EP1666616A1 - Fluid and its use to prepare hardmetals - Google Patents
Fluid and its use to prepare hardmetals Download PDFInfo
- Publication number
- EP1666616A1 EP1666616A1 EP05018858A EP05018858A EP1666616A1 EP 1666616 A1 EP1666616 A1 EP 1666616A1 EP 05018858 A EP05018858 A EP 05018858A EP 05018858 A EP05018858 A EP 05018858A EP 1666616 A1 EP1666616 A1 EP 1666616A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- liquid
- inhibitor
- weight
- gew
- powder
- 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
Links
- 239000012530 fluid Substances 0.000 title claims description 8
- 239000007788 liquid Substances 0.000 claims abstract description 56
- 239000000843 powder Substances 0.000 claims abstract description 39
- 239000003112 inhibitor Substances 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 239000000839 emulsion Substances 0.000 claims abstract description 19
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 10
- 150000003951 lactams Chemical class 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims description 16
- 239000001993 wax Substances 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- 150000001412 amines Chemical class 0.000 claims description 10
- 150000002739 metals Chemical class 0.000 claims description 9
- 239000012188 paraffin wax Substances 0.000 claims description 9
- -1 polyethylene Polymers 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- 150000001735 carboxylic acids Chemical class 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920001897 terpolymer Polymers 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims 2
- 229920002125 Sokalan® Polymers 0.000 claims 1
- 239000004584 polyacrylic acid Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 description 14
- 239000002245 particle Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 6
- 238000003801 milling Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 150000002462 imidazolines Chemical class 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000011805 ball Substances 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 150000002169 ethanolamines Chemical class 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- BNJOQKFENDDGSC-UHFFFAOYSA-N octadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCC(O)=O BNJOQKFENDDGSC-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000004482 other powder Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 150000003918 triazines Chemical class 0.000 description 2
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 description 2
- 150000000182 1,3,5-triazines Chemical class 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- MXRGSJAOLKBZLU-UHFFFAOYSA-N 3-ethenylazepan-2-one Chemical compound C=CC1CCCCNC1=O MXRGSJAOLKBZLU-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000010420 art technique Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- SUTMBHIETAEOMU-UHFFFAOYSA-N decanedioic acid;dodecanedioic acid Chemical compound OC(=O)CCCCCCCCC(O)=O.OC(=O)CCCCCCCCCCC(O)=O SUTMBHIETAEOMU-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229940083254 peripheral vasodilators imidazoline derivative Drugs 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/042—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling using a particular milling fluid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
Definitions
- the invention relates to the composition of a liquid and its use for the preparation of powder mixtures based on hard metal.
- hard metal or WC powder are treated with other metal powders, in particular cobalt powder to form a powder mixture, pressed the prepared powder mixture by pressing to form parts and then by sintering the moldings below the melting temperature of the hardmetal sintered to the desired product.
- the intimate mixture of the WC powder with the co-powder is in the foreground.
- segregations occur, in particular due to the different densities of the two powders.
- the powder mixture in order to produce as homogeneous and hard a material as possible from the cemented carbide, the powder mixture must be as homogeneous as possible.
- the WC / Co powder mixture is therefore mixed with the aid of liquids.
- This mixing process in a liquid is usually carried out today in so-called attritors, a type of ball mill, with the mixing of WC / Co powder mixture, grinding balls, liquid and Paraffin are filled.
- the mixing of the powders in the attritors presents itself as a combination of a mixing and a grinding process, so that the liquid, by means of which the powder mixture is mixed in the attritor, is also referred to as grinding liquid.
- the WC powder particles are comminuted and simultaneously mixed with the cobalt powder particles.
- liquids or grinding liquids
- organic liquids especially alcohols, such as hexane, heptane, ethyl alcohol or acetone are used.
- the paraffin dissolved in the organic liquid settles in the mixing / grinding process in the attritor to the WC and Co particles and acts u.a. as a pressing aid.
- the use of organic, especially alcoholic grinding liquids is associated with numerous disadvantages.
- Another disadvantage is the high material costs of the organic milling liquids and the high cost of their disposal or landfill.
- the object of the invention is to provide a way of using water as the mixing / milling liquid instead of the organic solvent previously used in the attritors for mixing and milling powder mixtures based on hard metal.
- the invention is based on the finding that the milling liquid previously used in attritors in the form of an organic liquid can then be replaced by water if the water is added to a suitable inhibitor, which surrounds the hard metal powder and prevents their hydrolysis.
- polyvinyllactam or a wax emulsion or carboxylic acid, amines or their derivatives are suitable inhibitors.
- the abovementioned substances encase both the hard metal powder particles and the other powder particles of the powder mixture, ie in particular the co-powder particles or regulate the oxygen attachment to the particles such that they do not or hardly hydrolyze in the water or undergo any other reaction with the water.
- the polyvinyl lactam used may be, for example, a polyvinyl caprolactam.
- the polyvinyllactam used may be a polyvinylpyrrolidone (PVP) or one or more of its co- or terpolymers, such as groups consisting of vinyl acetate, acrylate, methacrylate, acrylamide, methacrylamide, vinylimidazole, vinylcaprolactam, 3-methyl-1-vinylimidazoniummethylsulfate or other co- or terpolymers of polyvinylpyrrolidone.
- PVP polyvinylpyrrolidone
- the co-polymer content may range from 5 to 95% by weight.
- the polymers may, for example, have a molecular weight of from 1,000 to 5,000,000 daltons, preferably from 5,000 to 500,000 daltons.
- the wax emulsion may be a wax emulsion based on paraffin, oxidized paraffin, polyethylene, polypropylene, amide wax, e.g. Ethylene-bis-stearylamide, stearylamide, stearate or mixtures thereof.
- wax can only be used as an inhibitor in a generic liquid or grinding liquid if it is present as an emulsion in the liquid.
- the addition of wax in non-emulsified form would not result in distribution of the wax in the water. Accordingly, earlier attempts to use water as a liquid for processing hard metals failed the non-emulsified paraffin did not dissolve or disperse in the water.
- water as a liquid for the treatment of hard metals or as a grinding and mixing liquid in the treatment of hard metals leads to the fact that a complex encapsulation of the treatment units is no longer necessary. Furthermore, the water is much cheaper to buy than an organic liquid and its disposal is less expensive.
- the liquid according to the application as inhibitor may in particular also contain carboxylic acids and / or amines or their respective derivatives.
- carboxylic acid derivatives prove to be particularly effective inhibitors in the amine neutralized state.
- the carboxylic acids used may preferably be dicarboxylic acids and / or triazine derivatives.
- dicarboxylic acids may be, in particular, 1,8-octanedicarboxylic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid (sebacic acid), 1,11-undecanedicarboxylic acid, 1,12-dodecanecarboxylic acid and so on up to and including 1,16-hexadecanedicarboxylic acid.
- triazine derivatives in particular 1,3,5-triazine derivatives, in particular 1,3,5-triazine-2,4,6-triaminetricarboxylic acid, may be provided, for example.
- the amines used can preferably be ethanolamines and / or imidazolines.
- Ethanolamines may be, for example, in particular triethanolamine, diethanolamine, monoethanolamine and / or trishydroxymethylaminomethane.
- Imidazole units may also be provided with non-polymeric imidazole derivatives such as, for example, 2- (2-hepatadec-8-enyl-2-imidazolin-1-yl) ethanol. It is also possible for these latter to be provided with imidazole compounds, for example imidazoline derivatives, for example hydroxyethyl, aminoethyl and / or amidoethyl imidazole derivatives.
- alkyl radicals may be present residues of oil and tall oil fatty acids to octanoic acid.
- the abovementioned inhibitors are particularly effective if they are present in combination of amines and carboxylic acids, in each case in particular those of the abovementioned type.
- Stabilizers for example a cellulose
- dispersants for example based on acrylic
- the liquid according to the application can be used for the preparation of powder mixtures based on hard metals, for example for the preparation of carbides of titanium, of tantalum and of niobium.
- the liquid according to the application can be used for the preparation of hard metals based on monotungsten carbide and here in particular for the preparation of powder mixtures based on powders of monotungsten carbide and cobalt.
- the moist Powder mixture removed from the attritor and a drying unit, such as a spray-drying system, are supplied.
- the moist mixture is atomized to a granulate.
- the granules are fed to a shaping unit, usually a press, where they are pressed into the molded part.
- the wax emulsion in addition to its property as an inhibitor, simultaneously acts as an excellent pressing aid, whereby the homogeneity and green density of the pressed molded part at the same compacting pressure (compared to the pressing pressure or the properties of a molded part, according to the prior art Technique was prepared) is increased or only a lower pressing pressure is required to obtain the same properties in the molding that would be obtained without the use of a wax emulsion in the grinding fluid.
- the molding is finally subjected to a heat treatment and thereby sintered to the cemented carbide product.
- Inhibitor in the form of polyvinyllactam can be present, for example, in proportions of 0.5-50% by weight, that is to say, for example, in proportions of 1-10% by weight or 1-5% by weight in the liquid.
- Inhibitor in the form of a wax emulsion can be present for example in proportions of 0.5-66 wt .-%, that is, for example, in proportions of 1-25 wt .-% or 2-15 wt .-% in the liquid.
- Carboxylic acid for example, in proportions of 0.1 to 5 wt .-%, that is, for example, in proportions of 0.5 to 4 wt .-% in the liquid.
- Amines may, for example, in proportions of 0.1 to 7 wt .-%, that is, for example, in proportions of 0.5 to 5 wt .-% in the liquid.
- Dispersant may, for example, in proportions of 0.01-33 wt .-%, that is, for example, in proportions of 0.1-5 wt .-% or 0.5-3 wt .-% in the liquid.
- Stabilizer can be present for example in proportions of 0.01-33 wt .-%, that is, for example, in proportions of 0.05-6 wt .-% or of 0.1-3 wt .-% in the liquid.
- the liquid according to the application can be mixed with 3 to 5 times the amount of WC / Co powder particles to form a moist mixture.
- Inhibitor in the form of polyvinyl lactam in addition to the 100 wt .-% WC and Co-particles, for example, additionally with 0.01-10 wt .-%, that is, for example, also be contained with 0.1-2 wt .-% in the wet mixture.
- Inhibitor in the form of wax emulsion in addition to the 100 wt .-% WC and Co particles, for example, in addition to 0.1-20 wt .-%, that is, for example, 1-5 wt .-% in the wet mixture.
- the moist mixture in addition to the 100% by weight of WC and Co particles and the abovementioned components, it is possible for example in the moist mixture to contain 0.01-5% by weight, that is to say also 0.1-0.8% by weight of dispersant and / or or, for example, 0.01-5 wt .-%, that is, for example, 0.05-0.5 wt .-% stabilizer present.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cosmetics (AREA)
- Lubricants (AREA)
- Powder Metallurgy (AREA)
Abstract
Description
Die Erfindung betrifft die Zusammensetzung einer Flüssigkeit sowie deren Verwendung zur Aufbereitung von Pulvermischungen auf Hartmetallbasis.The invention relates to the composition of a liquid and its use for the preparation of powder mixtures based on hard metal.
Zur Herstellung hoch beanspruchter Produkte, beispielsweise hoch beanspruchter Werkzeuge wie etwa Schneidwerkzeuge, werden regelmäßig Sinterwerkstoffe auf der Basis von Hartmetallen eingesetzt.For the production of highly stressed products, for example highly stressed tools such as cutting tools, sintered materials based on hard metals are regularly used.
Als Hartmetalle werden vor allem die Carbide des Titan, des Tantals und des Niobs (TiC, TaC, NbC), insbesondere jedoch auch Monowolframcarbid (WC) verwendet.The carbides of titanium, of tantalum and of niobium (TiC, TaC, NbC), but in particular also monotungsten carbide (WC), are used as hard metals.
Zur Herstellung von Werkstoffen auf Hartmetallbasis, beispielsweise auf Basis WC, werden Hartmetall- bzw. WC-Pulver mit weiteren Metallpulvern, insbesondere Cobalt-Pulver zu einer Pulvermischung aufbereitet, die aufbereitete Pulvermischung durch Pressen zu Formteilen gepresst und anschließend durch Sintern der Formteile unterhalb der Schmelztemperatur des Hartmetalls zu dem gewünschten Produkt gesintert.For the production of materials based on hard metal, for example based on WC, hard metal or WC powder are treated with other metal powders, in particular cobalt powder to form a powder mixture, pressed the prepared powder mixture by pressing to form parts and then by sintering the moldings below the melting temperature of the hardmetal sintered to the desired product.
Soweit im folgenden auf die Aufbereitung von WC/Co-Pulvermischungen eingegangen wird, gelten die Ausführungen entsprechend für sonstige Pulvermischungen auf Hartmetallbasis.As far as the treatment of WC / Co powder mixtures is discussed below, the statements apply accordingly to other powder mixtures based on hard metal.
Die Zumischung von Cobalt-Pulver zum WC-Pulver ist notwendig, um die Sintereigenschaften des Formteiles zu verbessern. Die Sinterung eines Formteiles aus reinem WC-Pulver ist nicht möglich.The addition of cobalt powder to the WC powder is necessary to improve the sintering properties of the molded part. The sintering of a molded part of pure WC powder is not possible.
Bei der Aufbereitung steht die innige Mischung des WC-Pulvers mit dem Co-Pulver im Vordergrund. Bei der Mischung des WC-Pulvers und des Cobalt-Pulvers kommt es, insbesondere aufgrund der unterschiedlichen Dichten beider Pulver, zu Entmischungen. Zur Herstellung eines möglichst homogenen und harten Werkstoffes aus dem Hartmetall muss jedoch eine möglichst homogene Pulvermischung vorliegen.During the preparation, the intimate mixture of the WC powder with the co-powder is in the foreground. When mixing the WC powder and the cobalt powder, segregations occur, in particular due to the different densities of the two powders. However, in order to produce as homogeneous and hard a material as possible from the cemented carbide, the powder mixture must be as homogeneous as possible.
Die WC/Co-Pulvermischung wird daher unter Zuhilfenahme von Flüssigkeiten gemischt. Dieser Mischvorgang in einer Flüssigkeit erfolgt heutzutage üblicherweise in so genannten Attritoren, einer Art von Kugelmühle, die mit der zu vermischenden WC/Co-Pulvermischung, Mahlkugeln, Flüssigkeit und Paraffin gefüllt sind. Die Vermischung der Pulver in den Attritoren stellt sich als eine Kombination aus einem Misch- und einem Mahlvorgang dar, so dass die Flüssigkeit, unter deren Zuhilfenahme die Pulvermischung im Attritor gemischt wird, auch als Mahlflüssigkeit bezeichnet wird.The WC / Co powder mixture is therefore mixed with the aid of liquids. This mixing process in a liquid is usually carried out today in so-called attritors, a type of ball mill, with the mixing of WC / Co powder mixture, grinding balls, liquid and Paraffin are filled. The mixing of the powders in the attritors presents itself as a combination of a mixing and a grinding process, so that the liquid, by means of which the powder mixture is mixed in the attritor, is also referred to as grinding liquid.
Bei der Mischung beziehungsweise Mahlung im Attritor werden die WC-Pulverteilchen zerkleinert sowie gleichzeitig mit den Cobalt-Pulverteilchen vermischt.During mixing or grinding in the attritor, the WC powder particles are comminuted and simultaneously mixed with the cobalt powder particles.
Als Flüssigkeiten, beziehungsweise Mahlflüssigkeiten, werden üblicherweise organische Flüssigkeiten, insbesondere auch Alkohole, wie beispielsweise Hexan, Heptan, Ethylalkohol oder Aceton verwendet.As liquids, or grinding liquids, usually organic liquids, especially alcohols, such as hexane, heptane, ethyl alcohol or acetone are used.
Das in der organischen Flüssigkeit gelöste Paraffin legt sich beim Misch/Mahlvorgang im Attritor um die WC- und Co-Partikel und wirkt beim späteren Pressvorgang dadurch u.a. als Presshilfsmittel.The paraffin dissolved in the organic liquid settles in the mixing / grinding process in the attritor to the WC and Co particles and acts u.a. as a pressing aid.
Die Verwendung einer wässrigen Flüssigkeit als Mahlflüssigkeit kam bisher üblicherweise nicht in Frage, da die WC-Pulverteilchen in einer wässrigen Flüssigkeit beziehungsweise Mahlflüssigkeit teilweise hydrolysiert worden wären und die Eigenschaften eines hieraus hergestellten Produktes hierdurch nachteilig beeinflusst worden wären.The use of an aqueous liquid as milling liquid has hitherto usually been out of the question, since the WC powder particles would have been partially hydrolyzed in an aqueous liquid or milling liquid and the properties of a product produced therefrom would have been adversely affected by this.
Weiterhin kam die Verwendung einer wässrigen Mahlflüssigkeit nicht in Frage, da das Paraffin, das in der Mahlflüssigkeit regelmäßig vorhanden war, nur in organischen Flüssigkeiten, nicht jedoch in Wasser löslich gewesen wäre.Furthermore, the use of an aqueous grinding fluid was out of the question since the paraffin which was present regularly in the grinding fluid would have been soluble only in organic liquids but not in water.
Die Verwendung von organischen, insbesondere auch alkoholischen Mahlflüssigkeiten ist jedoch mit zahlreichen Nachteilen verbunden. So müssen die Attritoren sowie auch die den Attritoren verfahrenstechnisch nachgeschalteten Trocknungsanlagen, insbesondere beispielsweise die Sprühtrocknungsanlagen, aufwendig gekapselt werden, um ein Entweichen der brennbaren und explosiven organischen Flüssigkeiten aus den Aggregaten zu verhindern.However, the use of organic, especially alcoholic grinding liquids is associated with numerous disadvantages. Thus, the attritors as well as the attritors procedurally downstream drying equipment, in particular, for example, the spray drying systems, consuming encapsulated in order to prevent escape of the combustible and explosive organic liquids from the aggregates.
Weiterhin nachteilig sind die hohen Materialkosten der organischen Mahlflüssigkeiten sowie die hohen Kosten für deren Entsorgung beziehungsweise Deponierung.Another disadvantage is the high material costs of the organic milling liquids and the high cost of their disposal or landfill.
Ferner ist bei der bisher angewandten Aufbereitungstechnik für die Aufbereitung von Hartmetallen nachteilig, dass der Misch- beziehungsweise Mahlprozess im Attritor äußerst lange dauert, üblicherweise zwischen 6 und 36 Stunden.Furthermore, it is disadvantageous in the treatment technique used hitherto for the treatment of hard metals that the mixing or grinding process in the attritor takes extremely long, usually between 6 and 36 hours.
Der Erfindung liegt die Aufgabe zugrunde, einen Weg aufzuzeigen, wie statt des bisher in den Attritoren zur Vermischung und Mahlung von Pulvermischungen auf Hartmetallbasis eingesetzten organischen Lösemittels als Misch-/Mahlflüssigkeit Wasser verwendet werden kann.The object of the invention is to provide a way of using water as the mixing / milling liquid instead of the organic solvent previously used in the attritors for mixing and milling powder mixtures based on hard metal.
Erfindungsgemäß gelöst wird diese Aufgabe durch die zur Verfügungstellung einer Flüssigkeit zur Aufbereitung von Pulvermischungen auf Hartmetallbasis, enthaltend
- Wasser,
- Inhibitor in Form wenigstens eines der folgenden Stoffe:
- Polyvinyllactam, Wachsemulsion und
- gegebenenfalls weitere Stoffe.
Eine weitere Lösung liegt in der Zurverfügungstellung einer Flüssigkeit zur Aufbereitung von Pulvermischungen auf Hartmetallbasis, enthaltend - Wasser,
- Inhibitor in Form wenigstens eines der folgenden Stoffe:
- Carbonsäuren, Amine oder deren Derivate und
- gegebenenfalls weitere Stoffe.
- Water,
- Inhibitor in the form of at least one of the following substances:
- Polyvinyllactam, wax emulsion and
- optionally further substances.
Another solution lies in the provision of a liquid for the preparation of powder mixtures based on hard metal, containing - Water,
- Inhibitor in the form of at least one of the following substances:
- Carboxylic acids, amines or derivatives thereof and
- optionally further substances.
Der Erfindung liegt dabei die Erkenntnis zugrunde, dass die bisher in Attritoren verwendete Mahlflüssigkeit in Form einer organischen Flüssigkeit dann durch Wasser ersetzt werden kann, wenn dem Wasser ein geeigneter Inhibitor zugesetzt ist, der die Hartmetallpulverteilchen ummantelt und deren Hydrolyse hierdurch verhindert.The invention is based on the finding that the milling liquid previously used in attritors in the form of an organic liquid can then be replaced by water if the water is added to a suitable inhibitor, which surrounds the hard metal powder and prevents their hydrolysis.
Erfindungsgemäß wurde erkannt, dass Polyvinyllactam oder eine Wachsemulsion beziehungsweise Carbonsäure, Amine oder deren Derivate geeignete Inhibitoren sind.According to the invention, it has been recognized that polyvinyllactam or a wax emulsion or carboxylic acid, amines or their derivatives are suitable inhibitors.
Die vorgenannten Stoffe ummanteln sowohl die Hartmetall-Pulverteilchen als auch die sonstigen Pulverteilchen der Pulvermischung, insbesondere also beispielsweise die Co-Pulverteilchen beziehungsweise regulieren die Sauerstoffanlagerung an die Teilchen derart, dass diese im Wasser nicht oder kaum hydrolysieren beziehungsweise eine sonstige Reaktion mit dem Wasser eingehen.The abovementioned substances encase both the hard metal powder particles and the other powder particles of the powder mixture, ie in particular the co-powder particles or regulate the oxygen attachment to the particles such that they do not or hardly hydrolyze in the water or undergo any other reaction with the water.
Das verwendete Polyvinyllactam kann zum Beispiel ein Polyvinylcaprolactam sein. Alternativ oder kumulativ kann das verwendete Polyvinyllactam ein Polyvinylpyrrolidon (PVP) oder eines oder mehrere seiner Co- oder Terpolymere sein, wie zum Beispiel Gruppen bestehend aus Vinylacetat, Acrylat, Methacrylat, Acrylamid, Methacrylamid, Vinylimidazol, Vinylcaprolactam, 3-Methyl-1-Vinylimidazoniummethylsulfat oder andere Co- oder Terpolymere des Polyvinylpyrrolidon. Der Co-Polymeranteil, bezogen auf das Gesamtgewicht aus Polyvinylpyrrolidon und einem oder mehrere seiner Co- und/oder Terpolymere, kann sich in einem Bereich von 5 bis 95 Gew.-% bewegen. Die Polymere können beispielsweise ein Molekulargewicht von 1.000 bis 5.000.000 Dalton, vorzugsweise von 5.000 bis 500.000 Dalton besitzen.The polyvinyl lactam used may be, for example, a polyvinyl caprolactam. Alternatively or cumulatively, the polyvinyllactam used may be a polyvinylpyrrolidone (PVP) or one or more of its co- or terpolymers, such as groups consisting of vinyl acetate, acrylate, methacrylate, acrylamide, methacrylamide, vinylimidazole, vinylcaprolactam, 3-methyl-1-vinylimidazoniummethylsulfate or other co- or terpolymers of polyvinylpyrrolidone. The co-polymer content, based on the total weight of polyvinylpyrrolidone and one or more of its co- and / or terpolymers, may range from 5 to 95% by weight. The polymers may, for example, have a molecular weight of from 1,000 to 5,000,000 daltons, preferably from 5,000 to 500,000 daltons.
Die Wachsemulsion kann beispielsweise eine Wachsemulsion auf Basis von Paraffin, oxidiertem Paraffin, Polyethylen, Polypropylen, Amidwachs wie z.B. Ethylen-bis-stearylamid, Stearylamid, Stearat oder Mischungen daraus sein.For example, the wax emulsion may be a wax emulsion based on paraffin, oxidized paraffin, polyethylene, polypropylene, amide wax, e.g. Ethylene-bis-stearylamide, stearylamide, stearate or mixtures thereof.
Erfindungsgemäß wurde erkannt, dass Wachs als Inhibitor in einer gattungsgemäßen Flüssigkeit beziehungsweise Mahlflüssigkeit nur dann eingesetzt werden kann, wenn dieses als Emulsion in der Flüssigkeit vorliegt. Die Zugabe von Wachs in nicht-emulgierter Form würde zu keiner Verteilung des Wachses im Wasser führen. Entsprechend scheiterten frühere Versuche, Wasser als Flüssigkeit zur Aufbereitung von Hartmetallen zu verwenden, da sich das nicht-emulgierte Paraffin im Wasser nicht löste beziehungsweise verteilte.According to the invention, it has been recognized that wax can only be used as an inhibitor in a generic liquid or grinding liquid if it is present as an emulsion in the liquid. The addition of wax in non-emulsified form would not result in distribution of the wax in the water. Accordingly, earlier attempts to use water as a liquid for processing hard metals failed the non-emulsified paraffin did not dissolve or disperse in the water.
Die Verwendung von Wasser als Flüssigkeit zur Aufbereitung von Hartmetallen beziehungsweise als Mahl- und Mischflüssigkeit bei der Aufbereitung von Hartmetallen führt dazu, dass eine aufwendige Kapselung der Aufbereitungsaggregate nicht weiter notwendig ist. Ferner ist das Wasser wesentlich günstiger in der Anschaffung als eine organische Flüssigkeit und seine Entsorgung ist weniger aufwendig.The use of water as a liquid for the treatment of hard metals or as a grinding and mixing liquid in the treatment of hard metals leads to the fact that a complex encapsulation of the treatment units is no longer necessary. Furthermore, the water is much cheaper to buy than an organic liquid and its disposal is less expensive.
Gleichzeitig wurde festgestellt, dass der Misch- beziehungsweise Mahlprozess im Attritor deutlich auf nur mehr etwa 1 bis 3 Stunden Misch- beziehungsweise Mahlzeit verkürzt werden kann. Schließlich wurde bei Verwendung der anmeldungsgemäßen Flüssigkeit ein verbessertes Misch- beziehungsweise Mahlergebnis beobachtet.At the same time, it was found that the mixing or grinding process in the attritor can be reduced significantly to only about 1 to 3 hours mixing or meal. Finally, an improved mixing or grinding result was observed when using the liquid according to the application.
Kumulativ oder alternativ zu den vorgenannten Inhibitoren (Polyvinyllactam, Wachsemulsion) kann die anmeldungsgemäße Flüssigkeit als Inhibitor insbesondere auch Carbonsäuren und/oder Amine oder deren jeweilige Derivate enthalten. Insbesondere Carbonsäure-Derivate erweisen sich in dem mit Amin neutralisierten Zustand als besonders wirksame Inhibitoren.Cumulatively or alternatively to the abovementioned inhibitors (polyvinyl lactam, wax emulsion), the liquid according to the application as inhibitor may in particular also contain carboxylic acids and / or amines or their respective derivatives. In particular, carboxylic acid derivatives prove to be particularly effective inhibitors in the amine neutralized state.
Als Carbonsäuren können bevorzugt Dicarbonsäuren und/oder Triazinderivate eingesetzt werden. Dicarbonsäuren können beispielsweise insbesondere 1,8-Oktandicarbonsäure, 1,9-Nonandicarbonsäure, 1,10-Decandicarbonsäure (Sebacinsäure), 1,11-Undecandicarbonsäure, 1,12-Dodecancarbonsäure und so weiter bis einschließlich 1,16-Hexadecandicarbonsäure sein. Bezüglich der Triazinderivate können beispielsweise insbesondere 1,3,5-Triazinderivate, vor allem 1,3,5-Triazin-2,4,6-Triamintricarbonsäure vorgesehen sein.The carboxylic acids used may preferably be dicarboxylic acids and / or triazine derivatives. For example, dicarboxylic acids may be, in particular, 1,8-octanedicarboxylic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid (sebacic acid), 1,11-undecanedicarboxylic acid, 1,12-dodecanecarboxylic acid and so on up to and including 1,16-hexadecanedicarboxylic acid. With regard to the triazine derivatives, in particular 1,3,5-triazine derivatives, in particular 1,3,5-triazine-2,4,6-triaminetricarboxylic acid, may be provided, for example.
Als Amine können bevorzugt Ethanolamine und/oder Imidazoline eingesetzt werden. Ethanolamine können beispielsweise insbesondere Triethanolamin, Diethanolamin, Monoethanolamin und/oder Trishydroxymethylaminomethan sein. Bezüglich der Imidazoline können neben Polymere mitenthaltenden Imidazol-Einheiten auch nicht polymere Imidazol-Derivate, wie zum Beispiel 2-(2-Hepatadec-8-enyl-2-imidazolin-1-yl)ethanol vorgesehen sein. Es können auch diesen letzteren ähnliche Imidazolverbindungen vorgesehen sein, zum Beispiel Imidazolin-Derivate, wie zum Beispiel Hydroxyethyl-, Aminoethyl- und/oder Amidoethyl-Imdidazolderivate. Als Alkylreste können Reste von Öl- und Tallöl-Fettsäuren bis zur Octansäure vorhanden sein.The amines used can preferably be ethanolamines and / or imidazolines. Ethanolamines may be, for example, in particular triethanolamine, diethanolamine, monoethanolamine and / or trishydroxymethylaminomethane. With respect to the imidazolines, in addition to polymers may be included Imidazole units may also be provided with non-polymeric imidazole derivatives such as, for example, 2- (2-hepatadec-8-enyl-2-imidazolin-1-yl) ethanol. It is also possible for these latter to be provided with imidazole compounds, for example imidazoline derivatives, for example hydroxyethyl, aminoethyl and / or amidoethyl imidazole derivatives. As alkyl radicals may be present residues of oil and tall oil fatty acids to octanoic acid.
Erfindungsgemäß wurde festgestellt, dass die vorgenannten Inhibitoren besonders effektiv sind, wenn diese in Kombination von Aminen und Carbonsäuren, jeweils insbesondere solchen der vorgenannten Art, vorliegen.According to the invention, it has been found that the abovementioned inhibitors are particularly effective if they are present in combination of amines and carboxylic acids, in each case in particular those of the abovementioned type.
Als weitere in der anmeldungsgemäßen Flüssigkeit enthaltenden Stoffe kann beispielsweise Stabilisator (zum Beispiel eine Cellulose) und/oder Dispergiermittel (zum Beispiel auf Acryl-Basis) in der Flüssigkeit enthalten sein.Stabilizers (for example a cellulose) and / or dispersants (for example based on acrylic) may be present in the liquid as further substances contained in the liquid according to the application.
Die anmeldungsgemäße Flüssigkeit kann zur Aufbereitung von Pulvermischungen auf der Basis von Hartmetallen verwendet werden, beispielsweise zur Aufbereitung von Carbiden des Titans, des Tantals und des Niobs. Insbesondere kann die anmeldungsgemäße Flüssigkeit zur Aufbereitung von Hartmetallen auf Monowolframcarbid-Basis und hier insbesondere zur Aufbereitung von Pulvermischungen auf Basis von Pulvern aus Monowolframcarbid und Cobalt verwendet werden.The liquid according to the application can be used for the preparation of powder mixtures based on hard metals, for example for the preparation of carbides of titanium, of tantalum and of niobium. In particular, the liquid according to the application can be used for the preparation of hard metals based on monotungsten carbide and here in particular for the preparation of powder mixtures based on powders of monotungsten carbide and cobalt.
Nach der Aufbereitung beziehungsweise der Mischung des Hartmetalls beziehungsweise der Hartmetall-Pulvermischung im Attritor kann die feuchte Pulvermischung dem Attritor entnommen und einem Trocknungsaggregat, beispielsweise einer Sprühtrocknungsanlage, zugeführt werden.After the preparation or the mixture of the hard metal or the hard metal powder mixture in the attritor, the moist Powder mixture removed from the attritor and a drying unit, such as a spray-drying system, are supplied.
In der Trocknungsanlage, beispielsweise einer Sprühtrocknungsanlage, wird die feuchte Mischung zu einem Granulat verdüst.In the drying plant, for example a spray-drying plant, the moist mixture is atomized to a granulate.
Das Granulat wird einem Formgebungsaggregat, üblicherweise einer Presse zugeführt und dort zum Formteil gepresst.The granules are fed to a shaping unit, usually a press, where they are pressed into the molded part.
Es wurde festgestellt, dass die Wachsemulsion, neben ihrer Eigenschaft als Inhibitor, gleichzeitig als hervorragendes Presshilfsmittel agiert, wodurch die Homogenität und Gründichte beziehungsweise -festigkeit des gepressten Formteils bei gleichem Pressdruck (im Vergleich zum Pressdruck beziehungsweise den Eigenschaften eines Formteils, das nach dem Stand der Technik aufbereitet wurde) erhöht ist beziehungsweise nur ein geringerer Pressdruck erforderlich ist, um beim Formteil die gleichen Eigenschaften zu erhalten, die es ohne die Verwendung einer Wachsemulsion in der Mahlflüssigkeit erhalten würde.It was found that the wax emulsion, in addition to its property as an inhibitor, simultaneously acts as an excellent pressing aid, whereby the homogeneity and green density of the pressed molded part at the same compacting pressure (compared to the pressing pressure or the properties of a molded part, according to the prior art Technique was prepared) is increased or only a lower pressing pressure is required to obtain the same properties in the molding that would be obtained without the use of a wax emulsion in the grinding fluid.
Das Formteil wird schließlich einer Wärmebehandlung unterzogen und dabei zum Hartmetall-Produkt gesintert.The molding is finally subjected to a heat treatment and thereby sintered to the cemented carbide product.
Die anmeldungsgemäße Flüssigkeit kann beispielsweise wie folgt zusammengesetzt sein (die nachfolgenden Angaben in Gewichts-%, soweit nicht anders angegeben, bezogen auf das Gesamtgewicht der Flüssigkeit):
- Wasser: 25-99 Gew.-%, also beispielsweise auch 68-98 Gew.-% oder 85-95 Gew.-%;
- Inhibitor: 1-75 Gew.-%, also beispielsweise auch 2-32 Gew.-% oder 5-15 Gew.-%;
- Weitere Stoffe: 0-50 Gew.-%.
- Water: 25-99 wt .-%, that is, for example, 68-98 wt .-% or 85-95 wt .-%;
- Inhibitor: 1-75% by weight, for example also 2-32% by weight or 5-15% by weight;
- Other substances: 0-50 wt .-%.
Inhibitor in Form von Polyvinyllactam kann beispielsweise in Anteilen von 0,5-50 Gew.-%, also beispielsweise auch in Anteilen von 1-10 Gew.-% oder 1-5 Gew.-% in der Flüssigkeit vorliegen.Inhibitor in the form of polyvinyllactam can be present, for example, in proportions of 0.5-50% by weight, that is to say, for example, in proportions of 1-10% by weight or 1-5% by weight in the liquid.
Inhibitor in Form einer Wachsemulsion kann beispielsweise in Anteilen von 0,5-66 Gew.-%, also beispielsweise auch in Anteilen von 1-25 Gew.-% oder von 2-15 Gew.-% in der Flüssigkeit vorliegen.Inhibitor in the form of a wax emulsion can be present for example in proportions of 0.5-66 wt .-%, that is, for example, in proportions of 1-25 wt .-% or 2-15 wt .-% in the liquid.
Carbonsäure kann beispielsweise in Anteilen von 0,1 bis 5 Gew.-%, also beispielsweise auch in Anteilen von 0,5 bis 4 Gew.-% in der Flüssigkeit vorliegen.Carboxylic acid, for example, in proportions of 0.1 to 5 wt .-%, that is, for example, in proportions of 0.5 to 4 wt .-% in the liquid.
Amine können beispielsweise in Anteilen von 0,1 bis 7 Gew.-%, also beispielsweise auch in Anteilen von 0,5 bis 5 Gew.-% in der Flüssigkeit vorliegen.Amines may, for example, in proportions of 0.1 to 7 wt .-%, that is, for example, in proportions of 0.5 to 5 wt .-% in the liquid.
Dispergiermittel kann beispielsweise in Anteilen von 0,01-33 Gew.-%, also beispielsweise auch in Anteilen von 0,1-5 Gew.-% oder von 0,5-3 Gew.-% in der Flüssigkeit vorliegen.Dispersant may, for example, in proportions of 0.01-33 wt .-%, that is, for example, in proportions of 0.1-5 wt .-% or 0.5-3 wt .-% in the liquid.
Stabilisator kann beispielsweise in Anteilen von 0,01-33 Gew.-%, also beispielsweise auch in Anteilen von 0,05-6 Gew.-% oder von 0,1-3 Gew.-% in der Flüssigkeit vorliegen.Stabilizer can be present for example in proportions of 0.01-33 wt .-%, that is, for example, in proportions of 0.05-6 wt .-% or of 0.1-3 wt .-% in the liquid.
Die anmeldungsgemäße Flüssigkeit kann beispielsweise mit der 3- bis 5-fachen Menge an WC/Co-Pulverteilchen zur feuchten Mischung gemischt werden.For example, the liquid according to the application can be mixed with 3 to 5 times the amount of WC / Co powder particles to form a moist mixture.
Nachfolgend werden drei Beispiele von Zusammensetzungen für eine anmeldungsgemäße Flüssigkeit angegeben:
- Beispiel 1:
- Wasser: 88,9 Gew.-%;
- Inhibitor in Form von Polyvinylpyrrolidon, 2000 kDalton: 2,2 Gew.-%;
- Inhibitor in Form einer 50%-igen Paraffinemulsion: 8,9 Gew.-%.
- Beispiel 2:
- Wasser: 88,5 Gew.-%;
- Inhibitor in Form von Polyvinylcaprolactam, 100 kDalton: 2,2 Gew.-%;
- Inhibitor in Form einer 50%-igen Ethylen-bis-stearoylamid-Emulsion: 8,8 Gew.-%;
- Stabilisator in Form von Methylcellulose: 0,4 Gew.-%.
- Beispiel 3:
- Wasser: 87,7 Gew.-%;
- Inhibitor in Form von Vinylpyrrolidon/vinylimidazol-Copolymer 70kDalton: 2,2 Gew.-%;
- Inhibitor in Form einer 50%-igen Polyethylenemulsion: 8,8 Gew.-%;
- Dispergiermittel in Form von Polyammoniumacrylat: 0,9 Gew.-%;
- Stabilisator in Form von Methylhydroxypropylcellulose: 0,4 Gew.-%.
- Beispiel 4:
- Wasser: 88,2 Gew.-%;
- Inhibitor in Form einer 50%-igen Polyethylenemulsion: 7,6 Gew.-%;
- Carbonsäure in Form von 1,10-Decandicarbonsäure: 2,1 Gew.-%;
- Amin in Form von Triethanolamin: 2,1 Gew.-%.
- Example 1:
- Water: 88.9% by weight;
- Inhibitor in the form of polyvinylpyrrolidone, 2000 kDalton: 2.2% by weight;
- Inhibitor in the form of a 50% paraffin emulsion: 8.9% by weight.
- Example 2:
- Water: 88.5% by weight;
- Inhibitor in the form of polyvinylcaprolactam, 100 kDalton: 2.2% by weight;
- Inhibitor in the form of a 50% ethylene-bis-stearoylamide emulsion: 8.8% by weight;
- Stabilizer in the form of methylcellulose: 0.4% by weight.
- Example 3:
- Water: 87.7% by weight;
- Inhibitor in the form of vinylpyrrolidone / vinylimidazole copolymer 70kDalton: 2.2% by weight;
- Inhibitor in the form of a 50% polyethylene emulsion: 8.8% by weight;
- Dispersant in the form of polyammonium acrylate: 0.9% by weight;
- Stabilizer in the form of methylhydroxypropylcellulose: 0.4% by weight.
- Example 4:
- Water: 88.2% by weight;
- Inhibitor in the form of a 50% polyethylene emulsion: 7.6% by weight;
- Carboxylic acid in the form of 1,10-decanedicarboxylic acid: 2.1% by weight;
- Amine in the form of triethanolamine: 2.1% by weight.
In der feuchten Pulvermischung aus der anmeldungsgemäßen Flüssigkeit und der WC/Co-Pulvermischung können neben 100 Gew.-% WC- und Co-Partikeln beispielsweisezusätzlich die folgenden Teile an den Komponenten der Flüssigkeit vorliegen:
- 10-200 Gew.-%, also beispielsweise auch 15-70 oder 15-40 Gew.-% Wasser, bevorzugt deionisiertes Wasser und
- 0,01-30 Gew.-%, also beispielsweise auch 0,1-20 oder 1-7 Gew.-% Inhibitor in Form von Polyvinyllactam und/oder Wachsemulsion;
- 0-10 Gew.-% weitere Stoffe.
- 10-200 wt .-%, that is, for example, 15-70 or 15-40 wt .-% water, preferably deionized water and
- 0.01-30% by weight, for example also 0.1-20 or 1-7% by weight inhibitor in the form of polyvinyl lactam and / or wax emulsion;
- 0-10% by weight of other substances.
Inhibitor in Form von Polyvinyllactam kann neben den 100 Gew.-% WC- und Co-Partikeln beispielsweise zusätzlich mit 0,01-10 Gew.-%, also beispielsweise auch mit 0,1-2 Gew.-% in der feuchten Mischung enthalten sein. Inhibitor in Form von Wachsemulsion kann neben den 100 Gew.-% WC- und Co-Partikeln beispielsweise zusätzlich mit 0,1-20 Gew.-%, also beispielsweise auch mit 1-5 Gew.-% in der feuchten Mischung enthalten sein.Inhibitor in the form of polyvinyl lactam, in addition to the 100 wt .-% WC and Co-particles, for example, additionally with 0.01-10 wt .-%, that is, for example, also be contained with 0.1-2 wt .-% in the wet mixture. Inhibitor in the form of wax emulsion, in addition to the 100 wt .-% WC and Co particles, for example, in addition to 0.1-20 wt .-%, that is, for example, 1-5 wt .-% in the wet mixture.
Neben den 100 Gew.-% WC- und Co-Partikeln und den vorgenannten Komponenten können in der feuchten Mischung beispielsweise 0,01-5 Gew.-%, also beispielsweise auch 0,1-0,8 Gew.-% Dispergiermittel und/oder beispielsweise 0,01-5 Gew.-%, also beispielsweise auch 0,05-0,5 Gew.-% Stabilisator vorliegen.In addition to the 100% by weight of WC and Co particles and the abovementioned components, it is possible for example in the moist mixture to contain 0.01-5% by weight, that is to say also 0.1-0.8% by weight of dispersant and / or or, for example, 0.01-5 wt .-%, that is, for example, 0.05-0.5 wt .-% stabilizer present.
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DE102004053221A DE102004053221B3 (en) | 2004-11-04 | 2004-11-04 | Liquid and its use for the treatment of hard metals |
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DE102006043498A1 (en) * | 2006-09-12 | 2008-03-27 | Artur Wiegand | Dispersing machine and its use for the production of powder mixtures |
DE102006043581B4 (en) * | 2006-09-12 | 2011-11-03 | Artur Wiegand | Method and device for producing a cemented carbide or cermet mixture |
US9475945B2 (en) * | 2013-10-03 | 2016-10-25 | Kennametal Inc. | Aqueous slurry for making a powder of hard material |
IN2013CH04500A (en) | 2013-10-04 | 2015-04-10 | Kennametal India Ltd | |
WO2016049257A1 (en) | 2014-09-26 | 2016-03-31 | Henry Company, Llc | Powders from wax-based colloidal dispersions and their process of making |
WO2016070012A1 (en) | 2014-10-30 | 2016-05-06 | Henry Company, Llc | Phase-change materials from wax-based colloidal dispersions and their process of making |
WO2016094719A1 (en) | 2014-12-11 | 2016-06-16 | Henry Company, Llc | Phase-change materials from wax-based colloidal dispersions and their process of making |
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US7531022B2 (en) | 2009-05-12 |
DE102004053221B3 (en) | 2006-02-02 |
DE502005002035D1 (en) | 2008-01-03 |
EP1666616B1 (en) | 2007-11-21 |
US20060091579A1 (en) | 2006-05-04 |
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