EP0743352A1 - Schmiermittelzusammensetzung für die Anwendung auf Werkstücken bei der Heissumformung von Metallen - Google Patents
Schmiermittelzusammensetzung für die Anwendung auf Werkstücken bei der Heissumformung von Metallen Download PDFInfo
- Publication number
- EP0743352A1 EP0743352A1 EP96107611A EP96107611A EP0743352A1 EP 0743352 A1 EP0743352 A1 EP 0743352A1 EP 96107611 A EP96107611 A EP 96107611A EP 96107611 A EP96107611 A EP 96107611A EP 0743352 A1 EP0743352 A1 EP 0743352A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- lubricant composition
- water
- composition according
- sodium
- 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.)
- Granted
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- 239000000314 lubricant Substances 0.000 title claims description 40
- 239000000203 mixture Substances 0.000 title claims description 40
- 229910052751 metal Inorganic materials 0.000 title claims description 6
- 239000002184 metal Substances 0.000 title claims description 6
- 239000011521 glass Substances 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 19
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 16
- 229910021538 borax Inorganic materials 0.000 claims abstract description 15
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 15
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims abstract description 13
- 229910021383 artificial graphite Inorganic materials 0.000 claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 12
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 11
- 239000002562 thickening agent Substances 0.000 claims abstract description 11
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 9
- 229910021382 natural graphite Inorganic materials 0.000 claims abstract description 8
- 239000006185 dispersion Substances 0.000 claims description 15
- 239000011734 sodium Substances 0.000 claims description 15
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 14
- 229940045919 sodium polymetaphosphate Drugs 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 10
- 239000011591 potassium Substances 0.000 claims description 8
- 238000005461 lubrication Methods 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- 241001460678 Napo <wasp> Species 0.000 claims description 4
- 150000004676 glycans Chemical class 0.000 claims description 4
- 229920001282 polysaccharide Polymers 0.000 claims description 4
- 239000005017 polysaccharide Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 235000019983 sodium metaphosphate Nutrition 0.000 claims description 3
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 2
- 150000001447 alkali salts Chemical class 0.000 claims 1
- 229920000058 polyacrylate Polymers 0.000 claims 1
- 229940045916 polymetaphosphate Drugs 0.000 abstract 2
- 239000010687 lubricating oil Substances 0.000 abstract 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 12
- 238000009472 formulation Methods 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000004115 Sodium Silicate Substances 0.000 description 9
- 229910002804 graphite Inorganic materials 0.000 description 9
- 239000010439 graphite Substances 0.000 description 9
- 229910052911 sodium silicate Inorganic materials 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 235000019353 potassium silicate Nutrition 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 235000019830 sodium polyphosphate Nutrition 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000003115 biocidal effect Effects 0.000 description 5
- 239000003139 biocide Substances 0.000 description 5
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 5
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 5
- BANIDACEBXZGNK-UHFFFAOYSA-N 2-(diethylamino)ethyl 1-phenylcyclopentane-1-carboxylate;ethane-1,2-disulfonic acid Chemical compound OS(=O)(=O)CCS(O)(=O)=O.C=1C=CC=CC=1C1(C(=O)OCCN(CC)CC)CCCC1.C=1C=CC=CC=1C1(C(=O)OCCN(CC)CC)CCCC1 BANIDACEBXZGNK-UHFFFAOYSA-N 0.000 description 4
- 239000004111 Potassium silicate Substances 0.000 description 4
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 4
- 229910052912 lithium silicate Inorganic materials 0.000 description 4
- 229910052913 potassium silicate Inorganic materials 0.000 description 4
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 239000000230 xanthan gum Substances 0.000 description 3
- 229920001285 xanthan gum Polymers 0.000 description 3
- 229940082509 xanthan gum Drugs 0.000 description 3
- 235000010493 xanthan gum Nutrition 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 2
- -1 alkali metal salts Chemical class 0.000 description 2
- 229920013820 alkyl cellulose Polymers 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- AQMNWCRSESPIJM-UHFFFAOYSA-M sodium metaphosphate Chemical compound [Na+].[O-]P(=O)=O AQMNWCRSESPIJM-UHFFFAOYSA-M 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- CDMADVZSLOHIFP-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 CDMADVZSLOHIFP-UHFFFAOYSA-N 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229940005740 hexametaphosphate Drugs 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Classifications
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- 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
- C10M139/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00
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- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
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- C10M103/00—Lubricating compositions characterised by the base-material being an inorganic material
- C10M103/02—Carbon; Graphite
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- C10M125/24—Compounds containing phosphorus, arsenic or antimony
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- C10M125/26—Compounds containing silicon or boron, e.g. silica, sand
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- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
- C10M145/12—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
- C10M145/14—Acrylate; Methacrylate
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- C10M2201/0433—Sulfur; Selenenium; Tellurium used as base material
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- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
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- C10M2209/12—Polysaccharides, e.g. cellulose, biopolymers
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
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- C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
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- C10N2040/242—Hot working
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- C10N2040/244—Metal working of specific metals
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
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- C10N2040/245—Soft metals, e.g. aluminum
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
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- C10N2040/246—Iron or steel
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- C10N2040/20—Metal working
- C10N2040/244—Metal working of specific metals
- C10N2040/247—Stainless steel
Definitions
- the invention relates to a new lubricant composition for use on workpieces in the hot forming of metals, in particular for use in the hot rolling of blocks and profiles or in the production of hollow blocks in so-called shaping bench systems. Due to the fact that the metals to be processed have a surface temperature of approx. 800 ° C to 1300 ° C, the focus in practice has so far been on the lubrication of the tools, which are more accessible to classic lubrication at temperatures of maximum 400 ° C are. Although it is disclosed in the prior art, for example in CH-PS 660 023, that workpieces with temperatures above 600 ° C.
- the lubrication of the tools also has various difficulties.
- the application of the lubricant is often difficult because of the geometry of the tool alone, or low tool temperatures around 100 ° C do not allow proper formation of a lubricant film.
- large losses of lubricant are also the rule, which results in contamination of the waste water and a corresponding after-treatment of the waste water. Relatively large amounts of lubricant are therefore required for good lubrication.
- the glass frit is mainly used when the application temperatures are in the lower range from approx. 800 ° C. Then, due to the lower softening range of approx. 500 ° C to 700 ° C compared to glass powder, the film-forming properties of the glass frit come into full effect.
- the chemical frit of the glass frit is expediently an alkali-alkaline earth-alumo-boron silicate and is usually used in an average grain size d 50 of ⁇ 100 ⁇ m.
- glass powder and glass frit can be used in any mixing ratio within the specified limits.
- graphite Another important component is graphite. Both synthetic graphite and natural graphite can be used.
- the average grain size d 50 of the graphite used is expediently less than 100 ⁇ m.
- the water-soluble alkali silicates play an essential role as binders.
- a water-soluble sodium metapolyphosphate acts as a lubricant component that suppresses foaming.
- This is expediently understood to mean a compound having the general formula (NaPO 3 ) n in which n is less than 450. These compounds are also known under the name "hexametaphosphate” or "Graham's salt”.
- a water-insoluble sodium metapolyphosphate as a binder.
- Particularly suitable for this purpose are the compounds of the general formula (NaPO 3 ) n known under the name "Maddrell's salt", in which n is 40 to 70.
- a thickening agent expediently a polysaccharide or a polysaccharide derivative
- a thickening agent expediently a polysaccharide or a polysaccharide derivative
- Biopolysaccharides such as xanthan gum, rhamsan gum or an alkyl cellulose such as hydroxymethyl cellulose are expediently used.
- alkali metal salts of polyacrylic acid in particular sodium polyacrylates, can be added as thickeners.
- a commercially available biocide is expediently added to the lubricant composition.
- borax sodium tetraborate decahydrate
- the lubricant according to the invention is expediently used in the form of an aqueous dispersion with a solids content of preferably 20% to 50%. It is quite possible to vary the limits up and down.
- the dispersion can be produced in commercially available dispersing devices which enable high shear forces (cf., for example, EP-PS 218 989).
- the ready-to-use dispersion expediently has a viscosity in the range from 1000 MPas to 7000 MPas (Rheomat 15, 20 ° C., cell B, speed 5), but can be varied further by adding thickeners.
- the lubricant dispersion can be applied using known systems for spraying disperse systems (cf. e.g. EP-A 453 801).
- the lubricant composition disclosed above is used for use on workpieces which have surface temperatures of 800 ° C. to 1300 ° C., in the hot forming of metals, in particular in the hot rolling of blocks and profiles, or in the production of hollow blocks in so-called butt bench systems.
- the dispersion is applied to the workpiece immediately before the forming. Descaling the workpiece beforehand is an advantage but not essential. After the immediate evaporation of the water, a uniform, water-insoluble lubricating film forms on the workpiece surface within a few seconds, which is not affected by the subsequent forming process.
- Formulation 1 (suitable for workpieces with surface temperatures of 850 ° C - 1200 ° C).
- Formulation 2 (suitable for workpieces with surface temperatures of 1000 ° C - 1250 ° C)
- Formulation 3 (suitable for workpieces with surface temperatures of 1000 ° C - 1250 ° C)
- Comparative formulation 1 (according to CH-PS 660 023, example 1)
- Comparative formulation 2 (according to CH-PS 670 106, example 2)
- the formulations are placed on the 800 ° C to 1050 ° C hot surface of a steel block with the dimensions 29 cm x 6 cm x 3 cm, which is moved at 1.5 m / s, using a nozzle at a distance of 43 cm (pressure 50 bar) 1 to 4, and the comparison formulation 1 sprayed.
- the comparison formulation 2 is sprayed dry according to CH-PS 670 106.
- the lubricant film formed is evaluated according to the following classifications.
- Formulation Test result (class) 1 3 (from 850 ° C) 2nd 3 (from 1000 ° C) 3rd 3 (from 1000 ° C) 4th 3 (from 850 ° C) Comparison 1 1 Comparison 2 2nd
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Lubricants (AREA)
- Extrusion Of Metal (AREA)
- Mounting, Exchange, And Manufacturing Of Dies (AREA)
Abstract
Description
- Die Erfindung betrifft eine neue Schmiermittelzusammensetzung für die Anwendung auf Werkstücken bei der Heissumformung von Metallen, insbesondere für die Anwendung beim Warmwalzen von Blöcken und Profilen oder bei der Herstellung von Hohlblöcken in sogenannten Stossbankanlagen.
Aufgrund der Tatsache, dass die zu verarbeitenden Metalle eine Oberflächentemperatur von ca. 800 °C bis 1300 °C aufweisen, hat man sich in der Praxis bisher auf die Schmierung der Werkzeuge konzentriert, die mit Temperaturen von maximal 400 °C der klassischen Schmierung besser zugänglich sind.
Obwohl im Stand der Technik z.B. in der CH-PS 660 023 offenbart wird, dass mit der dort genannten Schmiermitteldispersion auch Werkstücke mit Temperaturen über 600 °C behandelt werden können, zeigt der Praxisvergleich keine Ausbildung eines wirksamen haftenden Schmiermittelfilms bei Temperaturen im Bereich von 800 °C bis 1300 °C. Die fehlende Haftung wird im wesentlichen verursacht durch die sofortige Pyrolyse der organischen Bestandteile, die eine Haftung des Films verunmöglicht. Die Pyrolyse der organischen Bestandteile mit der damit verbundenen Rauchentwicklung ist zudem für das Arbeitsumfeld eine sehr unangenehme Begleiterscheinung. Eine Ausbildung eines Schmiermitttelfilms war im Praxistest auch bei den in Pulverform applizierten Schmiermittel/Beizmittel-Zusammensetzungen der CH-PS 670 106 nicht festzustellen. Alleine die gleichmässige Applikation eines Pulvergemisches bildet in diesem Fall ein beträchtliches Erschwernis. - Aber auch die Schmierung der Werkzeuge ist je nach Werkzeugtyp mit verschiedenen Schwierigkeiten behaftet. So ist die Applikation des Schmiermittels alleine wegen der Geometrie des Werkzeuges vielfach erschwert oder tiefe Werkzeugtemperaturen um 100 °C erlauben keine richtige Ausbildung eines Schmiermittelfilms. Dadurch, dass die Werkzeuge dauernd mit grossen Mengen Kühlwasser behandelt werden, sind zudem grosse Verluste an Schmiermittel die Regel, was eine Kontamination des Abwassers und eine entsprechende Nachbehandlung des Abwassers mit sich bringt. Für eine gute Schmierung sind daher relativ grosse Mengen an Schmiermittel erforderlich.
- Es bestand folglich die Aufgabe, eine Schmiermittelzusammensetzung zu entwickeln, die die genannten Nachteile nicht aufweist und folglich geeignet ist Werkstücke mit Oberflächentemperaturen von 800 °C bis 1300 °C mit einem gleichmässigen, gut haftenden und wasserunlöslichen Schmiermittelfilm zu versehen.
- Die Aufgabe konnte gelöst werden mit den neuen Schmiermittelzusammensetzungen gemäß Patentanspruch 1, welche besteht aus:
- a1) 0-80 Gew.-% eines Glaspulvers
- a2) 0-50 Gew.-% einer Glasfritte
wobei der Anteil von zumindest einem der Bestandteile a1) oder a2) in der Schmiermittelzusammensetzung nicht 0 Gew.-% ist. - b) 10-25 Gew.-% natürlicher oder synthetischer Graphit
- c) 5-20 Gew.-% eines oder mehrerer Alkalisilikate der allgemeinen Formel Me2O n SiO2, worin Me Lithium, Kalium oder Natrium und n einen Zahlenwert zwischen 1 und 4 bedeutet.
- d) 1-6 Gew.-% eines wasserlöslichen Natriumpolymetaphosphates
- e) 0-3 Gew.-% eines wasserunlöslichen Natriumpolymetaphosphates
- f) 0,5-4 Gew.-% eines Verdickungsmittels
- g) 0-1 Gew.-% Borax
- Für die Anwendung bei Werkstücken mit Oberflächentemperaturen ab 800°C wird bevorzugt eine Schmiermittelzusammensetzung verwendet, welche besteht aus:
- a1) 0-20 Gew.-% eines Glaspulvers
- a2) 30-50 Gew.-% einer Glasfritte
- b) 20-25 Gew.-% natürlicher oder synthetischer Graphit
- c) 7-20 Gew.-% eines oder mehrerer Alkalisilikate der allgemeinen Formel Me2O n SiO2, worin Me Lithium, Kalium oder Natrium und n einen Zahlenwert zwischen 1 und 4 bedeutet.
- d) 2-6 Gew.-% eines wasserlöslichen Natriumpolymetaphosphates
- e) 0-1 Gew.-% eines wasserunlöslichen Natriumpolymetaphosphates
- f) 3-4 Gew.-% eines Verdickungsmittels
- g) 0,2-0,7 Gew.-% Borax
- Für die Anwendung bei Werkstücken mit Oberflächentemperaturen ab 1000°C wird bevorzugt eine Schmiermittelzusammensetzung verwendet, welche besteht aus:
- a1) 45-70 Gew.-% eines Glaspulvers
- a2) 0-20 Gew.-% einer Glasfritte
- b) 20-25 Gew.-% natürlicher oder synthetischer Graphit
- c) 7-20 Gew.-% eines oder mehrerer Alkalisilikate der allgemeinen Formel Me2O n SiO2, worin Me Lithium, Kalium oder Natrium und n einen Zahlenwert zwischen 1 und 4 bedeutet,
- d) 1 - 2 Gew.% eines wasserlöslichen Natriumpolymetaphosphates
- e) 0 - 1 Gew.% eines wasserunlöslichen Natriumpolymetaphosphates
- f) 1,5 - 2 Gew.% eines Verdickungsmittels
- g) 0 - 0,25 Gew.% Borax
- Als Glaspulver wird zweckmässig ein Normalglas mit einem durchschnittlichen Korndurchmesser d50 von <100µm und einem Erweichungsbereich von ca. 700 °C bis 900 °C verwendet (CAS Nr. 65997-17-3). Das Glaspulver ist massgeblich verantwortlich für die ausgezeichneten Filmeigenschaften des Schmiermittels. Durch seinen relativ hohen Erweichungspunkt gelangt es in zunehmender Menge dann zum Einsatz wenn die Oberflächentemperaturen des Werkstücks die 1000°C Grenze übersteigt.
- Im Gegensatz dazu findet die Glasfritte vorallem dann Anwendung, wenn die Anwendungstemperaturen im unteren Bereich ab ca. 800 °C liegen.
Dann kommen, aufgrund des im Vergleich zum Glaspulver tieferen Erweichungsbereichs von ca. 500 °C bis 700 °C, die filmbildenden Eigenschaften der Glasfritte voll zum tragen. Die Glasfritte ist zweckmässig von seiner chemischen Zusammensetzung her ein Alkali-Erdalkali-Alumo-Bor-Silikat und wird üblicherweise in einer durchschnittlichen Korngrösse d50 von <100µm angewendet. - Glaspulver und Glasfritte sind je nach Anwendung in den angegebenen Grenzen in beliebigen Mischverhältnissen einsetzbar.
- Ein weiterer wesentlicher Bestandteil bildet der Graphit. Es ist sowohl ein synthetischer Graphit als auch ein Naturgraphit anwendbar.
Zweckmässig ist die durchschnittliche Korngrösse d50 des verwendeten Graphits kleiner 100 µm. Von Vorteil wird ein Graphit mit hoher Kristallinität d. h. mit einer Kristallitlänge Lc von grösser 100 nm eingesetzt. - Eine wesentliche Funktion als Binder nehmen die wasserlöslichen Alkalisilikate ein. Es werden wasserlösliche Alkalisilikate, einzeln oder im Gemisch, der allgemeinen Formel
Me2O n SiO2
verwendet, worin Me Lithium, Kalium oder Natrium und n einen Zahlenwert zwischen 1 und 4 bedeutet. Bevorzugt kommt ein Natriummetasilikat der genannten allgemeinen Formel mit n = 1 - 1,5 oder ein Natriumsilikat mit n = 3,3 - 3,5 (Wasserglas) oder eine eutektische Mischung des genannten Natriumsilikate mit einem Kaliumsilikat der allgemeinen Formel K2O n SiO2 worin n 2,4 - 3 bedeutet und/oder einem Lithiumsilikat der allgemeinen Formel Li2O n SiO2, worin n 2,4 - 3 bedeutet, zur Anwendung.
Besonders bevorzugt wird eine Mischung der genannten bevorzugten Alkalisilikate im Verhältnis Natriumsilikat:Kaliumsilikat:Lithiumsilikat von 12,3% : 67,5% : 20,7% verwendet. - Als Schmiermittelbestandteil der die Schaumbildung unterdrückt, fungiert ein wasserlösliches Natriummetapolyphosphat. Zweckmässig wird darunter eine Verbindung mit der allgemeinen Formel (NaPO3)n worin n kleiner 450 ist, verstanden. Diese Verbindungen sind auch unter der Bezeichnung "Hexametaphosphat" oder "Grahamsches Salz" bekannt.
- Es ist desweiteren möglich ein wasserunlösliches Natriummetapolyphosphat als Binder zuzusetzen. Besonders geeignet sind dazu die unter dem Namen "Maddrellsches Salz" bekannten Verbindungen der allgemeinen Formel (NaPO3)n, worin n 40 bis 70 bedeutet.
- Der Zusatz eines Verdickungsmittels zweckmässig eines Polysaccharids oder eines Polysaccharidderivates ist entscheidend für die Gewährleistung einer konstanten Viskosität und Stabilität der Schmiermitteldispersion über einen weiten Temperaturbereich, sowie für die Verhinderung der Sedimentation der Feststoffanteile in der Dispersion. Zweckmässig finden Biopolysaccharide wie Xanthan-Gummi, Rhamsan-Gummi oder eine Alkylcellulose wie die Hydroxymethylcellulose, Anwendung.
- Mit einem entsprechenden Resultat lassen sich als Verdickungsmittel Alkalisalze der Polyacrylsäure, insbesondere Natriumpolyacrylate zusetzen.
- Zur Verhinderung eines bakteriellen Angriffs wird der Schmiermittelzusammensetzung zweckmässig ein handelsübliches Biocid in zugegeben.
- Schliesslich ist es möglich als Haftvermittler Borax (Natriumtetraborat-Decahydrat) zuzusetzen.
Das erfindungsgemässe Schmiermittel wird zweckmässig in Form einer wässrigen Dispersion mit einem Feststoffanteil von vorzugsweise 20% bis 50% angewendet. Es ist durchaus möglich, die Grenzen nach oben und unten zu variieren. Die Herstellung der Dispersion kann in handelsüblichen Dispergiergeräten, die hohe Scherkräfte ermöglichen, erfolgen (vgl. z.B. EP-PS 218 989).
Die anwendungsbereite Dispersion weist zweckmässig eine Viskosität im Bereich von 1000 MPas bis 7000 MPas (Rheomat 15, 20 °C, Zelle B, Geschwindigkeit 5) auf, kann aber über den Zusatz von Verdickungsmittel weiter variiert werden. - Die Applikation der Schmiermitteldispersion kann über bekannte Systeme zum Versprühen von dispersen Systemen erfolgen (vgl. z.B. EP-A 453 801).
- Erfindungsgemäss wird die vorstehend offenbarte Schmiermittelzusammensetzung für die Anwendung auf Werkstücken, die Oberflächentemperaturen von 800 °C bis 1300 °C aufweisen, bei der Heissumformung von Metallen, insbesondere beim Warmwalzen von Blöcken und Profilen oder bei der Herstellung von Hohlblöcken in sog. Stossbankanlagen verwendet. Die Auftragung der Dispersion auf das Werkstück erfolgt dabei unmittelbar vor der Umformung. Eine vorgängige Entzunderung des Werkstückes ist von Vorteil aber nicht zwingend. Nach dem sofortigen Verdampfen des Wassers bildet sich innert weniger Sekunden ein gleichmässiger, wasserunlöslicher Schmierfilm auf der Werkstückoberfläche aus, der durch den nachfolgenden Umformungsvorgang nicht beeinträchtigt wird.
- Die nachstehenden Viskositätsangaben wurden in einem Rheomat 15, 20 °C, Zelle B, Geschwindigkeit 5) gemessen.
-
- 49,17 Gew.% Glasfritte (Bindefritte K2244 mit d70 < 100µm, Schauer Co,A-Wien)
- 25,00 Gew.% Graphit (synthetischer Graphit T 75 mit d50 24µm, LONZA G&T,CH-Sins)
- 15,67 Gew.% Wasserglas (wasserlösl.Natriumsilikat Na2O n SiO2 mit n=3,3 - 3,5)
- 6,00 Gew.% wasserlösl. Natriumpolyphosphat (Alcopon, Benckiser-Knapsack, D-Ladenburg)
- 3,33 Gew.% Hydroxymethylcellulose (Dow Chemical)
- 0,67 Gew.% Borax
- 0,16 Gew.% Biozid
- Dispersion: % Gehalt in Wasser 20%
- Viskosität: 1000-2000 MPas
-
- 64,85 Gew.% Glaspulver (Glasmehl 300 mit d70 kleiner 63 µm der Mineralienwerke Kuppenheim)
- 24,94 Gew.% Graphit (synthetischer Graphit T 75 mit d50 24µm, LONZA G&T, CH-Sins)
- 6,98 Gew.% wasserlösl. Natriumsilikat (Na2O n SiO2 mit n=1 - 1,15)
- 1,67 Gew.% wasserlösl. Natriumpolyphosphat (Alcopon, Benckiser-Knapsack, D-Ladenburg
- 1,33 Gew.% Hydroxymethylcellulose (Dow Chemical)
- 0,22 Gew.% Xanthan-Gummi
- 0,01 Gew.% Biozid
- Dispersion: % Gehalt in Wasser 40%
- Viskosität: 1000 - 3000 MPas
-
- 47,78 Gew.% Glaspulver (Glasmehl 300 mit d70 kleiner 63 µm der Mineralienwerke Kuppenheim)
- 16,53 Gew.% Glasfritte (Bindefritte K2244 mit d70 < 100µm, Schauer Co., A-Wien)
- 24,84 Gew.% Graphit (synthetischer Graphit T 75 mit d50 24 µm, LONZA G&T, CH-Sins)
- 6,74 Gew.% wasserlösl. Alkalisilikatmischung (Natriumsilikat:Kaliumsilikat:Lithiumsilikat 12,3 : 67,5 : 20,7, Me2O n SiO2 mit n=2,7)
- 1,32 Gew.% wasserlösl. Natriumpolyphosphat (Alcopon, Benckiser-Knapsack, D-Ladenburg)
- 0,92 Gew.% waserunlösl. Natriumpolyphosphat (Dentphos M, Benckiser-Knapsack, D-Ladenburg)
- 0,25 Gew.% Borax
- 0,45 Gew.% Xanthan-Gummi
- 1,10 Gew.% Hydroxymethylcellulose (Dow Chemical)
- 0,07 Gew.% Biozid
- Dispersion: % Gehalt in Wasser 40%
- Viskosität: 2000 - 5000 MPas
-
- 49,53 Gew.% Glasfritte (Bindefritte K2244 mit d70 < 100 µm, Schauer Co., A-Wien)
- 24,76 Gew.% Graphit (synthetischer Graphit T 75 mit d50 24µm, LONZA G&T, CH-Sins)
- 6,74 Gew.% wasserlösl. Alkalisilikatmischung (Natriumsilikat:Kaliumsilikat:Lithiumsilikat 12,3 : 67,5 : 20,7, Me2O n SiO2 mit n=2,7)
- 2,64 Gew.% wasserlösl. Natriumpolyphosphat (Alcopon, Benckiser-Knapsack, D-Ladenburg
- 1,32 Gew.% waserunlösl. Natriumpolyphosphat (Dentphos M, Benckiser-Knapsack, D-Ladenburg)
- 0,66 Gew.% Borax
- 3,30 Gew.% Hydroxymethylcellulose (Dow Chemical)
- 0,71 Gew.% Natriumpolyacrylat (Carbopol, Goodrich Chemical)
- 0,14 Gew.% Biozid
- Dispersion: % Gehalt in Wasser 20%
- Viskosität: 2000 - 5000 MPas
-
- 54 Gew.% kristalliner Graphit
- 11 Gew.% Maddrellsches Salz
- 5 Gew.% Borax
- 10 Gew.% Natriumsilikat (Wasserglas SiO2/Na2O = 3,3)
- 18 Gew.% Polyethylen
- 2 Gew.% Alkylcellulose
- wässrige Dispersion mit Feststoffgehalt von 30 Gew.%
- Viskosität 1900 MPas
-
- 70 Gew.% Natriumtripolyphosphat (Na5P3O10)
- 4 Gew.% Graphit
- 26 Gew.% Na2B2O4 8 H2O
- Auf die 800 °C bis 1050 °C heisse Oberfläche eines vertikal, mit 1,5 m/s bewegten Stahlblocks mit den Masssen 29 cm x 6cm x 3cm werden über eine, im Abstand von 43 cm befindliche Düse (Druck 50 bar) die Formulationen 1 bis 4, sowie die Vergleichsformulation 1 aufgesprüht. Die Vergleichsformulation 2 wird trocken gesprüht gemäss CH-PS 670 106. Der gebildete Schmiermittelfilm wird nach den folgenden Klassierungen bewertet.
- Keine Bildung eines Schmiermittelfilms.
- Bildung eines brüchigen Schmiermittelfilms mit nur kurzzeitiger (wenige Sekunden) Haftung.
- Sofortige Bildung eines gleichmässigen, glasurähnlichen, gut haftenden Schmiermittelfilms mit hoher mechanischer Beständigkeit und hoher Wasserbeständigkeit.
-
Formulation Testergebnis (Klasse) 1 3 (ab 850 °C) 2 3 (ab 1000 °C) 3 3 (ab 1000 °C) 4 3 (ab 850 °C) Vergleich 1 1 Vergleich 2 2
Claims (12)
- Schmiermittelzusammensetzung für die Anwendung auf Werkstücken bei der Heissumformung von Metallen bestehend ausa1) 0-80 Gew.-% eines Glaspulversa2) 0-50 Gew.-% einer Glasfritte
wobei der Anteil von zumindest einem der Bestandteile a1) oder a2) in der Schmiermittelzusammensetzung nicht 0 Gew.-% istb) 10-25 Gew.-% natürlicher oder synthetischer Graphitc) 5-20 Gew.-% eines oder mehrerer Alkalisilikate der allgemeinen Formel Me2O n SiO2, worin Me Lithium, Kalium oder Natrium und n einen Zahlenwert zwischen 1 und 4 bedeutet.d) 1-6 Gew.-% eines wasserloslichen Natriumpolymetaphosphatese) 0-3 Gew.-% eines wasserunlöslichen Natriumpolymetaphosphatesf) 0,5-4 Gew.-% eines Verdickungsmittelsg) 0-1 Gew.-% Borax - Schmiermittelzusammensetzung nach Patentanspruch 1, dadurch gekennzeichnet, dass ein Glaspulver eingesetzt wird, das einen durchschnittlichen Korndurchmesser d50 von <100µm und einen Erweichungsbereich von ca. 700 °C - 900 °C aufweist
- Schmiermittelzusammensetzung nach Patentansprüchen 1 oder 2, dadurch gekennzeichnet, dass eine Glasfritte eingesetzt wird, die einen durchschnittlichen Korndurchmesser d50 von <100µm und einen Erweichungsbereich von ca. 500 °C - 700 °C aufweist.
- Schmiermittelzusammensetzung nach Patentansprüchen 1 - 3, dadurch gekennzeichnet, dass wasserlösliche Alkalisilikate, einzeln oder im Gemisch, der allgemeinen Formel Me2O n SiO2 verwendet werden, worin Me Lithium, Kalium oder Natrium und n einen Zahlenwert zwischen 1 und 4 bedeutet
- Schmiermittelzusammensetzung nach Patentansprüchen 1 - 4, dadurch gekennzeichnet, dass als wasserlösliches Natriumpolymetaphosphat ein Grahamsches Salz der allgemeinen Formel (NaPO3)n mit n kleiner 450 angewendet wird.
- Schmiermittelzusammensetzung nach Patentansprüchen 1 - 5, dadurch gekennzeichnet, dass als wasserunlösliches Natriumpolymetaphosphates ein Maddrellsches Salz der allgemeinen Formel (NaPO3)n mit n 40 bis 70 angewendet wird.
- Schmiermittelzusammensetzung nach Patentansprüchen 1 - 6, dadurch gekennzeichnet, dass als Verdickungsmittel ein Polysaccharid, ein Polysaccharidderivat oder ein Alkalisalz eines Polyacrylats verwendet wird.
- Schmiermittelzusammensetzung nach Patentansprüchen 1 - 7 in Form einer wässrigen Dispersion.
- Schmiermittelzusammensetzung nach Patentansprüchen 1 - 8 in Form einer wässrigen Dispersion mit einem Feststoffgehalt von 20% bis 50%.
- Schmiermittelzusammensetzung nach Patentansprüchen 1 - 9 zur Anwendung bei Werkstücken mit Oberflächentemperaturen ab 800 °C bestehend aus:a1) 0-20 Gew.-% eines Glaspulversa2) 30-50 Gew.-% einer Glasfritteb) 20-25 Gew.-% natürlicher oder synthetischer Graphitc) 7-20 Gew.-% eines oder mehrerer Alkalisilikate der allgemeinen Formel Me2O n SiO2, worin Me Lithium, Kalium oder Natrium und n einen Zahlenwert zwischen 1 und 4 bedeutet.d) 2-6 Gew.-% eines wasserlöslichen Natriumpolymetaphosphatese) 0-1 Gew.-% eines wasserunlöslichen Natrumpolymetaphosphatesf) 3-4 Gew.-% eines Verdickungsmittelsg) 0,2-0,7 Gew.-% Borax
- Schmiermittelzusammensetzung nach Patentansprüchen 1 - 9 zur Anwendung bei Werkstücken mit Oberflächentemperatur ab 1000 °C bestehend aus:a1) 45-70 Gew.-% eines Glaspulversa2) 0-20 Gew.-% einer Glasfritteb) 20-25 Gew.-% natürlicher oder synthetischer Graphitc) 7-20 Gew.-% eines oder mehrerer Alkalisililate der allgemeinen Formel Me2O n SiO2, worin Me Lithium, Kalium oder Natrium und n einen Zahlenwert zwischen 1 und 4 bedeutet.d) 1 - 2 Gew.% eines wasserlöslichen Natriumpolymetaphosphatese) 0 - 1 Gew.% eines wasserunlöslichen Natriumpolymetaphosphatesf) 1,5-2 Gew.-% eines Verdickungsmittelsg) 0-0,25 Gew.-% Borax
- Verwendung der Schmiermittelzusammensetzung gemäß Patentansprüchen 1 bis 11 zur direkten Schmierung von Werkstücken mit einer Oberflächentemperatur von ca. 800°C bis 1300°C bei der Heißumformung von Metallen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SI9630075T SI0743352T1 (en) | 1995-05-16 | 1996-05-13 | Lubricant composition suitable for application on metal workpieces during hot-forming |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1416/95 | 1995-05-16 | ||
| CH141695 | 1995-05-16 | ||
| CH141695 | 1995-05-16 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0743352A1 true EP0743352A1 (de) | 1996-11-20 |
| EP0743352B1 EP0743352B1 (de) | 1999-07-28 |
Family
ID=4209943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP96107611A Expired - Lifetime EP0743352B1 (de) | 1995-05-16 | 1996-05-13 | Schmiermittelzusammensetzung für die Anwendung auf Werkstücken bei der Heissumformung von Metallen |
Country Status (21)
| Country | Link |
|---|---|
| US (1) | US5691282A (de) |
| EP (1) | EP0743352B1 (de) |
| JP (1) | JP2930003B2 (de) |
| KR (1) | KR960041327A (de) |
| CN (1) | CN1063479C (de) |
| AR (1) | AR001910A1 (de) |
| AT (1) | ATE182612T1 (de) |
| BR (1) | BR9602185A (de) |
| CA (1) | CA2174825A1 (de) |
| CZ (1) | CZ140596A3 (de) |
| DE (1) | DE59602520D1 (de) |
| ES (1) | ES2136916T3 (de) |
| HU (1) | HU219309B (de) |
| NO (1) | NO962019L (de) |
| RO (1) | RO116817B1 (de) |
| RU (1) | RU2153525C2 (de) |
| SI (1) | SI0743352T1 (de) |
| SK (1) | SK61996A3 (de) |
| TR (1) | TR199600394A2 (de) |
| TW (1) | TW324739B (de) |
| ZA (1) | ZA963198B (de) |
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| EP4660286A1 (de) | 2024-06-03 | 2025-12-10 | Chemische Fabrik Budenheim KG | Entzunderungsmittel zur entfernung von zunder bei der heissverarbeitung von metallen |
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| US6330818B1 (en) | 1998-12-17 | 2001-12-18 | Materials And Manufacturing Technologies Solutions Company | Lubrication system for metalforming |
| CN1229298C (zh) * | 1999-01-27 | 2005-11-30 | 金伟华 | 利用废玻璃制备的无机粘结剂 |
| CN1091142C (zh) * | 1999-12-29 | 2002-09-18 | 宝山钢铁股份有限公司 | 金属热加工用润滑剂 |
| RU2232797C1 (ru) * | 2003-02-14 | 2004-07-20 | Федеральное государственное унитарное предприятие "Московское машиностроительное производственное предприятие "Салют" | Смазка для обработки металлов давлением |
| BRPI0609791B1 (pt) | 2005-03-31 | 2016-03-29 | Nippon Steel & Sumitomo Metal Corp | agente anticorrosão para trabalhar aço a quente, e método para trabalhar aço a quente e método de produção de tubos de aço sem costura empregando-se o referido agente |
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| JP5269341B2 (ja) * | 2006-04-24 | 2013-08-21 | 新日鐵住金株式会社 | 熱間押出加工用潤滑剤組成物 |
| BRPI0711407B1 (pt) * | 2006-04-24 | 2016-11-01 | Nippon Steel & Sumitomo Metal Corp | composição lubrificante para usinagem de metal aquecido, método de usinagem de metal aquecido e método para produção de tubo sem costura usando o método de usinagem de metal aquecido |
| TWI457431B (zh) * | 2008-01-30 | 2014-10-21 | Chemetall Gmbh | 將金屬表面施以一種潤滑劑組成物的方法 |
| TWI457433B (zh) * | 2008-01-30 | 2014-10-21 | Chemetall Gmbh | 將金屬表面施以一磷酸鹽層然後施以一潤滑劑層的方法 |
| CN101880580B (zh) * | 2010-06-28 | 2013-01-16 | 河南省长城特种润滑脂有限公司 | 超高温润滑脂及制备方法 |
| JP5482533B2 (ja) * | 2010-07-16 | 2014-05-07 | 新日鐵住金株式会社 | 酸化防止剤、酸化防止剤の製造方法及び金属材の製造方法 |
| CN102703180B (zh) * | 2012-05-25 | 2013-10-02 | 衡阳市金化科技有限公司 | 一种用于热轧无缝钢管的玻璃粉润滑剂 |
| CN102732367B (zh) * | 2012-05-25 | 2014-02-12 | 衡阳市金化科技有限公司 | 无石墨环保型芯棒润滑剂 |
| DE102013102897A1 (de) * | 2013-03-21 | 2014-09-25 | Chemische Fabrik Budenheim Kg | Zusammensetzung für den Schutz vor Zunder und als Schmiermittel für die Heißverarbeitung von Metallen |
| CN103225727B (zh) * | 2013-05-14 | 2015-08-26 | 江苏苏南重工机械科技有限公司 | 一种合金模锻用可粘贴绝热棉及其制造方法 |
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| CN104450143B (zh) * | 2014-11-28 | 2017-11-14 | 湖南金化科技集团有限公司 | 一种极压抗磨润滑剂 |
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-
1996
- 1996-04-22 ZA ZA963198A patent/ZA963198B/xx unknown
- 1996-04-23 CA CA002174825A patent/CA2174825A1/en not_active Abandoned
- 1996-05-08 BR BR9602185A patent/BR9602185A/pt active Search and Examination
- 1996-05-09 JP JP8115070A patent/JP2930003B2/ja not_active Expired - Lifetime
- 1996-05-10 AR AR33646996A patent/AR001910A1/es unknown
- 1996-05-13 KR KR1019960015815A patent/KR960041327A/ko not_active Withdrawn
- 1996-05-13 RO RO96-00972A patent/RO116817B1/ro unknown
- 1996-05-13 ES ES96107611T patent/ES2136916T3/es not_active Expired - Lifetime
- 1996-05-13 EP EP96107611A patent/EP0743352B1/de not_active Expired - Lifetime
- 1996-05-13 DE DE59602520T patent/DE59602520D1/de not_active Expired - Fee Related
- 1996-05-13 AT AT96107611T patent/ATE182612T1/de not_active IP Right Cessation
- 1996-05-13 SI SI9630075T patent/SI0743352T1/xx unknown
- 1996-05-13 SK SK619-96A patent/SK61996A3/sk unknown
- 1996-05-14 TR TR96/00394A patent/TR199600394A2/xx unknown
- 1996-05-15 TW TW085105769A patent/TW324739B/zh active
- 1996-05-15 CZ CZ961405A patent/CZ140596A3/cs unknown
- 1996-05-15 RU RU96109711/04A patent/RU2153525C2/ru active
- 1996-05-15 NO NO962019A patent/NO962019L/no not_active Application Discontinuation
- 1996-05-16 US US08/648,958 patent/US5691282A/en not_active Expired - Fee Related
- 1996-05-16 HU HU9601314A patent/HU219309B/hu not_active IP Right Cessation
- 1996-05-16 CN CN96106237A patent/CN1063479C/zh not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55161897A (en) * | 1979-06-04 | 1980-12-16 | Yutaka Oji | Composite lubricant for hot working |
| CH660023A5 (de) * | 1984-05-30 | 1987-03-13 | Lonza Ag | Hochtemperaturschmierstoff fuer die spanlose heissumformung von metallen. |
Non-Patent Citations (1)
| Title |
|---|
| PATENT ABSTRACTS OF JAPAN vol. 005, no. 035 (C - 046) 5 March 1981 (1981-03-05) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4660286A1 (de) | 2024-06-03 | 2025-12-10 | Chemische Fabrik Budenheim KG | Entzunderungsmittel zur entfernung von zunder bei der heissverarbeitung von metallen |
| WO2025252763A1 (de) | 2024-06-03 | 2025-12-11 | Chemische Fabrik Budenheim Kg | ENTZUNDERUNGSMITTEL ZUR ENTFERNUNG VON ZUNDER BEI DER HEIßVERARBEITUNG VON METALLEN |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1143107A (zh) | 1997-02-19 |
| HUP9601314A2 (en) | 1997-02-28 |
| KR960041327A (ko) | 1996-12-19 |
| CN1063479C (zh) | 2001-03-21 |
| HU9601314D0 (en) | 1996-07-29 |
| CA2174825A1 (en) | 1996-11-17 |
| TR199600394A2 (tr) | 1996-12-21 |
| JPH08311479A (ja) | 1996-11-26 |
| DE59602520D1 (de) | 1999-09-02 |
| ATE182612T1 (de) | 1999-08-15 |
| BR9602185A (pt) | 1998-04-07 |
| US5691282A (en) | 1997-11-25 |
| SK61996A3 (en) | 1997-07-09 |
| NO962019L (no) | 1996-11-18 |
| AR001910A1 (es) | 1997-12-10 |
| SI0743352T1 (en) | 1999-10-31 |
| JP2930003B2 (ja) | 1999-08-03 |
| ES2136916T3 (es) | 1999-12-01 |
| MX9601821A (es) | 1997-07-31 |
| CZ140596A3 (en) | 1996-12-11 |
| HUP9601314A3 (en) | 1998-07-28 |
| ZA963198B (en) | 1996-10-25 |
| NO962019D0 (no) | 1996-05-15 |
| RU2153525C2 (ru) | 2000-07-27 |
| TW324739B (en) | 1998-01-11 |
| EP0743352B1 (de) | 1999-07-28 |
| HU219309B (en) | 2001-03-28 |
| RO116817B1 (ro) | 2001-06-29 |
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