EP2976412B1 - Composition for the protection from scale and as lubricant for metal hot working - Google Patents
Composition for the protection from scale and as lubricant for metal hot working Download PDFInfo
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- EP2976412B1 EP2976412B1 EP14708889.2A EP14708889A EP2976412B1 EP 2976412 B1 EP2976412 B1 EP 2976412B1 EP 14708889 A EP14708889 A EP 14708889A EP 2976412 B1 EP2976412 B1 EP 2976412B1
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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
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/02—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic oxygen-containing compound
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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
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/12—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
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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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/04—Elements
- C10M2201/041—Carbon; Graphite; Carbon black
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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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/08—Inorganic acids or salts thereof
- C10M2201/084—Inorganic acids or salts thereof containing sulfur, selenium or tellurium
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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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/085—Phosphorus oxides, acids or salts
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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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/087—Boron oxides, acids or salts
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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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/10—Compounds containing silicon
- C10M2201/102—Silicates
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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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/12—Glass
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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
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
- C10M2207/122—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms monocarboxylic
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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
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
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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
- C10N2020/055—Particles related characteristics
- C10N2020/06—Particles of special shape or size
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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
- C10N2030/02—Pour-point; 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
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/04—Detergent property or dispersant property
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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
- C10N2030/70—Soluble oils
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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
- C10N2040/242—Hot working
Definitions
- the present invention relates to a composition for protection against scale and as a lubricant for the hot processing of metals.
- thermoforming metals especially steel
- in a temperature range of 500-1300 ° C such as rolling or drop forging
- it comes on the heated metal surface of the ambient air to the formation of scale which can be designed differently strong depending on the transfer time to the next process step
- a solid material is pierced and a hollow block is formed, which is then elongated in subsequent rolling steps.
- the danger of scale formation on the heated metal surface of the hollow block during the transfer to the Elongierrind is particularly high.
- this scale attack can lead to internal defects of the seamless pipe. For this reason, the resulting scale is blown out, for example, with compressed air or inert gas.
- lubricant or mordant or scale solvent on the inner surface of the hollow blocks.
- examples of such agents include graphite, boron nitride, molybdenum sulfide, silicates, sodium salts, alkali sulfates, saponified fatty acids or alkaline earth phosphates and mixtures thereof. Frequently alkali borates with different water of crystallization or boric acid are used.
- the forging process in particular of large and heavy parts, such.
- a contouring, wheel rolling and finish forging is at> 1200 ° C preheater, upset before the Hauptumform suitsen, cylindrical metal block in a preforming press, ie roughly preformed into a disk shape. Due to the process-related relatively long residence times of the heated parts it comes to the surface strong secondary delays that adversely affect the forming as well as the quality of the parts surfaces. If such a metal part before heating or the first forming step with lubricating, pickling, u. Coated with scale solvents of the aforementioned type, these negative influences reduce significantly.
- a lubricant for the hot processing of metals which contains a high proportion of water-soluble boron compounds, is for example in the WO 2008/000700 described.
- the object of the present invention was therefore to provide a composition acting as protection against scale and as a lubricant for the hot processing of metals, in which the risk potential based on the boron compounds previously used as constituents is reduced compared with the prior art, the good trickle and has flow behavior and good properties in terms of scale dissolution on heated metal surfaces and lubrication and applied in powder form allows a good coverage of the metal surface and requires little or no graphite.
- lubricant according to the invention may contain further constituents, as long as they do not significantly adversely affect the desired advantageous properties.
- the composition according to the invention is very well suited as an agent for protecting against scale and as a lubricant for the hot processing of metals, although they have no or, compared to known borate-based lubricants, only a very small optional amount of borates or boric acid having.
- the proportion of easily water-soluble borates, which entail a high hazard potential for humans and the environment, is considerably reduced or at best even completely excluded in the case of the composition according to the invention compared with known agents.
- the composition according to the invention forms the desired melt faster than in the case of known lubricants and ensures good lubrication and good protection against scale. This is achieved by the inventive combination of ingredients, it was surprising that the requirements for the lubrication and protection against scale of the composition despite the proportion of ground boron-silicate glass and the low proportion of boric acid or borate could be achieved.
- a particular advantage of the composition according to the invention consists in a significantly lower solubility of the borate portion compared to the prior art with comparable or even better effectiveness and functionality.
- This reduced solubility of the borate portion is achieved by a low or no amount of boric acid and / or boric acid salt according to component (e) and may be further modified by varying the ratio of the proportion of fatty acid and / or fatty acid salt of component (b) to boric acid and / or boric acid salt according to component (e).
- the borate content in the milled boron-silicate glass is extremely poorly water-soluble.
- the composition has a hemisphere point> 400 ° C.
- the hemisphere point is reached when a specimen in the examination of the ash melting behavior in the heating microscope has approximately the shape of a hemisphere.
- a hemisphere point> 400 ° C. of the composition according to the invention has the advantage that the melting point of the composition is not reached too early and a viscosity suitable for the application is maintained. If the hemisphere point of the composition is below 400 ° C., the viscosity of the melt in the range of use of 600-1300 ° C. is too low and a sufficient melt film is not obtained.
- Secondary and / or tertiary calcium phosphate compounds have surprisingly proven to be particularly suitable flow aids in a composition of the type according to the invention for the hot processing of metals.
- Monocalcium phosphate is unsuitable because it leads to clumping when humid.
- the calcium phosphate compound (a) is selected from hydroxy dia- betite [Ca 5 (PO 4 ) 3 OH] and tricalcium phosphate [Ca 3 (PO 4 ) 2 ], with hydroxy dia- pate being particularly preferred.
- the calcium phosphate compound (a) is contained in the composition in an amount of 1 to 5% by weight.
- the composition of the present invention further contains a fatty acid, a fatty acid salt or a mixture thereof in combination with the other ingredients. It has surprisingly been found that by using a fatty acid or a fatty acid salt, the agglomeration of the fine-grained powder can be significantly reduced and the storage stability can be improved. Without the applicant's being bound by theory, it is believed that the fatty acid or fatty acid salt attaches to the granules of one or more other constituents of the mixture and thus prevents or reduces clumping of the granules, preventing moisture from the granules and thereby improves the storage stability and the flow or flow behavior of the lubricant. In addition, it is believed that the fatty acid or fatty acid salt improves lubrication due to decomposition in the range of use of 600 - 1300 ° C and formation of a gas cushion.
- the fatty acid or fatty acid salt (b) is selected from saturated and unsaturated fatty acids containing 6 to 26 carbon atoms or their salts, preferably caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, Arachidic acid, behenic acid, lignoceric acid, cerotic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, icosenoic acid, erucic acid, nervonic acid, linoleic acid, linolenic acid, arachidonic acid, timnodonic acid, clupanodonic acid or salts thereof, provided that the fatty acid or the fatty acid salt is> 30 ° C is present as a solid.
- the fatty acid or the fatty acid salt is particularly preferably stearic acid or salts thereof.
- the fatty acid or fatty acid salt (b) is in an amount of 1 to 15 wt .-%, preferably from 1 to 10 wt .-%, particularly preferably from 3 to 7 wt .-% in of the composition.
- the milled boron-silicate glass (c) has a grain size with an average particle size D50 of ⁇ 300 ⁇ m.
- the milled boron-silicate glass improves the uniform distribution of the composition on the hot metal surface and reduces scale formation. At the high temperatures of metal processing, the composition forms a melt, the boron-silicate glass improving the rapid formation of the melt and ensuring it over a broader temperature range than known lubricants. If the average particle size of the milled boron-silicate glass in the composition is too large, the formation of the required melt after application of the composition may disadvantageously take too long.
- the boron-silicate glass (c) in an amount of 3 to 80 wt .-%, particularly preferably from 5 to 15 wt .-% in the mixture.
- the condensed alkali metal phosphates (d) are condensed sodium or potassium phosphates or mixtures thereof, preferably polyphosphates and / or pyrophosphates and / or metaphosphates or mixtures thereof, more preferably disodium pyrophosphate [Na 2 H 2 P 2 O 7 ] trisodium pyrophosphate [Na 3 HP 2 O 7 ], tetrasodium pyrophosphate [Na 4 P 2 O 7 ], sodium tripolyphosphate [Na 5 P 3 C 10 ], sodium trimetaphosphate [(NaPO 3 ) 3 ], sodium polyphosphate [(NaPO 3 ) n ] , Dipotassium pyrophosphate [K 2 H 2 P 2 O 7 ], tripotassium pyrophosphate [K 3 HP 2 O 7 ], tetrapotassium pyrophosphate [K 4 P 2 O 7 ], potassium tripolyphosphate [K 5
- the condensed alkali metal phosphates (d) in an amount of 40 to 80 wt .-%, preferably from 40 to 75 wt .-% in the mixture.
- the constituent (e) of the composition according to the invention is boric acid [H 3 BO 3 ], borax [Na 2 B 4 O 5 (OH) 4 .8H 2 O or Na 2 B 4 O 7 .10H 2 O], sodium borates such as Na 2 B 4 O 7 .5H 2 O, Na 2 B 4 O 7 (anhydrous), sodium metaborate [NaBO 2 .4H 2 O] boric anhydride [B 2 O 3 ] and Mixtures thereof selected.
- the mixture has an average particle size D50 of ⁇ 250 ⁇ m, preferably of ⁇ 200 ⁇ m. Due to the small average particle sizes of the constituents of the mixture according to the invention, the flow and flow behavior of the composition according to the invention compared to known lubricants is significantly improved, facilitates the spraying on surfaces as a powder and ensures better and more uniform layer formation or occupancy on the metal surface. At the same time, the combination of the constituents of the mixture according to the invention prevents or reduces clumping which has regularly occurred in the case of lubricants according to the prior art with small particle sizes and has led to considerable disadvantages.
- the mixture has an average particle size D50 of ⁇ 3 ⁇ m, preferably ⁇ 10 ⁇ m, particularly preferably ⁇ 15 ⁇ m. It has been found that too small average particle sizes can only be produced with great difficulty and at relatively high costs on the one hand and on the other hand they also increase the tendency to clumping again. An average particle size in the range of 20 to 50 microns has therefore proved to be optimal.
- the invention also includes the use of the inventive composition for the protection against scale and as a lubricant in the hot processing of metals, wherein the composition is applied in powder form to the metal, preferably inflated.
- the composition of the invention is characterized by more stable storage properties, faster melting in contact with the hot workpiece due to the larger surface, better inflatability and more uniform distribution on the surface of the workpiece as well as safer and more economical Dosage off.
- the dry, powdered use of the composition of the invention has the advantage that no unwanted cooling of the workpiece is carried by the liquid and also the additional step of preparing the application suspension is unnecessary ,
- the average particle size of the mixture or constituents of the composition according to the invention is determined by means of a Cilas Model 715/920 laser granulometer from Cilas. Inc. Approximately 80 mg of sample is suspended in 2-propanol and the measurement is made one minute after preparation of the suspension according to the manufacturer's instructions.
- Table 1 sets forth compositions according to the invention for protection against scale and as a lubricant for the hot processing of metals and comparative compositions.
- Table 2 gives parameters of the compositions given in Table 1. ⁇ b> ⁇ u>
- compositions (proportions of the components in% by weight) E1 (Erf.) E2 (Erf.) E3 (Erf.) V1 (Cf.) V2 (Cf.) (a) Ca Phosphate Compound Hydroxylapatite [Ca 5 (PO 4 ) 3 OH] 4 5 5 0 5 (b) Fatty acid, fatty acid salt magnesium stearate 7 5 5 0 5 Na / K soap 0 0 0 25 0 (c) ground borosilicate glass 1) 15 6 15 0 0 (d) condensed alkali phosphate sodium tripolyphosphate 71 80 75 0 75 (e) Boric acid, boric acid, sodium tetraborate anhydride 3 4 0 0 15 Sodium tetraborate decahydrate 0 0 0 40 0 (f) graphite 0 0 0 0 0 0 sodium sulphate 0 0 0 35 0 total 100 100 100 100 100 100 100 100 100
- the “required quantity used” given in Table 2 is defined as the quantity in “g”, based on the inner surface of the workpiece to be coated (hollow block), which is introduced on average into the hollow blocks to be machined by means of a suitable application technique, preferably according to the usual injector technology (injection). in “m 2 ".
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
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Description
Die vorliegende Erfindung betrifft eine Zusammensetzung für den Schutz vor Zunder und als Schmiermittel für die Heißverarbeitung von Metallen.The present invention relates to a composition for protection against scale and as a lubricant for the hot processing of metals.
Beim Warmverformen von Metallen, insbesondere von Stahl, in einem Temperaturbereich von 500-1300 °C, wie beispielsweise beim Walzen oder Gesenkschmieden, kommt es an der erhitzten Metalloberfläche an der Umgebungsluft zur Zunderbildung, die je nach Transferzeit zum nächsten Prozessschritt unterschiedlich stark ausgebildet sein kann. Bei Warmwalzverfahren von Stahl zur Herstellung von nahtlosen Rohren wird ein Vollmaterial durchstoßen und ein Hohlblock gebildet, der anschließend in nachfolgenden Walzschritten elongiert wird. Hier ist die Gefahr von Zunderbildung auf der erhitzten Metalloberfläche des Hohlblocks während der Überführung zu dem Elongierprozess besonders hoch. Bei den nachfolgenden Walzschritten kann dieser Zunderanfall zu Innenfehlern des nahtlosen Rohres führen. Aus diesem Grund wird der anfallende Zunder beispielsweise mit Druckluft oder Inertgas ausgeblasen. Zusätzlich werden unterschiedlichste Substanzen in Pulverform als Schmier- oder Beizmittel bzw. Zunderlösungsmittel auf die Innenoberfläche der Hohlblöcke aufgebracht. Beispiele für solche Mittel enthalten Graphit, Bornitrid, Molybdänsulfid, Silikate, Natriumsalze, Alkalisulfate, verseifte Fettsäuren oder Erdalkaliphosphate sowie Mischungen davon. Häufig kommen Alkaliborate mit unterschiedlichem Kristallwasser oder Borsäure zum Einsatz.When thermoforming metals, especially steel, in a temperature range of 500-1300 ° C, such as rolling or drop forging, it comes on the heated metal surface of the ambient air to the formation of scale, which can be designed differently strong depending on the transfer time to the next process step , In hot rolling of steel for the production of seamless tubes, a solid material is pierced and a hollow block is formed, which is then elongated in subsequent rolling steps. Here, the danger of scale formation on the heated metal surface of the hollow block during the transfer to the Elongierprozess is particularly high. In the subsequent rolling steps, this scale attack can lead to internal defects of the seamless pipe. For this reason, the resulting scale is blown out, for example, with compressed air or inert gas. In addition, a wide variety of substances are applied in powder form as a lubricant or mordant or scale solvent on the inner surface of the hollow blocks. Examples of such agents include graphite, boron nitride, molybdenum sulfide, silicates, sodium salts, alkali sulfates, saponified fatty acids or alkaline earth phosphates and mixtures thereof. Frequently alkali borates with different water of crystallization or boric acid are used.
In einem weiteren Anwendungsfeld, dem Schmiedeprozess, insbesondere von großen und schweren Teilen, wie z. B. Eisenbahnrädern, wird vor den Hauptumformschritten Konturschmieden, Radwalzen und Fertigschmieden ein auf >1200 °C vorerhitzer, zylinderförmiger Metallblock in einer Vorformpresse gestaucht, d. h. zu einer Scheibenform grob vorgeformt. Aufgrund der prozessbedingt relativ langen Verweilzeiten der erhitzen Teile kommt es an der Oberfläche zu starken Sekundärverzunderungen, welche die Umformung sowie die Qualität der Teileoberflächen negativ beeinflussen. Wird ein solches Metallteil vor der Erwärmung oder dem ersten Umformschritt mit Schmier-, Beiz-, u. Zunderlösemitteln der vorgenannten Art beschichtet, verringern sich diese negativen Einflüsse deutlich.In a further field of application, the forging process, in particular of large and heavy parts, such. As railway wheels, a contouring, wheel rolling and finish forging is at> 1200 ° C preheater, upset before the Hauptumformschritten, cylindrical metal block in a preforming press, ie roughly preformed into a disk shape. Due to the process-related relatively long residence times of the heated parts it comes to the surface strong secondary delays that adversely affect the forming as well as the quality of the parts surfaces. If such a metal part before heating or the first forming step with lubricating, pickling, u. Coated with scale solvents of the aforementioned type, these negative influences reduce significantly.
Um die schnelle Bildung einer Schmelze für die Schmierung und den Schutz vor Zunder zu gewährleisten, werden die vorgenannten Mittel durch Vernebelung als Pulver oder Granulat auf die glühenden Oberflächen aufgebracht. Dies hat zu Folge, dass die in den bekannten Mitteln enthaltenen Borverbindungen aufgrund der Wasserlöslichkeit und der schwierigen räumlichen Eindämmbarkeit ins Abwasser gelangen und ein Gefährdungspotenzial für Gewässer darstellen. Außerdem besteht beim Einsatz von Borsalzen und Borsäure bei der beschriebenen Applikation als Pulver oder Granulat Aspirationsgefahr. Studien lassen dabei auf eine Beeinträchtigung der Fruchtbarkeit und eine Gefährdung für das Kind im Mutterleib schließen und haben zur Einstufung der Borverbindungen und der damit aufgebauten Gemische als reproduktionstoxisch geführt. Diese Eigenschaften stellen damit eine signifikante Gefährdung für den Menschen und die Umwelt dar und sind sowohl für die Herstellung der Pulvermischungen, für die Lagerung, den Transport, die Handhabung, die Entsorgung, sowie den eigentlichen Einsatz und Zweck dieser Materialien in der Metallumformung relevant. Ein Schmiermittel für die Heißverarbeitung von Metallen, welches einen hohen Anteil an wasserlöslichen Borverbindungen enthält, ist beispielsweise in der
Viele Schmiermittel für die Heißverformung von Metallen enthalten Graphit aufgrund seiner guten Schmiereigenschaften und Temperaturstabilität. Allerdings hat Graphit erhebliche Nachteile, wie z. B. die Aufnahme von Graphitkohlenstoff in die bearbeitete Metalloberfläche, wodurch die Zusammensetzung und die Eigenschaften der Metalloberfläche verändert werden können. Darüber hinaus ist Graphit aus arbeitshygienischen Gründen unerwünscht, da das Graphitpulver leicht in die Umgebungsatmosphäre zerstäubt wird und für in der Nähe arbeitende Personen eine Rutschgefahr darstellt. Zudem kann der Graphitstaub die Funktionsfähigkeit von elektrischen Anlagen im Betrieb gefährden. Es wäre daher wünschenswert, ein Schmiermittel ohne Graphit oder mit einem möglichst niedrigen Graphitanteil bei gleichzeitig guter Schmierwirkung zur Verfügung zu stellen.Many lubricants for hot deformation of metals contain graphite because of its good lubricating properties and temperature stability. However, graphite has significant disadvantages, such. Example, the inclusion of graphite carbon in the machined metal surface, whereby the composition and the properties of the metal surface can be changed. In addition, graphite is undesirable for occupational hygiene reasons, since the graphite powder is easily atomized into the surrounding atmosphere and represents a danger of slipping for persons working nearby. In addition, the graphite dust can endanger the functionality of electrical systems during operation. It would therefore be desirable to provide a lubricant without graphite or with the lowest possible graphite content with good lubricity.
Weiterhin besitzen viele bekannte Schmiermittel aufgrund ihrer physikalischen Eigenschaften und Korngrößen kein gutes Riesel- bzw. Fließverhalten. Ein grobes Material mit hohen Korngrößen führt häufig zu einer unzureichenden und ungleichmäßigen Belegung der Metalloberfläche und damit zu einer schlechten Zunderreduzierung. Eine feinere Körnung hätte daher den Vorteil, dass eine bessere Schichtbildung erreicht werden kann. Bekannte feinkörnige Materialien mit kleinen Korngrößen, beispielsweise unter 50 µm, neigen jedoch häufig zu Verklumpung, insbesondere bei der Lagerung, weshalb sie nur schwer als Pulver auf die Metalloberfläche aufgesprüht werden können, was den Vorteil einer feinen Körnung bekannter Zusammensetzungen wieder zunichte macht.Furthermore, many known lubricants due to their physical properties and grain sizes no good trickle or flow behavior. A coarse material with high particle sizes often leads to an insufficient and uneven coverage of the metal surface and thus to a poor scale reduction. A finer grain size would therefore have the advantage that a better layer formation can be achieved. However, known fine-grained materials with small particle sizes, for example less than 50 μm, often tend to clump, in particular during storage, which is why they are difficult to spray as a powder on the metal surface, which negates the advantage of a fine grain size of known compositions again.
Die Aufgabe der vorliegenden Erfindung bestand daher darin, eine als Schutz vor Zunder und als Schmiermittel wirkende Zusammensetzung für die Heißverarbeitung von Metallen bereitzustellen, bei der das durch die bislang als Bestandteile verwendeten Borverbindungen begründete Gefährdungspotenzial gegenüber dem Stand der Technik vermindert ist, die gutes Riesel- und Fließverhalten aufweist und gute Eigenschaften hinsichtlich Zunderauflösung auf erhitzten Metalloberflächen und Schmierung besitzt und die in Pulverform aufgebracht eine gute Belegung der Metalloberfläche erlaubt und möglichst wenig oder gar keinen Graphit benötigt.The object of the present invention was therefore to provide a composition acting as protection against scale and as a lubricant for the hot processing of metals, in which the risk potential based on the boron compounds previously used as constituents is reduced compared with the prior art, the good trickle and has flow behavior and good properties in terms of scale dissolution on heated metal surfaces and lubrication and applied in powder form allows a good coverage of the metal surface and requires little or no graphite.
Gelöst wird diese Aufgabe erfindungsgemäß durch eine Zusammensetzung für den Schutz vor Zunder und als Schmiermittel für die Heißverarbeitung von Metallen, bestehend aus einem Gemisch von feinpulverigen Materialien, wobei das Gemisch wenigstens die folgenden Bestandteile enthält:
- (a) 0,5 bis 10 Gew.-% sekundäre oder tertiäre Calciumphosphatverbindung, Hydroxylapatit oder ein Gemisch davon,
- (b) 1 bis 35 Gew.-% Fettsäure, Fettsäuresalz oder ein Gemisch davon,
- (c) 1 bis 80 Gew.-% gemahlenes Bor-Silikatglas, welches bezogen auf das Bor-Silikatglas Na, B, Si und Al in den folgenden Gewichtsanteilen, ausgedrückt durch ihre jeweiligen Oxide, enthält:
- 1 bis 30 Gew.% Na2O,
- 2 bis 70 Gew.-% B2O3,
- 10 bis 70 Gew.-% SiO2 und
- 0 bis 10 Gew.-% Al2O3,
- (d) 40 bis 85 Gew.-% kondensierte Alkaliphosphate,
- (e) Borsäure, Borsäuresalz oder ein Gemisch davon in einer Menge entsprechend einem Borgehalt, ausgedrückt durch das Oxid, von 0 bis 3,2 Gew.-% B2O3,
- (f) nicht mehr als 10 Gew.-% Graphit,
- (a) 0.5 to 10% by weight of secondary or tertiary calcium phosphate compound, hydroxyapatite or a mixture thereof,
- (b) 1 to 35% by weight of fatty acid, fatty acid salt or a mixture thereof,
- (c) 1 to 80% by weight of ground boron-silicate glass which, based on the boron-silicate glass, contains Na, B, Si and Al in the following parts by weight, expressed by their respective oxides:
- 1 to 30% by weight of Na 2 O,
- From 2 to 70% by weight of B 2 O 3 ,
- 10 to 70 wt .-% SiO 2 and
- 0 to 10% by weight of Al 2 O 3 ,
- (d) 40 to 85% by weight of condensed alkali phosphates,
- (e) boric acid, boric acid salt or a mixture thereof in an amount corresponding to a boron content expressed by the oxide of from 0 to 3.2% by weight of B 2 O 3 ,
- (f) not more than 10% by weight of graphite,
Es versteht sich, dass der erfindungsgemäße Schmierstoff weitere Bestandteile enthalten kann, soweit diese die gewünschten vorteilhaften Eigenschaften nicht wesentlich nachteilig beeinflussen.It is understood that the lubricant according to the invention may contain further constituents, as long as they do not significantly adversely affect the desired advantageous properties.
Es hat sich überraschend gezeigt, dass sich die erfindungsgemäße Zusammensetzung sehr gut als Mittel für den Schutz vor Zunder und als Schmierstoff für die Heißverarbeitung von Metallen eignet, obwohl sie keinen oder im Vergleich zu bekannten Schmiermitteln auf Boratbasis nur sehr geringen optionalen Anteil an Boraten oder Borsäure aufweist. Der Anteil leicht wasserlöslicher Borate, die ein hohes Gefährdungspotential für Mensch und Umwelt mit sich bringen, ist bei der erfindungsgemäßen Zusammensetzung gegenüber bekannten Mitteln erheblich reduziert oder bestenfalls sogar völlig ausgeschlossen. Die erfindungsgemäße Zusammensetzung bildet beim Aufbringen auf die heiße Metalloberfläche schneller als bei bekannten Schmiermitteln die gewünschte Schmelze aus und sorgt für eine gute Schmierung und guten Schutz vor Zunder. Erreicht wird dies durch die erfindungsgemäße Kombination der Bestandteile, wobei es überraschend war, dass die Anforderungen an die Schmierung und den Schutz vor Zunder der Zusammensetzung trotz des Anteils an gemahlenem Bor-Silikatglas und des geringen Anteils an Borsäure oder Borat erzielt werden konnten.It has surprisingly been found that the composition according to the invention is very well suited as an agent for protecting against scale and as a lubricant for the hot processing of metals, although they have no or, compared to known borate-based lubricants, only a very small optional amount of borates or boric acid having. The proportion of easily water-soluble borates, which entail a high hazard potential for humans and the environment, is considerably reduced or at best even completely excluded in the case of the composition according to the invention compared with known agents. When applied to the hot metal surface, the composition according to the invention forms the desired melt faster than in the case of known lubricants and ensures good lubrication and good protection against scale. This is achieved by the inventive combination of ingredients, it was surprising that the requirements for the lubrication and protection against scale of the composition despite the proportion of ground boron-silicate glass and the low proportion of boric acid or borate could be achieved.
Ein besonderer Vorteil der erfindungsgemäßen Zusammensetzung besteht in einer gegenüber dem Stand der Technik deutlich reduzierten Löslichkeit des Boratanteils bei vergleichbarer oder sogar besserer Wirksamkeit und Funktionalität. Diese reduzierte Löslichkeit des Boratanteils wird durch einen niedrigen oder keinen Anteil an Borsäure und/oder Borsäuresalz gemäß Bestandteil (e) erzielt und kann weiterhin durch Variation des Verhältnisses des Anteils an Fettsäure und/oder Fettsäuresalz gemäß Bestandteil (b) zu Borsäure und/oder Borsäuresalz gemäß Bestandteil (e) beeinflusst werden. Der Boratanteil in dem gemahlenen Bor-Silikatglas ist äußerst schlecht wasserlöslich. Ein Vorteil der erfindungsgemäßen Zusammensetzung besteht daher darin, dass der Anwender aufgrund der geringen Boratlöslichkeit die üblicherweise hohen Anforderungen der geltenden Abwasserrichtlinien leichter erfüllen kann, beispielsweise gemäß EN ISO 11885:2007.A particular advantage of the composition according to the invention consists in a significantly lower solubility of the borate portion compared to the prior art with comparable or even better effectiveness and functionality. This reduced solubility of the borate portion is achieved by a low or no amount of boric acid and / or boric acid salt according to component (e) and may be further modified by varying the ratio of the proportion of fatty acid and / or fatty acid salt of component (b) to boric acid and / or boric acid salt according to component (e). The borate content in the milled boron-silicate glass is extremely poorly water-soluble. An advantage of the composition of the invention is therefore that the user due to the low borate solubility can easily meet the usually high requirements of the applicable wastewater guidelines, for example according to EN ISO 11885: 2007.
In einer weiteren bevorzugten Ausführungsform der Erfindung weist die Zusammensetzung einen Halbkugelpunkt > 400°C auf. Der Halbkugelpunkt ist erreicht, wenn ein Probekörper bei der Prüfung des Ascheschmelzverhaltens im Erhitzungsmikroskop annähernd die Form einer Halbkugel aufweist. Ein Halbkugelpunkt > 400°C der erfindungsgemäßen Zusammensetzung hat den Vorteil, dass der Schmelzpunkt der Zusammensetzung nicht zu früh erreicht wird und eine für die Anwendung geeignete Viskosität erhalten bleibt. Liegt der Halbkugelpunkt der Zusammensetzung unter 400 °C, ist die Viskosität der Schmelze im Einsatzbereich von 600 - 1300 °C zu niedrig und man erhält keinen ausreichenden Schmelzfilm.In a further preferred embodiment of the invention, the composition has a hemisphere point> 400 ° C. The hemisphere point is reached when a specimen in the examination of the ash melting behavior in the heating microscope has approximately the shape of a hemisphere. A hemisphere point> 400 ° C. of the composition according to the invention has the advantage that the melting point of the composition is not reached too early and a viscosity suitable for the application is maintained. If the hemisphere point of the composition is below 400 ° C., the viscosity of the melt in the range of use of 600-1300 ° C. is too low and a sufficient melt film is not obtained.
Sekundäre und/oder tertiäre Calciumphosphatverbindungen haben sich überraschenderweise als besonders geeignete Rieselhilfsmittel in einer Zusammensetzung der erfindungsgemäßen Art für die Heißverarbeitung von Metallen erwiesen. Monocalciumphosphat ist ungeeignet, da es bei Luftfeuchte zu Verklumpung führt.Secondary and / or tertiary calcium phosphate compounds have surprisingly proven to be particularly suitable flow aids in a composition of the type according to the invention for the hot processing of metals. Monocalcium phosphate is unsuitable because it leads to clumping when humid.
In einer bevorzugten Ausführungsform der Erfindung ist die Calciumphosphatverbindung (a) unter Hxdroxylapatit [Ca5(PO4)3OH] und Tricalciumphosphat [Ca3(PO4)2] ausgewählt, wobei Hxdroxylapatit besonders bevorzugt ist.In a preferred embodiment of the invention, the calcium phosphate compound (a) is selected from hydroxy dia- betite [Ca 5 (PO 4 ) 3 OH] and tricalcium phosphate [Ca 3 (PO 4 ) 2 ], with hydroxy dia- pate being particularly preferred.
In einer weiteren bevorzugten Ausführungsform der Erfindung ist die Calciumphosphatverbindung (a) in einer Menge von 1 bis 5 Gew.-% in der Zusammensetzung enthalten.In another preferred embodiment of the invention, the calcium phosphate compound (a) is contained in the composition in an amount of 1 to 5% by weight.
Die Zusammensetzung der vorliegenden Erfindung enthält weiterhin eine Fettsäure, ein Fettsäuresalz oder ein Gemisch davon in Kombination mit den übrigen Bestandteilen. Es hat sich überraschenderweise gezeigt, dass durch die Verwendung einer Fettsäure oder eines Fettsäuresalzes die Verklumpung des feinkörnigen Pulvers erheblich verringert und die Lagerungsbeständigkeit verbessert werden können. Ohne dass sich die Anmelderin hierdurch an eine Theorie gebunden fühlt, wird angenommen, dass sich die Fettsäure oder das Fettsäuresalz an die Körner eines oder mehrerer weiterer Bestandteile des Gemisches anlagert und auf diese Weise eine Verklumpung der Körner verhindert oder vermindert, Feuchtigkeit von den Körnern abhält und dadurch die Lagerungsbeständigkeit sowie das Riesel- bzw. Fließverhalten des Schmierstoffs verbessert. Zudem wird angenommen, dass die Fettsäure oder das Fettsäuresalz die Schmierung aufgrund von Zersetzung im Einsatzbereich von 600 - 1300 °C und Ausbildung eines Gaspolsters verbessert.The composition of the present invention further contains a fatty acid, a fatty acid salt or a mixture thereof in combination with the other ingredients. It has surprisingly been found that by using a fatty acid or a fatty acid salt, the agglomeration of the fine-grained powder can be significantly reduced and the storage stability can be improved. Without the applicant's being bound by theory, it is believed that the fatty acid or fatty acid salt attaches to the granules of one or more other constituents of the mixture and thus prevents or reduces clumping of the granules, preventing moisture from the granules and thereby improves the storage stability and the flow or flow behavior of the lubricant. In addition, it is believed that the fatty acid or fatty acid salt improves lubrication due to decomposition in the range of use of 600 - 1300 ° C and formation of a gas cushion.
In einer weiteren bevorzugten Ausführungsform der Erfindung ist die Fettsäure bzw. das Fettsäuresalz (b) unter gesättigten und ungesättigten Fettsäuren mit 6 bis 26 Kohlenstoffatomen bzw. deren Salzen, vorzugsweise unter Kapronsäure, Kaprylsäure, Kaprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Margarinsäure, Stearinsäure, Arachinsäure, Behensäure, Lignocerinsäure, Cerotinsäure, Palmitoleinsäure, Ölsäure, Elaidinsäure, Vaccensäure, Icosensäure, Erucasäure, Nervonsäure, Linolsäure, Linolensäure, Arachidonsäure, Timnodonsäure, Clupanodonsäure bzw. deren Salzen, ausgewählt, vorausgesetzt dass die Fettsäure bzw. das Fettsäuresalz bei einer Temperatur > 30 °C als Feststoff vorliegt. Besonders bevorzugt ist die Fettsäure bzw. das Fettsäuresalz Stearinsäure bzw. deren Salze.In a further preferred embodiment of the invention, the fatty acid or fatty acid salt (b) is selected from saturated and unsaturated fatty acids containing 6 to 26 carbon atoms or their salts, preferably caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, Arachidic acid, behenic acid, lignoceric acid, cerotic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, icosenoic acid, erucic acid, nervonic acid, linoleic acid, linolenic acid, arachidonic acid, timnodonic acid, clupanodonic acid or salts thereof, provided that the fatty acid or the fatty acid salt is> 30 ° C is present as a solid. The fatty acid or the fatty acid salt is particularly preferably stearic acid or salts thereof.
In einer weiteren bevorzugten Ausführungsform der Erfindung ist die Fettsäure bzw. das Fettsäuresalz (b) in einer Menge von 1 bis 15 Gew.-%, vorzugsweise von 1 bis 10 Gew.-%, besonders bevorzugt von 3 bis 7 Gew.-% in der Zusammensetzung enthalten.In a further preferred embodiment of the invention, the fatty acid or fatty acid salt (b) is in an amount of 1 to 15 wt .-%, preferably from 1 to 10 wt .-%, particularly preferably from 3 to 7 wt .-% in of the composition.
In einer weiteren bevorzugten Ausführungsform der Erfindung weist das gemahlene Bor-Silikatglas (c) eine Körnung mit einer mittleren Partikelgröße D50 von ≤ 300 µm auf. Das gemahlene Bor-Silikatglas verbessert die gleichmäßige Verteilung der Zusammensetzung auf der heißen Metalloberfläche und reduziert die Zunderbildung. Bei den hohen Temperaturen der Metallverarbeitung bildet die Zusammensetzung eine Schmelze, wobei das Bor-Silikatglas die schnelle Bildung der Schmelze verbessert und über einen breiteren Temperaturbereich als bei bekannten Schmiermitteln gewährleistet. Ist die mittlere Partikelgröße des gemahlenen Bor-Silikatglases in der Zusammensetzung zu groß, kann die Ausbildung der erforderlichen Schmelze nach dem Aufbringen der Zusammensetzung mit Nachteil zu lange dauern.In a further preferred embodiment of the invention, the milled boron-silicate glass (c) has a grain size with an average particle size D50 of ≦ 300 μm. The milled boron-silicate glass improves the uniform distribution of the composition on the hot metal surface and reduces scale formation. At the high temperatures of metal processing, the composition forms a melt, the boron-silicate glass improving the rapid formation of the melt and ensuring it over a broader temperature range than known lubricants. If the average particle size of the milled boron-silicate glass in the composition is too large, the formation of the required melt after application of the composition may disadvantageously take too long.
In einer weiteren bevorzugten Ausführungsform der Erfindung ist das Bor-Silikatglas (c) in einer Menge von 3 bis 80 Gew.-%, besonders bevorzugt von 5 bis 15 Gew.-% in dem Gemisch enthalten.In a further preferred embodiment of the invention, the boron-silicate glass (c) in an amount of 3 to 80 wt .-%, particularly preferably from 5 to 15 wt .-% in the mixture.
In einer weiteren bevorzugten Ausführungsform der Erfindung sind die kondensierten Alkaliphosphate (d) unter kondensierten Natrium- oder Kaliumphosphaten oder Gemischen davon, bevorzugt unter Polyphosphaten und/oder Pyrophosphaten und/oder Metaphosphaten oder Gemischen davon, besonders bevorzugt unter Dinatriumpyrophosphat [Na2H2P2O7] Trinatriumpyrophosphat [Na3HP2O7], Tetranatriumpyrophosphat [Na4P2O7], Natriumtripolyphosphat [Na5P3C10], Natriumtrimetaphosphat [(NaPO3)3], Natriumpolyphosphat [(NaPO3)n], Dikaliumpyrophosphat [K2H2P2O7], Trikaliumpyrophosphat [K3HP2O7], Tetrakaliumpyrophosphat [K4P2O7], Kaliumtripolyphosphat [K5P3O10], Kaliumtrimetaphosphat [(KPO3)3], Kaliumpolyphosphat [(KPO3)n] oder Gemischen davon ausgewählt, wobei Bestandteil (d) am bevorzugtesten Natriumtripolyphosphat [Na5P3O10] ist.In a further preferred embodiment of the invention, the condensed alkali metal phosphates (d) are condensed sodium or potassium phosphates or mixtures thereof, preferably polyphosphates and / or pyrophosphates and / or metaphosphates or mixtures thereof, more preferably disodium pyrophosphate [Na 2 H 2 P 2 O 7 ] trisodium pyrophosphate [Na 3 HP 2 O 7 ], tetrasodium pyrophosphate [Na 4 P 2 O 7 ], sodium tripolyphosphate [Na 5 P 3 C 10 ], sodium trimetaphosphate [(NaPO 3 ) 3 ], sodium polyphosphate [(NaPO 3 ) n ] , Dipotassium pyrophosphate [K 2 H 2 P 2 O 7 ], tripotassium pyrophosphate [K 3 HP 2 O 7 ], tetrapotassium pyrophosphate [K 4 P 2 O 7 ], potassium tripolyphosphate [K 5 P 3 O 10 ], potassium trimetaphosphate [(KPO 3 ) 3 ], Potassium polyphosphate [(KPO 3 ) n ] or mixtures thereof, wherein component (d) is most preferably sodium tripolyphosphate [Na 5 P 3 O 10 ].
Es hat sich gezeigt, dass die Verwendung eines Polyphosphats und/oder eines Pyrophosphats und/oder eines Metaphosphats in dem Gemisch der erfindungsgemäßen Zusammensetzung mit Vorteil unter anderem zur Zunderauflösung beiträgt.It has been found that the use of a polyphosphate and / or a pyrophosphate and / or a metaphosphate in the mixture of the composition according to the invention advantageously contributes, inter alia, to scaling.
In einer weiteren bevorzugten Ausführungsform der Erfindung sind die kondensierten Alkaliphosphate (d) in einer Menge von 40 bis 80 Gew.-%, vorzugsweise von 40 bis 75 Gew.-% in dem Gemisch enthalten.In a further preferred embodiment of the invention, the condensed alkali metal phosphates (d) in an amount of 40 to 80 wt .-%, preferably from 40 to 75 wt .-% in the mixture.
In einer weiteren bevorzugten Ausführungsform der Erfindung ist der Bestandteil (e) der erfindungsgemäßen Zusammensetzung, sofern enthalten, unter Borsäure [H3BO3], Borax [Na2B4O5(OH)4·8H2O bzw. Na2B4O7·10H2O], Natriumboraten, wie Na2B4O7·5H2O, Na2B4O7 (wasserfrei), Natriummetaborat [NaBO2·4H2O] Borsäureanhydrid [B2O3] und Gemischen davon ausgewählt.In a further preferred embodiment of the invention, the constituent (e) of the composition according to the invention, if present, is boric acid [H 3 BO 3 ], borax [Na 2 B 4 O 5 (OH) 4 .8H 2 O or Na 2 B 4 O 7 .10H 2 O], sodium borates such as Na 2 B 4 O 7 .5H 2 O, Na 2 B 4 O 7 (anhydrous), sodium metaborate [NaBO 2 .4H 2 O] boric anhydride [B 2 O 3 ] and Mixtures thereof selected.
In einer weiteren bevorzugten Ausführungsform der Erfindung weist das Gemisch eine mittlere Partikelgröße D50 von ≤ 250 µm, vorzugsweise von ≤ 200 µm auf. Durch die geringen mittleren Partikelgrößen der Bestandteile des erfindungsgemäßen Gemischs wird das Riesel- und Fließverhalten der erfindungsgemäßen Zusammensetzung gegenüber bekannten Schmierstoffen erheblich verbessert, das Aufsprühen auf Oberflächen als Pulver erleichtert und eine bessere und gleichmäßigere Schichtbildung bzw. Belegung auf der Metalloberfläche gewährleistet. Gleichzeitig wird durch die Kombination der erfindungsgemäßen Bestandteile des Gemischs eine Verklumpung verhindert oder vermindert, die bei Schmierstoffen nach dem Stand der Technik mit kleinen Korngrößen regelmäßig aufgetreten ist und zu erheblichen Nachteilen geführt hat.In a further preferred embodiment of the invention, the mixture has an average particle size D50 of ≦ 250 μm, preferably of ≦ 200 μm. Due to the small average particle sizes of the constituents of the mixture according to the invention, the flow and flow behavior of the composition according to the invention compared to known lubricants is significantly improved, facilitates the spraying on surfaces as a powder and ensures better and more uniform layer formation or occupancy on the metal surface. At the same time, the combination of the constituents of the mixture according to the invention prevents or reduces clumping which has regularly occurred in the case of lubricants according to the prior art with small particle sizes and has led to considerable disadvantages.
In einer weiteren bevorzugten Ausführungsform der Erfindung weist das Gemisch eine mittlere Partikelgröße D50 von ≥ 3 µm, vorzugsweise ≥ 10 µm, besonders bevorzugt ≥ 15 µm auf. Es hat sich gezeigt, dass zu geringe mittlere Partikelgrößen zum einen nur sehr aufwendig und unter verhältnismäßig hohen Kosten herstellbar sind und sie zum anderen auch die Neigung zur Verklumpung wieder erhöhen. Eine mittlere Partikelgröße im Bereich von 20 bis 50 µm hat sich daher als optimal erwiesen.In a further preferred embodiment of the invention, the mixture has an average particle size D50 of ≥ 3 μm, preferably ≥ 10 μm, particularly preferably ≥ 15 μm. It has been found that too small average particle sizes can only be produced with great difficulty and at relatively high costs on the one hand and on the other hand they also increase the tendency to clumping again. An average particle size in the range of 20 to 50 microns has therefore proved to be optimal.
Die Erfindung umfasst auch die Verwendung der erfindungsgemäßen Zusammensetzung für den Schutz vor Zunder und als Schmiermittel bei der Heißverarbeitung von Metallen, wobei die Zusammensetzung in Pulverform auf das Metall aufgebracht, vorzugsweise aufgeblasen wird. Im Gegensatz zu den häufig als Granulate eingesetzten Mitteln für die Heißverarbeitung von Metallen zeichnet sich die erfindungsgemäße Zusammensetzung durch stabilere Lagereigenschaften, schnelleres Aufschmelzen bei Kontakt mit dem heißen Werkstück aufgrund der größeren Oberfläche, bessere Verblasbarkeit und gleichmäßigere Verteilung auf der Oberfläche des Werkstückes sowie sicherere und sparsamere Dosierung aus. Gegenüber der ebenfalls bekannten Anwendung solcher Mittel in der Form von Suspensionen, beispielsweise in Wasser, bietet der trockene, pulverförmige Einsatz der erfindungsgemäßen Zusammensetzung den Vorteil, dass keine unerwünschte Kühlung des Werkstückes durch die Flüssigkeit erfolgt und sich auch der zusätzliche Arbeitsschritt der Zubereitung der Anwendungssuspension erübrigt.The invention also includes the use of the inventive composition for the protection against scale and as a lubricant in the hot processing of metals, wherein the composition is applied in powder form to the metal, preferably inflated. In contrast to the frequently used as granules means for the hot processing of metals, the composition of the invention is characterized by more stable storage properties, faster melting in contact with the hot workpiece due to the larger surface, better inflatability and more uniform distribution on the surface of the workpiece as well as safer and more economical Dosage off. Compared to the also known use of such agents in the form of suspensions, for example in water, the dry, powdered use of the composition of the invention has the advantage that no unwanted cooling of the workpiece is carried by the liquid and also the additional step of preparing the application suspension is unnecessary ,
Zur Prüfung der Verklumpungsneigung unter Produktionsbedingungen wurden Lagerversuche verschiedener Mischungen unter Produktionsbedingungen durchgeführt. Dafür wurden 150 g Probe im Klimaschrank (Typ 3821/15 der Firma Feutron) bei konstant 30 °C und 80% relativer Luftfeuchte für 0 h, 67 h und 96 h gelagert und anschließend ihre Agglomeratbildung (Rieselfähigkeit) in einem Siebtest sowie ihre Feuchteaufnahme anhand der Gewichtszunahme gegenüber der ursprünglichen Einwaage bestimmt.To test the tendency to agglomerate under production conditions, storage trials of various mixtures were carried out under production conditions. For this purpose, 150 g of sample were stored in a climate chamber (type 3821/15 from Feutron) at a constant 30 ° C. and 80% relative humidity for 0 h, 67 h and 96 h and then their agglomeration (free-flow) in a sieve test and their moisture absorption the weight gain compared to the original weight determined.
Erst die Gesamtbeurteilung von kombiniertem Lager- und Rieselverhalten einer jeweiligen Mischung lässt eine Aussage über ihre Qualität und Eignung unter Produktionsbedingungen zu.Only the overall assessment of combined storage and trickling behavior of a particular mixture allows a statement about its quality and suitability under production conditions.
Die Bestimmung der mittleren Partikelgröße des Gemischs bzw. der Bestandteile der erfindungsgemäßen Zusammensetzung erfolgt mittels eines Laser-Granulometers Cilas Modell 715/920 der Firma Cilas U.S. Inc. Circa 80 mg Probe werden in 2-Propanol suspendiert und die Messung eine Minute nach Herstellung der Suspension gemäß der Anleitung des Herstellers durchgeführt.The average particle size of the mixture or constituents of the composition according to the invention is determined by means of a Cilas Model 715/920 laser granulometer from Cilas. Inc. Approximately 80 mg of sample is suspended in 2-propanol and the measurement is made one minute after preparation of the suspension according to the manufacturer's instructions.
Die nachfolgende Tabelle 1 gibt erfindungsgemäße Zusammensetzungen für den Schutz vor Zunder und als Schmiermittel für die Heißverarbeitung von Metallen sowie Vergleichszusammensetzungen an. Tabelle 2 gibt Parameter der in Tabelle 1 angegebenen Zusammensetzungen an.
Die in Tabelle 2 angegebene "benötigte Einsatzmenge" ist definiert als die durchschnittlich in die zu bearbeitenden Hohlblöcke mittels geeigneter Aufbringungstechnik, vorzugsweise nach der üblichen Injektortechnologie (Einblasen), eingebrachte Menge in "g", bezogen auf die Innenoberfläche des zu beschichtenden Werkstücks (Hohlblocks) in "m2".The "required quantity used" given in Table 2 is defined as the quantity in "g", based on the inner surface of the workpiece to be coated (hollow block), which is introduced on average into the hollow blocks to be machined by means of a suitable application technique, preferably according to the usual injector technology (injection). in "m 2 ".
Die Eigenschaften Zunderlöseverhalten, Qualität der Innenrohre, Lagerstabilität und Rieselfähigkeit wurden anhand einer fünfstufigen Bewertungsskala mit den Bewertungsmöglichkeiten "sehr gut", "gut", "befriedigend", "ausreichend" und "schlecht" und die Viskosität der Schmelze wurde anhand einer dreistufigen Bewertungsskala mit den Bewertungsmöglichkeiten "hoch", "mittel" und "niedrig" eingestuft.The properties of scaling behavior, inner tube quality, storage stability and flowability were evaluated on the basis of a five-step rating scale with the evaluation possibilities "very good", "good", "satisfactory", "sufficient" and "poor", and the viscosity of the melt was determined using a three-stage evaluation scale the rating options "high", "medium" and "low".
Claims (14)
- A composition for protection from scale and as a lubricant for the hot processing of metals, consisting of a mixture of fine-powder materials, wherein the mixture contains at least the following constituents:(a) 0.5 to 10% by weight of secondary or tertiary calcium phosphate compound, hydroxyapatite or a mixture thereof,(b) 1 to 35% by weight of fatty acid, fatty acid salt or a mixture thereof,(c) 1 to 80% by weight of ground borosilicate glass which in relation to the borosilicate glass contains Na, B, Si and Al in the following proportions by weight expressed by their respective oxides:1 to 30% by weight of Na2O,2 to 70% by weight of B2O3,10 to 70% by weight of SiO2,, and0 to 10% by weight of Al2O3,(d) 40 to 85% by weight of condensed alkali metal phosphates,(e) boric acid, boric acid salt or a mixture thereof in an amount corresponding to a boron content, expressed by the oxide, of 0 to 3.2% by weight of B2O3,(f) not more than 10% by weight of graphite,wherein the mixture has a mean particle size D50 of ≤ 300 µm, measured according to the method as indicated in the description under the caption "Particle size determination".
- A composition according to claim 1 characterised in that the mixture contains not more than 5% by weight of graphite, preferably not more than 3% by weight of graphite, particularly preferably not more than 1% of graphite.
- A composition according to one of the preceding claims characterised in that the calcium phosphate compound (a) is selected from hydroxyapatite [Ca5(PO4)3OH] and tricalcium phosphate [Ca3(PO4)2], hydroxyapatite being particularly preferred.
- A composition according to one of the preceding claims characterised in that the secondary or tertiary calcium phosphate compound (a) is contained in the mixture in an amount of 1 to 5% by weight.
- A composition according to one of the preceding claims characterised in that the fatty acid or the fatty acid salt (b) is selected from saturated and unsaturated fatty acids having 6 to 26 carbon atoms or salts thereof, preferably from capric acid, caprylic acid, caprinic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachic acid, behenic acid, lignoceric acid, cerotic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, icosenic acid, erucic acid, nervonic acid, linoleic acid, linolenic acid, arachidonic acid, timnodonic acid, clupanodonic acid and salts thereof, provided that the fatty acid or the fatty acid salt is in the form of a solid at a temperature >30°C, wherein the fatty acid or the fatty acid salt is preferably stearic acid or salt thereof.
- A composition according to one of the preceding claims characterised in that the fatty acid or the fatty acid salt (b) is contained in the mixture in an amount of 1 to 15% by weight, preferably 1 to 10% by weight, particularly preferably 3 to 7% by weight.
- A composition according to one of the preceding claims characterised in that the ground borosilicate glass (c) has a grain with a mean particle size D50 of ≤ 300 µm.
- A composition according to one of the preceding claims characterised in that the borate glass frit (c) is contained in the mixture in an amount of 3 to 80% by weight, particularly preferably 5 to 15% by weight.
- A composition according to one of the preceding claims characterised in that the condensed alkali metal phosphates (d) are selected from condensed sodium or potassium phosphates or mixtures thereof, preferably from polyphosphates and/or pyrophosphates and/or metaphosphates or mixtures thereof, particularly preferably disodium pyrophosphate [Na2H2P2O7] trisodium pyrophosphate [Na3HP2O7], tetrasodium pyrophosphate [Na4P2O7], sodium tripolyphosphate [Na5P3O10], sodium trimetaphosphate [(NaPO3)3], sodium polyphosphate [(NaPO3)n], dipotassium pyrophosphate [K2H2P2O7], tripotassium pyrophosphate [K3HP2O7], tetrapotassium pyrophosphate [K4P2O7], potassium tripolyphosphate [K5P3O10], potassium trimetaphosphate [(KPO3)3], potassium polyphosphate [(KPO3)n] or mixtures thereof, wherein constituent (d) is most preferably sodium tripolyphosphate [Na5P3O10].
- A composition according to one of the preceding claims characterised in that the condensed alkali metal phosphates (d) are contained in the mixture in amount of 40 to 80% by weight, preferably 40 to 75% by weight.
- A composition according to one of the preceding claims characterised in that the constituent (e), if present, is selected from boric acid [H3BO3], borax [Na2BaO5(OH)4·8H2O or Na2B4O7·10H2O], sodium borates, such as Na2B4O7·5H2O, Na2B4O7 (water-free), sodium metaborate [NaBO2·4H2O] and boric acid anhydride [B2O3] and mixtures thereof.
- A composition according to one of the preceding claims characterised in that the mixture has a mean particle size D50 of ≤ 250 µm, preferably ≤ 200 µm.
- A composition according to one of the preceding claims characterised in that the mixture has a mean particle size D50 of ≥ 3 µm, preferably ≥ 10 µm, particularly preferably ≥ 15 µm.
- Use of the composition according to one of claims 1-13 for protection from scale and as a lubricant in the hot processing of metals, wherein the composition is applied, preferably blown, onto the material in powder form.
Applications Claiming Priority (2)
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DE102013102897.7A DE102013102897A1 (en) | 2013-03-21 | 2013-03-21 | Composition for protection against scale and as a lubricant for the hot processing of metals |
PCT/EP2014/054626 WO2014146927A1 (en) | 2013-03-21 | 2014-03-11 | Composition for protection from scale and as lubricant for hot processing metals |
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EP2976412A1 EP2976412A1 (en) | 2016-01-27 |
EP2976412B1 true EP2976412B1 (en) | 2016-08-17 |
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EP14708889.2A Active EP2976412B1 (en) | 2013-03-21 | 2014-03-11 | Composition for the protection from scale and as lubricant for metal hot working |
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US (1) | US10995297B2 (en) |
EP (1) | EP2976412B1 (en) |
JP (1) | JP5986337B2 (en) |
KR (1) | KR101652660B1 (en) |
CN (1) | CN105324470B (en) |
AR (1) | AR095489A1 (en) |
CA (1) | CA2904500C (en) |
DE (1) | DE102013102897A1 (en) |
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ES (1) | ES2590216T3 (en) |
HU (1) | HUE029378T2 (en) |
MX (1) | MX2015013371A (en) |
PL (1) | PL2976412T3 (en) |
SA (1) | SA515360884B1 (en) |
TW (1) | TW201500541A (en) |
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US11261397B2 (en) * | 2017-11-01 | 2022-03-01 | Moresco Corporation | Lubricant composition for plastic processing |
DE102020107159A1 (en) | 2020-03-16 | 2021-09-16 | Chemische Fabrik Budenheim Kg | Composition for lubricating and / or descaling in the hot working of metals |
CA3172826A1 (en) * | 2020-03-16 | 2021-09-23 | Chemische Fabrik Budenheim Kg | Composition for lubricating and/or descaling in hot processing of metals |
DE102021111658A1 (en) * | 2021-05-05 | 2022-11-10 | Chemische Fabrik Budenheim Kg | High temperature metal forming lubricant |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
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DE1290664B (en) * | 1966-02-18 | 1969-03-13 | Alchem Ltd | Method for applying a size from a suspension of heat-resistant particles and the size used therefor |
DE2430249C3 (en) * | 1974-06-24 | 1977-03-17 | Chemische Fabrik Budenheim Rudolf A. Oetker, 6501 Budenheim | HIGH TEMPERATURE LUBRICANT FOR THE HOT FORMING OF METALS |
CH629845A5 (en) * | 1977-10-26 | 1982-05-14 | Bbc Brown Boveri & Cie | High-temperature lubricant |
US4183236A (en) * | 1978-01-30 | 1980-01-15 | Trw Inc. | Method of isothermal forging |
CH660023A5 (en) | 1984-05-30 | 1987-03-13 | Lonza Ag | HIGH-TEMPERATURE LUBRICANT FOR CHIP-FREE HOT FORMING OF METALS. |
US4780226A (en) * | 1987-08-03 | 1988-10-25 | General Motors Corporation | Lubrication for hot working rare earth-transition metal alloys |
ZA963198B (en) * | 1995-05-16 | 1996-10-25 | Timcal Ltd | Lubricant composition for use on workpieces in the hot forming of metals |
EP0829528B1 (en) * | 1996-09-17 | 2003-06-18 | Chemische Fabrik Budenheim KG | Lubricating material for mandrel bars containing no graphite |
PL1725503T3 (en) * | 2004-11-01 | 2008-12-31 | The Morgan Crucible Company Plc | Modification of alkaline earth silicate fibres |
DE102004054495A1 (en) * | 2004-11-11 | 2006-05-24 | Degussa Ag | Sodium percarbonate particles with a thiosulfate containing shell layer |
DE102006030113B4 (en) * | 2006-06-28 | 2009-02-12 | Chemische Fabrik Budenheim Kg | Graphite-free high-temperature lubricant |
ES2314833T3 (en) * | 2006-07-27 | 2009-03-16 | Evonik Degussa Gmbh | PARTICLES WRAPPED BY SODIUM PERCARBONATE. |
DE102007051850A1 (en) * | 2007-10-30 | 2009-05-07 | Ashland-Südchemie-Kernfest GmbH | Molding compound with improved flowability |
-
2013
- 2013-03-21 DE DE102013102897.7A patent/DE102013102897A1/en not_active Withdrawn
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2014
- 2014-02-17 TW TW103105109A patent/TW201500541A/en unknown
- 2014-03-11 MX MX2015013371A patent/MX2015013371A/en unknown
- 2014-03-11 US US14/778,322 patent/US10995297B2/en active Active
- 2014-03-11 JP JP2016503601A patent/JP5986337B2/en active Active
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- 2014-03-11 EP EP14708889.2A patent/EP2976412B1/en active Active
- 2014-03-11 KR KR1020157030124A patent/KR101652660B1/en active IP Right Grant
- 2014-03-11 CA CA2904500A patent/CA2904500C/en active Active
- 2014-03-11 CN CN201480017118.3A patent/CN105324470B/en active Active
- 2014-03-11 WO PCT/EP2014/054626 patent/WO2014146927A1/en active Application Filing
- 2014-03-11 HU HUE14708889A patent/HUE029378T2/en unknown
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- 2014-03-11 EA EA201500964A patent/EA030719B1/en not_active IP Right Cessation
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CA2904500A1 (en) | 2014-09-25 |
EP2976412A1 (en) | 2016-01-27 |
EA030719B1 (en) | 2018-09-28 |
WO2014146927A1 (en) | 2014-09-25 |
HUE029378T2 (en) | 2017-02-28 |
US20160215232A1 (en) | 2016-07-28 |
AR095489A1 (en) | 2015-10-21 |
KR101652660B1 (en) | 2016-08-30 |
CN105324470A (en) | 2016-02-10 |
KR20150138850A (en) | 2015-12-10 |
CA2904500C (en) | 2017-03-28 |
MX2015013371A (en) | 2016-05-31 |
JP5986337B2 (en) | 2016-09-06 |
SA515360884B1 (en) | 2016-11-03 |
TW201500541A (en) | 2015-01-01 |
PL2976412T3 (en) | 2016-12-30 |
CN105324470B (en) | 2017-03-15 |
DE102013102897A1 (en) | 2014-09-25 |
EA201500964A1 (en) | 2016-05-31 |
US10995297B2 (en) | 2021-05-04 |
ES2590216T3 (en) | 2016-11-18 |
BR112015019739A2 (en) | 2017-07-18 |
JP2016519701A (en) | 2016-07-07 |
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