conventional lubricants can be specifically improved by using nanoparticles. An article by ZS Hu, JX Dong, G. X Chen (Tribology Intern. Vol. 31, No 7, pp 355-360) describes the use of amorphous iron oxide with a particle size of 20-50 nm to improve the abrasion resistance and Friction coefficient described. This material is obtained from ethanol by drying under supercritical conditions.
In dem Patent WO 92/01872 / US 5525246 wird Fe304 im Gemisch mit anderen Oxiden in einer Teilchengröße kleiner 2 μm eingesetzt. In WO 9114757 wird Eisenoxid in einer Konzentration von 1-30% und einer Teilchengröße von 10 μm beschrieben. JP 01083309/US 5468402 beschreibt den Einsatz von FeO und Fe3θ4 (>10 μm) für hot rolling-Prozesse. Fβ3θ4 mit Teilchengrößen von 1-5 μm wird von SU 765344 in Konzentrationen von 8-15% als festes Schmiermittel für magnetisierbare Oberflächen beschrieben.In the patent WO 92/01872 / US 5525246, Fe 3 0 4 is used in a mixture with other oxides in a particle size smaller than 2 μm. WO 9114757 describes iron oxide in a concentration of 1-30% and a particle size of 10 μm. JP 01083309 / US 5468402 describes the use of FeO and Fe 3 θ 4 (> 10 μm) for hot rolling processes. Fβ3θ 4 with particle sizes of 1-5 μm is described by SU 765344 in concentrations of 8-15% as a solid lubricant for magnetizable surfaces.
Die Herstellung magnetischer Nanopartikel, die erwünschtenfalls mit einer Schicht organischer Moleküle belegt sein können, sowie ihre Verwendung zur Herstellung magnetischer Flüssigkeiten sind aus einer großen Zahl von Veröffentlichungen bekannt. Der Artikel V. S. Zaitsev, D. S. Filimonov, J. A. Presnyakov, R. J. Gambino, B. Chu: „Physical and Chemical Properties of Magnetite and Magnetite-Polymer Nanoparticles and Their Colloidal Dispersions", J. Colloid Interface Sei, 212. 49 - 57 (1999) befaßt sich mit Herstellung und Eigenschaften von polymerbeschichteten Nanopartikeln aus Magnetit, die insbesondere als Kontrastmittel bei magnetischen Resonanzuntersuchungen eingesetzt werden können. Bei der Herstellung der Partikel, die auch nach einem kontinuierlichen Verfahren erfolgen kann, werden quatemäre Ammoniumsalze als Stabilisatoren eingesetzt. Bei geeigneter Wahl des Stabilisators werden wäßrige kolloide Suspensionen erhalten, die über Monate stabil sind. Separiert man die magnetischen Partikel und trocknet sie, können die erhaltenen Pulver unter Ultraschalleinwirkung wieder suspendiert werden. Eine Polymerbeschichtung erfolgt dadurch, daß man Acrylsäure und Hydroxyethylmethacrylat in Gegenwart der bereits vorgebildeten Nanopartikel polymehsiert.The production of magnetic nanoparticles, which can be coated with a layer of organic molecules if desired, and their use for the production of magnetic liquids are known from a large number of publications. The article VS Zaitsev, DS Filimonov, JA Presnyakov, RJ Gambino, B. Chu: "Physical and Chemical Properties of Magnetite and Magnetite-Polymer Nanoparticles and Their Colloidal Dispersions", J. Colloid Interface Sei, 212. 49 - 57 (1999) is concerned with the production and properties of polymer-coated nanoparticles made of magnetite, which can be used in particular as contrast agents in magnetic resonance examinations. Quaternary ammonium salts are used as stabilizers in the production of the particles, which can also be carried out by a continuous process Aqueous colloidal suspensions are obtained which are stable for months. If the magnetic particles are separated and dried, the powders obtained can be resuspended under the action of ultrasound el polymerized.
Das deutsche Gebrauchsmuster DE-U-93 21 479 offenbart eine magnetische Flüssigkeit auf wäßriger Basis, wobei magnetische Eisenoxidteilchen, die vorzugsweise eine Größe von 5 bis 20 nm aufweisen, durch eine erste monomolekulare Adsorptionsschicht aus gesättigten oder ungesättigten Fettsäuren und eine zweite Adsorptionsschicht aus oberflächenaktiven alkoxylierten Fettalkoholen stabilisiert sind.The German utility model DE-U-93 21 479 discloses an aqueous-based magnetic liquid, magnetic iron oxide particles, which preferably have a size of 5 to 20 nm, by a first monomolecular adsorption layer made of saturated or unsaturated fatty acids and a second adsorption layer made of surface-active alkoxylated Fatty alcohols are stabilized.
Die DE 199 23 625 beschreibt ein Verfahren zur Herstellung redispergierbarer Metalloxide oder Metallhydroxide mit einer volumengewichteten mittleren Kristallitgröße zwischen 1 und 20 nm, wobei man aus wäßrigen Lösungen von Metallsalzen durch Anheben des pH-Wertes mit einer Base in Gegenwart polymerer Carbonsäuren Metallhydroxid oder Metalloxid ausfällt und zumindest einen Teil der wäßrigen Phse von dem erhaltenen Metalioxid oder Metallhydroxid abtrennt.DE 199 23 625 describes a process for the preparation of redispersible metal oxides or metal hydroxides with a volume-weighted average crystallite size between 1 and 20 nm, where metal hydroxide or metal oxide is precipitated from aqueous solutions of metal salts by raising the pH with a base in the presence of polymeric carboxylic acids separates at least part of the aqueous phase from the metal oxide or metal hydroxide obtained.
Die vorliegende Erfindung hat zum Ziel, Schmiermittel sowie diese verwendende Schmierverfahren zur Verfügung zu stellen, bei denen eine verbesserte SchmierwirKunα erreicht wirc. Die Erfindung betrifft in einem ersten Aspekt olbasierte Schmiermittel für die Metallbearbeitung, die 0,1 bis 5 Gew.-% bezogen auf das anwendungsfertige Schmiermittel ferromagnetische oder ferrimagnetische Partikel mit einer volumengewichteten mittleren Kristallitgröße im Bereich von 2 bis 80 nm enthalten. Vorzugsweise liegt die volumengewichtete mittlere Kristallitgröße im Bereich von 8 bis 20 nm. Bei dem anwendungsfertigen Schmiermittel kann es sich um ein im wesentlichen wasserfreies Öl oder um eine ÖI-in-Wasser-Emulsion handeln.The aim of the present invention is to provide lubricants and lubricating methods using them, in which an improved lubricating effect is achieved. In a first aspect, the invention relates to oil-based lubricants for metalworking which contain 0.1 to 5% by weight, based on the ready-to-use lubricant, of ferromagnetic or ferrimagnetic particles with a volume-weighted average crystallite size in the range from 2 to 80 nm. The volume-weighted average crystallite size is preferably in the range from 8 to 20 nm. The ready-to-use lubricant can be an essentially anhydrous oil or an oil-in-water emulsion.
Die volumengewichtete mittlere Kristallitgröße ist mit Röntgenbeugungsverfahren, insbesondere über eine Scherrer-Analyse bestimmbar. Das Verfahren ist beispiels-weise beschrieben in: C. E. Krill, R. Birringer: „Measuring average grain sizes in nanocrystalline materials", Phil. Mag. A 77, S. 621 (1998). Demnach kann die volumengewichtete mittlere Kristallitgröße D bestimmt werden durch den Zusammenhang D = Kλ/ßcosθ.The volume-weighted average crystallite size can be determined using X-ray diffraction methods, in particular using a Scherrer analysis. The method is described, for example, in: CE Krill, R. Birringer: "Measuring average grain sizes in nanocrystalline materials", Phil. Mag. A 77, p. 621 (1998). Accordingly, the volume-weighted average crystallite size D can be determined by the relationship D = Kλ / ßcosθ.
Dabei ist λ die Wellenlänge der verwendeten Röntgenstrahlung, ß ist die volle Breite auf halber Höhe des Reflexes an der Beugungsposition 2Θ. K ist eine Konstante der Größenordnung 1 , deren genauer Wert von der Kristallform abhängt. Man kann diese Unbestimmtheit von K vermeiden, indem man die Linienverbreiterung als integrale Weite ß, bestimmt, wobei ß, definiert ist als die Fläche unter dem Röntgenbeugungsreflex, geteilt durch dessen maximaler Intensität l0:Here λ is the wavelength of the X-rays used, ß is the full width at half the height of the reflection at the diffraction position 2Θ. K is a constant of the order of 1, the exact value of which depends on the crystal shape. This indeterminacy of K can be avoided by determining the line broadening as an integral width ß, where ß is defined as the area under the X-ray diffraction reflex divided by its maximum intensity l 0 :
2Θ2 ß, = 1/l0 [ l(2θ)d(2θ) 2θι2Θ 2 ß, = 1 / l 0 [l (2θ) d (2θ) 2θι
Dabei sind die Größen 2θι und 2Θ2 die minimale unα maximale Winkeiposition des Bragg-Reflexes auf der 2Θ-Acnse. I(2Θ) ist die gemessene Intensität des Reflexes als Funktion von 29. Unier Verwendung von diesem Zusammenhang ergibt sich als Gleichung zur Bestimmung oer volumengewichteten mittleren Kristallitgröße D. D = λ/ßicosθThe sizes 2θι and 2Θ 2 are the minimum and maximum angle position of the Bragg reflex on the 2Θ lens. I (2Θ) is the measured intensity of the reflection as a function of 29. Using this relationship results in the equation for determining the volume-weighted average crystallite size D. D = λ / ßicosθ
Wegen der verbesserten Dispergierbarkeit in der Ölphase setzt man vorzugsweise solche ferromagnetischen oder ferrimagnetischen Partikel ein, die eine hydrophobierende organische Beschichtung aufweisen. Eine solche hydrophobierende organische Beschichtung kann beispielsweise erreicht werden durch Belegen der Partikel mit organischen Sulfon- oder Phosphonsäuren oder mit Alkoholen, die jeweils einen Alkylrest mit einer solchen Kettenlänge tragen, daß die Oberflächen der Partikel hydrophobiert werden und die Dispergierbarkeit der Partikel in der Ölphase verbessert wird. Dies ist beispielsweise bei Alkylresten mit Kettenlängen im Bereich von 8 bis 22 C-Atomen der Fall. Vorzugsweise setzt man jedoch solche ferromagnetischen oder ferrimagnetischen Partikel ein, deren hydrophobierende organische Beschichtung zumindest anteilig aus Carbonsäuren oder deren Anionen mit 8 bis 44, vorzugsweise mit 12 bis 22 C-Atomen besteht. Dies sind Kettenlängen, die man üblicherweise bei Fettsäuren oder sogenannten Dimerfettsäuren findet.Because of the improved dispersibility in the oil phase, preference is given to using ferromagnetic or ferrimagnetic particles which have a hydrophobic organic coating. Such a hydrophobic organic coating can be achieved, for example, by coating the particles with organic sulfonic or phosphonic acids or with alcohols, each carrying an alkyl radical with a chain length such that the surfaces of the particles are rendered hydrophobic and the dispersibility of the particles in the oil phase is improved , This is the case, for example, with alkyl radicals with chain lengths in the range from 8 to 22 carbon atoms. However, preference is given to using ferromagnetic or ferrimagnetic particles whose hydrophobizing organic coating consists at least in part of carboxylic acids or whose anions have 8 to 44, preferably 12 to 22, carbon atoms. These are chain lengths that are usually found in fatty acids or so-called dimer fatty acids.
Die ferromagnetischen oder ferrimagnetischen Partikel können ausgewählt sein aus jeweils dotiertem oder undotiertem Cobaltferrit, Manganferrit, Zinkferrit, Nickelferrit und γ-Fe2O3. Letzteres ist besonders bevorzugt.The ferromagnetic or ferrimagnetic particles can be selected from doped or undoped cobalt ferrite, manganese ferrite, zinc ferrite, nickel ferrite and γ-Fe 2 O 3 . The latter is particularly preferred.
Die Schmiermittel, in denen die ferromagnetischen oder ferrimagnetischen Nanopartikel dispergiert sind, können ein im wesentlichen wasserfreies Öl darstellen. Solche Öle sind auf dem betroffenen technischen Gebiet als Schneidoder Umformöle bekannt. Sie können weitere Additive enthalten, wie sie einleitend beispielhaft angeführt wurden. Da die ferromagnetischen oder ferrimagnetischen Nanopartikel wesentlich zur Schmierwirkung beitragen, kann das als Schmiermittel eingesetzte Öl wesentlich weniger EP-Additive als üblich enthalten oder sogar frei von solchen Additiven sein.The lubricants in which the ferromagnetic or ferrimagnetic nanoparticles are dispersed can be an essentially anhydrous oil. Such oils are known in the technical field concerned as cutting or forming oils. They can contain other additives, as exemplified in the introduction. Since the ferromagnetic or ferrimagnetic nanoparticles contribute significantly to the lubricating effect, the oil used as a lubricant can contain considerably fewer EP additives than usual or even be free of such additives.
In einer alternativen Ausführungsform stellen die Schmiermittel eine Öi-in-Wasser- Emulsion dar, wobei die ferromagnetischen oder ferrimagnetischen Partikel in der Ölphase dispergiert sind. Derartige Emulsionen werden üblicherweise dadurch hergestellt, daß man wasserarme oder wasserfreie Emuisionskonzentrate mit Wasser vermischt, wobei man üblicherweise pro Gewichtsteil Konzentrat 10 bis 50 Gewichtsteile Wasser verwendet. Im Sinne der Erfindung können zur Herstellung der ÖI-in-Wasser-Emulsionen Emulsionskonzentrate verwendet werden, die sich von dem im Stand der Technik bekannten und kommerziell erhältlichen Konzentraten lediglich dadurch unterscheiden, daß sie ferromagnetische oder ferrimagnetische Nanopartikel enthalten. Ansonsten können die Emulsionskonzentrate und die hieraus herstellbaren ÖI-in-Wasser-Emulsionen die auf dem betroffenen technischen Gebiet üblichen Komponenten enthalten, die vorstehend beispielhaft aufgezählt wurden. Jedoch kann auch in dieser Ausführungsform auf den Zusatz konventioneller EP-Additive zumindest weitgehend verzichtet werden.In an alternative embodiment, the lubricants are an oil-in-water emulsion, the ferromagnetic or ferrimagnetic particles being dispersed in the oil phase. Such emulsions are usually prepared by using low or anhydrous emulsion concentrates Mixed water, usually 10 to 50 parts by weight of water are used per part by weight of concentrate. For the purposes of the invention, emulsion concentrates can be used to produce the oil-in-water emulsions which differ from the concentrates known and commercially available only in that they contain ferromagnetic or ferrimagnetic nanoparticles. Otherwise, the emulsion concentrates and the oil-in-water emulsions which can be prepared therefrom may contain the components which are customary in the technical field concerned and which have been listed above by way of example. However, in this embodiment too, the addition of conventional EP additives can at least largely be dispensed with.
Das als Schmierstoff verwendete Öl bzw. die Ölphase der ÖI-in-Wasser- Emulsionen kann aus einem beliebigen Öl bestehen, wie es auf dem betroffenen Einsatzgebiet üblich ist. Beispielhaft genannt seien paraffinisches oder naphthenisches Mineralöl, synthetische Öle wie beispielsweise Polyolefine, Acetale oder Dialkylether oder Öl auf biologischer Basis, beispielsweise Esteröle, die in Pflanzen oder Tieren vorkommende Triglyceride oder Modifizierungsprodukte hiervon darstellen, Wachsester und Fettsäureester von Monoalkanolen mit 4 bis 12 C-Atomen, beispielsweise Talgfettsäure- ethylhexylester oder umgeestertes Rapsöl, sowie Fettsäureester von Polyolen, wobei als Polyolkomponente insbesondere Trimethyloipropan verwendet werden kann. Selbstverständlich können auch Gemische derartiger Öle eingesetzt werden.The oil used as a lubricant or the oil phase of the oil-in-water emulsions can consist of any oil, as is customary in the area of application concerned. Examples include paraffinic or naphthenic mineral oil, synthetic oils such as, for example, polyolefins, acetals or dialkyl ethers or biologically based oils, for example ester oils which are triglycerides or modification products thereof occurring in plants or animals, wax esters and fatty acid esters of monoalkanols having 4 to 12 carbon atoms , for example tallow fatty acid ethylhexyl ester or transesterified rapeseed oil, and also fatty acid esters of polyols, it being possible in particular to use trimethyloipropane as the polyol component. Mixtures of such oils can of course also be used.
Die Erfindung betrifft weiterhin die Verwendung einer Dispersion von ferromagnetischen oder ferrimagnetischen Partikeln mit einer volumengewichteten mittleren Kristallitgröße im Bereich von 2 bis 80 nm, vorzugsweise von 8 bis 20 nm in Öl zur Herstellung eines Schmiermitteis gemäß der vorstehenden Beschreibung. Bezüglich der Herstellverfahren für derartige Partikel und ihre fakultative Oberflächenbeschichtung gelten die vorstehenden Ausführungen. Vorzugsweise verwendet man zur Herstellung der Schmiermittel eine Dispersion von ferromaonetischen oder ferrimaonetischen Partikeln in Öl, die etwa 10 bis 35 Gew.-% der ferromagnetischen oder ferrimagnetischen Partikel bezogen auf das Gesamtgewicht der Dispersion enthält.The invention further relates to the use of a dispersion of ferromagnetic or ferrimagnetic particles with a volume-weighted average crystallite size in the range from 2 to 80 nm, preferably from 8 to 20 nm in oil for the production of a lubricant as described above. With regard to the production processes for such particles and their optional surface coating, the above statements apply. It is preferred to use a dispersion of ferromaonetic or ferrimaonetic particles in oil to produce the lubricants, which is about 10 to 35 Wt .-% of the ferromagnetic or ferrimagnetic particles based on the total weight of the dispersion contains.
Ein weiterer Asperkt der Erfindung liegt in einem Verfahren zum Umformen oder zur spanabhebenden Bearbeitung von Metallen unter Verwendung eines Werkzeugs und eines ölbasierten Schmiermittels, wobei man ein ölbasiertes Schmiermittel wie vorstehend beschrieben einsetzt, das ferromagnetische oder ferrimagnetische Nanopartikel enthält. Beispiele für die genannten Arbeitsverfahren „Umformen" und „spanabhebende Bearbeitung" wurden eingangs genannt.Another aspect of the invention resides in a process for forming or machining metals using a tool and an oil-based lubricant, using an oil-based lubricant as described above which contains ferromagnetic or ferrimagnetic nanoparticles. Examples of the above-mentioned working methods "forming" and "machining" were mentioned at the beginning.
Ein besonderer Vorteil der Erfindung zeigt sich dann, wenn das Werkzeug während des Umformens oder der spanabhebenden Bearbeitung von Metallen magnetisiert wird oder wenn, z. B. bei nichtmagnetischen Metallen, der Ort der Spanerzeugung einem Permanentmagnetfeld ausgesetzt wird. Dies kann beispielsweise elektromagnetisch erfolgen. Das magnetisierte Werkzeug zieht die aufgrund der Anwesenheit der ferromagnetischen oder ferrimagnetischen Nanopartikel ferromagnetische oder ferrimagnetische Ölphase an und hält sie so am Ort der Bearbeitung, also in der Tribozone, fest. Ein Abscheren der Ölphase wird hierdurch erschwert. Dieser Verfahrensaspekt ist besonders dann von Vorteil, wenn als Kühlschmierstoff eine ÖI-in-Wasser-Emulsion eingesetzt wird, deren Ölphase ferromagnetische oder ferrimagnetische Nanopartikel enthält. Durch Anlegen des Magnetfeldes an das Werkzeug bindet sich die ferromagnetische oder ferrimagnetische Ölphase an das Werkzeug. In der Tribozone liegt damit eine erwünschte besonders hohe Olkonzentration vor, während in der Peripherie der Tribozone ausreichend Wasserphase zur Kühlung zur Verfügung steht. Nach Abschalten des magnetischen (elektromagnetischen) Feldes lassen sich die entstandenen Späne gut durch die Kühlschmierflüssigkeit entfernen.A particular advantage of the invention shows itself when the tool is magnetized during the forming or machining of metals or when, for. B. in non-magnetic metals, the place of chip production is exposed to a permanent magnetic field. This can be done electromagnetically, for example. The magnetized tool attracts the ferromagnetic or ferrimagnetic oil phase due to the presence of the ferromagnetic or ferrimagnetic nanoparticles and thus holds them in place at the machining site, i.e. in the tribo zone. This makes it more difficult to shear off the oil phase. This process aspect is particularly advantageous if an oil-in-water emulsion is used as the cooling lubricant, the oil phase of which contains ferromagnetic or ferrimagnetic nanoparticles. By applying the magnetic field to the tool, the ferromagnetic or ferrimagnetic oil phase binds to the tool. A desired particularly high oil concentration is thus present in the tribozone, while sufficient water phase is available for cooling in the periphery of the tribozone. After switching off the magnetic (electromagnetic) field, the swarf can be easily removed with the cooling lubricant.
Ein weiterer Vorteil der Verwendung ferromagnetischer oder ferrimagnetischer Nanopartikel zur Herstellung ölbasierter Schmiermittel liegt darin, daß diese Nanopartikel biozide, insbesondere bakterezide Wirkung haben können. Hierdurch wird die Standzeit und die Verwendungsdauer der Schmierstoffe verbessert, ohne daß ein Zusatz herkömmlicher Konservierungsmittel, beispielsweise auf Basis von Formaldehydabspaltern, erforderlich ist. Demgemäß liegt ein weiterer Aspekt der Erfindung in einem Verfahren zum Umformen oder zur spanabhebenden Bearbeitung von Metallen unter Verwendung eines ölbasierten Schmiermittels, wobei das olbasierte Schmiermittel nicht mit einem üblichen Biozid versetzt wird. Dies ist besonders im Hinblick auf Arbeits- und Umweltschutz vorteilhaft.Another advantage of using ferromagnetic or ferrimagnetic nanoparticles for producing oil-based lubricants is that these nanoparticles can have a biocidal, in particular bactericidal, effect. As a result, the service life and the service life of the lubricants are improved without the addition of conventional preservatives, for example based on Formaldehyde releasing, is required. Accordingly, a further aspect of the invention resides in a method for forming or machining metals using an oil-based lubricant, the oil-based lubricant not being mixed with a conventional biocide. This is particularly advantageous in terms of occupational and environmental protection.
Die ferromagnetischen oder ferrimagnetischen Nanopartikel können nach bekannten Verfahren hergestellt und mit einer hydrophoben Beschichtung versehen werden. Beispielsweise sei das in DE 199 23 625 beschriebene Verfahren genannt. Gemäß diesem Dokument läßt sich das Herstellverfahren auch kontinuierlich betreiben, was eine erhöhte Wirtschaftlichkeit des Verfahrens bedeutet. Dabei geht man so vor, daß man aus wäßrigen Lösungen von Metallsalzen durch Anheben des pH-Wertes mit einer Base in Gegenwart polymerer Carbonsäuren Metallhydroxid oder Metalloxid kontinuierlich ausfällt, indem man a) ein erstes Behältnis mit der wäßrigen Lösung der Metallsalze und ein zweites Behältnis mit einer wäßrigen alkalischen Lösung einer Base und einer polymeren Carbonsäure bereitstellt, b) aus beiden Behältnissen kontinuierlich Lösung entnimmt und die beiden Lösungen in einer Mischstrecke vermischt und erwünschtenfalls c) in einem hinter der Mischstrecke liegenden Rohr die Fällreaktion abschließt.The ferromagnetic or ferrimagnetic nanoparticles can be produced by known processes and provided with a hydrophobic coating. For example, the method described in DE 199 23 625 may be mentioned. According to this document, the manufacturing process can also be operated continuously, which means increased efficiency of the process. The procedure is such that metal hydroxide or metal oxide is continuously precipitated from aqueous solutions of metal salts by raising the pH with a base in the presence of polymeric carboxylic acids by a) a first container with the aqueous solution of the metal salts and a second container with provides an aqueous alkaline solution of a base and a polymeric carboxylic acid, b) continuously removes solution from both containers and mixes the two solutions in a mixing section and, if desired c) closes the precipitation reaction in a tube behind the mixing section.
Spezielle Verfahren zur Herstellung und Hydrophobierung von ferromagnetischem oder ferrimagnetischem nanoskaligem γ-Fe203 sind die folgenden:Special processes for the production and hydrophobization of ferromagnetic or ferrimagnetic nanoscale γ-Fe 2 0 3 are the following:
Beispiel a:Example a:
6,48g FeCI3 werden in 40g Wasser gelöst. 3,97g FeCI2 *4H20 werden in einer Mischung aus 8ml entionisierten Wasser und 2ml 37 %iger Salzsäure gelöst. Kurz vor Einsatz der Lösungen im Fäliungsprozeß werden sie zu einer Mischung vereinigt.6.48g FeCI 3 are dissolved in 40g water. 3.97 g of FeCI 2 * 4H 2 0 are dissolved in a mixture of 8 ml of deionized water and 2 ml of 37% hydrochloric acid. Shortly before the solutions are used in the precipitation process, they are combined to form a mixture.
In einer Vorlage löst man 10,0g NaOH in 400m! Wasser. Nach Abkühlen auf RaumtemDeratur gießt die Eisensalziösung unter starKem Rühren zu, wobei sicn nanoskaliges Eisenoxid abscheidet. Der Niederschlag wird abzentrifugiert und mehrfach mit deionisiertem Wasser gewaschen. Anschließend wird der Niederschlag zu einer rührfähigen Suspension in Wasser aufgenommen und mit 1 ,11 g Laurinsäure auf 80 - 90 °C für eine halbe Stunde unter Rühren erwärmt. Nach erfolgtem Coating setzt sich der Niederschlag ab und überstehendes Wasser wird abdekantiert.In a template, 10.0 g of NaOH are dissolved in 400 m! Water. After cooling to room temperature, the iron salt solution is poured in with vigorous stirring, whereby deposits nanoscale iron oxide. The precipitate is centrifuged off and washed several times with deionized water. The precipitate is then taken up in a stirrable suspension in water and heated to 80-90 ° C. with 1.11 g of lauric acid for half an hour with stirring. After the coating has taken place, the precipitate settles out and the excess water is decanted off.
Den Rückstand nimmt man mit 70g Sojaöl auf. Mittels Ausschütteln und Zugabe von Wasser überführt man die gecoateten magnetischen Partikel in die Ölphase.The residue is taken up with 70g soybean oil. The coated magnetic particles are transferred into the oil phase by shaking and adding water.
Beispiel b:Example b:
6,48 g FeCI3 werden in 40 g Wasser gelöst. 3,97 g FeCI2 *4H20 werden in einer Mischung aus 8ml entionisierten Wasser und 2ml 37 %iger Salzsäure gelöst. Kurz vor Einsatz der Lösungen im Fällungsprozeß werden sie zu einer Mischung vereinigt.6.48 g FeCI 3 are dissolved in 40 g water. 3.97 g of FeCI 2 * 4H 2 0 are dissolved in a mixture of 8 ml of deionized water and 2 ml of 37% hydrochloric acid. Shortly before the solutions are used in the precipitation process, they are combined to form a mixture.
In einer Vorlage mischt man 80,0 g NH3 mit 320ml Wasser. Nach Abkühlen auf Raumtemperatur gießt die Eisensalzlösung unter starkem Rühren zu, wobei sich nanoskaliges Eisenoxid abscheidet. Der Niederschlag wird abzentrifugiert und mehrfach mit deionisiertem Wasser gewaschen. Anschließend wird der Niederschlag zu einer rührfähigen Suspension in Wasser aufgenommen und mit 2 g Isostearinsäure auf 80 - 90 °C für eine halbe Stunde unter Rühren erwärmt. Nach erfolgtem Coating setzt sich der Niederschlag ab und überstehendes Wasser wird abdekantiert.80.0 g of NH 3 are mixed with 320 ml of water in a template. After cooling to room temperature, the iron salt solution is poured in with vigorous stirring, nanoscale iron oxide separating out. The precipitate is centrifuged off and washed several times with deionized water. The precipitate is then taken up in a stirrable suspension in water and heated to 80-90 ° C. with 2 g of isostearic acid for half an hour with stirring. After the coating has taken place, the precipitate settles out and the excess water is decanted off.
Den Rückstand nimmt man mit 65 g Sojaöl auf. Mittels Ausschüttein und Zugabe von Wasser überführt man die gecoateten magnetischen Partikel in die Ölphase. AusführunosbeispieleThe residue is taken up with 65 g soybean oil. The coated magnetic particles are transferred into the oil phase by pouring out water and adding water. Ausführunosbeispiele
Als Eignungsprüfung wurde eine Reibverschleißprüfung nach Reichert durchgeführt. Dieses Verfahren dient zur Ermittlung des Druckaufnahmevermögens (EP-Verhalten), sowie zur Ermittlung der Haftfestigkeit von flüssigen Schmierstoffen. Hierbei wird eine Prüfrolle mittels eines Hebelsystems an einen umlaufenden Schleifring angepaßt, der mit seinem unteren Drittel in das zu prüfende Schmiermittel eintaucht. Vor Prüfbeginn wird die in Siedegrenzbenzin gereinigte Prüfrolle in die schwenkbare Halterung eingebaut. Die Halterung wird eingeschwenkt und festgeklemmt. Der Schleifring verbleibt mehrere Prüfläufe in der Vorrichtung eingespannt, wo er ebenfalls nach jedem Prüflauf mit Siedegrenzbenzin gereinigt wird. Die Prüfrolle wird durch langsames Aufbringen des Belastungsgewichtes (1 ,5 kg) auf den Schleifring gebracht. Das an der Reichertwaage befindliche Zählwerk wird auf 0 gestellt. Durch Einschalten des Motors versorgt der im Schmiermittel eingetauchte, rotierende Schleifring die Berührungstelle fortlaufend mit Schmiermittel. Beim Erreichen der Zahl 100 am Zählwerk (100 Meter Reibungsstrecke) wird die Prüfrolle vom Schleifring entfernt. Die Prüfrolle wird ausgebaut und die entstandene Schliffmarke mittels einer Meßlupe ausgemessen. Die Ellipsenfläche errechnet sich zu 0,785*Länge*Breite, oder wird mittels einer Zahlentabelle abgelesen. Es werden so viele Prüfläufe durchgeführt, bis sich die Ellipsenflächen der letzten 3 Prüfläufe nicht mehr als 10 % voneinander unterscheiden. Das Druckaufnahmevermögen ist um so größer, je kleiner die ermittelte Eliipsenfläche ist.A friction wear test according to Reichert was carried out as a suitability test. This procedure is used to determine the pressure absorption capacity (EP behavior) and to determine the adhesive strength of liquid lubricants. Here, a test roller is adapted to a rotating slip ring by means of a lever system, the lower third of which is immersed in the lubricant to be tested. Before the start of the test, the test roll, which has been cleaned in white spirit, is installed in the swiveling holder. The holder is swung in and clamped. The slip ring remains clamped in the device for several test runs, where it is also cleaned with white spirit after each test run. The test roller is placed on the slip ring by slowly applying the load weight (1.5 kg). The counter on the Reichertwaage is set to 0. When the motor is switched on, the rotating slip ring immersed in the lubricant continuously supplies the contact point with lubricant. When the number 100 is reached on the counter (100 meter friction distance), the test roller is removed from the slip ring. The test roller is removed and the cut mark is measured using a magnifying glass. The ellipse area is calculated as 0.785 * length * width, or is read off using a number table. So many test runs are carried out until the ellipse surfaces of the last 3 test runs do not differ from one another by more than 10%. The smaller the determined elliptical surface, the greater the pressure absorption capacity.
Als Schmierstoff wurden Kühlschmierstoffemulsionen in Form einer Öl-in-Wasser- Emulsion verwendet. Hierzu wurde ein Konzentrat nach folgender Zusammensetzung in den nachfolgend angegebenen Mengen mit Wasser versetzt: EmulsionskonzentratCooling lubricant emulsions in the form of an oil-in-water emulsion were used as the lubricant. For this purpose, a concentrate of the following composition was mixed with water in the amounts specified below: emulsion concentrate
13,8 Gew.-% Wasser13.8 wt% water
8,0 Gew.-% Monoethanolamin8.0% by weight monoethanolamine
5,0 Gew.-% Triethanolamin5.0% by weight triethanolamine
8,0 Gew.-% Borsäure8.0% by weight boric acid
0,2 Gew.-% Benzotriazol, 1 H, 2, 3-0.2% by weight benzotriazole, 1 H, 2, 3-
36,0 Gew.-% Mineralöl, paraffinisch36.0% by weight mineral oil, paraffinic
1 ,5 Gew.-% Fettalkohol (= FA) + 10 Ethylenoxid (= EO), Oleyl/Cetyl,1.5% by weight fatty alcohol (= FA) + 10 ethylene oxide (= EO), oleyl / cetyl,
Jodzahl (= JZ) 45/50Iodine number (= JZ) 45/50
2,0 Gew.-% Fettsäure (= FS), Capryl2.0% by weight of fatty acid (= FS), capryl
5,5 Gew.-% FS, Tallöl, 25 - 30 % Harz5.5% by weight FS, tall oil, 25-30% resin
2,0 Gew.-% Ethercarbonsäure-Gemisch 90,0 %-ig2.0 wt .-% ether carboxylic acid mixture 90.0%
1 ,0 Gew.-% Glycerin1.0% by weight glycerin
1 ,0 Gew.-% Diethylenglykolmonobutylether1.0% by weight of diethylene glycol monobutyl ether
8,0 Gew.-% FS-monoethanolamid + 1 ,5 EO, Tallöl-8.0% by weight of FS monoethanolamide + 1, 5 EO, tall oil
5,0 Gew.-% FA + 2 EO, Oleyl-Cetyl, pflanzlich5.0% by weight FA + 2 EO, oleyl-cetyl, vegetable
3,0 Gew.-% FA, Octyldodecyl, 2-3.0% by weight FA, octyldodecyl, 2-
Bezogen auf die anwendungsfertige Emulsion werden 5 Gew.-% dieses Konzentrats sowie gemäß Tabelle 1 0,63 bis 5 Gew.-% ferromagnetische oder ferrimagnetische Nanopartikel in Öl vermischt, die gemäß Herstellbeispiel a) erhalten wurden. Die Mischung aus Emulsionskonzentrat und ferromagnetische oder ferrimagnetische Nanopartikel enthaltendem Öl wird mit Wasser auf 100 Gew.-% aufgefüllt. Die Ergebnisse der Reib-Λ/erschleißprüfung an der Reichert- Waage sind in Tabelle 1 enthalten. Tabelle 1 :Based on the ready-to-use emulsion, 5% by weight of this concentrate and, according to Table 1, 0.63 to 5% by weight of ferromagnetic or ferrimagnetic nanoparticles are mixed in oil, which were obtained according to Preparation Example a). The mixture of emulsion concentrate and oil containing ferromagnetic or ferrimagnetic nanoparticles is made up to 100% by weight with water. The results of the friction / wear test on the Reichert balance are shown in Table 1. Table 1 :
Reib-/Verschleißprüfung an der Reic ert-WaageFriction / wear test on the Reic ert scales
(Füllvolumen 25 ml, 100 Meter Meßstrecke)(Filling volume 25 ml, 100 meter measuring section)
Die Proben werden folgendermaßen angesetzt:The samples are set up as follows:
Das Emulsionskonzentrat wird 5 %ig bezogen auf fertige Emulsion, hier 3 g eingesetzt. Das Ferrofluid wird in Konzentrationen an ferromagnetischen oder ferrimagnetischen Nanopartikeln von 0,63 % - 5 %, ebenfalls bezogen auf fertige Emulsion dazugegeben. Mit Wasser wird aufgefüllt, so daß in der Summe 60 g Emulsion entstehen. The emulsion concentrate is 5% based on the finished emulsion, here 3 g. The ferrofluid is added in concentrations of ferromagnetic or ferrimagnetic nanoparticles of 0.63% - 5%, also based on the finished emulsion. It is made up with water so that a total of 60 g of emulsion is formed.
Figure imgf000017_0001
Figure imgf000017_0001
Ergebnis: Die Schmierleistung verbessert sich deutlich beim Anlegen eines Magneten an den Prüfkörper. Damit wird das Schmiermittel (γ-Fe2O3 ) an dem Wirkort (in diesem Fall Prüfzylinder) fixiert.Result: The lubrication performance improves significantly when a magnet is placed on the test specimen. The lubricant (γ-Fe 2 O 3 ) is thus fixed at the place of action (in this case, test cylinder).
Die Angabe in der Spalte „Geräusch" gibt diejenige Laufstrecke der Prüfrolle an, bei der wegen mangelnder Schmierung ein Reibgeräusch auftritt. The information in the column "Noise" indicates the running distance of the test roller where there is friction noise due to insufficient lubrication.

Claims

Patentansprüche claims
1. Olbasierte Schmiermittel für die Metallbearbeitung, die 0,1 bis 5 Gew.-% bezogen auf das anwendungsfertige Schmiermittel ferromagnetische oder ferrimagnetische Partikel mit einer volumengewichteten mittleren Kristallitgröße im Bereich von 2 bis 80 nm enthalten.1. Oil-based lubricants for metalworking which contain 0.1 to 5% by weight, based on the ready-to-use lubricant, of ferromagnetic or ferrimagnetic particles with a volume-weighted average crystallite size in the range from 2 to 80 nm.
2. Schmiermittel nach Anspruch 1 , dadurch gekennzeichnet, daß die ferromagnetischen oder ferrimagnetischen Partikel ein volumengewichtete mittlere Kristallitgröße im Bereich von 8 bis 20 nm aufweisen.2. Lubricant according to claim 1, characterized in that the ferromagnetic or ferrimagnetic particles have a volume-weighted average crystallite size in the range from 8 to 20 nm.
3. Schmiermittel nach einem oder beiden der Ansprüche 1 und 2, dadurch gekennzeichnet, daß die ferromagnetischen oder ferrimagnetischen Partikel eine hydrophobierende organische Beschichtung aufweisen.3. Lubricant according to one or both of claims 1 and 2, characterized in that the ferromagnetic or ferrimagnetic particles have a hydrophobic organic coating.
4. Schmiermittel nach Anspruch 3, dadurch gekennzeichnet, daß die hydrophobierende organische Beschichtung zumindest anteilig aus Carbonsäuren oder deren Anionen mit 8 bis 44, vorzugsweise mit 12 bis 22 C- Atomen besteht.4. Lubricant according to claim 3, characterized in that the hydrophobizing organic coating consists at least partially of carboxylic acids or their anions with 8 to 44, preferably with 12 to 22 carbon atoms.
5. Schmiermittel nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die ferromagnetischen oder ferrimagnetischen Partikel ausgewählt sind aus jeweils dotiertem oder undotiertem Cobaltferrit, Manganferrit, Zinkferrit, Nickelferrit und gamma-Fe203.5. Lubricant according to one or more of claims 1 to 4, characterized in that the ferromagnetic or ferrimagnetic particles are selected from doped or undoped cobalt ferrite, manganese ferrite, zinc ferrite, nickel ferrite and gamma-Fe 2 0 3rd
6. Schmiermittel nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß sie ein im wesentlichen wasserfreies Öl darstellen.6. Lubricant according to one or more of claims 1 to 5, characterized in that they represent an essentially anhydrous oil.
7. Schmiermittel nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß sie eine ÖI-in-Wasser-Emuision darstellen, wobei die ferromagnetischen oder ferrimagnetischen Partikel in der Ölphase dispergiert sind. 7. Lubricant according to one or more of claims 1 to 5, characterized in that they represent an oil-in-water emission, the ferromagnetic or ferrimagnetic particles being dispersed in the oil phase.
8. Vewendung einer Dispersion von ferromagnetischen oder ferrimagnetischen Partikeln mit einer volumengewichteten mittleren Kristallitgröße im Bereich von 2 bis 80 nm in Öl zur Herstellung eines Schmiermittels nach einem oder mehreren der Ansprüche 1 bis 78. Use of a dispersion of ferromagnetic or ferrimagnetic particles with a volume-weighted average crystallite size in the range from 2 to 80 nm in oil for the production of a lubricant according to one or more of claims 1 to 7
9. Verfahren zum Umformen oder zur spanabhebenden Bearbeitung von Metallen unter Verwendung eines Werkzeugs und eines ölbasierten Schmiermittels, dadurch gekennzeichnet, daß als Schmiermittel ein Schmiermittel nach einem oder mehreren der Ansprüche 1 bis 7 eingesetzt wird.9. A method for forming or for machining metals using a tool and an oil-based lubricant, characterized in that a lubricant according to one or more of claims 1 to 7 is used as the lubricant.
10.Verfahren nach Anspruch 9, dadurch gekennzeichnet, daß das Werkzeug während des Umformens oder der spanabhebenden Bearbeitung von Metallen magnetisiert wird, oder daß der Ort der Spanerzeugung einem Permanentmagnetfeld ausgesetzt wird.10. The method according to claim 9, characterized in that the tool is magnetized during the forming or machining of metals, or that the location of the chip production is exposed to a permanent magnetic field.
11. Verfahren nach einem oder beiden der Ansprüche 9 und 10, dadurch gekennzeichnet, daß das olbasierte Schmiermittel nicht mit einem Bioeid versetzt wird. 11. The method according to one or both of claims 9 and 10, characterized in that the oil-based lubricant is not mixed with a bioid.
PCT/EP2000/009686 1999-10-12 2000-10-04 Lubricant for metal machining with ferromagnetic or ferrimagnetic nanoparticles WO2001027226A1 (en)

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US8507415B2 (en) 2005-05-03 2013-08-13 Southwest Research Institute Lubricant oils and greases containing nanoparticle additives
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