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US20100077887A1 - Metal formulations - Google Patents

Metal formulations Download PDF

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Publication number
US20100077887A1
US20100077887A1 US12/524,600 US52460008A US2010077887A1 US 20100077887 A1 US20100077887 A1 US 20100077887A1 US 52460008 A US52460008 A US 52460008A US 2010077887 A1 US2010077887 A1 US 2010077887A1
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Prior art keywords
cobalt
powders
powder
binder
elements
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Inventor
Frank Schrumpf
Benno Gries
Kai-Uwe Clauswitz
Bernd Mende
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HC Starck GmbH
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HC Starck GmbH
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Assigned to H.C. STARCK GMBH reassignment H.C. STARCK GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MENDE, BERND, SCHRUMPF, FRANK, GRIES, BENNO, CLAUSWITZ, KAI-UWE
Publication of US20100077887A1 publication Critical patent/US20100077887A1/en
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/067—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds comprising a particular metallic binder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/067—Metallic material containing free particles of non-metal elements, e.g. carbon, silicon, boron, phosphorus or arsenic
    • 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
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy

Definitions

  • Formulations comprising pulverulent hard materials and pulverulent binder metals are used industrially to produce, inter alia, cemented hard materials or spray powders for surface coating.
  • carbides by far the most frequently used carbide is tungsten carbide; others such as titanium, vanadium, chromium, tantalum and niobium carbide or their mixtures with one another or with tungsten carbide are usually used only as additives. It is also possible to use nitrides.
  • Cobalt is by far the most frequently used binder metal, but binder systems comprising 2 or 3 elements from among Fe, Co and Ni are also used; in spray powders also, for example, Mn, Al, Cr.
  • inorganic additives are metal powders such as tungsten, molybdenum, and also elemental carbon. If cemented hard material contains titanium carbonitride instead of tungsten carbide as main component, it is referred to as “cermet”. Further possible hard materials are borides.
  • binder metal in cemented hard materials and spray powders use is usually made of cobalt, but nickel or an alloy of Fe, Co and Ni can also be used.
  • the binder phase after sintering or thermal spraying contains proportions of, for example, tungsten, chromium, molybdenum and carbon derived from the hard material as a result of exchange of elements with the carbide phase in liquid-phase sintering or fusion.
  • Pulverulent binder metals used are either element powders such as iron, nickel or cobalt powders or else alloy powders.
  • the binder phase of spray powders can comprise not only the abovementioned elements and inorganic additives but also other elements such as Al, rare earths, yttrium.
  • cemented hard materials industry Over the decades, a statistically significant increased occurrence of pulmonary fibrosis having a specific appearance pattern has been observed in the cemented hard materials industry and has been associated with handling dust-like cemented hard material or handling dust-like formulations for producing cemented hard material.
  • the disease is also referred to as “cemented carbide lung” and was and is subject matter of numerous epidemiological studies and publications.
  • respirable dusts are set free due to the nature of the process. If the cemented hard material is machined by grinding in the sintered or presintered state, very fine, respirable dusts (“grinding dusts”) are likewise formed.
  • This object is achieved by a formulation comprising at least one hard material powder and at least 2 binder metal powders, characterized in that all the cobalt is present in the first binder metal powder and is prealloyed with one or more elements of groups 3 to 8 of the Periodic Table of the Elements and at least one further binder metal powder from the group consisting of powders of the elements Fe, Ni, Al, Mn, Cr and alloys of these elements with one another is present and the further binder metal powders do not contain any cobalt in unprealloyed form.
  • cobalt as binder metal in hard material/binder formulations loses its inhalation toxicity when it is prealloyed with iron or another element of groups 3 to 8 (transition groups IIIa to VIIIa) of the Periodic Table of the Elements, but not when these are present in unalloyed form alongside the cobalt.
  • all metals which are positioned to the left of cobalt in the Periodic Table and are preferably located in the same period produce a reduction in the corrosion tendency as a result of their less noble character while elements which are more noble, for example copper, have the opposite effect, which can even be confirmed in the case of alloyed-in copper which is present as an additional phase.
  • the alloying partner of cobalt in the first binder metal powder is advantageously an element of the fourth period and of groups 3 to 8 of the Periodic Table.
  • the alloying partner of cobalt in the first binder metal powder is particularly advantageously an element selected from the group consisting of Fe, Ni, Cr, Mn, Ti and Al.
  • the first binder metal powder can also contain further elements such as aluminium and/or copper.
  • binder metal powder Apart from the first binder metal powder, further binder metals are usually necessary. These are particularly advantageously selected from the group consisting of iron powders, nickel powders, FeNi alloy powders and prealloyed FeNi alloy powders.
  • the hard material is usually titanium carbide, vanadium carbide, molybdenum carbide, tungsten carbide or a mixture of these with one another.
  • These compounds are also known as catalysts for the reduction of oxygen and thus as catalysts for the oxidation of metals in aqueous media by the mechanism of oxygen reduction:
  • the at least one further added metal powder can contain Fe, Ni and, for example, further elements such as Al, Cr, Mn, Nb, Ta, Ti, but no cobalt except in the range of unavoidable and unintended impurities.
  • the first, cobalt-containing and completely alloyed binder metal powder preferably contains from 10% by weight to 50% by weight of cobalt. Particular preference is given to a ratio of iron to cobalt of 1:1 or more. Suitable compositions are, for example, FeCo 50/50, FeCoNi 90/5/5. This powder can additionally contain further elements of the iron group.
  • the further binder metal powder or powders which do not contain any cobalt in unprealloyed form is/are preferably iron- or nickel-based, i.e. the sum of the content of iron and nickel is at least 50%.
  • the remainder of the further powder or powders comprises a total of at least 50% of iron and nickel.
  • alloy powders of the composition for example, FeNi powders containing up to 30% of Fe, FeNi 50/50, FeNi 95/5.
  • the weight ratio of the first binder metal powder to the further powder or powders is preferably from 1:10 to 10:1, but particularly preferably from 1:5 to 5:1.
  • a person skilled in the art can choose the required ratios on the basis of the desired stoichiometry and the alloy powders available.
  • the further binder metal powders advantageously have a BET surface area of greater than 0.3 m 2 /g, more advantageously greater than 0.5 m 2 /g, in particular greater than 1 m 2 /g.
  • prealloyed powders which contain two or more elements from the group consisting of Fe, Co, Ni and represent the composition of the binder phase in respect of these elements is prior art as is the use of two or three element powders for producing this formulation. While the latter variant does not reduce the toxicity, the toxicity is reduced or eliminated by complete alloying of the binder system.
  • Such alloy powders from hydrogen reduction of oxides or other compounds are commercially available, but have considerable disadvantages compared to the element powders, for example higher oxygen contents and poor pressability.
  • Ni and Fe powders in particular can be produced by the carbonyl process and achieve very low oxygen contents since the reduction potential of carbon monoxide is greater than that of the hydrogen which is usually employed for producing fine alloy powders having specific surface areas of greater than 1 m 2 /g.
  • compositions which are obtained by a process for producing a hard material/binder mixture by use of a) at least one prealloyed powder selected from the group consisting of iron/cobalt and iron/nickel/cobalt; b) at least one element powder selected from the group consisting of iron and nickel or a prealloyed powder selected from the group consisting of iron/nickel which is different from component a); c) hard material powder, where the overall composition of the components a) and b) together contains a maximum of 90% of cobalt and a maximum of 70% by weight of nickel.
  • the iron content is advantageously at least 10% by weight.
  • the overall composition of the binder is max. 90% by weight of Co, max. 70% by weight of Ni and at least 10% by weight of Fe, where the iron content satisfies the inequality
  • one binder powder is lower in iron than the overall composition of the binder and the other binder powder is richer in iron than the overall composition of the binder and at least one binder powder is prealloyed from at least two elements selected from the group consisting of iron, nickel and cobalt.
  • Table 2 shows 54 formulations having the numbers 2.01 to 2.54 whose first binder metal powder, further binder metal powder and ratios of the alloy elements of the first binder metal powder and the second binder metal powder are identical to those of Table 1, with the first binder metal powder and the further binder metal powder being present in a ratio of 1:2.
  • the first alloy powder is FeCo 50/50
  • the further alloy powder is FeNi 30/70
  • the ratio of FeCo to FeNi is 1:2.
  • Table 3 shows 54 formulations having the numbers 3.01 to 3.54 whose first binder metal powder, further binder metal powder and ratios of the alloy elements of the first binder metal powder and the second binder metal powder are identical to those of Table 1, with the first binder metal powder and the further binder metal powder being present in a ratio of 2:1.
  • the first alloy powder is FeCo 50/50
  • the further alloy powder is FeNi 30/70
  • the ratio of FeCo to FeNi is 2:1.
  • the present invention therefore provides metal formulations comprising at least one hard material powder and at least 2 binder metal powders, characterized in that all the cobalt is present in the first binder metal powder and is prealloyed with one or more elements of groups 3 to 8 of the Periodic Table of the Elements which are elements of the fourth period and at least one further binder metal powder from the group consisting of powders of the elements Fe, Ni, Al, Mn, Cr and alloys of these elements with one another is present and the further binder metal powders do not contain any cobalt in unprealloyed form;
  • metal formulations comprising at least one hard material powder and at least 2 binder metal powders, characterized in that all the cobalt is present in the first binder metal powder and is prealloyed with one or more elements of groups 3 to 8 of the Periodic Table of the Elements and at least one further binder metal powder from the group consisting of powders of the elements Fe, Ni, Al, Mn, Cr and alloys of these elements with one another is present and the further binder metal powders do not contain any cobalt in unprealloyed form, where the free corrosion potential between the hard material and the first binder metal powder, measured in air-saturated water at atmospheric pressure and room temperature, is less than 0.300 volt (preferably less than 0.280 volt), with the hard material having the positive polarity; or metal formulations comprising at least one hard material powder and at least 2 binder metal powders, characterized in that all the cobalt is present in the first binder metal powder and is prealloyed with one or more elements of groups 3 to 8 of the Periodic Table of the Elements and at
  • the hard material present can be, in particular, titanium carbide, vanadium carbide, molybdenum carbide or tungsten carbide, which advantageously has a BET surface area of greater than 0.3 m 2 /g, preferably greater than 0.5 m 2 /g, particularly preferably greater than 1 m 2 /g.
  • the alloying partner of the cobalt in the first binder metal powder in the above metal formulations is an element of the fourth period
  • the alloying partner of the cobalt in the first binder metal powder in the above metal formulations is an element selected from the group consisting of Fe, Ni, Cr, Mn, Ti and Al; or the first binder metal powder in the above metal formulations can contain further alloyed elements, with aluminium and/or copper (Cu) being able to be used as further elements.
  • one or more further binder metal powders selected from the group consisting of iron powders, nickel powders, FeNi alloy powders and prealloyed FeNi alloy powders are present in addition to the first binder metal powder.
  • the free corrosion potential between the hard material and the first binder metal powder measured in air-saturated water at atmospheric pressure and room temperature, is less than 0.300 volt, with the hard material having the positive polarity.
  • Hard materials which can be present are, in particular, titanium carbide, vanadium carbide, molybdenum carbide or tungsten carbide, which advantageously have a BET surface area of greater than 0.3 m 2 /g, preferably greater than 0.5 m 2 /g, particularly preferably greater than 1 m 2 /g.
  • the weight ratio of the first binder metal powder to the further binder metal powder or powders is advantageously from 1:10 to 10:1.
  • All such metal formulations can advantageously contain: a) at least one prealloyed powder selected from the group consisting of iron/cobalt and iron/nickel/cobalt; b) at least one element powder selected from the group consisting of iron and nickel or a prealloyed powder comprising iron and nickel which is different from component a); c) hard material powder, where the overall composition of the components a) and b) together contains a maximum of 90% of cobalt and a maximum of 70% by weight of nickel.
  • the iron content is advantageously at least 10% by weight.
  • the overall composition of the binder is advantageously max. 90% by weight of Co, max. 70% by weight of Ni, and at least 10% by weight of Fe, where the iron content satisfies the inequality
  • At least two binder powders of which one binder powder is lower in iron than the overall composition of the binder and the other binder powder is richer in iron than the overall composition of the binder and at least one binder powder is prealloyed from at least two elements selected from the group consisting of iron, nickel and cobalt are used.
  • Such metal formulations are advantageous for various applications and such metal formulations can be used for producing cemented hard material or for producing porous sintered agglomerates.
  • Such a porous agglomerate can be obtained by sintering without pressing of one of the above metal formulations.
  • Thermal spray powders containing such a porous agglomerate which can be obtained by sintering without pressing of one of the above metal formulations and contains Al, yttrium and/or rare earths are also suitable.
  • the present invention further provides a method of controlling the toxic effect of cobalt-containing metal formulations, characterized in that one of the above metal formulations, advantageously metal formulations as shown in Tables 1 to 3, is used for producing cemented hard material or porous sintered agglomerates.
  • the present invention provides a method of controlling the toxic effect of cobalt-containing metal formulations, which is characterized in that the cobalt is prealloyed with one or more elements of groups 3 to 8 of the Periodic Table of the Elements in the metal formulation.
  • the present invention therefore also provides a method of controlling the toxic effect of cobalt-containing metal formulations, in which a metal formulation according to the invention, a porous agglomerate according to the invention or a thermal spray powder according to the invention is used for producing shaped bodies or coatings.
  • the toxicological effect is, in particular, pulmonary fibrosis and/or the disease cemented carbide lung.
  • the free corrosion potential between the hard material and the first binder metal powder, measured in air-saturated water at atmospheric pressure and room temperature, is, according to the invention, less than 0.380 volt, preferably less than 0.330 volt, in particular less than 0.300 and very particularly advantageously less than 0.280 volt, with tungsten carbide having the positive polarity.
  • FIG. 1 schematically shows the experimental set-up used.
  • Reference numeral 1 denotes the positive electrode composed of tungsten carbide (or another hard material)
  • 2 denotes the negative electrode composed of the binder metal, for example cobalt or the binder metal formulation according to the invention
  • 3 denotes the reaction medium, air-saturated tap water.
  • the contact voltage surprisingly decreases when the cobalt is alloyed with iron, even though iron is less noble than cobalt.
  • the reason for this phenomenon is not known. It is easy to see that the decreasing free corrosion potential results in the driving force of the corrosion phenomenon decreasing or corrosion proceeding more slowly, and the bioavailability likewise decreasing.
  • the free corrosion potential of the measurement set-up described in Example 4 can therefore serve as an indicator of the inhalation toxicity of a hard material/binder metal formulation which is to be expected.
  • a further indicator of the inhalation toxicity to be expected is the amount of dissolved binder metal which goes into solution as soon as a corresponding contact element is in contact with water in the presence of oxygen over a defined period of time.
  • the corrosion resistance which is determined by the chemical attack on the binder, can be improved by adding Cr carbide or Cr metal to the formulation.
  • the Cr is partly present in alloyed form in the binder after sintering or thermal spraying. If the Cr concentration in the binder is sufficiently high, which can be controlled by means of the carbon balance, the cemented hard material or the spray layer is then considerably more corrosion resistant, from which it can be concluded that the dust in the case of grinding such cemented hard materials or the overspray has to be significantly less toxic than pure WC—Co.
  • a further improvement in the corrosion resistance can be achieved by partial replacement of the cobalt by nickel, which is likewise industrial practice in the case of cemented hard material.
  • the acute toxic action of cemented hard material dusts can be correlated with the corrosion rates in the presence of water and oxygen.
  • the free corrosion potential can be reduced by alloying the cobalt with, for example, iron, as a result of which a cobalt-containing formulation in which the cobalt is prealloyed with iron is significantly less acutely inhalation toxic.
  • cemented hard material will be particularly inhalation toxic, including, in particular, the dust from the grinding machining of presintered cemented hard material parts (“grey machining”).
  • grey machining presintered cemented hard material parts
  • the formulation is pressed and sintered at a temperature below the melt eutectic (“presintering”) so that sufficient mechanical strength for the sintered body to be machined by grinding is obtained as a result of sinter bridges.
  • the sintered body is still porous, no longer contains any organic additives and the powders used have not yet equilibrated in the formulation, so that cobalt is still largely present in elemental form.
  • This combined with the porous structure of the grinding dust means that a very high inhalation toxicity is to be expected.
  • Spray powders sintered from granulated formulations are difficult to disperse in air because of their size, but the respirable fines formed as a result of internal friction during handling of the powders are very toxic (see Example 1e).
  • the formulations according to the invention can, for example, be used for producing cemented hard material or porous sintered agglomerates, with the porous sintered agglomerates being able to be advantageously used in thermal spray powders.
  • Cemented hard materials having binder systems based on FeCoNi offer, depending on the composition, technical advantages over purely cobalt-bonded materials in many applications and are therefore advantageous according to the invention.
  • Prealloyed powder is, according to the invention, a metal powder which contains the composition of the binder in respect of the Fe, Co and Ni contents in atomically dispersed form in each powder particle.
  • Prealloyed powders within the meaning of the invention can be alloy powders atomized from the melt or alloy powders obtainable by precipitation and reduction, for example as described in U.S. Pat. No. 6,554,885, EP-A-1079950 and the documents cited there, or be produced by other processes which are suitable in principle, e.g. carbonyl processes, plasma processes, CVD, etc., with alloy powders obtainable by precipitation and reduction, for example as described in U.S. Pat. No. 6,554,885, EP-A-1079950 and the documents cited there, being advantageous.
  • carbidic spray powders corresponds to the production of the granulated formulation in the production of cemented hard materials, but the granules are not pressed but instead sintered as such at temperatures either below or slightly above the lowest eutectic temperature and then classified.
  • the organic additives present are removed in the step.
  • the particles obtained in this way are still porous and have sinter necks between the particles representing the binder metal phase and the hard materials.
  • Spray powders can contain other elements such as Al, rare earths, yttrium, in addition to the abovementioned elements and inorganic additives in the binder phase.
  • Formulations for producing cemented hard materials and spray powders usually contain not only the abovementioned inorganic constituents but also organic additives such as paraffins, polyethylene glycols, inhibitors, which aid further processing and handling but are no longer present in the cemented hard material or after ignition in the spray powder. These formulations can have been granulated, e.g. by spray drying. It is also possible for plasticizers as are used in extrusion, for example polyethylenes and paraffin waxes, and bonding agents such as carboxylic acids and dispersants to be present.
  • Example a The highest toxicity is shown by Example a). Due to the way in which it is produced, it gives a maximum measure of contacts between the cobalt particles and the tungsten carbide particles.
  • Example b which as a powder mixture has far fewer contacts between cobalt particles and WC particles, is less toxic.
  • Example c) likewise displays, as a powder mixture but with a reduced cobalt content, a once again reduced effect.
  • Example d carried out using 2 concentrations, shows a further reduced toxic effect. Since the contact between the cobalt particles and the tungsten carbide particles would be very intensive due to the attritor milling, the reduced toxicity is attributed to hydrophobicization by the paraffin wax present (2% by weight corresponding to 25% by volume).
  • Example e shows the toxicity of a typical powder for thermal spraying. It should be noted here that only part of the powder can get into the lungs because of the comparatively coarse particles but a significant mortality nevertheless occurs.
  • Example a As a typical industrial grinding dust from final machining by grinding of cemented carbide, Example a) displays a comparatively very high toxicity.
  • the iron content of 12% is due to abrasion of grinding disks and other contamination, but not to final machining of cemented carbides having an iron-containing binder system.
  • the iron content is thus not prealloyed with the cobalt content.
  • This grinding dust is not a formulation within the meaning of the invention, since it has not been produced in a targeted manner and the cobalt content is not prealloyed with iron.
  • Example b produced using element powders Fe and Co, displays a toxicity of a similar order of magnitude to that of an attritor-milled formulation containing 5% of Co without further additives.
  • Example c) does not display any toxicity, even at 5 mg/l, although in this case the contact between the WC particles and the prealloyed FeCo particles is just as intensive as in Example 1a) and the composite was produced analogously.
  • Tungsten carbide powder was hot pressed at 2200° C. in a hot press to produce a solid body having a density of 15.68 g/cm 3 , which corresponds to the theoretical density.
  • cobalt metal powder and a prealloyed iron-cobalt metal powder were pressed at 1000° C. to give dense bodies having virtually the theoretical density.
  • the contact voltage of the electrochemical couple tungsten carbide/cobalt was measured by providing two solid pieces with power outlet electrodes for measuring the contact voltage and dipping this arrangement partly into air-saturated tap water.
  • the measurement was repeated with the cobalt piece being replaced by that produced from FeCo.
  • the measured value for the free corrosion potential was then 0.240 volt with the polarity being preserved.
  • a difference of 0.007 mV was measured, with reversal of the polarity occurring.
  • Example 4 demonstrates that the contact voltage or free corrosion potential between WC and cobalt, which according to the laws of electrochemistry which are known to those skilled in the art depends critically on the concentration of molecular oxygen in the water, makes an appreciable contribution.
  • the 0.33 V measured here compare well with the value of Mori et al. of from 0.301 to 0.384 V (R&HM 21, 135 (2003)) obtained from potentiometric measurements on cemented carbides.
  • the contact voltage surprisingly drops when the cobalt is alloyed with iron, although iron is less noble than cobalt. The reason for this phenomenon is not known. It can easily be seen that the decreasing free corrosion potential results in the driving force of the corrosion phenomenon decreasing or corrosion proceeding more slowly and the bioavailability likewise decreasing.
  • the free corrosion potential of the measurement set-up described in Example 4 can therefore serve as an indicator of the inhalation toxicity of a hard material/binder metal formulation which is to be expected.
  • a further indicator of the inhalation toxicity to be expected is the amount of dissolved binder metal which goes into solution as soon as a corresponding contact element is in contact with water in the presence of oxygen over a defined period of time.
  • FIG. 2 shows the aerosol concentrations plotted against the mortality rates and assigned to the examples.

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DE102007004937A DE102007004937B4 (de) 2007-01-26 2007-01-26 Metallformulierungen
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US9919358B2 (en) 2013-10-02 2018-03-20 H.C. Starck Gmbh Sintered molybdenum carbide-based spray powder

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DE102011112435B3 (de) * 2011-09-06 2012-10-25 H.C. Starck Gmbh Cermetpulver, Verfahren zur Herstellung eines Cermetpulvers, Verwendung der Cermetpulver, Verfahren zur Herstellung eines beschichteten Bauteils, Beschichtetes Bauteil
CN104400080B (zh) * 2014-09-23 2017-04-05 宁波市荣科迈特数控刀具有限公司 一种深孔钻
CN104625078B (zh) * 2015-02-14 2018-01-09 江苏和鹰机电科技有限公司 用于切削碳纤维或玻璃纤维的硬质合金刀具及其制备方法
CN104831216A (zh) * 2015-05-09 2015-08-12 芜湖鼎恒材料技术有限公司 一种Ni-Co-Mo-Mn纳米涂层材料及其制备方法
CN104831213A (zh) * 2015-05-09 2015-08-12 安徽鼎恒再制造产业技术研究院有限公司 一种Ni-Co-Mo-Mn材料及其制备方法
KR20190021816A (ko) * 2017-08-24 2019-03-06 주식회사 포스코 금속합금 분말과 그 제조방법
EP3748025A4 (de) * 2018-01-31 2021-10-27 Hitachi Metals, Ltd. Hartmetall und hartmetall-verbundwalze zum walzen
CN109280838B (zh) * 2018-11-30 2020-11-06 宇龙精机科技（浙江）有限公司 一种钛钴合金及其制备方法
CN111826569A (zh) * 2020-07-21 2020-10-27 广东正信硬质材料技术研发有限公司 一种耐磨高硬度硬质合金钻具及其制备方法

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US11207730B2 (en) 2011-05-27 2021-12-28 Höganäs Germany GmbH FeNi binder having universal usability
US9919358B2 (en) 2013-10-02 2018-03-20 H.C. Starck Gmbh Sintered molybdenum carbide-based spray powder

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CN101589166B (zh) 2013-06-26
MX2009007484A (es) 2009-07-22
WO2008090208A1 (de) 2008-07-31
EP2126148A1 (de) 2009-12-02
ZA200904268B (en) 2010-08-25
DE102007004937A1 (de) 2008-07-31
DE102007004937B4 (de) 2008-10-23
RU2009132002A (ru) 2011-03-10
JP2010516896A (ja) 2010-05-20
RU2483833C2 (ru) 2013-06-10
BRPI0807178A2 (pt) 2014-05-27
CA2674928A1 (en) 2008-07-31
KR20090107554A (ko) 2009-10-13
CN101589166A (zh) 2009-11-25

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