WO2001042402A1 - Emulsion et procede pour l'usinage de metaux - Google Patents

Emulsion et procede pour l'usinage de metaux Download PDF

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Publication number
WO2001042402A1
WO2001042402A1 PCT/EP2000/012026 EP0012026W WO0142402A1 WO 2001042402 A1 WO2001042402 A1 WO 2001042402A1 EP 0012026 W EP0012026 W EP 0012026W WO 0142402 A1 WO0142402 A1 WO 0142402A1
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WO
WIPO (PCT)
Prior art keywords
water
concentrate
weight
lubricant
emulsion
Prior art date
Application number
PCT/EP2000/012026
Other languages
German (de)
English (en)
Inventor
Jürgen Geke
Hans-Peter ÖLSCHER
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to AU26708/01A priority Critical patent/AU2670801A/en
Publication of WO2001042402A1 publication Critical patent/WO2001042402A1/fr

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Classifications

    • 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

Definitions

  • the invention relates to a cooling lubricant emulsion for the machining of metals and to a method for producing the emulsion.
  • Cooling lubricants are preparations / mixtures that are used in metal cutting and 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 generate heat that heats up the workpiece, the tool and, above all, the chips.
  • 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 which has an influence on the dimensional accuracy of the manufactured parts.
  • Another main task of cooling lubricants is to improve the service life of the tools, which 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 care than non-water-miscible cooling lubricants such as cutting oils, grinding oils and forming oils.
  • 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 represent an important group of additives for water-miscible cooling lubricants.
  • Common anti-corrosion 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, benzotriazoles, 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 lies in the lubricating effect (see the article by W. Klose: "Cooling lubricants on metal surfaces", messages from the Association of German Email Specialists, 41, Issue 11, pages 138-142 (1993)). Accordingly, the effect of the lubricating components is based on the formation of surface layers which have a lower shear strength than the base material and thus reduce friction and wear.
  • the spectrum of surface states ranges from adsorptively bound layers to chemical sorption to chemical reaction layers that create a solid 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. there 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.
  • 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 oriented perpendicular to the surface.
  • 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.
  • 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 not least occupational safety and environmental behavior. Manufacturers of cooling lubricant concentrates therefore have to manufacture many different types, keep them in stock and transport them in small batches. The user may have to discard usable emulsions if necessary changed materials a different type of cooling lubricant is required. This
  • the proportions of cutting oil to the proportions of water-miscible concentrate are preferably from 10 to 80 to 100 and in particular from 20 to 70 to 100.
  • the invention relates to a method for producing a water-mixed lubricant emulsion for metalworking, in which a) 2 to 15 parts by weight of a water-miscible concentrate of a lubricant emulsion are mixed with 98 to 85 parts by weight of water in order to obtain a mixture comprising 100 parts by weight, and then b) 1 to 14 parts by weight of a cutting oil immiscible with water
  • Dispersed mixture characterized in that the water-miscible concentrate of
  • composition of the emulsifier system and the molecular structure of the emulsifiers used must therefore meet stringent requirements.
  • fatty alcohol ethoxylates / propoxylates must be present which carry both 2 to 6 ethylene oxide units and 4 to 8 propylene oxide units.
  • These more hydrophilic components are to be combined with the more hydrophobic components
  • the approximate weight ratio given must be observed. Distillation residues of fatty alcohols with 12 to 24 carbon atoms are available from Henkel KGaA, Düsseldorf, under the name Pernil R RU.
  • the invention is therefore based on the fact that a water-mixed lubricant emulsion which contains the emulsifier system consisting of components c) and d) is first prepared from a water-miscible concentrate of a lubricant emulsion in accordance with sub-step a).
  • This lubricant emulsion does not contain water before or during use in accordance with sub-step b) miscible cutting oil dispersed in This can be done, for example, by stirring the cutting oil into the lubricant emulsion
  • Ultraturrax 10,000 to 20,000 revolutions per minute
  • high-speed rotor-stator systems are considered when using a
  • Ultraturrax is dispersed at 20,000 revolutions per minute for a period of about 1 to about 5 minutes. An alternative to this is ongoing
  • an emulsion concentrate can be used which, based on the total amount of the concentrate, contains about 15 to about 50% by weight of an oil component and 7 to 50% by weight. %, preferably 12 to 35% by weight of the emulsifier system consisting of components c) and d), a remaining remainder being formed to 100% by weight from water, corrosion inhibitors and / or further auxiliaries or active ingredients
  • the oil component of the concentrate of the water-miscible lubricant emulsion in sub-step a) can be selected, for example, from aliphatic or naphthenic mineral oils, esterols, polyolefins, acetals or dialkyl ethers
  • the concentrate of a water-miscible coolant emulsion used in sub-step a) can be composed of (details in% by weight) Concentrate 1
  • the water-miscible concentrate of the lubricant emulsion can contain one or more straight-chain or branched aliphatic carboxylic acids with 6 to 12 carbon atoms and / or aromatic carboxylic acids with 7 to 20 carbon atoms or their respective anions as corrosion inhibitors.
  • the water-miscible concentrate preferably contains these carboxylic acids or their anions in an amount of 8 to 35% by weight, in particular 15 to 30% by weight, based on the total amount of the concentrate, which makes up 100%.
  • the corrosion-inhibiting carboxylic acids can be straight-chain or branched. Mixtures of different acids can be particularly advantageous. Preferred examples of such carboxylic acids are caprylic acid, ethylhexanoic acid, isononanoic acid and isodecanoic acid.
  • the concentrate is preferably alkylphosphonic acids having 4 to 18 carbon atoms, preferably 6 to 12 carbon atoms -Atoms, or their salts.
  • the concentrate preferably contains these phosphonic acids or their anions in an amount of 0.1 to 4, preferably 0.4 to 2% by weight, based on the total amount of the concentrate, which makes up 100%.
  • a specific example of a suitable phosphonic acid is n-octylphosphonic acid.
  • Brass are suitable, it preferably contains non-ferrous metal inhibitors. These can be selected from the group of triazoles, in particular from
  • the concentrate then preferably contains about 0.1 to 1% by weight of non-ferrous metal inhibitors, based on the total amount of the concentrate, which makes up 100%.
  • the water-miscible concentrate of the lubricant emulsion can contain one or more ether carboxylic acids as an additional active ingredient. These are preferably selected from carboxymethylated alkoxylation products of alcohols having 6 to 22 carbon atoms in the alkyl radical and having an average of 1.5 to 12 alkylene oxide units.
  • the concentrate preferably contains these ether carboxylic acids in an amount such that the weight ratio of ether carboxylic acids to ethoxylates / propoxylates of fatty alcohols of group c) is in the range from 0.1: 1 to 1: 1.
  • the ether carboxylic acids can be represented by the general formula (I):
  • R is a saturated or unsaturated, linear or branched
  • A is hydrogen or a methyl group
  • n is a number in the range from 1.5 to 15 and m is an integer in the range from 1 to 3.
  • these ether carboxylic acids can be at least partially present as anions.
  • the ether carboxylic acids can have very different structures
  • it can be ether carboxylic acids from one
  • Fatty alcohol mixture with 12 to 14 carbon atoms in the alkyl group are derived, which was ethoxy-cured with an average of 2.5 ethylene oxide units and then acetyl-terminated.
  • the acetyl termination can be carried out, for example, by reacting the fatty alcohol ethoxylates with chloroacetic acid
  • ether carboxylic acids which can be used are acetyl-terminated ether carboxylic acids of oleyl alcohol, the average of which is 9
  • Ethylene oxide units was ethoxylated by caprylic alcohol, which averaged with 8
  • Ethylene oxide units has been ethoxylated or from hexyl alcohol, the average with 6
  • Ethylene oxide units have been ethoxylated. These ether carboxylic acids can be used individually or in a mixture with one another
  • ether carboxylic acid relate to the mixture of these acids.
  • the ether carboxylic acids as such or in the form of them relate to the mixture of these acids.
  • Alkali metal salts for example the sodium salts, can be used.
  • the water-immiscible cutting oil used in sub-step b) ester-based oils.
  • these are native triglycends, ie triglycides of plant or animal origin or modification products thereof, wax esters and fatty acid esters of monoalkanols with 4 to 18 carbon atoms in the alcohol part, for example tallow fatty acid ethylhexyl ester or transesterified rapeseed oil, as well as fatty acid esters of polyols, in particular trimethylolpropane can be used as the polyol component.
  • step b) mixtures of such oils can also be used.
  • the oils can contain additional auxiliaries, in particular EP additives, for example in the form of sulfurized compounds, antioxidants and corrosion inhibitors
  • EP additives for example in the form of sulfurized compounds, antioxidants and corrosion inhibitors
  • glycine is understood to mean glycine fatty acid esters, with "fatty acids” meaning saturated or mono- or polyunsaturated carboxylic acids with 12 to 22 carbon atoms
  • the process according to the invention is preferably carried out in such a way that fewer parts by weight of water-immiscible cutting oil are used than parts by weight of water-miscible concentrate.
  • the proportions of cutting oil and the proportions of water-miscible concentrate are from 10 to 80
  • the invention comprises a ready-to-use water-mixed cooling lubricant emulsion of the oil-in-water type, as can be produced directly by the user by the method described above.
  • the emulsion could also be produced centrally and transported to the individual users. This is uneconomical and ecologically disadvantageous because large amounts of water would have to be transported for this.
  • the shear conditions are preferably selected so that an oil-in-water emulsion is obtained at which more than 95% of the oil particles from the water-miscible concentrate are smaller than 0.7 ⁇ m and into which the water-immiscible cutting oil is dispersed in such a way that it is at least 50% in the form of droplets with a size in the range from 0.8 to 15 ⁇ m is present.
  • the emulsion acts like a "two-phase lubricant" with a finely emulsified O / W emulsion and coarsely dispersed cutting oil.
  • the droplet sizes of the cutting oil itself depend on the shear conditions and can therefore fluctuate. However, the ranges of the droplet sizes overlap, so that one at Particle size determination with light scattering methods, for example with a
  • Sympatec Helios Vectra device usually receives only one distribution maximum.
  • Particle size can also be determined by light microscopy or video microscopy.
  • the ready-to-use water-mixed cooling lubricant emulsion is therefore preferably characterized in that it is an oil-in-water emulsion in which more than 95% of the oil particles are smaller than 0.7 ⁇ m and in which the cutting oil which is not miscible with water is dispersed in such a way that that it is at least 50% in the form of particles with a size in the range of 0.5 to 15 microns.
  • the ready-to-use water-mixed lubricant emulsion can be used, for example, as a cooling lubricant in the machining of metals. If the cooling lubricant emulsion contains the light metal inhibitors described above, it can be used in particular as a cooling lubricant in the machining of light metals. If it contains the non-ferrous metal inhibitors also described above, it can be used as a cooling lubricant in the machining of non-ferrous metals.
  • the ready-to-use water-mixed lubricant emulsion can be used as a lubricant in the non-cutting and / or shaping processing of metals, for example in rolling or pressing processes.
  • the lubricant emulsion can also be used in very soft water, for example in water with a hardness below 8 ° dH, even at 0 ° dH, without foam problems occurring during use .
  • the lubricant emulsion produced according to the invention can also be used for water with a hardness above 8 ° dH.
  • the cooling lubricant emulsion additionally contains the ether carboxylic acids described above. This one
  • a lubricant emulsion which additionally contains these ether carboxylic acids, can be used in the entire hardness range of water that occurs practically.
  • the general advantage of using the emulsions produced according to the invention is that better friction wear values are obtained than with conventional emulsions without the addition of a water-immiscible cutting oil.
  • the lubricating effect can be controlled by the amount of cutting oil added. If there is an increased need for lubrication, the proportion of cutting oil which is not miscible with water in the dispersion is increased.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

L'invention concerne un procédé de production d'une émulsion lubrifiante aqueuse pour l'usinage de métaux. Selon ledit procédé: a) on mélange 2 à 15 parties en poids d'un concentré miscible avec l'eau d'une émulsion lubrifiante avec 85 à 98 parties en poids d'eau, pour obtenir un mélange présentant 100 parties en poids; puis b) on disperse dans ce mélange 1 à 14 parties en poids d'une huile de coupe non miscible avec l'eau, ce procédé se caractérisant en ce que le concentré d'émulsion lubrifiante miscible avec l'eau contient un système émulsifiant constitué des composants c) éthoxylates/propoxylates d'alcools gras présentant 8 à 18 atomes de carbone dans l'alcool avec 2 à 6 unités oxyde d'éthylène et 4 à 8 unités oxyde de propylène, et d) alcool gras et/ou propoxylates d'alcools gras présentant 12 à 28 atomes de C dans l'alcool, et 0 à 3 unités oxyde de propylène et/ou le résidu de distillation de ces alcools gras, selon un rapport pondéral c: d = 1: 0,3 à 0,3: 1. L'invention concerne également l'émulsion lubrifiante obtenue selon ce procédé et son utilisation.
PCT/EP2000/012026 1999-12-10 2000-11-30 Emulsion et procede pour l'usinage de metaux WO2001042402A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU26708/01A AU2670801A (en) 1999-12-10 2000-11-30 Metal working emulsion and metal working method

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19959590.9 1999-12-10
DE1999159590 DE19959590A1 (de) 1999-12-10 1999-12-10 Metallbehandlungsemulsion und Metallbearbeitungsverfahren

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WO2001042402A1 true WO2001042402A1 (fr) 2001-06-14

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PCT/EP2000/012026 WO2001042402A1 (fr) 1999-12-10 2000-11-30 Emulsion et procede pour l'usinage de metaux

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AU (1) AU2670801A (fr)
DE (1) DE19959590A1 (fr)
WO (1) WO2001042402A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19514413A1 (de) * 1994-04-20 1995-10-26 Sandoz Ag Neue oberflachenaktive Mittel
WO1998032527A1 (fr) * 1997-01-29 1998-07-30 Henkel Kommanditgesellschaft Auf Aktien Systeme emulsifiant a faible pouvoir moussant et concentre emulsifiable le contenant
WO2000008236A1 (fr) * 1998-08-05 2000-02-17 Henkel Kommanditgesellschaft Auf Aktien Agents et procedes pour l'usinage et le nettoyage des metaux ou leur traitement anticorrosion

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19514413A1 (de) * 1994-04-20 1995-10-26 Sandoz Ag Neue oberflachenaktive Mittel
WO1998032527A1 (fr) * 1997-01-29 1998-07-30 Henkel Kommanditgesellschaft Auf Aktien Systeme emulsifiant a faible pouvoir moussant et concentre emulsifiable le contenant
WO2000008236A1 (fr) * 1998-08-05 2000-02-17 Henkel Kommanditgesellschaft Auf Aktien Agents et procedes pour l'usinage et le nettoyage des metaux ou leur traitement anticorrosion

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Publication number Publication date
DE19959590A1 (de) 2001-06-13
AU2670801A (en) 2001-06-18

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