EP3957708A1 - Cooling lubricant for the cold rolling of aluminium - Google Patents
Cooling lubricant for the cold rolling of aluminium Download PDFInfo
- Publication number
- EP3957708A1 EP3957708A1 EP20191350.6A EP20191350A EP3957708A1 EP 3957708 A1 EP3957708 A1 EP 3957708A1 EP 20191350 A EP20191350 A EP 20191350A EP 3957708 A1 EP3957708 A1 EP 3957708A1
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- EP
- European Patent Office
- Prior art keywords
- cooling lubricant
- rolling
- aluminum
- glycol
- polyalkylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/24—Polyethers
- C10M145/26—Polyoxyalkylenes
- C10M145/34—Polyoxyalkylenes of two or more specified different types
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/24—Polyethers
- C10M145/26—Polyoxyalkylenes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/24—Polyethers
- C10M145/26—Polyoxyalkylenes
- C10M145/28—Polyoxyalkylenes of alkylene oxides containing 2 carbon atoms only
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/24—Polyethers
- C10M145/26—Polyoxyalkylenes
- C10M145/30—Polyoxyalkylenes of alkylene oxides containing 3 carbon atoms only
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/24—Polyethers
- C10M145/26—Polyoxyalkylenes
- C10M145/32—Polyoxyalkylenes of alkylene oxides containing 4 or more carbon atoms
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/24—Polyethers
- C10M145/26—Polyoxyalkylenes
- C10M145/36—Polyoxyalkylenes etherified
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/041—Mixtures of base-materials and additives the additives being macromolecular compounds only
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
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- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/106—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing four carbon atoms only
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/108—Polyethers, i.e. containing di- or higher polyoxyalkylene groups etherified
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; Viscosity index
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/09—Characteristics associated with water
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/09—Characteristics associated with water
- C10N2020/093—Insolubility in water
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/24—Emulsion properties
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/243—Cold working
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/244—Metal working of specific metals
- C10N2040/245—Soft metals, e.g. aluminum
Definitions
- the invention relates to a cooling lubricant (rolling oil) for the cold rolling of aluminum, a process for the production of an aluminum product free of visible defects caused by fatty acids and the use of the cooling lubricant for aluminum rolling.
- rolling emulsions and rolling oils are used as cooling lubricants, which have a major impact on the cost-effectiveness of production and the quality of the products.
- the coefficient of friction between the work roll and the rolling stock should be neither too high nor too low.
- a low coefficient of friction improves the lubrication in the roll gap, so that energy consumption, frictional heat and roll wear in the rolling process are reduced.
- Aluminum strips and foils are usually produced by rolling in a two-stage rolling process.
- an aluminum ingot is first rolled in several passes (passes) in a so-called hot rolling stand to form a blank or strip. This is then subjected to cold rolling into thinner strip or foil.
- the strip or foil can undergo other known treatment processes (annealing, thermal or chemical degreasing).
- a rolling emulsion (O/W) is usually used as a cooling lubricant in hot rolling and a rolling oil in cold rolling.
- O/W rolling emulsion
- Hydrocarbon-based rolling oils are used as cooling lubricants in cold rolling stands.
- Lubricating additives can be added to these rolling oils.
- Typical lubricating additives are, for example, fatty alcohols, fatty acids and fatty acid esters.
- fatty acids used regularly such as lauric acid, myristic acid, palmitic acid or stearic acid
- the fatty acids used regularly are solid at temperatures below 40 °C and only evaporate at temperatures well above 300 °C.
- Solid or pasty deposits of fatty acids and metal soaps formed from them can therefore occur on components in the roll stand that are not constantly flooded with rolling oil after the more volatile rolling oil has evaporated. If these solid or pasty deposits detach from the roll stand or pipelines and get onto the aluminum strip or aluminum foil, visible defects can appear on the rolling stock that can no longer be eliminated by the following process steps (further rolling passes, roll cutting, thermal or chemical degreasing). can become.
- a further disadvantage of a fatty acid as a lubricating additive is that it can react with the components of the rolling stock, in particular with the rolling debris formed during forming.
- Metal soaps mainly aluminum soaps, can form. After the alcohol has been oxidized to form an acid, fatty alcohols can also react with abraded aluminum to form aluminum soaps.
- the aluminum soaps formed from the fatty acids used and aluminum abrasion have only a limited and low solubility in cold rolling oil. They also form agglomerates with the aluminum debris. Store these poorly soluble metal soaps and the metal soaps/metal abrasion agglomerates are deposited on the components of the cold rolling stand and can form the deposits mentioned in pipes and tanks.
- metal soaps or metal soaps/metal abrasion agglomerates detach from components of the rolling mill, cold rolling mill or pipe walls and get onto the aluminum strip or aluminum foil, there can also be visually visible defects on the rolled stock, which can be caused by the subsequent process steps to completion of the tape or foil can no longer be removed.
- Filters such as horizontal pressure plate filters and filter aids such as kieselguhr, perlite and fuller's earth can be used for this purpose.
- Increasing soap content in the rolling oil is counteracted by increased use of bleaching earth filter aids. However, this shortens the filter service life and increases both the amount of filter aid required and the amount of filter waste produced.
- the EP 3 124 583 A1 describes a water-soluble metalworking fluid containing a dicarboxylic acid having a sulfide structure, a polyalkylene glycol, a polyhydric alcohol/polyalkylene oxide adduct, and a monocarboxylic acid.
- a water-soluble composition and not a mineral oil-based composition is thus described.
- the EP 0 484 542 A1 describes a lubricant for metalworking, which contains a fatty alcohol or a fatty acid in addition to a mineral oil and a straight-chain olefin.
- the lubricant described therein may contain glycols. Glycols are not included in the sample compositions in this document.
- a disadvantage of olefins in lubricants is that after the aluminum strip has been annealed, they lead to high residues from ignition on aluminum sheets.
- the EP 3 124 583 A1 describes a water-soluble metal treatment agent that may contain a polyalkylene glycol in addition to fatty acids and fatty alcohols.
- the object of the invention is to provide a cooling lubricant with which the visually visible defects on aluminum strips or aluminum foils, which are often caused by fatty acids and/or fatty alcohols in cold rolling processes, can be avoided without impairing the lubricating effect and tribological activity of the rolling oil.
- the subject matter of the invention is also a method for producing an aluminum product (aluminum strip or aluminum foil), in which the above-mentioned cooling lubricant is used for cold-rolling an aluminum strip.
- the subject of the invention is the use of the above-mentioned cooling lubricant for cold-rolling an aluminum strip into a thinner aluminum strip than the aluminum strip that has not yet been cold-rolled or into an aluminum foil (aluminum product).
- the aluminum product obtained is free from visually visible defects caused by fatty acids and fatty alcohols. It shows surprisingly high wettability for water and N-methyl-2-pyrrolidone (NMP). Furthermore, if a high surface energy of the aluminum foil surface is desired, the aluminum product does not need a corona treatment.
- the cooling lubricant according to the invention is oil-soluble; it is immiscible with water.
- the cooling lubricant according to the invention is free from straight-chain olefins, in particular free from alpha-olefins having 6 to 40 carbon atoms.
- essentially free of a fatty acid means that a fatty acid is present as a lubricating additive in a proportion of at most 0.2% by weight, preferably at most 0.1% by weight, based on the mass of the cooling lubricant .
- essentially free of a fatty alcohol means that a fatty alcohol is present as a lubricating additive in a proportion of at most 0.4% by weight, preferably at most 0.3% by weight, based on the mass of the cooling lubricant . If the fatty acid content and/or the fatty alcohol content in the lubricant according to the invention is above the maximum value specified above, the wetting properties of the aluminum product rolled therewith deteriorate.
- Aluminum products within the meaning of the invention are aluminum sheets, aluminum strips and aluminum foils which have been subjected to cold rolling.
- An aluminum foil can have a thickness of 4 to 100 ⁇ m, for example, or it can be thicker than 100 ⁇ m.
- the term aluminum within the meaning of the invention includes aluminum and aluminum alloys.
- Polyalkylene glycols to be used in the present invention include common polyalkylene glycols and compounds having a polyalkylene glycol structure such as polyoxyalkylene fatty alcohol ether (ethoxylated fatty alcohol).
- the alkylene residue in the polyalkylene glycol or polyalkylene oxide can be ethylene, propylene or butylene (polyethylene glycols, polypropylene glycols, polybutylene glycols).
- the fatty alcohol can contain from 8 to 20 carbon atoms.
- the fatty alcohol residue can be, for example, decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol. These compounds have lubricating and cooling properties when cold rolling aluminum.
- polyalkylene glycol used below includes polyalkylene glycols and compounds with a polyalkylene glycol structure.
- the polyalkylene glycols used according to the invention can have a kinematic viscosity of 5 mm 2 /s to 250 mm 2 /s, preferably 10 mm 2 /s to 200 mm 2 /s at 40.degree.
- the polyalkylene glycols used according to the invention are liquid at temperatures above 5° C. and are therefore easy to dose. They can be water-insoluble or water-soluble.
- ethoxylated fatty alcohols such as tetraethylene glycol monododecyl ether
- polyalkylene glycols or a compound containing polyalkylene oxide.
- ethoxylated fatty alcohols such as tetraethylene glycol monododecyl ether
- polyalkylene glycols or a compound containing polyalkylene oxide.
- Corresponding polyalkylene glycols are commercially available.
- the proportion of polyalkylene glycol in the rolling oil according to the invention can be up to 10% by weight, in particular 0.01 to 8% by weight and particularly preferably 0.1 to 5% by weight, based in each case on the mass of the rolling oil.
- the polyalkylene glycol therefore replaces the additives fatty acids and fatty alcohols usually found in cold rolling lubricants.
- the cooling lubricant according to the invention has a good lubricating effect or tribological effect without the aforementioned disadvantageous effects of fatty acids and fatty alcohols.
- the cooling lubricant according to the invention is based on a hydrocarbon base oil with a boiling point in the range from 180 to 300° C., measured according to DIN EN ISO 3405.
- the base oil contains straight-chain and branched hydrocarbons.
- the base oil may contain a mixture of hydrocarbons.
- the proportion of aromatics therein can preferably be less than 1% by weight, based on the mass of the base oil.
- the base oil can be a mineral oil or a synthetic oil. It can contain natural and/or synthetic n-paraffins and/or natural and/or synthetic isoparaffins.
- the kinematic viscosity of this low-aromatic hydrocarbon mixture can be 1.5 to 3.6 mm 2 /s at 20 °C. This kinematic viscosity provides good flow properties in the cold rolling mill and enables uniform lubrication and cooling.
- the proportion of the base oil in the cooling lubricant according to the invention can be 90% by weight or more, based on the mass of the cooling lubricant.
- the proportion of the base oil can be, for example, 90% by weight to 99% by weight of the mass of the cooling lubricant.
- the cooling lubricant according to the invention can contain customary additives to increase the high-pressure lubricating properties, antioxidants and conductivity improvers.
- Additives for enhancing extreme pressure lubricity include esters of C 10-14 straight chain saturated carboxylic acids. Such include, for example, butyl stearate and methyl dodecanoate. Methyl dodecanoate is particularly preferred. These can be contained in an amount of up to 10% by weight, preferably 1 to 8% by weight, based on the mass of the cooling lubricant.
- Suitable antioxidants include sterically hindered monohydric, dihydric and trihydric phenols and polynuclear phenols, especially tert-butyl phenols. A typical representative of this group is methylene-4,4'-bis-(2,6-di-tert-butylphenol).
- Other suitable antioxidants include amines such as diphenylamine, phenyl- ⁇ -naphthylamine, p,p'-tetramethyldiaminodiphenylmethane and N,N'-diphenyl-p-phenyldiamine.
- An antioxidant mentioned above can be used in combination with other antioxidants such as sulfides and polydisulfides in the usual concentrations.
- the cooling lubricant according to the invention allows the aluminum product obtained after cold rolling to be further processed for a number of applications without corona treatment being necessary. Nevertheless, a surface energy is achieved on the surface of the aluminum product, such as is found after corona treatment on aluminum products that have been cold rolled in the presence of fatty acids and fatty alcohols. In addition, the surface of the aluminum product has high wettability for water and N-methyl-2-pyrrolidone (NMP).
- NMP N-methyl-2-pyrrolidone
- the aluminum product contains residues of the polyalkylene glycol used in the cooling lubricant according to the invention on its surface.
- the amount of polyalkylene glycol on the aluminum product after cold rolling can be as high as 5 mg/m 2 or more. After the process according to the invention has been carried out, for example 0.01 mg/m 2 to 5 mg/m 2 of polyalkylene glycol or a compound containing a polyalkylene oxide structure can be present on the surface of the aluminum product.
- the lubricant according to the invention results in a significant reduction in the number of visually visible defects on the aluminum strips or aluminum foils produced. This is probably due to the fact that rolling oil components do not form deposits on the rolling stock that are difficult to remove. The omission of fatty alcohols appears to increase this reduction. Residues of the rolling oil according to the invention can be easily removed chemically or thermally from the surface of the rolling stock, or the surface of the rolling stock shows only a small amount of residue formation after thermal degreasing.
- the lubricating properties of the cooling lubricant according to the invention were determined using an MTM2 Mini-Traction machine from PCS Instruments in the standard configuration with a load-applying steel ball (diameter 19.05 mm) and an aluminum test disc rotating at different speeds.
- the load on the test disc from the ball (3 ⁇ 4"ball bearing steel AISI 52100 (100Cr6, 1.3505)) was set to 40N (0.5 GPa contact pressure) and coefficients of friction (RK) at different rolling speeds of.
- the following Table 1 shows the two mean values (MW) of the coefficients of friction measured at rolling speeds from 1 to 200 m/min.
- the disc was formed from an aluminum alloy AA1XXX.
- the slip/roll ratio (SRR) during the test was 50%.
- Table 1 lubricant sample Viscosity mm 2 /s RK MW 0.2-200m/min Drop size 5 ⁇ l water in mm Remarks 1 base oil 1.9 0.07; 0.08 3.1 lubricating film formation suboptimal; metal soaping 2 base oil + 0.9% fatty acid + 0.9% methyl laurate 1.9 0.06; 0.05 2.5 good lubricating film; more abrasion in the KSS but clean disc 3 rolling oil with 1% PAG* (visco 20 mm 2 /s at 40 °C) 1.9 0.05; 0.05 3.1 better lubricating film formation than pure rolling oil 4 rolling oil with 2% PAG* (visco 20 mm 2 /s at 40 °C] 1.9 0.04; 0.04 3.5 lubricating film formation good; hardly any track on the ball 5 rolling oil with 4% PAG* (visco 20 mm 2 /s at 40 °C) 2.0 0.03; 0.03 3.5 hardly any abrasion 6 rolling oil with 2% PAG compound** (
- Lubricant sample 2 provides a good lubricating film with more wear but with a clean disc.
- Lubricant sample 3 according to the invention provides better lubricating film formation. The same is true for sample 4, which moreover hardly shows any track on the ball. This also applies to sample 5, which gives hardly any abrasion.
- Samples 6 to 12 show good lubricating film formation. Samples 6 and 7 show some abrasion, sample 8 shows hardly any abrasion. Sample 6 shows acceptable water wetting, sample 7 good wetting and sample 8 very good water wetting. Sample 10 gives hardly any abrasion and hardly any track on the ball. Samples 11 and 12 provide little tracking on the ball.
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Abstract
Beschrieben wird ein Kühlschmierstoff für das Kaltwalzen von Aluminium, enthaltend- ein mineralölbasiertes oder synthetisches Grundöl,- einen Polyalkylenglykol oder eine eine Polyalkylenoxidstruktur enthaltende Verbindung, wobei- der Kühlschmierstoff nicht wasserlöslich oder mit Wasser mischbar ist und- der Kühlschmierstoff im Wesentlichen frei von Fettsäuren und Fettalkoholen ist.A cooling lubricant for the cold rolling of aluminum is described, containing - a mineral oil-based or synthetic base oil, - a polyalkylene glycol or a compound containing a polyalkylene oxide structure, wherein - the cooling lubricant is not water-soluble or miscible with water and - the cooling lubricant is essentially free of fatty acids and fatty alcohols is.
Description
Die Erfindung betrifft einen Kühlschmierstoff (Walzöl) für das Kaltwalzen von Aluminium, ein Verfahren zur Herstellung eines von durch Fettsäuren verursachten, visuell sichtbaren Fehlerbildern freien Aluminiumprodukts und die Verwendung des Kühlschmierstoffs zum Walzen von Aluminium.The invention relates to a cooling lubricant (rolling oil) for the cold rolling of aluminum, a process for the production of an aluminum product free of visible defects caused by fatty acids and the use of the cooling lubricant for aluminum rolling.
In Verfahren zur Herstellung von Aluminiumbändern und -folien werden Walzemulsionen und Walzöle als Kühlschmierstoff verwendet, die einen großen Einfluss auf die Wirtschaftlichkeit der Produktion und die Qualität der Erzeugnisse haben. Beim Walzen soll der Reibwert zwischen Arbeitswalze und Walzgut weder zu hoch noch zu niedrig sein. Ein niedriger Reibwert verbessert die Schmierung im Walzspalt, so dass Energieaufwand, Reibungswärme und Walzenverschleiß im Walzprozess verringert werden.In processes for the production of aluminum strips and foils, rolling emulsions and rolling oils are used as cooling lubricants, which have a major impact on the cost-effectiveness of production and the quality of the products. During rolling, the coefficient of friction between the work roll and the rolling stock should be neither too high nor too low. A low coefficient of friction improves the lubrication in the roll gap, so that energy consumption, frictional heat and roll wear in the rolling process are reduced.
Aluminiumbänder und -folien werden in der Regel in einem zweistufigen Walzverfahren durch Walzen erzeugt. Zur Herstellung eines Aluminiumbands oder einer Aluminiumfolie wird ein Aluminiumbarren zunächst in mehreren Durchgängen (Stichen) in einem sogenannten Warmwalzgerüst zu einer Platine oder einem Band gewalzt. Dieses wird anschließend einem Kaltwalzen zu einem dünneren Band oder einer Folie unterzogen. Darüber hinaus kann das Band oder die Folie noch weitere bekannte Behandlungsverfahren erfahren (Glühen, thermisches oder chemisches Entfetten).Aluminum strips and foils are usually produced by rolling in a two-stage rolling process. To produce aluminum strip or aluminum foil, an aluminum ingot is first rolled in several passes (passes) in a so-called hot rolling stand to form a blank or strip. This is then subjected to cold rolling into thinner strip or foil. In addition, the strip or foil can undergo other known treatment processes (annealing, thermal or chemical degreasing).
Beim Warmwalzen wird üblicherweise als Kühlschmiermittel eine Walzemulsion (O/W) und beim Kaltwalzen ein Walzöl verwendet. Im Verfahrensschritt des Warmwalzens erfolgt eine große Umformung des Aluminiumbarrens zu einem Aluminiumband. In Kaltwalzgerüsten werden als Kühlschmierstoffe kohlenwasserstoffbasierte Walzöle eingesetzt. Diesen Walzölen können Schmieradditive zugesetzt sein. Übliche Schmieradditive sind beispielsweise Fettalkohole, Fettsäuren und Fettsäureester.A rolling emulsion (O/W) is usually used as a cooling lubricant in hot rolling and a rolling oil in cold rolling. In the hot rolling process step, the aluminum ingot is deformed to form an aluminum strip. Hydrocarbon-based rolling oils are used as cooling lubricants in cold rolling stands. Lubricating additives can be added to these rolling oils. Typical lubricating additives are, for example, fatty alcohols, fatty acids and fatty acid esters.
Nachteilig am Einsatz von Fettsäuren ist, dass die regelmäßig verwendeten Fettsäuren wie Laurinsäure, Myristinsäure, Palmitinsäure oder Stearinsäure bei Temperaturen unterhalb von 40 °C als Feststoff vorliegen und erst bei Temperaturen deutlich über 300 °C verdampfen. An Bauteilen im Walzgerüst, die nicht ständig von Walzöl überspült werden, kann es daher nach Verdampfen des leichter flüchtigen Walzöls zu festen oder pastösen Ablagerungen von Fettsäuren und daraus gebildeten Metallseifen kommen. Wenn sich diese festen oder pastösen Ablagerungen vom Walzgerüst oder Rohrleitungen lösen und auf das Aluminiumband bzw. die Aluminiumfolie gelangen, können visuell sichtbare Fehlerbilder auf dem Walzgut entstehen, die durch die folgenden Prozessschritte (weitere Walzstiche, Rollenschneiden, thermisches oder chemisches Entfetten) nicht mehr beseitigt werden können.The disadvantage of using fatty acids is that the fatty acids used regularly, such as lauric acid, myristic acid, palmitic acid or stearic acid, are solid at temperatures below 40 °C and only evaporate at temperatures well above 300 °C. Solid or pasty deposits of fatty acids and metal soaps formed from them can therefore occur on components in the roll stand that are not constantly flooded with rolling oil after the more volatile rolling oil has evaporated. If these solid or pasty deposits detach from the roll stand or pipelines and get onto the aluminum strip or aluminum foil, visible defects can appear on the rolling stock that can no longer be eliminated by the following process steps (further rolling passes, roll cutting, thermal or chemical degreasing). can become.
Ein weiterer Nachteil einer Fettsäure als Schmieradditiv ist, dass diese mit den Bestandteilen des Walzguts, insbesondere mit dem während des Umformens gebildeten Walzabrieb, reagieren kann. Dabei können sich Metallseifen, hauptsächlich Aluminiumseifen, bilden. Auch Fettalkohole können nach Oxidation des Alkohols zur Säure mit Aluminiumabrieb zu Aluminiumseifen reagieren.A further disadvantage of a fatty acid as a lubricating additive is that it can react with the components of the rolling stock, in particular with the rolling debris formed during forming. Metal soaps, mainly aluminum soaps, can form. After the alcohol has been oxidized to form an acid, fatty alcohols can also react with abraded aluminum to form aluminum soaps.
Die aus den eingesetzten Fettsäuren und Aluminiumabrieb gebildeten Aluminiumseifen haben nur eine begrenzte und geringe Löslichkeit im Kaltwalzöl. Zudem bilden sie mit den Aluminium-Abriebteilchen Agglomerate. Diese schwerlöslichen Metallseifen und die Metallseifen/Metallabrieb-Agglomerate lagern sich an den Bauteilen des Kaltwalzgerüsts ab und können die genannten Ablagerungen in Rohrleitungen und Tanks bilden.The aluminum soaps formed from the fatty acids used and aluminum abrasion have only a limited and low solubility in cold rolling oil. They also form agglomerates with the aluminum debris. Store these poorly soluble metal soaps and the metal soaps/metal abrasion agglomerates are deposited on the components of the cold rolling stand and can form the deposits mentioned in pipes and tanks.
Wenn solche Metallseifen bzw. Metallseifen/Metallabrieb-Agglomerate sich von Bauteilen des Walzstuhls, Kaltwalzwerks oder von Rohrwandungen lösen und auf das Aluminiumband bzw. die Aluminiumfolie gelangen, kann es auch zu visuell sichtbaren Fehlerbildern auf dem Walzgut kommen, die durch die folgenden Prozessschritte zur Fertigstellung des Bands oder der Folie nicht mehr zu beseitigen sind. Zur Vermeidung solcher Oberflächendefekte ist es bekannt, Metallseifen und Metallabrieb aus dem Kaltwalzöl durch Filtrations- oder Destillationsverfahren abzutrennen. Dazu können Filter wie Horizontal-Druckplattenfiltern und Filterhilfsmitteln wie Kieselgur, Perlite und Bleicherden eingesetzt werden. Ansteigendem Seifengehalt im Walzöl wird durch erhöhten Einsatz von Bleicherde-Filterhilfsmittel entgegengewirkt. Dadurch wird jedoch die Filterstandzeit verkürzt und sowohl die Menge an benötigtem Filterhilfsmittel als auch die Menge des entstehenden Filterabfalls erhöht.If such metal soaps or metal soaps/metal abrasion agglomerates detach from components of the rolling mill, cold rolling mill or pipe walls and get onto the aluminum strip or aluminum foil, there can also be visually visible defects on the rolled stock, which can be caused by the subsequent process steps to completion of the tape or foil can no longer be removed. To avoid such surface defects, it is known to separate metal soaps and metal abrasion from the cold rolling oil by filtration or distillation processes. Filters such as horizontal pressure plate filters and filter aids such as kieselguhr, perlite and fuller's earth can be used for this purpose. Increasing soap content in the rolling oil is counteracted by increased use of bleaching earth filter aids. However, this shortens the filter service life and increases both the amount of filter aid required and the amount of filter waste produced.
Die
Die
Die
Mithin besteht ein Bedarf an neuen Schmieradditiven, die mit Aluminiumabrieb keine Reaktionsprodukte bilden und auch nicht mit anderen Bestandteilen des Walzöls reagieren.There is therefore a need for new lubricating additives which do not form any reaction products with abraded aluminum and also do not react with other components of the rolling oil.
Der Erfindung liegt die Aufgabe zugrunde, einen Kühlschmierstoff bereitzustellen, mit dem die in Kaltwalzverfahren durch Fettsäuren und/oder Fettalkohole häufig verursachten visuell sichtbaren Fehlerbilder auf Aluminiumbändern bzw. Aluminiumfolien vermieden werden können, ohne die Schmierwirkung und tribologische Aktivität des Walzöls zu beeinträchtigen.The object of the invention is to provide a cooling lubricant with which the visually visible defects on aluminum strips or aluminum foils, which are often caused by fatty acids and/or fatty alcohols in cold rolling processes, can be avoided without impairing the lubricating effect and tribological activity of the rolling oil.
Gelöst wird diese Aufgabe durch einen mineralölbasierten Kühlschmierstoff (Walzöl) für das Kaltwalzen von Aluminium. Dieser enthält
- ein mineralölbasiertes oder synthetisches Grundöl,
- einen Polyalkylenglykol oder eine eine Polyoxyalkylenstruktur enthaltende Verbindung, wobei
- der Kühlschmierstoff im Wesentlichen frei von Fettsäuren und Fettalkoholen ist.
- a mineral oil-based or synthetic base oil,
- a polyalkylene glycol or a compound containing a polyoxyalkylene structure, wherein
- the cooling lubricant is essentially free of fatty acids and fatty alcohols.
Gegenstand der Erfindung ist ferner ein Verfahren zur Herstellung eines Aluminiumprodukts (Aluminiumband oder Aluminiumfolie), in dem zum Kaltwalzen eines Aluminiumbands der oben genannte Kühlschmierstoff eingesetzt wird.The subject matter of the invention is also a method for producing an aluminum product (aluminum strip or aluminum foil), in which the above-mentioned cooling lubricant is used for cold-rolling an aluminum strip.
Gegenstand der Erfindung ist schließlich die Verwendung des oben genannten Kühlschmierstoffs für das Kaltwalzen eines Aluminiumbands zu einem dünneren Aluminiumband als das noch nicht kaltgewalzte Aluminiumband oder zu einer Aluminiumfolie (Aluminiumprodukt).Finally, the subject of the invention is the use of the above-mentioned cooling lubricant for cold-rolling an aluminum strip into a thinner aluminum strip than the aluminum strip that has not yet been cold-rolled or into an aluminum foil (aluminum product).
Das erhaltene Aluminiumprodukt ist frei von durch Fettsäuren und Fettalkoholen verursachten, visuell sichtbaren Fehlerbildern. Es weist eine überraschend hohe Benetzbarkeit für Wasser und N-Methyl-2-pyrrolidon (NMP) auf. Ferner benötigt das Aluminiumprodukt keine Coronabehandlung, wenn eine hohe Oberflächenenergie der Oberfläche der Aluminiumfolie gewünscht ist.The aluminum product obtained is free from visually visible defects caused by fatty acids and fatty alcohols. It shows surprisingly high wettability for water and N-methyl-2-pyrrolidone (NMP). Furthermore, if a high surface energy of the aluminum foil surface is desired, the aluminum product does not need a corona treatment.
Der erfindungsgemäße Kühlschmierstoff ist öllöslich; er ist nicht mit Wasser mischbar. Der erfindungsgemäße Kühlschmierstoff ist frei von geradkettigen Olefinen, insbesondere frei von alpha-Olefinen mit 6 bis 40 Kohlenstoffatomen.The cooling lubricant according to the invention is oil-soluble; it is immiscible with water. The cooling lubricant according to the invention is free from straight-chain olefins, in particular free from alpha-olefins having 6 to 40 carbon atoms.
Im Wesentlichen frei von einer Fettsäure bedeutet im Sinne der Erfindung, dass eine Fettsäure als Schmieradditiv in einem Anteil von höchstens 0,2 Gew.-%, vorzugsweise höchstens 0,1 Gew.-%, bezogen auf die Masse des Kühlschmierstoffs, darin enthalten sind. Im Wesentlichen frei von einem Fettalkohol bedeutet im Sinne der Erfindung, dass ein Fettalkohol als Schmieradditiv in einem Anteil von höchstens 0,4 Gew.-%, vorzugsweise höchstens 0,3 Gew.-%, bezogen auf die Masse des Kühlschmierstoffs, darin enthalten ist. Sind der Fettsäureanteil und/oder der Fettalkoholanteil im erfindungsgemäßen Schmierstoff oberhalb des zuvor angegebenen Höchstwerts verschlechtern sich die Benetzungseigenschaften des damit gewalzten Aluminiumprodukts.For the purposes of the invention, essentially free of a fatty acid means that a fatty acid is present as a lubricating additive in a proportion of at most 0.2% by weight, preferably at most 0.1% by weight, based on the mass of the cooling lubricant . For the purposes of the invention, essentially free of a fatty alcohol means that a fatty alcohol is present as a lubricating additive in a proportion of at most 0.4% by weight, preferably at most 0.3% by weight, based on the mass of the cooling lubricant . If the fatty acid content and/or the fatty alcohol content in the lubricant according to the invention is above the maximum value specified above, the wetting properties of the aluminum product rolled therewith deteriorate.
Aluminiumprodukte im Sinne der Erfindung sind Aluminiumbleche, Aluminiumbänder und Aluminiumfolien, die dem Kaltwalzen unterzogen worden sind. Eine Aluminiumfolie kann beispielsweise eine Dicke von 4 bis 100 µm aufweisen oder aber auch dicker sein als 100µm. Der Begriff Aluminium im Sinne der Erfindung umfasst Aluminium und Aluminiumlegierungen.Aluminum products within the meaning of the invention are aluminum sheets, aluminum strips and aluminum foils which have been subjected to cold rolling. An aluminum foil can have a thickness of 4 to 100 μm, for example, or it can be thicker than 100 μm. The term aluminum within the meaning of the invention includes aluminum and aluminum alloys.
Erfindungsgemäß zu verwendende Polyalkylenglykole umfassen übliche Polyalkylenglykole und Verbindungen mit einer Polyalkylenglykolstruktur wie Polyoxyalkylen-Fettalkoholether (ethoxylierter Fettalkohol). Der Alkylenrest im Polyalkylenglykol oder Polyalkylenoxid kann Ethylen, Propylen oder Butylen sein (Polyethylenglykole, Polypropylenglykole, Polybutylenglykole). Der Fettalkohol kann 8 bis 20 Kohlenstoffatome umfassen. Der Fettalkoholrest kann beispielsweise Decanol, Laurylalkohol, Myristylalkohol, Cetylalkohol, Stearylalkohol sein. Diese Verbindungen haben schmierende und kühlende Eigenschaften beim Kaltwalzen von Aluminium. Der nachfolgend verwendet Begriff Polyalkylenglykol umfasst Polyalkylenglykole und Verbindungen mit einer Polyalkylenglykolstruktur.Polyalkylene glycols to be used in the present invention include common polyalkylene glycols and compounds having a polyalkylene glycol structure such as polyoxyalkylene fatty alcohol ether (ethoxylated fatty alcohol). The alkylene residue in the polyalkylene glycol or polyalkylene oxide can be ethylene, propylene or butylene (polyethylene glycols, polypropylene glycols, polybutylene glycols). The fatty alcohol can contain from 8 to 20 carbon atoms. The fatty alcohol residue can be, for example, decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol. These compounds have lubricating and cooling properties when cold rolling aluminum. The term polyalkylene glycol used below includes polyalkylene glycols and compounds with a polyalkylene glycol structure.
Die erfindungsgemäß verwendeten Polyalkylenglykole können eine kinematische Viskosität von 5 mm2/s bis 250 mm2/s, vorzugsweise 10 mm2/s bis 200 mm2/s bei 40 °C aufweisen. Die erfindungsgemäß eingesetzten Polyalkylenglykole liegen oberhalb von 5 °C als Flüssigkeit vor und sind daher leicht zu dosieren. Sie können in Wasser unlöslich oder in Wasser löslich sein.The polyalkylene glycols used according to the invention can have a kinematic viscosity of 5 mm 2 /s to 250 mm 2 /s, preferably 10 mm 2 /s to 200 mm 2 /s at 40.degree. The polyalkylene glycols used according to the invention are liquid at temperatures above 5° C. and are therefore easy to dose. They can be water-insoluble or water-soluble.
Besonders bevorzugt werden als Polyalkylenglykole oder eine Polyalkylenoxid enthaltende Verbindung ethoxylierte Fettalkohole wie Tetraethylenglykolmonododecylether verwendet. Entsprechende Polyalkylenglykole sind im Handel erhältlich.Particular preference is given to using ethoxylated fatty alcohols such as tetraethylene glycol monododecyl ether as polyalkylene glycols or a compound containing polyalkylene oxide. Corresponding polyalkylene glycols are commercially available.
Der Anteil des Polyalkylenglykols im erfindungsgemäßen Walzöl kann bis zu 10 Gew.-%, insbesondere 0,01 bis 8 Gew.-% und besonders bevorzugt 0,1 bis 5 Gew.-%, jeweils bezogen auf die Masse des Walzöls, betragen. Das Polyalkylenglykol ersetzt mithin die üblicherweise in Kaltwalz-Schmierstoffen vorhandenen Additive Fettsäuren und Fettalkohole. Der erfindungsgemäße Kühlschmierstoff besitzt eine gute Schmierwirkung oder tribologische Wirkung ohne die zuvor genannten nachteiligen Wirkungen von Fettsäuren und Fettalkoholen.The proportion of polyalkylene glycol in the rolling oil according to the invention can be up to 10% by weight, in particular 0.01 to 8% by weight and particularly preferably 0.1 to 5% by weight, based in each case on the mass of the rolling oil. The polyalkylene glycol therefore replaces the additives fatty acids and fatty alcohols usually found in cold rolling lubricants. The cooling lubricant according to the invention has a good lubricating effect or tribological effect without the aforementioned disadvantageous effects of fatty acids and fatty alcohols.
Der erfindungsgemäße Kühlschmierstoff basiert auf einem Kohlenwasserstoff-Grundöl mit einer Siedelage im Bereich von 180 bis 300 °C, gemessen nach DIN EN ISO 3405. Das Grundöl enthält geradkettige und verzweigte Kohlenwasserstoffe. Das Grundöl kann ein Kohlenwasserstoffgemisch enthalten. Der Anteil an Aromaten darin kann vorzugsweise kleiner als 1 Gew.-%, bezogen auf die Masse des Grundöls, sein. Das Grundöl kann ein Mineralöl oder ein synthetisches Öl sein. Es kann natürliche und/oder synthetische n-Paraffine und/oder natürliche und/oder synthetische IsoParaffine enthalten.The cooling lubricant according to the invention is based on a hydrocarbon base oil with a boiling point in the range from 180 to 300° C., measured according to DIN EN ISO 3405. The base oil contains straight-chain and branched hydrocarbons. The base oil may contain a mixture of hydrocarbons. The proportion of aromatics therein can preferably be less than 1% by weight, based on the mass of the base oil. The base oil can be a mineral oil or a synthetic oil. It can contain natural and/or synthetic n-paraffins and/or natural and/or synthetic isoparaffins.
Die kinematische Viskosität dieses aromatenarmen Kohlenwasserstoffgemischs kann 1,5 bis 3,6 mm2/s bei 20 °C betragen. Diese kinematische Viskosität liefert gute Fließeigenschaften im Kaltwalzgerüst und ermöglicht eine gleichmäßige Schmierung und Kühlung. Der Anteil des Grundöls im erfindungsgemäßen Kühlschmierstoff kann 90 Gew.-% und mehr, bezogen auf die Masse des Kühlschmierstoffs ausmachen. Der Anteil des Grundöls kann beispielsweise 90 Gew.-% bis 99 Gew.-% der Masse des Kühlschmierstoffs betragen.The kinematic viscosity of this low-aromatic hydrocarbon mixture can be 1.5 to 3.6 mm 2 /s at 20 °C. This kinematic viscosity provides good flow properties in the cold rolling mill and enables uniform lubrication and cooling. The proportion of the base oil in the cooling lubricant according to the invention can be 90% by weight or more, based on the mass of the cooling lubricant. The proportion of the base oil can be, for example, 90% by weight to 99% by weight of the mass of the cooling lubricant.
Der erfindungsgemäße Kühlschmierstoff kann übliche Additive zur Steigerung der Hochdruck-Schmiereigenschaften, Antioxidantien und Leitfähigkeitsverbesserer enthalten.The cooling lubricant according to the invention can contain customary additives to increase the high-pressure lubricating properties, antioxidants and conductivity improvers.
Additive zur Steigerung der Hochdruck-Schmiereigenschaften umfassen Ester geradkettiger gesättigter C10-14-Carbonsäuren. Solche umfassen beispielsweise Butylstearat und Methyldodecanoat. Methyldodecanoat ist besonders bevorzugt. Diese können in einer Menge von bis zu 10 Gew.-%, vorzugsweise 1 bis 8 Gew.-%, bezogen auf die Masse des Kühlschmierstoffs enthalten sein.Additives for enhancing extreme pressure lubricity include esters of C 10-14 straight chain saturated carboxylic acids. Such include, for example, butyl stearate and methyl dodecanoate. Methyl dodecanoate is particularly preferred. These can be contained in an amount of up to 10% by weight, preferably 1 to 8% by weight, based on the mass of the cooling lubricant.
Geeignete Antioxidantien umfassen sterisch gehinderte einwertige, zweiwertige und dreiwerte Phenole und mehrkernige Phenole, insbesondere tert.-Butylphenole. Ein typischer Vertreter dieser Gruppe ist das Methylen-4,4'-bis-(2,6-di-tert-butylphenol). Weitere geeignet Antioxidantien umfassen Amine wie Diphenylamin, Phenyl-α-naphthylamin, p,p'-Tetramethyldiaminodiphenylmethan und N,N'-Diphenyl-p-phenyldiamin. Ein zuvor genanntes Antioxidans kann in Kombination mit weiteren Antioxidantien wie Sulfiden und Polydisulfiden in üblichen Konzentrationen eingesetzt werden.Suitable antioxidants include sterically hindered monohydric, dihydric and trihydric phenols and polynuclear phenols, especially tert-butyl phenols. A typical representative of this group is methylene-4,4'-bis-(2,6-di-tert-butylphenol). Other suitable antioxidants include amines such as diphenylamine, phenyl-α-naphthylamine, p,p'-tetramethyldiaminodiphenylmethane and N,N'-diphenyl-p-phenyldiamine. An antioxidant mentioned above can be used in combination with other antioxidants such as sulfides and polydisulfides in the usual concentrations.
Der erfindungsgemäße Kühlschmierstoff erlaubt die Weiterverarbeitung des nach dem Kaltwalzen erhaltenen Aluminiumprodukts für eine Reihe von Anwendungen, ohne dass eine Coronabehandlung erforderlich ist. Dennoch wird eine Oberflächenenergie auf der Oberfläche des Aluminiumprodukts erreicht, wie sie nach Coronabehandlung auf Aluminiumprodukten vorliegt, die in Gegenwart von Fettsäuren und Fettalkoholen kalt gewalzt worden sind. Darüber hinaus weist die Oberfläche des Alumiumprodukts eine hohe Benetzbarkeit für Wasser und N-Methyl-2-pyrrolidon (NMP) auf.The cooling lubricant according to the invention allows the aluminum product obtained after cold rolling to be further processed for a number of applications without corona treatment being necessary. Nevertheless, a surface energy is achieved on the surface of the aluminum product, such as is found after corona treatment on aluminum products that have been cold rolled in the presence of fatty acids and fatty alcohols. In addition, the surface of the aluminum product has high wettability for water and N-methyl-2-pyrrolidone (NMP).
Das Aluminiumprodukt enthält auf seiner Oberfläche Reste des im erfindungsgemäßen Kühlschmierstoff eingesetzten Polyalkylenglykols. Die Menge des Polyalkylenglykols auf dem Aluminiumprodukt nach dem Kaltwalzen kann bis zu 5 mg/m2 oder mehr betragen. Auf der Oberfläche des Aluminiumprodukts können sich nach Durchführung des erfindungsgemäßen Verfahrens beispielsweise 0,01 mg/m2 bis 5 mg/m2 Polyalkylenglykol oder eine Polyalkylenoxidstruktur enthaltende Verbindung befinden.The aluminum product contains residues of the polyalkylene glycol used in the cooling lubricant according to the invention on its surface. The amount of polyalkylene glycol on the aluminum product after cold rolling can be as high as 5 mg/m 2 or more. After the process according to the invention has been carried out, for example 0.01 mg/m 2 to 5 mg/m 2 of polyalkylene glycol or a compound containing a polyalkylene oxide structure can be present on the surface of the aluminum product.
Es wurde festgestellt, dass durch das erfindungsgemäße Schmiermittel eine deutliche Verringerung der Anzahl an visuell sichtbaren Fehlerbildern auf den hergestellten Aluminiumbändern bzw. Aluminiumfolien erfolgt. Das ist vermutlich darauf zurückzuführen, dass Walzölkomponenten keine schwer entfernbaren Ablagerungen auf dem Walzgut bilden. Das Weglassen von Fettalkoholen scheint diese Verringerung noch zu verstärken. Rückstände des erfindungsgemäßen Walzöls lassen sich chemisch oder thermisch gut von der Walzgutoberfläche entfernen bzw. die Walzgutoberfläche weist nach thermischer Entfettung nur eine geringe Rückstandsbildung auf.It has been found that the lubricant according to the invention results in a significant reduction in the number of visually visible defects on the aluminum strips or aluminum foils produced. This is probably due to the fact that rolling oil components do not form deposits on the rolling stock that are difficult to remove. The omission of fatty alcohols appears to increase this reduction. Residues of the rolling oil according to the invention can be easily removed chemically or thermally from the surface of the rolling stock, or the surface of the rolling stock shows only a small amount of residue formation after thermal degreasing.
Es ist sinnvoll, den erfindungsgemäßen Kühlschmierstoff vor seiner Verwendung auf mindestens etwa 40 ° C zu erwärmen. Das verringert seine Viskosität und erlaubt das schnellere Durchfließen des Walzenspalts.
Die folgenden Beispiele dienen der weiteren Erläuterung der Erfindung.It makes sense to heat the cooling lubricant according to the invention to at least about 40° C. before using it. This reduces its viscosity and allows it to flow through the nip more quickly.
The following examples serve to further illustrate the invention.
Die Schmiereigenschaften des erfindungsgemäßen Kühlschmierstoffs wurden mit einer MTM2 Mini-Traction Maschine der Firma PCS Instruments in der Standard-Konfiguration mit einer Last ausübenden Stahlkugel (Durchmesser 19,05 mm) und einer mit unterschiedlichen Geschwindigkeiten drehbaren Aluminiumprüf-Scheibe ermittelt. Die Belastung der Prüfscheibe durch die Kugel (¾"Kugellagerstahl AISI 52100 (100Cr6, 1.3505)) wurde auf 40N (0,5 GPa Kontaktdruck) eingestellt und Reibkoeffizienten (RK) bei unterschiedlichen Rollgeschwindigkeiten von. Wiedergeben sind in der folgenden Tabelle 1 die zwei Mittelwerte (MW) der bei Rollgeschwindigkeiten von 1 bis 200 m/min gemessenen Reibkoeffizienten. Die Scheibe war aus einer Aluminiumlegierung AA1XXX gebildet. Das Gleit/Roll-Verhältnis (SRR) während des Tests betrug 50%. Nach dem Tribotest wurde die Benetzbarkeit der Aluminiumprüfscheiben gegenüber Wasser geprüft. Hierzu wurde auf den Scheiben neben der Laufspur Tropfentests mit einem Tropfenvolumen von 5µl mit vollentsalztem Wasser durchgeführt. Die standardisierte Versuchsdurchführung entspricht der internen Arbeitsanweisung "Hydro CO 0620". Die kinematische Viskosität wurde gemäß DIN 51562 bei 40 °C gemessen.
** ein Polyethylengylkolmonodocylether mit einer kinematischen Viskosität von 20mm2/s bei 40°C
*** jeweils: Poly(proplylenglycol)monobutylether mit kin. Viskositäten von 33, 57 und 77 mm2/s bei 40°C
**** Mischung von Polyproplylenglycolen mit kin. Viskositäten von 75 und 225 mm2/s bei 40°C, Viskosität der Mischung ist 175 mm2/s bei 40°C
** a polyethylene glycol monodocyl ether with a kinematic viscosity of 20mm 2 /s at 40°C
*** each: poly(propylene glycol) monobutyl ether with kin. Viscosities of 33, 57 and 77 mm 2 /s at 40°C
**** Mixture of polypropylene glycols with kin. Viscosities of 75 and 225 mm 2 /s at 40°C, viscosity of the mixture is 175 mm 2 /s at 40°C
Die Schmierfilmbildung mit dem Grundöl allein ist suboptimal; es kommt zur Metallseifenbildung. Die Schmierstoffprobe 2 liefert einen guten Schmierfilm mit mehr Abrieb aber mit einer sauberen Scheibe. Die erfindungsgemäße Schmierstoffprobe 3 liefert eine bessere Schmierfilmbildung. Dasselbe gilt für die Probe 4, die darüber hinaus kaum eine Laufspur auf der Kugel zeigt. Das gilt auch für Probe 5, die kaum Abrieb liefert. Die Proben 6 bis 12 zeigen eine gute Schmierfilmausbildung. Proben 6 und 7etwas Abrieb, Probe 8 zeigt kaum Abrieb. Probe 6 zeigt eine akzeptable Benetzung mit Wasser, Probe 7 eine gute Benetzung und Probe 8 eine sehr gute Benetzung mit Wasser. Probe 10 liefert kaum Abrieb und kaum eine Laufspur auf der Kugel. Proben 11 und 12 liefern wenig Laufspur auf der Kugel.The lubricating film formation with the base oil alone is suboptimal; metal soap formation occurs. Lubricant sample 2 provides a good lubricating film with more wear but with a clean disc. Lubricant sample 3 according to the invention provides better lubricating film formation. The same is true for sample 4, which moreover hardly shows any track on the ball. This also applies to sample 5, which gives hardly any abrasion. Samples 6 to 12 show good lubricating film formation. Samples 6 and 7 show some abrasion, sample 8 shows hardly any abrasion. Sample 6 shows acceptable water wetting, sample 7 good wetting and sample 8 very good water wetting. Sample 10 gives hardly any abrasion and hardly any track on the ball. Samples 11 and 12 provide little tracking on the ball.
Auch in dem folgenden Versuch wurde eine Aluminiumfolie einer Legierung vom Typ AA1XXX zur Bestimmung des Benetzungswinkels auf der Oberfläche der Folie verwendet. Gemessen wurden die Kontaktwinkel (KW) bei der Benetzung mit Wasser und mit NMP. Die Bestimmung des Benetzungswinkels oder Kontaktwinkels erfolgte im Tropfentest bei einem Tropfenvolumen von 5 µl mit vollentsalztem Wasser oder NMP mit dem Drop Shape Analyzer DSA 10 der Krüss GmbH, Hamburg, Deutschland. Die Messungen sind Mittelwerte von Einzelmessungen an vier verschiedenen Positionen auf der Oberfläche der Folienprobe. Die Ergebnisse der Messungen sind in der folgenden Tabelle 2 gezeigt. Ferner wurde über die Bestimmung des Kontaktwinkels die Oberflächenenergie (SFE) ermittelt. Entsprechende Werte sind in der Tabelle 2 angegeben.
** Poly(propylenglycol)monobutylether
** Poly(propylene glycol) monobutyl ether
Die in der Tabelle 2 wiedergegebenen Ergebnisse zeigen, dass die Schmierstoffe mit einer Verbindung, die eine Polyalkylenoxidstruktur aufweist, zu Aluminiumprodukten mit erheblich geringeren Kontaktwinkeln zumindest für NMP führen. Das kann für bestimmte Anwendungen hilfreich sein.The results presented in Table 2 show that the lubricants with a compound having a polyalkylene oxide structure result in aluminum products with significantly lower contact angles, at least for NMP. This can be useful for certain applications.
Claims (9)
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP20191350.6A EP3957708A1 (en) | 2020-08-17 | 2020-08-17 | Cooling lubricant for the cold rolling of aluminium |
KR1020237008238A KR102636604B1 (en) | 2020-08-17 | 2021-08-17 | Cooling lubricant for aluminum cold rolling |
CA3191862A CA3191862C (en) | 2020-08-17 | 2021-08-17 | Cooling lubricant with polyalkylene glycol or ethoxylated fatty alcohol for cold rolling aluminum |
BR112023002718-7A BR112023002718B1 (en) | 2020-08-17 | 2021-08-17 | USE OF A COOLING LUBRICANT, AND METHOD FOR COLD ROLLING AN ALUMINUM PRODUCT FREE FROM VISUALLY DISCERNIBLE DEFECT PATTERNS CAUSED BY FATTY ACIDS |
JP2023512129A JP2023535646A (en) | 2020-08-17 | 2021-08-17 | Cooling lubricant for cold rolling aluminum |
EP21762692.8A EP4196558B1 (en) | 2020-08-17 | 2021-08-17 | Cooling lubricant for the cold rolling of aluminium |
PCT/EP2021/072781 WO2022038111A1 (en) | 2020-08-17 | 2021-08-17 | Cooling lubricant for cold rolling aluminum |
CN202180050723.0A CN115885025B (en) | 2020-08-17 | 2021-08-17 | Cooling lubricant for cold rolled aluminum |
US18/171,003 US20230203395A1 (en) | 2020-08-17 | 2023-02-17 | Cooling lubricant for cold rolling aluminum |
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EP20191350.6A EP3957708A1 (en) | 2020-08-17 | 2020-08-17 | Cooling lubricant for the cold rolling of aluminium |
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EP20191350.6A Withdrawn EP3957708A1 (en) | 2020-08-17 | 2020-08-17 | Cooling lubricant for the cold rolling of aluminium |
EP21762692.8A Active EP4196558B1 (en) | 2020-08-17 | 2021-08-17 | Cooling lubricant for the cold rolling of aluminium |
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EP21762692.8A Active EP4196558B1 (en) | 2020-08-17 | 2021-08-17 | Cooling lubricant for the cold rolling of aluminium |
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US (1) | US20230203395A1 (en) |
EP (2) | EP3957708A1 (en) |
JP (1) | JP2023535646A (en) |
KR (1) | KR102636604B1 (en) |
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WO (1) | WO2022038111A1 (en) |
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US4949566A (en) * | 1989-09-11 | 1990-08-21 | Robert Eichelbaum | Rolling mill lubrication |
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EP2978828A1 (en) * | 2013-05-23 | 2016-02-03 | Dow Global Technologies LLC | Polyalkylene glycols useful as lubricant additives for hydrocarbon base oils |
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GB8428621D0 (en) * | 1984-11-13 | 1984-12-19 | Alcan Int Ltd | Lubricant |
JP3133141B2 (en) * | 1992-04-03 | 2001-02-05 | 日石三菱株式会社 | Metalworking oil composition |
JPH09208984A (en) * | 1996-02-02 | 1997-08-12 | Nippon Steel Corp | Cold rolling oil composition, cold rolling oil emulsion and cold rolling |
JP3527936B2 (en) * | 1996-06-24 | 2004-05-17 | 新日本石油株式会社 | Metalworking oil composition |
US6059976A (en) * | 1997-08-28 | 2000-05-09 | Kaiser Aluminum & Chemical Corporation | Reclamation of spent aluminum rolling coolant oils, emulsions and dispersions |
JP4833487B2 (en) | 2001-09-21 | 2011-12-07 | Jx日鉱日石エネルギー株式会社 | Lubricating oil composition for aluminum processing |
JP2009242726A (en) * | 2008-03-31 | 2009-10-22 | Jfe Steel Corp | Lubricant for cold rolling and cold rolling method |
JP2009242700A (en) * | 2008-03-31 | 2009-10-22 | Jfe Steel Corp | Rolling oil for cold rolling, and cold rolling method |
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- 2020-08-17 EP EP20191350.6A patent/EP3957708A1/en not_active Withdrawn
-
2021
- 2021-08-17 KR KR1020237008238A patent/KR102636604B1/en active IP Right Grant
- 2021-08-17 WO PCT/EP2021/072781 patent/WO2022038111A1/en active Search and Examination
- 2021-08-17 EP EP21762692.8A patent/EP4196558B1/en active Active
- 2021-08-17 CA CA3191862A patent/CA3191862C/en active Active
- 2021-08-17 CN CN202180050723.0A patent/CN115885025B/en active Active
- 2021-08-17 JP JP2023512129A patent/JP2023535646A/en active Pending
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2023
- 2023-02-17 US US18/171,003 patent/US20230203395A1/en active Pending
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JP2023535646A (en) | 2023-08-18 |
CN115885025A (en) | 2023-03-31 |
EP4196558B1 (en) | 2024-06-19 |
US20230203395A1 (en) | 2023-06-29 |
CN115885025B (en) | 2024-05-24 |
CA3191862A1 (en) | 2022-02-24 |
WO2022038111A1 (en) | 2022-02-24 |
EP4196558A1 (en) | 2023-06-21 |
CA3191862C (en) | 2024-05-28 |
BR112023002718A2 (en) | 2023-03-14 |
KR102636604B1 (en) | 2024-02-16 |
KR20230052281A (en) | 2023-04-19 |
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