EP3041631A2 - Chromium metal powder - Google Patents

Chromium metal powder

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Publication number
EP3041631A2
EP3041631A2 EP14789128.7A EP14789128A EP3041631A2 EP 3041631 A2 EP3041631 A2 EP 3041631A2 EP 14789128 A EP14789128 A EP 14789128A EP 3041631 A2 EP3041631 A2 EP 3041631A2
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EP
European Patent Office
Prior art keywords
metal powder
mpa
chromium
powder
pressure
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
Application number
EP14789128.7A
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German (de)
French (fr)
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EP3041631B1 (en
Inventor
Michael O'sullivan
Lorenz Sigl
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Plansee SE
Original Assignee
Plansee SE
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Publication of EP3041631A2 publication Critical patent/EP3041631A2/en
Application granted granted Critical
Publication of EP3041631B1 publication Critical patent/EP3041631B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
    • C22B34/32—Obtaining chromium
    • 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
    • C22C1/045—Alloys based on refractory metals
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61H—PHYSICAL THERAPY APPARATUS, e.g. DEVICES FOR LOCATING OR STIMULATING REFLEX POINTS IN THE BODY; ARTIFICIAL RESPIRATION; MASSAGE; BATHING DEVICES FOR SPECIAL THERAPEUTIC OR HYGIENIC PURPOSES OR SPECIFIC PARTS OF THE BODY
    • A61H33/00—Bathing devices for special therapeutic or hygienic purposes
    • A61H33/06—Artificial hot-air or cold-air baths; Steam or gas baths or douches, e.g. sauna or Finnish baths
    • A61H33/063—Heaters specifically designed therefor
    • A61H33/065—Heaters specifically designed therefor with steam generators
    • 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
    • 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
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/06—Alloys based on chromium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C37/00—Cast-iron alloys
    • C22C37/06—Cast-iron alloys containing chromium
    • 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
    • B22F2201/00—Treatment under specific atmosphere
    • B22F2201/01—Reducing atmosphere
    • B22F2201/013—Hydrogen
    • 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
    • B22F2202/00—Treatment under specific physical conditions
    • 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
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/20—Refractory metals

Definitions

  • the present invention relates to a metal powder having a chromium content of at least 90% by mass and a process for its production.
  • the large-scale production of chromium metal powder from chromium oxides is currently only by aluminothermic (powder morphology see Figure 1) and electrolytic (powder morphology see Figure 2) method.
  • powders produced in this way have a poor pressing and sintering behavior.
  • electrolytic processes are environmentally harmful.
  • Increasingly stringent environmental regulations mean that this process is hardly acceptable economically and environmentally.
  • the present invention has therefore set itself the task of providing metal powder having a chromium content of at least 90% by mass, which can be processed well powder metallurgy, in particular by pressing and sintering.
  • a metal powder is to be provided with which complex-shaped and / or thin-walled components can be produced in a simple manner by powder metallurgy.
  • the metal powder should further be produced in a high metallic purity, in particular a metallic purity comparable or better than metal powder, which is obtained by electrolytic route.
  • the object is achieved by metal powder with a chromium content of at least 90% by mass, which is measured by a nanohardness of 0.005 / 5/1/5 EN ISO 14577-1 (2002 edition - Berkovich indenters and Oliver and Pharr's method) of ⁇ 4 GPa.
  • the hardness value refers to a metal powder, which is preferably subjected to no further treatment, such as an annealing.
  • the nanohardness HIT is preferably 0.005 / 5/1/5 ⁇ 3.7 GPa, more preferably ⁇ 3.4 GPa. For very high requirements, for example for very thin-walled components, a nanohardness HIT 0.005 / 5/1/5 of ⁇ 3, 1 GPa has proven itself.
  • a nanohardness of 0.005 / 5/1/5 of about 1.4 GPa can be realized.
  • the nanohardness is determined in the pure chromium phase. If there is no pure chromium phase, the nanohardness is determined in the chromium-rich (phase with the highest chromium content) phase.
  • the metal powder according to the invention thus has a significantly lower nanohardness compared with the nanohards of metal powder according to the prior art. Since the powder according to the invention can be produced without a downstream milling process, the specified nanohardness can be achieved even with very fine-grained powder having a BET surface area of preferably> 0.05 m 2 / g.
  • the information on the BET surface area in the context of this application relates to a BET measurement according to the standard (ISO 9277: 1995, measuring range: 0.01-300 m 2 / g, device: Gemini II 2370, baking temperature: 130 ° C., heating time : 2 hours, adsorptive: nitrogen, volumetric evaluation by five-point determination).
  • the object is further achieved by a metal powder having a chromium content of at least 90% by mass, which is determined by a green strength according to ASTM B 312-09 at a pressure of 550 MPa of at least 7 MPa, preferably at least 10 MPa, more preferably of at least 15 MPa , particularly particularly preferably of at least 20 MPa.
  • a metal powder having a chromium content of at least 90% by mass which is determined by a green strength according to ASTM B 312-09 at a pressure of 550 MPa of at least 7 MPa, preferably at least 10 MPa, more preferably of at least 15 MPa , particularly particularly preferably of at least 20 MPa.
  • metal powders having a green strength of up to about 50 MPa can be produced at a pressure of 550 MPa.
  • the ASTM B 312-09 leaves open whether a wax is used as pressing additive.
  • a wax was used as pressing additive, namely 0.6% by mass of an amide wax, namely LICOWAX® Micropowder
  • the green strength preferably has the following values: at least 8 MPa, preferably at least 13 MPa, at a compression pressure of 450 MPa; at least 6 MPa, preferably at least 1 1 MPa, at a compression pressure of 300 MPa; at least 4 MPa, preferably at least 6 MPa, at one Compressing pressure of 250 MPa and at least 2 MPa, preferably at least 2.5 MPa, at a pressure of 150 MPa.
  • Green strengths could be achieved at pressures of 450, 300 and 250 MPa of 18.5, 13.0 and 7.5 MPa and above.
  • the metal powder according to the invention can be processed in a simple manner by powder metallurgy, for example by pressing and sintering.
  • the metal powder according to the invention enables the simple and cost-effective production of powder metallurgy components with thin-walled areas, complex shape or relatively unfavorable pressing ratio.
  • the properties with regard to nanohardness and green strength can be achieved if the chromium content is at least 90% by mass and thus the content of other substances of 10% by mass is not exceeded.
  • the other substances are present in an advantageous manner separated from the chromium phase.
  • the other substance can be deposited in metallic or non-metallic form, preferably via a diffusion bond. Such powders are referred to as composite powder. Shares (advantageously ⁇ 5% by mass) of the other substance can also be dissolved in the chromium and form a chromium mixed crystal. Such powders are referred to as alloyed powders.
  • the metal powder then comprises a pure chromium phase and / or a chromium mixed crystal phase.
  • La 2 O 3 (up to 5 Ma%) or Cu (up to a maximum of 10 Ma%) may be mentioned, in the case of La 2 0 3 La (OH) 3 and in the case of Cu CuO mixed to form Cr 2 O 3 and the reduction are supplied.
  • La 2 O 3 up to 5 Ma%
  • Cu up to a maximum of 10 Ma%
  • other metals or non-metals are possible.
  • the metal powder preferably has both a green strength at a compacting pressure of 550 MPa of at least 7 MPa, preferably at least 10 MPa, more preferably of at least 15 MPa, particularly preferably of at least 20 MPa, and a nano-hardness HIT of 0.005 / 5/1/5 of ⁇ 4 GPa, preferably ⁇ 3.7 GPa, more preferably ⁇ 3.4 GPa, most preferably ⁇ 3, 1 GPa.
  • the metal powder according to the invention preferably has a sponge-like particle shape Z morphology (division of the particle shape / morphology see Powder Metallurgy Science; Randall M. German; MPIF; Princeton, 1994, second edition, page 63). This has a favorable effect on the green strength.
  • the metal powder has a BET surface without surface enlarging process of> 0.05 m 2 / g.
  • the BET surface area is> 0.07 m 2 / g.
  • BET surfaces of 0.25 m 2 / g and above could be achieved.
  • it without a surface-enlarging process, it can also be called "as produced” and means for the person skilled in the art that the metal powder was obtained directly from the process and, in particular, is no longer subjected to a grinding process Milling process form smooth fracture surfaces, which are not found in unmilled powder. According to the invention, only a deagglomeration is preferably provided.
  • the metal powder according to the invention has a metallic purity, i. a content of chromium based on other metals, of> 99.0 Ma%, preferably> 99.5 Ma%, more preferably ⁇ 99.9 Ma%, particularly preferably of> 99.99 Ma%.
  • Metallic purity here means the purity of the metal powder without consideration of non-metallic constituents such as, for example, O, C, N and H.
  • the oxygen content of metal powder according to the invention is preferably not more than 1500 pg / g of chromium, more preferably not more than 1000 pg / g of chromium. In a particularly preferred embodiment, the oxygen content is not more than 500 pg / g of chromium.
  • the achievable carbon content can be set very low and is preferably not more than 1 50 pg / g of chromium, more preferably not more than 100 pg / g of chromium. In a particularly preferred embodiment, the carbon content is not more than 50 pg / g chromium. In one embodiment, it can be provided that the metal powder is granulated.
  • the granulation can be carried out by customary methods, preferably by spray or build-up granulation (see also Powder Metallurgy Science, Randall M. German, MPIF, Princeton, 1994, second edition, pages 183 to 184). Under granules is the merger of individual powder particles to understand that are connected to each other, for example by means of a binder or by Sinterhals Struktur.
  • the metal powder has a bulk density of ⁇ 2.0 g / cm 3 .
  • the bulk density is preferably 0.1 to 2 g / cm 3 , more preferably 0.5 to 1.5 g / cm 3 . Since a comparatively high bulk density is achieved for the achievable particle size or BET surface area (preferably of> 0.05 m 2 / g), the powder has a good filling behavior during the pressing process.
  • the metal powder preferably has a compact density of> 80% of the theoretical density at 550 MPa compacting pressure. This makes it possible to produce components without high sintering shrinkage near net shape
  • the metal powder according to the invention can be prepared by reducing at least one compound of the group consisting of Cr oxide and Cr hydroxide, optionally with a mixed solid carbon source, under at least temporary exposure to hydrogen and hydrocarbon.
  • Preferred chromium oxide or chromium hydroxide are Cr (III) compounds in powder form, for example Cr 2 O 3 , CrOOH, Cr (OH) 3 or mixtures of chromium oxides and chromium hydroxides.
  • the preferred chromium source is Cr 2 O 3 .
  • the Cr 2 O 3 used has at least pigment quality.
  • the compound of the group consisting of Cr oxide and Cr hydroxide, optionally with a mixed solid carbon source, is preferably heated to a temperature T R of 1100 ° C. ⁇ T R ⁇ 1550 ° C. and optionally maintained at this temperature. Temperatures ⁇ 1 100 ° C or> 1550 ° C lead to deteriorated powder properties, or to a more uneconomical process. The reaction proceeds particularly well for industrial purposes when temperatures T R of about 1200 ° C to 1450 ° C are selected.
  • the degree of reduction R is defined as the ratio of the amount of oxygen in the chromium oxide or chromium hydroxide removed up to the time t, based on the total amount of oxygen present in the unreduced chromium compound:
  • the skilled person can easily determine the optimum combination of temperature and time for his furnace (continuous furnace, batch furnace, maximum achievable furnace temperature, etc.).
  • the reaction over substantially at least 30%, more preferably at least 50% of the reaction time is maintained substantially constant (isothermal) on T R.
  • the presence of hydrocarbon ensures that powder having the properties according to the invention is formed via a chemical transport process.
  • the total pressure of the reaction is advantageously 0.95 to 2 bar. Pressures above 2 bar adversely affect the economics of the process. Pressures below 0.95 bar have an adverse effect on the resulting hydrocarbon partial pressure, which in turn has a very unfavorable effect on the transport processes via the gas phase, which are of great importance for adjusting the powder properties of the invention (for example hardness, green strength, specific surface area) are. In addition, pressures below 0.95 bar adversely affect the process costs.
  • the hydrocarbon is present as CH 4 .
  • the hydrocarbon partial pressure is 5 to 500 mbar.
  • a hydrocarbon partial pressure ⁇ 5 mbar has an unfavorable effect on the powder properties, in particular the green strength.
  • a hydrocarbon partial pressure> 500 mbar leads to a high C content in the reduced powder.
  • the residual gas atmosphere is preferably hydrogen.
  • the action of hydrogen and hydrocarbon preferably takes place at least in the temperature range 800 ° C to 1050 ° C. In this temperature range, the hydrocarbon partial pressure is preferably from 5 to 500 mbar.
  • the reaction mixture forming from the starting materials is preferably at least 45 minutes, particularly preferably at least 60 minutes.
  • the hydrocarbon may be added to the reaction in gaseous form, preferably without admixing a solid carbon source.
  • the at least one compound of the group consisting of Cr oxide and Cr hydroxide is preferably reduced under at least temporary action of an H 2 -CH 4 gas mixture.
  • a H 2 / CH 4 volume ratio in the range 1 to 200, particularly advantageously from 1, 5 to 20 is selected.
  • the action of the H 2 -CH 4 gas mixture is preferably carried out at least temporarily during the heating phase to T R , the influence on the formation of the powder form, in particular in the temperature range 850 to 1000 ° C is very low.
  • T R is preferably switched to a pure hydrogen atmosphere, preferably with a dew point of ⁇ -40 ° C (measured in the gas supply). If T R is less than 1200X, switching to the pure hydrogen atmosphere is preferred when T R is reached .
  • the isothermal phase on T R and cooling to room temperature are advantageously carried out in a Wasserstoffatmosphinre. In particular, when cooling, it is advantageous to use hydrogen with a dew point ⁇ -40 ° C to avoid reoxidation.
  • a solid carbon source is admixed with the Cr oxide and / or Cr hydroxide. Preference is given here per mole of oxygen in the chromium compound between 0.75 and 1.25 mol, preferably between 0.90 and 1.05 moles of carbon used. This refers to the amount of carbon available for reaction with the chromium compound. In a particularly preferred embodiment, the ratio of O to C is slightly substoichiometric at about 0.98. It is preferably provided that the solid carbon source is selected from the group of carbon black, activated carbon, graphite, carbon-releasing compounds or mixtures thereof. As an example of a carbon releasing compound, chromium carbides such as Cr 3 C 2 , Cr 7 C 3 and Cr 2 3C 6 may be mentioned.
  • the powder mixture is heated to T R in an H 2 -containing atmosphere.
  • the H 2 pressure is preferably adjusted so that at least in the temperature range 800 ° to 1050 ° C, a CH 4 partial pressure of 5 to 500 mbar results.
  • the isothermal phase on T R and cooling to room temperature are again advantageously carried out in a hydrogen atmosphere. During these process phases, the presence of hydrocarbon is not required. Hydrogen prevents reoxidation processes during this process phase and during the cooling phase.
  • a hydrogen atmosphere with a dew point ⁇ -40 ° C. is preferably used.
  • FIG. 3 shows an SEM image of Cr 2 O 3 (pigment quality).
  • FIG. 6 shows the green strength of powder according to the invention (CP-181) in comparison with aluminothermically produced chromium powder (Cr-Std).
  • FIG. 7 shows the relative compacted density of powder according to the invention in FIG.
  • Figure 8 shows the time course of the reduction of Cr 2 0 3 to Cr at different temperatures according to the invention.
  • FIG. 9 shows the specific surface of various chromium powders according to the invention.
  • Example 1
  • Heating from 1200 ° C to T R and holding on T R was done by adding dry hydrogen with a dew point ⁇ -40 ° C, the pressure being about 1 bar.
  • the furnace cooling was also carried out under H 2 with a dew point ⁇ -40 ° C.
  • a metallic sponge was obtained, which could easily be deagglomerated to a powder.
  • the chromium metal powder thus produced is shown in FIG. The degree of reduction was> 99.0%, the carbon content 80 g / g and the oxygen content 1020 g / g.
  • An X-ray diffraction analysis provided only peaks for cubic body-centered (BCC) chromium metal.
  • the specific surface area was determined by BET method (according to ISO 9277: 1995, measuring range: 0.01-300 m 2 / g, device: Gemini II 2370, annealing temperature: 130 ° C., heating time: 2 hours, adsorptive: nitrogen, volumetric evaluation via five-point determination) and was 0.14 m 2 / g, the bulk density 1.2 g / cm 3 .
  • the nanohardness HIT 0.005 / 5/1/5 was determined according to EN ISO 14577-1 and was 3 GPa.
  • the green strength was determined according to ASTM B 312-09.
  • the compression additive used was 0.6% by mass LICOWAX® Micropowder PM (supplier Clariant, product number 107075, CAS No. 001 10-30-5). At a compacting pressure of 550 MPa, the green strength was 23.8 MPa, at 450 MPa 18.1 MPa, at 300 MPa 8.5 MPa, at 250 MPa 7.2 MPa and at 150 MPa 3.0 MPa.
  • Pigment-grade Cr 2 O 3 (Lanxess Bayoxide CGN-R) with a mean laser diffraction particle size d 50 of 0.9 ⁇ m was well blended with amorphous carbon black (Thermax ultra-pure N908 - Cancarb).
  • the carbon content of the mixture thus prepared was 0.99 mol / mol of O in Cr 2 O 3 . 12500 g of this mixture were in 80 min. to 800 ° C and then in 125 min. heated to 1050 ° C. The heating was carried out under the action of H 2 , wherein the H 2 pressure was adjusted so that in the temperature range 800 ° C to 1050 ° C, the measured mass spectrometry CH 4 partial pressure> 15 mbar amounted to.
  • the green strength was determined according to ASTM B 312-09.
  • the compression additive used was 0.6% by mass LICOWAX® Micropowder PM (supplier Clariant, product number 107075, CAS No. 001 0-30-5).
  • As pressing pressures 550 MPa, 450 MPa, 350 MPa, 250 MPa and 150 MPa were used.
  • FIG. 6 shows the measured fatigue properties in comparison with samples pressed with aluminothermically produced powder (Cr-Std).
  • the powder according to the invention (CP181) shows a green strength which is at least 5 times higher.
  • FIG. 7 shows the relative densities as a function of the compacting pressure in comparison to standard chromium metal powders (E-Cr: produced by electrolyzing, A-Cr: aluminothermically produced) having different particle sizes.
  • the BET specific surface area (ISO 9277: 1995, measuring range: 0.01-300 m 2 / g, apparatus: Gemini II 2370, baking temperature: 130 ° C., heating time: 2 hours, adsorptive: nitrogen, volumetric evaluation over 5-point determination) and the nanohardness ⁇ ⁇ 0.005 / 5/1/5 according to EN ISO 14577-1. Table 1 lists these characteristics and compares them with the properties of electrolytically produced chromium powders. Striking is the significantly lower nanohardness of the powder according to the invention. The particle size calculated from the BET surface area was 8.3 ⁇ m. Powder Type BET surface area 0 C Nanohardness
  • Chromium powder according to the invention 0,10 1064 114 2,92
  • Electrolytically produced chromium powder 0.1 1 736 87 5.32
  • Table 1 Properties of chromium powder according to the invention in comparison with electrolytically produced chromium powder
  • the holding times on T R were 30 min, 60 min, 90 min, 120 min and 180 min. Heating from 1000 ° C to T R and holding on T R was done by supplying dry hydrogen with a dew point ⁇ -40 ° C, the pressure was about 1 bar. The furnace cooling was also carried out under H 2 with a dew point ⁇ -40 ° C. The degree of reduction was determined as set out in the description. As can be seen from FIG. 8, an advantageous degree of reduction of> 95% at 1400 ° C., 1450 ° C. and 1480 ° C. already occurs with a holding time of 30 min. clearly exceeded. At 1350 ° C it takes about 80 min., At 1300 ° C about 160 min.

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Abstract

The invention relates to a metal powder having a chromium content of at least 90 Ma%, characterized by having a nano hardness according to EN ISO 14577-1 of ≤ 4 GPa and/or by a green strength measured according to ASTM B312-09 of at least 7 MPa at a compression pressure of 550 MPa.

Description

CHROMMETALLPULVER  CHROME METAL POWDER
Die vorliegende Erfindung betrifft ein Metallpulver mit einem Chromgehalt von zumindest 90 Ma% sowie ein Verfahren zu dessen Herstellung. Die großtechnische Herstellung von Chrommetallpulver aus Chromoxiden erfolgt derzeit nur durch aluminothermische (Pulvermorphologie siehe Figur 1 ) und elektrolytische (Pulvermorphologie siehe Figuren 2) Verfahren. So hergestellte Pulver weisen jedoch ein schlechtes Press- und Sinterverhalten auf. Zudem sind aufgrund des Einsatzes von Cr(VI)-Verbindungen elektrolytische Verfahren umweltbedenklich. Zunehmend strengere Umweltauflagen führen dazu, dass dieser Prozess wirtschaftlich und umwelttechnisch kaum mehr vertretbar ist. The present invention relates to a metal powder having a chromium content of at least 90% by mass and a process for its production. The large-scale production of chromium metal powder from chromium oxides is currently only by aluminothermic (powder morphology see Figure 1) and electrolytic (powder morphology see Figure 2) method. However, powders produced in this way have a poor pressing and sintering behavior. In addition, due to the use of Cr (VI) compounds electrolytic processes are environmentally harmful. Increasingly stringent environmental regulations mean that this process is hardly acceptable economically and environmentally.
Neben den bereits genannten Verfahren ist auch die Reduktion von Chromoxiden mit Wasserstoff und / oder Kohlenstoff (siehe beispielsweise: „Metallurgy of the Rarer Metals - Chromium"; Arthur Henry Sully; Butterworths Scientific Publications (1954), GB 512,502, JP 54013408 A, JP 07216474 A, JP 3934686 B2 und JP 06081052 A) beschrieben.  In addition to the processes already mentioned, the reduction of chromium oxides with hydrogen and / or carbon (see, for example: "Metallurgy of the Rare Metals - Chromium"; Arthur Henry Sully; Butterworths Scientific Publications (1954), GB 512,502, JP 54013408 A, JP 07216474 A, JP 3934686 B2 and JP 06081052 A).
Bis dato war es jedoch mit den bekannten Verfahren nicht möglich Chrommetallpulver herzustellen, das für anspruchsvolle, pulvermetallurgische Prozesse, zum Beispiel die Herstellung von dünnwandigen Bauteilen oder Bauteilen mit komplexer Form geeignet ist, insbesondere da die Grünfestigkeit bekannter Pulver zu niedrig und deren Härte zu hoch ist.  To date, however, it has not been possible with the known processes to produce chromium metal powder which is suitable for demanding powder metallurgical processes, for example the production of thin-walled components or components with complex shapes, especially since the green strength of known powders is too low and their hardness too high ,
Die vorliegende Erfindung hat es sich daher zur Aufgabe gestellt, Metallpulver mit einem Chromgehalt von zumindest 90 Ma% bereit zu stellen, welches sich gut pulvermetallurgisch, insbesondere durch Pressen und Sintern verarbeiten lässt. Im Besonderen soll ein Metallpulver bereitgestellt werden, mit dem komplex geformte und/oder dünnwandige Bauteile in einfacher Weise pulvermetallurgisch herstellbar sind. Das Metallpulver soll weiters in einem hohen metallischen Reinheitsgrad herstellbar sein, insbesondere einem metallischen Reinheitsgrad vergleichbar oder besser als Metallpulver, das nach elektrolytischem Weg gewonnen wird. Weiters ist es Aufgabe der Erfindung, ein Verfahren bereitzustellen, das für eine großtechnische, kostengünstige und umweltfreundliche Herstellung solcher Metallpulver geeignet ist. The present invention has therefore set itself the task of providing metal powder having a chromium content of at least 90% by mass, which can be processed well powder metallurgy, in particular by pressing and sintering. In particular, a metal powder is to be provided with which complex-shaped and / or thin-walled components can be produced in a simple manner by powder metallurgy. The metal powder should further be produced in a high metallic purity, in particular a metallic purity comparable or better than metal powder, which is obtained by electrolytic route. Furthermore, it is an object of the invention to provide a method which is suitable for large-scale, cost-effective and environmentally friendly production of such metal powder.
Die Aufgabe wird durch Metallpulver mit einem Chromgehalt von zumindest 90 Ma% gelöst, welches durch eine Nanohärte HIT 0,005/5/1/5 gemessen nach EN ISO 14577-1 (Ausgabestand 2002 - Berkovich-Eindringkörper und Auswerteverfahren nach Oliver und Pharr) von < 4 GPa gekennzeichnet ist. Der Härtewert bezieht sich dabei auf ein Metallpulver, das vorzugsweise keiner weiteren Nachbehandlung, wie beispielsweise einer Glühung unterzogen wird. Bevorzugt beträgt die Nanohärte HIT 0,005/5/1/5 ^ 3,7 GPa, besonders bevorzugt < 3,4 GPa. Bei sehr hohen Anforderungen, beispielsweise für sehr dünnwandige Bauteile, bewährt sich eine Nanohärte HIT 0,005/5/1/5 von < 3, 1 GPa. Bei sehr reinem Chrompulver lässt sich eine Nanohärte HIT 0,005/5/1/5 von in etwa 1 ,4 GPa realisieren. Die Nanohärte wird dabei in der reinen Chromphase bestimmt. Liegt keine reine Chromphase vor, wird die Nanohärte in der chromreichsten (Phase mit dem höchsten Chromgehalt) Phase bestimmt. Das erfindungsgemäße Metallpulver besitzt damit eine deutlich niedrigere Nanohärte verglichen mit den Nanohärten von Metallpulver gemäß dem Stand der Technik. Da das erfindungsgemäße Pulver ohne einen nachgelagerten Mahlprozess hergestellt werden kann, kann die angegebene Nanohärte auch bei sehr feinkörnigem Pulver mit einer Oberfläche nach BET von bevorzugt > 0,05 m2/g erzielt werden. Die Angaben zur Oberfläche nach BET im Rahmen dieser Anmeldung beziehen sich auf eine BET-Messung gemäß Norm (ISO 9277: 1995, Messbereich: 0,01 - 300 m2/g; Gerät: Gemini II 2370, Ausheiztemperatur: 130°C, Ausheizzeit: 2 Stunden; Adsorptiv: Stickstoff, volumetrische Auswertung über Fünfpunktbestimmung). The object is achieved by metal powder with a chromium content of at least 90% by mass, which is measured by a nanohardness of 0.005 / 5/1/5 EN ISO 14577-1 (2002 edition - Berkovich indenters and Oliver and Pharr's method) of <4 GPa. The hardness value refers to a metal powder, which is preferably subjected to no further treatment, such as an annealing. The nanohardness HIT is preferably 0.005 / 5/1/5 ^ 3.7 GPa, more preferably <3.4 GPa. For very high requirements, for example for very thin-walled components, a nanohardness HIT 0.005 / 5/1/5 of <3, 1 GPa has proven itself. For very pure chromium powder, a nanohardness of 0.005 / 5/1/5 of about 1.4 GPa can be realized. The nanohardness is determined in the pure chromium phase. If there is no pure chromium phase, the nanohardness is determined in the chromium-rich (phase with the highest chromium content) phase. The metal powder according to the invention thus has a significantly lower nanohardness compared with the nanohards of metal powder according to the prior art. Since the powder according to the invention can be produced without a downstream milling process, the specified nanohardness can be achieved even with very fine-grained powder having a BET surface area of preferably> 0.05 m 2 / g. The information on the BET surface area in the context of this application relates to a BET measurement according to the standard (ISO 9277: 1995, measuring range: 0.01-300 m 2 / g, device: Gemini II 2370, baking temperature: 130 ° C., heating time : 2 hours, adsorptive: nitrogen, volumetric evaluation by five-point determination).
Die Aufgabe wird weiters durch ein Metallpulver mit einem Chromgehalt von zumindest 90 Ma% gelöst, welches durch eine Grünfestigkeit gemessen nach ASTM B 312-09 bei einem Pressdruck von 550 MPa von zumindest 7 MPa, vorzugsweise zumindest 10 MPa, besonders bevorzugt von zumindest 15 MPa, insbesondere besonders bevorzugt von zumindest 20 MPa gekennzeichnet ist. Bei sehr reinem, grobkörnigen Chrompulver mit vergleichsweise hoher BET Oberfläche lassen sich bei einem Pressdruck von 550 MPa Metallpulver mit einer Grünfestigkeit von bis zu ca. 50 MPa realisieren. Die ASTM B 312-09 lässt dabei frei, ob ein Wachs als Presszusatz verwendet wird. Erfindungsgemäß wurde ein Wachs als Presszusatz verwendet und zwar 0,6 Ma% eines Amidwachses, nämlich LICOWAX® Micropowder PM (Lieferant Clariant, Produktnummer 107075, CAS- Nr. 001 10-30-5). The object is further achieved by a metal powder having a chromium content of at least 90% by mass, which is determined by a green strength according to ASTM B 312-09 at a pressure of 550 MPa of at least 7 MPa, preferably at least 10 MPa, more preferably of at least 15 MPa , particularly particularly preferably of at least 20 MPa. In the case of very pure, coarse-grained chromium powder with a comparatively high BET surface area, metal powders having a green strength of up to about 50 MPa can be produced at a pressure of 550 MPa. The ASTM B 312-09 leaves open whether a wax is used as pressing additive. According to the invention, a wax was used as pressing additive, namely 0.6% by mass of an amide wax, namely LICOWAX® Micropowder PM (supplier Clariant, product number 107075, CAS No. 001 10-30-5).
Des Weiteren weist die Grünfestigkeit bevorzugt folgende Werte auf: Zumindest 8 MPa, vorzugsweise zumindest 13 MPa, bei einem Pressdruck von 450 MPa; zumindest 6 MPa, vorzugsweise zumindest 1 1 MPa, bei einem Pressdruck von 300 MPa; zumindest 4 MPa, vorzugsweise zumindest 6 MPa, bei einem Pressdruck von 250 MPa und zumindest 2 MPa, vorzugsweise zumindest 2,5 MPa, bei einem Pressdruck von 150 MPa. Es konnten Grünfestigkeiten bei Pressdrücken von 450, 300 und 250 MPa von 18,5 13,0 und 7,5 MPa und darüber erzielt werden. Das erfindungsgemäße Metallpulver lässt sich in einfacher Weise pulvermetallurgisch, beispielsweise durch Pressen und Sintern verarbeiten. Insbesondere ermöglicht das erfindungsgemäße Metallpulver die einfache und kostengünstige pulvermetallurgische Herstellung von Bauteilen mit dünnwandigen Bereichen, komplexer Form oder vergleichsweise ungünstigem Pressverhältnis. Furthermore, the green strength preferably has the following values: at least 8 MPa, preferably at least 13 MPa, at a compression pressure of 450 MPa; at least 6 MPa, preferably at least 1 1 MPa, at a compression pressure of 300 MPa; at least 4 MPa, preferably at least 6 MPa, at one Compressing pressure of 250 MPa and at least 2 MPa, preferably at least 2.5 MPa, at a pressure of 150 MPa. Green strengths could be achieved at pressures of 450, 300 and 250 MPa of 18.5, 13.0 and 7.5 MPa and above. The metal powder according to the invention can be processed in a simple manner by powder metallurgy, for example by pressing and sintering. In particular, the metal powder according to the invention enables the simple and cost-effective production of powder metallurgy components with thin-walled areas, complex shape or relatively unfavorable pressing ratio.
Die Eigenschaften hinsichtlich Nanohärte und Grünfestigkeit können erzielt werden, wenn der Chromgehalt zumindest 90 Ma% beträgt und damit der Gehalt an sonstigen Stoffen von 10 Ma% nicht überschritten wird. Die sonstigen Stoffe liegen dabei in vorteilhafter Weise separiert von der Chromphase vor. Weiters kann der sonstige Stoff in metallischer oder nichtmetallischer Form, bevorzugt über eine Diffusionsbindung, angelagert sein. Derartige Pulver werden als Composite-Pulver bezeichnet. Anteile (in vorteilhafter Weise < 5 Ma%) des sonstigen Stoffs können auch im Chrom gelöst sein und einen Chrommischkristall bilden. Derartige Pulver werden als legierte Pulver bezeichnet. Das Metallpulver umfasst dann eine reine Chromphase und/oder eine Chrommischkristallphase. The properties with regard to nanohardness and green strength can be achieved if the chromium content is at least 90% by mass and thus the content of other substances of 10% by mass is not exceeded. The other substances are present in an advantageous manner separated from the chromium phase. Furthermore, the other substance can be deposited in metallic or non-metallic form, preferably via a diffusion bond. Such powders are referred to as composite powder. Shares (advantageously <5% by mass) of the other substance can also be dissolved in the chromium and form a chromium mixed crystal. Such powders are referred to as alloyed powders. The metal powder then comprises a pure chromium phase and / or a chromium mixed crystal phase.
Als Legierungsbestandteile können beispielhaft La203 (bis maximal 5 Ma%) oder Cu (bis maximal 10 Ma%) genannt werden, wobei im Falle von La203 La(OH)3 und im Falle von Cu CuO zu Cr203 gemischt und der Reduktion zugeführt werden. Selbstverständlich sind aber auch andere Metalle oder Nichtmetalle möglich. As alloying constituents, by way of example, La 2 O 3 (up to 5 Ma%) or Cu (up to a maximum of 10 Ma%) may be mentioned, in the case of La 2 0 3 La (OH) 3 and in the case of Cu CuO mixed to form Cr 2 O 3 and the reduction are supplied. Of course, other metals or non-metals are possible.
Bevorzugt weist das Metallpulver sowohl eine Grünfestigkeit bei einem Pressdruck von 550 MPa von zumindest 7 MPa, vorzugsweise zumindest 10 MPa, besonders bevorzugt von zumindest 15 MPa, insbesondere besonders bevorzugt von zumindest 20 MPa, als auch eine Nanohärte HIT 0,005/5/1/5 von < 4 GPa, bevorzugt < 3,7 GPa, besonders bevorzugt < 3,4 GPa, insbesondere besonders bevorzugt < 3, 1 GPa auf. The metal powder preferably has both a green strength at a compacting pressure of 550 MPa of at least 7 MPa, preferably at least 10 MPa, more preferably of at least 15 MPa, particularly preferably of at least 20 MPa, and a nano-hardness HIT of 0.005 / 5/1/5 of <4 GPa, preferably <3.7 GPa, more preferably <3.4 GPa, most preferably <3, 1 GPa.
Weiters weist das erfindungsgemäße Metallpulver bevorzugt eine schwammartige TeilchenformZ-morphologie auf (Einteilung der Teilchenform / -morphologie siehe Powder Metallurgy Science; Randall M. German; MPIF; Princeton, 1994, second edition, Seite 63). Dies wirkt sich günstig auf die Grünfestigkeit aus. Furthermore, the metal powder according to the invention preferably has a sponge-like particle shape Z morphology (division of the particle shape / morphology see Powder Metallurgy Science; Randall M. German; MPIF; Princeton, 1994, second edition, page 63). This has a favorable effect on the green strength.
Die Kombination aus schwammartiger Teilchenform/-morphologie und niedriger Härte erlaubt vergleichsweise hohe Pressdichten, aber vor allem eine sehr hohe Grünfestigkeit bei gegebener Dichte. The combination of sponge-like particle shape / morphology and low hardness allows comparatively high densities, but above all a very high green strength at a given density.
In einer bevorzugten Ausführungsvariante ist vorgesehen, dass das Metall pulver eine Oberfläche nach BET ohne oberflächenvergrößernden Vorgang von > 0,05 m2/g aufweist. Vorzugsweise ist die Oberfläche nach BET > 0,07 m2/g. Es konnten Oberflächen nach BET von 0,25 m2/g und darüber erreicht werden. Ohne oberflächenvergrößernden Vorgang kann in diesem Zusammenhang auch heißen„wie hergestellt" und bedeutet für den Fachmann, dass das Metallpulver direkt aus dem Verfahren gewonnen wurde und insbesondere keinem Mahlvorgang mehr unterzogen wird. Ein solcher Mahlvorgang ist an der Morphologie des Metallpulvers erkennbar, da sich beim Mahlvorgang glatte Bruchoberflächen bilden, die bei ungemahlenem Pulver nicht vorzufinden sind. Erfindungsgemäß ist bevorzugt lediglich eine Deagglomeration vorgesehen. In a preferred embodiment, it is provided that the metal powder has a BET surface without surface enlarging process of> 0.05 m 2 / g. Preferably, the BET surface area is> 0.07 m 2 / g. BET surfaces of 0.25 m 2 / g and above could be achieved. In this context, without a surface-enlarging process, it can also be called "as produced" and means for the person skilled in the art that the metal powder was obtained directly from the process and, in particular, is no longer subjected to a grinding process Milling process form smooth fracture surfaces, which are not found in unmilled powder. According to the invention, only a deagglomeration is preferably provided.
In einer Ausführungsvariante ist vorgesehen, dass das erfindungsgemäße Metallpulver eine metallische Reinheit, d.h. einen Gehalt an Chrom bezogen auf andere Metalle, von > 99,0 Ma%, vorzugsweise > 99,5 Ma%, besonders bevorzugt δ 99,9 Ma%, insbesondere bevorzugt von > 99,99 Ma% aufweist. Unter metallischer Reinheit ist dabei die Reinheit des Metallpulvers ohne Berücksichtigung nichtmetallischer Bestandteile wie beispielsweise O, C, N und H zu verstehen. In one embodiment, it is provided that the metal powder according to the invention has a metallic purity, i. a content of chromium based on other metals, of> 99.0 Ma%, preferably> 99.5 Ma%, more preferably δ 99.9 Ma%, particularly preferably of> 99.99 Ma%. Metallic purity here means the purity of the metal powder without consideration of non-metallic constituents such as, for example, O, C, N and H.
Der Sauerstoffgehalt von erfindungsgemäßem Metallpulver beträgt bevorzugt nicht mehr als 1500 pg/g Chrom, besonders bevorzugt nicht mehr als 1000 pg/g Chrom. In einer besonders bevorzugten Ausführungsvariante beträgt der Sauerstoffgehalt nicht mehr als 500 pg/g Chrom. Der erzielbare Kohlenstoffgehalt kann sehr niedrig eingestellt werden und beträgt bevorzugt nicht mehr als 1 50 pg/g Chrom, besonders bevorzugt nicht mehr als 100 pg/g Chrom. In einer besonders bevorzugten Ausführungsvariante beträgt der Kohlenstoffgehalt nicht mehr als 50 pg/g Chrom. In einer Ausführungsvariante kann vorgesehen sein, dass das Metallpulver granuliert ist. Die Granulation kann durch übliche Methoden, vorzugsweise durch Sprüh- oder Aufbaugranulation erfolgen (siehe dazu auch Powder Metallurgy Science; Randall M. German; MPIF; Princeton, 1994, second edition, Seiten 183 bis 184). Unter Granulat ist dabei der Zusammenschluss einzelner Pulverteilchen zu verstehen, die beispielsweise mittels eines Binders oder durch Sinterhalsbildung miteinander verbunden sind. The oxygen content of metal powder according to the invention is preferably not more than 1500 pg / g of chromium, more preferably not more than 1000 pg / g of chromium. In a particularly preferred embodiment, the oxygen content is not more than 500 pg / g of chromium. The achievable carbon content can be set very low and is preferably not more than 1 50 pg / g of chromium, more preferably not more than 100 pg / g of chromium. In a particularly preferred embodiment, the carbon content is not more than 50 pg / g chromium. In one embodiment, it can be provided that the metal powder is granulated. The granulation can be carried out by customary methods, preferably by spray or build-up granulation (see also Powder Metallurgy Science, Randall M. German, MPIF, Princeton, 1994, second edition, pages 183 to 184). Under granules is the merger of individual powder particles to understand that are connected to each other, for example by means of a binder or by Sinterhalsbildung.
In einer Ausführungsvariante weist das Metallpulver eine Schüttdichte von < 2,0 g/cm3 auf. Bevorzugt beträgt die Schüttdichte 0,1 bis 2 g/cm3, besonders bevorzugt 0,5 bis 1 ,5 g/cm3. Da eine für die erzielbare Partikelgröße bzw. BET Oberfläche (bevorzugt von > 0,05 m2/g) vergleichsweise hohe Schüttdichte erreicht wird, weist das Pulver beim Pressvorgang ein gutes Füllverhalten auf. In one embodiment, the metal powder has a bulk density of <2.0 g / cm 3 . The bulk density is preferably 0.1 to 2 g / cm 3 , more preferably 0.5 to 1.5 g / cm 3 . Since a comparatively high bulk density is achieved for the achievable particle size or BET surface area (preferably of> 0.05 m 2 / g), the powder has a good filling behavior during the pressing process.
Des Weiteren weist das Metallpulver bevorzugt eine Pressdichte von > 80 % der theoretischen Dichte bei 550 MPa Pressdruck auf. Damit ist es möglich, Bauteile ohne hohen Sinterschwund endkonturnah zu fertigen Furthermore, the metal powder preferably has a compact density of> 80% of the theoretical density at 550 MPa compacting pressure. This makes it possible to produce components without high sintering shrinkage near net shape
Das erfindungsgemäße Metallpulver lässt sich durch Reduktion zumindest einer Verbindung der Gruppe bestehend aus Cr-Oxid und Cr-Hydroxid, optional mit einer beigemischten festen Kohlenstoffquelle, unter zumindest zeitweiser Einwirkung von Wasserstoff und Kohlenwasserstoff herstellen. Als Chromoxid oder Chromhydroxid kommen bevorzugt Cr(lll)-Verbindungen in Pulverform in Frage, beispielsweise Cr2O3, CrOOH, Cr(OH)3 oder Mischungen aus Chromoxiden und Chromhydroxiden. Die bevorzugte Chromquelle ist Cr2O3. Für einen hohen Reinheitsgrad im Endprodukt ist bevorzugt vorgesehen, dass das verwendete Cr2O3 zumindest Pigmentqualität besitzt. The metal powder according to the invention can be prepared by reducing at least one compound of the group consisting of Cr oxide and Cr hydroxide, optionally with a mixed solid carbon source, under at least temporary exposure to hydrogen and hydrocarbon. Preferred chromium oxide or chromium hydroxide are Cr (III) compounds in powder form, for example Cr 2 O 3 , CrOOH, Cr (OH) 3 or mixtures of chromium oxides and chromium hydroxides. The preferred chromium source is Cr 2 O 3 . For a high degree of purity in the end product, it is preferably provided that the Cr 2 O 3 used has at least pigment quality.
Bevorzugt wird die Verbindung der Gruppe bestehend aus Cr-Oxid und Cr- Hydroxid, optional mit einer beigemischten festen Kohlenstoffquelle, auf eine Temperatur TR mit 1 100°C < TR < 1550°C erhitzt und optional auf dieser Temperatur gehalten. Temperaturen < 1 100°C bzw. > 1550°C führen zu verschlechterten Pulvereigenschaften, bzw. zu einem unwirtschaftlicheren Verfahren. Die Reaktion verläuft für industrielle Zwecke dann besonders gut ab, wenn Temperaturen TR von etwa 1200 °C bis 1450°C gewählt werden. The compound of the group consisting of Cr oxide and Cr hydroxide, optionally with a mixed solid carbon source, is preferably heated to a temperature T R of 1100 ° C. <T R <1550 ° C. and optionally maintained at this temperature. Temperatures <1 100 ° C or> 1550 ° C lead to deteriorated powder properties, or to a more uneconomical process. The reaction proceeds particularly well for industrial purposes when temperatures T R of about 1200 ° C to 1450 ° C are selected.
Während im unteren erfinderischen Temperaturbereich sehr lange Haltezeiten auf TR erforderlich sind, um einen vorteilhaften Reduktionsgrad von 90% einzustellen, kann im oberen erfinderischen Temperaturbereich die Haltezeit sehr kurz gewählt werden oder überhaupt entfallen. Der Reduktionsgrad R ist definiert als das Verhältnis der bis zum Zeitpunkt t im Chromoxid bzw. Chromhydroxid abgebauten Stoffmenge an Sauerstoff, bezogen auf die insgesamt vorhandene Sauerstoffmenge in der unreduzierten Chromverbindung: While in the lower inventive temperature range very long holding times to T R are required to set an advantageous degree of reduction of 90%, in the upper inventive temperature range, the holding time be chosen very short or omitted altogether. The degree of reduction R is defined as the ratio of the amount of oxygen in the chromium oxide or chromium hydroxide removed up to the time t, based on the total amount of oxygen present in the unreduced chromium compound:
%red (Mred> O/Ma O) X l00 % red ( Mred> O / Ma O ) X l00
%red Reduktionsgrad in % % red reduction rate in%
Mred, O Masse [g] O im reduzierten Pulver  Mred, O mass [g] O in the reduced powder
Ma, O _ Masse [g] O im Pulveransatz (vor der Reduktion)  Ma, O _ mass [g] O in powder formulation (before reduction)
Basierend auf den Beispielen kann der Fachmann in einfacher Weise die für seinen Ofen (Durchlaufofen, Batchofen, maximal erreichbare Ofentemperatur, ...) optimale Kombination aus Temperatur und Zeit bestimmen. Bevorzugt wird die Reaktion über zumindest 30%, insbesondere bevorzugt zumindest 50% der Reaktionszeit im Wesentlichen konstant (isotherm) auf TR gehalten. Based on the examples, the skilled person can easily determine the optimum combination of temperature and time for his furnace (continuous furnace, batch furnace, maximum achievable furnace temperature, etc.). Preferably, the reaction over substantially at least 30%, more preferably at least 50% of the reaction time is maintained substantially constant (isothermal) on T R.
Die Anwesenheit von Kohlenwasserstoff gewährleistet, dass über einen chemischen Transportprozess Pulver mit den erfindungsgemäßen Eigenschaften gebildet wird. Der Gesamtdruck der Reaktion beträgt in vorteilhafter Weise 0,95 bis 2 bar. Drücke über 2 bar wirken sich nachteilig auf die Wirtschaftlichkeit des Verfahrens aus. Drücke unter 0,95 bar wirken sich nachteilig auf den sich einstellenden Kohlenwasserstoff-Partialdruck aus, was sich wiederum sehr ungünstig auf die Transportprozesse über die Gasphase auswirkt, die zur Einstellung der erfindungsgemäßen Pulvereigenschaften (zum Beispiel Härte, Grünfestigkeit, spezifische Oberfläche) von großer Bedeutung sind. Zudem wirken sich Drücke unter 0,95 bar nachteilig auf die Prozesskosten aus.  The presence of hydrocarbon ensures that powder having the properties according to the invention is formed via a chemical transport process. The total pressure of the reaction is advantageously 0.95 to 2 bar. Pressures above 2 bar adversely affect the economics of the process. Pressures below 0.95 bar have an adverse effect on the resulting hydrocarbon partial pressure, which in turn has a very unfavorable effect on the transport processes via the gas phase, which are of great importance for adjusting the powder properties of the invention (for example hardness, green strength, specific surface area) are. In addition, pressures below 0.95 bar adversely affect the process costs.
Wie der Kohlenwasserstoff-Partialdruck in einfacher Weise eingestellt werden kann, geht aus den Beispielen hervor. In vorteilhafter Weise liegt der Kohlenwasserstoff als CH4 vor. Bevorzugt beträgt zumindest während des Aufheizvorgangs zumindest zeitweise der Kohlenwasserstoff-Partialdruck 5 bis 500 mbar. Ein Kohlenwasserstoff-Partialdruck < 5 mbar wirkt sich ungünstig auf die Pulvereigenschaften, insbesondere die Grünfestigkeit aus. Ein Kohlenwasserstoff-Partialdruck > 500 mbar führt zu einem hohen C-Gehalt im reduzierten Pulver. Die Restgasatmosphäre ist dabei bevorzugt Wasserstoff. Bevorzugt erfolgt die Einwirkung von Wasserstoff und Kohlenwasserstoff zumindest im Temperaturbereich 800°C bis 1050°C. Bevorzugt beträgt in diesem Temperaturbereich der Kohlenwasserstoff-Partialdruck 5 bis 500 mbar. Die sich aus den Ausgangsstoffen bildende Reaktionsmischung befindet dabei bevorzugt zumindest 45 min., insbesondere bevorzugt zumindest 60 min. in diesem Temperaturbereich. Diese Zeit schließt sowohl den Aufheizvorgang als auch etwaige isotherme Haltephasen in diesem Temperaturbereich ein. Mit den erfinderischen Verfahrensbedingungen ist gewährleistet, dass sich bei Temperaturen bevorzugt < TR zumindest eine Verbindung ausgewählt aus der Gruppe bestehend aus Cr-Oxid und Cr-Hydroxid unter Einwirkung von Wasserstoff und Kohlenwasserstoff zumindest teilweise zu Chromkarbid umsetzt. Bevorzugte Chromkarbide sind Cr3C2, Cr7C3 und Cr23C6. Die sich über den Kohlenwasserstoff-Partialdruck einstellende teilweise Bildung von Chromkarbid wirkt sich wiederum günstig auf die Pulvereigenschaften aus. Mit den erfinderischen Verfahrensbedingungen ist weiters gewährleistet, dass sich das Chromkarbid mit dem in der Reaktionsmischung vorhandenen und/oder zugemischten Cr-Oxid / Cr-Hydroxid zu Cr umsetzt, wobei dieser Prozess bei TR dominiert. How the hydrocarbon partial pressure can be adjusted easily can be seen from the examples. Advantageously, the hydrocarbon is present as CH 4 . Preferably, at least at times during the heating process, the hydrocarbon partial pressure is 5 to 500 mbar. A hydrocarbon partial pressure <5 mbar has an unfavorable effect on the powder properties, in particular the green strength. A hydrocarbon partial pressure> 500 mbar leads to a high C content in the reduced powder. The residual gas atmosphere is preferably hydrogen. The action of hydrogen and hydrocarbon preferably takes place at least in the temperature range 800 ° C to 1050 ° C. In this temperature range, the hydrocarbon partial pressure is preferably from 5 to 500 mbar. The reaction mixture forming from the starting materials is preferably at least 45 minutes, particularly preferably at least 60 minutes. in this temperature range. This time includes both the heating process and any isothermal holding phases in this temperature range. With the inventive process conditions it is ensured that at temperatures preferably <T R at least one compound selected from the group consisting of Cr oxide and Cr hydroxide at least partially converts to chromium carbide under the action of hydrogen and hydrocarbon. Preferred chromium carbides are Cr 3 C 2 , Cr 7 C 3 and Cr 2 3C 6 . The partial formation of chromium carbide, which occurs via the hydrocarbon partial pressure, in turn has a favorable effect on the powder properties. With the inventive process conditions it is further ensured that the chromium carbide reacts with the Cr oxide / Cr hydroxide present in the reaction mixture and / or admixed to form Cr, this process dominating at T R.
Der Kohlenwasserstoff kann der Reaktion gasförmig, bevorzugt ohne Zumischen einer festen Kohlenstoffquelle zugegeben werden. Bevorzugt wird dabei die zumindest eine Verbindung der Gruppe bestehend aus Cr-Oxid und Cr-Hydroxid unter zumindest zeitweiser Einwirkung eines H2-CH4 Gasgemisches reduziert. Vorteilhaft wird ein H2/CH4 Volumenverhältnis im Bereich 1 bis 200, besonders vorteilhaft von 1 ,5 bis 20 gewählt. Die Einwirkung des H2-CH4 Gasgemisches erfolgt dabei bevorzugt zumindest zeitweise während der Aufheizphase auf TR, wobei der Einfluss auf die Ausbildung der Pulverform insbesondere im Temperaturbereich 850 bis 1000°C sehr günstig ist. Wird eine Temperatur von ca. 1200°C erreicht, wird bevorzugt auf eine Rein-Wasserstoffatmosphäre, bevorzugt mit einem Taupunkt von < -40°C (gemessen im Bereich der Gaszufuhr) umgeschaltet. Liegt TR unter 1200X erfolgt das Umschalten auf die Rein-Wasserstoffatmosphäre bevorzugt bei Erreichen von TR. Die isotherme Phase auf TR und Abkühlen auf Raumtemperatur erfolgen vorteilhaft in einer Wasserstoffatmoshäre. Insbesondere beim Abkühlen ist es vorteilhaft, Wasserstoff mit einem Taupunkt < -40°C zu verwenden, um Rückoxidation zu vermeiden. The hydrocarbon may be added to the reaction in gaseous form, preferably without admixing a solid carbon source. The at least one compound of the group consisting of Cr oxide and Cr hydroxide is preferably reduced under at least temporary action of an H 2 -CH 4 gas mixture. Advantageously, a H 2 / CH 4 volume ratio in the range 1 to 200, particularly advantageously from 1, 5 to 20 is selected. The action of the H 2 -CH 4 gas mixture is preferably carried out at least temporarily during the heating phase to T R , the influence on the formation of the powder form, in particular in the temperature range 850 to 1000 ° C is very low. If a temperature of about 1200 ° C is reached, is preferably switched to a pure hydrogen atmosphere, preferably with a dew point of <-40 ° C (measured in the gas supply). If T R is less than 1200X, switching to the pure hydrogen atmosphere is preferred when T R is reached . The isothermal phase on T R and cooling to room temperature are advantageously carried out in a Wasserstoffatmoshäre. In particular, when cooling, it is advantageous to use hydrogen with a dew point <-40 ° C to avoid reoxidation.
In einer Ausführungsvariante wird dem Cr-Oxid und/oder Cr-Hydroxid eine feste Kohlenstoffquelle zugemischt. Bevorzugt wird dabei pro Mol Sauerstoff in der Chromverbindung zwischen 0,75 und 1 ,25 Mol, vorzugsweise zwischen 0,90 und 1 ,05 Mol an Kohlenstoff eingesetzt. Dabei ist die Menge an für die Reaktion mit der Chromverbindung verfügbaren Kohlenstoff gemeint. In einer besonders bevorzugten Ausführungsvariante ist das Verhältnis O zu C mit etwa 0,98 leicht unterstöchiometrisch. Bevorzugt ist vorgesehen, dass die feste Kohlenstoffquelle ausgewählt ist aus der Gruppe Ruß, Aktivkohle, Graphit, kohlenstofffreisetzende Verbindungen oder Mischungen daraus. Als Beispiel für eine kohlenstofffreisetzende Verbindung können Chromkarbide, wie zum Beispiel Cr3C2, Cr7C3 und Cr23C6 genannt werden. Die Pulvermischung wird in einer H2-haltigen Atmosphäre auf TR erhitzt. Der H2-Druck wird dabei bevorzugt so eingestellt, dass sich zumindest im Temperaturbereich 800° bis 1050°C ein CH4-Partialdruck von 5 bis 500 mbar ergibt. Die isotherme Phase auf TR und Abkühlen auf Raumtemperatur erfolgen wiederum vorteilhaft in einer Wasserstoffatmoshäre. Während dieser Prozessphasen ist die Anwesenheit von Kohlenwasserstoff nicht erforderlich. Wasserstoff verhindert während dieser Prozessphase und während der Abkühlphase Rückoxidationsprozesse. Während der Abkühlphase wird bevorzugt eine Wasserstoffatmosphäre mit einem Taupunkt < -40°C eingesetzt. In one embodiment variant, a solid carbon source is admixed with the Cr oxide and / or Cr hydroxide. Preference is given here per mole of oxygen in the chromium compound between 0.75 and 1.25 mol, preferably between 0.90 and 1.05 moles of carbon used. This refers to the amount of carbon available for reaction with the chromium compound. In a particularly preferred embodiment, the ratio of O to C is slightly substoichiometric at about 0.98. It is preferably provided that the solid carbon source is selected from the group of carbon black, activated carbon, graphite, carbon-releasing compounds or mixtures thereof. As an example of a carbon releasing compound, chromium carbides such as Cr 3 C 2 , Cr 7 C 3 and Cr 2 3C 6 may be mentioned. The powder mixture is heated to T R in an H 2 -containing atmosphere. The H 2 pressure is preferably adjusted so that at least in the temperature range 800 ° to 1050 ° C, a CH 4 partial pressure of 5 to 500 mbar results. The isothermal phase on T R and cooling to room temperature are again advantageously carried out in a hydrogen atmosphere. During these process phases, the presence of hydrocarbon is not required. Hydrogen prevents reoxidation processes during this process phase and during the cooling phase. During the cooling phase, a hydrogen atmosphere with a dew point <-40 ° C. is preferably used.
Weitere Vorteile und Details der Erfindung werden nachfolgend anhand von Beispielen und von Figuren erläutert. Further advantages and details of the invention are explained below with reference to examples and figures.
Figur 3 zeigt eine REM Aufnahme von Cr203 (Pigmentqualität). FIG. 3 shows an SEM image of Cr 2 O 3 (pigment quality).
Figur 4;5a,b zeigen REM Aufnahmen von nach dem erfindungsgemäßen  4, 5a, b show SEM images of the invention
Verfahren erhältlichen Metallpul  Method available metal powder
Figur 6 zeigt die Grünfestigkeit von erfindungsgemäßem Pulver (CP-181 ) im Vergleich zu aluminothermisch hergestelltem Chrompulver (Cr-Std).  FIG. 6 shows the green strength of powder according to the invention (CP-181) in comparison with aluminothermically produced chromium powder (Cr-Std).
Figur 7 zeigt die relative Pressdichte von Pulver gemäß Erfindung im  FIG. 7 shows the relative compacted density of powder according to the invention in FIG
Vergleich zu aluminothermisch (A-Cr) und elektrolytisch (E-Cr) hergestelltem Cr unterschiedlicher Reinheit (Angabe in Gew.%) und Pulverpartikelgröße.  Compared to aluminothermic (A-Cr) and electrolytic (E-Cr) produced Cr of different purity (in wt.%) And powder particle size.
Figur 8 zeigt den zeitlichen Verlauf der Reduktion von Cr203 zu Cr bei unterschiedlichen Temperaturen gemäß Erfindung. Figure 8 shows the time course of the reduction of Cr 2 0 3 to Cr at different temperatures according to the invention.
Figur 9 zeigt die spezifische Oberfläche von verschiedenen Chrompulvern gemäß Erfindung. Beispiel 1 : FIG. 9 shows the specific surface of various chromium powders according to the invention. Example 1 :
500 g Cr203 in Pigmentqualität (Lanxess Bayoxide CGN-R) mit einer mittleren, mittels Laserbeugung gemessenen Teilchengröße d50 von 0,9 μηι (Pulvermorphologie siehe Figur 3) wurde in H2(75vol.%)-CH4(25vol.%) (Durchflussrate 150 l/h, Druck ca. 1 bar) in 80 min. auf 800°C erhitzt. In weiterer Folge wurde die Reaktionsmischung langsam auf 1200X erhitzt, wobei sich die Reaktionsmischung 325 min. im Temperaturbereich 800 bis 1200°C befand. Danach wurde die Reaktionsmischung in 20 min. auf TR erhitzt mit TR= 1400°C. Die Haltezeit auf 1400°C betrug 180 min. Aufheizen von 1200°C auf TR und Halten auf TR erfolgten unter Zufuhr von trockenem Wasserstoff mit einem Taupunkt < -40°C, wobei der Druck ca. 1 bar betrug. Die Ofenabkühlung erfolgte ebenfalls unter H2 mit einem Taupunkt < -40°C. Es wurde ein metallischer Schwamm erhalten, der sehr leicht zu einem Pulver deagglomeriert werden konnte. Das so hergestellte Chrommetall-Pulver ist in Figur 4 wiedergeben. Der Reduktionsgrad betrug > 99,0 %, der Kohlenstoffgehalt 80 g/g und der Sauerstoffgehalt 1020 g/g. Eine Röntgenbeugungsanalyse lieferte nur Peaks für kubisch raumzentriertes (BCC) Chrommetall. Die spezifische Oberfläche wurde mittels BET-Verfahren (gemäß ISO 9277:1995, Messbereich: 0,01 - 300 m2/g; Gerät: Gemini II 2370, Ausheiztemperatur: 130°C, Ausheizzeit: 2 Stunden; Adsorptiv: Stickstoff, volumetrische Auswertung über Fünfpunktbestimmung) bestimmt und betrug 0,14 m2/g, die Schüttdichte 1 ,2 g/cm3. Die Nanohärte HIT 0.005/5/1/5 wurde nach EN ISO 14577-1 bestimmt und betrug 3 GPa. Die Grünfestigkeit wurde nach ASTM B 312-09 bestimmt. Als Presszusatz wurde 0,6 Ma% LICOWAX® Micropowder PM (Lieferant Clariant, Produktnummer 107075, CAS- Nr. 001 10-30-5) verwendet. Bei einem Pressdruck von 550 MPa betrug die Grünfestigkeit 23,8 MPa, bei 450 MPa 18,1 MPa, bei 300 MPa 8,5 MPa, bei 250 MPa 7,2 MPa und bei 150 MPa 3,0 MPa. 500 g of Cr 2 0 3 in pigment grade (Lanxess Bayoxide CGN-R) with a mean measured by laser diffraction particle size d 50 of 0.9 μηι (powder morphology see Figure 3) in H 2 (75vol.%) - CH 4 (25vol %) (Flow rate 150 l / h, pressure approx. 1 bar) in 80 min. heated to 800 ° C. Subsequently, the reaction mixture was slowly heated to 1200X, the reaction mixture being left for 325 min. in the temperature range 800 to 1200 ° C was. Thereafter, the reaction mixture was in 20 min. T R heated with T R = 1400 ° C. The holding time to 1400 ° C was 180 min. Heating from 1200 ° C to T R and holding on T R was done by adding dry hydrogen with a dew point <-40 ° C, the pressure being about 1 bar. The furnace cooling was also carried out under H 2 with a dew point <-40 ° C. A metallic sponge was obtained, which could easily be deagglomerated to a powder. The chromium metal powder thus produced is shown in FIG. The degree of reduction was> 99.0%, the carbon content 80 g / g and the oxygen content 1020 g / g. An X-ray diffraction analysis provided only peaks for cubic body-centered (BCC) chromium metal. The specific surface area was determined by BET method (according to ISO 9277: 1995, measuring range: 0.01-300 m 2 / g, device: Gemini II 2370, annealing temperature: 130 ° C., heating time: 2 hours, adsorptive: nitrogen, volumetric evaluation via five-point determination) and was 0.14 m 2 / g, the bulk density 1.2 g / cm 3 . The nanohardness HIT 0.005 / 5/1/5 was determined according to EN ISO 14577-1 and was 3 GPa. The green strength was determined according to ASTM B 312-09. The compression additive used was 0.6% by mass LICOWAX® Micropowder PM (supplier Clariant, product number 107075, CAS No. 001 10-30-5). At a compacting pressure of 550 MPa, the green strength was 23.8 MPa, at 450 MPa 18.1 MPa, at 300 MPa 8.5 MPa, at 250 MPa 7.2 MPa and at 150 MPa 3.0 MPa.
Beispiel 2: Example 2:
Cr2O3 in Pigmentqualität (Lanxess Bayoxide CGN-R) mit einer mittleren, mittels Laserbeugung gemessenen Teilchengröße d50 von 0,9 μηη wurde mit amorphem Ruß (Thermax ultra-pure N908 - Cancarb) gut vermengt. Der Kohlenstoffgehalt der so hergestellten Mischung betrug 0,99 Mol / Mol O in Cr2O3. 12500 g dieser Mischung wurden in 80 min. auf 800°C und danach in 125 min. auf 1050°C erhitzt. Das Aufheizen erfolgte unter Einwirkung von H2, wobei der H2-Druck so eingestellt wurde, dass im Temperaturbereich 800°C bis 1050°C der massenspektrometrisch gemessene CH4-Partialdruck > 15 mbar betrug. Der Gesamtdruck betrug dabei 1 , 1 bar. Danach wurde die Reaktionsmischung in 20 min. auf TR erhitzt mit TR= 1200°C. Die Haltezeit auf 1200X betrug 540 min. Aufheizen von 1000°C auf TR und Halten auf TR erfolgten unter Zufuhr von trockenem Wasserstoff mit einem Taupunkt < -40°C, wobei der Druck ca. 1 bar betrug. Die Ofenabkühlung erfolgte ebenfalls unter H2 mit einem Taupunkt < -40°C. Es wurde ein metallischer Schwamm erhalten, der sehr leicht zu einem Pulver deagglomeriert werden konnte. Das so hergestellte Chrommetall-Pulver ist in den Figuren 5 a,b wiedergeben. Der Kohlenstoff- und Sauerstoffgehalt sind in Tabelle 1 wiedergegeben. Die Röntgenbeugungsanalyse lieferte nur Peaks für kubisch raumzentriertes (BCC) Chrommetall. Die Grünfestigkeit wurde nach ASTM B 312-09 bestimmt. Als Presszusatz wurde 0,6 Ma% LICOWAX® Micropowder PM (Lieferant Clariant, Produktnummer 107075, CAS- Nr. 001 0-30-5) verwendet. Als Pressdrücke kamen dabei 550 MPa, 450 MPa, 350 MPa, 250 MPa und 150 MPa zur Anwendung. Figur 6 zeigt die gemessenen G rü nf estig keitswe rte im Vergleich zu Proben, die mit aluminothermisch hergestelltem Pulver (Cr-Std) gepresst wurden. Das erfindungsgemäße Pulver (CP181 ) zeigt dabei eine um das zumindest 5-fache höhere Grünfestigkeit. Pigment-grade Cr 2 O 3 (Lanxess Bayoxide CGN-R) with a mean laser diffraction particle size d 50 of 0.9 μm was well blended with amorphous carbon black (Thermax ultra-pure N908 - Cancarb). The carbon content of the mixture thus prepared was 0.99 mol / mol of O in Cr 2 O 3 . 12500 g of this mixture were in 80 min. to 800 ° C and then in 125 min. heated to 1050 ° C. The heating was carried out under the action of H 2 , wherein the H 2 pressure was adjusted so that in the temperature range 800 ° C to 1050 ° C, the measured mass spectrometry CH 4 partial pressure> 15 mbar amounted to. The total pressure was 1, 1 bar. Thereafter, the reaction mixture was in 20 min. T R heated with T R = 1200 ° C. The hold time at 1200X was 540 min. Heating from 1000 ° C to T R and holding on T R was done by supplying dry hydrogen with a dew point <-40 ° C, the pressure was about 1 bar. The furnace cooling was also carried out under H 2 with a dew point <-40 ° C. A metallic sponge was obtained, which could easily be deagglomerated to a powder. The chromium metal powder produced in this way is shown in FIGS. 5 a, b. The carbon and oxygen contents are given in Table 1. X-ray diffraction analysis only yielded peaks for cubic body-centered (BCC) chromium metal. The green strength was determined according to ASTM B 312-09. The compression additive used was 0.6% by mass LICOWAX® Micropowder PM (supplier Clariant, product number 107075, CAS No. 001 0-30-5). As pressing pressures 550 MPa, 450 MPa, 350 MPa, 250 MPa and 150 MPa were used. FIG. 6 shows the measured fatigue properties in comparison with samples pressed with aluminothermically produced powder (Cr-Std). The powder according to the invention (CP181) shows a green strength which is at least 5 times higher.
Der Pulveransatz (mit 0,6 Ma% LICOWAX® Micropowder PM Presszusatz) wurde weiters bei verschiedenen Drücken zu pillenförmigen Proben gepresst. In Figur 7 sind die relativen Pressdichten in Abhängigkeit vom Pressdruck im Vergleich zu Standard-Chrom-Metallpulver (E-Cr: elektrolytisch hergestellt; A- Cr: aluminothermisch hergestellt) mit unterschiedlichen Partikelgrößen dargestellt.  The powder formulation (with 0.6 Ma% LICOWAX® Micropowder PM Press Additive) was further pressed at various pressures into pill-shaped samples. FIG. 7 shows the relative densities as a function of the compacting pressure in comparison to standard chromium metal powders (E-Cr: produced by electrolyzing, A-Cr: aluminothermically produced) having different particle sizes.
Des Weiteren wurden die spezifische Oberfläche nach BET (ISO 9277:1995, Messbereich: 0,01 - 300 m2/g; Gerät: Gemini II 2370, Ausheiztemperatur: 130°C, Ausheizzeit: 2 Stunden; Adsorptiv: Stickstoff, volumetrische Auswertung über Fünfpunktbestimmung) und die Nanohärte Ηιτ 0,005/5/1/5 nach EN ISO 14577-1 bestimmt. In Tabelle 1 sind diese Merkmale aufgelistet und den Eigenschaften von auf elektrolytischem Weg hergestellten Chrompulver gegenübergestellt. Auffallend ist die deutlich niedrigere Nanohärte des erfindungsgemäßen Pulvers. Die aus der BET-Oberfläche berechnete Partikelgröße betrug 8,3 pm. Pulver Typ BET-Oberfläche 0 C Nanohärte Furthermore, the BET specific surface area (ISO 9277: 1995, measuring range: 0.01-300 m 2 / g, apparatus: Gemini II 2370, baking temperature: 130 ° C., heating time: 2 hours, adsorptive: nitrogen, volumetric evaluation over 5-point determination) and the nanohardness Η ιτ 0.005 / 5/1/5 according to EN ISO 14577-1. Table 1 lists these characteristics and compares them with the properties of electrolytically produced chromium powders. Striking is the significantly lower nanohardness of the powder according to the invention. The particle size calculated from the BET surface area was 8.3 μm. Powder Type BET surface area 0 C Nanohardness
[m2/g] [pg/g] [pg/g] [GPal[m 2 / g] [pg / g] [pg / g] [GPal
Erfindungsgemäßes Chrom-Pulver 0,10 1064 114 2,92 Chromium powder according to the invention 0,10 1064 114 2,92
(Beispiel 2) (Example 2)
Elektrolytisch hergestelltes Chrompulver, 0,1 1 736 87 5,32  Electrolytically produced chromium powder, 0.1 1 736 87 5.32
Partikelgröße < 45 μιτι Particle size <45 μιτι
Tabelle 1 : Eigenschaften von erfindungsgemäßem Chrompulver im Vergleich zu elektrolytisch hergestelltem Chrompulver Table 1: Properties of chromium powder according to the invention in comparison with electrolytically produced chromium powder
Beispiel 3: Example 3:
Jeweils 20 g einer Mischung gemäß Beispiel 2 wurden in einem Molybdän- Tiegel in 80 min. auf 800°C und danach in 125 min. auf 1050°C erhitzt. Das Aufheizen erfolgte unter Einwirkung vo H2, wobei der H2-Druck so eingestellt wurde, dass im Temperaturbereich 800°C bis 1050°C der massenspektrometrisch gemessene CH4-Partialdruck > 15 mbar betrug. Der Gesamtdruck betrug dabei 1 ,1 bar. Danach wurde die Reaktionsmischung mit einer Aufheizgeschwindigkeit von 10 K/min auf TR erhitzt. Als TR kamen dabei 1 150°C, 1250°C, 1300X, 1350°C, 1400°C, 1450°C und 1480°C zur Anwendung. Die Haltezeiten auf TR betrugen 30 min, 60 min, 90 min, 120 min und 180 min. Aufheizen von 1000°C auf TR und Halten auf TR erfolgten unter Zufuhr von trockenem Wasserstoff mit einem Taupunkt < -40°C, wobei der Druck ca. 1 bar betrug. Die Ofenabkühlung erfolgte ebenfalls unter H2 mit einem Taupunkt < -40°C. Der Reduktionsgrad wurde wie in der Beschreibung dargelegt bestimmt. Wie aus Figur 8 ersichtlich ist, wird ein vorteilhafter Reduktionsgrad von > 95% bei 1400°C, 1450°C und 1480°C bereits bei einer Haltezeit von 30 min. deutlich überschritten. Bei 1350°C bedarf es dazu ca. 80 min., bei 1300°C ca. 160 min. Bei 1250°C und 1 150°C bedarf es dazu in etwa 260 min. bzw. 350 min. (extrapolierte Werte). REM-Untersuchungen zeigten, dass die so hergestellten Pulver eine schwammartige Morphologie verbunden mit einer sehr hohen BET Oberfläche (siehe Figur 9) aufweisen. In each case 20 g of a mixture according to Example 2 were in a molybdenum crucible in 80 min. to 800 ° C and then in 125 min. heated to 1050 ° C. The heating was carried out under the action of H 2 , wherein the H 2 pressure was adjusted so that in the temperature range 800 ° C to 1050 ° C, the measured mass spectrometry CH 4 partial pressure> 15 mbar. The total pressure was 1, 1 bar. Thereafter, the reaction mixture was heated to T R at a heating rate of 10 K / min. The T R used were 1 150 ° C, 1250 ° C, 1300X, 1350 ° C, 1400 ° C, 1450 ° C and 1480 ° C. The holding times on T R were 30 min, 60 min, 90 min, 120 min and 180 min. Heating from 1000 ° C to T R and holding on T R was done by supplying dry hydrogen with a dew point <-40 ° C, the pressure was about 1 bar. The furnace cooling was also carried out under H 2 with a dew point <-40 ° C. The degree of reduction was determined as set out in the description. As can be seen from FIG. 8, an advantageous degree of reduction of> 95% at 1400 ° C., 1450 ° C. and 1480 ° C. already occurs with a holding time of 30 min. clearly exceeded. At 1350 ° C it takes about 80 min., At 1300 ° C about 160 min. At 1250 ° C and 1 150 ° C it takes about 260 min. or 350 min. (extrapolated values). SEM investigations showed that the powders thus produced have a sponge-like morphology associated with a very high BET surface area (see FIG. 9).

Claims

Patentansprüche  claims
1. Metallpulver mit einem Chromgehalt von zumindest 90 Ma%, 1. metal powder having a chromium content of at least 90% by mass,
gekennzeichnet durch eine Nanohärte HIT 0,005/5/1/5 nach  characterized by a nanohardness of HIT 0.005 / 5/1/5
EN ISO 14577-1 von < 4 GPa.  EN ISO 14577-1 of <4 GPa.
2. Metallpulver mit einem Chromgehalt von zumindest 90 Ma%, 2. metal powder with a chromium content of at least 90% by mass,
gekennzeichnet durch eine Grünfestigkeit gemessen nach  characterized by a green strength measured according to
ASTM B312-09 von zumindest 7 MPa bei einem Pressdruck von  ASTM B312-09 of at least 7 MPa at a pressure of
550 MPa.  550 MPa.
Metallpulver nach Anspruch 1 , gekennzeichnet durch eine Grünfestigkeit gemessen nach ASTM B312-09 von zumindest 7 MPa bei einem Metal powder according to claim 1, characterized by a green strength measured according to ASTM B312-09 of at least 7 MPa in one
Pressdruck von 550 MPa.  Pressing pressure of 550 MPa.
Metallpulver nach Anspruch 2, gekennzeichnet durch eine Metal powder according to claim 2, characterized by a
Nanohärte HIT 0,005/5/1/5 nach EN ISO 14577-1 von < 4 GPa.  Nanohardness HIT 0.005 / 5/1/5 according to EN ISO 14577-1 of <4 GPa.
Metallpulver nach einem der Ansprüche 1 bis 4, gekennzeichnet durch eine Grünfestigkeit gemessen nach ASTM B312-09 von zumindest 5 MPa bei einem Pressdruck von 550 MPa. Metal powder according to one of claims 1 to 4, characterized by a green strength measured according to ASTM B312-09 of at least 5 MPa at a pressure of 550 MPa.
Metallpulver nach einem der Ansprüche 1 bis 5, dadurch Metal powder according to one of claims 1 to 5, characterized
gekennzeichnet, dass das Metallpulver Chrompulver mit einer metallischen Reinheit > 99,0 Ma% ist.  characterized in that the metal powder is chromium powder with a metallic purity> 99.0 Ma%.
Metallpulver nach einem der Ansprüche 1 bis 6, dadurch Metal powder according to one of claims 1 to 6, characterized
gekennzeichnet, dass das Metallpulver als legiertes Pulver oder  characterized in that the metal powder as an alloyed powder or
Composite-Pulver vorliegt.  Composite powder is present.
8. Metallpulver nach einem der Ansprüche 1 bis 7, dadurch 8. metal powder according to one of claims 1 to 7, characterized
gekennzeichnet, dass das Metallpulver granuliert ist.  characterized in that the metal powder is granulated.
9. Metallpulver nach einem der Ansprüche 1 bis 8, gekennzeichnet durch eine Oberfläche nach BET, vorzugsweise ohne Oberflächenvergrößernden Vorgang, von > 0,05 m2/g. 9. Metal powder according to one of claims 1 to 8, characterized by a surface according to BET, preferably without Oberflächenvergrößernden process, of> 0.05 m 2 / g.
10. Metallpulver nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass die Pressdichte bei einem Pressdruck von 10. Metal powder according to one of claims 1 to 9, characterized in that the press density at a pressure of
550 MPa bei > 80 % der theoretischen Dichte liegt.  550 MPa is> 80% of the theoretical density.
1 . Verfahren zur Herstellung eines Metallpulvers nach einem der Ansprüche 1 bis 10 durch Reduktion zumindest einer Verbindung der Gruppe bestehend aus Cr-Oxid und Cr-Hydroxid, optional mit einer 1 . A process for producing a metal powder according to any one of claims 1 to 10 by reducing at least one compound of the group consisting of Cr oxide and Cr hydroxide, optionally with a
beigemischten festen Kohlenstoffquelle, unter zumindest zeitweiser Einwirkung von Wasserstoff und Kohlenwasserstoff. 12. Verfahren nach Anspruch 1 1 , dadurch gekennzeichnet, dass die  admixed solid carbon source, under at least temporary exposure to hydrogen and hydrocarbon. 12. The method according to claim 1 1, characterized in that the
Verbindung der Gruppe bestehend aus Cr-Oxid und Cr-Hydroxid, optional mit einer beigemischten festen Kohlenstoffquelle, auf eine Temperatur TR mit 1 100°C < TR < 1550°C erhitzt und optional auf dieser Temperatur gehalten wird, wobei zumindest während des Compound of the group consisting of Cr oxide and Cr hydroxide, optionally mixed with a solid carbon source, to a temperature T R at 1 100 ° C <T R <1550 ° C and optionally maintained at this temperature, wherein at least during the
Aufheizvorgangs zumindest zeitweise der Kohlenwasserstoff-Partialdruck Heating at least temporarily, the hydrocarbon partial pressure
5 bis 500 mbar beträgt. 5 to 500 mbar.
13. Verfahren nach Anspruch 1 1 oder 12, dadurch gekennzeichnet, dass die Einwirkung von Wasserstoff und Kohlenwasserstoff zumindest im 13. The method of claim 1 1 or 12, characterized in that the action of hydrogen and hydrocarbon at least in
Temperaturbereich 800 bis 1050°C erfolgt.  Temperature range 800 to 1050 ° C takes place.
14. Verfahren nach Anspruch 13, dadurch gekennzeichnet, dass zumindest im Temperaturbereich 800 bis 1050°C der Kohlenwasserstoff- Partialdruck 5 bis 500 mbar beträgt. 14. The method according to claim 13, characterized in that at least in the temperature range 800 to 1050 ° C, the hydrocarbon partial pressure is 5 to 500 mbar.
15. Verfahren nach einem der Ansprüche 12 bis 14, dadurch 15. The method according to any one of claims 12 to 14, characterized
gekennzeichnet, dass die Summe aus Aufheiz- und Haltezeit im  characterized in that the sum of heating and holding time in
Temperaturbereich 800°C bis 1050°C zumindest 45 min. beträgt. 16. Verfahren nach einem der Ansprüche 1 1 bis 15, dadurch  Temperature range 800 ° C to 1050 ° C at least 45 min. is. 16. The method according to any one of claims 1 1 to 15, characterized
gekennzeichnet, dass der Gesamtdruck 0,95 bis 2 bar beträgt.  characterized in that the total pressure is 0.95 to 2 bar.
17. Verfahren nach einem der Ansprüche 1 1 bis 16, dadurch 17. The method according to any one of claims 1 1 to 16, characterized
gekennzeichnet, dass die Verbindung der Gruppe bestehend aus Cr- Oxid und Cr-Hydroxid unter zumindest zeitweiser Einwirkung eines H2-in that the compound of the group consisting of Cr oxide and Cr hydroxide is at least temporarily exposed to an H 2
CH4 Gasgemisches reduziert wird. CH 4 gas mixture is reduced.
18. Verfahren nach Anspruch 17, dadurch gekennzeichnet, dass das H2/CH4 Volumenverhältnis 1 bis 200, insbesondere 1 ,5 bis 20 beträgt. 18. The method according to claim 17, characterized in that the H 2 / CH 4 volume ratio is 1 to 200, in particular 1, 5 to 20.
19. Verfahren nach einem der Ansprüche 1 1 bis 18, dadurch 19. The method according to any one of claims 1 1 to 18, characterized
gekennzeichnet, dass eine feste Kohlenstoffquelle beigemischt wird, die zumindest eine Komponente ist, ausgewählt aus der Gruppe bestehend aus Ruß, Aktivkohle, Graphit, kohlenstofffreisetzende Verbindung und Mischungen daraus.  characterized in that a solid carbon source is added which is at least one component selected from the group consisting of carbon black, activated carbon, graphite, carbon releasing compound and mixtures thereof.
20. Verfahren nach Anspruch 19, dadurch gekennzeichnet, dass pro Mol Sauerstoff im Chromoxid oder Chromhydroxid zwischen 0,75 und 1 ,25 Mol, vorzugsweise zwischen 0,90 und 1 ,05 Mol, an Kohlenstoff eingesetzt werden. 20. The method according to claim 19, characterized in that per mole of oxygen in the chromium oxide or chromium hydroxide between 0.75 and 1, 25 mol, preferably between 0.90 and 1, 05 mol, are used in carbon.
21. Verfahren nach einem der Ansprüche 1 1 bis 20, dadurch 21. The method according to any one of claims 1 1 to 20, characterized
gekennzeichnet, dass sich zumindest eine Verbindung ausgewählt aus der Gruppe bestehend aus Cr-Oxid und Cr-Hydroxid unter Einwirkung von Wasserstoff und Kohlenwasserstoff zumindest teilweise zu einem Chromkarbid ausgewählt aus der Gruppe bestehend aus Cr3C2, Cr7C3 und Cr23C6 umsetzt. characterized in that at least one compound selected from the group consisting of Cr oxide and Cr hydroxide under the action of hydrogen and hydrocarbon at least partially to a chromium carbide selected from the group consisting of Cr 3 C 2 , Cr 7 C 3 and Cr 2 3C 6 implements.
22. Verfahren nach Anspruch 21 , dadurch gekennzeichnet, dass sich das Chromkarbid mit zumindest einer Verbindung ausgewählt aus der Gruppe bestehend aus Cr-Oxid und Cr-Hydroxid zumindest teilweise zu Cr umsetzt. 22. The method according to claim 21, characterized in that the chromium carbide with at least one compound selected from the group consisting of Cr oxide and Cr hydroxide at least partially converts to Cr.
23. Verfahren nach einem der Ansprüche 1 1 bis 22, dadurch 23. The method according to any one of claims 1 1 to 22, characterized
gekennzeichnet, dass der Kohlenwasserstoff CH4 ist. characterized in that the hydrocarbon is CH 4 .
EP14789128.7A 2013-09-02 2014-08-19 Chromium metal powder Active EP3041631B1 (en)

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WO2015089534A2 (en) * 2013-12-20 2015-06-25 Plansee Se Coating material
CN111886088B (en) * 2018-03-23 2023-01-17 株式会社村田制作所 Iron alloy particles and method for producing iron alloy particles
CN111922350B (en) * 2020-09-22 2021-01-01 西安斯瑞先进铜合金科技有限公司 Preparation method of low-hydrochloric-acid-insoluble metal chromium powder
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