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EP2032679B1 - Graphite-free high-temperature lubricant - Google Patents

Graphite-free high-temperature lubricant Download PDF

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Publication number
EP2032679B1
EP2032679B1 EP07765571.0A EP07765571A EP2032679B1 EP 2032679 B1 EP2032679 B1 EP 2032679B1 EP 07765571 A EP07765571 A EP 07765571A EP 2032679 B1 EP2032679 B1 EP 2032679B1
Authority
EP
European Patent Office
Prior art keywords
acid
weight
mixture
temperature lubricant
lubricant according
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.)
Not-in-force
Application number
EP07765571.0A
Other languages
German (de)
French (fr)
Other versions
EP2032679A2 (en
Inventor
Steffen Bugner
Ralf Giskow
Bernd Schneider
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chemische Fabrik Budenhiem KG
Original Assignee
Chemische Fabrik Budenhiem KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chemische Fabrik Budenhiem KG filed Critical Chemische Fabrik Budenhiem KG
Priority to SI200731628T priority Critical patent/SI2032679T1/en
Priority to PL07765571T priority patent/PL2032679T3/en
Priority to EP14198677.8A priority patent/EP2878661A1/en
Publication of EP2032679A2 publication Critical patent/EP2032679A2/en
Application granted granted Critical
Publication of EP2032679B1 publication Critical patent/EP2032679B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • 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
    • 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
    • C10M2201/0853—Phosphorus oxides, acids or salts used as base material
    • 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
    • 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
    • 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
    • C10M2207/126—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 monocarboxylic
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/055—Particles related characteristics
    • C10N2020/06—Particles of special shape or size
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08—Resistance to extreme temperature
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10N2040/241—Manufacturing joint-less pipes
    • 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
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/08—Solids

Definitions

  • the present invention relates to a high-temperature lubricant for the hot processing of metals.
  • graphite Many lubricants for hot deformation of metals contain graphite because of its good lubricating properties.
  • 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.
  • graphite is undesirable for occupational hygiene reasons because the graphite powder is easily atomized into the ambient atmosphere and poses a health hazard to inhaled graphite powder for nearby workers.
  • the DD 292678 A5 discloses a coating for reducing the friction in the elastic or plastic deformation of metallic materials, consisting of a homogeneous solid mixture of thermal reaction products, produced by thermal action at 250 to 1600 ° C to a homogeneous mixture of (A) 0.02 to 28 parts by mass (B) 0.09 to 9.1 parts by mass alkali or ammonium borate, (C) 0.18 to 26 parts by mass alkali or ammonium phosphate, (D) 0.02 to 18 parts by mass of a polymeric organic compound and (E) O , 06 to 18 parts by mass of reaction products of the components AC, formed in aqueous solution at a pH> 6.5 and at a temperature ⁇ 80 ° C.
  • the object of the present invention was therefore to provide a high-temperature lubricant with good flow and flow behavior for scaling on heated metal surfaces, applied in powder form allows good occupancy of the metal surface and even after prolonged storage under production conditions still good flow and flow properties without has strong clumping and avoids the use of graphite.
  • the mixture according to the invention with the components (a), (b), (c) and (d) is particularly suitable as a lubricant for the hot processing of metals. It is understood that the lubricant of the invention may contain other ingredients, as far as they do not significantly adversely affect the desired advantageous properties.
  • Secondary and / or tertiary calcium phosphate compounds have surprisingly proven to be particularly suitable flow aids in a high-temperature lubricant 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 of the high-temperature lubricant according to the present invention is selected from hydroxy diaxbutate [Ca 5 (PO 4 ) 3 OH] and tricalcium phosphate [Ca 3 (PO 4 ) 2 ], with hydroxy diaxapatite being particularly preferred.
  • the mixture of the high-temperature lubricant according to the invention further contains a fatty acid or a fatty acid salt in combination with the other constituents. It has surprisingly been found that by using a fatty acid or a fatty acid salt, the agglomeration of the fine 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.
  • the fatty acid or the fatty acid salt is selected from saturated and unsaturated fatty acids having 6 to 26 carbon atoms or their salts. Particular preference is given to the fatty acid or the fatty acid salt among caproic acid, caprylic acid, capric 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, icosenoic acid, erucic acid, nervonic acid, linoleic acid, Linolenic acid, arachidonic acid, timnodonic acid, clupanodonic acid or salts thereof.
  • the fatty acid or the fatty acid salt is stearic acid or its salt, in particular magnesium stearate.
  • the fatty acid or the fatty acid salt is present at a temperature> 30 ° C as a solid.
  • the high-temperature lubricant according to the invention contains as further constituent boric acid, a boric acid salt (borate) and / or a mineral containing boric acid (borate).
  • 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
  • further 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] and boric anhydride [B 2 O 3 ].
  • boric acid a boric acid salt (borate) and / or a mineral containing a boric acid (borate) improves the uniform distribution of the lubricant on the metal surface and reduces scale formation. At high metalworking temperatures, the high temperature lubricant forms a melt.
  • the high-temperature lubricant according to the invention contains as further constituent alkali polyphosphates and / or alkali pyrophosphates and / or alkali metal metaphosphates, preferably of sodium or potassium.
  • alkali polyphosphates and / or alkali pyrophosphates and / or alkali metal metaphosphates preferably of sodium or potassium.
  • 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 O 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 ], tetra
  • the constituents of the mixture have an average particle size of ⁇ 150 ⁇ m. Preference is given to an average particle size of the constituents of the mixture of ⁇ 100 ⁇ m, particularly preferably ⁇ 50 ⁇ m. Due to the small mean particle sizes of the constituents of the mixture according to the invention, the flow and flow behavior of the high-temperature lubricant 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 constituents of the mixture of the high-temperature lubricant according to the invention have an average particle size of ⁇ 3 ⁇ m, preferably ⁇ 10 ⁇ m, particularly preferably ⁇ 15 ⁇ m. It has been found that too small average grain sizes can only be produced very costly and under relatively high costs and, on the other hand, they also increase the tendency to clumping again. An average grain size in the range of 20 to 50 microns has therefore proved to be optimal.
  • the secondary or tertiary calcium phosphate compound (a) is in an amount of 0.1 to 15% by weight, preferably 0.5 to 10% by weight, more preferably 1 to 5 Wt .-% in the mixture.
  • the fatty acid or fatty acid salt (b) is present in an amount of from 0.1 to 15% by weight, preferably from 1 to 10% by weight, more preferably from 3 to 7 Wt .-% in the mixture.
  • boric acid, boric acid salt (borate) and / or a mineral (c) containing boric acid (c) are present in an amount of from 5 to 30% by weight, preferably from 10 to 25% by weight. %, more preferably from 15 to 20 wt .-% in the mixture.
  • polyphosphate and / or pyrophosphate and / or metaphosphate in an amount of 70 to 85 wt .-%, particularly preferably from 75 to 80 wt .-% in the mixture.
  • the average particle size of the mixture or components of the mixture of the high-temperature lubricant according to the invention is determined by means of a Cilas Model 715/920 laser granulometer from Cilas US Inc. About 80 mg of sample are suspended in 2-propanol and the measurement taken for one minute after preparation of the suspension according to the instructions of the manufacturer. ⁇ b> ⁇ u> Table 1 ⁇ / u> ⁇ /b> Free-flowing and moisture absorption after different storage periods under production conditions Sample number composition Storage duration under production conditions; 30 ° C, 80% rel.

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

Description

Die vorliegende Erfindung betrifft einen Hochtemperatur-Schmierstoff für die Heißverarbeitung von Metallen.The present invention relates to a high-temperature lubricant for the hot processing of metals.

Hintergrund der ErfindungBackground of the invention

Beim Warmverformen von Metallen, insbesondere von Stahl, in einem Temperaturbereich von 700-1300°C kommt es an der erhitzten Metalloberfläche an der Umgebungsluft zur Zunderbildung. 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 auf die Innenoberfläche der Hohlblöcke aufgebracht. Beispiele für solche Schmier- oder Beizmittel enthalten Graphit, Bornitrid, Molybdänsulfid, Silikate oder Erdalkaliphosphate sowie Mischungen davon.In the hot forming of metals, especially steel, in a temperature range of 700-1300 ° C occurs on the heated metal surface in the ambient air to the formation of scale. 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 risk 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 to the inner surface of the hollow blocks. Examples of such lubricants or mordants include graphite, boron nitride, molybdenum sulfide, silicates or alkaline earth phosphates and mixtures thereof.

Viele Schmiermittel für die Heißverformung von Metallen enthalten Graphit aufgrund seiner guten Schmiereigenschaften. 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 zerstäübt wird und für in der Nähe arbeitende Personen eine Gesundheitsgefährdung durch Einatmen des Graphitpulvers darstellt.Many lubricants for hot deformation of metals contain graphite because of its good lubricating properties. 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 because the graphite powder is easily atomized into the ambient atmosphere and poses a health hazard to inhaled graphite powder for nearby workers.

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. Bekannte feinkörnige Materialien mit kleinen Korngrößen, beispielsweise unter 50 µm, neigen häufig zu Verklumpung, insbesondere bei Lagerung, weshalb sie nur schwer als Pulver auf die Metalloberfläche aufgesprüht werden können. Eine feinere Körnung hätte jedoch den Vorteil, daß eine bessere Schichtbildung erreicht werden kann, jedoch wird dieser Vorteil bei bekannten Zusammensetzungen mit feiner Körnung durch die starke Neigung zur Verklumpung wieder zunichte gemacht.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. Known fine-grained materials with small particle sizes, for example below 50 microns, often tend to clumping, especially during storage, which is why they can be difficult to spray on the metal surface as a powder. However, a finer grain size would have the advantage that a better layer formation can be achieved, but this advantage is nullified in known compositions with fine grain by the strong tendency to clumping again.

Die DD 292678 A5 offenbart einen Überzug zur Verminderung der Reibung bei der elastischen oder plastischen Verformung von metallischen Werkstoffen, bestehend aus einem homogenen Feststoffgemisch thermischer Umsetzungsprodukte, entstanden durch eine thermische Einwirkung bei 250 bis 1600°C auf eine homogene Mischung aus (A) 0,02 bis 28 Masseanteilen Fettsäuresalzen, (B) 0,09 bis 9,1 Masseanteilen Alkali- oder Ammoniumborat, (C) 0,18 bis 26 Masseanteilen Alkali- oder Ammoniumphosphat, (D) 0,02 bis 18 Masseanteilen einer polymeren organischen Verbindung und (E) 0,06 bis 18 Masseanteilen Reaktionsprodukten der Komponenten A-C, gebildet in wässriger Lösung bei einem pH-Wert > 6,5 und bei einer Temperatur < 80°C.The DD 292678 A5 discloses a coating for reducing the friction in the elastic or plastic deformation of metallic materials, consisting of a homogeneous solid mixture of thermal reaction products, produced by thermal action at 250 to 1600 ° C to a homogeneous mixture of (A) 0.02 to 28 parts by mass (B) 0.09 to 9.1 parts by mass alkali or ammonium borate, (C) 0.18 to 26 parts by mass alkali or ammonium phosphate, (D) 0.02 to 18 parts by mass of a polymeric organic compound and (E) O , 06 to 18 parts by mass of reaction products of the components AC, formed in aqueous solution at a pH> 6.5 and at a temperature <80 ° C.

Aufgabe der ErfindungObject of the invention

Die Aufgabe der vorliegenden Erfindung bestand daher darin, einen Hochtemperatur-Schmierstoff mit gutem Riesel- und Fließverhalten zur Zunderauflösung auf erhitzten Metalloberflächen bereitzustellen, der in Pulverform aufgebracht eine gute Belegung der Metalloberfläche erlaubt und auch nach längerer Lagerung unter Produktionsbedingungen noch gute Riesel- und Fließeigenschaften ohne starke Verklumpung aufweist und der die Verwendung von Graphit vermeidet.The object of the present invention was therefore to provide a high-temperature lubricant with good flow and flow behavior for scaling on heated metal surfaces, applied in powder form allows good occupancy of the metal surface and even after prolonged storage under production conditions still good flow and flow properties without has strong clumping and avoids the use of graphite.

Beschreibung der ErfindungDescription of the invention

Gelöst wird diese Aufgabe erfindungsgemäß durch einen Hochtemperatur-Schmierstoff für die Heißverarbeitung von Metallen, bestehend aus einem Gemisch von feinpulverigen Materialien, wobei das Gemisch wenigstens die folgenden Bestandteile enthält:

  1. (a) eine sekundäre und/oder tertiäre Calciumphosphatverbindung, ausgewählt unter Hydroxylapatit [Ca5(PO4)3OH] und Tricalciumphosphat [Ca3(PO4)2].
  2. (b) eine Fettsäure oder ein Fettsäuresalz,
  3. (c) Borsäure, ein Borsäuresalz (Borat) und/oder ein Borsäuresalz (Borat) enthaltendes Mineral und
  4. (d) Alkalipolyphosphate und/oder Alkalipyrophosphate und/oder Alkalimetaphosphate in einer Menge von 60 bis 95 Gew.-% in dem Gemisch,
und wobei die Bestandteile des Gemischs eine mittlere Korngröße von ≤ 150 µm aufweisen und der Schmierstoff keinen Zusatz von Graphit enthält.This object is achieved according to the invention by a high-temperature lubricant for the hot processing of metals, consisting of a mixture of pulverulent materials, wherein the mixture contains at least the following constituents:
  1. (a) a secondary and / or tertiary calcium phosphate compound selected from hydroxyapatite [Ca 5 (PO 4 ) 3 OH] and tricalcium phosphate [Ca 3 (PO 4 ) 2 ].
  2. (b) a fatty acid or a fatty acid salt,
  3. (c) boric acid, a borate salt (borate) and / or a boric acid borate containing mineral, and
  4. (d) alkali polyphosphates and / or alkali pyrophosphates and / or alkali metal metaphosphates in an amount of from 60 to 95% by weight in the mixture,
and wherein the components of the mixture have a mean particle size of ≤ 150 microns and the lubricant contains no addition of graphite.

Es hat sich überraschenderweise gezeigt, daß sich das erfindungsgemäße Gemisch mit den Bestandteile (a), (b), (c) und (d) als Schmierstoff für die Heißverarbeitung von Metallen besonders gut eignet. Es versteht sich, daß der erfindungsgemäße Schmierstoff weitere Bestandteile enthalten kann, soweit diese die gewünschten vorteilhaften Eigenschaften nicht wesentlich nachteilig beeinflussen.It has surprisingly been found that the mixture according to the invention with the components (a), (b), (c) and (d) is particularly suitable as a lubricant for the hot processing of metals. It is understood that the lubricant of the invention may contain other ingredients, as far as they do not significantly adversely affect the desired advantageous properties.

Sekundäre und/oder tertiäre Calciumphosphatverbindungen haben sich überraschenderweise als besonders geeignete Rieselhilfsmittel in einem Hochtemperatur-Schmierstoff der erfindungsgemäßen Art für die Heißverarbeitung von Metallen erwiesen. Monocalciumphosphat ist ungeeignet, da es bei Luftfeuchte zu Verklumpung führt. Die Calciumphosphatverbindung des erfindungsgemäßen Hochtemperatur-Schmierstoffes ist unter Hxdroxylapatit [Ca5(PO4)3OH] und Tricalciumphosphat [Ca3(PO4)2] ausgewählt, wobei Hxdroxylapatit besonders bevorzugt ist.Secondary and / or tertiary calcium phosphate compounds have surprisingly proven to be particularly suitable flow aids in a high-temperature lubricant 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 of the high-temperature lubricant according to the present invention is selected from hydroxy diaxbutate [Ca 5 (PO 4 ) 3 OH] and tricalcium phosphate [Ca 3 (PO 4 ) 2 ], with hydroxy diaxapatite being particularly preferred.

Das Gemisch des erfindungsgemäßen Hochtemperatur-Schmierstoffs enthält weiterhin eine Fettsäure oder ein Fettsäuresalz 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.The mixture of the high-temperature lubricant according to the invention further contains a fatty acid or a fatty acid salt in combination with the other constituents. It has surprisingly been found that by using a fatty acid or a fatty acid salt, the agglomeration of the fine 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 einer bevorzugten Ausführungsform des erfindungsgemäßen Hochtemperatur-Schmierstoffs ist die Fettsäure bzw. das Fettsäuresalz unter gesättigten und ungesättigten Fettsäuren mit 6 bis 26 Kohlenstoffatomen bzw. deren Salzen ausgewählt. Besonders bevorzugt ist die Fettsäure bzw. das Fettsäuresalz 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. Ganz besonders bevorzugt ist die Fettsäure bzw. das Fettsäuresalz Stearinsäure bzw. deren Salz, insbesondere Magnesiumstearat. Voraussetzung für die Auswahl ist, daß die Fettsäure bzw. das Fettsäuresalz bei einer Temperatur > 30°C als Feststoff vorliegt.In a preferred embodiment of the high-temperature lubricant according to the invention, the fatty acid or the fatty acid salt is selected from saturated and unsaturated fatty acids having 6 to 26 carbon atoms or their salts. Particular preference is given to the fatty acid or the fatty acid salt among caproic acid, caprylic acid, capric 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, icosenoic acid, erucic acid, nervonic acid, linoleic acid, Linolenic acid, arachidonic acid, timnodonic acid, clupanodonic acid or salts thereof. Most preferably, the fatty acid or the fatty acid salt is stearic acid or its salt, in particular magnesium stearate. Prerequisite for the selection is that the fatty acid or the fatty acid salt is present at a temperature> 30 ° C as a solid.

Der erfindungsgemäße Hochtemperatur-Schmierstoff enthält als weiteren Bestandteil Borsäure, ein Borsäuresalz (Borat) und/oder ein Borsäuresalz (Borat) enthaltendes Mineral. Besonders bevorzugt sind Borsäure [H3BO3], Borax [Na2B4O5(OH)48H2O bzw. Na2B4O7·10H2O], weitere Natriumborate, wie Na2B4O75H2O, Na2B4O7 (wasserfrei), Natriummetaborat [NaBO24H2O] und Borsäureanhydrid [B2O3]. Die erfindungsgemäße Verwendung von Borsäure, einem Borsäuresalz (Borat) und/oder einem ein Borsäuresalz (Borat) enthaltenden Mineral verbessert die gleichmäßige Verteilung des Schmiermittels auf der Metalloberfläche und reduziert die Zunderbildung. Bei den hohen Temperaturen der Metallverarbeitung bildet der Hochtemperatur-Schmierstoff eine Schmelze.The high-temperature lubricant according to the invention contains as further constituent boric acid, a boric acid salt (borate) and / or a mineral containing boric acid (borate). Particular preference is given to 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], further 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] and boric anhydride [B 2 O 3 ]. The use according to the invention of boric acid, a boric acid salt (borate) and / or a mineral containing a boric acid (borate) improves the uniform distribution of the lubricant on the metal surface and reduces scale formation. At high metalworking temperatures, the high temperature lubricant forms a melt.

Der erfindungsgemäße Hochtemperatur-Schmierstoff enthält als weiteren Bestandteil Alkalipolyphosphate und/oder Alkalipyrophosphate und/oder Alkalimetaphosphate, vorzugsweise von Natrium oder Kalium. Ganz besonders bevorzugt sind Dinatriumpyrophosphat [Na2H2P2O7], Trinatriumpyrophosphat [Na3HP2O7], Tetranatriumpyrophosphat [Na4P2O7], Natriumtripolyphosphat [Na5P3O10], Natriumtrimetaphosphat [(NaPO3)3], Natriumpolyphosphat [(NaPO3)n], Dikaliumpyrophosphat [K2H2P2O7], Trikaliumpyrophosphat [K3HP2O7], Tetrakaliumpyrophosphat [K4P2O7], Kaliumtripolyphosphat [K5P3O10], Kaliumtrimetaphosphat [(KPO3)3] und/oder Kaliumpolyphosphat [(KPO3)n], am bevorzugtesten Natriumtripolyphosphat [Na5P3O10]. Es hat sich gezeigt, daß die Verwendung eines Polyphosphats und/oder eines Pyrophosphats und/oder eines Metaphosphats in dem Gemisch des erfindungsgemäßen Hochtemperatur-Schmierstoffs mit Vorteil unter anderem zur Zunderauflösung beiträgt.The high-temperature lubricant according to the invention contains as further constituent alkali polyphosphates and / or alkali pyrophosphates and / or alkali metal metaphosphates, preferably of sodium or potassium. Very particularly preferred are 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 O 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 ] and / or potassium polyphosphate [(KPO 3 ) n ], most preferably sodium tripolyphosphate [Na 5 P 3 O 10 ]. It has been found that the use of a polyphosphate and / or a pyrophosphate and / or a metaphosphate in the mixture of the high-temperature lubricant according to the invention advantageously contributes, inter alia, to the scale dissolution.

In dem erfindungsgemäßen Hochtemperatur-Schmierstoff weisen die Bestandteile des Gemischs eine mittlere Korngröße von ≤ 150 µm auf. Bevorzugt ist eine mittlere Korngröße der Bestandteile des Gemischs von ≤ 100 µm, besonders bevorzugt von ≤ 50 µm. Durch die geringen mittleren Korngrößen der Bestandteile des erfindungsgemäßen Gemischs wird das Riesel- und Fließverhalten des erfindungsgemäßen Hochtemperatur-Schmierstoffs 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 the high-temperature lubricant according to the invention, the constituents of the mixture have an average particle size of ≦ 150 μm. Preference is given to an average particle size of the constituents of the mixture of ≦ 100 μm, particularly preferably ≦ 50 μm. Due to the small mean particle sizes of the constituents of the mixture according to the invention, the flow and flow behavior of the high-temperature lubricant 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.

Es ist weiterhin bevorzugt, wenn die Bestandteile des Gemischs des erfindungsgemäßen Hochtemperatur-Schmierstoffs eine mittlere Korngröße von ≥ 3 µm, vorzugsweise ≥10 µm, besonders bevorzugt ≥ 15 µm aufweisen. Es hat sich erwiesen, daß zu geringe mittlere Korngrößen 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 Korngröße im Bereich von 20 bis 50 µm hat sich daher als optimal erwiesen.It is furthermore preferred if the constituents of the mixture of the high-temperature lubricant according to the invention have an average particle size of ≥ 3 μm, preferably ≥ 10 μm, particularly preferably ≥ 15 μm. It has been found that too small average grain sizes can only be produced very costly and under relatively high costs and, on the other hand, they also increase the tendency to clumping again. An average grain size in the range of 20 to 50 microns has therefore proved to be optimal.

In einer bevorzugten Ausführungsform des erfindungsgemäßen Hochtemperatur-Schmierstoffs ist die sekundäre oder tertiäre Calciumphosphatverbindung (a) in einer Menge von 0,1 bis 15 Gew.-%, vorzugsweise von 0,5 bis 10 Gew.-%, besonders bevorzugt von 1 bis 5 Gew.-% in dem Gemisch enthalten.In a preferred embodiment of the high temperature lubricant of the present invention, the secondary or tertiary calcium phosphate compound (a) is in an amount of 0.1 to 15% by weight, preferably 0.5 to 10% by weight, more preferably 1 to 5 Wt .-% in the mixture.

In einer weiteren bevorzugten Ausführungsform des erfindungsgemäßen Hochtemperatur-Schmierstoffs ist die Fettsäure bzw. das Fettsäuresalz (b) in einer Menge von 0,1 bis 15 Gew.-%, vorzugsweise von 1 bis 10 Gew.-%, besonders bevorzugt von 3 bis 7 Gew.-% in dem Gemisch enthalten.In a further preferred embodiment of the high-temperature lubricant according to the invention, the fatty acid or fatty acid salt (b) is present in an amount of from 0.1 to 15% by weight, preferably from 1 to 10% by weight, more preferably from 3 to 7 Wt .-% in the mixture.

In einer weiteren bevorzugten Ausführungsform des erfindungsgemäßen Hochtemperatur-Schmierstoffs ist Borsäure, Borsäuresalz (Borat) und/oder ein Borsäuresalz (Borat) enthaltendes Mineral (c) in einer Menge von 5 bis 30 Gew.-%, vorzugsweise von 10 bis 25 Gew.-%, besonders bevorzugt von 15 bis 20 Gew.-% in dem Gemisch enthalten.In a further preferred embodiment of the high-temperature lubricant according to the invention, boric acid, boric acid salt (borate) and / or a mineral (c) containing boric acid (c) are present in an amount of from 5 to 30% by weight, preferably from 10 to 25% by weight. %, more preferably from 15 to 20 wt .-% in the mixture.

In einer weiteren bevorzugten Ausführungsform des erfindungsgemäßen Hochtemperatur-Schmierstoffs ist Polyphosphat und/oder Pyrophosphat und/oder Metaphosphat (d) in einer Menge von 70 bis 85 Gew.-%, besonders bevorzugt von 75 bis 80 Gew.-% in dem Gemisch enthalten.In a further preferred embodiment of the high-temperature lubricant according to the invention polyphosphate and / or pyrophosphate and / or metaphosphate (d) in an amount of 70 to 85 wt .-%, particularly preferably from 75 to 80 wt .-% in the mixture.

Lagerverhalten, Agglomeratbildung und FeuchteaufnahmeStorage behavior, agglomeration and moisture absorption

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. Die Ergebnisse der Untersuchung verschiedener Mischungen sind in Tabelle 1 gezeigt.Only the overall assessment of combined storage and trickling behavior of a particular mixture can be a statement about their quality and suitability under production conditions. The results of the examination of various mixtures are shown in Table 1.

KorngrößenbestimmungParticle size determination

Die Bestimmung der mittleren Korngröße des Gemischs bzw. der Bestandteile des Gemischs des erfindungsgemäßen Hochtemperatur-Schmierstoffs 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. Tabelle 1 Rieselfähigkeit und Feuchteaufnahme nach unterschiedlicher Lagerdauer unter Produktionsbedingungen Proben-Nummer Zusammensetzung Lagerdauer unter Produktionsbedingungen; 30°C, 80% rel. Luftfeuchte Siebrückstand bei Maschen- bzw. Lochweite von 250 µm 1) Feuchteaufnahme (Gew.-%) (%) von Einwaage (%) von Einwaage 1 82 % Natriumtripolyphosphat 0 h 5 0 18 % Borsäure (techn. Pulver) 67 h 89 17 (Stand der Technik) 96 h 87 20 2 74 % Natriumtripolyphosphat 0 h 2 0 16 % Borsäure (techn. Pulver) 67 h 67 11 5 % Tricalciumphosphat 5 % Magnesiumstearat 96 h 57 11 3 72 % Natriumtripolyphosphat 0 h 3 0 16 % Borsäure (techn. Pulver) 67 h 73 12 10 % Tricalciumphosphat 2 % Magnesiumstearat 96 h 71 10 4 72 % Natriumtripolyphosphat 0 h 4 0 16 % Borsäure (techn. Pulver) 67 h 59 12 2 % Tricalciumphosphat 10 % Magnesiumstearat 96 h 53 8 5 74 % Natriumtripolyphosphat 0 h 16 0 16 % Borax (techn. Pulver) 67 h 14 8 5 % Tricalciumphosphat 5 % Magnesiumstearat 96 h 13 13 1) Siebbedingungen: Probenmenge 2 g + Feuchtaufnahmemenge; Vibrationsamplitude 1 Skalenteil; Vibrationsdauer 70 sek. The average particle size of the mixture or components of the mixture of the high-temperature lubricant according to the invention is determined by means of a Cilas Model 715/920 laser granulometer from Cilas US Inc. About 80 mg of sample are suspended in 2-propanol and the measurement taken for one minute after preparation of the suspension according to the instructions of the manufacturer. <b><u> Table 1 </ u></b> Free-flowing and moisture absorption after different storage periods under production conditions Sample number composition Storage duration under production conditions; 30 ° C, 80% rel. humidity Sieve residue at mesh or hole width of 250 μm 1) moisture absorption (Wt .-%) (%) of weight (%) of weight 1 82% sodium tripolyphosphate 0 h 5 0 18% boric acid (technical powder) 67 h 89 17 (State of the art) 96 h 87 20 2 74% sodium tripolyphosphate 0 h 2 0 16% boric acid (technical powder) 67 h 67 11 5% tricalcium phosphate 5% magnesium stearate 96 h 57 11 3 72% sodium tripolyphosphate 0 h 3 0 16% boric acid (technical powder) 67 h 73 12 10% tricalcium phosphate 2% magnesium stearate 96 h 71 10 4 72% sodium tripolyphosphate 0 h 4 0 16% boric acid (technical powder) 67 h 59 12 2% tricalcium phosphate 10% magnesium stearate 96 h 53 8th 5 74% sodium tripolyphosphate 0 h 16 0 16% borax (technical powder) 67 h 14 8th 5% tricalcium phosphate 5% magnesium stearate 96 h 13 13 1) Screening conditions: sample quantity 2 g + wet pickup amount; Vibration amplitude 1 scale part; Vibration duration 70 sec.

Claims (11)

  1. A high-temperature lubricant for the hot processing of metals consisting of a mixture of fine-powder materials, wherein the mixture includes at least the following constituents:
    (a) a secondary and/or tertiary calcium phosphate compound selected from hydroxyapatite [Ca5(PO4)3OH] and tricalcium phosphate [Ca3(PO4)2],
    (b) a fatty acid or a fatty acid salt,
    (c) boric acid, a boric acid salt (borate) and/or a mineral containing boric acid salt (borate), and
    (d) alkali polyphosphates and/or alkali pyrophosphates and/or alkali metaphosphates in an amount of 60 to 95 % by weight in the mixture,
    and wherein the constituents of the mixture have a mean grain size of ≤ 150 µm and the lubricant does not contain any addition of graphite.
  2. A high-temperature lubricant according to one of the preceding claims characterized in that constituent (c) is selected from boric acid [HaBO3], borax [Na2B4O5(OH)48H2O or Na2B4O710H2O], sodium borates such as Na2B4O75H2O, Na2B4O7 (water-free), sodium metaborate [NaBO24H2O] and boric acid anhydride [B2O3] and mixtures thereof.
  3. A high-temperature lubricant according to one of the preceding claims characterized in that constituent (d) is selected from polyphosphates and/or pyrophosphates and/or metaphosphates of sodium or potassium, preferably from 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].
  4. A high-temperature lubricant according to one of the preceding claims characterized in that the fatty acid or the fatty acid salt is selected from saturated and unsaturated fatty acids with 6 to 26 carbon atoms and salts thereof, preferably from capronic acid, caprylic acid, capric 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, icosic 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 present as a solid at a temperature > 30° C.
  5. A high-temperature lubricant according to one of the preceding claims characterized in that the fatty acid or the fatty acid salt is stearic acid or salt thereof.
  6. A high-temperature lubricant according to one of the preceding claims characterized in that the secondary or tertiary calcium phosphate compound (a) is contained in the mixture in an amount of 0.1 to 15 % by weight, preferably 0.5 to 10 % by weight, particularly preferably 1 to 5 % by weight.
  7. A high-temperature lubricant according to one of the preceding claims characterized in that the fatty acid or the fatty acid salt (b) is contained in the mixture in an amount of 0.1 to 15 % by weight, preferably 1 to 10 % by weight, particularly preferably 3 to 7 % by weight.
  8. A high-temperature lubricant according to one of the preceding claims characterized in that boric acid, boric acid salt (borate) and/or a mineral (c) containing boric acid salt (borate) is contained in the mixture in an amount of 5 to 30 % by weight, preferably 10 to 25 % by weight, particularly preferably 15 to 20 % by weight.
  9. A high-temperature lubricant according to one of the preceding claims characterized in that polyphosphate and/or pyrophosphate and/or metaphosphate (d) is contained in the mixture in an amount of 70 to 85 % by weight, particularly preferably 75 to 80 % by weight.
  10. A high-temperature lubricant according to one of the preceding claims characterized in that the constituents of the mixture have a mean grain size of ≤ 100 µm, preferably ≤ 50 µm.
  11. A high-temperature lubricant according to one of the preceding claims characterized in that the constituents of the mixture have a mean grain size of ≥ 3 µm, preferably ≥ 10 µm, particularly preferably ≥ 15 µm.
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CN101479369A (en) 2009-07-08
US8940672B2 (en) 2015-01-27
WO2008000700A3 (en) 2008-02-28
US20100298181A1 (en) 2010-11-25
SI2032679T1 (en) 2015-04-30
RU2009102453A (en) 2010-08-10
WO2008000700A2 (en) 2008-01-03
ES2532847T3 (en) 2015-04-01
EP2878661A1 (en) 2015-06-03
DE102006030113B4 (en) 2009-02-12
DE102006030113A1 (en) 2008-01-03
EP2032679A2 (en) 2009-03-11
RU2458111C2 (en) 2012-08-10
PL2032679T3 (en) 2015-06-30
AR061694A1 (en) 2008-09-17

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